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2023 Volume 34 Issue 2
2023, 34(2): 107228
doi: 10.1016/j.cclet.2022.02.033
Abstract:
Defect-rich, highly porous two-dimensional carbon nanosheets (CNS) have attracted tremendous research interests in catalysis and environmental purification and other fields, because of their unique micromorphology, chemical stability and high specific surface area. Herein, in this work, we report a new solution to synthesize an ultrathin two-dimensional CNS with rich defects and abundant pores via two-step etching the Ti3AlC2 with the help of I2 and NaOH. The CNS thickness, specific surface area and pore volume could be all tunable by adding the amount of I2. And the highest specific surface area and pore volume of the synthesized 2D CNS can be achieved 1134.4 m2/g and 0.80 cm3/g, with a thickness of only 0.64 nm and a yield of 35.9%. When employed as the anodes for lithium-ion batteries, the synthesized CNS anodes exhibit good cycling and rate capabilities. This work provides a novel and facile strategy for synthesizing highly porous and defective 2D carbon materials with good lithium storage properties.
Defect-rich, highly porous two-dimensional carbon nanosheets (CNS) have attracted tremendous research interests in catalysis and environmental purification and other fields, because of their unique micromorphology, chemical stability and high specific surface area. Herein, in this work, we report a new solution to synthesize an ultrathin two-dimensional CNS with rich defects and abundant pores via two-step etching the Ti3AlC2 with the help of I2 and NaOH. The CNS thickness, specific surface area and pore volume could be all tunable by adding the amount of I2. And the highest specific surface area and pore volume of the synthesized 2D CNS can be achieved 1134.4 m2/g and 0.80 cm3/g, with a thickness of only 0.64 nm and a yield of 35.9%. When employed as the anodes for lithium-ion batteries, the synthesized CNS anodes exhibit good cycling and rate capabilities. This work provides a novel and facile strategy for synthesizing highly porous and defective 2D carbon materials with good lithium storage properties.
2023, 34(2): 107230
doi: 10.1016/j.cclet.2022.02.035
Abstract:
Platinum exhibits high electrocatalytic activity toward various reactions but might be poisoned by some species. This communication reports a new finding that the electrocatalytic activity of platinum for methanol oxidation will be largely lost in a lead-contaminated environment. This activity loss is demonstrated in an electrochemical cell using a lead counter electrode for measuring the activity of platinum electrode towards methanol oxidation. The recorded methanol oxidation current in this cell is significantly decreased compared with that using a platinum counter electrode. The possible mechanism is related to the adsorption of trace lead ions from the lead counter electrode, as confirmed by comparing the calculated binding energies of platinum and lead ions with oxygen ion. This report is of great importance for reliably designing and efficiently managing direct methanol fuel cells, because trace lead might be present in various components in the fuel cell systems or in air and attention should be paid to its negative effect.
Platinum exhibits high electrocatalytic activity toward various reactions but might be poisoned by some species. This communication reports a new finding that the electrocatalytic activity of platinum for methanol oxidation will be largely lost in a lead-contaminated environment. This activity loss is demonstrated in an electrochemical cell using a lead counter electrode for measuring the activity of platinum electrode towards methanol oxidation. The recorded methanol oxidation current in this cell is significantly decreased compared with that using a platinum counter electrode. The possible mechanism is related to the adsorption of trace lead ions from the lead counter electrode, as confirmed by comparing the calculated binding energies of platinum and lead ions with oxygen ion. This report is of great importance for reliably designing and efficiently managing direct methanol fuel cells, because trace lead might be present in various components in the fuel cell systems or in air and attention should be paid to its negative effect.
2023, 34(2): 107231
doi: 10.1016/j.cclet.2022.02.036
Abstract:
Polyoxometalates (POMs) are important inorganic photochromic materials to be potentially applied in photo-induced switch, energy storage, and even the detection of light. However, due to the limited sensitivity of POMs, it is difficult to realize the photochromic response to weak visible light. In this paper, by the coordination of solvated Pb(II), a new structure-defined chain-like polyoxomolybdate complex of [(Pb(DMF)4)3(P2Mo18O62)2]n (Pb3Mo18, DMF = dimethylformamide) has been demonstrated by a facile solvent-diffusion approach. By virtue of interactions between Pb(DMF)4 and polyoxoanions, Pb3Mo18 shows an ultrasensitive photochromic response to weak visible lights and forms the reduced 'heteropoly blue' species through ligand-to-metal charge transfer (LMCT) process. A new mechanism is firstly proposed here that the 6s orbital lone electron pair on Pb(II) can effectively stabilize the generated hole of oxygen atoms as a result of O→Mo charge transfer. Through the proposed mechanism, the LMCT barrier is drastically lowered and allows the coloration to be occurred even upon weak visible light. Also, because the conductivity of Pb3Mo18 enhances with the increase of reduction extent, its electrochemical impedance signals are proportionally response to irradiation intensity. Especially, for the first time, the polyoxomolybdate composite can be used to detect weak visible light, in which the optical signal can be converted into electrical signal output. Moreover, Pb3Mo18 can be drip-coated on the surface of the screen printed chip electrode, which is facile to the detection of light by portable devices compatible with computers, mobile phones and other electronic equipment. This work not only highlights a new approach to the molecular design of photochromic POMs by the coordination of metal ions with the effect of inert electron pair, but also lays a foundation to extend the application of POMs as light signal sensors.
Polyoxometalates (POMs) are important inorganic photochromic materials to be potentially applied in photo-induced switch, energy storage, and even the detection of light. However, due to the limited sensitivity of POMs, it is difficult to realize the photochromic response to weak visible light. In this paper, by the coordination of solvated Pb(II), a new structure-defined chain-like polyoxomolybdate complex of [(Pb(DMF)4)3(P2Mo18O62)2]n (Pb3Mo18, DMF = dimethylformamide) has been demonstrated by a facile solvent-diffusion approach. By virtue of interactions between Pb(DMF)4 and polyoxoanions, Pb3Mo18 shows an ultrasensitive photochromic response to weak visible lights and forms the reduced 'heteropoly blue' species through ligand-to-metal charge transfer (LMCT) process. A new mechanism is firstly proposed here that the 6s orbital lone electron pair on Pb(II) can effectively stabilize the generated hole of oxygen atoms as a result of O→Mo charge transfer. Through the proposed mechanism, the LMCT barrier is drastically lowered and allows the coloration to be occurred even upon weak visible light. Also, because the conductivity of Pb3Mo18 enhances with the increase of reduction extent, its electrochemical impedance signals are proportionally response to irradiation intensity. Especially, for the first time, the polyoxomolybdate composite can be used to detect weak visible light, in which the optical signal can be converted into electrical signal output. Moreover, Pb3Mo18 can be drip-coated on the surface of the screen printed chip electrode, which is facile to the detection of light by portable devices compatible with computers, mobile phones and other electronic equipment. This work not only highlights a new approach to the molecular design of photochromic POMs by the coordination of metal ions with the effect of inert electron pair, but also lays a foundation to extend the application of POMs as light signal sensors.
2023, 34(2): 107232
doi: 10.1016/j.cclet.2022.02.037
Abstract:
The polysulfide shuttle limits the development of lithium-sulfur (Li-S) batteries with high energy density and long lifespan. Herein, nitrogen doped hollow carbon nanospheres (NHCS) derived from polymerization of dopamine on SiO2 nanospheres are employed to modify the commercial polypropylene/polyethylene/polypropylene tri-layer separators (PP/PE/PP@NHCS). The abundant nitrogen heteroatoms in NHCS exhibit strong chemical adsorption toward polysulfides, which can effectively suppress the lithium polysulfides shuttle and further enhance the utilization of active sulfur. Lithium-sulfur batteries employing the PP/PE/PP@NHCS deliver an initial discharge capacity of 1355 mAh/g and retain high capacity of 921 mAh/g after 100 cycles at 0.2 C. At a high rate of 2 C, the lithium-sulfur batteries exhibit capacity of 461 mAh/g after 1000 cycles with a capacity fading rate of 0.049% per cycle. This work demonstrates that the NHCS coated PP/PE/PP separator is promising for future commercial applications of lithium-sulfur batteries with improved electrochemical performances.
The polysulfide shuttle limits the development of lithium-sulfur (Li-S) batteries with high energy density and long lifespan. Herein, nitrogen doped hollow carbon nanospheres (NHCS) derived from polymerization of dopamine on SiO2 nanospheres are employed to modify the commercial polypropylene/polyethylene/polypropylene tri-layer separators (PP/PE/PP@NHCS). The abundant nitrogen heteroatoms in NHCS exhibit strong chemical adsorption toward polysulfides, which can effectively suppress the lithium polysulfides shuttle and further enhance the utilization of active sulfur. Lithium-sulfur batteries employing the PP/PE/PP@NHCS deliver an initial discharge capacity of 1355 mAh/g and retain high capacity of 921 mAh/g after 100 cycles at 0.2 C. At a high rate of 2 C, the lithium-sulfur batteries exhibit capacity of 461 mAh/g after 1000 cycles with a capacity fading rate of 0.049% per cycle. This work demonstrates that the NHCS coated PP/PE/PP separator is promising for future commercial applications of lithium-sulfur batteries with improved electrochemical performances.
2023, 34(2): 107235
doi: 10.1016/j.cclet.2022.02.040
Abstract:
A novel air-stable n-type benzothiaphene endcapped azaarene (BTPQ) and its sulfonated derivative (BSPQ) were prepared via two pathways and characterized by NMR, UV–vis, fluorescence and cyclic voltammetry spectroscopy. Symmetrically introducing four nitrogen atoms into acenes, the semiconductor properties could be changed from p-type to n-type detected through the space charge limited current (SCLC) method. After sulfonation of BTPQ, BSPQ is with deeper frontier orbital energy levels and enhanced the electron mobility.
A novel air-stable n-type benzothiaphene endcapped azaarene (BTPQ) and its sulfonated derivative (BSPQ) were prepared via two pathways and characterized by NMR, UV–vis, fluorescence and cyclic voltammetry spectroscopy. Symmetrically introducing four nitrogen atoms into acenes, the semiconductor properties could be changed from p-type to n-type detected through the space charge limited current (SCLC) method. After sulfonation of BTPQ, BSPQ is with deeper frontier orbital energy levels and enhanced the electron mobility.
2023, 34(2): 107238
doi: 10.1016/j.cclet.2022.02.043
Abstract:
A series of DL-serine covalently modified multinuclear lanthanide implanted arsenotungstates K2[{Ln(H2O)7}2{As4W44O137(OH)18(H2O)2(DL-Ser)2}{Ln2(H2O)5(DL-Ser)}2]·65H2O (DL-Ser = DL-serine, Ln = La (1), Ce (2), Pr (3)) are obtained. Crystal structure analysis shows that these compounds are isomorphic and contain the basic [{As4W44O137(OH)18(H2O)2(DL-Ser)2}{Ln2(H2O)5(DL-Ser)}2]8– polyoxoanion constituted by two {As2W19O59(OH)8(H2O)}6‒ subunits, a [W6O23(OH)2(DL-Ser)2]14‒ fragment, and two embedded [Ln2(H2O)5(DL-Ser)]5+ groups, which further build into one dimensional linear chainlike structure via two peripheral Ln3+ ions. Most remarkably, these compounds exhibit rapid photochromic behaviors, which changed color quickly from white (1), yellow (2), green (3) to blue (1), brown (2) and glaucous (3) in ten minutes under UV irradiation, and that the colors gradually recovered in the dark for approximately 22 h.
A series of DL-serine covalently modified multinuclear lanthanide implanted arsenotungstates K2[{Ln(H2O)7}2{As4W44O137(OH)18(H2O)2(DL-Ser)2}{Ln2(H2O)5(DL-Ser)}2]·65H2O (DL-Ser = DL-serine, Ln = La (1), Ce (2), Pr (3)) are obtained. Crystal structure analysis shows that these compounds are isomorphic and contain the basic [{As4W44O137(OH)18(H2O)2(DL-Ser)2}{Ln2(H2O)5(DL-Ser)}2]8– polyoxoanion constituted by two {As2W19O59(OH)8(H2O)}6‒ subunits, a [W6O23(OH)2(DL-Ser)2]14‒ fragment, and two embedded [Ln2(H2O)5(DL-Ser)]5+ groups, which further build into one dimensional linear chainlike structure via two peripheral Ln3+ ions. Most remarkably, these compounds exhibit rapid photochromic behaviors, which changed color quickly from white (1), yellow (2), green (3) to blue (1), brown (2) and glaucous (3) in ten minutes under UV irradiation, and that the colors gradually recovered in the dark for approximately 22 h.
2023, 34(2): 107241
doi: 10.1016/j.cclet.2022.02.046
Abstract:
Developing bifunctional electrocatalysts for overall water splitting reaction is still highly desired but with large challenges. Herein, an amorphous FeCoNi-S electrocatalyst was developed using thioacetamide for the sulfuration of FeCoNi hydroxide during the hydrothermal process. The obtained catalyst exhibited an amorphous structure with hybrid bonds of metal-S bond and metal-O bonds in the catalyst system. The optimized catalyst showed a largely improved bifunctional catalytic ability to drive water splitting reaction in the alkaline electrolyte compared to the FeCoNi hydroxide. It required an overpotential of 280 mV and 80 mV (No-IR correction) to offer 10 mA/cm2 for water oxidation and reduction respectively; a low cell voltage of 1.55 V was required to reach 10 mA/cm2 for the water electrolysis with good stability for 12 h. Moreover, this catalyst system showed high catalytic stability, catalytic kinetics, and Faraday efficiency for water splitting reactions. Considering the very low intrinsic activity of FeCoNi hydroxide, the efficient bifunctional catalytic ability should result from the newly formed hybrid active sites of metallic metal-S species and the high valence state of metal oxide species. This work is effective in the bifunctional catalytic ability boosting for the transition metal materials by facile sulfuration in the hydrothermal approach.
Developing bifunctional electrocatalysts for overall water splitting reaction is still highly desired but with large challenges. Herein, an amorphous FeCoNi-S electrocatalyst was developed using thioacetamide for the sulfuration of FeCoNi hydroxide during the hydrothermal process. The obtained catalyst exhibited an amorphous structure with hybrid bonds of metal-S bond and metal-O bonds in the catalyst system. The optimized catalyst showed a largely improved bifunctional catalytic ability to drive water splitting reaction in the alkaline electrolyte compared to the FeCoNi hydroxide. It required an overpotential of 280 mV and 80 mV (No-IR correction) to offer 10 mA/cm2 for water oxidation and reduction respectively; a low cell voltage of 1.55 V was required to reach 10 mA/cm2 for the water electrolysis with good stability for 12 h. Moreover, this catalyst system showed high catalytic stability, catalytic kinetics, and Faraday efficiency for water splitting reactions. Considering the very low intrinsic activity of FeCoNi hydroxide, the efficient bifunctional catalytic ability should result from the newly formed hybrid active sites of metallic metal-S species and the high valence state of metal oxide species. This work is effective in the bifunctional catalytic ability boosting for the transition metal materials by facile sulfuration in the hydrothermal approach.
2023, 34(2): 107257
doi: 10.1016/j.cclet.2022.02.062
Abstract:
On-purpose propane dehydrogenation (PDH) has emerged as a profitable alternative to the traditional cracking of oil products for propylene production. By means of density functional theory (DFT) calculations, the present work demonstrates that Fe atoms may atomically disperse on MoS2 (Fe1/MoS2) and serve as a promising single-atom catalyst (SAC) for PDH. The catalytic activity of Fe1/MoS2 is attributed to the highly exposed d orbitals of single Fe atoms, while the propylene selectivity is originated from the kinetic inhibition of propylene dehydrogenation resulting from fast propenyl hydrogenation. The unique catalytic selectivity of Fe1/MoS2 may inspire further investigations of on-purpose dehydrogenations of propane on SACs.
On-purpose propane dehydrogenation (PDH) has emerged as a profitable alternative to the traditional cracking of oil products for propylene production. By means of density functional theory (DFT) calculations, the present work demonstrates that Fe atoms may atomically disperse on MoS2 (Fe1/MoS2) and serve as a promising single-atom catalyst (SAC) for PDH. The catalytic activity of Fe1/MoS2 is attributed to the highly exposed d orbitals of single Fe atoms, while the propylene selectivity is originated from the kinetic inhibition of propylene dehydrogenation resulting from fast propenyl hydrogenation. The unique catalytic selectivity of Fe1/MoS2 may inspire further investigations of on-purpose dehydrogenations of propane on SACs.
2023, 34(2): 107258
doi: 10.1016/j.cclet.2022.02.063
Abstract:
Rhein (Rhe), an anthraquinone derivative, exhibits excellent anti-inflammatory effects and other pharmacological activities, but its clinical application remains limited due to poor solubility. The present work aims at the improvement of solubility and oral bioavailability of Rhe through cocrystal formation. For this purpose, Rhe and matrine (Mat) were selected as pharmaceutical ingredient (API) and cocrystal former (CCF), respectively, and the Rhe-Mat cocrystal was synthesized and characterized by single crystal X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC). The formation mechanism of Rhe-Mat cocrystal was elucidated by molecular surface electrostatic potential (MSEP). It is worth mentioning that the 50-fold increment of dissolution in vitro was observed in pure water in the form of Rhe-Mat cocrystal. Furthermore, the in vivo studies revealed that Rhe-Mat cocrystal indicated the faster absorption rate and the higher peak blood concentration than the pure Rhe. Hence, it can be concluded that current study successfully improved the solubility and oral bioavailability of Rhe.
Rhein (Rhe), an anthraquinone derivative, exhibits excellent anti-inflammatory effects and other pharmacological activities, but its clinical application remains limited due to poor solubility. The present work aims at the improvement of solubility and oral bioavailability of Rhe through cocrystal formation. For this purpose, Rhe and matrine (Mat) were selected as pharmaceutical ingredient (API) and cocrystal former (CCF), respectively, and the Rhe-Mat cocrystal was synthesized and characterized by single crystal X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC). The formation mechanism of Rhe-Mat cocrystal was elucidated by molecular surface electrostatic potential (MSEP). It is worth mentioning that the 50-fold increment of dissolution in vitro was observed in pure water in the form of Rhe-Mat cocrystal. Furthermore, the in vivo studies revealed that Rhe-Mat cocrystal indicated the faster absorption rate and the higher peak blood concentration than the pure Rhe. Hence, it can be concluded that current study successfully improved the solubility and oral bioavailability of Rhe.
2023, 34(2): 107261
doi: 10.1016/j.cclet.2022.02.066
Abstract:
In this paper, Fe36Co44 nanocluster structure is used to catalyze the hydrolysis reaction of ammonia borane to produce H2. Firstly, we complete the construction of Fe36Co44 cluster structure and calculate the electronic properties of the cluster. By comparing the adsorption process of Ammonia Borane (AB) in active sites of the cluster, which have different Effective Coordination Number (ECN), the qualitative relationship between ECN and the catalytic activation of AB is clarified, and the optimal catalytic active site is obtained. Then, from the perspective of different reaction paths, we study the hydrolysis reaction of AB in multiple paths, and obtain 5 different reaction paths and energy profiles. The calculation results show that in the case of NH bond priority break (path 5), the reaction has the minimum rate-determining step (RDS) barrier (about 1.02 eV) and the entire reaction is exothermic (about 0.40 eV). So, path 5 is an optimal catalytic reaction path. This study will have an important guiding significance for the study of the AB hydrolysis reaction mechanism.
In this paper, Fe36Co44 nanocluster structure is used to catalyze the hydrolysis reaction of ammonia borane to produce H2. Firstly, we complete the construction of Fe36Co44 cluster structure and calculate the electronic properties of the cluster. By comparing the adsorption process of Ammonia Borane (AB) in active sites of the cluster, which have different Effective Coordination Number (ECN), the qualitative relationship between ECN and the catalytic activation of AB is clarified, and the optimal catalytic active site is obtained. Then, from the perspective of different reaction paths, we study the hydrolysis reaction of AB in multiple paths, and obtain 5 different reaction paths and energy profiles. The calculation results show that in the case of NH bond priority break (path 5), the reaction has the minimum rate-determining step (RDS) barrier (about 1.02 eV) and the entire reaction is exothermic (about 0.40 eV). So, path 5 is an optimal catalytic reaction path. This study will have an important guiding significance for the study of the AB hydrolysis reaction mechanism.
2023, 34(2): 107292
doi: 10.1016/j.cclet.2022.03.015
Abstract:
Artificial synapses with full synapse-like functionalities are of crucial importance for the implementation of neuromorphic computing and bioinspired intelligent systems. In particular, the development of artificial synapses with the capability to emulate multiplexed neural transmission is highly desirable, but remains challenging. In this work, we proposed a hybrid ambipolar synaptic transistor that combines two-dimensional (2D) molybdenum disulfide (MoS2) sheet and crystalline one-dimensional (1D) poly(3-hexylthiophene-2, 5-diyl) polymer nanowires (P3HT NWs) as dual excitatory channels. Essential synaptic functions, including excitatory postsynaptic current, paired-pulse facilitation, synaptic potentiation and depression, and dynamic filtering were emulated using the synaptic transistor. Benefitting from the dual excitatory channels of the synaptic transistor, the device achieved a fast switch between short-term and long-term memory by altering the charge carriers in the dual channels, i.e., electrons and holes. This emulated the multiplexed neural transmission of different excitatory neurotransmitters, e.g., dopamine and noradrenaline. The plasticity-switchable artificial synapse (PSAS) simulates the task-learning process of individuals under different motivations and the impact of success or failure on task learning and memory, which promises the potential to enable complex functionalities in future neuromorphic intelligent electronics.
Artificial synapses with full synapse-like functionalities are of crucial importance for the implementation of neuromorphic computing and bioinspired intelligent systems. In particular, the development of artificial synapses with the capability to emulate multiplexed neural transmission is highly desirable, but remains challenging. In this work, we proposed a hybrid ambipolar synaptic transistor that combines two-dimensional (2D) molybdenum disulfide (MoS2) sheet and crystalline one-dimensional (1D) poly(3-hexylthiophene-2, 5-diyl) polymer nanowires (P3HT NWs) as dual excitatory channels. Essential synaptic functions, including excitatory postsynaptic current, paired-pulse facilitation, synaptic potentiation and depression, and dynamic filtering were emulated using the synaptic transistor. Benefitting from the dual excitatory channels of the synaptic transistor, the device achieved a fast switch between short-term and long-term memory by altering the charge carriers in the dual channels, i.e., electrons and holes. This emulated the multiplexed neural transmission of different excitatory neurotransmitters, e.g., dopamine and noradrenaline. The plasticity-switchable artificial synapse (PSAS) simulates the task-learning process of individuals under different motivations and the impact of success or failure on task learning and memory, which promises the potential to enable complex functionalities in future neuromorphic intelligent electronics.
2023, 34(2): 107295
doi: 10.1016/j.cclet.2022.03.018
Abstract:
The morphology and heterojunction engineering are effective ways to boost the performance of Cu-based catalysts. Herein, we have reported the designed synthesis of two-dimensional Cu-CuO heterojunction nanosheets (2D Cu-CuO NS) based on 3-aminopropyl-triethoxysilane (APTES, KH550) aided synthetic strategy. The APTES can act as both the ligand and alkali (-OH) source to guide the large-scale synthesis of 2D Cu-based precursor, which can transform into 2D Cu-CuO NS by the controllable post-treatment. The Si species from APTES can protect the particles from the severe aggregation and growth, guaranteeing the formation of 2D sheets composed of small-sized Cu-CuO heterojunction (about 20 nm). The heterojunction interfaces can provide plentiful active sites to boost the catalytic ability. The 2D sheets can provide large accessible surface, being conducive to the contact of the catalyst and reactants. Benefiting from above virtues, the 2D Cu-CuO NS showed the superior catalytic performance for the reduction of a series of nitro compounds, being superior to most reported non-noble metal-based catalysts. Notably, it exhibited good re-cycled performance with no obvious performance degradation after 10 consecutive catalysis. The present study will be promising to promote the application of the Cu-based catalysts, due to its ability to control the morphology and potential for the large-scale synthesis.
The morphology and heterojunction engineering are effective ways to boost the performance of Cu-based catalysts. Herein, we have reported the designed synthesis of two-dimensional Cu-CuO heterojunction nanosheets (2D Cu-CuO NS) based on 3-aminopropyl-triethoxysilane (APTES, KH550) aided synthetic strategy. The APTES can act as both the ligand and alkali (-OH) source to guide the large-scale synthesis of 2D Cu-based precursor, which can transform into 2D Cu-CuO NS by the controllable post-treatment. The Si species from APTES can protect the particles from the severe aggregation and growth, guaranteeing the formation of 2D sheets composed of small-sized Cu-CuO heterojunction (about 20 nm). The heterojunction interfaces can provide plentiful active sites to boost the catalytic ability. The 2D sheets can provide large accessible surface, being conducive to the contact of the catalyst and reactants. Benefiting from above virtues, the 2D Cu-CuO NS showed the superior catalytic performance for the reduction of a series of nitro compounds, being superior to most reported non-noble metal-based catalysts. Notably, it exhibited good re-cycled performance with no obvious performance degradation after 10 consecutive catalysis. The present study will be promising to promote the application of the Cu-based catalysts, due to its ability to control the morphology and potential for the large-scale synthesis.
2023, 34(2): 107296
doi: 10.1016/j.cclet.2022.03.019
Abstract:
Acetylene (C2H2) and ethylene (C2H4) both are important chemical raw materials and energy fuel gasses. But the effective removement of trace C2H2 from C2H4 and the purification of C2H2 from carbon dioxide (CO2) are particularly challenging in the petrochemical industry. As a class of porous physical adsorbent, metal-organic frameworks (MOFs) have exhibited great success in separation and purification of light hydrocarbon gas. Herein, we rationally designed four novel MOFs by the strategy of pore space partition (PSP) via introducing triangular tri(pyridin-4-yl)-amine (TPA) into the 1D hexagonal channels of acs-type parent skeleton. By modulating the functional groups of linear dicarboxylate linkers for the parent skeleton, a series of isoreticular PSP-MOFs (SNNU-278−281) were successfully obtained. The synergistic effects of suitable pore size and Lewis basic functional groups make these MOFs ideal C2H2 adsorbents. The gas adsorption experimental results show that all MOFs have excellent C2H2 uptakes. Specially, SNNU-278 demonstrates a high C2H2 uptake of 149.7 cm3/g at 273 K and 1 atm. Meanwhile, SNNU-278−281 MOFs also show extremely great C2H2 separation from CO2 and C2H4. The optimized SNNU-281 with high-density hydroxy groups exhibits extraordinary C2H2/CO2 and C2H2/C2H4 dynamic breakthrough interval times up to 31 min/g and 17 min/g under 298 K and 1 bar.
Acetylene (C2H2) and ethylene (C2H4) both are important chemical raw materials and energy fuel gasses. But the effective removement of trace C2H2 from C2H4 and the purification of C2H2 from carbon dioxide (CO2) are particularly challenging in the petrochemical industry. As a class of porous physical adsorbent, metal-organic frameworks (MOFs) have exhibited great success in separation and purification of light hydrocarbon gas. Herein, we rationally designed four novel MOFs by the strategy of pore space partition (PSP) via introducing triangular tri(pyridin-4-yl)-amine (TPA) into the 1D hexagonal channels of acs-type parent skeleton. By modulating the functional groups of linear dicarboxylate linkers for the parent skeleton, a series of isoreticular PSP-MOFs (SNNU-278−281) were successfully obtained. The synergistic effects of suitable pore size and Lewis basic functional groups make these MOFs ideal C2H2 adsorbents. The gas adsorption experimental results show that all MOFs have excellent C2H2 uptakes. Specially, SNNU-278 demonstrates a high C2H2 uptake of 149.7 cm3/g at 273 K and 1 atm. Meanwhile, SNNU-278−281 MOFs also show extremely great C2H2 separation from CO2 and C2H4. The optimized SNNU-281 with high-density hydroxy groups exhibits extraordinary C2H2/CO2 and C2H2/C2H4 dynamic breakthrough interval times up to 31 min/g and 17 min/g under 298 K and 1 bar.
2023, 34(2): 107321
doi: 10.1016/j.cclet.2022.03.044
Abstract:
The effective design and synthesis of novel small-molecule donors (SMDs) is extremely essential for the in-depth study of the scientific problems of bulk heterojunction morphology and the improvement of photovoltaic performance in organic solar cells (OSCs). Importantly, developing a series of donors with different conjugated central donor (D) units is a remarkable strategy to obtain high-performance donors. Herein, two acceptor-donor-donor-acceptor (A-D-D-A) type oligomeric donors 2DTBDT and 2DTBDT-2T with two dithieno[2, 3-d: 2′, 3′-d']benzo[1, 2-b: 4, 5-b']dithiophene (DTBDT) as D units, without and with bithiophene as the π bridge respectively are designed and synthesized successfully. The central linked-DTBDT unit can provide a larger conjugated plane and promote π electron delocalization, which can effectively improve π-π interactions between donors and regulate the crystallinity. And we found that the π bridge provided 2DTBDT-2T with 12.31% efficiency that is already a high efficiency in OSCs, whereas 2DTBDT with merely 3.63% efficiency, both with 2, 2′-((2Z, 2′Z)-((12, 13-bis(2-ethylhexyl)-3, 9-diundecyl-12, 13-dihydro-[1,2,5]thiadiazolo[3, 4-e]thieno[2, "3′': 4′, 5′]thieno[2′, 3′: 4, 5]pyrrolo[3, 2-g]thieno[2′, 3′: 4, 5]thieno[3, 2-b]indole, 10-diyl)bis(methanylylidene))bis(5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-2, 1-diylidene)) dimalononitrile (Y6) as the acceptor. We conjecture that the main reason for the different device performance may be ascribed to the different molecular stacking orientation of the oligomeric donors and morphology features of the donors: Y6 blend films. Compared to the predominant face-on orientation of the 2DTBDT neat film, the 2DTBDT-2T neat film performed a preferential edge-on orientation, which obtained a smoother surface, stronger crystallinity and more uniform phase separation in the 2DTBDT-2T: Y6 blend films with nanofiber structure, which delivered higher and more balanced carrier mobilities, the more efficient exciton dissociation and reduced biomolecule recombination, therefore obtaining better power conversion efficiencies (PCEs). We speculate that the transformation of molecular stacking orientation of oligomeric donors is possibly due to that π bridge extended and twisted the molecular structure of 2DTDBT-2T, resulting in an edge-on orientation relative to the substrate. These findings demonstrate that the single-bond-linked donor strategy is an alternative method to design the donors towards high-performance OSCs.
The effective design and synthesis of novel small-molecule donors (SMDs) is extremely essential for the in-depth study of the scientific problems of bulk heterojunction morphology and the improvement of photovoltaic performance in organic solar cells (OSCs). Importantly, developing a series of donors with different conjugated central donor (D) units is a remarkable strategy to obtain high-performance donors. Herein, two acceptor-donor-donor-acceptor (A-D-D-A) type oligomeric donors 2DTBDT and 2DTBDT-2T with two dithieno[2, 3-d: 2′, 3′-d']benzo[1, 2-b: 4, 5-b']dithiophene (DTBDT) as D units, without and with bithiophene as the π bridge respectively are designed and synthesized successfully. The central linked-DTBDT unit can provide a larger conjugated plane and promote π electron delocalization, which can effectively improve π-π interactions between donors and regulate the crystallinity. And we found that the π bridge provided 2DTBDT-2T with 12.31% efficiency that is already a high efficiency in OSCs, whereas 2DTBDT with merely 3.63% efficiency, both with 2, 2′-((2Z, 2′Z)-((12, 13-bis(2-ethylhexyl)-3, 9-diundecyl-12, 13-dihydro-[1,2,5]thiadiazolo[3, 4-e]thieno[2, "3′': 4′, 5′]thieno[2′, 3′: 4, 5]pyrrolo[3, 2-g]thieno[2′, 3′: 4, 5]thieno[3, 2-b]indole, 10-diyl)bis(methanylylidene))bis(5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-2, 1-diylidene)) dimalononitrile (Y6) as the acceptor. We conjecture that the main reason for the different device performance may be ascribed to the different molecular stacking orientation of the oligomeric donors and morphology features of the donors: Y6 blend films. Compared to the predominant face-on orientation of the 2DTBDT neat film, the 2DTBDT-2T neat film performed a preferential edge-on orientation, which obtained a smoother surface, stronger crystallinity and more uniform phase separation in the 2DTBDT-2T: Y6 blend films with nanofiber structure, which delivered higher and more balanced carrier mobilities, the more efficient exciton dissociation and reduced biomolecule recombination, therefore obtaining better power conversion efficiencies (PCEs). We speculate that the transformation of molecular stacking orientation of oligomeric donors is possibly due to that π bridge extended and twisted the molecular structure of 2DTDBT-2T, resulting in an edge-on orientation relative to the substrate. These findings demonstrate that the single-bond-linked donor strategy is an alternative method to design the donors towards high-performance OSCs.
2023, 34(2): 107323
doi: 10.1016/j.cclet.2022.03.046
Abstract:
Photocatalytic hydrogen evolution from water splitting is a promising strategy for realizing the vision of carbon neutrality. Herein, a novel SrTiO3-SrCO3 n-n heterojunction was used for the first time for water splitting to generate H2. The heterojunction was synthesized by a soft chemical one-pot hydrothermal method. The SrTiO3-SrCO3 loading with 3 wt% Pt shows the maximum photocatalytic H2 evolution rate of 3.62 mmol h−1g−1 under simulated sunlight irradiation, which is 20.1 times higher than that of pristine SrTiO3. The apparent quantum efficiency of SrTiO3-SrCO3 reaches 21.73% at 313 nm, and it shows good stability during cyclic experiment. The formation of compact SrTiO3-SrCO3 heterojunction with strong interfacial electronic interaction promotes the transmission and separation of photo-generated carriers. The results of XPS, PL, PC, EIS and DFT support the mechanism of improving photocatalytic activity based on carrier dynamics. This work provides a facile and effective method to enhance the activity of SrTiO3-based heterojunction photocatalysts.
Photocatalytic hydrogen evolution from water splitting is a promising strategy for realizing the vision of carbon neutrality. Herein, a novel SrTiO3-SrCO3 n-n heterojunction was used for the first time for water splitting to generate H2. The heterojunction was synthesized by a soft chemical one-pot hydrothermal method. The SrTiO3-SrCO3 loading with 3 wt% Pt shows the maximum photocatalytic H2 evolution rate of 3.62 mmol h−1g−1 under simulated sunlight irradiation, which is 20.1 times higher than that of pristine SrTiO3. The apparent quantum efficiency of SrTiO3-SrCO3 reaches 21.73% at 313 nm, and it shows good stability during cyclic experiment. The formation of compact SrTiO3-SrCO3 heterojunction with strong interfacial electronic interaction promotes the transmission and separation of photo-generated carriers. The results of XPS, PL, PC, EIS and DFT support the mechanism of improving photocatalytic activity based on carrier dynamics. This work provides a facile and effective method to enhance the activity of SrTiO3-based heterojunction photocatalysts.
2023, 34(2): 107326
doi: 10.1016/j.cclet.2022.03.049
Abstract:
Pyrogenic carbonaceous matter (PCM) catalyzes azo dye decolorization by sulfide, but the nitrogen doping catalytic mechanisms are poorly understood. In this study, we found that stagnate time of azo dye methyl orange (MO) decolorization was reduced to 0.54-18.28 min in the presence of various nitrogen-doped graphenes (NGs), remarkably lower compared to graphene itself. Particularly, graphitic nitrogen played a critical role in NGs-catalyzed MO decolorization by sulfide. Gas chromatography-mass spectrometry and in-situ surface Raman analysis demonstrated that doping nitrogen, especially graphite one facilitated reactive intermediate polysulfides formation. This is attributed to the improved electron conductivity through graphitic nitrogen doping, and the enhanced interactions between sulfide and carbon atoms bonded to graphitic nitrogen. This study not only provides a better understanding of PCM impact on transformations and fates of organic pollutants in natural environments, but also offer a new regulation strategy for more efficient wastewater treatment processes in PCM-catalyzed engineering systems.
Pyrogenic carbonaceous matter (PCM) catalyzes azo dye decolorization by sulfide, but the nitrogen doping catalytic mechanisms are poorly understood. In this study, we found that stagnate time of azo dye methyl orange (MO) decolorization was reduced to 0.54-18.28 min in the presence of various nitrogen-doped graphenes (NGs), remarkably lower compared to graphene itself. Particularly, graphitic nitrogen played a critical role in NGs-catalyzed MO decolorization by sulfide. Gas chromatography-mass spectrometry and in-situ surface Raman analysis demonstrated that doping nitrogen, especially graphite one facilitated reactive intermediate polysulfides formation. This is attributed to the improved electron conductivity through graphitic nitrogen doping, and the enhanced interactions between sulfide and carbon atoms bonded to graphitic nitrogen. This study not only provides a better understanding of PCM impact on transformations and fates of organic pollutants in natural environments, but also offer a new regulation strategy for more efficient wastewater treatment processes in PCM-catalyzed engineering systems.
2023, 34(2): 107327
doi: 10.1016/j.cclet.2022.03.050
Abstract:
Graphene oxide (GO) with unique characteristics grasps striking potentials in both academic and industrial applications. After being released into natural waters, the dispersity and stability of GO might be altered by the chemical conditions in the receiving water bodies. In this review, we summarized that the aggregation of GO in aquatic environments is mostly dependent on properties of nanoparticles (size, structure, and functional groups) and complex water chemistry (pH, temperature, light, ionic strength, and dissolved organic matter). The knowledge about the aggregation/stability of GO is still insufficient due to the variations in GO properties and complex system of natural waters. Although studies about environmental transformation of graphene-related materials can be accessed but a systematic study taking into consideration the various factors of GO and aquatic systems responsible for aggregation of GO is still lacking. Therefore, we summarized that GO homoaggregation or heteroaggregation with other solid particles can affect the distribution in different depths of rivers and toxicity toward plankton or benthic organisms. More studies are needed to investigate the stability of GO in the long term, the effect of other nanomaterial on GO aggregation, the alteration of water constituents at different regions/time and its effect on GO aggregation, to understand the transportation and impact of GO in the environment.
Graphene oxide (GO) with unique characteristics grasps striking potentials in both academic and industrial applications. After being released into natural waters, the dispersity and stability of GO might be altered by the chemical conditions in the receiving water bodies. In this review, we summarized that the aggregation of GO in aquatic environments is mostly dependent on properties of nanoparticles (size, structure, and functional groups) and complex water chemistry (pH, temperature, light, ionic strength, and dissolved organic matter). The knowledge about the aggregation/stability of GO is still insufficient due to the variations in GO properties and complex system of natural waters. Although studies about environmental transformation of graphene-related materials can be accessed but a systematic study taking into consideration the various factors of GO and aquatic systems responsible for aggregation of GO is still lacking. Therefore, we summarized that GO homoaggregation or heteroaggregation with other solid particles can affect the distribution in different depths of rivers and toxicity toward plankton or benthic organisms. More studies are needed to investigate the stability of GO in the long term, the effect of other nanomaterial on GO aggregation, the alteration of water constituents at different regions/time and its effect on GO aggregation, to understand the transportation and impact of GO in the environment.
2023, 34(2): 107328
doi: 10.1016/j.cclet.2022.03.051
Abstract:
Through uncomplicated carbonation process, a carbon-embedded CoNiSe2/C nanosphere was synthesized from Ni-Co-MOF (metal-organic framework) precursor whose controllable structure and synergistic effect of bimetallic Ni/Co brought CoNiSe2/C anodes with high specific surface area (172.79 m2/g) and outstanding electrochemical performance. CoNiSe2/C anodes obtained reversible discharge capacities of 850.9 mAh/g at 0.1 A/g after cycling for 100 cycles. In addition, CoNiSe2/C exhibits excellent cycle stability and reversibility in the rate test at a current density of 0.1–2.0 A/g. When the current density returns to 0.5 A/g for 150 cycles, its discharge ratio the capacity is 330.8 mAh/g. Electrochemical impedance spectroscopy (EIS) tests suggested that CoNiSe2/C anodes had a lower charge transfer impedance of 130.02 Ω after 30 cycles. In-situ X-ray diffraction (XRD) tests confirmed the alloying mechanism of CoNiSe2/C which realized higher lithium storage capacity. This work affords substantial evidence for the extension of bimetallic selenides in secondary batteries, promoting the development of bimetallic selenides in anode materials for LIBs.
Through uncomplicated carbonation process, a carbon-embedded CoNiSe2/C nanosphere was synthesized from Ni-Co-MOF (metal-organic framework) precursor whose controllable structure and synergistic effect of bimetallic Ni/Co brought CoNiSe2/C anodes with high specific surface area (172.79 m2/g) and outstanding electrochemical performance. CoNiSe2/C anodes obtained reversible discharge capacities of 850.9 mAh/g at 0.1 A/g after cycling for 100 cycles. In addition, CoNiSe2/C exhibits excellent cycle stability and reversibility in the rate test at a current density of 0.1–2.0 A/g. When the current density returns to 0.5 A/g for 150 cycles, its discharge ratio the capacity is 330.8 mAh/g. Electrochemical impedance spectroscopy (EIS) tests suggested that CoNiSe2/C anodes had a lower charge transfer impedance of 130.02 Ω after 30 cycles. In-situ X-ray diffraction (XRD) tests confirmed the alloying mechanism of CoNiSe2/C which realized higher lithium storage capacity. This work affords substantial evidence for the extension of bimetallic selenides in secondary batteries, promoting the development of bimetallic selenides in anode materials for LIBs.
2023, 34(2): 107332
doi: 10.1016/j.cclet.2022.03.055
Abstract:
Prion diseases are fatal neurodegenerative diseases that can cause severe dementia. The misfolding and accumulation of the prion peptide (PrP)106–126 is crucial, and this process is closely relevant to biological membranes. However, how PrP106–126 aggregation is affected by the molecular chirality of phospholipid membrane is unknown. Thus, in this study, a pair of L- and D-aspartic acid (Asp)-modified 1, 2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) were synthesized to construct chiral liposomes. We discover that L-Asp-DPPE liposomes strongly inhibit the oligomerization and amyloidogenesis of PrP106–126, whether acting on monomers or oligomers, which rescues cytotoxicity induced by PrP106–126. By comparison, D-Asp-DPPE liposomes inhibit peptide oligomerization only at a high concentration and cannot prevent amyloidogenesis when acting on oligomers, which lead to pronounced cytotoxicity. Apoptosis experiment, dynamic change of intracellular Ca2+ (iCa2+) and Ca2+ release from endoplasmic reticulum (ER), reactive oxygen species (ROS) production, adsorption dynamics and affinity tests, and fluorescent imaging clearly disclose that molecular chirality of the liposomes dominates conformational transition of PrP106–126 from random coil to β-sheet, binding and adsorption of the monomers and oligomers, and subsequent fibrillation process, resulting in distinct inhibition effect in Ca2+ overload and release, ROS production and cell apoptosis. This work is the first to report that interfacial molecular chirality is a potentially crucial influence on the fibrillation process of PrP106–126 and its cell responses, whereas the convergence of chiral amino acids and liposomes can be considered potential inhibitors in prion diseases.
Prion diseases are fatal neurodegenerative diseases that can cause severe dementia. The misfolding and accumulation of the prion peptide (PrP)106–126 is crucial, and this process is closely relevant to biological membranes. However, how PrP106–126 aggregation is affected by the molecular chirality of phospholipid membrane is unknown. Thus, in this study, a pair of L- and D-aspartic acid (Asp)-modified 1, 2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) were synthesized to construct chiral liposomes. We discover that L-Asp-DPPE liposomes strongly inhibit the oligomerization and amyloidogenesis of PrP106–126, whether acting on monomers or oligomers, which rescues cytotoxicity induced by PrP106–126. By comparison, D-Asp-DPPE liposomes inhibit peptide oligomerization only at a high concentration and cannot prevent amyloidogenesis when acting on oligomers, which lead to pronounced cytotoxicity. Apoptosis experiment, dynamic change of intracellular Ca2+ (iCa2+) and Ca2+ release from endoplasmic reticulum (ER), reactive oxygen species (ROS) production, adsorption dynamics and affinity tests, and fluorescent imaging clearly disclose that molecular chirality of the liposomes dominates conformational transition of PrP106–126 from random coil to β-sheet, binding and adsorption of the monomers and oligomers, and subsequent fibrillation process, resulting in distinct inhibition effect in Ca2+ overload and release, ROS production and cell apoptosis. This work is the first to report that interfacial molecular chirality is a potentially crucial influence on the fibrillation process of PrP106–126 and its cell responses, whereas the convergence of chiral amino acids and liposomes can be considered potential inhibitors in prion diseases.
2023, 34(2): 107335
doi: 10.1016/j.cclet.2022.03.058
Abstract:
Metal-organic framework nanosheets (MOF NNs) offer potential opportunities for many applications, but an efficient strategy for the scalable preparation of few-layered two-dimensional (2D) MOF NNs are still a major challenge. Herein, we present an efficient top-down method for the synthesis of the Ni-BDC (Ni2(OH)2(1, 4-BDC); 1, 4-BDC = 1, 4-benzenedicarboxylate) nanosheets utilizing a novel thermal expansion-quench method of the flowerlike bulky MOFs in liquid N2. The obtained Ni-BDC nanosheets exhibit significantly enhanced photocatalytic performance of reductive CO2 deoxygenation (7.0 µmol h−1 mg−1) under visible light illumination compared with the bulky MOFs, due to much higher surface area for CO2 adsorption, more abundant active sites exposed and stronger electron transport ability of the nanosheets. More importantly, this synthetic strategy can be extended to fabricate other MOF nanosheets which also exhibit significantly improved performance for deoxygenative CO2 reduction compared to their bulky counterparts. This work may provide a guideline for preparing other 2D layered photocatalysts materials to realize energy conversion applications.
Metal-organic framework nanosheets (MOF NNs) offer potential opportunities for many applications, but an efficient strategy for the scalable preparation of few-layered two-dimensional (2D) MOF NNs are still a major challenge. Herein, we present an efficient top-down method for the synthesis of the Ni-BDC (Ni2(OH)2(1, 4-BDC); 1, 4-BDC = 1, 4-benzenedicarboxylate) nanosheets utilizing a novel thermal expansion-quench method of the flowerlike bulky MOFs in liquid N2. The obtained Ni-BDC nanosheets exhibit significantly enhanced photocatalytic performance of reductive CO2 deoxygenation (7.0 µmol h−1 mg−1) under visible light illumination compared with the bulky MOFs, due to much higher surface area for CO2 adsorption, more abundant active sites exposed and stronger electron transport ability of the nanosheets. More importantly, this synthetic strategy can be extended to fabricate other MOF nanosheets which also exhibit significantly improved performance for deoxygenative CO2 reduction compared to their bulky counterparts. This work may provide a guideline for preparing other 2D layered photocatalysts materials to realize energy conversion applications.
2023, 34(2): 107336
doi: 10.1016/j.cclet.2022.03.059
Abstract:
Intracellular pH undertakes critical functions in various biological and pathological processes. It is important to monitor intracellular pH fluctuations for understanding physiological and pathological processes. Here, one aldehyde-bearing cyclometalated iridium(Ⅲ) complex ([(4-pba)2Ir(dcphen)]PF6, 4-pba = 4-(2-pyridyl) benzaldehyde, dcphen = 4, 7-dichloro-1, 10-phenanthroline, probe 1) was synthesized and used to track intracellular pH fluctuations. Probe 1 displayed pH-dependent luminescence property in pH range of 1.81–6.81 with an evaluated pKa value of 4.30 in BR buffer-DMSO (v:v = 99:1). An intramolecular hydrogen bonds assisted pH-responsive mechanism was proposed for the pH-responsive behavior of probe 1. Probe 1 was successfully applied for imaging and tracking pH fluctuations in HeLa cells under external stimulation with fast response time, good photostability as well as low cytotoxicity and high cell permeability. This work demonstrates that aldehyde-bearing cyclometalated iridium(Ⅲ) complex can be used as alternative pH-responsive probe for real-time tracking intracellular pH fluctuations, which provides a strategy for the design of pH-responsive probe in versatile applications.
Intracellular pH undertakes critical functions in various biological and pathological processes. It is important to monitor intracellular pH fluctuations for understanding physiological and pathological processes. Here, one aldehyde-bearing cyclometalated iridium(Ⅲ) complex ([(4-pba)2Ir(dcphen)]PF6, 4-pba = 4-(2-pyridyl) benzaldehyde, dcphen = 4, 7-dichloro-1, 10-phenanthroline, probe 1) was synthesized and used to track intracellular pH fluctuations. Probe 1 displayed pH-dependent luminescence property in pH range of 1.81–6.81 with an evaluated pKa value of 4.30 in BR buffer-DMSO (v:v = 99:1). An intramolecular hydrogen bonds assisted pH-responsive mechanism was proposed for the pH-responsive behavior of probe 1. Probe 1 was successfully applied for imaging and tracking pH fluctuations in HeLa cells under external stimulation with fast response time, good photostability as well as low cytotoxicity and high cell permeability. This work demonstrates that aldehyde-bearing cyclometalated iridium(Ⅲ) complex can be used as alternative pH-responsive probe for real-time tracking intracellular pH fluctuations, which provides a strategy for the design of pH-responsive probe in versatile applications.
2023, 34(2): 107339
doi: 10.1016/j.cclet.2022.03.062
Abstract:
Constructing anodes with fast ions/electrons transfer paths is an effective strategy to achieve high-performance sodium ion batteries (SIBs)/potassium ion batteries (PIBs). Amorphous carbon is a promising candidate anode for SIBs/PIBs owing to its disordered carbon layers, abundant defects/pores, and low-cost resources. However, the larger radius of Na+/K+ leading to depressed kinetics and poor cycling performance, impeding their further applications. Herein, we propose an efficient strategy to construct of nitrogen, sulfur co-doped hollow carbon nanospheres (NS-HCS) involving an in situ growth of polydopamine on nano-Ni(OH)2 template with subsequent sulfur doping process. During the formation process, the produced Ni nanospheres play as the hard template and catalyst for the formation of hollow carbon nanosphere with partially graphite microcrystalline structure, while the sulfur doping process can enlarge the interlayer space and create more defects on the surface of carbon nanospheres, thus synchronous improve the Na+/K+ insertion and adsorption ability in NS-HCS. With the synergistic control of the enlarged interlayer spacing, high content of pyridinic N/pyrrolic N and graphitization, a hybrid storage mechanism facilitates the transport kinetics and endows the NS-HCS electrode with high capacities and good cycling stability in SIBs and PIB. Benefit from the multiple effects, NS-HCS exhibits the improved capacity of 274.8 mAh/g at 0.1 A/g and excellent cycling stability of 149.5 mAh/g after 5000 cycles at 2.5A/g in SIBs, as well as good potassium ion storage behavior with a high capacity retention of 76.5% after 700 cycles at 1.0 A/g, demonstrating the potential applications of NS-HCS for high-performance SIBs and PIBs
Constructing anodes with fast ions/electrons transfer paths is an effective strategy to achieve high-performance sodium ion batteries (SIBs)/potassium ion batteries (PIBs). Amorphous carbon is a promising candidate anode for SIBs/PIBs owing to its disordered carbon layers, abundant defects/pores, and low-cost resources. However, the larger radius of Na+/K+ leading to depressed kinetics and poor cycling performance, impeding their further applications. Herein, we propose an efficient strategy to construct of nitrogen, sulfur co-doped hollow carbon nanospheres (NS-HCS) involving an in situ growth of polydopamine on nano-Ni(OH)2 template with subsequent sulfur doping process. During the formation process, the produced Ni nanospheres play as the hard template and catalyst for the formation of hollow carbon nanosphere with partially graphite microcrystalline structure, while the sulfur doping process can enlarge the interlayer space and create more defects on the surface of carbon nanospheres, thus synchronous improve the Na+/K+ insertion and adsorption ability in NS-HCS. With the synergistic control of the enlarged interlayer spacing, high content of pyridinic N/pyrrolic N and graphitization, a hybrid storage mechanism facilitates the transport kinetics and endows the NS-HCS electrode with high capacities and good cycling stability in SIBs and PIB. Benefit from the multiple effects, NS-HCS exhibits the improved capacity of 274.8 mAh/g at 0.1 A/g and excellent cycling stability of 149.5 mAh/g after 5000 cycles at 2.5A/g in SIBs, as well as good potassium ion storage behavior with a high capacity retention of 76.5% after 700 cycles at 1.0 A/g, demonstrating the potential applications of NS-HCS for high-performance SIBs and PIBs
2023, 34(2): 107349
doi: 10.1016/j.cclet.2022.03.072
Abstract:
Previous studies demonstrated that three-dimensional (3D) multicellular tumor spheroids (MCTS) could more closely mimic solid tumors than two-dimensional (2D) cancer cells in terms of the spatial structure, extracellular matrix-cell interaction, and gene expression pattern. However, no study has been reported on the differences in lipid metabolism and distribution among 2D cancer cells, MCTS, and solid tumors. Here, we used HepG2 liver cancer cell lines to establish these three cancer models. The variations of lipid profiles and spatial distribution among them were explored by using mass spectrometry-based lipidomics and matrix-assisted laser desorption/ionization mass spectrometry imaging (MSI). The results revealed that MCTS, relative to 2D cells, had more shared lipid species with solid tumors. Furthermore, MCTS contained more comparable characteristics than 2D cells to solid tumors with respect to the relative abundance of most lipid classes and mass spectra patterns. MSI data showed that 46 of 71 lipids had similar spatial distribution between solid tumors and MCTS, while lipids in 2D cells had no specific spatial distribution. Interestingly, most of detected lipid species in sphingolipids and glycerolipids preferred locating in the necrotic region to the proliferative region of solid tumors and MCTS. Taken together, our study provides the evidence of lipid metabolism and distribution demonstrating that MCTS are a more suitable in vitro model to mimic solid tumors, which may offer insights into tumor metabolism and microenvironment.
Previous studies demonstrated that three-dimensional (3D) multicellular tumor spheroids (MCTS) could more closely mimic solid tumors than two-dimensional (2D) cancer cells in terms of the spatial structure, extracellular matrix-cell interaction, and gene expression pattern. However, no study has been reported on the differences in lipid metabolism and distribution among 2D cancer cells, MCTS, and solid tumors. Here, we used HepG2 liver cancer cell lines to establish these three cancer models. The variations of lipid profiles and spatial distribution among them were explored by using mass spectrometry-based lipidomics and matrix-assisted laser desorption/ionization mass spectrometry imaging (MSI). The results revealed that MCTS, relative to 2D cells, had more shared lipid species with solid tumors. Furthermore, MCTS contained more comparable characteristics than 2D cells to solid tumors with respect to the relative abundance of most lipid classes and mass spectra patterns. MSI data showed that 46 of 71 lipids had similar spatial distribution between solid tumors and MCTS, while lipids in 2D cells had no specific spatial distribution. Interestingly, most of detected lipid species in sphingolipids and glycerolipids preferred locating in the necrotic region to the proliferative region of solid tumors and MCTS. Taken together, our study provides the evidence of lipid metabolism and distribution demonstrating that MCTS are a more suitable in vitro model to mimic solid tumors, which may offer insights into tumor metabolism and microenvironment.
2023, 34(2): 107352
doi: 10.1016/j.cclet.2022.03.075
Abstract:
Exosome and inclusive cargoes have manifested significant function in different biological events. In particular, glycopeptides in exosome are closely associated with occurrence and development of various diseases. Developing advanced tools is highly desired to enrich glycopeptides from exosomes, and enrich exosomes from complex biological samples as well. In this work, integration of L-cysteine and titania onto the surface of magnetic nanoparticles is designed to realize the coefficient affinity towards exosomes and inclusive glycopeptides. Benefiting from the synergistic affinity, we separate exosomes from human urine concentrate directly, which was proved by the detection of three typical antigen markers of exosomes. Furthermore, hardly any exosomes remained on materials after ultrasonication, which confirmed the good capture performance of Fe3O4@TiO2@L-Cys and high release effect of direct lysis. Moreover, 146 glycopeptides corresponding to 77 glycoproteins were successfully identified from captured exosomes. These satisfactory results will inspire more efforts to be devoted to this field and will be extremely helpful to in-depth information excavation of biological markers, especially disease-related ones, through exosomes and inclusive glycopeptides.
Exosome and inclusive cargoes have manifested significant function in different biological events. In particular, glycopeptides in exosome are closely associated with occurrence and development of various diseases. Developing advanced tools is highly desired to enrich glycopeptides from exosomes, and enrich exosomes from complex biological samples as well. In this work, integration of L-cysteine and titania onto the surface of magnetic nanoparticles is designed to realize the coefficient affinity towards exosomes and inclusive glycopeptides. Benefiting from the synergistic affinity, we separate exosomes from human urine concentrate directly, which was proved by the detection of three typical antigen markers of exosomes. Furthermore, hardly any exosomes remained on materials after ultrasonication, which confirmed the good capture performance of Fe3O4@TiO2@L-Cys and high release effect of direct lysis. Moreover, 146 glycopeptides corresponding to 77 glycoproteins were successfully identified from captured exosomes. These satisfactory results will inspire more efforts to be devoted to this field and will be extremely helpful to in-depth information excavation of biological markers, especially disease-related ones, through exosomes and inclusive glycopeptides.
2023, 34(2): 107359
doi: 10.1016/j.cclet.2022.03.082
Abstract:
It is essential to develop efficient electrocatalysts to generate hydrogen from water electrolysis for hydrogen economy. In this work, platinum (Pt) and nickel (Ni) co-doped porous carbon nanofibers (Pt/Ni-PCNFs) with low Pt content were prepared via an electrospinning, carbonization and galvanic replacement reaction. Because of the high electrical conductivity, abundant electrochemical active sites and synergistic effect between Pt and Ni nanoparticles, the optimized Pt/Ni-PCNFs catalyst shows an excellent HER activity with overpotentials of 20 mV in 0.5 mol/L H2SO4 and 46 mV in 1 mol/L KOH at a current density of 10 mA/cm2. Furthermore, over 35-h long-term stability has been achieved without significant attenuation. This work provides a simple route to prepare highly efficient electrocatalysts for water splitting and has great prospects in the field of renewable energy.
It is essential to develop efficient electrocatalysts to generate hydrogen from water electrolysis for hydrogen economy. In this work, platinum (Pt) and nickel (Ni) co-doped porous carbon nanofibers (Pt/Ni-PCNFs) with low Pt content were prepared via an electrospinning, carbonization and galvanic replacement reaction. Because of the high electrical conductivity, abundant electrochemical active sites and synergistic effect between Pt and Ni nanoparticles, the optimized Pt/Ni-PCNFs catalyst shows an excellent HER activity with overpotentials of 20 mV in 0.5 mol/L H2SO4 and 46 mV in 1 mol/L KOH at a current density of 10 mA/cm2. Furthermore, over 35-h long-term stability has been achieved without significant attenuation. This work provides a simple route to prepare highly efficient electrocatalysts for water splitting and has great prospects in the field of renewable energy.
2023, 34(2): 107360
doi: 10.1016/j.cclet.2022.03.083
Abstract:
Screening of foodborne pathogens is important to prevent contaminated foods from their supply chains. In this study, a portable detection device was developed for rapid, sensitive and simple detection of viable Salmonella using a finger-actuated microfluidic chip and an improved recombinase aided amplification (RAA) assay. Improved propidium monoazide (PMAxx) was combined with RAA to enable this device to distinguish viable bacteria from dead ones. The modification of PMAxx into dead bacteria, the magnetic extraction of nucleic acids from viable bacteria and the RAA detection of extracted nucleic acids were performed using the microfluidic chip on its supporting device by finger press-release operations. The fluorescent signal resulting from RAA amplification of the nucleic acids was collected using a USB camera and analyzed using a self-developed smartphone App to quantitatively determine the bacterial concentration. This device could detect Salmonella typhimurium in spiked chicken meats from 1.3 × 102 CFU/mL to 1.3 × 107 CFU/mL in 2 h with a lower detection limit of 130 CFU/mL, and has shown its potential for on-site detection of foodborne pathogens.
Screening of foodborne pathogens is important to prevent contaminated foods from their supply chains. In this study, a portable detection device was developed for rapid, sensitive and simple detection of viable Salmonella using a finger-actuated microfluidic chip and an improved recombinase aided amplification (RAA) assay. Improved propidium monoazide (PMAxx) was combined with RAA to enable this device to distinguish viable bacteria from dead ones. The modification of PMAxx into dead bacteria, the magnetic extraction of nucleic acids from viable bacteria and the RAA detection of extracted nucleic acids were performed using the microfluidic chip on its supporting device by finger press-release operations. The fluorescent signal resulting from RAA amplification of the nucleic acids was collected using a USB camera and analyzed using a self-developed smartphone App to quantitatively determine the bacterial concentration. This device could detect Salmonella typhimurium in spiked chicken meats from 1.3 × 102 CFU/mL to 1.3 × 107 CFU/mL in 2 h with a lower detection limit of 130 CFU/mL, and has shown its potential for on-site detection of foodborne pathogens.
2023, 34(2): 107363
doi: 10.1016/j.cclet.2022.03.086
Abstract:
Graphene-polymer composites have attracted great attention as sensing materials due to their tailorable electrical conductivity, physicochemical properties, and sensitivity to geometric and functional changes. Herein, we report the first example of cylindrical monolithic polyimine vitrimer/graphene composites with excellent mechanical, compressive, rehealable and recyclable, and piezoresistive properties via simple infiltration of polymer monomers into the pores of graphene aerogel followed by thermal curing. The composites exhibit excellent durable compressibility (negligible reduction in the compression properties even after 3000 consecutive compression cycles), rapid recovery to the original size upon stress released, high compressive strength (up to 1.2 MPa), and high conductivity (up to 79 S/m). Excellent piezoresistive properties were observed, displaying consistent and reliable change of the electrical resistance with the compression ratio. Furthermore, rehealing with ~100% recovery of the compressive strength and electric conductivity was achieved under mild rehealing conditions, which is highly desired but has rarely been reported for electronic materials. The facile strategy for fabrication of rehealable monolithic polymer/GAs can open new possibilities for the sustainable development of composites with high electrical conductivity for various applications such as sensing, health monitoring, and movement detection.
Graphene-polymer composites have attracted great attention as sensing materials due to their tailorable electrical conductivity, physicochemical properties, and sensitivity to geometric and functional changes. Herein, we report the first example of cylindrical monolithic polyimine vitrimer/graphene composites with excellent mechanical, compressive, rehealable and recyclable, and piezoresistive properties via simple infiltration of polymer monomers into the pores of graphene aerogel followed by thermal curing. The composites exhibit excellent durable compressibility (negligible reduction in the compression properties even after 3000 consecutive compression cycles), rapid recovery to the original size upon stress released, high compressive strength (up to 1.2 MPa), and high conductivity (up to 79 S/m). Excellent piezoresistive properties were observed, displaying consistent and reliable change of the electrical resistance with the compression ratio. Furthermore, rehealing with ~100% recovery of the compressive strength and electric conductivity was achieved under mild rehealing conditions, which is highly desired but has rarely been reported for electronic materials. The facile strategy for fabrication of rehealable monolithic polymer/GAs can open new possibilities for the sustainable development of composites with high electrical conductivity for various applications such as sensing, health monitoring, and movement detection.
2023, 34(2): 107364
doi: 10.1016/j.cclet.2022.03.087
Abstract:
The development of high-performance non-precious metal-based robust bifunctional electrocatalyst for both hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) in alkaline media is essential for the electrochemical overall water splitting technologies. Herein, we demonstrate that the HER/OER performance of CoSe2 can be significantly enhanced by tuning the 3d-orbital electron filling degree through Mo doping. Both density functional theory (DFT) calculations and experimental results imply that the doping of Mo with higher proportion of the unoccupied d-orbital (Pun) could not only serve as the active center for water adsorption to enhance the water molecule activation, but also modulate the electronic structures of Co metal center leading to the optimized adsorption strength of *H. As expected, the obtained Mo-CoSe2 exhibits a remarkable bifunctional performance with overpotential of only 85 mV for HER and 245 mV for OER to achieve the current density of 10 mA/cm2 in alkaline media. This work will provide a valuable insight to design highly efficient bifunctional electrocatalyst towards HER and OER.
The development of high-performance non-precious metal-based robust bifunctional electrocatalyst for both hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) in alkaline media is essential for the electrochemical overall water splitting technologies. Herein, we demonstrate that the HER/OER performance of CoSe2 can be significantly enhanced by tuning the 3d-orbital electron filling degree through Mo doping. Both density functional theory (DFT) calculations and experimental results imply that the doping of Mo with higher proportion of the unoccupied d-orbital (Pun) could not only serve as the active center for water adsorption to enhance the water molecule activation, but also modulate the electronic structures of Co metal center leading to the optimized adsorption strength of *H. As expected, the obtained Mo-CoSe2 exhibits a remarkable bifunctional performance with overpotential of only 85 mV for HER and 245 mV for OER to achieve the current density of 10 mA/cm2 in alkaline media. This work will provide a valuable insight to design highly efficient bifunctional electrocatalyst towards HER and OER.
2023, 34(2): 107377
doi: 10.1016/j.cclet.2022.03.100
Abstract:
The cell surface membrane proteome is a class of proteins encoded by ~25% of all protein-coding genes in living organisms and plays a key role in mediating communication between the cells and their surrounding environment. However, most cell surface membrane proteins (CSMPs) are naturally expressed at very low levels compared with intracellular proteins. The difficulties in their purification with high specificity further hinder the understanding of their structure and function. In this study, we developed a new photolabeling probe to achieve efficient tagging and facile enrichment of the CSMPs. The probe is composed of a lipid tail for cell surface localization, a polyethylene glycol (PEG) spacer for increased water solubility, two 4-(N-maleimido)benzophenone (MBP) groups for UV-active tagging of the CSMPs, and a biotin tag for subsequent isolation. Application of this photolabeling probe resulted in the successful enrichment and identification of 3098 annotated CSMPs in HT22 cells with close to 70% selectivity. The proposed photolabeling probe and enrichment strategy were demonstrated to be a powerful method for deep cell surface proteome profiling, representing one of the largest groups of current drug targets.
The cell surface membrane proteome is a class of proteins encoded by ~25% of all protein-coding genes in living organisms and plays a key role in mediating communication between the cells and their surrounding environment. However, most cell surface membrane proteins (CSMPs) are naturally expressed at very low levels compared with intracellular proteins. The difficulties in their purification with high specificity further hinder the understanding of their structure and function. In this study, we developed a new photolabeling probe to achieve efficient tagging and facile enrichment of the CSMPs. The probe is composed of a lipid tail for cell surface localization, a polyethylene glycol (PEG) spacer for increased water solubility, two 4-(N-maleimido)benzophenone (MBP) groups for UV-active tagging of the CSMPs, and a biotin tag for subsequent isolation. Application of this photolabeling probe resulted in the successful enrichment and identification of 3098 annotated CSMPs in HT22 cells with close to 70% selectivity. The proposed photolabeling probe and enrichment strategy were demonstrated to be a powerful method for deep cell surface proteome profiling, representing one of the largest groups of current drug targets.
2023, 34(2): 107378
doi: 10.1016/j.cclet.2022.03.101
Abstract:
Black phosphorus (BP) as an uprising two-dimensional material exhibits attractive potential in the field of electrocatalysis due to the inherent advantages of high carrier mobility and abundant lone pair electrons. However, the exposed active electrons compel BP to be deactivated by oxidative degradation. Herein, the electronic signature of acceptor-donor heterointerfacial interactions between BP and Co3O4 is realized via wet ball milling. The preferential migration of active electrons from BP to Co3O4 is achieved at the heterointerface since the Fermi level of BP is higher than that of Co3O4. Such relative energetic consideration promotes reasonable oxygen electrocatalytic active sites. Moreover, it significantly suppresses the oxidative degradation of BP. Consequently, the resulting Co3O4/BP heterojunction possesses superior oxygen bifunctional electrocatalytic activity than its parent catalysts. Most importantly, this work promotes an efficient route towards BP-based multifunctional catalysts.
Black phosphorus (BP) as an uprising two-dimensional material exhibits attractive potential in the field of electrocatalysis due to the inherent advantages of high carrier mobility and abundant lone pair electrons. However, the exposed active electrons compel BP to be deactivated by oxidative degradation. Herein, the electronic signature of acceptor-donor heterointerfacial interactions between BP and Co3O4 is realized via wet ball milling. The preferential migration of active electrons from BP to Co3O4 is achieved at the heterointerface since the Fermi level of BP is higher than that of Co3O4. Such relative energetic consideration promotes reasonable oxygen electrocatalytic active sites. Moreover, it significantly suppresses the oxidative degradation of BP. Consequently, the resulting Co3O4/BP heterojunction possesses superior oxygen bifunctional electrocatalytic activity than its parent catalysts. Most importantly, this work promotes an efficient route towards BP-based multifunctional catalysts.
2023, 34(2): 107392
doi: 10.1016/j.cclet.2022.03.115
Abstract:
The freshness of seafood can be judged by detecting the concentration of triethylamine (TEA). In this work, 2D CuO porous nanosheets (CuO PNs) were prepared by a graphene oxide template method and their particle sizes were regulated by changing the calcination temperature. Their structure, morphology and gas sensing performances were investigated by various characterization methods. The response (Rg/Ra) of the gas sensor based on CuO PNs calcined at 700 ℃ was as high as 440-100 ppm TEA at the operating temperature of 40 ℃. The detection limit was as low as 0.25 ppm. In addition, the gas sensor has good selectivity and stability. The excellent TEA sensitivity is mainly resulted from the appropriate particle size and loose porous framework. This work not only paves the way to explore the novel low temperature TEA gas sensors, but also provides deep insight on improving the structure and properties of gas sensitive materials by controlling the calcination temperature.
The freshness of seafood can be judged by detecting the concentration of triethylamine (TEA). In this work, 2D CuO porous nanosheets (CuO PNs) were prepared by a graphene oxide template method and their particle sizes were regulated by changing the calcination temperature. Their structure, morphology and gas sensing performances were investigated by various characterization methods. The response (Rg/Ra) of the gas sensor based on CuO PNs calcined at 700 ℃ was as high as 440-100 ppm TEA at the operating temperature of 40 ℃. The detection limit was as low as 0.25 ppm. In addition, the gas sensor has good selectivity and stability. The excellent TEA sensitivity is mainly resulted from the appropriate particle size and loose porous framework. This work not only paves the way to explore the novel low temperature TEA gas sensors, but also provides deep insight on improving the structure and properties of gas sensitive materials by controlling the calcination temperature.
2023, 34(2): 107394
doi: 10.1016/j.cclet.2022.03.117
Abstract:
Photocatalytic recovery, a novel precious metal recycling technology, dedicates to solving the environmental and energy consumption problems caused by traditional technologies. The activation of molecular oxygen (O2) is one of the most critical steps in the whole process. Herein, we regulated the different adsorption intensity of oxygen on the surface by designing phosphate (PO43−) modified titanium oxide (TiO2). The results show that the adsorption of oxygen on the photocatalyst surface is gradually enhanced, which effectively improves the dissolution rate of precious metals. PO43− modification increased the photocatalytic dissolution rate of gold (Au) by 2.8 times. The photocatalytic activity of other precious metals dissolution (such as palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and iridium (Ir)) was also significantly improved. It is applied to the recovery of precious metals from spent catalysts and electronic devices to significantly promote the recovery efficiency. This indicates the direction for designing more efficient photocatalysts for precious metal recovery.
Photocatalytic recovery, a novel precious metal recycling technology, dedicates to solving the environmental and energy consumption problems caused by traditional technologies. The activation of molecular oxygen (O2) is one of the most critical steps in the whole process. Herein, we regulated the different adsorption intensity of oxygen on the surface by designing phosphate (PO43−) modified titanium oxide (TiO2). The results show that the adsorption of oxygen on the photocatalyst surface is gradually enhanced, which effectively improves the dissolution rate of precious metals. PO43− modification increased the photocatalytic dissolution rate of gold (Au) by 2.8 times. The photocatalytic activity of other precious metals dissolution (such as palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and iridium (Ir)) was also significantly improved. It is applied to the recovery of precious metals from spent catalysts and electronic devices to significantly promote the recovery efficiency. This indicates the direction for designing more efficient photocatalysts for precious metal recovery.
2023, 34(2): 107395
doi: 10.1016/j.cclet.2022.03.118
Abstract:
In order to realize the sulfur and water resistance and facilitate the CO oxidation reactions, the effects of strain on the adsorption of CO, O2, SO2 and H2O molecules on Ni single-atom-catalyst supported by single-carbon-vacancy graphene (Ni-SG) have been studied based on first principles calculations. It shows that the compressive strain increases the adsorption energies of all above mentioned molecules on Ni-SG, where SO2 is adsorbed more strongly on Ni-SG than CO. However, in the presence of tensile strain, the adsorption energies decreases significantly when the molecules (O2 and SO2) obtain electrons from Ni-SG, while the adsorption energies just slightly decrease when the molecules (CO and H2O) lose electrons to Ni-SG, which finally achieves the preferential adsorption of CO and O2 molecules on Ni-SG by tensile strain. In addition, with tensile strain increasing to 10%, the rate-limited energy barrier along Eley-Rideal (ER) path monotonically increases from 0.77 eV to 0.98 eV, while the rate-limited energy barrier along Langmuir-Hinshelwood (LH) path monotonically decreases from 0.54 eV to 0.44 eV, indicating that the tensile strain can facilitate the LH mechanism while imped the ER mechanism on Ni-SG. The Hirshfeld charge and orbital levels of O2 and CO molecules are modulated by the tensile strain, which plays an important role for the decreasing of energy barriers for CO oxidation. Overall, the tensile strain can enhance the sulfur and water resistance of Ni-SG, as well as boost the CO oxidation reactions.
In order to realize the sulfur and water resistance and facilitate the CO oxidation reactions, the effects of strain on the adsorption of CO, O2, SO2 and H2O molecules on Ni single-atom-catalyst supported by single-carbon-vacancy graphene (Ni-SG) have been studied based on first principles calculations. It shows that the compressive strain increases the adsorption energies of all above mentioned molecules on Ni-SG, where SO2 is adsorbed more strongly on Ni-SG than CO. However, in the presence of tensile strain, the adsorption energies decreases significantly when the molecules (O2 and SO2) obtain electrons from Ni-SG, while the adsorption energies just slightly decrease when the molecules (CO and H2O) lose electrons to Ni-SG, which finally achieves the preferential adsorption of CO and O2 molecules on Ni-SG by tensile strain. In addition, with tensile strain increasing to 10%, the rate-limited energy barrier along Eley-Rideal (ER) path monotonically increases from 0.77 eV to 0.98 eV, while the rate-limited energy barrier along Langmuir-Hinshelwood (LH) path monotonically decreases from 0.54 eV to 0.44 eV, indicating that the tensile strain can facilitate the LH mechanism while imped the ER mechanism on Ni-SG. The Hirshfeld charge and orbital levels of O2 and CO molecules are modulated by the tensile strain, which plays an important role for the decreasing of energy barriers for CO oxidation. Overall, the tensile strain can enhance the sulfur and water resistance of Ni-SG, as well as boost the CO oxidation reactions.
2023, 34(2): 107404
doi: 10.1016/j.cclet.2022.04.002
Abstract:
Hydroxyl radicals (•OH) generated on anode play a vital role in electrochemical oxidation (EO) of organic pollutants for water treatment. Inspired by the four-electron oxygen evolution reaction (OER), we supposed an anode-selection strategy to stabilize deeply oxidized states (*O and *OOH) which are beneficial to generating •OH. To verify the hypothesis, a candidate anode component (MIL-101(Cr), a well-known metal-organic framework with active variable-valence transition metal centers) was used to coat Ti/TiO2 plate to fabricate anodes. Compared to TiO2(101) plane on undecorated anode surface, fast and complete removal of aniline and phenol, and improved energy utilization were achieved on MIL-101(Cr)-coated-Ti/TiO2 anode. Mechanism investigation, including pollutant degradation pathways, showed the predominate contribution (69.60%–75.13%) of •OH in pollutant mineralization. Density functional theory (DFT) computations indicated Cr site in MIL-101(Cr) was more conducive to stabilizing *O and *OOH, leading to thermodynamical spontaneous generation of •OH. This work opens up an exciting avenue to explore •OH production, and supplies a useful guidance to the development of anode materials for EO process.
Hydroxyl radicals (•OH) generated on anode play a vital role in electrochemical oxidation (EO) of organic pollutants for water treatment. Inspired by the four-electron oxygen evolution reaction (OER), we supposed an anode-selection strategy to stabilize deeply oxidized states (*O and *OOH) which are beneficial to generating •OH. To verify the hypothesis, a candidate anode component (MIL-101(Cr), a well-known metal-organic framework with active variable-valence transition metal centers) was used to coat Ti/TiO2 plate to fabricate anodes. Compared to TiO2(101) plane on undecorated anode surface, fast and complete removal of aniline and phenol, and improved energy utilization were achieved on MIL-101(Cr)-coated-Ti/TiO2 anode. Mechanism investigation, including pollutant degradation pathways, showed the predominate contribution (69.60%–75.13%) of •OH in pollutant mineralization. Density functional theory (DFT) computations indicated Cr site in MIL-101(Cr) was more conducive to stabilizing *O and *OOH, leading to thermodynamical spontaneous generation of •OH. This work opens up an exciting avenue to explore •OH production, and supplies a useful guidance to the development of anode materials for EO process.
2023, 34(2): 107412
doi: 10.1016/j.cclet.2022.04.010
Abstract:
Finding transition metal catalysts for effective catalytic conversion of CO to CO2 has attracted much attention. MXene as a new 2D layered material of early transition metal carbides, nitrides, and carbo-nitrides is a robust support for achoring metal atoms. In this study, the electronic structure, geometries, thermodynamic stability, and catalytic activity of MXene (Mo2CS2) supported single noble metal atoms (NM = Ru, Rh, Pd, Ir, Pt and Au) have been systematically examined using first-principles calculations and ab initio molecular dynamic (AIMD) simulations. First, AIMD simulations and phonon spectra demonstrate the dynamic and thermal stabilities of Mo2CS2 monolayer. Three likely reaction pathways, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), and Termolecular Eley–Rideal (TER) for CO oxidation on the Ru1- and Ir1@Mo2CS2 SACs, have been studied in detail. It is found that CO oxidation mainly proceeds via the TER mechanism under mild reaction conditions. The corresponding rate-determining steps are the dissociation of the intermediate (OCO-Ru1-OCO) and formation of OCO-Ir1-OCO intermediate. The downshift d-band center of Ru1- and Ir1@Mo2CS2 help to enhance activity and improve catalytst stability. Moreover, a microkinetic study predicts a maximum CO oxidation rate of 4.01 × 102 s-1 and 4.15 × 103 s-1 (298.15 K) following the TER pathway for the Ru1- and Ir1@Mo2CS2 catalysts, respectively. This work provides guideline for fabricating and designing highly efficient SACs with superb catalyts using MXene materials.
Finding transition metal catalysts for effective catalytic conversion of CO to CO2 has attracted much attention. MXene as a new 2D layered material of early transition metal carbides, nitrides, and carbo-nitrides is a robust support for achoring metal atoms. In this study, the electronic structure, geometries, thermodynamic stability, and catalytic activity of MXene (Mo2CS2) supported single noble metal atoms (NM = Ru, Rh, Pd, Ir, Pt and Au) have been systematically examined using first-principles calculations and ab initio molecular dynamic (AIMD) simulations. First, AIMD simulations and phonon spectra demonstrate the dynamic and thermal stabilities of Mo2CS2 monolayer. Three likely reaction pathways, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), and Termolecular Eley–Rideal (TER) for CO oxidation on the Ru1- and Ir1@Mo2CS2 SACs, have been studied in detail. It is found that CO oxidation mainly proceeds via the TER mechanism under mild reaction conditions. The corresponding rate-determining steps are the dissociation of the intermediate (OCO-Ru1-OCO) and formation of OCO-Ir1-OCO intermediate. The downshift d-band center of Ru1- and Ir1@Mo2CS2 help to enhance activity and improve catalytst stability. Moreover, a microkinetic study predicts a maximum CO oxidation rate of 4.01 × 102 s-1 and 4.15 × 103 s-1 (298.15 K) following the TER pathway for the Ru1- and Ir1@Mo2CS2 catalysts, respectively. This work provides guideline for fabricating and designing highly efficient SACs with superb catalyts using MXene materials.
2023, 34(2): 107416
doi: 10.1016/j.cclet.2022.04.014
Abstract:
One-dimensional carbon nanofibers are widely applied as anode material in the energy storage field due to its unique structure and high conductivity. In this work, one-dimensional ZnSe@N-doped carbon nanofibers (ZnSe@NC NFs) are successfully synthesized by electrospinning and annealed without extra troublesome conditions. ZnSe nanocrystals are enfolded in the N-doped carbon nanofibers, which can act as a protective layer to avoid the volume expansion of active material and promote ion transport during the cycling process. More importantly, the as-synthesized ZnSe@NC NFs are served as the anode material and display the admirable storage properties for Na/K-ion batteries. The one-dimensional ZnSe@NC NFs material shows the high capacity of 237 mAh/g for Na-ion batteries at a current density of 1 A/g for 2000 cycles. Meanwhile, it also delivers a high discharge capacity of 337 mAh/g for K-ion batteries at 0.2 A/g for 300 cycles. Additionally, it is confirmed that the pseudocapacitive contribution of the nano-structure material is up to 54.5% at a scan rate of 0.6 mV/s through the cyclic voltammetry (CV) measurement in K-ion batteries.
One-dimensional carbon nanofibers are widely applied as anode material in the energy storage field due to its unique structure and high conductivity. In this work, one-dimensional ZnSe@N-doped carbon nanofibers (ZnSe@NC NFs) are successfully synthesized by electrospinning and annealed without extra troublesome conditions. ZnSe nanocrystals are enfolded in the N-doped carbon nanofibers, which can act as a protective layer to avoid the volume expansion of active material and promote ion transport during the cycling process. More importantly, the as-synthesized ZnSe@NC NFs are served as the anode material and display the admirable storage properties for Na/K-ion batteries. The one-dimensional ZnSe@NC NFs material shows the high capacity of 237 mAh/g for Na-ion batteries at a current density of 1 A/g for 2000 cycles. Meanwhile, it also delivers a high discharge capacity of 337 mAh/g for K-ion batteries at 0.2 A/g for 300 cycles. Additionally, it is confirmed that the pseudocapacitive contribution of the nano-structure material is up to 54.5% at a scan rate of 0.6 mV/s through the cyclic voltammetry (CV) measurement in K-ion batteries.
2023, 34(2): 107417
doi: 10.1016/j.cclet.2022.04.015
Abstract:
Photocatalytic fuel cell (PFC) holds great potential for the sustainable production of electricity and degradation of organic pollutants for solving global energy and environmental problems. However, the efficient photodegradation of organic dyes and antibiotic drugs, such as ciprofloxacin (CIP) and methylene blue (MB), remains challenging. Aiming at improving the separation efficiency of hole and electron for electricity generation in the PFC system, TiO2-NPs@NF-x photoanode was fabricated by a cost-effective and laborsaving hydrothermal approach. The as-fabricated photoanode demonstrated abundant active sites, enhanced light harvesting capacity and photogenerated charge carrier separation. At a CIP-HCl concentration of 10 mg/L and pH value of about 7, 85% of CIP-HCl can be efficiently removed after 3 h irradiation by 300 W Xe lamp. TiO2-NPs@NF-20 photoelectrode based PFC system exhibited an impressed ability to simultaneously degrade ciprofloxacin and generate electricity under light irradiation with an open circuit voltage of 1.021 V, short circuit current density and maximum power density of 2.4 mA/cm2, 0.357 mW/cm2, respectively. This work provided a cost-effective method for the treatment of organic waste and generation of electrical power.
Photocatalytic fuel cell (PFC) holds great potential for the sustainable production of electricity and degradation of organic pollutants for solving global energy and environmental problems. However, the efficient photodegradation of organic dyes and antibiotic drugs, such as ciprofloxacin (CIP) and methylene blue (MB), remains challenging. Aiming at improving the separation efficiency of hole and electron for electricity generation in the PFC system, TiO2-NPs@NF-x photoanode was fabricated by a cost-effective and laborsaving hydrothermal approach. The as-fabricated photoanode demonstrated abundant active sites, enhanced light harvesting capacity and photogenerated charge carrier separation. At a CIP-HCl concentration of 10 mg/L and pH value of about 7, 85% of CIP-HCl can be efficiently removed after 3 h irradiation by 300 W Xe lamp. TiO2-NPs@NF-20 photoelectrode based PFC system exhibited an impressed ability to simultaneously degrade ciprofloxacin and generate electricity under light irradiation with an open circuit voltage of 1.021 V, short circuit current density and maximum power density of 2.4 mA/cm2, 0.357 mW/cm2, respectively. This work provided a cost-effective method for the treatment of organic waste and generation of electrical power.
2023, 34(2): 107418
doi: 10.1016/j.cclet.2022.04.016
Abstract:
Sperm damage caused by reactive oxygen species (ROS) is one of the main causes of male infertility. Therefore, the level of ROS in sperm is an important indicator for the diagnosis and prognosis of male infertility. Herein, we constructed a single sperm ROS detection method (SSRDM) with an optical micro-probe fabricated via focused ion beam process. The micro-probe is used to separately excite fluorescence in the sperm and the area around the sperm after ROS staining, and the difference in fluorescence values can reflect the level of ROS in the sperm. We collected 102 semen samples and 72 of them were divided into asthenozoospermia and non-asthenozoospermia groups. SSRDM and flow cytometry were used to detect the ROS levels of the two groups. The results of SSRDM showed that the ROS levels of asthenozoospermia group were higher than that of non-asthenozoospermia group (P = 0.002), while the results of flow cytometry indicated no difference (P = 0.152). In terms of ROS levels, compared with flow cytometry, SSRDM has a stronger ability to distinguish between those two groups, providing a reliable basis for assessment of sperm quality. Another 30 semen samples were used to investigate temperature and temporal variability of SSRDM to ensure the stability and accuracy of this method. Overall, we have developed a method that can quantitatively detect fluorescent substances in sperm at the single-cell level supplying evidence for diagnosis and prognosis of male infertility.
Sperm damage caused by reactive oxygen species (ROS) is one of the main causes of male infertility. Therefore, the level of ROS in sperm is an important indicator for the diagnosis and prognosis of male infertility. Herein, we constructed a single sperm ROS detection method (SSRDM) with an optical micro-probe fabricated via focused ion beam process. The micro-probe is used to separately excite fluorescence in the sperm and the area around the sperm after ROS staining, and the difference in fluorescence values can reflect the level of ROS in the sperm. We collected 102 semen samples and 72 of them were divided into asthenozoospermia and non-asthenozoospermia groups. SSRDM and flow cytometry were used to detect the ROS levels of the two groups. The results of SSRDM showed that the ROS levels of asthenozoospermia group were higher than that of non-asthenozoospermia group (P = 0.002), while the results of flow cytometry indicated no difference (P = 0.152). In terms of ROS levels, compared with flow cytometry, SSRDM has a stronger ability to distinguish between those two groups, providing a reliable basis for assessment of sperm quality. Another 30 semen samples were used to investigate temperature and temporal variability of SSRDM to ensure the stability and accuracy of this method. Overall, we have developed a method that can quantitatively detect fluorescent substances in sperm at the single-cell level supplying evidence for diagnosis and prognosis of male infertility.
2023, 34(2): 107421
doi: 10.1016/j.cclet.2022.04.019
Abstract:
MicroRNAs (miRNAs) have attracted significant attention in biomedical research and clinical diagnosis. However, due to their inherent characteristics of low abundance and the high complexity of corresponding biological matrices, simultaneous detection of multiple miRNAs at low abundance is still a challenge. In this work, a method coupling exponential amplification reaction (EXPAR) with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is developed for label-free and simultaneous detection of multiple miRNAs. The assay can be performed under isothermal conditions in a single reaction tube, and finished in less than 30 min. It exhibits good quantification ability and with attomolar-level sensitivity for miRNAs detection. It also shows high specificity to distinguish miRNAs at single-nucleotide resolution. We used the method to detect the miRNA-21, let-7a, miRNA-100, and miRNA-125b in samples of spiked human serum and breast cancer cells (i.e., MCF-7, MDA-MB-231 and SK-BR-3). The quantification results were well consistent with the standard real-time fluorescence EXPAR. Consequently, the label-free mass-spectrometric platform could be a potential tool for miRNAs analysis in complex biological samples, and may be used for clinical diagnosis.
MicroRNAs (miRNAs) have attracted significant attention in biomedical research and clinical diagnosis. However, due to their inherent characteristics of low abundance and the high complexity of corresponding biological matrices, simultaneous detection of multiple miRNAs at low abundance is still a challenge. In this work, a method coupling exponential amplification reaction (EXPAR) with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is developed for label-free and simultaneous detection of multiple miRNAs. The assay can be performed under isothermal conditions in a single reaction tube, and finished in less than 30 min. It exhibits good quantification ability and with attomolar-level sensitivity for miRNAs detection. It also shows high specificity to distinguish miRNAs at single-nucleotide resolution. We used the method to detect the miRNA-21, let-7a, miRNA-100, and miRNA-125b in samples of spiked human serum and breast cancer cells (i.e., MCF-7, MDA-MB-231 and SK-BR-3). The quantification results were well consistent with the standard real-time fluorescence EXPAR. Consequently, the label-free mass-spectrometric platform could be a potential tool for miRNAs analysis in complex biological samples, and may be used for clinical diagnosis.
2023, 34(2): 107422
doi: 10.1016/j.cclet.2022.04.020
Abstract:
Developing the high activity, low cost and robust large-current-density-based electrocatalysts is of great significance for the industrial electrolytic water splitting. However, the current range of most reported materials is small, which makes it difficult for them to play their roles in practical applications. Here, a self-supported amorphous FexNi1-xMoO4/IF treated with ammonium fluoride (AF0.1-FNMO/IF) is synthesized by one-step hydrothermal method. With the help of NH4F, AF0.1-FNMO/IF exhibits a vertically cross-linked nanosheet with spherical structure. Electrochemical measurement shows that AF0.1-FNMO/IF affords a large current density ordeal and only need low overpotentials of 289 and 345 mV to reach a current response of 500 mA/cm2 for oxygen evolution reaction and hydrogen evolution reaction, respectively, together with long-time stability (both at 500, 1000 and 2000 mA/cm2) in 1.0 mol/L KOH solution. Using it as bifunctional catalyst for overall water splitting, the current densities of 100, 500, 1000 and 1500 mA/cm2 are achieved at a cell voltage of 1.71, 1.88, 1.94 and 1.97 V with excellent durability, which is much better than that of most published electrodes. The work provides valuable insight for designing higher activity nickel iron-based molybdate catalysts with large current density.
Developing the high activity, low cost and robust large-current-density-based electrocatalysts is of great significance for the industrial electrolytic water splitting. However, the current range of most reported materials is small, which makes it difficult for them to play their roles in practical applications. Here, a self-supported amorphous FexNi1-xMoO4/IF treated with ammonium fluoride (AF0.1-FNMO/IF) is synthesized by one-step hydrothermal method. With the help of NH4F, AF0.1-FNMO/IF exhibits a vertically cross-linked nanosheet with spherical structure. Electrochemical measurement shows that AF0.1-FNMO/IF affords a large current density ordeal and only need low overpotentials of 289 and 345 mV to reach a current response of 500 mA/cm2 for oxygen evolution reaction and hydrogen evolution reaction, respectively, together with long-time stability (both at 500, 1000 and 2000 mA/cm2) in 1.0 mol/L KOH solution. Using it as bifunctional catalyst for overall water splitting, the current densities of 100, 500, 1000 and 1500 mA/cm2 are achieved at a cell voltage of 1.71, 1.88, 1.94 and 1.97 V with excellent durability, which is much better than that of most published electrodes. The work provides valuable insight for designing higher activity nickel iron-based molybdate catalysts with large current density.
2023, 34(2): 107425
doi: 10.1016/j.cclet.2022.04.023
Abstract:
Metal oxides derived from metal-organic framework (MOF) have attracted considerable attention due to its excellent performance and unique structure. Doping is considered as an effective method to improve gas-sensing performance. However, nonmetal doped metal oxides derived from MOF as gas-sensing materials have not been reported. Within this work, N atoms were successfully doped into the lattice of ZnO nanoparticles using ZIF-8 as a self-sacrificial template through a thermal treatment process with the assistant of urea. The obtained N-ZnO exhibited competitive ethanol-sensing performance, in which the response value of N-ZnO-5 to 100 ppm ethanol reached 115 at 190 ℃ with a satisfactory selectivity. It was found that the N-doping in ZnO facilitated the formation of oxygen vacancy that promoted the generation of adsorbed oxygen species to achieve the enhanced gas-sensing performance. Besides, the larger specific surface area resulting from the size reduction during the urea-assisted pyrolysis process can also be responsible for the improving of the ethanol-sensing performance.
Metal oxides derived from metal-organic framework (MOF) have attracted considerable attention due to its excellent performance and unique structure. Doping is considered as an effective method to improve gas-sensing performance. However, nonmetal doped metal oxides derived from MOF as gas-sensing materials have not been reported. Within this work, N atoms were successfully doped into the lattice of ZnO nanoparticles using ZIF-8 as a self-sacrificial template through a thermal treatment process with the assistant of urea. The obtained N-ZnO exhibited competitive ethanol-sensing performance, in which the response value of N-ZnO-5 to 100 ppm ethanol reached 115 at 190 ℃ with a satisfactory selectivity. It was found that the N-doping in ZnO facilitated the formation of oxygen vacancy that promoted the generation of adsorbed oxygen species to achieve the enhanced gas-sensing performance. Besides, the larger specific surface area resulting from the size reduction during the urea-assisted pyrolysis process can also be responsible for the improving of the ethanol-sensing performance.
2023, 34(2): 107433
doi: 10.1016/j.cclet.2022.04.031
Abstract:
The removal of eight typical pharmaceuticals (PhACs) (i.e., ibuprofen (IBU), ketoprofen (KET), diclofenac (DIC), sulfadiazine (SD), sulfamethoxazole (SMX), trimethoprim (TMP), ciprofloxacin (CIP) and enoxacin (ENO)) in sulfur-driven autotrophic denitrification (SdAD) process were firstly investigated via long-term operation of bioreactor coupled with batch tests. The results indicated that IBU and KET can be effectively removed (removal efficiency > 50%) compared to other six PhACs in SdAD bioreactor. Biodegradation was the primary removal route for IBU and KET with the specific biodegradation rates of 5.3±0.7~18.1±1.8 µg g−1-VSS d−1 at initial concentrations of 25-200 µg/L. The biotransformation intermediates of IBU and KET were examined, and the results indicated that IBU was biotransformed to three intermediates via hydroxylation and carboxylation. KET biotransformation could be initiated from the reduction of the keto group following with a series of oxidation/reduction reactions, and five intermediates of KET were observed in this study. The microbial community composition in the system was markedly shifted when long-term exposure to PhACs. However, the functional microbes (e.g., genus Thiobacillus) showed high tolerance to PhACs, resulting in the high efficiency for PhACs, N and S removal during long-term SdAD reactor operation. The findings provide better insight into PhACs removal in SdAD process, especially IBU and KET, and open up an innovative opportunity for the treatment of PhACs-laden wastewater using sulfur-mediated biological process.
The removal of eight typical pharmaceuticals (PhACs) (i.e., ibuprofen (IBU), ketoprofen (KET), diclofenac (DIC), sulfadiazine (SD), sulfamethoxazole (SMX), trimethoprim (TMP), ciprofloxacin (CIP) and enoxacin (ENO)) in sulfur-driven autotrophic denitrification (SdAD) process were firstly investigated via long-term operation of bioreactor coupled with batch tests. The results indicated that IBU and KET can be effectively removed (removal efficiency > 50%) compared to other six PhACs in SdAD bioreactor. Biodegradation was the primary removal route for IBU and KET with the specific biodegradation rates of 5.3±0.7~18.1±1.8 µg g−1-VSS d−1 at initial concentrations of 25-200 µg/L. The biotransformation intermediates of IBU and KET were examined, and the results indicated that IBU was biotransformed to three intermediates via hydroxylation and carboxylation. KET biotransformation could be initiated from the reduction of the keto group following with a series of oxidation/reduction reactions, and five intermediates of KET were observed in this study. The microbial community composition in the system was markedly shifted when long-term exposure to PhACs. However, the functional microbes (e.g., genus Thiobacillus) showed high tolerance to PhACs, resulting in the high efficiency for PhACs, N and S removal during long-term SdAD reactor operation. The findings provide better insight into PhACs removal in SdAD process, especially IBU and KET, and open up an innovative opportunity for the treatment of PhACs-laden wastewater using sulfur-mediated biological process.
2023, 34(2): 107437
doi: 10.1016/j.cclet.2022.04.035
Abstract:
A series of monolithic MnO2/iron mesh (IM) catalysts for oxidation of toluene were successfully prepared by using in situ hydrothermal growth. MnO2 can grow firmly on the IM substrates surface with a shedding rate of only 0.14%. Due to the highest Oads and high-valent Mn4+ and Fe3+ elements, the temperature at 50% and 90% toluene conversion (T50% and T90%) was 252 and 265 ℃, respectively for the best performance catalyst (hydrothermal temperature of 80 ℃, hydrothermal time of 12 h, and precursor manganese ion concentration of 0.03 mol/L). The catalysts also presented good water resistance and cycle performance. In-situ DRIFTS results suggesting that toluene was first rapid transformed into the reaction intermediate species (benzoate species) and then converted to CO2 and H2O. Therefore, this work provides a new direction for the research and application of IM-based monolithic catalysts.
A series of monolithic MnO2/iron mesh (IM) catalysts for oxidation of toluene were successfully prepared by using in situ hydrothermal growth. MnO2 can grow firmly on the IM substrates surface with a shedding rate of only 0.14%. Due to the highest Oads and high-valent Mn4+ and Fe3+ elements, the temperature at 50% and 90% toluene conversion (T50% and T90%) was 252 and 265 ℃, respectively for the best performance catalyst (hydrothermal temperature of 80 ℃, hydrothermal time of 12 h, and precursor manganese ion concentration of 0.03 mol/L). The catalysts also presented good water resistance and cycle performance. In-situ DRIFTS results suggesting that toluene was first rapid transformed into the reaction intermediate species (benzoate species) and then converted to CO2 and H2O. Therefore, this work provides a new direction for the research and application of IM-based monolithic catalysts.
2023, 34(2): 107439
doi: 10.1016/j.cclet.2022.04.037
Abstract:
The horizontal flow anaerobic digester indicated that high ammonia (2923 mg/L) and SO42- (3653 mg/L) would influence the performance of methane production with food waste as substrates. Therefore, bottle anaerobic digestion reactors were carried out to investigate the effect of ammonia/sulfate concentrations on the methane production. Experimental results manifested that the anaerobic digesters with an ammonia concentration of 3500 mg/L or sulfate of 1600 mg/L showed the best performance of methane production, with an average methane yield of 0.32 and 0.33 L (g VS)-1 d-1, respectively. Specifically, a higher ammonia (6500 mg/L) or sulfate (1600-3500 mg/L) level hindered the bioconversion of C from liquid to gas phase (2.68% or 1.73% CH4-Gas, respectively), while insignificantly for the hydrolyzation of C and N from solid to liquid phase. Similar to sulfate, high ammonia nitrogen seriously inhibited the methanation process, leading to a significant carbon accumulation in the anaerobic reactor, especially for propionic acid. The predominant archaea Methanosarcina at genus level indicated that aceticlastic methanogenesis was the major methanogenic pathway. Meanwhile, high ammonia level suppressed the activity of Methanosarcina, while modest sulfate improved H2-consuming methanogens activity. A large fraction of unclassified bacteria within the Firmicutes (43.78%-63.17%) and Bacteroidetes (24.20%-33.30%) phylum played an important role in substrates hydrolysis.
The horizontal flow anaerobic digester indicated that high ammonia (2923 mg/L) and SO42- (3653 mg/L) would influence the performance of methane production with food waste as substrates. Therefore, bottle anaerobic digestion reactors were carried out to investigate the effect of ammonia/sulfate concentrations on the methane production. Experimental results manifested that the anaerobic digesters with an ammonia concentration of 3500 mg/L or sulfate of 1600 mg/L showed the best performance of methane production, with an average methane yield of 0.32 and 0.33 L (g VS)-1 d-1, respectively. Specifically, a higher ammonia (6500 mg/L) or sulfate (1600-3500 mg/L) level hindered the bioconversion of C from liquid to gas phase (2.68% or 1.73% CH4-Gas, respectively), while insignificantly for the hydrolyzation of C and N from solid to liquid phase. Similar to sulfate, high ammonia nitrogen seriously inhibited the methanation process, leading to a significant carbon accumulation in the anaerobic reactor, especially for propionic acid. The predominant archaea Methanosarcina at genus level indicated that aceticlastic methanogenesis was the major methanogenic pathway. Meanwhile, high ammonia level suppressed the activity of Methanosarcina, while modest sulfate improved H2-consuming methanogens activity. A large fraction of unclassified bacteria within the Firmicutes (43.78%-63.17%) and Bacteroidetes (24.20%-33.30%) phylum played an important role in substrates hydrolysis.
2023, 34(2): 107445
doi: 10.1016/j.cclet.2022.04.043
Abstract:
Due to the high decay rate of the non-radiative transition of long wavelengths, the molecular design of efficient and stable near-infrared (NIR) electroluminescent materials remains a big challenge. Herein, a new tetradentate cyclometalated platinum(Ⅱ) complex with an N∧C∧C∧N coordinated framework has been developed and used as a dopant for NIR organic light-emitting diodes (OLEDs). The complex exhibited a short-lived (0.5–1.5 μs) metal-to-ligand charge transfer (MLCT) excited state in doped and neat films. The resulting NIR OLEDs (λEL = 730 nm) achieved maximum external quantum efficiency (EQEmax) of 5.2% and radiance of 74626 mW sr-1 m–2. Of note, the device exhibited excellent stability with operational lifetime of 119 h for LT90. This work demonstrated the great potential of tetradentate platinum(Ⅱ) complexes in the field of NIR OLEDs.
Due to the high decay rate of the non-radiative transition of long wavelengths, the molecular design of efficient and stable near-infrared (NIR) electroluminescent materials remains a big challenge. Herein, a new tetradentate cyclometalated platinum(Ⅱ) complex with an N∧C∧C∧N coordinated framework has been developed and used as a dopant for NIR organic light-emitting diodes (OLEDs). The complex exhibited a short-lived (0.5–1.5 μs) metal-to-ligand charge transfer (MLCT) excited state in doped and neat films. The resulting NIR OLEDs (λEL = 730 nm) achieved maximum external quantum efficiency (EQEmax) of 5.2% and radiance of 74626 mW sr-1 m–2. Of note, the device exhibited excellent stability with operational lifetime of 119 h for LT90. This work demonstrated the great potential of tetradentate platinum(Ⅱ) complexes in the field of NIR OLEDs.
2023, 34(2): 107457
doi: 10.1016/j.cclet.2022.04.055
Abstract:
Spiropyrans (SPs) are a well-known class of photochromic compounds and have found widespread application due to their unique properties. However, for many conventional SPs, high energy ultraviolet (UV) light is commonly essential to drive photoisomerization, leading to poor fatigue resistance. Moreover, the practical application of spiropyrans is hindered by their fast fading speed due to the instability of closed forms (SP) or open forms (MC). Herein, we disclose a novel strategy to address these challenges through introducing both electron-donating substituents to stabilize the SP and dynamic coordination bonds to stabilize the MC. The resulting new spiropyrans complexes exhibit negative photochromic properties, with fast visible light response, good stability of both SP and MC, and significantly improved fatigue resistance.
Spiropyrans (SPs) are a well-known class of photochromic compounds and have found widespread application due to their unique properties. However, for many conventional SPs, high energy ultraviolet (UV) light is commonly essential to drive photoisomerization, leading to poor fatigue resistance. Moreover, the practical application of spiropyrans is hindered by their fast fading speed due to the instability of closed forms (SP) or open forms (MC). Herein, we disclose a novel strategy to address these challenges through introducing both electron-donating substituents to stabilize the SP and dynamic coordination bonds to stabilize the MC. The resulting new spiropyrans complexes exhibit negative photochromic properties, with fast visible light response, good stability of both SP and MC, and significantly improved fatigue resistance.
2023, 34(2): 107462
doi: 10.1016/j.cclet.2022.04.060
Abstract:
The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However, the exploration of N, S co-doped carbon with well-defined active sites and hierarchical porous structures are still limited. In this study, we prepared a series of edge-enriched N, S co-doped carbon materials through pyrolysis of thiourea (TU) encapsulated in zeolitic imidazolate frameworks (TU@ZIF) composites, which delivered very good oxygen reduction reaction (ORR) performance in alkaline medium with onset potential of 0.94 V vs. reversible hydrogen electrode (RHE), good stability and methanol tolerance. Density functional theory (DFT) calculations suggested that carbon atoms adjacent to N and S are probable active sites for ORR intermediates in edge-enriched N, S co-doped carbon materials because higher electron density can enhance O2 adsorption, lower formation barriers of intermediates, improving the ORR performance comparing to intact N, S co-doped carbon materials. This study might provide a new pathway for improving ORR activity by the integration engineering of edge sites, and electronic structure of heteroatom doped carbon electrocatalysts.
The development of carbon materials with high electrochemical performance for next-generation energy device is emerging, especially N, S co-doped carbon materials have sparked intensive attention. However, the exploration of N, S co-doped carbon with well-defined active sites and hierarchical porous structures are still limited. In this study, we prepared a series of edge-enriched N, S co-doped carbon materials through pyrolysis of thiourea (TU) encapsulated in zeolitic imidazolate frameworks (TU@ZIF) composites, which delivered very good oxygen reduction reaction (ORR) performance in alkaline medium with onset potential of 0.94 V vs. reversible hydrogen electrode (RHE), good stability and methanol tolerance. Density functional theory (DFT) calculations suggested that carbon atoms adjacent to N and S are probable active sites for ORR intermediates in edge-enriched N, S co-doped carbon materials because higher electron density can enhance O2 adsorption, lower formation barriers of intermediates, improving the ORR performance comparing to intact N, S co-doped carbon materials. This study might provide a new pathway for improving ORR activity by the integration engineering of edge sites, and electronic structure of heteroatom doped carbon electrocatalysts.
2023, 34(2): 107468
doi: 10.1016/j.cclet.2022.04.066
Abstract:
Realizing efficient charge separation and directional transfer is a challenge for single-component semiconductors. The spatial electric field generated by dipole moment could promote charge separation. Here, three-dimensional hierarchical CuCo2S4 microspheres with lattice distortion were prepared, and lattice distortion was modulated by changing feed Co/Cu molar ratios in synthesis. CuCo2S4 showed asymmetric crystal structure, leading to generation of dipole moment. The charge separation efficiency of CuCo2S4 was related to lattice distortion, and lattice expansion was in favor for charge separation. The CuCo2S4 with feed Cu/Co molar ratio of 1:4 (CCS-4) showed the maximum lattice expansion and exhibited the highest photocatalytic activity, which was attributable to the highest charge separation efficiency and the largest specific surface area. CCS-4 can remove 95.4% of tetracycline hydrochloride within 40 min photocatalysis, and effectively improve the biodegradability of pharmaceutical wastewater. Importantly, this study provides a new vision for constructing single-component photocatalysts with high photocatalytic performance.
Realizing efficient charge separation and directional transfer is a challenge for single-component semiconductors. The spatial electric field generated by dipole moment could promote charge separation. Here, three-dimensional hierarchical CuCo2S4 microspheres with lattice distortion were prepared, and lattice distortion was modulated by changing feed Co/Cu molar ratios in synthesis. CuCo2S4 showed asymmetric crystal structure, leading to generation of dipole moment. The charge separation efficiency of CuCo2S4 was related to lattice distortion, and lattice expansion was in favor for charge separation. The CuCo2S4 with feed Cu/Co molar ratio of 1:4 (CCS-4) showed the maximum lattice expansion and exhibited the highest photocatalytic activity, which was attributable to the highest charge separation efficiency and the largest specific surface area. CCS-4 can remove 95.4% of tetracycline hydrochloride within 40 min photocatalysis, and effectively improve the biodegradability of pharmaceutical wastewater. Importantly, this study provides a new vision for constructing single-component photocatalysts with high photocatalytic performance.
2023, 34(2): 107472
doi: 10.1016/j.cclet.2022.04.070
Abstract:
The unique structure of fluorescent proteins in which the fluorophore is encapsulated by the protein shell to restrict rotation and emit light inspired the screening of chromophores that selectively bind to biomolecules to generate fluorescence. In this paper, we report a curcuminoid-BF2-like fluorescent dye N-BF2 containing 4-dimethylaniline as an electron-donating group. When this dye is combined with HSA or BSA, the fluorescence is enhanced 90/112-fold, and the fluorescence quantum yield increases from < 0.001 to 0.16/0.19. Such a large change in fluorescence enhancement is due to the encapsulation of N-BF2 in the protein cavity by HSA/BSA, which inhibits the intramolecular rotation of the aniline moiety caused by charge transfer after the fluorophore is excited by light. N-BF2 has fast and strong binding to HSA or BSA and was found to be reversible in solution and intracellularly. Since N-BF2 also has the ability to target lipid droplets, the complex of N-BF2/HSA realizes the regulation of reversible lipid droplet staining in cells.
The unique structure of fluorescent proteins in which the fluorophore is encapsulated by the protein shell to restrict rotation and emit light inspired the screening of chromophores that selectively bind to biomolecules to generate fluorescence. In this paper, we report a curcuminoid-BF2-like fluorescent dye N-BF2 containing 4-dimethylaniline as an electron-donating group. When this dye is combined with HSA or BSA, the fluorescence is enhanced 90/112-fold, and the fluorescence quantum yield increases from < 0.001 to 0.16/0.19. Such a large change in fluorescence enhancement is due to the encapsulation of N-BF2 in the protein cavity by HSA/BSA, which inhibits the intramolecular rotation of the aniline moiety caused by charge transfer after the fluorophore is excited by light. N-BF2 has fast and strong binding to HSA or BSA and was found to be reversible in solution and intracellularly. Since N-BF2 also has the ability to target lipid droplets, the complex of N-BF2/HSA realizes the regulation of reversible lipid droplet staining in cells.
2023, 34(2): 107493
doi: 10.1016/j.cclet.2022.05.007
Abstract:
Aqueous rechargeable Zn//MnO2 batteries have been considered as the promising candidate for future energy storage system due to their economic and environmental merits. However, the high-performance Zn//MnO2 batteries are plagued by poor sluggish reaction kinetics and capacity degradation due to the strong electrostatic interactions and complicated reaction process. Herein, the synergistic effect of atom defects engineering and phase transformation mechanism is confirmed as the effective strategy to enhance ion/charge transfer kinetics and structural stability. Defects gradient controlling and electrochemically induced phase transformation from spinel to layered structure render the aqueous Zn//λ-MnO2 system delivers a high discharge capacity of 285 mAh/g and capacity retention of 81% after 500 cycles.
Aqueous rechargeable Zn//MnO2 batteries have been considered as the promising candidate for future energy storage system due to their economic and environmental merits. However, the high-performance Zn//MnO2 batteries are plagued by poor sluggish reaction kinetics and capacity degradation due to the strong electrostatic interactions and complicated reaction process. Herein, the synergistic effect of atom defects engineering and phase transformation mechanism is confirmed as the effective strategy to enhance ion/charge transfer kinetics and structural stability. Defects gradient controlling and electrochemically induced phase transformation from spinel to layered structure render the aqueous Zn//λ-MnO2 system delivers a high discharge capacity of 285 mAh/g and capacity retention of 81% after 500 cycles.
2023, 34(2): 107497
doi: 10.1016/j.cclet.2022.05.011
Abstract:
The most practical high-temperature proton exchange membranes (PEMs) are phosphoric acid (PA)-doped polymer electrolytes. However, due to the plasticizing effect of PA, it is a challenge to address the trade-off between the proton conductivity and the mechanical performance of these materials. Here, we report an effective strategy to fabricate robust high-temperature PEMs based on the in situ electrostatic crosslinking of polyoxometalates and polymers. A comb copolymer poly(ether-ether-ketone)-grafted-poly(2-ethyl-2-oxazoline) (PGE) with transformable side chains was synthesized and complexed with H3PW12O40 (PW) by electrostatic self-assembly, forming PGE/PW nanocomposite membranes with bicontinuous nanostructures. After a subsequent PA-treatment of these membranes, high-temperature PEMs of PGE/PW/PA ternary nanocomposites were obtained, in which the in situ electrostatic crosslinking effect between PW and PGE side chains was generated in the hydrophilic domains of the bicontinuous structures. The microphase separation structure and the electrostatic crosslinking feature endow the PGE/PW/PA membranes with excellent anhydrous proton conductive ability while retaining high mechanical performance. The membranes show a high proton conductivity of 42.5 mS/cm at 150 ℃ and a high tensile strength of 13 MPa. Our strategy can pave a new route based on electrostatic control to design nanostructured polymer electrolytes.
The most practical high-temperature proton exchange membranes (PEMs) are phosphoric acid (PA)-doped polymer electrolytes. However, due to the plasticizing effect of PA, it is a challenge to address the trade-off between the proton conductivity and the mechanical performance of these materials. Here, we report an effective strategy to fabricate robust high-temperature PEMs based on the in situ electrostatic crosslinking of polyoxometalates and polymers. A comb copolymer poly(ether-ether-ketone)-grafted-poly(2-ethyl-2-oxazoline) (PGE) with transformable side chains was synthesized and complexed with H3PW12O40 (PW) by electrostatic self-assembly, forming PGE/PW nanocomposite membranes with bicontinuous nanostructures. After a subsequent PA-treatment of these membranes, high-temperature PEMs of PGE/PW/PA ternary nanocomposites were obtained, in which the in situ electrostatic crosslinking effect between PW and PGE side chains was generated in the hydrophilic domains of the bicontinuous structures. The microphase separation structure and the electrostatic crosslinking feature endow the PGE/PW/PA membranes with excellent anhydrous proton conductive ability while retaining high mechanical performance. The membranes show a high proton conductivity of 42.5 mS/cm at 150 ℃ and a high tensile strength of 13 MPa. Our strategy can pave a new route based on electrostatic control to design nanostructured polymer electrolytes.
2023, 34(2): 107504
doi: 10.1016/j.cclet.2022.05.018
Abstract:
Isostructural multicomponent crystals provide a promising way for fine-tuning physicochemical properties, whereas their design remains quite challenging. The purpose of this work was to provide a new strategy for obtaining isostructural multicomponent crystals by introducing coformers with functional group positional isomerism. Five isostructural salts of an antitumor drug dimethylaminomicheliolide (DMAMCL) were reported and designed with a series of dihydroxybenzoic acid regioisomers for the first time, which were identified by power and single-crystal X-ray diffractions. Similar lattice parameters suggested these obtained salts may have the same crystal packing mode. The quantitative similarity parameters via XPac, CrystalCMP and Mercury program further proved these crystal structures are 3D isostructural. Hirshfeld surface maps and 2D fingerprint plots show that the isostructural salts have similar intermolecular interactions. Compared with DMAMCL, obvious improvement was observed in the thermal stability, hygroscopicity, and solubility of these isostructural salts. Meanwhile, isostructural crystals may have different physicochemical properties, even though the shape and molecular size are similar and the packing of crystal structures is equally matched.
Isostructural multicomponent crystals provide a promising way for fine-tuning physicochemical properties, whereas their design remains quite challenging. The purpose of this work was to provide a new strategy for obtaining isostructural multicomponent crystals by introducing coformers with functional group positional isomerism. Five isostructural salts of an antitumor drug dimethylaminomicheliolide (DMAMCL) were reported and designed with a series of dihydroxybenzoic acid regioisomers for the first time, which were identified by power and single-crystal X-ray diffractions. Similar lattice parameters suggested these obtained salts may have the same crystal packing mode. The quantitative similarity parameters via XPac, CrystalCMP and Mercury program further proved these crystal structures are 3D isostructural. Hirshfeld surface maps and 2D fingerprint plots show that the isostructural salts have similar intermolecular interactions. Compared with DMAMCL, obvious improvement was observed in the thermal stability, hygroscopicity, and solubility of these isostructural salts. Meanwhile, isostructural crystals may have different physicochemical properties, even though the shape and molecular size are similar and the packing of crystal structures is equally matched.
2023, 34(2): 107507
doi: 10.1016/j.cclet.2022.05.021
Abstract:
Acetaminophen (APAP), a classic nonsteroidal anti-inflammatory drug (NSAID), has attracted much attention due to the overdose-induced hepatotoxicity in the past several decades. N-Acetyl-p-benzoquinone imine (NAPQI), the P450-dependent metabolism of APAP, leads to GSH depletion, protein binding, mitochondrial oxidative stress, and eventually the liver injury. Herein, we develop a Fe-based metal-organic framework (MOF) to deliver and transform acetaminophen into toxic "chemo" drug through the cascade reaction for enhanced cancer therapy. In the acidic tumor microenvironment, the Fe-based MOF collapses and releases abundant Fe ions to generate hydroxyl radicals (•OH) via Fenton reaction, subsequently catalyzing nontoxic APAP into toxic NAPQI. Meanwhile, NAPQI depletes intracellular glutathione (GSH) rapidly, leading to alleviating the antioxidant ability of cancer cells and amplifying Fenton activity. The intracellular oxidative stress and the toxic metabolite of APAP can provide a synergistic effect on antitumor activity.
Acetaminophen (APAP), a classic nonsteroidal anti-inflammatory drug (NSAID), has attracted much attention due to the overdose-induced hepatotoxicity in the past several decades. N-Acetyl-p-benzoquinone imine (NAPQI), the P450-dependent metabolism of APAP, leads to GSH depletion, protein binding, mitochondrial oxidative stress, and eventually the liver injury. Herein, we develop a Fe-based metal-organic framework (MOF) to deliver and transform acetaminophen into toxic "chemo" drug through the cascade reaction for enhanced cancer therapy. In the acidic tumor microenvironment, the Fe-based MOF collapses and releases abundant Fe ions to generate hydroxyl radicals (•OH) via Fenton reaction, subsequently catalyzing nontoxic APAP into toxic NAPQI. Meanwhile, NAPQI depletes intracellular glutathione (GSH) rapidly, leading to alleviating the antioxidant ability of cancer cells and amplifying Fenton activity. The intracellular oxidative stress and the toxic metabolite of APAP can provide a synergistic effect on antitumor activity.
2023, 34(2): 107509
doi: 10.1016/j.cclet.2022.05.023
Abstract:
Three kinds of carbonized polymer dots (CPDs) synthesized via a one-pot process from o-phenylenediamine (OPD), m-phenylenediamine (MPD) and p-phenylenediamine (PPD) exhibit excitation-wavelength independent yellow, green and red emissions, respectively. In sharp contrast, two kinds of CPDs prepared via a hydrothermal process from citric acid (CA) and diethylenetriamine (DETA) exhibit obvious excitation-wavelength dependent emissions. Through the characterization and comparison of the two types of CPDs, it is concretely revealed that the polymer structure types during the formation of CPDs can effectively control the fluorescence excitation-wavelength independence/dependence. The homogeneous polymer structures contained in CPDs contribute to excitation-wavelength independence, whereas random copolymer structures contribute to excitation-wavelength dependence. These studies are of great significance for further understanding the polymer structures and designing unique optical properties of CPDs.
Three kinds of carbonized polymer dots (CPDs) synthesized via a one-pot process from o-phenylenediamine (OPD), m-phenylenediamine (MPD) and p-phenylenediamine (PPD) exhibit excitation-wavelength independent yellow, green and red emissions, respectively. In sharp contrast, two kinds of CPDs prepared via a hydrothermal process from citric acid (CA) and diethylenetriamine (DETA) exhibit obvious excitation-wavelength dependent emissions. Through the characterization and comparison of the two types of CPDs, it is concretely revealed that the polymer structure types during the formation of CPDs can effectively control the fluorescence excitation-wavelength independence/dependence. The homogeneous polymer structures contained in CPDs contribute to excitation-wavelength independence, whereas random copolymer structures contribute to excitation-wavelength dependence. These studies are of great significance for further understanding the polymer structures and designing unique optical properties of CPDs.
2023, 34(2): 107510
doi: 10.1016/j.cclet.2022.05.024
Abstract:
The serum cholesterol level is an important indicator of healthy and there is a great necessity for frequent cholesterol monitoring to some cardiovascular-related diseases, which puts forward higher requirements for point-of-care testing (POCT) of cholesterol. In this work, a cascade catalytic system of cholesterol is developed by encapsulation of cholesterol oxidase (ChOx) and PdCuAu nanoparticles into zeolitic imidazolate framework-L (ChOx/PCA@ZIF-L). Results indicate that ZIF-L carrier can significantly increase the catalytic activity of single or multiple enzymes, due to its high loading capacity and efficient molecular transport. Under the optimal conditions, the absorbance of reaction system performs linear relationships with the concentration of cholesterol in two intervals from 0.0005 mmol/L to 1.0000 mmol/L, with a limit of detection of 0.2176 µmol/L. The proposed colorimetric strategy based on ChOx/PCA@ZIF-L performs a good agreement with the results provided by chemiluminescence method for the serum cholesterol detection. Interestingly, a simple paper-based sensing system is constructed through a pre-reaction-transfer operation, which gets rid of the complex pre-processing requirements of traditional operations on filter paper. The presented strategy allows for the sensitive, convenient, costless assay of serum cholesterol, and paves a new way to design the POCT device for daily monitoring of healthy.
The serum cholesterol level is an important indicator of healthy and there is a great necessity for frequent cholesterol monitoring to some cardiovascular-related diseases, which puts forward higher requirements for point-of-care testing (POCT) of cholesterol. In this work, a cascade catalytic system of cholesterol is developed by encapsulation of cholesterol oxidase (ChOx) and PdCuAu nanoparticles into zeolitic imidazolate framework-L (ChOx/PCA@ZIF-L). Results indicate that ZIF-L carrier can significantly increase the catalytic activity of single or multiple enzymes, due to its high loading capacity and efficient molecular transport. Under the optimal conditions, the absorbance of reaction system performs linear relationships with the concentration of cholesterol in two intervals from 0.0005 mmol/L to 1.0000 mmol/L, with a limit of detection of 0.2176 µmol/L. The proposed colorimetric strategy based on ChOx/PCA@ZIF-L performs a good agreement with the results provided by chemiluminescence method for the serum cholesterol detection. Interestingly, a simple paper-based sensing system is constructed through a pre-reaction-transfer operation, which gets rid of the complex pre-processing requirements of traditional operations on filter paper. The presented strategy allows for the sensitive, convenient, costless assay of serum cholesterol, and paves a new way to design the POCT device for daily monitoring of healthy.
2023, 34(2): 107512
doi: 10.1016/j.cclet.2022.05.026
Abstract:
Eight polycyclic furanobutenolide-containing norcembrane diterpenoids featuring C19 frameworks (1–8) were rapidly recognized and isolated from the Hainan soft coral Sinularia sp. by the HSQC-based small molecule accurate recognition technology. Yonarolide A (1a), featuring an unprecedented 5/6/4/4/7 pentacyclic ring skeleton, was surprisingly obtained as a transformed product by leaving compound 1 under indoor natural light, and was further proved to be a [2 + 2] cycloaddition product of 1 by photochemical reaction. The absolute stereochemistry of 1a and the three known norcembrane diterpenoids 1, 4, and 7 were determined by using X-ray diffraction (XRD) analyses. Further, with the aid of XRD analysis, the structure of scabrolide B (2), which was previously reported of possessing 5/6/7 tricyclic skeleton, was firmly revised as 2a with the rare inelegane skeleton featured by the highly oxygenated 5/7/6 tricyclic carbocycle.
Eight polycyclic furanobutenolide-containing norcembrane diterpenoids featuring C19 frameworks (1–8) were rapidly recognized and isolated from the Hainan soft coral Sinularia sp. by the HSQC-based small molecule accurate recognition technology. Yonarolide A (1a), featuring an unprecedented 5/6/4/4/7 pentacyclic ring skeleton, was surprisingly obtained as a transformed product by leaving compound 1 under indoor natural light, and was further proved to be a [2 + 2] cycloaddition product of 1 by photochemical reaction. The absolute stereochemistry of 1a and the three known norcembrane diterpenoids 1, 4, and 7 were determined by using X-ray diffraction (XRD) analyses. Further, with the aid of XRD analysis, the structure of scabrolide B (2), which was previously reported of possessing 5/6/7 tricyclic skeleton, was firmly revised as 2a with the rare inelegane skeleton featured by the highly oxygenated 5/7/6 tricyclic carbocycle.
2023, 34(2): 107513
doi: 10.1016/j.cclet.2022.05.027
Abstract:
Hawanoids A‒E (1‒5), five highly cyclized diterpenoids were isolated from the deep-sea-derived fungus Paraconiothyrium hawaiiense FS482. Compounds 1 and 2 possessed an unprecedented tetracyclo[6.6.2.02,7.011,15]cetane carbon skeleton while 3 and 4 possessed an unusual 11, 14-macrocyclic ether moiety in phomactin family. Their structures including the stereo-chemistry were determined through spectroscopic analysis, X-ray diffractions and computational calculations. The plausible biosynthetic pathway was proposed based on the predicted biosynthetic gene cluster. All of the isolated compounds exhibited inhibitory activities against PAF-induced platelet aggregation. The molecular docking study was carried out understand the interaction between the PAF receptor and hawanoids with different skeletons.
Hawanoids A‒E (1‒5), five highly cyclized diterpenoids were isolated from the deep-sea-derived fungus Paraconiothyrium hawaiiense FS482. Compounds 1 and 2 possessed an unprecedented tetracyclo[6.6.2.02,7.011,15]cetane carbon skeleton while 3 and 4 possessed an unusual 11, 14-macrocyclic ether moiety in phomactin family. Their structures including the stereo-chemistry were determined through spectroscopic analysis, X-ray diffractions and computational calculations. The plausible biosynthetic pathway was proposed based on the predicted biosynthetic gene cluster. All of the isolated compounds exhibited inhibitory activities against PAF-induced platelet aggregation. The molecular docking study was carried out understand the interaction between the PAF receptor and hawanoids with different skeletons.
2023, 34(2): 107514
doi: 10.1016/j.cclet.2022.05.028
Abstract:
From ZINC database with a total of 1.8 million small molecules, four compounds are identified as prolyl hydroxylase 2 inhibitors through a virtual screening workflow that sequentially incorporates machine learning, molecular docking, and molecular dynamics. Among them, compound 103, (E)-5-(5-((2-(1H-tetrazol-5-yl)hydrazineylidene)methyl)furan-2-yl)isoindoline-1,3-dione, promotes the migration and capillary tube formation capacity of human umbilical vein endothelial cells through enhancing the stability of hypoxia inducible factor-1α and increasing the level of vascular endothelial growth factor.
From ZINC database with a total of 1.8 million small molecules, four compounds are identified as prolyl hydroxylase 2 inhibitors through a virtual screening workflow that sequentially incorporates machine learning, molecular docking, and molecular dynamics. Among them, compound 103, (E)-5-(5-((2-(1H-tetrazol-5-yl)hydrazineylidene)methyl)furan-2-yl)isoindoline-1,3-dione, promotes the migration and capillary tube formation capacity of human umbilical vein endothelial cells through enhancing the stability of hypoxia inducible factor-1α and increasing the level of vascular endothelial growth factor.
2023, 34(2): 107515
doi: 10.1016/j.cclet.2022.05.029
Abstract:
Triplet-triplet annihilation (TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared (NIR)-to-blue upconverted emission is preferred for most of the practical applications, but developing a NIR-to-blue TTA upconversion system is a challenging task in photochemistry. In this work, a thermally activated delayed fluorescence (TADF) material with intense visible-to-NIR absorption is demonstrated that shows a longer triplet state lifetime (32 µs) and high triplet state energy (ET = 1.55 eV). For the first time, a heavy atom-free NIR (λex > 650 nm) to blue (λem < 460 nm) TTA upconversion system was devised, employing the dimeric borondifluoride curcuminoid TADF material as triplet photosensitizer (PS) and a large anti-Stokes shift (0.88 eV) along with moderate upconversion yield was achieved. Our work provides the solution and guidance for the future development of purely organic heavy atom-free NIR activating TTA upconversion system for a wide array of applications.
Triplet-triplet annihilation (TTA) upconversion-based materials have potential application in the broad range of research areas, including photocatalysis and life sciences. However, near-infrared (NIR)-to-blue upconverted emission is preferred for most of the practical applications, but developing a NIR-to-blue TTA upconversion system is a challenging task in photochemistry. In this work, a thermally activated delayed fluorescence (TADF) material with intense visible-to-NIR absorption is demonstrated that shows a longer triplet state lifetime (32 µs) and high triplet state energy (ET = 1.55 eV). For the first time, a heavy atom-free NIR (λex > 650 nm) to blue (λem < 460 nm) TTA upconversion system was devised, employing the dimeric borondifluoride curcuminoid TADF material as triplet photosensitizer (PS) and a large anti-Stokes shift (0.88 eV) along with moderate upconversion yield was achieved. Our work provides the solution and guidance for the future development of purely organic heavy atom-free NIR activating TTA upconversion system for a wide array of applications.
2023, 34(2): 107516
doi: 10.1016/j.cclet.2022.05.030
Abstract:
Vercytochalasins A (1) and B (2), two biosynthetically related cytochalasins featuring novel structure and substituents, were isolated from the endozoic fungus Curvularia verruculosa which was associated with the deep-sea squat lobster Shinkaia crosnieri collected from the cold seep environment in South China sea. Their structures were elucidated by detailed interpretation of NMR spectroscopic and mass spectrometric data. The absolute configurations were confirmed by NOESY experiments as well as by DP4+ and ECD calculations. Differed from common cytochalasins, compound 1 is an uncommon secocytochalasin featuring the ester group cleaved between C-9 and C-23, and incorporating an additional oxygenated C4 unit which coupled with C-20 and C-22 to form a new substituted cyclohexenone moiety, while compound 2 contains an unusual 2‑hydroxy-3-oxobutan-2-yl unit at C-22. Both compounds are distinctive from the commonly described cytochalasins. Compound 1 exhibited potent activity against angiotensin-Ⅰ-converting enzyme (ACE) whereas compound 2 showed antibacterial activity. Molecular docking simulations were performed to explore the intermolecular interaction of compounds 1 and 2 with ACE.
Vercytochalasins A (1) and B (2), two biosynthetically related cytochalasins featuring novel structure and substituents, were isolated from the endozoic fungus Curvularia verruculosa which was associated with the deep-sea squat lobster Shinkaia crosnieri collected from the cold seep environment in South China sea. Their structures were elucidated by detailed interpretation of NMR spectroscopic and mass spectrometric data. The absolute configurations were confirmed by NOESY experiments as well as by DP4+ and ECD calculations. Differed from common cytochalasins, compound 1 is an uncommon secocytochalasin featuring the ester group cleaved between C-9 and C-23, and incorporating an additional oxygenated C4 unit which coupled with C-20 and C-22 to form a new substituted cyclohexenone moiety, while compound 2 contains an unusual 2‑hydroxy-3-oxobutan-2-yl unit at C-22. Both compounds are distinctive from the commonly described cytochalasins. Compound 1 exhibited potent activity against angiotensin-Ⅰ-converting enzyme (ACE) whereas compound 2 showed antibacterial activity. Molecular docking simulations were performed to explore the intermolecular interaction of compounds 1 and 2 with ACE.
2023, 34(2): 107517
doi: 10.1016/j.cclet.2022.05.031
Abstract:
G-quadruplex (G4) is widely known as a non-classical secondary structure of nucleic acid. With the in-depth study of G4, it is an urgent need for a phosphorescent probe with a high G4 binding ability to evaluate the level of G4 in the cytoplasm. Thus, this study designed and synthesized Ir-PDP where an Ir(Ⅲ) complex was used as a phosphorescent emitter. Meanwhile, two installed PDPs (pyridostatin derivatives) were used to improve the combination ability with G4 and reduced the cytotoxicity of the Ir(Ⅲ) complex. Compared with other nucleic acid secondary structures, Ir-PDP produced a higher phosphorescence lifetime after interacting with G4. Ir-PDP was distributed in the cytoplasm of living cells, and two-photon phosphorescence lifetime imaging can detect the binding events of the probe in the cytoplasm. The addition of G4 binder PDS significantly regulated cytoplasmic phosphorescence lifetime. The project explored a new sensing pathway to observe the binding manners of probes in the cytoplasm through the phosphorescence lifetime of probes.
G-quadruplex (G4) is widely known as a non-classical secondary structure of nucleic acid. With the in-depth study of G4, it is an urgent need for a phosphorescent probe with a high G4 binding ability to evaluate the level of G4 in the cytoplasm. Thus, this study designed and synthesized Ir-PDP where an Ir(Ⅲ) complex was used as a phosphorescent emitter. Meanwhile, two installed PDPs (pyridostatin derivatives) were used to improve the combination ability with G4 and reduced the cytotoxicity of the Ir(Ⅲ) complex. Compared with other nucleic acid secondary structures, Ir-PDP produced a higher phosphorescence lifetime after interacting with G4. Ir-PDP was distributed in the cytoplasm of living cells, and two-photon phosphorescence lifetime imaging can detect the binding events of the probe in the cytoplasm. The addition of G4 binder PDS significantly regulated cytoplasmic phosphorescence lifetime. The project explored a new sensing pathway to observe the binding manners of probes in the cytoplasm through the phosphorescence lifetime of probes.
2023, 34(2): 107519
doi: 10.1016/j.cclet.2022.05.033
Abstract:
The emission changes of fluorescent dyes under the influence of environmental changes or interaction with analytes are the basis for designing ratiometric fluorescent probes and logic gates. However, it is rare that only one external stimulus induces continuous fluorescent color changes in a fluorescent dye. In this paper, we report a cage-like molecule formed by two benzene rings and three imidazolium salts which produces continuous fluorescence wavelength changes when interacted with fluoride ions. Fluoride ions are first bound to the center of the cage under the action of anion-π interaction, and the (C−H)+···F– type ionic hydrogen bonds induce the blue-shift of fluorescence. The subsequent formation of C-F covalent bonds with fluoride ions makes the fluorophore wavelength continue to blue-shift, and finally obtains continuous multiple fluorescence changes caused by a single external stimulus. According to the fluorescence wavelength and intensity, six different fluorescence signal channels can be obtained, which can be encoded as six numbers from 0 to 5. We expect that this reaction process can find applications in quantitative anion recognition and molecular counters.
The emission changes of fluorescent dyes under the influence of environmental changes or interaction with analytes are the basis for designing ratiometric fluorescent probes and logic gates. However, it is rare that only one external stimulus induces continuous fluorescent color changes in a fluorescent dye. In this paper, we report a cage-like molecule formed by two benzene rings and three imidazolium salts which produces continuous fluorescence wavelength changes when interacted with fluoride ions. Fluoride ions are first bound to the center of the cage under the action of anion-π interaction, and the (C−H)+···F– type ionic hydrogen bonds induce the blue-shift of fluorescence. The subsequent formation of C-F covalent bonds with fluoride ions makes the fluorophore wavelength continue to blue-shift, and finally obtains continuous multiple fluorescence changes caused by a single external stimulus. According to the fluorescence wavelength and intensity, six different fluorescence signal channels can be obtained, which can be encoded as six numbers from 0 to 5. We expect that this reaction process can find applications in quantitative anion recognition and molecular counters.
2023, 34(2): 107520
doi: 10.1016/j.cclet.2022.05.034
Abstract:
We report the synthesis and characterization of a fan-shaped chiral nanographene 1, which is composed of 6 hexabenzocoronene subunits with 216 conjugated carbon atoms. In the dehydrocyclization reaction, 38 CC bonds are formed simultaneously. 1 exhibits strong panchromatic absorption from the ultraviolet to the near-infrared, with an absorption coefficient of 209,000 L mol−1 cm−1 at 564 nm. Optically pure samples, obtained via chiral HPLC, show distinct ECD signals (|Δε| = 704 L mol−1 cm−1 at 405 nm). Upon excitation, 1 emits near-infrared fluorescence at 820 nm with a quantum yield of 5.5%. These photophysical properties of 1 were analyzed with the assistance of DFT calculations.
We report the synthesis and characterization of a fan-shaped chiral nanographene 1, which is composed of 6 hexabenzocoronene subunits with 216 conjugated carbon atoms. In the dehydrocyclization reaction, 38 CC bonds are formed simultaneously. 1 exhibits strong panchromatic absorption from the ultraviolet to the near-infrared, with an absorption coefficient of 209,000 L mol−1 cm−1 at 564 nm. Optically pure samples, obtained via chiral HPLC, show distinct ECD signals (|Δε| = 704 L mol−1 cm−1 at 405 nm). Upon excitation, 1 emits near-infrared fluorescence at 820 nm with a quantum yield of 5.5%. These photophysical properties of 1 were analyzed with the assistance of DFT calculations.
2023, 34(2): 107521
doi: 10.1016/j.cclet.2022.05.035
Abstract:
Coordination-driven self-assembly was used to construct two metallacycles of a dicarboxylate-functionalized dibenzo-18-crown-6 in combination with either a 0° anthracene-based clip-type acceptor or a 60° phenanthrene-based acceptor. The angularities of these moieties make them suitable for the formation of a [2 + 2] rectangle and a [3 + 3] triangle, respectively. The synthesis, characterization and host-guest chemistry of two metallacycles were described and supported by 31P{1H}, 1H NMR spectra and electrospray mass spectrometry.
Coordination-driven self-assembly was used to construct two metallacycles of a dicarboxylate-functionalized dibenzo-18-crown-6 in combination with either a 0° anthracene-based clip-type acceptor or a 60° phenanthrene-based acceptor. The angularities of these moieties make them suitable for the formation of a [2 + 2] rectangle and a [3 + 3] triangle, respectively. The synthesis, characterization and host-guest chemistry of two metallacycles were described and supported by 31P{1H}, 1H NMR spectra and electrospray mass spectrometry.
2023, 34(2): 107528
doi: 10.1016/j.cclet.2022.05.042
Abstract:
Designing a multifunctional scaffold with osteogenic and angiogenic properties holds promise for ideal bone regeneration. Innovative scaffold was here constructed by immobilizing exosomes derived from human bone mesenchymal stem cells (hBMSCs) onto porous polymer meshes which developed by PLGA and Cu-based MOF (PLGA/CuBDC@Exo). The synthesized exosome-laden scaffold capable of providing a dual cooperative controllable release of bioactive copper ions and exosomes that promote osteogenesis and angiogenesis, thereby achieving cell-free bone regeneration. In vitro assay revealed the composite stent not only substantially upregulated the expression of osteogenic-related proteins (ALP, Runx2, Ocn) and VEGF in hBMSCs, but promoted the migration and tube formation of the human umbilical vein endothelial cells (HUVECs). In vivo evaluation further confirmed this scaffold dramatically stimulated bone regeneration and angiogenesis in critical-sized defects in rats. Altogether, this composite scaffold carrying therapeutic exosomes had an osteogenic-angiogenic coupling effect and offered a new idea for cell-free bone tissue engineering.
Designing a multifunctional scaffold with osteogenic and angiogenic properties holds promise for ideal bone regeneration. Innovative scaffold was here constructed by immobilizing exosomes derived from human bone mesenchymal stem cells (hBMSCs) onto porous polymer meshes which developed by PLGA and Cu-based MOF (PLGA/CuBDC@Exo). The synthesized exosome-laden scaffold capable of providing a dual cooperative controllable release of bioactive copper ions and exosomes that promote osteogenesis and angiogenesis, thereby achieving cell-free bone regeneration. In vitro assay revealed the composite stent not only substantially upregulated the expression of osteogenic-related proteins (ALP, Runx2, Ocn) and VEGF in hBMSCs, but promoted the migration and tube formation of the human umbilical vein endothelial cells (HUVECs). In vivo evaluation further confirmed this scaffold dramatically stimulated bone regeneration and angiogenesis in critical-sized defects in rats. Altogether, this composite scaffold carrying therapeutic exosomes had an osteogenic-angiogenic coupling effect and offered a new idea for cell-free bone tissue engineering.
2023, 34(2): 107529
doi: 10.1016/j.cclet.2022.05.043
Abstract:
Heat shock protein 90 (Hsp90) is an appealing anticancer drug target that provoked a tremendous wave of investigations. Geldanamycin (GA) is the first identified Hsp90 inhibitor that exhibited potent anti-cancer activity, but the off-target toxicity associated with the benzoquinone moiety hampered its clinical application. Until now, structure optimization of GA is still in need to fully exploit the therapeutic value of Hsp90. Due to the structural complexity and synthetic challenge of this compound family, conventional optimization is bound to be costly but high efficiency is expected to be reachable by combining the art of rational design and total synthesis. Described in this paper is our first attempt at this approach aiming at rational modification of the C6-position of GA. The binding affinities towards Hsp90 of compound 1 (C6-ethyl) and 2 (C6-methyl) were designed and predicted by using Discovery Studio. These compounds were synthesized and further subjected to a thorough in vitro biological evaluation. We found that compounds 1 and 2 bind to Hsp90 protein with the IC50 of 34.26 nmol/L and 163.7 nmol/L, respectively. Both compounds showed broad-spectrum antitumor effects. Replacing by ethyl, compound 1 exhibited more potent bioactivity than positive control GA, such as in G2/M cell cycle arrest, cell apoptosis and client proteins degradations. The results firstly indicated that the docking study is able to provide a precise prediction of Hsp90 affinities of GA analogues, and the C6 substituent of GA is not erasable without affecting its biological activity.
Heat shock protein 90 (Hsp90) is an appealing anticancer drug target that provoked a tremendous wave of investigations. Geldanamycin (GA) is the first identified Hsp90 inhibitor that exhibited potent anti-cancer activity, but the off-target toxicity associated with the benzoquinone moiety hampered its clinical application. Until now, structure optimization of GA is still in need to fully exploit the therapeutic value of Hsp90. Due to the structural complexity and synthetic challenge of this compound family, conventional optimization is bound to be costly but high efficiency is expected to be reachable by combining the art of rational design and total synthesis. Described in this paper is our first attempt at this approach aiming at rational modification of the C6-position of GA. The binding affinities towards Hsp90 of compound 1 (C6-ethyl) and 2 (C6-methyl) were designed and predicted by using Discovery Studio. These compounds were synthesized and further subjected to a thorough in vitro biological evaluation. We found that compounds 1 and 2 bind to Hsp90 protein with the IC50 of 34.26 nmol/L and 163.7 nmol/L, respectively. Both compounds showed broad-spectrum antitumor effects. Replacing by ethyl, compound 1 exhibited more potent bioactivity than positive control GA, such as in G2/M cell cycle arrest, cell apoptosis and client proteins degradations. The results firstly indicated that the docking study is able to provide a precise prediction of Hsp90 affinities of GA analogues, and the C6 substituent of GA is not erasable without affecting its biological activity.
2023, 34(2): 107533
doi: 10.1016/j.cclet.2022.05.047
Abstract:
Terminal deoxynucleotidyl transferase (TdT) has been characterized as template-independent polymerase using single-stranded DNA (ssDNA) as primers to generate random oligonucleotides. However, the extension performance of TdT to single-stranded RNA (ssRNA) is vague. By systematically comparing and contrasting the performance of TdT-catalyzed ssDNA and ssRNA extension, it is indicated that the catalytic efficiency of ssRNA as primers was about 3 times lower than ssDNA as primers. Collectively, it is believed that understanding the catalytic performance of TdT will help to design the strategy to synthesize chimeric DNA on 3′-OH of ssRNA, which becomes invaluable.
Terminal deoxynucleotidyl transferase (TdT) has been characterized as template-independent polymerase using single-stranded DNA (ssDNA) as primers to generate random oligonucleotides. However, the extension performance of TdT to single-stranded RNA (ssRNA) is vague. By systematically comparing and contrasting the performance of TdT-catalyzed ssDNA and ssRNA extension, it is indicated that the catalytic efficiency of ssRNA as primers was about 3 times lower than ssDNA as primers. Collectively, it is believed that understanding the catalytic performance of TdT will help to design the strategy to synthesize chimeric DNA on 3′-OH of ssRNA, which becomes invaluable.
2023, 34(2): 107534
doi: 10.1016/j.cclet.2022.05.048
Abstract:
The hydroarylation reaction of terminal alkynes with arylboronic acids catalyzed by low (400 ppm) loadings of palladium has been developed. The reaction is broad in scope and high-yielding, even on multi-gram scale. It is suitable for the synthesis of alkenes labeled with deuterium, and for the late-stage modification of bioactive molecules.
The hydroarylation reaction of terminal alkynes with arylboronic acids catalyzed by low (400 ppm) loadings of palladium has been developed. The reaction is broad in scope and high-yielding, even on multi-gram scale. It is suitable for the synthesis of alkenes labeled with deuterium, and for the late-stage modification of bioactive molecules.
Electrochemically mediated decarboxylative acylation of N-nitrosoanilines with α-oxocarboxylic acids
2023, 34(2): 107537
doi: 10.1016/j.cclet.2022.05.051
Abstract:
An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids was developed. The anodic oxidation of the Pd(Ⅱ) intermediate was found to be the key to complete the reaction. In this case, the N-nitroso group was observed to be an effective directing group for C–H activation reaction. Moreover, the synthetic transformation of derivatives of natural products (L-menthol, dehydroepiandrosterone, and pregnenolone) was successfully realized. Finally, flow electrochemical synthesis of some substrates was achieved.
An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N-nitrosoanilines with α-oxocarboxylic acids was developed. The anodic oxidation of the Pd(Ⅱ) intermediate was found to be the key to complete the reaction. In this case, the N-nitroso group was observed to be an effective directing group for C–H activation reaction. Moreover, the synthetic transformation of derivatives of natural products (L-menthol, dehydroepiandrosterone, and pregnenolone) was successfully realized. Finally, flow electrochemical synthesis of some substrates was achieved.
2023, 34(2): 107542
doi: 10.1016/j.cclet.2022.05.056
Abstract:
Cu2-xS nanostructures have been intensively studied as outstanding chemodynamic therapy (CDT) and good photothermal therapy (PTT) antibacterial agents due to their highly efficient Cu(Ⅰ)-initiated Fenton-like catalytic activity and good photothermal conversion property. However, they still suffer from shortage of Cu(Ⅰ) supply in the long-term and comparatively low inherent photothermal conversion efficiency. Herein, we constructed a self-enhanced synergistic PTT/CDT nanoplatform (Cu1.94S@MPN) by coating Cu1.94S nanoparticles with Fe(Ⅲ)/tannic acid based metal-polyphenol networks (MPN). Activated by the acidic bacterial infection microenvironment, Cu1.94S@MPN could be decomposed to continuously release Cu(Ⅱ), Fe(Ⅲ) ions and tannic acid. As the result of tannic acid-involved Cu and Fe redox cycling, Cu(Ⅰ)/Fe(Ⅱ)-rich CDT could be achieved through the highly accelerated catalytic Fenton/Fenton-like reactions. More importantly, experimental results demonstrated that Cu1.94S@MPN exhibited both excellent photothermal antibacterial and photothermal-enhanced CDT properties to eradicate bacteria in vitro and in vivo. Overall, this novel nanotherapeutics has great potential to become a clinic candidate for anti-infective therapy in future.
Cu2-xS nanostructures have been intensively studied as outstanding chemodynamic therapy (CDT) and good photothermal therapy (PTT) antibacterial agents due to their highly efficient Cu(Ⅰ)-initiated Fenton-like catalytic activity and good photothermal conversion property. However, they still suffer from shortage of Cu(Ⅰ) supply in the long-term and comparatively low inherent photothermal conversion efficiency. Herein, we constructed a self-enhanced synergistic PTT/CDT nanoplatform (Cu1.94S@MPN) by coating Cu1.94S nanoparticles with Fe(Ⅲ)/tannic acid based metal-polyphenol networks (MPN). Activated by the acidic bacterial infection microenvironment, Cu1.94S@MPN could be decomposed to continuously release Cu(Ⅱ), Fe(Ⅲ) ions and tannic acid. As the result of tannic acid-involved Cu and Fe redox cycling, Cu(Ⅰ)/Fe(Ⅱ)-rich CDT could be achieved through the highly accelerated catalytic Fenton/Fenton-like reactions. More importantly, experimental results demonstrated that Cu1.94S@MPN exhibited both excellent photothermal antibacterial and photothermal-enhanced CDT properties to eradicate bacteria in vitro and in vivo. Overall, this novel nanotherapeutics has great potential to become a clinic candidate for anti-infective therapy in future.
2023, 34(2): 107543
doi: 10.1016/j.cclet.2022.05.057
Abstract:
The abuse of antibiotics causes severe bacterial resistance, and the shortage of antibiotics has created a global public health crisis. This situation has prompted people to develop new antibacterial agents independent of traditional antibiotics. Here, we created a series of photosensitive azobenzene-quaternary ammonium salt smart antibacterial agents by connecting azobenzene with amines with different chain lengths to improve the antibacterial selectivity of quaternary ammonium salt (QAS) and prevent the accumulation of active QAS in the environment. After trans-cis isomerization, the solubility of the title compound (compound 4) increased and the antibacterial property enhanced. The experimental results suggested that the antibacterial effect of compound 4 was significantly enhanced after 365 nm light irradiation, and it had photosensitive intelligent antibacterial activity and could be reused. Notably, we did not obtain any mutants of Staphylococcus aureus or Escherichia coli resistant to compound 4. In general, compound 4 has the advantages of high yield, photo-controllable antibacterial properties, reusability, and does not induce bacterial resistance. This photosensitive antibacterial compound provides a new idea for the construction of intelligent disinfectants and is expected to be a candidate for disinfectants in public facilities and medical architecture.
The abuse of antibiotics causes severe bacterial resistance, and the shortage of antibiotics has created a global public health crisis. This situation has prompted people to develop new antibacterial agents independent of traditional antibiotics. Here, we created a series of photosensitive azobenzene-quaternary ammonium salt smart antibacterial agents by connecting azobenzene with amines with different chain lengths to improve the antibacterial selectivity of quaternary ammonium salt (QAS) and prevent the accumulation of active QAS in the environment. After trans-cis isomerization, the solubility of the title compound (compound 4) increased and the antibacterial property enhanced. The experimental results suggested that the antibacterial effect of compound 4 was significantly enhanced after 365 nm light irradiation, and it had photosensitive intelligent antibacterial activity and could be reused. Notably, we did not obtain any mutants of Staphylococcus aureus or Escherichia coli resistant to compound 4. In general, compound 4 has the advantages of high yield, photo-controllable antibacterial properties, reusability, and does not induce bacterial resistance. This photosensitive antibacterial compound provides a new idea for the construction of intelligent disinfectants and is expected to be a candidate for disinfectants in public facilities and medical architecture.
2023, 34(2): 107549
doi: 10.1016/j.cclet.2022.05.063
Abstract:
The hyperplasia and destruction of synovial tissue have an important impact on the development of rheumatoid arthritis (RA), the abnormal proliferation and migration of synovial fibroblast in synovial tissue is similar to tumor cells. Targeting anomalous synovial fibroblast and designing a high bioavailability nano drug delivery system can reduce the dosage for the treatment of rheumatoid arthritis and it is of great significance to reduce toxic and side effects and improve curative effect. In this experiment, the nobiletin-loaded tetrahedral framework nucleic acids cargo tank was established, carrying anti-inflammatory small molecule monomer drug nobiletin with minimal bioavailability. Both in vitro cell experiments and in vivo animal studies proved the nano cargo tank enhance the role of nobiletin in reducing the invasiveness of pathological synovial fibroblast and promote their apoptosis, effectively alleviate the disease development of rheumatoid arthritis.
The hyperplasia and destruction of synovial tissue have an important impact on the development of rheumatoid arthritis (RA), the abnormal proliferation and migration of synovial fibroblast in synovial tissue is similar to tumor cells. Targeting anomalous synovial fibroblast and designing a high bioavailability nano drug delivery system can reduce the dosage for the treatment of rheumatoid arthritis and it is of great significance to reduce toxic and side effects and improve curative effect. In this experiment, the nobiletin-loaded tetrahedral framework nucleic acids cargo tank was established, carrying anti-inflammatory small molecule monomer drug nobiletin with minimal bioavailability. Both in vitro cell experiments and in vivo animal studies proved the nano cargo tank enhance the role of nobiletin in reducing the invasiveness of pathological synovial fibroblast and promote their apoptosis, effectively alleviate the disease development of rheumatoid arthritis.
2023, 34(2): 107550
doi: 10.1016/j.cclet.2022.05.064
Abstract:
Polycyclic aromatic hydrocarbons (PAHs), are regarded as molecular fragments of graphene and are facilely available through chemical synthesis. Recently, it is found collective charge density oscillations with strong induced electromagnetic field display in PAH derivatives. This phenomenon, analogue to plasmonic excitation in metal, called molecular plasmonics, arise the significant interest of physicists. Instead of discussing its rich physics, this work aims at the application of molecular plasmon-like excitations in electrochromics and optoelectronics. We found that the energy and the intensity of plasmonic-like oscillation could be largely tuned by increasing the conjugation size along both the longitude/transverse axis in PAHs. Besides, the dimeric PAH demonstrates the possibility that molecular plasmonics could be designed using PAHs as building blocks for integration into larger molecular systems. Moreover, this work straightforwardly extends the molecular plasmonic-like property from CH composed PAHs to much more versatile planar conjugation systems with heteroatoms, achieving transferring between p-type and n-type organic semiconductors. Therefore, with the natural abundance, low cost, easily chemical synthesis of PAH derivatives, we believe this work paves the way for the application of molecular plasmonic-like properties in optoelectronics.
Polycyclic aromatic hydrocarbons (PAHs), are regarded as molecular fragments of graphene and are facilely available through chemical synthesis. Recently, it is found collective charge density oscillations with strong induced electromagnetic field display in PAH derivatives. This phenomenon, analogue to plasmonic excitation in metal, called molecular plasmonics, arise the significant interest of physicists. Instead of discussing its rich physics, this work aims at the application of molecular plasmon-like excitations in electrochromics and optoelectronics. We found that the energy and the intensity of plasmonic-like oscillation could be largely tuned by increasing the conjugation size along both the longitude/transverse axis in PAHs. Besides, the dimeric PAH demonstrates the possibility that molecular plasmonics could be designed using PAHs as building blocks for integration into larger molecular systems. Moreover, this work straightforwardly extends the molecular plasmonic-like property from CH composed PAHs to much more versatile planar conjugation systems with heteroatoms, achieving transferring between p-type and n-type organic semiconductors. Therefore, with the natural abundance, low cost, easily chemical synthesis of PAH derivatives, we believe this work paves the way for the application of molecular plasmonic-like properties in optoelectronics.
2023, 34(2): 107556
doi: 10.1016/j.cclet.2022.05.070
Abstract:
The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging. In this work, we report a facile and convenient solvothermal method to synthesize metal halides Cs2ZnX4 (X = Cl, Br) that however is PL innert at room temperature. Upon composition engineering utilizing Sn2+ as the dopant, the resulting Cs2ZnCl4: Sn not only emits strong deep-red PL peaked at 700 nm with the highest 99.4% PLQY among the similar materials so far, but also exhibits excellent structure stability in air (PLQY remains 96% after one year exposure to the atmosphere). Detailed experimental characterizations and theoretical calculations reveal that the deep-red emission stems from self-trapped excitons induced by the Sn2+ dopant. Particularly, triplet emission (3P2→1S0) from Sn-5s2 orbitals has been observed at low temperature due to the break of parity-forbidden transition. This work provides an important guidance for the development of deep-red light-emitting materials with low price, high efficiency and excellent stability.
The development of deep-red emitting lead-free metal-halide perovskites with high photoluminescence quantum yields (PLQYs) and outstanding stability remains a major challenge for displays and deep-tissue bioimaging. In this work, we report a facile and convenient solvothermal method to synthesize metal halides Cs2ZnX4 (X = Cl, Br) that however is PL innert at room temperature. Upon composition engineering utilizing Sn2+ as the dopant, the resulting Cs2ZnCl4: Sn not only emits strong deep-red PL peaked at 700 nm with the highest 99.4% PLQY among the similar materials so far, but also exhibits excellent structure stability in air (PLQY remains 96% after one year exposure to the atmosphere). Detailed experimental characterizations and theoretical calculations reveal that the deep-red emission stems from self-trapped excitons induced by the Sn2+ dopant. Particularly, triplet emission (3P2→1S0) from Sn-5s2 orbitals has been observed at low temperature due to the break of parity-forbidden transition. This work provides an important guidance for the development of deep-red light-emitting materials with low price, high efficiency and excellent stability.
2023, 34(2): 107557
doi: 10.1016/j.cclet.2022.05.071
Abstract:
Human serum albumin (HSA) has emerged as a pivotal biomarker and prognostic indicator for various human diseases. Real-time sensing and visual tracking of HSA in plasma or other biological systems will immensely facilitate the basic researchers and clinicians to better understand HSA-associated biological processes. Herein, a novel near-infrared (NIR) fluorescent probe (7-HTCF) was rationally constructed for light-up sensing and in-situ imaging of HSA in real samples, based on the principle of twisted intramolecular charge transfer (TICT). Under physiological conditions, 7-HTCF could be efficiently trapped by HSA to form a stable complex via binding on a non-drug binding site, while the complex emitted strong fluoresce signals around 670 nm. Further investigations demonstrated that 7-HTCF displayed a great combination of excellent selectivity and good chemical stability, as well as rapid fluorescent response and ultra-high sensitivity for HSA detection. Particularly, the newly developed light-up probe has been successfully utilized for quantitative detection of HSA in diluted plasma samples, while its readouts are hardly affected by the addition of therapeutic agents and herbal medicines. 7-HTCF is also successfully used for in-situ imaging of the reabsorbed HSA in living renal cells, while this dye exhibits good cell permeability and high resolution for in-situ imaging in living cells. Collectively, a novel TICT-based near-infrared fluorescent probe was devised for highly selective and ultra-sensitive sensing of HSA in plasma samples or imaging HSA in living cells, which offered a practical tool for clinical tests and for exploring HSA-associated biological processes.
Human serum albumin (HSA) has emerged as a pivotal biomarker and prognostic indicator for various human diseases. Real-time sensing and visual tracking of HSA in plasma or other biological systems will immensely facilitate the basic researchers and clinicians to better understand HSA-associated biological processes. Herein, a novel near-infrared (NIR) fluorescent probe (7-HTCF) was rationally constructed for light-up sensing and in-situ imaging of HSA in real samples, based on the principle of twisted intramolecular charge transfer (TICT). Under physiological conditions, 7-HTCF could be efficiently trapped by HSA to form a stable complex via binding on a non-drug binding site, while the complex emitted strong fluoresce signals around 670 nm. Further investigations demonstrated that 7-HTCF displayed a great combination of excellent selectivity and good chemical stability, as well as rapid fluorescent response and ultra-high sensitivity for HSA detection. Particularly, the newly developed light-up probe has been successfully utilized for quantitative detection of HSA in diluted plasma samples, while its readouts are hardly affected by the addition of therapeutic agents and herbal medicines. 7-HTCF is also successfully used for in-situ imaging of the reabsorbed HSA in living renal cells, while this dye exhibits good cell permeability and high resolution for in-situ imaging in living cells. Collectively, a novel TICT-based near-infrared fluorescent probe was devised for highly selective and ultra-sensitive sensing of HSA in plasma samples or imaging HSA in living cells, which offered a practical tool for clinical tests and for exploring HSA-associated biological processes.
2023, 34(2): 107558
doi: 10.1016/j.cclet.2022.05.072
Abstract:
Pillar[5]arene-based molecular universal joints (MUJs), bearing fused crown ether subring (MUJ1 and MUJ3) or a ring without ether oxygen atom (MUJ2), were synthesized and enantio‑differentiated. Significant chiral inversion was observed for the crown ether-fused MUJs upon the addition of equivalent cations Na+, showing an anisotropy (g) factor of 0.014, while alkyl subring-fused MUJ2 showed no CD inversions. Unprecedentedly, sodium ion triggered rolling-in motion of the subring to the pillar[5]arene cavity was verified, and the synergistic noncovalent interaction of cation-π interactions and CH···π interactions were responsible for the stabilized self-included conformers. The addition of MeOH or competitive hosts 15-crown-5 ether disassembled the complex of MUJ1 and Na+ followed by a rolling-out of the subring, which made the sodium-ion triggered chiroptical switching reversible.
Pillar[5]arene-based molecular universal joints (MUJs), bearing fused crown ether subring (MUJ1 and MUJ3) or a ring without ether oxygen atom (MUJ2), were synthesized and enantio‑differentiated. Significant chiral inversion was observed for the crown ether-fused MUJs upon the addition of equivalent cations Na+, showing an anisotropy (g) factor of 0.014, while alkyl subring-fused MUJ2 showed no CD inversions. Unprecedentedly, sodium ion triggered rolling-in motion of the subring to the pillar[5]arene cavity was verified, and the synergistic noncovalent interaction of cation-π interactions and CH···π interactions were responsible for the stabilized self-included conformers. The addition of MeOH or competitive hosts 15-crown-5 ether disassembled the complex of MUJ1 and Na+ followed by a rolling-out of the subring, which made the sodium-ion triggered chiroptical switching reversible.
2023, 34(2): 107560
doi: 10.1016/j.cclet.2022.05.074
Abstract:
Most of carbon dots (CDs) are synthesized in solutions, but the extensive use of solvents produces too much waste, needs complex purification and results in low yield. Particularly for the popular hydrothermal/solvothermal syntheses, safety issues hinder the large-scale production of CDs. Solid phase synthesis in air seems perfect to solve the above problems once for all, but nanoparticle growth in solid phase is always difficult to control. Here we suggest a new method to synthesize CDs in SBA-15 template, just by heating single carbon sources in air. Employing single carbon sources is important, which ensures both homogeneity of the nucleation and uniformity of the nanoparticle growth. The pores confinement of SBA-15 guarantees the uniform sizes of CDs, while the catalytic effect of SBA-15 accelerates the carbonization process of precursors. The products are easily extracted from the template by ethanol, and then the template can be recycled for the next synthesis after calcination. Various CDs are synthesized in this way by using different carbon sources and SBA-15 templates with different pore diameters, respectively. The results show that, the fluorescence properties of these CDs are determined by their composition and surface states, but not the particle sizes. This work opens a new avenue to synthesize uniform CDs in solid phase with high yield, low cost and tunable luminescence.
Most of carbon dots (CDs) are synthesized in solutions, but the extensive use of solvents produces too much waste, needs complex purification and results in low yield. Particularly for the popular hydrothermal/solvothermal syntheses, safety issues hinder the large-scale production of CDs. Solid phase synthesis in air seems perfect to solve the above problems once for all, but nanoparticle growth in solid phase is always difficult to control. Here we suggest a new method to synthesize CDs in SBA-15 template, just by heating single carbon sources in air. Employing single carbon sources is important, which ensures both homogeneity of the nucleation and uniformity of the nanoparticle growth. The pores confinement of SBA-15 guarantees the uniform sizes of CDs, while the catalytic effect of SBA-15 accelerates the carbonization process of precursors. The products are easily extracted from the template by ethanol, and then the template can be recycled for the next synthesis after calcination. Various CDs are synthesized in this way by using different carbon sources and SBA-15 templates with different pore diameters, respectively. The results show that, the fluorescence properties of these CDs are determined by their composition and surface states, but not the particle sizes. This work opens a new avenue to synthesize uniform CDs in solid phase with high yield, low cost and tunable luminescence.
2023, 34(2): 107562
doi: 10.1016/j.cclet.2022.05.076
Abstract:
Perpyrrospirone A (1) characterized an unprecedented 6/5/6/8/5/13/6 oxahexacyclic scaffold with a unique peroxide-bridged 8, 9-dioxa-2-azaspiro[4.7]dodecane core from marine-derived Penicillium citrinum. Compounds 2 and 3 possessed rare oxatetracyclic (6/5/6/5) skeleton fused with a 13-menbered-ring macrocyclic moiety. Their structure and absolute configurations were determined by comprehensive spectroscopic analyses, ECD data coupled with TD-DFT calculations and X-ray diffraction experiments. In addition, 7 showed cytotoxicity and induced apoptosis of Hela cells in a dose-dependent manner after a 48 h treatment.
Perpyrrospirone A (1) characterized an unprecedented 6/5/6/8/5/13/6 oxahexacyclic scaffold with a unique peroxide-bridged 8, 9-dioxa-2-azaspiro[4.7]dodecane core from marine-derived Penicillium citrinum. Compounds 2 and 3 possessed rare oxatetracyclic (6/5/6/5) skeleton fused with a 13-menbered-ring macrocyclic moiety. Their structure and absolute configurations were determined by comprehensive spectroscopic analyses, ECD data coupled with TD-DFT calculations and X-ray diffraction experiments. In addition, 7 showed cytotoxicity and induced apoptosis of Hela cells in a dose-dependent manner after a 48 h treatment.
2023, 34(2): 107568
doi: 10.1016/j.cclet.2022.05.082
Abstract:
Many previous studies have shown that the molecular structures of oligothiophene derivatives including molecular skeleton and alkyl chains have a significant effect on their self-assemblies on the surface. In this work, a series of linear oligothiophene derivatives (DCV-nT-Hex, n = 3~11) modified with terminal dicyanovinyls and alkyl chains were adopted to further investigate the different assembly behaviors at liquid-solid interface by scanning tunneling microscopy (STM). Interestingly, via the hydrogen bonding and van der Waals interactions, DCV-3T-Hex formed zigzag and flower structures while DCV-nT-Hex (n = 4~11) formed lamellar structures. Density functional theory (DFT) calculations show that for the most energetically favorable configurations of DCV-nT-Hex, the different distribution of alkyl chains affected intermolecular interactions, and ultimately led to the different assembled structures. The zigzag and flower structures of DCV-3T-Hex had preferential thermodynamic stability compared to other structures of DCV-nT-Hex (n = 4~11). In addition, self-assembled nanostructures of DCV-nT-Hex molecules with even numbers (n = 4, 6, 8, 10) were overall more stable than those with odd numbers (n = 5, 7, 9, 11), and the stability of the self-assembled structure was weakened with the extension of the molecular backbone, individually. The orientation of molecular alkyl chains was found to greatly affect the intermolecular interactions and thus leading to various self-assembly structures of DCV-nT-Hex (n = 3~11).
Many previous studies have shown that the molecular structures of oligothiophene derivatives including molecular skeleton and alkyl chains have a significant effect on their self-assemblies on the surface. In this work, a series of linear oligothiophene derivatives (DCV-nT-Hex, n = 3~11) modified with terminal dicyanovinyls and alkyl chains were adopted to further investigate the different assembly behaviors at liquid-solid interface by scanning tunneling microscopy (STM). Interestingly, via the hydrogen bonding and van der Waals interactions, DCV-3T-Hex formed zigzag and flower structures while DCV-nT-Hex (n = 4~11) formed lamellar structures. Density functional theory (DFT) calculations show that for the most energetically favorable configurations of DCV-nT-Hex, the different distribution of alkyl chains affected intermolecular interactions, and ultimately led to the different assembled structures. The zigzag and flower structures of DCV-3T-Hex had preferential thermodynamic stability compared to other structures of DCV-nT-Hex (n = 4~11). In addition, self-assembled nanostructures of DCV-nT-Hex molecules with even numbers (n = 4, 6, 8, 10) were overall more stable than those with odd numbers (n = 5, 7, 9, 11), and the stability of the self-assembled structure was weakened with the extension of the molecular backbone, individually. The orientation of molecular alkyl chains was found to greatly affect the intermolecular interactions and thus leading to various self-assembly structures of DCV-nT-Hex (n = 3~11).
2023, 34(2): 107587
doi: 10.1016/j.cclet.2022.06.010
Abstract:
Click chemistry has become a useful tool for diverse molecular linkage and modification, and the development of new click strategy that enable reversibility and multifunctionality is of high demand for the multifunction and drug release. Herein, compositionally clicking combined regioselective iridium-catalyzed azide-alkynthio cycloaddition (Ir-AAC) and disulfuration has been developed for the sequential linkage from N-acetylenethio phthalimides, naturally occurring thiols and readily available azides. This method has been successfully applied to the construction of drug hybrids, peptide modification and glycosylation. Furthermore, by the design of diacetylenethio phthalimide as a platform molecule, trifunctional conjugants were sequentially linked through independent Ir-AAC, disulfuration and Cu-AAC reaction for hydrophobic tagging ternary PROTACs.
Click chemistry has become a useful tool for diverse molecular linkage and modification, and the development of new click strategy that enable reversibility and multifunctionality is of high demand for the multifunction and drug release. Herein, compositionally clicking combined regioselective iridium-catalyzed azide-alkynthio cycloaddition (Ir-AAC) and disulfuration has been developed for the sequential linkage from N-acetylenethio phthalimides, naturally occurring thiols and readily available azides. This method has been successfully applied to the construction of drug hybrids, peptide modification and glycosylation. Furthermore, by the design of diacetylenethio phthalimide as a platform molecule, trifunctional conjugants were sequentially linked through independent Ir-AAC, disulfuration and Cu-AAC reaction for hydrophobic tagging ternary PROTACs.
2023, 34(2): 107590
doi: 10.1016/j.cclet.2022.06.013
Abstract:
To realize the handedness controllable circularly polarized luminescence (CPL) system remains challenging. Herein, the solvent-mediated CPL inversion and amplification systems were successfully constructed by camptothecin derivative (CPT-A). Due to the planar structure of N, N-dimethylformamide, it could co-assemble with CPT-A, resulting in the alteration of glum from ‒0.0082 to +0.0085 by increasing water content. While in the non-planar solvent (hexafluoroisopropanol), the glum was amplified to 0.034 with the increase in water content. Moreover, the CPT-A could react with the glutathione, resulting in the anticancer drug CPT to make it more toxic to the cancer cells. Overall, the handedness controllable CPL systems were realized by tuning the supramolecular self-assembly of a prodrug.
To realize the handedness controllable circularly polarized luminescence (CPL) system remains challenging. Herein, the solvent-mediated CPL inversion and amplification systems were successfully constructed by camptothecin derivative (CPT-A). Due to the planar structure of N, N-dimethylformamide, it could co-assemble with CPT-A, resulting in the alteration of glum from ‒0.0082 to +0.0085 by increasing water content. While in the non-planar solvent (hexafluoroisopropanol), the glum was amplified to 0.034 with the increase in water content. Moreover, the CPT-A could react with the glutathione, resulting in the anticancer drug CPT to make it more toxic to the cancer cells. Overall, the handedness controllable CPL systems were realized by tuning the supramolecular self-assembly of a prodrug.
2023, 34(2): 107594
doi: 10.1016/j.cclet.2022.06.017
Abstract:
Li metal has been regarded as the holy grail for the next-generation Li-ion battery. Li dendrites issues, however, impede its practical application. In general, prolonging the sand time of Li nucleation and regulating homogeneous Li+ flux are effective approaches to suppress the dendrites formation and growth. Regarding this view, a functional polypropylene (PP) separator is developed to regulate ion transportation via a newly designed Li-based metal-organic framework (Li-MOF) coating. The Li-MOF crystallizes in the orthorhombic space group P212121 and features a double-walled three-dimensional (3D) structure with 1D channels. The well-defined intrinsic nanochannels of Li-MOF and the steric-hinerance effect both restrict free migration of anions, contributing to a high Li+ transference number of 0.65, which improve the Sand time of Li nucleation. Meanwhile, the Li-MOF coating with uniform porous structure promotes homogeneous Li+ flux at the surface of Li metal. Furthermore, the Li-MOF coating layer helps to build solid-electrolyte interphase (SEI) layer that comprises of inorganic LiF and Li3N, which further prohibits the dendrites growth. Consequently, a highly stable Li plating/stripping cycling for over 1000 h is achieved. The functional separator also enables high-performance full lithium metal cells, the high-rate and long-stable cycling performance of LiNi0.8Mn0.1Co0.1 (NMC811)-Li and LiCoO2 (LCO)-Li cells further demonstrate the feasibility of this concept.
Li metal has been regarded as the holy grail for the next-generation Li-ion battery. Li dendrites issues, however, impede its practical application. In general, prolonging the sand time of Li nucleation and regulating homogeneous Li+ flux are effective approaches to suppress the dendrites formation and growth. Regarding this view, a functional polypropylene (PP) separator is developed to regulate ion transportation via a newly designed Li-based metal-organic framework (Li-MOF) coating. The Li-MOF crystallizes in the orthorhombic space group P212121 and features a double-walled three-dimensional (3D) structure with 1D channels. The well-defined intrinsic nanochannels of Li-MOF and the steric-hinerance effect both restrict free migration of anions, contributing to a high Li+ transference number of 0.65, which improve the Sand time of Li nucleation. Meanwhile, the Li-MOF coating with uniform porous structure promotes homogeneous Li+ flux at the surface of Li metal. Furthermore, the Li-MOF coating layer helps to build solid-electrolyte interphase (SEI) layer that comprises of inorganic LiF and Li3N, which further prohibits the dendrites growth. Consequently, a highly stable Li plating/stripping cycling for over 1000 h is achieved. The functional separator also enables high-performance full lithium metal cells, the high-rate and long-stable cycling performance of LiNi0.8Mn0.1Co0.1 (NMC811)-Li and LiCoO2 (LCO)-Li cells further demonstrate the feasibility of this concept.
2023, 34(2): 107598
doi: 10.1016/j.cclet.2022.06.021
Abstract:
A novel metabolic chemical reporter of Ac36deoGlcNAz was developed and confirmed as an effective probe for O-GlcNAc modification. Ac36deoGlcNAz labeling predominantly occurs in intracellular O-GlcNAcylated proteins rather than cell-surface glycoproteins. Of note, it could reduce the artificial S-glyco-modification compared to Ac4GalNAz and Ac4GlcNAz. This new reporter allows to be widely used in the field of proteomic identification of O-GlcNAcylation.
A novel metabolic chemical reporter of Ac36deoGlcNAz was developed and confirmed as an effective probe for O-GlcNAc modification. Ac36deoGlcNAz labeling predominantly occurs in intracellular O-GlcNAcylated proteins rather than cell-surface glycoproteins. Of note, it could reduce the artificial S-glyco-modification compared to Ac4GalNAz and Ac4GlcNAz. This new reporter allows to be widely used in the field of proteomic identification of O-GlcNAcylation.
2023, 34(2): 107599
doi: 10.1016/j.cclet.2022.06.022
Abstract:
A facile and environmentally friendly visible-light-induced three-component reaction of α-diazoesters, cyclic ethers and NaSCN to construct organic thiocyanates has been developed at room temperature. This reaction could occur under photocatalyst- and additive-free conditions to afford a number of organic thiocyanates with moderate to good yield and favorable functional group tolerance.
A facile and environmentally friendly visible-light-induced three-component reaction of α-diazoesters, cyclic ethers and NaSCN to construct organic thiocyanates has been developed at room temperature. This reaction could occur under photocatalyst- and additive-free conditions to afford a number of organic thiocyanates with moderate to good yield and favorable functional group tolerance.
2023, 34(2): 107608
doi: 10.1016/j.cclet.2022.06.031
Abstract:
A Cu-catalyzed chemoselective heterocyclization of o-cinnamoyl arylisocyanides with α-substituted tosylmethyl isocyanides is developed for the efficient synthesis benzopyrroloazepinones. An isocyanide insertion into the C–Cu bond of organocuprate intermediate is involved for the formation of the seven-membered azepinone ring.
A Cu-catalyzed chemoselective heterocyclization of o-cinnamoyl arylisocyanides with α-substituted tosylmethyl isocyanides is developed for the efficient synthesis benzopyrroloazepinones. An isocyanide insertion into the C–Cu bond of organocuprate intermediate is involved for the formation of the seven-membered azepinone ring.
2023, 34(2): 107640
doi: 10.1016/j.cclet.2022.06.063
Abstract:
A practical synthetic method for 4-thiocyanato-1H-pyrazoles through the electrochemical cascade reaction of hydrazines, 1, 3-diones and NH4SCN under metal-, chemical oxidant- and external electrolyte-free conditions was established. Importantly, both a gram-scale synthesis of 4-thiocyanato-1H-pyrazoles and five one-pot sequential transformations starting from hydrazine were successfully accomplished.
A practical synthetic method for 4-thiocyanato-1H-pyrazoles through the electrochemical cascade reaction of hydrazines, 1, 3-diones and NH4SCN under metal-, chemical oxidant- and external electrolyte-free conditions was established. Importantly, both a gram-scale synthesis of 4-thiocyanato-1H-pyrazoles and five one-pot sequential transformations starting from hydrazine were successfully accomplished.
2023, 34(2): 107704
doi: 10.1016/j.cclet.2022.07.047
Abstract:
Thermally regenerative batteries (TRBs) are promising for harvesting low-grade waste heat into electrical power. However, the ammonia crossover from anode to cathode causes self-discharge and then leads to the decay of capacity. To alleviate the ammonia crossover and improve electricity generation, a stable graphene oxide (GO) modified anion exchange membrane (AEM) was proposed. Compared with the original AEM, the GO modified AEM with a 39.5% lower ammonia permeability induces a 24.3% higher maximal power output and 20.2% higher energy density in TRBs. Together with the visualization result, it was demonstrated the ammonia crossover was effectively alleviated by GO modifying the AEM not at a cost of the reduced battery performance, indicating the promising application in future TRBs.
Thermally regenerative batteries (TRBs) are promising for harvesting low-grade waste heat into electrical power. However, the ammonia crossover from anode to cathode causes self-discharge and then leads to the decay of capacity. To alleviate the ammonia crossover and improve electricity generation, a stable graphene oxide (GO) modified anion exchange membrane (AEM) was proposed. Compared with the original AEM, the GO modified AEM with a 39.5% lower ammonia permeability induces a 24.3% higher maximal power output and 20.2% higher energy density in TRBs. Together with the visualization result, it was demonstrated the ammonia crossover was effectively alleviated by GO modifying the AEM not at a cost of the reduced battery performance, indicating the promising application in future TRBs.
2023, 34(2): 107709
doi: 10.1016/j.cclet.2022.07.052
Abstract:
With the help of the redox mediator, decoupled water-splitting allows O2 and H2 to be produced at different times, at different rates, and even in different cells, which promotes both the operation safety and the utilization of renewable power sources. However, the current densities and stabilities of these redox mediators are commonly low, which require further improvements for practical applications. Here, we propose to use supercapacitors as solid state redox mediators for decoupled water splitting. For demonstration, Na0.5MnO2 (pseudocapacitor) and active carbon (double layer capacitor), are both used as the redox mediator. These supercapacitors show superior current density (1 A/cm2) and ultralong cycle-life (8000 cycles) compared with commonly investigated battery-based mediators (NiOOH/Ni(OH)2). Our research proves supercapacitors can be used as redox relay with high current density and stability, which may bring new insights in the design of decoupled water splitting systems.
With the help of the redox mediator, decoupled water-splitting allows O2 and H2 to be produced at different times, at different rates, and even in different cells, which promotes both the operation safety and the utilization of renewable power sources. However, the current densities and stabilities of these redox mediators are commonly low, which require further improvements for practical applications. Here, we propose to use supercapacitors as solid state redox mediators for decoupled water splitting. For demonstration, Na0.5MnO2 (pseudocapacitor) and active carbon (double layer capacitor), are both used as the redox mediator. These supercapacitors show superior current density (1 A/cm2) and ultralong cycle-life (8000 cycles) compared with commonly investigated battery-based mediators (NiOOH/Ni(OH)2). Our research proves supercapacitors can be used as redox relay with high current density and stability, which may bring new insights in the design of decoupled water splitting systems.
2023, 34(2): 107721
doi: 10.1016/j.cclet.2022.08.001
Abstract:
Waste generation from food manufacturing facilities poses a serious hazard like environmental degradation, water pollution, and land pollution due to its high nutrient composition. Specifically, solid waste (powder) disposal requires additional energy sources in terms of scientific treatment, structured collection, and disposal packaging according to the safety regulation. Thus, this research discusses the viewpoint of integrating food processing waste as an organic carbon source with BG-11 medium for Chlorella vulgaris (FSP-E) growth. The food processing waste powders investigated in this study were obtained from milk, and biscuit manufacturing facilities. The culture medium was modified by combining both BG-11 and food processing waste powders to identify the optimal algal growth and biochemical content. Compared to the microalgae grown in BG-11 alone (IBG), the combination of biscuit waste and IBG produced higher biomass concentration (44%), with increased lipid (11%), protein (20%), and carbohydrate (57%) contents. Chlorella vulgaris was able to uptake nutrients from the culture medium with combination of food processing waste and IBG thus enhancing its growth. The results obtained also indicate that an integrated culture system using food processing waste and synthetic sources can generate energy out of waste by improving the bio-composition of the microalgae biomass.
Waste generation from food manufacturing facilities poses a serious hazard like environmental degradation, water pollution, and land pollution due to its high nutrient composition. Specifically, solid waste (powder) disposal requires additional energy sources in terms of scientific treatment, structured collection, and disposal packaging according to the safety regulation. Thus, this research discusses the viewpoint of integrating food processing waste as an organic carbon source with BG-11 medium for Chlorella vulgaris (FSP-E) growth. The food processing waste powders investigated in this study were obtained from milk, and biscuit manufacturing facilities. The culture medium was modified by combining both BG-11 and food processing waste powders to identify the optimal algal growth and biochemical content. Compared to the microalgae grown in BG-11 alone (IBG), the combination of biscuit waste and IBG produced higher biomass concentration (44%), with increased lipid (11%), protein (20%), and carbohydrate (57%) contents. Chlorella vulgaris was able to uptake nutrients from the culture medium with combination of food processing waste and IBG thus enhancing its growth. The results obtained also indicate that an integrated culture system using food processing waste and synthetic sources can generate energy out of waste by improving the bio-composition of the microalgae biomass.
2023, 34(2): 107749
doi: 10.1016/j.cclet.2022.107749
Abstract:
Hierarchical carbon material is used as a star cocatalyst in the field of photocatalysis due to its excellent catalytic properties. In this work, mesoporous carbon nitride sheet (MCNS) photocatalyst introduced nitrogen-doped hollow carbon spheres assembled with cobalt nanoparticles (Co@NHC) is synthesized by electrostatic adsorption. A series of characterizations are analyzed to display the structures, morphologies and optical properties of as-prepared materials. The photocatalytic activity of Co@NHC/MCNS material is evaluated with hydrogen evolution under visible light irradiation. The results indicate that 5 wt% Co@NHC/MCNS material reveals higher photocatalytic activity of hydrogen evolution rate of 3675 µmol/g with 4 h reaction time, which is 159 times than that of pure MCNS material. The carbon material with excellent charge transport properties can effectively accelerate the charge transfer from ultrathin MCNS to cobalt nanoparticles. The goal of improving the photocatalytic performance of Co@NHC/MCNS material is achieved. As a result, it provides a feasible and promised approach for doping transition metals to enhance photocatalytic activity.
Hierarchical carbon material is used as a star cocatalyst in the field of photocatalysis due to its excellent catalytic properties. In this work, mesoporous carbon nitride sheet (MCNS) photocatalyst introduced nitrogen-doped hollow carbon spheres assembled with cobalt nanoparticles (Co@NHC) is synthesized by electrostatic adsorption. A series of characterizations are analyzed to display the structures, morphologies and optical properties of as-prepared materials. The photocatalytic activity of Co@NHC/MCNS material is evaluated with hydrogen evolution under visible light irradiation. The results indicate that 5 wt% Co@NHC/MCNS material reveals higher photocatalytic activity of hydrogen evolution rate of 3675 µmol/g with 4 h reaction time, which is 159 times than that of pure MCNS material. The carbon material with excellent charge transport properties can effectively accelerate the charge transfer from ultrathin MCNS to cobalt nanoparticles. The goal of improving the photocatalytic performance of Co@NHC/MCNS material is achieved. As a result, it provides a feasible and promised approach for doping transition metals to enhance photocatalytic activity.
2023, 34(2): 107759
doi: 10.1016/j.cclet.2022.107759
Abstract:
Dinitrogen activation under mild conditions is important but extremely challenging due to the inert nature of the N≡N triple bond evidenced by high bond dissociation energy (945 kJ/mol) and large HOMO-LUMO gap (10.8 eV). In comparison with largely developed transition metal systems, the reported main group species on dinitrogen activation are rare. Here, we carry out density functional theory calculations on methyleneboranes to understand the reaction mechanisms of their dinitrogen activation. It is found that the methyleneboranes without any substituent at the boron atom performs best on dinitrogen activation, which could be contributed to its small singlet-triplet gap. In addition, strong correlations are achieved on dinitrogen activation between the singlet-triplet energy gap and the reaction energies for the formation of the end-on products as well as the side-on ones. The principal interacting orbital analysis suggests that methyleneboranes can mimic transition metals to cleave the NN triple bond. Our findings could be helpful for experimental chemists aiming at dinitrogen activation by main group species.
Dinitrogen activation under mild conditions is important but extremely challenging due to the inert nature of the N≡N triple bond evidenced by high bond dissociation energy (945 kJ/mol) and large HOMO-LUMO gap (10.8 eV). In comparison with largely developed transition metal systems, the reported main group species on dinitrogen activation are rare. Here, we carry out density functional theory calculations on methyleneboranes to understand the reaction mechanisms of their dinitrogen activation. It is found that the methyleneboranes without any substituent at the boron atom performs best on dinitrogen activation, which could be contributed to its small singlet-triplet gap. In addition, strong correlations are achieved on dinitrogen activation between the singlet-triplet energy gap and the reaction energies for the formation of the end-on products as well as the side-on ones. The principal interacting orbital analysis suggests that methyleneboranes can mimic transition metals to cleave the NN triple bond. Our findings could be helpful for experimental chemists aiming at dinitrogen activation by main group species.
2023, 34(2): 107779
doi: 10.1016/j.cclet.2022.107779
Abstract:
Atom- and step-economy in IBX assisted diversity-oriented synthesis is achieved with a versatile AQ auxiliary α-amino acid analogs offering rapid access to polycyclic spiro-quinolines featuring a quaternary stereocenter in 20%–91% yields under mild conditions via 7, 8-dearomatization of quinolines. Free of a preinstalled activation group is highlight of this intramolecular oxidation spiroannulation tandem reaction. This type of N-heterospirocycles, traditionally difficult to access, may open the door to a potentially interest scaffold for synthetic and medicinal chemistry.
Atom- and step-economy in IBX assisted diversity-oriented synthesis is achieved with a versatile AQ auxiliary α-amino acid analogs offering rapid access to polycyclic spiro-quinolines featuring a quaternary stereocenter in 20%–91% yields under mild conditions via 7, 8-dearomatization of quinolines. Free of a preinstalled activation group is highlight of this intramolecular oxidation spiroannulation tandem reaction. This type of N-heterospirocycles, traditionally difficult to access, may open the door to a potentially interest scaffold for synthetic and medicinal chemistry.
2023, 34(2): 107795
doi: 10.1016/j.cclet.2022.107795
Abstract:
Dynamic manipulation of enzymatic activity is a challenging task for applications in chemical and pharmaceutical industries due to the difficult modification and variable conformation of various enzymes. Here, we report a new strategy for reversible dynamic modulation of enzymatic activity by near-infrared light-induced photothermal conversion based on polyphenol-functionalized liquid metal nanodroplets (LM). The metal-phenolic nanocoating not only provides colloidal stability of LM nanodroplets but also generates nanointerfaces for the assembly of various enzymes on the LM nanodroplets. Upon near infrared (NIR) irradiation, the localized microenvironmental heating through photothermal effect of the LM nanodroplets allows tailoring the enzymatic activity without affecting the bulk temperature. A library of functional enzymes, including proteinase K, glucoamylase, glucose oxidase, and Bst DNA polymerase, is integrated to perform a reversible control and enhanced activities even after five times of cycles, demonstrating great potential in bacterial fermentation, bacteriostasis, and target gene amplification.
Dynamic manipulation of enzymatic activity is a challenging task for applications in chemical and pharmaceutical industries due to the difficult modification and variable conformation of various enzymes. Here, we report a new strategy for reversible dynamic modulation of enzymatic activity by near-infrared light-induced photothermal conversion based on polyphenol-functionalized liquid metal nanodroplets (LM). The metal-phenolic nanocoating not only provides colloidal stability of LM nanodroplets but also generates nanointerfaces for the assembly of various enzymes on the LM nanodroplets. Upon near infrared (NIR) irradiation, the localized microenvironmental heating through photothermal effect of the LM nanodroplets allows tailoring the enzymatic activity without affecting the bulk temperature. A library of functional enzymes, including proteinase K, glucoamylase, glucose oxidase, and Bst DNA polymerase, is integrated to perform a reversible control and enhanced activities even after five times of cycles, demonstrating great potential in bacterial fermentation, bacteriostasis, and target gene amplification.
2023, 34(2): 107872
doi: 10.1016/j.cclet.2022.107872
Abstract:
Macrocycle-based glycoclusters, on account of their promising anti-adhesive properties against bacteria, are potential therapeutic alternatives to classic antibiotics through the much less explored anti-adhesive strategy. In this study, a series of constitutionally-pure pentavalent glycoclusters was prepared by conjugating assorted azido-carbohydrates onto a penta-propargyl rim-differentiated pillar[5]arene (RD-P[5]) scaffold through Cu(I)-catalyzed azide–alkyne cycloaddition "click" reactions. Their binding towards therapeutically relevant bacterial lectins, such as LecA and LecB from Pseudomonas aeruginosa and concanavalin A (ConA), were evaluated subsequently by isothermal titration calorimetric studies. Most of these isomer-free RD-P[5] pentavalent glycoclusters, except the fucosylated ones, display good affinities to lectins. Nonetheless, the dissociation constants observed are similar to those displayed by an analogous pentavalent glycocluster consisting of four P[5] constitutional isomers, in which the RD-P[5] component merely accounts for 7% in the mixture. Our results revealed that high constitutional purity is not essential for achieving effective multivalent interactions between P[5]-based glycoclusters and lectins, presumably as a result of the conformationally labile nature of the P[5] scaffold. This information provides valuable design principles for low-cost and facile syntheses of glycosylated P[5]s for biomedical applications.
Macrocycle-based glycoclusters, on account of their promising anti-adhesive properties against bacteria, are potential therapeutic alternatives to classic antibiotics through the much less explored anti-adhesive strategy. In this study, a series of constitutionally-pure pentavalent glycoclusters was prepared by conjugating assorted azido-carbohydrates onto a penta-propargyl rim-differentiated pillar[5]arene (RD-P[5]) scaffold through Cu(I)-catalyzed azide–alkyne cycloaddition "click" reactions. Their binding towards therapeutically relevant bacterial lectins, such as LecA and LecB from Pseudomonas aeruginosa and concanavalin A (ConA), were evaluated subsequently by isothermal titration calorimetric studies. Most of these isomer-free RD-P[5] pentavalent glycoclusters, except the fucosylated ones, display good affinities to lectins. Nonetheless, the dissociation constants observed are similar to those displayed by an analogous pentavalent glycocluster consisting of four P[5] constitutional isomers, in which the RD-P[5] component merely accounts for 7% in the mixture. Our results revealed that high constitutional purity is not essential for achieving effective multivalent interactions between P[5]-based glycoclusters and lectins, presumably as a result of the conformationally labile nature of the P[5] scaffold. This information provides valuable design principles for low-cost and facile syntheses of glycosylated P[5]s for biomedical applications.
2023, 34(2): 107948
doi: 10.1016/j.cclet.2022.107948
Abstract:
The rapid prevalence of antibiotic resistance has led to a significant global health problem. Although colistin is the last resort antibiotic, it is limited by dose dependent toxicity. A critical approach to solve this problem is to use an antibiotic adjuvant, which is able to potentiate the activity of antibiotic and reduce the dosage of antibiotic. Herein, we reported a novel 2-aminothiazoyl piperidine adjuvant, which enhanced the activity of colistin against Acinetobacter baumannii (A. baumannii). Two pilot libraries of 40 compounds were prepared and their adjuvant activities were evaluated. The most potential compound 11j enabled to cause16-fold reduction in the minimum inhibitory concentration (MIC) of colistin at 8 µg/mL. Besides, time-kill curves exhibited that compound 11j had significant adjuvant activity to kill the bacteria. The predicted ADMET analysis showed that 2-aminothiazoyl piperidine derivatives had good drug-likeness and acceptable physicochemical properties. Furthermore, membrane permeability experiments demonstrated that compound 11j was beneficial for colistin to destroy the outer membrane of bacteria. Also, the comparative molecular similarity indices analysis (CoMSIA) and the density functional theory (DFT) calculations were conducted. The results drawn from these analyses indicated that the novel scaffold provided helpful information for the finding of new adjuvant lead.
The rapid prevalence of antibiotic resistance has led to a significant global health problem. Although colistin is the last resort antibiotic, it is limited by dose dependent toxicity. A critical approach to solve this problem is to use an antibiotic adjuvant, which is able to potentiate the activity of antibiotic and reduce the dosage of antibiotic. Herein, we reported a novel 2-aminothiazoyl piperidine adjuvant, which enhanced the activity of colistin against Acinetobacter baumannii (A. baumannii). Two pilot libraries of 40 compounds were prepared and their adjuvant activities were evaluated. The most potential compound 11j enabled to cause16-fold reduction in the minimum inhibitory concentration (MIC) of colistin at 8 µg/mL. Besides, time-kill curves exhibited that compound 11j had significant adjuvant activity to kill the bacteria. The predicted ADMET analysis showed that 2-aminothiazoyl piperidine derivatives had good drug-likeness and acceptable physicochemical properties. Furthermore, membrane permeability experiments demonstrated that compound 11j was beneficial for colistin to destroy the outer membrane of bacteria. Also, the comparative molecular similarity indices analysis (CoMSIA) and the density functional theory (DFT) calculations were conducted. The results drawn from these analyses indicated that the novel scaffold provided helpful information for the finding of new adjuvant lead.
2023, 34(2): 107993
doi: 10.1016/j.cclet.2022.107993
Abstract:
Lithium dendrite growth due to uneven electrodeposition usually leads to the potential hazard of internal short circuit and shorter lifetime of lithium-based batteries. Extensive efforts have been devoted to explore the effects of single or two factors on dendrite growth, involving the diffusion coefficient, exchange current density, electrolyte concentration, temperature, and applied voltage. However, these factors interrelate during battery operation, signifying that a understanding of how they jointly influence the electrodeposition is of paramount importance for the effective suppression of dendrites. Here, we incorporate the dependent relationships among key factors into the phase-field model to capture their synergistic effects on electrodeposition. All the simulations are implemented in our self-written MATLAB code under a unified modeling framework. Following this, five groups of experimentally common dendrite patterns are reproduced and the corresponding electrodeposition driving forces are identified. Unexpectedly, we find that with the decrease of the ratio of exchange current density (or applied voltage) to diffusion coefficient, the electrodeposition morphology changes from needle-like dendrites to columnar dendrites and to uniform deposition. The present phase-field simulation tends to depict the practical electrodeposition process, providing important insights into synergistic regulation to suppress dendrite growth.
Lithium dendrite growth due to uneven electrodeposition usually leads to the potential hazard of internal short circuit and shorter lifetime of lithium-based batteries. Extensive efforts have been devoted to explore the effects of single or two factors on dendrite growth, involving the diffusion coefficient, exchange current density, electrolyte concentration, temperature, and applied voltage. However, these factors interrelate during battery operation, signifying that a understanding of how they jointly influence the electrodeposition is of paramount importance for the effective suppression of dendrites. Here, we incorporate the dependent relationships among key factors into the phase-field model to capture their synergistic effects on electrodeposition. All the simulations are implemented in our self-written MATLAB code under a unified modeling framework. Following this, five groups of experimentally common dendrite patterns are reproduced and the corresponding electrodeposition driving forces are identified. Unexpectedly, we find that with the decrease of the ratio of exchange current density (or applied voltage) to diffusion coefficient, the electrodeposition morphology changes from needle-like dendrites to columnar dendrites and to uniform deposition. The present phase-field simulation tends to depict the practical electrodeposition process, providing important insights into synergistic regulation to suppress dendrite growth.
2023, 34(2): 107399
doi: 10.1016/j.cclet.2022.03.122
Abstract:
As an emerging energy storage device with high-safety aqueous electrolytes, low-cost, environmental benignity and large-reserves, the rechargeable aqueous zinc-ion batteries (AZIBs) have attracted more and more attention. Vanadium-based compounds are also supposed as the potential candidate cathode materials for AZIBs due to their wide variety of phases, variable crystal structures and high theoretical capacity. In this review, the recent progress in the development of vanadium-based materials was summarized, and the relationship between the crystal structure types of active materials and Zn-ion transport mechanism was highlighted. During the charge-discharge process, the different electrostatic repulsion between the cations of vanadium-based compounds with different crystal structures and Zn2+ results in a variety of the Zn-ion storage mechanisms, which can be significant guidance for designing the advanced battery-electrode materials for AZIBs. Furthermore, other factors associated with the storage mechanisms, such as electrolyte components and electrode morphology, are discussed. Finally, the strategies to improve the electrical conductivity, inhibit the dissolution and stabilize the crystal structure of vanadium-based compounds are proposed and the future prospects for developing high-energy-density AZIBs are presented.
As an emerging energy storage device with high-safety aqueous electrolytes, low-cost, environmental benignity and large-reserves, the rechargeable aqueous zinc-ion batteries (AZIBs) have attracted more and more attention. Vanadium-based compounds are also supposed as the potential candidate cathode materials for AZIBs due to their wide variety of phases, variable crystal structures and high theoretical capacity. In this review, the recent progress in the development of vanadium-based materials was summarized, and the relationship between the crystal structure types of active materials and Zn-ion transport mechanism was highlighted. During the charge-discharge process, the different electrostatic repulsion between the cations of vanadium-based compounds with different crystal structures and Zn2+ results in a variety of the Zn-ion storage mechanisms, which can be significant guidance for designing the advanced battery-electrode materials for AZIBs. Furthermore, other factors associated with the storage mechanisms, such as electrolyte components and electrode morphology, are discussed. Finally, the strategies to improve the electrical conductivity, inhibit the dissolution and stabilize the crystal structure of vanadium-based compounds are proposed and the future prospects for developing high-energy-density AZIBs are presented.
2023, 34(2): 107407
doi: 10.1016/j.cclet.2022.04.005
Abstract:
The growing food delivery service market has boosted the consumption of packaging materials, and this trend is projected to continue in the following years. The gap between industrial supply and consumer demand from a sustainable viewpoint leads to a need for agricultural cellulosic waste-based materials that bring the idea of trash-to-treasure to fruition. In this paper, we review up-to-date advancements surrounding the food delivery packaging that are derived from agricultural cellulosic waste. Two scenarios in which agricultural feedstock is used as a host or guest material are summarized, and sketch on the individual processing routine is depicted. We further evaluate how the chemical compositions and processing parameters influence the properties of the final products. Current challenges and gaps in developing sustainable packaging materials are identified, with perspectives on these important issues highlighting the importance of process innovation as well as economic and environmental-impact assessment for agricultural cellulosic waste to food delivery packaging.
The growing food delivery service market has boosted the consumption of packaging materials, and this trend is projected to continue in the following years. The gap between industrial supply and consumer demand from a sustainable viewpoint leads to a need for agricultural cellulosic waste-based materials that bring the idea of trash-to-treasure to fruition. In this paper, we review up-to-date advancements surrounding the food delivery packaging that are derived from agricultural cellulosic waste. Two scenarios in which agricultural feedstock is used as a host or guest material are summarized, and sketch on the individual processing routine is depicted. We further evaluate how the chemical compositions and processing parameters influence the properties of the final products. Current challenges and gaps in developing sustainable packaging materials are identified, with perspectives on these important issues highlighting the importance of process innovation as well as economic and environmental-impact assessment for agricultural cellulosic waste to food delivery packaging.
2023, 34(2): 107413
doi: 10.1016/j.cclet.2022.04.011
Abstract:
Lithium-oxygen (Li-O2) batteries are considered as the next generation for energy storages systems due to the higher theoretical energy density than that of Li-ion batteries. However, the high charge overpotential caused by the insulated Li2O2 results in low energy efficiency, side reaction from electrolyte and cathode, and therefore poor battery performance. Designing noble metal-based catalysts can be an effective strategy to develop high-performance Li-O2 batteries with low charge overpotentials and outstanding cycle stability. However, the charge mechanism for noble metal-based catalysts is not clear and even contradictory. Herein, several charge mechanisms of Li2O2 are first discussed. Subsequently, the possible charge processes of Li-O2 batteries with noble metal-based catalysts are illustrated. In addition, the future development for noble metal-based catalysts is outlined.
Lithium-oxygen (Li-O2) batteries are considered as the next generation for energy storages systems due to the higher theoretical energy density than that of Li-ion batteries. However, the high charge overpotential caused by the insulated Li2O2 results in low energy efficiency, side reaction from electrolyte and cathode, and therefore poor battery performance. Designing noble metal-based catalysts can be an effective strategy to develop high-performance Li-O2 batteries with low charge overpotentials and outstanding cycle stability. However, the charge mechanism for noble metal-based catalysts is not clear and even contradictory. Herein, several charge mechanisms of Li2O2 are first discussed. Subsequently, the possible charge processes of Li-O2 batteries with noble metal-based catalysts are illustrated. In addition, the future development for noble metal-based catalysts is outlined.
2023, 34(2): 107420
doi: 10.1016/j.cclet.2022.04.018
Abstract:
The conversion of carbon dioxide into useful fuels or chemical feedstocks is of great importance for achieving carbon emission peak and carbon neutrality. The harvesting and conversion of solar energy will provide a sustainable and environmentally friendly energy source for human production and living. Very recently, photothermal catalysis has been proved to exhibit great advantages in reducing the reaction temperature, promoting the catalytic activity, and manipulating the reaction pathway in comparison with traditional thermal catalysis. In this review, we firstly introduced the fundamental mechanisms and categories of photothermal catalysis to understand the synergy or the difference between photochemical and thermochemical reaction pathways. Subsequently, the criteria and strategies for photothermal catalyst design are discussed in order to inspire the development of high-efficiency photothermal catalytic route by achieving intense absorption of broadband solar energy spectrum and high conversion capability of solar-to-heat. Recent progress in CO2 reduction achieved by photothermal catalysis was summarized in terms of production types. In the end, the future challenges and perspectives of photothermal catalytic CO2 reduction are presented. We hope that this review will not only deepen the understanding of photothermal catalysis, but also inspire the design, preparation and application of high-performance photothermal catalysts, aiming at alleviating non-renewable fossil energy consumption and carbon emissions for early carbon emission peak and carbon neutrality.
The conversion of carbon dioxide into useful fuels or chemical feedstocks is of great importance for achieving carbon emission peak and carbon neutrality. The harvesting and conversion of solar energy will provide a sustainable and environmentally friendly energy source for human production and living. Very recently, photothermal catalysis has been proved to exhibit great advantages in reducing the reaction temperature, promoting the catalytic activity, and manipulating the reaction pathway in comparison with traditional thermal catalysis. In this review, we firstly introduced the fundamental mechanisms and categories of photothermal catalysis to understand the synergy or the difference between photochemical and thermochemical reaction pathways. Subsequently, the criteria and strategies for photothermal catalyst design are discussed in order to inspire the development of high-efficiency photothermal catalytic route by achieving intense absorption of broadband solar energy spectrum and high conversion capability of solar-to-heat. Recent progress in CO2 reduction achieved by photothermal catalysis was summarized in terms of production types. In the end, the future challenges and perspectives of photothermal catalytic CO2 reduction are presented. We hope that this review will not only deepen the understanding of photothermal catalysis, but also inspire the design, preparation and application of high-performance photothermal catalysts, aiming at alleviating non-renewable fossil energy consumption and carbon emissions for early carbon emission peak and carbon neutrality.
2023, 34(2): 107508
doi: 10.1016/j.cclet.2022.05.022
Abstract:
Exosome, which is a kind of extracellular vesicles with size around 40-160 nm, plays an important role in cell-to-cell communication in multiple diseases. Especially in tumor microenvironment, exosomes are the important pathway to transit proteins, nucleic acids and small molecules between different kinds of cells. Based on these characteristics, exosomes are served as both therapeutic agents and drug delivery systems in cancer therapy. In this review, the applications of exosomes as drug delivery systems in cancer therapy were summarized and classified according to the cell source of the exosomes, including normal cells, immune cells and tumor cells. Different modifications of exosomes and drug loading methods were presented. Finally, some challenges that hindered the clinical translation of exosomes were also discussed.
Exosome, which is a kind of extracellular vesicles with size around 40-160 nm, plays an important role in cell-to-cell communication in multiple diseases. Especially in tumor microenvironment, exosomes are the important pathway to transit proteins, nucleic acids and small molecules between different kinds of cells. Based on these characteristics, exosomes are served as both therapeutic agents and drug delivery systems in cancer therapy. In this review, the applications of exosomes as drug delivery systems in cancer therapy were summarized and classified according to the cell source of the exosomes, including normal cells, immune cells and tumor cells. Different modifications of exosomes and drug loading methods were presented. Finally, some challenges that hindered the clinical translation of exosomes were also discussed.
2023, 34(2): 107518
doi: 10.1016/j.cclet.2022.05.032
Abstract:
Decades have passed since the first nanoparticles-base medicine was approved for human cancer treatment, and the research and development of nanoparticles for drug delivery are always undergoing. Nowadays, the significant advances complicate nanoparticles' branches, including liposomes, solid lipid nanoparticles, inorganic nanoparticles, micelles, nanovaccines and nano-antibodies, etc. These nanoparticles show numerous capabilities in treatment and diagnosis of stubborn diseases like cancer and neurodegenerative diseases, emerging as novel drug carriers or therapeutic agents in future. In this review, the complicated branches of nanoparticles are classified and summarized, with their property and functions concluded. Besides, there are also some delivery strategies that make nanoparticles smarter and more efficient in drug delivery, and frontiers in these strategies are also summarized in this review. Except these excellent works in newly-produced drug delivery nanoparticles, some points of view and future expectations are made in the end.
Decades have passed since the first nanoparticles-base medicine was approved for human cancer treatment, and the research and development of nanoparticles for drug delivery are always undergoing. Nowadays, the significant advances complicate nanoparticles' branches, including liposomes, solid lipid nanoparticles, inorganic nanoparticles, micelles, nanovaccines and nano-antibodies, etc. These nanoparticles show numerous capabilities in treatment and diagnosis of stubborn diseases like cancer and neurodegenerative diseases, emerging as novel drug carriers or therapeutic agents in future. In this review, the complicated branches of nanoparticles are classified and summarized, with their property and functions concluded. Besides, there are also some delivery strategies that make nanoparticles smarter and more efficient in drug delivery, and frontiers in these strategies are also summarized in this review. Except these excellent works in newly-produced drug delivery nanoparticles, some points of view and future expectations are made in the end.
2023, 34(2): 107623
doi: 10.1016/j.cclet.2022.06.046
Abstract:
Amyloid proteins correlate with a series of degenerative diseases. Targeting amyloid aggregation has remained a hot topic in therapeutic studies. Numerous inhibitors have been developed, but very few have been approved for marketing. Meanwhile, the growing knowledge of amyloid structural characteristics provides a basis for the rational design of inhibitors. Here we introduce the high-resolution structural findings of amyloid fibrils in recent years and discuss the reported strategies toward rationally designed inhibitors based on amyloid-related structural studies.
Amyloid proteins correlate with a series of degenerative diseases. Targeting amyloid aggregation has remained a hot topic in therapeutic studies. Numerous inhibitors have been developed, but very few have been approved for marketing. Meanwhile, the growing knowledge of amyloid structural characteristics provides a basis for the rational design of inhibitors. Here we introduce the high-resolution structural findings of amyloid fibrils in recent years and discuss the reported strategies toward rationally designed inhibitors based on amyloid-related structural studies.
2023, 34(2): 107629
doi: 10.1016/j.cclet.2022.06.052
Abstract:
Aqueous zinc-ion batteries (AZIBs) have aroused significant research interest around the world in the past decade. The use of low-cost aqueous electrolytes and a metallic Zn anode with a suitable redox potential and high energy density make AZIBs a potential alternative to commercial Li-ion batteries in the development of next-generation batteries. However, owing to the narrow electrochemical stability window (ESW) of aqueous electrolytes, the choice of cathode materials is limited, because of which AZIBs exhibit a relatively low operating voltage and energy density. Hence, expanding the ESW of aqueous electrolytes is important for the development of practical AZIBs. This paper systematically reviews the electrolyte engineering strategies being explored to broaden the ESW of AZIBs. An in-depth analysis of high-voltage AZIBs is also presented. We suggest that the realization of high-voltage AZIBs depends on the synergistic development of suitable electrolytes and cathode materials. In addition, the cost associated with their fabrication as well as the use of standardized electrochemical tests should be considered during the design of high-voltage AZIBs.
Aqueous zinc-ion batteries (AZIBs) have aroused significant research interest around the world in the past decade. The use of low-cost aqueous electrolytes and a metallic Zn anode with a suitable redox potential and high energy density make AZIBs a potential alternative to commercial Li-ion batteries in the development of next-generation batteries. However, owing to the narrow electrochemical stability window (ESW) of aqueous electrolytes, the choice of cathode materials is limited, because of which AZIBs exhibit a relatively low operating voltage and energy density. Hence, expanding the ESW of aqueous electrolytes is important for the development of practical AZIBs. This paper systematically reviews the electrolyte engineering strategies being explored to broaden the ESW of AZIBs. An in-depth analysis of high-voltage AZIBs is also presented. We suggest that the realization of high-voltage AZIBs depends on the synergistic development of suitable electrolytes and cathode materials. In addition, the cost associated with their fabrication as well as the use of standardized electrochemical tests should be considered during the design of high-voltage AZIBs.
2023, 34(2): 107637
doi: 10.1016/j.cclet.2022.06.060
Abstract:
Carbocations such as tropylium and trityl cation, can be stable enough to be isolated and used without inert conditions. They can act as Lewis acids to lower the LUMO of electrophile, thus promoting reactions with nucleophiles. Additionally, the interaction between carbocations and alcohols can form Brønsted acids with enhanced acidity. Furthermore, electrophoto activation of TAC+ (trisaminocyclopropenium ion) delivers the excited radical dication TAC•2+*, which is a strong oxidant and capable of oxidizing a range of challenging substrates. Moreover, Pr-DMQA+ is disclosed as a versatile photoredox catalyst as its excited state can be quenched through both oxidation and reduction. This review summarizes recent advance in carbocation-catalyzed reactions. These developed methods provide an environmentally friendly pathway for the synthesis of valuable compounds and will inspire chemists to discover more interesting transformations promoted by carbocations.
Carbocations such as tropylium and trityl cation, can be stable enough to be isolated and used without inert conditions. They can act as Lewis acids to lower the LUMO of electrophile, thus promoting reactions with nucleophiles. Additionally, the interaction between carbocations and alcohols can form Brønsted acids with enhanced acidity. Furthermore, electrophoto activation of TAC+ (trisaminocyclopropenium ion) delivers the excited radical dication TAC•2+*, which is a strong oxidant and capable of oxidizing a range of challenging substrates. Moreover, Pr-DMQA+ is disclosed as a versatile photoredox catalyst as its excited state can be quenched through both oxidation and reduction. This review summarizes recent advance in carbocation-catalyzed reactions. These developed methods provide an environmentally friendly pathway for the synthesis of valuable compounds and will inspire chemists to discover more interesting transformations promoted by carbocations.
2023, 34(2): 107728
doi: 10.1016/j.cclet.2022.08.008
Abstract:
Polyanilines (PANIs) can be easily prepared from the available and cheap anilines via the oxidative polymerization reactions. Owing to the coordination of nitrogen in the material with metals, PANIs are widely used as the support of nano metal catalysts. In comparison with inorganic supports, the nano metals on PANIs were firmly anchored via the coordination bond so that they are not easily to lose during the reaction process. Moreover, since PANIs are versatile materials and their chemical features can be adjusted by introducing functional groups onto the monomers, the catalytic activities of the prepared catalysts are tunable. During the past decade, PANIs-supported nano metal catalysts have been widely applied in a variety of coupling reactions. This review aims to summarize the recent advances and give a perspective.
Polyanilines (PANIs) can be easily prepared from the available and cheap anilines via the oxidative polymerization reactions. Owing to the coordination of nitrogen in the material with metals, PANIs are widely used as the support of nano metal catalysts. In comparison with inorganic supports, the nano metals on PANIs were firmly anchored via the coordination bond so that they are not easily to lose during the reaction process. Moreover, since PANIs are versatile materials and their chemical features can be adjusted by introducing functional groups onto the monomers, the catalytic activities of the prepared catalysts are tunable. During the past decade, PANIs-supported nano metal catalysts have been widely applied in a variety of coupling reactions. This review aims to summarize the recent advances and give a perspective.
2023, 34(2): 108009
doi: 10.1016/j.cclet.2022.108009
Abstract:
Lanthanide metal-organic frameworks (Ln-MOFs), which is composed of organic bridging ligands and Ln3+ ions/clusters, is an important component of luminescent MOFs. Compared with transition metal ions, lanthanide ions have a higher coordination number and abundant coordination geometry. Moreover, Ln-MOFs have special characteristics such as good porosity, topological diversity, high surface area and highly adjustable structure. The energy transfer (ET) process in Ln-MOFs could be easily affected by the interaction between host framework and guest, resulting in the change of luminescence intensity or color. Over the past few decades, the features of Ln-MOFs open the door to a range of incredibly important applications. However, there are few reviews on systemic summary of the various applications of Ln-MOFs. In this paper, we summarized the latest progress of Ln-MOFs applications, including the Ln-MOFs in chemical and biological sensors, optical information devices and catalysis, respectively, and discussed design mechanism. The possible problems in current research are briefly prospected, hoping to provide some helpful guidance for the future development of Ln-MOF materials.
Lanthanide metal-organic frameworks (Ln-MOFs), which is composed of organic bridging ligands and Ln3+ ions/clusters, is an important component of luminescent MOFs. Compared with transition metal ions, lanthanide ions have a higher coordination number and abundant coordination geometry. Moreover, Ln-MOFs have special characteristics such as good porosity, topological diversity, high surface area and highly adjustable structure. The energy transfer (ET) process in Ln-MOFs could be easily affected by the interaction between host framework and guest, resulting in the change of luminescence intensity or color. Over the past few decades, the features of Ln-MOFs open the door to a range of incredibly important applications. However, there are few reviews on systemic summary of the various applications of Ln-MOFs. In this paper, we summarized the latest progress of Ln-MOFs applications, including the Ln-MOFs in chemical and biological sensors, optical information devices and catalysis, respectively, and discussed design mechanism. The possible problems in current research are briefly prospected, hoping to provide some helpful guidance for the future development of Ln-MOF materials.
2023, 34(2): 107739
doi: 10.1016/j.cclet.2022.08.019
Abstract:
2023, 34(2): 107936
doi: 10.1016/j.cclet.2022.107936
Abstract:
The issue about how outstanding scientists obtained innovative findings has drawn the interest of researchers in science, policy and scientometrics. Here, we attempt to address this question by using computational methods to measure the cognitive content and concepts of K. Barry Sharpless' research and estimate the knowledge flow of his click chemistry to other fields. First, we traced Sharpless' conceptual journey over time through topic modeling approach, mapping and clustering of the epistemic network from distant reading his publications. We find that connectivity and functions, the core features of click chemistry, are embodied in his constant search for simplicity. What makes simplicity possible is his continuous work with collaborators on reactivity and reaction mechanisms. Moreover, citation and link analysis show that click chemistry had a much richer impact on other research fields than what is generally acknowledged, and drew solutions to significant and practical questions back to chemistry from biology. Together with these findings, we propose that the click chemistry philosophy follows the way that values nature's principle. Chemistry has a clear-cut epistemic domain in modeling Nature. Thus, click chemistry as a concept on doing science beyond a connective technology goes across the boundaries between disciplines and impacts many other fields.
The issue about how outstanding scientists obtained innovative findings has drawn the interest of researchers in science, policy and scientometrics. Here, we attempt to address this question by using computational methods to measure the cognitive content and concepts of K. Barry Sharpless' research and estimate the knowledge flow of his click chemistry to other fields. First, we traced Sharpless' conceptual journey over time through topic modeling approach, mapping and clustering of the epistemic network from distant reading his publications. We find that connectivity and functions, the core features of click chemistry, are embodied in his constant search for simplicity. What makes simplicity possible is his continuous work with collaborators on reactivity and reaction mechanisms. Moreover, citation and link analysis show that click chemistry had a much richer impact on other research fields than what is generally acknowledged, and drew solutions to significant and practical questions back to chemistry from biology. Together with these findings, we propose that the click chemistry philosophy follows the way that values nature's principle. Chemistry has a clear-cut epistemic domain in modeling Nature. Thus, click chemistry as a concept on doing science beyond a connective technology goes across the boundaries between disciplines and impacts many other fields.
