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2026 Volume 37 Issue 3
2026, 37(3): 110623
doi: 10.1016/j.cclet.2024.110623
Abstract:
Transition metal sulfides (TMSs) are primitive composition of biocatalysts that are active for molecular hydrogen production. The development of non-precious TMSs with appropriate spatial ordering has great potentials to contribute high-level hydrogen generation. Herein, super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS2 nanosheet/Ni3S4 nanoparticle (Super-NiS/WS2/Ni3S4) with high spatial ordering and abundant plane- and edge-type WS2NiS and WS2Ni3S4 heterointerfaces were elaborately constructed though manipulating the sequential dissociation of phosphotungstic acid (PW12) as W precursor and nickel foam as Ni precursor in one pot. When evaluated for the electrocatalytic hydrogen evolution reaction (HER), the Super-NiS/WS2/Ni3S4 only required overpotentials of 57, 95, and 151 mV to drive HER in alkaline, acid, and neutral media, respectively, and presented favorable reaction kinetics and test stability. The theoretical and experimental results verify the adsorption and dissociation of water molecules are preferential on WS2-plane-related heterointerfaces. The Gibbs free energy (ΔGH*) analysis indicated the WS2-plane-NiS interface is thermodynamically optimal for HER. Moreover, the collaborations of the abundant plane- and edge-type active interfaces, the open nanosheet-based vertical array, and the phosphorus doping in Super-NiS/WS2/Ni3S4 strengthen mass transport and electron transfer in electrocatalysis. The polyoxometalates-based synthetic strategy will inspire the new vision for the rational design and construction of advanced functional materials.
Transition metal sulfides (TMSs) are primitive composition of biocatalysts that are active for molecular hydrogen production. The development of non-precious TMSs with appropriate spatial ordering has great potentials to contribute high-level hydrogen generation. Herein, super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS2 nanosheet/Ni3S4 nanoparticle (Super-NiS/WS2/Ni3S4) with high spatial ordering and abundant plane- and edge-type WS2NiS and WS2Ni3S4 heterointerfaces were elaborately constructed though manipulating the sequential dissociation of phosphotungstic acid (PW12) as W precursor and nickel foam as Ni precursor in one pot. When evaluated for the electrocatalytic hydrogen evolution reaction (HER), the Super-NiS/WS2/Ni3S4 only required overpotentials of 57, 95, and 151 mV to drive HER in alkaline, acid, and neutral media, respectively, and presented favorable reaction kinetics and test stability. The theoretical and experimental results verify the adsorption and dissociation of water molecules are preferential on WS2-plane-related heterointerfaces. The Gibbs free energy (ΔGH*) analysis indicated the WS2-plane-NiS interface is thermodynamically optimal for HER. Moreover, the collaborations of the abundant plane- and edge-type active interfaces, the open nanosheet-based vertical array, and the phosphorus doping in Super-NiS/WS2/Ni3S4 strengthen mass transport and electron transfer in electrocatalysis. The polyoxometalates-based synthetic strategy will inspire the new vision for the rational design and construction of advanced functional materials.
2026, 37(3): 110625
doi: 10.1016/j.cclet.2024.110625
Abstract:
The trithiocyanurate, (H2C3N3S3)-, exhibits a strong optical anisotropy but has a small HOMO-LUMO gap, limiting its application to the higher energy wavelength ranges. Herein, by applying an amino substitution strategy, we report that 2-amino-4,6-dimercapto-S-triazine, (H3C3N4S2)-, generates a series new compound: A2(H2C3N4S2)2•H2O (NH4, Ⅰ; K−Cs, Ⅱ−Ⅳ). Compound Ⅰ crystallizes in P21/n, while compounds Ⅱ–Ⅳ crystallize in P1. Their experimental optical band gaps (Eg) range from 3.52 eV to 3.65 eV, corresponding to a blue shift of 30~60 nm compared to those of the trithiocyanuric containing systems. Moreover, the birefringence of all compounds ranges from 0.440 to 0.510, indicating strong anisotropy. Notably, compound Ⅰ (Eg = 3.65 eV,\begin{document}$ \Delta n_{cal.}^{\max}$\end{document} \begin{document}$ \Delta n_{o b v.}^{(0 \overline{1} \overline{1})} $\end{document}
The trithiocyanurate, (H2C3N3S3)-, exhibits a strong optical anisotropy but has a small HOMO-LUMO gap, limiting its application to the higher energy wavelength ranges. Herein, by applying an amino substitution strategy, we report that 2-amino-4,6-dimercapto-S-triazine, (H3C3N4S2)-, generates a series new compound: A2(H2C3N4S2)2•H2O (NH4, Ⅰ; K−Cs, Ⅱ−Ⅳ). Compound Ⅰ crystallizes in P21/n, while compounds Ⅱ–Ⅳ crystallize in P1. Their experimental optical band gaps (Eg) range from 3.52 eV to 3.65 eV, corresponding to a blue shift of 30~60 nm compared to those of the trithiocyanuric containing systems. Moreover, the birefringence of all compounds ranges from 0.440 to 0.510, indicating strong anisotropy. Notably, compound Ⅰ (Eg = 3.65 eV,
2026, 37(3): 110626
doi: 10.1016/j.cclet.2024.110626
Abstract:
Garnet-type ceramic Li7La3Zr2O12 (LLZO) stands out as a potential solid-state electrolyte, offering a promising alternative to conventional flammable liquid electrolytes. However, its large interfacial resistance with electrodes remains a significant challenge. In this research, we have successfully in-situ fabricated polymeric interface layers on both cathode and anode sides with LLZO. By tuning the gel-polymer interphase via fluoroethylene carbonate (FEC), known as FGPE, we have established a rapid Li+ transport channel by enhancing the solid-solid interfacial contact. This FGPE layer exhibits exceptional ionic conductivity of 1.38 mS/cm and a high Li-ion transference number of 0.64. Furthermore, FGPE effectively mitigates concentration polarization under high currents, thereby enabling a higher capacity output. In comparison to gel-polymer interphases with dimethyl carbonate (DMC) as the solvent (referred to as GPE), the Li|FGPE|Li symmetrical cell has demonstrated superior stability in plating/strapping performance over 800 h at a current density of 0.1 mA/cm2. Moreover, the Li|FGPE|LLZO|FGPE|LiFePO4 cell has exhibited commendable rate capability and has maintained a high capacity retention of 98.94% at 0.5 C after 200 cycles. This study underscores an innovative approach in advancing in field of solid-state batteries, anticipated to be broadly applicable to other solid-state batteries by facilitating an abundance of robust solid-solid interfacial contacts.
Garnet-type ceramic Li7La3Zr2O12 (LLZO) stands out as a potential solid-state electrolyte, offering a promising alternative to conventional flammable liquid electrolytes. However, its large interfacial resistance with electrodes remains a significant challenge. In this research, we have successfully in-situ fabricated polymeric interface layers on both cathode and anode sides with LLZO. By tuning the gel-polymer interphase via fluoroethylene carbonate (FEC), known as FGPE, we have established a rapid Li+ transport channel by enhancing the solid-solid interfacial contact. This FGPE layer exhibits exceptional ionic conductivity of 1.38 mS/cm and a high Li-ion transference number of 0.64. Furthermore, FGPE effectively mitigates concentration polarization under high currents, thereby enabling a higher capacity output. In comparison to gel-polymer interphases with dimethyl carbonate (DMC) as the solvent (referred to as GPE), the Li|FGPE|Li symmetrical cell has demonstrated superior stability in plating/strapping performance over 800 h at a current density of 0.1 mA/cm2. Moreover, the Li|FGPE|LLZO|FGPE|LiFePO4 cell has exhibited commendable rate capability and has maintained a high capacity retention of 98.94% at 0.5 C after 200 cycles. This study underscores an innovative approach in advancing in field of solid-state batteries, anticipated to be broadly applicable to other solid-state batteries by facilitating an abundance of robust solid-solid interfacial contacts.
2026, 37(3): 110655
doi: 10.1016/j.cclet.2024.110655
Abstract:
Trapping and manipulating microscopic particles (micron or nano) in a liquid environment are of great significance for research and applications in nanoscience, engineering, and biomedicine. Although optical tweezers, magnetic tweezers, acoustic tweezers, etc. have been successfully developed, it is still challenging to separate, select, and manipulate micron and submicron particles with comparable morphologies and sizes in trace amounts of liquids with high viscosity and extremely tiny concentrations. Herein, an electric tweezer with measurable force was introduced in an environmental transmission electron microscope (ETEM) for trapping a single submicron particle in high viscosity liquids. The critical voltages for trapping SiO2 and TiO2 spheres were determined to be 75 V and 25 V, respectively, due to their dielectric characteristics. As a result, although TiO2 particles exhibited a similar size and morphology, they were able to be successfully separated from a mixed suspension of SiO2 and TiO2. Moreover, by applying a reasonable bias voltage to the electric tweezer and customizing the size and shape of the tweezer tip, individual 500, 750, and 1000 nm TiO2 spheres could be easily trapped from the corresponding TiO2 suspension. The displacements of atomic force microscope (AFM) cantilevers indicated that the forces to trapped a single particle gradually increased with the diameter of the particles. Additionally, the electric tweezer could precisely manipulate a single particle, and stack a specific structure on the top of the electric tweezer. When the electric tweezer was combined with an optical microscope, it could successfully transfer a 5 µm SiO2 sphere to a HeLa cell. Precisely trapping and manipulating micron and submicron particles is the foundation for fabricating microdevices to achieve specific functions, and it also show great potential for use in biological applications.
Trapping and manipulating microscopic particles (micron or nano) in a liquid environment are of great significance for research and applications in nanoscience, engineering, and biomedicine. Although optical tweezers, magnetic tweezers, acoustic tweezers, etc. have been successfully developed, it is still challenging to separate, select, and manipulate micron and submicron particles with comparable morphologies and sizes in trace amounts of liquids with high viscosity and extremely tiny concentrations. Herein, an electric tweezer with measurable force was introduced in an environmental transmission electron microscope (ETEM) for trapping a single submicron particle in high viscosity liquids. The critical voltages for trapping SiO2 and TiO2 spheres were determined to be 75 V and 25 V, respectively, due to their dielectric characteristics. As a result, although TiO2 particles exhibited a similar size and morphology, they were able to be successfully separated from a mixed suspension of SiO2 and TiO2. Moreover, by applying a reasonable bias voltage to the electric tweezer and customizing the size and shape of the tweezer tip, individual 500, 750, and 1000 nm TiO2 spheres could be easily trapped from the corresponding TiO2 suspension. The displacements of atomic force microscope (AFM) cantilevers indicated that the forces to trapped a single particle gradually increased with the diameter of the particles. Additionally, the electric tweezer could precisely manipulate a single particle, and stack a specific structure on the top of the electric tweezer. When the electric tweezer was combined with an optical microscope, it could successfully transfer a 5 µm SiO2 sphere to a HeLa cell. Precisely trapping and manipulating micron and submicron particles is the foundation for fabricating microdevices to achieve specific functions, and it also show great potential for use in biological applications.
2026, 37(3): 110666
doi: 10.1016/j.cclet.2024.110666
Abstract:
In order to cope with harsh situations without an external power supply, developing high-performance aqueous zinc batteries (AZBs) with chemically self-charging as a self-powered system is of great practical significance. Herein, we present the synthesis of a new porous organic polymer with hexaazatriphenylene hexacarboxylic acid trianhydride (HHAT) and 2,6-diaminoanthraquinone (DAAQ) units (HTAQ). Due to its π-conjugated aromatic structure with abundant redox-active centers and limited solubility in electrolytes, the constructed flexible and coin-type AZBs based on HTAQ cathodes display a superior volume energy density (8.7 mWh/cm3) and a higher energy density (104 Wh/kg), respectively, and excellent cycle life, where both Zn2+ and H+ ions participate in the cathode reaction. Impressively, the electric energy exhausted flexible Zn//HTAQ AZB can be chemically self-recharged by exposing the discharged HTAQ cathode to air, ascribing to the spontaneous redox reaction between O2 and the discharged HTAQ cathode. The exhausted flexible Zn//HTAQ AZB after air-charging for 30 h, can present a high discharge capacity of 294 mAh/g at 0.5 A/g, a higher self-charging cycle stability (15 cycles), a high-rate capability, and work well at hybrid modes (chemical or/and galvanostatic charging). Our work opens a new route to construct high-performance self-powered systems based on AZBs.
In order to cope with harsh situations without an external power supply, developing high-performance aqueous zinc batteries (AZBs) with chemically self-charging as a self-powered system is of great practical significance. Herein, we present the synthesis of a new porous organic polymer with hexaazatriphenylene hexacarboxylic acid trianhydride (HHAT) and 2,6-diaminoanthraquinone (DAAQ) units (HTAQ). Due to its π-conjugated aromatic structure with abundant redox-active centers and limited solubility in electrolytes, the constructed flexible and coin-type AZBs based on HTAQ cathodes display a superior volume energy density (8.7 mWh/cm3) and a higher energy density (104 Wh/kg), respectively, and excellent cycle life, where both Zn2+ and H+ ions participate in the cathode reaction. Impressively, the electric energy exhausted flexible Zn//HTAQ AZB can be chemically self-recharged by exposing the discharged HTAQ cathode to air, ascribing to the spontaneous redox reaction between O2 and the discharged HTAQ cathode. The exhausted flexible Zn//HTAQ AZB after air-charging for 30 h, can present a high discharge capacity of 294 mAh/g at 0.5 A/g, a higher self-charging cycle stability (15 cycles), a high-rate capability, and work well at hybrid modes (chemical or/and galvanostatic charging). Our work opens a new route to construct high-performance self-powered systems based on AZBs.
2026, 37(3): 110667
doi: 10.1016/j.cclet.2024.110667
Abstract:
The regulation of guest molecules on the self-assembly system of tetracarboxylic acid derivative (H4BDETP) at the liquid/solid interface was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Coronene (COR) guest molecules induced H4BDETP to transform from linear assembly structure to diversified nanoporous structures in which COR could be captured. And the regulation of pyridine guest molecules (DPE, BPYB, TYPY) on the mono-component assembly structure of H4BDETP was achieved by forming O–H···N hydrogen bonds with H4BDETP. The introduction of both COR and pyridine derivatives could destroy the hydrogen-bonded dimers of H4BDETP, and new O–H···O hydrogen bonds were formed between H4BDETP molecules. In addition, H4BDETP/pyridine co-assembly structures depended on the central bridging units and the number of pyridine groups in pyridine derivatives. Furthermore, H4BDETP/TYPY structure underwent structural transformation induced by COR and multi-component assembly structures with thermodynamic stability were constructed.
The regulation of guest molecules on the self-assembly system of tetracarboxylic acid derivative (H4BDETP) at the liquid/solid interface was studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Coronene (COR) guest molecules induced H4BDETP to transform from linear assembly structure to diversified nanoporous structures in which COR could be captured. And the regulation of pyridine guest molecules (DPE, BPYB, TYPY) on the mono-component assembly structure of H4BDETP was achieved by forming O–H···N hydrogen bonds with H4BDETP. The introduction of both COR and pyridine derivatives could destroy the hydrogen-bonded dimers of H4BDETP, and new O–H···O hydrogen bonds were formed between H4BDETP molecules. In addition, H4BDETP/pyridine co-assembly structures depended on the central bridging units and the number of pyridine groups in pyridine derivatives. Furthermore, H4BDETP/TYPY structure underwent structural transformation induced by COR and multi-component assembly structures with thermodynamic stability were constructed.
2026, 37(3): 110668
doi: 10.1016/j.cclet.2024.110668
Abstract:
The surficial inherent properties of TiO2 like exposed facet and crystalline state are vital for their surface reactions. However, efficiently controlling the specific crystal structure and the exposed crystal surface still faces big challenge. Here, the controlled solid phase transition of amorphous TiO2 to crystalline phase with exposed crystal facet (001) is achieved by photo-assisted atomic layer deposition (ALD) Pt process. Significantly, the obtained Pt/TiO2 film via photo-assisted treatment exhibits high sensing performance to NO and HF, and shows a lower optimized working temperature. The enhanced sensing performance is attributed to the metal-support strong interaction under oxidative atmosphere (O-SMSI). The facet effects leading to the unique distribution of charges at the interface combined with the catalytic effects result in the high sensing performance. This work provides a novel phase transition engineering strategy for regulating TiO2 from amorphous to crystalline phase, and the controllable synthesis of high Pt monatomic loading on TiO2 via ALD, which are critical for the accurate synthesis of efficient sensing and catalytic nanomaterials.
The surficial inherent properties of TiO2 like exposed facet and crystalline state are vital for their surface reactions. However, efficiently controlling the specific crystal structure and the exposed crystal surface still faces big challenge. Here, the controlled solid phase transition of amorphous TiO2 to crystalline phase with exposed crystal facet (001) is achieved by photo-assisted atomic layer deposition (ALD) Pt process. Significantly, the obtained Pt/TiO2 film via photo-assisted treatment exhibits high sensing performance to NO and HF, and shows a lower optimized working temperature. The enhanced sensing performance is attributed to the metal-support strong interaction under oxidative atmosphere (O-SMSI). The facet effects leading to the unique distribution of charges at the interface combined with the catalytic effects result in the high sensing performance. This work provides a novel phase transition engineering strategy for regulating TiO2 from amorphous to crystalline phase, and the controllable synthesis of high Pt monatomic loading on TiO2 via ALD, which are critical for the accurate synthesis of efficient sensing and catalytic nanomaterials.
2026, 37(3): 110681
doi: 10.1016/j.cclet.2024.110681
Abstract:
The emerging anode-free lithium metal battery (AFLMB) is very promising for the next-generation electrochemical energy storage technology due to its remarkable high-energy density. However, the current development of AFLMB is seriously hampered by the low Coulombic efficiency and limited lifespan caused mainly by the uncontrolled dendritic lithium growth and significant volume change during Li plating/stripping on the traditional current collector. Here, we report the design of a “breathable” three-dimensional (3D) lithium host with MnO2 nanoflake array for long-lifespan AFLMB. Specifically, a dense MnO2 nanoflake array stretchably grown on carbon cloth by an easy solution dipping method is constructed as a 3D current collector for AFLMBs. Both experimental and theoretical studies underlined that the Li2O/Mn nanoflake arrays produced spontaneously upon the initial lithiation can effectively guide uniform lithium nucleation and growth. Moreover, this unique 3D hierarchical structure expands/shrinks along with the lithium plating/stripping, accommodating the large volume expansion/shrinkage over the subsequent charge/discharge processes. As such, a dendrite-free lithium structure was achieved even at a high capacity of 10 mAh/cm2. More importantly, the as-constructed AFLMB with this current collector exhibits impressive cycling stability with 64% capacity retained after 200 cycles. This study offers new insights into constructing highly efficient 3D protective layers for metal anodes toward the practical feasibility of anode-free batteries.
The emerging anode-free lithium metal battery (AFLMB) is very promising for the next-generation electrochemical energy storage technology due to its remarkable high-energy density. However, the current development of AFLMB is seriously hampered by the low Coulombic efficiency and limited lifespan caused mainly by the uncontrolled dendritic lithium growth and significant volume change during Li plating/stripping on the traditional current collector. Here, we report the design of a “breathable” three-dimensional (3D) lithium host with MnO2 nanoflake array for long-lifespan AFLMB. Specifically, a dense MnO2 nanoflake array stretchably grown on carbon cloth by an easy solution dipping method is constructed as a 3D current collector for AFLMBs. Both experimental and theoretical studies underlined that the Li2O/Mn nanoflake arrays produced spontaneously upon the initial lithiation can effectively guide uniform lithium nucleation and growth. Moreover, this unique 3D hierarchical structure expands/shrinks along with the lithium plating/stripping, accommodating the large volume expansion/shrinkage over the subsequent charge/discharge processes. As such, a dendrite-free lithium structure was achieved even at a high capacity of 10 mAh/cm2. More importantly, the as-constructed AFLMB with this current collector exhibits impressive cycling stability with 64% capacity retained after 200 cycles. This study offers new insights into constructing highly efficient 3D protective layers for metal anodes toward the practical feasibility of anode-free batteries.
2026, 37(3): 110682
doi: 10.1016/j.cclet.2024.110682
Abstract:
Lead-free perovskite has become a shining pearl in the field of direct X-ray detection due to its non-toxicity and excellent optoelectronic properties. However, the high limit of detection (LoD) of X-ray detectors due to high current noise caused by high operating voltages is a major challenge to overcome. Here, we utilized a zero-dimensional lead-free perovskite ferroelectric material (NMP)3Sb2Br9 (1, NMP = N-methylpyrrolidine) to achieve ultra-low LoD self-driven X-ray detection. The self-driven detection mode without external bias has been proven to be an effective means of reducing LoD due to its low current noise characteristics. Additionally, the zero-dimensional distinctive isolated framework results in a high resistivity of 1.39 × 1011 Ω cm, which effectively reduces the current noise and suppresses ion migration. By further combining the ferroelectric-induced bulk photovoltaic effect, the 1-based detector achieves an ultra-low LoD X-ray detection of 84.1 nGyair/s under the self-driven mode, which represents a quite advanced level in the lead-free perovskite X-ray detection region. Our work successfully achieved ultra-low LoD self-driven X-ray detection by combining ferroelectricity with high resistance, providing a promising avenue for the development of low LoD X-ray detectors.
Lead-free perovskite has become a shining pearl in the field of direct X-ray detection due to its non-toxicity and excellent optoelectronic properties. However, the high limit of detection (LoD) of X-ray detectors due to high current noise caused by high operating voltages is a major challenge to overcome. Here, we utilized a zero-dimensional lead-free perovskite ferroelectric material (NMP)3Sb2Br9 (1, NMP = N-methylpyrrolidine) to achieve ultra-low LoD self-driven X-ray detection. The self-driven detection mode without external bias has been proven to be an effective means of reducing LoD due to its low current noise characteristics. Additionally, the zero-dimensional distinctive isolated framework results in a high resistivity of 1.39 × 1011 Ω cm, which effectively reduces the current noise and suppresses ion migration. By further combining the ferroelectric-induced bulk photovoltaic effect, the 1-based detector achieves an ultra-low LoD X-ray detection of 84.1 nGyair/s under the self-driven mode, which represents a quite advanced level in the lead-free perovskite X-ray detection region. Our work successfully achieved ultra-low LoD self-driven X-ray detection by combining ferroelectricity with high resistance, providing a promising avenue for the development of low LoD X-ray detectors.
2026, 37(3): 110702
doi: 10.1016/j.cclet.2024.110702
Abstract:
Rechargeable aqueous zinc-ion batteries (AZIBs) draw intensive attention due to their high security, low price and the abundant zinc source. However, the electrochemical behaviors of AZIBs are seriously affected by the cathode materials. Mn-based oxide cathodes have been extensively investigated owing to the superior electrochemical performances such as large theoretical capacity and high working voltage. In this work, we rationally design a high-performance cathode material using organic-inorganic co-modification strategy. The inorganic Al3+ ions and organic poly-vinylpyrrolidone (PVP) are successfully incorporated into the tunnel α-MnO2 structure. Structural characterizations and DFT calculations indicates that the Zn2+ adsorption energy in the Al3+/PVP co-intercalated tunnel α-MnO2 is effectively lowered when compared with the original material, facilitating fast ion diffusion and stable Zn2+ ion storage. Electrochemical tests indicate that the PVP-Al-MnO2 electrode exhibits excellent electrochemical performances, a capacity of 306.8 mAh/g at 0.3 A/g and 93.1% capacity retention over 2000 cycles at 1.0 A/g. In addition, the aqueous PVP-Al-MnO2||ZnClO4||Zn battery is able to operate properly at low temperature (-45 ℃). This work shows an encouraging strategy to the modification of materials for AZIBs and other multivalent ion systems.
Rechargeable aqueous zinc-ion batteries (AZIBs) draw intensive attention due to their high security, low price and the abundant zinc source. However, the electrochemical behaviors of AZIBs are seriously affected by the cathode materials. Mn-based oxide cathodes have been extensively investigated owing to the superior electrochemical performances such as large theoretical capacity and high working voltage. In this work, we rationally design a high-performance cathode material using organic-inorganic co-modification strategy. The inorganic Al3+ ions and organic poly-vinylpyrrolidone (PVP) are successfully incorporated into the tunnel α-MnO2 structure. Structural characterizations and DFT calculations indicates that the Zn2+ adsorption energy in the Al3+/PVP co-intercalated tunnel α-MnO2 is effectively lowered when compared with the original material, facilitating fast ion diffusion and stable Zn2+ ion storage. Electrochemical tests indicate that the PVP-Al-MnO2 electrode exhibits excellent electrochemical performances, a capacity of 306.8 mAh/g at 0.3 A/g and 93.1% capacity retention over 2000 cycles at 1.0 A/g. In addition, the aqueous PVP-Al-MnO2||ZnClO4||Zn battery is able to operate properly at low temperature (-45 ℃). This work shows an encouraging strategy to the modification of materials for AZIBs and other multivalent ion systems.
2026, 37(3): 110709
doi: 10.1016/j.cclet.2024.110709
Abstract:
The gas separation performance of metal-organic framework (MOF) adsorbents could be enhanced by tuning the pores, whereas the presence of moisture usually compromises the efficiency. Herein, two MOFs, Fe-BDC-TPT-BF4, Ni-BDC-TPT-TMA (TMA+ = (CH3)4N+), were synthesized by exchanging countering ions in parent MOFs, Fe-BDC-TPT-Cl and Ni-BDC-TPT-Me2NH2, respectively. Fe-BDC-TPT-BF4 and Ni-BDC-TPT-TMA exhibited a high C2H2 adsorption uptake of 203.1 cm3/g and 200.1 cm3/g at 298 K and 1 bar, and high C2H2/CO2 selectivity of 4.6 and 4.4. Humid breakthrough experiments revealed that high C2H2 productivity of high C2H2 purity was achieved on Ni-BDC-TPT-TMA at 35% relative humidity. Cycling dynamic breakthrough experiments demonstrate good recyclability of Ni-BDC-TPT-TMA for humid C2H2/CO2 separation. The alteration of countering ions changed the pore size and chemistry, leading to high C2H2 uptake, high C2H2 selectivity, and retained performance in the presence of moisture, making it a promising candidate for practical applications. This work highlights that ion exchange modification of MOFs has been developed as a facile and powerful strategy to optimize the inner pores for better performance in challenging separations.
The gas separation performance of metal-organic framework (MOF) adsorbents could be enhanced by tuning the pores, whereas the presence of moisture usually compromises the efficiency. Herein, two MOFs, Fe-BDC-TPT-BF4, Ni-BDC-TPT-TMA (TMA+ = (CH3)4N+), were synthesized by exchanging countering ions in parent MOFs, Fe-BDC-TPT-Cl and Ni-BDC-TPT-Me2NH2, respectively. Fe-BDC-TPT-BF4 and Ni-BDC-TPT-TMA exhibited a high C2H2 adsorption uptake of 203.1 cm3/g and 200.1 cm3/g at 298 K and 1 bar, and high C2H2/CO2 selectivity of 4.6 and 4.4. Humid breakthrough experiments revealed that high C2H2 productivity of high C2H2 purity was achieved on Ni-BDC-TPT-TMA at 35% relative humidity. Cycling dynamic breakthrough experiments demonstrate good recyclability of Ni-BDC-TPT-TMA for humid C2H2/CO2 separation. The alteration of countering ions changed the pore size and chemistry, leading to high C2H2 uptake, high C2H2 selectivity, and retained performance in the presence of moisture, making it a promising candidate for practical applications. This work highlights that ion exchange modification of MOFs has been developed as a facile and powerful strategy to optimize the inner pores for better performance in challenging separations.
2026, 37(3): 110710
doi: 10.1016/j.cclet.2024.110710
Abstract:
In this paper, a new series of donor-acceptor coordination polymers (DACPs), [Cd(dppz)(R-ndc)(H2O)]n (R = none, DZU-400; R = F, DZU-400-F; R = Br, DZU-400-Br; DZU is short for Dezhou University), [Cd(dppz)(adc)(H2O)]n (DZU-401), and {[Cd(dppz)(adb)0.5(HCOO)(H2O)]}n (DZU-402), have been successfully constructed through the combination of electron-deficient dipyrido[3,2-a: 2′,3′-c]phenazine (dppz) as an acceptor and various dicarboxylic ligands (H2ndc = 2,3-naphthalenedicarboxylic acid, F-H2ndc = 6,7-difluoronaphthalene-2,3-dicarboxylic acid, Br-H2ndc = 6,7-dibromonaphthalene-2,3-dicarboxylic acid, H2adc = 9,10-anthracenedicarboxylic acid, and H2adb = 4,4′-(anthracene-9,10-diyl)dibenzoic acid) with electron-rich planar aromatic rings as donors. Structural analyses reveal closely parallel arrangement of the planar acceptor and donor units in these DACPs, which could facilitate the through-space charge transfer (TSCT) interactions of the D-A systems and the corresponding luminescent properties. Interestingly, the DACPs show highly regulable donor dependent photoluminescence from blue to orange. Based on the TSCT based luminescence and the high thermal stability of the DACPs, their thermal-stimuli responsive emission properties were further studied. Photoluminescence intensity of the DACPs all present good linearity with temperature (298–473 K), as proved by variable temperature fluorescence spectra. Importantly, the temperature sensing process is reversible and recyclable, suggesting the promising applications of the DACPs as thermal-stimuli responsive materials.
In this paper, a new series of donor-acceptor coordination polymers (DACPs), [Cd(dppz)(R-ndc)(H2O)]n (R = none, DZU-400; R = F, DZU-400-F; R = Br, DZU-400-Br; DZU is short for Dezhou University), [Cd(dppz)(adc)(H2O)]n (DZU-401), and {[Cd(dppz)(adb)0.5(HCOO)(H2O)]}n (DZU-402), have been successfully constructed through the combination of electron-deficient dipyrido[3,2-a: 2′,3′-c]phenazine (dppz) as an acceptor and various dicarboxylic ligands (H2ndc = 2,3-naphthalenedicarboxylic acid, F-H2ndc = 6,7-difluoronaphthalene-2,3-dicarboxylic acid, Br-H2ndc = 6,7-dibromonaphthalene-2,3-dicarboxylic acid, H2adc = 9,10-anthracenedicarboxylic acid, and H2adb = 4,4′-(anthracene-9,10-diyl)dibenzoic acid) with electron-rich planar aromatic rings as donors. Structural analyses reveal closely parallel arrangement of the planar acceptor and donor units in these DACPs, which could facilitate the through-space charge transfer (TSCT) interactions of the D-A systems and the corresponding luminescent properties. Interestingly, the DACPs show highly regulable donor dependent photoluminescence from blue to orange. Based on the TSCT based luminescence and the high thermal stability of the DACPs, their thermal-stimuli responsive emission properties were further studied. Photoluminescence intensity of the DACPs all present good linearity with temperature (298–473 K), as proved by variable temperature fluorescence spectra. Importantly, the temperature sensing process is reversible and recyclable, suggesting the promising applications of the DACPs as thermal-stimuli responsive materials.
2026, 37(3): 110711
doi: 10.1016/j.cclet.2024.110711
Abstract:
Electrochemical two-electron oxygen reduction reaction (2e- ORR) is a green and attractive method for hydrogen peroxide synthesis. However, rapid and efficient development of high-performance catalyst remains a great challenge. Different from traditional trial and error methods, this study employs density functional theory and machine learning method to efficiently screen the promising main-group metal single-atom catalysts (SACs) and systematically investigate the influence of electronegativity of coordination atoms on the adsorption behavior of key intermediates in ORR process. It is found that the K SAC with N/B in the first coordination sphere and Sn SAC with N/C in the first coordination sphere and O in the second coordination sphere exhibit both excellent 2e- ORR activity and selectivity by showing extremely low overpotentials of 0.029 V and 0.064 V, respectively, as well as barrier-free processes from *OOH to H2O2. Bagging displays prominent advantages among seven popular algorithms because of its ensemble strategy. This provides a low-cost approach for designing and screening electrocatalyst candidates, and it will be informative for experimental study in the future to accelerate the development of catalysts for oxygen reduction and other types of reactions.
Electrochemical two-electron oxygen reduction reaction (2e- ORR) is a green and attractive method for hydrogen peroxide synthesis. However, rapid and efficient development of high-performance catalyst remains a great challenge. Different from traditional trial and error methods, this study employs density functional theory and machine learning method to efficiently screen the promising main-group metal single-atom catalysts (SACs) and systematically investigate the influence of electronegativity of coordination atoms on the adsorption behavior of key intermediates in ORR process. It is found that the K SAC with N/B in the first coordination sphere and Sn SAC with N/C in the first coordination sphere and O in the second coordination sphere exhibit both excellent 2e- ORR activity and selectivity by showing extremely low overpotentials of 0.029 V and 0.064 V, respectively, as well as barrier-free processes from *OOH to H2O2. Bagging displays prominent advantages among seven popular algorithms because of its ensemble strategy. This provides a low-cost approach for designing and screening electrocatalyst candidates, and it will be informative for experimental study in the future to accelerate the development of catalysts for oxygen reduction and other types of reactions.
2026, 37(3): 110728
doi: 10.1016/j.cclet.2024.110728
Abstract:
Cutting-edge high/pulsed power capacitors with satisfactory power density are fundamental units in modern power storage systems. However, a persistent challenge is how to overcome the trade-off between recoverable energy storage density (Wrec) and efficiency (η) for meeting the miniaturization and integration of advanced applications. Here, multiple local distortions including inhomogeneous functional nanoclusters, (anti)ferro-distortions and highly dynamic polar nanoregions are modulated through a high-entropy strategy to design a stable ergodic-relaxor-state-dominated structure. Of great importance, this strategy delay polarization saturation, reduces hysteresis and improves breakdown strength, so that an ultrahigh Wrec ~11.94 J/cm3 with a η ~ 82.4% is realized in Pb-free ergodic-relaxors. Moreover, a significant Vickers hardness of 10.04 GPa as well as superior temperature, cycling and frequency stabilities are also obtained. This work demonstrates that designing multiple local distortions via a high-entropy strategy is a promising way to realize superior comprehensive energy storage properties in high/pulsed power capacitors.
Cutting-edge high/pulsed power capacitors with satisfactory power density are fundamental units in modern power storage systems. However, a persistent challenge is how to overcome the trade-off between recoverable energy storage density (Wrec) and efficiency (η) for meeting the miniaturization and integration of advanced applications. Here, multiple local distortions including inhomogeneous functional nanoclusters, (anti)ferro-distortions and highly dynamic polar nanoregions are modulated through a high-entropy strategy to design a stable ergodic-relaxor-state-dominated structure. Of great importance, this strategy delay polarization saturation, reduces hysteresis and improves breakdown strength, so that an ultrahigh Wrec ~11.94 J/cm3 with a η ~ 82.4% is realized in Pb-free ergodic-relaxors. Moreover, a significant Vickers hardness of 10.04 GPa as well as superior temperature, cycling and frequency stabilities are also obtained. This work demonstrates that designing multiple local distortions via a high-entropy strategy is a promising way to realize superior comprehensive energy storage properties in high/pulsed power capacitors.
2026, 37(3): 110729
doi: 10.1016/j.cclet.2024.110729
Abstract:
Nickel-rich layered oxides are considered highly promising cathode materials for all-solid-state batteries (ASSBs) due to their high theoretical specific capacity and energy density. In this study, a comparison between polycrystalline and single-crystalline cathode materials was conducted. It was found that, during the charging process, ion transport at the interface of polycrystalline cathodes is significantly influenced by phase transitions and side reactions with the electrolyte, resulting in an irreversible increase in impedance after cycling. Furthermore, the structural stability of the cathode material affects internal ion diffusion kinetics, thereby influencing its electrochemical performance. Unlike single-crystalline materials, ion migration in polycrystalline materials must traverse anisotropic grain boundaries, which, due to anisotropic lattice contraction, evolve into intergranular cracks, leading to reduced ion diffusion kinetics and degraded electrochemical performance. In contrast, single-crystalline cathodes exhibit more stable interfacial resistance and uniform ion transport during charging, ensuring structural stability over long-term cycling. Consequently, at a 0.5 C rate, the single-crystalline cathode maintains a specific capacity of 143 mAh/g after 500 cycles, with a capacity retention of 89.2%, while preserving its intact single-crystal morphology. This study provides valuable new insights into the localized lithium-ion transport behavior in single-crystalline and polycrystalline cathode materials for sulfide-based all-solid-state batteries.
Nickel-rich layered oxides are considered highly promising cathode materials for all-solid-state batteries (ASSBs) due to their high theoretical specific capacity and energy density. In this study, a comparison between polycrystalline and single-crystalline cathode materials was conducted. It was found that, during the charging process, ion transport at the interface of polycrystalline cathodes is significantly influenced by phase transitions and side reactions with the electrolyte, resulting in an irreversible increase in impedance after cycling. Furthermore, the structural stability of the cathode material affects internal ion diffusion kinetics, thereby influencing its electrochemical performance. Unlike single-crystalline materials, ion migration in polycrystalline materials must traverse anisotropic grain boundaries, which, due to anisotropic lattice contraction, evolve into intergranular cracks, leading to reduced ion diffusion kinetics and degraded electrochemical performance. In contrast, single-crystalline cathodes exhibit more stable interfacial resistance and uniform ion transport during charging, ensuring structural stability over long-term cycling. Consequently, at a 0.5 C rate, the single-crystalline cathode maintains a specific capacity of 143 mAh/g after 500 cycles, with a capacity retention of 89.2%, while preserving its intact single-crystal morphology. This study provides valuable new insights into the localized lithium-ion transport behavior in single-crystalline and polycrystalline cathode materials for sulfide-based all-solid-state batteries.
2026, 37(3): 111033
doi: 10.1016/j.cclet.2025.111033
Abstract:
Interleukin-1 receptor-associated kinase 4 (IRAK4), a key target with both enzymatic and non-enzymatic functions, plays a pivotal role in autoimmune diseases. Previous studies have demonstrated that proteolysis-targeting chimera (PROTAC) molecules targeting IRAK4 can effectively eliminate both its enzymatic and non-enzymatic functions, showing promising therapeutic potential. However, the development of highly potent, synthetically accessible IRAK4-targeting degraders remains a challenge. In this work, through three rounds of PROTAC library construction, screening, and optimization, we successfully identified a representative compound, LZ-07, which proved to be a highly potent degrader with a half-maximal degradation concentration (DC50) value of 1.14 nmol/L. Notably, compared with KT-474, LZ-07 demonstrated comparable degradation activity and superior inhibition of cytokine production, while featuring a simpler synthetic route with optimized IRAK4 and cereblon (CRBN) ligands. LZ-07-induced degradation of IRAK4 led to marked suppression of key cytokines, including interleukin-6 (IL-6), IL-1β, tumor necrosis factor alpha (TNF-α), and IL-10. This study presents LZ-07 as a novel, highly efficient, and synthetically straightforward IRAK4-targeting degrader, offering a promising tool compound for the study of the potential treatment of autoimmune diseases.
Interleukin-1 receptor-associated kinase 4 (IRAK4), a key target with both enzymatic and non-enzymatic functions, plays a pivotal role in autoimmune diseases. Previous studies have demonstrated that proteolysis-targeting chimera (PROTAC) molecules targeting IRAK4 can effectively eliminate both its enzymatic and non-enzymatic functions, showing promising therapeutic potential. However, the development of highly potent, synthetically accessible IRAK4-targeting degraders remains a challenge. In this work, through three rounds of PROTAC library construction, screening, and optimization, we successfully identified a representative compound, LZ-07, which proved to be a highly potent degrader with a half-maximal degradation concentration (DC50) value of 1.14 nmol/L. Notably, compared with KT-474, LZ-07 demonstrated comparable degradation activity and superior inhibition of cytokine production, while featuring a simpler synthetic route with optimized IRAK4 and cereblon (CRBN) ligands. LZ-07-induced degradation of IRAK4 led to marked suppression of key cytokines, including interleukin-6 (IL-6), IL-1β, tumor necrosis factor alpha (TNF-α), and IL-10. This study presents LZ-07 as a novel, highly efficient, and synthetically straightforward IRAK4-targeting degrader, offering a promising tool compound for the study of the potential treatment of autoimmune diseases.
2026, 37(3): 111041
doi: 10.1016/j.cclet.2025.111041
Abstract:
Classic near-infrared dyes typically enhance their maxima absorption wavelength through the D-A system. Herein, introducing p-trifluoromethylphenyl group at 1,7-sites as electron-withdrawing group and julolidine at 3,5-sites as electron-donating group in aza-borondipyrromethene (aza-BODIPY) system, CF3-JLD with the donor-acceptor-acceptor (D-A-A’) system was prepared, which absorbs at 952 nm and emits at 1069 nm in dimethyl sulfoxide (DMSO) in the near infrared-Ⅱ (NIR-Ⅱ) region. According to the experimental observation and theoretical calculation, the D-A-A’ system for enhancing redshift of maxima absorption is found to be more effective than that of donor-acceptor-donor (D-A-D’) system. NIR-Ⅱ absorbing CF3-JLD was type Ⅰ photodynamic therapy/photothermal therapy (PDT/PTT) co-therapy reagent, with high photothermal conversion efficiency (η = 81%). Self-assembled nanoparticles (CF3-JLD NPs) can effectively induce 4T1 cell death in vitro, and the cellular morphology of tumor was destroyed and the proliferation-related protein was decreased in vivo under NIR irradiation by phototherapy. This strategy of the D-A-A’ system provides a guideline for developing organic fluorophores with enhanced NIR-Ⅱ absorption and type Ⅰ PDT/PTT co-therapy for 4T1 breast tumors.
Classic near-infrared dyes typically enhance their maxima absorption wavelength through the D-A system. Herein, introducing p-trifluoromethylphenyl group at 1,7-sites as electron-withdrawing group and julolidine at 3,5-sites as electron-donating group in aza-borondipyrromethene (aza-BODIPY) system, CF3-JLD with the donor-acceptor-acceptor (D-A-A’) system was prepared, which absorbs at 952 nm and emits at 1069 nm in dimethyl sulfoxide (DMSO) in the near infrared-Ⅱ (NIR-Ⅱ) region. According to the experimental observation and theoretical calculation, the D-A-A’ system for enhancing redshift of maxima absorption is found to be more effective than that of donor-acceptor-donor (D-A-D’) system. NIR-Ⅱ absorbing CF3-JLD was type Ⅰ photodynamic therapy/photothermal therapy (PDT/PTT) co-therapy reagent, with high photothermal conversion efficiency (η = 81%). Self-assembled nanoparticles (CF3-JLD NPs) can effectively induce 4T1 cell death in vitro, and the cellular morphology of tumor was destroyed and the proliferation-related protein was decreased in vivo under NIR irradiation by phototherapy. This strategy of the D-A-A’ system provides a guideline for developing organic fluorophores with enhanced NIR-Ⅱ absorption and type Ⅰ PDT/PTT co-therapy for 4T1 breast tumors.
2026, 37(3): 111061
doi: 10.1016/j.cclet.2025.111061
Abstract:
Quantitative visualization of pivotal biomarkers and accurate delineation of tumor lesion boundary are highly significant to assist surgeon precisely resect the tumors and reduce the risk of recurrence. Activatable fluorescent probes hold great promise for intraoperative guidance of tumor surgery with high signal-to-background ratio (SBR). Here, we report a γ-glutamyl transpeptidase (GGT)-activated fluorogenic probe Indol-Glu for quantitative visualization of GGT and fluorescence-guided tumor resection. The fluorescence of Indol-Glu was initially “off” state but was specifically activated by GGT to produce enhanced near-infrared (NIR) fluorescence (~37-fold at 741 nm). It is also accompanied by the formation of self-assemblies in the tumor microenvironment resulting in prolonged retention in tumor tissues, which was demonstrated to be able to apply for NIR imaging-guided surgical resection of GGT-overexpressed luciferase-transfected hepatocellular carcinoma (HCC/Luc) tumor. More notably, taking advantage of the ratiometric photoacoustic signal (PA690/PA800) characteristic of Indol-Glu under the digestion of GGT, quantitative visual assessment of GGT activities in various tumor models was achieved in living mice. We believe that this research work may offer a powerful tool for precise diagnosis and surgical resection of malignant tumors.
Quantitative visualization of pivotal biomarkers and accurate delineation of tumor lesion boundary are highly significant to assist surgeon precisely resect the tumors and reduce the risk of recurrence. Activatable fluorescent probes hold great promise for intraoperative guidance of tumor surgery with high signal-to-background ratio (SBR). Here, we report a γ-glutamyl transpeptidase (GGT)-activated fluorogenic probe Indol-Glu for quantitative visualization of GGT and fluorescence-guided tumor resection. The fluorescence of Indol-Glu was initially “off” state but was specifically activated by GGT to produce enhanced near-infrared (NIR) fluorescence (~37-fold at 741 nm). It is also accompanied by the formation of self-assemblies in the tumor microenvironment resulting in prolonged retention in tumor tissues, which was demonstrated to be able to apply for NIR imaging-guided surgical resection of GGT-overexpressed luciferase-transfected hepatocellular carcinoma (HCC/Luc) tumor. More notably, taking advantage of the ratiometric photoacoustic signal (PA690/PA800) characteristic of Indol-Glu under the digestion of GGT, quantitative visual assessment of GGT activities in various tumor models was achieved in living mice. We believe that this research work may offer a powerful tool for precise diagnosis and surgical resection of malignant tumors.
2026, 37(3): 111087
doi: 10.1016/j.cclet.2025.111087
Abstract:
The employment of low-frequency electrical stimulation therapy has been shown to elicit a pronounced depolarization of neurons, thereby initiating the regenerative signaling cascades within neural cells, which is favorable for the regeneration of neural cells. In this study, we designed the flexible triboelectric nanogenerator device (TENG) to treat injury of peripheral nerve, which is combined with mesoporous silica (H-SiO2), high dielectric performance of polydimethylsiloxane (PDMS), and connected to biocompatible and conductive polycaprolactone (PCL) conduit materials for limited power generation to neuro-bioelectric response adaptation. By adjusting the content of H-SiO2 and the amount of PDMS monomers, the electrical performance of the device is optimized. Through the charge collection effect of silica molecular sieve, the endogenous neural electric field in nerve injury was stabilized, ensuring the consistency of the electrical stimulation level that is crucial for maintaining resting membrane potential. In vitro experiments clearly demonstrated that electrical stimulation derived from the triboelectric nanogenerator significantly promotes cell proliferation. Further animal experiments confirmed that electrical stimulation can effectively treat sciatic nerve injury and accelerate axonal regeneration. Based on experimental outcomes, we have developed an implantable sciatic nerve system that can stably generate effective electrical pulses in response to rat movement through charge collection. This system regulates the electric field around the injured sciatic nerve, maintains the electric field threshold required for rapid nerve tissue repair, and accelerates the recovery of nerve function.
The employment of low-frequency electrical stimulation therapy has been shown to elicit a pronounced depolarization of neurons, thereby initiating the regenerative signaling cascades within neural cells, which is favorable for the regeneration of neural cells. In this study, we designed the flexible triboelectric nanogenerator device (TENG) to treat injury of peripheral nerve, which is combined with mesoporous silica (H-SiO2), high dielectric performance of polydimethylsiloxane (PDMS), and connected to biocompatible and conductive polycaprolactone (PCL) conduit materials for limited power generation to neuro-bioelectric response adaptation. By adjusting the content of H-SiO2 and the amount of PDMS monomers, the electrical performance of the device is optimized. Through the charge collection effect of silica molecular sieve, the endogenous neural electric field in nerve injury was stabilized, ensuring the consistency of the electrical stimulation level that is crucial for maintaining resting membrane potential. In vitro experiments clearly demonstrated that electrical stimulation derived from the triboelectric nanogenerator significantly promotes cell proliferation. Further animal experiments confirmed that electrical stimulation can effectively treat sciatic nerve injury and accelerate axonal regeneration. Based on experimental outcomes, we have developed an implantable sciatic nerve system that can stably generate effective electrical pulses in response to rat movement through charge collection. This system regulates the electric field around the injured sciatic nerve, maintains the electric field threshold required for rapid nerve tissue repair, and accelerates the recovery of nerve function.
2026, 37(3): 111151
doi: 10.1016/j.cclet.2025.111151
Abstract:
The design and synthesis of fully conjugated covalent organic cages (cCOCs) featuring sp2 carbon connections pose significant challenges due to the difficulties associated with forming stable CC bonds. In this study, we present a novel anthracene-based cCOC linked by CC bonds, synthesized directly through Knoevenagel condensation. Remarkably, this sp2c COC has shown exceptional performance as an n-type semiconductor, characterized by strong electronic delocalization, an optimized band structure, and extensive light absorption capabilities. It efficiently catalyzes the photodegradation of organic dyes and promotes the photoinduced aerobic oxidation of amines to imines. In comparison to imine-linked cCOCs with the same skeleton, the sp2c COC demonstrates distinct advantages as a next-generation photocatalyst, including enhanced chemical stability and superior photocatalytic performance. This research underscores the potential of Knoevenagel condensation in the development of innovative cCOCs, offering valuable insights for their applications in optoelectronic materials and catalysis.
The design and synthesis of fully conjugated covalent organic cages (cCOCs) featuring sp2 carbon connections pose significant challenges due to the difficulties associated with forming stable CC bonds. In this study, we present a novel anthracene-based cCOC linked by CC bonds, synthesized directly through Knoevenagel condensation. Remarkably, this sp2c COC has shown exceptional performance as an n-type semiconductor, characterized by strong electronic delocalization, an optimized band structure, and extensive light absorption capabilities. It efficiently catalyzes the photodegradation of organic dyes and promotes the photoinduced aerobic oxidation of amines to imines. In comparison to imine-linked cCOCs with the same skeleton, the sp2c COC demonstrates distinct advantages as a next-generation photocatalyst, including enhanced chemical stability and superior photocatalytic performance. This research underscores the potential of Knoevenagel condensation in the development of innovative cCOCs, offering valuable insights for their applications in optoelectronic materials and catalysis.
2026, 37(3): 111188
doi: 10.1016/j.cclet.2025.111188
Abstract:
Electrochemically converting nitrate to ammonia under ambient conditions is a hot topic. However, it suffers from low efficiency because of the multi-electron/proton transfer. Herein, high-load atomic Fe (16.45 wt%) in-situ grown on carbon fiber cloth (Fe1@MoS2/CFC) demonstrates super high activity and selectivity in electrochemical nitrate reduction to ammonia at -0.73 V vs. RHE. The maximum NH3 yield is 28.59 mg h-1 cm-2, and the corresponding NH3-Faradaic efficiency is 96.65% at 360 mA/cm2 partial current density. The electrode exhibits good durability during ten cycled tests of 1 h each. The X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), in-situ Raman analysis, and electron paramagnetic resonance (EPR) measurements reveal that the super high activity derives from the rich presence of active sites related to Fe-S and surrounding unsaturated Mo-S. Density functional theory (DFT) calculations show that the atomic Fe facilitates the water dissociation and provides sufficient active hydrogen for the edge Mo to boost nitrate reduction reaction (NO3-RR) activity, enhances NH3 selectivity, and decreases the energy barrier of NH3 desorption (rate-determining step) by regulating the coordination environment and electronic structure of the active Mo site. This stable and binder-free electrode with high dosage atomic Fe and rich edge Mo active sites is an attractive cathode for NO3-RR.
Electrochemically converting nitrate to ammonia under ambient conditions is a hot topic. However, it suffers from low efficiency because of the multi-electron/proton transfer. Herein, high-load atomic Fe (16.45 wt%) in-situ grown on carbon fiber cloth (Fe1@MoS2/CFC) demonstrates super high activity and selectivity in electrochemical nitrate reduction to ammonia at -0.73 V vs. RHE. The maximum NH3 yield is 28.59 mg h-1 cm-2, and the corresponding NH3-Faradaic efficiency is 96.65% at 360 mA/cm2 partial current density. The electrode exhibits good durability during ten cycled tests of 1 h each. The X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), in-situ Raman analysis, and electron paramagnetic resonance (EPR) measurements reveal that the super high activity derives from the rich presence of active sites related to Fe-S and surrounding unsaturated Mo-S. Density functional theory (DFT) calculations show that the atomic Fe facilitates the water dissociation and provides sufficient active hydrogen for the edge Mo to boost nitrate reduction reaction (NO3-RR) activity, enhances NH3 selectivity, and decreases the energy barrier of NH3 desorption (rate-determining step) by regulating the coordination environment and electronic structure of the active Mo site. This stable and binder-free electrode with high dosage atomic Fe and rich edge Mo active sites is an attractive cathode for NO3-RR.
2026, 37(3): 111195
doi: 10.1016/j.cclet.2025.111195
Abstract:
Photodynamic therapy (PDT) has attracted various attentions for cancer treatment, yet current strategies suffer many limitations including short retention time of photosensitizers, exacerbation of hypoxia due to oxygen consumption and restricted release of singlet oxygen under hypoxic conditions or in the absence of light. We present here a promising cancer therapy which not only reduces the frequency of drug administration and overall drug dosage through near-infrared (NIR) light-triggered drug immobilization in tumor sites, but also enhances anticancer efficacy by synergistic treatments through PDT and chemotherapeutic drug camptothecin. More importantly, endoperoxides generated in situ can not only persistently release singlet oxygen even in the absence of light, thereby augmenting PDT efficacy, but also release triplet oxygen to alleviate tumor hypoxia exacerbated by PDT. Its enhanced retention time was demonstrated both in vitro (96 h) and in vivo (240 h), with the duration adjustable by varying the light source. Notably, a single administration (3 mg/mL, 300 µL) during the entire treatment under low-power red light irradiation (11 mW/cm2) resulted in efficient suppression of the tumor growth and pulmonary metastasis. This NIR light-triggered long-acting platforms could be utilized for design of long-term disease imaging and therapy tools, and the in situ generated endoperoxide is promising for self-regulation of tumor hypoxia.
Photodynamic therapy (PDT) has attracted various attentions for cancer treatment, yet current strategies suffer many limitations including short retention time of photosensitizers, exacerbation of hypoxia due to oxygen consumption and restricted release of singlet oxygen under hypoxic conditions or in the absence of light. We present here a promising cancer therapy which not only reduces the frequency of drug administration and overall drug dosage through near-infrared (NIR) light-triggered drug immobilization in tumor sites, but also enhances anticancer efficacy by synergistic treatments through PDT and chemotherapeutic drug camptothecin. More importantly, endoperoxides generated in situ can not only persistently release singlet oxygen even in the absence of light, thereby augmenting PDT efficacy, but also release triplet oxygen to alleviate tumor hypoxia exacerbated by PDT. Its enhanced retention time was demonstrated both in vitro (96 h) and in vivo (240 h), with the duration adjustable by varying the light source. Notably, a single administration (3 mg/mL, 300 µL) during the entire treatment under low-power red light irradiation (11 mW/cm2) resulted in efficient suppression of the tumor growth and pulmonary metastasis. This NIR light-triggered long-acting platforms could be utilized for design of long-term disease imaging and therapy tools, and the in situ generated endoperoxide is promising for self-regulation of tumor hypoxia.
2026, 37(3): 111204
doi: 10.1016/j.cclet.2025.111204
Abstract:
Estrogen sulfotransferase (SULT1E1), an essential conjugative enzyme in mammals, plays a crucial role in both estrogen homeostasis and xenobiotic metabolism. Deciphering the dynamic changes in SULT1E1 function under specific physiological or pathological conditions and discovering SULT1E1 modulators require practical and highly efficient tools for sensing SULT1E1 in biological context. Herein, we showcase a scaffold-seeking and structural optimization strategy for the rational engineering of isoform-specific fluorescent substrates for SULT1E1. First, docking-based virtual screening coupled with biochemical assays suggested that N-butyl-4-hydroxyphenyl-1,8-naphthalimide (HPN) was a suitable scaffold for constructing the fluorescent substrates for SULT1E1, but this fluorophore could be metabolized by multiple SULT isoforms. To develop isoform-specific substrates for SULT1E1, various substituents were introduced on the north part of HPN to explore the structure-enzyme specificity relationships of HPN derivatives as SULT1E1 substrates. After molecular docking and experimental validation, an isoform-specific fluorescent substrate (HPN10) for SULT1E1 was successfully engineered. HPN10 demonstrated exceptional isoform-specificity, ultra-high sensitivity, and favorable signal-to-noise ratio (212). HPN10 excelled in the precise sensing of SULT1E1 activities in complex biological matrices, including cellular specimens and liver preparations. HPN10 immensely facilitated the discovery and characterization of SULT1E1 inhibitors, while tetrabromobisphenol A (TBBPA, half inhibitory concentration (IC50) = 31.5 ± 3.4 nmol/L) was identified as a potent SULT1E1 inhibitor that could strongly block SULT1E1 activities in living cells. Collectively, this work presents a practical and efficient strategy for the rational engineering of isoform-specific fluorescent substrates for target conjugative enzyme(s), while HPN10 emerges as a reliable SULT1E1-activatable tool for functional sensing and drug discovery.
Estrogen sulfotransferase (SULT1E1), an essential conjugative enzyme in mammals, plays a crucial role in both estrogen homeostasis and xenobiotic metabolism. Deciphering the dynamic changes in SULT1E1 function under specific physiological or pathological conditions and discovering SULT1E1 modulators require practical and highly efficient tools for sensing SULT1E1 in biological context. Herein, we showcase a scaffold-seeking and structural optimization strategy for the rational engineering of isoform-specific fluorescent substrates for SULT1E1. First, docking-based virtual screening coupled with biochemical assays suggested that N-butyl-4-hydroxyphenyl-1,8-naphthalimide (HPN) was a suitable scaffold for constructing the fluorescent substrates for SULT1E1, but this fluorophore could be metabolized by multiple SULT isoforms. To develop isoform-specific substrates for SULT1E1, various substituents were introduced on the north part of HPN to explore the structure-enzyme specificity relationships of HPN derivatives as SULT1E1 substrates. After molecular docking and experimental validation, an isoform-specific fluorescent substrate (HPN10) for SULT1E1 was successfully engineered. HPN10 demonstrated exceptional isoform-specificity, ultra-high sensitivity, and favorable signal-to-noise ratio (212). HPN10 excelled in the precise sensing of SULT1E1 activities in complex biological matrices, including cellular specimens and liver preparations. HPN10 immensely facilitated the discovery and characterization of SULT1E1 inhibitors, while tetrabromobisphenol A (TBBPA, half inhibitory concentration (IC50) = 31.5 ± 3.4 nmol/L) was identified as a potent SULT1E1 inhibitor that could strongly block SULT1E1 activities in living cells. Collectively, this work presents a practical and efficient strategy for the rational engineering of isoform-specific fluorescent substrates for target conjugative enzyme(s), while HPN10 emerges as a reliable SULT1E1-activatable tool for functional sensing and drug discovery.
2026, 37(3): 111214
doi: 10.1016/j.cclet.2025.111214
Abstract:
Given the immense potential of sonodynamic therapy (SDT) in cancer treatment, designing effective sonosensitizers (SNSs) and elucidating their mechanisms are crucial for advancing the field and enhancing anti-tumor responses. However, there are still several limitations that hinder the application of SDT, such as the activation of the hypoxia-inducible factor-1 (HIF-1) pathway. Herein, we designed an endoplasmic reticulum (ER)-targeted iridium(Ⅲ) SNS, C6IrAC, which exhibits specific toxicity towards tumor cells and excellent performance as a SNS. C6IrAC specifically targets the ER, causing ER stress, and under ultrasound (US) stimulation, the increased stress intensity enhances therapeutic efficacy. C6IrAC induces the degradation of HIF-1α and suppresses the HIF-1 pathway, thereby enhancing SDT. Furthermore, C6IrAC-induced ER stress leads to mitochondrial calcium overload, which subsequently results in the release of a large amount of mitochondrial DNA (mtDNA) into the cytoplasm, thereby activating the cyclic GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) pathway. Significant anti-tumor effects have been consistently observed both in vitro and in vivo. C6IrAC can effectively activate both the innate and adaptive immune systems, highlighting its substantial therapeutic potential. Taken together, this study provides a feasible method to overcome the limitations of SDT, and opens up new avenues for the design of SNSs.
Given the immense potential of sonodynamic therapy (SDT) in cancer treatment, designing effective sonosensitizers (SNSs) and elucidating their mechanisms are crucial for advancing the field and enhancing anti-tumor responses. However, there are still several limitations that hinder the application of SDT, such as the activation of the hypoxia-inducible factor-1 (HIF-1) pathway. Herein, we designed an endoplasmic reticulum (ER)-targeted iridium(Ⅲ) SNS, C6IrAC, which exhibits specific toxicity towards tumor cells and excellent performance as a SNS. C6IrAC specifically targets the ER, causing ER stress, and under ultrasound (US) stimulation, the increased stress intensity enhances therapeutic efficacy. C6IrAC induces the degradation of HIF-1α and suppresses the HIF-1 pathway, thereby enhancing SDT. Furthermore, C6IrAC-induced ER stress leads to mitochondrial calcium overload, which subsequently results in the release of a large amount of mitochondrial DNA (mtDNA) into the cytoplasm, thereby activating the cyclic GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) pathway. Significant anti-tumor effects have been consistently observed both in vitro and in vivo. C6IrAC can effectively activate both the innate and adaptive immune systems, highlighting its substantial therapeutic potential. Taken together, this study provides a feasible method to overcome the limitations of SDT, and opens up new avenues for the design of SNSs.
2026, 37(3): 111254
doi: 10.1016/j.cclet.2025.111254
Abstract:
Glioma, a highly aggressive brain tumor with a dismal prognosis, faces significant treatment hurdles due to the blood-brain barrier, which limits the efficient delivery of most medications. Diphtheria toxin receptor (DTR) is a specific receptor expressed both on brain microvascular endothelial cells and glioma, emerging as a potentially valuable target for targeted drug delivery system for glioma treatment. In this work, a short peptide (designated DTX) derived from diphtheria toxin, was rational designed and chemical synthesized based on the binding domain to DTR. The function of DTX as a ligand of DTR and the brain/glioma dual targeting efficacy were evaluated in vitro and in vivo. Furthermore, DTX was conjugated to vorinostat (SAHA) to enable its anti-glioma efficacy. The results demonstrated that DTX-SAHA can effectively cross the blood-brain barrier, exhibiting promising anti-glioma efficacy with good biocompatibility. This research confirmed the potential of DTX as the ligand for DTR-mediated intracranial drug delivery.
Glioma, a highly aggressive brain tumor with a dismal prognosis, faces significant treatment hurdles due to the blood-brain barrier, which limits the efficient delivery of most medications. Diphtheria toxin receptor (DTR) is a specific receptor expressed both on brain microvascular endothelial cells and glioma, emerging as a potentially valuable target for targeted drug delivery system for glioma treatment. In this work, a short peptide (designated DTX) derived from diphtheria toxin, was rational designed and chemical synthesized based on the binding domain to DTR. The function of DTX as a ligand of DTR and the brain/glioma dual targeting efficacy were evaluated in vitro and in vivo. Furthermore, DTX was conjugated to vorinostat (SAHA) to enable its anti-glioma efficacy. The results demonstrated that DTX-SAHA can effectively cross the blood-brain barrier, exhibiting promising anti-glioma efficacy with good biocompatibility. This research confirmed the potential of DTX as the ligand for DTR-mediated intracranial drug delivery.
2026, 37(3): 111258
doi: 10.1016/j.cclet.2025.111258
Abstract:
A new type of C2-symmetric chiral spirobiindole structure is developed, and excellent diastereoselectivities and enantioselectivities (>20:1 dr & >99% ee for all examples) were obtained via an asymmetric rhodium catalysis-intramolecular spirocyclization sequence. Selective synthesis of both spirobiindole enantiomers could be achieved using the same catalyst by simply switching the substrate combination.
A new type of C2-symmetric chiral spirobiindole structure is developed, and excellent diastereoselectivities and enantioselectivities (>20:1 dr & >99% ee for all examples) were obtained via an asymmetric rhodium catalysis-intramolecular spirocyclization sequence. Selective synthesis of both spirobiindole enantiomers could be achieved using the same catalyst by simply switching the substrate combination.
2026, 37(3): 111288
doi: 10.1016/j.cclet.2025.111288
Abstract:
Fluorine locates a pivotal position in modern medicinal chemistry due to its distinctive impact on the properties of organic molecules. This work described an efficient divergent palladium/XPhos-catalyzed ring-opening defluorinative cross-coupling of gem-difluorocyclopropanes with less nucleophilic fluorinated malonates or fluorobis(phenylsulfonyl)methane. The corresponding difluoro malonates and 2,4-difluorobutadienyl sulfones were obtained in good yields, respectively. Besides, this protocol also enabled the modification of structurally diverse complex molecules.
Fluorine locates a pivotal position in modern medicinal chemistry due to its distinctive impact on the properties of organic molecules. This work described an efficient divergent palladium/XPhos-catalyzed ring-opening defluorinative cross-coupling of gem-difluorocyclopropanes with less nucleophilic fluorinated malonates or fluorobis(phenylsulfonyl)methane. The corresponding difluoro malonates and 2,4-difluorobutadienyl sulfones were obtained in good yields, respectively. Besides, this protocol also enabled the modification of structurally diverse complex molecules.
2026, 37(3): 111299
doi: 10.1016/j.cclet.2025.111299
Abstract:
Immunosuppressive tumor microenvironment (TME) is a key regulator in the high recurrence and metastasis rate of breast cancer after microwave (MW) thermal therapy. Pyroptosis, a form of programmed cell death initiated by inflammasomes, which can activate tumor immunogenicity and reprogram immune TME. Here, we report an extremely simple Al-based metal-organic frameworks nano-immunoadjuvants (AM NIAs) that programmatically activate nucleotide-binding domain, leucine-rich-containing family, pyrin domain-containing-3 (NLRP3)-mediated pyroptosis to enhance MW-immunotherapy (MW-ICB). After entering the TME, AM NIAs programmed activation of NLRP3-mediated pyroptosis by inducing mitochondrial dysfunction, upregulating HSP90 and promoting lysosomal stress. Consequently, substantial amounts of lactate dehydrogenase, interleukin-18 (IL-18), and calreticulin are released, which improves immunosuppressive TME and hinders tumor cell proliferation by facilitating T-cell infiltration. The integration of immune checkpoint inhibitors with MW elicits potent immune responses, demonstrating high inhibition of both primary and distant tumors. Thus, a simple yet effective nano-immunoadjuvant is developed to enhance MW-ICB in breast cancer simply by NLRP3-mediated pyroptosis and immunosuppression reversal.
Immunosuppressive tumor microenvironment (TME) is a key regulator in the high recurrence and metastasis rate of breast cancer after microwave (MW) thermal therapy. Pyroptosis, a form of programmed cell death initiated by inflammasomes, which can activate tumor immunogenicity and reprogram immune TME. Here, we report an extremely simple Al-based metal-organic frameworks nano-immunoadjuvants (AM NIAs) that programmatically activate nucleotide-binding domain, leucine-rich-containing family, pyrin domain-containing-3 (NLRP3)-mediated pyroptosis to enhance MW-immunotherapy (MW-ICB). After entering the TME, AM NIAs programmed activation of NLRP3-mediated pyroptosis by inducing mitochondrial dysfunction, upregulating HSP90 and promoting lysosomal stress. Consequently, substantial amounts of lactate dehydrogenase, interleukin-18 (IL-18), and calreticulin are released, which improves immunosuppressive TME and hinders tumor cell proliferation by facilitating T-cell infiltration. The integration of immune checkpoint inhibitors with MW elicits potent immune responses, demonstrating high inhibition of both primary and distant tumors. Thus, a simple yet effective nano-immunoadjuvant is developed to enhance MW-ICB in breast cancer simply by NLRP3-mediated pyroptosis and immunosuppression reversal.
2026, 37(3): 111314
doi: 10.1016/j.cclet.2025.111314
Abstract:
Four novel Daphniphyllum alkaloids with highly rearranged skeletons involving a 6/5/7/7/5 pentacyclic scaffold (1), a 6/5/7/5/6/5/6 heptacyclic scaffold (2 and 4), and a 6/5/7/5/6/5 hexacyclic scaffold (3), were isolated from Daphniphyllum calycinum. Particularly, compound 1 contains a unique 13-oxa-17-aza-pentacyclo[7.6.4.112,15.04,8.09,15] eicosane core. Their structures were elucidated by comprehensive spectroscopic analyses, single-crystal X-ray diffraction, and electronic circular dichroism calculations. Putative biosynthetic pathways for compounds 1–4 were discussed with caldaphnidine C (5) as their biosynthetic precursor. Compound 2 markedly enhanced the survival of H9c2 cardiomyocytes under oxygen glucose deprivation and reoxygenation conditions. Mechanistic study revealed that 2 exerted its cardioprotective effects by activating the nuclear factor erythroid 2-related factor 2/heme oxygenase-1 (Nrf2/HO-1) antioxidant pathway, thereby enhancing cellular antioxidant capacity and alleviating oxidative stress induced by hypoxia.
Four novel Daphniphyllum alkaloids with highly rearranged skeletons involving a 6/5/7/7/5 pentacyclic scaffold (1), a 6/5/7/5/6/5/6 heptacyclic scaffold (2 and 4), and a 6/5/7/5/6/5 hexacyclic scaffold (3), were isolated from Daphniphyllum calycinum. Particularly, compound 1 contains a unique 13-oxa-17-aza-pentacyclo[7.6.4.112,15.04,8.09,15] eicosane core. Their structures were elucidated by comprehensive spectroscopic analyses, single-crystal X-ray diffraction, and electronic circular dichroism calculations. Putative biosynthetic pathways for compounds 1–4 were discussed with caldaphnidine C (5) as their biosynthetic precursor. Compound 2 markedly enhanced the survival of H9c2 cardiomyocytes under oxygen glucose deprivation and reoxygenation conditions. Mechanistic study revealed that 2 exerted its cardioprotective effects by activating the nuclear factor erythroid 2-related factor 2/heme oxygenase-1 (Nrf2/HO-1) antioxidant pathway, thereby enhancing cellular antioxidant capacity and alleviating oxidative stress induced by hypoxia.
2026, 37(3): 111339
doi: 10.1016/j.cclet.2025.111339
Abstract:
Chemodynamic therapy (CDT) represents a novel strategy for the safe treatment of malignant melanoma. It capitalizes on transition metal-catalyzed Fenton-like reactions to generate hydroxyl radicals (•OH) that directly eradicate tumor cells. However, its efficacy is hindered in the tumor microenvironment (TME) by low endogenous hydrogen peroxide (H2O2) levels and high glutathione (GSH) content. To overcome these limitations, an injectable self-healing adipic dihydrazide (ADH)-modified hyaluronic acid (HA) (HA-ADH)/aldehyde terminated polyethylene glycol (PEG-CHO)/PVP-cupric peroxide (CuO2) nanoparticles (HPC) hydrogel was developed. This hydrogel system is injectable, pH-responsive, self-healing, and enables sustained GSH depletion through dual Cu2+/•OH-mediated mechanisms. The HPC hydrogel system not only compensates for the TME's endogenous H2O2 deficiency through self-generated H2O2 but also disrupts redox homeostasis via GSH oxidation, thereby inactivating glutathione peroxidase 4 (GPX4) and promoting lipid peroxide accumulation to trigger ferroptosis in melanoma cells. Such a strategy represents a promising approach to achieve enhanced CDT and potent ferroptosis induction by synergizing dual GSH-depleting cycling and self-sufficient H2O2 generation.
Chemodynamic therapy (CDT) represents a novel strategy for the safe treatment of malignant melanoma. It capitalizes on transition metal-catalyzed Fenton-like reactions to generate hydroxyl radicals (•OH) that directly eradicate tumor cells. However, its efficacy is hindered in the tumor microenvironment (TME) by low endogenous hydrogen peroxide (H2O2) levels and high glutathione (GSH) content. To overcome these limitations, an injectable self-healing adipic dihydrazide (ADH)-modified hyaluronic acid (HA) (HA-ADH)/aldehyde terminated polyethylene glycol (PEG-CHO)/PVP-cupric peroxide (CuO2) nanoparticles (HPC) hydrogel was developed. This hydrogel system is injectable, pH-responsive, self-healing, and enables sustained GSH depletion through dual Cu2+/•OH-mediated mechanisms. The HPC hydrogel system not only compensates for the TME's endogenous H2O2 deficiency through self-generated H2O2 but also disrupts redox homeostasis via GSH oxidation, thereby inactivating glutathione peroxidase 4 (GPX4) and promoting lipid peroxide accumulation to trigger ferroptosis in melanoma cells. Such a strategy represents a promising approach to achieve enhanced CDT and potent ferroptosis induction by synergizing dual GSH-depleting cycling and self-sufficient H2O2 generation.
2026, 37(3): 111341
doi: 10.1016/j.cclet.2025.111341
Abstract:
Photocatalytic H2O2 production has emerged as a promising strategy for solar-to-H2O2 energy conversion. However, the inevitable requirement for aeration or sacrificial agents poses great challenges for its further application, particularly in environmental remediation process. Previous works often struggles to simultaneously balance the antibiotics degradation and H2O2 production. Herein, bifunctional TiO2 mesocrystal with oxygen vacancy (meso–TiO2-x) was prepared through a facile pyromellitic diimide assisted hydrothermal process. The well-aligned meso–TiO2-x superstructures with unique oxygen vacancies on the surface collectively facilitated the direct h+ oxidation and oxygen reduction reaction (ORR). The ciprofloxacin degradation through direct h+ oxidation boosted the separation of photogenerated carriers, which enhances the e- participation in ORR, resulting H2O2 production rate up to 904.2 µmol g−1 h−1. This work provides an ingenious strategy of constructing bifunctional catalyst to achieve synergistic antibiotics degradation and H2O2 production without the addition of exogenous reagents.
Photocatalytic H2O2 production has emerged as a promising strategy for solar-to-H2O2 energy conversion. However, the inevitable requirement for aeration or sacrificial agents poses great challenges for its further application, particularly in environmental remediation process. Previous works often struggles to simultaneously balance the antibiotics degradation and H2O2 production. Herein, bifunctional TiO2 mesocrystal with oxygen vacancy (meso–TiO2-x) was prepared through a facile pyromellitic diimide assisted hydrothermal process. The well-aligned meso–TiO2-x superstructures with unique oxygen vacancies on the surface collectively facilitated the direct h+ oxidation and oxygen reduction reaction (ORR). The ciprofloxacin degradation through direct h+ oxidation boosted the separation of photogenerated carriers, which enhances the e- participation in ORR, resulting H2O2 production rate up to 904.2 µmol g−1 h−1. This work provides an ingenious strategy of constructing bifunctional catalyst to achieve synergistic antibiotics degradation and H2O2 production without the addition of exogenous reagents.
2026, 37(3): 111358
doi: 10.1016/j.cclet.2025.111358
Abstract:
Probes that can undergo photoconversion in situ within cells are advantageous tools for live cell imaging in terms of precise spatial and temporal control. We herein present a new concept to construct photoconvertible probes based on intramolecular oxygen direct arylation within cells. Xanthones bearing aryls (XO-Ars) were designed and prepared. XO-Ars undergo oxygen direct arylation under visible light irradiation in cells to afford xanthene derivatives (XE-Ars). XO-Ars initially accumulate in the endoplasmic reticulum (ER) with green emission and then migrate to the mitochondria with bright red emission. Sequential single-cell lighting up experiments show high spatiotemporal control ability and utility in single or multi-cell tracking. In addition, the photoproducts irradiated with optimized wavelength light source show excellent photodynamic therapy effects. As the duration of light exposure increases, the cells begin to undergo apoptosis. These innovative photoconvertible probes capable of migrating from ER to mitochondria driven by light provide a feasible approach for the in-situ monitoring of subcellular physiological events and cell apoptosis.
Probes that can undergo photoconversion in situ within cells are advantageous tools for live cell imaging in terms of precise spatial and temporal control. We herein present a new concept to construct photoconvertible probes based on intramolecular oxygen direct arylation within cells. Xanthones bearing aryls (XO-Ars) were designed and prepared. XO-Ars undergo oxygen direct arylation under visible light irradiation in cells to afford xanthene derivatives (XE-Ars). XO-Ars initially accumulate in the endoplasmic reticulum (ER) with green emission and then migrate to the mitochondria with bright red emission. Sequential single-cell lighting up experiments show high spatiotemporal control ability and utility in single or multi-cell tracking. In addition, the photoproducts irradiated with optimized wavelength light source show excellent photodynamic therapy effects. As the duration of light exposure increases, the cells begin to undergo apoptosis. These innovative photoconvertible probes capable of migrating from ER to mitochondria driven by light provide a feasible approach for the in-situ monitoring of subcellular physiological events and cell apoptosis.
2026, 37(3): 111370
doi: 10.1016/j.cclet.2025.111370
Abstract:
To enhance the suitability of noble metal-based electrocatalysts for acidic overall water splitting, a Pt/Ir-based electrocatalyst incorporating Co and Pd anchored on Ti3C2Tx MXene (Ir/Co Pt Pd@MX) has been successfully synthesized. The incorporation of Co during the synthesis process increases the valence states of Ir and Pt, resulting in improved electrocatalytic performance. The Ir/Co Pt Pd@MX exhibits a low HER overpotential of 38 mV and an OER overpotential of 230 mV, outperforming commercial catalysts. The low noble metal containing electrocatalyst shows nearly 10 times the mass activity of Pt/C for HER and 35 times that of Ir/C for OER. The water splitting cell voltage is 1.46 V, with no observable decay after a 24-h stability test at 10 mA/cm2, establishing it as a top-tier noble metal-based electrocatalyst in acidic environments. Density functional theory (DFT) calculations indicate that Co facilitates the deposition of Ir, enhancing OER performance, while Pd restrict H+absorption of Ir, ensuring the stability. The energy barrier of the rate-determining steps for both the HER and OER decreases.
To enhance the suitability of noble metal-based electrocatalysts for acidic overall water splitting, a Pt/Ir-based electrocatalyst incorporating Co and Pd anchored on Ti3C2Tx MXene (Ir/Co Pt Pd@MX) has been successfully synthesized. The incorporation of Co during the synthesis process increases the valence states of Ir and Pt, resulting in improved electrocatalytic performance. The Ir/Co Pt Pd@MX exhibits a low HER overpotential of 38 mV and an OER overpotential of 230 mV, outperforming commercial catalysts. The low noble metal containing electrocatalyst shows nearly 10 times the mass activity of Pt/C for HER and 35 times that of Ir/C for OER. The water splitting cell voltage is 1.46 V, with no observable decay after a 24-h stability test at 10 mA/cm2, establishing it as a top-tier noble metal-based electrocatalyst in acidic environments. Density functional theory (DFT) calculations indicate that Co facilitates the deposition of Ir, enhancing OER performance, while Pd restrict H+absorption of Ir, ensuring the stability. The energy barrier of the rate-determining steps for both the HER and OER decreases.
2026, 37(3): 111375
doi: 10.1016/j.cclet.2025.111375
Abstract:
Specific interactions between the macrocycle backbone, solvent and counter anions control configurational interconversions of novel organoruthenium(Ⅱ) metallamacrocycles [Ru(η6-p-cymene)(µ2-m-bitmb)Cl]2·2X, m-bitmb = 1,3,5-trimethyl-2,4-di(imidazole-1-ylmethyl)benzene, X = Cl- (1·2Cl), NO3- (1·2NO3), CF3SO3- (1·2CF3SO3), PF6- (1·2PF6), or BF4- (1·2BF4). X-ray crystal structures reveal 1·2Cl in boat and chair conformations, 1·2NO3 in twist-boat and chair conformations, and 1·2CF3SO3 in a chair conformation. Chair/boat isomers of mono- and bis-DMSO adducts from 1·2Cl, 1·2CF3SO3 or 1·2NO3 in DMSO/H2O were separated and characterized. Slow anion-dependent interconversion of configurational isomers was observed in solution. Ligand field molecular mechanics and density functional theory calculations suggest an unusual macrochelate ring-opening isomerization mechanism. Such dynamic stimuli-responsive configurational changes offer scope for design of metallocycles for induced-fit recognition of biological targets.
Specific interactions between the macrocycle backbone, solvent and counter anions control configurational interconversions of novel organoruthenium(Ⅱ) metallamacrocycles [Ru(η6-p-cymene)(µ2-m-bitmb)Cl]2·2X, m-bitmb = 1,3,5-trimethyl-2,4-di(imidazole-1-ylmethyl)benzene, X = Cl- (1·2Cl), NO3- (1·2NO3), CF3SO3- (1·2CF3SO3), PF6- (1·2PF6), or BF4- (1·2BF4). X-ray crystal structures reveal 1·2Cl in boat and chair conformations, 1·2NO3 in twist-boat and chair conformations, and 1·2CF3SO3 in a chair conformation. Chair/boat isomers of mono- and bis-DMSO adducts from 1·2Cl, 1·2CF3SO3 or 1·2NO3 in DMSO/H2O were separated and characterized. Slow anion-dependent interconversion of configurational isomers was observed in solution. Ligand field molecular mechanics and density functional theory calculations suggest an unusual macrochelate ring-opening isomerization mechanism. Such dynamic stimuli-responsive configurational changes offer scope for design of metallocycles for induced-fit recognition of biological targets.
2026, 37(3): 111376
doi: 10.1016/j.cclet.2025.111376
Abstract:
Polycyclic pyrrole fused indolo[2,1-a]isoquinolins were efficiently generated from alkene-tethered indole derivatives and di–tert-butyldiaziridinone in up to 99% yield in the presence of Pd catalyst. The reaction likely proceeded via sequential Heck, CH activation, and amination process. Varying N-substituents of indole substrates led to indolo[3,2-b]indoles in up to 98% yields.
Polycyclic pyrrole fused indolo[2,1-a]isoquinolins were efficiently generated from alkene-tethered indole derivatives and di–tert-butyldiaziridinone in up to 99% yield in the presence of Pd catalyst. The reaction likely proceeded via sequential Heck, CH activation, and amination process. Varying N-substituents of indole substrates led to indolo[3,2-b]indoles in up to 98% yields.
2026, 37(3): 111378
doi: 10.1016/j.cclet.2025.111378
Abstract:
The extraction of uranium from seawater is essential for the sustainable development of the nuclear industry. Covalent organic frameworks (COFs) exhibit significant potential in uranium extraction from seawater due to their high stability, designability, and large specific surface area. Herein, a vinyl-decorated covalent organic framework, designated as COF-IHEP5, was synthesized through acid-catalyzed solvothermal method. COF-IHEP5-COOH was constructed by post-modification strategy through the "thiol-ene" click reaction, where COF-IHEP5-COOH contains hydrazone-carbonyl and flexible carboxylic acid chelating sites on pore wall. This modification facilitates synergistic adsorption of uranium by utilizing a "nano trap" that is embedded within the COF framework. The maximum adsorption capacity of the post-modified COF-IHEP5-COOH for UO22+ has reached 543.8 mg/g, representing a 1.5-fold increase compared to the unmodified COF-IHEP5. Additionally, COF-IHEP5-COOH demonstrates an extraction efficiency of approximately 80% for uranium from spiked natural seawater, featuring 4.5 times higher selectivity than vanadium. The DFT calculation results show that the adsorption of uranium orginated from the synergistic coordination of the skeleton in COF-IHEP5-COOH and carboxyl group on the side arm. This research highlights the remarkable potential of pore surface engineering in customizing active adsorption sites and offers new insights for the design of functionalized uranium adsorbents with superior binding affinity and adsorption capacities.
The extraction of uranium from seawater is essential for the sustainable development of the nuclear industry. Covalent organic frameworks (COFs) exhibit significant potential in uranium extraction from seawater due to their high stability, designability, and large specific surface area. Herein, a vinyl-decorated covalent organic framework, designated as COF-IHEP5, was synthesized through acid-catalyzed solvothermal method. COF-IHEP5-COOH was constructed by post-modification strategy through the "thiol-ene" click reaction, where COF-IHEP5-COOH contains hydrazone-carbonyl and flexible carboxylic acid chelating sites on pore wall. This modification facilitates synergistic adsorption of uranium by utilizing a "nano trap" that is embedded within the COF framework. The maximum adsorption capacity of the post-modified COF-IHEP5-COOH for UO22+ has reached 543.8 mg/g, representing a 1.5-fold increase compared to the unmodified COF-IHEP5. Additionally, COF-IHEP5-COOH demonstrates an extraction efficiency of approximately 80% for uranium from spiked natural seawater, featuring 4.5 times higher selectivity than vanadium. The DFT calculation results show that the adsorption of uranium orginated from the synergistic coordination of the skeleton in COF-IHEP5-COOH and carboxyl group on the side arm. This research highlights the remarkable potential of pore surface engineering in customizing active adsorption sites and offers new insights for the design of functionalized uranium adsorbents with superior binding affinity and adsorption capacities.
2026, 37(3): 111391
doi: 10.1016/j.cclet.2025.111391
Abstract:
In this study, we successfully construct a non-noble metal-based Schottky photocatalyst MX@MIL-125 (MX is shorted for Ti3C2 MXene) by combining the Ti-based metal-organic framework MIL-125(Ti) with Ti3C2 MXene. Leveraging the unique surface properties of MXene, a close and uniform distribution of nano-cake-like MIL-125(Ti) was achieved on the two-dimensional Ti3C2 MXene layers. The introduction of Ti3C2 MXene not only broadens the light absorption range but also adjusts the local coordination structure between the interfaces. This heterojunction significantly promotes the separation and transfer of photogenerated carriers. The photocatalytic N2 reduction efficiency of MX@MIL-125-20 is 11-fold higher than that of pristine MIL-125(Ti) (48.8 vs. 4.6 µmol gcat−1 h−1), and the photodegradation efficiency of tetracycline hydrochloride (TCH) is increased by about 18% (92.95% vs. 74.67%). This work may provide new insights for the design of innovative photocatalysts for various chemical redox reactions.
In this study, we successfully construct a non-noble metal-based Schottky photocatalyst MX@MIL-125 (MX is shorted for Ti3C2 MXene) by combining the Ti-based metal-organic framework MIL-125(Ti) with Ti3C2 MXene. Leveraging the unique surface properties of MXene, a close and uniform distribution of nano-cake-like MIL-125(Ti) was achieved on the two-dimensional Ti3C2 MXene layers. The introduction of Ti3C2 MXene not only broadens the light absorption range but also adjusts the local coordination structure between the interfaces. This heterojunction significantly promotes the separation and transfer of photogenerated carriers. The photocatalytic N2 reduction efficiency of MX@MIL-125-20 is 11-fold higher than that of pristine MIL-125(Ti) (48.8 vs. 4.6 µmol gcat−1 h−1), and the photodegradation efficiency of tetracycline hydrochloride (TCH) is increased by about 18% (92.95% vs. 74.67%). This work may provide new insights for the design of innovative photocatalysts for various chemical redox reactions.
2026, 37(3): 111397
doi: 10.1016/j.cclet.2025.111397
Abstract:
While TiO2 is a promising catalyst for electrocatalytic nitrate (NO3--N) reduction to NH3 (ENRR), how the crystalline phase (anatase (A) or rutile (R)) and surface oxygen vacancy (Ov) synergize in ENRR remains ambiguous. Herein a series of nitrogen-doped TiO2 catalysts with controlled phase composition and Ov number are prepared by calcinating titanium nitride powders in an air atmosphere at specific temperatures (N-TiO2-x, x = 450–750 ℃). Generally, higher temperatures lead to increased R-TiO2 content but decreased Ov number. The ENRR performances of these N-TiO2 are higher than that of pure A- and R-TiO2, and vary in volcano-like trends against both the R-TiO2 content and Ov number. Combined control experiments and theoretical simulation demonstrate that Ovs are the active sites for ENRR, but their functions differ between A-TiO2 and R-TiO2. Specifically, the Ovs on R-TiO2 are more active in NO3- conversion and renew more easily during reaction, while those on A-TiO2 perform better in proton adsorption. The synergy between Ovs on R-TiO2 and A-TiO2 promotes the ENRR on the phase-mixed N-TiO2. Furthermore, as the catalyst varies from N-TiO2–450 to -750, the overall efficacy of Ovs in proton transfer decreases due to the decreased number of Ovs on A-TiO2, while the mean activity and renewability of them improve as a higher proportion of Ovs are distributed on R-TiO2. The tug-of-war between the two opposing trends results in a peak ENRR performance on N-TiO2–650 (mass activity: 22.2 mgN h-1 gcat.-1; NH3-N selectivity: 98.8%; Faradaic efficiency: 79.4%). These findings offer a deeper understanding of ENRR on TiO2, and provide new insights for the design of efficient catalysts.
While TiO2 is a promising catalyst for electrocatalytic nitrate (NO3--N) reduction to NH3 (ENRR), how the crystalline phase (anatase (A) or rutile (R)) and surface oxygen vacancy (Ov) synergize in ENRR remains ambiguous. Herein a series of nitrogen-doped TiO2 catalysts with controlled phase composition and Ov number are prepared by calcinating titanium nitride powders in an air atmosphere at specific temperatures (N-TiO2-x, x = 450–750 ℃). Generally, higher temperatures lead to increased R-TiO2 content but decreased Ov number. The ENRR performances of these N-TiO2 are higher than that of pure A- and R-TiO2, and vary in volcano-like trends against both the R-TiO2 content and Ov number. Combined control experiments and theoretical simulation demonstrate that Ovs are the active sites for ENRR, but their functions differ between A-TiO2 and R-TiO2. Specifically, the Ovs on R-TiO2 are more active in NO3- conversion and renew more easily during reaction, while those on A-TiO2 perform better in proton adsorption. The synergy between Ovs on R-TiO2 and A-TiO2 promotes the ENRR on the phase-mixed N-TiO2. Furthermore, as the catalyst varies from N-TiO2–450 to -750, the overall efficacy of Ovs in proton transfer decreases due to the decreased number of Ovs on A-TiO2, while the mean activity and renewability of them improve as a higher proportion of Ovs are distributed on R-TiO2. The tug-of-war between the two opposing trends results in a peak ENRR performance on N-TiO2–650 (mass activity: 22.2 mgN h-1 gcat.-1; NH3-N selectivity: 98.8%; Faradaic efficiency: 79.4%). These findings offer a deeper understanding of ENRR on TiO2, and provide new insights for the design of efficient catalysts.
2026, 37(3): 111398
doi: 10.1016/j.cclet.2025.111398
Abstract:
Photocatalysis shows promising application in efficient reduction of nitrogen oxides (NOx). However, the sluggish selectivity in nitric oxide removal with reductants, resulting in the formation of undesired N2O byproducts, presents a great challenge. In this work, complete prohibition of nitric oxide generation in photo-removal of NO with carbon particulate is successfully achieved through the rational regulation of electron-trapping centers on TiO2 nanosheets (TNS) surface achieved by the surface reduction treatment with NaBH4. The efficient suppression (100%) of N2O generation is ascribed to the more stable N2O adsorption on the active (001) crystalline plane of TNS and the electron-capturing ability around oxygen vacancies based on the density functional theory (DFT) and experimental investigations. The existence of O2 and H2O effectively promote the photocatalytic activity of NO reduction but demonstrate no adverse effect on N2O suppression. The optimal photocatalytic NO reduction activity with the highest CO2 formation rate of 5.54 mg g−1 h−1 without N2O formation is achieved over the optimized 0.135-TNS. These investigations guide the development of feasible photocatalytic treatment of air pollutants, emphasizing the significance of managing electron capture and gas adsorption for efficient byproduct control in pollutants removal.
Photocatalysis shows promising application in efficient reduction of nitrogen oxides (NOx). However, the sluggish selectivity in nitric oxide removal with reductants, resulting in the formation of undesired N2O byproducts, presents a great challenge. In this work, complete prohibition of nitric oxide generation in photo-removal of NO with carbon particulate is successfully achieved through the rational regulation of electron-trapping centers on TiO2 nanosheets (TNS) surface achieved by the surface reduction treatment with NaBH4. The efficient suppression (100%) of N2O generation is ascribed to the more stable N2O adsorption on the active (001) crystalline plane of TNS and the electron-capturing ability around oxygen vacancies based on the density functional theory (DFT) and experimental investigations. The existence of O2 and H2O effectively promote the photocatalytic activity of NO reduction but demonstrate no adverse effect on N2O suppression. The optimal photocatalytic NO reduction activity with the highest CO2 formation rate of 5.54 mg g−1 h−1 without N2O formation is achieved over the optimized 0.135-TNS. These investigations guide the development of feasible photocatalytic treatment of air pollutants, emphasizing the significance of managing electron capture and gas adsorption for efficient byproduct control in pollutants removal.
2026, 37(3): 111404
doi: 10.1016/j.cclet.2025.111404
Abstract:
In situ therapeutic agent production strategy is promising to overcome the drawbacks of direct drug delivery. Hypoxia provides a great target for precise treatment of tumor. Here we report a copper ion competition-based nanoparticle (NP) for hypoxia-activated formation of diethyldithiocarbamate (DTC)-copper complex, an immunogenic cell death (ICD) inducer. The NP is composed of an amphiphilic hypoxia-responsive DTC precursor and a fluorescence quenched copper ion-chelated squaric acid. In hypoxic tumor cells, the azobenzene linker in DTC precursor can be cleaved through bioreduction, leading to DTC release and subsequent copper ion exchange between DTC and squaric acid. Simultaneous formation of toxic DTC-copper complexes and fluorescence recovery will allow for visualization of in situ therapeutic agents production. Furthermore, the DTC-copper complexes can induce ICD and promote cytotoxic T lymphocyte infiltration for cancer immunotherapy. This study not only provides a promising hypoxia-activated nanomedicine for precision cancer therapy, but also a visualization strategy for evaluating the treatment process.
In situ therapeutic agent production strategy is promising to overcome the drawbacks of direct drug delivery. Hypoxia provides a great target for precise treatment of tumor. Here we report a copper ion competition-based nanoparticle (NP) for hypoxia-activated formation of diethyldithiocarbamate (DTC)-copper complex, an immunogenic cell death (ICD) inducer. The NP is composed of an amphiphilic hypoxia-responsive DTC precursor and a fluorescence quenched copper ion-chelated squaric acid. In hypoxic tumor cells, the azobenzene linker in DTC precursor can be cleaved through bioreduction, leading to DTC release and subsequent copper ion exchange between DTC and squaric acid. Simultaneous formation of toxic DTC-copper complexes and fluorescence recovery will allow for visualization of in situ therapeutic agents production. Furthermore, the DTC-copper complexes can induce ICD and promote cytotoxic T lymphocyte infiltration for cancer immunotherapy. This study not only provides a promising hypoxia-activated nanomedicine for precision cancer therapy, but also a visualization strategy for evaluating the treatment process.
2026, 37(3): 111420
doi: 10.1016/j.cclet.2025.111420
Abstract:
Mechanosensitive channel proteins serve important physiological functions in biological systems. Building artificial transmembrane channels to mimic the function of natural channels would provide a new strategy for treating channel-related diseases. In this paper, we describe the design and construction of artificial channels derived from pillar[5]arene backbones with different flexibilities, which are determined by the alkyl chain length. Importantly, the ion transport activities of the channels can be activated by increasing the membrane curvature and tension, which endows the channel with mechano-gating behavior.
Mechanosensitive channel proteins serve important physiological functions in biological systems. Building artificial transmembrane channels to mimic the function of natural channels would provide a new strategy for treating channel-related diseases. In this paper, we describe the design and construction of artificial channels derived from pillar[5]arene backbones with different flexibilities, which are determined by the alkyl chain length. Importantly, the ion transport activities of the channels can be activated by increasing the membrane curvature and tension, which endows the channel with mechano-gating behavior.
2026, 37(3): 111427
doi: 10.1016/j.cclet.2025.111427
Abstract:
The development of advanced anti-counterfeiting technology using photochromic inorganic materials with dynamic optical signals has garnered significant interest, but the limited color response and un-controlled photochromic kinetics largely restrict their practical application. In this work, we report the design of photochromic supramolecular assembly based on host-guest chemistry, enabling kinetics-tunable time-encoded anti-counterfeiting. By co-assembling of photochromic tungsten oxide quantum dots (WO3 QDs) with cucurbit[7]uril (CB[7]), we developed a kinetics-tunable photochromic supramolecular assembly (WO3CB[7]). The WO3CB[7] assembly exhibits distinct photochromic kinetics compared to free WO3 QDs due to efficient suppression of photogenerated decomposition of water adsorbed on WO3 QDs, as verified by spectral and photophysical analysis. The photochromic kinetics can be readily modulated by adjusting the WO3 QDs to CB[7] ratio. The kinetics-tunable photochromic WO3CB[7] assembly has been successfully applied as innovative anti-counterfeiting materials for fabricating time-encoded anti-counterfeiting arrays and information encryption system. The irradiation time serves as a key parameter for decrypting the final information, thereby enhancing the complexity of replication and counterfeiting. This approach offers a simple, scalable and generalizable strategy for designing advanced optical anti-counterfeiting materials by integrating inorganic photochromic materials with the supramolecular strategy.
The development of advanced anti-counterfeiting technology using photochromic inorganic materials with dynamic optical signals has garnered significant interest, but the limited color response and un-controlled photochromic kinetics largely restrict their practical application. In this work, we report the design of photochromic supramolecular assembly based on host-guest chemistry, enabling kinetics-tunable time-encoded anti-counterfeiting. By co-assembling of photochromic tungsten oxide quantum dots (WO3 QDs) with cucurbit[7]uril (CB[7]), we developed a kinetics-tunable photochromic supramolecular assembly (WO3CB[7]). The WO3CB[7] assembly exhibits distinct photochromic kinetics compared to free WO3 QDs due to efficient suppression of photogenerated decomposition of water adsorbed on WO3 QDs, as verified by spectral and photophysical analysis. The photochromic kinetics can be readily modulated by adjusting the WO3 QDs to CB[7] ratio. The kinetics-tunable photochromic WO3CB[7] assembly has been successfully applied as innovative anti-counterfeiting materials for fabricating time-encoded anti-counterfeiting arrays and information encryption system. The irradiation time serves as a key parameter for decrypting the final information, thereby enhancing the complexity of replication and counterfeiting. This approach offers a simple, scalable and generalizable strategy for designing advanced optical anti-counterfeiting materials by integrating inorganic photochromic materials with the supramolecular strategy.
2026, 37(3): 111445
doi: 10.1016/j.cclet.2025.111445
Abstract:
The electrostatic repulsion between the anode and ammonia (NH4+) can cause chlorine radicals (Cl•) at the interface to self-compounding into low oxidating species, weakening the treatment performance of ammonia-nitrogen (NH4+-N) wastewater. This study introduces electron-rich elements into the tetrahedral sites (ATd2+) of spinel cobalt oxide (Co3O4) for efficient and selective NH4+-N mineralization induced by interfacial Cl•. Batch experiments, in-situ characterizations, and theoretical calculations confirm that CuTd2+ have moderate energy level matching and strong binding energy with NH4+ compared to NiTd2+ and ZnTd2+. NH4+ can effectively overcome electrostatic repulsion and enrich on CuxCo3-xO4 anode. More importantly, the interaction of CuTd2+-O-CoOh3+ weakens the binding of Cl• at CoOh3+ sites, promoting the desorption of Cl• from the anodic interface. As a result, NH4+-N is mineralized by Cl• into N2 with a rate of 4.4 × 10–2 min-1, superior to Co3O4 and commercial dimensionally stable anodes. Finally, the scale-up experiment using a continuous flow reactor realizes long-term stability for NH4+-N wastewater treatment, in which 100% of NH4+-N and 88.3% of total nitrogen can be continuously eliminated in 96 h. This study offers an in-depth understanding of interfacial reactions in the EC system and guides the design and synthesis of superior anodes for environmental remediation.
The electrostatic repulsion between the anode and ammonia (NH4+) can cause chlorine radicals (Cl•) at the interface to self-compounding into low oxidating species, weakening the treatment performance of ammonia-nitrogen (NH4+-N) wastewater. This study introduces electron-rich elements into the tetrahedral sites (ATd2+) of spinel cobalt oxide (Co3O4) for efficient and selective NH4+-N mineralization induced by interfacial Cl•. Batch experiments, in-situ characterizations, and theoretical calculations confirm that CuTd2+ have moderate energy level matching and strong binding energy with NH4+ compared to NiTd2+ and ZnTd2+. NH4+ can effectively overcome electrostatic repulsion and enrich on CuxCo3-xO4 anode. More importantly, the interaction of CuTd2+-O-CoOh3+ weakens the binding of Cl• at CoOh3+ sites, promoting the desorption of Cl• from the anodic interface. As a result, NH4+-N is mineralized by Cl• into N2 with a rate of 4.4 × 10–2 min-1, superior to Co3O4 and commercial dimensionally stable anodes. Finally, the scale-up experiment using a continuous flow reactor realizes long-term stability for NH4+-N wastewater treatment, in which 100% of NH4+-N and 88.3% of total nitrogen can be continuously eliminated in 96 h. This study offers an in-depth understanding of interfacial reactions in the EC system and guides the design and synthesis of superior anodes for environmental remediation.
2026, 37(3): 111446
doi: 10.1016/j.cclet.2025.111446
Abstract:
It is still challenging to develop nanomedicines with full-active and simple components to tackle osteoarthritis (OA) through restoration of inflammation and cartilage homeostasis. Here, we report the synthesis of a bioactive asymmetric phosphorus dendrimer bearing an azabisphosphonate (ABP) group, termed as G0.PD-ABP, by a divergent method for intracellular bromelain (Bro) delivery. The formed G0.PD-ABP/Bro nanocomplexes (NCs) exhibit a uniformly dispersed spherical shape with a mean size of 148.4 nm and can achieve more significant intracellular Bro delivery than symmetric phosphorus dendrimer (G0.PD) without ABP via the clathrin-mediated endocytosis pathway. Importantly, the NCs efficiently block the activation of inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), and nuclear factor kappa-B (NF-κB) by amplifying the anti-inflammatory function of Bro and synergizing with the immunomodulatory activity of dendrimers, thereby facilitating the polarization of macrophages towards M2 phenotype and down-regulating inflammatory cytokine secretion to lead to suppressed chondrocyte apoptosis. Compared with G0.PD/Bro NCs, an OA mouse model treated with G0.PD-ABP/Bro NCs demonstrates more remarkable alleviation of pathological features such as cartilage degradation, bone erosion, and synovial inflammation. This study emphasizes the positive contribution of structural asymmetry of phosphorus dendrimers in protein delivery and provides a viable strategy for the treatment of OA or other inflammatory diseases through enhanced immune modulation of macrophages.
It is still challenging to develop nanomedicines with full-active and simple components to tackle osteoarthritis (OA) through restoration of inflammation and cartilage homeostasis. Here, we report the synthesis of a bioactive asymmetric phosphorus dendrimer bearing an azabisphosphonate (ABP) group, termed as G0.PD-ABP, by a divergent method for intracellular bromelain (Bro) delivery. The formed G0.PD-ABP/Bro nanocomplexes (NCs) exhibit a uniformly dispersed spherical shape with a mean size of 148.4 nm and can achieve more significant intracellular Bro delivery than symmetric phosphorus dendrimer (G0.PD) without ABP via the clathrin-mediated endocytosis pathway. Importantly, the NCs efficiently block the activation of inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), and nuclear factor kappa-B (NF-κB) by amplifying the anti-inflammatory function of Bro and synergizing with the immunomodulatory activity of dendrimers, thereby facilitating the polarization of macrophages towards M2 phenotype and down-regulating inflammatory cytokine secretion to lead to suppressed chondrocyte apoptosis. Compared with G0.PD/Bro NCs, an OA mouse model treated with G0.PD-ABP/Bro NCs demonstrates more remarkable alleviation of pathological features such as cartilage degradation, bone erosion, and synovial inflammation. This study emphasizes the positive contribution of structural asymmetry of phosphorus dendrimers in protein delivery and provides a viable strategy for the treatment of OA or other inflammatory diseases through enhanced immune modulation of macrophages.
2026, 37(3): 111459
doi: 10.1016/j.cclet.2025.111459
Abstract:
Chronic kidney disease (CKD) is a progressive disease characterized by high rates of morbidity and mortality, often leading to various complications. Early home diagnosis and point-of-care prognosis are therefore crucial for monitoring CKD progression and managing patient outcomes. β2-microglobulin (B2M) levels offer a valuable indicator of renal function changes, however, their quantitative detection typically relies on sophisticated and costly laboratory instrumentation. Here, we present a universal and adaptable strategy for efficiently conjugating rare-earth-based nanoparticles with antibodies via a carboxymethyl β-cyclodextrin-mediated "self-assembly-followed-by-conjugation" approach. Cyclodextrin modification enhances the rigidity, hydrophilicity, and electrostatic repulsion of nanoparticles, significantly improving their colloidal stability and upconversion luminescence in aqueous solution. Moreover, the ample carboxyl groups on cyclodextrin offer multiple sites for covalent conjugation, resulting in a substantial enhancement in antibody loading capacity and improved immunoaffinity for biomarkers. Employing this methodology, we developed an antibody-conjugated nanoprobe for B2M and fabricated a fluorescent lateral flow strip. Subsequently, image acquisition and data analysis using a smartphone enabled sensitive and quantitative detection of B2M in artificial urine, achieving a detection limit of 2.7 ng/mL. This study provides a versatile strategy for the development of nanoparticle-based colorimetric/luminescent immunoassay probes.
Chronic kidney disease (CKD) is a progressive disease characterized by high rates of morbidity and mortality, often leading to various complications. Early home diagnosis and point-of-care prognosis are therefore crucial for monitoring CKD progression and managing patient outcomes. β2-microglobulin (B2M) levels offer a valuable indicator of renal function changes, however, their quantitative detection typically relies on sophisticated and costly laboratory instrumentation. Here, we present a universal and adaptable strategy for efficiently conjugating rare-earth-based nanoparticles with antibodies via a carboxymethyl β-cyclodextrin-mediated "self-assembly-followed-by-conjugation" approach. Cyclodextrin modification enhances the rigidity, hydrophilicity, and electrostatic repulsion of nanoparticles, significantly improving their colloidal stability and upconversion luminescence in aqueous solution. Moreover, the ample carboxyl groups on cyclodextrin offer multiple sites for covalent conjugation, resulting in a substantial enhancement in antibody loading capacity and improved immunoaffinity for biomarkers. Employing this methodology, we developed an antibody-conjugated nanoprobe for B2M and fabricated a fluorescent lateral flow strip. Subsequently, image acquisition and data analysis using a smartphone enabled sensitive and quantitative detection of B2M in artificial urine, achieving a detection limit of 2.7 ng/mL. This study provides a versatile strategy for the development of nanoparticle-based colorimetric/luminescent immunoassay probes.
2026, 37(3): 111496
doi: 10.1016/j.cclet.2025.111496
Abstract:
Traditional enzyme-nanozymes cascade assays for glucose detection are usually limited by pH incompatibility and operational complexity. Herein, we present a strategy based on hollow mesoporous Prussian blue (HMPB) nanozymes for one-step, dual-modal glucose sensing under neutral conditions. The rationally designed HMPB nanozymes exhibit intrinsic peroxidase-like activity at physiological pH (~7.4), inherent chromogenic properties and superior photothermal conversion efficiency. These features directly enable integration with glucose oxidase (GOx) for one-step glucose detection without intermediate pH adjustment. Additionally, the catalytic coupling of 4-aminoantipyrine/phenol oxidation products, enhanced by the intrinsic blue coloration of HMPB, generates vivid multicolorimetric responses for smartphone-based quantitative analysis. To enhance signal reliability, the photothermal properties of HMPB nanozymes are further ingeniously coupled with the thermal-responsive characteristics of oxidized 3,3′,5,5′-tetramethylbenzidine (oxTMB), establishing a dual-amplified thermal imaging platform through portable infrared thermal imager detection. HMPB nanozymes serve as both a catalytic activator and an intrinsic signal reporter, establish a new platform in dual-modal glucose monitoring. The platform demonstrates remarkable clinical adaptability through its smartphone-compatible colorimetric readout and portable thermal imaging capabilities, achieving a detection limit of 1.39 µmol/L (multicolorimetric modal) and 3.05 µmol/L (photothermometric modal) for glucose with robust reliability in human serum samples. This research overcomes the pH mismatch barrier in enzyme-nanozymes cascade system, and providing a cost-effective, instrument-flexible detection strategy that bridges laboratory research and point-of-care diagnostics.
Traditional enzyme-nanozymes cascade assays for glucose detection are usually limited by pH incompatibility and operational complexity. Herein, we present a strategy based on hollow mesoporous Prussian blue (HMPB) nanozymes for one-step, dual-modal glucose sensing under neutral conditions. The rationally designed HMPB nanozymes exhibit intrinsic peroxidase-like activity at physiological pH (~7.4), inherent chromogenic properties and superior photothermal conversion efficiency. These features directly enable integration with glucose oxidase (GOx) for one-step glucose detection without intermediate pH adjustment. Additionally, the catalytic coupling of 4-aminoantipyrine/phenol oxidation products, enhanced by the intrinsic blue coloration of HMPB, generates vivid multicolorimetric responses for smartphone-based quantitative analysis. To enhance signal reliability, the photothermal properties of HMPB nanozymes are further ingeniously coupled with the thermal-responsive characteristics of oxidized 3,3′,5,5′-tetramethylbenzidine (oxTMB), establishing a dual-amplified thermal imaging platform through portable infrared thermal imager detection. HMPB nanozymes serve as both a catalytic activator and an intrinsic signal reporter, establish a new platform in dual-modal glucose monitoring. The platform demonstrates remarkable clinical adaptability through its smartphone-compatible colorimetric readout and portable thermal imaging capabilities, achieving a detection limit of 1.39 µmol/L (multicolorimetric modal) and 3.05 µmol/L (photothermometric modal) for glucose with robust reliability in human serum samples. This research overcomes the pH mismatch barrier in enzyme-nanozymes cascade system, and providing a cost-effective, instrument-flexible detection strategy that bridges laboratory research and point-of-care diagnostics.
2026, 37(3): 111498
doi: 10.1016/j.cclet.2025.111498
Abstract:
Multi-substituted azetidines have been an under-utilized bioisosteres in modern drug entities, due to the scarcity of mild and stereo-controllable synthetic methods. The state-of-art aza-[2 + 2] cycloaddition suffers from two drawbacks, namely limited C=N scope and the dearth of stereochemical control. Herein, we extend a photocatalytic direct N-heteroarene dearomative aza-[2 + 2] cycloaddition under white light via energy transfer mechanism. A key protonic solvent triggered retro aza-[2 + 2] cycloaddition process was discovered and utilized as a stereochemical editing logic to address the challenge of diastereomeric control (controlling three contiguous stereocenters).
Multi-substituted azetidines have been an under-utilized bioisosteres in modern drug entities, due to the scarcity of mild and stereo-controllable synthetic methods. The state-of-art aza-[2 + 2] cycloaddition suffers from two drawbacks, namely limited C=N scope and the dearth of stereochemical control. Herein, we extend a photocatalytic direct N-heteroarene dearomative aza-[2 + 2] cycloaddition under white light via energy transfer mechanism. A key protonic solvent triggered retro aza-[2 + 2] cycloaddition process was discovered and utilized as a stereochemical editing logic to address the challenge of diastereomeric control (controlling three contiguous stereocenters).
2026, 37(3): 111502
doi: 10.1016/j.cclet.2025.111502
Abstract:
Multiple myeloma (MM) is a highly aggressive hematologic malignancy characterized by abnormal proliferation of malignant plasma cells. CD38, a transmembrane glycoprotein, is highly expressed on the surface of plasma cells and serves as a critical diagnostic and therapeutic target for MM. However, the masking of CD38 epitopes caused by therapeutic interventions often leads to false-negative results in clinical detection of CD38, compromising diagnostic accuracy and underscoring the urgent need for novel specific molecular tools. Herein, we reported a novel aptamer, CD38jd4a, specifically targeting CD38 with potential clinical applications. A series of high-affinity aptamers specifically binding CD38 were selected and identified through a highly efficient aptamer selection method with CD38 as the target. Among them, aptamer CD38jd4a exhibited the best performance, with a dissociation constant (Kd) value as low as 5.4 ± 0.6 nmol/L. Through siRNA-mediated knockdown experiments, CD38jd4a was further validated to specifically recognize native CD38 expressed on surface of cells. Furthermore, binding epitopes of CD38jd4a were confirmed to be distinct from those recognized by any of current therapeutic antibodies. This unique characteristic enabled the simultaneous application of CD38jd4a with therapeutic antibodies for CD38 detection on CD38-positive Ramos cells by flow cytometry without cross-interference. Importantly, clinical blood sample analysis revealed that CD38jd4a was capable of effectively detecting CD38 despite epitope masking, thereby overcoming limitations of conventional antibody-based detection methods. Given the small molecular size and excellent performance, CD38jd4a is expected to be a robust diagnostic tool for CD38 detection, offering a promising alternative for clinical diagnostics of CD38.
Multiple myeloma (MM) is a highly aggressive hematologic malignancy characterized by abnormal proliferation of malignant plasma cells. CD38, a transmembrane glycoprotein, is highly expressed on the surface of plasma cells and serves as a critical diagnostic and therapeutic target for MM. However, the masking of CD38 epitopes caused by therapeutic interventions often leads to false-negative results in clinical detection of CD38, compromising diagnostic accuracy and underscoring the urgent need for novel specific molecular tools. Herein, we reported a novel aptamer, CD38jd4a, specifically targeting CD38 with potential clinical applications. A series of high-affinity aptamers specifically binding CD38 were selected and identified through a highly efficient aptamer selection method with CD38 as the target. Among them, aptamer CD38jd4a exhibited the best performance, with a dissociation constant (Kd) value as low as 5.4 ± 0.6 nmol/L. Through siRNA-mediated knockdown experiments, CD38jd4a was further validated to specifically recognize native CD38 expressed on surface of cells. Furthermore, binding epitopes of CD38jd4a were confirmed to be distinct from those recognized by any of current therapeutic antibodies. This unique characteristic enabled the simultaneous application of CD38jd4a with therapeutic antibodies for CD38 detection on CD38-positive Ramos cells by flow cytometry without cross-interference. Importantly, clinical blood sample analysis revealed that CD38jd4a was capable of effectively detecting CD38 despite epitope masking, thereby overcoming limitations of conventional antibody-based detection methods. Given the small molecular size and excellent performance, CD38jd4a is expected to be a robust diagnostic tool for CD38 detection, offering a promising alternative for clinical diagnostics of CD38.
2026, 37(3): 111526
doi: 10.1016/j.cclet.2025.111526
Abstract:
According to the "New Coronavirus Pneumonia (COVID-19) Tenth Edition Diagnosis and Treatment Plan", residues from three prescriptions including Qingfei-Paidu Formula, Huashi-Baidu Formula, and Xuanfei-Zhixue Formula were selected as precursors for biochar preparation. The resulting Chinese medicine residue-derived biochars (CMR-BCs), prepared using different prescriptions and pyrolysis temperatures, were used to activate peracetic acid (PAA) for sulfamethoxazole (SMX) removal. Biochar (q800) produced from 800 ℃-treated Qingfei-Paidu Formula residue achieved ~60% SMX adsorption removal efficiency, outperforming other CMR-BCs. All prepared CMR-BC samples demonstrated oxidative degradation of SMX via activating PAA, with efficiencies ranging from ~20.8% to 45.5%, which might be ascribed to their abundant oxygen-containing functional groups and graphitic structures. Electro-chemical analysis and quenching tests indicated that the direct electron-transfer (DET) process was identified as the primary non-radical degradation mechanism. The formation of CMR-BCs-PAA* interfacial complexes enhanced the overall oxidation potential, facilitating the redox reaction between CMR-BCs-PAA* and SMX. In total, this study offers new insights into the non-radical mechanism of CMR-BC/PAA systems, presenting a potential solution for the resource utilization of Chinese medicine residue wastes.
According to the "New Coronavirus Pneumonia (COVID-19) Tenth Edition Diagnosis and Treatment Plan", residues from three prescriptions including Qingfei-Paidu Formula, Huashi-Baidu Formula, and Xuanfei-Zhixue Formula were selected as precursors for biochar preparation. The resulting Chinese medicine residue-derived biochars (CMR-BCs), prepared using different prescriptions and pyrolysis temperatures, were used to activate peracetic acid (PAA) for sulfamethoxazole (SMX) removal. Biochar (q800) produced from 800 ℃-treated Qingfei-Paidu Formula residue achieved ~60% SMX adsorption removal efficiency, outperforming other CMR-BCs. All prepared CMR-BC samples demonstrated oxidative degradation of SMX via activating PAA, with efficiencies ranging from ~20.8% to 45.5%, which might be ascribed to their abundant oxygen-containing functional groups and graphitic structures. Electro-chemical analysis and quenching tests indicated that the direct electron-transfer (DET) process was identified as the primary non-radical degradation mechanism. The formation of CMR-BCs-PAA* interfacial complexes enhanced the overall oxidation potential, facilitating the redox reaction between CMR-BCs-PAA* and SMX. In total, this study offers new insights into the non-radical mechanism of CMR-BC/PAA systems, presenting a potential solution for the resource utilization of Chinese medicine residue wastes.
2026, 37(3): 111536
doi: 10.1016/j.cclet.2025.111536
Abstract:
To deal with the problem of NO3− enrichment in water environment, electrochemical catalysis of nitrate reduction reaction (NO3RR) provides a possibility. However, this catalytic process requires efficient and highly selective NO3RR electrocatalysts to catalyze NO3− conversion. Consequently, the objective of this work is to search highly active NO3RR electrocatalysts by employing an efficient screening strategy using density functional theory methods. The catalytic activity is assessed by calculating limiting potential UL(NO3RR) and UL(HER). The research results indicate that Os2_C19N3 not only has excellent catalytic activity (UL(NO3RR) = −0.15 V), but also can effectively avoid the occurrence of competitive hydrogen evolution reaction. The NO3RR process of Os2_C19N3 is * + NO3− → *NO3 → *NO3H → NO2 → *NO2H → *NO → *NOH → *N → *NH → *NH2 → *NH3 → * + NH3. When Os2_C19N3 is in the condition of DFT-Sol, DFT-D, and DFT-D-Sol, the NO3RR process is * + NO3− → *NO3 → *NO3H → NO2 → *NO2H → *NO → *NOH → *NHOH → *NH2OH → *NH2 → *NH3 → * + NH3, and the UL(NO3RR) values are −0.06, −0.15, and −0.06 V, respectively. This research may offer potential reference values for the development of innovative NO3RR catalysts and the synthesis of NH3.
To deal with the problem of NO3− enrichment in water environment, electrochemical catalysis of nitrate reduction reaction (NO3RR) provides a possibility. However, this catalytic process requires efficient and highly selective NO3RR electrocatalysts to catalyze NO3− conversion. Consequently, the objective of this work is to search highly active NO3RR electrocatalysts by employing an efficient screening strategy using density functional theory methods. The catalytic activity is assessed by calculating limiting potential UL(NO3RR) and UL(HER). The research results indicate that Os2_C19N3 not only has excellent catalytic activity (UL(NO3RR) = −0.15 V), but also can effectively avoid the occurrence of competitive hydrogen evolution reaction. The NO3RR process of Os2_C19N3 is * + NO3− → *NO3 → *NO3H → NO2 → *NO2H → *NO → *NOH → *N → *NH → *NH2 → *NH3 → * + NH3. When Os2_C19N3 is in the condition of DFT-Sol, DFT-D, and DFT-D-Sol, the NO3RR process is * + NO3− → *NO3 → *NO3H → NO2 → *NO2H → *NO → *NOH → *NHOH → *NH2OH → *NH2 → *NH3 → * + NH3, and the UL(NO3RR) values are −0.06, −0.15, and −0.06 V, respectively. This research may offer potential reference values for the development of innovative NO3RR catalysts and the synthesis of NH3.
2026, 37(3): 111537
doi: 10.1016/j.cclet.2025.111537
Abstract:
Quenching experiments play an essential role in the probing of reactive oxygen species (ROS) in advanced oxidation processes (AOPs). However, inappropriate choice of quencher type and concentration will affect the judgement of the contribution of ROS. Herein, we systematically explored the direct reaction of quenchers with oxidants commonly used in AOPs (e.g., hydrogen peroxide (H2O2), peroxymonosulfate (PMS), and peroxydisulfate (PDS)). The experimental results showed that PMS had a noticeable reaction with methyl phenyl sulfoxide, dimethyl sulfoxide and furfuryl alcohol, and the second-order reaction rate constants between them were measured. Meanwhile, PDS and H2O2 were hardly consumed in the presence of various quenchers. Moreover, high-performance liquid chromatography measurements demonstrated that L-histidine, benzoquinone, and phenol would have the artifact of rapid PMS depletion due to the limitations of the test method. Furthermore, in response to the problems with the quenching experiments, some suggestions for the selection of quencher type and concentration were presented. This work is of great reference value in guiding the appropriate selection of quenchers in AOPs, which in turn facilitates the accurate investigation of ROS and reaction mechanisms.
Quenching experiments play an essential role in the probing of reactive oxygen species (ROS) in advanced oxidation processes (AOPs). However, inappropriate choice of quencher type and concentration will affect the judgement of the contribution of ROS. Herein, we systematically explored the direct reaction of quenchers with oxidants commonly used in AOPs (e.g., hydrogen peroxide (H2O2), peroxymonosulfate (PMS), and peroxydisulfate (PDS)). The experimental results showed that PMS had a noticeable reaction with methyl phenyl sulfoxide, dimethyl sulfoxide and furfuryl alcohol, and the second-order reaction rate constants between them were measured. Meanwhile, PDS and H2O2 were hardly consumed in the presence of various quenchers. Moreover, high-performance liquid chromatography measurements demonstrated that L-histidine, benzoquinone, and phenol would have the artifact of rapid PMS depletion due to the limitations of the test method. Furthermore, in response to the problems with the quenching experiments, some suggestions for the selection of quencher type and concentration were presented. This work is of great reference value in guiding the appropriate selection of quenchers in AOPs, which in turn facilitates the accurate investigation of ROS and reaction mechanisms.
2026, 37(3): 111542
doi: 10.1016/j.cclet.2025.111542
Abstract:
Antibiotic contamination in aquatic environments poses serious risks to ecosystems and public health, necessitating the development of effective removal technologies. In this study, a novel biochar-supported ferric oxyhydroxide (FeOOH/BC) composite catalyst was developed for the activation of peracetic acid (PAA) to degrade cefapirin (CFP), a widely used and persistent cephalosporin antibiotic. The catalyst featured highly dispersed FeOOH nanoparticles and enhanced interfacial electron transfer, enabling efficient activation of PAA through dual pathways involving both radical and non-radical species. FeOOH/BC-1 exhibited the highest catalytic activity, where high-valent iron, singlet oxygen, and surface-bound reactive species played the primary roles in CFP degradation. Fe(Ⅲ) active sites generate high-valent iron oxo, while N active sites in biochar accounted for the direct electron transfer. This work provides a new approach for activating PAA in the degradation of emerging contaminants and offers a feasible method for catalyst regeneration in wastewater treatment applications.
Antibiotic contamination in aquatic environments poses serious risks to ecosystems and public health, necessitating the development of effective removal technologies. In this study, a novel biochar-supported ferric oxyhydroxide (FeOOH/BC) composite catalyst was developed for the activation of peracetic acid (PAA) to degrade cefapirin (CFP), a widely used and persistent cephalosporin antibiotic. The catalyst featured highly dispersed FeOOH nanoparticles and enhanced interfacial electron transfer, enabling efficient activation of PAA through dual pathways involving both radical and non-radical species. FeOOH/BC-1 exhibited the highest catalytic activity, where high-valent iron, singlet oxygen, and surface-bound reactive species played the primary roles in CFP degradation. Fe(Ⅲ) active sites generate high-valent iron oxo, while N active sites in biochar accounted for the direct electron transfer. This work provides a new approach for activating PAA in the degradation of emerging contaminants and offers a feasible method for catalyst regeneration in wastewater treatment applications.
2026, 37(3): 111546
doi: 10.1016/j.cclet.2025.111546
Abstract:
Microplastics (MPs), which originate from plastic degradation, are becoming a significant environmental pollutant, and their prevalence is increasing rapidly. Humans can ingest MPs through various pathways and their presence has been detected in multiple human organs, raising concerns about the potential toxic effects associated with plastic consumption. Epigenetic modifications of nucleic acids play crucial roles in various biological processes, including gene expression and tumorigenesis. Previous studies have demonstrated that exposure to certain environmental pollutants can influence disease pathogenesis by affecting epigenetic factors, including modifications of nucleic acids. However, the impact of MPs on epigenetic modifications of nucleic acids remains largely unexplored. In this study, we systematically investigated the alterations in epigenetic modifications of DNA and RNA following exposure to polystyrene microplastics (PS-MPs). We utilized liquid chromatography-tandem mass spectrometry (LC-MS/MS) to simultaneously analyze two DNA epigenetic modifications of 5-methylcytosine (5mC) and 5-hydroxymethylcytosine (5hmC), along with twenty RNA epigenetic modifications from small RNA and nine epigenetic modifications from mRNA. We measured changes in the levels of DNA and RNA modifications across six tissues (heart, liver, spleen, lung, kidney, and intestine) in mice after PS-MPs exposure. The results indicated that exposure to PS-MPs significantly altered the landscape of epigenetic modifications in nucleic acids. Furthermore, we observed tissue-specific effects, suggesting that different organs respond uniquely to PS-MPs exposure. Additionally, the correlation patterns between DNA and RNA modifications changed following PS-MPs exposure. These findings provide valuable insights suggesting that PS-MPs exposure may alter the patterns of epigenetic modifications in nucleic acids, potentially leading to adverse health effects.
Microplastics (MPs), which originate from plastic degradation, are becoming a significant environmental pollutant, and their prevalence is increasing rapidly. Humans can ingest MPs through various pathways and their presence has been detected in multiple human organs, raising concerns about the potential toxic effects associated with plastic consumption. Epigenetic modifications of nucleic acids play crucial roles in various biological processes, including gene expression and tumorigenesis. Previous studies have demonstrated that exposure to certain environmental pollutants can influence disease pathogenesis by affecting epigenetic factors, including modifications of nucleic acids. However, the impact of MPs on epigenetic modifications of nucleic acids remains largely unexplored. In this study, we systematically investigated the alterations in epigenetic modifications of DNA and RNA following exposure to polystyrene microplastics (PS-MPs). We utilized liquid chromatography-tandem mass spectrometry (LC-MS/MS) to simultaneously analyze two DNA epigenetic modifications of 5-methylcytosine (5mC) and 5-hydroxymethylcytosine (5hmC), along with twenty RNA epigenetic modifications from small RNA and nine epigenetic modifications from mRNA. We measured changes in the levels of DNA and RNA modifications across six tissues (heart, liver, spleen, lung, kidney, and intestine) in mice after PS-MPs exposure. The results indicated that exposure to PS-MPs significantly altered the landscape of epigenetic modifications in nucleic acids. Furthermore, we observed tissue-specific effects, suggesting that different organs respond uniquely to PS-MPs exposure. Additionally, the correlation patterns between DNA and RNA modifications changed following PS-MPs exposure. These findings provide valuable insights suggesting that PS-MPs exposure may alter the patterns of epigenetic modifications in nucleic acids, potentially leading to adverse health effects.
2026, 37(3): 111548
doi: 10.1016/j.cclet.2025.111548
Abstract:
Nanomedicine preparation is a promising approach for the effective utilization of natural bioactive products. However, the successful fortification of natural products into nanocarriers in a host-guest manner remains a great challenge. Here, a 96-WP TFH/TM strategy integrating 96-well plate mediated thin-film hydration, turbidity measurement, stability evaluation, and relative quantification, was proposed to screen host-guest complexes. As a proof-of-concept, biomimetic bile acid-lecithin nanomicelles (BA-L NMs) were used as nanocarriers and 51 natural products were assayed for guest molecules. Muscone came out as the fit-for-purpose candidate to produce stable NMs, namely M-NMs. Following spectroscopic characterization and molecular dynamics calculation, hydrophobic interactions, hydrogen bonding, and salt bridges were demonstrated as the primary correlations amongst taurocholic acid, lecithin, and muscone. M-NMs exhibited significant in vitro and in vivo anti-inflammation features. Together, we developed a 96-WP TFH/TM strategy to achieve high-throughput host-guest complex screening, facilitating the development of natural product nanomicelles.
Nanomedicine preparation is a promising approach for the effective utilization of natural bioactive products. However, the successful fortification of natural products into nanocarriers in a host-guest manner remains a great challenge. Here, a 96-WP TFH/TM strategy integrating 96-well plate mediated thin-film hydration, turbidity measurement, stability evaluation, and relative quantification, was proposed to screen host-guest complexes. As a proof-of-concept, biomimetic bile acid-lecithin nanomicelles (BA-L NMs) were used as nanocarriers and 51 natural products were assayed for guest molecules. Muscone came out as the fit-for-purpose candidate to produce stable NMs, namely M-NMs. Following spectroscopic characterization and molecular dynamics calculation, hydrophobic interactions, hydrogen bonding, and salt bridges were demonstrated as the primary correlations amongst taurocholic acid, lecithin, and muscone. M-NMs exhibited significant in vitro and in vivo anti-inflammation features. Together, we developed a 96-WP TFH/TM strategy to achieve high-throughput host-guest complex screening, facilitating the development of natural product nanomicelles.
2026, 37(3): 111554
doi: 10.1016/j.cclet.2025.111554
Abstract:
In this study, two chiral cationic cage-shaped hosts were successfully self-assembled via imine condensation, achieving near-quantitative yields. Compared with the counterparts bearing a single imine bond, the intrinsic multivalency of the cage frameworks confers significant robustness to the cages, even when exposed to aqueous environments. Each cage features three relatively acidic CH protons oriented towards the interior cavity or clefts, enabling the efficient recognition of anionic guests through cooperative hydrogen bonding. The cage containing pyridinium functions adopts a pseudo face-in conformation, thus it accommodates anionic guests in its peripheral windows in a 1:2 stoichiometry. As a comparison, the cage containing imidazolium functions adopts an edge-in conformation, and thus recognizes the anions within the cavity in a 1:1 binding stoichiometry.
In this study, two chiral cationic cage-shaped hosts were successfully self-assembled via imine condensation, achieving near-quantitative yields. Compared with the counterparts bearing a single imine bond, the intrinsic multivalency of the cage frameworks confers significant robustness to the cages, even when exposed to aqueous environments. Each cage features three relatively acidic CH protons oriented towards the interior cavity or clefts, enabling the efficient recognition of anionic guests through cooperative hydrogen bonding. The cage containing pyridinium functions adopts a pseudo face-in conformation, thus it accommodates anionic guests in its peripheral windows in a 1:2 stoichiometry. As a comparison, the cage containing imidazolium functions adopts an edge-in conformation, and thus recognizes the anions within the cavity in a 1:1 binding stoichiometry.
2026, 37(3): 111566
doi: 10.1016/j.cclet.2025.111566
Abstract:
Immunogenic cell death (ICD) represents a specific form of tumor cell death that has the potential to elicit a tumor-specific immune response, resulting in a systemic anti-tumor effect and providing therapeutic benefits for metastatic lesions. The extensive research in this field has led to numerous studies confirming that during the induction of ICD, tumor cells can release damage-associated molecular patterns (DAMPs), which can be used as biomarkers to predict anti-cancer efficiency. However, few ratiometric fluorescent probes have been developed to tackle this fluctuation in living cells. In this study, we present a novel ratiometric fluorescence probe based on semiconducting polymer nanoparticles (SPNs) and carbon dots (CDs) for the sensing of DAMPs fluctuation in the ICD process by choosing adenosine triphosphate as a model. In this design, the fluorescence intensity of SPNs could not be affected by the change of target, while CDs could selectively respond to target, therefore realizing the ratiometric sensing of DAMPs. The ratiometric probe was successfully applied in real-time monitoring of the fluctuating concentration of DAMPs induced by doxorubicin in living cells. These results demonstrate that the ratiometric probe may become a promising agent for predicting anti-cancer efficiency.
Immunogenic cell death (ICD) represents a specific form of tumor cell death that has the potential to elicit a tumor-specific immune response, resulting in a systemic anti-tumor effect and providing therapeutic benefits for metastatic lesions. The extensive research in this field has led to numerous studies confirming that during the induction of ICD, tumor cells can release damage-associated molecular patterns (DAMPs), which can be used as biomarkers to predict anti-cancer efficiency. However, few ratiometric fluorescent probes have been developed to tackle this fluctuation in living cells. In this study, we present a novel ratiometric fluorescence probe based on semiconducting polymer nanoparticles (SPNs) and carbon dots (CDs) for the sensing of DAMPs fluctuation in the ICD process by choosing adenosine triphosphate as a model. In this design, the fluorescence intensity of SPNs could not be affected by the change of target, while CDs could selectively respond to target, therefore realizing the ratiometric sensing of DAMPs. The ratiometric probe was successfully applied in real-time monitoring of the fluctuating concentration of DAMPs induced by doxorubicin in living cells. These results demonstrate that the ratiometric probe may become a promising agent for predicting anti-cancer efficiency.
2026, 37(3): 111569
doi: 10.1016/j.cclet.2025.111569
Abstract:
Nanozymes-mediated catalytic therapy is an emerging approach for tumor treatment, but the performance of the nanozymes is limited by low enzyme catalytic efficiency, low reaction substrate concentration, and immunosuppressive features of the tumor microenvironment. Herein, a hollow gold nanorods loaded with oxygen-carrying hemoglobin (HAuHbO2) nanozyme with high enzyme catalytic efficiency is reported. In the tumor microenvironment, HAuHbO2 shows dual enzyme activities of glucose oxidase (GOD) and peroxidase (POD) for spontaneous cascade catalytic reactions to realize chemodynamic therapy (CDT). Meanwhile, it exerts excellent photothermal conversion ability for photothermal therapy (PTT). This study also reports the antitumor ability of HAuHbO2, including its mechanism of action in vivo. HAuHbO2 can induce the occurrence of immunogenic cell death (ICD) with the involvement of near-infrared light, which in turn induces the immune response of the organism. Overall, a simple, ingenious, and multifunctional nanozyme is designed in this study, which can provide a basis for applying nanozymes in antitumor therapy.
Nanozymes-mediated catalytic therapy is an emerging approach for tumor treatment, but the performance of the nanozymes is limited by low enzyme catalytic efficiency, low reaction substrate concentration, and immunosuppressive features of the tumor microenvironment. Herein, a hollow gold nanorods loaded with oxygen-carrying hemoglobin (HAuHbO2) nanozyme with high enzyme catalytic efficiency is reported. In the tumor microenvironment, HAuHbO2 shows dual enzyme activities of glucose oxidase (GOD) and peroxidase (POD) for spontaneous cascade catalytic reactions to realize chemodynamic therapy (CDT). Meanwhile, it exerts excellent photothermal conversion ability for photothermal therapy (PTT). This study also reports the antitumor ability of HAuHbO2, including its mechanism of action in vivo. HAuHbO2 can induce the occurrence of immunogenic cell death (ICD) with the involvement of near-infrared light, which in turn induces the immune response of the organism. Overall, a simple, ingenious, and multifunctional nanozyme is designed in this study, which can provide a basis for applying nanozymes in antitumor therapy.
2026, 37(3): 111598
doi: 10.1016/j.cclet.2025.111598
Abstract:
The heavy biofouling on electrochemical sensor surface poses a formidable challenge for biosensing in human blood. Herein, we designed a multilayer filtering-sensing sandwich patch that served as a versatile platform to surmount the substantial fouling constraints for detection in human blood. The patch integrated two functional layers: (i) Inspired by dialysis phenomenon, a filtering-mass transfer hydrophilic membrane with heterogeneous nanostructure was used to filter large-size substances (like cells, bacteria and microorganisms, etc.) and continuously pass through the rest of the biological fluid (like proteins, metabolites and inorganic salts, etc.). (ii) the polypeptide composite hydrogel (rGO/PEPG) on the screen-printed electrode (SPE) surface, with the modulation of -COOH and -NH2 groups, endowed a strong hydrophilic layer with electric neutrality to further facilitate the antifouling ability. Notably, the integration of the filtering porous membrane with the antifouling hydrogel ensures the strong antifouling ability of the electrochemical sensor in complex human blood. Furthermore, the self-healing property of the rGO/PEPG, relying on the physical π-π stacking forces, aligns the electrochemical sensor with practical needs. The constructed antifouling biosensor based on the filtering-sensing sandwich patch was successfully applied for the sensitive detection of cortisol in human blood, with an acceptable accuracy comparable to the enzyme-linked immunosorbent assay (ELISA) method. The strategy presented herein represent a promising advance along the road to construct effective antifouling biosensing devices with robust operation in diverse complex body fluids.
The heavy biofouling on electrochemical sensor surface poses a formidable challenge for biosensing in human blood. Herein, we designed a multilayer filtering-sensing sandwich patch that served as a versatile platform to surmount the substantial fouling constraints for detection in human blood. The patch integrated two functional layers: (i) Inspired by dialysis phenomenon, a filtering-mass transfer hydrophilic membrane with heterogeneous nanostructure was used to filter large-size substances (like cells, bacteria and microorganisms, etc.) and continuously pass through the rest of the biological fluid (like proteins, metabolites and inorganic salts, etc.). (ii) the polypeptide composite hydrogel (rGO/PEPG) on the screen-printed electrode (SPE) surface, with the modulation of -COOH and -NH2 groups, endowed a strong hydrophilic layer with electric neutrality to further facilitate the antifouling ability. Notably, the integration of the filtering porous membrane with the antifouling hydrogel ensures the strong antifouling ability of the electrochemical sensor in complex human blood. Furthermore, the self-healing property of the rGO/PEPG, relying on the physical π-π stacking forces, aligns the electrochemical sensor with practical needs. The constructed antifouling biosensor based on the filtering-sensing sandwich patch was successfully applied for the sensitive detection of cortisol in human blood, with an acceptable accuracy comparable to the enzyme-linked immunosorbent assay (ELISA) method. The strategy presented herein represent a promising advance along the road to construct effective antifouling biosensing devices with robust operation in diverse complex body fluids.
2026, 37(3): 111631
doi: 10.1016/j.cclet.2025.111631
Abstract:
To implement the principle of utilizing waste to address waste issues, porous carbon catalytic materials, prepared through a straightforward process involving NaOH-assisted microwave pyrolysis of ubiquitous waste plastics, were employed to degrade pollutants via peroxymonosulfate (PMS) activation. Polyethylene terephthalate (PET) derived P1S2 exhibited characteristics of defects enrichment and CO formation, while H1S2, prepared by carbonization of high-density polyethylene (HDPE), possessed a large number of COH and defects. Metal-free catalysts P1S2 and H1S2 exhibited excellent tetracycline (TC) degradation performance, with the rate constants up to 0.303 min-1 and 0.235 min-1. Interestingly, mechanism studies demonstrated that the types of waste plastic precursor had a significant impact on the pathways involved in TC degradation. Specifically, carbon defects in P1S2 dominated the electron transfer nonradial degradation pathway of TC; However, COH in H1S2 served as the reactive site for main active species SO4•−/•OH generation, initiating a free radical pathway. In addition, by combining Fukui function calculation and LC-MS test during the TC degradation process, the vulnerable sites attacked by active species were identified; different degradation routes of TC in nonradial and radial pathways were proposed and discussed. Furthermore, the toxicity of all intermediates was analyzed using the toxicity assessment software. This study offers fresh insights into the critical role of carbocatalysts derived from various waste plastics in both nonradical and radical activation processes of PMS.
To implement the principle of utilizing waste to address waste issues, porous carbon catalytic materials, prepared through a straightforward process involving NaOH-assisted microwave pyrolysis of ubiquitous waste plastics, were employed to degrade pollutants via peroxymonosulfate (PMS) activation. Polyethylene terephthalate (PET) derived P1S2 exhibited characteristics of defects enrichment and CO formation, while H1S2, prepared by carbonization of high-density polyethylene (HDPE), possessed a large number of COH and defects. Metal-free catalysts P1S2 and H1S2 exhibited excellent tetracycline (TC) degradation performance, with the rate constants up to 0.303 min-1 and 0.235 min-1. Interestingly, mechanism studies demonstrated that the types of waste plastic precursor had a significant impact on the pathways involved in TC degradation. Specifically, carbon defects in P1S2 dominated the electron transfer nonradial degradation pathway of TC; However, COH in H1S2 served as the reactive site for main active species SO4•−/•OH generation, initiating a free radical pathway. In addition, by combining Fukui function calculation and LC-MS test during the TC degradation process, the vulnerable sites attacked by active species were identified; different degradation routes of TC in nonradial and radial pathways were proposed and discussed. Furthermore, the toxicity of all intermediates was analyzed using the toxicity assessment software. This study offers fresh insights into the critical role of carbocatalysts derived from various waste plastics in both nonradical and radical activation processes of PMS.
2026, 37(3): 111693
doi: 10.1016/j.cclet.2025.111693
Abstract:
Nanozymes, particularly single-atom nanozymes (SAzymes), have gained attention as potential ferroptosis inducers for cancer therapy due to their high catalytic efficiency and selectivity. However, the catalytic activity of SAzymes is often limited by the symmetrical electronic structure at their active sites. To enhance their performance, heteroatom doping strategies have been applied to modulate the electronic properties of SAzyme catalysts. In this study, we synthesized sulfur-doped FNS SAzymes with an Fe-N-S-C asymmetric coordination structure through pyrolysis. Enzyme kinetics analysis and density functional theory calculations revealed that FNS SAzymes exhibit highly efficient peroxidase-like and glutathione oxidase-like activities. These nanozymes are capable of catalyzing the decomposition of H2O2 to produce reactive oxygen species and depleting glutathione (GSH), thereby inducing ferroptosis. The FNS SAzymes were combined with an alkyl radical (•R) initiator, 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (AIPH), and assembled into microneedle patches for enhanced ferroptosis therapy (FNSA-MN). Beyond the dual enzyme activities of FNS SAzymes, 808 nm laser activation induced a photothermal effect that facilitated the rapid dissociation of AIPH to generate •R. This FNSA-MN significantly enhanced lipid peroxidation within cells, thereby promoting ferroptosis. In vivo studies demonstrated significant suppression of tumor growth and strong anti-metastatic effects, highlighting a promising strategy for localized cancer therapy.
Nanozymes, particularly single-atom nanozymes (SAzymes), have gained attention as potential ferroptosis inducers for cancer therapy due to their high catalytic efficiency and selectivity. However, the catalytic activity of SAzymes is often limited by the symmetrical electronic structure at their active sites. To enhance their performance, heteroatom doping strategies have been applied to modulate the electronic properties of SAzyme catalysts. In this study, we synthesized sulfur-doped FNS SAzymes with an Fe-N-S-C asymmetric coordination structure through pyrolysis. Enzyme kinetics analysis and density functional theory calculations revealed that FNS SAzymes exhibit highly efficient peroxidase-like and glutathione oxidase-like activities. These nanozymes are capable of catalyzing the decomposition of H2O2 to produce reactive oxygen species and depleting glutathione (GSH), thereby inducing ferroptosis. The FNS SAzymes were combined with an alkyl radical (•R) initiator, 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (AIPH), and assembled into microneedle patches for enhanced ferroptosis therapy (FNSA-MN). Beyond the dual enzyme activities of FNS SAzymes, 808 nm laser activation induced a photothermal effect that facilitated the rapid dissociation of AIPH to generate •R. This FNSA-MN significantly enhanced lipid peroxidation within cells, thereby promoting ferroptosis. In vivo studies demonstrated significant suppression of tumor growth and strong anti-metastatic effects, highlighting a promising strategy for localized cancer therapy.
2026, 37(3): 111863
doi: 10.1016/j.cclet.2025.111863
Abstract:
Based on recently reported high-performance doubly concerted companion (DCC) dye XW96 constructed by covalently linking a porphyrin dye and an organic dye with hexyl chain protected phenothiazine and fluorenyl indoline donors, respectively, we herein employ a branched 2-ethylhexyl chain to realize better anti-charge-recombination and anti-aggregation abilities, achieving improved photovoltaic behavior. Thus, based on XW96, dye XW98 has been synthesized by introducing branched chains to the donors. As a result, the bulkier donors on both sub-dye units cause spatial repulsion, resulting in more severe twisting, decreased adsorption amount and lowered efficiency, compared to XW96. To reduce the steric hindrance, the linker between the two subdye units has been extended on the basis of XW98 (seven bonds) to give XW99 (eight bonds) and XW100 (nine bonds), affording considerably improved adsorption. Notably, XW99 affords an open-circuit voltage (VOC) of 784 mV, a short-circuit current density (JSC) of 22.08 mA/cm2, and a high power conversion efficiency (PCE) of 12.54%. Compared with XW99, dye XW100 exhibits a larger percentage of single anchoring despite its larger adsorption amount, leading to a lowered efficiency of 12.25%. This work indicates that combination of bulky branched chains on the donors with optimized linker length is essential for developing efficient DCC sensitizers.
Based on recently reported high-performance doubly concerted companion (DCC) dye XW96 constructed by covalently linking a porphyrin dye and an organic dye with hexyl chain protected phenothiazine and fluorenyl indoline donors, respectively, we herein employ a branched 2-ethylhexyl chain to realize better anti-charge-recombination and anti-aggregation abilities, achieving improved photovoltaic behavior. Thus, based on XW96, dye XW98 has been synthesized by introducing branched chains to the donors. As a result, the bulkier donors on both sub-dye units cause spatial repulsion, resulting in more severe twisting, decreased adsorption amount and lowered efficiency, compared to XW96. To reduce the steric hindrance, the linker between the two subdye units has been extended on the basis of XW98 (seven bonds) to give XW99 (eight bonds) and XW100 (nine bonds), affording considerably improved adsorption. Notably, XW99 affords an open-circuit voltage (VOC) of 784 mV, a short-circuit current density (JSC) of 22.08 mA/cm2, and a high power conversion efficiency (PCE) of 12.54%. Compared with XW99, dye XW100 exhibits a larger percentage of single anchoring despite its larger adsorption amount, leading to a lowered efficiency of 12.25%. This work indicates that combination of bulky branched chains on the donors with optimized linker length is essential for developing efficient DCC sensitizers.
2026, 37(3): 111893
doi: 10.1016/j.cclet.2025.111893
Abstract:
Chiral α-aryl ketone moieties are privileged structural motifs that are widely present in various biologically active natural products and pharmaceuticals. However, traditional carbonylation methods typically rely on the use of noble-metal catalysts and toxic and flammable CO gas as the carbonyl source. To overcomes these challenges, we disclose here a nickel-catalyzed enantioselective cross-hydroacylation of aryl alkenes with unactivated alkenes using isobutyl chloroformate as a safe CO source and electron acceptor. Two distinct alkenes and chloroformates are assembled efficiently in a chemo-, regio- and enantioselective manner, providing a scalable, environmentally friendly alternative for the enantioselective synthesis of α-aryl ketones. The approach proceeds under mild reaction conditions, uses abundant and readily available starting materials, and avoids the use of either toxic CO or metal carbonyl reagents. Mechanistic studies show that in situ generated nickel hydride complexes first undergoes hydrometalation/chain walking with aryl alkenes, followed by sequential migratory insertion of CO and unactivated alkenes, and finally cross-hydroacylated products are obtained through reductive elimination.
Chiral α-aryl ketone moieties are privileged structural motifs that are widely present in various biologically active natural products and pharmaceuticals. However, traditional carbonylation methods typically rely on the use of noble-metal catalysts and toxic and flammable CO gas as the carbonyl source. To overcomes these challenges, we disclose here a nickel-catalyzed enantioselective cross-hydroacylation of aryl alkenes with unactivated alkenes using isobutyl chloroformate as a safe CO source and electron acceptor. Two distinct alkenes and chloroformates are assembled efficiently in a chemo-, regio- and enantioselective manner, providing a scalable, environmentally friendly alternative for the enantioselective synthesis of α-aryl ketones. The approach proceeds under mild reaction conditions, uses abundant and readily available starting materials, and avoids the use of either toxic CO or metal carbonyl reagents. Mechanistic studies show that in situ generated nickel hydride complexes first undergoes hydrometalation/chain walking with aryl alkenes, followed by sequential migratory insertion of CO and unactivated alkenes, and finally cross-hydroacylated products are obtained through reductive elimination.
2026, 37(3): 111916
doi: 10.1016/j.cclet.2025.111916
Abstract:
Luminescent materials function as optical pressure sensors based on pressure-dependent emission. Optical pressure sensors offer a broad measurement range and non-contact operation but face limitations in sensitivity. In this study, we establish a selection principle based on low-dimensional structures and conduct a high-pressure evaluation of xCr3+-doped Sr9Ga1-x(PO4)7 (x = 0.2, 0.5, and 0.8) phosphor, demonstrating its exceptional pressure sensitivity. Upon excitation at 488 nm, Sr9Ga0.5(PO4)7:0.5Cr3+ displays a broad near-infrared emission peak centered at 840 nm. Specifically, the phosphor maintains its structural integrity under pressures up to 10.0 GPa, with a continuous blue shift. The fluorescence peak shifts from 839.5 nm to 757.9 nm, demonstrating a high-pressure sensitivity of 8.11 nm/GPa. These findings establish Sr9Ga0.5(PO4)7:0.5Cr3+ as a viable candidate for optical pressure sensor, thereby offering valuable insights into advancing optical sensor development through host selection.
Luminescent materials function as optical pressure sensors based on pressure-dependent emission. Optical pressure sensors offer a broad measurement range and non-contact operation but face limitations in sensitivity. In this study, we establish a selection principle based on low-dimensional structures and conduct a high-pressure evaluation of xCr3+-doped Sr9Ga1-x(PO4)7 (x = 0.2, 0.5, and 0.8) phosphor, demonstrating its exceptional pressure sensitivity. Upon excitation at 488 nm, Sr9Ga0.5(PO4)7:0.5Cr3+ displays a broad near-infrared emission peak centered at 840 nm. Specifically, the phosphor maintains its structural integrity under pressures up to 10.0 GPa, with a continuous blue shift. The fluorescence peak shifts from 839.5 nm to 757.9 nm, demonstrating a high-pressure sensitivity of 8.11 nm/GPa. These findings establish Sr9Ga0.5(PO4)7:0.5Cr3+ as a viable candidate for optical pressure sensor, thereby offering valuable insights into advancing optical sensor development through host selection.
2026, 37(3): 111921
doi: 10.1016/j.cclet.2025.111921
Abstract:
Hydrofunctionalization of unsaturated hydrocarbons via transition metal catalysis is a powerful route to prepare allyl skeletons, but is limited to mono- and two-component transformation models. Here we describe a novel protocol for the unprecedented three-component hydrofunctionalization via in situ formed diene species. Both amines and stabilized carbon nucleophiles undergo the assembled hydrofunctionalization with various olefins and alkenyl bromides through Pd-catalyzed tandem Heck coupling and outer-sphere allylation, generating allylic C–N and C–C bonds in reasonable yields and with excellent regioselectivities. In particular, the combination of assembled hydrofunctionalization and following derivatizations enables new access to a series of valuable substituted cyclic skeletons. Preliminary mechanistic studies support the in situ formation of critical conjugated diene intermediate for sequential hydrofunctionalization
Hydrofunctionalization of unsaturated hydrocarbons via transition metal catalysis is a powerful route to prepare allyl skeletons, but is limited to mono- and two-component transformation models. Here we describe a novel protocol for the unprecedented three-component hydrofunctionalization via in situ formed diene species. Both amines and stabilized carbon nucleophiles undergo the assembled hydrofunctionalization with various olefins and alkenyl bromides through Pd-catalyzed tandem Heck coupling and outer-sphere allylation, generating allylic C–N and C–C bonds in reasonable yields and with excellent regioselectivities. In particular, the combination of assembled hydrofunctionalization and following derivatizations enables new access to a series of valuable substituted cyclic skeletons. Preliminary mechanistic studies support the in situ formation of critical conjugated diene intermediate for sequential hydrofunctionalization
2026, 37(3): 111928
doi: 10.1016/j.cclet.2025.111928
Abstract:
Benzo[b]furans are significant scaffolds in drug molecules and are prevalent structural components in natural products. Chemically encoded non-natural peptidomimetics have a substantial impact on pharmaceuticals by offering enhanced stability, improved cell permeability, and resistance to enzymatic degradation. Consequently, a strategy for the sustainable assembly of benzo[b]furan/benzopyran-functionalized peptides through the electrochemical late-stage modification of alkyne-modified tyrosine oligopeptides is proposed. This approach facilitates the multifunctional integration of non-native tyrosine-derived substrates, as well as their subsequent functionalization. Notably, the resulting peptides exhibit favorable properties regarding biocompatibility and cellular uptake.
Benzo[b]furans are significant scaffolds in drug molecules and are prevalent structural components in natural products. Chemically encoded non-natural peptidomimetics have a substantial impact on pharmaceuticals by offering enhanced stability, improved cell permeability, and resistance to enzymatic degradation. Consequently, a strategy for the sustainable assembly of benzo[b]furan/benzopyran-functionalized peptides through the electrochemical late-stage modification of alkyne-modified tyrosine oligopeptides is proposed. This approach facilitates the multifunctional integration of non-native tyrosine-derived substrates, as well as their subsequent functionalization. Notably, the resulting peptides exhibit favorable properties regarding biocompatibility and cellular uptake.
2026, 37(3): 111947
doi: 10.1016/j.cclet.2025.111947
Abstract:
Developing passive cooling materials with dual functionality of high-performance thermal management and aesthetic appeal remains a critical challenge for sustainable development. Here, we present a hydrophobic force-driven assembly strategy to construct crack-free colloidal photonic crystals (CPCs) for colored passive daytime cooling (PDC) textiles. Monodispersed poly(styrene-hydroxypropyl acrylate-hexafluorobutyl methacrylate) (P(St-HPA-HFBMA)) colloidal particles with low surface energy (9 mN/m) and high monodispersity (PDI < 0.05) are synthesized via soap-free emulsion polymerization. The hexafluorobutyl terminal groups (C3F6) enable robust hydrophobicity (water contact angle: 124°), facilitating crack-free CPC assembly through hydrophobic driving force. By integrating the CPCs with SiO2 aerogel-embedded polyethylene oxide (PEO/SiO2 aerogel) fiber scaffold based on microfluidic spinning technology, a colored hybrid composite film is fabricated, achieving 0.76 solar reflectance and 0.84 thermal emissivity in the atmospheric window (8-13 µm). Outdoor evaluations demonstrate a sub-ambient cooling temperature of 4.1 ℃ under 732 W/m² solar intensity, reaching the desirable level of PDC materials. The hybrid composite film also exhibits angle-independent structural colors, mechanical robustness (tensile strength: 1.86 MPa), and scalable manufacturability. This work provides a paradigm for multifunctional PDC systems combining aesthetic versatility with sustainable cooling performance.
Developing passive cooling materials with dual functionality of high-performance thermal management and aesthetic appeal remains a critical challenge for sustainable development. Here, we present a hydrophobic force-driven assembly strategy to construct crack-free colloidal photonic crystals (CPCs) for colored passive daytime cooling (PDC) textiles. Monodispersed poly(styrene-hydroxypropyl acrylate-hexafluorobutyl methacrylate) (P(St-HPA-HFBMA)) colloidal particles with low surface energy (9 mN/m) and high monodispersity (PDI < 0.05) are synthesized via soap-free emulsion polymerization. The hexafluorobutyl terminal groups (C3F6) enable robust hydrophobicity (water contact angle: 124°), facilitating crack-free CPC assembly through hydrophobic driving force. By integrating the CPCs with SiO2 aerogel-embedded polyethylene oxide (PEO/SiO2 aerogel) fiber scaffold based on microfluidic spinning technology, a colored hybrid composite film is fabricated, achieving 0.76 solar reflectance and 0.84 thermal emissivity in the atmospheric window (8-13 µm). Outdoor evaluations demonstrate a sub-ambient cooling temperature of 4.1 ℃ under 732 W/m² solar intensity, reaching the desirable level of PDC materials. The hybrid composite film also exhibits angle-independent structural colors, mechanical robustness (tensile strength: 1.86 MPa), and scalable manufacturability. This work provides a paradigm for multifunctional PDC systems combining aesthetic versatility with sustainable cooling performance.
2026, 37(3): 111958
doi: 10.1016/j.cclet.2025.111958
Abstract:
Functionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO2 reduction reaction (CO2RR). However, it is always bound within an unfavorable linear scaling relationship of the synchronously changed adsorption energies of intermediates. To break it, a win-win diethylamine (DEA)-mediated strategy was proposed to functionalize surface Pd atoms by exchanging the residual oleylamine (OAm) on ultrafine Pd nanoparticles (Pd NPs) with DEA. The molecular dynamics simulations, coupled with in situ Fourier transform infrared spectroscopy results, revealed that DEA hindered less toward CO2 than H2O on Pd NPs surface, and induced more CO linear configuration intermediate (*COL), indicative of ease CO2 transport and CO desorption. Additionally, computational calculations implied that -NH- in DEA delocalized more electrons to surface Pd atoms and formed H-bond with *COOH, asynchronously changing the adsorption energies of *COOH and *CO, which enabled a CO Faraday efficiency (FECO) close to 100% in an ultrawide potential window and a stability of over 50 h with a FECO over 90%. This study dexterously addresses the residual issue of end-blocking agents on metal nanostructures from synthesis, and synchronously realizes the surface molecular functionalization, paving a smart avenue to design high-performance electrocatalysts.
Functionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO2 reduction reaction (CO2RR). However, it is always bound within an unfavorable linear scaling relationship of the synchronously changed adsorption energies of intermediates. To break it, a win-win diethylamine (DEA)-mediated strategy was proposed to functionalize surface Pd atoms by exchanging the residual oleylamine (OAm) on ultrafine Pd nanoparticles (Pd NPs) with DEA. The molecular dynamics simulations, coupled with in situ Fourier transform infrared spectroscopy results, revealed that DEA hindered less toward CO2 than H2O on Pd NPs surface, and induced more CO linear configuration intermediate (*COL), indicative of ease CO2 transport and CO desorption. Additionally, computational calculations implied that -NH- in DEA delocalized more electrons to surface Pd atoms and formed H-bond with *COOH, asynchronously changing the adsorption energies of *COOH and *CO, which enabled a CO Faraday efficiency (FECO) close to 100% in an ultrawide potential window and a stability of over 50 h with a FECO over 90%. This study dexterously addresses the residual issue of end-blocking agents on metal nanostructures from synthesis, and synchronously realizes the surface molecular functionalization, paving a smart avenue to design high-performance electrocatalysts.
2026, 37(3): 111963
doi: 10.1016/j.cclet.2025.111963
Abstract:
Given the emerging demand to “escape from flatland” for modern medicinal chemistry, both the catalytic construction of complex three-dimensional molecular architectures from planar aromatics and the bioisosteric substitution of aromatic ring with bicyclo[2.1.1]hexanes (BCHs) become increasingly valuable. Despite notable advancements in the cycloaddition reactions involving bicyclo[1.1.0]butanes (BCBs) and 2π-components, the application of easily accessible aromatic compounds in these transformations, particularly in an asymmetric manner, is still relatively unexplored. Herein, we report a nickel-catalyzed enantioselective polar dearomative (3 + 2) cycloaddition of BCBs with benzazoles and indoles. This protocol offers an efficient route for the synthesis of N,S- or N,N-heterocycles decorated fused aza-BCHs bearing two quaternary carbon centers. This approach stands out for its practicality and appeal due to the utilization of easily accessible starting materials and catalysts, broad substrate scope, easy scalability, and the employment of mild reaction conditions. Density functional theory (DFT) calculations offer crucial insights into the reaction mechanism and elucidate the factors governing the enantioselectivity within the dearomative cycloaddition process.
Given the emerging demand to “escape from flatland” for modern medicinal chemistry, both the catalytic construction of complex three-dimensional molecular architectures from planar aromatics and the bioisosteric substitution of aromatic ring with bicyclo[2.1.1]hexanes (BCHs) become increasingly valuable. Despite notable advancements in the cycloaddition reactions involving bicyclo[1.1.0]butanes (BCBs) and 2π-components, the application of easily accessible aromatic compounds in these transformations, particularly in an asymmetric manner, is still relatively unexplored. Herein, we report a nickel-catalyzed enantioselective polar dearomative (3 + 2) cycloaddition of BCBs with benzazoles and indoles. This protocol offers an efficient route for the synthesis of N,S- or N,N-heterocycles decorated fused aza-BCHs bearing two quaternary carbon centers. This approach stands out for its practicality and appeal due to the utilization of easily accessible starting materials and catalysts, broad substrate scope, easy scalability, and the employment of mild reaction conditions. Density functional theory (DFT) calculations offer crucial insights into the reaction mechanism and elucidate the factors governing the enantioselectivity within the dearomative cycloaddition process.
2026, 37(3): 112003
doi: 10.1016/j.cclet.2025.112003
Abstract:
A novel method for carbonylation of tertiary C(sp3)–H bonds in 2-aminophenyl-alkyl methanones with CO2 has been developed, enabling the synthesis of 2,4-quinolinediones featuring quaternary carbon centres. Building on this approach, a promising iridium(Ⅲ) complex involving carbon from CO2 was designed and synthesized. This complex, exhibiting a high photoluminescent quantum yield, was successfully applied in organic light-emitting diodes (OLEDs), achieving a high maximum luminance up to 12,010 cd/m2 and a maximum external quantum efficiency (EQE) of 13.95%.
A novel method for carbonylation of tertiary C(sp3)–H bonds in 2-aminophenyl-alkyl methanones with CO2 has been developed, enabling the synthesis of 2,4-quinolinediones featuring quaternary carbon centres. Building on this approach, a promising iridium(Ⅲ) complex involving carbon from CO2 was designed and synthesized. This complex, exhibiting a high photoluminescent quantum yield, was successfully applied in organic light-emitting diodes (OLEDs), achieving a high maximum luminance up to 12,010 cd/m2 and a maximum external quantum efficiency (EQE) of 13.95%.
2026, 37(3): 112018
doi: 10.1016/j.cclet.2025.112018
Abstract:
The α,β-butenolide moiety serves as a valuable electrophile in Michael additions and cycloadditions, enabling the direct and atom-economical construction of γ-butyrolactones—a unique structural motif prevalent in natural products. However, its susceptibility to aromatization limits its applications in complex natural products synthesis. Herein, we report the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, a stereoisomer of the natural product sinugyrosanolide A, in which the aromatization of α,β-butenolide moiety was inhibited. A mild acid-promoted intramolecular [5 + 2] cycloaddition could rapidly assemble the synthetically challenging 5,5,7,6 core found in several Sinularia diterpenoids. The key cycloaddition precursor was prepared through an unconventional sequence involving an aldol reaction of dihydropyranone acetal derivatives and aldehyde, followed by ring-closing metathesis (RCM). This research not only accomplishes the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, but also shows its potential for synthesizing other cembranoid and norcembranoid natural products. More importantly, it establishes an alternative approach toward synthesizing structurally complex molecules containing γ-butyrolactone moiety.
The α,β-butenolide moiety serves as a valuable electrophile in Michael additions and cycloadditions, enabling the direct and atom-economical construction of γ-butyrolactones—a unique structural motif prevalent in natural products. However, its susceptibility to aromatization limits its applications in complex natural products synthesis. Herein, we report the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, a stereoisomer of the natural product sinugyrosanolide A, in which the aromatization of α,β-butenolide moiety was inhibited. A mild acid-promoted intramolecular [5 + 2] cycloaddition could rapidly assemble the synthetically challenging 5,5,7,6 core found in several Sinularia diterpenoids. The key cycloaddition precursor was prepared through an unconventional sequence involving an aldol reaction of dihydropyranone acetal derivatives and aldehyde, followed by ring-closing metathesis (RCM). This research not only accomplishes the asymmetric synthesis of (–)-14-epi-sinugyrosanolide A, but also shows its potential for synthesizing other cembranoid and norcembranoid natural products. More importantly, it establishes an alternative approach toward synthesizing structurally complex molecules containing γ-butyrolactone moiety.
2026, 37(3): 112042
doi: 10.1016/j.cclet.2025.112042
Abstract:
Organic electrochemical transistor (OECT)-based inverters hold great promise for neural-machine interfaces due to their low operating voltage and compatibility with aqueous environments. However, unbalanced p-/n-channel characteristics hinder the inverter's voltage gain and fast switching. Here, a rational inverter design is presented, leveraging ion concentration to equilibrate p-n channel conductivity and kinetic doping in the OECT inverter, achieving an extremely high gain value of over 370 V/V under optimized driving conditions. Furthermore, a 3-stage ring oscillator constructed from these ion-equilibrated OECT inverters exhibits a rapid response time (stage delay < 0.6 ms) and a broad frequency response exceeding 300 Hz, matching the mechanoreceptor signals in human skin. The biocompatible output displays a sublinear reaction to static pressure pulses, indicating successful tactile recognition in live neurons. This work presents a practical strategy for constructing neural-compatible artificial logics through ion-concentration engineering, providing a platform for seamless neural-machine integration.
Organic electrochemical transistor (OECT)-based inverters hold great promise for neural-machine interfaces due to their low operating voltage and compatibility with aqueous environments. However, unbalanced p-/n-channel characteristics hinder the inverter's voltage gain and fast switching. Here, a rational inverter design is presented, leveraging ion concentration to equilibrate p-n channel conductivity and kinetic doping in the OECT inverter, achieving an extremely high gain value of over 370 V/V under optimized driving conditions. Furthermore, a 3-stage ring oscillator constructed from these ion-equilibrated OECT inverters exhibits a rapid response time (stage delay < 0.6 ms) and a broad frequency response exceeding 300 Hz, matching the mechanoreceptor signals in human skin. The biocompatible output displays a sublinear reaction to static pressure pulses, indicating successful tactile recognition in live neurons. This work presents a practical strategy for constructing neural-compatible artificial logics through ion-concentration engineering, providing a platform for seamless neural-machine integration.
2026, 37(3): 112114
doi: 10.1016/j.cclet.2025.112114
Abstract:
Supported noble‐metal catalysts often suffer from nanoparticle sintering, resulting in rapid deactivation under high‐temperature conditions. We report hierarchically porous spinel type high-entropy oxide (S-HEO) nanofibers, (CrMnFeCoMg)3O4, as robust supports for Pt nanoparticles. The porous structure (38.5 m2/g) endows thermal stability, preserving porosity after 880 ℃ calcination. The porous Pt/S-HEO-500 exhibits exceptional sinter-resistance. Under 500 ℃ calcination, Pt exhibits only a 0.2 nm growth increment, owing to the physical confinement and strong metal–support interactions. For Pt/S-HEO-500, the T50 (50% conversion temperature) for CO oxidation was merely 9 ℃ higher than that without calcination, with 100% conversion retained over 100 h of steady-state operation. These findings position porous spinel HEO nanofibers as a versatile platform for designing sinter-resistant noble-metal catalysts in high-temperature applications.
Supported noble‐metal catalysts often suffer from nanoparticle sintering, resulting in rapid deactivation under high‐temperature conditions. We report hierarchically porous spinel type high-entropy oxide (S-HEO) nanofibers, (CrMnFeCoMg)3O4, as robust supports for Pt nanoparticles. The porous structure (38.5 m2/g) endows thermal stability, preserving porosity after 880 ℃ calcination. The porous Pt/S-HEO-500 exhibits exceptional sinter-resistance. Under 500 ℃ calcination, Pt exhibits only a 0.2 nm growth increment, owing to the physical confinement and strong metal–support interactions. For Pt/S-HEO-500, the T50 (50% conversion temperature) for CO oxidation was merely 9 ℃ higher than that without calcination, with 100% conversion retained over 100 h of steady-state operation. These findings position porous spinel HEO nanofibers as a versatile platform for designing sinter-resistant noble-metal catalysts in high-temperature applications.
2026, 37(3): 110665
doi: 10.1016/j.cclet.2024.110665
Abstract:
Electrocatalytic carbon dioxide reduction reaction (eCO2RR) holds great promise in producing value-added chemicals, and achieving carbon neutrality. However, the efficiency of eCO2RR is often hindered by the sluggish oxygen evolution reaction (OER) at the anode. Thereby, various strategies have been developed to boost anode reaction, aiming to realize economic viability and reduce energy consumption in an eCO2RR electrolyzer. To give a comprehensive overview of anode engineering for optimizing eCO2RR, this review summarizes and discusses the cutting-edge anodic design strategies from recent research progress. They mainly include the direct substitution of OER to the value-added oxidation reaction of other small molecules, the introduction of photo/bio-assistance anodes, and the construction of metal-CO2 batteries. Furthermore, the emerging challenges and a forward-looking perspective on anode development by coupling renewable energy, sewage treatment and eCO2RR are also proposed.
Electrocatalytic carbon dioxide reduction reaction (eCO2RR) holds great promise in producing value-added chemicals, and achieving carbon neutrality. However, the efficiency of eCO2RR is often hindered by the sluggish oxygen evolution reaction (OER) at the anode. Thereby, various strategies have been developed to boost anode reaction, aiming to realize economic viability and reduce energy consumption in an eCO2RR electrolyzer. To give a comprehensive overview of anode engineering for optimizing eCO2RR, this review summarizes and discusses the cutting-edge anodic design strategies from recent research progress. They mainly include the direct substitution of OER to the value-added oxidation reaction of other small molecules, the introduction of photo/bio-assistance anodes, and the construction of metal-CO2 batteries. Furthermore, the emerging challenges and a forward-looking perspective on anode development by coupling renewable energy, sewage treatment and eCO2RR are also proposed.
2026, 37(3): 111170
doi: 10.1016/j.cclet.2025.111170
Abstract:
Peptides are increasingly favored as therapeutic agents due to their high efficacy, selectivity, and minimal side effects. However, they often face challenges related to poor stability and limited permeability through the gastrointestinal tract (GIT) and epithelia, necessitating parenteral administration. Despite this, there is a considerable demand for oral administration in clinical practice. To address the urgent clinical need for oral delivery, researchers have developed various technologies to surmount these challenges, including device-related systems, permeation enhancers (PEs), nanocarrier-based systems, and more. This review systematically explores the physiological barriers impacting peptide permeability and discusses the permeation-enhancing technologies designed to overcome them. It also reviews the oral peptide delivery systems currently available or under clinical investigation, offering insights into future developments in this field.
Peptides are increasingly favored as therapeutic agents due to their high efficacy, selectivity, and minimal side effects. However, they often face challenges related to poor stability and limited permeability through the gastrointestinal tract (GIT) and epithelia, necessitating parenteral administration. Despite this, there is a considerable demand for oral administration in clinical practice. To address the urgent clinical need for oral delivery, researchers have developed various technologies to surmount these challenges, including device-related systems, permeation enhancers (PEs), nanocarrier-based systems, and more. This review systematically explores the physiological barriers impacting peptide permeability and discusses the permeation-enhancing technologies designed to overcome them. It also reviews the oral peptide delivery systems currently available or under clinical investigation, offering insights into future developments in this field.
2026, 37(3): 111213
doi: 10.1016/j.cclet.2025.111213
Abstract:
Mucosal vaccines would be game-changing for blocking pathogenic transmission, prompting protection where microorganism first enters that those intramuscular ones could not be able to achieve. The exploration of the vaccines at mucosal surfaces is gaining momentum due to the unique immune reservoir they offer in a minimally invasive manner. Nevertheless, the application of mucosal vaccines faces challenges, including barriers such as degrading enzymes, mucus interference, and clearance mechanisms. The field of mucosal vaccination is still in its early stages, and its advancement will significantly benefit from foundational inquiries into immune activation mechanisms and the innovation of delivery technologies for optimal efficacy. It is highly central to design efficient systems for mucosal vaccine development, herein, this article offers the insights towards the status, bottlenecks and solutions in this field, the intricacies of the immune response, fundamental mechanisms, applications of the delivery strategies for various forms of mucosal vaccines are explored. Collectively, this review conducts systematical analysis on biological and chemical strategies designed to augment vaccine uptake across mucosal tissues, antigen design and delivery methods strengthening vaccination efficacy, with emphasis on the emerging mRNA mucosal vaccines, offering new insights into recent advancements, trends and future scenarios, aiming to harness mucosal immunity (MI) for comprehensive protection against infections and other diseases.
Mucosal vaccines would be game-changing for blocking pathogenic transmission, prompting protection where microorganism first enters that those intramuscular ones could not be able to achieve. The exploration of the vaccines at mucosal surfaces is gaining momentum due to the unique immune reservoir they offer in a minimally invasive manner. Nevertheless, the application of mucosal vaccines faces challenges, including barriers such as degrading enzymes, mucus interference, and clearance mechanisms. The field of mucosal vaccination is still in its early stages, and its advancement will significantly benefit from foundational inquiries into immune activation mechanisms and the innovation of delivery technologies for optimal efficacy. It is highly central to design efficient systems for mucosal vaccine development, herein, this article offers the insights towards the status, bottlenecks and solutions in this field, the intricacies of the immune response, fundamental mechanisms, applications of the delivery strategies for various forms of mucosal vaccines are explored. Collectively, this review conducts systematical analysis on biological and chemical strategies designed to augment vaccine uptake across mucosal tissues, antigen design and delivery methods strengthening vaccination efficacy, with emphasis on the emerging mRNA mucosal vaccines, offering new insights into recent advancements, trends and future scenarios, aiming to harness mucosal immunity (MI) for comprehensive protection against infections and other diseases.
2026, 37(3): 111298
doi: 10.1016/j.cclet.2025.111298
Abstract:
As an essential micronutrient, selenium (Se) plays crucial roles in maintaining cutaneous homeostasis through multifaceted mechanisms including redox regulation, immunomodulation, and anti-tumorigenic activity. While epidemiological and preclinical studies substantiate the therapeutic promise of Se in managing dermatological pathologies such as psoriasis, atopic dermatitis, and cutaneous malignancies, conventional Se formulations face translational challenges due to suboptimal bioavailability and dose-limiting hepatotoxicity. Recent advancements in nanobiotechnology have catalyzed the emergence of Se nanoparticles (SeNPs) as next-generation therapeutic platforms. These engineered nanostructures exhibit superior pharmacokinetic profiles characterized by enhanced epithelial permeability, stimuli-responsive drug release kinetics, and targeted biodistribution. This comprehensive review systematically examines: (1) pathophysiological barriers in dermatologic therapy; (2) Se-mediated molecular circuitry; (3) nano-enabled theranostic breakthroughs; (4) preclinical validation of SeNPs-based combinatorial regimens. By critically evaluating structure-activity relationships of various nanoformulations, we delineate a translational roadmap bridging nanomaterial design principles with clinical needs in precision dermatology. This synthesis aims to accelerate the clinical deployment of Se nanotechnology while addressing key regulatory and manufacturing challenges.
As an essential micronutrient, selenium (Se) plays crucial roles in maintaining cutaneous homeostasis through multifaceted mechanisms including redox regulation, immunomodulation, and anti-tumorigenic activity. While epidemiological and preclinical studies substantiate the therapeutic promise of Se in managing dermatological pathologies such as psoriasis, atopic dermatitis, and cutaneous malignancies, conventional Se formulations face translational challenges due to suboptimal bioavailability and dose-limiting hepatotoxicity. Recent advancements in nanobiotechnology have catalyzed the emergence of Se nanoparticles (SeNPs) as next-generation therapeutic platforms. These engineered nanostructures exhibit superior pharmacokinetic profiles characterized by enhanced epithelial permeability, stimuli-responsive drug release kinetics, and targeted biodistribution. This comprehensive review systematically examines: (1) pathophysiological barriers in dermatologic therapy; (2) Se-mediated molecular circuitry; (3) nano-enabled theranostic breakthroughs; (4) preclinical validation of SeNPs-based combinatorial regimens. By critically evaluating structure-activity relationships of various nanoformulations, we delineate a translational roadmap bridging nanomaterial design principles with clinical needs in precision dermatology. This synthesis aims to accelerate the clinical deployment of Se nanotechnology while addressing key regulatory and manufacturing challenges.
2026, 37(3): 111431
doi: 10.1016/j.cclet.2025.111431
Abstract:
Sewage sludge (SS) is a by-product of wastewater treatment. Recovering resources from SS, particularly nitrogen (N) and phosphorus (P), is emerging as a crucial approach to promoting carbon neutrality within the treatment sector. This need necessitates developing methods that not only recover these vital nutrients but also mitigate the release of nitrogenous pollutants. Our review addresses the recovery of N and P from SS, aiming to reduce the dissemination of harmful nitrogen compounds into the environment. We provide a comprehensive analysis of techniques ranging from ultrasonic treatment and aerobic/anaerobic digestion to thermochemical conversion methods such as incineration, pyrolysis, and gasification. We also evaluate strategies like bio-enhanced phosphorus recovery and electrochemical methods, with the dual goal of diminishing nitrogen emissions and reclaiming phosphorus from SS. The review synthesizes advanced techniques and strategies to support emission control and resource recovery, offering a comprehensive guide for advancing SS treatment technologies.
Sewage sludge (SS) is a by-product of wastewater treatment. Recovering resources from SS, particularly nitrogen (N) and phosphorus (P), is emerging as a crucial approach to promoting carbon neutrality within the treatment sector. This need necessitates developing methods that not only recover these vital nutrients but also mitigate the release of nitrogenous pollutants. Our review addresses the recovery of N and P from SS, aiming to reduce the dissemination of harmful nitrogen compounds into the environment. We provide a comprehensive analysis of techniques ranging from ultrasonic treatment and aerobic/anaerobic digestion to thermochemical conversion methods such as incineration, pyrolysis, and gasification. We also evaluate strategies like bio-enhanced phosphorus recovery and electrochemical methods, with the dual goal of diminishing nitrogen emissions and reclaiming phosphorus from SS. The review synthesizes advanced techniques and strategies to support emission control and resource recovery, offering a comprehensive guide for advancing SS treatment technologies.
2026, 37(3): 111549
doi: 10.1016/j.cclet.2025.111549
Abstract:
Residual ions introduced during catalyst synthesis can significantly impact both the structure and performance of the catalyst. Despite their crucial role, the effects of these residual ions are frequently overlooked in catalyst design and optimization. This review systematically surveys the characteristics and sources of typical residual ions in catalytic systems, including halogen anions, acidic anions, and alkali metal cations. It also examines their impact on both the supports and active metals of supported catalysts, as well as the alterations in surface, crystal structure, and chemical states of non-supported catalysts. The effects of residual ions on the performance of these catalysts in catalytic reactions such as oxidation and hydrogenation are discussed in detail. Additionally, the influence mechanism of residual ions on the catalysts is further explored, with a focus on their promotion and inhibition roles in catalytic processes, thus providing insights for the development of more efficient and durable catalysts. A summary finally provides an outlook on future approaches to advance catalyst preparation and mitigate the adverse effects of residual ions in catalysis.
Residual ions introduced during catalyst synthesis can significantly impact both the structure and performance of the catalyst. Despite their crucial role, the effects of these residual ions are frequently overlooked in catalyst design and optimization. This review systematically surveys the characteristics and sources of typical residual ions in catalytic systems, including halogen anions, acidic anions, and alkali metal cations. It also examines their impact on both the supports and active metals of supported catalysts, as well as the alterations in surface, crystal structure, and chemical states of non-supported catalysts. The effects of residual ions on the performance of these catalysts in catalytic reactions such as oxidation and hydrogenation are discussed in detail. Additionally, the influence mechanism of residual ions on the catalysts is further explored, with a focus on their promotion and inhibition roles in catalytic processes, thus providing insights for the development of more efficient and durable catalysts. A summary finally provides an outlook on future approaches to advance catalyst preparation and mitigate the adverse effects of residual ions in catalysis.
2026, 37(3): 111628
doi: 10.1016/j.cclet.2025.111628
Abstract:
Alzheimer’s disease (AD) is a progressive neurodegenerative disorder characterized by complex pathological features such as amyloid-β plaques and tau tangles. Early and accurate diagnosis is crucial for effective intervention, yet remains challenging. This review focuses on current and emerging imaging modalities used in AD detection, including positron emission tomography, single-photon emission computed tomography, magnetic resonance imaging (MRI), fluorescence imaging, photoacoustic imaging, and mass spectrometry imaging, with an emphasis on their mechanisms, advantages, and limitations. Special attention is given to the integration of nanotechnology with imaging platforms, highlighting how nanomaterials enhance diagnostic specificity, sensitivity, stability and therapeutic potential. The review also explores recent advances in multimodal imaging, artificial intelligence-assisted diagnostics, and future directions toward personalized and other non-invasive strategies for early AD diagnosis.
Alzheimer’s disease (AD) is a progressive neurodegenerative disorder characterized by complex pathological features such as amyloid-β plaques and tau tangles. Early and accurate diagnosis is crucial for effective intervention, yet remains challenging. This review focuses on current and emerging imaging modalities used in AD detection, including positron emission tomography, single-photon emission computed tomography, magnetic resonance imaging (MRI), fluorescence imaging, photoacoustic imaging, and mass spectrometry imaging, with an emphasis on their mechanisms, advantages, and limitations. Special attention is given to the integration of nanotechnology with imaging platforms, highlighting how nanomaterials enhance diagnostic specificity, sensitivity, stability and therapeutic potential. The review also explores recent advances in multimodal imaging, artificial intelligence-assisted diagnostics, and future directions toward personalized and other non-invasive strategies for early AD diagnosis.
2026, 37(3): 111723
doi: 10.1016/j.cclet.2025.111723
Abstract:
Osteoarthritis (OA), as a multifactorial degenerative joint disorder, is pathologically characterized by structural joint destruction and functional impairment, ultimately leading to chronic locomotor dysfunction. Clinically, intra-articular (IA) injection remains the preferred approach for localized OA treatment due to its advantages of high bioavailability, precise dosing, and minimal systemic side effects. However, frequent IA interventions may induce complications such as patient discomfort, pain, or even infection. Hydrogel materials, with their unique hydrophilic network structures and viscoelastic mechanical properties, are regarded as ideal joint cavity supplements and efficient drug carriers, making them a promising platform for localized therapy. This article systematically reviews recent advances in injectable hydrogel-based OA treatments. First, from a materials science perspective, it comprehensively analyzes the classification of injectable hydrogels (natural/synthetic polymers), their crosslinking mechanisms (chemical/physical/ionic), and environmental responsiveness (temperature/pH/ion triggers). Subsequently, it delves into their therapeutic potential in OA management, covering three major applications: controlled release of small-molecule drugs, cell delivery, and gene therapy. Despite the demonstrated prospects of hydrogels in OA therapy, attributed to their mechanical adaptability, biodegradability, and biocompatibility, key scientific challenges persist, particularly in maintaining IA mechanical homeostasis and long-term structural integrity. The review emphasizes that future research should focus on optimizing hydrogel architectures and enhancing delivery system functionalities to achieve sustained therapeutic efficacy in OA.
Osteoarthritis (OA), as a multifactorial degenerative joint disorder, is pathologically characterized by structural joint destruction and functional impairment, ultimately leading to chronic locomotor dysfunction. Clinically, intra-articular (IA) injection remains the preferred approach for localized OA treatment due to its advantages of high bioavailability, precise dosing, and minimal systemic side effects. However, frequent IA interventions may induce complications such as patient discomfort, pain, or even infection. Hydrogel materials, with their unique hydrophilic network structures and viscoelastic mechanical properties, are regarded as ideal joint cavity supplements and efficient drug carriers, making them a promising platform for localized therapy. This article systematically reviews recent advances in injectable hydrogel-based OA treatments. First, from a materials science perspective, it comprehensively analyzes the classification of injectable hydrogels (natural/synthetic polymers), their crosslinking mechanisms (chemical/physical/ionic), and environmental responsiveness (temperature/pH/ion triggers). Subsequently, it delves into their therapeutic potential in OA management, covering three major applications: controlled release of small-molecule drugs, cell delivery, and gene therapy. Despite the demonstrated prospects of hydrogels in OA therapy, attributed to their mechanical adaptability, biodegradability, and biocompatibility, key scientific challenges persist, particularly in maintaining IA mechanical homeostasis and long-term structural integrity. The review emphasizes that future research should focus on optimizing hydrogel architectures and enhancing delivery system functionalities to achieve sustained therapeutic efficacy in OA.
2026, 37(3): 111739
doi: 10.1016/j.cclet.2025.111739
Abstract:
Organoboron compounds have garnered significant attention in the fields of organic synthesis, materials science, medicinal chemistry and fine chemicals. In the past few decades, transition metal-catalyzed C–H borylation has been developed rapidly and efficiently. In recent years, in order to explore eco-friendly, economical and efficient method for constructing C–B bond, chemists are dedicated to developing metal-free BX3-mediated borylation. In this review, we present a systematic and comprehensive overview of the borylation driven by BX3 with different directing group auxiliary in the fields of organic synthesis and boron-containing organic materials since 2010, including (1) nitrogen directed C–H borylation, (2) oxygen directed C–H borylation, (3) sulfur directed C–H borylation and (4) phosphorus directed C–H borylation. The methods of borylation processes as well as the substance scopes, limits, and mechanisms of these routes are also discussed.
Organoboron compounds have garnered significant attention in the fields of organic synthesis, materials science, medicinal chemistry and fine chemicals. In the past few decades, transition metal-catalyzed C–H borylation has been developed rapidly and efficiently. In recent years, in order to explore eco-friendly, economical and efficient method for constructing C–B bond, chemists are dedicated to developing metal-free BX3-mediated borylation. In this review, we present a systematic and comprehensive overview of the borylation driven by BX3 with different directing group auxiliary in the fields of organic synthesis and boron-containing organic materials since 2010, including (1) nitrogen directed C–H borylation, (2) oxygen directed C–H borylation, (3) sulfur directed C–H borylation and (4) phosphorus directed C–H borylation. The methods of borylation processes as well as the substance scopes, limits, and mechanisms of these routes are also discussed.
2026, 37(3): 111793
doi: 10.1016/j.cclet.2025.111793
Abstract:
The asymmetric catalytic synthesis of planar chiral ferrocene derivatives has received dramatic attention in recent years. Transition metal-catalyzed asymmetric cross-coupling reactions and CH functionalization reactions have played significant roles in the stereoselective construction of planar chiral ferrocene derivatives. Transition metals such as copper, palladium, rhodium, iridium, gold, and platinum have been adopted as the effective catalysts in combination with various chiral ligands to achieve satisfactory yields and stereoselectivity. Organic catalysts have also shown great potential in the synthesis of planar chiral ferrocenes. Chiral amines and N-heterocyclic carbenes (NHCs) have been the key catalysts for facile access to multi-functional ferrocene derivatives. Some of the planar chiral ferrocene molecules obtained from the above methods have demonstrated promising applications in the development of novel ligands for asymmetric synthesis and pesticides for plant protection. This review provides an overview on the key progresses in the catalytic synthesis of planar chiral ferrocene derivatives using transition metal catalysts and organic catalysts. The merits, challenges and potential directions in the future development within this highly active research field are also discussed at the end of this review.
The asymmetric catalytic synthesis of planar chiral ferrocene derivatives has received dramatic attention in recent years. Transition metal-catalyzed asymmetric cross-coupling reactions and CH functionalization reactions have played significant roles in the stereoselective construction of planar chiral ferrocene derivatives. Transition metals such as copper, palladium, rhodium, iridium, gold, and platinum have been adopted as the effective catalysts in combination with various chiral ligands to achieve satisfactory yields and stereoselectivity. Organic catalysts have also shown great potential in the synthesis of planar chiral ferrocenes. Chiral amines and N-heterocyclic carbenes (NHCs) have been the key catalysts for facile access to multi-functional ferrocene derivatives. Some of the planar chiral ferrocene molecules obtained from the above methods have demonstrated promising applications in the development of novel ligands for asymmetric synthesis and pesticides for plant protection. This review provides an overview on the key progresses in the catalytic synthesis of planar chiral ferrocene derivatives using transition metal catalysts and organic catalysts. The merits, challenges and potential directions in the future development within this highly active research field are also discussed at the end of this review.
2026, 37(3): 111842
doi: 10.1016/j.cclet.2025.111842
Abstract:
Nanozymes are nanomaterials with enzyme-like catalytic activities that have rapidly advanced in the biomedical field in recent years due to their high stability, low cost, and catalytic versatility. As promising alternatives to natural enzymes, nanozymes have demonstrated unique advantages in infection control, cancer therapy, and tissue regeneration. This review systematically summarizes key advances in recent years in nanozyme-based catalytic therapeutics. We focus on their mechanisms and applications in combating bacterial, viral, and fungal infections via membrane lipid peroxidation, protein/genome damage, and biofilm disruption; in cancer treatment through chemodynamic therapy (CDT), tumor microenvironment modulation, and multimodal synergistic strategies; and in bone regeneration through antioxidant, anti-inflammatory, and osteoinductive functions. Moreover, we highlight the integration of nanozymes with hydrogels, scaffolds, and microrobotic systems to enhance therapeutic outcomes. Finally, current challenges such as targeting specificity, in vivo catalytic control, biosafety, and clinical translation are discussed to provide a comprehensive roadmap for future research and clinical development in catalytic nanomedicine.
Nanozymes are nanomaterials with enzyme-like catalytic activities that have rapidly advanced in the biomedical field in recent years due to their high stability, low cost, and catalytic versatility. As promising alternatives to natural enzymes, nanozymes have demonstrated unique advantages in infection control, cancer therapy, and tissue regeneration. This review systematically summarizes key advances in recent years in nanozyme-based catalytic therapeutics. We focus on their mechanisms and applications in combating bacterial, viral, and fungal infections via membrane lipid peroxidation, protein/genome damage, and biofilm disruption; in cancer treatment through chemodynamic therapy (CDT), tumor microenvironment modulation, and multimodal synergistic strategies; and in bone regeneration through antioxidant, anti-inflammatory, and osteoinductive functions. Moreover, we highlight the integration of nanozymes with hydrogels, scaffolds, and microrobotic systems to enhance therapeutic outcomes. Finally, current challenges such as targeting specificity, in vivo catalytic control, biosafety, and clinical translation are discussed to provide a comprehensive roadmap for future research and clinical development in catalytic nanomedicine.
2026, 37(3): 111905
doi: 10.1016/j.cclet.2025.111905
Abstract:
The advent of all-solid-state lithium metal batteries (ASSLMBs) holds promise for overcoming the safety hazards and energy density limitations faced by traditional lithium-ion batteries, thereby advancing the industrialization of next-generation energy storage technologies with high safety and specific energy. However, during practical application, three core challenges persist at the interface between the solid-state electrolytes (SSEs) and the lithium metal anode (LMA): Poor physical contact, interfacial side reactions, and growth of lithium dendrites. These interfacial issues constrain the overall performance of ASSLMBs and impede the commercialization process of this battery system. This review begins by examining the underlying mechanisms responsible for the interfacial problems between SSEs and LMA. Building on this foundation, optimization strategies and recent research progress are systematically introduced, classified according to the interfacial components: SSE-side optimizations, interface engineering, and LMA-side treatments. Finally, future research directions, strategies, and optimization schemes addressing the interfacial challenges between SSEs and LMA are prospected. This analysis aims to facilitate critical breakthroughs in the stability, cycling lifespan, and energy density of ASSLMBs, promoting their transition from laboratory innovation to commercial application.
The advent of all-solid-state lithium metal batteries (ASSLMBs) holds promise for overcoming the safety hazards and energy density limitations faced by traditional lithium-ion batteries, thereby advancing the industrialization of next-generation energy storage technologies with high safety and specific energy. However, during practical application, three core challenges persist at the interface between the solid-state electrolytes (SSEs) and the lithium metal anode (LMA): Poor physical contact, interfacial side reactions, and growth of lithium dendrites. These interfacial issues constrain the overall performance of ASSLMBs and impede the commercialization process of this battery system. This review begins by examining the underlying mechanisms responsible for the interfacial problems between SSEs and LMA. Building on this foundation, optimization strategies and recent research progress are systematically introduced, classified according to the interfacial components: SSE-side optimizations, interface engineering, and LMA-side treatments. Finally, future research directions, strategies, and optimization schemes addressing the interfacial challenges between SSEs and LMA are prospected. This analysis aims to facilitate critical breakthroughs in the stability, cycling lifespan, and energy density of ASSLMBs, promoting their transition from laboratory innovation to commercial application.
2026, 37(3): 111944
doi: 10.1016/j.cclet.2025.111944
Abstract:
Polymer surface modification constitutes a pivotal strategy for enhancing the efficacy of nanomedicine delivery, where intentional modifications (e.g., PEGylation, hyaluronic acid coating) are designed to optimize nanocarrier performance. However, conventional approaches remain constrained by the impermeable stratum corneum in transdermal applications. Dissolving microneedles (DMNs) circumvent this barrier by creating transient microchannels, thereby offering an innovative route for cutaneous nanocarriers administration. Nevertheless, the DMN polymeric matrix may unintentionally alter the physicochemical attributes of loaded nanocarriers via non-covalent interactions, giving rise to a distinct “polymer modification effect” (PME) that differs from purposeful surface engineering. Such unintended interfacial phenomena can modulate nanocarrier characteristics and, consequently, dictate their in vivo fate, including release kinetics, biodistribution, clearance, cellular uptake, and other interactions with the biological system. Herein, we review documented cases of DMN polymer-nanocarrier modifications, elucidate the underlying mechanisms and implications of PME, and propose rational strategies for its precise regulation. This conceptual framework is expected to guide the rational design of next-generation nanocarrier-loaded DMN delivery systems.
Polymer surface modification constitutes a pivotal strategy for enhancing the efficacy of nanomedicine delivery, where intentional modifications (e.g., PEGylation, hyaluronic acid coating) are designed to optimize nanocarrier performance. However, conventional approaches remain constrained by the impermeable stratum corneum in transdermal applications. Dissolving microneedles (DMNs) circumvent this barrier by creating transient microchannels, thereby offering an innovative route for cutaneous nanocarriers administration. Nevertheless, the DMN polymeric matrix may unintentionally alter the physicochemical attributes of loaded nanocarriers via non-covalent interactions, giving rise to a distinct “polymer modification effect” (PME) that differs from purposeful surface engineering. Such unintended interfacial phenomena can modulate nanocarrier characteristics and, consequently, dictate their in vivo fate, including release kinetics, biodistribution, clearance, cellular uptake, and other interactions with the biological system. Herein, we review documented cases of DMN polymer-nanocarrier modifications, elucidate the underlying mechanisms and implications of PME, and propose rational strategies for its precise regulation. This conceptual framework is expected to guide the rational design of next-generation nanocarrier-loaded DMN delivery systems.
2026, 37(3): 112021
doi: 10.1016/j.cclet.2025.112021
Abstract:
The hydrogen evolution reaction (HER) is a pivotal process for clean energy conversion, yet the development of efficient and cost-effective electrocatalysts remains a major challenge. Alloy catalysts, with their tunable electronic properties and promising catalytic performance, have shown great potential for HER. However, the design of component types and ratios, along with structural optimization, has largely relied on traditional trial-and-error approaches, which are very complex and time-consuming. The rise of machine learning (ML) provides an efficient strategy for discovering and optimizing alloy catalysts by enabling rapid analysis of extensive experimental and simulation datasets. This review highlights the recent advances in applying ML techniques for the design and optimization of alloy electrocatalysts for HER, covering binary and multinary (ternary, quaternary and high-entropy alloys). In particular, by employing supervised learning and deep learning techniques, ML has achieved remarkable success in the rapid screening of alloy catalysts and in improving prediction accuracy. It also demonstrates the merit and capability of ML in accelerating this process. In the end, we discuss current challenges and future prospects for integrating ML into advanced HER catalysis, highlighting its potential to revolutionize catalyst development and promote sustainable hydrogen energy solutions.
The hydrogen evolution reaction (HER) is a pivotal process for clean energy conversion, yet the development of efficient and cost-effective electrocatalysts remains a major challenge. Alloy catalysts, with their tunable electronic properties and promising catalytic performance, have shown great potential for HER. However, the design of component types and ratios, along with structural optimization, has largely relied on traditional trial-and-error approaches, which are very complex and time-consuming. The rise of machine learning (ML) provides an efficient strategy for discovering and optimizing alloy catalysts by enabling rapid analysis of extensive experimental and simulation datasets. This review highlights the recent advances in applying ML techniques for the design and optimization of alloy electrocatalysts for HER, covering binary and multinary (ternary, quaternary and high-entropy alloys). In particular, by employing supervised learning and deep learning techniques, ML has achieved remarkable success in the rapid screening of alloy catalysts and in improving prediction accuracy. It also demonstrates the merit and capability of ML in accelerating this process. In the end, we discuss current challenges and future prospects for integrating ML into advanced HER catalysis, highlighting its potential to revolutionize catalyst development and promote sustainable hydrogen energy solutions.
2026, 37(3): 112040
doi: 10.1016/j.cclet.2025.112040
Abstract:
Transforming sunlight into renewable energy sources like hydrogen and methane through photocatalytic water splitting and the CO2 conversion presents a promising prospect to tackle energy scarcity and environmental pollution caused by burning fossil fuels. As the core of the photocatalytic technique, photocatalysts design is most significant for acquiring the desirable catalytic performance and target products. Photonic crystals, also denoted as inverse opals and three-dimensionally ordered macroporous materials (3DOM), have been extensively applied in photocatalytic fields due to their distinct advantages. Specifically, photonic crystal possesses slow photons effect, rich reactive sites, and well-interconnected inner channels. Among the above advantages, the slow photons effect contributes the most essential role for accelerating photocatalytic reaction. However, how to design materials with maximized slow photons effect upon specific wavelength illumination is still in the infancy. Although some reviews about 3DOM photocatalysts have been published, a critical review focusing on tunable slow photons effects for efficient photocatalysis is still lacking. In this review, we highlighted recent advances in slow photons effect in boosting solar energy conversion. Meanwhile, the relevant mechanism and fundamentals of the slow photons effect are discussed. Finally, we present our vision of the future developments and challenges in this exciting research field.
Transforming sunlight into renewable energy sources like hydrogen and methane through photocatalytic water splitting and the CO2 conversion presents a promising prospect to tackle energy scarcity and environmental pollution caused by burning fossil fuels. As the core of the photocatalytic technique, photocatalysts design is most significant for acquiring the desirable catalytic performance and target products. Photonic crystals, also denoted as inverse opals and three-dimensionally ordered macroporous materials (3DOM), have been extensively applied in photocatalytic fields due to their distinct advantages. Specifically, photonic crystal possesses slow photons effect, rich reactive sites, and well-interconnected inner channels. Among the above advantages, the slow photons effect contributes the most essential role for accelerating photocatalytic reaction. However, how to design materials with maximized slow photons effect upon specific wavelength illumination is still in the infancy. Although some reviews about 3DOM photocatalysts have been published, a critical review focusing on tunable slow photons effects for efficient photocatalysis is still lacking. In this review, we highlighted recent advances in slow photons effect in boosting solar energy conversion. Meanwhile, the relevant mechanism and fundamentals of the slow photons effect are discussed. Finally, we present our vision of the future developments and challenges in this exciting research field.
2026, 37(3): 112049
doi: 10.1016/j.cclet.2025.112049
Abstract:
Essential oils (EOs) are widely present in aromatic plants and possess a wide range of significant pharmacological activities such as antibacterial, antioxidant and anti-tumor properties. They have broad application prospects in medical care, food, agriculture and other fields. However, their poor stability poses substantial challenges that significantly hinder their development and practical application. Metal-organic framework materials (MOFs), characterized by highly controllable structures, large specific surface areas, and stimuli-responsive release properties, have been extensively utilized in various fields such as drug delivery and food preservation. Due to their capacity to encapsulate and deliver EOs, MOFs have garnered considerable attention. In this review, we systematically summarize the structural features, types, and characteristics of MOFs, as well as the recent advancements in their application for controlled EO release. Furthermore, we focus on discussing engineering strategies aimed at enhancing the encapsulation, release, and delivery of EOs using MOFs. Finally, we briefly outline the existing challenges in the delivery of EOs using MOFs and present well-reasoned insights into prospective directions for future research.
Essential oils (EOs) are widely present in aromatic plants and possess a wide range of significant pharmacological activities such as antibacterial, antioxidant and anti-tumor properties. They have broad application prospects in medical care, food, agriculture and other fields. However, their poor stability poses substantial challenges that significantly hinder their development and practical application. Metal-organic framework materials (MOFs), characterized by highly controllable structures, large specific surface areas, and stimuli-responsive release properties, have been extensively utilized in various fields such as drug delivery and food preservation. Due to their capacity to encapsulate and deliver EOs, MOFs have garnered considerable attention. In this review, we systematically summarize the structural features, types, and characteristics of MOFs, as well as the recent advancements in their application for controlled EO release. Furthermore, we focus on discussing engineering strategies aimed at enhancing the encapsulation, release, and delivery of EOs using MOFs. Finally, we briefly outline the existing challenges in the delivery of EOs using MOFs and present well-reasoned insights into prospective directions for future research.
2026, 37(3): 112179
doi: 10.1016/j.cclet.2025.112179
Abstract:
Electrochemical reduction of carbon dioxide (CO2RR) into formate and related products is a crucial strategy for sustainable carbon utilization, yet the development of catalysts with both high efficiency and durability remains a central challenge. Among available candidates, two-dimensional (2D) bismuth (Bi) nanosheets stand out because of their earth abundance, low toxicity, and unique ability to stabilize *OCHO intermediates. In this review, we systematically summarize recent advances in the controlled synthesis of 2D Bi nanosheets, covering bottom-up chemical and electrochemical routes, top-down exfoliation, and physical/thermal methods, and highlight the application strategies that enable performance optimization, including defect/strain engineering, heteroatom doping, interface construction, heterostructure coupling, in situ reconstruction, and microenvironment regulation. We further integrate mechanistic insights from in situ/operando characterizations and density functional theory, which clarify the real active sites, dynamic reconstruction, and structure–activity relationships. Finally, we provide a forward-looking perspective on atomic-level structural control, understanding and regulating reconstruction, multi-scale architecture integration, expanding product selectivity beyond formate, device-level optimization, and data-driven catalyst discovery. By bridging synthesis, application strategies, and mechanistic understanding, this timely review establishes a comprehensive framework to guide the rational design of 2D Bi nanosheets and accelerate their translation toward industrially relevant CO2 electroreduction.
Electrochemical reduction of carbon dioxide (CO2RR) into formate and related products is a crucial strategy for sustainable carbon utilization, yet the development of catalysts with both high efficiency and durability remains a central challenge. Among available candidates, two-dimensional (2D) bismuth (Bi) nanosheets stand out because of their earth abundance, low toxicity, and unique ability to stabilize *OCHO intermediates. In this review, we systematically summarize recent advances in the controlled synthesis of 2D Bi nanosheets, covering bottom-up chemical and electrochemical routes, top-down exfoliation, and physical/thermal methods, and highlight the application strategies that enable performance optimization, including defect/strain engineering, heteroatom doping, interface construction, heterostructure coupling, in situ reconstruction, and microenvironment regulation. We further integrate mechanistic insights from in situ/operando characterizations and density functional theory, which clarify the real active sites, dynamic reconstruction, and structure–activity relationships. Finally, we provide a forward-looking perspective on atomic-level structural control, understanding and regulating reconstruction, multi-scale architecture integration, expanding product selectivity beyond formate, device-level optimization, and data-driven catalyst discovery. By bridging synthesis, application strategies, and mechanistic understanding, this timely review establishes a comprehensive framework to guide the rational design of 2D Bi nanosheets and accelerate their translation toward industrially relevant CO2 electroreduction.
2026, 37(3): 112181
doi: 10.1016/j.cclet.2025.112181
Abstract:
Porous materials, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), aerogels, and porous metal oxides, have been extensively explored as versatile platforms for energy conversion, storage, and environmental applications. Over the past five years, remarkable advances have been achieved in the design, synthesis, and functional optimization of these materials, opening new opportunities for practical implementation. In this roadmap, we focus on several key subtopics, including MOFs and COFs for supercapacitors and batteries, electrocatalysis and photocatalysis, heterojunction materials for charge separation, advanced electrocatalysts and photocatalysts based on aerogels, carbon aerogels for environmental remediation, and porous metal oxide nanomaterials for electrocatalysis. The current status, challenges, and opportunities in these areas are systematically summarized. Special attention is given to mechanistic insights, stability enhancement, conductivity improvement, and scalable fabrication strategies that are essential for bridging fundamental research and real-world applications. We believe this roadmap will provide valuable suggestions and updated knowledge for researchers, and offer useful inspiration to accelerate the development of porous materials for sustainable energy and environmental technologies toward 2030.
Porous materials, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), aerogels, and porous metal oxides, have been extensively explored as versatile platforms for energy conversion, storage, and environmental applications. Over the past five years, remarkable advances have been achieved in the design, synthesis, and functional optimization of these materials, opening new opportunities for practical implementation. In this roadmap, we focus on several key subtopics, including MOFs and COFs for supercapacitors and batteries, electrocatalysis and photocatalysis, heterojunction materials for charge separation, advanced electrocatalysts and photocatalysts based on aerogels, carbon aerogels for environmental remediation, and porous metal oxide nanomaterials for electrocatalysis. The current status, challenges, and opportunities in these areas are systematically summarized. Special attention is given to mechanistic insights, stability enhancement, conductivity improvement, and scalable fabrication strategies that are essential for bridging fundamental research and real-world applications. We believe this roadmap will provide valuable suggestions and updated knowledge for researchers, and offer useful inspiration to accelerate the development of porous materials for sustainable energy and environmental technologies toward 2030.
2026, 37(3): 112242
doi: 10.1016/j.cclet.2025.112242
Abstract:
Two-dimensional (2D) materials have rapidly emerged as transformative platforms for energy storage and conversion, owing to their atomic-scale thickness, tunable electronic structures, and versatile chemical functionalities. Over the past five years, remarkable advances in material synthesis, interface engineering, and device integration have unlocked new opportunities, yet challenges in stability, scalability, and performance optimization remain. In this roadmap, we provide an updated perspective toward 2030, systematically reviewing eleven representative 2D material classes, which can be broadly grouped into carbon-based materials, inorganic semiconductors, framework materials, and layered nanosheet systems. Their opportunities and challenges in electrochemical energy storage, photocatalysis, and electrocatalysis are highlighted. We believe this roadmap can enrich the development of 2D materials for sustainable energy technologies, and provide useful guidance for both fundamental studies and practical applications in the coming decade.
Two-dimensional (2D) materials have rapidly emerged as transformative platforms for energy storage and conversion, owing to their atomic-scale thickness, tunable electronic structures, and versatile chemical functionalities. Over the past five years, remarkable advances in material synthesis, interface engineering, and device integration have unlocked new opportunities, yet challenges in stability, scalability, and performance optimization remain. In this roadmap, we provide an updated perspective toward 2030, systematically reviewing eleven representative 2D material classes, which can be broadly grouped into carbon-based materials, inorganic semiconductors, framework materials, and layered nanosheet systems. Their opportunities and challenges in electrochemical energy storage, photocatalysis, and electrocatalysis are highlighted. We believe this roadmap can enrich the development of 2D materials for sustainable energy technologies, and provide useful guidance for both fundamental studies and practical applications in the coming decade.
2026, 37(3): 112243
doi: 10.1016/j.cclet.2025.112243
Abstract:
This review comprehensively summarizes the latest advancements in the synthesis and multifaceted applications of metal-organic frameworks (MOFs) for clean water. It systematically explores scalable synthesis methods, from solvothermal to green mechanochemical routes, and highlights the innovative transformation of waste into high-value MOFs. The article delves into the diverse functionalities of MOFs in water remediation, including the adsorptive and catalytic removal of heavy metals, organic pollutants, pharmaceuticals, PFASs, and micro/nano-plastics. Applications in sensing, radionuclide separation, oil-water separation, and advanced membrane technologies are also detailed. Furthermore, emerging roles in water capture, algal inhibition and resource recovery are discussed. Finally, the review provides a critical perspective on future challenges and opportunities, emphasizing sustainable synthesis, life-cycle assessment, and the integration of AI for the intelligent design of next-generation MOFs, paving the way for their transition from laboratory research to real-world water treatment solutions.
This review comprehensively summarizes the latest advancements in the synthesis and multifaceted applications of metal-organic frameworks (MOFs) for clean water. It systematically explores scalable synthesis methods, from solvothermal to green mechanochemical routes, and highlights the innovative transformation of waste into high-value MOFs. The article delves into the diverse functionalities of MOFs in water remediation, including the adsorptive and catalytic removal of heavy metals, organic pollutants, pharmaceuticals, PFASs, and micro/nano-plastics. Applications in sensing, radionuclide separation, oil-water separation, and advanced membrane technologies are also detailed. Furthermore, emerging roles in water capture, algal inhibition and resource recovery are discussed. Finally, the review provides a critical perspective on future challenges and opportunities, emphasizing sustainable synthesis, life-cycle assessment, and the integration of AI for the intelligent design of next-generation MOFs, paving the way for their transition from laboratory research to real-world water treatment solutions.
2026, 37(3): 112037
doi: 10.1016/j.cclet.2025.112037
Abstract:
2026, 37(3): 112132
doi: 10.1016/j.cclet.2025.112132
Abstract:
