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The first issue is scheduled to be published in Dec. 2018.
Call for Papers
CCS Chemistry is the flagship general journal for the cutting edge and fundamental research in the areas of chemica research facing global audiences published by Chinese Chemical Society. We call for excellent papers cover but not limited to synthetic chemistry, catalysis & surface chemistry, chemical theory and mechanism, chemical metrology, materials & energy chemistry, environmental chemistry, chemical biology, chemical engineering and industrial chemistry. Professional arrangement ensures that all papers can be reviewed and published online quickly and efficiently (one or two weeks).
Contact information:
Dr. Hao Linxiao, haolinxiao@iccas.ac.cn; +86-10-82449177-888
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2025, 36(6): 109741
doi: 10.1016/j.cclet.2024.109741
Abstract:
Achieving high energy densities for all-solid-state lithium batteries is restricted by the poor high voltage stability of solid electrolytes. Herein, F-doping strategy is successfully employed on Li3InCl6 to obtain enhanced voltage stability and electrode compatability towards bare LiNi0.7Mn0.2Co0.1O2 at high voltages. The optimized Li3InCl5.5F0.5 electrolyte exhibits a decreased conductivity of 1.00 mS/cm, a wider voltage window, and improved electrochemical performance in solid-state batteries when cycled at upper cut-off voltages of 4.5 and 4.8 V (vs. Li+/Li0). The generation of more stable LiInF4 phase in the cathode mixture of Li3InCl5.5F0.5-based battery ensures superior electrochemical performances compared to the Li3InCl6-based battery. The former battery exhibits a higher discharge capacity of 218.9 mAh/g and coulombic efficiency of 86.7% for the first cycle, and retains 80.0% of its original value after 100 cycles when cycled in the range of 3.0–4.5 V (vs. Li+/Li0). In contrast, the Li3InCl6-based battery exhibits lower capacities and faster degradation under the same conditions due to the formation of InCl3 phase with poor electrochemical stability. This work facilitates the advancement of high energy density solid-state battery technologies by utilizing high-voltage cathodes.
Achieving high energy densities for all-solid-state lithium batteries is restricted by the poor high voltage stability of solid electrolytes. Herein, F-doping strategy is successfully employed on Li3InCl6 to obtain enhanced voltage stability and electrode compatability towards bare LiNi0.7Mn0.2Co0.1O2 at high voltages. The optimized Li3InCl5.5F0.5 electrolyte exhibits a decreased conductivity of 1.00 mS/cm, a wider voltage window, and improved electrochemical performance in solid-state batteries when cycled at upper cut-off voltages of 4.5 and 4.8 V (vs. Li+/Li0). The generation of more stable LiInF4 phase in the cathode mixture of Li3InCl5.5F0.5-based battery ensures superior electrochemical performances compared to the Li3InCl6-based battery. The former battery exhibits a higher discharge capacity of 218.9 mAh/g and coulombic efficiency of 86.7% for the first cycle, and retains 80.0% of its original value after 100 cycles when cycled in the range of 3.0–4.5 V (vs. Li+/Li0). In contrast, the Li3InCl6-based battery exhibits lower capacities and faster degradation under the same conditions due to the formation of InCl3 phase with poor electrochemical stability. This work facilitates the advancement of high energy density solid-state battery technologies by utilizing high-voltage cathodes.
2025, 36(6): 109772
doi: 10.1016/j.cclet.2024.109772
Abstract:
Conductive hydrogel membranes with nanofluids channels represent one of the most promising capacitive electrodes due to their rapid kinetics of ion transport. The construction of these unique structures always requires new self-assembly behaviors with different building blocks, intriguing phenomena of colloidal chemistry. In this work, by delicately balancing the electrostatic repulsions between 2D inorganic nanosheets and the electrostatic adsorption with cations, we develop a general strategy to fabricate stable free-standing 1T molybdenum disulphide (MoS2) hydrogel membranes with abundant fluidic channels. Given the interpenetrating ionic transport network, the MoS2 hydrogel membranes exhibit a high-level capacitive performance 1.34 F/cm2 at an ultrahigh mass loading of 11.2 mg/cm2. Furthermore, the interlayer spacing of MoS2 in the hydrogel membranes can be controlled with ångström-scale precision using different cations, which can promote further fundamental studies and potential applications of the transition-metal dichalcogenides hydrogel membranes.
Conductive hydrogel membranes with nanofluids channels represent one of the most promising capacitive electrodes due to their rapid kinetics of ion transport. The construction of these unique structures always requires new self-assembly behaviors with different building blocks, intriguing phenomena of colloidal chemistry. In this work, by delicately balancing the electrostatic repulsions between 2D inorganic nanosheets and the electrostatic adsorption with cations, we develop a general strategy to fabricate stable free-standing 1T molybdenum disulphide (MoS2) hydrogel membranes with abundant fluidic channels. Given the interpenetrating ionic transport network, the MoS2 hydrogel membranes exhibit a high-level capacitive performance 1.34 F/cm2 at an ultrahigh mass loading of 11.2 mg/cm2. Furthermore, the interlayer spacing of MoS2 in the hydrogel membranes can be controlled with ångström-scale precision using different cations, which can promote further fundamental studies and potential applications of the transition-metal dichalcogenides hydrogel membranes.
2025, 36(6): 109891
doi: 10.1016/j.cclet.2024.109891
Abstract:
Spin-orbit coupling (SOC) plays a vital role in determining the ground state and forming novel electronic states of matter where heavy elements are involved. Here, the prototypical perovskite iridate oxide SrIrO3 is investigated to gain more insights into the SOC effect in the modification of electronic structure and corresponding magnetic and electrical properties. The high pressure metastable orthorhombic SrIrO3 is successfully stabilized by physical and chemical pressures, in which the chemical pressure is induced by Ru doping in Ir site and Mg substitution of Sr position. Detailed structural, magnetic, electrical characterizations and density functional theory (DFT) calculations reveal that the substitution of Ru for Ir renders an enhanced metallic characteristic, while the introduction of Mg into Sr site results in an insulating state with 10.1% negative magnetoresistance at 10 K under 7 T. Theoretical calculations indicate that Ru doping can weaken the SOC effect, leading to the decrease of orbital energy difference between J1/2 and J3/2, which is favorable for electron transport. On the contrary, Mg doping can enhance the SOC effect, inducing a metal-insulator-transition (MIT). The electronic phase transition is further revealed by DFT calculations, confirming that the strong SOC and electron-electron interactions can lead to the emergence of insulating state. These findings underline the intricate correlations between lattice degrees of freedom and SOC in determining the ground state, which effectively stimulate the physical pressure between like structures by chemical compression.
Spin-orbit coupling (SOC) plays a vital role in determining the ground state and forming novel electronic states of matter where heavy elements are involved. Here, the prototypical perovskite iridate oxide SrIrO3 is investigated to gain more insights into the SOC effect in the modification of electronic structure and corresponding magnetic and electrical properties. The high pressure metastable orthorhombic SrIrO3 is successfully stabilized by physical and chemical pressures, in which the chemical pressure is induced by Ru doping in Ir site and Mg substitution of Sr position. Detailed structural, magnetic, electrical characterizations and density functional theory (DFT) calculations reveal that the substitution of Ru for Ir renders an enhanced metallic characteristic, while the introduction of Mg into Sr site results in an insulating state with 10.1% negative magnetoresistance at 10 K under 7 T. Theoretical calculations indicate that Ru doping can weaken the SOC effect, leading to the decrease of orbital energy difference between J1/2 and J3/2, which is favorable for electron transport. On the contrary, Mg doping can enhance the SOC effect, inducing a metal-insulator-transition (MIT). The electronic phase transition is further revealed by DFT calculations, confirming that the strong SOC and electron-electron interactions can lead to the emergence of insulating state. These findings underline the intricate correlations between lattice degrees of freedom and SOC in determining the ground state, which effectively stimulate the physical pressure between like structures by chemical compression.
2025, 36(6): 109897
doi: 10.1016/j.cclet.2024.109897
Abstract:
Silicon-air batteries (SABs), a new type of semiconductor air battery, have a high energy density. However, some side reactions in SABs cause Si anodes to be covered by a passivation layer to prevent continuous discharge, and the anode utilization rate is low. In this work, reduced graphene oxide (RGO) fabricated via high-temperature annealing or L-ascorbic acid (L.AA) reduction was first used to obtain Si nanowires/RGO-1000 (Si NWs/RGO-1000) and Si nanowires/RGO-L.AA (Si NWs/RGO-L.AA) composite anodes for SABs. It was found that RGO suppressed the passivation and self-corrosion reactions and that SABs using Si NWs/RGO-L.AA as the anode can discharge for more than 700 h, breaking the previous performance of SABs, and that the specific capacity was increased by 90.8% compared to bare Si. This work provides a new solution for the design of high specific capacity SABs with nanostructures and anode protective layers.
Silicon-air batteries (SABs), a new type of semiconductor air battery, have a high energy density. However, some side reactions in SABs cause Si anodes to be covered by a passivation layer to prevent continuous discharge, and the anode utilization rate is low. In this work, reduced graphene oxide (RGO) fabricated via high-temperature annealing or L-ascorbic acid (L.AA) reduction was first used to obtain Si nanowires/RGO-1000 (Si NWs/RGO-1000) and Si nanowires/RGO-L.AA (Si NWs/RGO-L.AA) composite anodes for SABs. It was found that RGO suppressed the passivation and self-corrosion reactions and that SABs using Si NWs/RGO-L.AA as the anode can discharge for more than 700 h, breaking the previous performance of SABs, and that the specific capacity was increased by 90.8% compared to bare Si. This work provides a new solution for the design of high specific capacity SABs with nanostructures and anode protective layers.
2025, 36(6): 109987
doi: 10.1016/j.cclet.2024.109987
Abstract:
The ultra-high nickel cathode material has important application prospect in power lithium-ion batteries. However, the poor structural stability and serious surface/interfacial side reactions during long cycles severely hinder the material's practical application. In this paper, Cs+ doping and polymethyl methacrylate (PMMA) coating are used to synergistically modify the NCM955 material. The results show that the corresponding discharge specific capacity of NCMCs-2@P-2 material reaches 152.02 mAh/g at 1 C (1 C = 200 mA/g) and 125.66 mAh/g at 5 C after 300 cycles, and the capacity retention is 78.11% and 72.21%, respectively. In addition, it still maintains 156.36 mAh/g discharge specific capacity at 10 C, and these rate and cycle properties exceed those reported on ultra-high nickel cathode material. Moreover, NCMCs-2@P-2 material has higher migration energy barrier of Ni2+ and lower migration energy barrier of Li+ than that of NCM955 material. Therefore, NCMCs-2@P-2 material has excellent electrochemical properties, which has been proved by a series of structural characterization, theoretical calculation and performance test. The synergistic enhancement of Cs+ doping and PMMA coating accelerates lithium ion diffusion kinetics, stabilizes crystal structure, and inhabits surface/interface side reaction.
The ultra-high nickel cathode material has important application prospect in power lithium-ion batteries. However, the poor structural stability and serious surface/interfacial side reactions during long cycles severely hinder the material's practical application. In this paper, Cs+ doping and polymethyl methacrylate (PMMA) coating are used to synergistically modify the NCM955 material. The results show that the corresponding discharge specific capacity of NCMCs-2@P-2 material reaches 152.02 mAh/g at 1 C (1 C = 200 mA/g) and 125.66 mAh/g at 5 C after 300 cycles, and the capacity retention is 78.11% and 72.21%, respectively. In addition, it still maintains 156.36 mAh/g discharge specific capacity at 10 C, and these rate and cycle properties exceed those reported on ultra-high nickel cathode material. Moreover, NCMCs-2@P-2 material has higher migration energy barrier of Ni2+ and lower migration energy barrier of Li+ than that of NCM955 material. Therefore, NCMCs-2@P-2 material has excellent electrochemical properties, which has been proved by a series of structural characterization, theoretical calculation and performance test. The synergistic enhancement of Cs+ doping and PMMA coating accelerates lithium ion diffusion kinetics, stabilizes crystal structure, and inhabits surface/interface side reaction.
2025, 36(6): 109988
doi: 10.1016/j.cclet.2024.109988
Abstract:
Flexible zinc-ion batteries (FZIBs) have been acknowledged as a potential cornerstone for the future development of flexible energy storage, yet conventional FZIBs still encounter challenges, particularly concerning performance failure at low temperatures. To address these challenges, a novel anti-freezing leather gel electrolyte (AFLGE-30) is designed, incorporating ethanol as a hydrogen bonding acceptor. The AFLGE-30 demonstrates exceptional frost resistance while maintaining favorable flexibility even at −30 ℃; accordingly, the battery can achieve a high specific capacity of about 70 mAh/g. Cu//Zn battery exhibits remarkable stability at room temperature, retaining ~96% efficiency after 120 plating/stripping cycles at 1 mA/cm2. Concurrently, the Zn//Zn symmetric batteries demonstrate a lifespan of 4100 h at room temperature, which is attributed to the enhancement of Zn2+ deposition kinetics, restraining the formation of zinc dendrites. Furthermore, FZIBs exhibit minimal capacity loss even after bending, impacting, or burning. This work provides a promising strategy for designing low-temperature-resistant FZIBs.
Flexible zinc-ion batteries (FZIBs) have been acknowledged as a potential cornerstone for the future development of flexible energy storage, yet conventional FZIBs still encounter challenges, particularly concerning performance failure at low temperatures. To address these challenges, a novel anti-freezing leather gel electrolyte (AFLGE-30) is designed, incorporating ethanol as a hydrogen bonding acceptor. The AFLGE-30 demonstrates exceptional frost resistance while maintaining favorable flexibility even at −30 ℃; accordingly, the battery can achieve a high specific capacity of about 70 mAh/g. Cu//Zn battery exhibits remarkable stability at room temperature, retaining ~96% efficiency after 120 plating/stripping cycles at 1 mA/cm2. Concurrently, the Zn//Zn symmetric batteries demonstrate a lifespan of 4100 h at room temperature, which is attributed to the enhancement of Zn2+ deposition kinetics, restraining the formation of zinc dendrites. Furthermore, FZIBs exhibit minimal capacity loss even after bending, impacting, or burning. This work provides a promising strategy for designing low-temperature-resistant FZIBs.
2025, 36(6): 109989
doi: 10.1016/j.cclet.2024.109989
Abstract:
The sluggish reaction kinetics of the oxygen evolution reaction (OER) and methanol oxidation reaction (MOR) remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells. Considering the vital role of noble metals in electrocatalytic activity, this work focuses on the rational synthesis of Ni-noble metal composite nanocatalysts for overcoming the drawbacks of high cost and susceptible oxidized surfaces of noble metals. The inherent catalytic activity is improved by the altered electronic structure and effective active sites of the catalyst induced by the size effect of noble metal clusters. In particular, a series of Ni-noble metal nanocomposites are successfully synthesized by partially introducing noble metal into Ni with porous interfacial defects derived from Ni-Al layered double hydroxide (LDH). The Ni10Pd1 nanocomposite exhibits high OER catalytic activity with an overpotential of 0.279 V at 10 mA/cm2, surpassing Ni10Ag1 and Ni10Au1 counterparts. Furthermore, the average diameter of Pd clusters gradually increases from 5.57 nm to 44.44 nm with the increased proportion of doped Pd, leading to the passivation of catalytic activity due to the exacerbated surface oxidation of Pd in the form of Pd2+. After optimization, Ni10Pd1 delivers significantly enhanced OER and MOR electroactivities and long-term stability compared to that of Ni2Pd1, Ni1Pd1 and Ni1Pd2, which is conducive to the effective utilization of Pd and alleviation of surface oxidation.
The sluggish reaction kinetics of the oxygen evolution reaction (OER) and methanol oxidation reaction (MOR) remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells. Considering the vital role of noble metals in electrocatalytic activity, this work focuses on the rational synthesis of Ni-noble metal composite nanocatalysts for overcoming the drawbacks of high cost and susceptible oxidized surfaces of noble metals. The inherent catalytic activity is improved by the altered electronic structure and effective active sites of the catalyst induced by the size effect of noble metal clusters. In particular, a series of Ni-noble metal nanocomposites are successfully synthesized by partially introducing noble metal into Ni with porous interfacial defects derived from Ni-Al layered double hydroxide (LDH). The Ni10Pd1 nanocomposite exhibits high OER catalytic activity with an overpotential of 0.279 V at 10 mA/cm2, surpassing Ni10Ag1 and Ni10Au1 counterparts. Furthermore, the average diameter of Pd clusters gradually increases from 5.57 nm to 44.44 nm with the increased proportion of doped Pd, leading to the passivation of catalytic activity due to the exacerbated surface oxidation of Pd in the form of Pd2+. After optimization, Ni10Pd1 delivers significantly enhanced OER and MOR electroactivities and long-term stability compared to that of Ni2Pd1, Ni1Pd1 and Ni1Pd2, which is conducive to the effective utilization of Pd and alleviation of surface oxidation.
2025, 36(6): 110007
doi: 10.1016/j.cclet.2024.110007
Abstract:
Sodium metal batteries (SMBs) have drawn much attention as complement to lithium metal batteries for next generation high-energy batteries. However, it is still a big challenge to enhance their cycling stability without sufficient sodium reserve in anode, due to the non-uniform Na plating/stripping and uncontrolled Na dendrite growth. Herein, a dual layer host consists of sodiophilic graphene@antimony nanoparticles bottom layer and 3D polyacrylonitrile nanofiber top layer (PAN-G@Sb) is employed to enable highly reversible Na plating/stripping. Thanks to the uniform Na deposition, PAN-G@Sb delivers an outstanding average Coulombic efficiency of 99.8%, highly reversible Na plating/stripping for 1000 cycles at 2.0 mA/cm2, as well as over 1000 h of stable operation in symmetric cells. When paired with a high mass loading Na3V2(PO4)3 (NVP) cathode (16.2 mg/cm2), the full cell (N/P ratio = 1.4) also displays prominent capacity retention of 98.7% after 250 cycles with a high energy density of 284.6 Wh/kg. Moreover, PAN-G@SbNVP anode-free full cell also shows an excellent capacity retention of 91.0% after 50 cycles at 0.5 C, exhibiting the stable operation of high energy SMBs.
Sodium metal batteries (SMBs) have drawn much attention as complement to lithium metal batteries for next generation high-energy batteries. However, it is still a big challenge to enhance their cycling stability without sufficient sodium reserve in anode, due to the non-uniform Na plating/stripping and uncontrolled Na dendrite growth. Herein, a dual layer host consists of sodiophilic graphene@antimony nanoparticles bottom layer and 3D polyacrylonitrile nanofiber top layer (PAN-G@Sb) is employed to enable highly reversible Na plating/stripping. Thanks to the uniform Na deposition, PAN-G@Sb delivers an outstanding average Coulombic efficiency of 99.8%, highly reversible Na plating/stripping for 1000 cycles at 2.0 mA/cm2, as well as over 1000 h of stable operation in symmetric cells. When paired with a high mass loading Na3V2(PO4)3 (NVP) cathode (16.2 mg/cm2), the full cell (N/P ratio = 1.4) also displays prominent capacity retention of 98.7% after 250 cycles with a high energy density of 284.6 Wh/kg. Moreover, PAN-G@SbNVP anode-free full cell also shows an excellent capacity retention of 91.0% after 50 cycles at 0.5 C, exhibiting the stable operation of high energy SMBs.
2025, 36(6): 110008
doi: 10.1016/j.cclet.2024.110008
Abstract:
Solid-state batteries (SSBs) with thermal stable solid-state electrolytes (SSEs) show intrinsic capacity and great potential in energy density improvement. SSEs play critical role, however, their low ionic conductivity at room temperature and high brittleness hinder their further development. In this paper, polypropylene (PP)-polyvinylidene fluoride (PVDF)-Li1.3Al0.3Ti1.7(PO4)3 (LATP)-Lithium bis(trifluoromethane sulphonyl)imide (LiTFSI) multi-layered composite solid electrolyte (CSE) is prepared by a simple separator coating strategy. The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF, but also forms a solvation structure, which contributes to high ionic conductivity in a wide temperature. In addition, using a PP separator as the supporting film, the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited. The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10–4 S/cm at room temperature and significantly improves the mechanical properties, the tensile strength reaches 11.02 MPa. The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h. The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 mAh/g after 800 cycles at 2 C. This CSE has good cycle stability and excellent mechanical strength at room temperature, which provides an effective method to improve the performance of solid electrolytes under moderate condition.
Solid-state batteries (SSBs) with thermal stable solid-state electrolytes (SSEs) show intrinsic capacity and great potential in energy density improvement. SSEs play critical role, however, their low ionic conductivity at room temperature and high brittleness hinder their further development. In this paper, polypropylene (PP)-polyvinylidene fluoride (PVDF)-Li1.3Al0.3Ti1.7(PO4)3 (LATP)-Lithium bis(trifluoromethane sulphonyl)imide (LiTFSI) multi-layered composite solid electrolyte (CSE) is prepared by a simple separator coating strategy. The incorporation of LATP nanoparticle fillers and high concentration LiTFSI not only reduces the crystallinity of PVDF, but also forms a solvation structure, which contributes to high ionic conductivity in a wide temperature. In addition, using a PP separator as the supporting film, the mechanical strength of the electrolyte was improved and the growth of lithium dendrites are effectively inhibited. The results show that the CSE prepared in this paper has a high ionic conductivity of 6.38×10–4 S/cm at room temperature and significantly improves the mechanical properties, the tensile strength reaches 11.02 MPa. The cycle time of Li/Li symmetric cell assembled by CSE at room temperature can exceed 800 h. The Li/LFP full cell can cycle over 800 cycles and the specific capacity of Li/LFP full cell can still reach 120 mAh/g after 800 cycles at 2 C. This CSE has good cycle stability and excellent mechanical strength at room temperature, which provides an effective method to improve the performance of solid electrolytes under moderate condition.
2025, 36(6): 110009
doi: 10.1016/j.cclet.2024.110009
Abstract:
Lithium metal batteries, with their light mass anode and high theoretical specific capacity of 3860 mAh/g, have great potential for development in achieving high energy density. However, the generation of lithium dendrites and the loss of dead lithium pose a serious threat to the safety and long-cycle stability of batteries. Herein, we utilize the Lewis acid-base interaction principle for lithium-ion migration regulation. Through loading solid-acids onto molecular sieves to immobilize Lewis base (PF6−), we achieve accelerated dissociation of lithium salts and successfully increase the lithium ion transference number to 0.44. Lewis acid-base interaction helps lithium metal batteries achieve more uniform lithium deposition, with an average CE improved to 92.8%. The symmetrical cells can be plated/stripped stably for more than 800 h of cycling. Full cell with high surface-loaded LFP cathode (14 mg/cm2) exhibits impressively high capacity retention of 90.7% after 120 cycles at 0.5 C.
Lithium metal batteries, with their light mass anode and high theoretical specific capacity of 3860 mAh/g, have great potential for development in achieving high energy density. However, the generation of lithium dendrites and the loss of dead lithium pose a serious threat to the safety and long-cycle stability of batteries. Herein, we utilize the Lewis acid-base interaction principle for lithium-ion migration regulation. Through loading solid-acids onto molecular sieves to immobilize Lewis base (PF6−), we achieve accelerated dissociation of lithium salts and successfully increase the lithium ion transference number to 0.44. Lewis acid-base interaction helps lithium metal batteries achieve more uniform lithium deposition, with an average CE improved to 92.8%. The symmetrical cells can be plated/stripped stably for more than 800 h of cycling. Full cell with high surface-loaded LFP cathode (14 mg/cm2) exhibits impressively high capacity retention of 90.7% after 120 cycles at 0.5 C.
2025, 36(6): 110016
doi: 10.1016/j.cclet.2024.110016
Abstract:
Rationally design the morphology and structure of electroactive nanomaterials is an effective approach to enhance the performance of aqueous batteries. Herein, we co-engineered the hollow architecture and interlayer spacing of layered double hydroxides (LDH) to achieve high electrochemical activity. The hierarchical hollow LDH was prepared from bimetallic zeolitic imidazolate frameworks (ZIF) by a facile cation exchange strategy. Zn and Cu elements were selected as the second metals incorporated in Co-ZIF. The characteristics of the corresponding derivatives were studied. Besides, the transformation mechanism of CoZn-ZIF into nanosheet-assembled hollow CoZnNi LDH (denoted as CoZnNi-OH) was systematically investigated. Importantly, the interlayer spacing of CoZnNi-OH expands due to Zn2+ incorporation. The prepared CoZnNi-OH offers large surface area, exposed active sites, and rapid mass transfer/diffusion rate, which lead to a significant enhancement in the specific capacitance, rate performance, and cycle stability of CoZnNi-OH electrode. In addition, the aqueous alkaline CoZnNi-OH//Zn showed a maximum energy density/power density of 0.924 mWh/cm2, 8.479 mW/cm2. This work not only raises an insightful strategy for regulating the morphology and interlayer spacing of LDH, but also provides a reference of designing hollow nickel-based nanomaterials for aqueous batteries.
Rationally design the morphology and structure of electroactive nanomaterials is an effective approach to enhance the performance of aqueous batteries. Herein, we co-engineered the hollow architecture and interlayer spacing of layered double hydroxides (LDH) to achieve high electrochemical activity. The hierarchical hollow LDH was prepared from bimetallic zeolitic imidazolate frameworks (ZIF) by a facile cation exchange strategy. Zn and Cu elements were selected as the second metals incorporated in Co-ZIF. The characteristics of the corresponding derivatives were studied. Besides, the transformation mechanism of CoZn-ZIF into nanosheet-assembled hollow CoZnNi LDH (denoted as CoZnNi-OH) was systematically investigated. Importantly, the interlayer spacing of CoZnNi-OH expands due to Zn2+ incorporation. The prepared CoZnNi-OH offers large surface area, exposed active sites, and rapid mass transfer/diffusion rate, which lead to a significant enhancement in the specific capacitance, rate performance, and cycle stability of CoZnNi-OH electrode. In addition, the aqueous alkaline CoZnNi-OH//Zn showed a maximum energy density/power density of 0.924 mWh/cm2, 8.479 mW/cm2. This work not only raises an insightful strategy for regulating the morphology and interlayer spacing of LDH, but also provides a reference of designing hollow nickel-based nanomaterials for aqueous batteries.
2025, 36(6): 110040
doi: 10.1016/j.cclet.2024.110040
Abstract:
High-capacity Ni-rich layered cathodes LiNixCoyMn1−x−yO2 (NCM) have been widely recognized as highly promising candidates for lithium-ion batteries (LIBs). However, NCM cathodes are suffered from sluggish Li-ion kinetics and fast capacity decay. Herein, the Nb/Ti co-doping strategy has been proposed by formation energy analysis to enhance the mechanical and chemical integrities of NCM cathode. Nb/Ti co-doping facilitates Li-ion transport of NCM cathode for boosting the rate ability. Furthermore, the structure stability is prominently improved for the stronger Nb–O and Ti–O bonds, resulting from the suppressed sharp contraction of c axis, inhibited microcracks formation, and alleviated electrolyte corrosion. Inspired by the synergistic effect of Nb/Ti co-doping, the modified NCM exhibits superior comprehensive electrochemical performances. The Nb/Ti co-doping NCM exhibits an increased discharge capacity of 144.3 mAh/g at 10 C and an outstanding capacity retention remained 92.7% after 300 cycles at 1 C. This work offers a promising approach to developing high-performance cathode materials.
High-capacity Ni-rich layered cathodes LiNixCoyMn1−x−yO2 (NCM) have been widely recognized as highly promising candidates for lithium-ion batteries (LIBs). However, NCM cathodes are suffered from sluggish Li-ion kinetics and fast capacity decay. Herein, the Nb/Ti co-doping strategy has been proposed by formation energy analysis to enhance the mechanical and chemical integrities of NCM cathode. Nb/Ti co-doping facilitates Li-ion transport of NCM cathode for boosting the rate ability. Furthermore, the structure stability is prominently improved for the stronger Nb–O and Ti–O bonds, resulting from the suppressed sharp contraction of c axis, inhibited microcracks formation, and alleviated electrolyte corrosion. Inspired by the synergistic effect of Nb/Ti co-doping, the modified NCM exhibits superior comprehensive electrochemical performances. The Nb/Ti co-doping NCM exhibits an increased discharge capacity of 144.3 mAh/g at 10 C and an outstanding capacity retention remained 92.7% after 300 cycles at 1 C. This work offers a promising approach to developing high-performance cathode materials.
