The current strategy of co-delivering copper ions and disulfiram(DSF)to generate cytotoxic CuET faces limitations in achieving rapid and substantial CuET production,specifically in tumor lesions.To overcome this challenge,we introduce a novel burst-release cascade reactor composed of phase change materials(PCMs)encapsulating ultrasmall Cu_(2-x)Se nanoparticles(NPs)and DSF(DSF/Cu_(2-x)Se@PCM).Once triggered by second near-infrared(NIR-II)light irradiation,the reactor swiftly releases Cu_(2-x)Se NPs and DSF,enabling catalytic reactions that lead to the rapid and massive production of Cu_(2-x)Se-ET complexes,thereby achieving in situ chemotherapy.The mechanism of the burst reaction is due to the unique properties of ultrasmall Cu_(2-x)Se NPs,including their small size,multiple defects,and high surface activity.These characteristics allow DSF to be directly reduced and chelated on the surface defect sites of Cu_(2-x)Se,forming Cu_(2-x)Se-ET complexes without the need for copper ion release.Additionally,Cu_(2-x)Se-ET has demonstrated a similar(to CuET)anti-tumor activity through increased autophagy,but with even greater potency due to its unique two-dimensional-like structure.The light-triggered cascade of interlocking reactions,coupled with in situ explosive generation of tumor-suppressive substances mediated by the size and valence of Cu_(2-x)Se,presents a promising approach for the development of innovative nanoplatforms in the field of precise tumor chemotherapy.
Covalent organic frameworks(COFs)-based nanoreactors have attracted broad interest in many fields due to their voidconfinement effects.However,the inherent drawback of conventional nanoreactors is the lack of internal active sites,which limits their widespread utilization.Herein,we report the construction of hierarchical COF(EB-TFP)nanoreactor with pre-synthesized polyoxometalates(POM,[PV_(2)W_(10)O_(40)]^(5–)(PV_(2)W_(10)))clusters encapsulated inside of COF(POM@COF).PV_(2)W_(10)@EB-TFP anchors nucleophilic-group(Br–ions)and PV_(2)W_(10)anion cluster within the COF framework via electrostatic interactions,which not only simplifies the reaction system but also enhances catalytic efficiency.The reaction performance of the PV_(2)W_(10)@EB-TFP nanoreactor can be tuned to achieve excellent catalytic activity in CO_(2)cycloaddition reaction(CCR)for~97.63%conversion and~100%selectivity under visible light irradiation.A mechanistic study based on density functional theory(DFT)calculations and insitu characterization was also carried out.In summary,we have reported a method for achieving the uniform dispersion of POM single clusters into COF nanoreactor,demonstrating the potential of POM@COF nanoreactor for synergistic photothermal catalytic CO_(2)cycloaddition.
Tian WangYunqing ZhuWei WangJunfeng NiuZhiyi LuPeilei He
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.
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.
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.
Mengmeng LiuYuanyuan JiangZhuwei CaoLulu LiuHong ChenSheng Ye
Photothermal and photodynamic therapies(PTT/PDT)hold promise for localized tumor treatment,yet their full potential is hampered by limitations such as the hypoxic tumor microenvironment and inadequate systemic immune activation.Addressing these challenges,we present a novel near-infrared(NIR)-triggered RNS nanoreactor(PBNO-Ce6)to amplify the photodynamic and photothermal therapy efficacy against triple-negative breast cancer(TNBC).The designed PBNOCe6 combines sodium nitroprusside-doped Prussian Blue nanoparticles with Chlorin e6 to enable on-site RNS production through NIR-induced concurrent NO release and ROS generation.This not only enhances tumor cell eradication but also potentiates local and systemic antitumor immune responses,protecting mice from tumor rechallenge.Our in vivo evaluations revealed that treatment with PBNO-Ce6 leads to a remarkable 2.7-fold increase in cytotoxic T lymphocytes and a 62%decrease in regulatory T cells in comparison to the control PB-Ce6(Prussian Blue nanoparticles loaded with Chlorin e6),marking a substantial improvement over traditional PTT/PDT.As such,the PBNO-Ce6 nanoreactor represents a transformative approach for improving outcomes in TNBC and potentially other malignancies affected by similar barriers.
Tumor microenvironment(TME),as the“soil”of tumor growth and metastasis,exhibits significant differences from normal physiological conditions.However,how to manipulate the distinctions to achieve the accurate therapy of primary and metastatic tumors is still a challenge.Herein,an innovative nanoreactor(AH@MBTF)is developed to utilize the apparent differences(copper concentration and H_(2)O_(2)level)between tumor cells and normal cells to eliminate primary tumor based on H_(2)O_(2)-dependent photothermal-chemodynamic therapy and suppress metastatic tumor through copper complexation.This nanoreactor is constructed using functionalized MSN incorporating benzoyl thiourea(BTU),triphenylphosphine(TPP),and folic acid(FA),while being co-loaded with horseradish peroxidase(HRP)and its substrate ABTS.During therapy,the BTU moieties on AH@MBTF could capture excessive copper(highly correlated with tumor metastasis),presenting exceptional anti-metastasis activity.Simultaneously,the complexation between BTU and copper triggers the formation of cuprous ions,which further react with H_(2)O_(2)to generate cytotoxic hydroxyl radical(•OH),inhibiting tumor growth via che-modynamic therapy.Additionally,the stepwise targeting of FA and TPP guides AH@MBTF to accurately accu-mulate in tumor mitochondria,containing abnormally high levels of H_(2)O_(2).As a catalyst,HRP mediates the oxidation reaction between ABTS and H_(2)O_(2)to yield activated ABTS•^(+).Upon 808 nm laser irradiation,the activated ABTS•^(+)performs tumor-specific photothermal therapy,achieving the ablation of primary tumor by raising the tissue temperature.Collectively,this intelligent nanoreactor possesses profound potential in inhib-iting tumor progression and metastasis.
Jie LiuTianfeng YangHandan ZhangLin WengXiuhong PengTao LiuCheng ChengYanmin ZhangXin Chen
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.
Fenton reaction centered ferroptosis-apoptosis synergetic therapy has emerged as a promising tumor elimination strategy.However,the low intracellular Fenton level and accumulation of therapeutics at the lesion site greatly limit the efficacy of ferroptosis therapy.To overcome these two bottlenecks,an inhalable metal polyphenol network(MPN)-hybrid liposome,encoded as LDG,was proposed for enhancing the intracellular Fenton reaction level by co-delivering the ferroptosis inducer dihydroartemisinin(DHA)and the ferrous ion(Fe2+)donor MPN.The synthesized LDG had excellent nebulization performance which significantly improved the accumulation in the lungs,about 8.2 times of intravenous injection.In terms of anticancer mechanisms,MPN raised the intracellular level of Fe2+by constructing iron cycling in the weakly acidic environment of tumors.Triggered by Fe2+,DHA with peroxide-bridge structure underwent a high level of Fenton-like reaction,promoted the production of intracellular reactive oxygen species(ROS)and induced strong ferroptosis while cooperating with apoptosis.LDG exhibited extraordinary antitumor ability in an orthotopic lung tumor model,whose tumor inhibition efficiency was 1.53(P=0.0014)and 1.32(P=0.0183)times of the LG group(liposomes coated with gallic acid(GA)-Fe MPN)and LD group(liposomes loaded with DHA),respectively,showing the strongest anticancer effect.In conclusion,the constructed MPN-hybrid liposomes could be a potent custom nanoplatform for pulmonary delivery and underscored the great potential of ferroptosis-apoptosis synergetic therapy.
Producing fuels or chemicals via electrochemical carbon dioxide reduction reaction(CO_(2)RR)with renewable electricity has attracted great research interest due to its potential of alleviating the environmental and energy issues in a carbon–neutral manner[1].The CO_(2)RR is a proton-coupled electron transfer process with the simultaneous participation of multiple protons and electrons[2].
