Hydrazine oxidation reaction(HzOR)assisted hydrogen evolution reaction(HER)offers a feasible path for low power consumption to hydrogen production.Unfortunately however,the total electrooxidation of hydrazine in anode...Hydrazine oxidation reaction(HzOR)assisted hydrogen evolution reaction(HER)offers a feasible path for low power consumption to hydrogen production.Unfortunately however,the total electrooxidation of hydrazine in anode and the dissociation kinetics of water in cathode are critically depend on the interaction between the reaction intermediates and surface of catalysts,which are still challenging due to the totally different catalytic mechanisms.Herein,the[W–O]group with strong adsorption capacity is introduced into CoP nanoflakes to fabricate bifunctional catalyst,which possesses excellent catalytic performances towards both HER(185.60 mV at 1000 mA cm^(−2))and HzOR(78.99 mV at 10,00 mA cm^(−2))with the overall electrolyzer potential of 1.634 V lower than that of the water splitting system at 100 mA cm^(−2).The introduction of[W–O]groups,working as the adsorption sites for H2O dissociation and N2H4 dehydrogenation,leads to the formation of porous structure on CoP nanoflakes and regulates the electronic structure of Co through the linked O in[W–O]group as well,resultantly boosting the hydrogen production and HzOR.Moreover,a proof-of-concept direct hydrazine fuel cell-powered H_(2) production system has been assembled,realizing H_(2)evolution at a rate of 3.53 mmol cm^(−2)h^(−1)at room temperature without external electricity supply.展开更多
The current COVID-19 pandemic urges the extremely sensitive and prompt detection of SARS-CoV-2 virus.Here,we present a Human Angiotensin-converting-enzyme 2(ACE2)-functionalized gold“virus traps”nanostructure as an ...The current COVID-19 pandemic urges the extremely sensitive and prompt detection of SARS-CoV-2 virus.Here,we present a Human Angiotensin-converting-enzyme 2(ACE2)-functionalized gold“virus traps”nanostructure as an extremely sensitive SERS biosensor,to selectively capture and rapidly detect S-protein expressed coronavirus,such as the current SARS-CoV-2 in the contaminated water,down to the single-virus level.Such a SERS sensor features extraordinary 106-fold virus enrichment originating from high-affinity of ACE2 with S protein as well as“virus-traps”composed of oblique gold nanoneedles,and 109-fold enhancement of Raman signals originating from multi-component SERS effects.Furthermore,the identification standard of virus signals is established by machine-learning and identification techniques,resulting in an especially low detection limit of 80 copies mL^(−1) for the simulated contaminated water by SARS-CoV-2 virus with complex circumstance as short as 5 min,which is of great significance for achieving real-time monitoring and early warning of coronavirus.Moreover,here-developed method can be used to establish the identification standard for future unknown coronavirus,and immediately enable extremely sensitive and rapid detection of novel virus.展开更多
Photosynthesis of organic compounds in coupling with promoted hydrogen evolution under mild conditions of light irradiation is considered as one of the most efficient and promising approach to obtain high purity hydro...Photosynthesis of organic compounds in coupling with promoted hydrogen evolution under mild conditions of light irradiation is considered as one of the most efficient and promising approach to obtain high purity hydrogen and value-added chemicals concurrently by utilizing green solar energy.Here,we report the synthesis of Ni S nanoparticle-modified Cd S nanorod composites(Ni S/Cd S)as an efficient bifunctional catalyst for the highly selective photocatalytic synthesis of high-value-added product benzaldehyde(BAD)from aqueous solution of benzyl alcohol(BA)under oxygen-free conditions,in accompanying with the efficient hydrogen evolution.The synergetic catalytic effect between Ni S and Cd S is proposed to play an important role in elevating the photo-redox performance.The composition-optimized 30%Ni S/Cd S catalyst affords an extraordinarily high H;generation rate of 207.8μmol h^(-1)and a simultaneous BAD generation rate of 163.8μmol h^(-1)under visible light irradiation,which are respectively 139 and 950 times higher than those of Cd S without Ni S modification.To our knowledge,these are the highest photocatalytic production rates of both H_(2)and aldehyde ever reported on the concurrent photocatalytic of aldehyde synthesis and hydrogen evolution in green aqueous solution.This work provides a highly efficient photosynthesis strategy for the concurrent productions of high-value-added fine chemicals and hydrogen.展开更多
Among various earth-abundant and noble metal-free catalysts for oxygen reduction reaction(ORR),manganese-based oxides are promising candidates owing to the rich variety of manganese valence.Herein,an extremely facile ...Among various earth-abundant and noble metal-free catalysts for oxygen reduction reaction(ORR),manganese-based oxides are promising candidates owing to the rich variety of manganese valence.Herein,an extremely facile method for the synthesis of cubic and orthorhombic phase coexisting Mn(Ⅱ)O electrocatalyst as an efficient ORR catalyst was explored.The obtained MnO electrocatalyst with oxygen vacancies shows a significantly elevated ORR catalytic activity with a half-wave potential(E1/2) of as high as 0.895 V,in comparison with that of commercial Pt/C(E1/2=0.877 V).More impressively,the MnO electrocatalyst exhibits a marked activity enhancement after test under a constant applied potential for 1000 s thanks to the in situ generation and stable presence of high-valence manganese species(Mn^3+ and Mn^4+) during the electrochemical process,initiating a synergetic catalytic effect with oxygen vacancies,which is proved to largely accelerate the adsorption and reduction of O_2 molecules favoring the ORR activity elevation.Such an excellent ORR catalytic performance of this MnO electrocatalyst is applied in Zn-air battery,which shows an extra-high peak power density of 63.2 mW cm^-2 in comparison with that(47.4 m W cm^-2) of commercial Pt/C under identical test conditions.展开更多
The low immunogenicity of tumors remains one of the major limitations of cancer immunotherapy.Herein,we report a bacterial metabolisminitiated and photothermal-enhanced nanocatalytic therapy strategy to completely era...The low immunogenicity of tumors remains one of the major limitations of cancer immunotherapy.Herein,we report a bacterial metabolisminitiated and photothermal-enhanced nanocatalytic therapy strategy to completely eradicate primary tumor by triggering highly effective antitumor immune responses.Briefly,a microbiotic nanomedicine,designated as Cu_(2)O@ΔSt,has been constructed by conjugating PEGylated Cu_(2)O nanoparticles on the surface of an engineered Salmonella typhimurium strain(ΔSt).Owing to the natural hypoxia tropism ofΔSt,Cu_(2)O@ΔSt could selectively colonize hypoxic solid tumors,thus minimizing the adverse effects of the bacteria on normal tis-sues.Upon bacterial metabolism within the tumor,Cu_(2)O@ΔSt generates H_(2)S gas and other acidic substances in the tumor microenvironment(TME),which will in situ trigger the sulfidation of Cu_(2)O to form CuS facilitating tumor-specific photothermal therapy(PTT)under local NIR laser irradiation on the one hand.Meanwhile,the dissolved Cu+ions from Cu_(2)O into the acidified TME enables the nanocatalytic tumor therapy by catalyzing the Fenton-like reaction of decom-posing endogenous H_(2)O_(2) into cytotoxic hydroxyl radicals(·OH)on the other hand.Such a bacterial metabolism-triggered PTT-enhanced nanocatalytic treatment could effectively destroy tumor cells and induce a massive release of tumor antigens and damage-associated molecular patterns,thereby sensitizing tumors to checkpoint blockade(ICB)therapy.The combined nanocatalytic and ICB therapy results in the much-inhibited growth of distant and metastatic tumors,and more importantly,induces a powerful immunological memory effect after the primary tumor ablation.展开更多
The composite of Dy-α-sialon/10 wt pct nano-size SiC particles has been prepared from precursor powders of Si3N4, AIN, Al2O3, Dy2O3 and nano-size β-SiC. The hardness, toughness and bending strength of the composite ...The composite of Dy-α-sialon/10 wt pct nano-size SiC particles has been prepared from precursor powders of Si3N4, AIN, Al2O3, Dy2O3 and nano-size β-SiC. The hardness, toughness and bending strength of the composite at ambient temperature are a little higher than those of Dy-α-sialon.while the bending strength is maintained up to 1000℃ and about 2 times more than that of Dy-α-sialon at the same temperature. The fracture surfaces show that the grain size of the composite is smaller than that of Dy-α-sialon, and both Of them have predominately transgranular mode of fracture. It is believed that the decrease of the bending strength of Dy-α-sialon at elevated temperature is caused by the viscous flow of the grain boundary phase, while the addition of nanosize SiC particles effectively increases the viscosity of the grain boundary phase and therefore prevents the strength loss of Dy-α-sialon/nano-size SiC composites at elevated temperature展开更多
Electrocatalytic 2e−oxygen reduction reaction(2e−ORR)is a promising approach to producing H_(2)O_(2) at ambient temperature and pressure especially in acidic media,which,however,is hindered by the high cost of preciou...Electrocatalytic 2e−oxygen reduction reaction(2e−ORR)is a promising approach to producing H_(2)O_(2) at ambient temperature and pressure especially in acidic media,which,however,is hindered by the high cost of precious metal-based electrocatalysts.Hence,the development of efficient earth-abundant electrocatalysts and reaction mechanism exploration for H_(2)O_(2) production by 2e−ORR in acidic solution are critically important but remain challenging at present.In this work,NiSe_(2)has been developed as a novel and high-performance 2e−ORR electrocatalyst in acidic media,moreover,using nickel chalcogenides as the models,the influence of different anion species(Se_(2)^(2−),S22−,and O^(2−))on 2e−ORR electrocatalytic performance of the catalysts has been investigated.The synthesized NiSe_(2)exhibits outstanding 2e−ORR performance of high selectivity(90%)and long-term durability(12 h).The maximum H_(2)O_(2) concentration of NiSe_(2)reaches 988 ppm,which is the highest among all the reported transition metal chalcogenides.This work demonstrates a novel point of view in anion tuning for designing high-efficiency transition-metal-based electrocatalysts for 2e−ORR.展开更多
Ultrasound(US) imaging in combination with US contrast agents(UCAs) is a powerful tool in the modern biomedical field because of its high spatial resolution, easy access to patients and minimum invasiveness.The microb...Ultrasound(US) imaging in combination with US contrast agents(UCAs) is a powerful tool in the modern biomedical field because of its high spatial resolution, easy access to patients and minimum invasiveness.The microbubble-based UCAs have been widely used in clinical diagnosis; however, they are only limited to the blood pool imaging and not applicable to the tissue-penetrated imaging due to their large particle size and structural instability. Inorganic nanoparticles(NPs), such as silica,gold and Fe x O y, featured with both satisfactory echogenic properties and structural stability have the potential to be used as a new generation of UCAs. In this review, we present the most recent progresses in the tailored construction of inorganic UCAs and their biomedical applications in the US imaging-involved fields. Firstly, the typical inorganic NPs with different structures including solid, hollow and multiple-layer forms will be comprehensively introduced in terms of their structure design,physicochemical property, US imaging mechanism and diverse applications; secondly, the recent progress in exploring the gas-generating inorganic NP system for US imaging purpose will be reviewed, and these intelligent UCAs are multifunctional for simultaneous US imaging and disease therapy; thirdly, several nanocomposite platforms newly constructed by combining inorganic UCAs with other functional components will be presented anddiscussed. These multifunctional NPs are capable of further enhancing the imaging resolution by providing more comprehensive anatomical information simultaneously.Last but not the least, the design criteria for developing promising UCAs to satisfy both clinical demands and optimized US imaging capability will be discussed and summarized in this review.展开更多
Developing anode catalysts of substantially enhanced activity for hydrogen oxidation reaction(HOR)and anti-CO poisoning performance is of great importance for the application of proton exchange membrane fuel cells(PEM...Developing anode catalysts of substantially enhanced activity for hydrogen oxidation reaction(HOR)and anti-CO poisoning performance is of great importance for the application of proton exchange membrane fuel cells(PEMFCs).Herein,we report Pd cluster in situ decorated urchin-like W_(18)O_(49)(WO_(2.72))electrocatalysts by a photo-reduction method for high performance HOR.The synthesized Pd-WO_(2.72)-L composite of low loading amount of 0.44 wt.%Pd by Xenon light reduction exhibits markedly high HOR catalytic activity and stability in 0.5 M H_(2)SO_(4),and the specific HOR current density and mass activity of Pd-WO_(2.72)-L are~1.5 and~80 times those of 20 wt.%Pt/C catalyst,respectively.Moreover,excellent anti-CO poisoning ability has also been obtained.The excellent HOR activity and anti-CO poisoning performance of Pd-WO_(2.72)-L have been discussed mainly in terms of the dual synergetic catalytic effects between Pd and WO_(2.72):Pd activation to Pd^(δ+)by the electron transfer from Pd to W promotes the hydrogen adsorption and activation to H*species,which results in largely elevated HOR activity;Pd degradation due to the CO poisoning is effectively prevented by WO_(2.72),which is responsible for the excellent CO-tolerance performance.展开更多
The therapeutic outcomes of noninvasive sonodynamic therapy(SDT)are always compromised by tumor hypoxia,as well as inherent protective mechanisms of tumor.Herein,we report a simple cascade enzymatic approach of the co...The therapeutic outcomes of noninvasive sonodynamic therapy(SDT)are always compromised by tumor hypoxia,as well as inherent protective mechanisms of tumor.Herein,we report a simple cascade enzymatic approach of the concurrent glucose depletion and intratumoral oxygenation for starvation-sensitized and oxygenation-amplified sonodynamic therapy using a dual enzyme and sonosensitizer-loaded nanomedicine designated as GOD/CAT@ZPF-Lips.In particular,glucose oxidase-(GOD-)catalyzed glycolysis would cut off glucose supply within the tumor,resulting in the production of tumor hydrogen peroxide(H_(2)O_(2))while causing tumor cells starvation.The generated H_(2)O_(2)could subsequently be decomposed by catalase(CAT)to generate oxygen,which acts as reactants for the abundant singlet oxygen(^(1 O_(2))production by loaded sonosensitizer hematoporphyrin monomethyl ether(HMME)upon the US irradiation,performing largely elevated therapeutic outcomes of SDT.In the meantime,the severe energy deprivation enabled by GOD-catalyzed glucose depletion would prevent tumor cells from executing protective mechanisms to defend themselves and make the tumor cells sensitized and succumbed to the cytotoxicity of^(1 O_(2)).Eventually,GOD/CAT@ZPF-Lips demonstrate the excellent tumoral therapeutic effect of SDT in vivo without significant side effect through the cascade enzymatic starvation and oxygenation,and encouragingly,the tumor xenografts have been found completely eradicated in around 4 days by the intravenous injection of the nanomedicine without reoccurrence for as long as 20 days.展开更多
Hierarchically porous single-crystalline nanosized zeolites as heterogeneous catalysts show great potential in fine chemistry because they offer more rich hierarchically porous channels for the mass transfer and molec...Hierarchically porous single-crystalline nanosized zeolites as heterogeneous catalysts show great potential in fine chemistry because they offer more rich hierarchically porous channels for the mass transfer and molecular diffusion. However, the synthesis of hierarchically porous nanosized zeolites generally requires the assistance of templates acting as the mesoporogens, which limits its popularity. Herein,we report a one-pot and template-free synthesis of hierarchically porous single-crystalline nanosized zeolite beta only by introducing sodium carbonate in precursor solution. The resulted sample features the extraordinary properties, including the uniform nanocrystal(200–300 nm), high pore volume(0.65 cm^3g^(-1)) and the hierarchical pore-size distribution(e.g. 2–8 and 90–150 nm). After slicing processing, it is interestingly found that a large number of interconnected mesopores penetrate throughout whole material, which enables the hierarchically porous nanosized zeolite beta remarkably superior catalytic activity than the conventional zeolite beta in condensation of benzaldehyde with ethanol at room temperature. More importantly, this one-pot sodium carbonate-assisted synthetic strategy is highly versatile, which has also been successfully developed to synthesize hierarchically porous nanosized singlecrystalline zeolites ZSM-5 and TS.展开更多
CONSPECTUS:The goddess Venus has been known for her armless beauty.Such a unique artistic effect teaches us that the imperfection in one aspect may result in a great aesthetics in another aspect.The existence of struc...CONSPECTUS:The goddess Venus has been known for her armless beauty.Such a unique artistic effect teaches us that the imperfection in one aspect may result in a great aesthetics in another aspect.The existence of structural defects in nanomaterials(substitutional impurities and vacancies)endows them with diverse and fascinating physicochemical properties,such as optical properties and redox reaction capabilities.Therefore,defect engineering of controllably regulating the types and concentrations of defects in nanoparticles has been paid great attention in nanosynthetic chemistry for tailoring the performances of nanomaterials for diversified practical applications,such as biomedical applications.Mesoporous silica nanoparticles(MSNs)have been extensively applied as nanocarriers in biomedicine,due to their well-defined pore structure and particle morphology,extraordinarily large specific surface area and pore volume,tunable pore size,and framework composition.These nanoparticles have been considered as promising candidates for application in multiple therapeutic or diagnostic applications,by acting as drug carriers or supports for functional materials.The synthesis of MSN is usually based on sol−gel chemistry according to a bottom-up approach in a hydrothermal environment,where the silica precursor tetraethoxysilane molecules condense with each other and−Si−O−Si−bonds form consequently,under the assistance of surfactants as structural-directing agents,finally resulting in the formation of a mesoporous nanostructure.Accompanying the pore structure evolution,which has been being the major focus in the MSNs synthesis and application in the past decades,alternatively,the composition of MSN framework can also be elaborately engineered for the material functionalization and the application broadenings of MSNs,facilely by properly regulating the experimental conditions and reactants.Especially,the defect engineering of MSNs has been extensively explored very recently for broadening biomedical applications of these nanocarriers.In the last several years,our laboratory has developed three general strategies to engineer various functional chemical constituents in the MSN framework as structural defects,conferring the nanocarriers with multiple additional functions:(1)doping metal element M(M=Fe,Cu,Mn,Mg,Ca)in silica to form a−Si−O−M−metal silicate hybrid framework;(2)hybridizing organic group R(R=thioether,ethane,phenylene)in silica to fabricate a−Si−R−Si−molecularly organic−inorganic hybrid framework;(3)creating oxygen vacancies in silica by forming an oxygen-deficient framework abundant with−Si−Si−bonds.These material-engineering approaches have led to the generation of numbers of structural defects in the pristine silsesquioxane framework of MSNs,making these“defective nanoparticles”capable of presenting various unique physicochemical properties benefiting biomedical applications,such as triggered biodegradability for controlled drug release;catalytic performance for triggering in vivo chemical reactions generating therapeutic effects;paramagnetism for enabling magnetic resonance imaging;luminescent property for cell imaging,etc.In this Account,we will provide a concise and concentrated summary on the advances in the preparation of defective MSNs mainly in our laboratory,as well as the therapeutic and diagnostic applications of these versatile nanosystems,hoping to provide more inspirations to future nanomedicine design.展开更多
A simple sol-gel route was demonstrated for the synthesis of LiNb0.6Ti0.5O3 (M-phase) powder, using cheap and manageable starting materials at a relatively low temperature. The phase transitions in both chemical and...A simple sol-gel route was demonstrated for the synthesis of LiNb0.6Ti0.5O3 (M-phase) powder, using cheap and manageable starting materials at a relatively low temperature. The phase transitions in both chemical and solid-state processes were studied by X-ray diffraction (XRD) in detail. The results showed that in the sol-gel process the anatase TiO2 phase first appeared at 400 ℃ and then LiNbO3 solid solution (LiNbO3 55) emerged at 500 ℃. When calcined to 600 ℃, the M-phase started to appear along with the decrease of TiO2 and LiNbO3 ss. Single M-phase could be formed at 700℃, which is 300 ℃ lower than that by the traditional solid-state method. A plausible evolution mechanism of the as-synthesized powder in calcination was proposed. The produced powder has potential applications in microelectronics systems.展开更多
Targeted drug delivery has been widely explored for efficient tumor therapy with desired efficacy but minimized side effects. It is widely known that large numbers of DNA-toxins, such as doxorubicin, genes, reactive o...Targeted drug delivery has been widely explored for efficient tumor therapy with desired efficacy but minimized side effects. It is widely known that large numbers of DNA-toxins, such as doxorubicin, genes, reactive oxygen species, serving as therapeutic agents, can result in maximized therapeutic effects via the interaction directly with DNA helix. So after cellular uptake, these agents should be further delivered into cell nuclei to play their essential roles in damaging the DNA helix in cancer ceils. Here, we demonstrate the first paradigm estabJished in our laboratory in developing nucle- ar-targeted drug delivery systems (DDSs) based on MSNs for enhanced therapeutic efficiency in the hope of speeding their translation into the ctinics. Firstly, nuclear-targeting DDSs based on MSNs, capable of intranuclear accumulation and drug release therein, were designed and constructed for the first time, resulting in much enhanced anticancer effects both in vitro and in vivo. Such an MSNs-based and nuclear-targeted drug/agent delivery strategy was further applied to overcome multidrug resistance (MDR) of malignant tumors, intra-nuclearly deliver therapeutic genes, photosensitizers, radio-enhancement agents and photothermal agents to realize efficient gene therapy, photodynamic therapy, radiation therapy and photothermal therapy, respectively.展开更多
基金support of this research by National Natural Science Foundation of China(52172110)Key Research Program of Frontier Sciences,Chinese Academy of Sciences(ZDBS-LY-SLH029)+1 种基金the“Scientific and Technical Innovation Action Plan”Hong Kong,Macao and Taiwan Science&Technology Cooperation Project of Shanghai Science and Technology Committee(21520760500)BL14W1 beamline of Shanghai Synchrotron Radiation Facility(SSRF).
文摘Hydrazine oxidation reaction(HzOR)assisted hydrogen evolution reaction(HER)offers a feasible path for low power consumption to hydrogen production.Unfortunately however,the total electrooxidation of hydrazine in anode and the dissociation kinetics of water in cathode are critically depend on the interaction between the reaction intermediates and surface of catalysts,which are still challenging due to the totally different catalytic mechanisms.Herein,the[W–O]group with strong adsorption capacity is introduced into CoP nanoflakes to fabricate bifunctional catalyst,which possesses excellent catalytic performances towards both HER(185.60 mV at 1000 mA cm^(−2))and HzOR(78.99 mV at 10,00 mA cm^(−2))with the overall electrolyzer potential of 1.634 V lower than that of the water splitting system at 100 mA cm^(−2).The introduction of[W–O]groups,working as the adsorption sites for H2O dissociation and N2H4 dehydrogenation,leads to the formation of porous structure on CoP nanoflakes and regulates the electronic structure of Co through the linked O in[W–O]group as well,resultantly boosting the hydrogen production and HzOR.Moreover,a proof-of-concept direct hydrazine fuel cell-powered H_(2) production system has been assembled,realizing H_(2)evolution at a rate of 3.53 mmol cm^(−2)h^(−1)at room temperature without external electricity supply.
基金the National Natural Science Foundation of China(No.51471182)this work is also supported by Shanghai international science and Technology Cooperation Fund(No.17520711700)the National Key Research and Development Project(No.2017YFB0310600).
文摘The current COVID-19 pandemic urges the extremely sensitive and prompt detection of SARS-CoV-2 virus.Here,we present a Human Angiotensin-converting-enzyme 2(ACE2)-functionalized gold“virus traps”nanostructure as an extremely sensitive SERS biosensor,to selectively capture and rapidly detect S-protein expressed coronavirus,such as the current SARS-CoV-2 in the contaminated water,down to the single-virus level.Such a SERS sensor features extraordinary 106-fold virus enrichment originating from high-affinity of ACE2 with S protein as well as“virus-traps”composed of oblique gold nanoneedles,and 109-fold enhancement of Raman signals originating from multi-component SERS effects.Furthermore,the identification standard of virus signals is established by machine-learning and identification techniques,resulting in an especially low detection limit of 80 copies mL^(−1) for the simulated contaminated water by SARS-CoV-2 virus with complex circumstance as short as 5 min,which is of great significance for achieving real-time monitoring and early warning of coronavirus.Moreover,here-developed method can be used to establish the identification standard for future unknown coronavirus,and immediately enable extremely sensitive and rapid detection of novel virus.
基金This work was supported by the Natural Science Foundation of Shanghai(21ZR1418700)the China Postdoctoral Science Foundation funded project(2020T130193)the Fundamental Research Funds for the Central Universities。
文摘Photosynthesis of organic compounds in coupling with promoted hydrogen evolution under mild conditions of light irradiation is considered as one of the most efficient and promising approach to obtain high purity hydrogen and value-added chemicals concurrently by utilizing green solar energy.Here,we report the synthesis of Ni S nanoparticle-modified Cd S nanorod composites(Ni S/Cd S)as an efficient bifunctional catalyst for the highly selective photocatalytic synthesis of high-value-added product benzaldehyde(BAD)from aqueous solution of benzyl alcohol(BA)under oxygen-free conditions,in accompanying with the efficient hydrogen evolution.The synergetic catalytic effect between Ni S and Cd S is proposed to play an important role in elevating the photo-redox performance.The composition-optimized 30%Ni S/Cd S catalyst affords an extraordinarily high H;generation rate of 207.8μmol h^(-1)and a simultaneous BAD generation rate of 163.8μmol h^(-1)under visible light irradiation,which are respectively 139 and 950 times higher than those of Cd S without Ni S modification.To our knowledge,these are the highest photocatalytic production rates of both H_(2)and aldehyde ever reported on the concurrent photocatalytic of aldehyde synthesis and hydrogen evolution in green aqueous solution.This work provides a highly efficient photosynthesis strategy for the concurrent productions of high-value-added fine chemicals and hydrogen.
基金the support of this research by Natural Science Foundation of Shanghai (19ZR1479400)the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University (KF1818)the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing (Wuhan University of Technology)。
文摘Among various earth-abundant and noble metal-free catalysts for oxygen reduction reaction(ORR),manganese-based oxides are promising candidates owing to the rich variety of manganese valence.Herein,an extremely facile method for the synthesis of cubic and orthorhombic phase coexisting Mn(Ⅱ)O electrocatalyst as an efficient ORR catalyst was explored.The obtained MnO electrocatalyst with oxygen vacancies shows a significantly elevated ORR catalytic activity with a half-wave potential(E1/2) of as high as 0.895 V,in comparison with that of commercial Pt/C(E1/2=0.877 V).More impressively,the MnO electrocatalyst exhibits a marked activity enhancement after test under a constant applied potential for 1000 s thanks to the in situ generation and stable presence of high-valence manganese species(Mn^3+ and Mn^4+) during the electrochemical process,initiating a synergetic catalytic effect with oxygen vacancies,which is proved to largely accelerate the adsorption and reduction of O_2 molecules favoring the ORR activity elevation.Such an excellent ORR catalytic performance of this MnO electrocatalyst is applied in Zn-air battery,which shows an extra-high peak power density of 63.2 mW cm^-2 in comparison with that(47.4 m W cm^-2) of commercial Pt/C under identical test conditions.
基金Wencheng Wu and Yinying Pu contributed equally to this work.We greatly acknowledge the financial support from CAMS Innovation Fund for Medical Sciences(No.2021-I2M-5-012)National Natural Science Foundation of China(No.21835007)+2 种基金Key Research Program of Frontier Sciences,Chinese Academy of Sciences(No.ZDBS-LY-SLH029)Basic Research Program of Shanghai Municipal Government(No.21JC1406000)China National Postdoctoral Program for Innovative Talents(No.BX20220318).
文摘The low immunogenicity of tumors remains one of the major limitations of cancer immunotherapy.Herein,we report a bacterial metabolisminitiated and photothermal-enhanced nanocatalytic therapy strategy to completely eradicate primary tumor by triggering highly effective antitumor immune responses.Briefly,a microbiotic nanomedicine,designated as Cu_(2)O@ΔSt,has been constructed by conjugating PEGylated Cu_(2)O nanoparticles on the surface of an engineered Salmonella typhimurium strain(ΔSt).Owing to the natural hypoxia tropism ofΔSt,Cu_(2)O@ΔSt could selectively colonize hypoxic solid tumors,thus minimizing the adverse effects of the bacteria on normal tis-sues.Upon bacterial metabolism within the tumor,Cu_(2)O@ΔSt generates H_(2)S gas and other acidic substances in the tumor microenvironment(TME),which will in situ trigger the sulfidation of Cu_(2)O to form CuS facilitating tumor-specific photothermal therapy(PTT)under local NIR laser irradiation on the one hand.Meanwhile,the dissolved Cu+ions from Cu_(2)O into the acidified TME enables the nanocatalytic tumor therapy by catalyzing the Fenton-like reaction of decom-posing endogenous H_(2)O_(2) into cytotoxic hydroxyl radicals(·OH)on the other hand.Such a bacterial metabolism-triggered PTT-enhanced nanocatalytic treatment could effectively destroy tumor cells and induce a massive release of tumor antigens and damage-associated molecular patterns,thereby sensitizing tumors to checkpoint blockade(ICB)therapy.The combined nanocatalytic and ICB therapy results in the much-inhibited growth of distant and metastatic tumors,and more importantly,induces a powerful immunological memory effect after the primary tumor ablation.
文摘The composite of Dy-α-sialon/10 wt pct nano-size SiC particles has been prepared from precursor powders of Si3N4, AIN, Al2O3, Dy2O3 and nano-size β-SiC. The hardness, toughness and bending strength of the composite at ambient temperature are a little higher than those of Dy-α-sialon.while the bending strength is maintained up to 1000℃ and about 2 times more than that of Dy-α-sialon at the same temperature. The fracture surfaces show that the grain size of the composite is smaller than that of Dy-α-sialon, and both Of them have predominately transgranular mode of fracture. It is believed that the decrease of the bending strength of Dy-α-sialon at elevated temperature is caused by the viscous flow of the grain boundary phase, while the addition of nanosize SiC particles effectively increases the viscosity of the grain boundary phase and therefore prevents the strength loss of Dy-α-sialon/nano-size SiC composites at elevated temperature
基金supported by Shanghai Science and Technology Committee Rising-Star Program(No.22QA1403400)the Natural Science Foundation of Shanghai(No.21ZR1418700)the National Natural Science Foundation of China(No.52201271).
文摘Electrocatalytic 2e−oxygen reduction reaction(2e−ORR)is a promising approach to producing H_(2)O_(2) at ambient temperature and pressure especially in acidic media,which,however,is hindered by the high cost of precious metal-based electrocatalysts.Hence,the development of efficient earth-abundant electrocatalysts and reaction mechanism exploration for H_(2)O_(2) production by 2e−ORR in acidic solution are critically important but remain challenging at present.In this work,NiSe_(2)has been developed as a novel and high-performance 2e−ORR electrocatalyst in acidic media,moreover,using nickel chalcogenides as the models,the influence of different anion species(Se_(2)^(2−),S22−,and O^(2−))on 2e−ORR electrocatalytic performance of the catalysts has been investigated.The synthesized NiSe_(2)exhibits outstanding 2e−ORR performance of high selectivity(90%)and long-term durability(12 h).The maximum H_(2)O_(2) concentration of NiSe_(2)reaches 988 ppm,which is the highest among all the reported transition metal chalcogenides.This work demonstrates a novel point of view in anion tuning for designing high-efficiency transition-metal-based electrocatalysts for 2e−ORR.
基金financially supported by the National Key R&D Program of China (2016YFA0203700)the National Natural Science Foundation of China (51702099, 51672303 and 51722211)+5 种基金the Program of Shanghai Academic Research Leader (18XD1404300)Young Elite Scientist Sponsorship Program by CAST (2015QNRC001)Youth Innovation Promotion Association of the Chinese Academy of Sciences (2013169)Shanghai Sailing Program (17YF1403800)China Postdoctoral Science Foundation funded project (2017M611500)the Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure (SKL201702SIC)
基金supported by China National Funds for Distinguished Young Scientists(51225202)the National Natural Science Foundation of China(51402329)+1 种基金Science Foundation for Youth Scholar of State Key Laboratory of High Performance Ceramics and Superfine Microstructures(SKL201404)Shanghai Excellent Academic Leaders Program(14XD1403800)
文摘Ultrasound(US) imaging in combination with US contrast agents(UCAs) is a powerful tool in the modern biomedical field because of its high spatial resolution, easy access to patients and minimum invasiveness.The microbubble-based UCAs have been widely used in clinical diagnosis; however, they are only limited to the blood pool imaging and not applicable to the tissue-penetrated imaging due to their large particle size and structural instability. Inorganic nanoparticles(NPs), such as silica,gold and Fe x O y, featured with both satisfactory echogenic properties and structural stability have the potential to be used as a new generation of UCAs. In this review, we present the most recent progresses in the tailored construction of inorganic UCAs and their biomedical applications in the US imaging-involved fields. Firstly, the typical inorganic NPs with different structures including solid, hollow and multiple-layer forms will be comprehensively introduced in terms of their structure design,physicochemical property, US imaging mechanism and diverse applications; secondly, the recent progress in exploring the gas-generating inorganic NP system for US imaging purpose will be reviewed, and these intelligent UCAs are multifunctional for simultaneous US imaging and disease therapy; thirdly, several nanocomposite platforms newly constructed by combining inorganic UCAs with other functional components will be presented anddiscussed. These multifunctional NPs are capable of further enhancing the imaging resolution by providing more comprehensive anatomical information simultaneously.Last but not the least, the design criteria for developing promising UCAs to satisfy both clinical demands and optimized US imaging capability will be discussed and summarized in this review.
基金supported by the National Key Basic Research Program of China(2013CB933200)the Natural Science Foundation of Shanghai(16ZR1440600)+1 种基金the State key laboratory of heavy oil processing(SKLOP201402003)the National Natural Science Foundation of China(U1510107)
基金The authors gratefully acknowledged the support from the Natural Science Foundation of Shanghai(No.19ZR1479400)the State Key Laboratory for Modication of Chemical Fibers and Polymer Materials,Donghua University(No.KF1818)the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology).
文摘Developing anode catalysts of substantially enhanced activity for hydrogen oxidation reaction(HOR)and anti-CO poisoning performance is of great importance for the application of proton exchange membrane fuel cells(PEMFCs).Herein,we report Pd cluster in situ decorated urchin-like W_(18)O_(49)(WO_(2.72))electrocatalysts by a photo-reduction method for high performance HOR.The synthesized Pd-WO_(2.72)-L composite of low loading amount of 0.44 wt.%Pd by Xenon light reduction exhibits markedly high HOR catalytic activity and stability in 0.5 M H_(2)SO_(4),and the specific HOR current density and mass activity of Pd-WO_(2.72)-L are~1.5 and~80 times those of 20 wt.%Pt/C catalyst,respectively.Moreover,excellent anti-CO poisoning ability has also been obtained.The excellent HOR activity and anti-CO poisoning performance of Pd-WO_(2.72)-L have been discussed mainly in terms of the dual synergetic catalytic effects between Pd and WO_(2.72):Pd activation to Pd^(δ+)by the electron transfer from Pd to W promotes the hydrogen adsorption and activation to H*species,which results in largely elevated HOR activity;Pd degradation due to the CO poisoning is effectively prevented by WO_(2.72),which is responsible for the excellent CO-tolerance performance.
基金This work was supported by the National Basic Research Program of China (2013CB933200), the National High Technology Research and Development Program of China (2012AA062703), the National Natural Science Foundation of China (21177137) and the Youth Innovation Promotion Association CAS (2012200).
基金the financial support from the Natural Science Foundation of China(21835007)the Project of Shanghai Science and Technology Committee(17JC1404701).
文摘The therapeutic outcomes of noninvasive sonodynamic therapy(SDT)are always compromised by tumor hypoxia,as well as inherent protective mechanisms of tumor.Herein,we report a simple cascade enzymatic approach of the concurrent glucose depletion and intratumoral oxygenation for starvation-sensitized and oxygenation-amplified sonodynamic therapy using a dual enzyme and sonosensitizer-loaded nanomedicine designated as GOD/CAT@ZPF-Lips.In particular,glucose oxidase-(GOD-)catalyzed glycolysis would cut off glucose supply within the tumor,resulting in the production of tumor hydrogen peroxide(H_(2)O_(2))while causing tumor cells starvation.The generated H_(2)O_(2)could subsequently be decomposed by catalase(CAT)to generate oxygen,which acts as reactants for the abundant singlet oxygen(^(1 O_(2))production by loaded sonosensitizer hematoporphyrin monomethyl ether(HMME)upon the US irradiation,performing largely elevated therapeutic outcomes of SDT.In the meantime,the severe energy deprivation enabled by GOD-catalyzed glucose depletion would prevent tumor cells from executing protective mechanisms to defend themselves and make the tumor cells sensitized and succumbed to the cytotoxicity of^(1 O_(2)).Eventually,GOD/CAT@ZPF-Lips demonstrate the excellent tumoral therapeutic effect of SDT in vivo without significant side effect through the cascade enzymatic starvation and oxygenation,and encouragingly,the tumor xenografts have been found completely eradicated in around 4 days by the intravenous injection of the nanomedicine without reoccurrence for as long as 20 days.
基金sponsored by the National Key Basic Research Program of China(2013CB933200)China National Funds for Distinguished Young Scientists(51225202)+2 种基金National Natural Science Foundation of China(51502330)shanghai international cooperation project(16520710200)Science Foundation for Youth Scholar of State Key Laboratory of High Performance Ceramics and Superfine Microstructures(SKL201604)
文摘Hierarchically porous single-crystalline nanosized zeolites as heterogeneous catalysts show great potential in fine chemistry because they offer more rich hierarchically porous channels for the mass transfer and molecular diffusion. However, the synthesis of hierarchically porous nanosized zeolites generally requires the assistance of templates acting as the mesoporogens, which limits its popularity. Herein,we report a one-pot and template-free synthesis of hierarchically porous single-crystalline nanosized zeolite beta only by introducing sodium carbonate in precursor solution. The resulted sample features the extraordinary properties, including the uniform nanocrystal(200–300 nm), high pore volume(0.65 cm^3g^(-1)) and the hierarchical pore-size distribution(e.g. 2–8 and 90–150 nm). After slicing processing, it is interestingly found that a large number of interconnected mesopores penetrate throughout whole material, which enables the hierarchically porous nanosized zeolite beta remarkably superior catalytic activity than the conventional zeolite beta in condensation of benzaldehyde with ethanol at room temperature. More importantly, this one-pot sodium carbonate-assisted synthetic strategy is highly versatile, which has also been successfully developed to synthesize hierarchically porous nanosized singlecrystalline zeolites ZSM-5 and TS.
基金the financial support from the National Natural Science Foundation of China(Grant No.21835007)Key Research Program of Frontier Sciences,Chinese Academy of Sciences(Grant No.ZDBS-LY-SLH029)Shanghai Municipal Government S&T Project(Grant No.17JC1404701).
文摘CONSPECTUS:The goddess Venus has been known for her armless beauty.Such a unique artistic effect teaches us that the imperfection in one aspect may result in a great aesthetics in another aspect.The existence of structural defects in nanomaterials(substitutional impurities and vacancies)endows them with diverse and fascinating physicochemical properties,such as optical properties and redox reaction capabilities.Therefore,defect engineering of controllably regulating the types and concentrations of defects in nanoparticles has been paid great attention in nanosynthetic chemistry for tailoring the performances of nanomaterials for diversified practical applications,such as biomedical applications.Mesoporous silica nanoparticles(MSNs)have been extensively applied as nanocarriers in biomedicine,due to their well-defined pore structure and particle morphology,extraordinarily large specific surface area and pore volume,tunable pore size,and framework composition.These nanoparticles have been considered as promising candidates for application in multiple therapeutic or diagnostic applications,by acting as drug carriers or supports for functional materials.The synthesis of MSN is usually based on sol−gel chemistry according to a bottom-up approach in a hydrothermal environment,where the silica precursor tetraethoxysilane molecules condense with each other and−Si−O−Si−bonds form consequently,under the assistance of surfactants as structural-directing agents,finally resulting in the formation of a mesoporous nanostructure.Accompanying the pore structure evolution,which has been being the major focus in the MSNs synthesis and application in the past decades,alternatively,the composition of MSN framework can also be elaborately engineered for the material functionalization and the application broadenings of MSNs,facilely by properly regulating the experimental conditions and reactants.Especially,the defect engineering of MSNs has been extensively explored very recently for broadening biomedical applications of these nanocarriers.In the last several years,our laboratory has developed three general strategies to engineer various functional chemical constituents in the MSN framework as structural defects,conferring the nanocarriers with multiple additional functions:(1)doping metal element M(M=Fe,Cu,Mn,Mg,Ca)in silica to form a−Si−O−M−metal silicate hybrid framework;(2)hybridizing organic group R(R=thioether,ethane,phenylene)in silica to fabricate a−Si−R−Si−molecularly organic−inorganic hybrid framework;(3)creating oxygen vacancies in silica by forming an oxygen-deficient framework abundant with−Si−Si−bonds.These material-engineering approaches have led to the generation of numbers of structural defects in the pristine silsesquioxane framework of MSNs,making these“defective nanoparticles”capable of presenting various unique physicochemical properties benefiting biomedical applications,such as triggered biodegradability for controlled drug release;catalytic performance for triggering in vivo chemical reactions generating therapeutic effects;paramagnetism for enabling magnetic resonance imaging;luminescent property for cell imaging,etc.In this Account,we will provide a concise and concentrated summary on the advances in the preparation of defective MSNs mainly in our laboratory,as well as the therapeutic and diagnostic applications of these versatile nanosystems,hoping to provide more inspirations to future nanomedicine design.
文摘A simple sol-gel route was demonstrated for the synthesis of LiNb0.6Ti0.5O3 (M-phase) powder, using cheap and manageable starting materials at a relatively low temperature. The phase transitions in both chemical and solid-state processes were studied by X-ray diffraction (XRD) in detail. The results showed that in the sol-gel process the anatase TiO2 phase first appeared at 400 ℃ and then LiNbO3 solid solution (LiNbO3 55) emerged at 500 ℃. When calcined to 600 ℃, the M-phase started to appear along with the decrease of TiO2 and LiNbO3 ss. Single M-phase could be formed at 700℃, which is 300 ℃ lower than that by the traditional solid-state method. A plausible evolution mechanism of the as-synthesized powder in calcination was proposed. The produced powder has potential applications in microelectronics systems.
基金This work was financially supported by National Natural Science Foundation of China (Grant No. 51402338) and Youth Innovation Promotion Association CAS (Grant No. 2017299).
文摘Targeted drug delivery has been widely explored for efficient tumor therapy with desired efficacy but minimized side effects. It is widely known that large numbers of DNA-toxins, such as doxorubicin, genes, reactive oxygen species, serving as therapeutic agents, can result in maximized therapeutic effects via the interaction directly with DNA helix. So after cellular uptake, these agents should be further delivered into cell nuclei to play their essential roles in damaging the DNA helix in cancer ceils. Here, we demonstrate the first paradigm estabJished in our laboratory in developing nucle- ar-targeted drug delivery systems (DDSs) based on MSNs for enhanced therapeutic efficiency in the hope of speeding their translation into the ctinics. Firstly, nuclear-targeting DDSs based on MSNs, capable of intranuclear accumulation and drug release therein, were designed and constructed for the first time, resulting in much enhanced anticancer effects both in vitro and in vivo. Such an MSNs-based and nuclear-targeted drug/agent delivery strategy was further applied to overcome multidrug resistance (MDR) of malignant tumors, intra-nuclearly deliver therapeutic genes, photosensitizers, radio-enhancement agents and photothermal agents to realize efficient gene therapy, photodynamic therapy, radiation therapy and photothermal therapy, respectively.