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2023 Volume 34 Issue 10
2023, 34(10): 108134
doi: 10.1016/j.cclet.2023.108134
Abstract:
CRISPR/Cas system has been utilized to rationally manipulate intracellular genes, and it has been engineered as versatile and efficient gene editing tools with precise site-specificity and excellent targeting ability for therapeutics, diagnostics, and bioimaging. Here, the evolution and application of CRISPR/Cas systems were sketched chronologically. Landmark works were exemplified to illustrate the design principles of CRISPR/Cas systems. Furthermore, the delivery vectors of CRISPR/Cas system especially DNA nanomaterials-based vectors were categorized and illuminated. DNA nanomaterials are suitable for CRISPR/Cas system delivery via base pairing due to its sequence programmability and biocompatibility. Then the applications of CRISPR/Cas in diagnosis and genomic imaging were highlighted. At the end of the review, the challenges and opportunities of CRISPR/Cas systems were deeply discussed. We envision that the grant advances on CRISPR/Cas systems will promote the development of interdisciplinary fields in chemistry, biology and medicine.
CRISPR/Cas system has been utilized to rationally manipulate intracellular genes, and it has been engineered as versatile and efficient gene editing tools with precise site-specificity and excellent targeting ability for therapeutics, diagnostics, and bioimaging. Here, the evolution and application of CRISPR/Cas systems were sketched chronologically. Landmark works were exemplified to illustrate the design principles of CRISPR/Cas systems. Furthermore, the delivery vectors of CRISPR/Cas system especially DNA nanomaterials-based vectors were categorized and illuminated. DNA nanomaterials are suitable for CRISPR/Cas system delivery via base pairing due to its sequence programmability and biocompatibility. Then the applications of CRISPR/Cas in diagnosis and genomic imaging were highlighted. At the end of the review, the challenges and opportunities of CRISPR/Cas systems were deeply discussed. We envision that the grant advances on CRISPR/Cas systems will promote the development of interdisciplinary fields in chemistry, biology and medicine.
2023, 34(10): 108163
doi: 10.1016/j.cclet.2023.108163
Abstract:
Nonfullerene acceptors (NFAs), which usually possess symmetric skeletons, have drawn great attention in recent years due to their pronounced advantages over the fullerene counterparts. Moreover, breaking the symmetry of NFAs could fine tune the molecular dipole, solubility, energy level, intermolecular interaction, molecular packing, crystallinity, etc., and give rise to improved photovoltaic performance. Currently, there are three main strategies for the design of asymmetric NFAs. This review highlights the recent advances of high-performance asymmetric NFAs and briefly outlooks the materials exploration for the future.
Nonfullerene acceptors (NFAs), which usually possess symmetric skeletons, have drawn great attention in recent years due to their pronounced advantages over the fullerene counterparts. Moreover, breaking the symmetry of NFAs could fine tune the molecular dipole, solubility, energy level, intermolecular interaction, molecular packing, crystallinity, etc., and give rise to improved photovoltaic performance. Currently, there are three main strategies for the design of asymmetric NFAs. This review highlights the recent advances of high-performance asymmetric NFAs and briefly outlooks the materials exploration for the future.
2023, 34(10): 108238
doi: 10.1016/j.cclet.2023.108238
Abstract:
The appearance and spread of antibiotic-resistant pathogens known as antimicrobial resistance (AMR) is one of the major worldwide health crises that humanity have to deal with over the next decades. One of the main methods for addressing AMR is the effective screening for antimicrobial insensitivity in clinical and environmental monitoring. Current clinical laboratory procedures use traditional culture-based antibiotic susceptibility testing (AST) methods, which can take up to 24h to identify which drug is suitable for the infection inhibition. Therefore, it is vital to develop novel strategies that offer quick, simple, affordable, reliable, sensitive and accurate AMR monitoring. Sensors for AMR markers detection could possess the essential qualities for quickly identifying resistant microorganisms and could give vital data for the selection of antibacterial drugs administration. This review offers a summary of the innovative application of these AMR markers detection strategies focusing on healthcare and environmental surveillance for the AMR genotypic or phenotypic assessment.
The appearance and spread of antibiotic-resistant pathogens known as antimicrobial resistance (AMR) is one of the major worldwide health crises that humanity have to deal with over the next decades. One of the main methods for addressing AMR is the effective screening for antimicrobial insensitivity in clinical and environmental monitoring. Current clinical laboratory procedures use traditional culture-based antibiotic susceptibility testing (AST) methods, which can take up to 24h to identify which drug is suitable for the infection inhibition. Therefore, it is vital to develop novel strategies that offer quick, simple, affordable, reliable, sensitive and accurate AMR monitoring. Sensors for AMR markers detection could possess the essential qualities for quickly identifying resistant microorganisms and could give vital data for the selection of antibacterial drugs administration. This review offers a summary of the innovative application of these AMR markers detection strategies focusing on healthcare and environmental surveillance for the AMR genotypic or phenotypic assessment.
2023, 34(10): 108241
doi: 10.1016/j.cclet.2023.108241
Abstract:
It is established that monitoring blood glucose on a daily basis is one of the most effective solutions to prevent and treat diabetes. Consequently, developing a glucose sensing platform with outstanding sensing performance occupies an indispensable position for the early diagnosis and risk assessment of diabetes. Recently, biosensor has been deemed as a promising apparatus to acquire the signals for glucose monitoring based on 2D materials. However, it is unsatisfied to deploy some materials widely as a result of some inherent defects. Carbon nanotubes have comparatively high toxicity. MoS2 with unfavourable biocompatibility are still arduously implemented on being functionalized. Fortunately, MXene, a brand-new and rapidly developing two-dimensional material, exhibits marvellous application potential in the domain of biosensing. Therefore, it has exerted tremendous attention from diverse scientific fields owning to its remarkable properties, such as excellent hydrophilicity, metal-like conductivity, abundant surface functional groups, unique layered structure, large specific surface area and remarkable biocompatibility. This review mainly focuses on the main synthetic route of MXenes, as well as the recent advancements of biosensors involving MXenes as an electrode modifier for glucose detection. In addition, the promising prospects and challenges of glucose sensing technology based on MXenes are also discussed.
It is established that monitoring blood glucose on a daily basis is one of the most effective solutions to prevent and treat diabetes. Consequently, developing a glucose sensing platform with outstanding sensing performance occupies an indispensable position for the early diagnosis and risk assessment of diabetes. Recently, biosensor has been deemed as a promising apparatus to acquire the signals for glucose monitoring based on 2D materials. However, it is unsatisfied to deploy some materials widely as a result of some inherent defects. Carbon nanotubes have comparatively high toxicity. MoS2 with unfavourable biocompatibility are still arduously implemented on being functionalized. Fortunately, MXene, a brand-new and rapidly developing two-dimensional material, exhibits marvellous application potential in the domain of biosensing. Therefore, it has exerted tremendous attention from diverse scientific fields owning to its remarkable properties, such as excellent hydrophilicity, metal-like conductivity, abundant surface functional groups, unique layered structure, large specific surface area and remarkable biocompatibility. This review mainly focuses on the main synthetic route of MXenes, as well as the recent advancements of biosensors involving MXenes as an electrode modifier for glucose detection. In addition, the promising prospects and challenges of glucose sensing technology based on MXenes are also discussed.
2023, 34(10): 108359
doi: 10.1016/j.cclet.2023.108359
Abstract:
Neglected tropical diseases (NTDs) refer to infectious diseases caused by multiple pathogens that are prevalent in hot, humid climates in tropical areas. With the global economic growth and the improvement of public health status, eliminating neglected tropical diseases will be of great significance to the healthy development of human beings. However, the number of drugs and vaccines for NTDs treatment is extremely limited, so it is urgent to develop new drugs. Since most NTDs are caused by parasites, this paper selected parasitic diseases with high morbidity and mortality, and focused on new effective therapeutic targets and excellent lead compounds for these diseases. Schistosomiasis, human African trypanosomiasis (HAT), Chagas disease, leishmaniasis, filariasis and toxoplasmosis correspond to a series targets such as smHDAC8, thioredoxin glutathione reductase (TGR), T. cruzi glucokinase (TcGlcK), phosphofructokinase (PFK), type IB topoisomerase, cell division cycle-2-related Kinase, sterolmethyl transferase, calumenin, dihydrofolate reductase (DHFR) and Toxoplasma gondii farnesyl-diphosphate synthase (TgFPPs). In this paper, the pharmacological effects of typical lead compounds corresponding to each disease, the structural characteristics of the mother nucleus and the pharmacological activities of the substituent. In addition, the binding patterns of some involved targets (such as smHDAC8) with corresponding lead compounds (such as compound 13) and the signaling pathways associated with gluconeogenesis, glycolysis, and pentose phosphate pathways are analyzed in detail. In this paper, the interaction mechanism between the lead compounds and the target were thoroughly discussed, in order to provide the research ideas of potential anti-parasite compounds, and further improve the understanding and prevention ability of such diseases of NTDs.
Neglected tropical diseases (NTDs) refer to infectious diseases caused by multiple pathogens that are prevalent in hot, humid climates in tropical areas. With the global economic growth and the improvement of public health status, eliminating neglected tropical diseases will be of great significance to the healthy development of human beings. However, the number of drugs and vaccines for NTDs treatment is extremely limited, so it is urgent to develop new drugs. Since most NTDs are caused by parasites, this paper selected parasitic diseases with high morbidity and mortality, and focused on new effective therapeutic targets and excellent lead compounds for these diseases. Schistosomiasis, human African trypanosomiasis (HAT), Chagas disease, leishmaniasis, filariasis and toxoplasmosis correspond to a series targets such as smHDAC8, thioredoxin glutathione reductase (TGR), T. cruzi glucokinase (TcGlcK), phosphofructokinase (PFK), type IB topoisomerase, cell division cycle-2-related Kinase, sterolmethyl transferase, calumenin, dihydrofolate reductase (DHFR) and Toxoplasma gondii farnesyl-diphosphate synthase (TgFPPs). In this paper, the pharmacological effects of typical lead compounds corresponding to each disease, the structural characteristics of the mother nucleus and the pharmacological activities of the substituent. In addition, the binding patterns of some involved targets (such as smHDAC8) with corresponding lead compounds (such as compound 13) and the signaling pathways associated with gluconeogenesis, glycolysis, and pentose phosphate pathways are analyzed in detail. In this paper, the interaction mechanism between the lead compounds and the target were thoroughly discussed, in order to provide the research ideas of potential anti-parasite compounds, and further improve the understanding and prevention ability of such diseases of NTDs.
2023, 34(10): 108544
doi: 10.1016/j.cclet.2023.108544
Abstract:
Metal/nucleophilic Lewis base dual catalysis has been recognized as a reliable and promising strategy for finishing ideal organic synthesis over the past decades. The new strategy can usually achieve some chemical reactions that cannot be realized by the traditionally mono-catalytic system, dramatically expanding the synthetic utility of chemical transformations by leveraging additional activation modes. Thus considerable progress has been made in the synthesis of a wide range of heterocyclic and biologically active compounds by using the combination of diversely metal/nucleophilic Lewis base dual catalysts, including metal/phosphine, metal/N-heterocyclic carbene (NHC) and metal/tertiary amine dual catalysis systems. In this review, we describe a comprehensive and updated advance of metal/nucleophilic Lewis base dual catalytic annualtion reactions, meanwhile, the related mechanism and the application of these annulation strategies in natural product total synthesis will be highlighted in detail.
Metal/nucleophilic Lewis base dual catalysis has been recognized as a reliable and promising strategy for finishing ideal organic synthesis over the past decades. The new strategy can usually achieve some chemical reactions that cannot be realized by the traditionally mono-catalytic system, dramatically expanding the synthetic utility of chemical transformations by leveraging additional activation modes. Thus considerable progress has been made in the synthesis of a wide range of heterocyclic and biologically active compounds by using the combination of diversely metal/nucleophilic Lewis base dual catalysts, including metal/phosphine, metal/N-heterocyclic carbene (NHC) and metal/tertiary amine dual catalysis systems. In this review, we describe a comprehensive and updated advance of metal/nucleophilic Lewis base dual catalytic annualtion reactions, meanwhile, the related mechanism and the application of these annulation strategies in natural product total synthesis will be highlighted in detail.
2023, 34(10): 108559
doi: 10.1016/j.cclet.2023.108559
Abstract:
Compartmentalization in the biological world brings excellent efficiency and specificity to the formation of complex compounds, inspiring supramolecular chemists to continuously search for defined spaces that can mimic such natural binding sites. Bowl-shaped cavitands built up from resorcinarenes (RA) present rigid and preorganized concave surfaces, which are capable of mimicking the molecular recognition properties of enzymes. The versatile scaffold of RA endows the cavitand with terrific variety and excellent binding behavior. This review provides a comprehensive overview over the structural modification to date in the high attention field of RA-based cavitands development. Different strategies for synthesizing diverse cavitands, such as small cavity cavitands, wider cavity cavitands, deep cavity cavitands, biscavitands, and asymmetric cavitands, are discussed in details. Furthermore, insights into their applications including catalysis, separations and sensing are provided.
Compartmentalization in the biological world brings excellent efficiency and specificity to the formation of complex compounds, inspiring supramolecular chemists to continuously search for defined spaces that can mimic such natural binding sites. Bowl-shaped cavitands built up from resorcinarenes (RA) present rigid and preorganized concave surfaces, which are capable of mimicking the molecular recognition properties of enzymes. The versatile scaffold of RA endows the cavitand with terrific variety and excellent binding behavior. This review provides a comprehensive overview over the structural modification to date in the high attention field of RA-based cavitands development. Different strategies for synthesizing diverse cavitands, such as small cavity cavitands, wider cavity cavitands, deep cavity cavitands, biscavitands, and asymmetric cavitands, are discussed in details. Furthermore, insights into their applications including catalysis, separations and sensing are provided.
2023, 34(10): 108142
doi: 10.1016/j.cclet.2023.108142
Abstract:
Fe-NX/C electrocatalysts have aroused extensive interest in accelerating sluggish oxygen reduction reaction (ORR) kinetics as potential alternatives to platinum catalysts in rechargeable Zn-air batteries (ZABs). However, the low density and poor accessibility of Fe-NX sites have severely restricted the electrocatalytic performance of Fe-NX/C. Herein, Fe, N co-doped ordered mesoporous carbon fiber bundles are prepared through a ligand-assisted strategy with nitrogen-rich 1,10-phenanthroline as space isolation agent. 1,10-Phenanthroline reveals a six-membered heterocyclic structure containing abundant nitrogen species to tightly coordinate with Fe ions, which is conducive to achieving high-density Fe-NX sites. Meanwhile, the adoption of SBA-15 as hard-templates enables the catalysts with highly ordered channels and large specific surface areas, improving the accessibility of Fe-NX sites. The optimal catalyst (PDA-Fe-900) demonstrates a positive half-wave potential of 0.84 V (vs. RHE) in alkaline solution, outperforming the commercial Pt/C (0.83 V). In addition, PDA-Fe-900 delivers comparable ORR performance to commercial Pt/C in acidic electrolyte. Impressively, when PDA-Fe-900 is employed as an air cathode, it achieves large power densities of 163.0 mW/cm2 in liquid-state ZAB and 116.6 mW/cm2 in the flexible solid-state ZAB. This work provides an efficient ligand-assisted pathway for fabricating catalysts with dense and accessible Fe-NX sites as high-performance ORR electrocatalysts for ZABs.
Fe-NX/C electrocatalysts have aroused extensive interest in accelerating sluggish oxygen reduction reaction (ORR) kinetics as potential alternatives to platinum catalysts in rechargeable Zn-air batteries (ZABs). However, the low density and poor accessibility of Fe-NX sites have severely restricted the electrocatalytic performance of Fe-NX/C. Herein, Fe, N co-doped ordered mesoporous carbon fiber bundles are prepared through a ligand-assisted strategy with nitrogen-rich 1,10-phenanthroline as space isolation agent. 1,10-Phenanthroline reveals a six-membered heterocyclic structure containing abundant nitrogen species to tightly coordinate with Fe ions, which is conducive to achieving high-density Fe-NX sites. Meanwhile, the adoption of SBA-15 as hard-templates enables the catalysts with highly ordered channels and large specific surface areas, improving the accessibility of Fe-NX sites. The optimal catalyst (PDA-Fe-900) demonstrates a positive half-wave potential of 0.84 V (vs. RHE) in alkaline solution, outperforming the commercial Pt/C (0.83 V). In addition, PDA-Fe-900 delivers comparable ORR performance to commercial Pt/C in acidic electrolyte. Impressively, when PDA-Fe-900 is employed as an air cathode, it achieves large power densities of 163.0 mW/cm2 in liquid-state ZAB and 116.6 mW/cm2 in the flexible solid-state ZAB. This work provides an efficient ligand-assisted pathway for fabricating catalysts with dense and accessible Fe-NX sites as high-performance ORR electrocatalysts for ZABs.
2023, 34(10): 108143
doi: 10.1016/j.cclet.2023.108143
Abstract:
In recent years, vanadate has attracted the attention of researchers for its application in electrode materials due to its high specific capacity and layered crystal structure. Herein, a typical manganese vanadium oxides (MnV2O6) product is efficient synthesis via a simple one-step hydrothermal method at 200 ℃ for 16 h. The as-prepared MnV2O6 sample is found to be the unique one-dimensional fan-like superstructure consist of several nanorods. From a microcosmic point of view, VO6 octahedra sheets are connected by sharing edges which provides highly-open framework for rapid the intercalation and deintercalation of guest ions Therefore, stable MnV2O6 was prepared and used as a cathode material in aqueous zinc ion batteries, which displayed favorable specific discharge capacity, excellent coulombic efficiency and well cycling performance.
In recent years, vanadate has attracted the attention of researchers for its application in electrode materials due to its high specific capacity and layered crystal structure. Herein, a typical manganese vanadium oxides (MnV2O6) product is efficient synthesis via a simple one-step hydrothermal method at 200 ℃ for 16 h. The as-prepared MnV2O6 sample is found to be the unique one-dimensional fan-like superstructure consist of several nanorods. From a microcosmic point of view, VO6 octahedra sheets are connected by sharing edges which provides highly-open framework for rapid the intercalation and deintercalation of guest ions Therefore, stable MnV2O6 was prepared and used as a cathode material in aqueous zinc ion batteries, which displayed favorable specific discharge capacity, excellent coulombic efficiency and well cycling performance.
2023, 34(10): 108144
doi: 10.1016/j.cclet.2023.108144
Abstract:
Base pair mismatch has been regarded as the main source of DNA point mutations, where minor short-lived tautomers were usually involved. However, the detection and characterization of these unnatural species pose challenges to existing techniques. Here, by using systematic structural and ultrafast resonance Raman (RR) spectral analysis for the four possible conformers of guanine-cytosine base pairs, the prominent marker Raman bands were identified. We found that the hydrogen bonding vibrational region from 2300 cm−1 to 3700 cm−1 is ideal for the identification of these short live species. The marker bands provide direct evidence for the existence of the tautomer species, thus offering an effective strategy to detect the short-lived minor species. Ultrafast resonance Raman spectroscopy would be a powerful tool to provide direct evidence of critical dynamical details of complex systems involving protonation or tautomerization.
Base pair mismatch has been regarded as the main source of DNA point mutations, where minor short-lived tautomers were usually involved. However, the detection and characterization of these unnatural species pose challenges to existing techniques. Here, by using systematic structural and ultrafast resonance Raman (RR) spectral analysis for the four possible conformers of guanine-cytosine base pairs, the prominent marker Raman bands were identified. We found that the hydrogen bonding vibrational region from 2300 cm−1 to 3700 cm−1 is ideal for the identification of these short live species. The marker bands provide direct evidence for the existence of the tautomer species, thus offering an effective strategy to detect the short-lived minor species. Ultrafast resonance Raman spectroscopy would be a powerful tool to provide direct evidence of critical dynamical details of complex systems involving protonation or tautomerization.
2023, 34(10): 108147
doi: 10.1016/j.cclet.2023.108147
Abstract:
Benefitting from the tunable heterogeneous interface and electronic interaction, metal-polymer-based hybrid composites have attracted wide attention. It is highly desired to develop advanced synthesis methodology and understand the structure-performance relationship. Herein, with the aniline oligomer as the key enabler, we resolve the inferior dynamics issue in the Ag+-aniline reaction system, and successfully fabricate a sub-micron anisotropic eccentric Ag@polyaniline (PANI) particle (an average size up to 340 nm) at room temperature. We demonstrate the synergy mechanism of polyvinyl pyrrolidone and in-situ generated PANI for modifying the dynamic reaction interface. We further clarify the H+ concentration and the surfactant types serve as main descriptors to tune the reaction dynamics. Besides, by applying other aniline oligomers, a series of similar eccentric structures can also be obtained, indicative of the good applicability of our strategy. Such a sub-micron eccentric structure furnishes the Ag@PANI composites with sound performance for microwave absorption, as demonstrated by a minimum reflection loss (RL) value of −35 dB with an effective absorption bandwidth of 3.7 GHz. This study provides an inspiring scope/concept of eccentric microstructure engineering for better meeting the demands in the high-tech military, energy, environment fields, and beyond.
Benefitting from the tunable heterogeneous interface and electronic interaction, metal-polymer-based hybrid composites have attracted wide attention. It is highly desired to develop advanced synthesis methodology and understand the structure-performance relationship. Herein, with the aniline oligomer as the key enabler, we resolve the inferior dynamics issue in the Ag+-aniline reaction system, and successfully fabricate a sub-micron anisotropic eccentric Ag@polyaniline (PANI) particle (an average size up to 340 nm) at room temperature. We demonstrate the synergy mechanism of polyvinyl pyrrolidone and in-situ generated PANI for modifying the dynamic reaction interface. We further clarify the H+ concentration and the surfactant types serve as main descriptors to tune the reaction dynamics. Besides, by applying other aniline oligomers, a series of similar eccentric structures can also be obtained, indicative of the good applicability of our strategy. Such a sub-micron eccentric structure furnishes the Ag@PANI composites with sound performance for microwave absorption, as demonstrated by a minimum reflection loss (RL) value of −35 dB with an effective absorption bandwidth of 3.7 GHz. This study provides an inspiring scope/concept of eccentric microstructure engineering for better meeting the demands in the high-tech military, energy, environment fields, and beyond.
2023, 34(10): 108148
doi: 10.1016/j.cclet.2023.108148
Abstract:
Covalent organic frameworks (COFs) are promising crystalline materials for the light-driven hydrogen evolution reaction (HER) due to their tunable chemical structures and energy band gaps. However, deeply understanding corresponding mechanism is still challenging due to the multiple components and complicated electron transfer and reduction paths involved in photocatalytic HER. Here, the photocatalytic HER investigation has been reported based on three COFs catalysts, 1–3, which are prepared by benzo[1, 2-b: 3, 4-b': 5, 6-b']trithiophene-2, 5, 8-trialdehyde to react with C3 symmetric triamines including tris(4-aminophenyl)amine, 1, 3, 5-tris(4-aminophenyl)benzene, and (1, 3, 5-tris-(4-aminophenyl)triazine, respectively. As the isostructural hexagonal honeycomb-type COF of 2 and 3 reported previously, the crystal structure of 1 has been carefully correlated through the powder X-ray diffraction study with the help of theoretical simulations. 1 shows highly porous framework with Brunauer-Emmett-Teller surface area of 1249 m2/g. Moreover, the introduction of ascorbic acid into the photocatalytic system of COFs achieves the hydrogen evolution rate of 3.75, 12.16 and 20.2 mmol g–1 h–1 for 1–3, respectively. The important role of ascorbic acid in photocatalysis of HER is disclosed to protonate the imine linkages of these COFs, leading to the obvious absorbance red-shift and the improved charge separation efficiency together with reduced resistance in contrast to pristine materials according to the spectroscopic and electronic characterizations. These innovations of chemical and physical properties for these COFs are responsible for their excellent photocatalytic performance. These results elucidate that tiny modifications of COFs structures is able to greatly tune their band structures as well as catalytic properties, therefore providing an available approach for optimizing COFs functionalities.
Covalent organic frameworks (COFs) are promising crystalline materials for the light-driven hydrogen evolution reaction (HER) due to their tunable chemical structures and energy band gaps. However, deeply understanding corresponding mechanism is still challenging due to the multiple components and complicated electron transfer and reduction paths involved in photocatalytic HER. Here, the photocatalytic HER investigation has been reported based on three COFs catalysts, 1–3, which are prepared by benzo[1, 2-b: 3, 4-b': 5, 6-b']trithiophene-2, 5, 8-trialdehyde to react with C3 symmetric triamines including tris(4-aminophenyl)amine, 1, 3, 5-tris(4-aminophenyl)benzene, and (1, 3, 5-tris-(4-aminophenyl)triazine, respectively. As the isostructural hexagonal honeycomb-type COF of 2 and 3 reported previously, the crystal structure of 1 has been carefully correlated through the powder X-ray diffraction study with the help of theoretical simulations. 1 shows highly porous framework with Brunauer-Emmett-Teller surface area of 1249 m2/g. Moreover, the introduction of ascorbic acid into the photocatalytic system of COFs achieves the hydrogen evolution rate of 3.75, 12.16 and 20.2 mmol g–1 h–1 for 1–3, respectively. The important role of ascorbic acid in photocatalysis of HER is disclosed to protonate the imine linkages of these COFs, leading to the obvious absorbance red-shift and the improved charge separation efficiency together with reduced resistance in contrast to pristine materials according to the spectroscopic and electronic characterizations. These innovations of chemical and physical properties for these COFs are responsible for their excellent photocatalytic performance. These results elucidate that tiny modifications of COFs structures is able to greatly tune their band structures as well as catalytic properties, therefore providing an available approach for optimizing COFs functionalities.
2023, 34(10): 108153
doi: 10.1016/j.cclet.2023.108153
Abstract:
Glutathione depletion provides a promising strategy for the design of non-platinum anticancer drugs. Here we report a series of electrophilic (salen)osmium(Ⅵ) nitrides that react with glutathione to generate (salen)osmium(Ⅲ) ammine compounds. In vitro studies indicate that these osmium(Ⅵ) nitrides show comparable cytotoxicity to cisplatin against various carcinoma. Mechanistic studies with the representative compound [OsⅥ(N)(LH)(OH2)](PF6) (1, LH = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion) suggest that 1 induces glutathione depletion, reactive oxygen species generation, endoplasmic reticulum stress, and in turn triggers death receptor-mediated apoptosis and autophagy in lung cancer cells. In vivo evaluations show that 1 can inhibit tumor xenograft growth effectively with no body weight drop.
Glutathione depletion provides a promising strategy for the design of non-platinum anticancer drugs. Here we report a series of electrophilic (salen)osmium(Ⅵ) nitrides that react with glutathione to generate (salen)osmium(Ⅲ) ammine compounds. In vitro studies indicate that these osmium(Ⅵ) nitrides show comparable cytotoxicity to cisplatin against various carcinoma. Mechanistic studies with the representative compound [OsⅥ(N)(LH)(OH2)](PF6) (1, LH = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion) suggest that 1 induces glutathione depletion, reactive oxygen species generation, endoplasmic reticulum stress, and in turn triggers death receptor-mediated apoptosis and autophagy in lung cancer cells. In vivo evaluations show that 1 can inhibit tumor xenograft growth effectively with no body weight drop.
2023, 34(10): 108158
doi: 10.1016/j.cclet.2023.108158
Abstract:
Chemical upcycling of end-of-life poly(lactide) plastics to lactide, lactate ester and new poly(lactide) has been achieved by using magnesium bis[bis(trimethylsilyl)amide] [Mg(HMDS)2] as promoter. Mg(HMDS)2 showed high efficiency in L-lactide polymerization and poly(lactide) depolymerization. Mg(HMDS)2/Ph2CHOH catalytic system displayed high ring-opening selectivity and the characteristic of immortal polymerization. Taking advantage of transesterification, depolymerizations of end-of-life poly(lactide) plastics to lactate ester (polymer to value-added chemicals) and lactide (polymer to monomer) were achieved with high yields. Besides, a new "depolymerization-repolymerization" strategy was proposed to directly transform poly(lactide) into new poly(lactide). This work provides a theoretical basis for the design of polymerization and depolymerization catalysts and promotes the development of degradable polymers.
Chemical upcycling of end-of-life poly(lactide) plastics to lactide, lactate ester and new poly(lactide) has been achieved by using magnesium bis[bis(trimethylsilyl)amide] [Mg(HMDS)2] as promoter. Mg(HMDS)2 showed high efficiency in L-lactide polymerization and poly(lactide) depolymerization. Mg(HMDS)2/Ph2CHOH catalytic system displayed high ring-opening selectivity and the characteristic of immortal polymerization. Taking advantage of transesterification, depolymerizations of end-of-life poly(lactide) plastics to lactate ester (polymer to value-added chemicals) and lactide (polymer to monomer) were achieved with high yields. Besides, a new "depolymerization-repolymerization" strategy was proposed to directly transform poly(lactide) into new poly(lactide). This work provides a theoretical basis for the design of polymerization and depolymerization catalysts and promotes the development of degradable polymers.
2023, 34(10): 108181
doi: 10.1016/j.cclet.2023.108181
Abstract:
Simultaneous acquisition of fluorescence property and refractive index using a single surface plasmon coupled emission (SPCE) measurement has been achieved, thus achieving synchronicity in real time. The SPCE sensor was employed for monitoring the adsorption of volatile organic compounds (VOCs) by dye-encapsulated metal-organic frameworks (Dye@MOFs). Refractive index can reveal surface molecular adsorption and the fluorescence with information on refractive index can provide a comprehensive analysis of the adsorption events of VOCs on the interface. Meantime, the signal intensity can be amplified by combining the responses caused by changes in refractive index and the fluorescence property in parallel. This all-in-one method opens up a route to monitoring multiple processes simultaneously occurring on the interface.
Simultaneous acquisition of fluorescence property and refractive index using a single surface plasmon coupled emission (SPCE) measurement has been achieved, thus achieving synchronicity in real time. The SPCE sensor was employed for monitoring the adsorption of volatile organic compounds (VOCs) by dye-encapsulated metal-organic frameworks (Dye@MOFs). Refractive index can reveal surface molecular adsorption and the fluorescence with information on refractive index can provide a comprehensive analysis of the adsorption events of VOCs on the interface. Meantime, the signal intensity can be amplified by combining the responses caused by changes in refractive index and the fluorescence property in parallel. This all-in-one method opens up a route to monitoring multiple processes simultaneously occurring on the interface.
2023, 34(10): 108186
doi: 10.1016/j.cclet.2023.108186
Abstract:
Titanium dioxide (TiO2) has been widely investigated as a candidate for anode materials of sodium-ion batteries (SIBs) due to its low cost and high abundance. However, the intrinsic sluggish ion/electron transfer rate hinders its practical applications for high energy density storage devices. In contrast, antimony (Sb) shows high specific theoretical capacity (660 mAh/g) as well as excellent electron conductivity, but the large volume variation upon cycling usually leads to severe capacity fading. Herein, with the objective of achieving high-performance sodium storage anode materials, TiO2@C-Sb nanotablets with a small amount of Sb content (6.4 wt%) are developed through calcination Ti-metal–organic framework (MIL-125) derived TiO2@C/SbCl3 mixture under reductive atmosphere. Benefitting from the synergetic effect of well-dispersed Sb nanoparticles as well as robust porous TiO2@C substrate, the TiO2@C-Sb shows enhanced electron/ion transfer rate and predominantly pseudocapacitive sodium storage behavior, delivering a reversible capacity of 219 mAh/g at 0.5 A/g even after 1000 cycles. More significantly, this method may be commonly used to incorporate other alloy-based high-theoretical materials into MIL-125-derived TiO2@C, which is promising for developing high-energy-density TiO2-based energy storage devices.
Titanium dioxide (TiO2) has been widely investigated as a candidate for anode materials of sodium-ion batteries (SIBs) due to its low cost and high abundance. However, the intrinsic sluggish ion/electron transfer rate hinders its practical applications for high energy density storage devices. In contrast, antimony (Sb) shows high specific theoretical capacity (660 mAh/g) as well as excellent electron conductivity, but the large volume variation upon cycling usually leads to severe capacity fading. Herein, with the objective of achieving high-performance sodium storage anode materials, TiO2@C-Sb nanotablets with a small amount of Sb content (6.4 wt%) are developed through calcination Ti-metal–organic framework (MIL-125) derived TiO2@C/SbCl3 mixture under reductive atmosphere. Benefitting from the synergetic effect of well-dispersed Sb nanoparticles as well as robust porous TiO2@C substrate, the TiO2@C-Sb shows enhanced electron/ion transfer rate and predominantly pseudocapacitive sodium storage behavior, delivering a reversible capacity of 219 mAh/g at 0.5 A/g even after 1000 cycles. More significantly, this method may be commonly used to incorporate other alloy-based high-theoretical materials into MIL-125-derived TiO2@C, which is promising for developing high-energy-density TiO2-based energy storage devices.
2023, 34(10): 108187
doi: 10.1016/j.cclet.2023.108187
Abstract:
Lignin and its derivatives hold great potential in developing high performance porous carbon materials for supercapacitors due to the versatile features of high carbon content, abundant multifunctional groups, low cost, and environmental benefits. Unfortunately, their derived porous carbon generally has the features of unfavorable microporous-dominated morphologies and low specific surface area (SSA) attributed from the highly-branched structure of lignin, which are hardly suitable for the supercapacitors with ionic liquid (IL) electrolyte, leading to poor energy density and rate capability. Herein, porous carbon materials with desirable mesoporous contributions from sodium lignosulphonate are designed via a facile template method. Such rich mesoporisity carbon materials not only possess with three-dimensional interconnected network, large SSA, as well as favorable pore size distribution for accelerated ion and electron mass transfer, but also feature low heteroatom content for high electrochemical stability. Consequently, the optimal electrode exhibits a high capacitance of 166 F/g at 0.5 A/g, superior rate performance (59 Wh/kg at 59 kW/kg), as well as impressive cycle life with good capacitance retention of 93.1% in EMIBF4 electrolytes. The present work opens a new avenue to design porous carbon materials with high mesopore properties from lignin for effective compatibility with IL electrolyte in high-performance supercapacitors.
Lignin and its derivatives hold great potential in developing high performance porous carbon materials for supercapacitors due to the versatile features of high carbon content, abundant multifunctional groups, low cost, and environmental benefits. Unfortunately, their derived porous carbon generally has the features of unfavorable microporous-dominated morphologies and low specific surface area (SSA) attributed from the highly-branched structure of lignin, which are hardly suitable for the supercapacitors with ionic liquid (IL) electrolyte, leading to poor energy density and rate capability. Herein, porous carbon materials with desirable mesoporous contributions from sodium lignosulphonate are designed via a facile template method. Such rich mesoporisity carbon materials not only possess with three-dimensional interconnected network, large SSA, as well as favorable pore size distribution for accelerated ion and electron mass transfer, but also feature low heteroatom content for high electrochemical stability. Consequently, the optimal electrode exhibits a high capacitance of 166 F/g at 0.5 A/g, superior rate performance (59 Wh/kg at 59 kW/kg), as well as impressive cycle life with good capacitance retention of 93.1% in EMIBF4 electrolytes. The present work opens a new avenue to design porous carbon materials with high mesopore properties from lignin for effective compatibility with IL electrolyte in high-performance supercapacitors.
2023, 34(10): 108188
doi: 10.1016/j.cclet.2023.108188
Abstract:
Iron-chromium redox flow batteries (ICRFBs) possess advantages of high safety, long cycle time, and low-cost. Increasing Cr3+/Cr2+ reaction activity is suggested as one of the most promising strategies to improve the performance and prolong the lifetime of ICRFBs. To improve the slow reaction kinetics of the negative electrode, a type of defected carbon cloth with Bismuth (Bi) catalyst introduction is prepared by defect engineering method and electrochemical deposition, which provided defect sites and active sites to catalyze the redox couple's reaction of ICRFBs. Furthermore, this modified carbon cloth adsorbs Cr(Ⅲ) hydrate more easily, which has a more stable structure and can significantly improve the performance of ICRFBs. Both experimental analysis and theoretical calculation indicated that the modified electrode has excellent electrocatalytic ability, which can enhance the reaction rate of Cr3+/Cr2+, improve capacity retention and stabilize cycling performance. The capacity degradation rate of an ICRFB single cell with the modified electrodes is just 0.23% per cycle at a current density of 140 mA/cm2. Additionally, the energy efficiency (EE) remains around 83%, which is 8.45% higher than that of the pristine electrode assembled battery under 60 cycles. This work supplies a simple method to obtain a high-performance electrode material for ICRFBs and makes it a practical solution to promote ICFRBs large-scale commercialization process.
Iron-chromium redox flow batteries (ICRFBs) possess advantages of high safety, long cycle time, and low-cost. Increasing Cr3+/Cr2+ reaction activity is suggested as one of the most promising strategies to improve the performance and prolong the lifetime of ICRFBs. To improve the slow reaction kinetics of the negative electrode, a type of defected carbon cloth with Bismuth (Bi) catalyst introduction is prepared by defect engineering method and electrochemical deposition, which provided defect sites and active sites to catalyze the redox couple's reaction of ICRFBs. Furthermore, this modified carbon cloth adsorbs Cr(Ⅲ) hydrate more easily, which has a more stable structure and can significantly improve the performance of ICRFBs. Both experimental analysis and theoretical calculation indicated that the modified electrode has excellent electrocatalytic ability, which can enhance the reaction rate of Cr3+/Cr2+, improve capacity retention and stabilize cycling performance. The capacity degradation rate of an ICRFB single cell with the modified electrodes is just 0.23% per cycle at a current density of 140 mA/cm2. Additionally, the energy efficiency (EE) remains around 83%, which is 8.45% higher than that of the pristine electrode assembled battery under 60 cycles. This work supplies a simple method to obtain a high-performance electrode material for ICRFBs and makes it a practical solution to promote ICFRBs large-scale commercialization process.
2023, 34(10): 108195
doi: 10.1016/j.cclet.2023.108195
Abstract:
The effective removal and selective detection of explosive and toxic pollutant trinitrophenol (TNP) is an attractive but challenging field. Herein, a double-cavity nor-seco-cucurbit[10]uril (ns-Q[10])-based supramolecular assembly 8-HQ@ns-Q[10] was fabricated and its structure was characterized by X-ray single crystal diffraction. In this assembly, the stoichiometric ratio of ns-Q[10] and 8-hydroxyquinoline (8-HQ) is 1:2, which is also attributed to the special double-cavity structure of ns-Q[10]. The luminescence sensing experiments showed that 8-HQ@ns-Q[10] can be used as a good fluorescence-enhanced sensing material (enhanced 27-fold) for the rapid detection of explosives and the aqueous contaminant TNP, with a limit of detection (LOD) of 2.07 × 10−5 mol/L, without interference from other phenolic compounds. Furthermore, TNP can be efficiently removed in the presence of assembly 8-HQ@ns-Q[10], and the removal efficiency is more than 89%. Therefore, the supramolecular assembly 8-HQ@ns-Q[10], as a fluorescence-enhanced luminescence sensor and adsorption material, has rich research value and potential application prospect when applied to the detection and removal of TNP in aqueous environment.
The effective removal and selective detection of explosive and toxic pollutant trinitrophenol (TNP) is an attractive but challenging field. Herein, a double-cavity nor-seco-cucurbit[10]uril (ns-Q[10])-based supramolecular assembly 8-HQ@ns-Q[10] was fabricated and its structure was characterized by X-ray single crystal diffraction. In this assembly, the stoichiometric ratio of ns-Q[10] and 8-hydroxyquinoline (8-HQ) is 1:2, which is also attributed to the special double-cavity structure of ns-Q[10]. The luminescence sensing experiments showed that 8-HQ@ns-Q[10] can be used as a good fluorescence-enhanced sensing material (enhanced 27-fold) for the rapid detection of explosives and the aqueous contaminant TNP, with a limit of detection (LOD) of 2.07 × 10−5 mol/L, without interference from other phenolic compounds. Furthermore, TNP can be efficiently removed in the presence of assembly 8-HQ@ns-Q[10], and the removal efficiency is more than 89%. Therefore, the supramolecular assembly 8-HQ@ns-Q[10], as a fluorescence-enhanced luminescence sensor and adsorption material, has rich research value and potential application prospect when applied to the detection and removal of TNP in aqueous environment.
2023, 34(10): 108200
doi: 10.1016/j.cclet.2023.108200
Abstract:
DNAzyme machines play critical roles in the fields of cell imaging, disease diagnosis, and cancer therapy. However, the applications of DNAzyme machines are limited by the nucleases-induced degradation, non-specific binding of proteins, and insufficient provision of cofactors. Herein, protected DNAzyme machines with different cofactor designs (referred to as ProDs) were nanoengineered by the construction of multifunctional metal-phenolic nanoshells to deactivate the interferential proteins, including nucleases and non-specific binding proteins. Moreover, the nanoshells not only facilitate the cellular internalization of ProDs but provide specific metal ions acting as cofactors of the designed DNAzymes. Cellular imaging results demonstrated that ProDs could effectively and simultaneously monitor multiple tumor-related microRNAs in living cells. This facile and rapid strategy that encapsulates DNAzyme machines into the protective metal-phenolic nanoshells is anticipated to extend to a wide range of functional nucleic acids-based biomedical applications.
DNAzyme machines play critical roles in the fields of cell imaging, disease diagnosis, and cancer therapy. However, the applications of DNAzyme machines are limited by the nucleases-induced degradation, non-specific binding of proteins, and insufficient provision of cofactors. Herein, protected DNAzyme machines with different cofactor designs (referred to as ProDs) were nanoengineered by the construction of multifunctional metal-phenolic nanoshells to deactivate the interferential proteins, including nucleases and non-specific binding proteins. Moreover, the nanoshells not only facilitate the cellular internalization of ProDs but provide specific metal ions acting as cofactors of the designed DNAzymes. Cellular imaging results demonstrated that ProDs could effectively and simultaneously monitor multiple tumor-related microRNAs in living cells. This facile and rapid strategy that encapsulates DNAzyme machines into the protective metal-phenolic nanoshells is anticipated to extend to a wide range of functional nucleic acids-based biomedical applications.
2023, 34(10): 108203
doi: 10.1016/j.cclet.2023.108203
Abstract:
Mitochondria are essential for eukaryotic life as powerhouses for energy metabolism. Excessive mitochondrial hyperthermia and reactive oxygen species (ROS) production have been associated with aging, cancer, neurodegenerative diseases, and other disorders. Uncoupling protein 2 (UCP2) is the effector responsible for regulating cellular thermogenesis and ROS production via dissipating protons in an electrochemical gradient. A UCP2 inhibitor named genipin (GNP) is being researched for its effect on mitochondrial temperature, but little is known about its mechanisms. This study developed several molecular probes to explore the interactions between GNP and UCP2. The result indicated that the hemiacetal structure in GNP could selectively react with the ɛ-amine of lysine on the UCP2 proton leakage channel through ring-opening condensation at the mitochondrial, cellular, and animal levels. A notable feature of the reaction is its temperature sensitivity and ability to conjugate with UCP2 at high fever as lysine-specific covalent inhibitors that prevent mitochondrial thermogenesis. The result not only clarifies the existence of an antipyretic properties of GNP via its irreversible coupling to UCP2, but also reveals a bioorthogonal reaction of hemiacetal iridoid aglycone for selectively binding with the ɛ-amine of lysine on proteins.
Mitochondria are essential for eukaryotic life as powerhouses for energy metabolism. Excessive mitochondrial hyperthermia and reactive oxygen species (ROS) production have been associated with aging, cancer, neurodegenerative diseases, and other disorders. Uncoupling protein 2 (UCP2) is the effector responsible for regulating cellular thermogenesis and ROS production via dissipating protons in an electrochemical gradient. A UCP2 inhibitor named genipin (GNP) is being researched for its effect on mitochondrial temperature, but little is known about its mechanisms. This study developed several molecular probes to explore the interactions between GNP and UCP2. The result indicated that the hemiacetal structure in GNP could selectively react with the ɛ-amine of lysine on the UCP2 proton leakage channel through ring-opening condensation at the mitochondrial, cellular, and animal levels. A notable feature of the reaction is its temperature sensitivity and ability to conjugate with UCP2 at high fever as lysine-specific covalent inhibitors that prevent mitochondrial thermogenesis. The result not only clarifies the existence of an antipyretic properties of GNP via its irreversible coupling to UCP2, but also reveals a bioorthogonal reaction of hemiacetal iridoid aglycone for selectively binding with the ɛ-amine of lysine on proteins.
2023, 34(10): 108204
doi: 10.1016/j.cclet.2023.108204
Abstract:
Aromatic compounds such as phenols presented widely in coal chemical industry wastewater (CCW) render the treatment facing great challenge due to their biorefractory characteristics and potential risks to the environment and human health. Ozone-based advanced oxidation processes show promising for these pollutants removal, but the mineralization via ozonation alone is unsatisfactory and not cost-effective. Herein, a hybrid peroxi-coagulation/ozonation process (denoted as PCO) was developed using sacrificial iron plate as an anode and carbon black modified carbon felt as cathode in the presence of ozonation. An enhanced phenol removal of ~100% within 20 min and phenol mineralization of ~80% within 60 min were achieved with a low energy consumption of 0.35 kWh/g TOC. In this novel process, synergistic effect between ozonation and peroxi-coagulation was observed, and beside O3 direct oxidation, peroxone played a dominant role for phenol removal. In the PCO process, the hydrolyzed Fe species enhanced the generation of reactive oxygen species (ROS), while •OH was dominantly responsible for pollutant degradation. This process also illustrated high resistance to high ionic strength and better performance for TOC removal in real wastewater when compared with ozonation and peroxi-coagulation process. Therefore, this process is more cost-effective, being very promising for CCW treatment.
Aromatic compounds such as phenols presented widely in coal chemical industry wastewater (CCW) render the treatment facing great challenge due to their biorefractory characteristics and potential risks to the environment and human health. Ozone-based advanced oxidation processes show promising for these pollutants removal, but the mineralization via ozonation alone is unsatisfactory and not cost-effective. Herein, a hybrid peroxi-coagulation/ozonation process (denoted as PCO) was developed using sacrificial iron plate as an anode and carbon black modified carbon felt as cathode in the presence of ozonation. An enhanced phenol removal of ~100% within 20 min and phenol mineralization of ~80% within 60 min were achieved with a low energy consumption of 0.35 kWh/g TOC. In this novel process, synergistic effect between ozonation and peroxi-coagulation was observed, and beside O3 direct oxidation, peroxone played a dominant role for phenol removal. In the PCO process, the hydrolyzed Fe species enhanced the generation of reactive oxygen species (ROS), while •OH was dominantly responsible for pollutant degradation. This process also illustrated high resistance to high ionic strength and better performance for TOC removal in real wastewater when compared with ozonation and peroxi-coagulation process. Therefore, this process is more cost-effective, being very promising for CCW treatment.
2023, 34(10): 108209
doi: 10.1016/j.cclet.2023.108209
Abstract:
Peptide-drug conjugates (PDCs) composed of peptide, spacer and drug have gained extensive attention in the field of drug delivery owing to its precise control over the drug payload and architecture. However, the achievement of controllable and rapid drug release at targeted site by PDCs is still a great challenge for pharmaceutist. Herein, we introduced the histidine residue into PDCs to generate a supramolecular hydrogel via a pH-trigger strategy, which exhibited an autocatalytic effect to precisely tune drug release from PDCs hydrogel. Using indomethacin (Idm) as model drug, various PDCs (Y(Idm)EEH, Y(Idm)EEK and Y(Idm)EER) were synthesized and their self-assembling properties were investigated in terms of critical aggregation concentration (CAC), transmission electron microscopy (TEM) and rheometer. Introduction of histidine residue into PDCs presented a robust catalytic activity on the ester hydrolysis of p-nitrophenyl acetate in aqueous solution, as well conferred the autocatalytic capacity to hydrolyze the PDCs into active parent drug (Idm). Overall, we reported an autocatalytic activity of histidine residue to precisely tune drug release from PDCs hydrogels.
Peptide-drug conjugates (PDCs) composed of peptide, spacer and drug have gained extensive attention in the field of drug delivery owing to its precise control over the drug payload and architecture. However, the achievement of controllable and rapid drug release at targeted site by PDCs is still a great challenge for pharmaceutist. Herein, we introduced the histidine residue into PDCs to generate a supramolecular hydrogel via a pH-trigger strategy, which exhibited an autocatalytic effect to precisely tune drug release from PDCs hydrogel. Using indomethacin (Idm) as model drug, various PDCs (Y(Idm)EEH, Y(Idm)EEK and Y(Idm)EER) were synthesized and their self-assembling properties were investigated in terms of critical aggregation concentration (CAC), transmission electron microscopy (TEM) and rheometer. Introduction of histidine residue into PDCs presented a robust catalytic activity on the ester hydrolysis of p-nitrophenyl acetate in aqueous solution, as well conferred the autocatalytic capacity to hydrolyze the PDCs into active parent drug (Idm). Overall, we reported an autocatalytic activity of histidine residue to precisely tune drug release from PDCs hydrogels.
2023, 34(10): 108230
doi: 10.1016/j.cclet.2023.108230
Abstract:
Parkinson's disease (PD) is a complex neurological disorder that typically worsens with age. A wide range of pathologies makes PD a very heterogeneous condition, and there are currently no reliable diagnostic tests for this disease. The application of metabolomics to the study of PD has the potential to identify disease biomarkers through the systematic evaluation of metabolites. In this study, urine metabolic profiles of 215 urine samples from 104 PD patients and 111 healthy individuals were assessed based on liquid chromatography-mass spectrometry. The urine metabolic profile was first evaluated with partial least-squares discriminant analysis, and then we integrated the metabolomic data with ensemble machine learning techniques using the voting strategy to achieve better predictive performance. A combination of 8-metabolite predictive panel performed well with an accuracy of over 90.7%. Compared to control subjects, PD patients had higher levels of 3-methoxytyramine, N-acetyl-l-tyrosine, orotic acid, uric acid, vanillic acid, and xanthine, and lower levels of 3, 3-dimethylglutaric acid and imidazolelactic acid in their urine. The multi-metabolite prediction model developed in this study can serve as an initial point for future clinical studies.
Parkinson's disease (PD) is a complex neurological disorder that typically worsens with age. A wide range of pathologies makes PD a very heterogeneous condition, and there are currently no reliable diagnostic tests for this disease. The application of metabolomics to the study of PD has the potential to identify disease biomarkers through the systematic evaluation of metabolites. In this study, urine metabolic profiles of 215 urine samples from 104 PD patients and 111 healthy individuals were assessed based on liquid chromatography-mass spectrometry. The urine metabolic profile was first evaluated with partial least-squares discriminant analysis, and then we integrated the metabolomic data with ensemble machine learning techniques using the voting strategy to achieve better predictive performance. A combination of 8-metabolite predictive panel performed well with an accuracy of over 90.7%. Compared to control subjects, PD patients had higher levels of 3-methoxytyramine, N-acetyl-l-tyrosine, orotic acid, uric acid, vanillic acid, and xanthine, and lower levels of 3, 3-dimethylglutaric acid and imidazolelactic acid in their urine. The multi-metabolite prediction model developed in this study can serve as an initial point for future clinical studies.
2023, 34(10): 108234
doi: 10.1016/j.cclet.2023.108234
Abstract:
Finding improved therapeutic protocols against non-Hodgkin's lymphoma (NHL) remains an unmet clinical demand. Phototherapy is a promising alternative treatment for traditional clinical therapeutic methods, but the limited tissue penetration blocks the therapeutics. Inspired by the excellent physical and chemical properties of black phosphorus nanosheets (BPNSs), a fluorescence and thermal imaging guided photo-/sono-synergistic treatment platform BPNSs@PEG-SS-IR780/RGD is developed. This ingenious multifunctional theranostic platform not only exhibits outstanding photothermal conversion efficiency and highly efficient reactive oxygen species generation, but also has good biocompatibility, tumor-targeting and tumor microenvironment responsiveness. In addition, BPNSs@PEG-SS-IR780/RGD could actively target the tumor sites and generate excellent photothermal, photodynamic and sonodynamic therapeutic efficacy. Both in vitro and in vivo experiments indicate that BPNSs@PEG-SS-IR780/RGD can be a promising nanomaterial for NHL imaging and therapy. Taken together, this study not only expands the application field of black phosphorus materials, but also provides a possibility to design a new generation of NHL treatment regimens with clinical application potential.
Finding improved therapeutic protocols against non-Hodgkin's lymphoma (NHL) remains an unmet clinical demand. Phototherapy is a promising alternative treatment for traditional clinical therapeutic methods, but the limited tissue penetration blocks the therapeutics. Inspired by the excellent physical and chemical properties of black phosphorus nanosheets (BPNSs), a fluorescence and thermal imaging guided photo-/sono-synergistic treatment platform BPNSs@PEG-SS-IR780/RGD is developed. This ingenious multifunctional theranostic platform not only exhibits outstanding photothermal conversion efficiency and highly efficient reactive oxygen species generation, but also has good biocompatibility, tumor-targeting and tumor microenvironment responsiveness. In addition, BPNSs@PEG-SS-IR780/RGD could actively target the tumor sites and generate excellent photothermal, photodynamic and sonodynamic therapeutic efficacy. Both in vitro and in vivo experiments indicate that BPNSs@PEG-SS-IR780/RGD can be a promising nanomaterial for NHL imaging and therapy. Taken together, this study not only expands the application field of black phosphorus materials, but also provides a possibility to design a new generation of NHL treatment regimens with clinical application potential.
2023, 34(10): 108236
doi: 10.1016/j.cclet.2023.108236
Abstract:
Uncontrolled microglial activation is decisively involved in the neuroinflammatory pathogenesis of brain diseases. Consequently, suppression of microglial overactivation appears to be a strategy for the prevention of nerve injury. In this paper, a novel vanadium complex, vanadyl N-(p-N,N-dimethylaminophenylcarbamoylmethyl)iminodiacetate (VO(p-dmada)), was synthesized from vanadyl sulfate and N,N-dimethyl-p-phenylenediamine, which was structurally characterized by Fourier transform infrared spectrum and ESI-MS analysis. The effect of VO(p-dmada) on neuroinflammation was investigated by using the models of lipopolysaccharide (LPS)-induced BV2 microglial cells and BALB/c mice. Our data demonstrated that VO(p-dmada) significantly suppressed microglial activation by downregulating inflammatory mediators and associated proteins, and inactivating nuclear factor-κB (NF-κB) signaling pathway. VO(p-dmada) also upregulated peroxisome proliferator activated receptor gamma (PPARγ) by reducing transglutaminase 2 and heat shock protein 60 expression. Co-treatment with PPARγ antagonist GW9662 significantly impeded the inhibitory effect of VO(p-dmada) on LPS-induced neuroinflammation. These cumulative findings demonstrated that VO(p-dmada) is a potential new drug for the treatment of neuroinflammation-related neurodegenerative diseases.
Uncontrolled microglial activation is decisively involved in the neuroinflammatory pathogenesis of brain diseases. Consequently, suppression of microglial overactivation appears to be a strategy for the prevention of nerve injury. In this paper, a novel vanadium complex, vanadyl N-(p-N,N-dimethylaminophenylcarbamoylmethyl)iminodiacetate (VO(p-dmada)), was synthesized from vanadyl sulfate and N,N-dimethyl-p-phenylenediamine, which was structurally characterized by Fourier transform infrared spectrum and ESI-MS analysis. The effect of VO(p-dmada) on neuroinflammation was investigated by using the models of lipopolysaccharide (LPS)-induced BV2 microglial cells and BALB/c mice. Our data demonstrated that VO(p-dmada) significantly suppressed microglial activation by downregulating inflammatory mediators and associated proteins, and inactivating nuclear factor-κB (NF-κB) signaling pathway. VO(p-dmada) also upregulated peroxisome proliferator activated receptor gamma (PPARγ) by reducing transglutaminase 2 and heat shock protein 60 expression. Co-treatment with PPARγ antagonist GW9662 significantly impeded the inhibitory effect of VO(p-dmada) on LPS-induced neuroinflammation. These cumulative findings demonstrated that VO(p-dmada) is a potential new drug for the treatment of neuroinflammation-related neurodegenerative diseases.
2023, 34(10): 108239
doi: 10.1016/j.cclet.2023.108239
Abstract:
Carbon dots (CDs), a new building unit, have been revolutionizing the fields of biomedicine, bioimaging, and optoelectronics with their excellent physical, chemical, and biological properties. However, the difficulty of preparing excitation-dependent full-spectrum fluorescent CDs has seriously hindered their further research in fluorescence emission mechanisms and biomedicine. Here, we report full-spectrum fluorescent CDs that exhibit controlled emission changes from purple (380 nm) to red (613 nm) at room temperature by changing the excitation wavelength, and the excitation dependence was closely related to the regulation of sp2 and sp3 hybrid carbon structures by β-cyclodextrin-related groups. In addition, by regulating the content of β-cyclodextrin, the optimal quantum yields of full-spectrum fluorescent CDs were 8.97%, 8.35%, 7.90%, 9.69% and 17.4% at the excitation wavelengths of 340, 350, 390, 410 and 540 nm, respectively. Due to their excellent biocompatibility and color tunability, full-spectrum fluorescent CDs emitted bright and steady purple, blue, green, yellow, and red fluorescence in MCF-7 cells. Moreover, we optimized the imaging conditions of CDs and mitochondrial-specific dyes; and realized the mitochondrial-targeted co-localization imaging of purple, blue and green fluorescence. After that, we also explored the effect of full-spectrum fluorescent CDs in vivo fluorescence imaging through the intratumorally, subcutaneously, and caudal vein, and found that full-spectrum fluorescent CDs had good fluorescence imaging ability in vivo.
Carbon dots (CDs), a new building unit, have been revolutionizing the fields of biomedicine, bioimaging, and optoelectronics with their excellent physical, chemical, and biological properties. However, the difficulty of preparing excitation-dependent full-spectrum fluorescent CDs has seriously hindered their further research in fluorescence emission mechanisms and biomedicine. Here, we report full-spectrum fluorescent CDs that exhibit controlled emission changes from purple (380 nm) to red (613 nm) at room temperature by changing the excitation wavelength, and the excitation dependence was closely related to the regulation of sp2 and sp3 hybrid carbon structures by β-cyclodextrin-related groups. In addition, by regulating the content of β-cyclodextrin, the optimal quantum yields of full-spectrum fluorescent CDs were 8.97%, 8.35%, 7.90%, 9.69% and 17.4% at the excitation wavelengths of 340, 350, 390, 410 and 540 nm, respectively. Due to their excellent biocompatibility and color tunability, full-spectrum fluorescent CDs emitted bright and steady purple, blue, green, yellow, and red fluorescence in MCF-7 cells. Moreover, we optimized the imaging conditions of CDs and mitochondrial-specific dyes; and realized the mitochondrial-targeted co-localization imaging of purple, blue and green fluorescence. After that, we also explored the effect of full-spectrum fluorescent CDs in vivo fluorescence imaging through the intratumorally, subcutaneously, and caudal vein, and found that full-spectrum fluorescent CDs had good fluorescence imaging ability in vivo.
2023, 34(10): 108243
doi: 10.1016/j.cclet.2023.108243
Abstract:
Inosine is a vital RNA modification across three kingdoms of life. It has been demonstrated that inosine plays important roles in modulation of the fate of RNAs. In the current study, we developed a highly sensitive method to determine inosine in a single cell by N-cyclohexyl-N'-β-(4-methylmorpholinium)ethylcarbodiimide p-toluenesulfonate (CMCT) derivatization in combination with mass spectrometry analysis. The results showed that the detection sensitivity of inosine was increased by 556-fold after CMCT derivatization, with the limit of detection (LOD) being 4.5 amol. With the established method, we could detect inosine from 13.0 pg of total RNA of HEK293T cells. Meanwhile, inosine in RNA from a single cell could also be clearly detected due to the improved detection sensitivity. Moreover, we found the level of inosine in RNA of sleep-deprived mice was significantly increased compared to the control mice, indicating that inosine is associated with sleep behavior and might be a potential indicator of sleep disorder. Taken together, the chemical derivatization coupled with mass spectrometry analysis offers a valuable tool in determination of endogenous RNA modifications in a single cell, which should benefit the functional study of RNA modification in rare clinical samples.
Inosine is a vital RNA modification across three kingdoms of life. It has been demonstrated that inosine plays important roles in modulation of the fate of RNAs. In the current study, we developed a highly sensitive method to determine inosine in a single cell by N-cyclohexyl-N'-β-(4-methylmorpholinium)ethylcarbodiimide p-toluenesulfonate (CMCT) derivatization in combination with mass spectrometry analysis. The results showed that the detection sensitivity of inosine was increased by 556-fold after CMCT derivatization, with the limit of detection (LOD) being 4.5 amol. With the established method, we could detect inosine from 13.0 pg of total RNA of HEK293T cells. Meanwhile, inosine in RNA from a single cell could also be clearly detected due to the improved detection sensitivity. Moreover, we found the level of inosine in RNA of sleep-deprived mice was significantly increased compared to the control mice, indicating that inosine is associated with sleep behavior and might be a potential indicator of sleep disorder. Taken together, the chemical derivatization coupled with mass spectrometry analysis offers a valuable tool in determination of endogenous RNA modifications in a single cell, which should benefit the functional study of RNA modification in rare clinical samples.
2023, 34(10): 108246
doi: 10.1016/j.cclet.2023.108246
Abstract:
As one of the 2D transition metal sulfides, 1T phase MoS2 nanosheets (NSs) have been studied because of their distinguished conductivity and suitable electronic structure. Nevertheless, the active sites are limited to a small number of edge sites only, while the basal plane is catalytically inert. Herein, we report that boron (B) doped 1T phase MoS2 NSs can replace precious metals as a co-catalyst to assist in photocatalytic H2 production of 2D layered g-C3N4 nanosheets (g-C3N4 NSs). The H2 evolution rate of prepared B-MoS2@g-C3N4 composites with 15 wt% B-MoS2 (B-MoS2@g-C3N4–15, 1612.75 µmol h−1 g−1) is 52.33 times of pure g-C3N4 NSs (30.82 µmol h−1 g−1). Furthermore, the apparent quantum efficiency (AQE) of B-MoS2@g-C3N4–15 composites under the light at λ = 370 nm is calculated and reaches 5.54%. The excellent photocatalytic performance of B-MoS2@g-C3N4–15 composites is attributed to the B ions doping inducing the distortion of 1T phase MoS2 crystal, which can activate more base planes to offer more active sites for H2 evolution reaction (HER). This work of B-MoS2@g-C3N4 composites offers experience in the progress of effective and low-price photocatalysts for HER.
As one of the 2D transition metal sulfides, 1T phase MoS2 nanosheets (NSs) have been studied because of their distinguished conductivity and suitable electronic structure. Nevertheless, the active sites are limited to a small number of edge sites only, while the basal plane is catalytically inert. Herein, we report that boron (B) doped 1T phase MoS2 NSs can replace precious metals as a co-catalyst to assist in photocatalytic H2 production of 2D layered g-C3N4 nanosheets (g-C3N4 NSs). The H2 evolution rate of prepared B-MoS2@g-C3N4 composites with 15 wt% B-MoS2 (B-MoS2@g-C3N4–15, 1612.75 µmol h−1 g−1) is 52.33 times of pure g-C3N4 NSs (30.82 µmol h−1 g−1). Furthermore, the apparent quantum efficiency (AQE) of B-MoS2@g-C3N4–15 composites under the light at λ = 370 nm is calculated and reaches 5.54%. The excellent photocatalytic performance of B-MoS2@g-C3N4–15 composites is attributed to the B ions doping inducing the distortion of 1T phase MoS2 crystal, which can activate more base planes to offer more active sites for H2 evolution reaction (HER). This work of B-MoS2@g-C3N4 composites offers experience in the progress of effective and low-price photocatalysts for HER.
2023, 34(10): 108247
doi: 10.1016/j.cclet.2023.108247
Abstract:
Activation of (bi)sulfite (S(Ⅳ)) by metal oxides is strongly limited by low electrons utilization. In this study, two carbon-supported cobalt ferrites spinels (CoFe2O4 QDs-GO and CoFe2O4 MOFs-CNTs) have been successfully synthesized by one-step solvothermal method. It was found that both catalysts could efficiently activate S(Ⅳ), with rapid reductive dechlorination and then oxidative degradation of a recalcitrant antibiotic chloramphenicol (CAP). Characterizations revealed that CoFe2O4 spinels were tightly coated on the carbon bases (GO and CNTs), with effectiveness of the internal transfer of electrons. O2˙− was identified for the reductive dechlorination of CAP, with simultaneously detection of both •OH and SO4˙− responsible for further oxidative degradation. The sulfur oxygen radical conversion reactions and molecular oxygen activation would occur together upon the carbon-based spinels. Spatial-separated interfacial reductive-oxidation of CAP would occur with dechlorination of CAP by O2˙− on the carbon bases, and oxidative degradation of intermediates by SO4˙−/•OH upon the CoFe2O4 catalysts.
Activation of (bi)sulfite (S(Ⅳ)) by metal oxides is strongly limited by low electrons utilization. In this study, two carbon-supported cobalt ferrites spinels (CoFe2O4 QDs-GO and CoFe2O4 MOFs-CNTs) have been successfully synthesized by one-step solvothermal method. It was found that both catalysts could efficiently activate S(Ⅳ), with rapid reductive dechlorination and then oxidative degradation of a recalcitrant antibiotic chloramphenicol (CAP). Characterizations revealed that CoFe2O4 spinels were tightly coated on the carbon bases (GO and CNTs), with effectiveness of the internal transfer of electrons. O2˙− was identified for the reductive dechlorination of CAP, with simultaneously detection of both •OH and SO4˙− responsible for further oxidative degradation. The sulfur oxygen radical conversion reactions and molecular oxygen activation would occur together upon the carbon-based spinels. Spatial-separated interfacial reductive-oxidation of CAP would occur with dechlorination of CAP by O2˙− on the carbon bases, and oxidative degradation of intermediates by SO4˙−/•OH upon the CoFe2O4 catalysts.
2023, 34(10): 108262
doi: 10.1016/j.cclet.2023.108262
Abstract:
To achieve smart and personalized medicine, the development of hydrogel dressings with sensing properties and biotherapeutic properties that can act as a sensor to monitor of human health in real-time while speeding up wound healing face great challenge. In the present study, a biocompatible dual-network composite hydrogel (DNCGel) sensor was obtained via a simple process. The dual network hydrogel is constructed by the interpenetration of a flexible network formed of poly(vinyl alcohol) (PVA) physical cross-linked by repeated freeze-thawing and a rigid network of iron-chelated xanthan gum (XG) impregnated with Fe3+ interpenetration. The pure PVA/XG hydrogels were chelated with ferric ions by immersion to improve the gel strength (compressive modulus and tensile modulus can reach up to 0.62 MPa and 0.079 MPa, respectively), conductivity (conductivity values ranging from 9 × 10-4 S/cm to 1 × 10-3 S/cm) and bacterial inhibition properties (up to 98.56%). Subsequently, the effects of the ratio of PVA and XG and the immersion time of Fe3+ on the hydrogels were investigated, and DNGel3 was given the most priority on a comprehensive consideration. It was demonstrated that the DNCGel exhibit good biocompatibility in vitro, effectively facilitate wound healing in vivo (up to 97.8% healing rate) under electrical stimulation, and monitors human movement in real time. This work provides a novel avenue to explore multifunctional intelligent hydrogels that hold great promise in biomedical fields such as smart wound dressings and flexible wearable sensors.
To achieve smart and personalized medicine, the development of hydrogel dressings with sensing properties and biotherapeutic properties that can act as a sensor to monitor of human health in real-time while speeding up wound healing face great challenge. In the present study, a biocompatible dual-network composite hydrogel (DNCGel) sensor was obtained via a simple process. The dual network hydrogel is constructed by the interpenetration of a flexible network formed of poly(vinyl alcohol) (PVA) physical cross-linked by repeated freeze-thawing and a rigid network of iron-chelated xanthan gum (XG) impregnated with Fe3+ interpenetration. The pure PVA/XG hydrogels were chelated with ferric ions by immersion to improve the gel strength (compressive modulus and tensile modulus can reach up to 0.62 MPa and 0.079 MPa, respectively), conductivity (conductivity values ranging from 9 × 10-4 S/cm to 1 × 10-3 S/cm) and bacterial inhibition properties (up to 98.56%). Subsequently, the effects of the ratio of PVA and XG and the immersion time of Fe3+ on the hydrogels were investigated, and DNGel3 was given the most priority on a comprehensive consideration. It was demonstrated that the DNCGel exhibit good biocompatibility in vitro, effectively facilitate wound healing in vivo (up to 97.8% healing rate) under electrical stimulation, and monitors human movement in real time. This work provides a novel avenue to explore multifunctional intelligent hydrogels that hold great promise in biomedical fields such as smart wound dressings and flexible wearable sensors.
2023, 34(10): 108274
doi: 10.1016/j.cclet.2023.108274
Abstract:
Regenerating spent graphite (SG) from retired lithium-ion batteries (LIBs) can effectively avoid resource waste. However, the technology is challenged by the impurity content and energy consumption. In this study, micro-expanded graphite (MEG) was synthesized by one-step oxidation method using waste LIBs anode graphite as material and perchloric acid as intercalation and oxidant agent. Then, its performance as a LIBs anode material were investigated as well as the greenhouse gas (GHG) emissions of the whole process were calculated. Perchloric acid was successfully embedded in the SG during the reaction, which effectively removed the impurities in the graphite. Defects introduced during intercalation and delamination, such as nanopores and intercrystalline cracks. Both provide additional space for Li ions during charging and discharging, thereby promoting capacity enhancement. The prepared MEG expresses a rate capability as high as 340.32 mAh/g at a current density of 0.1 C and still retains 81.73% of the capacity after 100 cycles at a current density of 1 C. Additionally, the GHG emissions of the synthesis process of this article and other literatures are compared. The results demonstrated that perchloric acid treatment process provides a low-carbon, time- and energy-saving approach for regenerated SG as battery grade material.
Regenerating spent graphite (SG) from retired lithium-ion batteries (LIBs) can effectively avoid resource waste. However, the technology is challenged by the impurity content and energy consumption. In this study, micro-expanded graphite (MEG) was synthesized by one-step oxidation method using waste LIBs anode graphite as material and perchloric acid as intercalation and oxidant agent. Then, its performance as a LIBs anode material were investigated as well as the greenhouse gas (GHG) emissions of the whole process were calculated. Perchloric acid was successfully embedded in the SG during the reaction, which effectively removed the impurities in the graphite. Defects introduced during intercalation and delamination, such as nanopores and intercrystalline cracks. Both provide additional space for Li ions during charging and discharging, thereby promoting capacity enhancement. The prepared MEG expresses a rate capability as high as 340.32 mAh/g at a current density of 0.1 C and still retains 81.73% of the capacity after 100 cycles at a current density of 1 C. Additionally, the GHG emissions of the synthesis process of this article and other literatures are compared. The results demonstrated that perchloric acid treatment process provides a low-carbon, time- and energy-saving approach for regenerated SG as battery grade material.
2023, 34(10): 108293
doi: 10.1016/j.cclet.2023.108293
Abstract:
We report two air-stable nickel(Ⅱ) half-sandwich complexes, Cp*Ni(1,2-Cy2PC6H4O) (1) and Cp*Ni(1,2-Ph2PC6H4NH) (2), for cooperative B-H bond activation and their applications in catalytic hydroboration of unsaturated organic compounds. Both 1 and 2 react with HBpin by adding the B-H bond across the Ni−X bond (X = O or N), giving rise to the 18-electron Ni(Ⅱ)−H active species, [H1(Bpin)] and [H2(Bpin)]. Subtle tuning of the Ni−X pair and the supporting ancillary phosphine have a significant effect on the reactivity and catalytic performance of Cp*Ni(1,2-R2PC6H4X). Unlike [H2(Bpin)], the activation of HBpin in [H1(Bpin)] is reversible, which enables the Ni−O complex to be an effective cooperative catalyst in the hydroboration of N-heteroarenes, and as well as ketones and imines.
We report two air-stable nickel(Ⅱ) half-sandwich complexes, Cp*Ni(1,2-Cy2PC6H4O) (1) and Cp*Ni(1,2-Ph2PC6H4NH) (2), for cooperative B-H bond activation and their applications in catalytic hydroboration of unsaturated organic compounds. Both 1 and 2 react with HBpin by adding the B-H bond across the Ni−X bond (X = O or N), giving rise to the 18-electron Ni(Ⅱ)−H active species, [H1(Bpin)] and [H2(Bpin)]. Subtle tuning of the Ni−X pair and the supporting ancillary phosphine have a significant effect on the reactivity and catalytic performance of Cp*Ni(1,2-R2PC6H4X). Unlike [H2(Bpin)], the activation of HBpin in [H1(Bpin)] is reversible, which enables the Ni−O complex to be an effective cooperative catalyst in the hydroboration of N-heteroarenes, and as well as ketones and imines.
2023, 34(10): 108297
doi: 10.1016/j.cclet.2023.108297
Abstract:
A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.
A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.
2023, 34(10): 108315
doi: 10.1016/j.cclet.2023.108315
Abstract:
Heme responsible for the dioxygen fixation, transport and conversion is a metalloporphyrin complex highly dependent on its diverse geometry of ligand. In this work, a trans-ortho-di-strapped zinc porphyrin with dome-like deformation was synthesized by thermodynamically controlling the formation of trans-precursor of porphyrinogen. Its single-crystal structure demonstrated that the asymmetric treatment of porphyrin achieves three goals of creating two secondary coordination sphere (SCS) bulks, maintaining a unique dome deformation, and making atomic out-of-plane deviation. In this way, this metallic complex integrates at least three key features of the pocket structure, the differentiated axial ligations, and the ring distortion, making it an ideal heme analog.
Heme responsible for the dioxygen fixation, transport and conversion is a metalloporphyrin complex highly dependent on its diverse geometry of ligand. In this work, a trans-ortho-di-strapped zinc porphyrin with dome-like deformation was synthesized by thermodynamically controlling the formation of trans-precursor of porphyrinogen. Its single-crystal structure demonstrated that the asymmetric treatment of porphyrin achieves three goals of creating two secondary coordination sphere (SCS) bulks, maintaining a unique dome deformation, and making atomic out-of-plane deviation. In this way, this metallic complex integrates at least three key features of the pocket structure, the differentiated axial ligations, and the ring distortion, making it an ideal heme analog.
2023, 34(10): 108316
doi: 10.1016/j.cclet.2023.108316
Abstract:
NaClO has been widely used to restore membrane flux in practical membrane cleaning processes, which would induce the formation of toxic halogenated byproducts. In this study, we proposed a novel heat-activated peroxydisulfate (heat/PDS) process to clean the membrane fouling derived from humic acid (HA). The results show that the combination of heat and PDS can achieve almost 100% recovery of permeate flux after soaking the HA-fouled membrane in 1 mmol/L PDS solution at 50 ℃ for 2 h, which is attributed to the changes of HA structure and enhanced detachment of foulants from membranes. The properties of different treated membranes are characterized by scanning electron microscopy (SEM), atomic force microscope (AFM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS), demonstrating that the reversible and irreversible foulants could be effectively removed by heat/PDS cleaning. The filtration process and fouling mechanism of the cleaned membrane were close to that of the virgin membrane, illustrating the good reusability of the cleaned membrane. Additionally, heat/PDS which can avoid the generation of halogenated byproducts shows comparable performance to NaClO on membrane cleaning and high performance for the removal of fouling caused by sodium alginate (SA), HA-bovine serum albumin (BSA)-SA mixture and algae, further suggesting that heat/PDS would be a potential alternative for membrane cleaning in practical application.
NaClO has been widely used to restore membrane flux in practical membrane cleaning processes, which would induce the formation of toxic halogenated byproducts. In this study, we proposed a novel heat-activated peroxydisulfate (heat/PDS) process to clean the membrane fouling derived from humic acid (HA). The results show that the combination of heat and PDS can achieve almost 100% recovery of permeate flux after soaking the HA-fouled membrane in 1 mmol/L PDS solution at 50 ℃ for 2 h, which is attributed to the changes of HA structure and enhanced detachment of foulants from membranes. The properties of different treated membranes are characterized by scanning electron microscopy (SEM), atomic force microscope (AFM), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS), demonstrating that the reversible and irreversible foulants could be effectively removed by heat/PDS cleaning. The filtration process and fouling mechanism of the cleaned membrane were close to that of the virgin membrane, illustrating the good reusability of the cleaned membrane. Additionally, heat/PDS which can avoid the generation of halogenated byproducts shows comparable performance to NaClO on membrane cleaning and high performance for the removal of fouling caused by sodium alginate (SA), HA-bovine serum albumin (BSA)-SA mixture and algae, further suggesting that heat/PDS would be a potential alternative for membrane cleaning in practical application.
2023, 34(10): 108339
doi: 10.1016/j.cclet.2023.108339
Abstract:
This report describes the oxidative cyclopalladation activation of a C≡C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway in-volves an oxidative cyclopalladation to generate a palladacyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. The reaction pathway proposed herein is kinetically favorable relative to the commonly proposed alkyne insertion mode. Furthermore, the Laplacians of the electron density, interaction region indicators, Mayer bond orders, and localized orbital bonding are evaluated to determine the reaction processes and characterize the key intermediates. Theoretical calculations indicate covalent bonding between a Pd(Ⅱ) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.
This report describes the oxidative cyclopalladation activation of a C≡C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway in-volves an oxidative cyclopalladation to generate a palladacyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. The reaction pathway proposed herein is kinetically favorable relative to the commonly proposed alkyne insertion mode. Furthermore, the Laplacians of the electron density, interaction region indicators, Mayer bond orders, and localized orbital bonding are evaluated to determine the reaction processes and characterize the key intermediates. Theoretical calculations indicate covalent bonding between a Pd(Ⅱ) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.
2023, 34(10): 108400
doi: 10.1016/j.cclet.2023.108400
Abstract:
The construction of an integrated nanoplatform with controlled fungicide delivery features in the specific microenvironment produced by fungal pathogens is a highly desirable strategy to improve the utilization of fungicides. Herein, we report a supramolecular fungicide delivery system based on benzimidazole-modified NH2-MIL-101(Fe) metal–organic frameworks (B-MIL-101(Fe) MOFs) as carriers loaded with osthole (OS), and β-cyclodextrin (β-CD) as nanovalves to form β-CD@B-MIL-101(Fe)-OS. The nanoplatform can release the loaded OS for fungus control through self-degradation of the MOFs skeleton in an oxalic acid microenvironment produced by Botrytis cinerea. The experimental results exhibit that the constructed supramolecular fungicide delivery system could effectively inhibit mycelial growth and protect the tomatoes from infection by B. cinerea during the ripening stage. This strategy constructs a facile and integrated supramolecular drug delivery system for B. cinerea control and opens up a new avenue for the sustainable development of modern agriculture.
The construction of an integrated nanoplatform with controlled fungicide delivery features in the specific microenvironment produced by fungal pathogens is a highly desirable strategy to improve the utilization of fungicides. Herein, we report a supramolecular fungicide delivery system based on benzimidazole-modified NH2-MIL-101(Fe) metal–organic frameworks (B-MIL-101(Fe) MOFs) as carriers loaded with osthole (OS), and β-cyclodextrin (β-CD) as nanovalves to form β-CD@B-MIL-101(Fe)-OS. The nanoplatform can release the loaded OS for fungus control through self-degradation of the MOFs skeleton in an oxalic acid microenvironment produced by Botrytis cinerea. The experimental results exhibit that the constructed supramolecular fungicide delivery system could effectively inhibit mycelial growth and protect the tomatoes from infection by B. cinerea during the ripening stage. This strategy constructs a facile and integrated supramolecular drug delivery system for B. cinerea control and opens up a new avenue for the sustainable development of modern agriculture.
2023, 34(10): 108411
doi: 10.1016/j.cclet.2023.108411
Abstract:
With the rapid development of economy, industrial and agricultural pollutants have caused great damage to the ecological environment and the normal development of organisms, posing a serious threat to global public health. Therefore, rapid and sensitive detection of pollutants is very important for environmental safety and people’s health. A stable multi-response fluorescence sensor (RhB@1) with dual emission characteristics was constructed by embedding RhB guest molecules in Zn-MOF using a simple one-pot method. XRD, IR, XPS, Raman and other characterization methods were used to demonstrate the formation of composite materials. The sensor has two fluorescence emission peaks at 415 nm and 575 nm under the excitation of 316 nm. It has high sensitivity and low detection limit (7.94 and 7.82 nmol/L, respectively) in the detection of fluazinam (FLU) and Fe3+. The mechanism of fluorescence quenching may be due to the synergistic effect of IFE and PET. Outstandingly, when ascorbate acid (AA) was added to the quenching system of Fe3+ and RhB@1, its fluorescence gradually recovered, forming the unique “on-off-on” sensor. Therefore, RhB@1 has a fast fluorescence response and good stability, making it potentially useful in practical application and biosensors. More significantly, using Fe3+ and AA as chemical input signals, a binary intelligent logic gate device has been developed based on the “on-off-on” response mode of RhB@1, which extends the application of logic gate switching devices in the chemical field. In addition, a visual portable test paper with good selectivity and high sensitivity was developed, which can be used for rapid detection of FLU, showing its broad application prospect.
With the rapid development of economy, industrial and agricultural pollutants have caused great damage to the ecological environment and the normal development of organisms, posing a serious threat to global public health. Therefore, rapid and sensitive detection of pollutants is very important for environmental safety and people’s health. A stable multi-response fluorescence sensor (RhB@1) with dual emission characteristics was constructed by embedding RhB guest molecules in Zn-MOF using a simple one-pot method. XRD, IR, XPS, Raman and other characterization methods were used to demonstrate the formation of composite materials. The sensor has two fluorescence emission peaks at 415 nm and 575 nm under the excitation of 316 nm. It has high sensitivity and low detection limit (7.94 and 7.82 nmol/L, respectively) in the detection of fluazinam (FLU) and Fe3+. The mechanism of fluorescence quenching may be due to the synergistic effect of IFE and PET. Outstandingly, when ascorbate acid (AA) was added to the quenching system of Fe3+ and RhB@1, its fluorescence gradually recovered, forming the unique “on-off-on” sensor. Therefore, RhB@1 has a fast fluorescence response and good stability, making it potentially useful in practical application and biosensors. More significantly, using Fe3+ and AA as chemical input signals, a binary intelligent logic gate device has been developed based on the “on-off-on” response mode of RhB@1, which extends the application of logic gate switching devices in the chemical field. In addition, a visual portable test paper with good selectivity and high sensitivity was developed, which can be used for rapid detection of FLU, showing its broad application prospect.
2023, 34(10): 108489
doi: 10.1016/j.cclet.2023.108489
Abstract:
Catalyzed by cerium ammonium nitrate (CAN), the oxidative cracking reaction of alkenes occurred to produce carbonyls in good yields under mild conditions. The reaction employed molecular oxygen (O2) as the safe and clean oxidant. The catalyst dosage was reduced to as low as 0.5 mol%, while no additive was required. Thus, it may afford a generally green synthetic approach for introducing oxygen into organic molecules as well as the biomass degradation and the resource recycling from the C=C bond-containing waste polymers. X-ray photoelectron spectroscopy (XPS) analysis and control experiments demonstrated that the process proceeded via a single electron transfer (SET) reaction-initiated free radical reaction mechanism. In the process, both Ce and NO3− acted as the oxygen carrier to promote the oxidation reaction. The application of the abundantly existed nitrate in CAN was found to be the key for reducing the catalyst loading.
Catalyzed by cerium ammonium nitrate (CAN), the oxidative cracking reaction of alkenes occurred to produce carbonyls in good yields under mild conditions. The reaction employed molecular oxygen (O2) as the safe and clean oxidant. The catalyst dosage was reduced to as low as 0.5 mol%, while no additive was required. Thus, it may afford a generally green synthetic approach for introducing oxygen into organic molecules as well as the biomass degradation and the resource recycling from the C=C bond-containing waste polymers. X-ray photoelectron spectroscopy (XPS) analysis and control experiments demonstrated that the process proceeded via a single electron transfer (SET) reaction-initiated free radical reaction mechanism. In the process, both Ce and NO3− acted as the oxygen carrier to promote the oxidation reaction. The application of the abundantly existed nitrate in CAN was found to be the key for reducing the catalyst loading.
2023, 34(10): 108490
doi: 10.1016/j.cclet.2023.108490
Abstract:
The synthesis methods of α-fluoro-arylketones were well-established through electrophilic/nucleophilic fluorination and transition metal catalyzed cross-coupling. However, due to the site selectivity and substrate restriction, only a few cases have been developed to afford α-alkyl-α-fluoro-alkylketones. Herein, we report a general and efficient method of preparing diverse α-alkyl-α-fluoro-alkylketones via nickel-catalyzed reductive coupling reaction of monofluoroalkyl triflates with low-cost industrial raw material alkyl carboxylic acids. These transformations demonstrate high efficiency, mild conditions, and excellent functional group compatibility. This strategy provides a general and efficient method for the synthesis of α-alkyl-α-fluoro-alkylketones.
The synthesis methods of α-fluoro-arylketones were well-established through electrophilic/nucleophilic fluorination and transition metal catalyzed cross-coupling. However, due to the site selectivity and substrate restriction, only a few cases have been developed to afford α-alkyl-α-fluoro-alkylketones. Herein, we report a general and efficient method of preparing diverse α-alkyl-α-fluoro-alkylketones via nickel-catalyzed reductive coupling reaction of monofluoroalkyl triflates with low-cost industrial raw material alkyl carboxylic acids. These transformations demonstrate high efficiency, mild conditions, and excellent functional group compatibility. This strategy provides a general and efficient method for the synthesis of α-alkyl-α-fluoro-alkylketones.
A highly selective fluorescent probe for visualizing dry eye disease-associated viscosity variations
2023, 34(10): 108516
doi: 10.1016/j.cclet.2023.108516
Abstract:
Dry eye disease (DED) is a multifactorial chronic inflammatory disease of the ocular surface with complex and unclear etiology. The development of reliable detection tools for the pathology of DED will benefit its treatment, but it is still lacking. In parallel, it has been discovered recently that viscosity changes are involved in inflammation processes. In this regard, we constructed a fluorescent probe V5 with an asymmetric donor-acceptor-donor (D-A-D) feature after rational structural modulation for viscosity detection during DED progression. The probe manifested a remarkable fluorescence enhancement (110 folds) in highly viscous conditions without interferences from polarity and reactive species. Specifically, no aggregation effect of the probe was found in glycerol. Moreover, viscosity increment in human corneal epithelial cells (HCECs) induced by hyperosmosis and inflammation was monitored, and ferroptosis in HCECs also led to the viscosity elevation. A reactive oxygen species (ROS)-dependent viscosity changes during DED progression is demonstrated. Finally, viscosity change in corneal epithelial cell layer from mice treated by scopolamine was also visualized for the first time. We anticipate this work can provide a new lens to the pathogenesis study and diagnosis of DED and other ophthalmic diseases using fluorescence methods.
Dry eye disease (DED) is a multifactorial chronic inflammatory disease of the ocular surface with complex and unclear etiology. The development of reliable detection tools for the pathology of DED will benefit its treatment, but it is still lacking. In parallel, it has been discovered recently that viscosity changes are involved in inflammation processes. In this regard, we constructed a fluorescent probe V5 with an asymmetric donor-acceptor-donor (D-A-D) feature after rational structural modulation for viscosity detection during DED progression. The probe manifested a remarkable fluorescence enhancement (110 folds) in highly viscous conditions without interferences from polarity and reactive species. Specifically, no aggregation effect of the probe was found in glycerol. Moreover, viscosity increment in human corneal epithelial cells (HCECs) induced by hyperosmosis and inflammation was monitored, and ferroptosis in HCECs also led to the viscosity elevation. A reactive oxygen species (ROS)-dependent viscosity changes during DED progression is demonstrated. Finally, viscosity change in corneal epithelial cell layer from mice treated by scopolamine was also visualized for the first time. We anticipate this work can provide a new lens to the pathogenesis study and diagnosis of DED and other ophthalmic diseases using fluorescence methods.
2023, 34(10): 108518
doi: 10.1016/j.cclet.2023.108518
Abstract:
Photodynamic therapy (PDT) has shown great application potential in cancer treatment and the important manifestation of PDT in the inhibition of tumors is the activation of immunogenic cell death (ICD) effects. However, the strategy is limited in the innate hypoxic tumor microenvironment. There are two key elements for the realization of enhanced PDT: specific cellular uptake and release of the photosensitizer in the tumor, and a sufficient amount of oxygen to ensure photodynamic efficiency. Herein, self-oxygenated biomimetic nanoparticles (CS@M NPs) co-assembled by photosensitizer prodrug (Ce6-S-S-LA) and squalene (SQ) were engineered. In the treatment of triple negative breast cancer (TNBC), the oxygen carried by SQ can be converted to reactive oxygen species (ROS). Meanwhile, glutathione (GSH) consumption during transformation from Ce6-S-S-LA to chlorin e6 (Ce6) avoided the depletion of ROS. The co-assembled (CS NPs) were encapsulated by homologous tumor cell membrane to improve the tumor targeting. The results showed that the ICD effect of CS@M NPs was confirmed by the significant release of calreticulin (CRT) and high mobility group protein B1 (HMGB1), and it significantly activated the immune system by inhibiting the hypoxia inducible factor-1alpha (HIF-1α)-CD39-CD73-adenosine a2a receptor (A2AR) pathway, which not only promoted the maturation of dendritic cells (DC) and the presentation of tumor specific antigens, but also induced effective immune infiltration of tumors. Overall, the integrated nanoplatform implements the concept of multiple advantages of tumor targeting, reactive drug release, and synergistic photodynamic therapy-immunotherapy, which can achieve nearly 90% tumor suppression rate in orthotopic TNBC models.
Photodynamic therapy (PDT) has shown great application potential in cancer treatment and the important manifestation of PDT in the inhibition of tumors is the activation of immunogenic cell death (ICD) effects. However, the strategy is limited in the innate hypoxic tumor microenvironment. There are two key elements for the realization of enhanced PDT: specific cellular uptake and release of the photosensitizer in the tumor, and a sufficient amount of oxygen to ensure photodynamic efficiency. Herein, self-oxygenated biomimetic nanoparticles (CS@M NPs) co-assembled by photosensitizer prodrug (Ce6-S-S-LA) and squalene (SQ) were engineered. In the treatment of triple negative breast cancer (TNBC), the oxygen carried by SQ can be converted to reactive oxygen species (ROS). Meanwhile, glutathione (GSH) consumption during transformation from Ce6-S-S-LA to chlorin e6 (Ce6) avoided the depletion of ROS. The co-assembled (CS NPs) were encapsulated by homologous tumor cell membrane to improve the tumor targeting. The results showed that the ICD effect of CS@M NPs was confirmed by the significant release of calreticulin (CRT) and high mobility group protein B1 (HMGB1), and it significantly activated the immune system by inhibiting the hypoxia inducible factor-1alpha (HIF-1α)-CD39-CD73-adenosine a2a receptor (A2AR) pathway, which not only promoted the maturation of dendritic cells (DC) and the presentation of tumor specific antigens, but also induced effective immune infiltration of tumors. Overall, the integrated nanoplatform implements the concept of multiple advantages of tumor targeting, reactive drug release, and synergistic photodynamic therapy-immunotherapy, which can achieve nearly 90% tumor suppression rate in orthotopic TNBC models.
2023, 34(10): 108562
doi: 10.1016/j.cclet.2023.108562
Abstract:
Visible-light heterogeneous photocatalyst with high activity and selectivity is crucial for the development of organic transformations, but remains a formidable challenge. Herein, a simple and effective strategy was developed to integrate tetrazine moiety, a visible light active unit, into robust metal-organic frameworks (2D MOF-1(M), M = Co, Mn, Zn, and 3D MOF-2(Co)). MOF-1 series are isomorphous 2D porous frameworks, and MOF-2(Co) displays 3D porous framework. Interestingly, benefiting from the oxidative active species of O2•−, these MOFs all exhibit obviously highly enhanced photocatalytic activities toward the straightforward condensation of o-aminothiophenol and aromatic aldehydes at room temperature in EtOH under visible-white-light irradiation. Notably, compared to 3D MOF, the 2D layered MOF-1(Co) exhibited more excellent catalytic activity with a wide range of substrates possessing preeminent tolerance of steric hindrance. Most impressively, MOF-1(Co) can be recycled at least five times without significant loss of catalytic activity or crystallinity, exhibiting excellent stability and reusability. This study sheds light on the wide-ranging prospects of visible light active 2D MOFs as green photocatalysts for the preparation of fine chemicals.
Visible-light heterogeneous photocatalyst with high activity and selectivity is crucial for the development of organic transformations, but remains a formidable challenge. Herein, a simple and effective strategy was developed to integrate tetrazine moiety, a visible light active unit, into robust metal-organic frameworks (2D MOF-1(M), M = Co, Mn, Zn, and 3D MOF-2(Co)). MOF-1 series are isomorphous 2D porous frameworks, and MOF-2(Co) displays 3D porous framework. Interestingly, benefiting from the oxidative active species of O2•−, these MOFs all exhibit obviously highly enhanced photocatalytic activities toward the straightforward condensation of o-aminothiophenol and aromatic aldehydes at room temperature in EtOH under visible-white-light irradiation. Notably, compared to 3D MOF, the 2D layered MOF-1(Co) exhibited more excellent catalytic activity with a wide range of substrates possessing preeminent tolerance of steric hindrance. Most impressively, MOF-1(Co) can be recycled at least five times without significant loss of catalytic activity or crystallinity, exhibiting excellent stability and reusability. This study sheds light on the wide-ranging prospects of visible light active 2D MOFs as green photocatalysts for the preparation of fine chemicals.
2023, 34(10): 108586
doi: 10.1016/j.cclet.2023.108586
Abstract:
The rechargeable Li-O2 battery endowed with high theoretical specific energy density has sparked intense research interest as a promising energy storage system. However, the intrinsic high activity of Li anode, especially to moisture, usually leads to inferior electrochemical performance of Li-O2 battery in humid environments, hindering its widespread application. To settle the trouble of poor moisture tolerance, fabricating a water-proof layer on the Li-metal anode could be an effective tactic. Herein, a facile strategy for constructing an ibuprofen-based protective layer on the Li anode has been proposed to realize highly rechargeable Li-O2 battery in humid atmosphere. Due to the in-situ reaction between ibuprofen reagent and metallic Li, the protective layer with a thickness of ~30 μm has been uniformly deposited on the surface of Li anode. Particularly, the protective layer, consisting of a large amount of hydrophobic alkyl group and benzene ring, can significantly resist water ingress and enhance the electrochemical stability of Li anode. As a result, the Li-O2 battery based on the protected Li anode achieves a long cycle life of 210 h (21 cycles at 1000 mAh/g, 200 mA/g) in highly moist atmosphere with relative humidity (RH) of 68%. This convenient and efficient strategy offers novel design concept of water-resistant metal anode, and paves the way to the promising future prospect for the high-energy Li-O2 battery implementing in the ambient atmosphere.
The rechargeable Li-O2 battery endowed with high theoretical specific energy density has sparked intense research interest as a promising energy storage system. However, the intrinsic high activity of Li anode, especially to moisture, usually leads to inferior electrochemical performance of Li-O2 battery in humid environments, hindering its widespread application. To settle the trouble of poor moisture tolerance, fabricating a water-proof layer on the Li-metal anode could be an effective tactic. Herein, a facile strategy for constructing an ibuprofen-based protective layer on the Li anode has been proposed to realize highly rechargeable Li-O2 battery in humid atmosphere. Due to the in-situ reaction between ibuprofen reagent and metallic Li, the protective layer with a thickness of ~30 μm has been uniformly deposited on the surface of Li anode. Particularly, the protective layer, consisting of a large amount of hydrophobic alkyl group and benzene ring, can significantly resist water ingress and enhance the electrochemical stability of Li anode. As a result, the Li-O2 battery based on the protected Li anode achieves a long cycle life of 210 h (21 cycles at 1000 mAh/g, 200 mA/g) in highly moist atmosphere with relative humidity (RH) of 68%. This convenient and efficient strategy offers novel design concept of water-resistant metal anode, and paves the way to the promising future prospect for the high-energy Li-O2 battery implementing in the ambient atmosphere.
2023, 34(10): 108592
doi: 10.1016/j.cclet.2023.108592
Abstract:
Triple-negative breast cancer (TNBC) lacks specific regimens for targeted therapy. Repeat chemotherapy promotes the evolution of TNBC into highly chemo-resistant tumors that metastasize to multiple organs simultaneously. Herein, polyacrylic acid-coated ultrasmall superparamagnetic iron-oxide nanoparticles (PAA@IONs) and dual-targeting doxorubicin liposomes achieved chemo–immunotherapy through intermittent administration. They inhibited tumor-drug resistance and multiorgan-specific metastasis significantly by targeting tumors and the microenvironment. We deciphered an immunosuppressive pre-metastatic niche and discovered that PAA@IONs could target tumors, tumor-draining lymph nodes (TDLNs), the liver, bone, and lungs. They promoted the polarization of macrophages into M1 macrophages in these organs and tissues. This action remodeled the immunosuppressive microenvironment and induced a sustained immune response, thereby reducing organ-specific metastasis. Overcoming the disadvantages of doxorubicin-induced cardiotoxicity as well as low tumor specificity, dual peptide-modified liposomes could target CD206 and CD13 simultaneously, and reverse chemo-resistance. These properties resulted in a significant decrease in the numbers of myeloid-derived suppressor cells (MDSCs) and cancer stem cells (CSCs) in the liver, lungs, and bone, thereby reducing protein expression of Ki-67 in TDLNs, and dramatically increasing the number of cluster of differentiation (CD)8+T cells and CD8+ T cell/T-regulatory-cell ratio in tumors and TDLNs (P < 0.0001). Compared with the control (P < 0.05 and P < 0.01, respectively) or free drug (P < 0.0001 and P < 0.01, respectively), multi-organ metastases were suppressed significantly, tumor-growth rate reduced, and survival prolonged. Our drug-delivery system overcame TNBC chemo-resistance and inhibited multiorgan-specific metastases. It circumvents the lack of effective therapeutic targets, the problem of patient selection due to a low mutation rate, and can simultaneously offer the possibility of avoiding surgery and considerable postoperative complications.
Triple-negative breast cancer (TNBC) lacks specific regimens for targeted therapy. Repeat chemotherapy promotes the evolution of TNBC into highly chemo-resistant tumors that metastasize to multiple organs simultaneously. Herein, polyacrylic acid-coated ultrasmall superparamagnetic iron-oxide nanoparticles (PAA@IONs) and dual-targeting doxorubicin liposomes achieved chemo–immunotherapy through intermittent administration. They inhibited tumor-drug resistance and multiorgan-specific metastasis significantly by targeting tumors and the microenvironment. We deciphered an immunosuppressive pre-metastatic niche and discovered that PAA@IONs could target tumors, tumor-draining lymph nodes (TDLNs), the liver, bone, and lungs. They promoted the polarization of macrophages into M1 macrophages in these organs and tissues. This action remodeled the immunosuppressive microenvironment and induced a sustained immune response, thereby reducing organ-specific metastasis. Overcoming the disadvantages of doxorubicin-induced cardiotoxicity as well as low tumor specificity, dual peptide-modified liposomes could target CD206 and CD13 simultaneously, and reverse chemo-resistance. These properties resulted in a significant decrease in the numbers of myeloid-derived suppressor cells (MDSCs) and cancer stem cells (CSCs) in the liver, lungs, and bone, thereby reducing protein expression of Ki-67 in TDLNs, and dramatically increasing the number of cluster of differentiation (CD)8+T cells and CD8+ T cell/T-regulatory-cell ratio in tumors and TDLNs (P < 0.0001). Compared with the control (P < 0.05 and P < 0.01, respectively) or free drug (P < 0.0001 and P < 0.01, respectively), multi-organ metastases were suppressed significantly, tumor-growth rate reduced, and survival prolonged. Our drug-delivery system overcame TNBC chemo-resistance and inhibited multiorgan-specific metastases. It circumvents the lack of effective therapeutic targets, the problem of patient selection due to a low mutation rate, and can simultaneously offer the possibility of avoiding surgery and considerable postoperative complications.
2023, 34(10): 108828
doi: 10.1016/j.cclet.2023.108828
Abstract:
