Enhanced Catalytic Activity of Gold@Polydopamine Nanoreactors with Multi-compartment Structure Under NIR Irradiation

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.

Construction of a Cu@hollow TS-1 nanoreactor based on a hierarchical full-spectrum solar light utilization strategy for photothermal synergistic artificial photosynthesis

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.

Tailoring polysulfide trapping and kinetics by engineering hollow carbon bubble nanoreactors for high-energy Li-S pouch cells

Despite great progress of lithium-sulfur(Li-S)battery performance at the laboratory-level,both key parameters and challenges at cell scales to achieve practical high energy density require high-sulfur-loading cathodes and lean electrolytes.Herein,a novel carbon foam integrated by hollow carbon bubble nanoreactors with ultrahigh pore volume of 6.9 cm3·g−1 is meticulously designed for ultrahigh sulfur content up to 96 wt.%.Tailoring polysulfide trapping and ion/electron transport kinetics during the charge-discharge process can be achieved by adjusting the wall thickness of hollow carbon bubbles.And a further in-depth understanding of electrochemical reaction mechanism for the cathode is impelled by the in-situ Raman spectroscopy.As a result,the as-prepared cathode delivers high specific capacitances of 1,269 and 695 mAh·g−1 at 0.1 and 5 C,respectively.Furthermore,Li-S pouch cells with high areal sulfur loading of 6.9 mg·cm−2 yield exceptional practical energy density of 382 Wh·kg−1 under lean electrolyte of 3.5µL·mg−1,which demonstrates the great potential for realistic high-energy Li-S batteries.

CoP@SiO2nanoreactors: A core-shell structure for efficient electrocatalytic oxygen evolution reaction

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 Co3O4@SiO2 as precursor,core-shell structured CoP@SiO2 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 NaH2PO2 was greatly enhanced.The obtained product displays a low overpotential of 280 mV at a current density of 10 mA/cm2 and a Tafel value 89 mV/dec in alkaline conditions.The easy available CoP@SiO2 with outstanding catalytic performance and stability possesses huge potential in future electrochemical applications.

Nanoreactors derived from silica-protection-assisted metal-organic framework

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@SiO2(JS) and to encapsulate metal oxide nanoparticles(Co3O4) into nanoreactors(SiO2).ZIF-67 crystals provide a cobalt species;SiO2 was first used as a protective layer of ZIF-67 and then as a nanoreactor for metastable metal oxide nanoparticles.On this basis,Co3O4@SiO2 with dodecahedron morphology were synthesized by calcining JS at different tempe ratures,followed by a hydrothermal reaction to obtain Co3(OH)4Si2O5.Subsequently,CoSx and CoP-SiO2 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.

Catalysis under shell： Improved CO oxidation reaction confined in Pt@h-BN core-shell nanoreactors

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 O2 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.

Controlled synthesis of Pt-loaded yolk-shell TiO_(2)@SiO_(2) nanoreactors as effective photocatalysts for hydrogen generation

Yolk-shell and hollow structures are powerful platforms for controlled release,confined nanocatalysis,and optical and electronic applications.This contribution describes a fabrication strategy for a yolk-shell nanoreactor(NR)using a post decoration approach.The widely studied yolk-shell structure of silica-coated TiO_(2)(TiO_(2)@SiO_(2))was used as a model.At first,anatase TiO_(2) spheres were prepared,and subsequently were given a continuous coating of carbonaceous and silica layers.Finally,the carbonaceous layer was removed to produce a yolk-shell structure TiO_(2)@SiO_(2).By using an in-situ photodeposition method,Pt-encased spheres(Pt-TiO_(2)@SiO_(2))were synthesized with Pt nanoparticles grown on the surface of the TiO_(2) core,which contained void spaces suitable for use as NRs.The NR showed enhanced hydrogen production with a rate of 24.56 mmol·g^(-1)·h^(-1) in the presence of a sacrificial agent under simulated sunlight.This strategy holds the potential to be extended for the synthesis of other yolk-shell photocatalytic NRs with different metal oxides.

Core-Sheath CeO_(2)/SiO_(2) Nanofibers as Nanoreactors for Stabilizing Sinter‑Resistant Pt,Enhanced Catalytic Oxidation and Water Remediation

One-dimensional(1D)oxide nanofibers have attracted much attention in recent years but are still hampered by the difficulty in the expansion to 2D or 3D dimensions.Herein,ultrathin CeO_(2)/SiO_(2)nanofibers with intriguing core-sheath structures were simply fabricated by a facile single-spinneret electrospinning method and were subsequently integrated as 2D nanofi-brous mats and 3D sponges.Introducing secondary oxide(i.e.,SiO_(2))could induce a unique fine structure and further inhibit the sintering of CeO_(2)nanocrystals,endowing the resultant dual-oxide nanofibers with high porosity,good flexibility,and enriched oxygen defects.Benefiting from the core-sheath structure and dual-oxide component,the CeO_(2)/SiO_(2)nanofibers could stabilize 2.59 nm-Pt clusters against sintering at 600℃.Once assembled into a 2D mat,the nanofibers could efficiently decrease the soot oxidation temperature by 63℃.Moreover,the core-sheath CeO_(2)/SiO_(2)nanofibers can be readily integrated with graphene nanosheets into a 3D sponge via a gas foaming protocol,showing 218.5 mg/g of adsorption capacity toward Rhodamine B molecules.This work shed lights on the versatile applications of oxide nanofibers toward clean energy ultili-zation and low-carbon development.

Boosting ferroptosis and microtubule inhibition for antitumor therapy via a carrier-free supermolecule nanoreactor

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.

Inorganic Nanozyme with Combined Self-Oxygenation/Degradable Capabilities for Sensitized Cancer Immunochemotherapy

Recently emerged cancer immunochemotherapy has provided enormous new possibilities to replace traditional chemotherapy in fighting tumor.However,the treatment efficacy is hampered by tumor hypoxiainduced immunosuppression in tumor microenvironment(TME).Herein,we fabricated a self-oxygenation/degradable inorganic nanozyme with a core-shell structure to relieve tumor hypoxia in cancer immunochemotherapy.By integrating the biocompatible CaO2 as the oxygen-storing component,this strategy is more effective than the earlier designed nanocarriers for delivering oxygen or H2O2,and thus provides remarkable oxygenation and long-term capability in relieving hypoxia throughout the tumor tissue.Consequently,in vivo tests validate that the delivery system can successfully relieve hypoxia and reverse the immunosuppressive TME to favor antitumor immune responses,leading to enhanced chemoimmunotherapy with cytotoxic T lymphocyte-associated antigen 4 blockade.Overall,a facile,robust and effective strategy is proposed to improve tumor oxygenation by using self-decomposable and biocompatible inorganic nanozyme reactor,which will not only provide an innovative pathway to relieve intratumoral hypoxia,but also present potential applications in other oxygen-favored cancer therapies or oxygen deficiency-originated diseases.

A MXene-Based Bionic Cascaded-Enzyme Nanoreactor for Tumor Phototherapy/Enzyme Dynamic Therapy and Hypoxia-Activated Chemotherapy

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.

A confined growth strategy to construct 3DOM SiO_(2) nanoreactor insitu embedded Co_(3)O_(4) nanoparticles catalyst for the catalytic combustion of VOCs:Superior H_(2)O and SO_(2) resistance

SO_(2)poisoning is a common problem in the catalytic combustion of volatile organic compounds(VOCs).In this work,we took three-dimensionally ordered macroporous and mesoporous(3DOM)SiO_(2)as the nanoreactor to protect active sites from SO_(2)erosion in the catalytic combustion of benzene.Simultaneously,the confined growth of metal active nanoparticles in the multi-stage pore is also full of challenges.And we successfully confined Co_(3)O_(4)nanoparticles(NPs)in macroporous and mesoporous channels.Interestingly,the precursors’growth in the pore was controlled and nanoreactors with different pore sizes were prepared by adjusting the loading amount and preparation methods.It is discovered that the Co_(3)O_(4)NPs confined in 3DOM SiO_(2)nanoreactor showed superior sulfur and water resistance.Density functional theory(DFT)calculations verified that the Co-Si catalyst had high SO_(2)adsorption energy(-0.48 eV),which illustrated that SO_(2)was hard to attach to the surface of the Co-Si catalyst.The SiO_(2)nanoreactor had low SO_(2)adsorption energy(-5.15 eV),which indicated that SO_(2)was easily absorbed on SiO_(2)nanoreactor.This illustrated that the SiO_(2)nanoreactor could protect effectively active sites from SO_(2)erosion.

Electrospun advanced nanomaterials for in situ transmission electron microscopy:Progress and perspectives

Electrospun nanofibers(NFs)have shown excellent properties including high porosity,abundant active sites,controllable diameter,uniform and designable structure,high mechanical strength,and superior resistance to external destruction,which are ideal nanoreactors for in situ characterizations.Among various techniques,in situ transmission electron microscopy(TEM)has enabled operando observation at the atomic level due to its high temporal and spatial resolution combined with excellent sensitivity,which is of great importance for rational materials design and performance improvement.In this review,the basic knowledge of in situ TEM techniques and the advantages of electrospun nanoreactors for in situ TEM characterization are first introduced.The recent development in electrospun nanoreactors for studying the physical properties,structural evolution,phase transition,and formation mechanisms of materials using in situ TEM is then summarized.The electrochemical behaviors of carbon nanofibers(CNFs),metal/metal oxide NFs,and solidelectrolyte interphase for different rechargeable batteries are highlighted.Finally,challenges faced by electrospun nanoreactors for in situ TEM characterization are discussed and potential solutions are proposed to advance this field.

Synthesis of cycloparaphenylene under spatial nanoconfinement

Suzuki coupling reactions between symmetrical monomers were conducted in various mesoporous silica nanoreactors grafted with palladium catalysts,enabling the selective formation of[12]cycloparaphenylene precursor with separate yield up to 25%in one-pot reactions,much higher than that in homogeneous reaction.The spatial nanoconfinement of the nanoreactors promotes the macrocyclization while limits the concomitant linear oligomer formation,offering more possibilities for the synthesis of macrocycles from symmetrical monomers in one-pot reaction.

Time-resolved luminescent nanoprobes based on lanthanide nucleotide self-assemblies for alkaline phosphatase detection

Currently,enzyme-responsive nanomaterials have shown great promise in prognosis or diagnosis of disease biomarker.However,the great obstacle for conventional enzyme-responsive nanomaterials frequently lies in autofluorescence interference,poor monodispersity,uncontrollable size and morphology,low optical stability,and biotoxicity,which fundamentally impede their practical application in biological systems.To overcome these deficiencies,we proposed a novel strategy for reliable and precise detection of an enzyme disease biomarker,alkaline phosphatase(ALP),through lanthanide(Ln^(3+))nucleotide nanoparticles(LNNPs)with extremely improved monodispersity and uniformity,which were achieved by the coordination self-assembly between ATP and Ln^(3+)inside micellar nanoreactor.Specifically,for ATP-Ce/Tb LNNPs,highly improved photoluminescence(PL)emission of Tb^(3+)can be achieved via efficient Ce^(3+)sensitization.We demonstrated that ALP could specifically cleave the phosphorus–oxygen(P–O)bonds of ATP and result in the collapse of ATP-Ce/Tb scaffold,finally leading to the PL quenching of Tb^(3+).By taking advantage of time-resolved(TR)PL technique,the fabricated ATP-Ce/Tb LNNPs presented superior selectivity and sensitivity for the ALP bioassay in complicated serum samples,thus revealing the great potential of ATP-Ce/Tb LNNPs in the areas of ALP-related disease prognosis and diagnosis.

Zeolites for food applications:A review Cristian

Zeolites have been little investigated for food applications,despite their chemical composition is similar to clays and clay minerals,which have been extensively analyzed for various applications,including food.Zeolites can be distinguished from clay materials,since the former have a porous microstructure characterized by intracrystalline cavities and channels,while the latter have a laminar microstructure.The goal of this review paper was to give a comprehensive perspective in terms of the different food applications found so far for zeolites,namely:antimicrobial materials,ethylene scavengers,fillers for food packaging materials,food nanoreactors,food substance sensors,immobilizers and stabilizers of active compounds and enzymes,molecular sieves for the pretreatment of food samples,as well as intelligent food contact materials.The main food applications from zeolites are related to their good properties as adsorbent materials,and these properties can be altered and tuned by ion exchange,surface organo-modification,among others,for a specific designed application.Zeolites for food applications have been investigated primarily as antimicrobial materials,concentrators of target analytes and sensors for food substances.However,the other potential food applications indicated above from zeolites are booming,since they are harmless materials recognized by various organizations.

Plasmonic coupling-enhanced in situ photothermal nanoreactor with shape selective catalysis for C–C coupling reaction

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.

A pH-switched mesoporous nanoreactor for synergetic therapy

作为 pH 敏感的药搬运人的一种新类型，锌氧化物 nanoparticles (ZnO NP ) 收到了许多注意。ZnO NP 在生理的 pH 是稳定的，但是能在酸的肿瘤环境快速溶解(pH < 6 ) 产生细胞毒素的锌离子和反应的氧种类(ROS ) 。然而，蛋白质日冕通常引起 ZnO NP 的非特定的降级，它更加限制了他们的申请。此处， pH 敏感的 nanoreactor 的一种新类型(ZnO-DOX@F-mSiO 2-FA), 瞄准了减少 ZnO NP 的非特定的降级，被介绍。在酸的肿瘤环境(pH < 6 ) ，它能释放有效地杀死癌症房间的细胞毒素的锌离子， ROS，和 anticancer 药。另外，从荧光黄 isothiocyanate (FITC ) 射出的荧光标记 mesoporous 为硅石(F-mSiO 2) 和 doxorubicin (纪录影片) 能被用来监视 anticancer 药的版本行为。这份报告提供一个新方法避免 ZnO NP 的非特定的降级，导致由利用导致 NPs 的氧化应力和指向的药释放的 ZnO 的合作治疗。

Nanovoid-confinement and click-activated nanoreactor for synchronous delivery of prodrug pairs and precise photodynamic therapy

Bioorthogonal cleavage reaction-triggered prodrug activation by the pretargeted methods can achieve accurate cancer therapy.However,the click and release efficiency of these methods in vivo is limited by the space-time dislocation of bioorthogonal prodrug-trigger pairs within the tumor area,caused by their asynchronous administration and inconsistent accumulation for most delivery systems.We herein created a nanovoid-confinement and click-activated(NCCA)core–shell nanoreactor by incorporating prodrugs within zeolitic imidazolate framework-90(ZIF-90)as core and coating tetrazine-based covalent organic framework(COF)as shell.After surface modification of aptamer polymer,the NCCA nanoreactor enabled the sufficient delivery of photodynamic prodrugs within tumor.Notably,the core of ZIF-90 was decomposed by tumor acidic environment,inducing the high-efficiency activation of photodynamic prodrugs via nanoconfined bioorthogonal reaction with tetrazine-based COF shell.As a result,such photodynamic agents are efficiently and safely accumulated into tumor and specifically activated for precise photodynamic therapy of cancer cells and tumor bearing mice with minimizing toxic side effect.Taken together,such NCCA nanoreactor clearly demonstrates the critical feasibility to realize the synchronous delivery of both prodrugs and triggers for precise treatment,which most of delivery systems are not able to afford.

High-performance cascade nanoreactor based on halloysite nanotubes-integrated enzyme-nanozyme microsystem

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.