Nuclear energy provides a competitive path for reduction of CO_(2)with water,whereas the high-efficiency utilization of radioly tic ally produced active species for oriented transformation remains challenging.Herein,w...Nuclear energy provides a competitive path for reduction of CO_(2)with water,whereas the high-efficiency utilization of radioly tic ally produced active species for oriented transformation remains challenging.Herein,we report the assembling of yttrium-decorated bimetallic MOFs via one-step hydrothermal strategy,which can act as a sensitized nanoreactor for syngas production under y-ray irradiation.The flower-shaped CuNi-MOF matrix with tunable metal centers exposed plentiful cooperative active sites for CO_(2)binding,and its nanopetals enabled the well dispersion of Y_(2)O_(3)nanoparticles on the surfaces.The introduction of high-Z element Y enhanced the secondary electron scattering and promoted the water radiolysis to produce more hydrated electrons(e_(aq)^(-)),thus accelerating the initial CO_(2)activation to CO_(2)^(·-).Moreover,the in situ formed coupling interlayer provided a fast charge transfer channel between Y_(2)O_(3)and the MOF framework,which facilitated the interfacial electron migration for intermediate generation and subsequent CO_(2)conversion.By regulating the contents of Cu and Y_(2)O_(3)within the nanocomposites,the affinity toward CO_(2)and the product compositions could be modulated.As a result,the optimal 7CN-2Y catalyst achieved a high syngas evolution rate of 311.07μmol g^(-1)with a H_(2)/CO ratio of 2.7:1 at an absorbed dose of 4 kGy.The present study offered a feasible route for the efficient transformation of CO_(2)into valuable chemicals and the design of viable catalysts for ionizing radiation.展开更多
Traditional microtubule inhibitors fail to significantly enhance+e effect of colorectal cancer;hence,new and efficient strategies are necessary.In+is study,a supramolecular nanoreactor(DOC@TA-Fe^(3+))based on tannic a...Traditional microtubule inhibitors fail to significantly enhance+e effect of colorectal cancer;hence,new and efficient strategies are necessary.In+is study,a supramolecular nanoreactor(DOC@TA-Fe^(3+))based on tannic acid(TA),iron ion(Fe^(3+)),and docetaxel(DOC)wi+microtubule inhibition,reactive oxygen species(ROS)generation,and gluta+ione peroxidase 4(GPX4)inhibition,is prepared for ferroptosis/apoptosis treatment.After internalization by CT26 cells,+e DOC@TA-Fe^(3+)nanoreactor escapes from+e lysosomes to release payloads.+e subsequent Fe^(3+)/Fe^(2+)conversion mediated by TA reducibility can trigger+e Fenton reaction to enhance+e ROS concentration.Additionally,Fe^(3+)can consume gluta+ione to repress+e activity of GPX4 to induce ferroptosis.Meanwhile,+e released DOC controls microtubule dynamics to activate+e apoptosis pa+way.+e superior in vivo antitumor efficacy of DOC@TA-Fe^(3+)nanoreactor in terms of tumor grow+inhibition and improved survival is verified in CT26 tumor-bearing mouse model.+erefore,+e nanoreactor can act as an effective apoptosis and ferroptosis inducer for application in colorectal cancer+erapy.展开更多
Metallic phosphides as a crucial class of metal-like compounds show high electric conductivity and electrochemical properties.It is of significant benefit to understanding the relationship between the electrocatalytic...Metallic phosphides as a crucial class of metal-like compounds show high electric conductivity and electrochemical properties.It is of significant benefit to understanding the relationship between the electrocatalytic performance and phosphating degree of precursors.In this work,using Co_(3)O_(4)@SiO_(2)as precursor,core-shell structured CoP@SiO_(2)nanoreactors with outstanding oxygen evolution reaction performance were synthesized through a facile calcination method.The electrocatalytic performance of CoP@SiO2 modified electrode that treated with 500 mg NaH_(2)PO_(2)was greatly enhanced.The obtained product displays a low overpotential of 280 mV at a current density of 10 mA/cm^(2)and a Tafel value 89 mV/dec in alkaline conditions.The easy available CoP@SiO_(2)with outstanding catalytic performance and stability possesses huge potential in future electrochemical applications.展开更多
The enzyme-mediated elevation of reactive oxygen species(ROS)at the tumor sites has become an emerging strategy for regulating intracellular redox status for anticancer treatment.Herein,we proposed a camouflaged bioni...The enzyme-mediated elevation of reactive oxygen species(ROS)at the tumor sites has become an emerging strategy for regulating intracellular redox status for anticancer treatment.Herein,we proposed a camouflaged bionic cascaded-enzyme nanoreactor based on Ti_(3)C_(2)nanosheets for combined tumor enzyme dynamic therapy(EDT),phototherapy and deoxygenation-activated chemotherapy.Briefly,glucose oxidase(GOX)and chloroperoxidase(CPO)were chemically conjugated onto Ti_(3)C_(2)nanosheets,where the deoxygenation-activated drug tirapazamine(TPZ)was also loaded,and the Ti_(3)C_(2)-GOX-CPO/TPZ(TGCT)was embedded into nanosized cancer cell-derived membrane vesicles with high-expressed CD47(m_eTGCT).Due to biomimetic membrane camouflage and CD47 overexpression,m_eTGCT exhibited superior immune escape and homologous targeting capacities,which could effectively enhance the tumor preferential targeting and internalization.Once internalized into tumor cells,the cascade reaction of GOX and CPO could generate HClO for efficient EDT.Simultaneously,additional laser irradiation could accelerate the enzymic-catalytic reaction rate and increase the generation of singlet oxygen(~1O_(2)).Furthermore,local hypoxia environment with the oxygen depletion by EDT would activate deoxygenation-sensitive prodrug for additional chemotherapy.Consequently,m_eTGCT exhibits amplified synergistic therapeutic effects of tumor phototherapy,EDT and chemotherapy for efficient tumor inhibition.This intelligent cascaded-enzyme nanoreactor provides a promising approach to achieve concurrent and significant antitumor therapy.展开更多
Yolk‐shell structured nanoparticles are of immense scientific and technological interests because of their unique architecture and myriad of applications.This review summarizes recent progresses in the use of yolk‐s...Yolk‐shell structured nanoparticles are of immense scientific and technological interests because of their unique architecture and myriad of applications.This review summarizes recent progresses in the use of yolk‐shell structured nanoparticles as nanoreactors for various chemical reactions.A very brief overview of synthetic strategies is provided with emphasis on recent research progress in the last five years.Catalytic applications of these yolk‐shell structured nanoreactors are then discussed by covering photocatalysis,methane reforming and electrochemical conversion.The state of the art research and perspective in future development are also highlighted.展开更多
An efficient diketene ring-opening synthesis of polyhydroquinoline derivatives using SBA-15 sulfonic acid modified mesoporous substrates a green and reusable catalyst in a single-pot four-component coupling reaction o...An efficient diketene ring-opening synthesis of polyhydroquinoline derivatives using SBA-15 sulfonic acid modified mesoporous substrates a green and reusable catalyst in a single-pot four-component coupling reaction of diketene,alcohol,enamine,and aldehydes is reported.Dihydropyridine derivatives based on neat adduct of diketene,alcohols and aldehydes using SBA-15/SO_3H nanoreactor as catalyst via a four-component reactions are also synthesized.The advantages of the present method include the use of a small amount catalyst,simple procedure with an easy filterable work-up,waste-free,green and direct synthetic method with an excellent yield of products with efficient use of catalyst and a short reaction time.展开更多
The rational design of efficient bimetallic nanoparticle(NP)catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction.Here,we re...The rational design of efficient bimetallic nanoparticle(NP)catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction.Here,we report the rational design of nanoreactors comprising hollow carbon sphere-confined PtNi bimetallic NPs(PtNi@HCS)as highly efficient catalysts for hydrogen generation via ammonia borane hydrolysis in water.Using both density functional theory calculations and molecular dynamics simulations,the effects of an active PtNi combination and the critical synergistic role of a hollow carbon shell on the molecule diffusion adsorption behaviors are explored.Kinetic isotope effects and theoretical calculations allow the clarification of the mechanism,with oxidative addition of an O-H bond of water to the catalyst surface being the rate-determining step.The remarkable catalytic activity of the PtNi@HCS nanoreactor was also utilized for successful tandem catalytic hydrogenation reactions,using in situ-generated H_(2) from ammonia borane with high efficiency.The concerted design,theoretical calculations,and experimental work presented here shed light on the rational elaboration of efficient nanocatalysts and contribute to the establishment of a circular carbon economy using green hydrogen.展开更多
Titanium dioxide(TiO_(2))hollow nanoparticles present significant potential for photocatalytic applications while their straightforward preparation with precise structure control is still challenging.This work reports...Titanium dioxide(TiO_(2))hollow nanoparticles present significant potential for photocatalytic applications while their straightforward preparation with precise structure control is still challenging.This work reports the approach to preparing tunable hollow TiO_(2) nanospheres by utilization of spherical polyelectrolyte brushes(SPB)as nanoreactors and templates.During the preparation,the evolution of the structure was characterized by small angle X-ray scattering(SAXS),and in combination with dynamic light scattering and transmission electron microscopy.The formation of TiO_(2) shell within the brush(SPB@TiO_(2))is confirmed by the significant increase of the electron density,and its internal structure has been analyzed by fitting SAXS data,which can be influenced by Titanium precursors and ammonia concentration.After calcining SPB@TiO_(2) in a muffle furnace,hollow TiO_(2) nanospheres are produced,and their transition to the anatase crystal form is triggered,as confirmed by X-ray diffraction analysis.Utilizing the advantages of their hollow structure,these TiO_(2) nanospheres exhibit exceptional catalytic degradation efficiency of methylene blue(MB),tetracycline(TC),and 2,4-dichlorophenoxyacetic acid(2,4-D),and also demonstrate excellent recyclability.展开更多
Photothermal conversion(PTC)nanostructures have great potential for applications in many fields,and therefore,they have attracted tremendous attention.However,the construction of a PTC nanoreactor with multi-compartme...Photothermal conversion(PTC)nanostructures have great potential for applications in many fields,and therefore,they have attracted tremendous attention.However,the construction of a PTC nanoreactor with multi-compartment structure to achieve the combination of unique chemical properties and structural feature is still challenging due to the synthetic difficulties.Herein,we designed and synthesized a catalytically active,PTC gold(Au)@polydopamine(PDA)nanoreactor driven by infrared irradiation using assembled PS-b-P2VP nanosphere as soft template.The particles exhibit multi-compartment structure which is revealed by 3D electron tomography characterization technique.They feature permeable shells with tunable shell thickness.Full kinetics for the reduction reaction of 4-nitrophenol has been investigated using these particles as nanoreactors and compared with other reported systems.Notably,a remarkable acceleration of the catalytic reaction upon near-infrared irradiation is demonstrated,which reveals for the first time the importance of the synergistic effect of photothermal conversion and complex inner structure to the kinetics of the catalytic reduction.The ease of synthesis and fresh insights into catalysis will promote a new platform for novel nanoreactor studies.展开更多
Various enzymatic reactions or enzymatic cascade reactions occur efficiently in biological microsystems due to space constraints or orderly transfer of intermediate products. Inspired by this, the horseradish peroxida...Various enzymatic reactions or enzymatic cascade reactions occur efficiently in biological microsystems due to space constraints or orderly transfer of intermediate products. Inspired by this, the horseradish peroxidase(HRP)-like nanozyme(Fe-aminoclay) was in situ synthesized on the surface of alkali-activated halloysite nanotubes and the natural enzyme(glucose oxidase, GOx) was immobilized on it to construct a high-efficiency GOx-Fe AC@AHNTs cascade nanoreactor. In which, Fe AC@AHNTs can not only be used as a carrier for immobilized enzymes, but also help its catalytic activity to cooperate with glucose oxidase in a cascade reaction. The microcompartments and substrate channel effect of this enzyme-nanozyme microsystem exhibit a superior catalytic performance than that of natural enzyme system, and exhibits excellent long-term stability and recyclability. Subsequently, the GOx-Fe AC@AHNTs cascade nanoreactor was employed as a glucose colorimetric platform, which displayed a low detection limit(0.47 μmol/L)in glucose detection. This enzyme-nanoenzyme nanoreactor provides a simple and effective example for constructing a multi-enzyme system with limited space, and lays the foundation for subsequent research in the fields of biological analysis and catalysis.展开更多
The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosyn...The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosynthesis by coupling both photochemistry and thermochemistry.However,strategies for maximizing the use of solar spectra with different frequencies in photothermal catalysis are urgently needed.Here,a hierarchical full-spectrum solar light utilization strategy is proposed.Based on this strategy,a Cu@hollow titanium silicalite-1 zeolite(TS-1)nanoreactor with spatially separated photo/thermal catalytic sites is designed to realize high-efficiency photothermal catalytic artificial photosynthesis.The space-time yield of alcohol products over the optimal catalyst reached 64.4μmol g−1 h−1,with the selectivity of CH3CH2OH of 69.5%.This rationally designed hierarchical utilization strategy for solar light can be summarized as follows:(1)high-energy ultraviolet light is utilized to drive the initial and difficult CO_(2) activation step on the TS-1 shell;(2)visible light can induce the localized surface plasmon resonance effect on plasmonic Cu to generate hot electrons for H2O dissociation and subsequent reaction steps;and(3)low-energy near-infrared light is converted into heat by the simulated greenhouse effect by cavities to accelerate the carrier dynamics.This work provides some scientific and experimental bases for research on novel,highly efficient photothermal catalysts for artificial photosynthesis.展开更多
Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improv...Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improvement of HER performance.Here,we synthesized monodisperse hollow Mo_(2)C nanoreactors,in which the carbon dots(CD)were in situ formed onto the surface of Mo_(2)C through carburization reactions.According to finite element simulation and analysis,the CD@Mo_(2)C possesses better mesoscale diffusion properties than Mo_(2)C alone.The optimized CD@Mo_(2)C nanoreactor demonstrates superior HER performance in alkaline electrolyte with a low overpotential of 57 mV at 10 mA cm^(−2),which is better than most Mo_(2)C-based electrocatalysts.Moreover,CD@Mo_(2)C exhibits excellent electrochemical stability during 240 h,confirmed by operando Raman and X-ray diffraction(XRD).Density functional theory(DFT)calculations show that carbon dots cause the d-band center of CD@Mo_(2)C to shift away from Fermi level,promoting water dissociation and the desorption of H^(*).This study provides a reasonable strategy towards high-activity Mo-based HER eletrocatalysts by modulating the strength of Mo–H bonds.展开更多
The construction of highly stable and regular nanoreactors is a major challenge.In this work,we use a facile template protection method to obtain ZIF-67@SiO_(2)(JS)and to encapsulate metal oxide nanoparticles(Co_(3)O_...The construction of highly stable and regular nanoreactors is a major challenge.In this work,we use a facile template protection method to obtain ZIF-67@SiO_(2)(JS)and to encapsulate metal oxide nanoparticles(Co_(3)O_(4))into nanoreactors(SiO_(2)).ZIF-67 crystals provide a cobalt species;SiO_(2)was first used as a protective layer of ZIF-67 and then as a nanoreactor for metastable metal oxide nanoparticles.On this basis,Co_(3)O_(4)@SiO_(2)with dodecahedron morphology were synthesized by calcining JS at different tempe ratures,followed by a hydrothermal reaction to obtain Co_(3)(OH)4Si_(2)O_(5).Subsequently,CoSx and CoP-SiO_(2)were fabricated through sulfuration and phosphorization.The results in this work show that nanoreactors derived from metal-organic frameworks(MOFs)with a rational structure have broad development prospects.展开更多
Two discrete octahedral metallo-supramolecular cages were designed and constructed by using truxene-based pyridine L with enPd(NO_(3))_(2)or enPt(NO_(3))_(2),followed by detailed NMR,MS,UV absorption,and fluorescence ...Two discrete octahedral metallo-supramolecular cages were designed and constructed by using truxene-based pyridine L with enPd(NO_(3))_(2)or enPt(NO_(3))_(2),followed by detailed NMR,MS,UV absorption,and fluorescence spectroscopy.Owing to the determined cavity size and excellent optical performance of cages,the resulting supramolecular cages were confirmed to be the light-harvesting system based on Foster resonance energy-transfer(FRET).The developed cages display good water solubilities and can act as nanoreactors and light-harvesting systems to catalyze the difluoromethylation of quinoxalin-2(1H)-ones with sodium difluoromethanesulfinate under the irradiation of sunlight.Compared with eosin Y alone,this system displayed enhanced catalytic activity in catalyzing the difluoromethylation,which realizes the simulation of the photosynthesis process.展开更多
Carbon monoxide (CO) therapy has emerged asa promising approach in cancer treatment. Selecting suitablenanocarriers for delivering manganese carbonyl (MnCO), aCO donor, while simultaneously regulating CO release andco...Carbon monoxide (CO) therapy has emerged asa promising approach in cancer treatment. Selecting suitablenanocarriers for delivering manganese carbonyl (MnCO), aCO donor, while simultaneously regulating CO release andcompensating for hydrogen peroxide (H2O2) and acidity in thetumor microenvironment is crucial for enhancing the effectivenessof CO therapy. In this study, a tumor microenvironment-responsive core-shell structured cascade nanoreactorwas designed and synthesized using mesoporous polydopamine(MPDA) as a nanocarrier, followed by loading ofMnCO and glucose oxidase-encapsulated zeolite imidazolateframework-8 (GOx@ZIF-8) nanoparticles. Upon enteringcancer cells, the protective shell of GOx@ZIF-8 degrades inresponse to the acidic tumor environment, releasing GOx.GOx catalyzes the conversion of endogenous glucose intogluconic acid and H2O2, accelerating energy starvation in tumorcells. This process, in turn, promotes the reaction betweenMnCO and H2O2, resulting in in-situ amplified release of CO.Additionally, the excellent photothermal properties of MPDAenable photothermal therapy. This comprehensive antitumorstrategy represents a promising advancement in the field ofCO-based cancer therapy.展开更多
Nanoreactors have attracted extensive research and attention in the field of catalysis due to their unique surface/interface structures and physicochemical properties.However,conventional nanoreactors have limited cat...Nanoreactors have attracted extensive research and attention in the field of catalysis due to their unique surface/interface structures and physicochemical properties.However,conventional nanoreactors have limited catalytic performance due to the confinement of their active components in the“nanochamber”.Herein,low-content active metal(AM,AM=Pd,Cu)decorated yolk-shelled FeCoNiOx(AM/FeCoNiOx)nanoreactors with magnetic recycling properties are synthesized through a simple two-step method.The obtained AM/FeCoNiOxnanospheres are characterized by their distinctive structure and the integration of two kinds of catalytically active components,namely the active FeCoNiOxsubstrate and the well-dispersed AMs in the whole yolk-shelled substrate.These nanospheres can be utilized as nanoreactors in two types of organic reactions(i.e.,reduction and oxidation).During the catalytic reduction of prototypical nitrogen-containing unsaturated organic compounds(e.g.,4-nitrophenol)using sodium borohydride,the Pd/FeCoNiOxnanoreactors demonstrate high activity over Cu/FeCoNiOxand FeCoNiOxcounterparts.The catalytic efficiency significantly surpasses that of a variety of magnetic metalbased nanocatalysts reported recently.Meanwhile,the Pd/FeCoNiOxnanoreactors demonstrate remarkable stability and broadspectrum catalytic capability towards reduction of the other nitrogen-containing unsaturated compounds,including eight substituted nitrobenzenes and two azo dyes.Furthermore,the Pd/FeCoNiOxnanoreactors exhibit exceptional catalytic activity and selectivity in promoting the oxidation of benzyl alcohol.This research provides an effective strategy for the rational design and fabrication of a dual-active-component nanoreactor with simple recycling,which is of practical significance for future sustainable industrial applications.展开更多
Metal-organic frameworks(MOFs)have emerged as superior hosting matrices for atomically precise nanoclusters(NCs)encapsulation,offering excellent physical and chemical protections for advanced catalysis.Nevertheless,th...Metal-organic frameworks(MOFs)have emerged as superior hosting matrices for atomically precise nanoclusters(NCs)encapsulation,offering excellent physical and chemical protections for advanced catalysis.Nevertheless,the MOF coating significantly reduces the NC catalytic efficiency due to the diffusion barriers and the confined microenvironments.Herein,a hierarchically engineered MOF nanoreactor was constructed by controlled structural etching for NC immobilization.This nanoreactor possesses hierarchical pores to accelerate the diffusion rate of reactants and creates hollow structures to unleash the confined NC molecules from the rigid MOF network to a capacious microenvironment.The enhanced mass transfer,improved freedom of NCs,and outstanding stability collectively boosted the catalytic activity of the nanoreactor.By controlling the etching time,freestanding Pd8@zeolitic imidazolate framework-8(ZIF-8)-TA10 displayed a catalytic efficiency that was 3.17 times greater than that of the initial confined Pd8@ZIF-8 and even better than free Pd8.This work opens a new strategy to reduce the inherent limitations of porous matrixes for developing high-performance catalysts.展开更多
Core-shell nanostructures consisting of active metal cores and protective shells often exhibit enhanced catalytic performance, in which reactants can access a small part of the core surfaces through the pores in the s...Core-shell nanostructures consisting of active metal cores and protective shells often exhibit enhanced catalytic performance, in which reactants can access a small part of the core surfaces through the pores in the shells. In this study, we show that Pt nanoparticles （NPs） can be embedded into few-layer hexagonal boron nitride （h-BN） overlayers, forming Pt@h-BN core-shell nanocatalysts. The h-BN shells not only protect the Pt NPs under harsh conditions but also allow gaseous molecules such as CO and 02 to access a large part of the Pt surfaces through a facile intercalation process. As a result, the Pt@h-BN nanostructures act as nanoreactors, and CO oxidation reactions with improved activity, selectivity, and stability occur at the core-shell interfaces. The confinement effect exerted by the h-BN shells promotes the Pt-catalyzed reactions. Our work suggests that two-dimensional shells can function as robust but flexible covers on nanocatalyst surfaces and tune the surface reactivity.展开更多
Carbon-carbon(C–C)coupling reactions represent one of the most powerful tools for the synthesis of complex natural products,bioactive molecules developed as drugs and agrochemicals.In this work,a multifunctional nano...Carbon-carbon(C–C)coupling reactions represent one of the most powerful tools for the synthesis of complex natural products,bioactive molecules developed as drugs and agrochemicals.In this work,a multifunctional nanoreactor for C–C coupling reaction was successfully fabricated via encapsulating the core-shell Cu@Ni nanocubes into ZIF-8(Cu@Ni@ZIF-8).In this nanoreactor,Ni shell of the core-shell Cu@Ni nanocubes was the catalytical active center,and Cu core was in situ heating source for the catalyst by absorbing the visible light.Moreover,benefiting from the plasmonic resonance effect between Cu@Ni nanocubes encapsulated in ZIF-8,the absorption range of nanoreactor was widened and the utilization rate of visible light was enhanced.Most importantly,the microporous structure of ZIF-8 provided shape-selective of reactant.This composite was used for the highly shape-selective and stable photocatalysed C–C coupling reaction of boric acid under visible light irradiation.After five cycles,the nanoreactor still remained high catalytical activity.This Cu@Ni@ZIF-8 nanoreactor opens a way for photocatalytic C–C coupling reactions with shape-selectivity.展开更多
Zinc oxide nanoparticles （ZnO NPs）, as a new type of pH-sensitive drug carrier, have received much attention. ZnO NPs are stable at physiological pH, but can dissolve quickly in the acidic tumor environment （pH 〈 ...Zinc oxide nanoparticles （ZnO NPs）, as a new type of pH-sensitive drug carrier, have received much attention. ZnO NPs are stable at physiological pH, but can dissolve quickly in the acidic tumor environment （pH 〈 6） to generate cytotoxic zinc ions and reactive oxygen species （ROS）. However, the protein corona usually causes the non-specific degradation of ZnO NPs, which has limited their application considerably. Herein, a new type of pH-sensitive nanoreactor （ZnO-DOX@F-mSiO2-FA）, aimed at reducing the non-specific degradation of ZnO NPs, is presented. In the acidic tumor environment （pH 〈 6）, it can release cytotoxic zinc ions, ROS, and anticancer drugs to kill cancer cells effectively. In addition, the fluorescence emitted from fluorescein isothiocyanate （FITC）-labeled mesoporous silica （F-mSiO2） and doxorubicin （DOX） can be used to monitor the release behavior of the anticancer drug. This report provides a new method to avoid the non-specific degradation of ZnO NPs, resulting in synergetic therapy by taking advantage of ZnO NPs-induced oxidative stress and targeted drug release.展开更多
基金financially supported by the National Natural Science Foundation of China(No.21908092)the Natural Science Foundation of Jiangsu Province(No.BK20242043)+2 种基金the China Postdoctoral Science Foundation(No.2022M711614)Jiangsu Funding Program for Excellent Postdoctoral Talent(No.2022ZB194)the Fundamental Research Funds for the Central Universities at NUAA(No.NZ2024038)
文摘Nuclear energy provides a competitive path for reduction of CO_(2)with water,whereas the high-efficiency utilization of radioly tic ally produced active species for oriented transformation remains challenging.Herein,we report the assembling of yttrium-decorated bimetallic MOFs via one-step hydrothermal strategy,which can act as a sensitized nanoreactor for syngas production under y-ray irradiation.The flower-shaped CuNi-MOF matrix with tunable metal centers exposed plentiful cooperative active sites for CO_(2)binding,and its nanopetals enabled the well dispersion of Y_(2)O_(3)nanoparticles on the surfaces.The introduction of high-Z element Y enhanced the secondary electron scattering and promoted the water radiolysis to produce more hydrated electrons(e_(aq)^(-)),thus accelerating the initial CO_(2)activation to CO_(2)^(·-).Moreover,the in situ formed coupling interlayer provided a fast charge transfer channel between Y_(2)O_(3)and the MOF framework,which facilitated the interfacial electron migration for intermediate generation and subsequent CO_(2)conversion.By regulating the contents of Cu and Y_(2)O_(3)within the nanocomposites,the affinity toward CO_(2)and the product compositions could be modulated.As a result,the optimal 7CN-2Y catalyst achieved a high syngas evolution rate of 311.07μmol g^(-1)with a H_(2)/CO ratio of 2.7:1 at an absorbed dose of 4 kGy.The present study offered a feasible route for the efficient transformation of CO_(2)into valuable chemicals and the design of viable catalysts for ionizing radiation.
基金supported by the National Natural Science Foundation of China(Grant Nos.:31971308,81960769,and U1903211)National S&T Major Project(Grant No.:2019ZX09301-147),Luzhou Science and Technology Plan(Grant No.:2018CDLZ10)Sichuan Science and Technology Program(Grant No.:2021YFS0081).
文摘Traditional microtubule inhibitors fail to significantly enhance+e effect of colorectal cancer;hence,new and efficient strategies are necessary.In+is study,a supramolecular nanoreactor(DOC@TA-Fe^(3+))based on tannic acid(TA),iron ion(Fe^(3+)),and docetaxel(DOC)wi+microtubule inhibition,reactive oxygen species(ROS)generation,and gluta+ione peroxidase 4(GPX4)inhibition,is prepared for ferroptosis/apoptosis treatment.After internalization by CT26 cells,+e DOC@TA-Fe^(3+)nanoreactor escapes from+e lysosomes to release payloads.+e subsequent Fe^(3+)/Fe^(2+)conversion mediated by TA reducibility can trigger+e Fenton reaction to enhance+e ROS concentration.Additionally,Fe^(3+)can consume gluta+ione to repress+e activity of GPX4 to induce ferroptosis.Meanwhile,+e released DOC controls microtubule dynamics to activate+e apoptosis pa+way.+e superior in vivo antitumor efficacy of DOC@TA-Fe^(3+)nanoreactor in terms of tumor grow+inhibition and improved survival is verified in CT26 tumor-bearing mouse model.+erefore,+e nanoreactor can act as an effective apoptosis and ferroptosis inducer for application in colorectal cancer+erapy.
基金supported by the National Natural Science Foundation of China(Nos.U1904215,21671170 and 21673203)the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP)+4 种基金Program for New Century Excellent Talents of the University in China(No.NCET-13-0645)the Six Talent Plan(No.2015XCL-030)Qinglan Project of JiangsuProgram for Colleges Natural Science Research in Jiangsu Province(No.18KJB150036)the Science and Technology Innovation Foster Foundation of Yangzhou University(No.2016CXJ010)。
文摘Metallic phosphides as a crucial class of metal-like compounds show high electric conductivity and electrochemical properties.It is of significant benefit to understanding the relationship between the electrocatalytic performance and phosphating degree of precursors.In this work,using Co_(3)O_(4)@SiO_(2)as precursor,core-shell structured CoP@SiO_(2)nanoreactors with outstanding oxygen evolution reaction performance were synthesized through a facile calcination method.The electrocatalytic performance of CoP@SiO2 modified electrode that treated with 500 mg NaH_(2)PO_(2)was greatly enhanced.The obtained product displays a low overpotential of 280 mV at a current density of 10 mA/cm^(2)and a Tafel value 89 mV/dec in alkaline conditions.The easy available CoP@SiO_(2)with outstanding catalytic performance and stability possesses huge potential in future electrochemical applications.
基金This work was supported by the National Natural Science Foundation of China(51773231)Shenzhen Science and Technology Project(JCYJ20190807160801664)the Project of Key Laboratory of Sensing Technology and Biomedical Instruments of Guangdong Province(2011A060901013).
文摘The enzyme-mediated elevation of reactive oxygen species(ROS)at the tumor sites has become an emerging strategy for regulating intracellular redox status for anticancer treatment.Herein,we proposed a camouflaged bionic cascaded-enzyme nanoreactor based on Ti_(3)C_(2)nanosheets for combined tumor enzyme dynamic therapy(EDT),phototherapy and deoxygenation-activated chemotherapy.Briefly,glucose oxidase(GOX)and chloroperoxidase(CPO)were chemically conjugated onto Ti_(3)C_(2)nanosheets,where the deoxygenation-activated drug tirapazamine(TPZ)was also loaded,and the Ti_(3)C_(2)-GOX-CPO/TPZ(TGCT)was embedded into nanosized cancer cell-derived membrane vesicles with high-expressed CD47(m_eTGCT).Due to biomimetic membrane camouflage and CD47 overexpression,m_eTGCT exhibited superior immune escape and homologous targeting capacities,which could effectively enhance the tumor preferential targeting and internalization.Once internalized into tumor cells,the cascade reaction of GOX and CPO could generate HClO for efficient EDT.Simultaneously,additional laser irradiation could accelerate the enzymic-catalytic reaction rate and increase the generation of singlet oxygen(~1O_(2)).Furthermore,local hypoxia environment with the oxygen depletion by EDT would activate deoxygenation-sensitive prodrug for additional chemotherapy.Consequently,m_eTGCT exhibits amplified synergistic therapeutic effects of tumor phototherapy,EDT and chemotherapy for efficient tumor inhibition.This intelligent cascaded-enzyme nanoreactor provides a promising approach to achieve concurrent and significant antitumor therapy.
文摘Yolk‐shell structured nanoparticles are of immense scientific and technological interests because of their unique architecture and myriad of applications.This review summarizes recent progresses in the use of yolk‐shell structured nanoparticles as nanoreactors for various chemical reactions.A very brief overview of synthetic strategies is provided with emphasis on recent research progress in the last five years.Catalytic applications of these yolk‐shell structured nanoreactors are then discussed by covering photocatalysis,methane reforming and electrochemical conversion.The state of the art research and perspective in future development are also highlighted.
文摘An efficient diketene ring-opening synthesis of polyhydroquinoline derivatives using SBA-15 sulfonic acid modified mesoporous substrates a green and reusable catalyst in a single-pot four-component coupling reaction of diketene,alcohol,enamine,and aldehydes is reported.Dihydropyridine derivatives based on neat adduct of diketene,alcohols and aldehydes using SBA-15/SO_3H nanoreactor as catalyst via a four-component reactions are also synthesized.The advantages of the present method include the use of a small amount catalyst,simple procedure with an easy filterable work-up,waste-free,green and direct synthetic method with an excellent yield of products with efficient use of catalyst and a short reaction time.
基金Financial support was received from the National Key R&D Program of China (2021YFC2902505)the start-up funding by Beijing University of Technology (Changlong Wang)。
文摘The rational design of efficient bimetallic nanoparticle(NP)catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction.Here,we report the rational design of nanoreactors comprising hollow carbon sphere-confined PtNi bimetallic NPs(PtNi@HCS)as highly efficient catalysts for hydrogen generation via ammonia borane hydrolysis in water.Using both density functional theory calculations and molecular dynamics simulations,the effects of an active PtNi combination and the critical synergistic role of a hollow carbon shell on the molecule diffusion adsorption behaviors are explored.Kinetic isotope effects and theoretical calculations allow the clarification of the mechanism,with oxidative addition of an O-H bond of water to the catalyst surface being the rate-determining step.The remarkable catalytic activity of the PtNi@HCS nanoreactor was also utilized for successful tandem catalytic hydrogenation reactions,using in situ-generated H_(2) from ammonia borane with high efficiency.The concerted design,theoretical calculations,and experimental work presented here shed light on the rational elaboration of efficient nanocatalysts and contribute to the establishment of a circular carbon economy using green hydrogen.
基金funded by the National Key Research and Development Program of China,grant number 2023YFD1700303.
文摘Titanium dioxide(TiO_(2))hollow nanoparticles present significant potential for photocatalytic applications while their straightforward preparation with precise structure control is still challenging.This work reports the approach to preparing tunable hollow TiO_(2) nanospheres by utilization of spherical polyelectrolyte brushes(SPB)as nanoreactors and templates.During the preparation,the evolution of the structure was characterized by small angle X-ray scattering(SAXS),and in combination with dynamic light scattering and transmission electron microscopy.The formation of TiO_(2) shell within the brush(SPB@TiO_(2))is confirmed by the significant increase of the electron density,and its internal structure has been analyzed by fitting SAXS data,which can be influenced by Titanium precursors and ammonia concentration.After calcining SPB@TiO_(2) in a muffle furnace,hollow TiO_(2) nanospheres are produced,and their transition to the anatase crystal form is triggered,as confirmed by X-ray diffraction analysis.Utilizing the advantages of their hollow structure,these TiO_(2) nanospheres exhibit exceptional catalytic degradation efficiency of methylene blue(MB),tetracycline(TC),and 2,4-dichlorophenoxyacetic acid(2,4-D),and also demonstrate excellent recyclability.
基金support from the DFG through SFB 951 Hybrid Inorganic/Organic Systems for OptoElectronics(HIOS)funding by the European Research Council(ERC)Consolidator Grant with Project Number 646659-NANOREACTORthe Joint Lab for Structural Research at the Integrative Research Institute for the Sciences(IRIS Adlershof).
文摘Photothermal conversion(PTC)nanostructures have great potential for applications in many fields,and therefore,they have attracted tremendous attention.However,the construction of a PTC nanoreactor with multi-compartment structure to achieve the combination of unique chemical properties and structural feature is still challenging due to the synthetic difficulties.Herein,we designed and synthesized a catalytically active,PTC gold(Au)@polydopamine(PDA)nanoreactor driven by infrared irradiation using assembled PS-b-P2VP nanosphere as soft template.The particles exhibit multi-compartment structure which is revealed by 3D electron tomography characterization technique.They feature permeable shells with tunable shell thickness.Full kinetics for the reduction reaction of 4-nitrophenol has been investigated using these particles as nanoreactors and compared with other reported systems.Notably,a remarkable acceleration of the catalytic reaction upon near-infrared irradiation is demonstrated,which reveals for the first time the importance of the synergistic effect of photothermal conversion and complex inner structure to the kinetics of the catalytic reduction.The ease of synthesis and fresh insights into catalysis will promote a new platform for novel nanoreactor studies.
基金supported by the National Natural Science Foundation of China (NSFC,Nos.42061134018,42011530085 and 41877323)the Russian Science Foundation (RSF,No.21-4700019,Russia)the Sichuan Science and Technology Program (No.2019JDJQ0056,China)。
文摘Various enzymatic reactions or enzymatic cascade reactions occur efficiently in biological microsystems due to space constraints or orderly transfer of intermediate products. Inspired by this, the horseradish peroxidase(HRP)-like nanozyme(Fe-aminoclay) was in situ synthesized on the surface of alkali-activated halloysite nanotubes and the natural enzyme(glucose oxidase, GOx) was immobilized on it to construct a high-efficiency GOx-Fe AC@AHNTs cascade nanoreactor. In which, Fe AC@AHNTs can not only be used as a carrier for immobilized enzymes, but also help its catalytic activity to cooperate with glucose oxidase in a cascade reaction. The microcompartments and substrate channel effect of this enzyme-nanozyme microsystem exhibit a superior catalytic performance than that of natural enzyme system, and exhibits excellent long-term stability and recyclability. Subsequently, the GOx-Fe AC@AHNTs cascade nanoreactor was employed as a glucose colorimetric platform, which displayed a low detection limit(0.47 μmol/L)in glucose detection. This enzyme-nanoenzyme nanoreactor provides a simple and effective example for constructing a multi-enzyme system with limited space, and lays the foundation for subsequent research in the fields of biological analysis and catalysis.
基金supported by the National Natural Science Foundation of China(Grant Nos.21908052 and 22108200)the Key Program of the Natural Science Foundation of Hebei Province(Grant No.B2020209017)+2 种基金the Project of Science and Technology Innovation Team,Tangshan(Grant No.20130203D)the Natural Science Foundation of Zhejiang Province(Grant No.LQ22B060013)and the Science and Technology Project of Hebei Education Department(Grant No.QN2021113).
文摘The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosynthesis by coupling both photochemistry and thermochemistry.However,strategies for maximizing the use of solar spectra with different frequencies in photothermal catalysis are urgently needed.Here,a hierarchical full-spectrum solar light utilization strategy is proposed.Based on this strategy,a Cu@hollow titanium silicalite-1 zeolite(TS-1)nanoreactor with spatially separated photo/thermal catalytic sites is designed to realize high-efficiency photothermal catalytic artificial photosynthesis.The space-time yield of alcohol products over the optimal catalyst reached 64.4μmol g−1 h−1,with the selectivity of CH3CH2OH of 69.5%.This rationally designed hierarchical utilization strategy for solar light can be summarized as follows:(1)high-energy ultraviolet light is utilized to drive the initial and difficult CO_(2) activation step on the TS-1 shell;(2)visible light can induce the localized surface plasmon resonance effect on plasmonic Cu to generate hot electrons for H2O dissociation and subsequent reaction steps;and(3)low-energy near-infrared light is converted into heat by the simulated greenhouse effect by cavities to accelerate the carrier dynamics.This work provides some scientific and experimental bases for research on novel,highly efficient photothermal catalysts for artificial photosynthesis.
基金financially supported by the National Natural Science Foundation of China (22372001)Starting Fund for Scientific Research of High-Level Talents, Anhui Agricultural University (rc382108)+1 种基金Anhui Provincial Key Research and Development Plan (2022e07020037)Innovation and Entrepreneurship Training Program for College Students (X202310364204, S202210364046, X202310364209)
文摘Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improvement of HER performance.Here,we synthesized monodisperse hollow Mo_(2)C nanoreactors,in which the carbon dots(CD)were in situ formed onto the surface of Mo_(2)C through carburization reactions.According to finite element simulation and analysis,the CD@Mo_(2)C possesses better mesoscale diffusion properties than Mo_(2)C alone.The optimized CD@Mo_(2)C nanoreactor demonstrates superior HER performance in alkaline electrolyte with a low overpotential of 57 mV at 10 mA cm^(−2),which is better than most Mo_(2)C-based electrocatalysts.Moreover,CD@Mo_(2)C exhibits excellent electrochemical stability during 240 h,confirmed by operando Raman and X-ray diffraction(XRD).Density functional theory(DFT)calculations show that carbon dots cause the d-band center of CD@Mo_(2)C to shift away from Fermi level,promoting water dissociation and the desorption of H^(*).This study provides a reasonable strategy towards high-activity Mo-based HER eletrocatalysts by modulating the strength of Mo–H bonds.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.21671170,21673203)the Topnotch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP)+2 种基金Program for New Century Excellent Talents of the University in China(NCET,No.13-0645)the Six Talent Plan(No.2015-XCL-030)Qinglan Project。
文摘The construction of highly stable and regular nanoreactors is a major challenge.In this work,we use a facile template protection method to obtain ZIF-67@SiO_(2)(JS)and to encapsulate metal oxide nanoparticles(Co_(3)O_(4))into nanoreactors(SiO_(2)).ZIF-67 crystals provide a cobalt species;SiO_(2)was first used as a protective layer of ZIF-67 and then as a nanoreactor for metastable metal oxide nanoparticles.On this basis,Co_(3)O_(4)@SiO_(2)with dodecahedron morphology were synthesized by calcining JS at different tempe ratures,followed by a hydrothermal reaction to obtain Co_(3)(OH)4Si_(2)O_(5).Subsequently,CoSx and CoP-SiO_(2)were fabricated through sulfuration and phosphorization.The results in this work show that nanoreactors derived from metal-organic frameworks(MOFs)with a rational structure have broad development prospects.
基金National Natural Science Foundation of China(Nos.22101267,21672192,21803059,U2004191,U1904212 and 21801063)for financial support.
文摘Two discrete octahedral metallo-supramolecular cages were designed and constructed by using truxene-based pyridine L with enPd(NO_(3))_(2)or enPt(NO_(3))_(2),followed by detailed NMR,MS,UV absorption,and fluorescence spectroscopy.Owing to the determined cavity size and excellent optical performance of cages,the resulting supramolecular cages were confirmed to be the light-harvesting system based on Foster resonance energy-transfer(FRET).The developed cages display good water solubilities and can act as nanoreactors and light-harvesting systems to catalyze the difluoromethylation of quinoxalin-2(1H)-ones with sodium difluoromethanesulfinate under the irradiation of sunlight.Compared with eosin Y alone,this system displayed enhanced catalytic activity in catalyzing the difluoromethylation,which realizes the simulation of the photosynthesis process.
基金supported by the National Natural Science Foundation of China (21971153 and 22371172)the Major Basic Research Projects of Shandong Provincial Natural Science Foundation (ZR2020ZD32)+2 种基金the Taishan Scholars Climbing Program of Shandong Provincethe Natural Science Foundation of Shandong Province (ZR2021QB035)the financial support from the China Scholarship Council (202108370157)。
文摘Carbon monoxide (CO) therapy has emerged asa promising approach in cancer treatment. Selecting suitablenanocarriers for delivering manganese carbonyl (MnCO), aCO donor, while simultaneously regulating CO release andcompensating for hydrogen peroxide (H2O2) and acidity in thetumor microenvironment is crucial for enhancing the effectivenessof CO therapy. In this study, a tumor microenvironment-responsive core-shell structured cascade nanoreactorwas designed and synthesized using mesoporous polydopamine(MPDA) as a nanocarrier, followed by loading ofMnCO and glucose oxidase-encapsulated zeolite imidazolateframework-8 (GOx@ZIF-8) nanoparticles. Upon enteringcancer cells, the protective shell of GOx@ZIF-8 degrades inresponse to the acidic tumor environment, releasing GOx.GOx catalyzes the conversion of endogenous glucose intogluconic acid and H2O2, accelerating energy starvation in tumorcells. This process, in turn, promotes the reaction betweenMnCO and H2O2, resulting in in-situ amplified release of CO.Additionally, the excellent photothermal properties of MPDAenable photothermal therapy. This comprehensive antitumorstrategy represents a promising advancement in the field ofCO-based cancer therapy.
基金supported by the Key Research and Development Program of Hubei Province(Grant No.2022BAA026)the Open/Innovation Project of Key Laboratory of Novel Biomass-Based Environmental and Energy Materials in Petroleum and Chemical Industry(Grant No.2022BEEA06)。
文摘Nanoreactors have attracted extensive research and attention in the field of catalysis due to their unique surface/interface structures and physicochemical properties.However,conventional nanoreactors have limited catalytic performance due to the confinement of their active components in the“nanochamber”.Herein,low-content active metal(AM,AM=Pd,Cu)decorated yolk-shelled FeCoNiOx(AM/FeCoNiOx)nanoreactors with magnetic recycling properties are synthesized through a simple two-step method.The obtained AM/FeCoNiOxnanospheres are characterized by their distinctive structure and the integration of two kinds of catalytically active components,namely the active FeCoNiOxsubstrate and the well-dispersed AMs in the whole yolk-shelled substrate.These nanospheres can be utilized as nanoreactors in two types of organic reactions(i.e.,reduction and oxidation).During the catalytic reduction of prototypical nitrogen-containing unsaturated organic compounds(e.g.,4-nitrophenol)using sodium borohydride,the Pd/FeCoNiOxnanoreactors demonstrate high activity over Cu/FeCoNiOxand FeCoNiOxcounterparts.The catalytic efficiency significantly surpasses that of a variety of magnetic metalbased nanocatalysts reported recently.Meanwhile,the Pd/FeCoNiOxnanoreactors demonstrate remarkable stability and broadspectrum catalytic capability towards reduction of the other nitrogen-containing unsaturated compounds,including eight substituted nitrobenzenes and two azo dyes.Furthermore,the Pd/FeCoNiOxnanoreactors exhibit exceptional catalytic activity and selectivity in promoting the oxidation of benzyl alcohol.This research provides an effective strategy for the rational design and fabrication of a dual-active-component nanoreactor with simple recycling,which is of practical significance for future sustainable industrial applications.
基金financial support by the National Natural Science Foundation of China(Nos.22305003 and 21972001)the China Postdoctoral Science Foundation(No.2023M740009).
文摘Metal-organic frameworks(MOFs)have emerged as superior hosting matrices for atomically precise nanoclusters(NCs)encapsulation,offering excellent physical and chemical protections for advanced catalysis.Nevertheless,the MOF coating significantly reduces the NC catalytic efficiency due to the diffusion barriers and the confined microenvironments.Herein,a hierarchically engineered MOF nanoreactor was constructed by controlled structural etching for NC immobilization.This nanoreactor possesses hierarchical pores to accelerate the diffusion rate of reactants and creates hollow structures to unleash the confined NC molecules from the rigid MOF network to a capacious microenvironment.The enhanced mass transfer,improved freedom of NCs,and outstanding stability collectively boosted the catalytic activity of the nanoreactor.By controlling the etching time,freestanding Pd8@zeolitic imidazolate framework-8(ZIF-8)-TA10 displayed a catalytic efficiency that was 3.17 times greater than that of the initial confined Pd8@ZIF-8 and even better than free Pd8.This work opens a new strategy to reduce the inherent limitations of porous matrixes for developing high-performance catalysts.
基金Acknowledgements This work was financially supported by the National Natural Science Foundation of China （Nos. 21373208, 91545204, 21688102, and 21621063）, and Ministry of Science and Technology of China （Nos. 2016YFA0200200, 2013CB834603, and 2013CB933100）, and the Strategic Priority Research Program of the Chinese Academy of Sciences （No. XDB17020200）.
文摘Core-shell nanostructures consisting of active metal cores and protective shells often exhibit enhanced catalytic performance, in which reactants can access a small part of the core surfaces through the pores in the shells. In this study, we show that Pt nanoparticles （NPs） can be embedded into few-layer hexagonal boron nitride （h-BN） overlayers, forming Pt@h-BN core-shell nanocatalysts. The h-BN shells not only protect the Pt NPs under harsh conditions but also allow gaseous molecules such as CO and 02 to access a large part of the Pt surfaces through a facile intercalation process. As a result, the Pt@h-BN nanostructures act as nanoreactors, and CO oxidation reactions with improved activity, selectivity, and stability occur at the core-shell interfaces. The confinement effect exerted by the h-BN shells promotes the Pt-catalyzed reactions. Our work suggests that two-dimensional shells can function as robust but flexible covers on nanocatalyst surfaces and tune the surface reactivity.
基金We gratefully acknowledge the financial support from the Beijing Natural Science Foundation(No.2182061)Science Foundation of China University of Petroleum,Bejing(No.2462019BJRC001).
文摘Carbon-carbon(C–C)coupling reactions represent one of the most powerful tools for the synthesis of complex natural products,bioactive molecules developed as drugs and agrochemicals.In this work,a multifunctional nanoreactor for C–C coupling reaction was successfully fabricated via encapsulating the core-shell Cu@Ni nanocubes into ZIF-8(Cu@Ni@ZIF-8).In this nanoreactor,Ni shell of the core-shell Cu@Ni nanocubes was the catalytical active center,and Cu core was in situ heating source for the catalyst by absorbing the visible light.Moreover,benefiting from the plasmonic resonance effect between Cu@Ni nanocubes encapsulated in ZIF-8,the absorption range of nanoreactor was widened and the utilization rate of visible light was enhanced.Most importantly,the microporous structure of ZIF-8 provided shape-selective of reactant.This composite was used for the highly shape-selective and stable photocatalysed C–C coupling reaction of boric acid under visible light irradiation.After five cycles,the nanoreactor still remained high catalytical activity.This Cu@Ni@ZIF-8 nanoreactor opens a way for photocatalytic C–C coupling reactions with shape-selectivity.
文摘Zinc oxide nanoparticles （ZnO NPs）, as a new type of pH-sensitive drug carrier, have received much attention. ZnO NPs are stable at physiological pH, but can dissolve quickly in the acidic tumor environment （pH 〈 6） to generate cytotoxic zinc ions and reactive oxygen species （ROS）. However, the protein corona usually causes the non-specific degradation of ZnO NPs, which has limited their application considerably. Herein, a new type of pH-sensitive nanoreactor （ZnO-DOX@F-mSiO2-FA）, aimed at reducing the non-specific degradation of ZnO NPs, is presented. In the acidic tumor environment （pH 〈 6）, it can release cytotoxic zinc ions, ROS, and anticancer drugs to kill cancer cells effectively. In addition, the fluorescence emitted from fluorescein isothiocyanate （FITC）-labeled mesoporous silica （F-mSiO2） and doxorubicin （DOX） can be used to monitor the release behavior of the anticancer drug. This report provides a new method to avoid the non-specific degradation of ZnO NPs, resulting in synergetic therapy by taking advantage of ZnO NPs-induced oxidative stress and targeted drug release.