2025, 36(6): 110041
doi: 10.1016/j.cclet.2024.110041
Abstract:
For realizing the goals of “carbon peak” and “carbon neutrality”, lithium-ion batteries (LIB) with LiFePO4 as the cathode material have been widely applied. However, this has also led to a large number of spent lithium-ion batteries, and the safe disposal of spent lithium-ion batteries is an urgent issue. Currently, the main reason for the capacity decay of LiFePO4 materials is the Li deficiency and the formation of the Fe3+ phase. In order to address this issue, we performed high-temperature calcination of the discarded lithium iron phosphate cathode material in a carbon dioxide environment to reduce or partially remove the carbon coating on its surface. Subsequently, mechanical grinding was conducted to ensure thorough mixing of the lithium source with the discarded lithium iron phosphate. The reaction between CO2 and the carbon coating produced a reducing atmosphere, reducing Fe3+ to Fe2+ and thereby reducing the content of Fe3+. The Fe3+ content in the repaired LiFePO4 material is reduced. The crystal structure of spent LiFePO4 cathode materials was repaired more completely compare with the traditional pretreatment method, and the repaired LiFePO4 material shows good electrochemical performance and cycling stability. Under 0.1 C conditions, the initial capacity can reach 149.1 mAh/g. It can be reintroduced for commercial use.
For realizing the goals of “carbon peak” and “carbon neutrality”, lithium-ion batteries (LIB) with LiFePO4 as the cathode material have been widely applied. However, this has also led to a large number of spent lithium-ion batteries, and the safe disposal of spent lithium-ion batteries is an urgent issue. Currently, the main reason for the capacity decay of LiFePO4 materials is the Li deficiency and the formation of the Fe3+ phase. In order to address this issue, we performed high-temperature calcination of the discarded lithium iron phosphate cathode material in a carbon dioxide environment to reduce or partially remove the carbon coating on its surface. Subsequently, mechanical grinding was conducted to ensure thorough mixing of the lithium source with the discarded lithium iron phosphate. The reaction between CO2 and the carbon coating produced a reducing atmosphere, reducing Fe3+ to Fe2+ and thereby reducing the content of Fe3+. The Fe3+ content in the repaired LiFePO4 material is reduced. The crystal structure of spent LiFePO4 cathode materials was repaired more completely compare with the traditional pretreatment method, and the repaired LiFePO4 material shows good electrochemical performance and cycling stability. Under 0.1 C conditions, the initial capacity can reach 149.1 mAh/g. It can be reintroduced for commercial use.
2025, 36(6): 110042
doi: 10.1016/j.cclet.2024.110042
Abstract:
Urea-assisted water electrolysis offers a promising route to reduce energy consumption for hydrogen production and meanwhile treat urea-rich wastewater. Herein, we devised a shear force-involved polyoxometalate-organic supramolecular self-assembly strategy to fabricate 3D hierarchical porous nanoribbon assembly Mn-VN cardoons. A bimetallic polyoxovanadate (POV) with the inherent structural feature of Mn surrounded by [VO6] octahedrons was introduced to trigger precise Mn incorporation in VN lattice, thereby achieving simultaneous morphology engineering and electronic structure modulation. The lattice contraction of VN caused by Mn incorporation drives electron redistribution. The unique hierarchical architecture with modulated electronic structure that provides more exposed active sites, facilitates mass and charge transfer, and optimizes the associated adsorption behavior. Mn-VN exhibits excellent activity with low overpotentials of 86 mV and 1.346 V at 10 mA/cm2 for hydrogen evolution reaction (HER) and urea oxidation reaction (UOR), respectively. Accordingly, in the two-electrode urea-assisted water electrolyzer utilizing Mn-VN as a bifunctional catalyst, hydrogen production can occur at low voltage (1.456 V@10 mA/cm2), which has the advantages of energy saving and competitive durability over traditional water electrolysis. This work provides a simple and mild route to construct nanostructures and modulate electronic structure for designing high-efficiency electrocatalysts.
Urea-assisted water electrolysis offers a promising route to reduce energy consumption for hydrogen production and meanwhile treat urea-rich wastewater. Herein, we devised a shear force-involved polyoxometalate-organic supramolecular self-assembly strategy to fabricate 3D hierarchical porous nanoribbon assembly Mn-VN cardoons. A bimetallic polyoxovanadate (POV) with the inherent structural feature of Mn surrounded by [VO6] octahedrons was introduced to trigger precise Mn incorporation in VN lattice, thereby achieving simultaneous morphology engineering and electronic structure modulation. The lattice contraction of VN caused by Mn incorporation drives electron redistribution. The unique hierarchical architecture with modulated electronic structure that provides more exposed active sites, facilitates mass and charge transfer, and optimizes the associated adsorption behavior. Mn-VN exhibits excellent activity with low overpotentials of 86 mV and 1.346 V at 10 mA/cm2 for hydrogen evolution reaction (HER) and urea oxidation reaction (UOR), respectively. Accordingly, in the two-electrode urea-assisted water electrolyzer utilizing Mn-VN as a bifunctional catalyst, hydrogen production can occur at low voltage (1.456 V@10 mA/cm2), which has the advantages of energy saving and competitive durability over traditional water electrolysis. This work provides a simple and mild route to construct nanostructures and modulate electronic structure for designing high-efficiency electrocatalysts.
2025, 36(6): 110048
doi: 10.1016/j.cclet.2024.110048
Abstract:
In the practical operations of the sodium ion (Na+) batteries (SIBs), the fast transport of Na+ is desired for the rate performance, because the other ions in an electrolyte are electrochemically inert. In this study, we use molecular dynamics simulations to investigate the partial conductivity of Na+ (σNa+) in the salt-in-ionic liquid electrolytes (SILEs) composed of 1-ethyl-3-methylimidazolium (EMIM+) and bis(fluorosulfonyl)imide (FSI−) with various molar fraction of NaFSI. The simulations show that while the ionic conductivity of the SILE decreases monotonically with the increase of salt fraction of NaFSI, σNa+ peaks in the SILE with 0.5 molar fraction of NaFSI. Detailed analyses indicate that with the increase of salt fraction, the coordination structure of FSI− around Na+ changed from bidentate manner to monodentate manner which weakens the binding of FSI− to Na+. The effects are two folds. On one hand, the increased monodentate coordinations cause a large aggregate that hinders the transport of Na+ within the aggregate; on the other hand, the large aggregate captures most FSI− to form percolating ion network, and thus leaves a small portion of Na+’s that are not in the large aggregate to be more "free" to transport in the SILE.
In the practical operations of the sodium ion (Na+) batteries (SIBs), the fast transport of Na+ is desired for the rate performance, because the other ions in an electrolyte are electrochemically inert. In this study, we use molecular dynamics simulations to investigate the partial conductivity of Na+ (σNa+) in the salt-in-ionic liquid electrolytes (SILEs) composed of 1-ethyl-3-methylimidazolium (EMIM+) and bis(fluorosulfonyl)imide (FSI−) with various molar fraction of NaFSI. The simulations show that while the ionic conductivity of the SILE decreases monotonically with the increase of salt fraction of NaFSI, σNa+ peaks in the SILE with 0.5 molar fraction of NaFSI. Detailed analyses indicate that with the increase of salt fraction, the coordination structure of FSI− around Na+ changed from bidentate manner to monodentate manner which weakens the binding of FSI− to Na+. The effects are two folds. On one hand, the increased monodentate coordinations cause a large aggregate that hinders the transport of Na+ within the aggregate; on the other hand, the large aggregate captures most FSI− to form percolating ion network, and thus leaves a small portion of Na+’s that are not in the large aggregate to be more "free" to transport in the SILE.
2025, 36(6): 110062
doi: 10.1016/j.cclet.2024.110062
Abstract:
Transition metal selenides are considered promising electrochemical energy storage materials due to their excellent rate properties and high capacity based on multi-step conversion reactions. However, its practical applications are hampered by poor conductivity and large volume variation for Na+ storage, which resulting fast capacity decay. Herein, a facile metal-organic framework (MOF) derived method is explored to embed Cu2-xSe@C particles into a carbon nanobelts matrix. Such carbon encapsulated nanobelts' structural moderate integral electronic conductivity and maintained the structure from collapsing during Na+ insertion/extraction. Furthermore, the porous structure of these nanobelts endows enough void space to mitigate volume stress and provide more diffusion channels for Na+/electrons transporting. Due to the unique structure, these Cu2-xSe@C nanobelts achieved ultra-stable cycling performance (170.7 mAh/g at 1.0 A/g after 1000 cycles) and superior rate capability (94.6 mAh/g at 8 A/g) for sodium-ion batteries. The kinetic analysis reveals that these Cu2-xSe@C nanobelts with considerable pesoudecapactive contribution benefit the rapid sodiation/desodiation. This rational design strategy broadens an avenue for the development of metal selenide materials for energy storage devices.
Transition metal selenides are considered promising electrochemical energy storage materials due to their excellent rate properties and high capacity based on multi-step conversion reactions. However, its practical applications are hampered by poor conductivity and large volume variation for Na+ storage, which resulting fast capacity decay. Herein, a facile metal-organic framework (MOF) derived method is explored to embed Cu2-xSe@C particles into a carbon nanobelts matrix. Such carbon encapsulated nanobelts' structural moderate integral electronic conductivity and maintained the structure from collapsing during Na+ insertion/extraction. Furthermore, the porous structure of these nanobelts endows enough void space to mitigate volume stress and provide more diffusion channels for Na+/electrons transporting. Due to the unique structure, these Cu2-xSe@C nanobelts achieved ultra-stable cycling performance (170.7 mAh/g at 1.0 A/g after 1000 cycles) and superior rate capability (94.6 mAh/g at 8 A/g) for sodium-ion batteries. The kinetic analysis reveals that these Cu2-xSe@C nanobelts with considerable pesoudecapactive contribution benefit the rapid sodiation/desodiation. This rational design strategy broadens an avenue for the development of metal selenide materials for energy storage devices.
2025, 36(6): 110063
doi: 10.1016/j.cclet.2024.110063
Abstract:
Nickel-rich cathode materials have received widespread attention due to their high energy density. However, the poor rate capability and inferior cycle stability seriously hinder their large-scale application. The traditional co-precipitation method for preparing them has a long process and easily arises agglomeration leading to inhomogeneous element distribution. Here, a novel precursor containing Li element was prepared by ultrafast spray pyrolysis (SP) in 3–5 s. Then the precursor was used to synthesize pristine LiNi0.9Co0.05Mn0.05O2 (NCM90) and 1% Mg modified LiNi0.9Co0.05Mn0.05O2 (NCM90-Mg1). This method gets rid of mixing Li/Mg source and the precursor prepared by common co-precipitation, thus could achieve homogeneous lithiation and Mg2+ doping. The cell parameter c is expanded, and the cation disorder is reduced after Mg2+ doping. Furthermore, the harmful H2-H3 phase transition in NCM90-Mg1 is also well suppressed. As a result, the obtained NCM90-Mg1 shows better electrochemical performance than NCM90. Within 2.8–4.3 V (25 ℃), the specific discharge capacity of NCM90-Mg1 at 5 C is as high as 169.1 mAh/g, and an outstanding capacity retention of 70.0% (10.0% higher than NCM90) can be obtained after 400 cycles at 0.5 C. At 45 ℃, a capacity retention of 81.9% after 100 cycles at 1 C is recorded for NCM90-Mg1. Moreover, the NCM90-Mg1 also exhibits superior cycle stability when cycled at high cut-off voltage (4.5 V, 25 ℃), possessing the capacity retention of 79.2% after 200 cycles at 1 C. Therefore, SP can be proposed as a powerful method for the preparation of multi-element materials for next-generation high energy density LIBs.
Nickel-rich cathode materials have received widespread attention due to their high energy density. However, the poor rate capability and inferior cycle stability seriously hinder their large-scale application. The traditional co-precipitation method for preparing them has a long process and easily arises agglomeration leading to inhomogeneous element distribution. Here, a novel precursor containing Li element was prepared by ultrafast spray pyrolysis (SP) in 3–5 s. Then the precursor was used to synthesize pristine LiNi0.9Co0.05Mn0.05O2 (NCM90) and 1% Mg modified LiNi0.9Co0.05Mn0.05O2 (NCM90-Mg1). This method gets rid of mixing Li/Mg source and the precursor prepared by common co-precipitation, thus could achieve homogeneous lithiation and Mg2+ doping. The cell parameter c is expanded, and the cation disorder is reduced after Mg2+ doping. Furthermore, the harmful H2-H3 phase transition in NCM90-Mg1 is also well suppressed. As a result, the obtained NCM90-Mg1 shows better electrochemical performance than NCM90. Within 2.8–4.3 V (25 ℃), the specific discharge capacity of NCM90-Mg1 at 5 C is as high as 169.1 mAh/g, and an outstanding capacity retention of 70.0% (10.0% higher than NCM90) can be obtained after 400 cycles at 0.5 C. At 45 ℃, a capacity retention of 81.9% after 100 cycles at 1 C is recorded for NCM90-Mg1. Moreover, the NCM90-Mg1 also exhibits superior cycle stability when cycled at high cut-off voltage (4.5 V, 25 ℃), possessing the capacity retention of 79.2% after 200 cycles at 1 C. Therefore, SP can be proposed as a powerful method for the preparation of multi-element materials for next-generation high energy density LIBs.
2025, 36(6): 110065
doi: 10.1016/j.cclet.2024.110065
Abstract:
Despite significant progress has been achieved regarding the shuttle-effect of lithium polysulfides, the suppressed specific capacity and retarded redox kinetics under high sulfur loading still threat the actual energy density and power density of lithium-sulfur batteries. In this study, a graham condenser-inspired carbon@WS2 host with coil-in-tube structure was designed and synthesized using anodic aluminum oxide (AAO) membrane with vertically aligned nanopores as template. The vertical array of carbon nanotubes with internal carbon coils not only leads to efficient charge transfer across through the thickness of the cathode, but also provides significant confinement to polysulfide diffusion towards both the lateral and longitudinal directions. Few-layer WS2 in the carbon coils perform a synergistic role in suppressing the shuttle-effect as well as boosting the cathodic kinetics. As a result, high specific capacity (1180 mAh/g at 0.1 C) and long-cycling stability at 0.5 C for 500 cycles has been achieved at 3 mgS/cm2. Impressive areal capacity of 7.4 mAh/cm2 has been demonstrated when the sulfur loading reaches 8.4 mg/cm2. The unique coil-in-tube structure developed in this work provides a new solution for high sulfur loading cathode towards practical lithium-sulfur batteries.
Despite significant progress has been achieved regarding the shuttle-effect of lithium polysulfides, the suppressed specific capacity and retarded redox kinetics under high sulfur loading still threat the actual energy density and power density of lithium-sulfur batteries. In this study, a graham condenser-inspired carbon@WS2 host with coil-in-tube structure was designed and synthesized using anodic aluminum oxide (AAO) membrane with vertically aligned nanopores as template. The vertical array of carbon nanotubes with internal carbon coils not only leads to efficient charge transfer across through the thickness of the cathode, but also provides significant confinement to polysulfide diffusion towards both the lateral and longitudinal directions. Few-layer WS2 in the carbon coils perform a synergistic role in suppressing the shuttle-effect as well as boosting the cathodic kinetics. As a result, high specific capacity (1180 mAh/g at 0.1 C) and long-cycling stability at 0.5 C for 500 cycles has been achieved at 3 mgS/cm2. Impressive areal capacity of 7.4 mAh/cm2 has been demonstrated when the sulfur loading reaches 8.4 mg/cm2. The unique coil-in-tube structure developed in this work provides a new solution for high sulfur loading cathode towards practical lithium-sulfur batteries.
2025, 36(6): 110066
doi: 10.1016/j.cclet.2024.110066
Abstract:
The excited state dynamics and critically regulated factors of reverse intersystem crossing (RISC) in through-space charge transfer (TSCT) molecules have received insufficient attention. Here, five molecules of through space/bond charge transfer inducing thermally activated delayed fluorescence (TADF) are prepared, and their excited state charge transfer processes are studied by ultrafast transient absorption and theoretical calculations. DM-Z has a larger ∆EST, leading to a longer lifetime of intersystem crossing (ISC), resulting in the lowest photoluminescence quantum yield (PLQY). Oppositely, ISC and RISC are demonstrated to take place with shorter lifetimes for TSCT molecules. The face-to-face π-π stacking interactions and electron communication enable DM-B and DM-BX to have an efficient RISC, increasing the weight coefficient of RISC from 1.7% (DM-X) to close to 50% (DM-B and DM-BX) in the solvents, which make DM-BX and DM-B to have a high PLQY. However, partial local excitation in the donor center is observed and the charge transfer is decreased for DM-G and DM-X. The triplet excited state (DM-G) or singlet excited state (DM-X) mainly undergoes inactivation through a non-radiative relaxation process, resulting in less RISC and low PLQY. This work provides theoretical hints to enhance the RISC process in the TADF materials.
The excited state dynamics and critically regulated factors of reverse intersystem crossing (RISC) in through-space charge transfer (TSCT) molecules have received insufficient attention. Here, five molecules of through space/bond charge transfer inducing thermally activated delayed fluorescence (TADF) are prepared, and their excited state charge transfer processes are studied by ultrafast transient absorption and theoretical calculations. DM-Z has a larger ∆EST, leading to a longer lifetime of intersystem crossing (ISC), resulting in the lowest photoluminescence quantum yield (PLQY). Oppositely, ISC and RISC are demonstrated to take place with shorter lifetimes for TSCT molecules. The face-to-face π-π stacking interactions and electron communication enable DM-B and DM-BX to have an efficient RISC, increasing the weight coefficient of RISC from 1.7% (DM-X) to close to 50% (DM-B and DM-BX) in the solvents, which make DM-BX and DM-B to have a high PLQY. However, partial local excitation in the donor center is observed and the charge transfer is decreased for DM-G and DM-X. The triplet excited state (DM-G) or singlet excited state (DM-X) mainly undergoes inactivation through a non-radiative relaxation process, resulting in less RISC and low PLQY. This work provides theoretical hints to enhance the RISC process in the TADF materials.
2025, 36(6): 110088
doi: 10.1016/j.cclet.2024.110088
Abstract:
TiO2 has been widely studied as one of the most promising anode materials for lithium-ion batteries (LIBs) due to good structural stability and small volume changes. However, its applications are still greatly affected by its poor electrical conductivity. In this work, ultrasmall TiO2 quantum dots (QDs) are firmly grown onto 2D Ti3C2Tx nanosheets (A-TiO2/Ti3C2Tx), benefiting from the positive regulation of (3-aminopropyl)triethoxysilane (APTES). Interestingly, SiO2 nanoparticles produced by the hydrolysis of APTES can strengthen the strong coupling of TiO2 QDs with Ti3C2Tx, thereby enhancing the structural integrity of the composite. As expected, the A-TiO2/Ti3C2Tx composite demonstrates an exceptional lithium storage performance, achieving a high capacity of 425.4 mAh/g for 400 cycles at 0.1 A/g, and an outstanding long-term cycling stability. In-situ electrochemical impedance spectroscopy and theoretical analysis unconver that the superior lithium storage performance is attributed to its unique heterostructure and in-situ N doping derived from APTES, which not only reduces the Li+ adsorption energy, but also gives the fast charge transfer dynamics.
TiO2 has been widely studied as one of the most promising anode materials for lithium-ion batteries (LIBs) due to good structural stability and small volume changes. However, its applications are still greatly affected by its poor electrical conductivity. In this work, ultrasmall TiO2 quantum dots (QDs) are firmly grown onto 2D Ti3C2Tx nanosheets (A-TiO2/Ti3C2Tx), benefiting from the positive regulation of (3-aminopropyl)triethoxysilane (APTES). Interestingly, SiO2 nanoparticles produced by the hydrolysis of APTES can strengthen the strong coupling of TiO2 QDs with Ti3C2Tx, thereby enhancing the structural integrity of the composite. As expected, the A-TiO2/Ti3C2Tx composite demonstrates an exceptional lithium storage performance, achieving a high capacity of 425.4 mAh/g for 400 cycles at 0.1 A/g, and an outstanding long-term cycling stability. In-situ electrochemical impedance spectroscopy and theoretical analysis unconver that the superior lithium storage performance is attributed to its unique heterostructure and in-situ N doping derived from APTES, which not only reduces the Li+ adsorption energy, but also gives the fast charge transfer dynamics.
2025, 36(6): 110185
doi: 10.1016/j.cclet.2024.110185
Abstract:
As a kind of emerging energy storage devices, Aqueous zinc ion batteries possess the characteristics of safety, low cost and environmental friendliness. However, their further application is restricted by the sluggish electrochemical reaction kinetics and low conductivity. In this work, we prepare two H3.78V6O13 electrode materials with many active sites, which promotes the kinetics of ion diffusion and then improves the capacity of the cell. The as-obtained HVO-PVP electrode possess a capacity of 393.2 and 285.9 mAh/g at 0.2 and 5.0 A/g, respectively. Moreover, the assembled Zn//HVO-PVP cells also indicate excellent specific capacity and cycle stability at different operating temperatures (0–60 ℃).
As a kind of emerging energy storage devices, Aqueous zinc ion batteries possess the characteristics of safety, low cost and environmental friendliness. However, their further application is restricted by the sluggish electrochemical reaction kinetics and low conductivity. In this work, we prepare two H3.78V6O13 electrode materials with many active sites, which promotes the kinetics of ion diffusion and then improves the capacity of the cell. The as-obtained HVO-PVP electrode possess a capacity of 393.2 and 285.9 mAh/g at 0.2 and 5.0 A/g, respectively. Moreover, the assembled Zn//HVO-PVP cells also indicate excellent specific capacity and cycle stability at different operating temperatures (0–60 ℃).
2025, 36(6): 110251
doi: 10.1016/j.cclet.2024.110251
Abstract:
Small interfering RNA (siRNA), a promising revolutionary therapy, faces delivery obstacles due to its poor targeting, strong charge negativity and macromolecular nature. Clinical-approved siRNAs can now only be delivered to the liver mediated by the chemically conjugated N-acetylgalactosamine (GalNAc) ligand, the conjugate can be effectively uptaken into cells through interaction with asialoglycoprotein receptor (ASGPR) highly expressed on liver hepatocytes. To further explore an efficient non-hepatic targeted delivery strategy, in this study, we designed a delivery system that chemically conjugated p53 siRNA to renal tubular cell-targeting peptides for targeting the kidney, which was suitable for industrial transformation. Results showed that peptide-siRNA conjugate could specifically enter renal tubular epithelial cells and silence target genes. In cisplatin-induced acute kidney injury (AKI) mice, peptide-siRNA conjugate blocked the p53-mediated apoptotic pathway and alleviated renal damage. The innovative proposed system to conjugate kidney-targeting peptides with siRNA achieved the efficient kidney-targeted delivery of siRNA and provided a prospective choice for treating AKI.
Small interfering RNA (siRNA), a promising revolutionary therapy, faces delivery obstacles due to its poor targeting, strong charge negativity and macromolecular nature. Clinical-approved siRNAs can now only be delivered to the liver mediated by the chemically conjugated N-acetylgalactosamine (GalNAc) ligand, the conjugate can be effectively uptaken into cells through interaction with asialoglycoprotein receptor (ASGPR) highly expressed on liver hepatocytes. To further explore an efficient non-hepatic targeted delivery strategy, in this study, we designed a delivery system that chemically conjugated p53 siRNA to renal tubular cell-targeting peptides for targeting the kidney, which was suitable for industrial transformation. Results showed that peptide-siRNA conjugate could specifically enter renal tubular epithelial cells and silence target genes. In cisplatin-induced acute kidney injury (AKI) mice, peptide-siRNA conjugate blocked the p53-mediated apoptotic pathway and alleviated renal damage. The innovative proposed system to conjugate kidney-targeting peptides with siRNA achieved the efficient kidney-targeted delivery of siRNA and provided a prospective choice for treating AKI.
2025, 36(6): 110252
doi: 10.1016/j.cclet.2024.110252
Abstract:
Asperfilasin A (1), featuring a unique 5/5 cyclopenta[c]pyrrol-one bicyclic core, represents a newly discovered skeletal cytochalasan isolated from Aspergillus flavipes. The enantioselective total synthesis was efficiently accomplished from the key intermediate (S)-6 with three contiguous stereocenters in 5 steps and the synthetic 1 induced G2/M-phase cell cycle arrest of HT29 cells and apoptosis of HL60 and NB4 cells by activation of caspase-3 and degradation of PARP. (S)-6, bearing three contiguous chiral centers, was efficiently constructed by a novel Nazarov cyclization reaction containing basic nitrogen, which was less developed, primarily due to the incompatibility of basic nitrogen under acidic reaction conditions. This reaction allows a wide range of pentadienone substrates containing basic nitrogen to undergo Nazarov cyclization in a single regioselective and diastereoselective manner and is capable of generating three stereocenters simultaneously. Furthermore, the mechanism of the Nazarov cyclization and the origin of the regio- and diastereoselectivity were elucidated by DFT calculations and deuteration experiments, providing valuable insights into the reaction and serving as a guide for future applications involving substrates containing basic nitrogen.
Asperfilasin A (1), featuring a unique 5/5 cyclopenta[c]pyrrol-one bicyclic core, represents a newly discovered skeletal cytochalasan isolated from Aspergillus flavipes. The enantioselective total synthesis was efficiently accomplished from the key intermediate (S)-6 with three contiguous stereocenters in 5 steps and the synthetic 1 induced G2/M-phase cell cycle arrest of HT29 cells and apoptosis of HL60 and NB4 cells by activation of caspase-3 and degradation of PARP. (S)-6, bearing three contiguous chiral centers, was efficiently constructed by a novel Nazarov cyclization reaction containing basic nitrogen, which was less developed, primarily due to the incompatibility of basic nitrogen under acidic reaction conditions. This reaction allows a wide range of pentadienone substrates containing basic nitrogen to undergo Nazarov cyclization in a single regioselective and diastereoselective manner and is capable of generating three stereocenters simultaneously. Furthermore, the mechanism of the Nazarov cyclization and the origin of the regio- and diastereoselectivity were elucidated by DFT calculations and deuteration experiments, providing valuable insights into the reaction and serving as a guide for future applications involving substrates containing basic nitrogen.
2025, 36(6): 110259
doi: 10.1016/j.cclet.2024.110259
Abstract:
Molecularly imprinted polymers (MIPs) are a kind of synthetic receptors possessing wide application prospects in proteins recognition. However, there are still great challenges in proteins imprinting due to their large size and easy conformation change. In this study, we explored epitope-oriented MIP based on host-guest interaction (hg-MIP) and constructed a novel hg-MIP-SERS (surface-enhanced Raman scatting) approach for efficiently recognizing the terminal epitopes of neuron-specific enolase (NSE), a well-known disease biomarker for small cell lung cancer, neuroblstom, and Alzheimer's disease. The C- and N-terminal epitopes of NSE were modified with 4-(phenylazo) benzoic acid, then they were used as the templates and immobilized on β-cyclodextrin-functionalized substrates. The imprinted layer was formed by polymerization of various functional monomers. Combined with SERS detection, an antibody-free sandwich assay based on hg-MIP was successfully used to detect the concentration of NSE in human serums, with the advantages of simple operation, small sample volume (5 µL), wide linear range (1–104 ng/mL) and a limit of detection as low as 0.01 ng/mL. The developed epitope-oriented hg-MIP-SERS approach can also be extended to other proteins, expanding the imprinting method of proteins, and has a broad development space in the field of protein separation and detection.
Molecularly imprinted polymers (MIPs) are a kind of synthetic receptors possessing wide application prospects in proteins recognition. However, there are still great challenges in proteins imprinting due to their large size and easy conformation change. In this study, we explored epitope-oriented MIP based on host-guest interaction (hg-MIP) and constructed a novel hg-MIP-SERS (surface-enhanced Raman scatting) approach for efficiently recognizing the terminal epitopes of neuron-specific enolase (NSE), a well-known disease biomarker for small cell lung cancer, neuroblstom, and Alzheimer's disease. The C- and N-terminal epitopes of NSE were modified with 4-(phenylazo) benzoic acid, then they were used as the templates and immobilized on β-cyclodextrin-functionalized substrates. The imprinted layer was formed by polymerization of various functional monomers. Combined with SERS detection, an antibody-free sandwich assay based on hg-MIP was successfully used to detect the concentration of NSE in human serums, with the advantages of simple operation, small sample volume (5 µL), wide linear range (1–104 ng/mL) and a limit of detection as low as 0.01 ng/mL. The developed epitope-oriented hg-MIP-SERS approach can also be extended to other proteins, expanding the imprinting method of proteins, and has a broad development space in the field of protein separation and detection.
2025, 36(6): 110280
doi: 10.1016/j.cclet.2024.110280
Abstract:
Proteolysis-targeting chimera (PROTAC) has emerged as an efficient strategy to accurately control intracellular protein levels. However, conventional PROTACs are generally limited by nonspecific protein degradation and off-tissue side effects. Particularly, there is a lack of effective chemical tools for visualizing protein degradation. Herein, a near-infrared fluorescent and theranostic PROTAC (PRO-S-DCM) was designed for imaging the degradation of bromodomain-containing protein 4 (BRD4). PRO-S-DCM could be tumor-specifically activated and exhibited favorable imaging effects both in vitro and in vivo. PRO-S-DCM was proven to be a theranostic probe, which potently inhibited growth, invasion and migration of HeLa cells and induced cell apoptosis.
Proteolysis-targeting chimera (PROTAC) has emerged as an efficient strategy to accurately control intracellular protein levels. However, conventional PROTACs are generally limited by nonspecific protein degradation and off-tissue side effects. Particularly, there is a lack of effective chemical tools for visualizing protein degradation. Herein, a near-infrared fluorescent and theranostic PROTAC (PRO-S-DCM) was designed for imaging the degradation of bromodomain-containing protein 4 (BRD4). PRO-S-DCM could be tumor-specifically activated and exhibited favorable imaging effects both in vitro and in vivo. PRO-S-DCM was proven to be a theranostic probe, which potently inhibited growth, invasion and migration of HeLa cells and induced cell apoptosis.
2025, 36(6): 110281
doi: 10.1016/j.cclet.2024.110281
Abstract:
The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching (ACQ). In this study, an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters (Au NCs). Interestingly, the gold ion complexes coated with proteins of low isoelectric point (pI) nucleate at the secondary structure of proteins with high pI through ionic exchange within cells, generating fluorescent Au NCs. It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs, the distance between Au NCs can be controlled, avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ. This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects. Therefore, this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.
The potential of metal nanoclusters in biomedical applications is limited due to aggregation-caused quenching (ACQ). In this study, an in situ self-assembled pitaya structure was proposed to obtain stable fluorescence emission through protein coronas-controlled distance between gold nanoclusters (Au NCs). Interestingly, the gold ion complexes coated with proteins of low isoelectric point (pI) nucleate at the secondary structure of proteins with high pI through ionic exchange within cells, generating fluorescent Au NCs. It is worth noting that due to the steric hindrance formed by the protein coronas on the surface of Au NCs, the distance between Au NCs can be controlled, avoiding electron transfer caused by close proximity of Au NCs and inhibiting fluorescence ACQ. This strategy can achieve fluorescence imaging of clinical tissue samples without observable side effects. Therefore, this study proposes a distance-controllable self-assembled pitaya structure to provide a new approach for Au NCs with stable fluorescence.
2025, 36(6): 110285
doi: 10.1016/j.cclet.2024.110285
Abstract:
As PEGylated liposomes have witnessed remarkable advancements in drug delivery, their immunogenicity has emerged as a notable challenge. In this study, we discovered that a simple pre-injection of folic acid (FA) effectively mitigated the immunogenicity of PEGylated liposomes and enhanced their in vivo performance by tolerating splenic marginal zone B cells. FA specifically inhibited the internalization of PEGylated liposomes by splenic marginal zone B cells, thereby reducing splenic lymphocyte proliferation and specific IgM secretion. This modulation alleviated IgM-mediated accelerated blood clearance and adverse accumulation of the PEGylated liposomes in the skin. These findings provide new insights into the immunomodulatory effects of FA and promising avenues to enhance the efficacy and safety of PEGylated liposomal nanomedicines.
As PEGylated liposomes have witnessed remarkable advancements in drug delivery, their immunogenicity has emerged as a notable challenge. In this study, we discovered that a simple pre-injection of folic acid (FA) effectively mitigated the immunogenicity of PEGylated liposomes and enhanced their in vivo performance by tolerating splenic marginal zone B cells. FA specifically inhibited the internalization of PEGylated liposomes by splenic marginal zone B cells, thereby reducing splenic lymphocyte proliferation and specific IgM secretion. This modulation alleviated IgM-mediated accelerated blood clearance and adverse accumulation of the PEGylated liposomes in the skin. These findings provide new insights into the immunomodulatory effects of FA and promising avenues to enhance the efficacy and safety of PEGylated liposomal nanomedicines.
2025, 36(6): 110286
doi: 10.1016/j.cclet.2024.110286
Abstract:
Bacterial infection, insufficient angiogenesis, and oxidative damage are generally regarded as key issues that impede wound healing, making it necessary to prepare new biomaterials to simultaneously address these problems. In this work, monodispersed CeO2@CuS nanocomposites (NCs) were successfully prepared with tannin (TA) as the reductant and linker. Due to abundant oxygen vacancies in CeO2 and the polyphenolic structure of TA, the TA-CeO2@CuS NCs exhibited a remarkable antioxidant ability to scavenge excessive reactive oxygen species (ROS), which would likely induce serious inflammation. In addition, the TA-CeO2@CuS NCs demonstrated excellent antibacterial capability with near-infrared ray (NIR) irradiation, and the released copper ions could promote the regeneration of blood vessels. These synergistic effects indicated that the synthesized TA-CeO2@CuS NCs could serve as a promising biomaterial for multimodal wound therapy.
Bacterial infection, insufficient angiogenesis, and oxidative damage are generally regarded as key issues that impede wound healing, making it necessary to prepare new biomaterials to simultaneously address these problems. In this work, monodispersed CeO2@CuS nanocomposites (NCs) were successfully prepared with tannin (TA) as the reductant and linker. Due to abundant oxygen vacancies in CeO2 and the polyphenolic structure of TA, the TA-CeO2@CuS NCs exhibited a remarkable antioxidant ability to scavenge excessive reactive oxygen species (ROS), which would likely induce serious inflammation. In addition, the TA-CeO2@CuS NCs demonstrated excellent antibacterial capability with near-infrared ray (NIR) irradiation, and the released copper ions could promote the regeneration of blood vessels. These synergistic effects indicated that the synthesized TA-CeO2@CuS NCs could serve as a promising biomaterial for multimodal wound therapy.
2025, 36(6): 110290
doi: 10.1016/j.cclet.2024.110290
Abstract:
Currently, it is still a challenge to develop an organic photosensitizer (PS) with outstanding near-infrared absorption, low O2 dependence, precise tumor targeting and rapid clearance through the kidney to improve the overall outcome of phototherapy. In this study, we have designed an organic PS (NcPB) with an excellent near-infrared light absorption through a refined molecular strategy. Meanwhile, NcPB was assembled into nanoparticles with different sizes (NanoNcPB-1 and NanoNcPB-0) by a supramolecular modulation strategy. As the results, the nanoparticle with an ultra-small size (NanoNcPB-1) generated a large number of superoxide anion (O2•−) in a low-O2-dependent manner and release plenty of heat. Furthermore, the results of in vivo experiments demonstrated that NanoNcPB-1 actively accumulated in tumor tissues and showed a 92% tumor inhibition after photodynamic and photothermal combination therapy. More importantly, NanoNcPB-1 could be rapidly cleared from the body of mice via the renal pathway, which alleviates potential side effects of prolonged retention of PS in the circulation.
Currently, it is still a challenge to develop an organic photosensitizer (PS) with outstanding near-infrared absorption, low O2 dependence, precise tumor targeting and rapid clearance through the kidney to improve the overall outcome of phototherapy. In this study, we have designed an organic PS (NcPB) with an excellent near-infrared light absorption through a refined molecular strategy. Meanwhile, NcPB was assembled into nanoparticles with different sizes (NanoNcPB-1 and NanoNcPB-0) by a supramolecular modulation strategy. As the results, the nanoparticle with an ultra-small size (NanoNcPB-1) generated a large number of superoxide anion (O2•−) in a low-O2-dependent manner and release plenty of heat. Furthermore, the results of in vivo experiments demonstrated that NanoNcPB-1 actively accumulated in tumor tissues and showed a 92% tumor inhibition after photodynamic and photothermal combination therapy. More importantly, NanoNcPB-1 could be rapidly cleared from the body of mice via the renal pathway, which alleviates potential side effects of prolonged retention of PS in the circulation.
2025, 36(6): 110297
doi: 10.1016/j.cclet.2024.110297
Abstract:
Receptor tyrosine kinases (RTKs) are biological enzymes expressed on cell membranes that can influence cellular signaling, and their overexpression in tumor cells makes them a key route to assess relevant tumor processes. The development of a delivery system that targets and accumulates in RTKs overexpressing-cells at the on-target site is significant for the monitoring of tumor progression and clinical applications through longer tumor site signaling response under low injection frequency. Here, a host-guest nanoscale fluorescent probe SNI@ZIF-8 based on zeolitic imidazolate framework-8 (ZIF-8) and a fluorescent probe SNI constructed from receptor tyrosine kinase inhibitor was proposed and prepared for targeting RTKs and enabling prolonged fluorescence imaging in vivo. The folded conformation of the probe SNI resulted in low background fluorescence, and the unfolding of the SNI conformation upon insertion of the RTKs active pocket showed significant fluorescence enhancement thus enabling real-time detection of RTKs. The host-guest system SNI@ZIF-8 could release guest molecules due to the presence of the enzyme, emphasizing the reporting of stable fluorescent signals over time under low injection frequency. SNI@ZIF-8 could provide a signal response on the cell membrane of RTKs overexpressing cells without interference from other substances, and provided a longer fluorescent signal than SNI at equivalent number of injections in tumor-bearing mice. The host-guest system SNI@ZIF-8, with its obvious tumor site enrichment ability and clear fluorescence imaging ability, could be successfully applied to the detection of RTKs on cell membranes in biological systems, providing a new strategy for determining the process of tumor development in clinical applications.
Receptor tyrosine kinases (RTKs) are biological enzymes expressed on cell membranes that can influence cellular signaling, and their overexpression in tumor cells makes them a key route to assess relevant tumor processes. The development of a delivery system that targets and accumulates in RTKs overexpressing-cells at the on-target site is significant for the monitoring of tumor progression and clinical applications through longer tumor site signaling response under low injection frequency. Here, a host-guest nanoscale fluorescent probe SNI@ZIF-8 based on zeolitic imidazolate framework-8 (ZIF-8) and a fluorescent probe SNI constructed from receptor tyrosine kinase inhibitor was proposed and prepared for targeting RTKs and enabling prolonged fluorescence imaging in vivo. The folded conformation of the probe SNI resulted in low background fluorescence, and the unfolding of the SNI conformation upon insertion of the RTKs active pocket showed significant fluorescence enhancement thus enabling real-time detection of RTKs. The host-guest system SNI@ZIF-8 could release guest molecules due to the presence of the enzyme, emphasizing the reporting of stable fluorescent signals over time under low injection frequency. SNI@ZIF-8 could provide a signal response on the cell membrane of RTKs overexpressing cells without interference from other substances, and provided a longer fluorescent signal than SNI at equivalent number of injections in tumor-bearing mice. The host-guest system SNI@ZIF-8, with its obvious tumor site enrichment ability and clear fluorescence imaging ability, could be successfully applied to the detection of RTKs on cell membranes in biological systems, providing a new strategy for determining the process of tumor development in clinical applications.
2025, 36(6): 110301
doi: 10.1016/j.cclet.2024.110301
Abstract:
Breath analysis can be used to diagnose diseases non-invasively. Accurate measurement of volatolomics is critical for breath analysis to be a gold standard. Tedlar bags (TB) are often used to collect breath samples, but they emit contaminants that affect accuracy. This issue was overlooked in previous studies. We found contamination issues with TB (e.g., siloxanes and aromatic impurities) that affect the identification of volatile organic compounds (VOCs) due to impurities. Then, home-designed equipment (HD) made with poly-tetrafluoride (PTFE) and quartz glass for breath collection was developed and employed in clinical trials. 15 healthy individuals and 32 non-small cell lung cancer (NSCLC) patients at IA stage participated in this study. 610 VOCs can be collected through TB, which is less than HD (1109 VOCs), demonstrating that the inner wall of the TB easily adsorbs VOCs, leading to decreased detection concentrations. Otherwise, utilizing orthogonal partial least squares discriminant analysis (OPLS-DA), we identified chemical markers with significant discriminatory power (VIP > 1.5, P < 0.05). The HD method identified 12 target VOCs, surpassing the 3 target VOCs discerned by the TB method. A model combined with a machine learning algorithm for distinguishing early-stage lung cancer patients was established based on biomarkers, which were selected based on OPLS-DA. The results showed strong predictive capabilities for the HD-based model. It indicated that 12 biomarkers derived from the HD model were more effective in distinguishing NSCLC patients, with an AUC value of 0.92, compared to the AUC value of 0.5 from 3 markers obtained from the TB model. The sensitivity and specificity in the confusion matrix reached 100% and 80% for the HD test, but TB test reached only 40% and 60%. This work demonstrated that optimizing and standardizing VOCs collection methodology from breath of lung cancer patients is essential to identify actual volatiles, which could promote disease volatolomics worldwide.
Breath analysis can be used to diagnose diseases non-invasively. Accurate measurement of volatolomics is critical for breath analysis to be a gold standard. Tedlar bags (TB) are often used to collect breath samples, but they emit contaminants that affect accuracy. This issue was overlooked in previous studies. We found contamination issues with TB (e.g., siloxanes and aromatic impurities) that affect the identification of volatile organic compounds (VOCs) due to impurities. Then, home-designed equipment (HD) made with poly-tetrafluoride (PTFE) and quartz glass for breath collection was developed and employed in clinical trials. 15 healthy individuals and 32 non-small cell lung cancer (NSCLC) patients at IA stage participated in this study. 610 VOCs can be collected through TB, which is less than HD (1109 VOCs), demonstrating that the inner wall of the TB easily adsorbs VOCs, leading to decreased detection concentrations. Otherwise, utilizing orthogonal partial least squares discriminant analysis (OPLS-DA), we identified chemical markers with significant discriminatory power (VIP > 1.5, P < 0.05). The HD method identified 12 target VOCs, surpassing the 3 target VOCs discerned by the TB method. A model combined with a machine learning algorithm for distinguishing early-stage lung cancer patients was established based on biomarkers, which were selected based on OPLS-DA. The results showed strong predictive capabilities for the HD-based model. It indicated that 12 biomarkers derived from the HD model were more effective in distinguishing NSCLC patients, with an AUC value of 0.92, compared to the AUC value of 0.5 from 3 markers obtained from the TB model. The sensitivity and specificity in the confusion matrix reached 100% and 80% for the HD test, but TB test reached only 40% and 60%. This work demonstrated that optimizing and standardizing VOCs collection methodology from breath of lung cancer patients is essential to identify actual volatiles, which could promote disease volatolomics worldwide.
Synergistic effects of oxygen vacancies and Pd single atoms on Pd@TiO2−x for efficient HER catalysis
2025, 36(6): 110309
doi: 10.1016/j.cclet.2024.110309
Abstract:
Electrocatalytic water splitting for hydrogen production is a key approach to tackling the current energy crisis. Among the catalysts, the traditional Pd@C catalysts are remarkable for their efficiency in hydrogen evolution. However, the high cost and scarcity of Pd catalysts, as well as the instability caused by the corrosiveness of carbon-based substrates, hinder their large-scale application. To overcome this challenge, an effective strategy is to construct highly dispersed Pd single atoms to improve palladium utilization and choose more stable materials as supports. In this study, TiO2−x carriers with abundant oxygen vacancies were prepared and loaded with Pd by photoreduction deposition. Adjusting the palladium content resulted in three forms of Pd-loaded TiO2−x: nanoparticles (Pd@TiO2−x(6%, 10%)), nanoclusters (Pd@TiO2−x(3%)) and single atoms (Pd@TiO2−x(1.5%)). The oxygen vacancies improved the stability of the titanium dioxide materials by providing more active hydrogen adsorption sites and increasing the affinity of Pd for active hydrogen. Single atom loading increased the frequency of oxygen holes in the support and the high activity of monatomic Pd promoted the adsorption of active hydrogen and facilitated the formation of active hydrogen intermediates. The synergistic effect of single atoms and oxygen vacancies improved the stability and catalytic activity of the composite material. Pd@TiO2−x(1.5%) showed outstanding performance in hydrogen evolution in an acidic medium with an overpotential of only 24 mV at a current density of 10 mA/cm2 and a low Tafel rise of 41.9 mV/dec. This study provides an effective strategy for the development of high-performance hydrogen evolution (HER) catalysts.
Electrocatalytic water splitting for hydrogen production is a key approach to tackling the current energy crisis. Among the catalysts, the traditional Pd@C catalysts are remarkable for their efficiency in hydrogen evolution. However, the high cost and scarcity of Pd catalysts, as well as the instability caused by the corrosiveness of carbon-based substrates, hinder their large-scale application. To overcome this challenge, an effective strategy is to construct highly dispersed Pd single atoms to improve palladium utilization and choose more stable materials as supports. In this study, TiO2−x carriers with abundant oxygen vacancies were prepared and loaded with Pd by photoreduction deposition. Adjusting the palladium content resulted in three forms of Pd-loaded TiO2−x: nanoparticles (Pd@TiO2−x(6%, 10%)), nanoclusters (Pd@TiO2−x(3%)) and single atoms (Pd@TiO2−x(1.5%)). The oxygen vacancies improved the stability of the titanium dioxide materials by providing more active hydrogen adsorption sites and increasing the affinity of Pd for active hydrogen. Single atom loading increased the frequency of oxygen holes in the support and the high activity of monatomic Pd promoted the adsorption of active hydrogen and facilitated the formation of active hydrogen intermediates. The synergistic effect of single atoms and oxygen vacancies improved the stability and catalytic activity of the composite material. Pd@TiO2−x(1.5%) showed outstanding performance in hydrogen evolution in an acidic medium with an overpotential of only 24 mV at a current density of 10 mA/cm2 and a low Tafel rise of 41.9 mV/dec. This study provides an effective strategy for the development of high-performance hydrogen evolution (HER) catalysts.
2025, 36(6): 110315
doi: 10.1016/j.cclet.2024.110315
Abstract:
The efficacy of photodynamic therapy (PDT) for breast tumors is hindered by challenges such as inadequate tumor targeting, limited treatment depth, and strong oxygen dependence. Herein, a promising photosensitizer VP-B was developed to simultaneously address all the aforementioned issues for the treatment of hypoxic deep-seated breast tumors. The biotinylated photosensitizer VP-B not only exhibited precise targeting towards breast tumor tissue, but also efficiently triggered the generation of abundant 1O2 and O2−• under 690 nm red light irradiation. Indeed, the red light penetration ability enabled VP-B to achieve successful application in a mouse orthotopic breast tumor model. After intravenous administration, VP-B can selectively target tumor tissues and significantly inhibit the growth of hypoxic deep-seated tumors. Therefore, this new type Ⅰ & Ⅱ photosensitizer could boost fluorescence-guided photodynamic therapy of other hypoxic solid tumors.
The efficacy of photodynamic therapy (PDT) for breast tumors is hindered by challenges such as inadequate tumor targeting, limited treatment depth, and strong oxygen dependence. Herein, a promising photosensitizer VP-B was developed to simultaneously address all the aforementioned issues for the treatment of hypoxic deep-seated breast tumors. The biotinylated photosensitizer VP-B not only exhibited precise targeting towards breast tumor tissue, but also efficiently triggered the generation of abundant 1O2 and O2−• under 690 nm red light irradiation. Indeed, the red light penetration ability enabled VP-B to achieve successful application in a mouse orthotopic breast tumor model. After intravenous administration, VP-B can selectively target tumor tissues and significantly inhibit the growth of hypoxic deep-seated tumors. Therefore, this new type Ⅰ & Ⅱ photosensitizer could boost fluorescence-guided photodynamic therapy of other hypoxic solid tumors.
2025, 36(6): 110316
doi: 10.1016/j.cclet.2024.110316
Abstract:
Venetoclax (Vene), a BCL-2 inhibitor, is widely used as a chemotherapeutic drug in acute myeloid leukemia (AML). However, its treatment specificity for leukemia cells is limited, often leading to side effects and treatment resistance. In this study, we utilized l-phenylalanine as an efficient nanocarrier to enhance the delivery of Vene, forming the complex Vene@8P6. This complex was then applied to AML mouse models and human AML cell lines. The in vitro analysis showed that THP-1 and HL60 cells rapidly absorbed the Vene@8P6 nanoparticles. This absorption resulted in severe DNA damage, increased reactive oxygen species (ROS) production, elevated apoptosis rates, and decreased cell proliferation compared to the administration of Vene alone. In vivo studies demonstrated that Vene@8P6 more efficiently targeted leukemia cells than normal hematopoietic cells within the bone marrow and other major organs in AML mice, as evidenced by bioluminescence imaging and flow cytometry analysis. Furthermore, Vene@8P6 treatment resulted in reduced drug side effects and improved therapeutic efficacy in AML mice. Overall, Vene@8P6 represents a novel and efficient therapeutic agent for AML, offering enhanced leukemia target specificity, reduced side effects, and improved treatment outcomes.
Venetoclax (Vene), a BCL-2 inhibitor, is widely used as a chemotherapeutic drug in acute myeloid leukemia (AML). However, its treatment specificity for leukemia cells is limited, often leading to side effects and treatment resistance. In this study, we utilized l-phenylalanine as an efficient nanocarrier to enhance the delivery of Vene, forming the complex Vene@8P6. This complex was then applied to AML mouse models and human AML cell lines. The in vitro analysis showed that THP-1 and HL60 cells rapidly absorbed the Vene@8P6 nanoparticles. This absorption resulted in severe DNA damage, increased reactive oxygen species (ROS) production, elevated apoptosis rates, and decreased cell proliferation compared to the administration of Vene alone. In vivo studies demonstrated that Vene@8P6 more efficiently targeted leukemia cells than normal hematopoietic cells within the bone marrow and other major organs in AML mice, as evidenced by bioluminescence imaging and flow cytometry analysis. Furthermore, Vene@8P6 treatment resulted in reduced drug side effects and improved therapeutic efficacy in AML mice. Overall, Vene@8P6 represents a novel and efficient therapeutic agent for AML, offering enhanced leukemia target specificity, reduced side effects, and improved treatment outcomes.
2025, 36(6): 110317
doi: 10.1016/j.cclet.2024.110317
Abstract:
Programmed cell death protein 1/programmed cell death 1 ligand 1(PD-1/PD-L1) protein-protein interaction represents an appealing target for cancer therapy. Several antibody drugs have been developed to target this interaction, but they are less effective in the treatment of melanoma. To overcome the limitations, the first proteolysis-targeting chimeric (PROTAC) small molecules simultaneously targeting PD-L1 and Src homology phosphotyrosyl phosphatase 2 (SHP2) were designed. By employment of PD-1/PD-L1 inhibitors BMS01 or BMS-37, SHP2 inhibitor SHP099 and E3 ligase ligands, a series of potent PD-L1 and SHP2 dual PROTACs were synthesized. The most promising compounds BS-7C-V2 and BS327V2 efficiently induced PD-L1 and SHP2 degradation and demonstrated significantly improved immune potency in B16-F10 and A375 cell lines. More importantly, the efficacy of BS-7C-V2 and BS327V2 in a B16-F10 transplanted mouse model was further evaluated based on their degradation ability in vivo. Taken together, our work qualifies the new dual PROTACs as a potent degrader of PD-L1 and SHP2. The biological and mechanism investigations with BS-7C-V2 and BS327V2 prove that dual PROTACs can play an anti-tumor role in vivo and in vitro, and can provide a new therapeutic strategy for melanoma.
Programmed cell death protein 1/programmed cell death 1 ligand 1(PD-1/PD-L1) protein-protein interaction represents an appealing target for cancer therapy. Several antibody drugs have been developed to target this interaction, but they are less effective in the treatment of melanoma. To overcome the limitations, the first proteolysis-targeting chimeric (PROTAC) small molecules simultaneously targeting PD-L1 and Src homology phosphotyrosyl phosphatase 2 (SHP2) were designed. By employment of PD-1/PD-L1 inhibitors BMS01 or BMS-37, SHP2 inhibitor SHP099 and E3 ligase ligands, a series of potent PD-L1 and SHP2 dual PROTACs were synthesized. The most promising compounds BS-7C-V2 and BS327V2 efficiently induced PD-L1 and SHP2 degradation and demonstrated significantly improved immune potency in B16-F10 and A375 cell lines. More importantly, the efficacy of BS-7C-V2 and BS327V2 in a B16-F10 transplanted mouse model was further evaluated based on their degradation ability in vivo. Taken together, our work qualifies the new dual PROTACs as a potent degrader of PD-L1 and SHP2. The biological and mechanism investigations with BS-7C-V2 and BS327V2 prove that dual PROTACs can play an anti-tumor role in vivo and in vitro, and can provide a new therapeutic strategy for melanoma.
2025, 36(6): 110320
doi: 10.1016/j.cclet.2024.110320
Abstract:
H2O2 is an environmentally friendly oxidizing agent with minimal secondary pollution; however, its application has always been constrained by factors such as storage and transportation. In this study, we propose an innovative method for storing and releasing H2O2 using hydrogels. Commercial hydrogels (sodium polyacrylate) can undergo swelling and absorb H2O2 in aqueous solutions, and the swollen hydrogel can continuously release H2O2 under osmotic pressure. And the characteristics of osmotic pressure drive ensure the recyclability of hydrogel for H2O2 storage. Experimental results demonstrate that H2O2 can stably exist within the hydrogel for an extended period, and this strategy helps to avoid explosion the risk and potential environmental hazards during the transportation of H2O2. Finally, experiments confirm that the hydrogel controlled sustained release of H2O2 is effective in both Fenton reactions and the process of bacterial inactivation. This work introduces new ideas for the storage of H2O2, and the sustained release of H2O2 may have significant implications in the fields of healthcare, environmental science, catalysis, and beyond.
H2O2 is an environmentally friendly oxidizing agent with minimal secondary pollution; however, its application has always been constrained by factors such as storage and transportation. In this study, we propose an innovative method for storing and releasing H2O2 using hydrogels. Commercial hydrogels (sodium polyacrylate) can undergo swelling and absorb H2O2 in aqueous solutions, and the swollen hydrogel can continuously release H2O2 under osmotic pressure. And the characteristics of osmotic pressure drive ensure the recyclability of hydrogel for H2O2 storage. Experimental results demonstrate that H2O2 can stably exist within the hydrogel for an extended period, and this strategy helps to avoid explosion the risk and potential environmental hazards during the transportation of H2O2. Finally, experiments confirm that the hydrogel controlled sustained release of H2O2 is effective in both Fenton reactions and the process of bacterial inactivation. This work introduces new ideas for the storage of H2O2, and the sustained release of H2O2 may have significant implications in the fields of healthcare, environmental science, catalysis, and beyond.
2025, 36(6): 110322
doi: 10.1016/j.cclet.2024.110322
Abstract:
Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation, they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery. Therefore, the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts. In this work, an efficient catalyst was developed with Co-Nx configuration facilely reconstructed on the surface of Co3O4 (Co-Nx/Co3O4), which exhibited superior catalytic activity. We further fixed the highly efficient Co-Nx/Co3O4 onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability. Results indicated that the inorganic ceramic membrane (CM) can achieve high water flux of 710 L m-2 h-1, and the similar water flux can be achieved by Co-Nx/Co3O4/CM even without the pressure extraction. We also employed the Co-Nx/Co3O4/CM system to the wastewater secondary effluent, and the pollutant in complicated secondary effluent could be highly removed by the Co-Nx/Co3O4/CM system. This paper provides a new point of view for the application of metal-based catalysts with M-Nx coordination in catalytic reaction device.
Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation, they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery. Therefore, the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts. In this work, an efficient catalyst was developed with Co-Nx configuration facilely reconstructed on the surface of Co3O4 (Co-Nx/Co3O4), which exhibited superior catalytic activity. We further fixed the highly efficient Co-Nx/Co3O4 onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability. Results indicated that the inorganic ceramic membrane (CM) can achieve high water flux of 710 L m-2 h-1, and the similar water flux can be achieved by Co-Nx/Co3O4/CM even without the pressure extraction. We also employed the Co-Nx/Co3O4/CM system to the wastewater secondary effluent, and the pollutant in complicated secondary effluent could be highly removed by the Co-Nx/Co3O4/CM system. This paper provides a new point of view for the application of metal-based catalysts with M-Nx coordination in catalytic reaction device.
2025, 36(6): 110333
doi: 10.1016/j.cclet.2024.110333
Abstract:
Although diverse signal-amplified methods have been committed to improve the sensitivity of surface plasmon resonance (SPR) biosensing, introducing convenient and robust signal amplification strategy into SPR biosensing remains challenging. Here, a novel nanozyme-triggered polymerization amplification strategy was proposed for constructing highly sensitive surface plasmon resonance (SPR) immunosensor. In detail, Au@Pd core-shell nanooctahedra nanozyme with superior peroxidase (POD)-like activity was synthesized and utilized as a label probe. Simultaneously, Au@Pd core-shell nanooctahedra nanozyme can catalyze the decomposition of H2O2 to form hydroxyl radicals (•OH) that triggers the polymerization of aniline to form polyaniline attaching on the surface of sensor chip, significantly amplifying SPR responses. The sensitivity of SPR immunosensor was enhanced by nanozyme-triggered polymerization amplification strategy. Using human immunoglobulin G (HIgG) as a model, the constructed SPR immunosensor obtains a wide linear range of 0.005–1.0 µg/mL with low detection limit of 0.106 ng/mL. This research provides new sights on establishing sensitive SPR immunosensor and may evokes more inspiration for developing signal amplification methods based on nanozyme in biosensing.
Although diverse signal-amplified methods have been committed to improve the sensitivity of surface plasmon resonance (SPR) biosensing, introducing convenient and robust signal amplification strategy into SPR biosensing remains challenging. Here, a novel nanozyme-triggered polymerization amplification strategy was proposed for constructing highly sensitive surface plasmon resonance (SPR) immunosensor. In detail, Au@Pd core-shell nanooctahedra nanozyme with superior peroxidase (POD)-like activity was synthesized and utilized as a label probe. Simultaneously, Au@Pd core-shell nanooctahedra nanozyme can catalyze the decomposition of H2O2 to form hydroxyl radicals (•OH) that triggers the polymerization of aniline to form polyaniline attaching on the surface of sensor chip, significantly amplifying SPR responses. The sensitivity of SPR immunosensor was enhanced by nanozyme-triggered polymerization amplification strategy. Using human immunoglobulin G (HIgG) as a model, the constructed SPR immunosensor obtains a wide linear range of 0.005–1.0 µg/mL with low detection limit of 0.106 ng/mL. This research provides new sights on establishing sensitive SPR immunosensor and may evokes more inspiration for developing signal amplification methods based on nanozyme in biosensing.
2025, 36(6): 110335
doi: 10.1016/j.cclet.2024.110335
Abstract:
Invasive fibroblast-like synoviocytes (FLS), inflammatory macrophages and osteoclasts are the main three contributors to rheumatoid arthritis (RA) progression by promoting synovial inflammation and destructing cartilage and bone. Targeting these three cell types for restoring the inflammatory homeostasis microenvironment may be a promising anti-RA strategy. Herein, we prepared a reactive oxygen species (ROS)-responsive micelles (DPTM) to co-load dexamethasone (DEX) and pristimerin (PRI) for RA therapy. This ROS-responsive system exhibits the following advantages: (1) It makes use of the "ELVIS" effect for passive delivery and targeting the ROS environment of RA-related cells to rapidly release the payload drugs DEX and PRI. (2) Compared with free drugs, DPTM showed stronger effect on the inhibition of RA-FLS proliferation and the promotion of RA-FLS apoptosis. Moreover, DPTM could significantly weaken the migration ability of RA-FLS as indicated by the results of wound healing assay and transwell assay. (3) DPTM exerted stronger cellular uptake and anti-inflammatory effect in M1 macrophages. (4) In the model studying receptor activator of nuclear factor kappa-B ligand (RANKL)-induced differentiation of bone marrow-derived macrophages (BMDMs) to osteoclasts, DPTM showed a stronger inhibitory activity on osteoclast formation as compared to free drugs. Taken together, these results highlighted the potential of DPTM for targeted RA therapy via inhibition of RA-FLS abnormal activation, macrophage polarization and osteoclastogenesis.
Invasive fibroblast-like synoviocytes (FLS), inflammatory macrophages and osteoclasts are the main three contributors to rheumatoid arthritis (RA) progression by promoting synovial inflammation and destructing cartilage and bone. Targeting these three cell types for restoring the inflammatory homeostasis microenvironment may be a promising anti-RA strategy. Herein, we prepared a reactive oxygen species (ROS)-responsive micelles (DPTM) to co-load dexamethasone (DEX) and pristimerin (PRI) for RA therapy. This ROS-responsive system exhibits the following advantages: (1) It makes use of the "ELVIS" effect for passive delivery and targeting the ROS environment of RA-related cells to rapidly release the payload drugs DEX and PRI. (2) Compared with free drugs, DPTM showed stronger effect on the inhibition of RA-FLS proliferation and the promotion of RA-FLS apoptosis. Moreover, DPTM could significantly weaken the migration ability of RA-FLS as indicated by the results of wound healing assay and transwell assay. (3) DPTM exerted stronger cellular uptake and anti-inflammatory effect in M1 macrophages. (4) In the model studying receptor activator of nuclear factor kappa-B ligand (RANKL)-induced differentiation of bone marrow-derived macrophages (BMDMs) to osteoclasts, DPTM showed a stronger inhibitory activity on osteoclast formation as compared to free drugs. Taken together, these results highlighted the potential of DPTM for targeted RA therapy via inhibition of RA-FLS abnormal activation, macrophage polarization and osteoclastogenesis.
2025, 36(6): 110337
doi: 10.1016/j.cclet.2024.110337
Abstract:
The significance of axial chiral compounds in asymmetric organic catalysis, functional materials, and pharmaceutical useful molecules has encouraged advancements in the atroposelective synthesis of such compounds. Herein, we report the first atroposelective construction of axially chiral N-aryl benzimidazoles catalyzed by a polymer-supported chiral phosphoric acid. A varied library of atropisomers has been synthesized in 30%-96% yield with 58%-98% enantiomeric excess (ee) under a straightforward reaction setup (without the use of molecular sieves). Notably, even after 12 cycles, the immobilized catalyst maintained its reactivity and selectivity (TON > 540).
The significance of axial chiral compounds in asymmetric organic catalysis, functional materials, and pharmaceutical useful molecules has encouraged advancements in the atroposelective synthesis of such compounds. Herein, we report the first atroposelective construction of axially chiral N-aryl benzimidazoles catalyzed by a polymer-supported chiral phosphoric acid. A varied library of atropisomers has been synthesized in 30%-96% yield with 58%-98% enantiomeric excess (ee) under a straightforward reaction setup (without the use of molecular sieves). Notably, even after 12 cycles, the immobilized catalyst maintained its reactivity and selectivity (TON > 540).
2025, 36(6): 110338
doi: 10.1016/j.cclet.2024.110338
Abstract:
Benziodazole-triflate, as a novel heterocyclic hypervalent iodine(Ⅲ) reagent, was prepared from the reaction of hypervalent chloroiodine(Ⅲ) with silver triflate under mild conditions. The structure of this new reagent was elucidated by NMR spectroscopy and X-ray crystallography, and its reactions with diverse α-electron withdrawing group substituted carbonyl compounds were investigated. The results implied that benziodazole-triflate could be selectively used as both a 2-iodobenzamido-transfer reagent for the synthesis of oxazole compounds, and a triflate-transfer reagent for the triflation of β-keto-sulfones. Ionic mechanistic pathways, supported by density functional theory (DFT) calculations, were proposed to account for the divergent selectivities of the transformations.
Benziodazole-triflate, as a novel heterocyclic hypervalent iodine(Ⅲ) reagent, was prepared from the reaction of hypervalent chloroiodine(Ⅲ) with silver triflate under mild conditions. The structure of this new reagent was elucidated by NMR spectroscopy and X-ray crystallography, and its reactions with diverse α-electron withdrawing group substituted carbonyl compounds were investigated. The results implied that benziodazole-triflate could be selectively used as both a 2-iodobenzamido-transfer reagent for the synthesis of oxazole compounds, and a triflate-transfer reagent for the triflation of β-keto-sulfones. Ionic mechanistic pathways, supported by density functional theory (DFT) calculations, were proposed to account for the divergent selectivities of the transformations.
2025, 36(6): 110339
doi: 10.1016/j.cclet.2024.110339
Abstract:
Regioselevtive functionalization of perylene diimides (PDIs) at bay area often requires multistep synthesis and strenuous recrystallization. Direct bromination of perylene diimides only afford the 1, 6 and 1, 7-regioisomers. More importantly, the 1, 6-dibromo regioisomers could only be separated by preparative HPLC. Herein, we report a promising strategy for constructing Janus backbone of BN-doped perylene diimide derivatives. This Janus-type configuration results in the unique regioselective functionalization of BN-JPDIs, which yields exclusively the 1, 6-regioisomers. Further investigation shows that the Janus-type configuration leads to a net dipole moment of 1.94 D and intramolecular charge transfer, which causes substantial changes on the optoelectronic properties. Moreover, the single crystal organic field-effect transistors based on BN-JPDIs exhibit electron mobilities up to 0.57 cm2 V−1 s−1, showcasing their potential as versatile building block towards high-performance n-type organic semiconductors.
Regioselevtive functionalization of perylene diimides (PDIs) at bay area often requires multistep synthesis and strenuous recrystallization. Direct bromination of perylene diimides only afford the 1, 6 and 1, 7-regioisomers. More importantly, the 1, 6-dibromo regioisomers could only be separated by preparative HPLC. Herein, we report a promising strategy for constructing Janus backbone of BN-doped perylene diimide derivatives. This Janus-type configuration results in the unique regioselective functionalization of BN-JPDIs, which yields exclusively the 1, 6-regioisomers. Further investigation shows that the Janus-type configuration leads to a net dipole moment of 1.94 D and intramolecular charge transfer, which causes substantial changes on the optoelectronic properties. Moreover, the single crystal organic field-effect transistors based on BN-JPDIs exhibit electron mobilities up to 0.57 cm2 V−1 s−1, showcasing their potential as versatile building block towards high-performance n-type organic semiconductors.
2025, 36(6): 110341
doi: 10.1016/j.cclet.2024.110341
Abstract:
Fluorescence imaging-guided photodynamic therapy holds great promise for application in precise cancer diagnosis and treatment, which has motivated high requirements for phototheranostic agents. However, current photosensitizers (PSs) generally face limitations such as short emission wavelength and inadequate reactive oxygen species (ROS) production. Aggregation-caused quenching issue also hinders the phototheranostic efficiency of PSs. Herein, the π-bridge modulation strategy is proposed to construct ionic PSs with enhanced bioimaging and therapeutic outcomes. Two donor-π-acceptor (D-π-A) molecules TPCPY and TFCPY were obtained by incorporating phenyl and furan units as π-bridge, respectively. Both PSs feature aggregation-induced near-infrared emission. Under light irradiation, TPCPY and TFCPY can produce both type Ⅰ and Ⅱ ROS. Introducing furan ring in TFCPY enhances the ROS generation capacity by type Ⅰ photosensitization process, which is consistent with the reduced energy gap between singlet and triplet states from theoretical calculation. Furthermore, TFCPY can achieve quick cellular uptake, accumulate in mitochondria, and then efficiently kill cancer cells, which is superior to TPCPY. Consequently, TFCPY exhibited good antitumor outcomes and excellent in vivo fluorescence imaging ability. This work provides an efficient molecular engineering of introducing heterocycles into the D-π-A skeleton to develop high-performance PSs with both type Ⅰ and Ⅱ ROS generation.
Fluorescence imaging-guided photodynamic therapy holds great promise for application in precise cancer diagnosis and treatment, which has motivated high requirements for phototheranostic agents. However, current photosensitizers (PSs) generally face limitations such as short emission wavelength and inadequate reactive oxygen species (ROS) production. Aggregation-caused quenching issue also hinders the phototheranostic efficiency of PSs. Herein, the π-bridge modulation strategy is proposed to construct ionic PSs with enhanced bioimaging and therapeutic outcomes. Two donor-π-acceptor (D-π-A) molecules TPCPY and TFCPY were obtained by incorporating phenyl and furan units as π-bridge, respectively. Both PSs feature aggregation-induced near-infrared emission. Under light irradiation, TPCPY and TFCPY can produce both type Ⅰ and Ⅱ ROS. Introducing furan ring in TFCPY enhances the ROS generation capacity by type Ⅰ photosensitization process, which is consistent with the reduced energy gap between singlet and triplet states from theoretical calculation. Furthermore, TFCPY can achieve quick cellular uptake, accumulate in mitochondria, and then efficiently kill cancer cells, which is superior to TPCPY. Consequently, TFCPY exhibited good antitumor outcomes and excellent in vivo fluorescence imaging ability. This work provides an efficient molecular engineering of introducing heterocycles into the D-π-A skeleton to develop high-performance PSs with both type Ⅰ and Ⅱ ROS generation.
2025, 36(6): 110343
doi: 10.1016/j.cclet.2024.110343
Abstract:
Carbon dots (CDs)-based composites have shown impressive performance in fields of information encryption and sensing, however, a great challenge is to simultaneously implement multi-mode luminescence and room-temperature phosphorescence (RTP) detection in single system due to the formidable synthesis. Herein, a multifunctional composite of Eu&CDs@pRHO has been designed by co-assembly strategy and prepared via a facile calcination and impregnation treatment. Eu&CDs@pRHO exhibits intense fluorescence (FL) and RTP coming from two individual luminous centers, Eu3+ in the free pores and CDs in the interrupted structure of RHO zeolite. Unique four-mode color outputs including pink (Eu3+, ex. 254 nm), light violet (CDs, ex. 365 nm), blue (CDs, 254 nm off), and green (CDs, 365 nm off) could be realized, on the basis of it, a preliminary application of advanced information encoding has been demonstrated. Given the free pores of matrix and stable RTP in water of confined CDs, a visual RTP detection of Fe3+ ions is achieved with the detection limit as low as 9.8 µmol/L. This work has opened up a new perspective for the strategic amalgamation of luminous guests with porous zeolite to construct the advanced functional materials.
Carbon dots (CDs)-based composites have shown impressive performance in fields of information encryption and sensing, however, a great challenge is to simultaneously implement multi-mode luminescence and room-temperature phosphorescence (RTP) detection in single system due to the formidable synthesis. Herein, a multifunctional composite of Eu&CDs@pRHO has been designed by co-assembly strategy and prepared via a facile calcination and impregnation treatment. Eu&CDs@pRHO exhibits intense fluorescence (FL) and RTP coming from two individual luminous centers, Eu3+ in the free pores and CDs in the interrupted structure of RHO zeolite. Unique four-mode color outputs including pink (Eu3+, ex. 254 nm), light violet (CDs, ex. 365 nm), blue (CDs, 254 nm off), and green (CDs, 365 nm off) could be realized, on the basis of it, a preliminary application of advanced information encoding has been demonstrated. Given the free pores of matrix and stable RTP in water of confined CDs, a visual RTP detection of Fe3+ ions is achieved with the detection limit as low as 9.8 µmol/L. This work has opened up a new perspective for the strategic amalgamation of luminous guests with porous zeolite to construct the advanced functional materials.
2025, 36(6): 110347
doi: 10.1016/j.cclet.2024.110347
Abstract:
Electrochemical nitrate reduction (NO3RR) offers a promising avenue for treating nitrate-contaminated water and recovering ammonia (NH3), yet the complexities of direct electron transfer (DET) and hydrogen atom transfer (HAT) mechanisms crucial for efficiency remain elusive. This study bridges the gap with a combined experimental and theoretical approach, elucidating the impact of catalyst structure on NO3RR pathways. We discover that catalysts favoring strong NO3− adsorption and efficient water dissociation were more inclined towards DET, enhancing denitrification. The Fe@Fe3O4/FF cathode, leveraging the synergistic interplay between metallic Fe and Fe3O4, excelled in NO3RR via DET, achieving an NH3 yield of 0.28 mmol h−1 cm−2 and a Faradaic efficiency of 95.7% for NH3 at -1.6 V (vs. SCE), with minimal nitrite accumulation at 100 mmol/L nitrate. Conversely, the Fe/FF and Fe3O4/CC cathodes showed reduced NH3 production and increased nitrite levels, attributed to the lack of Fe3O4 and metallic Fe, respectively, resulting in a dominant HAT mechanism. Moreover, Fe@Fe3O4/FF facilitated complete denitrification in real wastewater treatment by harnessing Cl− for electrochemically mediated breakpoint chlorination. This research not only deepens our understanding of NO3RR mechanisms but also paves the way for designing superior nitrate reduction catalysts.
Electrochemical nitrate reduction (NO3RR) offers a promising avenue for treating nitrate-contaminated water and recovering ammonia (NH3), yet the complexities of direct electron transfer (DET) and hydrogen atom transfer (HAT) mechanisms crucial for efficiency remain elusive. This study bridges the gap with a combined experimental and theoretical approach, elucidating the impact of catalyst structure on NO3RR pathways. We discover that catalysts favoring strong NO3− adsorption and efficient water dissociation were more inclined towards DET, enhancing denitrification. The Fe@Fe3O4/FF cathode, leveraging the synergistic interplay between metallic Fe and Fe3O4, excelled in NO3RR via DET, achieving an NH3 yield of 0.28 mmol h−1 cm−2 and a Faradaic efficiency of 95.7% for NH3 at -1.6 V (vs. SCE), with minimal nitrite accumulation at 100 mmol/L nitrate. Conversely, the Fe/FF and Fe3O4/CC cathodes showed reduced NH3 production and increased nitrite levels, attributed to the lack of Fe3O4 and metallic Fe, respectively, resulting in a dominant HAT mechanism. Moreover, Fe@Fe3O4/FF facilitated complete denitrification in real wastewater treatment by harnessing Cl− for electrochemically mediated breakpoint chlorination. This research not only deepens our understanding of NO3RR mechanisms but also paves the way for designing superior nitrate reduction catalysts.
2025, 36(6): 110348
doi: 10.1016/j.cclet.2024.110348
Abstract:
Studies widely acknowledge the enhancement of permanganate (Mn(Ⅶ)) oxidation of organic contaminants by coexisting matrices in water. This study investigated the positive influence of Mn(Ⅱ), a common soluble metal ion, on the removal of trace organic pollutants by Mn(Ⅶ). Results showed that introducing 20 µmol/L Mn(Ⅱ) at pH 5.0 accelerated trace organic pollutant removal by promoting colloidal MnO2 formation. UV−vis spectrum, quenching, and probe experiments confirmed role of MnO2 in sulfamethoxazole (SMX) oxidation, with Mn(Ⅲ) playing a predominant role. Meanwhile, in situ-generated MnO2 facilitated Mn(Ⅶ)* formation, enhancing oxidation performance, as indicated by Raman spectroscopy and electrochemical analysis. Eleven transformation products (TPs) of SMX in the Mn(Ⅶ)/Mn(Ⅱ) process were detected by UPLC-QTOF-MS/MS. Subsequently, the reaction pathways of SMX were elucidated through Fukui index analysis and the identification of TPs. Additionally, toxicity simulations with Toxicity Estimation Software Tool (T.E.S.T.) software revealed significantly lower cytotoxicity of TPs of SMX compared to the parent compound. This study unveils an effective strategy to enhance Mn(Ⅶ)-mediated degradation of organic pollutants in water, elucidating Mn(Ⅱ)-induced Mn(Ⅶ) activation mechanisms.
Studies widely acknowledge the enhancement of permanganate (Mn(Ⅶ)) oxidation of organic contaminants by coexisting matrices in water. This study investigated the positive influence of Mn(Ⅱ), a common soluble metal ion, on the removal of trace organic pollutants by Mn(Ⅶ). Results showed that introducing 20 µmol/L Mn(Ⅱ) at pH 5.0 accelerated trace organic pollutant removal by promoting colloidal MnO2 formation. UV−vis spectrum, quenching, and probe experiments confirmed role of MnO2 in sulfamethoxazole (SMX) oxidation, with Mn(Ⅲ) playing a predominant role. Meanwhile, in situ-generated MnO2 facilitated Mn(Ⅶ)* formation, enhancing oxidation performance, as indicated by Raman spectroscopy and electrochemical analysis. Eleven transformation products (TPs) of SMX in the Mn(Ⅶ)/Mn(Ⅱ) process were detected by UPLC-QTOF-MS/MS. Subsequently, the reaction pathways of SMX were elucidated through Fukui index analysis and the identification of TPs. Additionally, toxicity simulations with Toxicity Estimation Software Tool (T.E.S.T.) software revealed significantly lower cytotoxicity of TPs of SMX compared to the parent compound. This study unveils an effective strategy to enhance Mn(Ⅶ)-mediated degradation of organic pollutants in water, elucidating Mn(Ⅱ)-induced Mn(Ⅶ) activation mechanisms.
2025, 36(6): 110349
doi: 10.1016/j.cclet.2024.110349
Abstract:
Metal halide perovskite nanocrystals (MHP NCs) are of great candidates in photocatalytic applications due to their extreme light utilization efficiency. However, the instability towards humid environment severely restrict their practical application. Herein, the CsPbBr3/CsPb2Br5 heteronanocrystals (HNCs) were successfully encapsulated into ZIF-8 through a thermal injection method via controlling the molar ratio of Cs+/Pb2+. The surface of ZIF-8 was then modified with hydrophobic copolymer of poly(methyl methacrylate) (PMMA) to improve the water stability. Benefiting from the intimate interfacial interaction and staggered energy band structure, the type-Ⅱ heterojunction of CsPbBr3/CsPb2Br5 guarantees efficient separation and migration of photogenerated electron/hole pairs. Meanwhile, the formation of Z-scheme heterojunction between ZIF-8 and CsPbBr3/CsPb2Br5 HNCs contributes to the adsorption and enrichment of pollutants, further accelerates the photocatalytic antibiotic degradation efficiency towards tetracycline hydrochloride (TCH) in aqueous solution. Nearly 87% of TCH (40 mg/L, 50 mL) was degraded by 40 mg catalyst within 100 min. This work offers a feasible approach in assembling high-performance MHP NCs-based efficient photocatalyst with expanding application in aqueous solution.
Metal halide perovskite nanocrystals (MHP NCs) are of great candidates in photocatalytic applications due to their extreme light utilization efficiency. However, the instability towards humid environment severely restrict their practical application. Herein, the CsPbBr3/CsPb2Br5 heteronanocrystals (HNCs) were successfully encapsulated into ZIF-8 through a thermal injection method via controlling the molar ratio of Cs+/Pb2+. The surface of ZIF-8 was then modified with hydrophobic copolymer of poly(methyl methacrylate) (PMMA) to improve the water stability. Benefiting from the intimate interfacial interaction and staggered energy band structure, the type-Ⅱ heterojunction of CsPbBr3/CsPb2Br5 guarantees efficient separation and migration of photogenerated electron/hole pairs. Meanwhile, the formation of Z-scheme heterojunction between ZIF-8 and CsPbBr3/CsPb2Br5 HNCs contributes to the adsorption and enrichment of pollutants, further accelerates the photocatalytic antibiotic degradation efficiency towards tetracycline hydrochloride (TCH) in aqueous solution. Nearly 87% of TCH (40 mg/L, 50 mL) was degraded by 40 mg catalyst within 100 min. This work offers a feasible approach in assembling high-performance MHP NCs-based efficient photocatalyst with expanding application in aqueous solution.
2025, 36(6): 110350
doi: 10.1016/j.cclet.2024.110350
Abstract:
In the fight against bacterial infections, it is critical to effectively disrupt biofilms. However, disruption of biofilms becomes exceptionally difficult due to the low permeability of therapeutic agents. Herein, we present a self-propelled nanovesicle (PCL-PLG@CHX) strategy for eliminating biofilms and further expediting the healing of wounds. PCL-PLG@CHX is synthesized by assembling vesicles from amphiphilic polymers, which incorporate both poly-ε-caprolactone and guanidinated-poly-ε-lysine (PCL-PLG) and are infused with chlorhexidine (CHX). Upon application to sites of bacterial infection, PCL-PLG@CHX, abundant in guanidinium structures, effectively accumulates on the negatively charged surface of biofilms. It interacts with reactive oxygen species (ROS) within the biofilm, leading to nitric oxide (NO) production. The generated NO cannot only propel the nanovesicle to penetrate deeper into the biofilm, but also act as a signaling molecule to disperse the biofilm, working in conjunction with the subsequent release of CHX for an enhanced antibacterial impact. Following the eradication of bacteria, the residual guanidine component continues to produce small quantities of NO, facilitating angiogenesis and epithelial growth, thereby accelerating the healing of wounds. Together, our study shows that PCL-PLG@CHX utilizes the potential of guanidine moieties to efficiently break down biofilms and support tissue restoration, tackling the pivotal challenge of biofilm-related diseases.
In the fight against bacterial infections, it is critical to effectively disrupt biofilms. However, disruption of biofilms becomes exceptionally difficult due to the low permeability of therapeutic agents. Herein, we present a self-propelled nanovesicle (PCL-PLG@CHX) strategy for eliminating biofilms and further expediting the healing of wounds. PCL-PLG@CHX is synthesized by assembling vesicles from amphiphilic polymers, which incorporate both poly-ε-caprolactone and guanidinated-poly-ε-lysine (PCL-PLG) and are infused with chlorhexidine (CHX). Upon application to sites of bacterial infection, PCL-PLG@CHX, abundant in guanidinium structures, effectively accumulates on the negatively charged surface of biofilms. It interacts with reactive oxygen species (ROS) within the biofilm, leading to nitric oxide (NO) production. The generated NO cannot only propel the nanovesicle to penetrate deeper into the biofilm, but also act as a signaling molecule to disperse the biofilm, working in conjunction with the subsequent release of CHX for an enhanced antibacterial impact. Following the eradication of bacteria, the residual guanidine component continues to produce small quantities of NO, facilitating angiogenesis and epithelial growth, thereby accelerating the healing of wounds. Together, our study shows that PCL-PLG@CHX utilizes the potential of guanidine moieties to efficiently break down biofilms and support tissue restoration, tackling the pivotal challenge of biofilm-related diseases.
2025, 36(6): 110352
doi: 10.1016/j.cclet.2024.110352
Abstract:
A novel organocatalytic asymmetric approach to oxazoline derivatives that proceeds through Mannich/annulation reaction of N-acylimines with 3-chlorooxindoles is presented. This strategy provides an efficient and convenient method to access enantioenriched oxazolines such as valuable chiral S, N-oxazoline ligand as well as Ferrox ligand in high yields with excellent enantio– and diastereroselectivity. Furthermore, the optically active oxazoline products can be converted to valuable 1, 2-amino alcohols. More importantly, the synthetic utility of this transformation is demonstrated in the expeditious assembly of chiral Phox-type ligand, which shows excellent catalytic activities.
A novel organocatalytic asymmetric approach to oxazoline derivatives that proceeds through Mannich/annulation reaction of N-acylimines with 3-chlorooxindoles is presented. This strategy provides an efficient and convenient method to access enantioenriched oxazolines such as valuable chiral S, N-oxazoline ligand as well as Ferrox ligand in high yields with excellent enantio– and diastereroselectivity. Furthermore, the optically active oxazoline products can be converted to valuable 1, 2-amino alcohols. More importantly, the synthetic utility of this transformation is demonstrated in the expeditious assembly of chiral Phox-type ligand, which shows excellent catalytic activities.
2025, 36(6): 110354
doi: 10.1016/j.cclet.2024.110354
Abstract:
Herein, we report the design and synthesis of alternating donor-acceptor nanorings [3]C-NA and [4]C-NA, along with a reference linear molecule [3]L-NA, via electrochemical oxidation-induced reductive elimination of alkynyl platinum(Ⅱ) complexes. Unlike [3]L-NA, which exhibits charge defects at its end-groups, the cyclic structures of [3]C-NA and [4]C-NA facilitate enhanced electron delocalization, enabling efficient charge transfer in low-polarity toluene. In the polar solvent dichloromethane (DCM), the increased flexibility of [4]C-NA promotes intramolecular charge transfer and suppresses charge recombination. The observed faster intramolecular charge transfer and slower charge recombination rates in these nanoring acceptor materials suggest their potential for improving the power conversion efficiency of organic solar cells, providing valuable insights for the design of nanoring acceptor materials.
Herein, we report the design and synthesis of alternating donor-acceptor nanorings [3]C-NA and [4]C-NA, along with a reference linear molecule [3]L-NA, via electrochemical oxidation-induced reductive elimination of alkynyl platinum(Ⅱ) complexes. Unlike [3]L-NA, which exhibits charge defects at its end-groups, the cyclic structures of [3]C-NA and [4]C-NA facilitate enhanced electron delocalization, enabling efficient charge transfer in low-polarity toluene. In the polar solvent dichloromethane (DCM), the increased flexibility of [4]C-NA promotes intramolecular charge transfer and suppresses charge recombination. The observed faster intramolecular charge transfer and slower charge recombination rates in these nanoring acceptor materials suggest their potential for improving the power conversion efficiency of organic solar cells, providing valuable insights for the design of nanoring acceptor materials.
2025, 36(6): 110366
doi: 10.1016/j.cclet.2024.110366
Abstract:
Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) is an attractive technology for the visualization of metabolite distributions in tissues. However, detection and identification of low-abundance or poorly ionized metabolites remains challenging. Although on-tissue chemical derivatization (OTCD) holds great promise for improving MALDI MS detection sensitivity and selectivity by modification of specific chemical groups, the available methods for subsequent metabolite annotation are limited. Herein, a laser-assisted chemical transfer (LACT)-based parallel OTCD strategy was established for visualizing and annotating carbonyl metabolites in murine brain tissues. Girard's T and Girard's P reagents were applied for parallel OTCD to generate the characteristic m/z pairs with a 19.969 Da mass shift (±0.020 Da tolerance) for rapid recognition of derivatized metabolites. The similarity of spatial distribution patterns of each m/z pair was further statistically evaluated to remove the ambiguous annotations due to the occurrence of interference compounds. As a result, 90 ion pairs were annotated as candidate carbonyl metabolites, 66 were previously known and 24 were potential unreported carbonyls. Furthermore, the spatial alterations of carbonyl metabolites in the ischemic rat brain were successfully visualized and characterized, including small molecule aldehydes and ketones, long-chain fatty aldehydes, and monosaccharides. This further emphasizes great potential of parallel OTCD strategy for efficient and confident molecular annotation of spatial submetabolomics data associated with brain diseases.
Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) is an attractive technology for the visualization of metabolite distributions in tissues. However, detection and identification of low-abundance or poorly ionized metabolites remains challenging. Although on-tissue chemical derivatization (OTCD) holds great promise for improving MALDI MS detection sensitivity and selectivity by modification of specific chemical groups, the available methods for subsequent metabolite annotation are limited. Herein, a laser-assisted chemical transfer (LACT)-based parallel OTCD strategy was established for visualizing and annotating carbonyl metabolites in murine brain tissues. Girard's T and Girard's P reagents were applied for parallel OTCD to generate the characteristic m/z pairs with a 19.969 Da mass shift (±0.020 Da tolerance) for rapid recognition of derivatized metabolites. The similarity of spatial distribution patterns of each m/z pair was further statistically evaluated to remove the ambiguous annotations due to the occurrence of interference compounds. As a result, 90 ion pairs were annotated as candidate carbonyl metabolites, 66 were previously known and 24 were potential unreported carbonyls. Furthermore, the spatial alterations of carbonyl metabolites in the ischemic rat brain were successfully visualized and characterized, including small molecule aldehydes and ketones, long-chain fatty aldehydes, and monosaccharides. This further emphasizes great potential of parallel OTCD strategy for efficient and confident molecular annotation of spatial submetabolomics data associated with brain diseases.
2025, 36(6): 110367
doi: 10.1016/j.cclet.2024.110367
Abstract:
Degradation of nitrobenzene (NB) via Fenton-like reaction is considered as an efficient approach for contaminated groundwater remediation. However, the poor stability of H2O2 limits the application of traditional Fenton reactions in soil and groundwater due to the transportation risks of H2O2. In this study, we synthesized a controlled release nano calcium peroxide (nCP) by coating it with polydopamine (PDA) as a solid H2O2 to construct a Fe(Ⅱ)/PDA@nCP Fenton-like system for contaminants degradation. The phenol-quinone transformations of catechol groups on the PDA surface facilitated the Fe(Ⅱ)/Fe(Ⅲ) cycle, resulting in enhanced generation of hydroxyl radicals (HO) and effective long-term degradation of NB. Moreover, the PDA shell modulated the nCP decomposition rate and inhibited sharp pH fluctuations, and the NB removal efficiency was achieved up to 96.8% at pH ranging from 3.0 to 9.0. This study demonstrated the promising application potential of PDA@nCP as a solid-controlled release H2O2 source in Fenton-like system for groundwater contamination remediation.
Degradation of nitrobenzene (NB) via Fenton-like reaction is considered as an efficient approach for contaminated groundwater remediation. However, the poor stability of H2O2 limits the application of traditional Fenton reactions in soil and groundwater due to the transportation risks of H2O2. In this study, we synthesized a controlled release nano calcium peroxide (nCP) by coating it with polydopamine (PDA) as a solid H2O2 to construct a Fe(Ⅱ)/PDA@nCP Fenton-like system for contaminants degradation. The phenol-quinone transformations of catechol groups on the PDA surface facilitated the Fe(Ⅱ)/Fe(Ⅲ) cycle, resulting in enhanced generation of hydroxyl radicals (HO) and effective long-term degradation of NB. Moreover, the PDA shell modulated the nCP decomposition rate and inhibited sharp pH fluctuations, and the NB removal efficiency was achieved up to 96.8% at pH ranging from 3.0 to 9.0. This study demonstrated the promising application potential of PDA@nCP as a solid-controlled release H2O2 source in Fenton-like system for groundwater contamination remediation.
2025, 36(6): 110375
doi: 10.1016/j.cclet.2024.110375
Abstract:
Pure organic materials with ultralong room-temperature phosphorescence (RTP) and persistent luminescence in broad color gamut exhibit tremendous potential and broad application prospects due to their unique optical properties. This article proposes a simple strategy, polyatomic synergistic effect, to endow persistent luminescent materials with ultralong lifetime and broad color-tunability through polyatomic synergistic effect and non-traditional phosphorescence resonance energy transfer (PRET). By leveraging the polyatomic synergistic effect to enhance the intersystem crossing (ISC) in bibenzimidazole (BBI) derivatives and suppress the non-radiative transition process, ultralong persistent room-temperature phosphorescence has been successfully achieved after incorporating BBI-Cl-M into poly(methyl methacrylate) (PMMA) to form a rigid matrix(BBI-Cl-M@PMMA). Specifically, the ester functionalized bibenzimidazole with modified chlorine on molecular skeleton (BBI-Cl-M) demonstrates a remarkable phosphorescent lifetime (τp) of up to 256.4 ms. In addition, the behaviors and mechanism of RTP via polyatomic synergistic effect have been further understood by theoretical calculation and single crystal analysis. Subsequently, utilizing BBI-Cl-M as the energy donor and Rhodamine B (RB) as the energy acceptor, persistent and multicolor organic afterglow covering from green to red has been realized successfully by simply regulating the doping composition and concentration of PRET systems. These RTP materials have also been applied in underwater afterglow emission and multilevel anti-counterfeiting technology successfully.
Pure organic materials with ultralong room-temperature phosphorescence (RTP) and persistent luminescence in broad color gamut exhibit tremendous potential and broad application prospects due to their unique optical properties. This article proposes a simple strategy, polyatomic synergistic effect, to endow persistent luminescent materials with ultralong lifetime and broad color-tunability through polyatomic synergistic effect and non-traditional phosphorescence resonance energy transfer (PRET). By leveraging the polyatomic synergistic effect to enhance the intersystem crossing (ISC) in bibenzimidazole (BBI) derivatives and suppress the non-radiative transition process, ultralong persistent room-temperature phosphorescence has been successfully achieved after incorporating BBI-Cl-M into poly(methyl methacrylate) (PMMA) to form a rigid matrix(BBI-Cl-M@PMMA). Specifically, the ester functionalized bibenzimidazole with modified chlorine on molecular skeleton (BBI-Cl-M) demonstrates a remarkable phosphorescent lifetime (τp) of up to 256.4 ms. In addition, the behaviors and mechanism of RTP via polyatomic synergistic effect have been further understood by theoretical calculation and single crystal analysis. Subsequently, utilizing BBI-Cl-M as the energy donor and Rhodamine B (RB) as the energy acceptor, persistent and multicolor organic afterglow covering from green to red has been realized successfully by simply regulating the doping composition and concentration of PRET systems. These RTP materials have also been applied in underwater afterglow emission and multilevel anti-counterfeiting technology successfully.
2025, 36(6): 110376
doi: 10.1016/j.cclet.2024.110376
Abstract:
Intracellular bacteria (ICB), cloaked by the protective barriers of host cells, pose a formidable challenge to selective and efficient eradication. The employment of activatable photosensitizers based antibacterial photodynamic therapy (aPDT) holds significant potential for selective imaging and photo-inactivation of ICB while minimizing side effects on normal cells. Drawing inspiration from the elevated hypochlorous acid (HClO) levels in ICB infected phagocytes, herein we firstly designed and synthesized a series of HClO-responsive dinuclear Ru(Ⅱ) complexes (Ru1-Ru3) to achieve such a goal. Initially, the luminescence, 1O2 generation and aPDT activity of these Ru(Ⅱ) complexes were suppressed due to the quenching effect of the azo group, but were recovered after reaction with HClO in solutions or within ICB infected phagocytes. The detailed results revealed that Ru1 and Ru3 could not only selectively visualize ICB, but also demonstrated remarkable aPDT activity against ICB, surpassing vancomycin both in vitro and in vivo.
Intracellular bacteria (ICB), cloaked by the protective barriers of host cells, pose a formidable challenge to selective and efficient eradication. The employment of activatable photosensitizers based antibacterial photodynamic therapy (aPDT) holds significant potential for selective imaging and photo-inactivation of ICB while minimizing side effects on normal cells. Drawing inspiration from the elevated hypochlorous acid (HClO) levels in ICB infected phagocytes, herein we firstly designed and synthesized a series of HClO-responsive dinuclear Ru(Ⅱ) complexes (Ru1-Ru3) to achieve such a goal. Initially, the luminescence, 1O2 generation and aPDT activity of these Ru(Ⅱ) complexes were suppressed due to the quenching effect of the azo group, but were recovered after reaction with HClO in solutions or within ICB infected phagocytes. The detailed results revealed that Ru1 and Ru3 could not only selectively visualize ICB, but also demonstrated remarkable aPDT activity against ICB, surpassing vancomycin both in vitro and in vivo.
2025, 36(6): 110377
doi: 10.1016/j.cclet.2024.110377
Abstract:
The asymmetric conjugate additions of aryl Grignard reagents to trisubstituted enones by chiral P, N ligand L6 with low catalyst loading (0.25–1.0 mol%) are disclosed. Chiral 2-ester chromanone and its analogs bearing a quaternary stereogenic centers at C2 position were produced in high to excellent yields, enantioselectivities and high turnover number. The notable features of this reaction include its broad substrate scope, complete 1, 4-addition regioselectivities, applicability to both batch and flow for large scale synthesis. This report develops an efficient strategy to apply aryl Grignard reagents in asymmetric 1, 4-conjugation reactions and provides a direct method to incorporate quaternary chiral centers toward the synthesis of biologically relevant chromanone derivatives.
The asymmetric conjugate additions of aryl Grignard reagents to trisubstituted enones by chiral P, N ligand L6 with low catalyst loading (0.25–1.0 mol%) are disclosed. Chiral 2-ester chromanone and its analogs bearing a quaternary stereogenic centers at C2 position were produced in high to excellent yields, enantioselectivities and high turnover number. The notable features of this reaction include its broad substrate scope, complete 1, 4-addition regioselectivities, applicability to both batch and flow for large scale synthesis. This report develops an efficient strategy to apply aryl Grignard reagents in asymmetric 1, 4-conjugation reactions and provides a direct method to incorporate quaternary chiral centers toward the synthesis of biologically relevant chromanone derivatives.
2025, 36(6): 110382
doi: 10.1016/j.cclet.2024.110382
Abstract:
2, 6-Diisopropylaniline reacts with an open-cage fullerene derivative with a 11-membered orifice and forms an open-cage derivative containing one imino group on the rim of the expanded orifice. Further treatment with Lewis acids leads to open-cage fullerenes with an 18-membered orifice. Instead of the direct addition process observed before for less bulky anilines, an electron transfer process takes place in the initial step in the present reaction with bulky 2, 6-diisopropylaniline. As a result, the chemo-selectivity is completely different affording the mono imino open-cage derivative selectively.
2, 6-Diisopropylaniline reacts with an open-cage fullerene derivative with a 11-membered orifice and forms an open-cage derivative containing one imino group on the rim of the expanded orifice. Further treatment with Lewis acids leads to open-cage fullerenes with an 18-membered orifice. Instead of the direct addition process observed before for less bulky anilines, an electron transfer process takes place in the initial step in the present reaction with bulky 2, 6-diisopropylaniline. As a result, the chemo-selectivity is completely different affording the mono imino open-cage derivative selectively.
2025, 36(6): 110383
doi: 10.1016/j.cclet.2024.110383
Abstract:
Photoredox-mediated reversible-deactivation radical polymerization (RDRP) is an effective approach to synthesize polymers with defined composition and architecture. Current photoinduced RDRP primarily depends on outer-sphere electron transfer or homolysis mechanisms. Herein, we describe an example of iodine-mediated RDRP facilitated by photoinduced charge transfer complex (CTC) catalysis. The approach uses cheap and easily accessible N-heterocyclic nitrenium salt (NHN+···I-) as the photoactive CTC. Upon the irradiation of visible light, NHN+···I- undergoes single electron transfer to generate NHN• and I• radicals. The NHN• radical activates dormant Pn-I polymers via inner-sphere single electron transfer, leading to the propagating Pn• radical for chain growth and the I- anion for recovering the CTC, and the I• radical deactivates the polymerization via coupling with Pn•.
Photoredox-mediated reversible-deactivation radical polymerization (RDRP) is an effective approach to synthesize polymers with defined composition and architecture. Current photoinduced RDRP primarily depends on outer-sphere electron transfer or homolysis mechanisms. Herein, we describe an example of iodine-mediated RDRP facilitated by photoinduced charge transfer complex (CTC) catalysis. The approach uses cheap and easily accessible N-heterocyclic nitrenium salt (NHN+···I-) as the photoactive CTC. Upon the irradiation of visible light, NHN+···I- undergoes single electron transfer to generate NHN• and I• radicals. The NHN• radical activates dormant Pn-I polymers via inner-sphere single electron transfer, leading to the propagating Pn• radical for chain growth and the I- anion for recovering the CTC, and the I• radical deactivates the polymerization via coupling with Pn•.
2025, 36(6): 110391
doi: 10.1016/j.cclet.2024.110391
Abstract:
Halide solid-state electrolytes (HSSEs) with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries (ASSLBs). However, they suffer from poor processability, mechanical durability and humidity stability, hindering their large-scale applications. Here, we introduce a dry-processing fibrillation strategy using hydrophobic polytetrafluoroethylene (PTFE) binder to encapsulate Li3InCl6 (LIC) particles (the most representative HSSE). By manipulating the fibrillating process, only 0.5 wt% PTFE is sufficient to prepare free-standing LIC-PTFE (LIC-P) HSSEs. Additionally, LIC-P demonstrates excellent mechanical durability and humidity resistance. They can maintain their shapes after being exposed to humid atmosphere for 30 min, meanwhile still exhibit high ionic conductivity of > 0.2 mS/cm at 25 ℃. Consequently, the LIC-P-based ASSLBs deliver a high specific capacity of 126.6 mAh/g at 0.1 C and long cyclability of 200 cycles at 0.2 C. More importantly, the ASSLBs using moisture-exposed LIC-P can still operate properly by exhibiting a high capacity-retention of 87.7% after 100 cycles under 0.2 C. Furthermore, for the first time, we unravel the LIC interfacial morphology evolution upon cycling because the good mechanical durability enables a facile separation of LIC-P from ASSLBs after testing.
Halide solid-state electrolytes (HSSEs) with excellent ionic conductivity and high voltage stability are promising for all-solid-state Li-ion batteries (ASSLBs). However, they suffer from poor processability, mechanical durability and humidity stability, hindering their large-scale applications. Here, we introduce a dry-processing fibrillation strategy using hydrophobic polytetrafluoroethylene (PTFE) binder to encapsulate Li3InCl6 (LIC) particles (the most representative HSSE). By manipulating the fibrillating process, only 0.5 wt% PTFE is sufficient to prepare free-standing LIC-PTFE (LIC-P) HSSEs. Additionally, LIC-P demonstrates excellent mechanical durability and humidity resistance. They can maintain their shapes after being exposed to humid atmosphere for 30 min, meanwhile still exhibit high ionic conductivity of > 0.2 mS/cm at 25 ℃. Consequently, the LIC-P-based ASSLBs deliver a high specific capacity of 126.6 mAh/g at 0.1 C and long cyclability of 200 cycles at 0.2 C. More importantly, the ASSLBs using moisture-exposed LIC-P can still operate properly by exhibiting a high capacity-retention of 87.7% after 100 cycles under 0.2 C. Furthermore, for the first time, we unravel the LIC interfacial morphology evolution upon cycling because the good mechanical durability enables a facile separation of LIC-P from ASSLBs after testing.
2025, 36(6): 110393
doi: 10.1016/j.cclet.2024.110393
Abstract:
Chemotherapy is the cornerstone of cancer treatment, and paclitaxel (PTX), as a first-line broad-spectrum chemotherapy drug, is widely used in the treatment of multiple tumors in the clinic. However, unsatisfactory efficacy and drug resistance of single chemotherapy have severely hampered the clinical progress of PTX. Herein, three-in-one naringenin (NAR)-loaded PTX polymer prodrug micelles were constructed for efficient and synergistic antitumor therapy. Firstly, the polymer prodrug micelles could simultaneously act as nanoreservoirs for two hydrophobic drugs, PTX and NAR. Secondly, the polymer prodrug micelles enabled dual-responsive intelligent release of PTX and NAR triggered by reduction and acid. Finally, released PTX and NAR exerted synergistic antitumor effects for reversing tumor resistance, while NAR enhanced the immune and anti-inflammatory functions of polymer prodrug micelles. Due to the cascade-enhanced chemotherapeutic augmentation, the intelligent-responsive nanoreservoir proved to be an excellent antitumor therapeutic platform. This work was of great interest for designing superior chemotherapeutic augmentation regimens.
Chemotherapy is the cornerstone of cancer treatment, and paclitaxel (PTX), as a first-line broad-spectrum chemotherapy drug, is widely used in the treatment of multiple tumors in the clinic. However, unsatisfactory efficacy and drug resistance of single chemotherapy have severely hampered the clinical progress of PTX. Herein, three-in-one naringenin (NAR)-loaded PTX polymer prodrug micelles were constructed for efficient and synergistic antitumor therapy. Firstly, the polymer prodrug micelles could simultaneously act as nanoreservoirs for two hydrophobic drugs, PTX and NAR. Secondly, the polymer prodrug micelles enabled dual-responsive intelligent release of PTX and NAR triggered by reduction and acid. Finally, released PTX and NAR exerted synergistic antitumor effects for reversing tumor resistance, while NAR enhanced the immune and anti-inflammatory functions of polymer prodrug micelles. Due to the cascade-enhanced chemotherapeutic augmentation, the intelligent-responsive nanoreservoir proved to be an excellent antitumor therapeutic platform. This work was of great interest for designing superior chemotherapeutic augmentation regimens.
2025, 36(6): 110398
doi: 10.1016/j.cclet.2024.110398
Abstract:
A porous lanthanum (La) carbonate-carbon composite (LaCC) was prepared by vacuum-freeze-drying and pyrolysis techniques to remove phosphorus (P) from wastewater. Using polyethylene glycol as a carbon skeleton template, and the organic ligands are removed during pyrolysis, resulting in the creation of many pore structures. The LaCC showed excellent P removal performance and selectivity over a wide pH range (3–10). It exhibited a rapid adsorption rate and could hold up to 119.5 mg P/g. Fixed-bed column experiments showed that under dynamic conditions, just 1 g of LaCC effectively treated 60 L of P-contaminated wastewater with an initial concentration of 2 mg/L, meeting the primary discharge standard of <0.5 mg/L according to the comprehensive sewage guidelines of China. Bacterial experiments showed that the LaCC could inhibit the growth of Escherichia coli, indicating that it has both P removal and bacterial inhibition effects, which can greatly improve the application range of adsorbents.
A porous lanthanum (La) carbonate-carbon composite (LaCC) was prepared by vacuum-freeze-drying and pyrolysis techniques to remove phosphorus (P) from wastewater. Using polyethylene glycol as a carbon skeleton template, and the organic ligands are removed during pyrolysis, resulting in the creation of many pore structures. The LaCC showed excellent P removal performance and selectivity over a wide pH range (3–10). It exhibited a rapid adsorption rate and could hold up to 119.5 mg P/g. Fixed-bed column experiments showed that under dynamic conditions, just 1 g of LaCC effectively treated 60 L of P-contaminated wastewater with an initial concentration of 2 mg/L, meeting the primary discharge standard of <0.5 mg/L according to the comprehensive sewage guidelines of China. Bacterial experiments showed that the LaCC could inhibit the growth of Escherichia coli, indicating that it has both P removal and bacterial inhibition effects, which can greatly improve the application range of adsorbents.
2025, 36(6): 110399
doi: 10.1016/j.cclet.2024.110399
Abstract:
Electrocatalytic nitrate reduction reaction (NO3−RR) is a green and competitive method for removing nitrate from water, requiring highly active and long-term stable electrocatalysts. In this work, we report a Cu0 nanorod catalyst with disordered structure (re-Cu NRs), prepared by electrochemical in situ reconfiguration of copper-based nitrides (Cu3N NRs). The amorphous structure allows the exposure of abundant active sites to enhance the electrocatalytic activity because of the disordered atomic arrangement. At a potential of −1.2 V vs. Ag/AgCl, the re-Cu NRs catalyst achieved nearly 100% nitrate conversion within 120 min at a low nitrate concentration (50 mg/L), without the accumulation of nitrite. In-situ DEMS detection reveals that the NO3−RR on re-Cu NRs followed the pathway of *NO3−→ *NO2−→ *NO → *N → *NH → *NH2 → *NH3. Furthermore, combining this proposed pathway with electrochlorination could efficiently transform ammonia into harmless N2 (~99.41%). Theoretical calculations confirm that the amorphous structure on the surface of re-Cu NRs catalysts can facilitate strongly adsorbed nitrate, weaken the rate-determining step of *NH3 → NH3, and suppress hydrogen evolution reaction (HER). This study provides a new approach for designing efficient and stable amorphous catalysts for electrocatalytic nitrate reduction.
Electrocatalytic nitrate reduction reaction (NO3−RR) is a green and competitive method for removing nitrate from water, requiring highly active and long-term stable electrocatalysts. In this work, we report a Cu0 nanorod catalyst with disordered structure (re-Cu NRs), prepared by electrochemical in situ reconfiguration of copper-based nitrides (Cu3N NRs). The amorphous structure allows the exposure of abundant active sites to enhance the electrocatalytic activity because of the disordered atomic arrangement. At a potential of −1.2 V vs. Ag/AgCl, the re-Cu NRs catalyst achieved nearly 100% nitrate conversion within 120 min at a low nitrate concentration (50 mg/L), without the accumulation of nitrite. In-situ DEMS detection reveals that the NO3−RR on re-Cu NRs followed the pathway of *NO3−→ *NO2−→ *NO → *N → *NH → *NH2 → *NH3. Furthermore, combining this proposed pathway with electrochlorination could efficiently transform ammonia into harmless N2 (~99.41%). Theoretical calculations confirm that the amorphous structure on the surface of re-Cu NRs catalysts can facilitate strongly adsorbed nitrate, weaken the rate-determining step of *NH3 → NH3, and suppress hydrogen evolution reaction (HER). This study provides a new approach for designing efficient and stable amorphous catalysts for electrocatalytic nitrate reduction.
2025, 36(6): 110408
doi: 10.1016/j.cclet.2024.110408
Abstract:
Mitochondria are crucial organelles responsible for maintaining cell growth, and their homeostasis is closely linked to pH regulation. Physiologically, mitochondria exhibit a weakly alkaline state (pH~8.0). However, when subjected to stress stimuli that cause damage, cells initiate the process of mitophagy, resulting in mitochondrial acidification. Therefore, monitoring changes in mitochondrial pH to comprehend the physiological processes associated with mitophagy is essential. In this study, we developed an asymmetric pentamethine cyanine dye Cy5.5-H-CyN as a probe for continuous monitoring of mitophagy in living cells. By incorporating an azaindole structure into the dye molecule, a ratiometric fluorescence response was achieved that is specifically responsive to pH variations while preserving its ability to target mitochondria and emit near-infrared fluorescence. Through various methods inducing mitophagy, Cy5.5-H-CyN was employed to determine mitochondrial pH quantitatively, demonstrating its suitability as an ideal probe for continuous monitoring of mitophagy in living cells.
Mitochondria are crucial organelles responsible for maintaining cell growth, and their homeostasis is closely linked to pH regulation. Physiologically, mitochondria exhibit a weakly alkaline state (pH~8.0). However, when subjected to stress stimuli that cause damage, cells initiate the process of mitophagy, resulting in mitochondrial acidification. Therefore, monitoring changes in mitochondrial pH to comprehend the physiological processes associated with mitophagy is essential. In this study, we developed an asymmetric pentamethine cyanine dye Cy5.5-H-CyN as a probe for continuous monitoring of mitophagy in living cells. By incorporating an azaindole structure into the dye molecule, a ratiometric fluorescence response was achieved that is specifically responsive to pH variations while preserving its ability to target mitochondria and emit near-infrared fluorescence. Through various methods inducing mitophagy, Cy5.5-H-CyN was employed to determine mitochondrial pH quantitatively, demonstrating its suitability as an ideal probe for continuous monitoring of mitophagy in living cells.
2025, 36(6): 110424
doi: 10.1016/j.cclet.2024.110424
Abstract:
A novel photocatalytic energy transfer-driven radical relay strategy has been introduced for the chemo- and regioselective 1, 4-difunctionalization of carbon-sulfur double bonds. This represents the first instance of radical-mediated dual-functionalization of X-Y type unsaturated bonds, enabling the synthesis of complex linear molecules with CO, CN, and C-S bonds in a single operation. The method surpasses traditional approaches by avoiding the need for thiourea intermediates and the harsh conditions typically associated with them. The developed strategy exemplifies versatility, being applicable to 1, 4-oxyamination, 1, 4-diamination, and 1, 4-sulfonamination reactions, and has demonstrated compatibility with over 60 different substrates. The research also elucidates the role of electronic complementarity between radicals and receptors in achieving high selectivity in 1, 4-difunctionalization reactions. This study significantly advances the field of bifunctionalization and remote difunctionalization reactions, with profound implications for the development of pharmaceuticals and materials science.
A novel photocatalytic energy transfer-driven radical relay strategy has been introduced for the chemo- and regioselective 1, 4-difunctionalization of carbon-sulfur double bonds. This represents the first instance of radical-mediated dual-functionalization of X-Y type unsaturated bonds, enabling the synthesis of complex linear molecules with CO, CN, and C-S bonds in a single operation. The method surpasses traditional approaches by avoiding the need for thiourea intermediates and the harsh conditions typically associated with them. The developed strategy exemplifies versatility, being applicable to 1, 4-oxyamination, 1, 4-diamination, and 1, 4-sulfonamination reactions, and has demonstrated compatibility with over 60 different substrates. The research also elucidates the role of electronic complementarity between radicals and receptors in achieving high selectivity in 1, 4-difunctionalization reactions. This study significantly advances the field of bifunctionalization and remote difunctionalization reactions, with profound implications for the development of pharmaceuticals and materials science.
2025, 36(6): 110464
doi: 10.1016/j.cclet.2024.110464
Abstract:
A renewable fluorescent material (G⊂CP5L) has been constructed via supramolecular assembly between a new derivative of pillararene, namely leggero pillar[5]arene, as the host molecule (CP5L) and a tetraphenylethylene (TPE)-based ditopic guest (G). This new material can simultaneously perform efficient detection and separation of silver(Ⅰ) from aqueous environments. Possessing an electron-rich cavity and two cytosine groups modified on both rims, CP5L functions as the host-guest binding site for G and offers exclusive coordination sites for further interaction with Ag+. Adding Ag+ to the system undergoes dramatic fluorescence enhancement due to the mechanism of supramolecular assembly-induced enhanced emission (SAIEE). This fluorescence enhancement allows for efficient and visualized detection following a "light-up" pattern, achieving a limit of detection (LOD) of 1.3 × 10–7 mol/L, which is fully in line with the World Health Organization's drinking water standard of 9 × 10–7 mol/L. In addition, G⊂CP5L also shows strong anti-interference capability against other cationic species. For the separation of Ag+ from aqueous systems, G⊂CP5L displays exceptional adsorption efficiency (97%) and reliable recovery performance, demonstrating excellent recyclability after five experimental cycles without compromising its adsorption activity
A renewable fluorescent material (G⊂CP5L) has been constructed via supramolecular assembly between a new derivative of pillararene, namely leggero pillar[5]arene, as the host molecule (CP5L) and a tetraphenylethylene (TPE)-based ditopic guest (G). This new material can simultaneously perform efficient detection and separation of silver(Ⅰ) from aqueous environments. Possessing an electron-rich cavity and two cytosine groups modified on both rims, CP5L functions as the host-guest binding site for G and offers exclusive coordination sites for further interaction with Ag+. Adding Ag+ to the system undergoes dramatic fluorescence enhancement due to the mechanism of supramolecular assembly-induced enhanced emission (SAIEE). This fluorescence enhancement allows for efficient and visualized detection following a "light-up" pattern, achieving a limit of detection (LOD) of 1.3 × 10–7 mol/L, which is fully in line with the World Health Organization's drinking water standard of 9 × 10–7 mol/L. In addition, G⊂CP5L also shows strong anti-interference capability against other cationic species. For the separation of Ag+ from aqueous systems, G⊂CP5L displays exceptional adsorption efficiency (97%) and reliable recovery performance, demonstrating excellent recyclability after five experimental cycles without compromising its adsorption activity
2025, 36(6): 110465
doi: 10.1016/j.cclet.2024.110465
Abstract:
Three monomers, namely A2, B2, and GH, were designed and synthesized. By utilizing double host-guest interactions, the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer (SLP) at high concentrations. Long fibers could be pulled from the concentrated SLP solution. Upon the addition of PdCl2(PhCN)2 into the SLP solution, a structural transformation occurred from SLP to a supramolecular crosslinked polymer (SCP) through metal coordination interaction. This transformation induced fluorescence quenching, test paper strips for ion detection experiment confirmed that the SLP had good detection ability for Pd2+. Furthermore, the SCP underwent a transformation into a gel when the concentration exceeded 145 mmol/L. The SCP gel demonstrated sensitivity to different stimuli, such as K+ ions and changes in temperature, accompanied by a reversible transition between sol and gel states. Additionally, rheological analyses indicated that the gel possessed favorable self-healing properties.
Three monomers, namely A2, B2, and GH, were designed and synthesized. By utilizing double host-guest interactions, the monomers A2+B2+GH underwent self-assembly to form a supramolecular linear polymer (SLP) at high concentrations. Long fibers could be pulled from the concentrated SLP solution. Upon the addition of PdCl2(PhCN)2 into the SLP solution, a structural transformation occurred from SLP to a supramolecular crosslinked polymer (SCP) through metal coordination interaction. This transformation induced fluorescence quenching, test paper strips for ion detection experiment confirmed that the SLP had good detection ability for Pd2+. Furthermore, the SCP underwent a transformation into a gel when the concentration exceeded 145 mmol/L. The SCP gel demonstrated sensitivity to different stimuli, such as K+ ions and changes in temperature, accompanied by a reversible transition between sol and gel states. Additionally, rheological analyses indicated that the gel possessed favorable self-healing properties.
2025, 36(6): 110514
doi: 10.1016/j.cclet.2024.110514
Abstract:
Electrocatalysis for nitrate (NO3–) removal from wastewater faces the challenge of merging efficient reduction and high selectivity to nitrogen (N2) with economic viability in a durable catalyst. In this study, bimetallic PdCu/TiOx composite catalysts were synthesized with varying Pd and Cu ratios through electrochemical deposition on defective TiOx nanotube arrays. Denitrification experiments demonstrated that the Pd1Cu1/TiOx catalyst exhibited the highest NO3– removal rate (81.2%) and N2 selectivity (67.2%) among all tested catalysts. Leveraging the exceptional light-responsive property of TiOx, the introduction of light energy as an assisting factor in electrocatalysis further augmented the NO3– treatment rate, resulting in a higher NO3– removal rate of 95.1% and N2 selectivity of approximately 90%. Compared to individual electrocatalysis and photocatalysis systems, the overpotential for the catalytic interface active *H formation in the photo-assisted electrocatalysis system was remarkably reduced, thus accelerating electron migration and promoting NO3– reduction kinetics. Economic analysis revealed an energy consumption of 2.74 kWh/mol and a corresponding energy consumption per order (EEO) of 0.79 kWh/m3 for the Pd1Cu1/TiOx catalyst to reduce 25.2 mg/L of NO3–-N in water to N2, showcasing remarkable competitiveness and economic advantages over other water treatment technologies. This study developed the PdCu/TiOx electrocatalysts with high NO3– removal rates and N2 selectivity, particularly when combined with light energy, the efficiency and selectivity were significantly enhanced, offering a competitive and economically viable solution for wastewater treatment.
Electrocatalysis for nitrate (NO3–) removal from wastewater faces the challenge of merging efficient reduction and high selectivity to nitrogen (N2) with economic viability in a durable catalyst. In this study, bimetallic PdCu/TiOx composite catalysts were synthesized with varying Pd and Cu ratios through electrochemical deposition on defective TiOx nanotube arrays. Denitrification experiments demonstrated that the Pd1Cu1/TiOx catalyst exhibited the highest NO3– removal rate (81.2%) and N2 selectivity (67.2%) among all tested catalysts. Leveraging the exceptional light-responsive property of TiOx, the introduction of light energy as an assisting factor in electrocatalysis further augmented the NO3– treatment rate, resulting in a higher NO3– removal rate of 95.1% and N2 selectivity of approximately 90%. Compared to individual electrocatalysis and photocatalysis systems, the overpotential for the catalytic interface active *H formation in the photo-assisted electrocatalysis system was remarkably reduced, thus accelerating electron migration and promoting NO3– reduction kinetics. Economic analysis revealed an energy consumption of 2.74 kWh/mol and a corresponding energy consumption per order (EEO) of 0.79 kWh/m3 for the Pd1Cu1/TiOx catalyst to reduce 25.2 mg/L of NO3–-N in water to N2, showcasing remarkable competitiveness and economic advantages over other water treatment technologies. This study developed the PdCu/TiOx electrocatalysts with high NO3– removal rates and N2 selectivity, particularly when combined with light energy, the efficiency and selectivity were significantly enhanced, offering a competitive and economically viable solution for wastewater treatment.
2025, 36(6): 110540
doi: 10.1016/j.cclet.2024.110540
Abstract:
2-Azabicyclo[2.1.1]hexanes (aza-BCHs) are constrained pyrrolidine analogues with improved physicochemical characteristics in drug design. Here, we report a direct visible light-mediated photocycloaddition of 4-aza-coumarins with mono- or disubstituted bicyclo[1.1.0]butanes for synthesizing aza-BCHs without an external catalyst. The introduction of the ester group on 4-azacoumarin is critical for direct imine excitation and versatile synthetic utility. Preliminary mechanistic studies indicated that the reaction took place primarily at the triplet hypersurface.
2-Azabicyclo[2.1.1]hexanes (aza-BCHs) are constrained pyrrolidine analogues with improved physicochemical characteristics in drug design. Here, we report a direct visible light-mediated photocycloaddition of 4-aza-coumarins with mono- or disubstituted bicyclo[1.1.0]butanes for synthesizing aza-BCHs without an external catalyst. The introduction of the ester group on 4-azacoumarin is critical for direct imine excitation and versatile synthetic utility. Preliminary mechanistic studies indicated that the reaction took place primarily at the triplet hypersurface.
2025, 36(6): 110541
doi: 10.1016/j.cclet.2024.110541
Abstract:
A new oxidative N-heterocyclic carbene (NHC)-catalyzed high-order [7 + 3] annulation reaction of γ-indolyl phenols as 1, 7-dinucleophiles and α, β‐alkynals with the aid of Sc(OTf)3 is reported, enabling the highly regioselective access to unprecedented polyarene-fused ten-membered lactams bearing a bridged aryl-aryl-indole scaffold in moderate to good yields. This protocol demonstrates a broad substrate scope, good compatibility with substituents and complete regioselectivity, providing an organocatalytic modular synthetic strategy for creating medium-sized lactams.
A new oxidative N-heterocyclic carbene (NHC)-catalyzed high-order [7 + 3] annulation reaction of γ-indolyl phenols as 1, 7-dinucleophiles and α, β‐alkynals with the aid of Sc(OTf)3 is reported, enabling the highly regioselective access to unprecedented polyarene-fused ten-membered lactams bearing a bridged aryl-aryl-indole scaffold in moderate to good yields. This protocol demonstrates a broad substrate scope, good compatibility with substituents and complete regioselectivity, providing an organocatalytic modular synthetic strategy for creating medium-sized lactams.
2025, 36(6): 110582
doi: 10.1016/j.cclet.2024.110582
Abstract:
A convenient photocatalytic multi-component reaction of alkenes, quinoxalin-2(1H)-ones, and diazo compounds has been developed in the presence of water. A number of ester-containing quinoxalin-2(1H)-ones could be efficiently obtained in moderate to good yields at room temperature. This metal-free visible-light-driven tandem reaction was conducted through proton-coupled electron transfer (PCET) process using water as the hydrogen donor and 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as the photocatalyst.
A convenient photocatalytic multi-component reaction of alkenes, quinoxalin-2(1H)-ones, and diazo compounds has been developed in the presence of water. A number of ester-containing quinoxalin-2(1H)-ones could be efficiently obtained in moderate to good yields at room temperature. This metal-free visible-light-driven tandem reaction was conducted through proton-coupled electron transfer (PCET) process using water as the hydrogen donor and 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as the photocatalyst.
2025, 36(6): 110593
doi: 10.1016/j.cclet.2024.110593
Abstract:
Selective catalytic transfer hydrogenation (CTH) of carbonyl compounds to obtain specific alcohols holds significant importance across various fields. Achieving multiple selectivity in CTH is particularly crucial, but full of great challenge. Herein, a cationic In-captured Zr-porphyrin framework (1) with nanosized pores/cages was successfully constructed and showed high structure stability. Catalytic investigations revealed that 1 displayed highly multi-selective CTH of aldehydes and ketones containing both chemo- and size selectivity for the first time. The CTH of aldehydes and ketones exhibited remarkable reductive selectivity of 99% towards CO bonds into CHOH in the presence of -NO2, -CN and CC groups. Through tuning the reaction conditions, 1 also exhibited highly selective reduction of 97% for -CHO groups in the simultaneous presence of -CHO and -COCH3 groups in intra- and intermolecular settings. Remarkably, reductive selectivity towards -CHO group remained prominent among five concurrent unsaturated groups mentioned above. Additionally, the definite pore size of 1 facilitated volume control of substrates, enabling size selectivity. 1 as a heterogeneous catalyst was further confirmed by leaching tests, and maintained high activity even after being used for at least six cycles. Mechanistic studies have revealed that Zr6O8 clusters served as the catalytic centers and the observed chemoselectivity mainly results from the synergistic effect of distinct metal sites within 1. The heightened selectivity towards -CHO over -COCH3 can be attributed to the easier realization of transfer hydrogenation processes for -CHO compared to -COCH3.
Selective catalytic transfer hydrogenation (CTH) of carbonyl compounds to obtain specific alcohols holds significant importance across various fields. Achieving multiple selectivity in CTH is particularly crucial, but full of great challenge. Herein, a cationic In-captured Zr-porphyrin framework (1) with nanosized pores/cages was successfully constructed and showed high structure stability. Catalytic investigations revealed that 1 displayed highly multi-selective CTH of aldehydes and ketones containing both chemo- and size selectivity for the first time. The CTH of aldehydes and ketones exhibited remarkable reductive selectivity of 99% towards CO bonds into CHOH in the presence of -NO2, -CN and CC groups. Through tuning the reaction conditions, 1 also exhibited highly selective reduction of 97% for -CHO groups in the simultaneous presence of -CHO and -COCH3 groups in intra- and intermolecular settings. Remarkably, reductive selectivity towards -CHO group remained prominent among five concurrent unsaturated groups mentioned above. Additionally, the definite pore size of 1 facilitated volume control of substrates, enabling size selectivity. 1 as a heterogeneous catalyst was further confirmed by leaching tests, and maintained high activity even after being used for at least six cycles. Mechanistic studies have revealed that Zr6O8 clusters served as the catalytic centers and the observed chemoselectivity mainly results from the synergistic effect of distinct metal sites within 1. The heightened selectivity towards -CHO over -COCH3 can be attributed to the easier realization of transfer hydrogenation processes for -CHO compared to -COCH3.
2025, 36(6): 110641
doi: 10.1016/j.cclet.2024.110641
Abstract:
Boron-doped diamond (BDD) is a well-known anode material with a high pollutant degradation ability for electrochemical oxidation wastewater treatment. Nevertheless, the cost of production and mechanical strength of BDD membranes remain unsatisfactory. Magnetic BDD particles derived from industrial waste may represent a promising alternative to BDD membranes, although the challenge remains in assembling these particles into a usable electrode. In this study, magnetic BDD particles were attracted to a Ti/RuO2-IrO2 electrode using a magnet, thus constituting a novel 2.5-dimensional (2.5D) electrode. To ascertain the structure-activity relationship of the novel electrode, essential characterizations, multi-physics simulations, pollutant degradation and electrosynthesis experiments were conducted. The results indicate that an appropriate quantity of BDD particles (0.1 g/cm2) can enhance the number of active sites by approximately 20%. A strong synergistic effect was observed between the Ti/RuO2-IrO2 and BDD particles in the degradation of various pollutants, including azo dye, p-benzoquinone, succinic acid and four kinds of real wastewaters, as well as glycerol conversion. The joint active sites on the interface between Ti/RuO2-IrO2 and BDD particles, as well as the inner active sites on BDD particles, have been identified as crucial in the mineralization of pollutants and the generation of value-added products. The optimal amount of BDD particles (0.1 g/cm2) is sufficient to preserve the joint active sites and to maintain an adequate polarization on the BDD particles. Nevertheless, the hybrid feature of the 2.5D electrode is diminished when a greater quantity of BDD particles (0.3 g/cm2) is loaded.
Boron-doped diamond (BDD) is a well-known anode material with a high pollutant degradation ability for electrochemical oxidation wastewater treatment. Nevertheless, the cost of production and mechanical strength of BDD membranes remain unsatisfactory. Magnetic BDD particles derived from industrial waste may represent a promising alternative to BDD membranes, although the challenge remains in assembling these particles into a usable electrode. In this study, magnetic BDD particles were attracted to a Ti/RuO2-IrO2 electrode using a magnet, thus constituting a novel 2.5-dimensional (2.5D) electrode. To ascertain the structure-activity relationship of the novel electrode, essential characterizations, multi-physics simulations, pollutant degradation and electrosynthesis experiments were conducted. The results indicate that an appropriate quantity of BDD particles (0.1 g/cm2) can enhance the number of active sites by approximately 20%. A strong synergistic effect was observed between the Ti/RuO2-IrO2 and BDD particles in the degradation of various pollutants, including azo dye, p-benzoquinone, succinic acid and four kinds of real wastewaters, as well as glycerol conversion. The joint active sites on the interface between Ti/RuO2-IrO2 and BDD particles, as well as the inner active sites on BDD particles, have been identified as crucial in the mineralization of pollutants and the generation of value-added products. The optimal amount of BDD particles (0.1 g/cm2) is sufficient to preserve the joint active sites and to maintain an adequate polarization on the BDD particles. Nevertheless, the hybrid feature of the 2.5D electrode is diminished when a greater quantity of BDD particles (0.3 g/cm2) is loaded.
2025, 36(6): 110669
doi: 10.1016/j.cclet.2024.110669
Abstract:
Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries, attributed to its high theoretical specific capacity and low electrochemical potential. However, safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries. Current research efforts primarily focus on altering the solvated structure of Li+ by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier, expedite the desolvation process, and suppress the growth of lithium dendrites. Nevertheless, an integrated approach that combines the advantages of these two strategies remains elusive. In this study, we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process, reduce the nucleation barrier of Li+, and modulate its solvated structure. This approach enhanced the inorganic compound content in the solid electrolyte interphase (SEI) on lithium foil surfaces, leading to stable Li+ deposition and stripping. Specifically, LiCu cells demonstrated excellent cycle life and Coulombic efficiency (97.28% and 98.59%, respectively) at 0.5 mA/cm2@0.5 mAh/cm2 and 1 mA/cm2@1 mAh/cm2 for 410 and 240 cycles, respectively. LiLi symmetrical cells showed no short circuit at 1 mA/cm2@1 mAh/cm2 for 1150 h, and LiLFP full cells retained 68.9% of their capacity (104.6 mAh/g) after 250 cycles at N/P (1.1:1.0) with a current density of 1 C.
Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries, attributed to its high theoretical specific capacity and low electrochemical potential. However, safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries. Current research efforts primarily focus on altering the solvated structure of Li+ by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier, expedite the desolvation process, and suppress the growth of lithium dendrites. Nevertheless, an integrated approach that combines the advantages of these two strategies remains elusive. In this study, we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process, reduce the nucleation barrier of Li+, and modulate its solvated structure. This approach enhanced the inorganic compound content in the solid electrolyte interphase (SEI) on lithium foil surfaces, leading to stable Li+ deposition and stripping. Specifically, LiCu cells demonstrated excellent cycle life and Coulombic efficiency (97.28% and 98.59%, respectively) at 0.5 mA/cm2@0.5 mAh/cm2 and 1 mA/cm2@1 mAh/cm2 for 410 and 240 cycles, respectively. LiLi symmetrical cells showed no short circuit at 1 mA/cm2@1 mAh/cm2 for 1150 h, and LiLFP full cells retained 68.9% of their capacity (104.6 mAh/g) after 250 cycles at N/P (1.1:1.0) with a current density of 1 C.
2025, 36(6): 110684
doi: 10.1016/j.cclet.2024.110684
Abstract:
Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies, post-modification induced topological transformations have never been explored in the context of [2]catenane topologies. In this study, we present a novel supramolecular transformation between a Hopf link and a macrocycle, induced by the Diels–Alder click reaction. By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent, we successfully integrated tetrazine moieties into the metalla[2]catenane structure. We demonstrated that the introduction of 2,5-norbornadiene (NBD) as an external stimulus allows for the transformation of the novel metalla[2]catenane, featuring reactive tetrazine sites, into the corresponding monomeric ring through post-modification for the first time. The synthetic results are corroborated by single-crystal X-ray diffraction analysis, ESI-TOF/MS, elemental analysis, and detailed solution-state NMR techniques.
Although supramolecular transformations have been emerged as a potent strategy for transitioning between various topologies, post-modification induced topological transformations have never been explored in the context of [2]catenane topologies. In this study, we present a novel supramolecular transformation between a Hopf link and a macrocycle, induced by the Diels–Alder click reaction. By strategically selecting the half-sandwich ruthenium binuclear fragment B as a rigid capping agent, we successfully integrated tetrazine moieties into the metalla[2]catenane structure. We demonstrated that the introduction of 2,5-norbornadiene (NBD) as an external stimulus allows for the transformation of the novel metalla[2]catenane, featuring reactive tetrazine sites, into the corresponding monomeric ring through post-modification for the first time. The synthetic results are corroborated by single-crystal X-ray diffraction analysis, ESI-TOF/MS, elemental analysis, and detailed solution-state NMR techniques.
2025, 36(6): 110763
doi: 10.1016/j.cclet.2024.110763
Abstract:
Aryl-ether bonds are facile to attack by oxidizing radicals, thus stimulating the exploitation of ether-free polymers as proton exchange membranes (PEMs) for the long-lasting operation of fuel cells. In this study, a novel class of PEMs derived from all-carbon fluorinated backbone polymers containing sulfide-linked alkyl sulfonic acid side chains have been developed through a straightforward and effective synthetic procedure. The sulfide-linked alkyl sulfonate groups were tethered to the poly(triphenylene pentafluorophenyl) backbone through a quantified and site-specific para-fluoro-thiol click reaction. Owing to the existence of obvious phase separation morphology between hydrophobic main chain and hydrophilic sulfonate groups in the side chains, resulting PEMs demonstrated favorable proton conductivity of 142.5 mS/cm at 80 ℃, while maintaining excellent dimensional stability with an in-plane swelling ratio of <17% as well as a through-plane swelling ratio of <25%. They also exhibit elevated thermal decomposition temperatures (Td5% exceeding 300 ℃) alongside high tensile strength (>50 MPa). Furthermore, the ether-free full-carbon fluorinated main chain and the -S- group in the side chain, which serves as an effective free-radical scavenger, providing good chemical stability during Fenton's test. The PEMs achieved a maximum power density of 407 mW/cm2 in a single H2/air fuel cell, and an open-circuit voltage decline rate of 0.275 mV/h in a durability test at 30% RH and 80 ℃. Concurrently, the hydrogen crossover current density is only 1/3 of that of Nafion 212. These findings reveal that the resulted PEMs display considerable antioxidative properties along with commendable performance, with prospective applications in proton exchange membrane fuel cells.
Aryl-ether bonds are facile to attack by oxidizing radicals, thus stimulating the exploitation of ether-free polymers as proton exchange membranes (PEMs) for the long-lasting operation of fuel cells. In this study, a novel class of PEMs derived from all-carbon fluorinated backbone polymers containing sulfide-linked alkyl sulfonic acid side chains have been developed through a straightforward and effective synthetic procedure. The sulfide-linked alkyl sulfonate groups were tethered to the poly(triphenylene pentafluorophenyl) backbone through a quantified and site-specific para-fluoro-thiol click reaction. Owing to the existence of obvious phase separation morphology between hydrophobic main chain and hydrophilic sulfonate groups in the side chains, resulting PEMs demonstrated favorable proton conductivity of 142.5 mS/cm at 80 ℃, while maintaining excellent dimensional stability with an in-plane swelling ratio of <17% as well as a through-plane swelling ratio of <25%. They also exhibit elevated thermal decomposition temperatures (Td5% exceeding 300 ℃) alongside high tensile strength (>50 MPa). Furthermore, the ether-free full-carbon fluorinated main chain and the -S- group in the side chain, which serves as an effective free-radical scavenger, providing good chemical stability during Fenton's test. The PEMs achieved a maximum power density of 407 mW/cm2 in a single H2/air fuel cell, and an open-circuit voltage decline rate of 0.275 mV/h in a durability test at 30% RH and 80 ℃. Concurrently, the hydrogen crossover current density is only 1/3 of that of Nafion 212. These findings reveal that the resulted PEMs display considerable antioxidative properties along with commendable performance, with prospective applications in proton exchange membrane fuel cells.
2025, 36(6): 110816
doi: 10.1016/j.cclet.2025.110816
Abstract:
Single-molecule junctions are building blocks for constructing molecular devices. However, intermolecular interactions like winding bring additional interference among the surrounding molecules, which inhibits the intrinsic coherent transport through single-molecule junctions. Here, we employed a nanocavity (dimethoxypillar[5]arene, DMP[5]), which is analogous to electric cables, to confine the conformation of flexible chains (1,8-diaminooctane, DAO) via host-guest interaction. Single-molecule conductance measurements indicate that the conductance of DAO encapsulated with DMP[5] is as high as that of pure DAO, as reproduced by theoretical simulations. Intriguingly, the molecular lengths of the DAO encapsulated with DMP[5] increase from 1.13 nm to 1.46 nm compared with the pure DAO, indicating that DMP[5] keeps DAO upright-standing via the confinement effect. This work provides a new strategy to decouple the intermolecular interaction by employing an insulating sheath, enabling the high-density integration of single-molecule devices.
Single-molecule junctions are building blocks for constructing molecular devices. However, intermolecular interactions like winding bring additional interference among the surrounding molecules, which inhibits the intrinsic coherent transport through single-molecule junctions. Here, we employed a nanocavity (dimethoxypillar[5]arene, DMP[5]), which is analogous to electric cables, to confine the conformation of flexible chains (1,8-diaminooctane, DAO) via host-guest interaction. Single-molecule conductance measurements indicate that the conductance of DAO encapsulated with DMP[5] is as high as that of pure DAO, as reproduced by theoretical simulations. Intriguingly, the molecular lengths of the DAO encapsulated with DMP[5] increase from 1.13 nm to 1.46 nm compared with the pure DAO, indicating that DMP[5] keeps DAO upright-standing via the confinement effect. This work provides a new strategy to decouple the intermolecular interaction by employing an insulating sheath, enabling the high-density integration of single-molecule devices.
2025, 36(6): 110817
doi: 10.1016/j.cclet.2025.110817
Abstract:
A pair of asymmetric rigid carbazole-benzonitrile-based emitters were synthesized by strategically alternating donor and acceptor groups along the molecular edges. The spin-flip process is accelerated by both the formation of localized and delocalized charge transfer states due to linearly positioned donors and strong spin-orbital coupling between different excitation feature of the lowest singlet and triplet excited states. This molecular architecture results in a remarkable short delayed lifespan of around 100 ns. The application of the two emitters in organic light-emitting diodes (OLEDs) achieves the highest external quantum efficiencies of 13.0% for the green emitter and 9.1% for the sky-blue emitter. Impressively, these devices maintain their high efficiency even at high luminance levels. The sustained efficiency is ascribed to the effective suppression of exciton quenching by substantially shortening delayed lifespan. These findings underscore the practical utility of the molecular design strategy that incorporates alternate donor and acceptor groups at the molecular periphery for shortening delayed fluorescence lifetime, and hold great promise for the development of high-performance OLEDs.
A pair of asymmetric rigid carbazole-benzonitrile-based emitters were synthesized by strategically alternating donor and acceptor groups along the molecular edges. The spin-flip process is accelerated by both the formation of localized and delocalized charge transfer states due to linearly positioned donors and strong spin-orbital coupling between different excitation feature of the lowest singlet and triplet excited states. This molecular architecture results in a remarkable short delayed lifespan of around 100 ns. The application of the two emitters in organic light-emitting diodes (OLEDs) achieves the highest external quantum efficiencies of 13.0% for the green emitter and 9.1% for the sky-blue emitter. Impressively, these devices maintain their high efficiency even at high luminance levels. The sustained efficiency is ascribed to the effective suppression of exciton quenching by substantially shortening delayed lifespan. These findings underscore the practical utility of the molecular design strategy that incorporates alternate donor and acceptor groups at the molecular periphery for shortening delayed fluorescence lifetime, and hold great promise for the development of high-performance OLEDs.
2025, 36(6): 110818
doi: 10.1016/j.cclet.2025.110818
Abstract:
Electromagnetic wave-absorbing materials (EWAMs) are susceptible to failure in complex chemical environments. It is urgent to develop composites with high-efficiency electromagnetic wave (EMW) absorption and strong corrosion resistance. In the work, polyaniline (PANI) is in-situ polymerized on the surface of oxidized carbon nanohorns (ox-CNHs) to create a core-shell composite of ox-CNHs@PANI. By adjusting the thickness of the PANI shell and effectively regulating the electromagnetic parameters of the composite material, excellent impedance matching and efficient EMW absorption are achieved. At a thickness of 2.22 mm, the composite exhibits a reflection loss peak (RLmin) and a maximum effective absorption broadband (EAB) of −66.7 dB and 5.68 GHz, respectively. Additionally, the dense PANI shell effectively prevents contact between the corrosive medium and ox-CNHs, which significantly reduces the possibility of corrosion. Due to the formation of the ox-CNHs/PANI interface, the ox-CNHs@PANI composite exhibits strong corrosion resistance under acidic, alkaline, and neutral conditions. The ox-CNHs@PANI composite exhibits excellent EMW absorption and strong corrosion resistance, offering a new approach to developing advanced bifunctional materials.
Electromagnetic wave-absorbing materials (EWAMs) are susceptible to failure in complex chemical environments. It is urgent to develop composites with high-efficiency electromagnetic wave (EMW) absorption and strong corrosion resistance. In the work, polyaniline (PANI) is in-situ polymerized on the surface of oxidized carbon nanohorns (ox-CNHs) to create a core-shell composite of ox-CNHs@PANI. By adjusting the thickness of the PANI shell and effectively regulating the electromagnetic parameters of the composite material, excellent impedance matching and efficient EMW absorption are achieved. At a thickness of 2.22 mm, the composite exhibits a reflection loss peak (RLmin) and a maximum effective absorption broadband (EAB) of −66.7 dB and 5.68 GHz, respectively. Additionally, the dense PANI shell effectively prevents contact between the corrosive medium and ox-CNHs, which significantly reduces the possibility of corrosion. Due to the formation of the ox-CNHs/PANI interface, the ox-CNHs@PANI composite exhibits strong corrosion resistance under acidic, alkaline, and neutral conditions. The ox-CNHs@PANI composite exhibits excellent EMW absorption and strong corrosion resistance, offering a new approach to developing advanced bifunctional materials.
2025, 36(6): 110836
doi: 10.1016/j.cclet.2025.110836
Abstract:
Molecular catalysts can effectively steer the electrocatalytic acetylene semihydrogenation into ethylene, but realizing high Faradaic efficiency (FE) at industrial current densities remains a challenge. Herein, we report a ligand engineering strategy that utilizes polymeric N-heterocyclic carbene (NHC) as a hydrophobic ligand to modulate the microenvironment of Cu sites. This polymeric NHC imparts appropriate hydrophobic properties for the chelated Cu sites, thereby moderating the H2O transport and enabling easy access of acetylene. Consequently, the polymeric NHC chelated Cu exhibits an FEethylene of ~97% at a current density of 500 mA/cm2 in a flow cell. Particularly in a zero-gap reactor, the FEethylene consistently exceeds 86% across current densities from 100 mA/cm2 to 400 mA/cm2, reaching an optimal FEethylene of 98% at 200 mA/cm2 and achieving durable operation for 155 h at 100 mA/cm2. This work provides a promising paradigm to regulate the microenvironment of molecular catalysts for improving electrocatalytic performances under industrial current densities.
Molecular catalysts can effectively steer the electrocatalytic acetylene semihydrogenation into ethylene, but realizing high Faradaic efficiency (FE) at industrial current densities remains a challenge. Herein, we report a ligand engineering strategy that utilizes polymeric N-heterocyclic carbene (NHC) as a hydrophobic ligand to modulate the microenvironment of Cu sites. This polymeric NHC imparts appropriate hydrophobic properties for the chelated Cu sites, thereby moderating the H2O transport and enabling easy access of acetylene. Consequently, the polymeric NHC chelated Cu exhibits an FEethylene of ~97% at a current density of 500 mA/cm2 in a flow cell. Particularly in a zero-gap reactor, the FEethylene consistently exceeds 86% across current densities from 100 mA/cm2 to 400 mA/cm2, reaching an optimal FEethylene of 98% at 200 mA/cm2 and achieving durable operation for 155 h at 100 mA/cm2. This work provides a promising paradigm to regulate the microenvironment of molecular catalysts for improving electrocatalytic performances under industrial current densities.
2025, 36(6): 110838
doi: 10.1016/j.cclet.2025.110838
Abstract:
Recently, CsPbBr3 perovskite solar cells (PSCs) have garnered attention due to cost-effectiveness and reliability. However, hole transport limitations lead to charge recombination and lower power conversion efficiency (PCE). Defects in the CsPbBr3 layer, poor hole transport at the interface with carbon electrodes, and energy level differences hinder performance. Optimizing the perovskite layer using electron-donating organic molecules containing -NH2 groups enhances efficiency and stability by passivating defects and modulating lattice structure. In this work, tetra(4-aminophenyl)ethylene (TPE) and tetra(4-aminobiphenyl)ethylene (TPE-Ph) were employed to optimize the CsPbBr3/carbon electrode interface. Their strong electron-donating properties and amino groups facilitate hole transfer and defect passivation, boosting PCE to 9.38% and enhancing stability.
Recently, CsPbBr3 perovskite solar cells (PSCs) have garnered attention due to cost-effectiveness and reliability. However, hole transport limitations lead to charge recombination and lower power conversion efficiency (PCE). Defects in the CsPbBr3 layer, poor hole transport at the interface with carbon electrodes, and energy level differences hinder performance. Optimizing the perovskite layer using electron-donating organic molecules containing -NH2 groups enhances efficiency and stability by passivating defects and modulating lattice structure. In this work, tetra(4-aminophenyl)ethylene (TPE) and tetra(4-aminobiphenyl)ethylene (TPE-Ph) were employed to optimize the CsPbBr3/carbon electrode interface. Their strong electron-donating properties and amino groups facilitate hole transfer and defect passivation, boosting PCE to 9.38% and enhancing stability.
2025, 36(6): 110905
doi: 10.1016/j.cclet.2025.110905
Abstract:
Epoxy resin is widely used in electronic packaging due to its exceptional performance, particularly the low-temperature curable thiol/epoxy system, which effectively minimizes thermal damage to sensitive electronic components. However, the majority of commercial thiol curing agents contain hydrolysable ester bonds and lack rigid structures, which induces most of thiol/epoxy systems still suffering from unsatisfactory heat resistance and hygrothermal resistance, significantly hindering their application in electronic packaging. In this study, we synthesized a tetrafunctional thiol compound, bis[3-(3-sulfanylpropyl)-4-(3-sulfanylpropoxy)phenyl]sulfone (TMBPS) with rigid and ester-free structures to replace traditional commercial thiol curing agents, pentaerythritol tetra(3-mercaptopropionate) (PETMP). Compared to the PETMP/epoxy system, the TMBPS/epoxy system exhibited superior comprehensive properties. The rigid structures of bisphenol S-type tetrathiol enhanced the heat resistance and mechanical properties of TMBPS/epoxy resin cured products, outperforming those of PETMP/epoxy resin cured products. Notably, the glass transition temperature of TMBPS/epoxy resin cured products was 74.2 ℃ which was 11.8 ℃ higher than that of PETMP cured products. Moreover, the ester-free structure in TMBPS contributed to its enhanced resistance to chemicals and hygrothermal conditions. After undergoing 1000 h of high-temperature and high-humidity aging, the tensile strength and adhesion strength of TMBPS-cured products were 73.33 MPa and 3.39 MPa, respectively exceeding 100% and 40% of their initial values, while PETMP-cured products exhibited a complete loss of both tensile strength and adhesion strength. This study provides a strategy for obtaining thermosetting polymers that can be cured at low temperatures and exhibit excellent comprehensive properties.
Epoxy resin is widely used in electronic packaging due to its exceptional performance, particularly the low-temperature curable thiol/epoxy system, which effectively minimizes thermal damage to sensitive electronic components. However, the majority of commercial thiol curing agents contain hydrolysable ester bonds and lack rigid structures, which induces most of thiol/epoxy systems still suffering from unsatisfactory heat resistance and hygrothermal resistance, significantly hindering their application in electronic packaging. In this study, we synthesized a tetrafunctional thiol compound, bis[3-(3-sulfanylpropyl)-4-(3-sulfanylpropoxy)phenyl]sulfone (TMBPS) with rigid and ester-free structures to replace traditional commercial thiol curing agents, pentaerythritol tetra(3-mercaptopropionate) (PETMP). Compared to the PETMP/epoxy system, the TMBPS/epoxy system exhibited superior comprehensive properties. The rigid structures of bisphenol S-type tetrathiol enhanced the heat resistance and mechanical properties of TMBPS/epoxy resin cured products, outperforming those of PETMP/epoxy resin cured products. Notably, the glass transition temperature of TMBPS/epoxy resin cured products was 74.2 ℃ which was 11.8 ℃ higher than that of PETMP cured products. Moreover, the ester-free structure in TMBPS contributed to its enhanced resistance to chemicals and hygrothermal conditions. After undergoing 1000 h of high-temperature and high-humidity aging, the tensile strength and adhesion strength of TMBPS-cured products were 73.33 MPa and 3.39 MPa, respectively exceeding 100% and 40% of their initial values, while PETMP-cured products exhibited a complete loss of both tensile strength and adhesion strength. This study provides a strategy for obtaining thermosetting polymers that can be cured at low temperatures and exhibit excellent comprehensive properties.
2025, 36(6): 110922
doi: 10.1016/j.cclet.2025.110922
Abstract:
Rapid carrier recombination and slow charge transfer dynamics have significantly reduced the performance of photocatalytic hydrogen production. Construction of heterojunctions via utilizing the sulfur-edge and metal-edge sites of metal sulfide semiconductor for improving photocatalytic activity remains a significant challenge. Herein, a novel ZnIn2S4/MnS S-scheme heterojunction was prepared by hydrothermal synthesis to accelerate charge carrier transfer for efficient photocatalysis. Notably, ZnIn2S4/MnS exhibited excellent photocatalytic hydrogen evolution activity (7.95 mmol g−1 h−1) under visible light irradiation (≥420 nm), up to 4.7 times higher than that of pure ZnIn2S4. Additionally, cycling experiments showed that ZM-2 remained high stability after four cycles. Density-functional theory (DFT) calculations and in situ XPS results confirm the formation of S-scheme heterojunction, indicating that the tight interfacial contact between ZnIn2S4 and MnS with the presence of Mn-S bonds (the unsaturated Mn edges of MnS and the uncoordinated S atoms in the edge of ZnIn2S4) promoted faster charge transfer. Besides, the unsaturated S atom on the surface of MnS is an active site with strong H+ binding ability, which can effectively reduce the overpotential or activation barrier for hydrogen evolution. This study illustrates the critical influence of the interfacial Mn-S bond on the ZnIn2S4/MnS S-scheme heterojunction to achieve efficient photocatalytic hydrogen production and provides relevant guidance for carrying out rational structural/interfacial modulation.
Rapid carrier recombination and slow charge transfer dynamics have significantly reduced the performance of photocatalytic hydrogen production. Construction of heterojunctions via utilizing the sulfur-edge and metal-edge sites of metal sulfide semiconductor for improving photocatalytic activity remains a significant challenge. Herein, a novel ZnIn2S4/MnS S-scheme heterojunction was prepared by hydrothermal synthesis to accelerate charge carrier transfer for efficient photocatalysis. Notably, ZnIn2S4/MnS exhibited excellent photocatalytic hydrogen evolution activity (7.95 mmol g−1 h−1) under visible light irradiation (≥420 nm), up to 4.7 times higher than that of pure ZnIn2S4. Additionally, cycling experiments showed that ZM-2 remained high stability after four cycles. Density-functional theory (DFT) calculations and in situ XPS results confirm the formation of S-scheme heterojunction, indicating that the tight interfacial contact between ZnIn2S4 and MnS with the presence of Mn-S bonds (the unsaturated Mn edges of MnS and the uncoordinated S atoms in the edge of ZnIn2S4) promoted faster charge transfer. Besides, the unsaturated S atom on the surface of MnS is an active site with strong H+ binding ability, which can effectively reduce the overpotential or activation barrier for hydrogen evolution. This study illustrates the critical influence of the interfacial Mn-S bond on the ZnIn2S4/MnS S-scheme heterojunction to achieve efficient photocatalytic hydrogen production and provides relevant guidance for carrying out rational structural/interfacial modulation.
Reduction of methane emission from microbial fuel cells during sulfamethoxazole wastewater treatment
2025, 36(6): 110997
doi: 10.1016/j.cclet.2025.110997
Abstract:
Carbon emissions from wastewater treatment contribute to global warming and have received widespread attention. It is necessary to seek low-carbon wastewater treatment technologies. Microbial fuel cells (MFC) and osmotic microbial fuel cells (OsMFC) are low-carbon technologies that enable both wastewater treatment and energy recovery. In this study, MFC and OsMFC were used to treat sulfamethoxazole (SMX) wastewater, and direct carbon emissions during operation was calculated. The highest SMX removal rate can reach about 40%. Simultaneously, the CH4 emission factor was significantly reduced to <6 g CO2/kg of chemical oxygen demand. The accumulation of SMX-degrading bacteria competed with methanogens for carbon source utilization, leading to a significant decrease in the relative abundance of methanogens. It is hoped that this study can provide a sustainable approach to antibiotic wastewater treatment and promote the development of low-carbon wastewater treatment technologies.
Carbon emissions from wastewater treatment contribute to global warming and have received widespread attention. It is necessary to seek low-carbon wastewater treatment technologies. Microbial fuel cells (MFC) and osmotic microbial fuel cells (OsMFC) are low-carbon technologies that enable both wastewater treatment and energy recovery. In this study, MFC and OsMFC were used to treat sulfamethoxazole (SMX) wastewater, and direct carbon emissions during operation was calculated. The highest SMX removal rate can reach about 40%. Simultaneously, the CH4 emission factor was significantly reduced to <6 g CO2/kg of chemical oxygen demand. The accumulation of SMX-degrading bacteria competed with methanogens for carbon source utilization, leading to a significant decrease in the relative abundance of methanogens. It is hoped that this study can provide a sustainable approach to antibiotic wastewater treatment and promote the development of low-carbon wastewater treatment technologies.
2025, 36(6): 111059
doi: 10.1016/j.cclet.2025.111059
Abstract:
Broadband photothermal and photoacoustic agents in the near-infrared (NIR) biowindow are of significance for cancer phototheranostics. In this work, PtCu nanosheets with an average lateral size of less than 10 nm are synthesized as NIR photothermal and photoacoustic agents in vivo, which show strong light absorption from NIR-Ⅰ to NIR-Ⅱ biowindows with the photothermal conversion efficiencies of 20.4% under 808 nm laser and 32.7% under 1064 nm laser. PtCu nanosheets functionalized with folic acid-modified thiol-poly(ethylene glycol) (SH-PEG-FA) present good biocompatibility and 4T1 tumor-targeted effect, which give high-contrast photoacoustic imaging and efficient photothermal ablation of 4T1 tumor in both NIR-Ⅰ and NIR-Ⅱ biowindows. Our work significantly broadens applications of noble metal-based nanomaterials in the fields of cancer phototheranostics by rationally designing their structures and modulating their physicochemical properties.
Broadband photothermal and photoacoustic agents in the near-infrared (NIR) biowindow are of significance for cancer phototheranostics. In this work, PtCu nanosheets with an average lateral size of less than 10 nm are synthesized as NIR photothermal and photoacoustic agents in vivo, which show strong light absorption from NIR-Ⅰ to NIR-Ⅱ biowindows with the photothermal conversion efficiencies of 20.4% under 808 nm laser and 32.7% under 1064 nm laser. PtCu nanosheets functionalized with folic acid-modified thiol-poly(ethylene glycol) (SH-PEG-FA) present good biocompatibility and 4T1 tumor-targeted effect, which give high-contrast photoacoustic imaging and efficient photothermal ablation of 4T1 tumor in both NIR-Ⅰ and NIR-Ⅱ biowindows. Our work significantly broadens applications of noble metal-based nanomaterials in the fields of cancer phototheranostics by rationally designing their structures and modulating their physicochemical properties.
2025, 36(6): 111182
doi: 10.1016/j.cclet.2025.111182
Abstract:
Protein damage repair and prevention are important objectives in skin care industry. Skin protein damage or modifications such as glycation, carbonylation or oxidation, have a significant impact on its function, therefore directly influencing various skin functions or properties including skin appearance. However, there is a lack of comprehensive methods to visualize and assess the protein damage. In this article, we present a three-channel imaging approach to simultaneously visualize and quantitatively evaluate protein oxidation, protein glycation and carbonylation in a full-thickness skin model. We successfully visualized and quantified the impact of the multiple stimuli (ultraviolet radiation A (UVA) and/or methylglyoxal) as well as treatment effect of positive control (vitamins C and E) with this method. Our findings indicate that multiple stimuli exhibit synergistic effects on protein damage. Furthermore, we evaluated a unique combination of skin care ingredients which demonstrated an excellent efficacy in resisting protein damage. Further research revealed that three ingredients of the combination upregulate autophagy in cells, which may contribute to remove damaged proteins and maintain protein quality homeostasis. This method provides a holistic assessment of protein damages and can be employed to evaluate the impact of various stimuli or to assess the efficacy of skin care ingredients in mitigating such damage.
Protein damage repair and prevention are important objectives in skin care industry. Skin protein damage or modifications such as glycation, carbonylation or oxidation, have a significant impact on its function, therefore directly influencing various skin functions or properties including skin appearance. However, there is a lack of comprehensive methods to visualize and assess the protein damage. In this article, we present a three-channel imaging approach to simultaneously visualize and quantitatively evaluate protein oxidation, protein glycation and carbonylation in a full-thickness skin model. We successfully visualized and quantified the impact of the multiple stimuli (ultraviolet radiation A (UVA) and/or methylglyoxal) as well as treatment effect of positive control (vitamins C and E) with this method. Our findings indicate that multiple stimuli exhibit synergistic effects on protein damage. Furthermore, we evaluated a unique combination of skin care ingredients which demonstrated an excellent efficacy in resisting protein damage. Further research revealed that three ingredients of the combination upregulate autophagy in cells, which may contribute to remove damaged proteins and maintain protein quality homeostasis. This method provides a holistic assessment of protein damages and can be employed to evaluate the impact of various stimuli or to assess the efficacy of skin care ingredients in mitigating such damage.
2025, 36(6): 109997
doi: 10.1016/j.cclet.2024.109997
Abstract:
Sodium metal has been widely studied in the field of batteries due to its high theoretical specific capacity (~1,166 mAh/g), low redox potential (-2.71 V compared to standard hydrogen electrode), and low-cost advantages. However, problems such as unstable solid electrolyte interface (SEI), uncontrolled dendrite growth, and side reactions between solid-liquid interfaces have hindered the practical application of sodium metal anodes (SMAs). Currently, lots of strategies have been developed to achieve stabilized sodium metal anodes. Among these strategies, modified metal current collectors (MCCs) stand out due to their unique role in accommodating volumetric fluctuations with superior structure, lowering the energy barrier for sodium nucleation, and providing guided uniform sodium deposition. In this review, we first introduced three common metal-based current collectors applied to SMAs. Then, we summarized strategies to improve sodium deposition behavior by optimally engineering the surface of MCCs, including surface loading, surface structural design, and surface engineering for functional modification. We have followed the latest research progress and summarized surface optimization cases on different MCCs and their applications in battery systems.
Sodium metal has been widely studied in the field of batteries due to its high theoretical specific capacity (~1,166 mAh/g), low redox potential (-2.71 V compared to standard hydrogen electrode), and low-cost advantages. However, problems such as unstable solid electrolyte interface (SEI), uncontrolled dendrite growth, and side reactions between solid-liquid interfaces have hindered the practical application of sodium metal anodes (SMAs). Currently, lots of strategies have been developed to achieve stabilized sodium metal anodes. Among these strategies, modified metal current collectors (MCCs) stand out due to their unique role in accommodating volumetric fluctuations with superior structure, lowering the energy barrier for sodium nucleation, and providing guided uniform sodium deposition. In this review, we first introduced three common metal-based current collectors applied to SMAs. Then, we summarized strategies to improve sodium deposition behavior by optimally engineering the surface of MCCs, including surface loading, surface structural design, and surface engineering for functional modification. We have followed the latest research progress and summarized surface optimization cases on different MCCs and their applications in battery systems.
2025, 36(6): 110006
doi: 10.1016/j.cclet.2024.110006
Abstract:
For large-scale energy storage devices, all-solid-state sodium-ion batteries (SIBs) have been revered for the abundant resources, low cost, safety performance and a wide operating temperature range. Na-ion solid-state electrolytes (Na-ion SSEs) are the critical parts and mostly determine the electrochemical performance of SIBs. Among the studied ones, inorganic Na-ion SSEs stand out for their good safety performance and high ionic conductivity. In this review, we outline the research progress of inorganic SSEs in SIBs based on the perspectives of crystal structure, performance optimization, synthesis methods, all-solid-state SIBs, interface modification and related characterization techniques. We hope to provide some ideas for the design of future high-performance Na-ion SSEs.
For large-scale energy storage devices, all-solid-state sodium-ion batteries (SIBs) have been revered for the abundant resources, low cost, safety performance and a wide operating temperature range. Na-ion solid-state electrolytes (Na-ion SSEs) are the critical parts and mostly determine the electrochemical performance of SIBs. Among the studied ones, inorganic Na-ion SSEs stand out for their good safety performance and high ionic conductivity. In this review, we outline the research progress of inorganic SSEs in SIBs based on the perspectives of crystal structure, performance optimization, synthesis methods, all-solid-state SIBs, interface modification and related characterization techniques. We hope to provide some ideas for the design of future high-performance Na-ion SSEs.
2025, 36(6): 110039
doi: 10.1016/j.cclet.2024.110039
Abstract:
With the development of science and technology, there is an increasing demand for energy storage batteries. Aqueous zinc-ion batteries (AZIBs) are expected to become the next generation of commercialized energy storage devices due to their advantages. The aqueous zinc ion battery is generally composed of zinc metal as the anode, active material as the cathode, and aqueous electrolyte. However, there are still many problems with the cathode/anode material and voltage window of the battery, which limit its use. This review introduces the recent research progress of zinc-ion batteries, including the advantages and disadvantages, energy storage mechanisms, and common cathode/anode materials, electrolytes, etc. It also gives a summary of the current research status of each material and provides solutions to the problems they face. Finally, it looks at the future direction and methods to optimize the performance of zinc-ion full batteries.
With the development of science and technology, there is an increasing demand for energy storage batteries. Aqueous zinc-ion batteries (AZIBs) are expected to become the next generation of commercialized energy storage devices due to their advantages. The aqueous zinc ion battery is generally composed of zinc metal as the anode, active material as the cathode, and aqueous electrolyte. However, there are still many problems with the cathode/anode material and voltage window of the battery, which limit its use. This review introduces the recent research progress of zinc-ion batteries, including the advantages and disadvantages, energy storage mechanisms, and common cathode/anode materials, electrolytes, etc. It also gives a summary of the current research status of each material and provides solutions to the problems they face. Finally, it looks at the future direction and methods to optimize the performance of zinc-ion full batteries.
2025, 36(6): 110049
doi: 10.1016/j.cclet.2024.110049
Abstract:
Multi-metal porous crystalline materials (MPCM), integrating the functions of both multi-metal centres and porous crystalline materials (e.g., metal-organic frameworks (MOFs) and covalent organic frameworks (COFs)), are an extended class of porous materials that have attracted much attention for a broad range of applications. Owing to the advantages of these materials, they generally display high porosity, multi-metal active sites, well-tuned functions, and pre-designable structures, etc., serving as desired platforms for the study of structure-property relationships. In view of the clean and sustainable target, a series of MPCM have been explored as electrocatalysts for electrocatalytic reactions like hydrogen evolution reaction, oxygen evolution reaction and electrocatalytic CO2 reduction reaction. Concerning the progress achieved for MPCM in electrocatalytic field during past years, this review will provide a brief introduction on the recent breakthrough of MPCM based electrocatalysts including their synthesis methods, structure design, component/morphology tuning, electrocatalytic property and structure-property relationship, etc. Besides, it will also conclude the current challenges and present perspectives for the MPCM based electrocatalysts, which might promote the development of porous crystalline materials in electrocatalysis and hope to provide new insights for scientists in related fields.
Multi-metal porous crystalline materials (MPCM), integrating the functions of both multi-metal centres and porous crystalline materials (e.g., metal-organic frameworks (MOFs) and covalent organic frameworks (COFs)), are an extended class of porous materials that have attracted much attention for a broad range of applications. Owing to the advantages of these materials, they generally display high porosity, multi-metal active sites, well-tuned functions, and pre-designable structures, etc., serving as desired platforms for the study of structure-property relationships. In view of the clean and sustainable target, a series of MPCM have been explored as electrocatalysts for electrocatalytic reactions like hydrogen evolution reaction, oxygen evolution reaction and electrocatalytic CO2 reduction reaction. Concerning the progress achieved for MPCM in electrocatalytic field during past years, this review will provide a brief introduction on the recent breakthrough of MPCM based electrocatalysts including their synthesis methods, structure design, component/morphology tuning, electrocatalytic property and structure-property relationship, etc. Besides, it will also conclude the current challenges and present perspectives for the MPCM based electrocatalysts, which might promote the development of porous crystalline materials in electrocatalysis and hope to provide new insights for scientists in related fields.
2025, 36(6): 110070
doi: 10.1016/j.cclet.2024.110070
Abstract:
Protein glycosylation and phosphorylation, as two of the most important protein post-translational modifications (PTMs), play key roles in living organisms. However, glycopeptides and phosphopeptides have low abundance in biological samples. In addition, the low ionization efficiency and the severe signal interference in the presence of other peptides present great difficulties for their direct mass spectrometry (MS) analysis. Therefore, it is important to develop feasible enrichment strategies to pretreat glycopeptides and phosphopeptides in complex samples before MS detection. This paper reviews the application of various magnetic nanomaterials (MNMs) in glycopeptides and phosphopeptides in the last decade, with emphasis on the enrichment principles, the design and synthesis process of the materials, and the effectiveness of the application in biological samples. In addition, possible future trends and potential challenges are presented.
Protein glycosylation and phosphorylation, as two of the most important protein post-translational modifications (PTMs), play key roles in living organisms. However, glycopeptides and phosphopeptides have low abundance in biological samples. In addition, the low ionization efficiency and the severe signal interference in the presence of other peptides present great difficulties for their direct mass spectrometry (MS) analysis. Therefore, it is important to develop feasible enrichment strategies to pretreat glycopeptides and phosphopeptides in complex samples before MS detection. This paper reviews the application of various magnetic nanomaterials (MNMs) in glycopeptides and phosphopeptides in the last decade, with emphasis on the enrichment principles, the design and synthesis process of the materials, and the effectiveness of the application in biological samples. In addition, possible future trends and potential challenges are presented.
2025, 36(6): 110215
doi: 10.1016/j.cclet.2024.110215
Abstract:
Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries. However, it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles, which seriously limits the actual energy density of sulfide all-solid-state lithium batteries (ASSLBs). Fortunately, the preparation of sulfide-polymer composite solid electrolyte (SPCSE) membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties. In this review, recent progress of SPCSE membranes for ASSLBs is summarized. The classification of components in SPCSE membranes is first introduced briefly. Then, the preparation methods of SPCSE membranes are categorized according to process characteristics, in which the challenges of different methods and their corresponding solutions are carefully reviewed. The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance. Finally, we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.
Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries. However, it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles, which seriously limits the actual energy density of sulfide all-solid-state lithium batteries (ASSLBs). Fortunately, the preparation of sulfide-polymer composite solid electrolyte (SPCSE) membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties. In this review, recent progress of SPCSE membranes for ASSLBs is summarized. The classification of components in SPCSE membranes is first introduced briefly. Then, the preparation methods of SPCSE membranes are categorized according to process characteristics, in which the challenges of different methods and their corresponding solutions are carefully reviewed. The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance. Finally, we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.
Recent trends of biodegradable mesoporous silica based nanoplatforms for enhanced tumor theranostics
2025, 36(6): 110221
doi: 10.1016/j.cclet.2024.110221
Abstract:
Mesoporous silica nanoparticles (MSNs) are thought to be an attractive drug delivery material because of their advantages including high specific surface area, tunable pore size and morphology, easy surface modification and good biocompatibility. However, as a result of the poor biodegradability of MSNs, their biomedical applications are limited. To break the bottleneck of limited biomedical applications of MSNs, more and more researchers tend to design biodegradable MSNs (b-MSNs) nanosystems to obtain biodegradable as well as safe and reliable drug delivery carriers. In this review, we focused on summarizing strategies to improve the degradability of MSNs and innovatively proposed a series of advantages of b-MSNs, including controlled cargo release behavior, multifunctional frameworks, nano-catalysis, bio-imaging capabilities and enhanced therapeutic effects. Based on these advantages, we have innovatively summarized the applications of b-MSNs for enhanced tumor theranostics, including enhanced chemotherapy, delivery of nanosensitizers, gas molecules and biomacromolecules, initiation of immune response, synergistic therapies and image-guided tumor diagnostics. Finally, the challenges and further clinical translation potential of nanosystems based on b-MSNs are fully discussed and prospected. We believe that such b-MSNs delivery carriers will provide a timely reference for further applications in tumor theranostics.
Mesoporous silica nanoparticles (MSNs) are thought to be an attractive drug delivery material because of their advantages including high specific surface area, tunable pore size and morphology, easy surface modification and good biocompatibility. However, as a result of the poor biodegradability of MSNs, their biomedical applications are limited. To break the bottleneck of limited biomedical applications of MSNs, more and more researchers tend to design biodegradable MSNs (b-MSNs) nanosystems to obtain biodegradable as well as safe and reliable drug delivery carriers. In this review, we focused on summarizing strategies to improve the degradability of MSNs and innovatively proposed a series of advantages of b-MSNs, including controlled cargo release behavior, multifunctional frameworks, nano-catalysis, bio-imaging capabilities and enhanced therapeutic effects. Based on these advantages, we have innovatively summarized the applications of b-MSNs for enhanced tumor theranostics, including enhanced chemotherapy, delivery of nanosensitizers, gas molecules and biomacromolecules, initiation of immune response, synergistic therapies and image-guided tumor diagnostics. Finally, the challenges and further clinical translation potential of nanosystems based on b-MSNs are fully discussed and prospected. We believe that such b-MSNs delivery carriers will provide a timely reference for further applications in tumor theranostics.
2025, 36(6): 110224
doi: 10.1016/j.cclet.2024.110224
Abstract:
Natural phytoconstituents exhibit distinct advantages in the management and prevention of inflammatory bowel disease (IBD), attributed to their robust biological activity, multi-target effects, and elevated safety profile. Although promising, the clinical application of phytoconstituents have been impeded by poor water solubility, low oral bioavailability, and inadequate colonic targeting. Recent advancements in nanotechnology has offered prospective avenues for the application of phytoconstituents in the treatment of IBD. A common strategy involves encapsulating or conjugating phytoconstituents with nanocarriers to enhance their stability, prolong intestinal retention, and facilitate targeted delivery to colonic inflammatory tissues. Furthermore, drawing inspiration from the self-assembling nanostructures that emerge during the decoction process of Chinese herbs, a variety of natural active compounds-based nanoassemblies have been developed for the treatment of IBD. They exhibit high drug-loading capacities and surmount the challenges posed by poor water solubility and low bioavailability. Notably, phyto-derived nanovesicles, owing to their unique structure and biological functions, can serve as therapeutic agents or novel delivery vehicles for the treatment of IBD. Consequently, this review provides an extensive overview of emerging phytoconstituent-derived nano-medicines/vesicles for the treatment of IBD, intending to offer novel insights for the clinical management of IBD.
Natural phytoconstituents exhibit distinct advantages in the management and prevention of inflammatory bowel disease (IBD), attributed to their robust biological activity, multi-target effects, and elevated safety profile. Although promising, the clinical application of phytoconstituents have been impeded by poor water solubility, low oral bioavailability, and inadequate colonic targeting. Recent advancements in nanotechnology has offered prospective avenues for the application of phytoconstituents in the treatment of IBD. A common strategy involves encapsulating or conjugating phytoconstituents with nanocarriers to enhance their stability, prolong intestinal retention, and facilitate targeted delivery to colonic inflammatory tissues. Furthermore, drawing inspiration from the self-assembling nanostructures that emerge during the decoction process of Chinese herbs, a variety of natural active compounds-based nanoassemblies have been developed for the treatment of IBD. They exhibit high drug-loading capacities and surmount the challenges posed by poor water solubility and low bioavailability. Notably, phyto-derived nanovesicles, owing to their unique structure and biological functions, can serve as therapeutic agents or novel delivery vehicles for the treatment of IBD. Consequently, this review provides an extensive overview of emerging phytoconstituent-derived nano-medicines/vesicles for the treatment of IBD, intending to offer novel insights for the clinical management of IBD.
2025, 36(6): 110229
doi: 10.1016/j.cclet.2024.110229
Abstract:
As one of the most common gynecological malignancies, peritoneal metastasis is a common feature and cause of high mortality in ovarian cancer (OC). Currently, the standard treatment for OC and its peritoneal metastasis is maximal cytoreductive surgery (CRS) combined with platinum-based chemotherapy. Compared with intravenous chemotherapy, traditional intraperitoneal (IP) chemotherapy exhibits obvious pharmacokinetic (PK) advantages and systemic safety and has shown significant survival benefits in several clinical studies of OC patients. However, there remain several challenges in traditional IP chemotherapy, such as insufficient drug retention, a lack of tumor targeting, inadequate drug penetration, gastrointestinal toxicity, and limited inhibition of tumor metastasis and chemoresistance. Nanomedicine-based IP targeting delivery systems, through specific drug carrier design with tumor cells and tumor environment (TME) targeting, make it possible to overcome these challenges and maximize local therapy efficacy while reducing side effects. In this review article, the rationale and challenges of nanomedicine-based IP chemotherapies, as well as their in vivo fate after IP administration, which are crucial for their rational design and clinical translation, are firstly discussed. Then, current strategies for nanomedicine-based targeting delivery systems and the relevant clinical trials in IP chemotherapy are summarized. Finally, the future directions of the nanomedicine-based IP targeting delivery system for OC and its peritoneal metastasis are proposed, expecting to improve the clinical development of IP chemotherapy.
As one of the most common gynecological malignancies, peritoneal metastasis is a common feature and cause of high mortality in ovarian cancer (OC). Currently, the standard treatment for OC and its peritoneal metastasis is maximal cytoreductive surgery (CRS) combined with platinum-based chemotherapy. Compared with intravenous chemotherapy, traditional intraperitoneal (IP) chemotherapy exhibits obvious pharmacokinetic (PK) advantages and systemic safety and has shown significant survival benefits in several clinical studies of OC patients. However, there remain several challenges in traditional IP chemotherapy, such as insufficient drug retention, a lack of tumor targeting, inadequate drug penetration, gastrointestinal toxicity, and limited inhibition of tumor metastasis and chemoresistance. Nanomedicine-based IP targeting delivery systems, through specific drug carrier design with tumor cells and tumor environment (TME) targeting, make it possible to overcome these challenges and maximize local therapy efficacy while reducing side effects. In this review article, the rationale and challenges of nanomedicine-based IP chemotherapies, as well as their in vivo fate after IP administration, which are crucial for their rational design and clinical translation, are firstly discussed. Then, current strategies for nanomedicine-based targeting delivery systems and the relevant clinical trials in IP chemotherapy are summarized. Finally, the future directions of the nanomedicine-based IP targeting delivery system for OC and its peritoneal metastasis are proposed, expecting to improve the clinical development of IP chemotherapy.
2025, 36(6): 110294
doi: 10.1016/j.cclet.2024.110294
Abstract:
Covalent organic frameworks (COFs) are crystalline porous polymeric materials composed of organic monomers connected by strong covalent bonds and offer high stability, good crystallinity, a large specific surface area, and controllable structures. COFs are widely used in the fields of adsorption and separation, catalysis, photovoltaics, and drug-delivery. The structural regulation and performance optimization of COFs can be realized through the modification of ligands and the selection of linkage methods. In which, the types of linkage are closely related to the stability and performance of COFs. In this review, nitrogen-containing linkage-bonds (NCLBs) in COFs are divided into N-containing double bonds, N-containing conjugated rings and N-containing unconjugated rings. The association between structure and performance of COFs is elaborated and the synthesis methods of COFs are systematically summarized. Moreover, the structural design, theoretical prediction and machinable application of COFs are prospected
Covalent organic frameworks (COFs) are crystalline porous polymeric materials composed of organic monomers connected by strong covalent bonds and offer high stability, good crystallinity, a large specific surface area, and controllable structures. COFs are widely used in the fields of adsorption and separation, catalysis, photovoltaics, and drug-delivery. The structural regulation and performance optimization of COFs can be realized through the modification of ligands and the selection of linkage methods. In which, the types of linkage are closely related to the stability and performance of COFs. In this review, nitrogen-containing linkage-bonds (NCLBs) in COFs are divided into N-containing double bonds, N-containing conjugated rings and N-containing unconjugated rings. The association between structure and performance of COFs is elaborated and the synthesis methods of COFs are systematically summarized. Moreover, the structural design, theoretical prediction and machinable application of COFs are prospected
2025, 36(6): 110319
doi: 10.1016/j.cclet.2024.110319
Abstract:
Pollutants contained in wastewater pose serious harm to the environment. Graphene-based water treatment materials show significant advantages in wastewater treatment. However, with the development of graphene-based materials, its progress in water treatment has reached a bottleneck. The challenge lies in effectively enhancing its performance in water treatment and ensuring its practicality. By employing biomimetic approaches, some exceptional properties and structures found in nature can be mimicked in graphene materials, effectively enhancing graphene’s adsorption and mechanical properties. Current biomimetic methods include biomimetic mineralization, self-assembly, and templating. unfortunately, all of the above methods suffer from the disadvantages of complexity and poor bionic effect. Nevertheless, 3D printing, a form of additive manufacturing (AM) technology, offers integrated molding and excellent biomimetic performance in creating biomimetic materials. This paper will cover the following aspects: (1) An overview of objects suitable for bionics in terms of functional and structural aspects, along with their properties, and a discussion of various bionic objects combined with graphene materials in water treatment and related research; (2) a comparison of different methods for preparing graphene-based bionic materials; (3) an examination of the current drawbacks and limitations of graphene-based biomimetic materials; and (4) a conclusion and future prospects, exploring the potential of using 3D printing technology to produce graphene biomimetic materials. This review aims to serve as a guide for effectively leveraging natural inspirations to create graphene-based biomimetic materials and enhance graphene properties.
Pollutants contained in wastewater pose serious harm to the environment. Graphene-based water treatment materials show significant advantages in wastewater treatment. However, with the development of graphene-based materials, its progress in water treatment has reached a bottleneck. The challenge lies in effectively enhancing its performance in water treatment and ensuring its practicality. By employing biomimetic approaches, some exceptional properties and structures found in nature can be mimicked in graphene materials, effectively enhancing graphene’s adsorption and mechanical properties. Current biomimetic methods include biomimetic mineralization, self-assembly, and templating. unfortunately, all of the above methods suffer from the disadvantages of complexity and poor bionic effect. Nevertheless, 3D printing, a form of additive manufacturing (AM) technology, offers integrated molding and excellent biomimetic performance in creating biomimetic materials. This paper will cover the following aspects: (1) An overview of objects suitable for bionics in terms of functional and structural aspects, along with their properties, and a discussion of various bionic objects combined with graphene materials in water treatment and related research; (2) a comparison of different methods for preparing graphene-based bionic materials; (3) an examination of the current drawbacks and limitations of graphene-based biomimetic materials; and (4) a conclusion and future prospects, exploring the potential of using 3D printing technology to produce graphene biomimetic materials. This review aims to serve as a guide for effectively leveraging natural inspirations to create graphene-based biomimetic materials and enhance graphene properties.
2025, 36(6): 110321
doi: 10.1016/j.cclet.2024.110321
Abstract:
Graphene quantum dots (GQDs) are a class of promising carbon-based nanomaterials that have attracted considerable interest from researchers due to their excellent physical, chemical, and biological properties. However, the high cost, toxicity, and laborious preparation process of GQDs also limit their widespread use. To address this issue, the actual research directions consist in replacing traditional non-renewable feedstocks via screening cheap, easily available, and renewable biomass materials based on the concept of resource conservation and environmental friendliness. Herein, the state-of-the-art technologies in the green preparation of GQDs using biomass as carbon source are reported. Initially, the green synthesis strategies as well as the structural, optical, and biosafety properties of GQDs are discussed in detail. Subsequently, the most representative applications of GQDs in energy and environmental remediation fields are summarized. Finally, the current challenges and future potential of the GQDs are presented.
Graphene quantum dots (GQDs) are a class of promising carbon-based nanomaterials that have attracted considerable interest from researchers due to their excellent physical, chemical, and biological properties. However, the high cost, toxicity, and laborious preparation process of GQDs also limit their widespread use. To address this issue, the actual research directions consist in replacing traditional non-renewable feedstocks via screening cheap, easily available, and renewable biomass materials based on the concept of resource conservation and environmental friendliness. Herein, the state-of-the-art technologies in the green preparation of GQDs using biomass as carbon source are reported. Initially, the green synthesis strategies as well as the structural, optical, and biosafety properties of GQDs are discussed in detail. Subsequently, the most representative applications of GQDs in energy and environmental remediation fields are summarized. Finally, the current challenges and future potential of the GQDs are presented.
2025, 36(6): 110374
doi: 10.1016/j.cclet.2024.110374
Abstract:
Advanced oxidation processes (AOPs) governed by peroxide activation to produce highly oxidative active species have been extensively explored for environmental remediation. Nevertheless, the low diffusion rates, inadequate interactions of the reactants, and limited active site exposure hinder treatment efficiency. Porous carbocatalysts with high specific surface area, tunable pore size, and programmable active sites demonstrate outstanding performance in activating diverse types of peroxides to generate active species for treatment of aqueous organic pollutants. The pore-rich structures enhance reaction kinetics for peroxide activation by facilitating diffusion of the reactants and their interactions. Additionally, the structural flexibility of porous structures favors the accommodation of highly dispersed metal species and allows for precise tuning of the microenvironment around the active sites, which further enhances the catalytic activity. This review critically summarizes the recent research progress in the applications of engineered porous carbocatalysts for peroxide activation and outlines the prevailing pore construction methods in carbocatalysts. Moreover, engineering strategies to regulate the mass transfer efficiency and fine-tune the microenvironment around the active sites are systematically addressed to enhance their catalytic peroxide activation performances. Challenges and future research opportunities pertaining to the design, optimization, mechanistic investigation, and practical application of porous carbocatalysts in peroxide activation are also proposed.
Advanced oxidation processes (AOPs) governed by peroxide activation to produce highly oxidative active species have been extensively explored for environmental remediation. Nevertheless, the low diffusion rates, inadequate interactions of the reactants, and limited active site exposure hinder treatment efficiency. Porous carbocatalysts with high specific surface area, tunable pore size, and programmable active sites demonstrate outstanding performance in activating diverse types of peroxides to generate active species for treatment of aqueous organic pollutants. The pore-rich structures enhance reaction kinetics for peroxide activation by facilitating diffusion of the reactants and their interactions. Additionally, the structural flexibility of porous structures favors the accommodation of highly dispersed metal species and allows for precise tuning of the microenvironment around the active sites, which further enhances the catalytic activity. This review critically summarizes the recent research progress in the applications of engineered porous carbocatalysts for peroxide activation and outlines the prevailing pore construction methods in carbocatalysts. Moreover, engineering strategies to regulate the mass transfer efficiency and fine-tune the microenvironment around the active sites are systematically addressed to enhance their catalytic peroxide activation performances. Challenges and future research opportunities pertaining to the design, optimization, mechanistic investigation, and practical application of porous carbocatalysts in peroxide activation are also proposed.
2025, 36(6): 110392
doi: 10.1016/j.cclet.2024.110392
Abstract:
Electrochemical water splitting presents a promising, environmentally friendly alternative to fossil fuels for hydrogen production. However, the efficiency is constrained by the sluggish kinetics and high overpotentials associated with the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). While noble metal catalysts, such as Pt for HER and Ir for OER, currently offer superior performance, their widespread adoption is hindered by high cost and scarcity. This has spurred research into cost-effective alternatives, with a focus on understanding the underlying electrocatalytic mechanisms. MXenes, a class of two-dimensional materials, have emerged as promising candidates for electrocatalytic water splitting due to their unique physical and chemical properties. However, research in this field remains largely experimental, lacking a comprehensive understanding of fundamental mechanisms. This knowledge gap impedes the development of high-efficiency electrocatalysts and necessitates further investigation. This review systematically examines recent advancements in MXene-based nanohybrids for electrocatalytic water splitting, covering synthetic methods, structure-property relationships, and performance enhancement strategies. It encompasses both precious and non-noble metal-based systems for HER, OER, and overall water splitting applications. Additionally, this review addresses current challenges, opportunities, and future research directions for MXene-based nanohybrids. By providing comprehensive insights into the development of high-performance MXene-based electrocatalysts, this review aims to accelerate progress in the field of electrochemical water splitting. It serves as a valuable resource for researchers and engineers working towards more efficient and sustainable hydrogen production technologies, potentially contributing to the broader goal of transitioning away from fossil fuels towards cleaner energy sources.
Electrochemical water splitting presents a promising, environmentally friendly alternative to fossil fuels for hydrogen production. However, the efficiency is constrained by the sluggish kinetics and high overpotentials associated with the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). While noble metal catalysts, such as Pt for HER and Ir for OER, currently offer superior performance, their widespread adoption is hindered by high cost and scarcity. This has spurred research into cost-effective alternatives, with a focus on understanding the underlying electrocatalytic mechanisms. MXenes, a class of two-dimensional materials, have emerged as promising candidates for electrocatalytic water splitting due to their unique physical and chemical properties. However, research in this field remains largely experimental, lacking a comprehensive understanding of fundamental mechanisms. This knowledge gap impedes the development of high-efficiency electrocatalysts and necessitates further investigation. This review systematically examines recent advancements in MXene-based nanohybrids for electrocatalytic water splitting, covering synthetic methods, structure-property relationships, and performance enhancement strategies. It encompasses both precious and non-noble metal-based systems for HER, OER, and overall water splitting applications. Additionally, this review addresses current challenges, opportunities, and future research directions for MXene-based nanohybrids. By providing comprehensive insights into the development of high-performance MXene-based electrocatalysts, this review aims to accelerate progress in the field of electrochemical water splitting. It serves as a valuable resource for researchers and engineers working towards more efficient and sustainable hydrogen production technologies, potentially contributing to the broader goal of transitioning away from fossil fuels towards cleaner energy sources.
2025, 36(6): 110543
doi: 10.1016/j.cclet.2024.110543
Abstract:
The transition metal-catalyzed C-H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step- and atom-economy, the abundance of hydrocarbon compounds, and the potential for late-stage functionalization of complex organic molecules. The ortho- and meta-C-H activation and functionalization of aromatic compounds have been widely explored in recent years, however the distal para-C-H activation and functionalization has remained a significant challenge because of the difficulty in forming energetically favorable metallacyclic transition states. The utilization of appropriate directing groups or templates as well as the meticulous design of catalysts and ligands has proven to be effective in transition-metal-catalyzed remote para-C-H bonds activation and functionalization of aromatic compounds. This review aims to summarize the strategies for controlling para-selective C-H functionalization using the directing group, template engineering, and catalyst/ligand design under transition metals catalysis in recent years.
The transition metal-catalyzed C-H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step- and atom-economy, the abundance of hydrocarbon compounds, and the potential for late-stage functionalization of complex organic molecules. The ortho- and meta-C-H activation and functionalization of aromatic compounds have been widely explored in recent years, however the distal para-C-H activation and functionalization has remained a significant challenge because of the difficulty in forming energetically favorable metallacyclic transition states. The utilization of appropriate directing groups or templates as well as the meticulous design of catalysts and ligands has proven to be effective in transition-metal-catalyzed remote para-C-H bonds activation and functionalization of aromatic compounds. This review aims to summarize the strategies for controlling para-selective C-H functionalization using the directing group, template engineering, and catalyst/ligand design under transition metals catalysis in recent years.
2025, 36(6): 110600
doi: 10.1016/j.cclet.2024.110600
Abstract:
Supramolecular luminescent materials (SLMs) exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches, making them highly attractive in the field of luminescent materials. In recent years, the novel macrocyclic arenes characterized by unique electron-rich structures, ease of derivatization, tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials. The incorporation of macrocyclic arenes into SLMs leads to simple preparation process, diverse photophysical phenomena and sophisticated regulatory mechanisms, which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials. In this review, the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies, including host-guest complexes, supramolecular polymers, nanoparticles, and other assemblies. Moreover, some insights into future directions for this research area will also be offered.
Supramolecular luminescent materials (SLMs) exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches, making them highly attractive in the field of luminescent materials. In recent years, the novel macrocyclic arenes characterized by unique electron-rich structures, ease of derivatization, tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials. The incorporation of macrocyclic arenes into SLMs leads to simple preparation process, diverse photophysical phenomena and sophisticated regulatory mechanisms, which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials. In this review, the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies, including host-guest complexes, supramolecular polymers, nanoparticles, and other assemblies. Moreover, some insights into future directions for this research area will also be offered.
2025, 36(6): 110798
doi: 10.1016/j.cclet.2024.110798
Abstract:
Quantum dots (QDs), a type of nanoscale semiconductor material with unique optical and electrical properties like adjustable emission and high photoluminescence quantum yields, are suitable for applications in optoelectronics. However, QDs are typically degraded under humid and high-temperature circumstances, greatly limiting their practical value. Coating the QD surface with an inorganic silica layer is a feasible method for improving stability and endurance in a variety of applications. This paper comprehensively reviews silica coating methodologies on QD surfaces and explores their applications in optoelectronic domains. Firstly, the paper provides mainstream silica coating approaches, which can be divided into two categories: in-situ hydrolysis of silylating reagents on QD surfaces and template techniques for encapsulation QDs. Subsequently, the recent applications of the silica-coated QDs on optoelectronic fields including light-emitting diodes, solar cells, photodetectors were discussed. Finally, it reviews recent advances in silica-coated QD technology and prospects for future applications.
Quantum dots (QDs), a type of nanoscale semiconductor material with unique optical and electrical properties like adjustable emission and high photoluminescence quantum yields, are suitable for applications in optoelectronics. However, QDs are typically degraded under humid and high-temperature circumstances, greatly limiting their practical value. Coating the QD surface with an inorganic silica layer is a feasible method for improving stability and endurance in a variety of applications. This paper comprehensively reviews silica coating methodologies on QD surfaces and explores their applications in optoelectronic domains. Firstly, the paper provides mainstream silica coating approaches, which can be divided into two categories: in-situ hydrolysis of silylating reagents on QD surfaces and template techniques for encapsulation QDs. Subsequently, the recent applications of the silica-coated QDs on optoelectronic fields including light-emitting diodes, solar cells, photodetectors were discussed. Finally, it reviews recent advances in silica-coated QD technology and prospects for future applications.
Metal single-atom catalysts derived from silicon-based materials for advanced oxidation applications
2025, 36(6): 110898
doi: 10.1016/j.cclet.2025.110898
Abstract:
Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites, thus meeting fundamental requirements for practical application. The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts (SACs) prepared based on silicon-based materials (mesoporous silica, silicon-based minerals, and organosilicon materials) has unique advantages such as structural stability (especially important under strong oxidation conditions) and environmental protection. In this paper, the preparation strategies for the silicon-based SACs were assessed first, and the structural characteristics of various silicon-based SACs are systematically discussed, their application process and mechanism in Fenton-like process to achieve water purification are investigated, and the progress of Fenton-like process in density functional theory (DFT) of silicon-based derived single atom catalysts is summarized. In this paper, the preparation strategies and applications of silicon-based derived SACs are analyzed in depth, and their oxidation activities and pathways to different pollutants in water are reviewed. In addition, this paper also summarizes the device design and application of silicon-based derived SACs, and prospects the future development of silicon-based SACs in Fenton-like applications.
Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites, thus meeting fundamental requirements for practical application. The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts (SACs) prepared based on silicon-based materials (mesoporous silica, silicon-based minerals, and organosilicon materials) has unique advantages such as structural stability (especially important under strong oxidation conditions) and environmental protection. In this paper, the preparation strategies for the silicon-based SACs were assessed first, and the structural characteristics of various silicon-based SACs are systematically discussed, their application process and mechanism in Fenton-like process to achieve water purification are investigated, and the progress of Fenton-like process in density functional theory (DFT) of silicon-based derived single atom catalysts is summarized. In this paper, the preparation strategies and applications of silicon-based derived SACs are analyzed in depth, and their oxidation activities and pathways to different pollutants in water are reviewed. In addition, this paper also summarizes the device design and application of silicon-based derived SACs, and prospects the future development of silicon-based SACs in Fenton-like applications.
2025, 36(6): 110906
doi: 10.1016/j.cclet.2025.110906
Abstract:
Organic semiconductor materials have demonstrated extensive potential in the field of gas sensors due to the advantages including designable chemical structure, tunable physical and chemical properties. Through density functional theory (DFT) calculations, researchers can investigate gas sensing mechanisms, optimize, and predict the electronic structures and response characteristics of these materials, and thereby identify candidate materials with promising gas sensing applications for targeted design. This review concentrates on three primary applications of DFT technology in the realm of organic semiconductor-based gas sensors: (1) Investigating the sensing mechanisms by analyzing the interactions between gas molecules and sensing materials through DFT, (2) simulating the dynamic responses of gas molecules, which involves the behavior on the sensing interface using DFT combined with other computational methods to explore adsorption and diffusion processes, and (3) exploring and designing sensitive materials by employing DFT for screening and predicting chemical structures, thereby developing new sensing materials with exceptional performance. Furthermore, this review examines current research outcomes and anticipates the extensive application prospects of DFT technology in the domain of organic semiconductor-based gas sensors. These efforts are expected to provide valuable insights for further in-depth exploration of DFT applications in sensor technology, thereby fostering significant advancements and innovations in the field.
Organic semiconductor materials have demonstrated extensive potential in the field of gas sensors due to the advantages including designable chemical structure, tunable physical and chemical properties. Through density functional theory (DFT) calculations, researchers can investigate gas sensing mechanisms, optimize, and predict the electronic structures and response characteristics of these materials, and thereby identify candidate materials with promising gas sensing applications for targeted design. This review concentrates on three primary applications of DFT technology in the realm of organic semiconductor-based gas sensors: (1) Investigating the sensing mechanisms by analyzing the interactions between gas molecules and sensing materials through DFT, (2) simulating the dynamic responses of gas molecules, which involves the behavior on the sensing interface using DFT combined with other computational methods to explore adsorption and diffusion processes, and (3) exploring and designing sensitive materials by employing DFT for screening and predicting chemical structures, thereby developing new sensing materials with exceptional performance. Furthermore, this review examines current research outcomes and anticipates the extensive application prospects of DFT technology in the domain of organic semiconductor-based gas sensors. These efforts are expected to provide valuable insights for further in-depth exploration of DFT applications in sensor technology, thereby fostering significant advancements and innovations in the field.
2025, 36(6): 110920
doi: 10.1016/j.cclet.2025.110920
Abstract:
Bacterial pneumonia is one of the most common infectious diseases, a great threat to the health of children and the elderly. In the clinic, due to the extensive use of antibiotics, multi-drug-resistant bacteria have increased in large numbers, seriously affects the treatment of patients with bacterial pneumonia. With the development of nanomedicine, it shows great potential in the treatment of bacterial pneumonia. In this review, it initially comprehensively describes the pathological process of bacterial pneumonia and the current status of its clinical treatment. Then it summarizes the strategies of nanomedicine for the treatment of bacterial pneumonia, including inorganic nanomaterials, polymer nanoparticles, natural source nanomaterials and artificial antimicrobial peptides, with a focus on novel nanomaterials for the treatment of bacterial pneumonia (biomimetic nanomaterials, nanovaccines and genetically engineered nanomaterials). Finally, the prospect of nanomedicine for bacterial pneumonia therapy is discussed in the hope of providing new ideas for the clinical treatment of bacterial pneumonia.
Bacterial pneumonia is one of the most common infectious diseases, a great threat to the health of children and the elderly. In the clinic, due to the extensive use of antibiotics, multi-drug-resistant bacteria have increased in large numbers, seriously affects the treatment of patients with bacterial pneumonia. With the development of nanomedicine, it shows great potential in the treatment of bacterial pneumonia. In this review, it initially comprehensively describes the pathological process of bacterial pneumonia and the current status of its clinical treatment. Then it summarizes the strategies of nanomedicine for the treatment of bacterial pneumonia, including inorganic nanomaterials, polymer nanoparticles, natural source nanomaterials and artificial antimicrobial peptides, with a focus on novel nanomaterials for the treatment of bacterial pneumonia (biomimetic nanomaterials, nanovaccines and genetically engineered nanomaterials). Finally, the prospect of nanomedicine for bacterial pneumonia therapy is discussed in the hope of providing new ideas for the clinical treatment of bacterial pneumonia.
2025, 36(6): 110654
doi: 10.1016/j.cclet.2024.110654
Abstract:
2025, 36(6): 110823
doi: 10.1016/j.cclet.2025.110823
Abstract:
2025, 36(6): 110950
doi: 10.1016/j.cclet.2025.110950
Abstract:
2025, 36(6): 111004
doi: 10.1016/j.cclet.2025.111004
Abstract:
2025, 36(6): 111007
doi: 10.1016/j.cclet.2025.111007
Abstract:
2025, 36(6): 111026
doi: 10.1016/j.cclet.2025.111026
Abstract:
2025, 36(6): 110868
doi: 10.1016/j.cclet.2025.110868
Abstract:
