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2022 Volume 33 Issue 6
2022, 33(6): 2763-2764
doi: 10.1016/j.cclet.2022.03.094
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2022, 33(6): 2765-2772
doi: 10.1016/j.cclet.2021.12.092
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The works on the procedure of fluorescent sensors for the detection of biological analytes are extremely momentous. Among diverse analytical approaches, fluorescence is the most eye-catching due to its high sensitivity, selectivity, rapidity, robustness, ease of measurement and non-destructive approaches. Herein, we show different fluorescent probes synthesized for estimation and detection of biological analytes (H2S, SO32−/HSO3−, H2O2, HOCl, HNO, ONOO−). These probes were constructed by masking the functional groups (hydroxyl and amino) of fluorophore and formation of active C=C, C=N, C=O and N=N for specific analytes. In this review we concentrate on synthesis of the probe, their photophysical properties and applications to biological studies.
The works on the procedure of fluorescent sensors for the detection of biological analytes are extremely momentous. Among diverse analytical approaches, fluorescence is the most eye-catching due to its high sensitivity, selectivity, rapidity, robustness, ease of measurement and non-destructive approaches. Herein, we show different fluorescent probes synthesized for estimation and detection of biological analytes (H2S, SO32−/HSO3−, H2O2, HOCl, HNO, ONOO−). These probes were constructed by masking the functional groups (hydroxyl and amino) of fluorophore and formation of active C=C, C=N, C=O and N=N for specific analytes. In this review we concentrate on synthesis of the probe, their photophysical properties and applications to biological studies.
2022, 33(6): 2773-2782
doi: 10.1016/j.cclet.2022.01.011
Abstract:
Cardiac toxicity is one of the most common side effects of anticancer drugs. Cardiac toxicity results dysfunction of heart including hypotension, heart failure, and even cause death in extreme cases. The potential risk of cardiotoxicity is a huge concern in chemotherapeutics mediated cancer treatment. The individual with any pre-existing cardiac issues are excluded from clinical trials due to the potential risk of cardiotoxicity. Because of the potential cardiotoxicity, there is an emerging need for alternatives of some very potent anticancer drugs (doxorubicin/DOX, 5-fluorouracil/5FU, trastuzumab). While a patient is being treated with anticancer drugs, early blood screening, biomarker detection, and careful monitoring of cardiac functions are necessary to be able to avoid any irreversible cardiac damage. Therefore, early detection methodology to monitor cardiotoxicity in real-time, and a drug formulation that prevent interaction between drug and cardiac cell, seemingly have potential to mitigate the risk. In this review, we have summarized the cardiotoxicity of the most used anticancer drugs, their pathophysiology and some of the conventional and newer screening methods available to manage an individual patient in clinic. We have also incorporated our perspective on how a rationale designing of biomolecules can be used to overcome the cardiotoxicity generated chemotherapeutics.
Cardiac toxicity is one of the most common side effects of anticancer drugs. Cardiac toxicity results dysfunction of heart including hypotension, heart failure, and even cause death in extreme cases. The potential risk of cardiotoxicity is a huge concern in chemotherapeutics mediated cancer treatment. The individual with any pre-existing cardiac issues are excluded from clinical trials due to the potential risk of cardiotoxicity. Because of the potential cardiotoxicity, there is an emerging need for alternatives of some very potent anticancer drugs (doxorubicin/DOX, 5-fluorouracil/5FU, trastuzumab). While a patient is being treated with anticancer drugs, early blood screening, biomarker detection, and careful monitoring of cardiac functions are necessary to be able to avoid any irreversible cardiac damage. Therefore, early detection methodology to monitor cardiotoxicity in real-time, and a drug formulation that prevent interaction between drug and cardiac cell, seemingly have potential to mitigate the risk. In this review, we have summarized the cardiotoxicity of the most used anticancer drugs, their pathophysiology and some of the conventional and newer screening methods available to manage an individual patient in clinic. We have also incorporated our perspective on how a rationale designing of biomolecules can be used to overcome the cardiotoxicity generated chemotherapeutics.
2022, 33(6): 2783-2798
doi: 10.1016/j.cclet.2021.12.057
Abstract:
Malignant tumors, with the characteristics of easy metastasis and recurrence, are a serious threat to health of mankind. It is urgent to develop promising clinical cancer targeted agents with combination of rapid diagnosis and efficient therapies. Compared with the conventional photosensitizing agents, the recent advances of nanoagents based on transition metal-oxide clusters possess unique structural and electronic properties, greatly improving cancer survival rate, meanwhile, keeping high contrast imaging. This review provides a brief introduction of metal-oxide clusters, including both nanoclusters to molecular clusters, specifically polyoxometalates (POMs). Subsequently, biocompatibility of metal-oxide clusters is emphasized from aspects of endocytosis, macropinocytosis, and phagocytosis. Through the classification of late and early transition metals oxide clusters, recent outcomes of light-guided nanoagents are represented with their intriguing chemical and optical properties in their diagnosing and photochemotherapy performance. It shed light on the summary of next generation multifunctional cancer targeting agents' developments as well as outlook of materials selection trends and research direction in the future.
Malignant tumors, with the characteristics of easy metastasis and recurrence, are a serious threat to health of mankind. It is urgent to develop promising clinical cancer targeted agents with combination of rapid diagnosis and efficient therapies. Compared with the conventional photosensitizing agents, the recent advances of nanoagents based on transition metal-oxide clusters possess unique structural and electronic properties, greatly improving cancer survival rate, meanwhile, keeping high contrast imaging. This review provides a brief introduction of metal-oxide clusters, including both nanoclusters to molecular clusters, specifically polyoxometalates (POMs). Subsequently, biocompatibility of metal-oxide clusters is emphasized from aspects of endocytosis, macropinocytosis, and phagocytosis. Through the classification of late and early transition metals oxide clusters, recent outcomes of light-guided nanoagents are represented with their intriguing chemical and optical properties in their diagnosing and photochemotherapy performance. It shed light on the summary of next generation multifunctional cancer targeting agents' developments as well as outlook of materials selection trends and research direction in the future.
2022, 33(6): 2799-2806
doi: 10.1016/j.cclet.2021.09.066
Abstract:
In the field of cell studies, there is a burgeoning trend to further downscale the investigation from a single-cell level to a sub-single-cell level. Subcellular matter is the basic content in cells and correlates with cell heterogeneity. Sub-single cellular studies focus on the subcellular matter in single cells and aim to understand the details and heterogeneity of individual cells in terms of the subcellular matter or even at the single component/vesicle/molecule level. Hence, sub-single cellular studies can provide deeper insights into fundamental cell biology and the development of new diagnostic and therapeutic technologies and applications. Nonetheless, the contents of a single cell are not only ultra-small in volume but also extremely complex in composition, far exceeding the capabilities of most tools used in current cell studies. We believe that nanofluidics holds great potential in providing ideal tools for sub-single cellular studies, not only because of their capability to handle femtoliter/attoliter-scale samples, but also because of their possibility to manipulate and analyze subcellular matters at the single component/vesicle/molecule level in a high-throughput manner. In this review, we summarize the efforts in the field of nanofluidics for sub-single cellular studies, focusing on nascent progress and critical technologies that have the potential to overcome the technical bottlenecks. Some challenges and future opportunities to integrate with information sciences are also discussed.
In the field of cell studies, there is a burgeoning trend to further downscale the investigation from a single-cell level to a sub-single-cell level. Subcellular matter is the basic content in cells and correlates with cell heterogeneity. Sub-single cellular studies focus on the subcellular matter in single cells and aim to understand the details and heterogeneity of individual cells in terms of the subcellular matter or even at the single component/vesicle/molecule level. Hence, sub-single cellular studies can provide deeper insights into fundamental cell biology and the development of new diagnostic and therapeutic technologies and applications. Nonetheless, the contents of a single cell are not only ultra-small in volume but also extremely complex in composition, far exceeding the capabilities of most tools used in current cell studies. We believe that nanofluidics holds great potential in providing ideal tools for sub-single cellular studies, not only because of their capability to handle femtoliter/attoliter-scale samples, but also because of their possibility to manipulate and analyze subcellular matters at the single component/vesicle/molecule level in a high-throughput manner. In this review, we summarize the efforts in the field of nanofluidics for sub-single cellular studies, focusing on nascent progress and critical technologies that have the potential to overcome the technical bottlenecks. Some challenges and future opportunities to integrate with information sciences are also discussed.
2022, 33(6): 2807-2816
doi: 10.1016/j.cclet.2021.11.060
Abstract:
Due to the frequent occurrence of oil spills and the large-scale production of oily wastewater, the treatment of oily sewage has become an important issue for sustainable development. Recently, materials prepared from lignocellulosic biomass (LCB) for oil-water separation have been found to be effective due to their high separation efficiency, good recyclability, and superior sustainability. However, few reviews have focused on the advantages and limitations of LCB for sewage treatment. This review summarizes the performance of modified LCB in oily wastewater treatment, in terms of the advanced modification methods applied and the structural dimensions of LCB materials according to the principle of superwetting oil-water separation. Research on the preparation technologies, separation mechanisms, and treatment efficiency of different LCB materials are briefly summarized, along with the characteristics of different LCB material types for oily wastewater treatment. Finally, the future prospects and challenges faced in the development of LCB materials are discussed.
Due to the frequent occurrence of oil spills and the large-scale production of oily wastewater, the treatment of oily sewage has become an important issue for sustainable development. Recently, materials prepared from lignocellulosic biomass (LCB) for oil-water separation have been found to be effective due to their high separation efficiency, good recyclability, and superior sustainability. However, few reviews have focused on the advantages and limitations of LCB for sewage treatment. This review summarizes the performance of modified LCB in oily wastewater treatment, in terms of the advanced modification methods applied and the structural dimensions of LCB materials according to the principle of superwetting oil-water separation. Research on the preparation technologies, separation mechanisms, and treatment efficiency of different LCB materials are briefly summarized, along with the characteristics of different LCB material types for oily wastewater treatment. Finally, the future prospects and challenges faced in the development of LCB materials are discussed.
2022, 33(6): 2817-2831
doi: 10.1016/j.cclet.2021.11.033
Abstract:
Pathogenic bacteria pose a global threat to public health and attract considerable attention in terms of food safety. Rapid and highly sensitive strategies for detecting pathogenic bacteria must be urgently developed to ensure food safety and public health. Microchips offer significant advantages for pathogenic bacterial detection in terms of speed and sensitivity compared with those of traditional techniques. Microfluidic devices, in particular, have attracted significant attention for the detection of pathogenic bacteria owing to their ease of operation, high throughput, cost-effectiveness, and high sensitivity. This review summarizes representative articles on the analysis of pathogenic bacteria using microchip-based systems. A detailed and comprehensive overview of microchip-based techniques for the detection of pathogenic bacteria is presented herein, and their advantages and disadvantages are discussed to compare their applications. The accomplishments and shortcomings of these microchips have been highlighted, and the direction of development and prospects of the analysis of pathogenic bacteria have been examined. The content of this review is anticipated to provide constructive suggestions for further development of highly effective and advanced microchip-based strategies for detecting pathogenic bacteria.
Pathogenic bacteria pose a global threat to public health and attract considerable attention in terms of food safety. Rapid and highly sensitive strategies for detecting pathogenic bacteria must be urgently developed to ensure food safety and public health. Microchips offer significant advantages for pathogenic bacterial detection in terms of speed and sensitivity compared with those of traditional techniques. Microfluidic devices, in particular, have attracted significant attention for the detection of pathogenic bacteria owing to their ease of operation, high throughput, cost-effectiveness, and high sensitivity. This review summarizes representative articles on the analysis of pathogenic bacteria using microchip-based systems. A detailed and comprehensive overview of microchip-based techniques for the detection of pathogenic bacteria is presented herein, and their advantages and disadvantages are discussed to compare their applications. The accomplishments and shortcomings of these microchips have been highlighted, and the direction of development and prospects of the analysis of pathogenic bacteria have been examined. The content of this review is anticipated to provide constructive suggestions for further development of highly effective and advanced microchip-based strategies for detecting pathogenic bacteria.
2022, 33(6): 2832-2844
doi: 10.1016/j.cclet.2021.10.013
Abstract:
Inspired by the biosystems, the artificial smart membrane to control the mass transport and molecular conversion has attracted increasing attention in the fields of membrane separation, desalination, nanofiltration, healthcare and environmental remediation. However, the trade-off limitations in polymeric membranes greatly hinder the development of smart membranes with high permeability and manipulability. Recently, inspired by the unique physical/chemical properties of two-dimensional (2D) materials, 2D materials-based smart membranes (2DSMs) with the ability of intelligent regulation under different stimuli are highly suitable for membrane applications. According to the desired properties, the 2DSMs with abundant functional groups can be designed through chemical modification to change the original properties and obtain tunable interlayer spacings under different external conditions. In this review, we summarize the recent progress on artificial smart membranes based on 2D materials. The design concept and fabrication strategy of 2DSMs are first introduced. Following that, the developed 2DSMs are introduced and classified by the type of responsive stimuli, including pH, magnetic field, electric field, light and temperature. Then, the 2DSMs exhibiting unique performances as membrane separation, pressure sensors, blue energy harvesting, photoelectrochemical sensors and biomimetic devices are presented. Finally, the perspectives and challenges in the developments of 2DSMs are discussed
Inspired by the biosystems, the artificial smart membrane to control the mass transport and molecular conversion has attracted increasing attention in the fields of membrane separation, desalination, nanofiltration, healthcare and environmental remediation. However, the trade-off limitations in polymeric membranes greatly hinder the development of smart membranes with high permeability and manipulability. Recently, inspired by the unique physical/chemical properties of two-dimensional (2D) materials, 2D materials-based smart membranes (2DSMs) with the ability of intelligent regulation under different stimuli are highly suitable for membrane applications. According to the desired properties, the 2DSMs with abundant functional groups can be designed through chemical modification to change the original properties and obtain tunable interlayer spacings under different external conditions. In this review, we summarize the recent progress on artificial smart membranes based on 2D materials. The design concept and fabrication strategy of 2DSMs are first introduced. Following that, the developed 2DSMs are introduced and classified by the type of responsive stimuli, including pH, magnetic field, electric field, light and temperature. Then, the 2DSMs exhibiting unique performances as membrane separation, pressure sensors, blue energy harvesting, photoelectrochemical sensors and biomimetic devices are presented. Finally, the perspectives and challenges in the developments of 2DSMs are discussed
2022, 33(6): 2845-2855
doi: 10.1016/j.cclet.2021.10.034
Abstract:
Oxygen evolution reaction (OER) is pivotal to drive green hydrogen generation from water electrolysis, but yet is strictly overshadowed by the sluggish reaction kinetics. Earth-abundant and cut-price transition-metal compounds, particularly CoFe layered-double-hydroxides (LDHs), show the distinct superiorities in contrast to noble metals and their derivatives. In this review, we firstly underline their fundamental issues in electrocatalytic water oxidation, including CoFe LDHs crystal structure, the surface of (hydr)oxides confined to OER and the controversial roles of Fe species, aiming at understanding the structure-related activity and catalytic mechanism. Advanced approaches for optimizing OER activity of CoFe LDHs are then comprehensively overviewed, which will shed light on the different working mechanisms and provide a concise analysis of their unique advantages. Finally, a perspective on the future development of CoFe LDHs electrocatalysts is offered. We hope this review can give a concise and explicit guidance for the development of transition-metal-based electrocatalysts in the energy field.
Oxygen evolution reaction (OER) is pivotal to drive green hydrogen generation from water electrolysis, but yet is strictly overshadowed by the sluggish reaction kinetics. Earth-abundant and cut-price transition-metal compounds, particularly CoFe layered-double-hydroxides (LDHs), show the distinct superiorities in contrast to noble metals and their derivatives. In this review, we firstly underline their fundamental issues in electrocatalytic water oxidation, including CoFe LDHs crystal structure, the surface of (hydr)oxides confined to OER and the controversial roles of Fe species, aiming at understanding the structure-related activity and catalytic mechanism. Advanced approaches for optimizing OER activity of CoFe LDHs are then comprehensively overviewed, which will shed light on the different working mechanisms and provide a concise analysis of their unique advantages. Finally, a perspective on the future development of CoFe LDHs electrocatalysts is offered. We hope this review can give a concise and explicit guidance for the development of transition-metal-based electrocatalysts in the energy field.
2022, 33(6): 2856-2866
doi: 10.1016/j.cclet.2022.02.065
Abstract:
Covalent organic frameworks (COFs) have been attracting growing concerns since the first report in 2005. With the well-defined and ordered structures, COFs express big potential in mass transport, storage/separation and energy conversion applications. From the perspective of both theory and application, the construction of crystalline COFs with high quality and variety is highly worth to be devoted to. To give insight into the crystalline process of COFs and deeply understand the factors of COFs crystallization, this review was concentrated on the recent progress in construction of crystalline COFs. Accordingly, the types and crystallization process of COFs were summarized firstly. And then the factors on crystallinity and the measures for improving the crystallinity of COFs were classified and discussed in detail. Finally, the perspectives for the development of COFs in further was given at the end of this review.
Covalent organic frameworks (COFs) have been attracting growing concerns since the first report in 2005. With the well-defined and ordered structures, COFs express big potential in mass transport, storage/separation and energy conversion applications. From the perspective of both theory and application, the construction of crystalline COFs with high quality and variety is highly worth to be devoted to. To give insight into the crystalline process of COFs and deeply understand the factors of COFs crystallization, this review was concentrated on the recent progress in construction of crystalline COFs. Accordingly, the types and crystallization process of COFs were summarized firstly. And then the factors on crystallinity and the measures for improving the crystallinity of COFs were classified and discussed in detail. Finally, the perspectives for the development of COFs in further was given at the end of this review.
2022, 33(6): 2867-2882
doi: 10.1016/j.cclet.2021.10.060
Abstract:
Two-dimensional (2D) covalent organic framework nanosheets (CONs) are attracting increasing research attention because of their unique properties derived from their ultrathin thickness, high surface-to-volume atomic ratio, and extremely large surface area. 2D CONs can provide high transport pathways for charge carriers (e.g., electrons, holes and ions) through either the conjugated skeletons or the open channels. Therefore, they have shown great potential in energy related applications. In this review, we firstly introduce the recent developments and characteristics of 2D CONs by focusing on the two typical synthetic methods, i.e., top-down and bottom-up methods. Then, the energy-related applications in energy storage and conversion of 2D CONs are summarized. Finally, we give our personal views on the challenges and perspectives for the future research of 2D CONs and their composites.
Two-dimensional (2D) covalent organic framework nanosheets (CONs) are attracting increasing research attention because of their unique properties derived from their ultrathin thickness, high surface-to-volume atomic ratio, and extremely large surface area. 2D CONs can provide high transport pathways for charge carriers (e.g., electrons, holes and ions) through either the conjugated skeletons or the open channels. Therefore, they have shown great potential in energy related applications. In this review, we firstly introduce the recent developments and characteristics of 2D CONs by focusing on the two typical synthetic methods, i.e., top-down and bottom-up methods. Then, the energy-related applications in energy storage and conversion of 2D CONs are summarized. Finally, we give our personal views on the challenges and perspectives for the future research of 2D CONs and their composites.
2022, 33(6): 2883-2892
doi: 10.1016/j.cclet.2021.10.006
Abstract:
Metabolites can directly reflect and modulate cell responses and phenotypical changes by influencing energy balances, intercellular signals, and many other cellular functions throughout the lifespan of cells. Taking into account the heterogeneity of cells, single-cell metabolite analysis offers an insight into the functional process within one cell. Microfluidics as a powerful tool has attracted significant interest in the single-cell metabolite analysis field. The microfluidic platform is possible to observe, classify, and stimulate individual cells. It can also transport single-cell to subsequent analysis steps in a fast and controllable way to determine and analyze the composition and content of metabolites. The reviews of topics in microfluidics for single-cell metabolite analysis have been published in the past few years. However, most of them focused on metabolite analysis with mass spectrometry. Here, we covered the advances of microfluidic devices for single-cell metabolite analysis, with a focus on single-cell isolation and manipulation. What is more, we summarized the detection methods and applications of single-cell metabolites.
Metabolites can directly reflect and modulate cell responses and phenotypical changes by influencing energy balances, intercellular signals, and many other cellular functions throughout the lifespan of cells. Taking into account the heterogeneity of cells, single-cell metabolite analysis offers an insight into the functional process within one cell. Microfluidics as a powerful tool has attracted significant interest in the single-cell metabolite analysis field. The microfluidic platform is possible to observe, classify, and stimulate individual cells. It can also transport single-cell to subsequent analysis steps in a fast and controllable way to determine and analyze the composition and content of metabolites. The reviews of topics in microfluidics for single-cell metabolite analysis have been published in the past few years. However, most of them focused on metabolite analysis with mass spectrometry. Here, we covered the advances of microfluidic devices for single-cell metabolite analysis, with a focus on single-cell isolation and manipulation. What is more, we summarized the detection methods and applications of single-cell metabolites.
2022, 33(6): 2893-2900
doi: 10.1016/j.cclet.2021.09.058
Abstract:
Extracellular vesicles (EVs) are membrane vesicles secreted by cells, playing critical roles in mediating intercellular communications for various physiological and pathological processes. Most of the EV analysis is currently performed at the bulk level, obscuring the origin of the EVs and diverse characteristics of the individual extracellular vesicle. Technologies to analyze the extracellular vesicles at the single-cell and single-vesicle levels are needed to evaluate EV comprehensively and decode the heterogeneity underlying EV secretion. Microfluidic platforms that could control and manipulate fluids at the microscale provide an efficient way to achieve the aims. Various microfluidics-based technologies are emerging to realize single-cell EV secretion analysis and single EV analysis, which would be summarized in this mini-review.
Extracellular vesicles (EVs) are membrane vesicles secreted by cells, playing critical roles in mediating intercellular communications for various physiological and pathological processes. Most of the EV analysis is currently performed at the bulk level, obscuring the origin of the EVs and diverse characteristics of the individual extracellular vesicle. Technologies to analyze the extracellular vesicles at the single-cell and single-vesicle levels are needed to evaluate EV comprehensively and decode the heterogeneity underlying EV secretion. Microfluidic platforms that could control and manipulate fluids at the microscale provide an efficient way to achieve the aims. Various microfluidics-based technologies are emerging to realize single-cell EV secretion analysis and single EV analysis, which would be summarized in this mini-review.
2022, 33(6): 2901-2905
doi: 10.1016/j.cclet.2021.10.028
Abstract:
As human stem cells with the special pluripotency play important roles in the innovative drug discovery and regenerative medicine, development of extracellular matrix (ECM) mimetics or functional materials that can support stem cell growth and propagation is of high significance. Despite numerous efforts spent, one major limitation restricting the wide applications of stem cells to the clinical translation is the lack of efficient strategies for low cost and large-scale stem cell production under xeno-free culture conditions. Herein, we reported a new strategy with peptides-modified polystyrene-based polymers coated onto the surface of coverslips for the growth and reproduction of human embryonic stem cells (hESCs). The modified peptides are the active parts of proteins which has been shown to contribute to the pluripotent stem cell attachment or proliferation. The peptides were linked to the glass coverslips coated by the polymer materials via chemical crosslinking, and the composite substrates successfully maintain the long-term growth of HUES-7, H7 and DF699. Our study shows that the coating of polystyrene-derived polymer modified by our developed peptides is a good matrix for long-term growth and reproduction of stem cells. This polystyrene-derived polymer substrate can be produced in large scale and stored for a long time. The most important thing is that it can support the growth of undifferentiated human pluripotent stem cells (hPSCs) for more than ten passages, which could provide a new and relatively easy way to amplify hESCs in vitro.
As human stem cells with the special pluripotency play important roles in the innovative drug discovery and regenerative medicine, development of extracellular matrix (ECM) mimetics or functional materials that can support stem cell growth and propagation is of high significance. Despite numerous efforts spent, one major limitation restricting the wide applications of stem cells to the clinical translation is the lack of efficient strategies for low cost and large-scale stem cell production under xeno-free culture conditions. Herein, we reported a new strategy with peptides-modified polystyrene-based polymers coated onto the surface of coverslips for the growth and reproduction of human embryonic stem cells (hESCs). The modified peptides are the active parts of proteins which has been shown to contribute to the pluripotent stem cell attachment or proliferation. The peptides were linked to the glass coverslips coated by the polymer materials via chemical crosslinking, and the composite substrates successfully maintain the long-term growth of HUES-7, H7 and DF699. Our study shows that the coating of polystyrene-derived polymer modified by our developed peptides is a good matrix for long-term growth and reproduction of stem cells. This polystyrene-derived polymer substrate can be produced in large scale and stored for a long time. The most important thing is that it can support the growth of undifferentiated human pluripotent stem cells (hPSCs) for more than ten passages, which could provide a new and relatively easy way to amplify hESCs in vitro.
2022, 33(6): 2906-2910
doi: 10.1016/j.cclet.2021.10.031
Abstract:
Dimethyl ether (DME), as a promising alternative to diesel fuel and liquefied petroleum gas, has attracted considerable attention in catalysis domain. The catalytic direct synthesis of DME from syngas is an up-and-coming route but remains a challenge. In this work, we firstly prepared a Cu-embedded porous Al2O3 bifunctional catalyst (Cu@Al2O3-dp) by filling Cu-1, 3, 5-benzenetricarboxylate metal-organic framework (Cu-BTC MOF) with Al(OH)3 followed by a two-step calcination process (400 ℃ for 4 h and 600 ℃ for 1 h), exhibiting excellent catalytic performance for direct synthesis of DME from syngas. Cu@Al2O3-dp catalyst demonstrates much higher CO conversion (25.7% vs. 15.4%) and extremely higher DME selectivity (90.4% vs. 63.9%) with the increased catalytic stability compared to the supported Cu catalyst on MOF-derived porous Al2O3 (Cu/Al2O3) prepared by incipient wetness impregnation method, ascribed to the unique embedding-type structure, promoted Cu dispersion and stronger metal-support interaction. This work not only provides an efficient syngas-to-DME catalyst, but also paves a new way for designing highly-efficient core-shell bifunctional catalysts for diverse consecutive reactions.
Dimethyl ether (DME), as a promising alternative to diesel fuel and liquefied petroleum gas, has attracted considerable attention in catalysis domain. The catalytic direct synthesis of DME from syngas is an up-and-coming route but remains a challenge. In this work, we firstly prepared a Cu-embedded porous Al2O3 bifunctional catalyst (Cu@Al2O3-dp) by filling Cu-1, 3, 5-benzenetricarboxylate metal-organic framework (Cu-BTC MOF) with Al(OH)3 followed by a two-step calcination process (400 ℃ for 4 h and 600 ℃ for 1 h), exhibiting excellent catalytic performance for direct synthesis of DME from syngas. Cu@Al2O3-dp catalyst demonstrates much higher CO conversion (25.7% vs. 15.4%) and extremely higher DME selectivity (90.4% vs. 63.9%) with the increased catalytic stability compared to the supported Cu catalyst on MOF-derived porous Al2O3 (Cu/Al2O3) prepared by incipient wetness impregnation method, ascribed to the unique embedding-type structure, promoted Cu dispersion and stronger metal-support interaction. This work not only provides an efficient syngas-to-DME catalyst, but also paves a new way for designing highly-efficient core-shell bifunctional catalysts for diverse consecutive reactions.
2022, 33(6): 2911-2914
doi: 10.1016/j.cclet.2021.10.049
Abstract:
Selective hydrogenation of substituted nitroarenes is an important reaction to obtain amines. Supported metal catalysts are wildly used in this reaction because the surface structure of supports can tune the properties of the supported metal nanoparticles (NPs) and promote the selectivity to amines. Herein, Pt NPs were immobilized on FeOOH, Fe3O4 and α-Fe2O3 nanorods to synthesize a series of iron compounds supported Pt catalysts by liquid phase reduction method. Chemoselective hydrogenation of 3-nitrostyrene to 3-aminostyrene was used as probe reaction to evaluate the performance of the catalysts. The results show that Pt/FeOOH exhibits the highest selectivity and activity. FeOOH support with pores and -OH groups can tune the electronic structure of Pt NPs. The positive charge of Pt NPs supported on FeOOH is key factor for improving the catalytic performance.
Selective hydrogenation of substituted nitroarenes is an important reaction to obtain amines. Supported metal catalysts are wildly used in this reaction because the surface structure of supports can tune the properties of the supported metal nanoparticles (NPs) and promote the selectivity to amines. Herein, Pt NPs were immobilized on FeOOH, Fe3O4 and α-Fe2O3 nanorods to synthesize a series of iron compounds supported Pt catalysts by liquid phase reduction method. Chemoselective hydrogenation of 3-nitrostyrene to 3-aminostyrene was used as probe reaction to evaluate the performance of the catalysts. The results show that Pt/FeOOH exhibits the highest selectivity and activity. FeOOH support with pores and -OH groups can tune the electronic structure of Pt NPs. The positive charge of Pt NPs supported on FeOOH is key factor for improving the catalytic performance.
2022, 33(6): 2915-2918
doi: 10.1016/j.cclet.2021.10.061
Abstract:
The photocatalytic reduction of CO2 to energy-rich chemicals is highly appealing for alleviation of energy crisis and environment pollution. The introduction of different active sites is a key factor to determine the reaction activity and selectivity. Here, we demonstrate the metal ion-dependent performance for photocatalytic CO2 reduction by anchoring transition metal ions (Co2+ and Ni2+) in an amine-functionalized boron imidazolate framework (BIF-43). As a result, Ni@BIF-43 realized a high selectivity of 90.2% for the CO2-to-CO, while Co@BIF-43 achieved more efficient conversion with a high CO production rate of 2036.0 µmol g−1 h−1. Significantly, precise control of isolated metal site on a well-defined structure through coordination-assisted strategies enables us to better understand the specific effects of different metal-ion species on photoreduction of CO2 as well as the catalytic mechanism.
The photocatalytic reduction of CO2 to energy-rich chemicals is highly appealing for alleviation of energy crisis and environment pollution. The introduction of different active sites is a key factor to determine the reaction activity and selectivity. Here, we demonstrate the metal ion-dependent performance for photocatalytic CO2 reduction by anchoring transition metal ions (Co2+ and Ni2+) in an amine-functionalized boron imidazolate framework (BIF-43). As a result, Ni@BIF-43 realized a high selectivity of 90.2% for the CO2-to-CO, while Co@BIF-43 achieved more efficient conversion with a high CO production rate of 2036.0 µmol g−1 h−1. Significantly, precise control of isolated metal site on a well-defined structure through coordination-assisted strategies enables us to better understand the specific effects of different metal-ion species on photoreduction of CO2 as well as the catalytic mechanism.
2022, 33(6): 2919-2922
doi: 10.1016/j.cclet.2021.10.072
Abstract:
Valeriaquinone A (1), an unprecedented anthraquinone-coumarin hybrid, was isolated from the roots of Knoxia valerianoides. Its structure was determined by extensive spectroscopic analyses and X-ray diffraction. The plausible biosynthetic pathways for 1 were proposed. Compound 1 exhibited strong protein tyrosine phosphatase 1B (PTP1B) inhibition with high selectivity (> 30 fold) over homologous T cell protein tyrosine phosphatase (TCPTP) potentially by binding to an allosteric site predicted by kinetic analysis and molecular docking. Moreover, compound 1 showed significant cytotoxic activities against three human hepatoma cell lines (HepG2, QGY-7703, and SMMC-7721) with half maximal inhibitory concentration (IC50) values of 1.39 ± 0.2, 10.34 ± 2.09, and 5.56 ± 0.47 µmol/L, respectively.
Valeriaquinone A (1), an unprecedented anthraquinone-coumarin hybrid, was isolated from the roots of Knoxia valerianoides. Its structure was determined by extensive spectroscopic analyses and X-ray diffraction. The plausible biosynthetic pathways for 1 were proposed. Compound 1 exhibited strong protein tyrosine phosphatase 1B (PTP1B) inhibition with high selectivity (> 30 fold) over homologous T cell protein tyrosine phosphatase (TCPTP) potentially by binding to an allosteric site predicted by kinetic analysis and molecular docking. Moreover, compound 1 showed significant cytotoxic activities against three human hepatoma cell lines (HepG2, QGY-7703, and SMMC-7721) with half maximal inhibitory concentration (IC50) values of 1.39 ± 0.2, 10.34 ± 2.09, and 5.56 ± 0.47 µmol/L, respectively.
2022, 33(6): 2923-2927
doi: 10.1016/j.cclet.2021.10.085
Abstract:
Sophoralines A-C, three novel [2 + 2] cycloaddition dimers of matrine-based alkaloids with an unprecedented 6/6/6/6/4/6/6/6/6 nonacyclic skeleton containing 11 stereogenic centers, were isolated from Sophora alopecuroides. Their structures were determined by spectroscopic methods, and the absolute configurations were further determined by single-crystal X-ray diffraction analysis for 1 and quantum chemical calculations of electronic circular dichroism (ECD) spectra for 2 and 3. Moreover, 1 exhibited excellent hepatoprotective activities in acetaminophen-induced liver injury in vitro and in vivo.
Sophoralines A-C, three novel [2 + 2] cycloaddition dimers of matrine-based alkaloids with an unprecedented 6/6/6/6/4/6/6/6/6 nonacyclic skeleton containing 11 stereogenic centers, were isolated from Sophora alopecuroides. Their structures were determined by spectroscopic methods, and the absolute configurations were further determined by single-crystal X-ray diffraction analysis for 1 and quantum chemical calculations of electronic circular dichroism (ECD) spectra for 2 and 3. Moreover, 1 exhibited excellent hepatoprotective activities in acetaminophen-induced liver injury in vitro and in vivo.
2022, 33(6): 2928-2932
doi: 10.1016/j.cclet.2021.10.090
Abstract:
Coordination polymers (CPs) have great potential to be used in electrocatalysis owing to their designable compositions and structures. It is highly challenging to apply CPs as electrocatalysts for oxygen evolution reaction (OER) on account of insufficient catalytic efficiency and relatively poor stability of current electrocatalysts. Herein, through a mixed-metal strategy, one-dimensional CoNi1--HIPA with dual active sites was synthesized and studied for OER electrocatalysts. By changing the metal ratio of CoNi1--HIPA, the OER performance was well regulated. The optimized Co1/2Ni1/2-HIPA exhibited minimum reaction activation energy, and represented an overpotential of 367 mV to reach 10 mA/cm2 at 25 ℃. Moreover, an overpotential of 314 mV at 10 mA/cm2 was obtained from Co1/2Ni1/2-HIPA at 55 ℃. This mixed-metal strategy provides a feasible way for adjusting the electronic states of the electrocatalysts to improve the electrocatalytic OER performance.
Coordination polymers (CPs) have great potential to be used in electrocatalysis owing to their designable compositions and structures. It is highly challenging to apply CPs as electrocatalysts for oxygen evolution reaction (OER) on account of insufficient catalytic efficiency and relatively poor stability of current electrocatalysts. Herein, through a mixed-metal strategy, one-dimensional CoNi1--HIPA with dual active sites was synthesized and studied for OER electrocatalysts. By changing the metal ratio of CoNi1--HIPA, the OER performance was well regulated. The optimized Co1/2Ni1/2-HIPA exhibited minimum reaction activation energy, and represented an overpotential of 367 mV to reach 10 mA/cm2 at 25 ℃. Moreover, an overpotential of 314 mV at 10 mA/cm2 was obtained from Co1/2Ni1/2-HIPA at 55 ℃. This mixed-metal strategy provides a feasible way for adjusting the electronic states of the electrocatalysts to improve the electrocatalytic OER performance.
2022, 33(6): 2933-2936
doi: 10.1016/j.cclet.2021.10.089
Abstract:
Aprotic Li-CO2 batteries have attracted growing interest due to their high theoretical energy density and its ability to use green house gas CO2 for energy storage. However, the poor ability of activating CO2 in organic electrolyte often leads to the premature termination of CO2 reduction reaction (CO2RR) directly. Here in this work, cetyl trimethyl ammonium bromide (CTAB) was introduced into a dimethyl sulfoxide (DMSO) based Li-CO2 battery for the first time to enhance the CO2RR. Significantly improved electrochemical performances, including reduced discharge over-potential and increased discharge capacity, can be achieved with the addition of CTAB. Ab initio molecular dynamics (AIMD) simulations show that quaternary ammonium group CTA+ can accelerate CO2 reduction process by forming more stable contact ion pair (CIP) with CO2-, reducing the energy barrier for CO2RR, thus improving the CO2 reduction process. In addition, adding CTA+ is also favorable for the solution-phase growth of discharge products because of the improved migration ability of stable CTA+-CO2- CIP in the electrolyte, which is beneficial for improving the utilization ratio of cathode. This work could facilitate the development of CO2RR by providing a novel understanding of CO2RR mechanism in organic system.
Aprotic Li-CO2 batteries have attracted growing interest due to their high theoretical energy density and its ability to use green house gas CO2 for energy storage. However, the poor ability of activating CO2 in organic electrolyte often leads to the premature termination of CO2 reduction reaction (CO2RR) directly. Here in this work, cetyl trimethyl ammonium bromide (CTAB) was introduced into a dimethyl sulfoxide (DMSO) based Li-CO2 battery for the first time to enhance the CO2RR. Significantly improved electrochemical performances, including reduced discharge over-potential and increased discharge capacity, can be achieved with the addition of CTAB. Ab initio molecular dynamics (AIMD) simulations show that quaternary ammonium group CTA+ can accelerate CO2 reduction process by forming more stable contact ion pair (CIP) with CO2-, reducing the energy barrier for CO2RR, thus improving the CO2 reduction process. In addition, adding CTA+ is also favorable for the solution-phase growth of discharge products because of the improved migration ability of stable CTA+-CO2- CIP in the electrolyte, which is beneficial for improving the utilization ratio of cathode. This work could facilitate the development of CO2RR by providing a novel understanding of CO2RR mechanism in organic system.
2022, 33(6): 2937-2941
doi: 10.1016/j.cclet.2021.12.091
Abstract:
Uncontrollable hemorrhage remains staple trouble in surgical procedures and a leading cause after major trauma. The bleeding issue may trigger various pathologic scenarios that can lead to tissue morbidities and mortalities, and currently available on-site hemostatic agents are confined to a narrow therapeutic index and may carry the risk of immunogenicity. Inspired by the crucial role of platelets in the process of thrombus, a platelet-mimetic plateletsome with wound targeting and blood coagulation properties is developed for hemorrhage control. Plateletsome is formulated by integrating platelet membranes with functionalized synthetic liposomes and exhibits superior wound targeting and effective hemostasis properties. It presents less blood loss and shorter hemostasis time than the platelet membrane vehicles or the conventional liposomes in the mouse tail transection model. The strong homing of the biomimetic plateletsome to the thrombus was also confirmed, demonstrating the potential of this engineered cell membrane vesicle as a biomimetic hemostat for bleeding treatment.
Uncontrollable hemorrhage remains staple trouble in surgical procedures and a leading cause after major trauma. The bleeding issue may trigger various pathologic scenarios that can lead to tissue morbidities and mortalities, and currently available on-site hemostatic agents are confined to a narrow therapeutic index and may carry the risk of immunogenicity. Inspired by the crucial role of platelets in the process of thrombus, a platelet-mimetic plateletsome with wound targeting and blood coagulation properties is developed for hemorrhage control. Plateletsome is formulated by integrating platelet membranes with functionalized synthetic liposomes and exhibits superior wound targeting and effective hemostasis properties. It presents less blood loss and shorter hemostasis time than the platelet membrane vehicles or the conventional liposomes in the mouse tail transection model. The strong homing of the biomimetic plateletsome to the thrombus was also confirmed, demonstrating the potential of this engineered cell membrane vesicle as a biomimetic hemostat for bleeding treatment.
2022, 33(6): 2942-2948
doi: 10.1016/j.cclet.2021.12.094
Abstract:
Waste utilization is not only the protection of the environment and the practice of green chemistry, but also one of the ways to develop new materials. Herein, we report two biomass carbon dots which prepared from bee pollen waste by one-step hydrothermal method. The new two carbon dots were used in sensing, cell imaging and plant growth regulation. The differences in the structure and properties of the two carbon dots were evaluated by TEM, XPS, TG and various spectroscopic methods. Both two carbon dots contain abundant functional groups, polyatomic doping, excellent water solubility and stable photoluminescence. Due to these good properties, we have demonstrated its versatile applications in Fe3+ sensing, cell imaging and plant growth regulation. It shows sensitive and specific Fe3+ responsiveness and good biocompatibility. This research provides a green and simple method for the recycling and reuse of bee pollen waste, and also provides a reference for the application of biomass carbon dots.
Waste utilization is not only the protection of the environment and the practice of green chemistry, but also one of the ways to develop new materials. Herein, we report two biomass carbon dots which prepared from bee pollen waste by one-step hydrothermal method. The new two carbon dots were used in sensing, cell imaging and plant growth regulation. The differences in the structure and properties of the two carbon dots were evaluated by TEM, XPS, TG and various spectroscopic methods. Both two carbon dots contain abundant functional groups, polyatomic doping, excellent water solubility and stable photoluminescence. Due to these good properties, we have demonstrated its versatile applications in Fe3+ sensing, cell imaging and plant growth regulation. It shows sensitive and specific Fe3+ responsiveness and good biocompatibility. This research provides a green and simple method for the recycling and reuse of bee pollen waste, and also provides a reference for the application of biomass carbon dots.
2022, 33(6): 2949-2953
doi: 10.1016/j.cclet.2021.12.098
Abstract:
Cystic echinococcosis (CE) is one of the most harmful and life-threatening helminths. As the essential therapeutics, chemotherapy is always difficult to achieve desired anti-echinococcal effect due to the problems that the echinococcus granulosus cyst laminated layer makes the drug difficult to infiltrate and the poor solubility of drugs. In this study, we established a "breaking-then-curing" anti-echinococcal treatment strategy for efficient CE therapy. The photodynamic therapy (PDT) was used as a breaker to produce toxic reactive oxygen species (ROS) and damage the laminated layer of protoscolices (PSCs), leading to enhanced infiltration of albendazole sulfoxide nanoparticles (ABZSO NPs). Then, ABZSO NP was worked as curer for efficient anti-echinococcal treatment. As a result, the breaking-then-curing treatment strategy could generate more intracellular ROS in PSCs induced by plenty of ABZSO NPs, greatly increasing the mortality rate of PSCs in a shorter time than using ABZSO NPs alone, leading to the attenuation of laminated layer and finally disintegrating PSCs. We believe the "breaking-then-curing" strategy will suggest great potential in the treatment of CE and provide a new sight for anti-echinococcal treatment.
Cystic echinococcosis (CE) is one of the most harmful and life-threatening helminths. As the essential therapeutics, chemotherapy is always difficult to achieve desired anti-echinococcal effect due to the problems that the echinococcus granulosus cyst laminated layer makes the drug difficult to infiltrate and the poor solubility of drugs. In this study, we established a "breaking-then-curing" anti-echinococcal treatment strategy for efficient CE therapy. The photodynamic therapy (PDT) was used as a breaker to produce toxic reactive oxygen species (ROS) and damage the laminated layer of protoscolices (PSCs), leading to enhanced infiltration of albendazole sulfoxide nanoparticles (ABZSO NPs). Then, ABZSO NP was worked as curer for efficient anti-echinococcal treatment. As a result, the breaking-then-curing treatment strategy could generate more intracellular ROS in PSCs induced by plenty of ABZSO NPs, greatly increasing the mortality rate of PSCs in a shorter time than using ABZSO NPs alone, leading to the attenuation of laminated layer and finally disintegrating PSCs. We believe the "breaking-then-curing" strategy will suggest great potential in the treatment of CE and provide a new sight for anti-echinococcal treatment.
2022, 33(6): 2954-2958
doi: 10.1016/j.cclet.2021.12.090
Abstract:
In this work, we developed a novel photoelectrochemical (PEC) sensor based on n-p organic semiconductor heterojunction for sensitive detecting MCF-7 cancer cells. BTA-C4Ph and PM6 were designed as photoactive materials to form n-p heterojunction, which greatly enhanced the photoelectric conversion efficiency. Antibody-modified magnetic nanoparticles were utilized to capture and separate MCF-7 cells from samples. Detection of MCF-7 is ascribed to the loading of MCF-7 onto BTA-C4Ph-PM6 modified electrode that resulted in the decrease of photocurrent intensity. The PEC immunosensor displayed a linear concentration ranging from 50 cell/mL to 1 × 104 cell/mL with a limit of detection (LOD) of 41 cell/mL (S/N = 3) for MCF-7. Additionally, the senor also exhibited good stability, excellent selectivity and prominent reproducibility. Furthermore, the sensor was successfully applied to detect MCF-7 in whole blood. This work illustrates that n-p heterojunction of organic semiconductor may find wide applications for the preparation of different photoelectrochemical sensors.
In this work, we developed a novel photoelectrochemical (PEC) sensor based on n-p organic semiconductor heterojunction for sensitive detecting MCF-7 cancer cells. BTA-C4Ph and PM6 were designed as photoactive materials to form n-p heterojunction, which greatly enhanced the photoelectric conversion efficiency. Antibody-modified magnetic nanoparticles were utilized to capture and separate MCF-7 cells from samples. Detection of MCF-7 is ascribed to the loading of MCF-7 onto BTA-C4Ph-PM6 modified electrode that resulted in the decrease of photocurrent intensity. The PEC immunosensor displayed a linear concentration ranging from 50 cell/mL to 1 × 104 cell/mL with a limit of detection (LOD) of 41 cell/mL (S/N = 3) for MCF-7. Additionally, the senor also exhibited good stability, excellent selectivity and prominent reproducibility. Furthermore, the sensor was successfully applied to detect MCF-7 in whole blood. This work illustrates that n-p heterojunction of organic semiconductor may find wide applications for the preparation of different photoelectrochemical sensors.
2022, 33(6): 2959-2964
doi: 10.1016/j.cclet.2021.12.096
Abstract:
Compared with traditional photodynamic therapy (PDT), ultrasound (US) triggered sonodynamic therapy (SDT) has a wide application prospect in tumor therapy because of its deeper penetration depth. Herein, a novel MnSiO3-Pt (MP) nanocomposite composed of MnSiO3 nanosphere and noble metallic Pt was successfully constructed. After modification with bovine serum albumin (BSA) and chlorine e6 (Ce6), the multifunctional nanoplatform MnSiO3-Pt@BSA-Ce6 (MPBC) realized the magnetic resonance imaging (MRI)-guided synergetic SDT/chemodynamic therapy (CDT). In this nanoplatform, sonosensitizer Ce6 can generate singlet oxygen (1O2) to kill cancer cells under US irradiation. Meanwhile, the loaded Pt has the ability to catalyze the decomposition of overexpressed hydrogen peroxide (H2O2) in tumor microenvironment (TME) to produce oxygen (O2), which can conquer tumor hypoxia and promote the SDT-induced 1O2 production. In addition, MP can degrade in mildly acidic and reductive TME, causing the release of Mn2+. The released Mn2+ not only can be used for MRI, but also can generate hydroxyl radical (∙OH) for CDT by Fenton-like reaction. The multifunctional nanoplatform MPBC has high biological safety and good anticancer effect, which displays the great latent capacity in biological application.
Compared with traditional photodynamic therapy (PDT), ultrasound (US) triggered sonodynamic therapy (SDT) has a wide application prospect in tumor therapy because of its deeper penetration depth. Herein, a novel MnSiO3-Pt (MP) nanocomposite composed of MnSiO3 nanosphere and noble metallic Pt was successfully constructed. After modification with bovine serum albumin (BSA) and chlorine e6 (Ce6), the multifunctional nanoplatform MnSiO3-Pt@BSA-Ce6 (MPBC) realized the magnetic resonance imaging (MRI)-guided synergetic SDT/chemodynamic therapy (CDT). In this nanoplatform, sonosensitizer Ce6 can generate singlet oxygen (1O2) to kill cancer cells under US irradiation. Meanwhile, the loaded Pt has the ability to catalyze the decomposition of overexpressed hydrogen peroxide (H2O2) in tumor microenvironment (TME) to produce oxygen (O2), which can conquer tumor hypoxia and promote the SDT-induced 1O2 production. In addition, MP can degrade in mildly acidic and reductive TME, causing the release of Mn2+. The released Mn2+ not only can be used for MRI, but also can generate hydroxyl radical (∙OH) for CDT by Fenton-like reaction. The multifunctional nanoplatform MPBC has high biological safety and good anticancer effect, which displays the great latent capacity in biological application.
2022, 33(6): 2965-2968
doi: 10.1016/j.cclet.2021.12.097
Abstract:
Pure organic room-temperature phosphorescence (RTP) materials have attracted wide attention owing to their excellent luminescent properties and great potential in various applications. In this work, iminostilbene and its analogues are applied to realize RTP emission by copolymerizing with acrylamide. It can be concluded that the growth of alkane chain in monomers can enhance the lifetime and photoluminescence quantum yield of RTP emission, and polymers with the larger conjugated structure of the monomer show a longer RTP emission wavelength. This work provides a series of new pure organic RTP materials and might provide new thoughts for designing more advanced and superior RTP materials.
Pure organic room-temperature phosphorescence (RTP) materials have attracted wide attention owing to their excellent luminescent properties and great potential in various applications. In this work, iminostilbene and its analogues are applied to realize RTP emission by copolymerizing with acrylamide. It can be concluded that the growth of alkane chain in monomers can enhance the lifetime and photoluminescence quantum yield of RTP emission, and polymers with the larger conjugated structure of the monomer show a longer RTP emission wavelength. This work provides a series of new pure organic RTP materials and might provide new thoughts for designing more advanced and superior RTP materials.
2022, 33(6): 2969-2974
doi: 10.1016/j.cclet.2021.12.099
Abstract:
The abnormal activation of JAK2 kinase is closely related to the occurrence and progression of myeloproliferative neoplasms (MPNs). At present, there is still an obvious unmet medical need for selective JAK2 inhibitors in clinic. In this paper, a class of 2-aminopyridine derivatives as potent and selective JAK2 inhibitors was obtained by combining drug design, synthesis and structure-activity relationship studies based on the previously identified lead Crizotinib. Among them, 21b exhibited high inhibitory activity against JAK2 with an IC50 of 9 nmol/L, moreover, it showed 276- and 184-fold selectivity over JAK1 and JAK3, respectively. Besides, 21b had a significant antiproliferative activity against HEL cells, and also inhibited the phosphorylation of JAK2 and its down-stream signaling pathway. These results indicated that 2-aminopyridine compound 21b had the potential to be developed as a selective JAK2 inhibitor for further study.
The abnormal activation of JAK2 kinase is closely related to the occurrence and progression of myeloproliferative neoplasms (MPNs). At present, there is still an obvious unmet medical need for selective JAK2 inhibitors in clinic. In this paper, a class of 2-aminopyridine derivatives as potent and selective JAK2 inhibitors was obtained by combining drug design, synthesis and structure-activity relationship studies based on the previously identified lead Crizotinib. Among them, 21b exhibited high inhibitory activity against JAK2 with an IC50 of 9 nmol/L, moreover, it showed 276- and 184-fold selectivity over JAK1 and JAK3, respectively. Besides, 21b had a significant antiproliferative activity against HEL cells, and also inhibited the phosphorylation of JAK2 and its down-stream signaling pathway. These results indicated that 2-aminopyridine compound 21b had the potential to be developed as a selective JAK2 inhibitor for further study.
2022, 33(6): 2975-2981
doi: 10.1016/j.cclet.2021.12.086
Abstract:
Medical cotton dressing is cheap and widely used in diversified fields, but in the application of promoting wound healing, the continuous research of multifunctional medical cotton dressing is still of great significance. Here, we developed a fresh type of antibacterial cotton dressing through a succinct strategy based on chemically anchoring polyhexamethylene biguanide (PHMB). Intriguingly, after PHMB modification, the cotton dressing exhibited outstanding antibacterial performance which could maintain > 99.99% antibacterial rate after several treatments, including washing 50 times, repeated use 10 times, UV irradiation for 7 days, cationic dyes dying, and conditioned under 90 ℃ water bath for 2 h. In addition, the water contact angle of cotton dressing increased dramatically from 0° to 111°, which could facilitate bacterial adhesion, thus further enhance the antibacterial efficiency, and easily remove the bacterial debris. Apart from that, the developed cotton dressing showed good cytocompatibility, promoted blood clotting and expression of platelets, and promoted the wound healing process in the infection intervened skin wound model. Taken together, this antibacterial cotton dressing with desirable blood clotting, sustained protection against bacterial infection and bacterial removal features shows the potential to be a candidate for infected skin wound healing.
Medical cotton dressing is cheap and widely used in diversified fields, but in the application of promoting wound healing, the continuous research of multifunctional medical cotton dressing is still of great significance. Here, we developed a fresh type of antibacterial cotton dressing through a succinct strategy based on chemically anchoring polyhexamethylene biguanide (PHMB). Intriguingly, after PHMB modification, the cotton dressing exhibited outstanding antibacterial performance which could maintain > 99.99% antibacterial rate after several treatments, including washing 50 times, repeated use 10 times, UV irradiation for 7 days, cationic dyes dying, and conditioned under 90 ℃ water bath for 2 h. In addition, the water contact angle of cotton dressing increased dramatically from 0° to 111°, which could facilitate bacterial adhesion, thus further enhance the antibacterial efficiency, and easily remove the bacterial debris. Apart from that, the developed cotton dressing showed good cytocompatibility, promoted blood clotting and expression of platelets, and promoted the wound healing process in the infection intervened skin wound model. Taken together, this antibacterial cotton dressing with desirable blood clotting, sustained protection against bacterial infection and bacterial removal features shows the potential to be a candidate for infected skin wound healing.
2022, 33(6): 2982-2986
doi: 10.1016/j.cclet.2022.02.031
Abstract:
A [3 + 2]/[2 + 1] cycloaddition reaction of gem-difluorocyclopropenes is presented, offering a mild and efficient approach to accessing tri- and tetra-substituted 4-fluoropyridines in moderate to good yields with excellent regioselectivity. Multiple synthetic applications, including process-scale reactions, modification of bioactive molecules, derivatization reactions and synthesis of the analogue of the PKM2 modulator, are subsequently described.
A [3 + 2]/[2 + 1] cycloaddition reaction of gem-difluorocyclopropenes is presented, offering a mild and efficient approach to accessing tri- and tetra-substituted 4-fluoropyridines in moderate to good yields with excellent regioselectivity. Multiple synthetic applications, including process-scale reactions, modification of bioactive molecules, derivatization reactions and synthesis of the analogue of the PKM2 modulator, are subsequently described.
2022, 33(6): 2987-2992
doi: 10.1016/j.cclet.2022.01.068
Abstract:
A rhodium-catalyzed [4 + 3] cycloaddition reaction between N-methoxybenzamides and gem-difluorocyclopropenes is described. The reaction offers a mild and efficient approach towards the synthesis of fluorinated 2H-azepin-2-ones with broad substrate scope. A consecutive HOAc-assisted CN bond formation and fluorine elimination are involved as key steps for success as illustrated by detailed DFT studies.
A rhodium-catalyzed [4 + 3] cycloaddition reaction between N-methoxybenzamides and gem-difluorocyclopropenes is described. The reaction offers a mild and efficient approach towards the synthesis of fluorinated 2H-azepin-2-ones with broad substrate scope. A consecutive HOAc-assisted CN bond formation and fluorine elimination are involved as key steps for success as illustrated by detailed DFT studies.
2022, 33(6): 2993-2996
doi: 10.1016/j.cclet.2021.10.069
Abstract:
Naphthyridine-fused bisimidazolium salts were designed and synthesized for the first time. The study of the Cu(Ⅱ) and Pd(Ⅱ) complexes demonstrated that the deprotonated dicarbene ligands are rigid chelating C, C-ligands with strong electron-donating ability in analogy with the classic phenanthroline N, N-ligands.
Naphthyridine-fused bisimidazolium salts were designed and synthesized for the first time. The study of the Cu(Ⅱ) and Pd(Ⅱ) complexes demonstrated that the deprotonated dicarbene ligands are rigid chelating C, C-ligands with strong electron-donating ability in analogy with the classic phenanthroline N, N-ligands.
2022, 33(6): 2997-3002
doi: 10.1016/j.cclet.2021.11.070
Abstract:
Copper-catalyzed divergent annulations between α-diketones and alkynyl α-diketones have been achieved, delivering a series of highly functionalized and biologically important cis-hexahydro-2H-cyclopenta[b]furan (HCPF) and 2-hydroxydihydrofuran-3(2H)-one (HDFO) products with high levels of stereoselectivity under identical conditions. The protocol features the use of earth-abundant copper catalyst, mild conditions, shortening synthetic routes in constructing different molecular frameworks, and reducing the corresponding possible waste production. The substituents of the nucleophilic α-diketones play crucial roles in switching the reaction pathways.
Copper-catalyzed divergent annulations between α-diketones and alkynyl α-diketones have been achieved, delivering a series of highly functionalized and biologically important cis-hexahydro-2H-cyclopenta[b]furan (HCPF) and 2-hydroxydihydrofuran-3(2H)-one (HDFO) products with high levels of stereoselectivity under identical conditions. The protocol features the use of earth-abundant copper catalyst, mild conditions, shortening synthetic routes in constructing different molecular frameworks, and reducing the corresponding possible waste production. The substituents of the nucleophilic α-diketones play crucial roles in switching the reaction pathways.
2022, 33(6): 3003-3006
doi: 10.1016/j.cclet.2021.11.087
Abstract:
Neuromuscular blocking agents (NMBAs) are extensively used during anesthesia to improve surgical conditions by relaxing skeletal muscle movements. Rapid neuromuscular recovery after surgery is desirable to facilitate the recovery of muscle function and prevent residual blockade. Decamethonium (C10) is a classic NMBA, which has been restricted over the past decades ascribed to lack of a suitable antidote in clinic. Herein we used carboxylatopillar[6]arene (CP6A) to reverse neuromuscular blocker effect of C10 through direct host-guest encapsulation. NMR and isothermal titration calorimetry served to confirm the complexation between CP6A and C10 with robust affinity [(1.07 ± 0.14) × 107 L/mol]. The CP6A was further used as a reversal agent of C10, which facilitated to decrease C10 concentration in mice blood and excrete via urinary clearance, resulting in rapid recovery from muscle relaxation. These favorable outcomes might lead us to suggest that this supramolecular strategy could allow patients to regain lucidity much faster than spontaneous recovery from anesthesia.
Neuromuscular blocking agents (NMBAs) are extensively used during anesthesia to improve surgical conditions by relaxing skeletal muscle movements. Rapid neuromuscular recovery after surgery is desirable to facilitate the recovery of muscle function and prevent residual blockade. Decamethonium (C10) is a classic NMBA, which has been restricted over the past decades ascribed to lack of a suitable antidote in clinic. Herein we used carboxylatopillar[6]arene (CP6A) to reverse neuromuscular blocker effect of C10 through direct host-guest encapsulation. NMR and isothermal titration calorimetry served to confirm the complexation between CP6A and C10 with robust affinity [(1.07 ± 0.14) × 107 L/mol]. The CP6A was further used as a reversal agent of C10, which facilitated to decrease C10 concentration in mice blood and excrete via urinary clearance, resulting in rapid recovery from muscle relaxation. These favorable outcomes might lead us to suggest that this supramolecular strategy could allow patients to regain lucidity much faster than spontaneous recovery from anesthesia.
2022, 33(6): 3007-3011
doi: 10.1016/j.cclet.2021.12.002
Abstract:
A hexafluoroisopropanol (HFIP)-catalyzed highly diastereoselective formal [4 + 2] cyclization between ortho-hydroxyphenyl para-quinone methides and difluoroenoxysilanes is developed. This tandem protocol provides a simple and straightforward approach to assemble diverse multiply functionalized difluorinated chromans with high to excellent diastereoselectivity by employing difluoroenoxysilane as a new C2 synthon.
A hexafluoroisopropanol (HFIP)-catalyzed highly diastereoselective formal [4 + 2] cyclization between ortho-hydroxyphenyl para-quinone methides and difluoroenoxysilanes is developed. This tandem protocol provides a simple and straightforward approach to assemble diverse multiply functionalized difluorinated chromans with high to excellent diastereoselectivity by employing difluoroenoxysilane as a new C2 synthon.
2022, 33(6): 3012-3016
doi: 10.1016/j.cclet.2021.12.006
Abstract:
The first example of stereoconvergent 1, 3-dipolar cycloaddition of nitrile oxides and nitrile imines with E/Z isomeric mixture of electron-deficient olefins is reported, delivering isoxazolines and pyrazolines bearing two vicinal stereogenic tertiary and trifluoromethylated quaternary carbon centers with perfect regio- and diastereoselectivities. The possibility of concerted cycloaddition/epimerization sequence under basic condition to form the thermodynamically stable diastereomers is excluded through some control experiments and DFT calculations, and a stepwise mechanism is proposed.
The first example of stereoconvergent 1, 3-dipolar cycloaddition of nitrile oxides and nitrile imines with E/Z isomeric mixture of electron-deficient olefins is reported, delivering isoxazolines and pyrazolines bearing two vicinal stereogenic tertiary and trifluoromethylated quaternary carbon centers with perfect regio- and diastereoselectivities. The possibility of concerted cycloaddition/epimerization sequence under basic condition to form the thermodynamically stable diastereomers is excluded through some control experiments and DFT calculations, and a stepwise mechanism is proposed.
2022, 33(6): 3017-3020
doi: 10.1016/j.cclet.2021.12.011
Abstract:
A new type of covalent organic framework (COF) was achieved using combination of structrally rigid and conformationally othorganal building blocks. The N-2-aryl-substituted triazole derivative (NAT-CHO) was prepared with co-planar conformation among the three aromatic rings as the "flat" building block. The 4, 4′, 4′′, 4′′′-(ethene-1, 1, 2, 2-tetrayl)tetraaniline) (ETTA) was applied as the "twist" building block. A 2D sheet of network was obtained through imine formation. The resulting NAT-COF gave excellent thermal and chemical stability, survived aqueous solutions from pH 5 to 13. With large-size building blocks, the porous framework NAT-COF gave efficient gas adsorption with excellent selectivity of C3 propane over C1 me-thane, suggesting its potential application for selective gas capture and separation.
A new type of covalent organic framework (COF) was achieved using combination of structrally rigid and conformationally othorganal building blocks. The N-2-aryl-substituted triazole derivative (NAT-CHO) was prepared with co-planar conformation among the three aromatic rings as the "flat" building block. The 4, 4′, 4′′, 4′′′-(ethene-1, 1, 2, 2-tetrayl)tetraaniline) (ETTA) was applied as the "twist" building block. A 2D sheet of network was obtained through imine formation. The resulting NAT-COF gave excellent thermal and chemical stability, survived aqueous solutions from pH 5 to 13. With large-size building blocks, the porous framework NAT-COF gave efficient gas adsorption with excellent selectivity of C3 propane over C1 me-thane, suggesting its potential application for selective gas capture and separation.
2022, 33(6): 3021-3025
doi: 10.1016/j.cclet.2021.12.012
Abstract:
MeOTf-catalyzed formal [4 + 2] annulation of styrene oxides with alkynes to afford polysubstituted naphthalenes has been realized, which undergoes sequential electrophilic cyclization/ring expansion. A range of substrates were tolerated in the formation of naphthalene derivatives with high regioselectivity in satisfactory yields. The reaction could also be carried out on gram scale.
MeOTf-catalyzed formal [4 + 2] annulation of styrene oxides with alkynes to afford polysubstituted naphthalenes has been realized, which undergoes sequential electrophilic cyclization/ring expansion. A range of substrates were tolerated in the formation of naphthalene derivatives with high regioselectivity in satisfactory yields. The reaction could also be carried out on gram scale.
2022, 33(6): 3026-3030
doi: 10.1016/j.cclet.2021.09.039
Abstract:
DNA-functionalized gold nanoparticles are one of the most versatile bionanomaterials for biomedical and clinical diagnosis. Herein, we discovered that the performance of DNAzyme cleaving the substrate is highly related to its length. This intriguing phenomenon only appears at the interfaces of DNA-functionalized gold nanoparticles. We systematically investigated the causes of this phenomenon. We conjectured that the DNAzyme with extended nucleotides that do not match its substrate strand is vulnerable to non-specific adsorption, electrostatic repulsion, and steric hindrance. Based on our improved understanding of this phenomenon, we have successfully developed a highly sensitive and specific amplifiable biosensor to detect human apurinic/apyrimidinic endonuclease 1.
DNA-functionalized gold nanoparticles are one of the most versatile bionanomaterials for biomedical and clinical diagnosis. Herein, we discovered that the performance of DNAzyme cleaving the substrate is highly related to its length. This intriguing phenomenon only appears at the interfaces of DNA-functionalized gold nanoparticles. We systematically investigated the causes of this phenomenon. We conjectured that the DNAzyme with extended nucleotides that do not match its substrate strand is vulnerable to non-specific adsorption, electrostatic repulsion, and steric hindrance. Based on our improved understanding of this phenomenon, we have successfully developed a highly sensitive and specific amplifiable biosensor to detect human apurinic/apyrimidinic endonuclease 1.
2022, 33(6): 3031-3034
doi: 10.1016/j.cclet.2021.09.022
Abstract:
Aromatic carboxylic acids (ACAs) may be as transformed key metabolites via gut microbiome for playing better pharmacological effects. However, it's rare to achieve high-specificity, high-sensitivity, and high-throughput detection simultaneously, especially, for tracing trace ACAs in gut microbiome. In this work, firstly, a novel dual-template and double-shelled molecularly imprinted 96-well microplates (DDMIPs) was designed and amplified signal for p-hydroxybenzoic acid (PBA) and 3, 4, 5-trimethoxycinnamic acid (TMA). Additionally, the DDMIPs and a stable isotope labeling derivatization (SILD) method combined with the ultra-high performance liquid chromatography triple quadrupole tandem mass spectrometry (UHPLC-TQ MS) was firstly stepwise integrated, achieving high-effective, high-sensitive, and high-throughput study of gut microbiome metabolism. The whole strategy showed lower limits of detections (LODs) up to 1000 folds than the traditional method, and revealed a more real metabolism-time profile of PBA and TMA by 3-step signal amplification. The platform also laid the foundation for fast, simple, high-selective, high-effective, and high-throughput metabolism and pharmacological research.
Aromatic carboxylic acids (ACAs) may be as transformed key metabolites via gut microbiome for playing better pharmacological effects. However, it's rare to achieve high-specificity, high-sensitivity, and high-throughput detection simultaneously, especially, for tracing trace ACAs in gut microbiome. In this work, firstly, a novel dual-template and double-shelled molecularly imprinted 96-well microplates (DDMIPs) was designed and amplified signal for p-hydroxybenzoic acid (PBA) and 3, 4, 5-trimethoxycinnamic acid (TMA). Additionally, the DDMIPs and a stable isotope labeling derivatization (SILD) method combined with the ultra-high performance liquid chromatography triple quadrupole tandem mass spectrometry (UHPLC-TQ MS) was firstly stepwise integrated, achieving high-effective, high-sensitive, and high-throughput study of gut microbiome metabolism. The whole strategy showed lower limits of detections (LODs) up to 1000 folds than the traditional method, and revealed a more real metabolism-time profile of PBA and TMA by 3-step signal amplification. The platform also laid the foundation for fast, simple, high-selective, high-effective, and high-throughput metabolism and pharmacological research.
2022, 33(6): 3035-3038
doi: 10.1016/j.cclet.2021.09.024
Abstract:
In this paper, Ni3S2 nanosheet (NS) was generated by chemical etching with sodium sulfide directly on the nickel foam (NF), which was induced by dielectric barrier discharge plasma in liquid. Compared with other chemical etching methods of nickel-based nanomaterials, this method was not only rapid (40 min) and mild (at room temperature and atmospheric pressure), but also showed consistent stability and good reproducibility. The Ni3S2 NS/NF electrode showed excellent performance in the electrochemical detection of formaldehyde under alkaline conditions. It had a good linear relationship with the concentration of formaldehyde in the range of 0.002-5.45 mmol/L (R2 = 0.9957) and the limit of detection (LOD) was 1.23 µmol/L (S/N = 3). The sensitivity was 1286.9 µA L mmol‒1 cm‒2, and the response time was about 5 s. The plasma-induced chemical etching strategy provides a simple and stable electrode preparation method, which has great application prospects in nonenzymatic electrochemical sensors.
In this paper, Ni3S2 nanosheet (NS) was generated by chemical etching with sodium sulfide directly on the nickel foam (NF), which was induced by dielectric barrier discharge plasma in liquid. Compared with other chemical etching methods of nickel-based nanomaterials, this method was not only rapid (40 min) and mild (at room temperature and atmospheric pressure), but also showed consistent stability and good reproducibility. The Ni3S2 NS/NF electrode showed excellent performance in the electrochemical detection of formaldehyde under alkaline conditions. It had a good linear relationship with the concentration of formaldehyde in the range of 0.002-5.45 mmol/L (R2 = 0.9957) and the limit of detection (LOD) was 1.23 µmol/L (S/N = 3). The sensitivity was 1286.9 µA L mmol‒1 cm‒2, and the response time was about 5 s. The plasma-induced chemical etching strategy provides a simple and stable electrode preparation method, which has great application prospects in nonenzymatic electrochemical sensors.
2022, 33(6): 3039-3042
doi: 10.1016/j.cclet.2021.09.033
Abstract:
Excellent optical properties involving strong visible light response and superior carrier transport endow metal halide perovskites (MHP) with a fascinating prospect in the field of photocatalysis. Nevertheless, the poor stability of MHP nanocrystals (NCs) in water-contained system, especially without the protection of long alkyl chain ligands, severely restricts their photocatalytic performance. In this context, we report an effortless strategy for the generation of ligand-free MHP NCs based photocatalyst with high water tolerance, by coating PbI2 on the surface of ligand-free formamidinium lead bromide (FAPbBr3) NCs via the facile procedure of in-situ conversion with the aid of ZnI2. Under the protection of PbI2 layer, the resultant FAPbBr3/PbI2 composite exhibits significantly ameliorated stability in an artificial photosynthesis system with CO2 and H2O vapor as feedstocks. Moreover, the formation of compact PbI2 layer can accelerate the separation of photogenerated carriers in FAPbBr3 NCs, bringing forth a remarkable improvement of CO2 photoreduction efficiency with an impressive electron consumption yield of 2053 µmol/g in the absence of organic sacrificial agents, which is 7-fold over that of pristine FAPbBr3 NCs.
Excellent optical properties involving strong visible light response and superior carrier transport endow metal halide perovskites (MHP) with a fascinating prospect in the field of photocatalysis. Nevertheless, the poor stability of MHP nanocrystals (NCs) in water-contained system, especially without the protection of long alkyl chain ligands, severely restricts their photocatalytic performance. In this context, we report an effortless strategy for the generation of ligand-free MHP NCs based photocatalyst with high water tolerance, by coating PbI2 on the surface of ligand-free formamidinium lead bromide (FAPbBr3) NCs via the facile procedure of in-situ conversion with the aid of ZnI2. Under the protection of PbI2 layer, the resultant FAPbBr3/PbI2 composite exhibits significantly ameliorated stability in an artificial photosynthesis system with CO2 and H2O vapor as feedstocks. Moreover, the formation of compact PbI2 layer can accelerate the separation of photogenerated carriers in FAPbBr3 NCs, bringing forth a remarkable improvement of CO2 photoreduction efficiency with an impressive electron consumption yield of 2053 µmol/g in the absence of organic sacrificial agents, which is 7-fold over that of pristine FAPbBr3 NCs.
2022, 33(6): 3043-3048
doi: 10.1016/j.cclet.2021.09.038
Abstract:
Enzyme assisted DNA probes are powerful tools in molecular diagnostics for their simplicity, rapidity, and low detection limit. However, cost of probes, difficulty in optimization and disturbance of secondary structure hindered the wider application of enzyme assisted DNA probes. To solve the problems, we designed a new system named shared-probe system. By introducing two unlabeled single stranded DNA named Sh1 and Sh2 as the bridge between probe and the substrate, the same sequence of dually labeled probe with stable performance was shared for different mutations, thus sparing the expense and time cost on designing, synthesizing and optimizing corresponding probes. Besides, the hybridization between Sh1 and the substrate could overcome secondary structures, which guaranteed the detection of different substrates. The performance and generality of the design were tested by low abundance detection in synthetic single DNA samples and the limit of detection was 0.05% for PTENR130Q, EGFR-L858R and 0.02% for BRCA1-NM007294.3. In genomic DNA samples, the limit of detection of 0.1% can be achieved for EGFR-L858R, demonstrating the potential of clinical application in our design.
Enzyme assisted DNA probes are powerful tools in molecular diagnostics for their simplicity, rapidity, and low detection limit. However, cost of probes, difficulty in optimization and disturbance of secondary structure hindered the wider application of enzyme assisted DNA probes. To solve the problems, we designed a new system named shared-probe system. By introducing two unlabeled single stranded DNA named Sh1 and Sh2 as the bridge between probe and the substrate, the same sequence of dually labeled probe with stable performance was shared for different mutations, thus sparing the expense and time cost on designing, synthesizing and optimizing corresponding probes. Besides, the hybridization between Sh1 and the substrate could overcome secondary structures, which guaranteed the detection of different substrates. The performance and generality of the design were tested by low abundance detection in synthetic single DNA samples and the limit of detection was 0.05% for PTENR130Q, EGFR-L858R and 0.02% for BRCA1-NM007294.3. In genomic DNA samples, the limit of detection of 0.1% can be achieved for EGFR-L858R, demonstrating the potential of clinical application in our design.
2022, 33(6): 3049-3052
doi: 10.1016/j.cclet.2021.09.047
Abstract:
Several 2D nanosheets of porphyrin MOFs with various transition-metal clusters as metal nodes were prepared via a simple solvothermal method to apply in the photocatalytic hydrogen evolution, in which the hydrogen production rate of the optimal NS-Cu was as high as 15.39 mmol g−1 h−1. A series of experimental technologies especially cyclic voltammetry (CV) and Mott-Schottky (M-S) had been adopted to investigate the charge-transfer property of photo-generated electron-hole pairs, it was found that the uniformly dispersed Cu-clusters nodes in the original 2D MOFs played a key role in the electron transfer process, that was, the photo-generated electron transferred from excited state eosin-Y to the Cu-clusters nodes for the efficient hydrogen evolution. The excellent photocatalytic performance could be attributed to the reversible oxidation-–reduction process of CuⅡ/CuⅠ, which had excellent electron-receiving and electron-outputting capabilities. Our results provided a novel avenue to adapt the uniformly dispersed metal nodes in the original MOFs as cost-effective noble-metal-free cocatalysts with very high atom-utilization efficiency to improve the photocatalytic hydrogen evolution performance in dye-sensitized system.
Several 2D nanosheets of porphyrin MOFs with various transition-metal clusters as metal nodes were prepared via a simple solvothermal method to apply in the photocatalytic hydrogen evolution, in which the hydrogen production rate of the optimal NS-Cu was as high as 15.39 mmol g−1 h−1. A series of experimental technologies especially cyclic voltammetry (CV) and Mott-Schottky (M-S) had been adopted to investigate the charge-transfer property of photo-generated electron-hole pairs, it was found that the uniformly dispersed Cu-clusters nodes in the original 2D MOFs played a key role in the electron transfer process, that was, the photo-generated electron transferred from excited state eosin-Y to the Cu-clusters nodes for the efficient hydrogen evolution. The excellent photocatalytic performance could be attributed to the reversible oxidation-–reduction process of CuⅡ/CuⅠ, which had excellent electron-receiving and electron-outputting capabilities. Our results provided a novel avenue to adapt the uniformly dispersed metal nodes in the original MOFs as cost-effective noble-metal-free cocatalysts with very high atom-utilization efficiency to improve the photocatalytic hydrogen evolution performance in dye-sensitized system.
2022, 33(6): 3053-3060
doi: 10.1016/j.cclet.2021.09.043
Abstract:
Conversion of hexavalent chromium (Cr(Ⅵ)) to trivalent chromium (Cr(Ⅲ)) is an effective way to reduce its environmental risk, especially via photoreduction process. However, over a wide range of pH values, it is still a great challenge to achieve a high removal rate, and the disposal of produced Cr(Ⅲ) should be concerned. In this work, we implemented a high removal rate at 98% for Cr(Ⅵ) and total chromium (Cr(T)) over a wide pH range (4–10) through the synergistic effect of adsorption, photoreduction and immobilization on the surface of BiOBr0.25I0.75. The substitution of bromine by iodine reduced the adsorption energy of Cr(Ⅵ) on BiOBr0.25I0.75, promoting the adsorption of Cr(Ⅵ). Meanwhile, the introduced iodine upshifted the conduction band (CB), enhancing the reduction ability for Cr(Ⅵ) to Cr(Ⅲ). The negative surface of BiOBr0.25I0.75 can capture Cr(Ⅲ), achieving a high removal rate for Cr(T). The pH-independent feature for Cr(Ⅵ) and Cr(Ⅲ) removal make BiOBr0.25I0.75 a potential material for chromium-containing wastewater treatment. This work provides an effective strategy for removing chromium over a wide pH range.
Conversion of hexavalent chromium (Cr(Ⅵ)) to trivalent chromium (Cr(Ⅲ)) is an effective way to reduce its environmental risk, especially via photoreduction process. However, over a wide range of pH values, it is still a great challenge to achieve a high removal rate, and the disposal of produced Cr(Ⅲ) should be concerned. In this work, we implemented a high removal rate at 98% for Cr(Ⅵ) and total chromium (Cr(T)) over a wide pH range (4–10) through the synergistic effect of adsorption, photoreduction and immobilization on the surface of BiOBr0.25I0.75. The substitution of bromine by iodine reduced the adsorption energy of Cr(Ⅵ) on BiOBr0.25I0.75, promoting the adsorption of Cr(Ⅵ). Meanwhile, the introduced iodine upshifted the conduction band (CB), enhancing the reduction ability for Cr(Ⅵ) to Cr(Ⅲ). The negative surface of BiOBr0.25I0.75 can capture Cr(Ⅲ), achieving a high removal rate for Cr(T). The pH-independent feature for Cr(Ⅵ) and Cr(Ⅲ) removal make BiOBr0.25I0.75 a potential material for chromium-containing wastewater treatment. This work provides an effective strategy for removing chromium over a wide pH range.
2022, 33(6): 3061-3064
doi: 10.1016/j.cclet.2021.09.057
Abstract:
Owing to the exorbitant overpotential and serious carrier recombination of graphitic carbon nitride (g-C3N4), noble metal (NM) is usually served as the H2 evolution co-catalyst. Although the NM (such as Pt) nanoparticles can reduce the H2 evolution overpotential, the weak van der Waals interaction between Pt and g-C3N4 makes against the charge transfer. Herein, the solvothermal method is developed to achieve semi-chemical interaction between Pt and g-C3N4 nanotube (Pt-CNNT) for fast charge transfer. Moreover, the generated in-plane homojunction of CNNT can accelerate charge separation and restrain recombination. Meanwhile, the metallic Pt is an excellent H2 evolution co-catalyst. Photo/electrochemical tests verify that the semi-chemical interaction can improve photogenerated charge separation and transferability of CNNT. As a result, the photocatalytic H2 evolution turnover frequency (TOF) of Pt-CNNT under visible light irradiation reaches up to 918 h−1, which is one of the highest in the g-C3N4-based photocatalysts. This work provides a new idea to improve the charge transfer for efficient photocatalytic H2 evolution.
Owing to the exorbitant overpotential and serious carrier recombination of graphitic carbon nitride (g-C3N4), noble metal (NM) is usually served as the H2 evolution co-catalyst. Although the NM (such as Pt) nanoparticles can reduce the H2 evolution overpotential, the weak van der Waals interaction between Pt and g-C3N4 makes against the charge transfer. Herein, the solvothermal method is developed to achieve semi-chemical interaction between Pt and g-C3N4 nanotube (Pt-CNNT) for fast charge transfer. Moreover, the generated in-plane homojunction of CNNT can accelerate charge separation and restrain recombination. Meanwhile, the metallic Pt is an excellent H2 evolution co-catalyst. Photo/electrochemical tests verify that the semi-chemical interaction can improve photogenerated charge separation and transferability of CNNT. As a result, the photocatalytic H2 evolution turnover frequency (TOF) of Pt-CNNT under visible light irradiation reaches up to 918 h−1, which is one of the highest in the g-C3N4-based photocatalysts. This work provides a new idea to improve the charge transfer for efficient photocatalytic H2 evolution.
2022, 33(6): 3065-3072
doi: 10.1016/j.cclet.2021.09.056
Abstract:
The catalytic elimination of nitrogen-containing volatile organic compounds (NVOCs) still encounters bottlenecks in NOx formation and low N2 selectivity. Here, a series of Cu-promoted Ce-Zr mixed oxide catalysts were synthesized using a simple precipitation approach, and n-butylamine was adopted as the probe pollutant to evaluate their catalytic performance. The CeCu10%ZrOx catalyst exhibited the best catalytic activity, with 100% n-butylamine conversion and 90% N2 selectivity at 250 ℃. Concurrently, this sample also displayed good water resistance. A detailed characterization of the catalyst was performed through a series of experimental studies and theoretical calculations. The addition of Cu increased the redox property and promoted the production of oxygen vacancies, all of which were favorable for the greatest n-butylamine selective catalytic oxidation performance. The changes of oxygen vacancies over CeCu10%ZrOx in reaction process were studied by in situ Raman spectra. Moreover, in situ diffuse reflectance infrared Fourier transform spectra (DRIFTs) and theoretical calculations were employed to explore the reaction mechanism of n-butylamine selective oxidation. The high activity and selectivity of this catalyst confirm the practical feasibility of the selective oxidation of n-butylamine to CO2 and N2, and the exploration of the reaction mechanism provides new insights into the further design of catalysts.
The catalytic elimination of nitrogen-containing volatile organic compounds (NVOCs) still encounters bottlenecks in NOx formation and low N2 selectivity. Here, a series of Cu-promoted Ce-Zr mixed oxide catalysts were synthesized using a simple precipitation approach, and n-butylamine was adopted as the probe pollutant to evaluate their catalytic performance. The CeCu10%ZrOx catalyst exhibited the best catalytic activity, with 100% n-butylamine conversion and 90% N2 selectivity at 250 ℃. Concurrently, this sample also displayed good water resistance. A detailed characterization of the catalyst was performed through a series of experimental studies and theoretical calculations. The addition of Cu increased the redox property and promoted the production of oxygen vacancies, all of which were favorable for the greatest n-butylamine selective catalytic oxidation performance. The changes of oxygen vacancies over CeCu10%ZrOx in reaction process were studied by in situ Raman spectra. Moreover, in situ diffuse reflectance infrared Fourier transform spectra (DRIFTs) and theoretical calculations were employed to explore the reaction mechanism of n-butylamine selective oxidation. The high activity and selectivity of this catalyst confirm the practical feasibility of the selective oxidation of n-butylamine to CO2 and N2, and the exploration of the reaction mechanism provides new insights into the further design of catalysts.
2022, 33(6): 3073-3077
doi: 10.1016/j.cclet.2021.09.051
Abstract:
An efficient photo-Fenton catalyst (FeS2@HTCN) was designed by maximizing the synergistic effect of FeS2 nanoparticles and hollow tubular g-C3N4 (HTCN). Molecule self-assembly and molten salts-assisted calcination were used to engineering the hollow structured g-C3N4 before anchoring FeS2 nanoparticles on the walls of HTCN via reflux method. Compared to bulk g-C3N4, the unique structure of HTCN and heterojunction in the composite endowed FeS2@HTCN with more active sites and abundant channels for electron transfer and charge separation. The enriched electrons can improve the Fe3+ recycling and boost Fe2+ catalyzed •OH production via H2O2. As-prepared photo-Fenton catalyst was successfully applied to the treatment of industrial paint wastewater. The paint wastewater with its COD as high as 8200 mg/L can be effectively degraded with 0.2 mol/L H2O2 in 90 min under visible light irradiation. The photo-Fenton system was further evaluated according to the process stability and economic benefit, proving that the strategy presented in this work would be applicable to the treatment of real wastewater.
An efficient photo-Fenton catalyst (FeS2@HTCN) was designed by maximizing the synergistic effect of FeS2 nanoparticles and hollow tubular g-C3N4 (HTCN). Molecule self-assembly and molten salts-assisted calcination were used to engineering the hollow structured g-C3N4 before anchoring FeS2 nanoparticles on the walls of HTCN via reflux method. Compared to bulk g-C3N4, the unique structure of HTCN and heterojunction in the composite endowed FeS2@HTCN with more active sites and abundant channels for electron transfer and charge separation. The enriched electrons can improve the Fe3+ recycling and boost Fe2+ catalyzed •OH production via H2O2. As-prepared photo-Fenton catalyst was successfully applied to the treatment of industrial paint wastewater. The paint wastewater with its COD as high as 8200 mg/L can be effectively degraded with 0.2 mol/L H2O2 in 90 min under visible light irradiation. The photo-Fenton system was further evaluated according to the process stability and economic benefit, proving that the strategy presented in this work would be applicable to the treatment of real wastewater.
AuNP aggregation-induced quantitative colorimetric aptasensing of sulfadimethoxine with a smartphone
2022, 33(6): 3078-3082
doi: 10.1016/j.cclet.2021.09.061
Abstract:
A gold nanoparticle (AuNP) aggregation-induced colorimetric aptasensing method for quantitative detection of sulfadimethoxine (SDM) with a smartphone was developed. AuNPs were complexed with aptamers which protected AuNPs from aggregating in high-concentration salt solutions. In the presence of SDM, SDM bound with the aptamer on the surface of AuNPs with higher affinity, which competitively desorbed the aptamer from the AuNP surface and resulted in AuNPs aggregation, accompanied with a color change from red to purple-blue. The R, G and B values of images taken by a smartphone camera were analyzed with an app on the smartphone, and were utilized for quantitative analysis of SDM. Under the optimized conditions, the colorimetric aptasensing method using a smartphone showed high sensitivity for SDM, with the limit of detection of 0.023 ppm, lower than the allowed maximum SDM residue limit. This study provides a simple, fast, and easy to read method for on-site quantitative biochemical and cellular analysis.
A gold nanoparticle (AuNP) aggregation-induced colorimetric aptasensing method for quantitative detection of sulfadimethoxine (SDM) with a smartphone was developed. AuNPs were complexed with aptamers which protected AuNPs from aggregating in high-concentration salt solutions. In the presence of SDM, SDM bound with the aptamer on the surface of AuNPs with higher affinity, which competitively desorbed the aptamer from the AuNP surface and resulted in AuNPs aggregation, accompanied with a color change from red to purple-blue. The R, G and B values of images taken by a smartphone camera were analyzed with an app on the smartphone, and were utilized for quantitative analysis of SDM. Under the optimized conditions, the colorimetric aptasensing method using a smartphone showed high sensitivity for SDM, with the limit of detection of 0.023 ppm, lower than the allowed maximum SDM residue limit. This study provides a simple, fast, and easy to read method for on-site quantitative biochemical and cellular analysis.
2022, 33(6): 3083-3086
doi: 10.1016/j.cclet.2021.09.065
Abstract:
Microfluidic devices have become a powerful tool for chemical and biologic applications. To control different functional parts on the microchip, valve plays a key role in the device. In conventional methods, physio-mechanical valves are usually used on microfluidic chip. Herein, we reported a chemo-mechanical switchable valve on microfluidic chip by using a thermally responsive block copolymer. The wettability changes of capillary with copolymer modification on inner surface were investigated to verify the function as a valve. Capillaries with modification of poly-(N-isopropylacrylamide-co-hexafluoroisopropyl acrylate) (P(NIPAAm-co-HFIPA)) with a 20% HFIPA was demonstrated capable of control aqueous solution stop or go through. Then short capillaries with copolymer modification were integrated in microchannels as valves. With the temperature changing around lower critical solution temperature (LCST), the integrated chemo-mechanical switchable valve exhibited excellent "OPEN–CLOSE'' behavior for microflow control. After optimization of the block copolymer sequences and molar ratio, a switching time as low as 20 s was achieved. The developed micro valve was demonstrated effective for flow control on microchip.
Microfluidic devices have become a powerful tool for chemical and biologic applications. To control different functional parts on the microchip, valve plays a key role in the device. In conventional methods, physio-mechanical valves are usually used on microfluidic chip. Herein, we reported a chemo-mechanical switchable valve on microfluidic chip by using a thermally responsive block copolymer. The wettability changes of capillary with copolymer modification on inner surface were investigated to verify the function as a valve. Capillaries with modification of poly-(N-isopropylacrylamide-co-hexafluoroisopropyl acrylate) (P(NIPAAm-co-HFIPA)) with a 20% HFIPA was demonstrated capable of control aqueous solution stop or go through. Then short capillaries with copolymer modification were integrated in microchannels as valves. With the temperature changing around lower critical solution temperature (LCST), the integrated chemo-mechanical switchable valve exhibited excellent "OPEN–CLOSE'' behavior for microflow control. After optimization of the block copolymer sequences and molar ratio, a switching time as low as 20 s was achieved. The developed micro valve was demonstrated effective for flow control on microchip.
2022, 33(6): 3087-3090
doi: 10.1016/j.cclet.2021.09.072
Abstract:
Mn-Si-MEL zeolite was developed as a bi-functional adsorption-catalytic oxidation material for volatile organic compounds (VOCs) elimination due to its good hydrophobicity & good organophileproperty brought by the substitution of Mn for Al in zeolite and the superior catalytic oxidation property endowed by the existence of Mn species. Various Mn-Si-MEL samples were obtained by introducing Mn to MEL crystallization system via different ways. It was found the incorporated Mn ways have a significant effect on the behavior of Mn being involved in the crystallization of MEL and finally influenced the distribution of Mn in zeolite as well the physicochemical properties of product zeolite. The seeding method (Mn-S2(Seed)) is favorable for the good incorporation and uniform distribution of Mn in zeolite while both recrystallization method (Mn-S2(RC)) and direct synthesis method (Mn-S2(DH)) are favorable for obtaining more reducible Mn species and surface adsorbed oxygen species. The Mn amount incorporated into zeolite follows Mn-S2(RC) (1.96 wt%) > Mn-S2(Seed) (1.07 wt%) ≈ Mn-S2(DH) (0.97 wt%), the adsorption capacity of various samples follows Mn-S2(Seed) (83.3 μmol/g) ≈ Mn-S2(RC) (82.1 μmol/g) > Mn-S2(DH) (76.1 μmol/g), while the catalytic oxidation ability of three samples follows Mn-S2(RC) ≈ Mn-S2(DH) > Mn-S2(Seed). Furthermore, Mn-S2(RC) which exhibits both superior adsorption capacity and catalytic oxidation ability shows good hydrophobicity and superior recyclability, demonstrating its great potential to be applied in the VOCs elimination by an enrichment-degradation route.
Mn-Si-MEL zeolite was developed as a bi-functional adsorption-catalytic oxidation material for volatile organic compounds (VOCs) elimination due to its good hydrophobicity & good organophileproperty brought by the substitution of Mn for Al in zeolite and the superior catalytic oxidation property endowed by the existence of Mn species. Various Mn-Si-MEL samples were obtained by introducing Mn to MEL crystallization system via different ways. It was found the incorporated Mn ways have a significant effect on the behavior of Mn being involved in the crystallization of MEL and finally influenced the distribution of Mn in zeolite as well the physicochemical properties of product zeolite. The seeding method (Mn-S2(Seed)) is favorable for the good incorporation and uniform distribution of Mn in zeolite while both recrystallization method (Mn-S2(RC)) and direct synthesis method (Mn-S2(DH)) are favorable for obtaining more reducible Mn species and surface adsorbed oxygen species. The Mn amount incorporated into zeolite follows Mn-S2(RC) (1.96 wt%) > Mn-S2(Seed) (1.07 wt%) ≈ Mn-S2(DH) (0.97 wt%), the adsorption capacity of various samples follows Mn-S2(Seed) (83.3 μmol/g) ≈ Mn-S2(RC) (82.1 μmol/g) > Mn-S2(DH) (76.1 μmol/g), while the catalytic oxidation ability of three samples follows Mn-S2(RC) ≈ Mn-S2(DH) > Mn-S2(Seed). Furthermore, Mn-S2(RC) which exhibits both superior adsorption capacity and catalytic oxidation ability shows good hydrophobicity and superior recyclability, demonstrating its great potential to be applied in the VOCs elimination by an enrichment-degradation route.
2022, 33(6): 3091-3096
doi: 10.1016/j.cclet.2021.09.080
Abstract:
The cellular response to the complex extracellular microenvironment is highly dynamic in time and type of extracellular matrix. Accurately reconstructing this process and analyzing the changes in receptor conformation on the cell membrane surface and intracellular or intercellular signaling has been a major challenge in analytical chemistry and biophysical methodology. In this paper, a time-coded multi-concentration microfluidic chemical waveform generator was developed for the dynamic signaling probing with single-cell array of high temporal resolution, high throughput, and multi-concentration combination stimulation. Based on innovative microchannel structure, sophisticated external control methods and multiplexing technology, the system not only allowed for temporally sequential permutations of the four concentrations of stimuli (time code), but also generated pulsed and continuous waveforms at different frequencies in a highly controllable manner. Furthermore, the single-cell trap array was set up to efficiently capture cells in suspension, dramatically increasing throughput and reducing experiment preparation time. The maximum frequency of the platform was 1 Hz, and one cell could be stimulated at multiple frequencies. To show the ability of the system to investigate rapid biochemical events in high throughput, pulse stimulation and continuous stimulation of different frequencies and different time codes, combined with four concentrations of histamine (HA), were generated for probing G protein-coupled receptor (GPCR) signaling in HeLa cells. Then, statistical analysis was performed for the mean peak height and mean peak area of the cellular response. We believe that the time-coded multi-concentration microfluidic chemical waveform generator will provide a novel strategy for analytical chemistry, biophysics, cell signaling, and individualized medicine applications.
The cellular response to the complex extracellular microenvironment is highly dynamic in time and type of extracellular matrix. Accurately reconstructing this process and analyzing the changes in receptor conformation on the cell membrane surface and intracellular or intercellular signaling has been a major challenge in analytical chemistry and biophysical methodology. In this paper, a time-coded multi-concentration microfluidic chemical waveform generator was developed for the dynamic signaling probing with single-cell array of high temporal resolution, high throughput, and multi-concentration combination stimulation. Based on innovative microchannel structure, sophisticated external control methods and multiplexing technology, the system not only allowed for temporally sequential permutations of the four concentrations of stimuli (time code), but also generated pulsed and continuous waveforms at different frequencies in a highly controllable manner. Furthermore, the single-cell trap array was set up to efficiently capture cells in suspension, dramatically increasing throughput and reducing experiment preparation time. The maximum frequency of the platform was 1 Hz, and one cell could be stimulated at multiple frequencies. To show the ability of the system to investigate rapid biochemical events in high throughput, pulse stimulation and continuous stimulation of different frequencies and different time codes, combined with four concentrations of histamine (HA), were generated for probing G protein-coupled receptor (GPCR) signaling in HeLa cells. Then, statistical analysis was performed for the mean peak height and mean peak area of the cellular response. We believe that the time-coded multi-concentration microfluidic chemical waveform generator will provide a novel strategy for analytical chemistry, biophysics, cell signaling, and individualized medicine applications.
2022, 33(6): 3097-3100
doi: 10.1016/j.cclet.2021.09.099
Abstract:
In this work, a modification method of H3PO4 plus H2O2 (PHP) was introduced to targetedly form abundant oxygenated functional groups (OFGs) on biochar, and methylene blue (MB) was employed as a model pollutant for adsorption to reflect the modification performance. Results indicated that parent biochars, especially derived from lower temperatures, substantially underwent oxidative modification by PHP, and OFGs were targetedly produced. Correspondingly, approximately 21.5-fold MB adsorption capacity was achieved by PHP-modified biochar comparing with its parent biochar. To evaluate the compatibility of PHP-modification, coefficient of variation (CV) based on MB adsorption capacity by the biochar from various precursors was calculated, in which the CV of PHP-modified biochars was 0.0038 comparing to 0.64 of the corresponding parent biochars. These results suggested that the PHP method displayed the excellent feedstock compatibility on biochar modification. The maximum MB adsorption capacity was 454.1 mg/g when the H3PO4 and H2O2 fraction in PHP were 65.2% and 7.0%; the modification was further intensified by promoting temperature and duration. Besides, average 94.5% H3PO4 was recovered after 10-batch modification, implying 1.0 kg H3PO4 (85%) in PHP can maximally modify 2.37 kg biochar. Overall, this work offered a novel method to tailor biochar towards OFGs-rich surface for efficient adsorption.
In this work, a modification method of H3PO4 plus H2O2 (PHP) was introduced to targetedly form abundant oxygenated functional groups (OFGs) on biochar, and methylene blue (MB) was employed as a model pollutant for adsorption to reflect the modification performance. Results indicated that parent biochars, especially derived from lower temperatures, substantially underwent oxidative modification by PHP, and OFGs were targetedly produced. Correspondingly, approximately 21.5-fold MB adsorption capacity was achieved by PHP-modified biochar comparing with its parent biochar. To evaluate the compatibility of PHP-modification, coefficient of variation (CV) based on MB adsorption capacity by the biochar from various precursors was calculated, in which the CV of PHP-modified biochars was 0.0038 comparing to 0.64 of the corresponding parent biochars. These results suggested that the PHP method displayed the excellent feedstock compatibility on biochar modification. The maximum MB adsorption capacity was 454.1 mg/g when the H3PO4 and H2O2 fraction in PHP were 65.2% and 7.0%; the modification was further intensified by promoting temperature and duration. Besides, average 94.5% H3PO4 was recovered after 10-batch modification, implying 1.0 kg H3PO4 (85%) in PHP can maximally modify 2.37 kg biochar. Overall, this work offered a novel method to tailor biochar towards OFGs-rich surface for efficient adsorption.
2022, 33(6): 3101-3105
doi: 10.1016/j.cclet.2021.09.060
Abstract:
Nicotine ingested from smoking exerts neuroprotection and developmental neurotoxicity in central nervous system. It can produce several changes of cognitive behaviors through regulating the release of different neurotransmitters in the brain. However, the effects of nicotine exposure or withdrawal on neurotransmitter metabolism of hippocampus are still unclear. In this study, we real-time evaluated the dynamic alterations in neurotransmitter metabolism of hippocampal neuronal (HT22) cells induced by nicotine exposure and withdrawal at relevant exposure levels of smoking and secondhand smoke by using a microfluidic chip-coupled with liquid chromatography-mass spectrometry (MC-LC-MS) system. We found HT22 cells mainly released related neurotransmitters of tryptophan and choline metabolism, both nicotine exposure and withdraw altered its neurotransmitters and their metabolites release. Exposure to nicotine mainly altered the secretion of serotonin, kynurenic acid, choline and acetylcholine of HT22 cells to improve hippocampal dependent cognition, and the change are closely related to the dose and duration of exposure. Moreover, the altered metabolites could rapidly recover after nicotine withdrawal, but picolinic acid was elevated. MC-LC-MS system used in present study showed a greater advantage to detect unstable metabolites than conventional method by using in vitro model, and the results of dynamic alterations of neurotransmitter metabolism induced by nicotine might provide a potential targets for drug development of neuroprotection or cognitive improvement.
Nicotine ingested from smoking exerts neuroprotection and developmental neurotoxicity in central nervous system. It can produce several changes of cognitive behaviors through regulating the release of different neurotransmitters in the brain. However, the effects of nicotine exposure or withdrawal on neurotransmitter metabolism of hippocampus are still unclear. In this study, we real-time evaluated the dynamic alterations in neurotransmitter metabolism of hippocampal neuronal (HT22) cells induced by nicotine exposure and withdrawal at relevant exposure levels of smoking and secondhand smoke by using a microfluidic chip-coupled with liquid chromatography-mass spectrometry (MC-LC-MS) system. We found HT22 cells mainly released related neurotransmitters of tryptophan and choline metabolism, both nicotine exposure and withdraw altered its neurotransmitters and their metabolites release. Exposure to nicotine mainly altered the secretion of serotonin, kynurenic acid, choline and acetylcholine of HT22 cells to improve hippocampal dependent cognition, and the change are closely related to the dose and duration of exposure. Moreover, the altered metabolites could rapidly recover after nicotine withdrawal, but picolinic acid was elevated. MC-LC-MS system used in present study showed a greater advantage to detect unstable metabolites than conventional method by using in vitro model, and the results of dynamic alterations of neurotransmitter metabolism induced by nicotine might provide a potential targets for drug development of neuroprotection or cognitive improvement.
2022, 33(6): 3106-3112
doi: 10.1016/j.cclet.2021.09.097
Abstract:
Considering that cathode of microbial electrochemical system (MES) is a good electrons source for methane production via direct/indirect electron transfer to electroactive microorganisms, and that Fe(0) is also a confirmed electron donor for some electroactive microorganisms through metal-microbe direct electron transfer (DET), Fe(0)-cathode was equipped into an MES digester to enhance cathodic methane production. The results of this study indicated that the potential DET participator, Clostridium possibly obtained electrons directly from Fe(0)-cathode via metal-microbe electrons transfer, then transferred electrons directly to the definite DET participators, Methanosarcina/Methanothrix via microbe-microbe electrons transfer for CH4 production. In addition, Methanobacterium is another specially enriched methanogen on Fe(0)-cathode, which might obtain electrons directly from Fe(0)-cathode to produce CH4 via metal/electrode-microbe DET. The increment of conductivity of cathodic sludge in Fe(0)-cathode MES digester (R1) further confirmed the enrichment of electroactive microorganisms participating in DET process. As a consequence, a higher CH4 production (1205–1508 mL/d) and chemical oxygen demand (COD) removal (79.0%-93.8%) were achieved in R1 compared with graphite-cathode MES digester (R2, 720–1090 mL/d and 63.6%-85.6%) and the conventional anaerobic digester (R3, 384–428 mL/d and 35.2%-41.0%). In addition, energy efficiency calculated indicated that the output energy of CH4 production was 8.16 folds of electricity input in Fe(0)-cathode MES digester.
Considering that cathode of microbial electrochemical system (MES) is a good electrons source for methane production via direct/indirect electron transfer to electroactive microorganisms, and that Fe(0) is also a confirmed electron donor for some electroactive microorganisms through metal-microbe direct electron transfer (DET), Fe(0)-cathode was equipped into an MES digester to enhance cathodic methane production. The results of this study indicated that the potential DET participator, Clostridium possibly obtained electrons directly from Fe(0)-cathode via metal-microbe electrons transfer, then transferred electrons directly to the definite DET participators, Methanosarcina/Methanothrix via microbe-microbe electrons transfer for CH4 production. In addition, Methanobacterium is another specially enriched methanogen on Fe(0)-cathode, which might obtain electrons directly from Fe(0)-cathode to produce CH4 via metal/electrode-microbe DET. The increment of conductivity of cathodic sludge in Fe(0)-cathode MES digester (R1) further confirmed the enrichment of electroactive microorganisms participating in DET process. As a consequence, a higher CH4 production (1205–1508 mL/d) and chemical oxygen demand (COD) removal (79.0%-93.8%) were achieved in R1 compared with graphite-cathode MES digester (R2, 720–1090 mL/d and 63.6%-85.6%) and the conventional anaerobic digester (R3, 384–428 mL/d and 35.2%-41.0%). In addition, energy efficiency calculated indicated that the output energy of CH4 production was 8.16 folds of electricity input in Fe(0)-cathode MES digester.
2022, 33(6): 3113-3118
doi: 10.1016/j.cclet.2021.10.005
Abstract:
The nitrogen-doped carbon derived from graphitic carbon nitride (g-C3N4) has been widely deployed in activating peroxymonosulfate (PMS) to remove organic pollutants. However, the instability of g-C3N4 at high temperature brings challenges to the preparation of materials. The nitrogen-doped graphitic carbon nanosheets (N-GC750) were synthesized by magnesium thermal denitrification. Magnesium undergoes the displacement reaction with small molecules produced by the pyrolysis of g-C3N4, thereby effectively fixing carbon on the in-situ template of Mg3N2 and avoiding direct product volatilization. N-GC750 exhibited excellent performance during the PMS activation process and bisphenol A (BPA, 0.2 g/L) could be thoroughly removed in 30 min. A wide range of pH (3–11), temperature (10–40 ℃) and common anions were employed in studying the impact on system. Additionally, N-GC750 showed satisfactory reusability in cycle tests and promising applicability in real water samples. Quenching experiments and electron paramagnetic resonance (EPR) measurements indicated that singlet oxygen was the main active species coupled with partial electron transfer in N-GC750/PMS system. Furtherly, the oxidation products were identified, and their ecotoxicity was evaluated. This work is expected to provide a reference for the feasibility of preparing g-C3N4 derived carbon materials and meaningful for PMS activation.
The nitrogen-doped carbon derived from graphitic carbon nitride (g-C3N4) has been widely deployed in activating peroxymonosulfate (PMS) to remove organic pollutants. However, the instability of g-C3N4 at high temperature brings challenges to the preparation of materials. The nitrogen-doped graphitic carbon nanosheets (N-GC750) were synthesized by magnesium thermal denitrification. Magnesium undergoes the displacement reaction with small molecules produced by the pyrolysis of g-C3N4, thereby effectively fixing carbon on the in-situ template of Mg3N2 and avoiding direct product volatilization. N-GC750 exhibited excellent performance during the PMS activation process and bisphenol A (BPA, 0.2 g/L) could be thoroughly removed in 30 min. A wide range of pH (3–11), temperature (10–40 ℃) and common anions were employed in studying the impact on system. Additionally, N-GC750 showed satisfactory reusability in cycle tests and promising applicability in real water samples. Quenching experiments and electron paramagnetic resonance (EPR) measurements indicated that singlet oxygen was the main active species coupled with partial electron transfer in N-GC750/PMS system. Furtherly, the oxidation products were identified, and their ecotoxicity was evaluated. This work is expected to provide a reference for the feasibility of preparing g-C3N4 derived carbon materials and meaningful for PMS activation.
2022, 33(6): 3119-3122
doi: 10.1016/j.cclet.2021.10.007
Abstract:
Fabrication of selective adsorption coatings plays a crucial role in solid-phase microextraction (SPME). Herein, new strategies were developed for the in-situ fabrication of novel cobalt-based carbonaceous coatings on the nickel-titanium alloy (NiTi) fiber substrate using ZIF-67 as a precursor and template through the chemical reaction of ZIF-67 with glucose, dopamine (DA) and melamine, respectively. The adsorption performance of the resulting coatings was evaluated using representative aromatic compounds coupled to high-performance liquid chromatography (HPLC) with ultraviolet detection (HPLC-UV). The results clearly demonstrated that the adsorption selectivity was subject to the surface elemental composition of the fiber coatings. The cobalt and nitrogen co-doped carbonaceous coating showed better adsorption selectivity for ultraviolet filters. In contrast, the cobalt-doped carbonaceous coating exhibited higher adsorption selectivity for polycyclic aromatic hydrocarbons. The fabricated fibers present higher mechanical stability and higher adsorption capability for model analytes than the commercial polydimethylsiloxane and polyacrylate fibers. These new strategies will continue to expand the NiTi fibers as versatile fiber substrates for metal-organic frameworks (MOFs)-derived coating materials with controllable nanostructures and tunable properties.
Fabrication of selective adsorption coatings plays a crucial role in solid-phase microextraction (SPME). Herein, new strategies were developed for the in-situ fabrication of novel cobalt-based carbonaceous coatings on the nickel-titanium alloy (NiTi) fiber substrate using ZIF-67 as a precursor and template through the chemical reaction of ZIF-67 with glucose, dopamine (DA) and melamine, respectively. The adsorption performance of the resulting coatings was evaluated using representative aromatic compounds coupled to high-performance liquid chromatography (HPLC) with ultraviolet detection (HPLC-UV). The results clearly demonstrated that the adsorption selectivity was subject to the surface elemental composition of the fiber coatings. The cobalt and nitrogen co-doped carbonaceous coating showed better adsorption selectivity for ultraviolet filters. In contrast, the cobalt-doped carbonaceous coating exhibited higher adsorption selectivity for polycyclic aromatic hydrocarbons. The fabricated fibers present higher mechanical stability and higher adsorption capability for model analytes than the commercial polydimethylsiloxane and polyacrylate fibers. These new strategies will continue to expand the NiTi fibers as versatile fiber substrates for metal-organic frameworks (MOFs)-derived coating materials with controllable nanostructures and tunable properties.
2022, 33(6): 3123-3126
doi: 10.1016/j.cclet.2021.10.008
Abstract:
High performance liquid chromatography-mass spectrometry is one of the most commonly used strategies for lipid analysis. The development of versatile chromatographic stationary phases to meet the increasing demands for separation of complex lipids is very important. Styrene-maleic acid (SMA) copolymer is an amphiphilic polymer, which has been proven to have the ability to solubilize lipid molecules of various structures. In this study, styrene-maleic anhydride copolymer coated silica was first prepared by the thiol-ene click reaction. With l-cysteine hydrochloride or dodecanol as the post-modification reagents, Sil-SMA-amino acid and Sil-SMA-dodecanol stationary phase materials were further successfully fabricated via nucleophilic ring-opening reaction. The Fourier-transform infrared, thermogravimetric analysis, and elemental analysis results confirmed the two stationary phase materials were successfully prepared. Furthermore, both the Sil-SMA-dodecanol column and the Sil-SMA-amino acid column possessed reversed-phase/hydrophilic interaction/ion exchange mixed-mode retention mechanisms. The column efficiency of the Sil-SMA-derivatives columns reached 77,300 N/m. Based on the mixed-mode retention characteristics, the Sil-SMA-derivatives columns achieved both the lipid classes and species separation via a single column. The Sil-SMA-amino acid column was further successfully used to separate lipid extract from gastric cancer cell membrane. All these results demonstrated that the SMA-based stationary phase materials have a good potential for use in lipid separation.
High performance liquid chromatography-mass spectrometry is one of the most commonly used strategies for lipid analysis. The development of versatile chromatographic stationary phases to meet the increasing demands for separation of complex lipids is very important. Styrene-maleic acid (SMA) copolymer is an amphiphilic polymer, which has been proven to have the ability to solubilize lipid molecules of various structures. In this study, styrene-maleic anhydride copolymer coated silica was first prepared by the thiol-ene click reaction. With l-cysteine hydrochloride or dodecanol as the post-modification reagents, Sil-SMA-amino acid and Sil-SMA-dodecanol stationary phase materials were further successfully fabricated via nucleophilic ring-opening reaction. The Fourier-transform infrared, thermogravimetric analysis, and elemental analysis results confirmed the two stationary phase materials were successfully prepared. Furthermore, both the Sil-SMA-dodecanol column and the Sil-SMA-amino acid column possessed reversed-phase/hydrophilic interaction/ion exchange mixed-mode retention mechanisms. The column efficiency of the Sil-SMA-derivatives columns reached 77,300 N/m. Based on the mixed-mode retention characteristics, the Sil-SMA-derivatives columns achieved both the lipid classes and species separation via a single column. The Sil-SMA-amino acid column was further successfully used to separate lipid extract from gastric cancer cell membrane. All these results demonstrated that the SMA-based stationary phase materials have a good potential for use in lipid separation.
2022, 33(6): 3127-3132
doi: 10.1016/j.cclet.2021.10.009
Abstract:
The efficient remediation of heavy metal complexes in water has become a difficult and challenging task owing to their high stability and strong mobility. In this study, a novel strategy was employed for highly efficient removal of Cu-citrate by using intimately coupled photocatalysis and biodegradation (ICPB) system with non-woven cotton fabric as a carrier. Experimental results showed that the ICPB system caused 94% Cu removal, which was higher than those of single photocatalysis. After 5 cycles, Cu removal efficiency could still reach 78% within 5 h. The existence of 0–40 mg/L citrate had negligible influence, whereas the presence of 60–100 mg/L citrate exhibited a limited adverse effect on Cu removal (~70%). The decomplexation of Cu-citrate was realized via the function of free radicals and microorganisms. Two main processes, such as bio-adsorption of Cu2+ by microorganisms, deposition of Cu0 on the surface of material, played important role in Cu removal from aqueous solution. The dominant microorganisms in the system were Proteobacteria, Actinobacteria, Bacteroidetes, Chloroflexi, Chlorophyta, Planctomycetes, and Verrucomicrobia. Furthermore, the performance of ICPB system was also validated through treatment of other heavy metal complexes. This study provided a feasible strategy for the decontamination of heavy metal complexes in wastewater.
The efficient remediation of heavy metal complexes in water has become a difficult and challenging task owing to their high stability and strong mobility. In this study, a novel strategy was employed for highly efficient removal of Cu-citrate by using intimately coupled photocatalysis and biodegradation (ICPB) system with non-woven cotton fabric as a carrier. Experimental results showed that the ICPB system caused 94% Cu removal, which was higher than those of single photocatalysis. After 5 cycles, Cu removal efficiency could still reach 78% within 5 h. The existence of 0–40 mg/L citrate had negligible influence, whereas the presence of 60–100 mg/L citrate exhibited a limited adverse effect on Cu removal (~70%). The decomplexation of Cu-citrate was realized via the function of free radicals and microorganisms. Two main processes, such as bio-adsorption of Cu2+ by microorganisms, deposition of Cu0 on the surface of material, played important role in Cu removal from aqueous solution. The dominant microorganisms in the system were Proteobacteria, Actinobacteria, Bacteroidetes, Chloroflexi, Chlorophyta, Planctomycetes, and Verrucomicrobia. Furthermore, the performance of ICPB system was also validated through treatment of other heavy metal complexes. This study provided a feasible strategy for the decontamination of heavy metal complexes in wastewater.
2022, 33(6): 3133-3138
doi: 10.1016/j.cclet.2021.10.026
Abstract:
Concentration gradient and fluid shear stress (FSS) for cell microenvironment were investigated through microfluidic technology. The Darcy–Weisbach equation combined with computational fluid dynamics modeling was exploited to design the microfluidic chip, and the FSS distribution on the cell model with varying micro-channels (triangular, conical, and elliptical). The diffusion with the incompressible laminar flow model by solving the time-dependent diffusion–convection equation was applied to simulate the gradient profiles of concentration in the micro-channels. For the study of single cell in-depth, the FSS was investigated by the usage of polystyrene particles and the concentration diffusion distribution was studied by the usage of different colors of dyes. A successful agreement between model simulations and experimental data was obtained. Finally, based on the established method, the communication between individual cells was envisaged and modeled. The developed method provides valuable insights and allows to continuously improve the design of microfluidic devices for the study of single cell, the occurrence and development of tumors, and therapeutic applications.
Concentration gradient and fluid shear stress (FSS) for cell microenvironment were investigated through microfluidic technology. The Darcy–Weisbach equation combined with computational fluid dynamics modeling was exploited to design the microfluidic chip, and the FSS distribution on the cell model with varying micro-channels (triangular, conical, and elliptical). The diffusion with the incompressible laminar flow model by solving the time-dependent diffusion–convection equation was applied to simulate the gradient profiles of concentration in the micro-channels. For the study of single cell in-depth, the FSS was investigated by the usage of polystyrene particles and the concentration diffusion distribution was studied by the usage of different colors of dyes. A successful agreement between model simulations and experimental data was obtained. Finally, based on the established method, the communication between individual cells was envisaged and modeled. The developed method provides valuable insights and allows to continuously improve the design of microfluidic devices for the study of single cell, the occurrence and development of tumors, and therapeutic applications.
2022, 33(6): 3139-3143
doi: 10.1016/j.cclet.2021.10.001
Abstract:
Gestational diabetes mellitus (GDM), a frequently-occurring disease during pregnancy, may cause some adverse healthy outcome of both mother and offspring. However, the knowledge about metabolite alterations during the pathogenesis and development process is limited. Here, a large longitudinal non-targeted metabolomics study of 195 pregnant women (64 women with subsequently developed GDM and 131 healthy controls) was conducted. Each participant provided urine samples at three timepoints during early, middle and late pregnancy, respectively. The metabolic profiles of 585 urine samples (195 × 3) were measured by using ultra-high performance liquid chromatography coupled with Orbitrap high-resolution mass spectrometry. Among the 56 identified metabolites, the levels of eight metabolites increased and three ones decreased in the first trimester, the concentration of one metabolite increased and those of 20 decreased in the second trimester, as well as the levels of five metabolites increased and two decreased in the third trimester. After false discovery rate correction, the levels of valine and 5-acetamidovalerate in GDM group significantly increased in the first trimester, the levels of 1-methylguanine and 1, 3-dihydro-(2H)-indol-2-one significantly decreased in the second trimester and three metabolites (threonine, OH-octanedioyl-carnitine and pimelylcarnitine) increased and N-acetyltryptophan decreased in the third trimester, respectively. Six metabolites, such as pantothenic acid and threonine, had significant interaction effects between gestational stage (different trimester) and group (GDM or control). The differential metabolites were involved in "tryptophan metabolism", "purine metabolism", "valine, leucine and isoleucine degradation" and other pathways. The findings may provide insights into further pathogenesis study of GDM.
Gestational diabetes mellitus (GDM), a frequently-occurring disease during pregnancy, may cause some adverse healthy outcome of both mother and offspring. However, the knowledge about metabolite alterations during the pathogenesis and development process is limited. Here, a large longitudinal non-targeted metabolomics study of 195 pregnant women (64 women with subsequently developed GDM and 131 healthy controls) was conducted. Each participant provided urine samples at three timepoints during early, middle and late pregnancy, respectively. The metabolic profiles of 585 urine samples (195 × 3) were measured by using ultra-high performance liquid chromatography coupled with Orbitrap high-resolution mass spectrometry. Among the 56 identified metabolites, the levels of eight metabolites increased and three ones decreased in the first trimester, the concentration of one metabolite increased and those of 20 decreased in the second trimester, as well as the levels of five metabolites increased and two decreased in the third trimester. After false discovery rate correction, the levels of valine and 5-acetamidovalerate in GDM group significantly increased in the first trimester, the levels of 1-methylguanine and 1, 3-dihydro-(2H)-indol-2-one significantly decreased in the second trimester and three metabolites (threonine, OH-octanedioyl-carnitine and pimelylcarnitine) increased and N-acetyltryptophan decreased in the third trimester, respectively. Six metabolites, such as pantothenic acid and threonine, had significant interaction effects between gestational stage (different trimester) and group (GDM or control). The differential metabolites were involved in "tryptophan metabolism", "purine metabolism", "valine, leucine and isoleucine degradation" and other pathways. The findings may provide insights into further pathogenesis study of GDM.
2022, 33(6): 3144-3150
doi: 10.1016/j.cclet.2021.10.027
Abstract:
The simplification of localized surface plasmon resonance (LSPR) detection can further promote the development of optical biosensing application in point-of-care testing. In this study, we proposed a simple light emitting diode (LED) based single-wavelength LSPR sensor modulated with bio-electron transfers for the detection of electroactive biomolecules. Indium tin oxide electrode loaded with nanocomposites of polyaniline coated gold nanorod was used as LSPR chip, and the applied electric potential was scanned at the LSPR chip for single-wavelength LSPR biosensing. Under the scanning of applied potentials, biological electron transfer of redox reaction was employed to demonstrate the bioelectronic modulation of single-wavelength LSPR for selective electroactive biomolecule detection. Without any additional recognition material, electroactive biomolecules uric acid and dopamine were detected directly with a sensitivity of 5.05 μmol/L and 7.11 μmol/L at their specific oxidation potentials, respectively. With the simplified optical configuration and selective bioelectronic modulation, the single-wavelength LSPR sensor is promising for the development of simple, low-cost, and high specificity optical biosensor for point-of-care testing of electroactive biomolecules.
The simplification of localized surface plasmon resonance (LSPR) detection can further promote the development of optical biosensing application in point-of-care testing. In this study, we proposed a simple light emitting diode (LED) based single-wavelength LSPR sensor modulated with bio-electron transfers for the detection of electroactive biomolecules. Indium tin oxide electrode loaded with nanocomposites of polyaniline coated gold nanorod was used as LSPR chip, and the applied electric potential was scanned at the LSPR chip for single-wavelength LSPR biosensing. Under the scanning of applied potentials, biological electron transfer of redox reaction was employed to demonstrate the bioelectronic modulation of single-wavelength LSPR for selective electroactive biomolecule detection. Without any additional recognition material, electroactive biomolecules uric acid and dopamine were detected directly with a sensitivity of 5.05 μmol/L and 7.11 μmol/L at their specific oxidation potentials, respectively. With the simplified optical configuration and selective bioelectronic modulation, the single-wavelength LSPR sensor is promising for the development of simple, low-cost, and high specificity optical biosensor for point-of-care testing of electroactive biomolecules.
2022, 33(6): 3151-3155
doi: 10.1016/j.cclet.2021.10.038
Abstract:
We propose a concept for ligase detection by conversion of aggregation-based homogeneous analysis into surface-tethered electrochemical assay through streptavidin (SA)-biotin interaction. Sortase A (SrtA) served as the model analyte and two biotinylated peptides (bio-LPETGG and GGGK-bio) were used as the substrates. SrtA-catalyzed ligation of the peptide substrates led to the generation of bio-LPETGGGK-bio. The ligation product (bio-LPETGGGK-bio) induced the aggregation and color change of SA-modified gold nanoparticles (AuNPs) through the SA-biotin interactions, which could be assayed by the colorimetric method. Furthermore, we found that the bio-LPETGGGK-bio could trigger the assembly of tetrameric SA proteins with the formation of the (SA-bio-LPETGGGK-bio)n assemblies through the same interactions. The above results were further confirmed by atomic force microscopy and fluorescent imaging. The insulated assemblies were in-situ fabricated at the SA-modified gold electrode, thus hindering the electron transfer of [Fe(CN)6]3−/4− and leading to an increase in the electron-transfer resistance. The capability of the method for the detection of SrtA both in vitro and Staphylococcus aureus (S. aureus) has been demonstrated. SrtA with a concentration down to 1 pmol/L has been determined by the electrochemical analysis, which is lower than that achieved by the colorimetric assay (50 pmol/L). By integrating the advantages of homogeneous reaction and heterogeneous detection, the strategy serves as an ideal means for the fabrication of various sensing platforms by adopting biotin-labeled and sequence-specific peptide or nucleic acid substrates.
We propose a concept for ligase detection by conversion of aggregation-based homogeneous analysis into surface-tethered electrochemical assay through streptavidin (SA)-biotin interaction. Sortase A (SrtA) served as the model analyte and two biotinylated peptides (bio-LPETGG and GGGK-bio) were used as the substrates. SrtA-catalyzed ligation of the peptide substrates led to the generation of bio-LPETGGGK-bio. The ligation product (bio-LPETGGGK-bio) induced the aggregation and color change of SA-modified gold nanoparticles (AuNPs) through the SA-biotin interactions, which could be assayed by the colorimetric method. Furthermore, we found that the bio-LPETGGGK-bio could trigger the assembly of tetrameric SA proteins with the formation of the (SA-bio-LPETGGGK-bio)n assemblies through the same interactions. The above results were further confirmed by atomic force microscopy and fluorescent imaging. The insulated assemblies were in-situ fabricated at the SA-modified gold electrode, thus hindering the electron transfer of [Fe(CN)6]3−/4− and leading to an increase in the electron-transfer resistance. The capability of the method for the detection of SrtA both in vitro and Staphylococcus aureus (S. aureus) has been demonstrated. SrtA with a concentration down to 1 pmol/L has been determined by the electrochemical analysis, which is lower than that achieved by the colorimetric assay (50 pmol/L). By integrating the advantages of homogeneous reaction and heterogeneous detection, the strategy serves as an ideal means for the fabrication of various sensing platforms by adopting biotin-labeled and sequence-specific peptide or nucleic acid substrates.
2022, 33(6): 3156-3160
doi: 10.1016/j.cclet.2021.10.064
Abstract:
Rapid screening of foodborne pathogens is of great significance to ensure food safety. A microfluidic biosensor based on immunomagnetic separation, enzyme catalysis and electrochemical impedance analysis was developed for rapid and sensitive detection of S. typhimurium. First, the bacterial sample, the magnetic nanoparticles (MNPs) modified with capture antibodies, and the enzymatic probes modified with detection antibodies and glucose oxidase (GOx) were simultaneously injected into the microfluidic chip, followed by mixing and incubation to form MNP-bacteria-probe sandwich complexes. Then, glucose with high impedance was injected into the chip and catalyzed by the GOx on the complexes into hydrogen peroxide with high impedance and gluconic acid with low impedance, which was finally measured using the low-cost interdigitated microelectrode and the electrochemical impedance analyzer to determine the target bacteria. Under the optimal conditions, this biosensor could quantitatively detect S. typhimurium at the concentrations from 1.6 × 102 CFU/mL to 1.6 × 106 CFU/mL in 1 h with the low detection limit of 73 CFU/mL. Besides, this biosensor was demonstrated with good feasibility for practical applications by detecting the S. typhimurium spiked chicken meat samples.
Rapid screening of foodborne pathogens is of great significance to ensure food safety. A microfluidic biosensor based on immunomagnetic separation, enzyme catalysis and electrochemical impedance analysis was developed for rapid and sensitive detection of S. typhimurium. First, the bacterial sample, the magnetic nanoparticles (MNPs) modified with capture antibodies, and the enzymatic probes modified with detection antibodies and glucose oxidase (GOx) were simultaneously injected into the microfluidic chip, followed by mixing and incubation to form MNP-bacteria-probe sandwich complexes. Then, glucose with high impedance was injected into the chip and catalyzed by the GOx on the complexes into hydrogen peroxide with high impedance and gluconic acid with low impedance, which was finally measured using the low-cost interdigitated microelectrode and the electrochemical impedance analyzer to determine the target bacteria. Under the optimal conditions, this biosensor could quantitatively detect S. typhimurium at the concentrations from 1.6 × 102 CFU/mL to 1.6 × 106 CFU/mL in 1 h with the low detection limit of 73 CFU/mL. Besides, this biosensor was demonstrated with good feasibility for practical applications by detecting the S. typhimurium spiked chicken meat samples.
2022, 33(6): 3161-3166
doi: 10.1016/j.cclet.2021.10.082
Abstract:
Bismuth-rich Bi5O7Br is a promising photocatalyst for pollutant removal owing to its stability and appropriate band structure in comparison with bismuth oxybromide. However, bulk-phase Bi5O7Br suffers from poor light absorption and high charge recombination rates resulting in poor activity. Elemental doping is a powerful strategy to enhance photocatalytic activity. In this study, we prepared a series of Br auto-doped ultrathin Bi5O7Br nanotubes and explored the effect of Br doping on photocatalytic NO removal. The optimal doping content was determined via a photocatalytic NO removal experiment, which revealed the optimal ratio of Bi and Br was approximately 3:1. In situ diffuse reflectance infrared Fourier transform spectroscopy (In situ DRIFT) and density functional theory (DFT) studies revealed that NO removal mechanism catalyzed by Br doped Bi5O7Br. Our work presents a new strategy for the enhancement of photocatalytic pollutant degradation by bismuth oxyhalide photocatalysts.
Bismuth-rich Bi5O7Br is a promising photocatalyst for pollutant removal owing to its stability and appropriate band structure in comparison with bismuth oxybromide. However, bulk-phase Bi5O7Br suffers from poor light absorption and high charge recombination rates resulting in poor activity. Elemental doping is a powerful strategy to enhance photocatalytic activity. In this study, we prepared a series of Br auto-doped ultrathin Bi5O7Br nanotubes and explored the effect of Br doping on photocatalytic NO removal. The optimal doping content was determined via a photocatalytic NO removal experiment, which revealed the optimal ratio of Bi and Br was approximately 3:1. In situ diffuse reflectance infrared Fourier transform spectroscopy (In situ DRIFT) and density functional theory (DFT) studies revealed that NO removal mechanism catalyzed by Br doped Bi5O7Br. Our work presents a new strategy for the enhancement of photocatalytic pollutant degradation by bismuth oxyhalide photocatalysts.
2022, 33(6): 3167-3171
doi: 10.1016/j.cclet.2021.11.029
Abstract:
Liver is the foremost organ of human being for drug metabolism, and it played a significant role in toxicity evaluation of drugs. Establishing a liver model in vitro can accelerate the process of the drug screening and new drug research and development. We provide a 3D printing based hepatic sinusoid-on-a-chip microdevice that reconstitutes organ-level liver functions to create a drug screening model of toxicity evaluation on chip. The microfluidic device, which recapitulates the hepatic sinusoid microenvironment, consists of PET polyporous membranes which mimic the perisinusoidal space, and experience fluid flow to mimic the hepatic arterial capillaries. The PET membrane was used to separate the hepatocyte and endotheliocyte. The endotheliocyte was cultured on the downside of the membrane and the hepatocyte were 3D seeded on the membrane via the 3D printer. This device was used to reproduce the in vitro liver model for drug toxicity assays. The expression of several biomarkers of liver was compared with the monoculture and 2D cultured conditions, and the results reveal that this organ-on-a-chip microdevice mimics the drug hepatoxicity that has not been possible by 2D cell-based and animal models, providing a useful platform for screening the drugs and developing an effective therapy in hepatopathy.
Liver is the foremost organ of human being for drug metabolism, and it played a significant role in toxicity evaluation of drugs. Establishing a liver model in vitro can accelerate the process of the drug screening and new drug research and development. We provide a 3D printing based hepatic sinusoid-on-a-chip microdevice that reconstitutes organ-level liver functions to create a drug screening model of toxicity evaluation on chip. The microfluidic device, which recapitulates the hepatic sinusoid microenvironment, consists of PET polyporous membranes which mimic the perisinusoidal space, and experience fluid flow to mimic the hepatic arterial capillaries. The PET membrane was used to separate the hepatocyte and endotheliocyte. The endotheliocyte was cultured on the downside of the membrane and the hepatocyte were 3D seeded on the membrane via the 3D printer. This device was used to reproduce the in vitro liver model for drug toxicity assays. The expression of several biomarkers of liver was compared with the monoculture and 2D cultured conditions, and the results reveal that this organ-on-a-chip microdevice mimics the drug hepatoxicity that has not been possible by 2D cell-based and animal models, providing a useful platform for screening the drugs and developing an effective therapy in hepatopathy.
2022, 33(6): 3172-3176
doi: 10.1016/j.cclet.2021.11.072
Abstract:
Peracetic acid (PAA)-based system is becoming an emerging advanced oxidation process (AOP) for effective removal of organic contaminants from water. Various approaches have been tested to activate PAA, while no previous researches reported the application of metal-organic frameworks (MOFs) materials for PAA activation. In this study, zeolitic imidazole framework (ZIF)-67, a representative MOFs, was facile synthesized via direct-mixing method at room temperature, and tested for PAA activation and sulfachloropyridazine (SCP) degradation. The as-synthesized ZIF-67 exhibited excellent performance for PAA activation and SCP degradation with 100% of SCP degraded within 3 min, owing to the specific MOFs structure and abundant Co2+ sites. The pseudo-first-order kinetic model was applied to fit the kinetic data, with rate constant k1 of ZIF-67 activated PAA system 34.2 and 156.5 times higher than those of conventional Co3O4 activated PAA and direct oxidation by PAA. Radical quenching experiments and electron paramagnetic resonance (EPR) analysis indicated that CH3C(O)OO· played a major role in this PAA activation system. Then, the Fukui index based on density functional theory (DFT) calculation was used to predict the possible reaction sites of SCP for electrophilic attack by CH3C(O)OO·. In addition, the degradation pathway of SCP was proposed based on Fukui index values and intermediates detection, which mainly included the S-N bond cleavage and SO2 extrusion and followed by further oxidation, dechlorination, and hydroxylation. Therefore, ZIF-67 activated PAA is a novel strategy and holds strong potential for the removal of emerging organic contaminants (EOCs) from water.
Peracetic acid (PAA)-based system is becoming an emerging advanced oxidation process (AOP) for effective removal of organic contaminants from water. Various approaches have been tested to activate PAA, while no previous researches reported the application of metal-organic frameworks (MOFs) materials for PAA activation. In this study, zeolitic imidazole framework (ZIF)-67, a representative MOFs, was facile synthesized via direct-mixing method at room temperature, and tested for PAA activation and sulfachloropyridazine (SCP) degradation. The as-synthesized ZIF-67 exhibited excellent performance for PAA activation and SCP degradation with 100% of SCP degraded within 3 min, owing to the specific MOFs structure and abundant Co2+ sites. The pseudo-first-order kinetic model was applied to fit the kinetic data, with rate constant k1 of ZIF-67 activated PAA system 34.2 and 156.5 times higher than those of conventional Co3O4 activated PAA and direct oxidation by PAA. Radical quenching experiments and electron paramagnetic resonance (EPR) analysis indicated that CH3C(O)OO· played a major role in this PAA activation system. Then, the Fukui index based on density functional theory (DFT) calculation was used to predict the possible reaction sites of SCP for electrophilic attack by CH3C(O)OO·. In addition, the degradation pathway of SCP was proposed based on Fukui index values and intermediates detection, which mainly included the S-N bond cleavage and SO2 extrusion and followed by further oxidation, dechlorination, and hydroxylation. Therefore, ZIF-67 activated PAA is a novel strategy and holds strong potential for the removal of emerging organic contaminants (EOCs) from water.
The protective effect of icariin on glucocorticoid-damaged BMECs explored by microfluidic organ chip
2022, 33(6): 3177-3182
doi: 10.1016/j.cclet.2021.11.093
Abstract:
Osteonecrosis of the femoral head (ONFH) is a devastating musculoskeletal disease characterized by the impaired circulation of bone. The purpose of this study was to explore the underlying mechanisms of the protective effect of icariin on the glucocorticoid-induced injury of bone microvascular endothelial cells (BMECs). Normal BMECs were extracted from the femoral heads by enzymatic isolation and magnetic-activated cell sorting methods. Dexamethasone and icariin were used to intervene BMECs in microfluidic organ chips, and phalloidin staining was conducted to observe the cell morphology and viability. Then next-generation transcriptome sequencing and real-time quantitative reverse transcription-polymerase chain reaction (qRT-PCR) were performed to identify the differentially expressed genes (DEGs) in different groups. Through the microfluidic organ chip, it can be observed that after dexamethasone intervention, the filamentous structure in cell fibers disappeared and the cell morphology changed from spindle to round until death. Icariin could relieve these changes and showed a protective effect on glucocorticoid-damaged BMECs. In addition, 201 DEGs were detected between the icariin protection group and the dexamethasone group, which were significantly enriched in 17 signaling pathways. 8 of the top ten selected hub genes (IL6, PTGS2, VEGFA, etc.) were confirmed by qRT-PCR. Transcription factors (TFs)-gene network showed 63 connections between 18 TFs and 12 DEGs. For instance, GATA2 could regulate 5 DEGs. The associations between 92 miRNA and 12 DEGs were visualized in a miRNA-gene network. The hub miRNA, has-mir-335–5p was predicted to interact with 8 DEGs (PTGS2, VEGFA, etc.). Microfluidic organ chips could provide excellent morphological results for cell experiments, by which it could be observed that icariin showed a protective effect on the glucocorticoid-induced injury of BMECs. Beside, these DEGs, possible regulatory TF (GATA2, FOXC1, etc.) and miRNA (has-mir-335–5p) might be dysregulated in the initiation of ONFH and have prospective importance in ONFH diagnosis and therapy.
Osteonecrosis of the femoral head (ONFH) is a devastating musculoskeletal disease characterized by the impaired circulation of bone. The purpose of this study was to explore the underlying mechanisms of the protective effect of icariin on the glucocorticoid-induced injury of bone microvascular endothelial cells (BMECs). Normal BMECs were extracted from the femoral heads by enzymatic isolation and magnetic-activated cell sorting methods. Dexamethasone and icariin were used to intervene BMECs in microfluidic organ chips, and phalloidin staining was conducted to observe the cell morphology and viability. Then next-generation transcriptome sequencing and real-time quantitative reverse transcription-polymerase chain reaction (qRT-PCR) were performed to identify the differentially expressed genes (DEGs) in different groups. Through the microfluidic organ chip, it can be observed that after dexamethasone intervention, the filamentous structure in cell fibers disappeared and the cell morphology changed from spindle to round until death. Icariin could relieve these changes and showed a protective effect on glucocorticoid-damaged BMECs. In addition, 201 DEGs were detected between the icariin protection group and the dexamethasone group, which were significantly enriched in 17 signaling pathways. 8 of the top ten selected hub genes (IL6, PTGS2, VEGFA, etc.) were confirmed by qRT-PCR. Transcription factors (TFs)-gene network showed 63 connections between 18 TFs and 12 DEGs. For instance, GATA2 could regulate 5 DEGs. The associations between 92 miRNA and 12 DEGs were visualized in a miRNA-gene network. The hub miRNA, has-mir-335–5p was predicted to interact with 8 DEGs (PTGS2, VEGFA, etc.). Microfluidic organ chips could provide excellent morphological results for cell experiments, by which it could be observed that icariin showed a protective effect on the glucocorticoid-induced injury of BMECs. Beside, these DEGs, possible regulatory TF (GATA2, FOXC1, etc.) and miRNA (has-mir-335–5p) might be dysregulated in the initiation of ONFH and have prospective importance in ONFH diagnosis and therapy.
2022, 33(6): 3183-3187
doi: 10.1016/j.cclet.2021.11.092
Abstract:
Simultaneous and quantitative detection of multiple exosomal microRNAs (miRNAs) was successfully performed by a surface-enhanced Raman scattering (SERS) assay consisting of Raman probes and capture probes. In this design, the asymmetric core-shell structured Au@Au@Ag nanoparticles were first synthesized by layer-by-layer self-assembly method and modified with different Raman molecules and recognition sequences (polyA-DNA) to prepare the surface-enhanced Raman probes. Then, the streptavidin-modified magnetic beads were used to immobilize the biotinylated DNA capture sequences (biotin-DNA) to obtain capture probes. In the presence of target exosomal miRNAs, the Raman probes and capture probes could bind to the target exosomal miRNAs in the partial hybridization manner. Thus, the developed SERS sensor could indicate the target miRNAs levels in the buffer solution. Using breast cancer-related miRNAs as model targets, the limits of detection of this sensor were determined to be 1.076 fmol/L for synthetic miR-21, 0.068 fmol/L for synthetic miR-126, and 4.57 fmol/L for synthetic miR-1246, respectively. Such SERS sensors were further employed to detect the miR-21 in 20% human serum and the extraction solution of exosomes, respectively. Therefore, simultaneous and multiplex detection of cancer-related exosomal miRNAs by this assay could provide new opportunities for further biomedical applications.
Simultaneous and quantitative detection of multiple exosomal microRNAs (miRNAs) was successfully performed by a surface-enhanced Raman scattering (SERS) assay consisting of Raman probes and capture probes. In this design, the asymmetric core-shell structured Au@Au@Ag nanoparticles were first synthesized by layer-by-layer self-assembly method and modified with different Raman molecules and recognition sequences (polyA-DNA) to prepare the surface-enhanced Raman probes. Then, the streptavidin-modified magnetic beads were used to immobilize the biotinylated DNA capture sequences (biotin-DNA) to obtain capture probes. In the presence of target exosomal miRNAs, the Raman probes and capture probes could bind to the target exosomal miRNAs in the partial hybridization manner. Thus, the developed SERS sensor could indicate the target miRNAs levels in the buffer solution. Using breast cancer-related miRNAs as model targets, the limits of detection of this sensor were determined to be 1.076 fmol/L for synthetic miR-21, 0.068 fmol/L for synthetic miR-126, and 4.57 fmol/L for synthetic miR-1246, respectively. Such SERS sensors were further employed to detect the miR-21 in 20% human serum and the extraction solution of exosomes, respectively. Therefore, simultaneous and multiplex detection of cancer-related exosomal miRNAs by this assay could provide new opportunities for further biomedical applications.
2022, 33(6): 3188-3192
doi: 10.1016/j.cclet.2021.12.045
Abstract:
Exosomes are now raising focus as a prospective biomarker for cancer diagnostics and prognosis owing to its unique bio-origin and composition. Exosomes take part in cellular communication and receptor mediation and transfer their cargos (e.g., proteins, mRNA and DNA). Quantitative analysis of tumor-related nucleic acid mutations can be a potential method to cancer diagnosis and prognosis in early stages. Here we present an integrated microfluidic system for exosome on-chip isolation and lung cancer RNA analysis through droplet digital PCR (ddPCR). Gradient dilution experiments show great linearity over a large concentration range with R2 = 0.9998. Utilizing the system, four cell lines and two mutation targets were parallelly detected for mutation analysis. The experiments demonstrated mutation heterogeneity and the results were agree with cell researches. These results proved our integrated microfluidic system as a promising means for early cancer diagnosis and prognosis in the era of liquid biopsy.
Exosomes are now raising focus as a prospective biomarker for cancer diagnostics and prognosis owing to its unique bio-origin and composition. Exosomes take part in cellular communication and receptor mediation and transfer their cargos (e.g., proteins, mRNA and DNA). Quantitative analysis of tumor-related nucleic acid mutations can be a potential method to cancer diagnosis and prognosis in early stages. Here we present an integrated microfluidic system for exosome on-chip isolation and lung cancer RNA analysis through droplet digital PCR (ddPCR). Gradient dilution experiments show great linearity over a large concentration range with R2 = 0.9998. Utilizing the system, four cell lines and two mutation targets were parallelly detected for mutation analysis. The experiments demonstrated mutation heterogeneity and the results were agree with cell researches. These results proved our integrated microfluidic system as a promising means for early cancer diagnosis and prognosis in the era of liquid biopsy.
2022, 33(6): 3193-3196
doi: 10.1016/j.cclet.2021.12.070
Abstract:
The temperature monitoring of treated cancer cells is critical in photothermal therapy. Current methods of detecting intracellular temperatures have low accuracy and poor spatial resolution, which limits their application to photothermal therapy. Herein, a strategy for targeted recognition and selective capture of MCF-7 breast cancer cells based on fluorescent polymer poly(N-isopropylacrylamide-benzoxadiazole-2-vinyl-4,4-dimethyl azlactone, PNMV) and modified gold nanobipyramids (AuNBPs-PNMV) was developed for temperature sensing during photothermal therapy. A mucin-1 protein aptamer (Apt) was applied to selectively target mucin-1 protein overexpressed on the surfaces of the MCF-7 cells, which can reduce interference by affinity interaction between the Apt and proteins. During photothermal therapy, the significant AuNBPs photothermal effect increases the fluorescence intensity of PNMV with temperature. Irradiation of MCF-7 cells cultured with AuNBPs-PNMV@Apt by an 808 nm laser increases the temperature of the system, while the cells can be inactivated because of the remarkable AuNBPs-PNMV@Apt photothermal effect. The results indicate that variation in the fluorescence of AuNBPs-PNMV@Apt can be applied as thermometers to monitor the intracellular effect of photothermal therapy.
The temperature monitoring of treated cancer cells is critical in photothermal therapy. Current methods of detecting intracellular temperatures have low accuracy and poor spatial resolution, which limits their application to photothermal therapy. Herein, a strategy for targeted recognition and selective capture of MCF-7 breast cancer cells based on fluorescent polymer poly(N-isopropylacrylamide-benzoxadiazole-2-vinyl-4,4-dimethyl azlactone, PNMV) and modified gold nanobipyramids (AuNBPs-PNMV) was developed for temperature sensing during photothermal therapy. A mucin-1 protein aptamer (Apt) was applied to selectively target mucin-1 protein overexpressed on the surfaces of the MCF-7 cells, which can reduce interference by affinity interaction between the Apt and proteins. During photothermal therapy, the significant AuNBPs photothermal effect increases the fluorescence intensity of PNMV with temperature. Irradiation of MCF-7 cells cultured with AuNBPs-PNMV@Apt by an 808 nm laser increases the temperature of the system, while the cells can be inactivated because of the remarkable AuNBPs-PNMV@Apt photothermal effect. The results indicate that variation in the fluorescence of AuNBPs-PNMV@Apt can be applied as thermometers to monitor the intracellular effect of photothermal therapy.
2022, 33(6): 3197-3202
doi: 10.1016/j.cclet.2021.10.014
Abstract:
Transition metal selenides attract significant attention as advanced anode materials for sodium-ion batteries (SIBs) in recent years due to their appropriate working potential and high theoretic capacity. However, the poor structural stability and rate capability limit their further practical applications. Herein, zeolite imidazole framework-8/zeolite imidazole framework-67 is used as a template to prepare Co0.85Se and ZnSe nanoparticles embed in N-doped carbon matrix successfully, and then coated a carbon layer (ZCS@NC@C) by in-situ polymerization. One side, the N-doped carbon matrix with rich pore structure not only shorten the diffusion path of Na+ and improve the conductivity of the electrode, but also prevent structural collapse and agglomeration of active particles during the sodium insertion/extraction process. On the other side, the carbon shell preparation by coating can form a protective layer to buffer the volumetric stress generated in the electrochemical process and further improve the electrical conductivity. As a result, the as-prepared ZCS@NC@C anode material exhibits an excellent electrochemical performance for SIBs. This investigation provides a promising approach to optimize the electrochemical performance of SIBs by incorporating active metal compounds into conductive carbons to form multidimensional structure.
Transition metal selenides attract significant attention as advanced anode materials for sodium-ion batteries (SIBs) in recent years due to their appropriate working potential and high theoretic capacity. However, the poor structural stability and rate capability limit their further practical applications. Herein, zeolite imidazole framework-8/zeolite imidazole framework-67 is used as a template to prepare Co0.85Se and ZnSe nanoparticles embed in N-doped carbon matrix successfully, and then coated a carbon layer (ZCS@NC@C) by in-situ polymerization. One side, the N-doped carbon matrix with rich pore structure not only shorten the diffusion path of Na+ and improve the conductivity of the electrode, but also prevent structural collapse and agglomeration of active particles during the sodium insertion/extraction process. On the other side, the carbon shell preparation by coating can form a protective layer to buffer the volumetric stress generated in the electrochemical process and further improve the electrical conductivity. As a result, the as-prepared ZCS@NC@C anode material exhibits an excellent electrochemical performance for SIBs. This investigation provides a promising approach to optimize the electrochemical performance of SIBs by incorporating active metal compounds into conductive carbons to form multidimensional structure.
2022, 33(6): 3203-3206
doi: 10.1016/j.cclet.2021.10.015
Abstract:
Tuning white-light emission via free radicals is still a challenge in molecular-based functional materials. Herein, a new photoactive Zn2+ oxalate-based chain containing a polypyridine ligand was designed and synthesized with remarkably bifunctional photochromism and photo-actuated greenish white-light emission after UV, sunlight or Xe lamp light irradiation at room temperature. The photo-actuated coloration process was induced by the photogeneration of stable radicals originated from intermolecular electron transfers from oxalate components to the protonated polypyridine units, as demonstrated by UV–vis, IR, electron spin resonance and X-ray photoelectron spectra and magnetic measurements. Importantly, the on/off greenish white light emission (WLE) could be reversibly switched by generation and elimination of radicals via light irradiation and heat treatment, providing a feasible strategy for designing photoswitchable light emission diodes materials.
Tuning white-light emission via free radicals is still a challenge in molecular-based functional materials. Herein, a new photoactive Zn2+ oxalate-based chain containing a polypyridine ligand was designed and synthesized with remarkably bifunctional photochromism and photo-actuated greenish white-light emission after UV, sunlight or Xe lamp light irradiation at room temperature. The photo-actuated coloration process was induced by the photogeneration of stable radicals originated from intermolecular electron transfers from oxalate components to the protonated polypyridine units, as demonstrated by UV–vis, IR, electron spin resonance and X-ray photoelectron spectra and magnetic measurements. Importantly, the on/off greenish white light emission (WLE) could be reversibly switched by generation and elimination of radicals via light irradiation and heat treatment, providing a feasible strategy for designing photoswitchable light emission diodes materials.
2022, 33(6): 3207-3211
doi: 10.1016/j.cclet.2021.10.012
Abstract:
The specific crystalline form of a compound remarkably affects its physicochemical properties. Therefore, a detailed analysis of the structural features and intermolecular interactions of a multi-component crystal is feasible to understand the relationships among the structure, physicochemical properties and the formation mechanism. In the present study, three novel cocrystal salt solvates of rhein and berberine were reported for the first time. Various solid characterizations and theoretical computations based on density functional theory (DFT) were carried out to demonstrate the intermolecular interactions. The theoretical computation shows that the strongest interaction existed between berberine cation and rhein anion, and the electrostatic interaction play a dominant role. However, no salt bond was observed between them. Further intrinsic dissolution rate analysis in water shows that the monohydrate exhibits 17 times enhancement in comparison with rhein. The rhein and berberine combined in ionic state in cocrystal salt is the main reason for the solubility improvement. This paper suggests that the interactions between the different components can be visualized and qualitatively and quantitatively analyzed by theoretical computation, which is helpful to understand the relationship between stereochemical structure and physicochemical properties of multi-component complex.
The specific crystalline form of a compound remarkably affects its physicochemical properties. Therefore, a detailed analysis of the structural features and intermolecular interactions of a multi-component crystal is feasible to understand the relationships among the structure, physicochemical properties and the formation mechanism. In the present study, three novel cocrystal salt solvates of rhein and berberine were reported for the first time. Various solid characterizations and theoretical computations based on density functional theory (DFT) were carried out to demonstrate the intermolecular interactions. The theoretical computation shows that the strongest interaction existed between berberine cation and rhein anion, and the electrostatic interaction play a dominant role. However, no salt bond was observed between them. Further intrinsic dissolution rate analysis in water shows that the monohydrate exhibits 17 times enhancement in comparison with rhein. The rhein and berberine combined in ionic state in cocrystal salt is the main reason for the solubility improvement. This paper suggests that the interactions between the different components can be visualized and qualitatively and quantitatively analyzed by theoretical computation, which is helpful to understand the relationship between stereochemical structure and physicochemical properties of multi-component complex.
2022, 33(6): 3212-3216
doi: 10.1016/j.cclet.2021.10.035
Abstract:
Bismuth sulfide (Bi2S3) is a promising anode material for high-performance potassium ion batteries due to its high theoretical capacity. However, the poor conductivity and substantial volume expansion hinder its practical application. We proposed an iodine-doped graphene encapsulated Bi2S3 nanorods composite (Bi2S3/IG) as an efficient anode for PIBs. The uniform-sized Bi2S3 nanorods evenly in-situ encapsulated in iodine-doped graphene framework, facilitating the electron transportation and structural stability. The potassium storage performance was evaluated in three electrolytes, with the best option of 5 mol/L KFSI in DME. The reversible capacity of representative Bi2S3/IG reached 453.5 mAh/g at 50 mA/g. Meanwhile, it could deliver an initial reversible capacity of 413.6 mAh/g at 100 mA/g, which maintained 256.9 mAh/g after 200 cycles. The proposed strategy contributes to improving potassium storage performance of metal sulfide anodes.
Bismuth sulfide (Bi2S3) is a promising anode material for high-performance potassium ion batteries due to its high theoretical capacity. However, the poor conductivity and substantial volume expansion hinder its practical application. We proposed an iodine-doped graphene encapsulated Bi2S3 nanorods composite (Bi2S3/IG) as an efficient anode for PIBs. The uniform-sized Bi2S3 nanorods evenly in-situ encapsulated in iodine-doped graphene framework, facilitating the electron transportation and structural stability. The potassium storage performance was evaluated in three electrolytes, with the best option of 5 mol/L KFSI in DME. The reversible capacity of representative Bi2S3/IG reached 453.5 mAh/g at 50 mA/g. Meanwhile, it could deliver an initial reversible capacity of 413.6 mAh/g at 100 mA/g, which maintained 256.9 mAh/g after 200 cycles. The proposed strategy contributes to improving potassium storage performance of metal sulfide anodes.
2022, 33(6): 3217-3220
doi: 10.1016/j.cclet.2021.10.041
Abstract:
Iron chalcogenides have attracted great interest as potential substitutes of nature enzymes in the colorimetric biological sensing due to their unique chemodynamic characteristics. Herein, we report the preparation of ultrathin FeS nanosheets (NSs) by a simple one-pot hydrothermal method and the prepared FeS NSs exhibit strong Fenton-reaction activity to catalyze hydrogen peroxide (H2O2) for generation of hydroxyl radical (•OH). Based on the chromogenic reaction of resultant •OH with 3, 3′, 5, 5′-tetramethylbenzidine (TMB), we develop colorimetric biosensors for highly sensitive detection of H2O2 and glutathione (GSH). The fabricated biosensors show wide linear ranges for the detection of H2O2 (5–150 µmol/L) and GSH (5–50 µmol/L). Their detection limits for H2O2 and GSH reach as low as 0.19 µmol/L and 0.14 µmol/L, respectively. The experimental results of sensing intracellular H2O2 and GSH demonstrate that this colorimetric method can realize the accurate detection of H2O2 and GSH in normal cells (L02 and 3T3) and cancer cells (MCF-7 and HeLa). Our results have demonstrated that the synthesized FeS NSs is a promising material to construct colorimetric biosensors for the sensitive detection of H2O2 and GSH, holding great promising for medical diagnosis in cancer therapy.
Iron chalcogenides have attracted great interest as potential substitutes of nature enzymes in the colorimetric biological sensing due to their unique chemodynamic characteristics. Herein, we report the preparation of ultrathin FeS nanosheets (NSs) by a simple one-pot hydrothermal method and the prepared FeS NSs exhibit strong Fenton-reaction activity to catalyze hydrogen peroxide (H2O2) for generation of hydroxyl radical (•OH). Based on the chromogenic reaction of resultant •OH with 3, 3′, 5, 5′-tetramethylbenzidine (TMB), we develop colorimetric biosensors for highly sensitive detection of H2O2 and glutathione (GSH). The fabricated biosensors show wide linear ranges for the detection of H2O2 (5–150 µmol/L) and GSH (5–50 µmol/L). Their detection limits for H2O2 and GSH reach as low as 0.19 µmol/L and 0.14 µmol/L, respectively. The experimental results of sensing intracellular H2O2 and GSH demonstrate that this colorimetric method can realize the accurate detection of H2O2 and GSH in normal cells (L02 and 3T3) and cancer cells (MCF-7 and HeLa). Our results have demonstrated that the synthesized FeS NSs is a promising material to construct colorimetric biosensors for the sensitive detection of H2O2 and GSH, holding great promising for medical diagnosis in cancer therapy.
2022, 33(6): 3221-3226
doi: 10.1016/j.cclet.2021.10.033
Abstract:
Semiconductor electrocatalysis with weak conductivity can accumulate extremely high carriers at semiconductor-electrolyte interface by self-gating effect, which strongly promotes electrocatalytic efficiency. The correlation between semiconductor carrier mobility and electrocatalysis performance is still unclear. Herein atomic-thin transition metal dichalcogenides based composites have been developed for hydrogen evolution reaction (HER) performed with on-chip microdevices. Electrical and electrochemical measurement of individual flack verified the key role of high carrier mobility for enhanced HER activity. Carrier mobility regulation further demonstrated its high dependence with HER performance under self-gating. Our study provides new insight into the carrier mobility of the semiconductor in the electrocatalysis, paving the way for designing high-performance semiconductor catalysts.
Semiconductor electrocatalysis with weak conductivity can accumulate extremely high carriers at semiconductor-electrolyte interface by self-gating effect, which strongly promotes electrocatalytic efficiency. The correlation between semiconductor carrier mobility and electrocatalysis performance is still unclear. Herein atomic-thin transition metal dichalcogenides based composites have been developed for hydrogen evolution reaction (HER) performed with on-chip microdevices. Electrical and electrochemical measurement of individual flack verified the key role of high carrier mobility for enhanced HER activity. Carrier mobility regulation further demonstrated its high dependence with HER performance under self-gating. Our study provides new insight into the carrier mobility of the semiconductor in the electrocatalysis, paving the way for designing high-performance semiconductor catalysts.
2022, 33(6): 3227-3230
doi: 10.1016/j.cclet.2021.10.042
Abstract:
Two primitive metal-organic frameworks (MOFs), NiL1 and NiL2, based on Ni8O6-cluster and ditopic pyrazolate linkers, L1 (with rigid alkyne arms) and L2 (with flexible alkyne chains), were prepared. The proton conductivities of these MOFs in pristine form and imidazole-encapsulated forms, Im@NiL1 and Im@NiL2, were measured and compared. Upon introduction of imidazole molecules, the proton conductivity could be increased by 3 to 5 orders of magnitude and reached as high as 1.72 × 10−2 S/cm (at 98% RH and 80 ℃). Also, whether imidazole molecules were introduced or not, Ni8O6-based MOFs with L2 in general gave better proton conductivity than those with L1 signifying that flexible side arms indeed assist proton conduction probably via establishment of efficient proton-conducting channels along with formation of highly ordered domains of water/imidazole molecules within the network cavities. Beyond the active Ni8O6-cluster, tuning flexibility of linker pendants serves as an alternative approach to regulate/modulate the proton conductivity of MOFs.
Two primitive metal-organic frameworks (MOFs), NiL1 and NiL2, based on Ni8O6-cluster and ditopic pyrazolate linkers, L1 (with rigid alkyne arms) and L2 (with flexible alkyne chains), were prepared. The proton conductivities of these MOFs in pristine form and imidazole-encapsulated forms, Im@NiL1 and Im@NiL2, were measured and compared. Upon introduction of imidazole molecules, the proton conductivity could be increased by 3 to 5 orders of magnitude and reached as high as 1.72 × 10−2 S/cm (at 98% RH and 80 ℃). Also, whether imidazole molecules were introduced or not, Ni8O6-based MOFs with L2 in general gave better proton conductivity than those with L1 signifying that flexible side arms indeed assist proton conduction probably via establishment of efficient proton-conducting channels along with formation of highly ordered domains of water/imidazole molecules within the network cavities. Beyond the active Ni8O6-cluster, tuning flexibility of linker pendants serves as an alternative approach to regulate/modulate the proton conductivity of MOFs.
2022, 33(6): 3231-3235
doi: 10.1016/j.cclet.2021.10.046
Abstract:
Tailor-made advanced electrocatalysts with high active and stable for hydrogen evolution reaction (HER) play a key role in the development of hydrogen economy. Herein, a N, P-co-doped molybdenum carbide confined in porous carbon matrix (N, P-Mo2C/NPC) with a hierarchical structure is prepared by a resources recovery process. The N, P-Mo2C/NPC compound exhibits outstanding HER activity with a low overpotential of 84 mV to achieve 10 mA/cm2, and excellent stability in alkaline media. The electrochemical measurements confirm that the enhanced HER activity of N, P-Mo2C/NPC is ascribe to the synergy of N, P-codoped and porous carbon matrix. Density functional theory calculations further reveal that the electron density of active sites on Mo2C can be regulated by the N/P doping, leading to optimal H adsorption strength. In this work, the proof-of-concept resource utilization, a microorganism derived molybdenum carbide electrocatalyst for HER is fabricated, which may inaugurate a new way for designing electrocatalysts by the utilization of solid waste.
Tailor-made advanced electrocatalysts with high active and stable for hydrogen evolution reaction (HER) play a key role in the development of hydrogen economy. Herein, a N, P-co-doped molybdenum carbide confined in porous carbon matrix (N, P-Mo2C/NPC) with a hierarchical structure is prepared by a resources recovery process. The N, P-Mo2C/NPC compound exhibits outstanding HER activity with a low overpotential of 84 mV to achieve 10 mA/cm2, and excellent stability in alkaline media. The electrochemical measurements confirm that the enhanced HER activity of N, P-Mo2C/NPC is ascribe to the synergy of N, P-codoped and porous carbon matrix. Density functional theory calculations further reveal that the electron density of active sites on Mo2C can be regulated by the N/P doping, leading to optimal H adsorption strength. In this work, the proof-of-concept resource utilization, a microorganism derived molybdenum carbide electrocatalyst for HER is fabricated, which may inaugurate a new way for designing electrocatalysts by the utilization of solid waste.
2022, 33(6): 3236-3240
doi: 10.1016/j.cclet.2021.10.039
Abstract:
Silicon (Si) is regarded as the potential anode for lithium-ion batteries (LIBs), due to the remarkable theoretical specific capacity and low voltage plateau. However, the rapid capacity decay resulting from volume variation and slow electron/ion transportation of Si limit its practical application. Here, matryoshka-type carbon-stabilized hollow silicon spheres (Si/C/Si/C) are synthesized by an aluminothermic reduction and calcination process. The Si/C/Si/C anode materials prepared at 500 ℃ (Si/C/Si/C-500) exhibit unique structures, in which amorphous region and porous structure are preserved in the Si layers. The anode based on Si/C/Si/C-500 displays an initial specific capacity of 2792 mAh/g at a current density of 100 mA/g. At 1000 mA/g, this anode retains a reversible capacity of 1673 mAh/g, 86.9% of the initial capacity after 200 cycles. Such synthetic strategy can be employed to fabricate other high-capacity anode materials with large volume variation during charge/discharge process
Silicon (Si) is regarded as the potential anode for lithium-ion batteries (LIBs), due to the remarkable theoretical specific capacity and low voltage plateau. However, the rapid capacity decay resulting from volume variation and slow electron/ion transportation of Si limit its practical application. Here, matryoshka-type carbon-stabilized hollow silicon spheres (Si/C/Si/C) are synthesized by an aluminothermic reduction and calcination process. The Si/C/Si/C anode materials prepared at 500 ℃ (Si/C/Si/C-500) exhibit unique structures, in which amorphous region and porous structure are preserved in the Si layers. The anode based on Si/C/Si/C-500 displays an initial specific capacity of 2792 mAh/g at a current density of 100 mA/g. At 1000 mA/g, this anode retains a reversible capacity of 1673 mAh/g, 86.9% of the initial capacity after 200 cycles. Such synthetic strategy can be employed to fabricate other high-capacity anode materials with large volume variation during charge/discharge process
2022, 33(6): 3241-3244
doi: 10.1016/j.cclet.2021.10.059
Abstract:
The urgent need for immediate personal protection against chemical warfare agents (CWAs) spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices. Herein, as a new concept for CWA decontamination catalyst design, sub-nanoscale, catalytically active zirconium-oxo molecular clusters are covalently integrated in flexible polymer network as crosslinkers for the full exposure of catalytic sites as well as robust framework structures. The obtained membrane catalysts exhibit high swelling ratio with aqueous content as 84 wt% and therefore, demonstrate quasi-homogeneous catalytic activity toward the rapid hydrolysis of both CWA, soman (GD) (t1/2 = 5.0 min) and CWA simulant, methyl paraoxon (DMNP) (t1/2 = 8.9 min). Meanwhile, due to the covalent nature of cross-linkages and the high flexibility of polymer strands, the membranes possess promising mechanical strength and toughness that can stand the impact of high gas pressures and show high permeation for both CO2 and O2, enabling their extended applications in the field of collective/personal protective materials with body comfort.
The urgent need for immediate personal protection against chemical warfare agents (CWAs) spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices. Herein, as a new concept for CWA decontamination catalyst design, sub-nanoscale, catalytically active zirconium-oxo molecular clusters are covalently integrated in flexible polymer network as crosslinkers for the full exposure of catalytic sites as well as robust framework structures. The obtained membrane catalysts exhibit high swelling ratio with aqueous content as 84 wt% and therefore, demonstrate quasi-homogeneous catalytic activity toward the rapid hydrolysis of both CWA, soman (GD) (t1/2 = 5.0 min) and CWA simulant, methyl paraoxon (DMNP) (t1/2 = 8.9 min). Meanwhile, due to the covalent nature of cross-linkages and the high flexibility of polymer strands, the membranes possess promising mechanical strength and toughness that can stand the impact of high gas pressures and show high permeation for both CO2 and O2, enabling their extended applications in the field of collective/personal protective materials with body comfort.
2022, 33(6): 3245-3248
doi: 10.1016/j.cclet.2021.10.079
Abstract:
Biomass-derived dynamic covalent thermoset has been considered as a promising solution to the high dependence on fossil resources and the difficulty in recyclability after curing of conventional bisphenol A epoxy resins. However, the design and preparation of a dynamic covalent biobased epoxy thermoset with both comparable thermal and mechanical performances to bisphenol A epoxy resins and reprocessibility remains a significant challenge. Herein, based on imine chemistry, a novel Schiff base-containing dynamic covalent epoxy thermoset was facilely fabricated from biobased protocatechualdehyde and synthetic siloxane diamine. Due to the more reactive epoxides in the epoxy monomer than in bisphenol A epoxy oligomer, the thermoset exhibited a high cross-linking density, resulting in high thermal stability and glass transition temperature. The rigid aromatic Schiff base moieties endowed the thermoset with excellent mechanical properties: Thanks to the plasticization of the flexible siloxane, the thermoset displayed high impact strength. Meanwhile, owing to the high segmental mobility, the fast exchange of imine bonds was guaranteed; and the thermoset was able to be recycled through reprocessing. Taking these features, this work provided great potential for designing and preparing sustainable substitutes for bisphenol A epoxy resins in the high-performance applications.
Biomass-derived dynamic covalent thermoset has been considered as a promising solution to the high dependence on fossil resources and the difficulty in recyclability after curing of conventional bisphenol A epoxy resins. However, the design and preparation of a dynamic covalent biobased epoxy thermoset with both comparable thermal and mechanical performances to bisphenol A epoxy resins and reprocessibility remains a significant challenge. Herein, based on imine chemistry, a novel Schiff base-containing dynamic covalent epoxy thermoset was facilely fabricated from biobased protocatechualdehyde and synthetic siloxane diamine. Due to the more reactive epoxides in the epoxy monomer than in bisphenol A epoxy oligomer, the thermoset exhibited a high cross-linking density, resulting in high thermal stability and glass transition temperature. The rigid aromatic Schiff base moieties endowed the thermoset with excellent mechanical properties: Thanks to the plasticization of the flexible siloxane, the thermoset displayed high impact strength. Meanwhile, owing to the high segmental mobility, the fast exchange of imine bonds was guaranteed; and the thermoset was able to be recycled through reprocessing. Taking these features, this work provided great potential for designing and preparing sustainable substitutes for bisphenol A epoxy resins in the high-performance applications.
2022, 33(6): 3249-3254
doi: 10.1016/j.cclet.2021.10.075
Abstract:
Well-defined two-dimensional (2D) cobalt oxalate (CoC2O4·2H2O) nanosheets exhibit more excellent property than common bulk cobalt oxalate due to high specific surface areas and high-efficient transport of ion and electron. However, the delicate control of the 2D morphology of CoC2O4·2H2O during their synthesis remains challenging. Herein, 2D CoC2O4·2H2O nanosheets (M1), grown by straightforward chemical precipitation, can be tuned from three-dimensional (3D) structure during their synthesis with no templates or capping agents. This control is obtained by rationally changing the ratio of reactants with ethylene glycol as solvent. Moreover, Co3O4/CoC2O4 composites (M1-250) have been fabricated through low-temperature thermal treatment of the M1 precursor in air, which possess porous surfaces with the 2D morphology maintained. Benefiting from the porous surfaces, more redox-active sites and better electrical conductivity of Co3O4, the constructed M1-250//AC aqueous device manifest improved kinetics of the electrochemistry process with energy density of 27.9 Wh/kg at 550.7 W/kg and good cycling stability with sustaining 73.0 mAh/g after 5000 cycles.
Well-defined two-dimensional (2D) cobalt oxalate (CoC2O4·2H2O) nanosheets exhibit more excellent property than common bulk cobalt oxalate due to high specific surface areas and high-efficient transport of ion and electron. However, the delicate control of the 2D morphology of CoC2O4·2H2O during their synthesis remains challenging. Herein, 2D CoC2O4·2H2O nanosheets (M1), grown by straightforward chemical precipitation, can be tuned from three-dimensional (3D) structure during their synthesis with no templates or capping agents. This control is obtained by rationally changing the ratio of reactants with ethylene glycol as solvent. Moreover, Co3O4/CoC2O4 composites (M1-250) have been fabricated through low-temperature thermal treatment of the M1 precursor in air, which possess porous surfaces with the 2D morphology maintained. Benefiting from the porous surfaces, more redox-active sites and better electrical conductivity of Co3O4, the constructed M1-250//AC aqueous device manifest improved kinetics of the electrochemistry process with energy density of 27.9 Wh/kg at 550.7 W/kg and good cycling stability with sustaining 73.0 mAh/g after 5000 cycles.
2022, 33(6): 3255-3258
doi: 10.1016/j.cclet.2021.10.076
Abstract:
Micro-nano-level photonic waveguide regulation is essential for future on-chip photonic integrated systems and is still of great challenges. We report a molecular design strategy, changing the position of the methyl substituent makes the arrangement of the three isomer molecules different in their respective crystals. Based on this strategy, three sheet-like crystals with different polygonal morphologies were prepared via solution self-assembly approach. The in-depth optical measurements demonstrated that these three microsheet crystals have different 2D optical waveguide performances related to the shapes. Our work provides a feasible design strategy and material preparation method for realizing precise 2D optical waveguide modulation, which lays the foundation for complex photonic integrated systems in the future.
Micro-nano-level photonic waveguide regulation is essential for future on-chip photonic integrated systems and is still of great challenges. We report a molecular design strategy, changing the position of the methyl substituent makes the arrangement of the three isomer molecules different in their respective crystals. Based on this strategy, three sheet-like crystals with different polygonal morphologies were prepared via solution self-assembly approach. The in-depth optical measurements demonstrated that these three microsheet crystals have different 2D optical waveguide performances related to the shapes. Our work provides a feasible design strategy and material preparation method for realizing precise 2D optical waveguide modulation, which lays the foundation for complex photonic integrated systems in the future.
2022, 33(6): 3259-3262
doi: 10.1016/j.cclet.2021.10.091
Abstract:
The thermal decomposition of AgNO3 is known to produce metallic Ag, but single-atomic dispersion is hard to achieve instead of the aggregation state of nanoparticles. Herein, we develop an efficient approach to thermally generate and stabilize single Ag atoms via the coordination effect. Two desired Co-Ag phosphonates [Ag2ⅠCo2Ⅲ(notpH3)2(NO3)]X [X = NO3− (1) or ClO4− (2)] were synthesized by solid-phase grinding method or solution crystallization. Both crystal structures reveal slightly different packing arrangements of various lattice anions and identical one-dimensional (1-D) coordination chains, formed in each case by the coordination of Ag(Ⅰ) to the metalloligand Co(notpH3) and NO3− anion. The number of Ag(Ⅰ) ions connected to each NO3− anion reduces from 5 in bulk AgNO3 to 2 in compounds 1 and 2, leading to the AgNO3 component stepwise decomposition at a lower temperature (< 300 ℃). During the thermal decomposition, the changes of supermolecular structures and Ag oxidation states were monitored by PXRD, IR and XAFS measurements. The most interesting finding is that 1 and 2 can retain chain structures and harvest Ag(0) atoms in the chain by controlling decomposition temperatures (220 ℃ for 1 and 254 ℃ for 2).
The thermal decomposition of AgNO3 is known to produce metallic Ag, but single-atomic dispersion is hard to achieve instead of the aggregation state of nanoparticles. Herein, we develop an efficient approach to thermally generate and stabilize single Ag atoms via the coordination effect. Two desired Co-Ag phosphonates [Ag2ⅠCo2Ⅲ(notpH3)2(NO3)]X [X = NO3− (1) or ClO4− (2)] were synthesized by solid-phase grinding method or solution crystallization. Both crystal structures reveal slightly different packing arrangements of various lattice anions and identical one-dimensional (1-D) coordination chains, formed in each case by the coordination of Ag(Ⅰ) to the metalloligand Co(notpH3) and NO3− anion. The number of Ag(Ⅰ) ions connected to each NO3− anion reduces from 5 in bulk AgNO3 to 2 in compounds 1 and 2, leading to the AgNO3 component stepwise decomposition at a lower temperature (< 300 ℃). During the thermal decomposition, the changes of supermolecular structures and Ag oxidation states were monitored by PXRD, IR and XAFS measurements. The most interesting finding is that 1 and 2 can retain chain structures and harvest Ag(0) atoms in the chain by controlling decomposition temperatures (220 ℃ for 1 and 254 ℃ for 2).
2022, 33(6): 3263-3266
doi: 10.1016/j.cclet.2021.10.092
Abstract:
Understanding the impact of substituents on the quantum interference effect at single molecule scale is of great importance for the design of molecular devices. In this work, three platinum(Ⅱ) complexes with –H, –NH2 and –NO2 groups on conductive backbones were designed and synthesized. Single-molecule conductance, which was measured using scanning tunnelling microscope break junction (STM-BJ) technique, demonstrated a conductance freeze phenomenon under the variation of substituents. Theoretical study revealed that, despite the electronic effect of the substituents shifting the energy level of molecular orbital, the quantum interference effect vanished the influence of electronic effect on the conductance and eventually leaded to the conductance freeze.
Understanding the impact of substituents on the quantum interference effect at single molecule scale is of great importance for the design of molecular devices. In this work, three platinum(Ⅱ) complexes with –H, –NH2 and –NO2 groups on conductive backbones were designed and synthesized. Single-molecule conductance, which was measured using scanning tunnelling microscope break junction (STM-BJ) technique, demonstrated a conductance freeze phenomenon under the variation of substituents. Theoretical study revealed that, despite the electronic effect of the substituents shifting the energy level of molecular orbital, the quantum interference effect vanished the influence of electronic effect on the conductance and eventually leaded to the conductance freeze.
2022, 33(6): 3267-3271
doi: 10.1016/j.cclet.2021.11.001
Abstract:
Aggregation-induced emission (AIE) based luminescent materials are generating intensive interest due to their unique fluorescence in the aggregation state. Herein we report a strategy of dynamic covalent chemistry (DCC) controlled AIE luminogens for the regulation of multicolor emission in reversible covalent polymer networks. Tetraphenylethene derived ring-chain tautomers were prepared, and the emission was readily controlled through multimode, such as changing the solvent, adding the base, and dynamic covalent reactions with amines. Moreover, the construction of dynamic covalent cross-linked luminescent hydrogels with tunable fluorescent, self-healing, and mechanical properties, was realized. The combination of AIE and aggregation-caused quenching (ACQ) fluorophores in the polymer network further enabled the realization of a multicolor modulator, including white emission, in both solution and gel states. The strategies and results presented should find utility in dynamic assemblies, polymer networks, chemical sensing, and responsive materials.
Aggregation-induced emission (AIE) based luminescent materials are generating intensive interest due to their unique fluorescence in the aggregation state. Herein we report a strategy of dynamic covalent chemistry (DCC) controlled AIE luminogens for the regulation of multicolor emission in reversible covalent polymer networks. Tetraphenylethene derived ring-chain tautomers were prepared, and the emission was readily controlled through multimode, such as changing the solvent, adding the base, and dynamic covalent reactions with amines. Moreover, the construction of dynamic covalent cross-linked luminescent hydrogels with tunable fluorescent, self-healing, and mechanical properties, was realized. The combination of AIE and aggregation-caused quenching (ACQ) fluorophores in the polymer network further enabled the realization of a multicolor modulator, including white emission, in both solution and gel states. The strategies and results presented should find utility in dynamic assemblies, polymer networks, chemical sensing, and responsive materials.
2022, 33(6): 3272-3276
doi: 10.1016/j.cclet.2021.10.084
Abstract:
The selection and development of cathode of alkaline zinc batteries (AZBs) is still hindered and often leads to poor rate capability and short cycle life. Here, amorphous hollow nickel-cobalt-based sulfides nanocages with nanosheet arrays (AM-NCS) are designed and constructed with ZIF-67 as the self-template to exchange with Ni2+ and S2− by using a two-step ion exchange method. The synthesized AM-NCS possess the high specific capacity (160 mAh/g at 2 A/g), and the assembled battery has excellent rate performance (146 mAh/g reversible capacity at 5 A/g). The assembled device has excellent rate performance (155 mAh/g at 2 A/g) and long cycling stability (7000 cycles, 62.5% of initial capacity). The excellent electrochemical properties of the electrode materials are mainly attributed to the unique structure, in particular, polyhedron structure with hollow structure can improve the cyclic stability, and the amorphous structure can expose more reactive sites on the surfaces of nickel, cobalt and sulfur. This work provides a new strategy for the design and fabrication of high performance cathode materials for AZBs.
The selection and development of cathode of alkaline zinc batteries (AZBs) is still hindered and often leads to poor rate capability and short cycle life. Here, amorphous hollow nickel-cobalt-based sulfides nanocages with nanosheet arrays (AM-NCS) are designed and constructed with ZIF-67 as the self-template to exchange with Ni2+ and S2− by using a two-step ion exchange method. The synthesized AM-NCS possess the high specific capacity (160 mAh/g at 2 A/g), and the assembled battery has excellent rate performance (146 mAh/g reversible capacity at 5 A/g). The assembled device has excellent rate performance (155 mAh/g at 2 A/g) and long cycling stability (7000 cycles, 62.5% of initial capacity). The excellent electrochemical properties of the electrode materials are mainly attributed to the unique structure, in particular, polyhedron structure with hollow structure can improve the cyclic stability, and the amorphous structure can expose more reactive sites on the surfaces of nickel, cobalt and sulfur. This work provides a new strategy for the design and fabrication of high performance cathode materials for AZBs.
2022, 33(6): 3277-3280
doi: 10.1016/j.cclet.2021.11.004
Abstract:
Photodynamic therapy (PDT) has been gaining popularity in both scientific research and clinic applications due to its non-invasiveness and spatiotemporal targeting properties. Nevertheless, the local hypoxic microenvironment in tumor tissue impedes PDT universality. To overcome this drawback, a 2-pyridone-bearing BODIPY photosensitizer was synthesized rationally and introduced to polyethyleneglycol-b-poly(aspartic acid) to form a photosensitizer-1O2 generation, storage/release agent dual-loading system (PEG-b-PAsp-BODIPY). The investigation of the PDT effect at different illumination conditions in vitro and in vivo revealed that the system tremendously inhibited tumor proliferation, indicating that this new PEG-b-PAsp-BODIPY could act as a potentially effective photo therapeutic system for cancer therapeutics.
Photodynamic therapy (PDT) has been gaining popularity in both scientific research and clinic applications due to its non-invasiveness and spatiotemporal targeting properties. Nevertheless, the local hypoxic microenvironment in tumor tissue impedes PDT universality. To overcome this drawback, a 2-pyridone-bearing BODIPY photosensitizer was synthesized rationally and introduced to polyethyleneglycol-b-poly(aspartic acid) to form a photosensitizer-1O2 generation, storage/release agent dual-loading system (PEG-b-PAsp-BODIPY). The investigation of the PDT effect at different illumination conditions in vitro and in vivo revealed that the system tremendously inhibited tumor proliferation, indicating that this new PEG-b-PAsp-BODIPY could act as a potentially effective photo therapeutic system for cancer therapeutics.
2022, 33(6): 3281-3286
doi: 10.1016/j.cclet.2022.02.055
Abstract:
Ammonia borane (NH3BH3, AB) has been considered to be a promising chemical hydrogen storage material. Based on density functional theory, a series of transition metal atoms supported P3C (P3C_O) sheet is systematically investigated to screen out the most promising catalyst for dehydrogenation of AB. The results indicate that the Os/P3C and Os/P3C_O could be an efficient single atom catalyst (SACs) and the stepwise reaction pathway with free energy barrier of 2.07 and 1.54 eV respectively. Remarkably, the rate constant further quantitatively confirmed the real situation of the first step of dehydrogenation of AB on the Os/P3C and Os/P3C_O substrates. We found that kf1 at 400 K is equivalent to kf2 at 800 K, which greatly improves the temperature of the first step of AB dehydrogenation on P3C_O. We hope this work can provide a promising method for the design of catalysts for AB dehydrogenation reactions on the surface of two-dimensional materials (2D).
Ammonia borane (NH3BH3, AB) has been considered to be a promising chemical hydrogen storage material. Based on density functional theory, a series of transition metal atoms supported P3C (P3C_O) sheet is systematically investigated to screen out the most promising catalyst for dehydrogenation of AB. The results indicate that the Os/P3C and Os/P3C_O could be an efficient single atom catalyst (SACs) and the stepwise reaction pathway with free energy barrier of 2.07 and 1.54 eV respectively. Remarkably, the rate constant further quantitatively confirmed the real situation of the first step of dehydrogenation of AB on the Os/P3C and Os/P3C_O substrates. We found that kf1 at 400 K is equivalent to kf2 at 800 K, which greatly improves the temperature of the first step of AB dehydrogenation on P3C_O. We hope this work can provide a promising method for the design of catalysts for AB dehydrogenation reactions on the surface of two-dimensional materials (2D).
2022, 33(6): 3287-3290
doi: 10.1016/j.cclet.2022.03.065
Abstract:
Dendrite growth in lithium-ion batteries may bring thermal run-away especially at high current densities, which remains the major bottleneck to implement safe and fast charging for portable electronic devices or electronical vehicles. Designing dendrite inhibition separators with proper pore size is considered to be one of the most promising strategies to guarantee the battery safety. However, due to the impossible observation of lithium-ion distribution under separator by experiments, the underlying dendrite inhibition mechanism is still not fully understood. Here, we apply the phase-field model, which takes the separator phase into account to construct the electrochemical system total free energy, to study the ion re-distribution behavior of porous separator and understand the pore size inhibition effect on lithium dendrite. The numerical results indicate that separator with smaller pore size is beneficial to smoother electrodeposition, since the lithium-ion concentration on the electrode surface is more uniform under denser separator pores, when their sizes is larger than the critical nucleus. The proposed model could capture the physicochemical process of electrodeposition under multiphase structures, so it could also be used to explore dendrite growth under composite electrodes and composite solid electrolytes.
Dendrite growth in lithium-ion batteries may bring thermal run-away especially at high current densities, which remains the major bottleneck to implement safe and fast charging for portable electronic devices or electronical vehicles. Designing dendrite inhibition separators with proper pore size is considered to be one of the most promising strategies to guarantee the battery safety. However, due to the impossible observation of lithium-ion distribution under separator by experiments, the underlying dendrite inhibition mechanism is still not fully understood. Here, we apply the phase-field model, which takes the separator phase into account to construct the electrochemical system total free energy, to study the ion re-distribution behavior of porous separator and understand the pore size inhibition effect on lithium dendrite. The numerical results indicate that separator with smaller pore size is beneficial to smoother electrodeposition, since the lithium-ion concentration on the electrode surface is more uniform under denser separator pores, when their sizes is larger than the critical nucleus. The proposed model could capture the physicochemical process of electrodeposition under multiphase structures, so it could also be used to explore dendrite growth under composite electrodes and composite solid electrolytes.
2022, 33(6): 3291-3295
doi: 10.1016/j.cclet.2021.12.015
Abstract:
Metal-organic framework materials (MOFs), such as zeolitic imidazolate framework (ZIF), have been widely used in energy storage due to their advantages such as high structural stability, large specific surface, more active sites and skeleton structures. Herein, a novel two-dimensional (2D) CoCu-ZIF was synthesized by a facile solvothermal method. The as-prepared CoCu-ZIF nanosheets exhibit an ultrahigh reversible capacity of 2287.4 mAh/g and remains at 1172.1 mAh/g after 300 cycles at a current density of 100 mA/g, far better than that of the single Co-ZIF and Cu-ZIF. Additionally, the specific discharge capacity of CoCu-ZIF nanosheets can maintain at about 590 mAh/g after 1000 cycles at the current density of 2 A/g. Owing to the synergistic effect of two metals, function of nitrogen in the molecular and self-assembly 2D nanosheets, our research can provide strong support for the practical application of CoCu-ZIF materials in lithium ion batteries.
Metal-organic framework materials (MOFs), such as zeolitic imidazolate framework (ZIF), have been widely used in energy storage due to their advantages such as high structural stability, large specific surface, more active sites and skeleton structures. Herein, a novel two-dimensional (2D) CoCu-ZIF was synthesized by a facile solvothermal method. The as-prepared CoCu-ZIF nanosheets exhibit an ultrahigh reversible capacity of 2287.4 mAh/g and remains at 1172.1 mAh/g after 300 cycles at a current density of 100 mA/g, far better than that of the single Co-ZIF and Cu-ZIF. Additionally, the specific discharge capacity of CoCu-ZIF nanosheets can maintain at about 590 mAh/g after 1000 cycles at the current density of 2 A/g. Owing to the synergistic effect of two metals, function of nitrogen in the molecular and self-assembly 2D nanosheets, our research can provide strong support for the practical application of CoCu-ZIF materials in lithium ion batteries.
2022, 33(6): 3296-3296
doi: 10.1016/j.cclet.2022.03.066
Abstract:
