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2023 Volume 34 Issue 6
2023, 34(6): 107630
doi: 10.1016/j.cclet.2022.06.053
Abstract:
Developing redox switches that not only perform specific mechanical movements but also drive important chemical reactions is important but a great challenge. Herein, we report a redox pair of cobalt species (CoⅢ/CoⅡ) that switches through photo-dehydrogenation of alcohol and hydrogenation of azo-ligand. The cobalt species is equipped with a flexible azo-ligand containing two bulky planar substituents. A planar oxidated sate (CoⅢ species) can be photo-reduced to a saddle-like reduced state (CoⅡ) with alcohol molecules as electron donors, and in turn the CoⅢ species can be recovered with azo-ligand as oxidant under acidic surrounding. Both the redox states of the pair are isolated and characterized by single crystal X-ray diffraction. In the switching cycle, alcohol is oxidized to aldehyde by azo-ligand through proton coupled electron transfer and the cobalt complex acts as a redox catalyst. These results provide important insights into alcohol dehydrogenation catalyzed by redox complexes.
Developing redox switches that not only perform specific mechanical movements but also drive important chemical reactions is important but a great challenge. Herein, we report a redox pair of cobalt species (CoⅢ/CoⅡ) that switches through photo-dehydrogenation of alcohol and hydrogenation of azo-ligand. The cobalt species is equipped with a flexible azo-ligand containing two bulky planar substituents. A planar oxidated sate (CoⅢ species) can be photo-reduced to a saddle-like reduced state (CoⅡ) with alcohol molecules as electron donors, and in turn the CoⅢ species can be recovered with azo-ligand as oxidant under acidic surrounding. Both the redox states of the pair are isolated and characterized by single crystal X-ray diffraction. In the switching cycle, alcohol is oxidized to aldehyde by azo-ligand through proton coupled electron transfer and the cobalt complex acts as a redox catalyst. These results provide important insights into alcohol dehydrogenation catalyzed by redox complexes.
2023, 34(6): 107633
doi: 10.1016/j.cclet.2022.06.056
Abstract:
Efficient cathode-catalysts with multi-functional properties are essential for Li-CO2 battery, while the construction of them with simultaneously enhanced CO2 reduction and evolution kinetics is still challenging. Here, a kind of hybrid nanosheets based on Ru nanoparticles, Fe-TAPP and grapheme oxide (GO) has been designed through a one-pot self-assembly strategy. The Ru, Fe-porphyrin and GO based hybrid nanosheets (denoted as Ru/Fe-TAPP@GO) with integrated multi-components offer characteristics of ultrathin thickness (~4 nm), high electro-redox property, uniformly dispersed morphology, and high electrical conductivity, etc. These features endow Ru/Fe-TAPP@GO with ultra-low overpotential (0.82 V) and fully reversible discharge/charge property with a high specific-capacity of 39,000 mAh/g within 2.0–4.5 V at 100 mA/g, which are much superior to Ru@GO and Fe-TAPP@GO. The achieved performance was presented as one of the best cathode-catalysts reported to date. The synergistically enhanced activity originated from the integrated hybrid nanosheets may provide a new pathway for designing efficient cathode-catalysts for Li-CO2 batteries.
Efficient cathode-catalysts with multi-functional properties are essential for Li-CO2 battery, while the construction of them with simultaneously enhanced CO2 reduction and evolution kinetics is still challenging. Here, a kind of hybrid nanosheets based on Ru nanoparticles, Fe-TAPP and grapheme oxide (GO) has been designed through a one-pot self-assembly strategy. The Ru, Fe-porphyrin and GO based hybrid nanosheets (denoted as Ru/Fe-TAPP@GO) with integrated multi-components offer characteristics of ultrathin thickness (~4 nm), high electro-redox property, uniformly dispersed morphology, and high electrical conductivity, etc. These features endow Ru/Fe-TAPP@GO with ultra-low overpotential (0.82 V) and fully reversible discharge/charge property with a high specific-capacity of 39,000 mAh/g within 2.0–4.5 V at 100 mA/g, which are much superior to Ru@GO and Fe-TAPP@GO. The achieved performance was presented as one of the best cathode-catalysts reported to date. The synergistically enhanced activity originated from the integrated hybrid nanosheets may provide a new pathway for designing efficient cathode-catalysts for Li-CO2 batteries.
2023, 34(6): 107634
doi: 10.1016/j.cclet.2022.06.057
Abstract:
Through-space charge transfer (TSCT) is regarded as an effective way to develop thermally activated delayed fluorescence (TADF) emitters. Based on this strategy, many molecular frameworks have been proposed, among which spirobased scaffolds have been extensively studied due to their unique advantages. In this work, we developed three emitters SPS, SPO, and SPON, which were constructed with the same donor and various acceptors to explore the influence of acceptor modulation at the C9 position of fluorene for spirostructure TSCT emitters. The results show that the acceptor with too weak electron-withdrawing ability will cause the emitter to not have TADF properties, while the acceptor with too much steric hindrance will weaken the face-to-face π-π stacking interaction between donor/acceptor (D/A). Since SPO balances the electron-withdrawing strength and steric hindrance of the acceptor, it achieves the highest external quantum efficiency (EQE) of 17.75%. This work shows that appropriate acceptor selection is essential for the TADF properties and high efficiency of the spirobased scaffold TSCT emitter
Through-space charge transfer (TSCT) is regarded as an effective way to develop thermally activated delayed fluorescence (TADF) emitters. Based on this strategy, many molecular frameworks have been proposed, among which spirobased scaffolds have been extensively studied due to their unique advantages. In this work, we developed three emitters SPS, SPO, and SPON, which were constructed with the same donor and various acceptors to explore the influence of acceptor modulation at the C9 position of fluorene for spirostructure TSCT emitters. The results show that the acceptor with too weak electron-withdrawing ability will cause the emitter to not have TADF properties, while the acceptor with too much steric hindrance will weaken the face-to-face π-π stacking interaction between donor/acceptor (D/A). Since SPO balances the electron-withdrawing strength and steric hindrance of the acceptor, it achieves the highest external quantum efficiency (EQE) of 17.75%. This work shows that appropriate acceptor selection is essential for the TADF properties and high efficiency of the spirobased scaffold TSCT emitter
2023, 34(6): 107635
doi: 10.1016/j.cclet.2022.06.058
Abstract:
Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid (H2pba), FICN-6, a metal-organic framework containing both Cu2(O2CR)4 and Cu3(OH)(pyz)3(O2CR) secondary building units (SBUs), was synthesized. FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other. Presence of Cu3 clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.
Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid (H2pba), FICN-6, a metal-organic framework containing both Cu2(O2CR)4 and Cu3(OH)(pyz)3(O2CR) secondary building units (SBUs), was synthesized. FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other. Presence of Cu3 clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.
2023, 34(6): 107641
doi: 10.1016/j.cclet.2022.06.064
Abstract:
The domain purity, material crystallinity and distribution at the interface between the active layer and the transport layer have an important impact on the performance of organic solar cells (OSCs) and organic photodetectors (OPDs), while this focal issue has received less attention in previous studies. From this perspective, a new method to simultaneously enhance the performance of OSC and OPD is proposed, namely, using a sequential deposition method to first construct a compact stacking structure of dual-donor (D18-Cl:PTO2) eutectic in the donor layer, and then induce the ordered deposition of the acceptor (Y6). Compared with the conventional bulk heterojunction (BHJ), the active layer realized by this method not only improves the crystallinity and stacking order of the constituent material on the surface of the transport layer, but also regulates a good vertical distribution, which is conducive to improving the charge transport and extraction efficiency, reducing the leakage current, and enhancing the stability of the device. As a result, the OSC device based on the D18-Cl:PTO2/Y6 structure achieves a power conversion efficiency of up to 17.65% and good light-degradation stability, which is much better than that of BHJ-based OSC (PCE of 16.37%). For the OPD, the dark current at reverse bias is reduced by more than an order of magnitude, and the maximum responsivity is improved to 0.52 A/W through the optimization of the donor phase at the interface. Moreover, the strategy does not require additional post-processing compared to the BHJ preparation, which reduces the device construction cost and process complexity, providing an effective way for developing high-performance organic optoelectronic devices.
The domain purity, material crystallinity and distribution at the interface between the active layer and the transport layer have an important impact on the performance of organic solar cells (OSCs) and organic photodetectors (OPDs), while this focal issue has received less attention in previous studies. From this perspective, a new method to simultaneously enhance the performance of OSC and OPD is proposed, namely, using a sequential deposition method to first construct a compact stacking structure of dual-donor (D18-Cl:PTO2) eutectic in the donor layer, and then induce the ordered deposition of the acceptor (Y6). Compared with the conventional bulk heterojunction (BHJ), the active layer realized by this method not only improves the crystallinity and stacking order of the constituent material on the surface of the transport layer, but also regulates a good vertical distribution, which is conducive to improving the charge transport and extraction efficiency, reducing the leakage current, and enhancing the stability of the device. As a result, the OSC device based on the D18-Cl:PTO2/Y6 structure achieves a power conversion efficiency of up to 17.65% and good light-degradation stability, which is much better than that of BHJ-based OSC (PCE of 16.37%). For the OPD, the dark current at reverse bias is reduced by more than an order of magnitude, and the maximum responsivity is improved to 0.52 A/W through the optimization of the donor phase at the interface. Moreover, the strategy does not require additional post-processing compared to the BHJ preparation, which reduces the device construction cost and process complexity, providing an effective way for developing high-performance organic optoelectronic devices.
2023, 34(6): 107642
doi: 10.1016/j.cclet.2022.06.065
Abstract:
Fluoranthenes have attracted tremendous attention due to their unique optoelectronic properties and extensive applications. Although several synthetic methodologies have been developed for the preparation of fluoranthene derivatives, it is still unfavorable to functionalize the fluoranthene framework at different positions due to the relatively low selectivity and reactivity. Herein, a catalyst-free intramolecular [4 + 2] annulation between thiophenes and alkynes is developed towards the synthesis of fluoranthenes. Altogether 20 examples have been demonstrated using this method. Various functional groups can be precisely introduced into the fluoranthene skeleton at different positions by simply tuning the substituents on the thiophenes and alkynes. The conjugation of the fluoranthene can be facilely extended through different directions. Furthermore, the feasibility of this [4 + 2] annulation reaction is also investigated by density functional theory calculations. Therefore, this protocol provides not only a synthetic methodology towards fluoranthenes with substituents functionalized at different positions, but also an effective pathway to construct large polycyclic aromatic hydrocarbons containing fluoranthene moieties.
Fluoranthenes have attracted tremendous attention due to their unique optoelectronic properties and extensive applications. Although several synthetic methodologies have been developed for the preparation of fluoranthene derivatives, it is still unfavorable to functionalize the fluoranthene framework at different positions due to the relatively low selectivity and reactivity. Herein, a catalyst-free intramolecular [4 + 2] annulation between thiophenes and alkynes is developed towards the synthesis of fluoranthenes. Altogether 20 examples have been demonstrated using this method. Various functional groups can be precisely introduced into the fluoranthene skeleton at different positions by simply tuning the substituents on the thiophenes and alkynes. The conjugation of the fluoranthene can be facilely extended through different directions. Furthermore, the feasibility of this [4 + 2] annulation reaction is also investigated by density functional theory calculations. Therefore, this protocol provides not only a synthetic methodology towards fluoranthenes with substituents functionalized at different positions, but also an effective pathway to construct large polycyclic aromatic hydrocarbons containing fluoranthene moieties.
2023, 34(6): 107643
doi: 10.1016/j.cclet.2022.06.066
Abstract:
Two-dimensional electride Ca2N has strong electron transfer ability and low work function, which is a potential candidate for hydrogen evolution reaction (HER) catalyst. In this work, based on density functional theory calculations, we adopt two strategies to improve the HER catalytic activity of Ca2N monolayer: introducing Ca or N vacancy and doping transition metal atoms (TM, refers to Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Ru, Hf, Ta and W). Interestingly, the Gibbs free energy ΔGH* of Ca2N monolayer after introducing N vacancy is reduced to -0.146 eV, showing good HER catalytic activity. It is highlighted that, the HER catalytic activity of Ca2N monolayer can be further enhanced with TM doping, the Gibbs free energy ΔGH* of single Mo and double Mn doped Ca2N are predicted to be 0.119 and 0.139 eV, respectively. The present results will provide good theoretical guidance for the HER catalysis applications of two-dimensional electride Ca2N monolayer.
Two-dimensional electride Ca2N has strong electron transfer ability and low work function, which is a potential candidate for hydrogen evolution reaction (HER) catalyst. In this work, based on density functional theory calculations, we adopt two strategies to improve the HER catalytic activity of Ca2N monolayer: introducing Ca or N vacancy and doping transition metal atoms (TM, refers to Ti, V, Cr, Mn, Fe, Zr, Nb, Mo, Ru, Hf, Ta and W). Interestingly, the Gibbs free energy ΔGH* of Ca2N monolayer after introducing N vacancy is reduced to -0.146 eV, showing good HER catalytic activity. It is highlighted that, the HER catalytic activity of Ca2N monolayer can be further enhanced with TM doping, the Gibbs free energy ΔGH* of single Mo and double Mn doped Ca2N are predicted to be 0.119 and 0.139 eV, respectively. The present results will provide good theoretical guidance for the HER catalysis applications of two-dimensional electride Ca2N monolayer.
2023, 34(6): 107644
doi: 10.1016/j.cclet.2022.06.067
Abstract:
Two bis-naphthalimide-based supramolecular gelators (NN-3 and NN-4) with a little difference of position of amino groups were designed and synthesized for the detection of oxaloyl chloride and phosgene. Energy transfer could be occurred between two naphthalimide groups in molecules NN-3 and NN-4. Yellow gels NN-3 and NN-4 were formed in some mixed solvents, and nanofibers with different size were obtained in these gels. The self-assembly processes of NN-3 and NN-4 in different solvents were investigated by UV-vis absorption, fluorescent spectra, SEM, FTIR, XRD and NMR. Gelators NN-3 and NN-4 could selectively detect oxaloyl chloride in solution and film states, but detect phosgene only in solution. NN-3 exhibited the ratiometric detection ability towards oxaloyl chloride and phosgene with the low limit of detection (LOD) of 210 nmol/L and 90 nmol/L, respectively. NN-4 as the corresponding control sample, it owned the higher LOD towards oxaloyl chloride and phosgene of 12.4 µmol/L and 64 µmol/L, respectively. Interestingly, films NN-3 and NN-4 could sensitively detect oxaloyl chloride gases with the low LOD of 2.0 ppm and 8.34 ppm, respectively. The detection mechanisms of NN-3 and NN-4 were well studied by 1H NMR titration, HRMS and theoretical calculation.
Two bis-naphthalimide-based supramolecular gelators (NN-3 and NN-4) with a little difference of position of amino groups were designed and synthesized for the detection of oxaloyl chloride and phosgene. Energy transfer could be occurred between two naphthalimide groups in molecules NN-3 and NN-4. Yellow gels NN-3 and NN-4 were formed in some mixed solvents, and nanofibers with different size were obtained in these gels. The self-assembly processes of NN-3 and NN-4 in different solvents were investigated by UV-vis absorption, fluorescent spectra, SEM, FTIR, XRD and NMR. Gelators NN-3 and NN-4 could selectively detect oxaloyl chloride in solution and film states, but detect phosgene only in solution. NN-3 exhibited the ratiometric detection ability towards oxaloyl chloride and phosgene with the low limit of detection (LOD) of 210 nmol/L and 90 nmol/L, respectively. NN-4 as the corresponding control sample, it owned the higher LOD towards oxaloyl chloride and phosgene of 12.4 µmol/L and 64 µmol/L, respectively. Interestingly, films NN-3 and NN-4 could sensitively detect oxaloyl chloride gases with the low LOD of 2.0 ppm and 8.34 ppm, respectively. The detection mechanisms of NN-3 and NN-4 were well studied by 1H NMR titration, HRMS and theoretical calculation.
2023, 34(6): 107659
doi: 10.1016/j.cclet.2022.07.002
Abstract:
The electrochemical nitrogen reduction reaction (NRR) for the ammonia production under ambient conditions is regarded as a sustainable alternative to the industrial Haber–Bosch process. However, the electrocatalytic systems that efficiently catalyze nitrogen reduction remain elusive. In the work, the nitrogen reduction activity of the transition metal decorated bismuthene TM@Bis is fully investigated by means of density functional theory calculations. Our results demonstrate that W@Bis delivers the best efficiency, wherein the potential-determining step is located at the last protonation step of *NH2 + H+ + e– → *NH3 via the distal mechanism with the limiting potential UL of 0.26 V. Furthermore, the dopants of Re and Os are also promising candidates for experimental synthesis due to its good selectivity, in despite of the slightly higher UL of NRR with the value of 0.55 V. However, the candidates of Ti, V, Nb and Mo delivered the relative lower UL of 0.35, 0.37, 0.41 and 0.43 V might be suffered from the side hydrogen evolution reaction. More interestingly, a volcano curve is established between UL and valence electrons of metal elements wherein W with 4 electrons in d band located at the summit. Such phenomenon originates from the underlying acceptance-back donation mechanism. Therefore, our work provides a fundament understanding for the material design for nitrogen reduction electrocatalysis.
The electrochemical nitrogen reduction reaction (NRR) for the ammonia production under ambient conditions is regarded as a sustainable alternative to the industrial Haber–Bosch process. However, the electrocatalytic systems that efficiently catalyze nitrogen reduction remain elusive. In the work, the nitrogen reduction activity of the transition metal decorated bismuthene TM@Bis is fully investigated by means of density functional theory calculations. Our results demonstrate that W@Bis delivers the best efficiency, wherein the potential-determining step is located at the last protonation step of *NH2 + H+ + e– → *NH3 via the distal mechanism with the limiting potential UL of 0.26 V. Furthermore, the dopants of Re and Os are also promising candidates for experimental synthesis due to its good selectivity, in despite of the slightly higher UL of NRR with the value of 0.55 V. However, the candidates of Ti, V, Nb and Mo delivered the relative lower UL of 0.35, 0.37, 0.41 and 0.43 V might be suffered from the side hydrogen evolution reaction. More interestingly, a volcano curve is established between UL and valence electrons of metal elements wherein W with 4 electrons in d band located at the summit. Such phenomenon originates from the underlying acceptance-back donation mechanism. Therefore, our work provides a fundament understanding for the material design for nitrogen reduction electrocatalysis.
2023, 34(6): 107667
doi: 10.1016/j.cclet.2022.07.010
Abstract:
Nanopore detection is a hot issue in current research. One of the challenges is how to slow down the transport velocity of nanoparticles in nanopores. In this paper, we propose a functional group modified nanopore. That means a polyelectrolyte brush layer is grafted on the surface of the nanopore to change the surface charge properties. The existing studies generally set the charge density of the brush layer to a fixed value. On the contrary, in this paper, we consider an essential property of the brush layer: the volume charge density is adjustable with pH. Thus, the charge property of the brush layer will change with the local H+ concentration. Based on this, we established a mathematical model to study the transport of nanoparticles in polyelectrolyte brush layer modified nanopores. We found that pH can effectively adjust the charge density and even the polarity of the brush layer. A larger pH can reduce the transport velocity of nanoparticles and improve the blockade degree of ion current. The grafting density does not change the polarity of the brush charge. The larger the grafting density, the greater the charge density of the brush layer, and the blockade degree of ion current is also more obvious. The polyelectrolyte brush layer modified nanopores in this paper can effectively reduce the nanoparticle transport velocity and retain the essential ion current characteristics, such as ion current blockade and enhancement.
Nanopore detection is a hot issue in current research. One of the challenges is how to slow down the transport velocity of nanoparticles in nanopores. In this paper, we propose a functional group modified nanopore. That means a polyelectrolyte brush layer is grafted on the surface of the nanopore to change the surface charge properties. The existing studies generally set the charge density of the brush layer to a fixed value. On the contrary, in this paper, we consider an essential property of the brush layer: the volume charge density is adjustable with pH. Thus, the charge property of the brush layer will change with the local H+ concentration. Based on this, we established a mathematical model to study the transport of nanoparticles in polyelectrolyte brush layer modified nanopores. We found that pH can effectively adjust the charge density and even the polarity of the brush layer. A larger pH can reduce the transport velocity of nanoparticles and improve the blockade degree of ion current. The grafting density does not change the polarity of the brush charge. The larger the grafting density, the greater the charge density of the brush layer, and the blockade degree of ion current is also more obvious. The polyelectrolyte brush layer modified nanopores in this paper can effectively reduce the nanoparticle transport velocity and retain the essential ion current characteristics, such as ion current blockade and enhancement.
2023, 34(6): 107668
doi: 10.1016/j.cclet.2022.07.011
Abstract:
Voriconazole (VZL) is a second-generation and broad-spectrum triazole against fungal infections. Being a BCS (biopharmaceutics classification system) class Ⅱ compound, the poor aqueous solubility has limited its bioavailability and clinical efficacy. Aims to overcome this disadvantage, a cocrystallization strategy based on crystal engineering principles has resulted in five new multi-component crystals of VZL with maleic acid, L-tartaric, protocatechuic, gallic, and 3,5-dinitrobenzoic acids. Structure analysis revealed that the hydroxyl/carboxylic acid···triazole N3 hydrogen bonding interaction appears as a main supramolecular heterosynthon in the VZL multi-component crystals with organic acids. And VZL molecule has a flexible conformation in each of the five multi-component structures. The newly synthesized multi-component crystals showed impressive solubility improvement compared to that of the raw material of VZL. Molecular electrostatic potential surfaces (MEPS) analysis based on density functional (DFT) calculations revealed that hydrogen bond interactions in cocrystals mainly involved pairwise interactions in the global maxima and minima sites, but this rule is not always followed. This study indicates the potential of cocrystals to improve the solubility and dissolution rate of VZL
Voriconazole (VZL) is a second-generation and broad-spectrum triazole against fungal infections. Being a BCS (biopharmaceutics classification system) class Ⅱ compound, the poor aqueous solubility has limited its bioavailability and clinical efficacy. Aims to overcome this disadvantage, a cocrystallization strategy based on crystal engineering principles has resulted in five new multi-component crystals of VZL with maleic acid, L-tartaric, protocatechuic, gallic, and 3,5-dinitrobenzoic acids. Structure analysis revealed that the hydroxyl/carboxylic acid···triazole N3 hydrogen bonding interaction appears as a main supramolecular heterosynthon in the VZL multi-component crystals with organic acids. And VZL molecule has a flexible conformation in each of the five multi-component structures. The newly synthesized multi-component crystals showed impressive solubility improvement compared to that of the raw material of VZL. Molecular electrostatic potential surfaces (MEPS) analysis based on density functional (DFT) calculations revealed that hydrogen bond interactions in cocrystals mainly involved pairwise interactions in the global maxima and minima sites, but this rule is not always followed. This study indicates the potential of cocrystals to improve the solubility and dissolution rate of VZL
2023, 34(6): 107669
doi: 10.1016/j.cclet.2022.07.012
Abstract:
Zinc-ion batteries are under current research focus because of their uniqueness in low cost and high safety. However, the pursuing of high-performance cathode materials of aqueous Zinc ion batteries (AZBs) with low cost, high energy density and long cycle life has become the key problem to be solved. Herein we synthesized a series of amorphous nickel borate (AM-NiBO) nanosheets by varying corrosion time with in-situ electrochemical corrosion method. The AM-NiBO-T13 as electrode material possesses a high areal capacity of 0.65 mAh/cm2 with the capacity retention of 95.1% after 2000 cycles. In addition, the assembled AM-NiBO-T13//Zn provides high energy density (0.77 mWh/cm2 at 1.76 mW/cm2). The high areal capacity and better cycling performance can be owing to the amorphous nanosheets structure and the stable coordination characteristics of boron and oxygen in borate materials. It shows that amorphous nickel borate nanosheets have great prospects in the field of energy storage.
Zinc-ion batteries are under current research focus because of their uniqueness in low cost and high safety. However, the pursuing of high-performance cathode materials of aqueous Zinc ion batteries (AZBs) with low cost, high energy density and long cycle life has become the key problem to be solved. Herein we synthesized a series of amorphous nickel borate (AM-NiBO) nanosheets by varying corrosion time with in-situ electrochemical corrosion method. The AM-NiBO-T13 as electrode material possesses a high areal capacity of 0.65 mAh/cm2 with the capacity retention of 95.1% after 2000 cycles. In addition, the assembled AM-NiBO-T13//Zn provides high energy density (0.77 mWh/cm2 at 1.76 mW/cm2). The high areal capacity and better cycling performance can be owing to the amorphous nanosheets structure and the stable coordination characteristics of boron and oxygen in borate materials. It shows that amorphous nickel borate nanosheets have great prospects in the field of energy storage.
2023, 34(6): 107675
doi: 10.1016/j.cclet.2022.07.018
Abstract:
MOF-based composites have aroused widespread concern due to their controllable morphology and pore characteristics. Nevertheless, the poor conductivity and volume expansion hinder its practical application in LIBs. Herein a classical structure HKUST-1, as the precursor, was used to fabricate quasi-Cu-MOF composite through a facile thermal decomposition strategy. The results showed that quasi-Cu-MOF composite had superior reversible specific capacity (627.5 mAh/g at 100 mA/g) and outstanding cycle stability (514.6 mAh/g at 500 mA/g after 400 cycles) as anodes for LIBs. The results demonstrated that the low-temperature calcination strategy played a significant role in morphology retaining during cycling and the derived copper framework play a crucial part in conductivity improvement. This work is helpful to the design of high-performance electrodes with advanced three-dimensional hierarchical structures.
MOF-based composites have aroused widespread concern due to their controllable morphology and pore characteristics. Nevertheless, the poor conductivity and volume expansion hinder its practical application in LIBs. Herein a classical structure HKUST-1, as the precursor, was used to fabricate quasi-Cu-MOF composite through a facile thermal decomposition strategy. The results showed that quasi-Cu-MOF composite had superior reversible specific capacity (627.5 mAh/g at 100 mA/g) and outstanding cycle stability (514.6 mAh/g at 500 mA/g after 400 cycles) as anodes for LIBs. The results demonstrated that the low-temperature calcination strategy played a significant role in morphology retaining during cycling and the derived copper framework play a crucial part in conductivity improvement. This work is helpful to the design of high-performance electrodes with advanced three-dimensional hierarchical structures.
2023, 34(6): 107676
doi: 10.1016/j.cclet.2022.07.019
Abstract:
Organic-inorganic hybrid perovskites (OIHPs) materials with high phase transition temperature (Tp) have been widely studied in the field of molecular switches, solar energy and electric power. At present, the OIHPs with high Tp are generally constructed through molecular design, which can be applied to a wide temperature range. Here, three one-dimensional (1D) OIHPs [R-ClEQ]PbCl3 (Tp = 442 K), [R-ClEQ]PbBr3 (Tp= 499 K) and [R-ClEQ]PbI3 (Tp above m.p.) (R-ClEQ = (R)-N-chloroethyl-3-quinuclidinol) with different Tp are obtained by regulating the halogen-halogen interaction and hydrogen bonding in the system. Especially in [R-ClEQ]PbX3 (X = Cl, Br and I) crystal system, all the halogen bonds tend to form at approximately 180°angles and the strength of halogen bonding is found to be increased from 1.59 × 10–3 Hartree to 2.35 × 10–3 Hartree with increased atom number from Cl to I. The synergistic effect of halogen bonding and hydrogen bonding provide a useful strategy for the design OIHPs phase transition materials with high Tp.
Organic-inorganic hybrid perovskites (OIHPs) materials with high phase transition temperature (Tp) have been widely studied in the field of molecular switches, solar energy and electric power. At present, the OIHPs with high Tp are generally constructed through molecular design, which can be applied to a wide temperature range. Here, three one-dimensional (1D) OIHPs [R-ClEQ]PbCl3 (Tp = 442 K), [R-ClEQ]PbBr3 (Tp= 499 K) and [R-ClEQ]PbI3 (Tp above m.p.) (R-ClEQ = (R)-N-chloroethyl-3-quinuclidinol) with different Tp are obtained by regulating the halogen-halogen interaction and hydrogen bonding in the system. Especially in [R-ClEQ]PbX3 (X = Cl, Br and I) crystal system, all the halogen bonds tend to form at approximately 180°angles and the strength of halogen bonding is found to be increased from 1.59 × 10–3 Hartree to 2.35 × 10–3 Hartree with increased atom number from Cl to I. The synergistic effect of halogen bonding and hydrogen bonding provide a useful strategy for the design OIHPs phase transition materials with high Tp.
2023, 34(6): 107681
doi: 10.1016/j.cclet.2022.07.024
Abstract:
Single atom catalysts (SACs) with atomically dispersed transition metals on nitrogen-doped carbon supports have recently emerged as highly active non-noble metal electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), showing great application potential in Zn-air batteries. However, because of the complex structure-performance relationships of carbon-based SACs in the oxygen electrocatalytic reactions, the contribution of different metal atoms to the catalytic activity of SACs in Zn-air batteries still remains ambiguous. In this study, SACs with atomically dispersed transition metals on nitrogen-doped graphene sheets (M-N@Gs, M = Co, Fe and Ni), featured with similar physicochemical properties and M-N@C configurations, are obtained. By comparing the on-set potentials and the maximum current, we observed that the ORR activity is in the order of Co-N@G > Fe-N@G > Ni-N@G, while the OER activity is in the order of Co-N@G > Ni-N@G > Fe-N@G. The Zn-air batteries with Co-N@G as the air cathode catalysts outperform those with the Fe-N@G and Ni-N@G. This is due to the accelerated charge transfer between Co-N@C active sites and the oxygen-containing reactants. This study could improve our understanding of the design of more efficient bifunctional electrocatalysts for Zn-air batteries at the atomic level.
Single atom catalysts (SACs) with atomically dispersed transition metals on nitrogen-doped carbon supports have recently emerged as highly active non-noble metal electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), showing great application potential in Zn-air batteries. However, because of the complex structure-performance relationships of carbon-based SACs in the oxygen electrocatalytic reactions, the contribution of different metal atoms to the catalytic activity of SACs in Zn-air batteries still remains ambiguous. In this study, SACs with atomically dispersed transition metals on nitrogen-doped graphene sheets (M-N@Gs, M = Co, Fe and Ni), featured with similar physicochemical properties and M-N@C configurations, are obtained. By comparing the on-set potentials and the maximum current, we observed that the ORR activity is in the order of Co-N@G > Fe-N@G > Ni-N@G, while the OER activity is in the order of Co-N@G > Ni-N@G > Fe-N@G. The Zn-air batteries with Co-N@G as the air cathode catalysts outperform those with the Fe-N@G and Ni-N@G. This is due to the accelerated charge transfer between Co-N@C active sites and the oxygen-containing reactants. This study could improve our understanding of the design of more efficient bifunctional electrocatalysts for Zn-air batteries at the atomic level.
2023, 34(6): 107685
doi: 10.1016/j.cclet.2022.07.028
Abstract:
It is greatly desired to develop novel gadolinium-based contrast agents (GBCAs) as improved platforms for magnetic resonance imaging (MRI). Herein, we report the syntheses of a series of nonionic cyclen-based GBCAs by precisely tuning carboxylate group on DO3A-pyridine scaffold. [Gd-DO3A-4cp] is isolated which adopts an octadentate coordination mode with a free carboxylate group at 4-position of pyridine. It shows the r1 relaxivity of 5.8 (mmol/L)−1 s-1 (3 T, 25 ℃), which is 75% higher than 3.3 (mmol/L)−1 s-1 of the clinic used [Gd-DOTA]. The possible mechanisms behind the enhanced relaxivity are investigated and proposed by structure-property relationship studies. After validation of low cytotoxicity and considerable kinetic inertness, in-vivo studies are further examined, demonstrating its good MRI performance, biodistribution as well as the way of excretion.
It is greatly desired to develop novel gadolinium-based contrast agents (GBCAs) as improved platforms for magnetic resonance imaging (MRI). Herein, we report the syntheses of a series of nonionic cyclen-based GBCAs by precisely tuning carboxylate group on DO3A-pyridine scaffold. [Gd-DO3A-4cp] is isolated which adopts an octadentate coordination mode with a free carboxylate group at 4-position of pyridine. It shows the r1 relaxivity of 5.8 (mmol/L)−1 s-1 (3 T, 25 ℃), which is 75% higher than 3.3 (mmol/L)−1 s-1 of the clinic used [Gd-DOTA]. The possible mechanisms behind the enhanced relaxivity are investigated and proposed by structure-property relationship studies. After validation of low cytotoxicity and considerable kinetic inertness, in-vivo studies are further examined, demonstrating its good MRI performance, biodistribution as well as the way of excretion.
2023, 34(6): 107686
doi: 10.1016/j.cclet.2022.07.029
Abstract:
Herein we report a covalent cage TPE-Zn4 based on a tetraphenylethylene molecule via subcomponent self-assembly, which is templated by zinc ions. TPE-Zn4 features a quadrangular prismatic cage structure, which is characterized by NMR, mass spectrum, and single-crystal X-ray diffractions. TPE-Zn4 emitted orange fluorescence (λem = 620 nm) in DMSO solution under the irradiation of UV light (λex = 395 nm) and can be applied as a fluorescence sensor for selectively detecting Pd2+. The fluorescence of TPE-Zn4 was quenched by Pd2+ in DMSO solution, and a very low detection limit of 62.3 nM was achieved. Mechanism studies reveal that the Pd2+ can replace the Zn2+, and the heavy atom effect and chelation-enhanced quenching effect between the Pd2+ and the cage probably cause the fluorescence quenching.
Herein we report a covalent cage TPE-Zn4 based on a tetraphenylethylene molecule via subcomponent self-assembly, which is templated by zinc ions. TPE-Zn4 features a quadrangular prismatic cage structure, which is characterized by NMR, mass spectrum, and single-crystal X-ray diffractions. TPE-Zn4 emitted orange fluorescence (λem = 620 nm) in DMSO solution under the irradiation of UV light (λex = 395 nm) and can be applied as a fluorescence sensor for selectively detecting Pd2+. The fluorescence of TPE-Zn4 was quenched by Pd2+ in DMSO solution, and a very low detection limit of 62.3 nM was achieved. Mechanism studies reveal that the Pd2+ can replace the Zn2+, and the heavy atom effect and chelation-enhanced quenching effect between the Pd2+ and the cage probably cause the fluorescence quenching.
2023, 34(6): 107690
doi: 10.1016/j.cclet.2022.07.033
Abstract:
A series of linear poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene) (PEO113-b-PVBC130-b-PtBSx or E113V130Tx) triblock terpolymers with various lengths x (=20, 33, 66, 104, 215) of PtBS block were synthesized via a two-step reversible addition-fragmentation chain transfer (RAFT) polymerization. The E113V130T triblock terpolymers were non-crystalline because the PVBC and PtBS blocks strongly hindered the crystallization of PEO block. The effects of PtBS block length x on the phase structures of E113V130Tx triblock terpolymers were investigated by combined techniques of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). It was found that with increasing x from 20 to 215, the phase structure of E113V130Tx triblock terpolymers became more ordered and changed from disordered structure, hexagonally-packed cylinder (HEX), hexagonally perforated layer (HPL), to lamellar (LAM) phase structures. Temperature-variable SAXS measurements showed that the HEX, HPL and LAM phase structures obtained for E113V130T66, E113V130T104 and E113V130T215 by thermal annealing, respectively, were thermodynamically stable in the temperature range of 30–170 ℃.
A series of linear poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene) (PEO113-b-PVBC130-b-PtBSx or E113V130Tx) triblock terpolymers with various lengths x (=20, 33, 66, 104, 215) of PtBS block were synthesized via a two-step reversible addition-fragmentation chain transfer (RAFT) polymerization. The E113V130T triblock terpolymers were non-crystalline because the PVBC and PtBS blocks strongly hindered the crystallization of PEO block. The effects of PtBS block length x on the phase structures of E113V130Tx triblock terpolymers were investigated by combined techniques of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). It was found that with increasing x from 20 to 215, the phase structure of E113V130Tx triblock terpolymers became more ordered and changed from disordered structure, hexagonally-packed cylinder (HEX), hexagonally perforated layer (HPL), to lamellar (LAM) phase structures. Temperature-variable SAXS measurements showed that the HEX, HPL and LAM phase structures obtained for E113V130T66, E113V130T104 and E113V130T215 by thermal annealing, respectively, were thermodynamically stable in the temperature range of 30–170 ℃.
2023, 34(6): 107692
doi: 10.1016/j.cclet.2022.07.035
Abstract:
One-step assembly of organic-ligand modified Pd-Keggin-POMs has been rarely reported, so as for their applications in catalytic benzothiadiazole generation and derived cell-imaging probing. Herein, three Pd-Keggin-POMs (compounds 1–3) have been successfully synthesized via a one-step assembly strategy. Thus-obtained Pd-Keggin-POMs with well-defined structures and heterogeneous properties enable highly efficient catalytic benzothiadiazole generation. Specifically, compound 3 showed outstanding catalytic activities in Suzuki-Miyaura coupling reactions for the generation of benzothiadiazole derivatives (yields, 90%-97%) and was represented as one of the best catalysts reported to date. Consequently, the obtained benzothiadiazoles were used as the bio-probe for tracking lipid droplets in living-cells and exhibited large Stokes shifts (130 nm), low cytotoxicity and good targeting, which could be also applied to mark the distribution of LDs in living HeLa cells. Systematic investigations clearly decipher the functions of Pd-Keggin-POMs toward finding novel bio-probe materials, highlighting a new insight into the generation of sustainable materials in life-science.
One-step assembly of organic-ligand modified Pd-Keggin-POMs has been rarely reported, so as for their applications in catalytic benzothiadiazole generation and derived cell-imaging probing. Herein, three Pd-Keggin-POMs (compounds 1–3) have been successfully synthesized via a one-step assembly strategy. Thus-obtained Pd-Keggin-POMs with well-defined structures and heterogeneous properties enable highly efficient catalytic benzothiadiazole generation. Specifically, compound 3 showed outstanding catalytic activities in Suzuki-Miyaura coupling reactions for the generation of benzothiadiazole derivatives (yields, 90%-97%) and was represented as one of the best catalysts reported to date. Consequently, the obtained benzothiadiazoles were used as the bio-probe for tracking lipid droplets in living-cells and exhibited large Stokes shifts (130 nm), low cytotoxicity and good targeting, which could be also applied to mark the distribution of LDs in living HeLa cells. Systematic investigations clearly decipher the functions of Pd-Keggin-POMs toward finding novel bio-probe materials, highlighting a new insight into the generation of sustainable materials in life-science.
2023, 34(6): 107702
doi: 10.1016/j.cclet.2022.07.045
Abstract:
A series of heterotrinuclear Ti2Ni(CO)n– (n = 6–9) carbonyls have been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectroscopy. Quantum chemical calculations have been carried out to identify the structures and understand the experimental spectral features. The results indicate that a building block of Ti-Ti-Ni-C four-membered ring with the C atom bonded to Ti, Ti, and Ni is dominated in the n = 6–8 complexes, whereas a structural motif of Ti-Ti-Ni triangle core is preferred in n = 9. These complexes are found to be capable of simultaneously accommodating all the main modes of metal-CO coordination (i.e., terminal, bridging, and side-on modes), where the corresponding mode points to the weak, moderate, high CO bond activation, respectively. The number of CO ligands for a specific bonding mode varies with the cluster size. These findings have important implications for molecular-level understanding of the interaction of CO with alloy surfaces/interfaces and tuning the appropriate CO activation via the selection of different metals.
A series of heterotrinuclear Ti2Ni(CO)n– (n = 6–9) carbonyls have been generated via a laser vaporization supersonic cluster source and characterized by mass-selected photoelectron velocity-map imaging spectroscopy. Quantum chemical calculations have been carried out to identify the structures and understand the experimental spectral features. The results indicate that a building block of Ti-Ti-Ni-C four-membered ring with the C atom bonded to Ti, Ti, and Ni is dominated in the n = 6–8 complexes, whereas a structural motif of Ti-Ti-Ni triangle core is preferred in n = 9. These complexes are found to be capable of simultaneously accommodating all the main modes of metal-CO coordination (i.e., terminal, bridging, and side-on modes), where the corresponding mode points to the weak, moderate, high CO bond activation, respectively. The number of CO ligands for a specific bonding mode varies with the cluster size. These findings have important implications for molecular-level understanding of the interaction of CO with alloy surfaces/interfaces and tuning the appropriate CO activation via the selection of different metals.
2023, 34(6): 107703
doi: 10.1016/j.cclet.2022.07.046
Abstract:
Aqueous zinc-ion batteries (ZIBs) has been regarded as a promising energy storage system for large-scale application due to the advantages of low cost and high safety. However, the growth of Zn dendrite, hydrogen evolution and passivation issues induce the poor electrochemical performance of ZIBs. Herein, a Na3Zr2Si2PO12 (NZSP) protection layer with high ionic conductivity of 2.94 mS/cm on Zn metal anode was fabricated by drop casting approach. The protection layer prevents Zn dendrites formation, hydrogen evolution as well as passivation, and facilitates a fast Zn2+ transport. As a result, the symmetric cells based on NZSP-coated Zn show a stable cycling over 1360 h at 0.5 mA/cm2 with 0.5 mAh/cm2 and 1000 h even at a high current density of 5 mA/cm2 with 2 mAh/cm2. Moreover, the full cells combined with V2O5-based cathode displays high capacities and high rate capability. This work offers a facile and effective approach to stabilizing Zn metal anode for enhanced ZIBs.
Aqueous zinc-ion batteries (ZIBs) has been regarded as a promising energy storage system for large-scale application due to the advantages of low cost and high safety. However, the growth of Zn dendrite, hydrogen evolution and passivation issues induce the poor electrochemical performance of ZIBs. Herein, a Na3Zr2Si2PO12 (NZSP) protection layer with high ionic conductivity of 2.94 mS/cm on Zn metal anode was fabricated by drop casting approach. The protection layer prevents Zn dendrites formation, hydrogen evolution as well as passivation, and facilitates a fast Zn2+ transport. As a result, the symmetric cells based on NZSP-coated Zn show a stable cycling over 1360 h at 0.5 mA/cm2 with 0.5 mAh/cm2 and 1000 h even at a high current density of 5 mA/cm2 with 2 mAh/cm2. Moreover, the full cells combined with V2O5-based cathode displays high capacities and high rate capability. This work offers a facile and effective approach to stabilizing Zn metal anode for enhanced ZIBs.
Direct reuse of LiFePO4 cathode materials from spent lithium-ion batteries: Extracting Li from brine
2023, 34(6): 107706
doi: 10.1016/j.cclet.2022.07.049
Abstract:
Due to the serious imbalance between demand and supply of lithium, lithium extraction from brine has become a research hotspot. With the demand for power lithium-ion batteries (LIBs) increased rapidly, a large number of spent LiFePO4 power batteries have been scrapped and entered the recycling stage. Herein, a novel and efficient strategy is proposed to extract lithium from brine by directly reusing spent LiFePO4 powder without any treatment. Various electrochemical test results show that spent LiFePO4 electrode has appropriate lithium capacity (14.62 mgLi/gLiFePO4), excellent separation performance (αLi-Na = 210.5) and low energy consumption (0.768 Wh/gLi) in electrochemical lithium extraction from simulated brine. This work not only provides a novel idea for lithium extraction from brine, but also develops an effective strategy for recycling spent LIBs. The concept of from waste to wealth is of great significance to the development of recycling the spent batteries.
Due to the serious imbalance between demand and supply of lithium, lithium extraction from brine has become a research hotspot. With the demand for power lithium-ion batteries (LIBs) increased rapidly, a large number of spent LiFePO4 power batteries have been scrapped and entered the recycling stage. Herein, a novel and efficient strategy is proposed to extract lithium from brine by directly reusing spent LiFePO4 powder without any treatment. Various electrochemical test results show that spent LiFePO4 electrode has appropriate lithium capacity (14.62 mgLi/gLiFePO4), excellent separation performance (αLi-Na = 210.5) and low energy consumption (0.768 Wh/gLi) in electrochemical lithium extraction from simulated brine. This work not only provides a novel idea for lithium extraction from brine, but also develops an effective strategy for recycling spent LIBs. The concept of from waste to wealth is of great significance to the development of recycling the spent batteries.
2023, 34(6): 107711
doi: 10.1016/j.cclet.2022.07.054
Abstract:
Increasing the charging cut-off potential of lithium cobalt oxide (LiCoO2, LCO) can effectively improve the energy density of the lithium-ion batteries, which are the mainstream energy storage devices used in 3C electronic products. However, the continuous decomposition of the electrolyte and dissolution of Co from the electrode will occur at high-potential operation, which deteriorate the performances of LCO. Here, a cathode-electrolyte interface (CEI) layer containing MgF2 is constructed to enhance the electrochemical stability of LCO at 4.6 V (vs. Li+/Li). The Mg2+ added to the cathode gradually releases into the electrolyte during cycling, which forms a stable MgF2-rich protective layer. In addition, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TTE) is added to the electrolyte acting as a F source to increase the content of MgF2 in the CEI layer. The MgF2-rich CEI layer effectively suppresses the decomposition of electrolyte components and the dissolution of Co of LCO, which makes the Li||LiCoO2 (Li||LCO) cell cycled stably at 3~4.6 V (vs. Li+/Li) in 200 cycles with a retention of 83.9%.
Increasing the charging cut-off potential of lithium cobalt oxide (LiCoO2, LCO) can effectively improve the energy density of the lithium-ion batteries, which are the mainstream energy storage devices used in 3C electronic products. However, the continuous decomposition of the electrolyte and dissolution of Co from the electrode will occur at high-potential operation, which deteriorate the performances of LCO. Here, a cathode-electrolyte interface (CEI) layer containing MgF2 is constructed to enhance the electrochemical stability of LCO at 4.6 V (vs. Li+/Li). The Mg2+ added to the cathode gradually releases into the electrolyte during cycling, which forms a stable MgF2-rich protective layer. In addition, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TTE) is added to the electrolyte acting as a F source to increase the content of MgF2 in the CEI layer. The MgF2-rich CEI layer effectively suppresses the decomposition of electrolyte components and the dissolution of Co of LCO, which makes the Li||LiCoO2 (Li||LCO) cell cycled stably at 3~4.6 V (vs. Li+/Li) in 200 cycles with a retention of 83.9%.
2023, 34(6): 107717
doi: 10.1016/j.cclet.2022.07.060
Abstract:
Developing efficient and stable electrocatalyst to hydrogen evolution reaction adaptable for electrolytes with different pH is a big challenge. In this work, a hierarchically structured ternary nanohybrid composed of flower-like Ru nanoparticles, rigid macrocyclic cucurbit[6]uril (CB[6]) and carboxylated multi-walled carbon nanotubes (MWCNTs) was successfully prepared by chemical wet method. Benefited by the structural merits of flower-like Ru nanoparticles exposed abundant active sites supported by the MWCNTs holding superior mass transport and electrons transfer ability as well as the existence of CB[6], the obtained catalyst exhibited outstanding HER activities with overpotentials of 27, 37 and 70 mV at −10 mA/cm2 in alkaline, acidic, and neutral electrolytes, respectively. Under the same electrocatalytic operation conditions, the HER performance is comparable or superior to commercial Pt/C catalyst (47, 27 and 49 mV). Besides, chronopotentiometric and accelerated stability test also revealed its extraordinary stability, which could be further employed for electrocatalytic procedure in a broad pH range.
Developing efficient and stable electrocatalyst to hydrogen evolution reaction adaptable for electrolytes with different pH is a big challenge. In this work, a hierarchically structured ternary nanohybrid composed of flower-like Ru nanoparticles, rigid macrocyclic cucurbit[6]uril (CB[6]) and carboxylated multi-walled carbon nanotubes (MWCNTs) was successfully prepared by chemical wet method. Benefited by the structural merits of flower-like Ru nanoparticles exposed abundant active sites supported by the MWCNTs holding superior mass transport and electrons transfer ability as well as the existence of CB[6], the obtained catalyst exhibited outstanding HER activities with overpotentials of 27, 37 and 70 mV at −10 mA/cm2 in alkaline, acidic, and neutral electrolytes, respectively. Under the same electrocatalytic operation conditions, the HER performance is comparable or superior to commercial Pt/C catalyst (47, 27 and 49 mV). Besides, chronopotentiometric and accelerated stability test also revealed its extraordinary stability, which could be further employed for electrocatalytic procedure in a broad pH range.
2023, 34(6): 107718
doi: 10.1016/j.cclet.2022.07.061
Abstract:
The Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) layered cathodes endow Li-ion batteries (LIBs) with high energy density. However, they usually suffer from limited ion-diffusion and structural instability during cycling. Although doping strategy can effectively alleviate these issues, the coupling effects of multi-element doping and the corresponding performance enhancement mechanism have been yet unclear. Here, we report a Zr/Ti dual-doped NCM811 cathode material (ZT-NCM811), in which Zr-ion is doped into both transition metal (TM) layers and lithium layers and Ti-ion is only distributed in TM layers. The dual-doping can effectively enhance crystal structure stability via inhibiting the lattice collapse along c-axis and decreasing the Li/Ni disorder. Meantime, the lattice oxygen escape is also greatly reduced due to the presence of stronger Zr-O and Ti-O bonds, further mitigating the crystal surface parasitic reactions with electrolyte. The resultant ZT-NCM811 exhibits high specific capacity of 124 mAh/g at even 10 C, much higher than undoped and single-doped NCM811, and a retention of 98.8% at 1 C after 100 cycles. The assembled ZT-NCM811/graphite full cell also delivers superior battery performances and durability.
The Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) layered cathodes endow Li-ion batteries (LIBs) with high energy density. However, they usually suffer from limited ion-diffusion and structural instability during cycling. Although doping strategy can effectively alleviate these issues, the coupling effects of multi-element doping and the corresponding performance enhancement mechanism have been yet unclear. Here, we report a Zr/Ti dual-doped NCM811 cathode material (ZT-NCM811), in which Zr-ion is doped into both transition metal (TM) layers and lithium layers and Ti-ion is only distributed in TM layers. The dual-doping can effectively enhance crystal structure stability via inhibiting the lattice collapse along c-axis and decreasing the Li/Ni disorder. Meantime, the lattice oxygen escape is also greatly reduced due to the presence of stronger Zr-O and Ti-O bonds, further mitigating the crystal surface parasitic reactions with electrolyte. The resultant ZT-NCM811 exhibits high specific capacity of 124 mAh/g at even 10 C, much higher than undoped and single-doped NCM811, and a retention of 98.8% at 1 C after 100 cycles. The assembled ZT-NCM811/graphite full cell also delivers superior battery performances and durability.
2023, 34(6): 107756
doi: 10.1016/j.cclet.2022.107756
Abstract:
Carbon materials derived from biomass waste are considered as potential electrocatalysts for applications in zinc-air batteries (ZABs) due to their low cost and good catalytic activity. Here, we reported the preparation of gel-based catalysts through utilizing hydrolyzed waste leather powder cross-linked with metallic salt solutions. After calcination, iron-nickel alloy anchored in nitrogen-doped porous carbon catalysts (FeNi@NDC) was achieved. Compared with commercial Pt/C catalyst, FeNi@NDC-800 exhibited lower E1/2 (0.77 V) and better durability. More importantly, the resulting FeNi@NDC-800-based alkaline ZABs achieved power density of 93.01 mW/cm2 and open circuit voltage of 1.45 V, which the FeNi@NDC-800-based neutral ZAB displayed a charge/discharge cycle stability of 275 h. This work opens up the possibility of rational design and preparation of low-cost and high-performance electrocatalysts from recyclable leather waste.
Carbon materials derived from biomass waste are considered as potential electrocatalysts for applications in zinc-air batteries (ZABs) due to their low cost and good catalytic activity. Here, we reported the preparation of gel-based catalysts through utilizing hydrolyzed waste leather powder cross-linked with metallic salt solutions. After calcination, iron-nickel alloy anchored in nitrogen-doped porous carbon catalysts (FeNi@NDC) was achieved. Compared with commercial Pt/C catalyst, FeNi@NDC-800 exhibited lower E1/2 (0.77 V) and better durability. More importantly, the resulting FeNi@NDC-800-based alkaline ZABs achieved power density of 93.01 mW/cm2 and open circuit voltage of 1.45 V, which the FeNi@NDC-800-based neutral ZAB displayed a charge/discharge cycle stability of 275 h. This work opens up the possibility of rational design and preparation of low-cost and high-performance electrocatalysts from recyclable leather waste.
2023, 34(6): 107793
doi: 10.1016/j.cclet.2022.107793
Abstract:
Lithium-rich manganese-based material shows great potential as the high specific cathode materials due to its low cost, environmental friendliness, high operating voltage and simple preparation process. However, the poor capacity retention and cycling performance caused by its unstable structure during cycling restrict the commercialization. In this work, Li1.2Ni0.16Mn0.56Co0.08O2 was synthesized utilizing a Co-precipitation method and different amount of La(PO3)3 (La(PO3)3 = 2 wt%, 4 wt% and 6 wt%) was selected as the coating layer to resolve the above issues. During the calcination process, La(PO3)3 reacts with impurities such as LiOH and Li2CO3 on the lithium-rich surface to reduce the residual lithium on the surface, thus improving the interfacial stability, slowing down the corrosion of the electrolyte, and finally enhancing its electrochemical performance. The cathode materials coated with 4% of La(PO3)3 showed the best electrochemical performance in terms of capacity retention and cycling performance compared to the pristine NCM. The high initial discharge capacity of 214.21 mAh/g and capacity retention of 94.2% after 100 cycles at 0.1 C can be obtained. This work provides an effective strategy to protect the cathode from corrosion and will promote its further practical applications in high specific Li-ion batteries.
Lithium-rich manganese-based material shows great potential as the high specific cathode materials due to its low cost, environmental friendliness, high operating voltage and simple preparation process. However, the poor capacity retention and cycling performance caused by its unstable structure during cycling restrict the commercialization. In this work, Li1.2Ni0.16Mn0.56Co0.08O2 was synthesized utilizing a Co-precipitation method and different amount of La(PO3)3 (La(PO3)3 = 2 wt%, 4 wt% and 6 wt%) was selected as the coating layer to resolve the above issues. During the calcination process, La(PO3)3 reacts with impurities such as LiOH and Li2CO3 on the lithium-rich surface to reduce the residual lithium on the surface, thus improving the interfacial stability, slowing down the corrosion of the electrolyte, and finally enhancing its electrochemical performance. The cathode materials coated with 4% of La(PO3)3 showed the best electrochemical performance in terms of capacity retention and cycling performance compared to the pristine NCM. The high initial discharge capacity of 214.21 mAh/g and capacity retention of 94.2% after 100 cycles at 0.1 C can be obtained. This work provides an effective strategy to protect the cathode from corrosion and will promote its further practical applications in high specific Li-ion batteries.
2023, 34(6): 107828
doi: 10.1016/j.cclet.2022.107828
Abstract:
Local delivery of nanomedicines holds therapeutic promise for colorectal cancer (CRC). However, it presents tremendous challenges due to the existence of multiple physiological barriers, especially intracellular obstacles, including intracellular trafficking, subcellular accumulation, and drug release. Herein, we report a multifunctional nanoparticle (CMSNR) by wrapping the mesoporous silica nanorod with cell membrane derived from CRC cells for improved chemotherapy. Compared with their naked counterparts, the cell membrane endowed CMSNR with homotypic targeting and improved cellular uptake capacities. Due to the rod-like shape, CMSNR achieved superior colorectal mucus permeability, enhanced tumor accumulation, and boosted cellular uptake than their spherical counterparts. Moreover, the internalized CMSNR underwent robust intracellular trafficking and gained augmented motility toward the nucleus, leading to efficient perinuclear accumulation and a subsequent 5.6-fold higher nuclear accumulation of loaded drug than that of nanospheres. In the orthotopic colorectal tumor-bearing nude mice, rectally administrated mefuparib hydrochloride (MPH)-loaded CMSNR traversed the colorectal mucus, penetrated the tumor tissue, and successfully aggregated in the perinuclear region of cancer cells, thus exhibiting significantly improved antitumor outcomes. Our findings highlight the shape-based design of cell membrane-coated nanoparticles that can address sequential drug delivery barriers has a promising future in cancer nanomedicine.
Local delivery of nanomedicines holds therapeutic promise for colorectal cancer (CRC). However, it presents tremendous challenges due to the existence of multiple physiological barriers, especially intracellular obstacles, including intracellular trafficking, subcellular accumulation, and drug release. Herein, we report a multifunctional nanoparticle (CMSNR) by wrapping the mesoporous silica nanorod with cell membrane derived from CRC cells for improved chemotherapy. Compared with their naked counterparts, the cell membrane endowed CMSNR with homotypic targeting and improved cellular uptake capacities. Due to the rod-like shape, CMSNR achieved superior colorectal mucus permeability, enhanced tumor accumulation, and boosted cellular uptake than their spherical counterparts. Moreover, the internalized CMSNR underwent robust intracellular trafficking and gained augmented motility toward the nucleus, leading to efficient perinuclear accumulation and a subsequent 5.6-fold higher nuclear accumulation of loaded drug than that of nanospheres. In the orthotopic colorectal tumor-bearing nude mice, rectally administrated mefuparib hydrochloride (MPH)-loaded CMSNR traversed the colorectal mucus, penetrated the tumor tissue, and successfully aggregated in the perinuclear region of cancer cells, thus exhibiting significantly improved antitumor outcomes. Our findings highlight the shape-based design of cell membrane-coated nanoparticles that can address sequential drug delivery barriers has a promising future in cancer nanomedicine.
2023, 34(6): 107866
doi: 10.1016/j.cclet.2022.107866
Abstract:
As nanocarriers, nanomicelles play vital roles in the toolbox of drug delivery. The stability of nanomicelles affects the nanomedicines’ bioactivity. Therefore, it is important to understand the stability of nanomicelles for further improvements. Here, we report a strategy to construct new nanomicelles (NM) by introducing aggregation-induced emission (AIE) functional group tetraphenylethylene (TPE) in the component polymer vitamin E (d-α-tocopheryl polyethylene glycol 1000 succinate) (TPGS). The stability of doxorubicin (DOX) loaded nanomicelles DOX@NM in different conditions was studied by fluorescence analysis. The fluorescence changes of DOX@NM are ‘seesaw-like’ when they transform between assembled and disassembled forms. In the assembled form, TPE gives emission from AIE effect, while in the disassembled form, the fluorescence of DOX is observed due to the disappearance of ACQ effect.
As nanocarriers, nanomicelles play vital roles in the toolbox of drug delivery. The stability of nanomicelles affects the nanomedicines’ bioactivity. Therefore, it is important to understand the stability of nanomicelles for further improvements. Here, we report a strategy to construct new nanomicelles (NM) by introducing aggregation-induced emission (AIE) functional group tetraphenylethylene (TPE) in the component polymer vitamin E (d-α-tocopheryl polyethylene glycol 1000 succinate) (TPGS). The stability of doxorubicin (DOX) loaded nanomicelles DOX@NM in different conditions was studied by fluorescence analysis. The fluorescence changes of DOX@NM are ‘seesaw-like’ when they transform between assembled and disassembled forms. In the assembled form, TPE gives emission from AIE effect, while in the disassembled form, the fluorescence of DOX is observed due to the disappearance of ACQ effect.
2023, 34(6): 107867
doi: 10.1016/j.cclet.2022.107867
Abstract:
By introducing a naphthothiadiazole (NT) unit as the main building block, a non-doped and red emissive conjugated polymer poly(9,9-dihexylfluorene-alt-naphthothiadiazole) (PFNT) is readily obtained through a two-step synthesis. Since the NT unit has a large twist angle with its neighboring segment, the aggregation-induced quenching (AIQ) effect of PFNT can be effectively suppressed in the condensed state. As a result, the corresponding PFNT polymer dot (Pdot) exhibits a high fluorescence quantum yield of 53.2% with peak emission at 616 nm, which is one of the most efficient red Pdots known. PFNT Pdot shows good biocompatibility and can be employed for living cell fluorescent imaging with high brightness. It also can be used for specific subcellular organelle imaging through immunofluorescence labeling. Furthermore, the PFNT Pdot demonstrates much better photostability for long-time cell fluorescence imaging than commercial red dyes. The high performances of PFNT Pdot make it a promising fluorescent probe for practical bioapplications.
By introducing a naphthothiadiazole (NT) unit as the main building block, a non-doped and red emissive conjugated polymer poly(9,9-dihexylfluorene-alt-naphthothiadiazole) (PFNT) is readily obtained through a two-step synthesis. Since the NT unit has a large twist angle with its neighboring segment, the aggregation-induced quenching (AIQ) effect of PFNT can be effectively suppressed in the condensed state. As a result, the corresponding PFNT polymer dot (Pdot) exhibits a high fluorescence quantum yield of 53.2% with peak emission at 616 nm, which is one of the most efficient red Pdots known. PFNT Pdot shows good biocompatibility and can be employed for living cell fluorescent imaging with high brightness. It also can be used for specific subcellular organelle imaging through immunofluorescence labeling. Furthermore, the PFNT Pdot demonstrates much better photostability for long-time cell fluorescence imaging than commercial red dyes. The high performances of PFNT Pdot make it a promising fluorescent probe for practical bioapplications.
2023, 34(6): 107868
doi: 10.1016/j.cclet.2022.107868
Abstract:
Twenty-four novel neonicotinoid analogues with nitromethylene and five-membered aromatic heterocycles were designed and synthesized. All target molecular structures have been confirmed by analytical and spectral data. Some compounds exhibited notable insecticidal activities against aphid (Aphis medicaginis) and brown planthopper (Nilaparvata lugens). The aqueous stability test confirmed that the stabilities of those compounds were superior to the leading compound, and the photostability was even better than that of imidacloprid.
Twenty-four novel neonicotinoid analogues with nitromethylene and five-membered aromatic heterocycles were designed and synthesized. All target molecular structures have been confirmed by analytical and spectral data. Some compounds exhibited notable insecticidal activities against aphid (Aphis medicaginis) and brown planthopper (Nilaparvata lugens). The aqueous stability test confirmed that the stabilities of those compounds were superior to the leading compound, and the photostability was even better than that of imidacloprid.
2023, 34(6): 107887
doi: 10.1016/j.cclet.2022.107887
Abstract:
Schisandrin A is a natural dibenzocyclooctene lignan with potent neuroprotective activity. However, the specific mechanisms or direct target proteins have not been clarified up to now. In this study, we designed and synthesized the probes of schisandrin A with photoreactive diazirine and clickable alkyne to identify its direct target in SH-SY5Y cells by employing activity-based protein profiling (ABPP) technique. Ykt6 was prominent among the 13 proteins obtained with high confidence and we confirmed Ykt6 as the direct target of schisandrin A by CETSA, IF, SPR and knockdown assay. Functionally, schisandrin A protected the cells against the injury induced by glutamate by regulating autophagy via Ykt6. This discovery may provide a novel therapeutic option for various neuronal cell damage-mediated diseases.
Schisandrin A is a natural dibenzocyclooctene lignan with potent neuroprotective activity. However, the specific mechanisms or direct target proteins have not been clarified up to now. In this study, we designed and synthesized the probes of schisandrin A with photoreactive diazirine and clickable alkyne to identify its direct target in SH-SY5Y cells by employing activity-based protein profiling (ABPP) technique. Ykt6 was prominent among the 13 proteins obtained with high confidence and we confirmed Ykt6 as the direct target of schisandrin A by CETSA, IF, SPR and knockdown assay. Functionally, schisandrin A protected the cells against the injury induced by glutamate by regulating autophagy via Ykt6. This discovery may provide a novel therapeutic option for various neuronal cell damage-mediated diseases.
2023, 34(6): 107888
doi: 10.1016/j.cclet.2022.107888
Abstract:
Nitrogen electro-reduction reaction (NERR) is a promising alternative method for ammonia production to the Haber–Bosch approach due to mild reaction conditions and free harmful by-product emission. A formidable challenge in bringing NERR closer to the practical application is developing an electro-catalyst which can simultaneously improve the Faraday efficiency and reduce the reaction over-potential. Herein, we fabricated a catalyst of nitrogen-doped carbon dots modified copper-phosphate nanoflower petals (CuPo-NCDs NF) via a self-assembly method. The flower structure endowed the CuPo-NCDs NF with large specific surface area, and thus enabled more active sites to be exposed. In particular, we demonstrated that the NCDs modified CuPo petals with flower-like structure can accelerate the interfacial proton-electron transfer, suppressing the competing hydrogen evolution reaction and promoting the desired NERR process. Ultimately, for the CuPo-NCDs NF catalyzed NERR, the FENH3 and the reaction potential both were boosted, the resultant energy efficiency of NERR reached a record-breaking value of 56.5%, and the NH3 yield rate increased by 7 times compared to NCDs. This study provides a novel catalyst with a new pathway to boost the NERR.
Nitrogen electro-reduction reaction (NERR) is a promising alternative method for ammonia production to the Haber–Bosch approach due to mild reaction conditions and free harmful by-product emission. A formidable challenge in bringing NERR closer to the practical application is developing an electro-catalyst which can simultaneously improve the Faraday efficiency and reduce the reaction over-potential. Herein, we fabricated a catalyst of nitrogen-doped carbon dots modified copper-phosphate nanoflower petals (CuPo-NCDs NF) via a self-assembly method. The flower structure endowed the CuPo-NCDs NF with large specific surface area, and thus enabled more active sites to be exposed. In particular, we demonstrated that the NCDs modified CuPo petals with flower-like structure can accelerate the interfacial proton-electron transfer, suppressing the competing hydrogen evolution reaction and promoting the desired NERR process. Ultimately, for the CuPo-NCDs NF catalyzed NERR, the FENH3 and the reaction potential both were boosted, the resultant energy efficiency of NERR reached a record-breaking value of 56.5%, and the NH3 yield rate increased by 7 times compared to NCDs. This study provides a novel catalyst with a new pathway to boost the NERR.
2023, 34(6): 107889
doi: 10.1016/j.cclet.2022.107889
Abstract:
Various phototheranostics have recently been developed for phototherapy. Through proper molecular design, the photochemical and photophysical properties of these phototheranostics can be promoted. Herein, an acceptor-donor-acceptor (A-D-A)-structured dye, BTP-4F-DMO, was synthesized and prepared into water-soluble nanoparticles (NPs). The obtained BTP-4F-DMO NPs had strong absorption from 650 nm to 850 nm and a fluorescence emission peak at ~900 nm that tailed to ~1100 nm. The NPs showed a superhigh photothermal conversion efficiency of 90.5% ± 5% and could simultaneously generate •OH and 1O2 with a 1O2 generation quantum yield of 4.6% under 808 nm laser irradiation. Due to these advanced properties, BTP-4F-DMO NPs can switch the role of autophagy from pro-survival to pro-death, thereby further promoting cancer cell death. These features make BTP-4F-DMO NPs a promising multifunctional phototheranostic agent for NIR-Ⅱ fluorescence/photoacoustic dual-mode imaging-guided synergetic photodynamic/photothermal therapy. In general, this work provides a strategy for expanding the biomedical applications of organic A-D-A-structured phototheranostics.
Various phototheranostics have recently been developed for phototherapy. Through proper molecular design, the photochemical and photophysical properties of these phototheranostics can be promoted. Herein, an acceptor-donor-acceptor (A-D-A)-structured dye, BTP-4F-DMO, was synthesized and prepared into water-soluble nanoparticles (NPs). The obtained BTP-4F-DMO NPs had strong absorption from 650 nm to 850 nm and a fluorescence emission peak at ~900 nm that tailed to ~1100 nm. The NPs showed a superhigh photothermal conversion efficiency of 90.5% ± 5% and could simultaneously generate •OH and 1O2 with a 1O2 generation quantum yield of 4.6% under 808 nm laser irradiation. Due to these advanced properties, BTP-4F-DMO NPs can switch the role of autophagy from pro-survival to pro-death, thereby further promoting cancer cell death. These features make BTP-4F-DMO NPs a promising multifunctional phototheranostic agent for NIR-Ⅱ fluorescence/photoacoustic dual-mode imaging-guided synergetic photodynamic/photothermal therapy. In general, this work provides a strategy for expanding the biomedical applications of organic A-D-A-structured phototheranostics.
2023, 34(6): 107890
doi: 10.1016/j.cclet.2022.107890
Abstract:
The massive use of polyhexamethylene guanidine (PHMG), as a typical bactericidal agent, raised environmental concerns to the public. This work comprehensively revealed the hormesis effects of PHMG occurred in waste activated sludge (WAS) on the generation of volatile fatty acids (VFAs) during anaerobic fermentation. The low level of PHMG (100 mg/g TSS) significantly promoted the VFAs generation (1283 mg COD/L, compared with 337 mg COD/L in the control) via synchronously facilitating the solubilization, hydrolysis, and acidification steps but inhibiting methanogenesis. Metagenomic analysis showed that the functional anaerobe (i.e., Bacteroides, Macellibacteroide and Parabacteroide) and corresponding genetic expressions responsible for extracellular hydrolysis (i.e., clpP), membrane transport (i.e., ffh and gspF), intracellular substrates metabolism (i.e., ald and paaF) and VFAs biosynthesis (i.e., ACACA and FASN) were enhanced in the optimal presence of PHMG. Moreover, the anaerobic species could respond and adapt to low PHMG stimuli via quorum sensing (i.e., cqsA, rpfC and rpfG), and thus maintain the high microbial metabolic activities. However, they were unable to tolerate the toxicity of excessive PHMG, resulting in the extremely low VFAs production. This work enlightened the effects of emerging pollutants on WAS fermentation at the genetic levels, and provided guidance on the WAS treatment and resource recovery.
The massive use of polyhexamethylene guanidine (PHMG), as a typical bactericidal agent, raised environmental concerns to the public. This work comprehensively revealed the hormesis effects of PHMG occurred in waste activated sludge (WAS) on the generation of volatile fatty acids (VFAs) during anaerobic fermentation. The low level of PHMG (100 mg/g TSS) significantly promoted the VFAs generation (1283 mg COD/L, compared with 337 mg COD/L in the control) via synchronously facilitating the solubilization, hydrolysis, and acidification steps but inhibiting methanogenesis. Metagenomic analysis showed that the functional anaerobe (i.e., Bacteroides, Macellibacteroide and Parabacteroide) and corresponding genetic expressions responsible for extracellular hydrolysis (i.e., clpP), membrane transport (i.e., ffh and gspF), intracellular substrates metabolism (i.e., ald and paaF) and VFAs biosynthesis (i.e., ACACA and FASN) were enhanced in the optimal presence of PHMG. Moreover, the anaerobic species could respond and adapt to low PHMG stimuli via quorum sensing (i.e., cqsA, rpfC and rpfG), and thus maintain the high microbial metabolic activities. However, they were unable to tolerate the toxicity of excessive PHMG, resulting in the extremely low VFAs production. This work enlightened the effects of emerging pollutants on WAS fermentation at the genetic levels, and provided guidance on the WAS treatment and resource recovery.
2023, 34(6): 107892
doi: 10.1016/j.cclet.2022.107892
Abstract:
Conductive hydrogels have shown great prospects as wearable flexible sensors. Nevertheless, it is still a challenge to construct hydrogel-based sensor with great mechanical strength and high strain sensitivity. Herein, an ion-conducting hydrogel was fabricated by introducing gelatin-dialdehyde β-cyclodextrin (Gel-DACD) into polyvinyl alcohol-borax (PVA-borax) hydrogel network. Natural Gel-DACD network acted as mechanical deformation force through non-covalent cross-linking to endow the polyvinyl alcohol-borax/gelatin-dialdehyde β-cyclodextrin hydrogel (PGBCDH) with excellent mechanical stress (1.35 MPa), stretchability (400%), toughness (1.84 MJ/m3) and great fatigue resistance (200% strain for 100 cycles). Surprisingly, PGBCDH displayed good conductivity of 0.31 S/m after adding DACD to hydrogel network. As sensor, it showed rapid response (168 ms), high strain sensitivity (gage factor (GF) = 8.57 in the strain range of 200%-250%) and reliable sensing stability (100% strain for 200 cycles). Importantly, PGBCDH-based sensor can accurately monitor complex body movements (knee, elbow, wrist and finger joints) and large-scale subtle movements (speech, swallow, breath and facial expressions). Thus, PGBCDH shows great potential for human monitoring with high precision.
Conductive hydrogels have shown great prospects as wearable flexible sensors. Nevertheless, it is still a challenge to construct hydrogel-based sensor with great mechanical strength and high strain sensitivity. Herein, an ion-conducting hydrogel was fabricated by introducing gelatin-dialdehyde β-cyclodextrin (Gel-DACD) into polyvinyl alcohol-borax (PVA-borax) hydrogel network. Natural Gel-DACD network acted as mechanical deformation force through non-covalent cross-linking to endow the polyvinyl alcohol-borax/gelatin-dialdehyde β-cyclodextrin hydrogel (PGBCDH) with excellent mechanical stress (1.35 MPa), stretchability (400%), toughness (1.84 MJ/m3) and great fatigue resistance (200% strain for 100 cycles). Surprisingly, PGBCDH displayed good conductivity of 0.31 S/m after adding DACD to hydrogel network. As sensor, it showed rapid response (168 ms), high strain sensitivity (gage factor (GF) = 8.57 in the strain range of 200%-250%) and reliable sensing stability (100% strain for 200 cycles). Importantly, PGBCDH-based sensor can accurately monitor complex body movements (knee, elbow, wrist and finger joints) and large-scale subtle movements (speech, swallow, breath and facial expressions). Thus, PGBCDH shows great potential for human monitoring with high precision.
2023, 34(6): 107893
doi: 10.1016/j.cclet.2022.107893
Abstract:
Rational regulation of stable graphitic carbon nitride (CN) for superior peroxymonosulfate (PMS) activation is important in the catalytic degradation of water contaminants. In this work, the copper oxide and oxygen co-doped graphitic carbon nitride (CuO/O-CN) was prepared via one-step synthesis and applied in activating PMS for oxytetracycline (OTC) degradation, displaying superior catalytic performance. Systematic characterization and theoretical calculations indicated that the synergistic effect between the oxygen site of CN and CuO can modulate the electronic structure of the whole composite further facilitating the formation of non-radical 1O2 and various reactive radicals. Results of the influencing factor experiments revealed that CuO/O-CN has a strong resistance to the environmental impact. The degradation efficiency of OTC in the real water environment even exceeded that in the deionized water. After four successive runs of the optimal catalyst, the OTC removal rate was still as high as 91.3%. This work developed a high-efficiency PMS activator to remove refractory pollutants via both radical pathway and non-radical pathway, which showed a promising potential in the treatment of wastewaters.
Rational regulation of stable graphitic carbon nitride (CN) for superior peroxymonosulfate (PMS) activation is important in the catalytic degradation of water contaminants. In this work, the copper oxide and oxygen co-doped graphitic carbon nitride (CuO/O-CN) was prepared via one-step synthesis and applied in activating PMS for oxytetracycline (OTC) degradation, displaying superior catalytic performance. Systematic characterization and theoretical calculations indicated that the synergistic effect between the oxygen site of CN and CuO can modulate the electronic structure of the whole composite further facilitating the formation of non-radical 1O2 and various reactive radicals. Results of the influencing factor experiments revealed that CuO/O-CN has a strong resistance to the environmental impact. The degradation efficiency of OTC in the real water environment even exceeded that in the deionized water. After four successive runs of the optimal catalyst, the OTC removal rate was still as high as 91.3%. This work developed a high-efficiency PMS activator to remove refractory pollutants via both radical pathway and non-radical pathway, which showed a promising potential in the treatment of wastewaters.
2023, 34(6): 107895
doi: 10.1016/j.cclet.2022.107895
Abstract:
Glioma is a malignant primary brain tumor that is extremely harmful to human beings. Therefore, studying the invasiveness of glioma cells is of great significance for the diagnosis and treatment of glioma. In this work, TiO2/Nb2C was prepared as a SERS substrate and combined with microfluidic chip to construct an invasion model capable of monitoring glioma invasion in real time. Both experimental data and density function theory (DFT) calculations showed that the significant SERS-enhancing effect of TiO2/Nb2C on methylene blue (MB) originated from the chemical magnification (CM) mechanism when MB was used as the adsorbed molecule. Based on this, we achieved a highly sensitive and targeted detection of vascular endothelial growth factor (VEGF), a biomarker for glioma with a low detection limit of 3.7 pg/mL, then quantified the invasive process in real time by detecting VEGF. Meanwhile, the depletion of reactive oxygen species (ROS) by TiO2/Nb2C can inhibit the invasion of glioma cells. For the first time, the invasion model combines SERS technology with microfluidic technology, while monitoring the cell invasion process in real time, the invasion process can be quantified by detecting the VEGF secreted by glioma cells during the invasion process, realizing the integration of diagnosis and treatment, and establish a new model for the biomedical analysis, clinical diagnosis and treatment of glioma.
Glioma is a malignant primary brain tumor that is extremely harmful to human beings. Therefore, studying the invasiveness of glioma cells is of great significance for the diagnosis and treatment of glioma. In this work, TiO2/Nb2C was prepared as a SERS substrate and combined with microfluidic chip to construct an invasion model capable of monitoring glioma invasion in real time. Both experimental data and density function theory (DFT) calculations showed that the significant SERS-enhancing effect of TiO2/Nb2C on methylene blue (MB) originated from the chemical magnification (CM) mechanism when MB was used as the adsorbed molecule. Based on this, we achieved a highly sensitive and targeted detection of vascular endothelial growth factor (VEGF), a biomarker for glioma with a low detection limit of 3.7 pg/mL, then quantified the invasive process in real time by detecting VEGF. Meanwhile, the depletion of reactive oxygen species (ROS) by TiO2/Nb2C can inhibit the invasion of glioma cells. For the first time, the invasion model combines SERS technology with microfluidic technology, while monitoring the cell invasion process in real time, the invasion process can be quantified by detecting the VEGF secreted by glioma cells during the invasion process, realizing the integration of diagnosis and treatment, and establish a new model for the biomedical analysis, clinical diagnosis and treatment of glioma.
A new insight into the promoting effects of transition metal phosphides in methanol electrooxidation
2023, 34(6): 107899
doi: 10.1016/j.cclet.2022.107899
Abstract:
The construction of highly active catalysts for methanol oxidation reaction (MOR) is central to direct methanol fuel cells. Tremendous progress has been made in transition metal phosphides (TMPs) based catalysts. However, TMPs would be partially damaged and transformed into new substances (e.g., Pt-M-P composite, where M represents a second transition metal) during Pt deposition process. This would pose a large obstacle to the cognition of the real promoting effects of TMPs in MOR. Herein, Co2P co-catalysts (Pt-P/Co2P@NPC, where NPC stands for N and P co-doped carbon) and Pt-Co-P composite catalysts (Pt-Co-P/NPC) were controllably synthesized. Electrocatalysis tests show that the Pt-Co-P/NPC exhibits superior MOR activity as high as 1016 mA/mgPt, significantly exceeding that of Pt-P/Co2P@NPC (345 mA/mgPt). This result indicates that the promoting effect is ascribed primarily to the resultant Pt-Co-P composite, in sharply contrast to previous viewpoint that Co2P itself improves the activity. Further mechanistic studies reveal that Pt-Co-P/NPC exhibits much stronger electron interaction and thus manifesting a remarkably weaker CO absorption than Pt-P/Co2P@NPC and Pt/C. Moreover, Pt-Co-P is also more capable of producing oxygen-containing adsorbate and thus accelerating the removal of surface-bonded CO*, ultimately boosting the MOR performance.
The construction of highly active catalysts for methanol oxidation reaction (MOR) is central to direct methanol fuel cells. Tremendous progress has been made in transition metal phosphides (TMPs) based catalysts. However, TMPs would be partially damaged and transformed into new substances (e.g., Pt-M-P composite, where M represents a second transition metal) during Pt deposition process. This would pose a large obstacle to the cognition of the real promoting effects of TMPs in MOR. Herein, Co2P co-catalysts (Pt-P/Co2P@NPC, where NPC stands for N and P co-doped carbon) and Pt-Co-P composite catalysts (Pt-Co-P/NPC) were controllably synthesized. Electrocatalysis tests show that the Pt-Co-P/NPC exhibits superior MOR activity as high as 1016 mA/mgPt, significantly exceeding that of Pt-P/Co2P@NPC (345 mA/mgPt). This result indicates that the promoting effect is ascribed primarily to the resultant Pt-Co-P composite, in sharply contrast to previous viewpoint that Co2P itself improves the activity. Further mechanistic studies reveal that Pt-Co-P/NPC exhibits much stronger electron interaction and thus manifesting a remarkably weaker CO absorption than Pt-P/Co2P@NPC and Pt/C. Moreover, Pt-Co-P is also more capable of producing oxygen-containing adsorbate and thus accelerating the removal of surface-bonded CO*, ultimately boosting the MOR performance.
2023, 34(6): 107900
doi: 10.1016/j.cclet.2022.107900
Abstract:
Development of high-performance solid state luminescent carbon-based nanomaterials remains challenging. Here, strong blue-green fluorescent carbonized polymer dots (CPDs) from o-aminobenzenethiol and thiosalicylic acid (oABT-TSA-CPDs) with an absolute photoluminescence quantum yield (PLQY) of 76% in solid state without matrix were synthesized. Through adjusting the reaction temperature and time, the PL centers were proved to be carbon core state and surface state associated to carbonyl group which was the source of strong fluorescence emission in solid state. The mechanism of the unique phenomenon of enhanced emission from ethanol solution (PLQY = 7%) to powder (PLQY = 76%) was investigated by analyzing the chemical properties and structures of oABT-TSA-CPDs at different temperatures and oABT-TSA-CPDs/PVC composites, and was confirmed as fixation of PL centers.
Development of high-performance solid state luminescent carbon-based nanomaterials remains challenging. Here, strong blue-green fluorescent carbonized polymer dots (CPDs) from o-aminobenzenethiol and thiosalicylic acid (oABT-TSA-CPDs) with an absolute photoluminescence quantum yield (PLQY) of 76% in solid state without matrix were synthesized. Through adjusting the reaction temperature and time, the PL centers were proved to be carbon core state and surface state associated to carbonyl group which was the source of strong fluorescence emission in solid state. The mechanism of the unique phenomenon of enhanced emission from ethanol solution (PLQY = 7%) to powder (PLQY = 76%) was investigated by analyzing the chemical properties and structures of oABT-TSA-CPDs at different temperatures and oABT-TSA-CPDs/PVC composites, and was confirmed as fixation of PL centers.
2023, 34(6): 107901
doi: 10.1016/j.cclet.2022.107901
Abstract:
Atomically precise metal nanoclusters (NCs) have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties, discrete energy band structure, and quantum confinement effect, which are distinct from conventional metal nanoparticles (NPs). Nevertheless, metal NCs suffer from photoinduced self-oxidative aggregation accompanied by in-situ transformation to metal NPs, markedly reducing the photosensitization of metal NCs. Herein, maneuvering the generic instability of metal NCs, we perform the charge transport impetus comparison between atomically precise metal NCs and plasmonic metal NPs counterpart obtained from in-situ self-transformation of metal NCs in photoelectrochemical (PEC) water splitting reaction. For conceptual demonstration, we proposed two quintessential heterostructures, which include TNTAs-Au25 heterostructure fabricated by electrostatically depositing glutathione (GSH)-protected Au25(GSH)18 NCs on the TiO2 nanotube arrays (TNTAs) substrate, and TNTAs-Au heterostructure constructed by triggering self-transformation of Au25(GSH)18 NCs to plasmonic Au NPs in TNTAs-Au25 via calcination. The results indicate that photoelectrons produced over Au25 NCs are superior to hot electrons of plasmonic Au NPs in stimulating the interracial charge transport toward solar water oxidation. This is mainly ascribed to the significantly accelerated carrier transport kinetics, prolonged carrier lifespan, and substantial photosensitization effect of Au25 NCs compared with plasmonic Au NPs, resulting in the considerably enhanced PEC water splitting performance of TNTAs-Au25 relative to plasmonic TNTAs-Au counterpart under visible light irradiation. Our work would provide important implications for rationally designing atomically precise metal NCs-based photosystems toward solar energy conversion.
Atomically precise metal nanoclusters (NCs) have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties, discrete energy band structure, and quantum confinement effect, which are distinct from conventional metal nanoparticles (NPs). Nevertheless, metal NCs suffer from photoinduced self-oxidative aggregation accompanied by in-situ transformation to metal NPs, markedly reducing the photosensitization of metal NCs. Herein, maneuvering the generic instability of metal NCs, we perform the charge transport impetus comparison between atomically precise metal NCs and plasmonic metal NPs counterpart obtained from in-situ self-transformation of metal NCs in photoelectrochemical (PEC) water splitting reaction. For conceptual demonstration, we proposed two quintessential heterostructures, which include TNTAs-Au25 heterostructure fabricated by electrostatically depositing glutathione (GSH)-protected Au25(GSH)18 NCs on the TiO2 nanotube arrays (TNTAs) substrate, and TNTAs-Au heterostructure constructed by triggering self-transformation of Au25(GSH)18 NCs to plasmonic Au NPs in TNTAs-Au25 via calcination. The results indicate that photoelectrons produced over Au25 NCs are superior to hot electrons of plasmonic Au NPs in stimulating the interracial charge transport toward solar water oxidation. This is mainly ascribed to the significantly accelerated carrier transport kinetics, prolonged carrier lifespan, and substantial photosensitization effect of Au25 NCs compared with plasmonic Au NPs, resulting in the considerably enhanced PEC water splitting performance of TNTAs-Au25 relative to plasmonic TNTAs-Au counterpart under visible light irradiation. Our work would provide important implications for rationally designing atomically precise metal NCs-based photosystems toward solar energy conversion.
2023, 34(6): 107903
doi: 10.1016/j.cclet.2022.107903
Abstract:
Quantum dots (QDs) based heterojunction is a candidate for the photocatalytic CO2 reduction, owing to the large extinction coefficient and easy modification of band structures. However, the van der Waals interaction causes the large charge resistance and strong recombination centers between QDs and host materials, which makes the poor photocatalytic performance. Herein, a covalent bonded CdSeTe QDs and NH2-UiO-66 heterojunction (NUC-x) is constructed through an acylamino (-CONH-). The results indicate that the acylamino between NH2-UiO-66 and CdSeTe QDs can serve as the transfer channels for the photogenerated charges and stabilize the QDs. The optimized NUC-1200 achieved a CO generation rate of 228.68 µmol/g, which is 13 and 4 times higher than that of NH2-UiO-66 and CdSeTe QDs, respectively. This work provides a new avenue for efficient and stable photocatalysis of QDs.
Quantum dots (QDs) based heterojunction is a candidate for the photocatalytic CO2 reduction, owing to the large extinction coefficient and easy modification of band structures. However, the van der Waals interaction causes the large charge resistance and strong recombination centers between QDs and host materials, which makes the poor photocatalytic performance. Herein, a covalent bonded CdSeTe QDs and NH2-UiO-66 heterojunction (NUC-x) is constructed through an acylamino (-CONH-). The results indicate that the acylamino between NH2-UiO-66 and CdSeTe QDs can serve as the transfer channels for the photogenerated charges and stabilize the QDs. The optimized NUC-1200 achieved a CO generation rate of 228.68 µmol/g, which is 13 and 4 times higher than that of NH2-UiO-66 and CdSeTe QDs, respectively. This work provides a new avenue for efficient and stable photocatalysis of QDs.
2023, 34(6): 107905
doi: 10.1016/j.cclet.2022.107905
Abstract:
This work demonstrates a two-step method to produce oxide-derived Cu nanowires on Cu mesh surface to offer a monolithic catalyst that outstandingly improves the hydrogen production from reforming formaldehyde and water under ambient conditions. Our results not only reveal that the special oxide-derived nanostructure can significantly improve the formaldehyde reforming performance of Cu, but also display that the hydrogen production has a linear relationship with oxygen pressure. Specially, a maximum of 36 times increment in hydrogen generation rate is observed than that without oxygen during the reaction. Density functional theory calculations show that the formaldehyde molecule is adsorbed on Cu surface only when the adsorbed oxygen is in adjacency, and hydrogen release process is the rate-determining step. This work highlights that the activity of deliberately synthesized catalyst can further be promoted by dynamic chemical modulation of surface states during working.
This work demonstrates a two-step method to produce oxide-derived Cu nanowires on Cu mesh surface to offer a monolithic catalyst that outstandingly improves the hydrogen production from reforming formaldehyde and water under ambient conditions. Our results not only reveal that the special oxide-derived nanostructure can significantly improve the formaldehyde reforming performance of Cu, but also display that the hydrogen production has a linear relationship with oxygen pressure. Specially, a maximum of 36 times increment in hydrogen generation rate is observed than that without oxygen during the reaction. Density functional theory calculations show that the formaldehyde molecule is adsorbed on Cu surface only when the adsorbed oxygen is in adjacency, and hydrogen release process is the rate-determining step. This work highlights that the activity of deliberately synthesized catalyst can further be promoted by dynamic chemical modulation of surface states during working.
2023, 34(6): 107906
doi: 10.1016/j.cclet.2022.107906
Abstract:
DNAzyme amplifiers have been extensively explored as a useful sensing platform, but single DNAzyme amplifier is limited in biosensing applications by its low sensitivity. Herein, a cascade DNAzyme amplifier was designed by exploiting concurrent amplification cycle principles of toehold-mediated strand displacement reaction (TSDR) and Zn2+-assisted DNAzyme cycle with lower cost and simpler procedures. Compared with single DNAzyme amplifier, the proposed TSDR-propelled cascade DNAzyme amplifier exhibited higher sensitivity by releasing more DNAzyme through TSDR to cleave substrate strand during the DNAzyme cycle. Base on this, let-7a could be sensitively detected in the range of 5–50 nmol/L with a detection limit of 64 pmol/L. Furthermore, the dual signal amplification strategy of the cascade DNAzyme amplifier exhibited excellent selectivity to distinguish single-base mismatched DNA strands, which has been successfully applied to the determination of let-7a in blood serum, showing high promise in early cancer diagnosis.
DNAzyme amplifiers have been extensively explored as a useful sensing platform, but single DNAzyme amplifier is limited in biosensing applications by its low sensitivity. Herein, a cascade DNAzyme amplifier was designed by exploiting concurrent amplification cycle principles of toehold-mediated strand displacement reaction (TSDR) and Zn2+-assisted DNAzyme cycle with lower cost and simpler procedures. Compared with single DNAzyme amplifier, the proposed TSDR-propelled cascade DNAzyme amplifier exhibited higher sensitivity by releasing more DNAzyme through TSDR to cleave substrate strand during the DNAzyme cycle. Base on this, let-7a could be sensitively detected in the range of 5–50 nmol/L with a detection limit of 64 pmol/L. Furthermore, the dual signal amplification strategy of the cascade DNAzyme amplifier exhibited excellent selectivity to distinguish single-base mismatched DNA strands, which has been successfully applied to the determination of let-7a in blood serum, showing high promise in early cancer diagnosis.
2023, 34(6): 107907
doi: 10.1016/j.cclet.2022.107907
Abstract:
The application of metal-organic frameworks (MOFs) nanozymes in biosensing has been extensively investigated, however, till now there is still no report on photoelectrochemical (PEC) sensing based on enzyme memetic properties of MOFs. To further expand the utilization of MOFs nanozymes in biosensing, we developed a label-free homogenous PEC aptasensor for the detection of VEGF165, an important cancer biomarker, based on the DNA-regulated peroxidase-mimetic activity of Fe-MIL-88, a type of MOFs. In this strategy, the peroxidase-mimetic property of MOFs is integrated with the label-free homogeneous PEC sensing approach, and highly sensitive detection of VEGF165 is obtained with a detection limit down to 33 fg/mL, superior or comparable to the previously reported values. Moreover, this approach displays outstanding specificity, and has been successfully used to detect VEGF165 added in diluted serum samples. As far as we know, it is the first example to employ the peroxidase-like activity of MOFs in PEC biosensing, which may find potential application in bioanalysis and early disease diagnosis.
The application of metal-organic frameworks (MOFs) nanozymes in biosensing has been extensively investigated, however, till now there is still no report on photoelectrochemical (PEC) sensing based on enzyme memetic properties of MOFs. To further expand the utilization of MOFs nanozymes in biosensing, we developed a label-free homogenous PEC aptasensor for the detection of VEGF165, an important cancer biomarker, based on the DNA-regulated peroxidase-mimetic activity of Fe-MIL-88, a type of MOFs. In this strategy, the peroxidase-mimetic property of MOFs is integrated with the label-free homogeneous PEC sensing approach, and highly sensitive detection of VEGF165 is obtained with a detection limit down to 33 fg/mL, superior or comparable to the previously reported values. Moreover, this approach displays outstanding specificity, and has been successfully used to detect VEGF165 added in diluted serum samples. As far as we know, it is the first example to employ the peroxidase-like activity of MOFs in PEC biosensing, which may find potential application in bioanalysis and early disease diagnosis.
2023, 34(6): 107912
doi: 10.1016/j.cclet.2022.107912
Abstract:
Suzuki coupling reactions between symmetrical monomers were conducted in various mesoporous silica nanoreactors grafted with palladium catalysts, enabling the selective formation of [12]cycloparaphenylene precursor with separate yield up to 25% in one-pot reactions, much higher than that in homogeneous reaction. The spatial nanoconfinement of the nanoreactors promotes the macrocyclization while limits the concomitant linear oligomer formation, offering more possibilities for the synthesis of macrocycles from symmetrical monomers in one-pot reaction.
Suzuki coupling reactions between symmetrical monomers were conducted in various mesoporous silica nanoreactors grafted with palladium catalysts, enabling the selective formation of [12]cycloparaphenylene precursor with separate yield up to 25% in one-pot reactions, much higher than that in homogeneous reaction. The spatial nanoconfinement of the nanoreactors promotes the macrocyclization while limits the concomitant linear oligomer formation, offering more possibilities for the synthesis of macrocycles from symmetrical monomers in one-pot reaction.
2023, 34(6): 107914
doi: 10.1016/j.cclet.2022.107914
Abstract:
A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earth-abundant nickel catalyst. The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with (RO)2P(O)–Ni–H or R2P(O)O–Ni–H species, respectively. Under the Ni/Xantphos catalysis, 4,1-hydrophosphorylation is selectively obtained while the adding of acid can promote reactions towards 1,2-addition. By employing an additional Pd–H catalysis, 2,1-hydrophosphorylation is also an accessible task in one-pot reaction. Mechanistic studies and analysis have also been performed to interpret the origin of the regioselective regulation. This work highlights the arts in accessing different regioisomers by diverting common elementary reaction steps.
A regiodivergent hydrophosphorylation of enynes with phosphites has been developed using earth-abundant nickel catalyst. The manipulation of regioselectivity can be achieved by regulating the insertion order of alkyne bonds with (RO)2P(O)–Ni–H or R2P(O)O–Ni–H species, respectively. Under the Ni/Xantphos catalysis, 4,1-hydrophosphorylation is selectively obtained while the adding of acid can promote reactions towards 1,2-addition. By employing an additional Pd–H catalysis, 2,1-hydrophosphorylation is also an accessible task in one-pot reaction. Mechanistic studies and analysis have also been performed to interpret the origin of the regioselective regulation. This work highlights the arts in accessing different regioisomers by diverting common elementary reaction steps.
2023, 34(6): 107915
doi: 10.1016/j.cclet.2022.107915
Abstract:
The biocompatibility and biodegradability of peptide self-assembled materials makes them suitable for many biological applications, such as targeted drug delivery, bioimaging, and tracking of therapeutic agents. According to our previous research, self-assembled fluorescent peptide nanoparticles can overcome the intrinsic optical properties of peptides. However, monochromatic fluorescent nanomaterials have many limitations as luminescent agents in biomedical applications. Therefore, combining different fluorescent species into one nanostructure to prepare fluorescent nanoparticles with multiple emission wavelengths has become a very attractive research area in the bioimaging field. In this study, the tetrapeptide Trp-Trp-Trp-Trp (WWWW) was self-assembled into multicolor fluorescent nanoparticles (TPNPs). The results have demonstrated that TPNPs have the blue, green, red and near infrared (NIR) fluorescence emission wavelength. Moreover, TPNPs have shown excellent performance in multicolor bioimaging, biocompatibility, and photostability. The facile preparation and multicolor fluorescence features make TPNPs potentially useful in multiplex bioanalysis and diagnostics.
The biocompatibility and biodegradability of peptide self-assembled materials makes them suitable for many biological applications, such as targeted drug delivery, bioimaging, and tracking of therapeutic agents. According to our previous research, self-assembled fluorescent peptide nanoparticles can overcome the intrinsic optical properties of peptides. However, monochromatic fluorescent nanomaterials have many limitations as luminescent agents in biomedical applications. Therefore, combining different fluorescent species into one nanostructure to prepare fluorescent nanoparticles with multiple emission wavelengths has become a very attractive research area in the bioimaging field. In this study, the tetrapeptide Trp-Trp-Trp-Trp (WWWW) was self-assembled into multicolor fluorescent nanoparticles (TPNPs). The results have demonstrated that TPNPs have the blue, green, red and near infrared (NIR) fluorescence emission wavelength. Moreover, TPNPs have shown excellent performance in multicolor bioimaging, biocompatibility, and photostability. The facile preparation and multicolor fluorescence features make TPNPs potentially useful in multiplex bioanalysis and diagnostics.
2023, 34(6): 107921
doi: 10.1016/j.cclet.2022.107921
Abstract:
Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxene-pended base ligands. Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(p-phenylene-vinylene) (u-COPV) suspended by the truxene skeleton, the resulting supramolecular cages were confirmed to exhibit significant aggregation-induced emission (AIE) accompanied by an interesting solvatochromic fluorescent behavior as well as a porous honeycomb-like state during aggregation. In particular, the anti-counterfeiting performance and emission behaviors of the cages in the solid state under external hydrostatic pressure were investigated.
Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxene-pended base ligands. Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(p-phenylene-vinylene) (u-COPV) suspended by the truxene skeleton, the resulting supramolecular cages were confirmed to exhibit significant aggregation-induced emission (AIE) accompanied by an interesting solvatochromic fluorescent behavior as well as a porous honeycomb-like state during aggregation. In particular, the anti-counterfeiting performance and emission behaviors of the cages in the solid state under external hydrostatic pressure were investigated.
2023, 34(6): 107922
doi: 10.1016/j.cclet.2022.107922
Abstract:
As a strong oxidizer, hypochlorite (ClO–) are widely employed as bleaching agents and disinfectants. Determination of ClO– is required to ensure bactericidal effects and avoid hazards caused by excessive residual chlorine. Herein, the derivative bicyclic 2-pyridone, namely DHIP-Py, was prepared successfully to establish a new ClO–-quantitative method. The probe exhibits excellent ClO– selectivity over other ROS and anions/cations, high sensitivity (LOD = 1.32 µmol/L), fast response (<5 s), and wide-pH tolerance (pH 4~10). Benefit from its good water solubility, DHIP-Py is well suited for water sample analysis and has been successfully applied to detect ClO– in real-world food and environmental samples, including tap water, bottled water and river water. The detection results were essentially identical to that of obtained from traditional DPD method. Moreover, visual detection of ClO– via filter paper-based solid sensor and imaging of ClO– in Escherichia coli were also achieved by DHIP-Py. These satisfactory results demonstrate that this bicyclic 2-pyridone-based hypochlorite probe is a promising free chlorine chemosensor with great potential for analytical applications.
As a strong oxidizer, hypochlorite (ClO–) are widely employed as bleaching agents and disinfectants. Determination of ClO– is required to ensure bactericidal effects and avoid hazards caused by excessive residual chlorine. Herein, the derivative bicyclic 2-pyridone, namely DHIP-Py, was prepared successfully to establish a new ClO–-quantitative method. The probe exhibits excellent ClO– selectivity over other ROS and anions/cations, high sensitivity (LOD = 1.32 µmol/L), fast response (<5 s), and wide-pH tolerance (pH 4~10). Benefit from its good water solubility, DHIP-Py is well suited for water sample analysis and has been successfully applied to detect ClO– in real-world food and environmental samples, including tap water, bottled water and river water. The detection results were essentially identical to that of obtained from traditional DPD method. Moreover, visual detection of ClO– via filter paper-based solid sensor and imaging of ClO– in Escherichia coli were also achieved by DHIP-Py. These satisfactory results demonstrate that this bicyclic 2-pyridone-based hypochlorite probe is a promising free chlorine chemosensor with great potential for analytical applications.
2023, 34(6): 107923
doi: 10.1016/j.cclet.2022.107923
Abstract:
The abnormal activation of BRD4 accelerates the progression of acute myeloid leukemia (AML), developing more precise therapeutics to intervene BRD4 promise to be an excellent opportunity to avoid current limitations of chemotherapy in clinic. Herein, a range of small-molecule PROTACs with the privileged 8-methyl-pyrrolo[1,2-a]pyrazin-1(2H)-one scaffold were rationally designed, which harbored different carbon or ethylenedioxy chains to degrade BRD4 mediated by the E3 ubiquitin ligase CRBN. Among them, the most potential B24 exhibited remarkable BRD4 degradation and excellent anti-proliferative activities in MV4-11 cells, with values of DC50 and IC50 for 0.75 nmol/L and 0.4 nmol/L, respectively, which were better than the BRD4 inhibitor (+)-JQ-1. Notably, this compound could time-dependently degrade the target protein in the BRD4-, CRBN-, and proteasome-dependent manner. Besides, B24 dramatically decreased the level of proto-oncogene c-Myc, and induced cell apoptosis by arresting the cell cycle in G0/G1 phase, down-regulating Bcl-2 and up-regulating Bax to amplify apoptotic effectors. This proof-of-concept study also highlighted the feasibility of BRD4-based PROTACs as a more powerful strategy against AML.
The abnormal activation of BRD4 accelerates the progression of acute myeloid leukemia (AML), developing more precise therapeutics to intervene BRD4 promise to be an excellent opportunity to avoid current limitations of chemotherapy in clinic. Herein, a range of small-molecule PROTACs with the privileged 8-methyl-pyrrolo[1,2-a]pyrazin-1(2H)-one scaffold were rationally designed, which harbored different carbon or ethylenedioxy chains to degrade BRD4 mediated by the E3 ubiquitin ligase CRBN. Among them, the most potential B24 exhibited remarkable BRD4 degradation and excellent anti-proliferative activities in MV4-11 cells, with values of DC50 and IC50 for 0.75 nmol/L and 0.4 nmol/L, respectively, which were better than the BRD4 inhibitor (+)-JQ-1. Notably, this compound could time-dependently degrade the target protein in the BRD4-, CRBN-, and proteasome-dependent manner. Besides, B24 dramatically decreased the level of proto-oncogene c-Myc, and induced cell apoptosis by arresting the cell cycle in G0/G1 phase, down-regulating Bcl-2 and up-regulating Bax to amplify apoptotic effectors. This proof-of-concept study also highlighted the feasibility of BRD4-based PROTACs as a more powerful strategy against AML.
2023, 34(6): 107924
doi: 10.1016/j.cclet.2022.107924
Abstract:
Ibrutinib is a first-line treatment drug for B-cell malignancies. However, resistance to ibrutinib has been reported due to BTKC481S mutation. Although PROTAC strategy is expected to overcome this clinical resistance, it has limitations such as large molecular weight and moderate bioactivity, which restrict its potential clinical application. Herein, we report a new type of potent BTKC481S-targeting PROTAC degrader. Through design, computer-assisted optimization and SAR studies, we have developed a representative BTKC481S degrader L6 with a much smaller molecular weight and improved solubility. Notably, L6 demonstrates better BTK degrading activity and lower IC50 value in ibrutinib-resistant cell line than the first-generation BTK degrader P13I. Optimization strategy of L6 provides a general approach in the development of PROTACs targeting BTK and other proteins for future study.
Ibrutinib is a first-line treatment drug for B-cell malignancies. However, resistance to ibrutinib has been reported due to BTKC481S mutation. Although PROTAC strategy is expected to overcome this clinical resistance, it has limitations such as large molecular weight and moderate bioactivity, which restrict its potential clinical application. Herein, we report a new type of potent BTKC481S-targeting PROTAC degrader. Through design, computer-assisted optimization and SAR studies, we have developed a representative BTKC481S degrader L6 with a much smaller molecular weight and improved solubility. Notably, L6 demonstrates better BTK degrading activity and lower IC50 value in ibrutinib-resistant cell line than the first-generation BTK degrader P13I. Optimization strategy of L6 provides a general approach in the development of PROTACs targeting BTK and other proteins for future study.
2023, 34(6): 107931
doi: 10.1016/j.cclet.2022.107931
Abstract:
As a high-flux operation mode of thin film composite-forward osmosis (TFC-FO) membrane, active layer facing draw solution (AL-DS) mode suffers from the severe membrane fouling tendency, which is not addressed well. Here, we introduced a photocatalyst (Anatase titanium dioxide, A-TiO2) onto the support layer of TFC-FO membrane via the bonding of polydopamine (PDA) and polytetrafluoroethylene (PTFE), and prepared two photocatalytic membranes, A-TiO2/PDA@TFC and A-TiO2/PTFE@TFC. Compared with the pristine TFC-FO membrane, both A-TiO2/PDA @TFC and A-TiO2/PTFE@TFC had an improved water permeability (10.5 L m−2h−1 and 9.5 L m−2 h−1, respectively) and reduced reverse NaCl flux salt (0.8 g m−2 h−1 and 0.7 g m−2 h−1, respectively) in the AL-DS mode using 1 mol/L NaCl as draw solution and pure water as feed solution. Moreover, in the 16 h fouling experiment using 200 ppm bovine serum albumin (BSA) solution as a representative pollutant, the flux decline rate of both photocatalytic membranes was dramatically alleviated from 39.7% and 21.7% in the darkness to 8.5% and 9.7% under UV irradiation, respectively, indicating a significant anti-fouling capacity of photocatalytic effect. In all, the presence of A-TiO2 endowed membrane with high permeability, high rejection efficiency and excellent anti-fouling capacity under UV spotlight. As bonding agent, PTFE provided the modified membrane with a high photocatalytic effect and high self-cleaning capacity, while PDA increased the membrane permeability and protected membrane against photocatalytic damage. This work provides a simple and feasible method to improve the anti-fouling capacity of TFC-FO membrane in AL-DS mode.
As a high-flux operation mode of thin film composite-forward osmosis (TFC-FO) membrane, active layer facing draw solution (AL-DS) mode suffers from the severe membrane fouling tendency, which is not addressed well. Here, we introduced a photocatalyst (Anatase titanium dioxide, A-TiO2) onto the support layer of TFC-FO membrane via the bonding of polydopamine (PDA) and polytetrafluoroethylene (PTFE), and prepared two photocatalytic membranes, A-TiO2/PDA@TFC and A-TiO2/PTFE@TFC. Compared with the pristine TFC-FO membrane, both A-TiO2/PDA @TFC and A-TiO2/PTFE@TFC had an improved water permeability (10.5 L m−2h−1 and 9.5 L m−2 h−1, respectively) and reduced reverse NaCl flux salt (0.8 g m−2 h−1 and 0.7 g m−2 h−1, respectively) in the AL-DS mode using 1 mol/L NaCl as draw solution and pure water as feed solution. Moreover, in the 16 h fouling experiment using 200 ppm bovine serum albumin (BSA) solution as a representative pollutant, the flux decline rate of both photocatalytic membranes was dramatically alleviated from 39.7% and 21.7% in the darkness to 8.5% and 9.7% under UV irradiation, respectively, indicating a significant anti-fouling capacity of photocatalytic effect. In all, the presence of A-TiO2 endowed membrane with high permeability, high rejection efficiency and excellent anti-fouling capacity under UV spotlight. As bonding agent, PTFE provided the modified membrane with a high photocatalytic effect and high self-cleaning capacity, while PDA increased the membrane permeability and protected membrane against photocatalytic damage. This work provides a simple and feasible method to improve the anti-fouling capacity of TFC-FO membrane in AL-DS mode.
2023, 34(6): 107932
doi: 10.1016/j.cclet.2022.107932
Abstract:
Microscale zero valent iron (mFe0) is one of the most potential water pollution remediation materials, but the effective utilization ability of electrons released by mFe0 in the reduction of hexavalent chromium (Cr(Ⅵ)) is not satisfactory. Here, we find the microscale iron-copper (mFe/Cu) bimetals coated with copper on the surface of mFe0 can significantly improve the effective utilization of electrons released by mFe0. Electrochemical analysis displays that copper plating on the surface of mFe/Cu can promote the release the electrons from mFe0 and reduce the impedance of mFe0. Spin-polarized density functional theory (DFT) calculation reveals that Cu on the surface of mFe/Cu bimetals promotes the release of electrons from mFe0 and reduces the adsorption energy of Fe to Cr. As the electron transporter, moreover, Cu can always attract Cr to the hollow position near itself of the Fe surface, which could promote the effective utilization of electrons released by Fe. Effective utilization ability of electrons in mFe/Cu system is 12.5 times higher than that in mFe0 system. Our findings provide another basis for the efficient reduction of Cr(Ⅵ) by mFe/Cu bimetals, which could promote the application and popularization of mFe/Cu bimetals.
Microscale zero valent iron (mFe0) is one of the most potential water pollution remediation materials, but the effective utilization ability of electrons released by mFe0 in the reduction of hexavalent chromium (Cr(Ⅵ)) is not satisfactory. Here, we find the microscale iron-copper (mFe/Cu) bimetals coated with copper on the surface of mFe0 can significantly improve the effective utilization of electrons released by mFe0. Electrochemical analysis displays that copper plating on the surface of mFe/Cu can promote the release the electrons from mFe0 and reduce the impedance of mFe0. Spin-polarized density functional theory (DFT) calculation reveals that Cu on the surface of mFe/Cu bimetals promotes the release of electrons from mFe0 and reduces the adsorption energy of Fe to Cr. As the electron transporter, moreover, Cu can always attract Cr to the hollow position near itself of the Fe surface, which could promote the effective utilization of electrons released by Fe. Effective utilization ability of electrons in mFe/Cu system is 12.5 times higher than that in mFe0 system. Our findings provide another basis for the efficient reduction of Cr(Ⅵ) by mFe/Cu bimetals, which could promote the application and popularization of mFe/Cu bimetals.
2023, 34(6): 107933
doi: 10.1016/j.cclet.2022.107933
Abstract:
Defect passivation is one of the important strategies to improve the efficiency and stability of perovskite solar cells. In this work, 2,6-di–tert–butyl–4-methylphenol (BHT) as antioxidant was introduced into the perovskite precursor solution to improve the quality of the prepared perovskite films, so that these films performed a larger and uniform grain size. Moreover, the −OH functional group in BHT interacts with I−, thus reducing the density of defect states and inhibiting the non-radiative recombination. The presence of hydrophobic groups in BHT protects the film from moisture erosion and improves the long-term stability of PSCs devices. The maximum photoelectric conversion efficiency of the constructed ITO/SnO2/BHT-MAPbI3/Carbon device is 16.88%, and the unpackaged cell maintains the initial efficiency of 99.3% after 698 h of storage under the environmental condition of 30% humidity. This work provides an efficient approach to improve the performance of printable hole transport layer-free carbon electrode perovskite solar cells.
Defect passivation is one of the important strategies to improve the efficiency and stability of perovskite solar cells. In this work, 2,6-di–tert–butyl–4-methylphenol (BHT) as antioxidant was introduced into the perovskite precursor solution to improve the quality of the prepared perovskite films, so that these films performed a larger and uniform grain size. Moreover, the −OH functional group in BHT interacts with I−, thus reducing the density of defect states and inhibiting the non-radiative recombination. The presence of hydrophobic groups in BHT protects the film from moisture erosion and improves the long-term stability of PSCs devices. The maximum photoelectric conversion efficiency of the constructed ITO/SnO2/BHT-MAPbI3/Carbon device is 16.88%, and the unpackaged cell maintains the initial efficiency of 99.3% after 698 h of storage under the environmental condition of 30% humidity. This work provides an efficient approach to improve the performance of printable hole transport layer-free carbon electrode perovskite solar cells.
2023, 34(6): 107934
doi: 10.1016/j.cclet.2022.107934
Abstract:
Realizing both a high emission efficiency and luminescence dissymmetry factor (glum) in circularly polarized solution processable organic light-emitting diodes (CP-OLEDs) remains a significant challenge. In this contribution, two chiral phosphorescent liquid crystals based on cyclometalated platinum complexes are prepared, in which the chiral s-2-methyl-1-butyl group is introduced into the cyclometalating ligand and the mesogenic fragment is attached to the periphery of the ancillary ligand. The platinum complexes exhibit both smectic and chiral nematic phases as evidenced by polarized optical microscopy, differential scanning calorimetry and small-angle X-ray diffraction. Remarkably, a high photoluminescent quantum efficiency of over 78% and clear circularly polarized luminescent signal with gPL of about 10–2 are observed for the complexes. Further, solution-processed CP-OLEDs show maximum external quantum efficiencies (EQE) of over 15% and strong circularly polarized electroluminescent signals with a gEL ≈ 10–2. This research demonstrates that both liquid crystallinity and the number of chiral centers play key roles in improving the chiroptical property, paving the way for a new approach for the design of high-efficiency CPL emitters.
Realizing both a high emission efficiency and luminescence dissymmetry factor (glum) in circularly polarized solution processable organic light-emitting diodes (CP-OLEDs) remains a significant challenge. In this contribution, two chiral phosphorescent liquid crystals based on cyclometalated platinum complexes are prepared, in which the chiral s-2-methyl-1-butyl group is introduced into the cyclometalating ligand and the mesogenic fragment is attached to the periphery of the ancillary ligand. The platinum complexes exhibit both smectic and chiral nematic phases as evidenced by polarized optical microscopy, differential scanning calorimetry and small-angle X-ray diffraction. Remarkably, a high photoluminescent quantum efficiency of over 78% and clear circularly polarized luminescent signal with gPL of about 10–2 are observed for the complexes. Further, solution-processed CP-OLEDs show maximum external quantum efficiencies (EQE) of over 15% and strong circularly polarized electroluminescent signals with a gEL ≈ 10–2. This research demonstrates that both liquid crystallinity and the number of chiral centers play key roles in improving the chiroptical property, paving the way for a new approach for the design of high-efficiency CPL emitters.
2023, 34(6): 107935
doi: 10.1016/j.cclet.2022.107935
Abstract:
A facile and elegant method for synthesis of novel N–aryl phenothiazine derivatives from 2-phenylindolizines and phenothiazines through direct electrochemical oxidation has been developed. This approach was performed smoothly at room temperature without external oxidant and catalyst. Cyclic voltammetry and in situ FTIR techniques were applied to analyze the cross-coupling process of phenothiazines and 2-phenylindolizines, which helped to select the appropriate reaction potential. Under the optimized conditions, a broad range of substrates were well tolerated, affording the desired products in moderate to excellent isolated yields (up to 91%) with high regioselectivity. Meanwhile, a plausible mechanism involving a radical pathway has been proposed.
A facile and elegant method for synthesis of novel N–aryl phenothiazine derivatives from 2-phenylindolizines and phenothiazines through direct electrochemical oxidation has been developed. This approach was performed smoothly at room temperature without external oxidant and catalyst. Cyclic voltammetry and in situ FTIR techniques were applied to analyze the cross-coupling process of phenothiazines and 2-phenylindolizines, which helped to select the appropriate reaction potential. Under the optimized conditions, a broad range of substrates were well tolerated, affording the desired products in moderate to excellent isolated yields (up to 91%) with high regioselectivity. Meanwhile, a plausible mechanism involving a radical pathway has been proposed.
2023, 34(6): 107938
doi: 10.1016/j.cclet.2022.107938
Abstract:
Bacterial antimicrobial resistance (AMR) is a severe threat to global health and development. Under the stimulation of antibiotics, bacterial cells can undergo filamentation and generate daughter cells with stronger AMR. The current research on bacterial AMR mechanism is mainly conducted with a population of cells. However, bacterial cells exhibit heteroresistance, making the study at population level not reliable. Herein, we developed single bacterial cell metabolic profiling by mass spectrometry (MS) to study bacterial AMR at single-cell level. By utilizing a microprobe controlled by a microoperation platform, single filamentous extended spectrum beta-lactamase (ESBL) producing Escherichia coli (ESBL-E. coli) cells generated by ceftriaxone sodium stimulation can be extracted and spray-ionized for MS analysis. Heterogeneous among ESBL-E. coli cells under the same antibiotic stimulus condition was observed from mass spectra as well as cell morphology. The metabolic profiles by MS of different individual cells can be clustered into subgroups well in accordance with bacterial cell length. Metabolic pathways including arginine and proline metabolism, as well as cysteine and methionine metabolism were disclosed to play an important role in the bacterial SOS-associated filamentation against antibiotics. The microprobe electrospray ionization-MS-based single bacterial cell analysis method is promising in the study of various bacterial AMR mechanism and can reveal the heterogeneity of bacterial AMR from-cell-to-cell.
Bacterial antimicrobial resistance (AMR) is a severe threat to global health and development. Under the stimulation of antibiotics, bacterial cells can undergo filamentation and generate daughter cells with stronger AMR. The current research on bacterial AMR mechanism is mainly conducted with a population of cells. However, bacterial cells exhibit heteroresistance, making the study at population level not reliable. Herein, we developed single bacterial cell metabolic profiling by mass spectrometry (MS) to study bacterial AMR at single-cell level. By utilizing a microprobe controlled by a microoperation platform, single filamentous extended spectrum beta-lactamase (ESBL) producing Escherichia coli (ESBL-E. coli) cells generated by ceftriaxone sodium stimulation can be extracted and spray-ionized for MS analysis. Heterogeneous among ESBL-E. coli cells under the same antibiotic stimulus condition was observed from mass spectra as well as cell morphology. The metabolic profiles by MS of different individual cells can be clustered into subgroups well in accordance with bacterial cell length. Metabolic pathways including arginine and proline metabolism, as well as cysteine and methionine metabolism were disclosed to play an important role in the bacterial SOS-associated filamentation against antibiotics. The microprobe electrospray ionization-MS-based single bacterial cell analysis method is promising in the study of various bacterial AMR mechanism and can reveal the heterogeneity of bacterial AMR from-cell-to-cell.
2023, 34(6): 107939
doi: 10.1016/j.cclet.2022.107939
Abstract:
The water promotion effects, where water can provide a solution-mediated reaction pathway in various heterogeneous chemical catalysis, have been presented and attracted wide attention recently, yet, the rational design of catalysts with a certain ability of enhancing water-induced reaction process is full of challenges and difficulties. Here, we show that by incorporating alkali (Na, K) cations as an electronic and/or structural promoter into Pd/rGO-ZnCr2O4 (rGO, reduced graphene oxide), the obtained Pd(Na)/rGO-ZnCr2O4 as a representative example demonstrates an outstanding benzyl alcohol oxidation activity in the Pickering emulsion system in comparison to the alkali-free counterpart. The response experiments of water injection confirm the enhanced activity, and the Na-modified catalyst can further enhance the promotion effects of water on the reaction. The effects of alkali cations for Pd nanoparticles are identified and deciphered by a series of experimental characterizations (XPS, in situ CO-DRIFTS, and CO-TPR coupled with MS), showing that there is abundant −OH on the surface of the catalyst, which is stabilized by the formation of Pd−OHx. The alkali-stabilized Pd−OHx is helpful to enhance the water-induced reaction process. According to the results of in situ Raman as well as UV-vis absorption spectra, the Na-modulated Pd(Na)/rGO-ZnCr2O4 enables the beneficial characteristics for distorting the benzyl alcohol structure and enhancing the adsorption of benzyl alcohol. Further, the mechanism for enhanced water promotion effects is rationally proposed. The strategy of alkali cations-modified catalysts can provide a new direction to effectively enhance the chemical reaction involving small molecule water.
The water promotion effects, where water can provide a solution-mediated reaction pathway in various heterogeneous chemical catalysis, have been presented and attracted wide attention recently, yet, the rational design of catalysts with a certain ability of enhancing water-induced reaction process is full of challenges and difficulties. Here, we show that by incorporating alkali (Na, K) cations as an electronic and/or structural promoter into Pd/rGO-ZnCr2O4 (rGO, reduced graphene oxide), the obtained Pd(Na)/rGO-ZnCr2O4 as a representative example demonstrates an outstanding benzyl alcohol oxidation activity in the Pickering emulsion system in comparison to the alkali-free counterpart. The response experiments of water injection confirm the enhanced activity, and the Na-modified catalyst can further enhance the promotion effects of water on the reaction. The effects of alkali cations for Pd nanoparticles are identified and deciphered by a series of experimental characterizations (XPS, in situ CO-DRIFTS, and CO-TPR coupled with MS), showing that there is abundant −OH on the surface of the catalyst, which is stabilized by the formation of Pd−OHx. The alkali-stabilized Pd−OHx is helpful to enhance the water-induced reaction process. According to the results of in situ Raman as well as UV-vis absorption spectra, the Na-modulated Pd(Na)/rGO-ZnCr2O4 enables the beneficial characteristics for distorting the benzyl alcohol structure and enhancing the adsorption of benzyl alcohol. Further, the mechanism for enhanced water promotion effects is rationally proposed. The strategy of alkali cations-modified catalysts can provide a new direction to effectively enhance the chemical reaction involving small molecule water.
2023, 34(6): 107949
doi: 10.1016/j.cclet.2022.107949
Abstract:
The application of fluorescent probes for in vivo retinal imaging is of great importance, which could provide direct and crucial imaging evidence for a better understanding of common eye diseases. Herein, a group of bright organic luminogens with typical electron-donating (D) and electron-accepting (A) structures (abbreviated as LDs-BDM, LDs-BTM, and LDs-BHM) was synthesized through a simple single-step reaction. They were found to be efficient solid-state emitters with high fluorescence quantum yields of above 70% (e.g., 83.7% for LDs-BTM). Their light-emission properties could be tuned by the modulation of π-conjugation effect with methoxy groups at different substituent positions. Their resulting fluorescent nanoparticles (NPs) were demonstrated as specific lipid droplets (LDs) targeting probes with high brightness, good biocompatibility, and satisfactory photostability. LDs-BTM NPs with a large two-photon absorption cross section (σ2 = 249 GM) were further utilized as ultrabright two-photon fluorescence (2PF) nanoprobes for in vivo retina imaging of live zebrafish by NIR excitation at an ultralow concentration (0.5 µmol/L). Integrated histological structures at the tissue level and corresponding fine details at the cellular level of the embryonic retina of live zebrafish were clearly demonstrated. This is the first report of using ultrabright LDs-targeting nanoprobes to accurately measure fine details in the retina with 2PF microscopic technique. These good results are anticipated to open up a new avenue in the development of efficient 2PF emitters for non-invasive bioimaging of living animals.
The application of fluorescent probes for in vivo retinal imaging is of great importance, which could provide direct and crucial imaging evidence for a better understanding of common eye diseases. Herein, a group of bright organic luminogens with typical electron-donating (D) and electron-accepting (A) structures (abbreviated as LDs-BDM, LDs-BTM, and LDs-BHM) was synthesized through a simple single-step reaction. They were found to be efficient solid-state emitters with high fluorescence quantum yields of above 70% (e.g., 83.7% for LDs-BTM). Their light-emission properties could be tuned by the modulation of π-conjugation effect with methoxy groups at different substituent positions. Their resulting fluorescent nanoparticles (NPs) were demonstrated as specific lipid droplets (LDs) targeting probes with high brightness, good biocompatibility, and satisfactory photostability. LDs-BTM NPs with a large two-photon absorption cross section (σ2 = 249 GM) were further utilized as ultrabright two-photon fluorescence (2PF) nanoprobes for in vivo retina imaging of live zebrafish by NIR excitation at an ultralow concentration (0.5 µmol/L). Integrated histological structures at the tissue level and corresponding fine details at the cellular level of the embryonic retina of live zebrafish were clearly demonstrated. This is the first report of using ultrabright LDs-targeting nanoprobes to accurately measure fine details in the retina with 2PF microscopic technique. These good results are anticipated to open up a new avenue in the development of efficient 2PF emitters for non-invasive bioimaging of living animals.
2023, 34(6): 107954
doi: 10.1016/j.cclet.2022.107954
Abstract:
Inhibiting the side reactions while promoting hydrogenation are the main target for the production of functional anilines from nitroarenes; consequently, the preparation of an ideal catalyst to improve chemical selectivity is one of the hot issues. In this work, we provided an easy-to-prepare catalyst with N-doped carbon layers, where the FexOy nanoparticles were encapsulated and distributed uniformly. The structural features of catalyst were characterized by several techniques, and the selected catalyst was next applied to the hydrogenation of nitrobenzene under varied conditions, involving temperature, holding period and H2 pressure. Subsequently, we conducted the synthesis of more than 16 substrates for the corresponding anilines with varied functional groups. The hydrogenation protocol to gram-scale synthesis as well as lifecycle performance were also demonstrated in the batch reactor, together with the explanation of its catalytic mechanisms. Overall, the present work provides an available preparation of simple but highly efficient catalysts for the production or aromatic amines, which will be benefit for the sustainable development of this field in near future.
Inhibiting the side reactions while promoting hydrogenation are the main target for the production of functional anilines from nitroarenes; consequently, the preparation of an ideal catalyst to improve chemical selectivity is one of the hot issues. In this work, we provided an easy-to-prepare catalyst with N-doped carbon layers, where the FexOy nanoparticles were encapsulated and distributed uniformly. The structural features of catalyst were characterized by several techniques, and the selected catalyst was next applied to the hydrogenation of nitrobenzene under varied conditions, involving temperature, holding period and H2 pressure. Subsequently, we conducted the synthesis of more than 16 substrates for the corresponding anilines with varied functional groups. The hydrogenation protocol to gram-scale synthesis as well as lifecycle performance were also demonstrated in the batch reactor, together with the explanation of its catalytic mechanisms. Overall, the present work provides an available preparation of simple but highly efficient catalysts for the production or aromatic amines, which will be benefit for the sustainable development of this field in near future.
2023, 34(6): 107955
doi: 10.1016/j.cclet.2022.107955
Abstract:
Benzimidazole amino acid derivatives behave as supramolecular hosts to include organic acids via complementary hydrogen bonding whereby supramolecular chirality and chiroptical properties could be manipulated. Organic acids enhanced the chiral assembly that showed tunable circularly polarized luminescence with high dissymmetry g-factors at 10-2 grade.
Benzimidazole amino acid derivatives behave as supramolecular hosts to include organic acids via complementary hydrogen bonding whereby supramolecular chirality and chiroptical properties could be manipulated. Organic acids enhanced the chiral assembly that showed tunable circularly polarized luminescence with high dissymmetry g-factors at 10-2 grade.
2023, 34(6): 107956
doi: 10.1016/j.cclet.2022.107956
Abstract:
As an attractive C1 synthon, carbon dioxide (CO2) has been extensively used in organic synthesis to produce carboxylic acids. In this research, stereoselective electrochemical carboxylation of α,β-unsaturated sulfones has been developed under transition-metal-free conditions. All the cinnamic acids and the derivatives are obtained selectively in the E-configuration. Besides, arylpropiolates also can be produced from alkynyl sulfones.
As an attractive C1 synthon, carbon dioxide (CO2) has been extensively used in organic synthesis to produce carboxylic acids. In this research, stereoselective electrochemical carboxylation of α,β-unsaturated sulfones has been developed under transition-metal-free conditions. All the cinnamic acids and the derivatives are obtained selectively in the E-configuration. Besides, arylpropiolates also can be produced from alkynyl sulfones.
2023, 34(6): 107957
doi: 10.1016/j.cclet.2022.107957
Abstract:
Herein, an intense electrochemiluminescence (ECL) was achieved based on Pt hollow nanospheres/rubrene nanoleaves (Pt HNSs/Rub NLs) without the addition of any coreactant, which was employed for ultrasensitive detection of carcinoembryonic antigen (CEA) coupled with an M-shaped DNA walker (M-DNA walker) as signal switch. Specifically, in comparison with platinum nanoparticles (Pt NPs), Pt HNSs revealed excellent catalytic performance and pore confinement-enhanced ECL, which could significantly amplify ECL intensity of Rub NLs/dissolved O2 (DO) binary system. Then, the tracks and M-DNA walker were confined on the Pt HNSs simultaneously to promote the reaction efficiency, whose M-structure boosted the interaction sites between walking strands and tracks and reduced the rigidity of their recognition. Once the CEA approached the sensing interface, the M-DNA walker was activated based on highly specific aptamer recognition to recover ECL intensity with the assistance of exonuclease Ⅲ (Exo Ⅲ). As proof of concept, the "on-off-on" switch aptasensor was constructed for CEA detection with a low detection limit of 0.20 fg/mL. The principle of the constructed ECL aptasensor also enables a universal platform for sensitive detection of other tumor markers.
Herein, an intense electrochemiluminescence (ECL) was achieved based on Pt hollow nanospheres/rubrene nanoleaves (Pt HNSs/Rub NLs) without the addition of any coreactant, which was employed for ultrasensitive detection of carcinoembryonic antigen (CEA) coupled with an M-shaped DNA walker (M-DNA walker) as signal switch. Specifically, in comparison with platinum nanoparticles (Pt NPs), Pt HNSs revealed excellent catalytic performance and pore confinement-enhanced ECL, which could significantly amplify ECL intensity of Rub NLs/dissolved O2 (DO) binary system. Then, the tracks and M-DNA walker were confined on the Pt HNSs simultaneously to promote the reaction efficiency, whose M-structure boosted the interaction sites between walking strands and tracks and reduced the rigidity of their recognition. Once the CEA approached the sensing interface, the M-DNA walker was activated based on highly specific aptamer recognition to recover ECL intensity with the assistance of exonuclease Ⅲ (Exo Ⅲ). As proof of concept, the "on-off-on" switch aptasensor was constructed for CEA detection with a low detection limit of 0.20 fg/mL. The principle of the constructed ECL aptasensor also enables a universal platform for sensitive detection of other tumor markers.
2023, 34(6): 107958
doi: 10.1016/j.cclet.2022.107958
Abstract:
Developing efficient photosensitizers for C–P bond construction is highly important and remains a challenge due to the urgently needed for the synthesis of modified nucleosides, nucleotides, and other phosphine-containing ligands. Herein, two pyrene-tethered bismoviologen derivatives (Py-BiV2+) were designed and synthesized for visible-light-induced C–P bonds formation. The photochemical and electrochemical properties of Py-BiV2+ were studied systemically, certifying fine-tunable opto-electronic properties through the number of pyrene groups (4, n = 1; 6, n = 2). The prepared Py-BiV2+ showed strong light absorption, while retaining good redox features and chromic response features that were inherent to viologens. 4 exhibited accelerated photoinduced electron transfer in the presence of the electron donor (pyrene) and the generated 4' (radical cation) showed higher stability. Accordingly, Py-BiV2+ directly served as photosensitizers for the first time in the visible-light-induced C(sp3)–P and C(sp2)–P bonds formation. As expected, these novel viologen derivatives exhibited good catalytic performance and good substrate expansibility under ambient conditions.
Developing efficient photosensitizers for C–P bond construction is highly important and remains a challenge due to the urgently needed for the synthesis of modified nucleosides, nucleotides, and other phosphine-containing ligands. Herein, two pyrene-tethered bismoviologen derivatives (Py-BiV2+) were designed and synthesized for visible-light-induced C–P bonds formation. The photochemical and electrochemical properties of Py-BiV2+ were studied systemically, certifying fine-tunable opto-electronic properties through the number of pyrene groups (4, n = 1; 6, n = 2). The prepared Py-BiV2+ showed strong light absorption, while retaining good redox features and chromic response features that were inherent to viologens. 4 exhibited accelerated photoinduced electron transfer in the presence of the electron donor (pyrene) and the generated 4' (radical cation) showed higher stability. Accordingly, Py-BiV2+ directly served as photosensitizers for the first time in the visible-light-induced C(sp3)–P and C(sp2)–P bonds formation. As expected, these novel viologen derivatives exhibited good catalytic performance and good substrate expansibility under ambient conditions.
2023, 34(6): 107960
doi: 10.1016/j.cclet.2022.107960
Abstract:
Difluorocarbene has emerged as a valuable intermediate to synthesize fluorides. However, difluorocarbene-derived synthesis of 19F/18F-trifluoromethyl triazoles has not been explored. Herein, we reported the Cu(I)-promoted difluorocarbene-derived 19F/18F-trifluoromethylation of iodotriazoles using KF/K18F as the fluorine source. This approach rapidly generated a wide range of 5-trifluoromethyl-1, 2, 3-triazoles in good yields showing high functional group compatibility. The reaction was effective for late-stage functionalization of bioactive molecules and 18F-trifluoromethylation of iodotriazoles. This work provides a practical synthetic methodology for the development of triazole drugs and 18F-radiotracers for positron emission tomography.
Difluorocarbene has emerged as a valuable intermediate to synthesize fluorides. However, difluorocarbene-derived synthesis of 19F/18F-trifluoromethyl triazoles has not been explored. Herein, we reported the Cu(I)-promoted difluorocarbene-derived 19F/18F-trifluoromethylation of iodotriazoles using KF/K18F as the fluorine source. This approach rapidly generated a wide range of 5-trifluoromethyl-1, 2, 3-triazoles in good yields showing high functional group compatibility. The reaction was effective for late-stage functionalization of bioactive molecules and 18F-trifluoromethylation of iodotriazoles. This work provides a practical synthetic methodology for the development of triazole drugs and 18F-radiotracers for positron emission tomography.
2023, 34(6): 107962
doi: 10.1016/j.cclet.2022.107962
Abstract:
Artificial photosynthesis of valuable chemicals from CO2 is a potential way to achieve sustainable carbon cycle. The CO2 conversion activity is still inhibited by the sluggish charge kinetics and poor CO2 activation. Herein, Ag nanoparticles coupled BiOBr have been constructed by in-situ photoreduction strategy. The crafting of interface between Ag nanoparticles and BiOBr nanosheets, achieving an ultra-fast charge transfer. The BiOBr semiconductor excited electrons and plasmonic Ag nanoparticles generated high-energy hot electrons synchronous accelerates the C=O double bond activation. Thus, the optimized Ag/BiOBr-2 heterostructure shows excellent CO2 photoreduction activity with CO production of 133.75 and 6.83 µmol/g under 5 h of 300 W Xe lamp and visible light (λ > 400 nm) irradiation, which is 1.51 and 2.81 folds versus the pristine BiOBr, respectively. The mechanism of CO2 photoreduction was in-depth understood through in-situ FT-IR spectrum and density functional theory calculations. This study provides some new perspectives into efficient photocatalytic CO2 reduction.
Artificial photosynthesis of valuable chemicals from CO2 is a potential way to achieve sustainable carbon cycle. The CO2 conversion activity is still inhibited by the sluggish charge kinetics and poor CO2 activation. Herein, Ag nanoparticles coupled BiOBr have been constructed by in-situ photoreduction strategy. The crafting of interface between Ag nanoparticles and BiOBr nanosheets, achieving an ultra-fast charge transfer. The BiOBr semiconductor excited electrons and plasmonic Ag nanoparticles generated high-energy hot electrons synchronous accelerates the C=O double bond activation. Thus, the optimized Ag/BiOBr-2 heterostructure shows excellent CO2 photoreduction activity with CO production of 133.75 and 6.83 µmol/g under 5 h of 300 W Xe lamp and visible light (λ > 400 nm) irradiation, which is 1.51 and 2.81 folds versus the pristine BiOBr, respectively. The mechanism of CO2 photoreduction was in-depth understood through in-situ FT-IR spectrum and density functional theory calculations. This study provides some new perspectives into efficient photocatalytic CO2 reduction.
2023, 34(6): 107963
doi: 10.1016/j.cclet.2022.107963
Abstract:
Developing an efficient Zn-based catalyst modified with Trifluoromethanesulfonic acid (TfOH) ligand is extremely desirable for the acetylene hydration reaction. In this paper, with the use of a simple impregnation method, a series of Zn-TfOH/AC catalysts were synthesized, and the Zn-1.5TfOH/AC catalyst demonstrated the optimal catalytic performance with 96% acetylene conversion in the hydration of acetylene. The X-ray absorption fine structure (XAFS) spectra of the fresh Zn-1.5TfOH/AC catalysts demonstrated the establishment of the Zn-O4 coordination structure. According to the characterization results, TfOH ligands effectively inhibited carbon accumulation and Zinc loss, improved acidic sites and the dispersion of active metal, and produced more catalytic active site. Furthermore, the hydration reaction mechanism of Zn-TfOH/AC catalyst with Zn(OTf)2, TfO-ZnCl, and TfO-ZnOH complex configurations was explored by the Density Functional Theory (DFT) method, which showed that the activation barrier increased sequentially TfO-ZnOH < Zn(OTf)2 < TfO-ZnCl. Importantly, the OH− in TfO-ZnOH is involved in the reaction and regenerated by the dissociation of H2O, which lowers the energy barrier. This will provide a reference to design more efficient nonmercury catalysts for acetylene hydration.
Developing an efficient Zn-based catalyst modified with Trifluoromethanesulfonic acid (TfOH) ligand is extremely desirable for the acetylene hydration reaction. In this paper, with the use of a simple impregnation method, a series of Zn-TfOH/AC catalysts were synthesized, and the Zn-1.5TfOH/AC catalyst demonstrated the optimal catalytic performance with 96% acetylene conversion in the hydration of acetylene. The X-ray absorption fine structure (XAFS) spectra of the fresh Zn-1.5TfOH/AC catalysts demonstrated the establishment of the Zn-O4 coordination structure. According to the characterization results, TfOH ligands effectively inhibited carbon accumulation and Zinc loss, improved acidic sites and the dispersion of active metal, and produced more catalytic active site. Furthermore, the hydration reaction mechanism of Zn-TfOH/AC catalyst with Zn(OTf)2, TfO-ZnCl, and TfO-ZnOH complex configurations was explored by the Density Functional Theory (DFT) method, which showed that the activation barrier increased sequentially TfO-ZnOH < Zn(OTf)2 < TfO-ZnCl. Importantly, the OH− in TfO-ZnOH is involved in the reaction and regenerated by the dissociation of H2O, which lowers the energy barrier. This will provide a reference to design more efficient nonmercury catalysts for acetylene hydration.
2023, 34(6): 107967
doi: 10.1016/j.cclet.2022.107967
Abstract:
The NO gas is easily oxidized to form toxic by-products (NO2) during the oxidation process, which are adsorbed on the catalyst surface and inhibit the subsequent reaction. For photocatalytic NO removal, a significant challenge is to achieve catalytic stability while maintaining high conversion efficiency. Here, we fabricated a (BiO)2CO3/β-Bi2O3 heterostructure that enables efficient charge transfer and promotes the NO removal. We propose that the catalytic stability depends on the heterojunction structure, which is able to generate interfacial charge transfer channels. In addition, we further introduce graphene quantum dots on the heterojunction structure, which further strengthens the interfacial charge transfer dynamics and finally realizes that the NO2 byproduct could gain electrons and convert to the final product (nitrite or nitrate). This composite structure not only exhibits high activity for NO removal but also maintains long-term stability under visible light.
The NO gas is easily oxidized to form toxic by-products (NO2) during the oxidation process, which are adsorbed on the catalyst surface and inhibit the subsequent reaction. For photocatalytic NO removal, a significant challenge is to achieve catalytic stability while maintaining high conversion efficiency. Here, we fabricated a (BiO)2CO3/β-Bi2O3 heterostructure that enables efficient charge transfer and promotes the NO removal. We propose that the catalytic stability depends on the heterojunction structure, which is able to generate interfacial charge transfer channels. In addition, we further introduce graphene quantum dots on the heterojunction structure, which further strengthens the interfacial charge transfer dynamics and finally realizes that the NO2 byproduct could gain electrons and convert to the final product (nitrite or nitrate). This composite structure not only exhibits high activity for NO removal but also maintains long-term stability under visible light.
2023, 34(6): 107969
doi: 10.1016/j.cclet.2022.107969
Abstract:
Designing single-atom nanozymes with densely exposed metal atom active sites and enhancing catalytic activity to detect pollutants remain a serious challenge. Herein, we reported a single-atom nanozyme with layered stacked Fe/Cu dual active sites (Fe/Cu-NC SAzyme) synthesized via hydrothermal and high-temperature pyrolysis using folic acid as a template. Compared with Fe-NC and Cu-NC SAzyme, Fe/Cu-NC SAzyme has higher peroxidase-like activity, which indicates that the doping of synthesized Fe/Cu bimetals can improve the catalytic activity and that the atomic loading of Fe and Cu in Fe/Cu-NC is 5.5 wt% and 2.27 wt%, respectively. When S2− is added to the Fe/Cu-NC catalytic system, a high-sensitivity and high-selectivity S2− colorimetric sensing platform can be established, with a wide linear range (0.09–6 µmol/L) and a low detection limit (30 nmol/L), which can be used to detect S2− in environmental water samples. What's more, the Fe/Cu-NC SAzyme can activate peroxymonosulfate (PMS) to degrade 99.9% of rhodamine B (RhB) within 10 min with a degradation kinetics of 0.5943 min−1. This work details attractive applications in Fe/Cu-NC SAzyme colorimetric sensing and dye degradation.
Designing single-atom nanozymes with densely exposed metal atom active sites and enhancing catalytic activity to detect pollutants remain a serious challenge. Herein, we reported a single-atom nanozyme with layered stacked Fe/Cu dual active sites (Fe/Cu-NC SAzyme) synthesized via hydrothermal and high-temperature pyrolysis using folic acid as a template. Compared with Fe-NC and Cu-NC SAzyme, Fe/Cu-NC SAzyme has higher peroxidase-like activity, which indicates that the doping of synthesized Fe/Cu bimetals can improve the catalytic activity and that the atomic loading of Fe and Cu in Fe/Cu-NC is 5.5 wt% and 2.27 wt%, respectively. When S2− is added to the Fe/Cu-NC catalytic system, a high-sensitivity and high-selectivity S2− colorimetric sensing platform can be established, with a wide linear range (0.09–6 µmol/L) and a low detection limit (30 nmol/L), which can be used to detect S2− in environmental water samples. What's more, the Fe/Cu-NC SAzyme can activate peroxymonosulfate (PMS) to degrade 99.9% of rhodamine B (RhB) within 10 min with a degradation kinetics of 0.5943 min−1. This work details attractive applications in Fe/Cu-NC SAzyme colorimetric sensing and dye degradation.
2023, 34(6): 107982
doi: 10.1016/j.cclet.2022.107982
Abstract:
A family of the 3, 6-branched Fuzi α-glucans including the pentasaccharide repeating unit as well as its di- and trimers were efficiently achieved via a one-pot and convergent glycosylation strategy. All the protected α-glucans up to 15-mer were assembled with high yields and excellent α-stereoselectivity, which was secured by the synergistic α-directing effects of the TolSCl/AgOTf promotion system and the steric β-facial shielding of bulky saccharide residues linked at the 6-O-position of glucosyl donors. Moreover, the 3, 6-branched architecture of glycosyl donor was revealed to be more favorable for the α-selective glucosidation of primary hydroxyl group, especially in the case of large oligosaccharide acceptor. The structurally well-defined synthetic α-glucans would be useful for various biological studies.
A family of the 3, 6-branched Fuzi α-glucans including the pentasaccharide repeating unit as well as its di- and trimers were efficiently achieved via a one-pot and convergent glycosylation strategy. All the protected α-glucans up to 15-mer were assembled with high yields and excellent α-stereoselectivity, which was secured by the synergistic α-directing effects of the TolSCl/AgOTf promotion system and the steric β-facial shielding of bulky saccharide residues linked at the 6-O-position of glucosyl donors. Moreover, the 3, 6-branched architecture of glycosyl donor was revealed to be more favorable for the α-selective glucosidation of primary hydroxyl group, especially in the case of large oligosaccharide acceptor. The structurally well-defined synthetic α-glucans would be useful for various biological studies.
2023, 34(6): 107983
doi: 10.1016/j.cclet.2022.107983
Abstract:
The co-crystallization of quercetin (Qur) with a flexible molecule 4-(4-pyridinyldisulfanyl) pyridine (DPDS) in different solvents and conditions was investigated, yielded five multi-component crystalline phases and characterized with X-ray diffractions and thermal analysis. Although the crystal system of Qur-DPDS-MeOH and Qur-DPDS-Dioxane is the same, the desolvation results revealed that Qur-DPDS-MeOH transformed to Qur-DPDS when MeOH solvent molecules escape from the lattice, while Qur-DPDS-Dioxane transformed to Qur-DPDS-Ⅱ through a similar process, which is same with Qur-DPDS-THF. These two cocrystal polymorphs Qur-DPDS and Qur-DPDS-Ⅱ obey an enantiotropic relationship. Moreover, the formation of cocrystal solvates improves the packing efficiency of crystals. Crystal structure analysis showed that hydrogen bonds and conformations of the corresponding parent molecules play a major role in molecular assembly and crystal packing patterns, thus bring different physicochemical properties. Finally, the fluorescence spectra and quantum-chemical calculations were carried out to explore the difference in the optical-physical properties.
The co-crystallization of quercetin (Qur) with a flexible molecule 4-(4-pyridinyldisulfanyl) pyridine (DPDS) in different solvents and conditions was investigated, yielded five multi-component crystalline phases and characterized with X-ray diffractions and thermal analysis. Although the crystal system of Qur-DPDS-MeOH and Qur-DPDS-Dioxane is the same, the desolvation results revealed that Qur-DPDS-MeOH transformed to Qur-DPDS when MeOH solvent molecules escape from the lattice, while Qur-DPDS-Dioxane transformed to Qur-DPDS-Ⅱ through a similar process, which is same with Qur-DPDS-THF. These two cocrystal polymorphs Qur-DPDS and Qur-DPDS-Ⅱ obey an enantiotropic relationship. Moreover, the formation of cocrystal solvates improves the packing efficiency of crystals. Crystal structure analysis showed that hydrogen bonds and conformations of the corresponding parent molecules play a major role in molecular assembly and crystal packing patterns, thus bring different physicochemical properties. Finally, the fluorescence spectra and quantum-chemical calculations were carried out to explore the difference in the optical-physical properties.
2023, 34(6): 107984
doi: 10.1016/j.cclet.2022.107984
Abstract:
Trifluoromethylation/sulfonylation of alkynes from trifluoromethyl thianthrenium triflate and sulfur dioxide under extremely mild reaction conditions provides a facile access to trifluoromethyl-substituted vinyl sulfonohydrazides in moderate to good yields. This multicomponent reaction of trifluoromethyl thianthrenium triflate, alkynes, sulfur dioxide and hydrazines proceeds efficiently under visible light irradiation in the presence of photocatalyst at room temperature with broad substrate scope and excellent functional group compatibility. This reaction is highly stereoselective, and only (E)-isomers are obtained. Additionally, these trifluoromethyl-substituted vinyl sulfonohydrazides are further evaluated for anti-bacteria activity. In vitro activities of these compounds against Staphylococcus aureus (G+) and Escherichia coli (G−) are examined.
Trifluoromethylation/sulfonylation of alkynes from trifluoromethyl thianthrenium triflate and sulfur dioxide under extremely mild reaction conditions provides a facile access to trifluoromethyl-substituted vinyl sulfonohydrazides in moderate to good yields. This multicomponent reaction of trifluoromethyl thianthrenium triflate, alkynes, sulfur dioxide and hydrazines proceeds efficiently under visible light irradiation in the presence of photocatalyst at room temperature with broad substrate scope and excellent functional group compatibility. This reaction is highly stereoselective, and only (E)-isomers are obtained. Additionally, these trifluoromethyl-substituted vinyl sulfonohydrazides are further evaluated for anti-bacteria activity. In vitro activities of these compounds against Staphylococcus aureus (G+) and Escherichia coli (G−) are examined.
2023, 34(6): 107992
doi: 10.1016/j.cclet.2022.107992
Abstract:
Cardiovascular disease (CVD) is a global health problem and is thought to be responsible for almost half of all deaths in the world. Nevertheless, currently available diagnostic methods for CVD are strongly depended on clinical observation and monitoring, which commonly result in false diagnosis. Herein, an attractive strategy of a metal-organic framework (MOF) nanofilm-based laser desorption/ionization mass spectrometry (LDI-MS) was developed for enhancing serum metabolic profiling, which could provide precise diagnosis and molecular subtyping of CVD. The porous MOF nanofilm fabricated on indium-tin oxide (ITO) glass possessed enhanced ionization efficiency and size-exclusion effect, which endowed it as substrate with high sensitivity and selectivity for serum metabolites. Furthermore, the MOF nanofilm with uniform surface and high orientation provided high-quality and high-reproducibility serum metabolic profiles (SMPs) without any tedious pretreatment. Further analysis of extracted serum metabolic fingerprints could successfully distinguish patients with CVD from healthy controls and also differentiate two major subtypes of CVD. This work not only extends the application of MOF nanofilm as an attractive MS probe, but also provide an alternative way for precise diagnosis of CVD in molecular level.
Cardiovascular disease (CVD) is a global health problem and is thought to be responsible for almost half of all deaths in the world. Nevertheless, currently available diagnostic methods for CVD are strongly depended on clinical observation and monitoring, which commonly result in false diagnosis. Herein, an attractive strategy of a metal-organic framework (MOF) nanofilm-based laser desorption/ionization mass spectrometry (LDI-MS) was developed for enhancing serum metabolic profiling, which could provide precise diagnosis and molecular subtyping of CVD. The porous MOF nanofilm fabricated on indium-tin oxide (ITO) glass possessed enhanced ionization efficiency and size-exclusion effect, which endowed it as substrate with high sensitivity and selectivity for serum metabolites. Furthermore, the MOF nanofilm with uniform surface and high orientation provided high-quality and high-reproducibility serum metabolic profiles (SMPs) without any tedious pretreatment. Further analysis of extracted serum metabolic fingerprints could successfully distinguish patients with CVD from healthy controls and also differentiate two major subtypes of CVD. This work not only extends the application of MOF nanofilm as an attractive MS probe, but also provide an alternative way for precise diagnosis of CVD in molecular level.
2023, 34(6): 107995
doi: 10.1016/j.cclet.2022.107995
Abstract:
As a monoatomic bridge, fluoride ion can transmit efficient magnetic interaction between lanthanide ions but its effect on tuning the magnetization dynamics has not been well understood. Herein, two monofluoride-bridged dinuclear dysprosium complexes [Dy2F(bbpen)2(EtOH)2]Br·EtOH (1) and [Dy2F(bbppy)2]Br·2EtOH (2) with Dy-F-Dy angles of ~178° and their diamagnetic-ion diluted analogues 1´ and 2´ were synthesized. Magnetic studies reveal that 1 and 1´ barely show any magnetization dynamics, but 2 and 2´ exhibit strong magnetization dynamics. Systematical experimental analysis combined with ab initio calculations reveals that the different magnetization dynamics between 1 and 2 mainly originate from the effect of magnetic anisotropy by terminal ligand and bridging group of the chelating ligand, and the fluoride bridge can effectively suppress the quantum tunneling of the magnetization and turn on Orbach process in 2.
As a monoatomic bridge, fluoride ion can transmit efficient magnetic interaction between lanthanide ions but its effect on tuning the magnetization dynamics has not been well understood. Herein, two monofluoride-bridged dinuclear dysprosium complexes [Dy2F(bbpen)2(EtOH)2]Br·EtOH (1) and [Dy2F(bbppy)2]Br·2EtOH (2) with Dy-F-Dy angles of ~178° and their diamagnetic-ion diluted analogues 1´ and 2´ were synthesized. Magnetic studies reveal that 1 and 1´ barely show any magnetization dynamics, but 2 and 2´ exhibit strong magnetization dynamics. Systematical experimental analysis combined with ab initio calculations reveals that the different magnetization dynamics between 1 and 2 mainly originate from the effect of magnetic anisotropy by terminal ligand and bridging group of the chelating ligand, and the fluoride bridge can effectively suppress the quantum tunneling of the magnetization and turn on Orbach process in 2.
2023, 34(6): 107997
doi: 10.1016/j.cclet.2022.107997
Abstract:
Levofloxacin (LVFX) as a representative drug of quinolone antibiotics is widely used in clinical, and its residues enriched in water bodies and sideline products seriously damage human health. It is imperative to develop a real-time/on-site sensing method for monitoring residual antibiotics. Here, we report a portable sensing platform by utilizing a composite fluorescent nanoprobe constructed by the cerium ions (Ce3+) coordination functionalized CdTe quantum dots (QDs) for the visual and quantitative detection of LVFX residues. This fluorescent probe provides a distinct color variation from red to green, which shows a good linear relationship to LVFX residues concentrations in the range of 0-6.0 µmol/L with a sensitive limit of detection (LOD) of 16.3 nmol/L. The smartphone platform with Color Analyzer App installed, which could accomplish quantified detection of LVFX in water, milk, and raw pork with a LOD of 27.9 nmol/L. The facile sensing method we proposed realizes rapid visualization of antibiotics residual in the environment and provides a practical application pathway in food safety and human health.
Levofloxacin (LVFX) as a representative drug of quinolone antibiotics is widely used in clinical, and its residues enriched in water bodies and sideline products seriously damage human health. It is imperative to develop a real-time/on-site sensing method for monitoring residual antibiotics. Here, we report a portable sensing platform by utilizing a composite fluorescent nanoprobe constructed by the cerium ions (Ce3+) coordination functionalized CdTe quantum dots (QDs) for the visual and quantitative detection of LVFX residues. This fluorescent probe provides a distinct color variation from red to green, which shows a good linear relationship to LVFX residues concentrations in the range of 0-6.0 µmol/L with a sensitive limit of detection (LOD) of 16.3 nmol/L. The smartphone platform with Color Analyzer App installed, which could accomplish quantified detection of LVFX in water, milk, and raw pork with a LOD of 27.9 nmol/L. The facile sensing method we proposed realizes rapid visualization of antibiotics residual in the environment and provides a practical application pathway in food safety and human health.
2023, 34(6): 107998
doi: 10.1016/j.cclet.2022.107998
Abstract:
In the context of the circular economy, the huge amounts of biomass waste should be converted into value-added materials and energy to diminish pollution, atmospheric CO2 levels and costly waste disposal. Biological imaging usually uses expensive and toxic chemicals e.g., organic dyes, semiconductor quantum dots, calling for safer, greener, cheaper fluorescent probes for biological imaging in vitro and in vivo. In these regards, carbon quantum dots (CQDs)-based fluorescent probes using biomass waste as a precursor may have much higher potential. Here we transformed the biomass waste of peach leaves into value-added fluorescent CQDs through a low-cost and green one-step hydrothermal process. The obtained CQDs show excitation-dependent photoluminescence properties with a fluorescence lifetime of 5.96 ns and a quantum yield of 7.71% without any passivation. In addition, the CQDs have a fine size of 1.9 nm with good hydrophilicity and high fluorescent stability over pH 4.0–11.0 range. Fluorescence imaging of in vitro cell cultures and in vivo with zebrafish show that CQDs possess ultra-low toxicity and remarkable performance for biological imaging. Even when CQDs present at a concentration as high as 500 µg/mL, the organism can still maintain more than 90% activity both in vitro and in vivo, and present bright fluorescence. The cheaper, greener, ultra-low toxicity CQDs developed in this work is a potential candidate for biological imaging in vitro and in vivo.
In the context of the circular economy, the huge amounts of biomass waste should be converted into value-added materials and energy to diminish pollution, atmospheric CO2 levels and costly waste disposal. Biological imaging usually uses expensive and toxic chemicals e.g., organic dyes, semiconductor quantum dots, calling for safer, greener, cheaper fluorescent probes for biological imaging in vitro and in vivo. In these regards, carbon quantum dots (CQDs)-based fluorescent probes using biomass waste as a precursor may have much higher potential. Here we transformed the biomass waste of peach leaves into value-added fluorescent CQDs through a low-cost and green one-step hydrothermal process. The obtained CQDs show excitation-dependent photoluminescence properties with a fluorescence lifetime of 5.96 ns and a quantum yield of 7.71% without any passivation. In addition, the CQDs have a fine size of 1.9 nm with good hydrophilicity and high fluorescent stability over pH 4.0–11.0 range. Fluorescence imaging of in vitro cell cultures and in vivo with zebrafish show that CQDs possess ultra-low toxicity and remarkable performance for biological imaging. Even when CQDs present at a concentration as high as 500 µg/mL, the organism can still maintain more than 90% activity both in vitro and in vivo, and present bright fluorescence. The cheaper, greener, ultra-low toxicity CQDs developed in this work is a potential candidate for biological imaging in vitro and in vivo.
2023, 34(6): 108001
doi: 10.1016/j.cclet.2022.108001
Abstract:
Due to its difficulty and complexity, the cleavage and subsequent functionalization of the C(sp3)-C(sp3) single bond has received less attention than the CC bond formation reactions that have been extensively studied. Herein, by utilizing Cu/g-C3N4 nanometric semiconductor as a recyclable photocatalyst, an aerobic oxidative CC bond cleavage of aldehydes was developed with the promotion of amines under visible light irradiation. Based on the reaction, phenylacetaldehyde was selected as a highly efficient formylation reagent for amines. Under blue light irradiation, good to excellent yields of formamides were achieved for various amines in 1 atm oxygen atmosphere at room temperature. This methodology offers a practical, neutral and gentle alternative to the preparation of formamides.
Due to its difficulty and complexity, the cleavage and subsequent functionalization of the C(sp3)-C(sp3) single bond has received less attention than the CC bond formation reactions that have been extensively studied. Herein, by utilizing Cu/g-C3N4 nanometric semiconductor as a recyclable photocatalyst, an aerobic oxidative CC bond cleavage of aldehydes was developed with the promotion of amines under visible light irradiation. Based on the reaction, phenylacetaldehyde was selected as a highly efficient formylation reagent for amines. Under blue light irradiation, good to excellent yields of formamides were achieved for various amines in 1 atm oxygen atmosphere at room temperature. This methodology offers a practical, neutral and gentle alternative to the preparation of formamides.
2023, 34(6): 108002
doi: 10.1016/j.cclet.2022.108002
Abstract:
The lantern-shaped cage Pd2L4 and tweezer-like PdL2 can be synthesized from the trans- and cis-isomer of an azobenzene-containing ligand, respectively, which were characterized by 1H, 13C, 1H-1H COSY, DOSY NMR spectroscopies, high-resolution ESI-MS and density function theory (DFT) calculations. The interconversion of Pd2L4 and PdL2 can be achieved via the cis-trans isomerization of the azobenzene unit on the ligand upon alternative irradiation of light 365 nm or 420 nm.
The lantern-shaped cage Pd2L4 and tweezer-like PdL2 can be synthesized from the trans- and cis-isomer of an azobenzene-containing ligand, respectively, which were characterized by 1H, 13C, 1H-1H COSY, DOSY NMR spectroscopies, high-resolution ESI-MS and density function theory (DFT) calculations. The interconversion of Pd2L4 and PdL2 can be achieved via the cis-trans isomerization of the azobenzene unit on the ligand upon alternative irradiation of light 365 nm or 420 nm.
2023, 34(6): 108007
doi: 10.1016/j.cclet.2022.108007
Abstract:
Water splitting by photoelectrochemical (PEC) processes to convert solar energy into hydrogen energy using semiconductors is regarded as one of the most ideal methods to solve the current energy crisis and has attracted widespread attention. Herein, Co-based metal-organic framework (Co(bpdc)(H2O)4 (Co-MOF) nanosheets as passivation layers were in-situ constructed on the surface of BiVO4 films through an uncomplicated hydrothermal method (Co-MOF/BiVO4). Under AM 1.5G illumination, synthesized Co-MOF/BiVO4 electrode exhibited a 4-fold higher photocurrent than bare BiVO4, measuring 6.0 mA/cm2 at 1.23 V vs. RHE in 1 mol/L potassium borate electrolyte (pH 9.5) solution. Moreover, the Co-MOF/BiVO4 film demonstrated a 96% charge separation efficiency, a result caused by an inhibited recombination rate of photogenerated electrons and holes by the addition of Co-MOF nanosheets. This work provides an idea for depositing inexpensive 2D Co-MOF nanosheets on the photoanode as an excellent passivation layer for solar fuel production.
Water splitting by photoelectrochemical (PEC) processes to convert solar energy into hydrogen energy using semiconductors is regarded as one of the most ideal methods to solve the current energy crisis and has attracted widespread attention. Herein, Co-based metal-organic framework (Co(bpdc)(H2O)4 (Co-MOF) nanosheets as passivation layers were in-situ constructed on the surface of BiVO4 films through an uncomplicated hydrothermal method (Co-MOF/BiVO4). Under AM 1.5G illumination, synthesized Co-MOF/BiVO4 electrode exhibited a 4-fold higher photocurrent than bare BiVO4, measuring 6.0 mA/cm2 at 1.23 V vs. RHE in 1 mol/L potassium borate electrolyte (pH 9.5) solution. Moreover, the Co-MOF/BiVO4 film demonstrated a 96% charge separation efficiency, a result caused by an inhibited recombination rate of photogenerated electrons and holes by the addition of Co-MOF nanosheets. This work provides an idea for depositing inexpensive 2D Co-MOF nanosheets on the photoanode as an excellent passivation layer for solar fuel production.
2023, 34(6): 108010
doi: 10.1016/j.cclet.2022.108010
Abstract:
Activity-based Ubiquitin probes (Ub-ABPs) carrying a reporter group have emerged as effective tools for the investigation of deubiquitinating enzymes (DUBs), such as studying the molecular mechanism of DUBs, profiling new DUBs. But so far, the synthesis of commonly used biotin-bearing Ub-ABPs is a technical challenge. Here, we report a one-pot semi-synthetic strategy for the acquiring of Ub-ABPs carrying a biotin tag through sequential enzymatic ligation, N-S acyl transfer and aminolysis reaction without any purification steps. These probes enable to capture the different family of DUBs for enrichment and immunoblotting using the attached biotin tag.
Activity-based Ubiquitin probes (Ub-ABPs) carrying a reporter group have emerged as effective tools for the investigation of deubiquitinating enzymes (DUBs), such as studying the molecular mechanism of DUBs, profiling new DUBs. But so far, the synthesis of commonly used biotin-bearing Ub-ABPs is a technical challenge. Here, we report a one-pot semi-synthetic strategy for the acquiring of Ub-ABPs carrying a biotin tag through sequential enzymatic ligation, N-S acyl transfer and aminolysis reaction without any purification steps. These probes enable to capture the different family of DUBs for enrichment and immunoblotting using the attached biotin tag.
2023, 34(6): 108014
doi: 10.1016/j.cclet.2022.108014
Abstract:
A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4 + 3] annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time, and used to produce a range of hitherto unreported precedented β-monofluorinated benzo[b]azepin-5-ones with good yields and complete regioselectivity. This approach features a broad substrate scope, good functional group tolerance, and high regioselectivity, which may include Rh(Ⅲ)-catalyzed aldehydic C−H activation, tandem site-/regioselective insertion, defluorinated ring-scission, and 1, 2-elimination.
A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4 + 3] annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time, and used to produce a range of hitherto unreported precedented β-monofluorinated benzo[b]azepin-5-ones with good yields and complete regioselectivity. This approach features a broad substrate scope, good functional group tolerance, and high regioselectivity, which may include Rh(Ⅲ)-catalyzed aldehydic C−H activation, tandem site-/regioselective insertion, defluorinated ring-scission, and 1, 2-elimination.
2023, 34(6): 108017
doi: 10.1016/j.cclet.2022.108017
Abstract:
The Ni−Al bimetallic catalysis of intramolecular enantioselective and regioselective C−H cyclization of 4-oxoquinazolines with tethered alkenes has been successfully developed. Some new secondary phosphine oxides (SPOs) with large steric hindrance (SPO6-11) were designed and successfully synthesized from readily available chiral amines or amino acids. The developed chiral SPOs as ligands or preligands demonstrate much higher efficiency in the asymmetric catalytic reactions than the reported traditional ones. A new class of chiral tricyclic pyrroloquinazolinones were obtained in up to 95% yield and 99% ee.
The Ni−Al bimetallic catalysis of intramolecular enantioselective and regioselective C−H cyclization of 4-oxoquinazolines with tethered alkenes has been successfully developed. Some new secondary phosphine oxides (SPOs) with large steric hindrance (SPO6-11) were designed and successfully synthesized from readily available chiral amines or amino acids. The developed chiral SPOs as ligands or preligands demonstrate much higher efficiency in the asymmetric catalytic reactions than the reported traditional ones. A new class of chiral tricyclic pyrroloquinazolinones were obtained in up to 95% yield and 99% ee.
2023, 34(6): 108096
doi: 10.1016/j.cclet.2022.108096
Abstract:
A novel route of enzalutamide was developed in five steps. Starting from 4-amino-2-(trifluoromethyl)benzonitrile (7) and Boc-2-aminoisobutyric acid (16), condensation, deprotection, Ullmann coupling, cyclization and amination provided enzalutamide in 41.0% total yield. This route avoids the using of toxic chemical, unstable intermediate and high-risk reaction. It is a potential efficient and economical procedure for industrialization.
A novel route of enzalutamide was developed in five steps. Starting from 4-amino-2-(trifluoromethyl)benzonitrile (7) and Boc-2-aminoisobutyric acid (16), condensation, deprotection, Ullmann coupling, cyclization and amination provided enzalutamide in 41.0% total yield. This route avoids the using of toxic chemical, unstable intermediate and high-risk reaction. It is a potential efficient and economical procedure for industrialization.
2023, 34(6): 108109
doi: 10.1016/j.cclet.2022.108109
Abstract:
Heterogeneous Fenton has been widely used in the disposal of organic pollutants, however, slow regeneration of Fe(Ⅱ) remains limitation for its practical application of long-term treatment. Herein, we come up with a novel Fe-based heterogeneous Fenton catalyst named as FeSxOy-X (X is the ratio of ethylene glycol to N, N-dimethylformamide). With the help of the abundant defect electrons in Sulfur vacancies, Fe(Ⅱ) regeneration on the surface of FeSxOy-1:1 was accelerated, resulting in a stable proportion of Fe(Ⅱ) on the surface, which maintained continuously stable generation of hydroxyl radical (•OH) and singlet oxygen (1O2). Thus, without any organic reagents or cocatalysts, FeSxOy-1:1 based Fenton system achieved effective long-term degradation of 560 mg/L quinoline within only 7 days, which was evidently better than reported FeS and SV-FeS2 (SV: Sulfur vacancy). The system had excellent adaptability to water quality and the COD removal rate of biochemical wastewater was as high as 79.8%.
Heterogeneous Fenton has been widely used in the disposal of organic pollutants, however, slow regeneration of Fe(Ⅱ) remains limitation for its practical application of long-term treatment. Herein, we come up with a novel Fe-based heterogeneous Fenton catalyst named as FeSxOy-X (X is the ratio of ethylene glycol to N, N-dimethylformamide). With the help of the abundant defect electrons in Sulfur vacancies, Fe(Ⅱ) regeneration on the surface of FeSxOy-1:1 was accelerated, resulting in a stable proportion of Fe(Ⅱ) on the surface, which maintained continuously stable generation of hydroxyl radical (•OH) and singlet oxygen (1O2). Thus, without any organic reagents or cocatalysts, FeSxOy-1:1 based Fenton system achieved effective long-term degradation of 560 mg/L quinoline within only 7 days, which was evidently better than reported FeS and SV-FeS2 (SV: Sulfur vacancy). The system had excellent adaptability to water quality and the COD removal rate of biochemical wastewater was as high as 79.8%.
2023, 34(6): 107687
doi: 10.1016/j.cclet.2022.07.030
Abstract:
Diketopyrrolopyrrole (DPP) and related derivatives have drawn great attention due to their applications in organic optical /electronic materials. Progress in these materials is associated with developments in the syntheses of the DPP family. Chemical modification of DPP at nitrogen atom, including N-alkylation and N-arylation, is an effective strategy to improve its physical and chemical properties, such as solubility, optical and semiconducting properties. However, N-arylation of DPPs remains challenging compared to the easily accessible N-alkylation. Herein, the synthesis of N-aryl DPP derivatives and correlated π-expanded DPPs are summarized, and their optical/electronic properties are introduced. The future perspectives of N-aryl DPP derivatives are also discussed.
Diketopyrrolopyrrole (DPP) and related derivatives have drawn great attention due to their applications in organic optical /electronic materials. Progress in these materials is associated with developments in the syntheses of the DPP family. Chemical modification of DPP at nitrogen atom, including N-alkylation and N-arylation, is an effective strategy to improve its physical and chemical properties, such as solubility, optical and semiconducting properties. However, N-arylation of DPPs remains challenging compared to the easily accessible N-alkylation. Herein, the synthesis of N-aryl DPP derivatives and correlated π-expanded DPPs are summarized, and their optical/electronic properties are introduced. The future perspectives of N-aryl DPP derivatives are also discussed.
2023, 34(6): 107757
doi: 10.1016/j.cclet.2022.107757
Abstract:
The electrochemical CO2 reduction reaction (CO2ER) is an emerging process that involves utilizing CO2 to produce valuable chemicals and fuels by consuming excess electricity from renewable sources. Recently, Cu and Cu-based nanoparticles, as earth-abundant and economical metal sources, have been attracting significant interest. The chemical and physical properties of Cu-based nanoparticles are modified by different strategies, and CO2 can be converted into multicarbon products. Among various Cu-based nanoparticles, Cu-based metal-organic frameworks (MOFs) are gaining increasing interest in the field of catalysis because of their textural, topological, and electrocatalytic properties. In this minireview, we summarized and highlighted the main achievements in the research on Cu-based MOFs and their advantages in the CO2ER as electrocatalysts, supports, or precursors.
The electrochemical CO2 reduction reaction (CO2ER) is an emerging process that involves utilizing CO2 to produce valuable chemicals and fuels by consuming excess electricity from renewable sources. Recently, Cu and Cu-based nanoparticles, as earth-abundant and economical metal sources, have been attracting significant interest. The chemical and physical properties of Cu-based nanoparticles are modified by different strategies, and CO2 can be converted into multicarbon products. Among various Cu-based nanoparticles, Cu-based metal-organic frameworks (MOFs) are gaining increasing interest in the field of catalysis because of their textural, topological, and electrocatalytic properties. In this minireview, we summarized and highlighted the main achievements in the research on Cu-based MOFs and their advantages in the CO2ER as electrocatalysts, supports, or precursors.
2023, 34(6): 107904
doi: 10.1016/j.cclet.2022.107904
Abstract:
Over the last 50 years, the explosive adoption of modern agricultural practices has led to an enormous increase in the emission of non-biodegradable and highly biotoxic ions into the hydrosphere. Excess intake of such ions, even essential trace elements such as Cu2+ and F−, can have serious consequences on human health. Therefore, to ensure safe drinking water and regulate wastewater discharge, photoelectrochemical (PEC) online sensors were developed, with advantages such as low energy consumption, inherent miniaturization, simple instrumentation, and fast response. However, there is no publicly available systematic review of the recent advances in PEC ion sensors available in the literature since January 2017. Thus, this review covers the various strategies that have been used to enhance the sensitivity, selectivity, and limit of detection for PEC ion sensors. The photoelectrochemically active materials, conductive substrates, electronic transfer, and performance of various PEC sensors are discussed in detail and divided into sections based on the measurement principle and detected ion species. We conclude this review by highlighting the challenges and potential future avenues of research associated with the development of novel high-performance PEC sensors.
Over the last 50 years, the explosive adoption of modern agricultural practices has led to an enormous increase in the emission of non-biodegradable and highly biotoxic ions into the hydrosphere. Excess intake of such ions, even essential trace elements such as Cu2+ and F−, can have serious consequences on human health. Therefore, to ensure safe drinking water and regulate wastewater discharge, photoelectrochemical (PEC) online sensors were developed, with advantages such as low energy consumption, inherent miniaturization, simple instrumentation, and fast response. However, there is no publicly available systematic review of the recent advances in PEC ion sensors available in the literature since January 2017. Thus, this review covers the various strategies that have been used to enhance the sensitivity, selectivity, and limit of detection for PEC ion sensors. The photoelectrochemically active materials, conductive substrates, electronic transfer, and performance of various PEC sensors are discussed in detail and divided into sections based on the measurement principle and detected ion species. We conclude this review by highlighting the challenges and potential future avenues of research associated with the development of novel high-performance PEC sensors.
2023, 34(6): 107908
doi: 10.1016/j.cclet.2022.107908
Abstract:
Nitrate (NO3−) is widely found in wastewater, which is harmful to human health and water environmental. Electrochemical reduction can convert NO3− to high value-added ammonia (NH3)/ammonium (NH4+) for pollutant removal and resource recovery. Currently, electrochemical nitrate reduction to produce ammonia (ENRA) is mostly focused on the preparation of high-performance catalysts, while ignoring the prerequisite for industrial application as the stable operation and optimal regulation of the process. Therefore, the review focused on wastewater treatment, based on the mechanism of electrochemical nitrate reduction for ammonia production and reactor construction (reactor, power supply system), then summarized the operation control strategies (such as reduction potential, nitrate concentration, inorganic ions, pH) that should be noted for ENRA. Finally, the challenges (system structure, economy) and prospects (ammonia recovery process, construction of large-scale ENRA system, application of real wastewater) of the field as it moves towards commercialization were discussed. It is hoped that this review will facilitate the scaling up of ENRA in the wastewater treatment field.
Nitrate (NO3−) is widely found in wastewater, which is harmful to human health and water environmental. Electrochemical reduction can convert NO3− to high value-added ammonia (NH3)/ammonium (NH4+) for pollutant removal and resource recovery. Currently, electrochemical nitrate reduction to produce ammonia (ENRA) is mostly focused on the preparation of high-performance catalysts, while ignoring the prerequisite for industrial application as the stable operation and optimal regulation of the process. Therefore, the review focused on wastewater treatment, based on the mechanism of electrochemical nitrate reduction for ammonia production and reactor construction (reactor, power supply system), then summarized the operation control strategies (such as reduction potential, nitrate concentration, inorganic ions, pH) that should be noted for ENRA. Finally, the challenges (system structure, economy) and prospects (ammonia recovery process, construction of large-scale ENRA system, application of real wastewater) of the field as it moves towards commercialization were discussed. It is hoped that this review will facilitate the scaling up of ENRA in the wastewater treatment field.
2023, 34(6): 107925
doi: 10.1016/j.cclet.2022.107925
Abstract:
As the main target cells of immune regulation, macrophages play an important role in the bone regeneration process. Macrophages can be polarized into the M1 and M2 types under the stimulation of different factors. They have proinflammatory and anti-inflammatory effects, respectively, and play key roles in different stages of bone regeneration. The ratio of M1 to M2 macrophages can be regulated by immunomodulatory biomaterials to promote bone repair and regeneration. In this paper, we review the recent literature on the chemical, physical and biological properties of biomaterials and the regulation of macrophage polarization under the influence of other factors. We also cover new methods for preparing immunomodulatory biomaterials for bone regeneration. This paper will provide new design ideas for the development of biomaterials with immunological properties and will support the clinical translation of bone-related medical biomaterials.
As the main target cells of immune regulation, macrophages play an important role in the bone regeneration process. Macrophages can be polarized into the M1 and M2 types under the stimulation of different factors. They have proinflammatory and anti-inflammatory effects, respectively, and play key roles in different stages of bone regeneration. The ratio of M1 to M2 macrophages can be regulated by immunomodulatory biomaterials to promote bone repair and regeneration. In this paper, we review the recent literature on the chemical, physical and biological properties of biomaterials and the regulation of macrophage polarization under the influence of other factors. We also cover new methods for preparing immunomodulatory biomaterials for bone regeneration. This paper will provide new design ideas for the development of biomaterials with immunological properties and will support the clinical translation of bone-related medical biomaterials.
2023, 34(6): 107926
doi: 10.1016/j.cclet.2022.107926
Abstract:
Extracellular vesicles (EVs) are cell-derived nanosized vesicles widely recognized for their critical roles in various pathophysiological processes. Molecular analysis of EVs is currently being considered an emerging tool for diseases diagnosis. However, the small size and heterogeneity of EVs has staggered the EVs research for diseases diagnosis. DNA nanotechnology enables self-assembly of versatile DNA nanostructures and has shown enormous potential in assisting EVs biosensing. In this review, we briefly introduce the recent advances in DNA nanotechnology approaches for EVs detection. The approaches were categorized based on the dimension of DNA nanostructures. We provide critical evaluation of these approaches, and summarize the pros and cons of specific methods. Further, we discuss the challenges and future perspectives in this field.
Extracellular vesicles (EVs) are cell-derived nanosized vesicles widely recognized for their critical roles in various pathophysiological processes. Molecular analysis of EVs is currently being considered an emerging tool for diseases diagnosis. However, the small size and heterogeneity of EVs has staggered the EVs research for diseases diagnosis. DNA nanotechnology enables self-assembly of versatile DNA nanostructures and has shown enormous potential in assisting EVs biosensing. In this review, we briefly introduce the recent advances in DNA nanotechnology approaches for EVs detection. The approaches were categorized based on the dimension of DNA nanostructures. We provide critical evaluation of these approaches, and summarize the pros and cons of specific methods. Further, we discuss the challenges and future perspectives in this field.
2023, 34(6): 107927
doi: 10.1016/j.cclet.2022.107927
Abstract:
Proteolysis targeting chimeras (PROTACs) are bifunctional degrader molecules via hijacking the ubiquitin-proteasome system (UPS) to specifically eliminate targeted proteins. PROTACs have gained momentum as a new modality of attractive technologies in the drug discovery landscape, since it allows to degrade disease-related proteins effectively. Although some PROTACs drugs reached the clinical research, they are still facing some bottlenecks and challenges that should not be neglected, such as poor oral bioavailability and potential toxic side effects. To overcome these limitations, herein, we provide an overview of recent strategies for improving the durability of PROTACs by enhancing cell permeability and reducing toxic side effects. Meanwhile, the impact of these strategies on improving oral bioavailability as well as their advantages and drawbacks will also be discussed. This review will give a useful reference toolbox for PROTACs design and further promote its clinical application.
Proteolysis targeting chimeras (PROTACs) are bifunctional degrader molecules via hijacking the ubiquitin-proteasome system (UPS) to specifically eliminate targeted proteins. PROTACs have gained momentum as a new modality of attractive technologies in the drug discovery landscape, since it allows to degrade disease-related proteins effectively. Although some PROTACs drugs reached the clinical research, they are still facing some bottlenecks and challenges that should not be neglected, such as poor oral bioavailability and potential toxic side effects. To overcome these limitations, herein, we provide an overview of recent strategies for improving the durability of PROTACs by enhancing cell permeability and reducing toxic side effects. Meanwhile, the impact of these strategies on improving oral bioavailability as well as their advantages and drawbacks will also be discussed. This review will give a useful reference toolbox for PROTACs design and further promote its clinical application.
2023, 34(6): 107953
doi: 10.1016/j.cclet.2022.107953
Abstract:
As one of the top global health problems, the effective treatment of cancer is one of the most urgent clinical challenges. Currently, the main treatments for cancer include surgery, chemotherapy, radiotherapy, and gene therapy etc. Chemotherapy is one of the most commonly used treatments, however it has limitations such as highly toxic side effects and low drug utilization rate that limit its application. Gene therapy, as an emerging cancer treatment, has limitations such as drug instability, off-target effects and low internalization efficiency. Poly(amino acid)s carriers with good biocompatibility, degradability and multifunctionality as drug carriers have received much attention, as they can reduce the toxic side effects of chemotherapy, improve drug utilization, and enhance the internalization efficiency and utilization of gene drugs. However, little attention has been paid to the nature of the carriers themselves. This paper reviews the immunomodulatory, anti-inflammatory, antioxidant, internalization-promoting and apoptosis-promoting functions of poly(amino acid)s drug carriers in tumor therapy to provide a theoretical basis for different carrier-drug-adapted synergistic therapies.
As one of the top global health problems, the effective treatment of cancer is one of the most urgent clinical challenges. Currently, the main treatments for cancer include surgery, chemotherapy, radiotherapy, and gene therapy etc. Chemotherapy is one of the most commonly used treatments, however it has limitations such as highly toxic side effects and low drug utilization rate that limit its application. Gene therapy, as an emerging cancer treatment, has limitations such as drug instability, off-target effects and low internalization efficiency. Poly(amino acid)s carriers with good biocompatibility, degradability and multifunctionality as drug carriers have received much attention, as they can reduce the toxic side effects of chemotherapy, improve drug utilization, and enhance the internalization efficiency and utilization of gene drugs. However, little attention has been paid to the nature of the carriers themselves. This paper reviews the immunomodulatory, anti-inflammatory, antioxidant, internalization-promoting and apoptosis-promoting functions of poly(amino acid)s drug carriers in tumor therapy to provide a theoretical basis for different carrier-drug-adapted synergistic therapies.
2023, 34(6): 107959
doi: 10.1016/j.cclet.2022.107959
Abstract:
Metal-based catalysis, including homogeneous and heterogeneous catalysis, plays a significant role in the modern chemical industry. Heterogeneous catalysis is widely used due to the high efficiency, easy catalyst separation and recycling. However, the metal-utilization efficiency for conventional heterogeneous catalysts needs further improvement compared to homogeneous catalyst. To tackle this, the pursing of heterogenizing homogeneous catalysts has always been attractive but challenging. As a recently emerging class of catalytic material, single-atom catalysts (SACs) are expected to bridge homogeneous and heterogeneous catalytic process in organic reactions and have arguably become the most active new frontier in catalysis field. In this review, a brief introduction and development history of single-atom catalysis and SACs involved organic reactions are documented. In addition, recent advances in SACs and their practical applications in organic reactions such as oxidation, reduction, addition, coupling reaction, and other organic reactions are thoroughly reviewed. To understand structure-property relationships of single-atom catalysis in organic reactions, active sites or coordination structure, metal atom-utilization efficiency (e.g., turnover frequency, TOF calculated based on active metal) and catalytic performance (e.g., conversion and selectivity) of SACs are comprehensively summarized. Furthermore, the application limitations, development trends, future challenges and perspective of SAC for organic reaction are discussed.
Metal-based catalysis, including homogeneous and heterogeneous catalysis, plays a significant role in the modern chemical industry. Heterogeneous catalysis is widely used due to the high efficiency, easy catalyst separation and recycling. However, the metal-utilization efficiency for conventional heterogeneous catalysts needs further improvement compared to homogeneous catalyst. To tackle this, the pursing of heterogenizing homogeneous catalysts has always been attractive but challenging. As a recently emerging class of catalytic material, single-atom catalysts (SACs) are expected to bridge homogeneous and heterogeneous catalytic process in organic reactions and have arguably become the most active new frontier in catalysis field. In this review, a brief introduction and development history of single-atom catalysis and SACs involved organic reactions are documented. In addition, recent advances in SACs and their practical applications in organic reactions such as oxidation, reduction, addition, coupling reaction, and other organic reactions are thoroughly reviewed. To understand structure-property relationships of single-atom catalysis in organic reactions, active sites or coordination structure, metal atom-utilization efficiency (e.g., turnover frequency, TOF calculated based on active metal) and catalytic performance (e.g., conversion and selectivity) of SACs are comprehensively summarized. Furthermore, the application limitations, development trends, future challenges and perspective of SAC for organic reaction are discussed.
2023, 34(6): 107978
doi: 10.1016/j.cclet.2022.107978
Abstract:
Sodium-ion batteries (SIBs) have received significant attention in large-scale energy storage due to their low cost and abundant resources. To obtain high-performance SIBs, many intensive studies about electrode materials have been carried out, especially the cathode material. As various types of cathode material for SIBs, a 3D open framework structural Na3V2(PO4)2F3 (NVPF) with Na superionic conductor (NASICON) structure is a promising cathode material owing to its high operating potential and high energy density. However, its electrochemical properties are severely limited by the poor electronic conductivity due to the insulated [PO4] tetrahedral unit. In this review, the challenges and strategies for NVPF are presented, and the synthetic strategy for NVPF is also analyzed in detail. Furthermore, recent developments of modification research to enhance their electrochemical performance are discussed, including designing the crystal structure, adjusting the electrode structure, and optimizing the electrolyte components. Finally, further research and application for future development of NVPF are prospected.
Sodium-ion batteries (SIBs) have received significant attention in large-scale energy storage due to their low cost and abundant resources. To obtain high-performance SIBs, many intensive studies about electrode materials have been carried out, especially the cathode material. As various types of cathode material for SIBs, a 3D open framework structural Na3V2(PO4)2F3 (NVPF) with Na superionic conductor (NASICON) structure is a promising cathode material owing to its high operating potential and high energy density. However, its electrochemical properties are severely limited by the poor electronic conductivity due to the insulated [PO4] tetrahedral unit. In this review, the challenges and strategies for NVPF are presented, and the synthetic strategy for NVPF is also analyzed in detail. Furthermore, recent developments of modification research to enhance their electrochemical performance are discussed, including designing the crystal structure, adjusting the electrode structure, and optimizing the electrolyte components. Finally, further research and application for future development of NVPF are prospected.
2023, 34(6): 108000
doi: 10.1016/j.cclet.2022.108000
Abstract:
Atmospheric pollutants can deteriorate air quality and put human health at risk. There is a growing need for green, economical, and efficient technologies, among which catalytic elimination technology is the most promising, to remove atmospheric pollutants. Two-dimensional transition metal oxides (2D TMOs) have recently become attractive catalysts due to their highly exposed active sites, excellent reactant transport properties, and extraordinary catalytic performance. This review systematically summarizes the top-down and bottom-up preparation methods of 2D TMOs and focuses on the specific applications of 2D TMOs in the catalytic elimination of atmospheric inorganic pollutants and volatile organic pollutants. The development of 2D TMOs in the catalytic elimination of atmospheric pollutants is prospected. This review is expected to provide design insights into efficient 2D TMOs to remove atmospheric pollutants.
Atmospheric pollutants can deteriorate air quality and put human health at risk. There is a growing need for green, economical, and efficient technologies, among which catalytic elimination technology is the most promising, to remove atmospheric pollutants. Two-dimensional transition metal oxides (2D TMOs) have recently become attractive catalysts due to their highly exposed active sites, excellent reactant transport properties, and extraordinary catalytic performance. This review systematically summarizes the top-down and bottom-up preparation methods of 2D TMOs and focuses on the specific applications of 2D TMOs in the catalytic elimination of atmospheric inorganic pollutants and volatile organic pollutants. The development of 2D TMOs in the catalytic elimination of atmospheric pollutants is prospected. This review is expected to provide design insights into efficient 2D TMOs to remove atmospheric pollutants.
2023, 34(6): 108003
doi: 10.1016/j.cclet.2022.108003
Abstract:
Benzo[b]thiophene fused compounds with a unique active heterocyclic skeleton have wide applications in the fields of medicinal chemistry, organic synthesis, and organic functional materials, which resulted in rapid development of many efficient methods for the construction of benzo[b]thiophene-fused heterocycles in recent years. Among these methods, the domino reaction of benzo[b]thiophene derivatives is a practical and powerful synthetic route to access benzo[b]thiophene-fused heterocycles by virtue of the particularity of sulfur atom. This review summarizes the latest developments in the construction of benzo[b]thiophene-fused heterocycles by ring formation at the C2-C3-position of benzo[b]thiophene derivatives in the past decade. Additionally, this review is divided into four parts according to the four kinds of benzo[b]thiophene derivatives used, including thioaurone, thioisatin, substituted benzo[b]thiophene, and azadiene.
Benzo[b]thiophene fused compounds with a unique active heterocyclic skeleton have wide applications in the fields of medicinal chemistry, organic synthesis, and organic functional materials, which resulted in rapid development of many efficient methods for the construction of benzo[b]thiophene-fused heterocycles in recent years. Among these methods, the domino reaction of benzo[b]thiophene derivatives is a practical and powerful synthetic route to access benzo[b]thiophene-fused heterocycles by virtue of the particularity of sulfur atom. This review summarizes the latest developments in the construction of benzo[b]thiophene-fused heterocycles by ring formation at the C2-C3-position of benzo[b]thiophene derivatives in the past decade. Additionally, this review is divided into four parts according to the four kinds of benzo[b]thiophene derivatives used, including thioaurone, thioisatin, substituted benzo[b]thiophene, and azadiene.
2023, 34(6): 108026
doi: 10.1016/j.cclet.2022.108026
Abstract:
Bicyclic peptides, a class of polypeptides with two loops within their structure, have emerged as powerful tools in the development of new peptide drugs. They have the potential to bind to challenged drug targets, with antibody-like affinity and selectivity. Meanwhile, bicyclic peptides possess small molecule-like access to chemical synthesis, which is conducive to large-scale synthesis and screening. In the last five years, bicyclic peptide technology has been increasingly developed, and researchers have carried out a variety of studies to elucidate the potential functions of bicyclic peptides. With the continuous development of synthetic methods and the advances of new technology to build bicyclic peptide libraries, bicyclic peptides are now becoming widely used in the development of new drugs for various diseases. This perspective provides an overview of the structure types, synthesis and applications of bicyclic peptides in current drug development, and our own views on future challenges of bicyclic peptides.
Bicyclic peptides, a class of polypeptides with two loops within their structure, have emerged as powerful tools in the development of new peptide drugs. They have the potential to bind to challenged drug targets, with antibody-like affinity and selectivity. Meanwhile, bicyclic peptides possess small molecule-like access to chemical synthesis, which is conducive to large-scale synthesis and screening. In the last five years, bicyclic peptide technology has been increasingly developed, and researchers have carried out a variety of studies to elucidate the potential functions of bicyclic peptides. With the continuous development of synthetic methods and the advances of new technology to build bicyclic peptide libraries, bicyclic peptides are now becoming widely used in the development of new drugs for various diseases. This perspective provides an overview of the structure types, synthesis and applications of bicyclic peptides in current drug development, and our own views on future challenges of bicyclic peptides.
2023, 34(6): 108041
doi: 10.1016/j.cclet.2022.108041
Abstract:
Chirality is one of the most important features of the nature. The recognition of enantiomers plays significant roles in the field of life science, pharmaceutical analysis and food chemistry. Among various recognition methods, fluorescence spectrometry has attracted much attention of researchers thanks to its high sensitivity and easy operation. Compared with traditional fluorescent probes, chiral molecules with aggregation-induced emission (AIE) have drawn increasing interests due to their huge potential in high-efficiency chemo/biosensors and solid emitters. Chiral AIE luminogens (AIEgens) can not only discriminate two enantiomers with excellent enantioselectivity, but also show general applicability for many chiral analytes, such as chiral acids, amino acids, amines, alcohols. In this review, we mainly summarized the recent development of chiral probes with AIE properties, including chiral tetraphenylethylene (TPE) derivatives, α-cyanostilbene derivatives, Schiff base derivatives and other AIEgens. Their synthetic routes, recognition capabilities and possible working mechanisms were well discussed. It is envisioned that the present review can give some significant guidance for design and synthesis of chiral AIEgens with good enantioselectivity and inspire more readers to join the research of chiral AIE.
Chirality is one of the most important features of the nature. The recognition of enantiomers plays significant roles in the field of life science, pharmaceutical analysis and food chemistry. Among various recognition methods, fluorescence spectrometry has attracted much attention of researchers thanks to its high sensitivity and easy operation. Compared with traditional fluorescent probes, chiral molecules with aggregation-induced emission (AIE) have drawn increasing interests due to their huge potential in high-efficiency chemo/biosensors and solid emitters. Chiral AIE luminogens (AIEgens) can not only discriminate two enantiomers with excellent enantioselectivity, but also show general applicability for many chiral analytes, such as chiral acids, amino acids, amines, alcohols. In this review, we mainly summarized the recent development of chiral probes with AIE properties, including chiral tetraphenylethylene (TPE) derivatives, α-cyanostilbene derivatives, Schiff base derivatives and other AIEgens. Their synthetic routes, recognition capabilities and possible working mechanisms were well discussed. It is envisioned that the present review can give some significant guidance for design and synthesis of chiral AIEgens with good enantioselectivity and inspire more readers to join the research of chiral AIE.
2023, 34(6): 108103
doi: 10.1016/j.cclet.2022.108103
Abstract:
Microneedles are considered to be an effective, convenient, non-invasive, biosafety and compliant medical technology for vaccinations, biomarker testing, medical aesthetics and other related fields. Nonetheless, further clinical and commercial translation of regular microneedles is hampered by challenges in manufacturability, cost variability, insufficient comfort, contamination and so on. Recent innovations in functional biomaterials and chemical engineering technologies have been applied to develop extensible and swellable hydrogel-forming microneedles, achieving precise and controlled drug delivery and localized sampling from the target tissues. In this review, we systematically summarize the latest development of the extensible and swellable hydrogel-forming microneedles, including deep point-of-care testing, drug deployment, wound healing and mucoadhesion improvement. In addition, further analysis of the challenges and prospects for clinical application of current strategies is well presented. It is believed that the combined efforts of engineering, material, pharmaceutical and clinical research will contribute to the future success of this clinical and commercial translation.
Microneedles are considered to be an effective, convenient, non-invasive, biosafety and compliant medical technology for vaccinations, biomarker testing, medical aesthetics and other related fields. Nonetheless, further clinical and commercial translation of regular microneedles is hampered by challenges in manufacturability, cost variability, insufficient comfort, contamination and so on. Recent innovations in functional biomaterials and chemical engineering technologies have been applied to develop extensible and swellable hydrogel-forming microneedles, achieving precise and controlled drug delivery and localized sampling from the target tissues. In this review, we systematically summarize the latest development of the extensible and swellable hydrogel-forming microneedles, including deep point-of-care testing, drug deployment, wound healing and mucoadhesion improvement. In addition, further analysis of the challenges and prospects for clinical application of current strategies is well presented. It is believed that the combined efforts of engineering, material, pharmaceutical and clinical research will contribute to the future success of this clinical and commercial translation.
2023, 34(6): 107928
doi: 10.1016/j.cclet.2022.107928
Abstract:
2023, 34(6): 108089
doi: 10.1016/j.cclet.2022.108089
Abstract:
