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2023 Volume 34 Issue 9
2023, 34(9): 108083
doi: 10.1016/j.cclet.2022.108083
Abstract:
Selenium, an element belonging to the same group in the periodic table as sulfur, has a high electronic conductivity (1 × 10−5 S/cm) and a high volumetric energy density (3253 mAh/cm3), which is a prospective cathode material for high-energy all-solid-state rechargeable batteries. However, its wide use is hindered by large volume expansion and low utilization rate. In this work, Se-infused nitrogen-doped hierarchical meso-microporous carbon composites (Se/NHPC) are prepared by a melt-diffusion process. Amorphous Se is uniformly dispersed in meso-micropores of NHPC with a high mass loading of 81%. All-solid-state Li-Se batteries fabricated by using Se/NHPC as the cathode, a Li-In alloy as the anode, and Li6PS5Cl as the solid-state electrolyte, deliver a highly reversible capacity of 621 mAh/g (92% of theoretical capacity), a good rate capability and a high capacity retention value of 80.9% after 100 cycles. It is found that the capacity decay of Se cathode is mainly related to the interfacial degradation and the separation of Se from the carbon substrate, as suggested by the continuous increase of interfacial resistance and the structural transformation from amorphous Sen chains to Se8 rings initial discharge/charge cycle and then to the trigonally crystalline Se chains structure after the long-term cycles.
Selenium, an element belonging to the same group in the periodic table as sulfur, has a high electronic conductivity (1 × 10−5 S/cm) and a high volumetric energy density (3253 mAh/cm3), which is a prospective cathode material for high-energy all-solid-state rechargeable batteries. However, its wide use is hindered by large volume expansion and low utilization rate. In this work, Se-infused nitrogen-doped hierarchical meso-microporous carbon composites (Se/NHPC) are prepared by a melt-diffusion process. Amorphous Se is uniformly dispersed in meso-micropores of NHPC with a high mass loading of 81%. All-solid-state Li-Se batteries fabricated by using Se/NHPC as the cathode, a Li-In alloy as the anode, and Li6PS5Cl as the solid-state electrolyte, deliver a highly reversible capacity of 621 mAh/g (92% of theoretical capacity), a good rate capability and a high capacity retention value of 80.9% after 100 cycles. It is found that the capacity decay of Se cathode is mainly related to the interfacial degradation and the separation of Se from the carbon substrate, as suggested by the continuous increase of interfacial resistance and the structural transformation from amorphous Sen chains to Se8 rings initial discharge/charge cycle and then to the trigonally crystalline Se chains structure after the long-term cycles.
2023, 34(9): 108084
doi: 10.1016/j.cclet.2022.108084
Abstract:
Functional carbon nanomaterials have become the stars of many active research fields, such as electronics, energy, catalysis, imaging, sensing and biomedicine. Herein, a facile and one-pot strategy for generating ferromagnetic nanoparticles loaded on N-doped carbon nanosheets (Fe-N-CNS) is presented by salt-assisted high-temperature carbonization of natural silk proteins. Due to their graphitic structures, N-doping and ferromagnetic nanoparticles (FeNx, FeOy, FeCz), the silk-derived Fe-N-CNS can act as excellent mimics of both peroxidase and oxidase. Benefiting from the combined character of the graphene-like structures and enzyme-like activities, Fe-N-CNS can be further applied to highly efficient dye removal via synergistic adsorption and degradation. Meanwhile, the as-prepared Fe-N-CNS with intrinsic magnetism and electrical conductivity can also serve as an efficient electromagnetic wave absorption agent. The broadest effective absorption bandwidth (EAB) of as-obtained absorbing material yields a 6.73 GHz with 1 mm thickness, with a maximum reflection loss of −37.33 dB (11.41 GHz). The EAB can cover 2~18 GHz with a tunable absorber thickness from 1.0 mm to 5.0 mm. Collectively, Fe-N-CNS, as a dual-functional material, can tackle the aggravating environmental pollution issues of both dyes and electromagnetic waves.
Functional carbon nanomaterials have become the stars of many active research fields, such as electronics, energy, catalysis, imaging, sensing and biomedicine. Herein, a facile and one-pot strategy for generating ferromagnetic nanoparticles loaded on N-doped carbon nanosheets (Fe-N-CNS) is presented by salt-assisted high-temperature carbonization of natural silk proteins. Due to their graphitic structures, N-doping and ferromagnetic nanoparticles (FeNx, FeOy, FeCz), the silk-derived Fe-N-CNS can act as excellent mimics of both peroxidase and oxidase. Benefiting from the combined character of the graphene-like structures and enzyme-like activities, Fe-N-CNS can be further applied to highly efficient dye removal via synergistic adsorption and degradation. Meanwhile, the as-prepared Fe-N-CNS with intrinsic magnetism and electrical conductivity can also serve as an efficient electromagnetic wave absorption agent. The broadest effective absorption bandwidth (EAB) of as-obtained absorbing material yields a 6.73 GHz with 1 mm thickness, with a maximum reflection loss of −37.33 dB (11.41 GHz). The EAB can cover 2~18 GHz with a tunable absorber thickness from 1.0 mm to 5.0 mm. Collectively, Fe-N-CNS, as a dual-functional material, can tackle the aggravating environmental pollution issues of both dyes and electromagnetic waves.
2023, 34(9): 108085
doi: 10.1016/j.cclet.2022.108085
Abstract:
Metal-support interaction (MSI) is an efficient way in heterogeneous catalysis and electrocatalysis to modulate the electronic structure of metal for enhanced catalytic activity. However, there are still great challenges in promoting the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) simultaneously by this way. Herein, Fe-doped Co3O4 supported Ru (Ru/FeCo) catalysts are synthesized by MSI strategies to further improve the electrocatalytic activity and stability of the catalysts. The results show that the optimized Ru/FeCo catalyst exhibits the best catalytic performance. The HER and OER tests at 10 mA/cm2 in 1 mol/L KOH solution show excellent overpotentials of 155 mV and 283 mV, respectively. The activity and stability enhancement can be attributed to the MSI that effectively modify the electronic structure and improve interfacial electron transfer between Ru and Fe-doped Co3O4 (FeCo). This work provides an innovative direction for the design of high-efficiency bifunctional electrocatalysts by virtue of the MSI.
Metal-support interaction (MSI) is an efficient way in heterogeneous catalysis and electrocatalysis to modulate the electronic structure of metal for enhanced catalytic activity. However, there are still great challenges in promoting the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) simultaneously by this way. Herein, Fe-doped Co3O4 supported Ru (Ru/FeCo) catalysts are synthesized by MSI strategies to further improve the electrocatalytic activity and stability of the catalysts. The results show that the optimized Ru/FeCo catalyst exhibits the best catalytic performance. The HER and OER tests at 10 mA/cm2 in 1 mol/L KOH solution show excellent overpotentials of 155 mV and 283 mV, respectively. The activity and stability enhancement can be attributed to the MSI that effectively modify the electronic structure and improve interfacial electron transfer between Ru and Fe-doped Co3O4 (FeCo). This work provides an innovative direction for the design of high-efficiency bifunctional electrocatalysts by virtue of the MSI.
2023, 34(9): 108095
doi: 10.1016/j.cclet.2022.108095
Abstract:
Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries (PIBs) because of their abundant, recyclable and highly customizable characteristics. However, small molecular organics are easily solubilized in organic electrolytes, resulting in a low capacity and poor stability. Herein, the folic acid-based supermolecules (SM-FAs) are successfully prepared by a hydrothermal assisted self-assembly strategy. Due to multi-locus hydrogen bonds (HBs) and the cyclized π-conjugated interactions, the structural stability of SM-FAs has been significantly improved, and the solubility in carbonate electrolytes has been effectively inhibited. As an anode for PIB, the SM-FA-6 sample exhibits a large capacity (206 mAh/g at 50 mA/g) and an outstanding cycle stability (capacity retention of 91% after 1000 cycles at 50 mA/g). More impressively, an integrative storage mechanism which combines both the general enolization reaction between C=O groups and K+, and the atypical π–K+ interaction within the assembled conjugation framework, is unraveled for potassium ion accumulation. It is envisioned that this facile self-assemble strategy opens up a promising avenue to modulate the stability of small molecular organic electrodes with enhanced storage capacity.
Organics present significant prospects as environmentally friendly and sustainable electrode materials for potassium ion batteries (PIBs) because of their abundant, recyclable and highly customizable characteristics. However, small molecular organics are easily solubilized in organic electrolytes, resulting in a low capacity and poor stability. Herein, the folic acid-based supermolecules (SM-FAs) are successfully prepared by a hydrothermal assisted self-assembly strategy. Due to multi-locus hydrogen bonds (HBs) and the cyclized π-conjugated interactions, the structural stability of SM-FAs has been significantly improved, and the solubility in carbonate electrolytes has been effectively inhibited. As an anode for PIB, the SM-FA-6 sample exhibits a large capacity (206 mAh/g at 50 mA/g) and an outstanding cycle stability (capacity retention of 91% after 1000 cycles at 50 mA/g). More impressively, an integrative storage mechanism which combines both the general enolization reaction between C=O groups and K+, and the atypical π–K+ interaction within the assembled conjugation framework, is unraveled for potassium ion accumulation. It is envisioned that this facile self-assemble strategy opens up a promising avenue to modulate the stability of small molecular organic electrodes with enhanced storage capacity.
2023, 34(9): 108100
doi: 10.1016/j.cclet.2022.108100
Abstract:
Most porous conductive frameworks are highly anisotropic in their structures thus leading to anisotropic charge transport. Here we report a supramolecular self-assembly which is constructed by intermolecular hydrogen bonding and π···π interactions. This material features a chiral, porous, cubic framework structure with π-stacked helical columns along all of the three Cartesian coordinates. As a result, isotropic charge transport with an electrical conductivity (σ) of 2.1 × 10–7 S/cm is achieved. By achieving isotropic charge transport in a π-stacked supramolecular assembly, these results provide a new type of isotropic conductive framework materials alternative to conductive metal-organic frameworks (MOFs).
Most porous conductive frameworks are highly anisotropic in their structures thus leading to anisotropic charge transport. Here we report a supramolecular self-assembly which is constructed by intermolecular hydrogen bonding and π···π interactions. This material features a chiral, porous, cubic framework structure with π-stacked helical columns along all of the three Cartesian coordinates. As a result, isotropic charge transport with an electrical conductivity (σ) of 2.1 × 10–7 S/cm is achieved. By achieving isotropic charge transport in a π-stacked supramolecular assembly, these results provide a new type of isotropic conductive framework materials alternative to conductive metal-organic frameworks (MOFs).
2023, 34(9): 108101
doi: 10.1016/j.cclet.2022.108101
Abstract:
Most catalytic processes are achieved by heating the whole reaction systems including the entire reactor, substrate and solvent, which leads to energy loss and obvious heat transfer limits. In this study, induction heating was employed to boost the catalytic Suzuki-Miyaura cross-coupling reactions by using conductive superparamagnetic microspheres with loaded Pd nanoparticles as heterogeneous catalysts. It was found that, at the same apparent reaction temperatures, the reactions by adopting the induction heating all exhibit better catalytic performance with higher conversion and yield, as compared to the reactions using conventional joule heating. The improvement is mainly attributed to the localized heating effect endowed by high efficiency of the heat transfer from the heat source to catalytic sites, which dissipates the electromagnetic energy through Néel relaxation mechanism. Moreover, it has be found that the reactions have been largely accelerated, resulting in much shorter reaction time required to approach a given value of reactant conversion. These results indicate that the unique heating method based on the superparamagnetic nanomaterials as both the inductive component and catalyst support holds a promising application for fast and efficient heterogeneous catalytic process, and exhibits potential for improving energy transfer efficiency and reducing the side reactions attributed to the uneven temperature profile.
Most catalytic processes are achieved by heating the whole reaction systems including the entire reactor, substrate and solvent, which leads to energy loss and obvious heat transfer limits. In this study, induction heating was employed to boost the catalytic Suzuki-Miyaura cross-coupling reactions by using conductive superparamagnetic microspheres with loaded Pd nanoparticles as heterogeneous catalysts. It was found that, at the same apparent reaction temperatures, the reactions by adopting the induction heating all exhibit better catalytic performance with higher conversion and yield, as compared to the reactions using conventional joule heating. The improvement is mainly attributed to the localized heating effect endowed by high efficiency of the heat transfer from the heat source to catalytic sites, which dissipates the electromagnetic energy through Néel relaxation mechanism. Moreover, it has be found that the reactions have been largely accelerated, resulting in much shorter reaction time required to approach a given value of reactant conversion. These results indicate that the unique heating method based on the superparamagnetic nanomaterials as both the inductive component and catalyst support holds a promising application for fast and efficient heterogeneous catalytic process, and exhibits potential for improving energy transfer efficiency and reducing the side reactions attributed to the uneven temperature profile.
2023, 34(9): 108127
doi: 10.1016/j.cclet.2022.108127
Abstract:
Multifunctional switchable materials are attracting tremendous interest because of their great application potential in signal processing, information encryption, and smart devices. Here, we reported an organic-inorganic hybrid thermochromic ferroelastic crystal, [TMIm][CuCl4] (TMIm = 1,1,3,3-tetramethylimidazolidinium), which undergoes two reversible phase transitions at 333 K and 419 K, respectively. Intriguingly, these three phases experience a remarkable ferroelastic-paraelastic-ferroelastic (2/m-mmm-2/m) transition, which remains relatively unexplored in ferroelastics. Moreover, the ferroelastic domains can be simultaneously switched under temperature and stress stimuli. Meanwhile, [TMIm][CuCl4] exhibits thermochromic phenomenon, endowing it with extra spectral encryption possibilities during information processing. Combined with dielectric switching behavior, [TMIm][CuCl4] are promising for practical applications in memory devices, next-generation sensors, and encryption technology.
Multifunctional switchable materials are attracting tremendous interest because of their great application potential in signal processing, information encryption, and smart devices. Here, we reported an organic-inorganic hybrid thermochromic ferroelastic crystal, [TMIm][CuCl4] (TMIm = 1,1,3,3-tetramethylimidazolidinium), which undergoes two reversible phase transitions at 333 K and 419 K, respectively. Intriguingly, these three phases experience a remarkable ferroelastic-paraelastic-ferroelastic (2/m-mmm-2/m) transition, which remains relatively unexplored in ferroelastics. Moreover, the ferroelastic domains can be simultaneously switched under temperature and stress stimuli. Meanwhile, [TMIm][CuCl4] exhibits thermochromic phenomenon, endowing it with extra spectral encryption possibilities during information processing. Combined with dielectric switching behavior, [TMIm][CuCl4] are promising for practical applications in memory devices, next-generation sensors, and encryption technology.
2023, 34(9): 108128
doi: 10.1016/j.cclet.2022.108128
Abstract:
Hydrogenation reactions play crucial roles on chemical synthesis and pollutant elimination. The improvement of the ability to activate reactants and increase of the contact probability between the catalysts and reactants are positive to improve the catalytic performance. Herein, we have reported the design of two-dimensional porous Ni-Ni3N-NiMoN heterojunction sheets (2D Mo-Ni based nanosheets) for efficient catalytic hydrogenation of the aromatic nitro-compounds. The heterojunction interfaces provide plentiful active sites to improve the activating ability of the catalyst on the reactants. Additionally, the 2D porous structure facilitates not only the contact of catalytic sites with reactants but also mass transfer and diffusion, both of which are favorable to accelerating the hydrogenation process. As a result, the optimized sample of 2D Mo-Ni sheet exhibits good activity for the hydrogenation of aromatic nitro-compounds by converting 0.2 mmol/L (30 mL) of p-nitrophenol to p-aminophenol within 45 s with good recyclability. The activation energy and the reaction rate at 25 ℃ is 31.11 kJ/mol and 0.0796 s-1, respectively, both of which surpass most of reported non-noble metal catalysts and rivals with most noble metal-based catalysts. The combination of late and early transition metals provides an innovative way to obtain outstanding catalysts for the hydrogenation.
Hydrogenation reactions play crucial roles on chemical synthesis and pollutant elimination. The improvement of the ability to activate reactants and increase of the contact probability between the catalysts and reactants are positive to improve the catalytic performance. Herein, we have reported the design of two-dimensional porous Ni-Ni3N-NiMoN heterojunction sheets (2D Mo-Ni based nanosheets) for efficient catalytic hydrogenation of the aromatic nitro-compounds. The heterojunction interfaces provide plentiful active sites to improve the activating ability of the catalyst on the reactants. Additionally, the 2D porous structure facilitates not only the contact of catalytic sites with reactants but also mass transfer and diffusion, both of which are favorable to accelerating the hydrogenation process. As a result, the optimized sample of 2D Mo-Ni sheet exhibits good activity for the hydrogenation of aromatic nitro-compounds by converting 0.2 mmol/L (30 mL) of p-nitrophenol to p-aminophenol within 45 s with good recyclability. The activation energy and the reaction rate at 25 ℃ is 31.11 kJ/mol and 0.0796 s-1, respectively, both of which surpass most of reported non-noble metal catalysts and rivals with most noble metal-based catalysts. The combination of late and early transition metals provides an innovative way to obtain outstanding catalysts for the hydrogenation.
2023, 34(9): 108130
doi: 10.1016/j.cclet.2023.108130
Abstract:
Acid-catalyzed tandem reactions were established by employing a novel class of 2-arylglycerol derivative, 5-aryl-1, 3-dioxan-5-ol, as versatile 1, 3-biselectrophile. In the reactions, 5-aryl-1, 3-dioxan-5-ol works like atropaldehydes or 2-aryl malondialdehydes, and can react with 2-naphthols and β-keto amides, allowing the synthesis of 4H-chromenes and 5-aryl-2-pyridinones. High yields, good functional group tolerance, broad substrate scope and simple reaction operation make this protocol attractive.
Acid-catalyzed tandem reactions were established by employing a novel class of 2-arylglycerol derivative, 5-aryl-1, 3-dioxan-5-ol, as versatile 1, 3-biselectrophile. In the reactions, 5-aryl-1, 3-dioxan-5-ol works like atropaldehydes or 2-aryl malondialdehydes, and can react with 2-naphthols and β-keto amides, allowing the synthesis of 4H-chromenes and 5-aryl-2-pyridinones. High yields, good functional group tolerance, broad substrate scope and simple reaction operation make this protocol attractive.
2023, 34(9): 108131
doi: 10.1016/j.cclet.2023.108131
Abstract:
The visible light induced multicomponent reaction of styrene, carbon disulfide, amine and ethyl difluorobromoacetate for the synthesis of thiodifluoroesters is disclosed. This developed protocol offers a facile and general route to access various valuable thiodifluoroesters in moderate to good yields. Preliminary mechanistic studies revealed that a radical process might be involved in this transformation.
The visible light induced multicomponent reaction of styrene, carbon disulfide, amine and ethyl difluorobromoacetate for the synthesis of thiodifluoroesters is disclosed. This developed protocol offers a facile and general route to access various valuable thiodifluoroesters in moderate to good yields. Preliminary mechanistic studies revealed that a radical process might be involved in this transformation.
2023, 34(9): 108133
doi: 10.1016/j.cclet.2023.108133
Abstract:
Multiple myeloma (MM) is the second most common hematological tumor characterized by the proliferation of monoclonal plasma cells. Melphalan (MEL) is commonly used in the treatment of MM and is especially essential for patients undergoing autologous stem cell transplantation (ASCT). Although many drugs for MM have been developed in recent years, chemotherapy followed by ASCT remains the optimal option. Melphalan, the backbone of the conditioning regimen, brings severe toxicities at a high dose. Nanodrug delivery systems enable drugs to be highly effective and have low toxicity. In this study, methoxy poly(ethylene glycol)-poly(D, L-lactide) copolymer (MPEG-PDLLA) was chosen to encapsulate melphalan, and the characteristics, effectiveness, and safety of MEL/MPEG-PDLLA in vitro and in vivo were investigated. MEL/MPEG-PDLLA showed slow release and was easily engulfed by MM cells despite a result of the antitumor assay comparable to that of free melphalan in vitro. The in vivo results showed that MEL/MPEG-PDLLA could significantly alleviate tumor burden and prolong survival time without increasing the toxicity to vital organs. In addition, MEL/MPEG-PDLLA could significantly reduce the damage to the intestinal mucosa caused by melphalan. In conclusion, MEL/MPEG-PDLLA shows improved antitumor activity and has the potential to alleviate pains of MM patients undergoing ASCT.
Multiple myeloma (MM) is the second most common hematological tumor characterized by the proliferation of monoclonal plasma cells. Melphalan (MEL) is commonly used in the treatment of MM and is especially essential for patients undergoing autologous stem cell transplantation (ASCT). Although many drugs for MM have been developed in recent years, chemotherapy followed by ASCT remains the optimal option. Melphalan, the backbone of the conditioning regimen, brings severe toxicities at a high dose. Nanodrug delivery systems enable drugs to be highly effective and have low toxicity. In this study, methoxy poly(ethylene glycol)-poly(D, L-lactide) copolymer (MPEG-PDLLA) was chosen to encapsulate melphalan, and the characteristics, effectiveness, and safety of MEL/MPEG-PDLLA in vitro and in vivo were investigated. MEL/MPEG-PDLLA showed slow release and was easily engulfed by MM cells despite a result of the antitumor assay comparable to that of free melphalan in vitro. The in vivo results showed that MEL/MPEG-PDLLA could significantly alleviate tumor burden and prolong survival time without increasing the toxicity to vital organs. In addition, MEL/MPEG-PDLLA could significantly reduce the damage to the intestinal mucosa caused by melphalan. In conclusion, MEL/MPEG-PDLLA shows improved antitumor activity and has the potential to alleviate pains of MM patients undergoing ASCT.
2023, 34(9): 108135
doi: 10.1016/j.cclet.2023.108135
Abstract:
Engineering small-molecule drugs into nanoparticulate formulations provides an unprecedented opportunity to improve the performance of traditional chemo drugs, but suffers from poor compatibility between drugs and nanocarriers. Stimuli-responsive mPEG-PDLLA–drug conjugate-based nanomedicines can facilitate the exploitation of beneficial properties of the carrier and enable the practical fabrication of highly efficacious self-assembled nanomedicines. However, the influence of hydrophobic length on the performance of this type of nanomedicine is little known. Here we synthesized two acid-sensitive ketal-linked mPEG-PDLLA–docetaxel prodrugs with different lengths of PDLLA, and engineered them into self-assembled sub-20 nm micellar nanomedicines for breast cancer chemotherapy. We found that the nanomedicine consisting of a mPEG-PDLLA–docetaxel prodrug with the shorter length of PDLLA stood out due to its potent cytotoxicity, deep penetration into multicellular spheroids, and improved in vivo anticancer performance. Additionally, our prodrug-based nanomedicines outperformed the generic formulation of commercial Nanoxel in terms of safety profile, tolerated doses, and tumor suppression. Our findings indicate that the hydrophobic content of a polymeric prodrug nanomedicine plays an important role in the performance of the nanomedicine, and should be instructive for developing polymeric prodrug-based nanomedicines with clinical translational potential.
Engineering small-molecule drugs into nanoparticulate formulations provides an unprecedented opportunity to improve the performance of traditional chemo drugs, but suffers from poor compatibility between drugs and nanocarriers. Stimuli-responsive mPEG-PDLLA–drug conjugate-based nanomedicines can facilitate the exploitation of beneficial properties of the carrier and enable the practical fabrication of highly efficacious self-assembled nanomedicines. However, the influence of hydrophobic length on the performance of this type of nanomedicine is little known. Here we synthesized two acid-sensitive ketal-linked mPEG-PDLLA–docetaxel prodrugs with different lengths of PDLLA, and engineered them into self-assembled sub-20 nm micellar nanomedicines for breast cancer chemotherapy. We found that the nanomedicine consisting of a mPEG-PDLLA–docetaxel prodrug with the shorter length of PDLLA stood out due to its potent cytotoxicity, deep penetration into multicellular spheroids, and improved in vivo anticancer performance. Additionally, our prodrug-based nanomedicines outperformed the generic formulation of commercial Nanoxel in terms of safety profile, tolerated doses, and tumor suppression. Our findings indicate that the hydrophobic content of a polymeric prodrug nanomedicine plays an important role in the performance of the nanomedicine, and should be instructive for developing polymeric prodrug-based nanomedicines with clinical translational potential.
2023, 34(9): 108139
doi: 10.1016/j.cclet.2023.108139
Abstract:
An algorithm capable of predicting and optimizing the gradient separation of LC × LC system was developed in this paper. Two groups of structural analogues, five ginsenosides as well as eight bisphenols, which were difficult to discriminate in routine analysis, were used to verify the effectiveness of the proposed algorithm in fast separation optimization. Average errors of retention times below 1% were found in the retention prediction for all types of gradient programs, implying that the theory could lead to high quality in prediction of the retention times under gradients elution. Meanwhile, 84% of relative average deviations (RADs) between the predicted peak width and the measured ones were less than 20%. The larger deviation occurred at the time when the peak appeared while the gradient of the mobile phase changed, which led the deviations increased to 20%–42%. In all, method development and optimization for LC × LC tandem system was realized by the homemade user-friendly software. The present protocol may turn on great opportunities for the convenient method development in analysis of trace structural analogues in environmental, food and biological samples.
An algorithm capable of predicting and optimizing the gradient separation of LC × LC system was developed in this paper. Two groups of structural analogues, five ginsenosides as well as eight bisphenols, which were difficult to discriminate in routine analysis, were used to verify the effectiveness of the proposed algorithm in fast separation optimization. Average errors of retention times below 1% were found in the retention prediction for all types of gradient programs, implying that the theory could lead to high quality in prediction of the retention times under gradients elution. Meanwhile, 84% of relative average deviations (RADs) between the predicted peak width and the measured ones were less than 20%. The larger deviation occurred at the time when the peak appeared while the gradient of the mobile phase changed, which led the deviations increased to 20%–42%. In all, method development and optimization for LC × LC tandem system was realized by the homemade user-friendly software. The present protocol may turn on great opportunities for the convenient method development in analysis of trace structural analogues in environmental, food and biological samples.
2023, 34(9): 108140
doi: 10.1016/j.cclet.2023.108140
Abstract:
2023, 34(9): 108141
doi: 10.1016/j.cclet.2023.108141
Abstract:
Compared with other types of breast cancer, triple-negative breast cancer (TNBC) has the characteristics of a high degree of malignancy and poor prognosis. Early diagnosis of TNBC through biological markers and timely development of effective treatment methods can reduce its mortality. Many Research experiments have confirmed that some specific miRNA expression profiles in TNBC can used as markers for early diagnosis. However, detecting the expression profiles of multiple groups of miRNAs according to traditional detection methods is complicated and consumes many samples. To address this issue, we developed a method for high-throughput, high-sensitivity quantitative detection of multiple sets of miRNAs (including miR-16, miR-21, miR-92, miR-199, and miR-342) specifically expressed in TNBC by rolling circle amplification (RCA) on fluorescence-encoded microspheres. Through the optimization of reaction system conditions, the developed method showed an extensive linear dynamic range and high sensitivity for all five miRNAs with the lowest limit of detection of 2 fmol/L. Meanwhile, this high-throughput detection method also appeared reasonable specificity. Only in the presence of a specific target miRNA, the fluorescence signal on the correspondingly encoded microspheres is significantly increased, while the fluorescence signal on other non-correspondingly encoded microspheres is almost negligible. Furthermore, this process exhibited good recovery and reproducibility in serum. The advantages of this method allow us to more conveniently obtain the expression profiles of multiple groups of TNBC-associated miRNAs, which is beneficial for the early detection of TNBC.
Compared with other types of breast cancer, triple-negative breast cancer (TNBC) has the characteristics of a high degree of malignancy and poor prognosis. Early diagnosis of TNBC through biological markers and timely development of effective treatment methods can reduce its mortality. Many Research experiments have confirmed that some specific miRNA expression profiles in TNBC can used as markers for early diagnosis. However, detecting the expression profiles of multiple groups of miRNAs according to traditional detection methods is complicated and consumes many samples. To address this issue, we developed a method for high-throughput, high-sensitivity quantitative detection of multiple sets of miRNAs (including miR-16, miR-21, miR-92, miR-199, and miR-342) specifically expressed in TNBC by rolling circle amplification (RCA) on fluorescence-encoded microspheres. Through the optimization of reaction system conditions, the developed method showed an extensive linear dynamic range and high sensitivity for all five miRNAs with the lowest limit of detection of 2 fmol/L. Meanwhile, this high-throughput detection method also appeared reasonable specificity. Only in the presence of a specific target miRNA, the fluorescence signal on the correspondingly encoded microspheres is significantly increased, while the fluorescence signal on other non-correspondingly encoded microspheres is almost negligible. Furthermore, this process exhibited good recovery and reproducibility in serum. The advantages of this method allow us to more conveniently obtain the expression profiles of multiple groups of TNBC-associated miRNAs, which is beneficial for the early detection of TNBC.
Carbon dots and polyurethane composite for photo-induced elimination of uranium under air atmosphere
2023, 34(9): 108146
doi: 10.1016/j.cclet.2023.108146
Abstract:
Uranium is the main fuel of nuclear power and elimination uranium from nuclear wastewater is significant both in environmental protection and fuel recycle. Here we report for the first time the synthesis of carbon dots/polyurethane (CDs/PU) composite materials for the photoinduced elimination of uranium from water. Irradiated with visible light, CDs/PU could eliminate uranium efficiently with the generation of (UO2)O2·2H2O as solid products in air. The further investigated mechanism showed that the addition of CDs/PU could produce more H2O2 under visible light, which reacted with uranyl ions to form (UO2)O2·2H2O. Importantly, the sponge-like CDs/PU could be easily removed from water with high reusability as the elimination efficiency remained above 95% after 5 cycles. CDs/PU also displayed good selectivity in the presence of other metal ions. Our work affords exciting strategies for developing photocatalysts and eliminating uranium from water.
Uranium is the main fuel of nuclear power and elimination uranium from nuclear wastewater is significant both in environmental protection and fuel recycle. Here we report for the first time the synthesis of carbon dots/polyurethane (CDs/PU) composite materials for the photoinduced elimination of uranium from water. Irradiated with visible light, CDs/PU could eliminate uranium efficiently with the generation of (UO2)O2·2H2O as solid products in air. The further investigated mechanism showed that the addition of CDs/PU could produce more H2O2 under visible light, which reacted with uranyl ions to form (UO2)O2·2H2O. Importantly, the sponge-like CDs/PU could be easily removed from water with high reusability as the elimination efficiency remained above 95% after 5 cycles. CDs/PU also displayed good selectivity in the presence of other metal ions. Our work affords exciting strategies for developing photocatalysts and eliminating uranium from water.
2023, 34(9): 108150
doi: 10.1016/j.cclet.2023.108150
Abstract:
Herein, copper-catalyzed 1,4-protosilylation and 1,4-protoborylation of enynic orthoesters have been developed. The enynic orthoesters as precursors of unstable enynic esters were applied to produce the functionalized 2, 3-allenoate products. Meanwhile, the asymmetric 1,4-protosilylation of enynic orthoesters with PhMe2Si-Bpin was also studied. The chiral monopyridine imidazoline ligand was efficient to provide the asymmetric 1,4-protosilylation products with high enantioselectivity.
Herein, copper-catalyzed 1,4-protosilylation and 1,4-protoborylation of enynic orthoesters have been developed. The enynic orthoesters as precursors of unstable enynic esters were applied to produce the functionalized 2, 3-allenoate products. Meanwhile, the asymmetric 1,4-protosilylation of enynic orthoesters with PhMe2Si-Bpin was also studied. The chiral monopyridine imidazoline ligand was efficient to provide the asymmetric 1,4-protosilylation products with high enantioselectivity.
2023, 34(9): 108151
doi: 10.1016/j.cclet.2023.108151
Abstract:
Li metal is considered an ideal anode material because of its high theoretical capacity and low electrode potential. However, the practical usage of Li metal as an anode is severely limited because of inevitable parasitic side reactions with electrolyte and dendrites formation. At present, single-component artificial solid electrolyte interphase cannot simultaneously meet the multiple functions of promoting ion conduction, guiding lithium ion deposition, inhibiting dendrite growth, and reducing interface side reactions. Therefore, multi-component design on Li metal surface is widely investigated to achieve long-term cycling. Herein, we report a Li2Ga-carbonate polymer interphase layer to solve volume changes, Li dendrites formation and side-reactions. As a result, the Li symmetric cell can be stabilized at 3.0 mA/cm2 in carbonate electrolyte with limited volume of 20 µL. Coupled with 13.6 mg/cm2 (loading of 2 mAh/cm2) LiFePO4 cathode, discharge capacity retains at 90% for over 150 cycles under limited electrolyte conditions. With such an alloy-polymer interphase layer, higher energy density Li metal batteries become prominent in the near future.
Li metal is considered an ideal anode material because of its high theoretical capacity and low electrode potential. However, the practical usage of Li metal as an anode is severely limited because of inevitable parasitic side reactions with electrolyte and dendrites formation. At present, single-component artificial solid electrolyte interphase cannot simultaneously meet the multiple functions of promoting ion conduction, guiding lithium ion deposition, inhibiting dendrite growth, and reducing interface side reactions. Therefore, multi-component design on Li metal surface is widely investigated to achieve long-term cycling. Herein, we report a Li2Ga-carbonate polymer interphase layer to solve volume changes, Li dendrites formation and side-reactions. As a result, the Li symmetric cell can be stabilized at 3.0 mA/cm2 in carbonate electrolyte with limited volume of 20 µL. Coupled with 13.6 mg/cm2 (loading of 2 mAh/cm2) LiFePO4 cathode, discharge capacity retains at 90% for over 150 cycles under limited electrolyte conditions. With such an alloy-polymer interphase layer, higher energy density Li metal batteries become prominent in the near future.
2023, 34(9): 108154
doi: 10.1016/j.cclet.2023.108154
Abstract:
Fluorescence-guided surgery calls for development of near-infrared fluorophores. Despite the wide-spread application and a safe clinical record of Indocyanine Green (ICG), its maximal absorption wavelength at 780 nm is rather short and longer-wavelength dyes are desired to exploit such benefits as low photo-toxicity and deep penetration depth. Here, we report ECY, a stable deep near-infrared (NIR) fluorochromic scaffold absorbing/emitting at 836/871 nm with a fluorescence quantum yield of 16% in CH2Cl2. ECY was further rationally engineered for biological distribution specificity. Analogous bearing different numbers of sulfonate group or a polyethylene glycol chain were synthesized. By screening this focused library upon intravenous injection to BALB/c mice, ECYS2 was identified to be a suitable candidate for bioimaging of organs involved in hepatobiliary excretion, and ECYPEG was found to be a superior candidate for vasculature imaging. They have potentials in intraoperative imaging.
Fluorescence-guided surgery calls for development of near-infrared fluorophores. Despite the wide-spread application and a safe clinical record of Indocyanine Green (ICG), its maximal absorption wavelength at 780 nm is rather short and longer-wavelength dyes are desired to exploit such benefits as low photo-toxicity and deep penetration depth. Here, we report ECY, a stable deep near-infrared (NIR) fluorochromic scaffold absorbing/emitting at 836/871 nm with a fluorescence quantum yield of 16% in CH2Cl2. ECY was further rationally engineered for biological distribution specificity. Analogous bearing different numbers of sulfonate group or a polyethylene glycol chain were synthesized. By screening this focused library upon intravenous injection to BALB/c mice, ECYS2 was identified to be a suitable candidate for bioimaging of organs involved in hepatobiliary excretion, and ECYPEG was found to be a superior candidate for vasculature imaging. They have potentials in intraoperative imaging.
2023, 34(9): 108155
doi: 10.1016/j.cclet.2023.108155
Abstract:
Developing multiplex sensing technique is of great significance for fast sample analysis. However, the broad emissions of most chemiluminescence (CL) luminophores make the multiplex CL analysis be difficult. In this work, a simple and sensitive CL analytical method has been developed for the simultaneous determination of Tb3+ and Eu3+ thanking to their narrow band emission. The technique was based on a mixed CL system of periodate (IO4−)-hydrogen peroxide (H2O2)-rare earth complexes, in which the reactive oxygen species (ROSs) especially singlet oxygen (1O2) can transfer its energy to the complex of Tb3+/Eu3+-ethylenediaminetetraacetic acid disodium salt (EDTA) and then produce the characteristic emissions of Tb3+ and Eu3+ without cross-interference. The further experiment found that the CL emissions of Tb3+ and Eu3+ could be catalyzed by the gold nanoparticles (AuNPs) via enhancing the yield of 1O2. The CL intensities of Tb3+ (at 490 nm) and Eu3+ (at 620 nm) increased linearly with concentration of Tb3+ and Eu3+. After the optimization of the CL sensing conditions, the limits of detection (LOD) were 5.0 × 10−9 mol/L and 8.0 × 10−7 mol/L for Tb3+ and Eu3+, respectively. Finally, the method has been applied for measuring the contents of Tb3+ and Eu3+ in leaching solution of mine sample and Tb3+/Eu3+-contained nanomaterials with satisfactory results. The present system provides a new CL technique for multiplex sensing with simplicity and high sensitivity.
Developing multiplex sensing technique is of great significance for fast sample analysis. However, the broad emissions of most chemiluminescence (CL) luminophores make the multiplex CL analysis be difficult. In this work, a simple and sensitive CL analytical method has been developed for the simultaneous determination of Tb3+ and Eu3+ thanking to their narrow band emission. The technique was based on a mixed CL system of periodate (IO4−)-hydrogen peroxide (H2O2)-rare earth complexes, in which the reactive oxygen species (ROSs) especially singlet oxygen (1O2) can transfer its energy to the complex of Tb3+/Eu3+-ethylenediaminetetraacetic acid disodium salt (EDTA) and then produce the characteristic emissions of Tb3+ and Eu3+ without cross-interference. The further experiment found that the CL emissions of Tb3+ and Eu3+ could be catalyzed by the gold nanoparticles (AuNPs) via enhancing the yield of 1O2. The CL intensities of Tb3+ (at 490 nm) and Eu3+ (at 620 nm) increased linearly with concentration of Tb3+ and Eu3+. After the optimization of the CL sensing conditions, the limits of detection (LOD) were 5.0 × 10−9 mol/L and 8.0 × 10−7 mol/L for Tb3+ and Eu3+, respectively. Finally, the method has been applied for measuring the contents of Tb3+ and Eu3+ in leaching solution of mine sample and Tb3+/Eu3+-contained nanomaterials with satisfactory results. The present system provides a new CL technique for multiplex sensing with simplicity and high sensitivity.
2023, 34(9): 108160
doi: 10.1016/j.cclet.2023.108160
Abstract:
An amphiphilic AIE photosensitizer has been successfully developed, which allows for easily inserting into the bacterial membranes. Binding experiments with phospholipid preliminary demonstrates its membrane specificity. As expected, it is proved to possess a broad-spectrum bacterial staining performance and photodynamic antibacterial activity toward S. aureus and E. coli.
An amphiphilic AIE photosensitizer has been successfully developed, which allows for easily inserting into the bacterial membranes. Binding experiments with phospholipid preliminary demonstrates its membrane specificity. As expected, it is proved to possess a broad-spectrum bacterial staining performance and photodynamic antibacterial activity toward S. aureus and E. coli.
2023, 34(9): 108161
doi: 10.1016/j.cclet.2023.108161
Abstract:
Glycolysis inhibition can effectively block the energy supply and interrupt tumorigenesis in many types of cancers. However, when glycolysis is inhibited, tumor cells will break down glutamine as the raw material for the replenishment pathway to maintain the tricarboxylic acid cycle ensuring energy supply, therefore inducing ineffective interruption of metabolic. Herein, we designed glutamine transporter antagonist l-γ-glutamyl-p-nitroanilide (GPNA) loaded and 4T1 cancer cell membrane coated iridium oxide nanoparticles (IrO2-GPNA@CCM) to realize a comprehensive inhibition of tumor energy supply which synergistically mediated by glycolysis and glutamine cycle. IrO2 NPs were used to catalyze the O2 generation by facilitating the decomposition of endogenous H2O2 in tumor cells, which further downregulated the expression of HIF-1α and PI3K/pAKT to interrupt the generation of lactate. Meanwhile, the loaded GPNA was released under NIR irradiation to bind to alanine-serine-cysteine transporter (ASCT2) for glutamine uptake suppression, therefore realizing the comprehensive dysfunction of cell metabolism. Moreover, both in vitro and in vivo results convinced the thorough energy inhibition effect based on IrO2-GPNA@CCM NPs, which provided an inspiring strategy for future construction of tumor therapeutic regimen.
Glycolysis inhibition can effectively block the energy supply and interrupt tumorigenesis in many types of cancers. However, when glycolysis is inhibited, tumor cells will break down glutamine as the raw material for the replenishment pathway to maintain the tricarboxylic acid cycle ensuring energy supply, therefore inducing ineffective interruption of metabolic. Herein, we designed glutamine transporter antagonist l-γ-glutamyl-p-nitroanilide (GPNA) loaded and 4T1 cancer cell membrane coated iridium oxide nanoparticles (IrO2-GPNA@CCM) to realize a comprehensive inhibition of tumor energy supply which synergistically mediated by glycolysis and glutamine cycle. IrO2 NPs were used to catalyze the O2 generation by facilitating the decomposition of endogenous H2O2 in tumor cells, which further downregulated the expression of HIF-1α and PI3K/pAKT to interrupt the generation of lactate. Meanwhile, the loaded GPNA was released under NIR irradiation to bind to alanine-serine-cysteine transporter (ASCT2) for glutamine uptake suppression, therefore realizing the comprehensive dysfunction of cell metabolism. Moreover, both in vitro and in vivo results convinced the thorough energy inhibition effect based on IrO2-GPNA@CCM NPs, which provided an inspiring strategy for future construction of tumor therapeutic regimen.
2023, 34(9): 108166
doi: 10.1016/j.cclet.2023.108166
Abstract:
In this study, two novel spherical/hollow metal-organic frameworks were successfully synthesized, and further modified by a mild non-covalent modification strategy with dopamine and 1, 4-benzenedithiol (BDT) as polymeric monomers to obtain pBDT@PDA-Ni-MOF and pBDT@PDA-Ni/Co-MOF, respectively. The results showed that the above MOFs possessed extremely fast adsorption rates and ideal adsorption capacities for sulfonamides (SAs) and the modified MOFs exhibited enhanced adsorption capacities for SAs owing to a large number of additional functional groups. Then, benefit of their regular morphology and size, a facile syringe-assisted dispersive solid phase extraction (S-DSPE) method was developed for efficient detection of SAs, which will provide a powerful tool for monitoring trace level of SAs in aqueous environment.
In this study, two novel spherical/hollow metal-organic frameworks were successfully synthesized, and further modified by a mild non-covalent modification strategy with dopamine and 1, 4-benzenedithiol (BDT) as polymeric monomers to obtain pBDT@PDA-Ni-MOF and pBDT@PDA-Ni/Co-MOF, respectively. The results showed that the above MOFs possessed extremely fast adsorption rates and ideal adsorption capacities for sulfonamides (SAs) and the modified MOFs exhibited enhanced adsorption capacities for SAs owing to a large number of additional functional groups. Then, benefit of their regular morphology and size, a facile syringe-assisted dispersive solid phase extraction (S-DSPE) method was developed for efficient detection of SAs, which will provide a powerful tool for monitoring trace level of SAs in aqueous environment.
2023, 34(9): 108167
doi: 10.1016/j.cclet.2023.108167
Abstract:
The precise synthesis of polymer with narrow molecular weight distribution (Đ) and well-defined architectures is very essential to exploring the functions and properties of polymer materials. Here, a universal polymerization method capable of low Đ and reactive hydrogen compatibility is reported by introducing super-Grignard reagents (R2Mg·LiCl) into polymer chemistry. Under mild conditions, various monomers, including nonpolar polystyrene and 4-methoxystyrene that cannot be initiated by Grignard reagents, and polar methacrylate, are successfully polymerized with full monomer conversion and low Đ. This approach is amenable to wide varieties of initiators, polymerization temperature, and feed ratio, which makes it attractive for applications in polymer synthesis. By adding methanol and water during the polymerization process, the reactive hydrogen compatibility of this method is confirmed, which makes this method avoid the rigorous restriction on polymerization conditions of anionic polymerization. Moreover, chain extension polymerization and block copolymerization are achieved and demonstrate the livingness of chain propagation, enabling the facile synthesis of well-defined macromolecular architectures. This work therefore expands the methodology libraries of living polymerization, which may cause inspirations to polymer science.
The precise synthesis of polymer with narrow molecular weight distribution (Đ) and well-defined architectures is very essential to exploring the functions and properties of polymer materials. Here, a universal polymerization method capable of low Đ and reactive hydrogen compatibility is reported by introducing super-Grignard reagents (R2Mg·LiCl) into polymer chemistry. Under mild conditions, various monomers, including nonpolar polystyrene and 4-methoxystyrene that cannot be initiated by Grignard reagents, and polar methacrylate, are successfully polymerized with full monomer conversion and low Đ. This approach is amenable to wide varieties of initiators, polymerization temperature, and feed ratio, which makes it attractive for applications in polymer synthesis. By adding methanol and water during the polymerization process, the reactive hydrogen compatibility of this method is confirmed, which makes this method avoid the rigorous restriction on polymerization conditions of anionic polymerization. Moreover, chain extension polymerization and block copolymerization are achieved and demonstrate the livingness of chain propagation, enabling the facile synthesis of well-defined macromolecular architectures. This work therefore expands the methodology libraries of living polymerization, which may cause inspirations to polymer science.
2023, 34(9): 108178
doi: 10.1016/j.cclet.2023.108178
Abstract:
We report here a generic, green synthesis of 17 valuable syn-aryl-(2S,3R)-2–chloro-3–hydroxy esters (syn-(2S,3R)-1) in 73%-99% isolated yields along with 6.1:1–83:1 dr and 31%~ > 99% ee, through dynamic reductive kinetic resolution of racemic aryl α–chloro β-keto esters (2) catalyzed by an engineered ketoreductase which was obtained via epPCR-based directed evolution. The hectogram scale synthesis of syn-(2S,3R)-1b at a substrate concentration of 120 g/L showcased the application potential of the biocatalytic method developed presently.
We report here a generic, green synthesis of 17 valuable syn-aryl-(2S,3R)-2–chloro-3–hydroxy esters (syn-(2S,3R)-1) in 73%-99% isolated yields along with 6.1:1–83:1 dr and 31%~ > 99% ee, through dynamic reductive kinetic resolution of racemic aryl α–chloro β-keto esters (2) catalyzed by an engineered ketoreductase which was obtained via epPCR-based directed evolution. The hectogram scale synthesis of syn-(2S,3R)-1b at a substrate concentration of 120 g/L showcased the application potential of the biocatalytic method developed presently.
2023, 34(9): 108192
doi: 10.1016/j.cclet.2023.108192
Abstract:
Macromolecular drugs have attracted great interest as biotherapy to cure previously untreatable diseases. For clinical translation, biomacromolecules encounter several common druggability difficulties, such as in vivo instability and poor penetration to cross physiologic barriers, thus requiring sophisticated systems for drug delivery. Inspired by the natural biomineralization via interaction between inorganic ions and biomacromolecules, herein we rationally screened biocompatible transition metals to biomineralize with carbonate for macromolecules loading. Among the metal ions, Cu2+ was found to be the best candidate, and its superiority over the widely studied Ca2+ minerals was also demonstrated. Capitalized on this finding, copper carbonate nanoparticles were prepared via a simple mixing process to co-load glucose oxidase (GOx) and a HIF-α DNAzyme (DZ), achieving ultra-high loading capacity of 61%. Upon encapsulation into nanoparticles, enzymatic activity of both drugs was passivated to avoid potential side-effects during circulation, while the drugs could be rapidly released within 1 h in response to acidic pH to fully recover their activities. The nanoparticles could accumulate into tumor via intravenous injection, facilitate the cell membrane penetration, and release the payloads of GOx, DZ and Cu2+ inside cells to exert a series of anti-tumor effects. GOx caused tumor starvation by catalytic glucose consumption, and the concomitantly generated H2O2 byproduct boosted the Cu2+-mediated chemodynamic therapy (CDT). Meanwhile, the DZ silenced HIF-α expression to sensitize both starvation therapy and CDT. As a result, a synergistic tumor growth inhibition was achieved. This work provides a simple method to prepare biomineralized nanoparticles, and offers a general approach for macromolecular drugs delivery via Cu2+-based biomineralization.
Macromolecular drugs have attracted great interest as biotherapy to cure previously untreatable diseases. For clinical translation, biomacromolecules encounter several common druggability difficulties, such as in vivo instability and poor penetration to cross physiologic barriers, thus requiring sophisticated systems for drug delivery. Inspired by the natural biomineralization via interaction between inorganic ions and biomacromolecules, herein we rationally screened biocompatible transition metals to biomineralize with carbonate for macromolecules loading. Among the metal ions, Cu2+ was found to be the best candidate, and its superiority over the widely studied Ca2+ minerals was also demonstrated. Capitalized on this finding, copper carbonate nanoparticles were prepared via a simple mixing process to co-load glucose oxidase (GOx) and a HIF-α DNAzyme (DZ), achieving ultra-high loading capacity of 61%. Upon encapsulation into nanoparticles, enzymatic activity of both drugs was passivated to avoid potential side-effects during circulation, while the drugs could be rapidly released within 1 h in response to acidic pH to fully recover their activities. The nanoparticles could accumulate into tumor via intravenous injection, facilitate the cell membrane penetration, and release the payloads of GOx, DZ and Cu2+ inside cells to exert a series of anti-tumor effects. GOx caused tumor starvation by catalytic glucose consumption, and the concomitantly generated H2O2 byproduct boosted the Cu2+-mediated chemodynamic therapy (CDT). Meanwhile, the DZ silenced HIF-α expression to sensitize both starvation therapy and CDT. As a result, a synergistic tumor growth inhibition was achieved. This work provides a simple method to prepare biomineralized nanoparticles, and offers a general approach for macromolecular drugs delivery via Cu2+-based biomineralization.
2023, 34(9): 108196
doi: 10.1016/j.cclet.2023.108196
Abstract:
Photocatalytic dual-functional reaction under visible light irradiation represents a sustainable development strategy. In detail, H2 production coupled with benzylamine oxidation can remarkably lower the cost by replacing sacrificial agents. In this work, CdS quantum dots (CdS QDs) were successfully loaded onto the surface of a porphyrinic metal-organic framework (Pd-PCN-222) by the electrostatic self-assembly at room temperature. The consequent Pd-PCN-222/CdS heterojunction composites displayed superb photocatalytic activity under visible light irradiation, achieving a H2 production and benzylamine oxidation rate of 5069 and 3717 µmol g−1 h−1 with > 99% selectivity in 3 h. There is no noticeable loss of catalytic capability during three successive runs. Mechanistic studies by in situ electron spin resonance and X-ray photoelectron spectroscopy disclosed that CdS QDs injected photoexcited electrons to Pd-PCN-222 and then Zr6 clusters under visible-light irradiation, and thus CdS QDs and Zr6 clusters behave as the photocatalytic oxidation and reduction centers, respectively.
Photocatalytic dual-functional reaction under visible light irradiation represents a sustainable development strategy. In detail, H2 production coupled with benzylamine oxidation can remarkably lower the cost by replacing sacrificial agents. In this work, CdS quantum dots (CdS QDs) were successfully loaded onto the surface of a porphyrinic metal-organic framework (Pd-PCN-222) by the electrostatic self-assembly at room temperature. The consequent Pd-PCN-222/CdS heterojunction composites displayed superb photocatalytic activity under visible light irradiation, achieving a H2 production and benzylamine oxidation rate of 5069 and 3717 µmol g−1 h−1 with > 99% selectivity in 3 h. There is no noticeable loss of catalytic capability during three successive runs. Mechanistic studies by in situ electron spin resonance and X-ray photoelectron spectroscopy disclosed that CdS QDs injected photoexcited electrons to Pd-PCN-222 and then Zr6 clusters under visible-light irradiation, and thus CdS QDs and Zr6 clusters behave as the photocatalytic oxidation and reduction centers, respectively.
2023, 34(9): 108197
doi: 10.1016/j.cclet.2023.108197
Abstract:
Applying the fluorescent carbon dots as smart materials in anticancer therapy is of great interest. However, carbon dots for multimodal synergistic anticancer therapy, especially for the triple modality, is rarely reported. Herein, we successfully synthesized OCDs by citric acid and (1R, 2S)-2-amino-1,2-diphenylethan-1-ol, which show aggregation-induced emission property and two-photon fluorescence imaging. Meanwhile, OCDs are ideal photosensitizers for photothermal therapy under 808 nm and Type Ⅰ photodynamic therapy with white light. Hydroxyl radicals, generated by Type Ⅰ photodynamic therapy based on OCDs can transform protumoral M2 macrophages into antitumoral M1 macrophages, which exhibited immunotherapy ability. The synergism trimodal of OCDs results in potent anticancer efficacy, showing great potential in cancer therapy.
Applying the fluorescent carbon dots as smart materials in anticancer therapy is of great interest. However, carbon dots for multimodal synergistic anticancer therapy, especially for the triple modality, is rarely reported. Herein, we successfully synthesized OCDs by citric acid and (1R, 2S)-2-amino-1,2-diphenylethan-1-ol, which show aggregation-induced emission property and two-photon fluorescence imaging. Meanwhile, OCDs are ideal photosensitizers for photothermal therapy under 808 nm and Type Ⅰ photodynamic therapy with white light. Hydroxyl radicals, generated by Type Ⅰ photodynamic therapy based on OCDs can transform protumoral M2 macrophages into antitumoral M1 macrophages, which exhibited immunotherapy ability. The synergism trimodal of OCDs results in potent anticancer efficacy, showing great potential in cancer therapy.
2023, 34(9): 108223
doi: 10.1016/j.cclet.2023.108223
Abstract:
Forming J-aggregates by organic monomer is a fascinating strategy to urge spectroscopic redshift with respect to that of the monomer. Herein, we designed 1,7-diphenyl-substituted meso–CF3-BDP monomer confirmed by X-ray crystallographic analysis. The low-barrier rotation of the –CF3 group in meso–CF3-BDP 1 significantly enhances the non-radiative efficiency, and the photothermal conversion efficiency (PCE) of the self-assembled nanoparticles (1-NPs: λabs = 746 nm) by J-aggregates was 82%. 1-NPs could effectively block cell cycle progression, inhibit cancer cell proliferation and trigger cell apoptosis under low power laser irradiation (0.2 W/cm2). This study proposes an alternate molecular design platform by J-aggregates to promote PCE through the insertion of rotating segment and trigger the cancer cells apoptosis in photothermal therapy at low power laser density.
Forming J-aggregates by organic monomer is a fascinating strategy to urge spectroscopic redshift with respect to that of the monomer. Herein, we designed 1,7-diphenyl-substituted meso–CF3-BDP monomer confirmed by X-ray crystallographic analysis. The low-barrier rotation of the –CF3 group in meso–CF3-BDP 1 significantly enhances the non-radiative efficiency, and the photothermal conversion efficiency (PCE) of the self-assembled nanoparticles (1-NPs: λabs = 746 nm) by J-aggregates was 82%. 1-NPs could effectively block cell cycle progression, inhibit cancer cell proliferation and trigger cell apoptosis under low power laser irradiation (0.2 W/cm2). This study proposes an alternate molecular design platform by J-aggregates to promote PCE through the insertion of rotating segment and trigger the cancer cells apoptosis in photothermal therapy at low power laser density.
2023, 34(9): 108229
doi: 10.1016/j.cclet.2023.108229
Abstract:
The misuse of antibiotics and oxygen-lacking in aquaculture causes serious water environmental problems. Herein, a piezoelectic odd-layered MoS2 is prepared and applied to piezo-catalytic remove tinidazole (TNZ) and other antibiotic pollutants with aeration as a piezo-driving force. About 89.6% of TNZ can be degraded by MoS2 under aeration in the presence of dissolved oxygen with a reaction rate constant of 0.15 min−1, which is 2.4 times higher than that under N2 atmosphere and quiescence conditions. Quenching experiments and electron paramagnetic resonance (EPR) tests identify that singlet oxygen (1O2) and superoxide radical (O2•−) are dominant reactive oxygen species in MoS2/aeration system. These results demonstrate that MoS2 can trigger a piezoelectric effect and produce charge carriers to generate reactive oxygen species with dissolved oxygen (DO) for contaminant degradation with the turbulence and water bubbles rupture driven by aeration.
The misuse of antibiotics and oxygen-lacking in aquaculture causes serious water environmental problems. Herein, a piezoelectic odd-layered MoS2 is prepared and applied to piezo-catalytic remove tinidazole (TNZ) and other antibiotic pollutants with aeration as a piezo-driving force. About 89.6% of TNZ can be degraded by MoS2 under aeration in the presence of dissolved oxygen with a reaction rate constant of 0.15 min−1, which is 2.4 times higher than that under N2 atmosphere and quiescence conditions. Quenching experiments and electron paramagnetic resonance (EPR) tests identify that singlet oxygen (1O2) and superoxide radical (O2•−) are dominant reactive oxygen species in MoS2/aeration system. These results demonstrate that MoS2 can trigger a piezoelectric effect and produce charge carriers to generate reactive oxygen species with dissolved oxygen (DO) for contaminant degradation with the turbulence and water bubbles rupture driven by aeration.
2023, 34(9): 108335
doi: 10.1016/j.cclet.2023.108335
Abstract:
Herein, we report an efficient photochemical method for the synthesis of poly-substituted pyrazoles through a multicomponent reaction of acceptor-only diazoalkanes, alkynes, and solvents (cyclic ethers or nitriles). The key to this success was driven by the photolysis of acceptor-only diazoalkanes to form free carbene species and the fast in situ [3 + 2]-cycloaddition formation of nucleophilic NH pyrazole derivatives. This work also serves as an entry to allow future reaction design on the combination of carbene reactivity of diazoalkanes with their other reaction modes.
Herein, we report an efficient photochemical method for the synthesis of poly-substituted pyrazoles through a multicomponent reaction of acceptor-only diazoalkanes, alkynes, and solvents (cyclic ethers or nitriles). The key to this success was driven by the photolysis of acceptor-only diazoalkanes to form free carbene species and the fast in situ [3 + 2]-cycloaddition formation of nucleophilic NH pyrazole derivatives. This work also serves as an entry to allow future reaction design on the combination of carbene reactivity of diazoalkanes with their other reaction modes.
2023, 34(9): 108344
doi: 10.1016/j.cclet.2023.108344
Abstract:
Photothermal therapy (PTT) induces thermoresistance through cellular heat shock response, which impairs the therapeutic efficacy of the PTT. To resolve this problem, we developed a photothermal theranostics (denoted as PMH), which integrated the photothermal conversion agent of PdMo bimetallene with histone deacetylase 6 (HDAC6) selected inhibitor (ACY-1215), showing the synergistic antitumor effect both in vitro and in vivo. Mechanistically, under the photoacoustic imaging (PA) navigation, the released ACY-1215 triggered by NIR laser irradiation decrease the heat shock proteins (HSPs) expression and weaken the HDAC6-regulated HSP90 deacetylation, thus hindering the degradation of PTT-induced misfolded or unfold proteins through proteasome dependent pathway. Moreover, mild photothermal therapy (mPTT) treatment compromised the autophagy, which induced by HDAC6 inhibition, leading to mPTT-induced misfolded or unfold proteins further accumulation. Given that inhibition of HDAC6 plus mPTT contribute to tumor eradication. This study develops a promising combination strategy based on mPTT for future cancer treatment.
Photothermal therapy (PTT) induces thermoresistance through cellular heat shock response, which impairs the therapeutic efficacy of the PTT. To resolve this problem, we developed a photothermal theranostics (denoted as PMH), which integrated the photothermal conversion agent of PdMo bimetallene with histone deacetylase 6 (HDAC6) selected inhibitor (ACY-1215), showing the synergistic antitumor effect both in vitro and in vivo. Mechanistically, under the photoacoustic imaging (PA) navigation, the released ACY-1215 triggered by NIR laser irradiation decrease the heat shock proteins (HSPs) expression and weaken the HDAC6-regulated HSP90 deacetylation, thus hindering the degradation of PTT-induced misfolded or unfold proteins through proteasome dependent pathway. Moreover, mild photothermal therapy (mPTT) treatment compromised the autophagy, which induced by HDAC6 inhibition, leading to mPTT-induced misfolded or unfold proteins further accumulation. Given that inhibition of HDAC6 plus mPTT contribute to tumor eradication. This study develops a promising combination strategy based on mPTT for future cancer treatment.
2023, 34(9): 108413
doi: 10.1016/j.cclet.2023.108413
Abstract:
Bioorthogonal reactions can take place in biological environments without interfering with biochemical processes. In this study, Pd(PPh3)2Cl2 was used as a bioorthogonal catalyst to in situ transform the stable N-heterocyclic carbene (NHC)-gold(I)-alkyne complex 5 to its active species which can effectively inhibit thioredoxin reductase (TrxR) and exhibit significant anticancer bioactivity in hepatocellular carcinoma (HCC).
Bioorthogonal reactions can take place in biological environments without interfering with biochemical processes. In this study, Pd(PPh3)2Cl2 was used as a bioorthogonal catalyst to in situ transform the stable N-heterocyclic carbene (NHC)-gold(I)-alkyne complex 5 to its active species which can effectively inhibit thioredoxin reductase (TrxR) and exhibit significant anticancer bioactivity in hepatocellular carcinoma (HCC).
2023, 34(9): 108621
doi: 10.1016/j.cclet.2023.108621
Abstract:
A phytochemical investigation on Isodon flavidus led to the isolation of flavidanolide A (1), a rearranged diterpenoid featuring a six/seven/five-membered tricyclic skeleton, together with flavidanolide B (2), an uncommon heterodimeric diterpenoid consisting of a norabietane and a seco-isopimarane monomeric units. Their structures were elucidated by extensive spectroscopic data and single-crystal X-ray diffraction analyses. Their plausible biosynthetic routes were also proposed. In the bioassay, flavidanolide B was found to exhibit good inhibitory effect against lipopolysaccharide (LPS)-induced nitric oxide (NO) production in RAW264.7 cells comparable to positive control pyrrolidinedithiocarbamate ammonium (PDTC), which provided evidence for the medicinal value of I. flavidus as a folk medicine for treating inflammatory diseases.
A phytochemical investigation on Isodon flavidus led to the isolation of flavidanolide A (1), a rearranged diterpenoid featuring a six/seven/five-membered tricyclic skeleton, together with flavidanolide B (2), an uncommon heterodimeric diterpenoid consisting of a norabietane and a seco-isopimarane monomeric units. Their structures were elucidated by extensive spectroscopic data and single-crystal X-ray diffraction analyses. Their plausible biosynthetic routes were also proposed. In the bioassay, flavidanolide B was found to exhibit good inhibitory effect against lipopolysaccharide (LPS)-induced nitric oxide (NO) production in RAW264.7 cells comparable to positive control pyrrolidinedithiocarbamate ammonium (PDTC), which provided evidence for the medicinal value of I. flavidus as a folk medicine for treating inflammatory diseases.
2023, 34(9): 108094
doi: 10.1016/j.cclet.2022.108094
Abstract:
Organic field-effect transistors (OFETs) refer to field-effect transistors that use organic semiconductors as channel materials. Owing to the advantages of organic materials such as solution processability and intrinsic flexibility, OFETs are expected to be applicable in emergent technologies including wearable electronics and sensors, flexible displays, internet-of-things, neuromorphic computing, etc. Improving the electrical performance and developing multifunctionalities of OFETs are two major and closely relevant aspects for OFETs-related research. The former one aims for investigating the device physics and expanding the horizons of OFETs, while the later one is critical for leading OFETs into practical and emergent applications. The development in each of the two aspects would undoubtfully promote the other and bring more confidence for future development of OFETs. Hence, this review is divided into two parts that respectively summarize the recent progress in high-performance OFETs and multifunctional OFETs.
Organic field-effect transistors (OFETs) refer to field-effect transistors that use organic semiconductors as channel materials. Owing to the advantages of organic materials such as solution processability and intrinsic flexibility, OFETs are expected to be applicable in emergent technologies including wearable electronics and sensors, flexible displays, internet-of-things, neuromorphic computing, etc. Improving the electrical performance and developing multifunctionalities of OFETs are two major and closely relevant aspects for OFETs-related research. The former one aims for investigating the device physics and expanding the horizons of OFETs, while the later one is critical for leading OFETs into practical and emergent applications. The development in each of the two aspects would undoubtfully promote the other and bring more confidence for future development of OFETs. Hence, this review is divided into two parts that respectively summarize the recent progress in high-performance OFETs and multifunctional OFETs.
2023, 34(9): 108137
doi: 10.1016/j.cclet.2023.108137
Abstract:
Ultrasonography is an important complement to clinical diagnosis, and the application of microbubbles effectively improved diagnostic accuracy in echography. In scientific research, the sizes of microbubbles range from nanometers to microns. By optimizing the fabrication process, bubble sizes and ultrasound parameters, microbubbles can also be used for drug delivery and therapeutic monitoring. In this review, we summarize the recent advances in the diagnosis and treatment of microbubbles according to their different components. Modification of microbubble shells allows for more accurate imaging and detection and the combined utilization of US-targeted MB destruction (UTMD) allows for non-invasive, precise and targeted delivery of drug molecules to pathological tissues. These features pave the way for the emerge of theranostic microbubbles by combination of functional compositions and the application of multifunctional materials. Theranostic microbubbles allow for the simultaneous process of diagnosis, visualization of drug delivery and therapeutic monitoring. Ultimately, theranostic microbubbles are promising in clinical practice and would enhance contrast-enhanced US (CEUS) to a new qualitative level.
Ultrasonography is an important complement to clinical diagnosis, and the application of microbubbles effectively improved diagnostic accuracy in echography. In scientific research, the sizes of microbubbles range from nanometers to microns. By optimizing the fabrication process, bubble sizes and ultrasound parameters, microbubbles can also be used for drug delivery and therapeutic monitoring. In this review, we summarize the recent advances in the diagnosis and treatment of microbubbles according to their different components. Modification of microbubble shells allows for more accurate imaging and detection and the combined utilization of US-targeted MB destruction (UTMD) allows for non-invasive, precise and targeted delivery of drug molecules to pathological tissues. These features pave the way for the emerge of theranostic microbubbles by combination of functional compositions and the application of multifunctional materials. Theranostic microbubbles allow for the simultaneous process of diagnosis, visualization of drug delivery and therapeutic monitoring. Ultimately, theranostic microbubbles are promising in clinical practice and would enhance contrast-enhanced US (CEUS) to a new qualitative level.
2023, 34(9): 108156
doi: 10.1016/j.cclet.2023.108156
Abstract:
Hydrogen evolution from water electrolysis has become an important reaction for the green energy revolution. Traditional precious metals and their compounds are excellent catalysts for producing hydrogen; however, their high cost limits their large-scale practical application. Therefore, the development of affordable electrocatalysts to replace these precious metals is important. Transition metal phosphides (TMPs) have shown remarkable performance for hydrogen evolution and garnered considerable interest in the field of electrolysis. Based on the detailed introduction of TMPs in previous studies, we have systematically summarized the preparation methods, improvement methods, and development opportunities of TMPs and proposed “stimulatory factors” as a fundamental factor affecting the performance of TMPs herein. As the core of this research, “stimulatory factors” can provide numerous solutions to improve the performance of TMP materials and provide a good starting point for TMP research.
Hydrogen evolution from water electrolysis has become an important reaction for the green energy revolution. Traditional precious metals and their compounds are excellent catalysts for producing hydrogen; however, their high cost limits their large-scale practical application. Therefore, the development of affordable electrocatalysts to replace these precious metals is important. Transition metal phosphides (TMPs) have shown remarkable performance for hydrogen evolution and garnered considerable interest in the field of electrolysis. Based on the detailed introduction of TMPs in previous studies, we have systematically summarized the preparation methods, improvement methods, and development opportunities of TMPs and proposed “stimulatory factors” as a fundamental factor affecting the performance of TMPs herein. As the core of this research, “stimulatory factors” can provide numerous solutions to improve the performance of TMP materials and provide a good starting point for TMP research.
2023, 34(9): 108157
doi: 10.1016/j.cclet.2023.108157
Abstract:
This work reported the lanthanide ion (Gd3+) doped tungsten trioxide (Gd-WO3) nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H2O2 production. With doped lanthanide ion (Gd3+), Gd-WO3 showed a much broad and enhanced solar light absorption, which not only promoted the photocatalytic degradation efficiency of organic compounds, but also provided a suitable bandgap for direct reduction of oxygen to H2O2. Additionally, the isolated Gd3+ on WO3 surface can efficiently weaken the *OOH binding energy, increasing the activity and selectivity of direct reduction of oxygen to H2O2, with a rate of 0.58 mmol L−1 g−1 h−1. The in-situ generated H2O2 can be subsequently converted to •OH based on Fenton reaction, further contributed to the overall removal of organic pollutants. Our results demonstrate a cascade photocatalytic oxidation-Fenton reaction which can efficiently utilize photo-generated electrons and holes for organic pollutants treatment.
This work reported the lanthanide ion (Gd3+) doped tungsten trioxide (Gd-WO3) nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H2O2 production. With doped lanthanide ion (Gd3+), Gd-WO3 showed a much broad and enhanced solar light absorption, which not only promoted the photocatalytic degradation efficiency of organic compounds, but also provided a suitable bandgap for direct reduction of oxygen to H2O2. Additionally, the isolated Gd3+ on WO3 surface can efficiently weaken the *OOH binding energy, increasing the activity and selectivity of direct reduction of oxygen to H2O2, with a rate of 0.58 mmol L−1 g−1 h−1. The in-situ generated H2O2 can be subsequently converted to •OH based on Fenton reaction, further contributed to the overall removal of organic pollutants. Our results demonstrate a cascade photocatalytic oxidation-Fenton reaction which can efficiently utilize photo-generated electrons and holes for organic pollutants treatment.
2023, 34(9): 108159
doi: 10.1016/j.cclet.2023.108159
Abstract:
In-depth exploration of the relationship among different adsorption sites is conducive to design of efficient adsorbents for target pollutants removal from water. In this study, the experiments, multivariate non-linear regression and density functional theory calculations are applied to explore the possible synergistic effects of three nitrogen (N)-containing sites on cow dung biochar surface for sulfamethoxazole (SMX) adsorption. Notably, a strong synergistic effect between pyridinic N and pyrrolic N sites was found for sulfamethoxazole adsorption. The adsorption energies of SMX on four pyrrolic N-coupled pyridinic N structures were −1.02, −0.41, −0.49 and −0.72 eV, much higher than the sum of adsorption energies (−0.31 eV) on pyrrolic N and pyridinic N. Besides, the alteration of Mulliken charge revealed that the simultaneous presence of pyridinic N and pyrrolic N improved the electron transfer remarkably from −0.459 e and 0.094 e to −0.649 e and 0.186 e, benefiting for SMX adsorption. This work firstly explored the possible synergies of adsorption sites on biochar surface for organic contaminants removal from water, which shed new lights on the adsorption mechanism and provided valuable information to design efficient adsorbents in the field of water treatment.
In-depth exploration of the relationship among different adsorption sites is conducive to design of efficient adsorbents for target pollutants removal from water. In this study, the experiments, multivariate non-linear regression and density functional theory calculations are applied to explore the possible synergistic effects of three nitrogen (N)-containing sites on cow dung biochar surface for sulfamethoxazole (SMX) adsorption. Notably, a strong synergistic effect between pyridinic N and pyrrolic N sites was found for sulfamethoxazole adsorption. The adsorption energies of SMX on four pyrrolic N-coupled pyridinic N structures were −1.02, −0.41, −0.49 and −0.72 eV, much higher than the sum of adsorption energies (−0.31 eV) on pyrrolic N and pyridinic N. Besides, the alteration of Mulliken charge revealed that the simultaneous presence of pyridinic N and pyrrolic N improved the electron transfer remarkably from −0.459 e and 0.094 e to −0.649 e and 0.186 e, benefiting for SMX adsorption. This work firstly explored the possible synergies of adsorption sites on biochar surface for organic contaminants removal from water, which shed new lights on the adsorption mechanism and provided valuable information to design efficient adsorbents in the field of water treatment.
2023, 34(9): 108162
doi: 10.1016/j.cclet.2023.108162
Abstract:
The electro-peroxone technology, a novel type of advanced oxidation technology, is widely used in wastewater treatment. Herein, this paper reviews the advantages and problems of the electro-peroxone technology compared with electrochemical oxidation technology, ozonation technology, and traditional peroxone technology. Due to the high kinetics of pollutant degradation, the electro-peroxone process can reduce the reaction time and energy consumption of pollutant treatment in wastewater. The electro-peroxone technology can promote pollutant degradation and mineralization, which shows obvious synergistic effects of electrochemical oxidation and ozonation for wastewater treatment. Most importantly, the research mechanism of the electro-peroxone technology is systematically introduced from two aspects of cathode reaction and bulk reaction. The influence of experimental parameters on the wastewater treatment effect is also discussed. Finally, the potential applications and future research directions of the electro-peroxone technology in the wastewater field are proposed. The electro-peroxone process can offer a highly efficient and energy saving water treatment method to improve the performance of existing ozonation and electrochemical systems and has therefore become a promising electrochemical advanced oxidation process for wastewater treatment.
The electro-peroxone technology, a novel type of advanced oxidation technology, is widely used in wastewater treatment. Herein, this paper reviews the advantages and problems of the electro-peroxone technology compared with electrochemical oxidation technology, ozonation technology, and traditional peroxone technology. Due to the high kinetics of pollutant degradation, the electro-peroxone process can reduce the reaction time and energy consumption of pollutant treatment in wastewater. The electro-peroxone technology can promote pollutant degradation and mineralization, which shows obvious synergistic effects of electrochemical oxidation and ozonation for wastewater treatment. Most importantly, the research mechanism of the electro-peroxone technology is systematically introduced from two aspects of cathode reaction and bulk reaction. The influence of experimental parameters on the wastewater treatment effect is also discussed. Finally, the potential applications and future research directions of the electro-peroxone technology in the wastewater field are proposed. The electro-peroxone process can offer a highly efficient and energy saving water treatment method to improve the performance of existing ozonation and electrochemical systems and has therefore become a promising electrochemical advanced oxidation process for wastewater treatment.
2023, 34(9): 108165
doi: 10.1016/j.cclet.2023.108165
Abstract:
Integrating discrete plasmonic nanoparticles into assemblies can induce plasmonic coupling that produces collective plasmonic properties, which are not available for single nanoparticles. Theoretical analysis revealed that plasmonic coupling derived from assemblies could produce stronger electromagnetic field enhancement effects. Thus, plasmonic assemblies enable better performance in plasmon-based applications, such as enhanced fluorescence and Raman effects. This makes them hold great potential for trace analyte detection and nanomedicine. Herein, we focus on the recent advances in various plasmonic nanoassembles such as dimers, tetramers, and core-satellite structures, and discuss their applications in biosensing and cell imaging. The fabrication strategies for self-assembled plasmonic nanostructures are described, including top-down strategies, self-assembly methods linked by DNA, ligand, polymer, amino acid, or proteins, and chemical overgrowth methods. Thereafter, their applications in biosensor and cell imaging based on dark-field imaging, surface-enhanced Raman scattering, plasmonic circular dichroism, and fluorescence imaging are discussed. Finally, the remaining challenges and prospects are elucidated.
Integrating discrete plasmonic nanoparticles into assemblies can induce plasmonic coupling that produces collective plasmonic properties, which are not available for single nanoparticles. Theoretical analysis revealed that plasmonic coupling derived from assemblies could produce stronger electromagnetic field enhancement effects. Thus, plasmonic assemblies enable better performance in plasmon-based applications, such as enhanced fluorescence and Raman effects. This makes them hold great potential for trace analyte detection and nanomedicine. Herein, we focus on the recent advances in various plasmonic nanoassembles such as dimers, tetramers, and core-satellite structures, and discuss their applications in biosensing and cell imaging. The fabrication strategies for self-assembled plasmonic nanostructures are described, including top-down strategies, self-assembly methods linked by DNA, ligand, polymer, amino acid, or proteins, and chemical overgrowth methods. Thereafter, their applications in biosensor and cell imaging based on dark-field imaging, surface-enhanced Raman scattering, plasmonic circular dichroism, and fluorescence imaging are discussed. Finally, the remaining challenges and prospects are elucidated.
2023, 34(9): 108180
doi: 10.1016/j.cclet.2023.108180
Abstract:
Photoimmunotherapy is an emerging treatment modality that uses photothermal, photodynamic and photochemical processes to fight against cancer by eliciting a robust host immune response. Recently, various nanoformulations of biomaterials have been rationally designed as highly effective photosensitive agents, immunoadjuvants or carriers to enhance phototherapeutic efficacy, boost immune stimulation, amplify nano-permeability and monitor cancer progression in situ. Nevertheless, relying solely on a single-modality therapy may not completely ablate primary tumors, and the metastasis and recurrence of tumors remain a serious challenge. To solve this issue, the strategy of combining photoimmunotherapy with other immunotherapies, such as immune checkpoint blockade, chimeric antigen receptor-T cell or cytokine therapy, can greatly enhance the effectiveness of oncology treatment and reduce the traditional adverse effects. Thus, it is very valuable to summarize the research progress in biomaterial-assisted combination photoimmunotherapy for clinical translation. In this review, the recent advances in constructing multifunctional nano-biomaterials for combinatorial photoimmunotherapy of cancer are summarized. Furthermore, the opportunities, challenges, future trends and prospects in this field are also analyzed to pave the way for advancing the next generation of clinical cancer management strategies.
Photoimmunotherapy is an emerging treatment modality that uses photothermal, photodynamic and photochemical processes to fight against cancer by eliciting a robust host immune response. Recently, various nanoformulations of biomaterials have been rationally designed as highly effective photosensitive agents, immunoadjuvants or carriers to enhance phototherapeutic efficacy, boost immune stimulation, amplify nano-permeability and monitor cancer progression in situ. Nevertheless, relying solely on a single-modality therapy may not completely ablate primary tumors, and the metastasis and recurrence of tumors remain a serious challenge. To solve this issue, the strategy of combining photoimmunotherapy with other immunotherapies, such as immune checkpoint blockade, chimeric antigen receptor-T cell or cytokine therapy, can greatly enhance the effectiveness of oncology treatment and reduce the traditional adverse effects. Thus, it is very valuable to summarize the research progress in biomaterial-assisted combination photoimmunotherapy for clinical translation. In this review, the recent advances in constructing multifunctional nano-biomaterials for combinatorial photoimmunotherapy of cancer are summarized. Furthermore, the opportunities, challenges, future trends and prospects in this field are also analyzed to pave the way for advancing the next generation of clinical cancer management strategies.
2023, 34(9): 108199
doi: 10.1016/j.cclet.2023.108199
Abstract:
Two dimensional (2D) materials are promising gas sensing materials, but the most of them need to be heated to show promising sensing performance. Sensing structures with high sensing performance at room-temperature are urgent. Here, another 2D material, violet phosphorus (VP) nanoflake is investigated as gas sensing material. The VP nanoflakes have been effectively ablated to have layers of 1–5 layers by laser ablation in glycol. The VP nanoflakes are combined with graphene to form VP/G heterostructures-based NO sensor. An ultra-high gauge factor of 3 × 107 for ppb-level sensing and high resistance response of 59.21% with ultra-short recovery time of 6s for ppm-level sensing have been obtained. The sensing mechanism is also analysed by density functional theory (DFT) calculations. The adsorption energy of VP/G is calculated to be −0.788 eV, resulting in electrons migration from P to N to form a P−N bond in the gap between VP and graphene sheet. This work provides a facile approach to ablate VP for mass production. The as-produced structures have also provided potential gas sensors with ultrasensitive performance as ppb-level room-temperature sensors.
Two dimensional (2D) materials are promising gas sensing materials, but the most of them need to be heated to show promising sensing performance. Sensing structures with high sensing performance at room-temperature are urgent. Here, another 2D material, violet phosphorus (VP) nanoflake is investigated as gas sensing material. The VP nanoflakes have been effectively ablated to have layers of 1–5 layers by laser ablation in glycol. The VP nanoflakes are combined with graphene to form VP/G heterostructures-based NO sensor. An ultra-high gauge factor of 3 × 107 for ppb-level sensing and high resistance response of 59.21% with ultra-short recovery time of 6s for ppm-level sensing have been obtained. The sensing mechanism is also analysed by density functional theory (DFT) calculations. The adsorption energy of VP/G is calculated to be −0.788 eV, resulting in electrons migration from P to N to form a P−N bond in the gap between VP and graphene sheet. This work provides a facile approach to ablate VP for mass production. The as-produced structures have also provided potential gas sensors with ultrasensitive performance as ppb-level room-temperature sensors.
2023, 34(9): 108202
doi: 10.1016/j.cclet.2023.108202
Abstract:
Adoptive immunotherapy expressing synthetic chimeric antigen receptors (CAR) on T cells through in vitro modifications represents a new and innovative strategy in cancer treatment. This new approach enables T cells to recognize and bind tumor antigens via a single-chain variable fragment recognition domain, circumventing the restriction of major histocompatibility complex. This review summarized the structure/design of CAR-T cells and the evolution process this technology went through, displaying the theoretical foundation for CAR-T therapy, the marketed products and the latest preclinical and clinical research progress. Finally, we provided perspectives on this technology's development and potential future applications, especially for treating hematological malignant and solid tumors.
Adoptive immunotherapy expressing synthetic chimeric antigen receptors (CAR) on T cells through in vitro modifications represents a new and innovative strategy in cancer treatment. This new approach enables T cells to recognize and bind tumor antigens via a single-chain variable fragment recognition domain, circumventing the restriction of major histocompatibility complex. This review summarized the structure/design of CAR-T cells and the evolution process this technology went through, displaying the theoretical foundation for CAR-T therapy, the marketed products and the latest preclinical and clinical research progress. Finally, we provided perspectives on this technology's development and potential future applications, especially for treating hematological malignant and solid tumors.
2023, 34(9): 108205
doi: 10.1016/j.cclet.2023.108205
Abstract:
Stroke is a common disease and is the major cause of death and disability. It occurs and generates devastating neurological deficits when cerebral blood vessel is blocked (ischemic stroke, IS) or ruptured (hemorrhagic stroke, HS). Hydrogel, being biodegradable and biocompatible, have shown attractive advantages in stroke therapy as a new biomaterial with desirable mechanical properties and tunability of structure, owing to special ability to load different cargoes for multiple treatment strategies, such as pharmacotherapy based on drug-delivery systems and cell therapy including mesenchymal stem cells (MSCs) and neural progenitor cells (NPCs) for improving functional outcomes. However, a comprehensive review of the functional hydrogel for treatment of stroke is still lacking. Therefore, in this work, the main pathological mechanisms of stroke including IS and HS are comprehensively described. The benefits of hydrogel for stroke treatment are also summarized regarding the natural advantages and the delivery advantages. Simultaneously, the application development of hydrogel for treatment of stroke is highlighted. Finally, the unique considerations and challenges in the design and application of hydrogel is discussed for treatment of stroke and clinical application in the future.
Stroke is a common disease and is the major cause of death and disability. It occurs and generates devastating neurological deficits when cerebral blood vessel is blocked (ischemic stroke, IS) or ruptured (hemorrhagic stroke, HS). Hydrogel, being biodegradable and biocompatible, have shown attractive advantages in stroke therapy as a new biomaterial with desirable mechanical properties and tunability of structure, owing to special ability to load different cargoes for multiple treatment strategies, such as pharmacotherapy based on drug-delivery systems and cell therapy including mesenchymal stem cells (MSCs) and neural progenitor cells (NPCs) for improving functional outcomes. However, a comprehensive review of the functional hydrogel for treatment of stroke is still lacking. Therefore, in this work, the main pathological mechanisms of stroke including IS and HS are comprehensively described. The benefits of hydrogel for stroke treatment are also summarized regarding the natural advantages and the delivery advantages. Simultaneously, the application development of hydrogel for treatment of stroke is highlighted. Finally, the unique considerations and challenges in the design and application of hydrogel is discussed for treatment of stroke and clinical application in the future.
2023, 34(9): 108285
doi: 10.1016/j.cclet.2023.108285
Abstract:
Transition metal sulfides are demonstrated to play an increasingly important role in boosting the deployment of ecofriendly electrocatalytic energy conversion technologies. It is also widely recognized that the introduction of vacancies is now becoming an important and valid approach to promote the electrocatalytic performance. In this review, the significance of sulfur vacancies on the enhancement of catalytic performance via four main functionalities, including tuning the electronic structure, tailoring the active sites, improving the electrical conductivity, and regulating surface reconstruction, is comprehensively summarized. Many effective strategies for the sulfur vacancy engineering, such as plasma treatment, heteroatom doping, and chemical reduction are also comprehensively provided. Subsequently, recent achievements in sulfur vacancy fabrication on various hotspot electrocatalytic reactions are also systematically discussed. Finally, a summary of the recent progress and challenges of this interesting field are organized, which hopes to guide the future development of more efficient metal sulfide electrocatalysts.
Transition metal sulfides are demonstrated to play an increasingly important role in boosting the deployment of ecofriendly electrocatalytic energy conversion technologies. It is also widely recognized that the introduction of vacancies is now becoming an important and valid approach to promote the electrocatalytic performance. In this review, the significance of sulfur vacancies on the enhancement of catalytic performance via four main functionalities, including tuning the electronic structure, tailoring the active sites, improving the electrical conductivity, and regulating surface reconstruction, is comprehensively summarized. Many effective strategies for the sulfur vacancy engineering, such as plasma treatment, heteroatom doping, and chemical reduction are also comprehensively provided. Subsequently, recent achievements in sulfur vacancy fabrication on various hotspot electrocatalytic reactions are also systematically discussed. Finally, a summary of the recent progress and challenges of this interesting field are organized, which hopes to guide the future development of more efficient metal sulfide electrocatalysts.
2023, 34(9): 108300
doi: 10.1016/j.cclet.2023.108300
Abstract:
The cancer cells realize their proliferation and metastasis activities based on the special redox adaptation to increased reactive oxygen species (ROS) level, which inversely makes them sensitive to external interference with their redox state. In view of this, in recent decades, researchers have made great efforts to construct a series of novel nanoplatform-based ROS-mediated cancer therapies through increasing ROS generation and inhibiting the ROS elimination. Besides, the multidrug resistance and thermoresistance of tumor are closely related to tumor redox state. Recently, numerous works have shown that ROS regulation in cancer cells can intervene in the expression, function and stability of related proteins to achieve reversal of tumor resistance. In this review, the recent researches about ROS-regulating nanoagents on cancer therapy and tumor resistance alleviation have been well summarized. Finally, the challenges and research directions of ROS-regulating nanoagents for future clinical translation are also discussed.
The cancer cells realize their proliferation and metastasis activities based on the special redox adaptation to increased reactive oxygen species (ROS) level, which inversely makes them sensitive to external interference with their redox state. In view of this, in recent decades, researchers have made great efforts to construct a series of novel nanoplatform-based ROS-mediated cancer therapies through increasing ROS generation and inhibiting the ROS elimination. Besides, the multidrug resistance and thermoresistance of tumor are closely related to tumor redox state. Recently, numerous works have shown that ROS regulation in cancer cells can intervene in the expression, function and stability of related proteins to achieve reversal of tumor resistance. In this review, the recent researches about ROS-regulating nanoagents on cancer therapy and tumor resistance alleviation have been well summarized. Finally, the challenges and research directions of ROS-regulating nanoagents for future clinical translation are also discussed.
2023, 34(9): 108396
doi: 10.1016/j.cclet.2023.108396
Abstract:
Furocoumarins are an important class of heterocyclic compounds with a fused tricyclic structure of coumarin and furan rings. They are commonly found in bioactive natural products and have a diverse range of biological and pharmaceutical properties, including cytotoxicity, photosensitivity, insecticidal, antibacterial, and antifungal activity, among others. The elegant linear/angular tricyclic skeleton and superior pharmacological properties, make them ideal for building and developing advanced biological scaffolds for biomedical applications. As a result, the family of furocoumarins has been the focus of intensive research, and lots of encouraging progress have been achieved in recent years. This review summarizes the most recent methods reported for the synthesis of the furocoumarin derivative family, along with their applications in medicinal chemistry covering from 2018 to 2022.
Furocoumarins are an important class of heterocyclic compounds with a fused tricyclic structure of coumarin and furan rings. They are commonly found in bioactive natural products and have a diverse range of biological and pharmaceutical properties, including cytotoxicity, photosensitivity, insecticidal, antibacterial, and antifungal activity, among others. The elegant linear/angular tricyclic skeleton and superior pharmacological properties, make them ideal for building and developing advanced biological scaffolds for biomedical applications. As a result, the family of furocoumarins has been the focus of intensive research, and lots of encouraging progress have been achieved in recent years. This review summarizes the most recent methods reported for the synthesis of the furocoumarin derivative family, along with their applications in medicinal chemistry covering from 2018 to 2022.
2023, 34(9): 108509
doi: 10.1016/j.cclet.2023.108509
Abstract:
A simple, practical and eco-friendly visible light-induced alkylation of N-sulfonyl ketamine under metal-, additive-, external photocatalyst-free conditions was developed. This photocatalytic method utilized low cost and abundant alkanes as the atom economy alkyl sources with H2O2 as the environmentally beneficial oxidant, allowing for the efficient construction of diverse valuable 4-alkylated sulfonyl ketamines. The N-sulfonyl ketamine played a dual role of reactant and photocatalyst, thus simplifying the reaction system.
A simple, practical and eco-friendly visible light-induced alkylation of N-sulfonyl ketamine under metal-, additive-, external photocatalyst-free conditions was developed. This photocatalytic method utilized low cost and abundant alkanes as the atom economy alkyl sources with H2O2 as the environmentally beneficial oxidant, allowing for the efficient construction of diverse valuable 4-alkylated sulfonyl ketamines. The N-sulfonyl ketamine played a dual role of reactant and photocatalyst, thus simplifying the reaction system.
2023, 34(9): 108563
doi: 10.1016/j.cclet.2023.108563
Abstract:
Peracetic acid (CH3C(O)OOH, PAA)-based heterogeneous advanced oxidation process (AOP) has attacked intensive interests due to production of various reactive species. Herein, Co(OH)2 nanoparticles decorated biochar (Co(OH)2/BC) was fabricated by a simple and controllable method, which was used to degrade tetracycline hydrochloride (TTCH) in water through PAA activation. The results indicated that 100% TTCH (C0 = 10 µmol/L) degradation efficiency was realized within 7 min at pH 7, with a high kinetic rate constant (k1) of 0.64 min−1 by the optimized Co(OH)2/BC. Material characterizations suggested that Co(OH)2 nanoparticle was successfully decorated on biochar, leading to more active sites and electronic structure alteration of biochar, thus greatly promoting the catalytic cleavage of PAA for radicals production. Then, the reactive oxygen species (ROS) quenching experiments and electron paramagnetic resonance (EPR) analysis demonstrated the key species were alkoxyl radicals (R–O•, mainly CH3CO2• and CH3CO3•), HO• and 1O2 in this system. Besides, density functional theory (DFT) calculation on Fukui index further revealed that the vulnerable sites of TTCH and three possible degradation pathways were proposed. This study can provide a new strategy for synthesis functional materials in PAA activation AOPs for removal of antibiotics in water.
Peracetic acid (CH3C(O)OOH, PAA)-based heterogeneous advanced oxidation process (AOP) has attacked intensive interests due to production of various reactive species. Herein, Co(OH)2 nanoparticles decorated biochar (Co(OH)2/BC) was fabricated by a simple and controllable method, which was used to degrade tetracycline hydrochloride (TTCH) in water through PAA activation. The results indicated that 100% TTCH (C0 = 10 µmol/L) degradation efficiency was realized within 7 min at pH 7, with a high kinetic rate constant (k1) of 0.64 min−1 by the optimized Co(OH)2/BC. Material characterizations suggested that Co(OH)2 nanoparticle was successfully decorated on biochar, leading to more active sites and electronic structure alteration of biochar, thus greatly promoting the catalytic cleavage of PAA for radicals production. Then, the reactive oxygen species (ROS) quenching experiments and electron paramagnetic resonance (EPR) analysis demonstrated the key species were alkoxyl radicals (R–O•, mainly CH3CO2• and CH3CO3•), HO• and 1O2 in this system. Besides, density functional theory (DFT) calculation on Fukui index further revealed that the vulnerable sites of TTCH and three possible degradation pathways were proposed. This study can provide a new strategy for synthesis functional materials in PAA activation AOPs for removal of antibiotics in water.
2023, 34(9): 108182
doi: 10.1016/j.cclet.2023.108182
Abstract:
2023, 34(9): 108327
doi: 10.1016/j.cclet.2023.108327
Abstract:
2023, 34(9): 108365
doi: 10.1016/j.cclet.2023.108365
Abstract:
