Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.

Advances in the study of HOR reaction mechanisms under alkaline conditions

Hydrogen energy is an important energy carrier,which is an ideal choice to meet energy demand and reduce harmful gas emissions.The green recycling of hydrogen energy depends on water electrolysis and hydrogen fuel cells,which involves hydrogen oxidation reaction(HOR)and hydrogen evolution reaction(HER).The activity of HER/HOR in alkaline electrolyte,however,exhibits a significantly lower magnitude(2–3 orders)compared to that observed in an acidic medium,which hinders the development of alkaline water electrolysis and alkaline membrane fuel cells.Therefore,comprehending the characteristics of HOR/HER activity in alkaline electrolytes and elucidating its underlyingmechanismis a prerequisite for the designof advanced electrocatalysts.Based on this background,this reviewwill briefly summarize the explanations and controversies about the basic HOR mechanism,including bifunctional mechanismand hydrogen binding energy theory.Moreover,the crucial affecting factors of theHOR kinetics,such as dband center theory,interfacial water recombination,alkali metal cations and electronic effects,are discussed.Thus,based on the above theories,the design principle,catalytic performance,and latest progress ofHOR electrocatalysts are summarized.An outlook and future research perspectives of advanced catalysts for hydrogen energy recycling are addressed.This reviewis helpful to understand the latest development ofHORmechanismand design cost-effective and high-performance HOR electrocatalysts towards the production of clean renewable energies.

Engineering the Active Sites of MOF-derived Catalysts:From Oxygen Activation to Activate Metal-Air Batteries

The electrochemical processes of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)play a crucial role in various energy storage and conversion systems.However,the inherently slow kinetics of reversible oxygen reactions present an urgent demand for the development of efficient oxygen electrocatalysts.Recently,metal-organic framework(MOF)derivatives have attracted extensive attention in electrocatalysis research due to their unique porous structure,abundant active sites,and tunable structural properties.Especially,the optimization of the electronic structure of active sites in MOF derivatives has been proven as an effective strategy to enhance the catalytic activity.In this review,we provide an overview of the electronic structure optimization strategies for active sites in MOF derivatives as advanced catalysts in various O—O bond activation reactions,including the construction of synergistic effects between multiple sites,the development of heterogeneous interfaces,the utilization of metal support interactions,and the precise modulation of organic ligands surrounding catalytic active sites at the atomic level.Furthermore,this review offers theoretical insights into the oxygen activation and catalytic mechanisms of MOF derivatives,as well as the identification of active sites.Finally,the potential challenges and prospects of MOF derivatives in electrocatalysis are discussed.This review contributes to the understanding and advancement of efficient oxygen electrocatalysis in energy systems.

Molecular structure and application of covalent organic frameworks(COFs)in tumor therapy

The field of nanomedicine has emerged as a vital component in cancer treatment modalities over the past decades.Covalent organic frameworks(COFs)at the nanoscale have become a novel and promising category of biomaterials in the field of nanomedicine.Their distinctive properties,such as low density,exceptional porosity,crystalline structure,remarkable thermal stability,versatile functionality,and biocompatibility,contribute to their significant potential in cancer therapy applications.This review firstly discusses COFs with various morphologies in theranostic applications.The primary morphologies of COFs for tumors treatment can be categorized into four types:nanospheres,nanosheets,nano-rods/tubes and nanoparticles.Furthermore,we review recent research articles and systematically discuss recent advancements in COFs for chemotherapy,chemodynamic therapy,photodynamic therapy,photothermal therapy and combination therapy.In conclusion,we outline the current obstacles and potential future directions for this distinctive research area.

Nb_(2)O_(5) nanocrystals decorated graphene composites as anode materials for high-performance dual-ion batteries

Niobium oxide(Nb_(2)O_(5))is a promising material in photocatalytic,solar cell,electronic like electron field emitters,and especially lithium-ion batteries(LIBs)because of its adjustable morphologies,controllable crystal type,stable structure,and environmental friendliness.However,its low electrical conductivity lowers the rate performance and limits the practical applications in LIBs.Herein,we present a one-step solid-state synthesis of orthogonal Nb_(2)O_(5) nanocrystals/graphene composites(Nb_(2)O_(5)/G)as high-performance anode materials in LIBs.Benefiting from the nanoscale crystalline structure Nb_(2)O_(5) and highly-conductive graphene substrate,the as-prepared Nb_(2)O_(5)/G exhibits excellent electrochemical performances.Impressively,a reversible structural phase transition between orthogonal Nb_(2)O_(5) and tetragonal Li1-xNbO_(2)(0<x<1)was verified by ex-situ transmission electron microscopy(TEM)and X-ray photoelectron spectroscopy(XPS).After coupling with graphite cathode based on PF6-intercalation/deintercalation mechanisms,Nb_(2)O_(5)/G||graphite dual-ion batteries(DIBs)full cell delivers good electrochemical performance in terms of cyclic performance and rate capability.We believe this work can provide a clear route towards developing advanced transition metal oxide/graphene composite anode and a comprehension of its electrochemical reaction mechanism.

Facile Synthesis of Mo2C Nanocrystals Embedded in Nanopo- rous Carbon Network for Efficient Hydrogen Evolution

Exploring facile and easily-scalable methods for synthesizing earth-abundant, cost-effective and efficient hy- drogen evolution reaction （HER） electrocatalysts is essential for the mass production of hydrogen as a clean and sustainable energy carrier. We report here a simple strategy to produce Mo2C nanocrystals embedded in carbon network （Mo2C@C） by the direct pyrolysis of ammonium molybdate and polyvinylpyrrolidone （PVP）. It is found that PVP can be effectively used as a single source to form carbides and carbon network. The long polymer chain and coordinating capability with transition metal of PVP make it possible to form connected porous carbon network and well-dispersed MozC nanocrystals in several nanometers. The carbonization of PVP not only effectively in-situ prevents the aggregation of Mo2C nanocrystals during their formation, but also provides conductive porous matrix. As a result, the Mo2C@C composite exhibits the superior electrocatalytic performance for HER, which can be as- cribed to the large number of active sites from plenty of small MORC nanocrystals and the efficient mass and elec- tron transport network from carbon matrix. This strategy may inspire the exploration of cost-effective functional polymer as single source for both carbon precursor and nanostructure-directed reagent to mass-produce well-defined metal carbides nanostructures embedded in porous carbon network for energy applications.

Microscale Chemical Features of Sediment-Water Interface in Hongfeng Lake

In situ microscale distributions of 02, H2S, pH and redox potential in sediments of Hongfeng Lake, SW China, were investigated using the powerful microsensor technique. Our results show that O2 was depleted within the top 3.9 mm in surface sediments, and H2S was subsequently detected at -6.0 mm depth, and reached its maximum concentrations at -25 mm. The degradation of organic matter and reduction of sulfate might be the major pathways of producing H2S in sediments, pH rapidly reduced in surface layers mainly due to H＋ release in the oxidation of organic matter. Eh also decreased sharply in surface sediments, probabl indicating the coexistence of Fe and Mn oxides with O2 in aerobic region. Furthermore, the programme of PROFILE was applied to model the 02 gradient, and good fit was obtained between the simulative values and the factual values both in sediments and in the diffusive boundary layer （DBL）. The results indicate that the depth-integrated O2 consumption rates within sediments were 0.083 and 0.134 nmol·m-3·s-1 in site S1 and site S2, respectively. In addition, there were distinct DBL in two sediment profiles, with 1.2 mm thickness in S1 and 0.9 mm thickness in S2. The diffusive fluxes of O2 within the DBL were 67.13 nmol·m-2·s-1 in S1 and 88.54 nmol·m-2·s-1 in S2.

A boronate-modified renewable nanointerface for ultrasensitive electrochemical assay of cellulase activity

The saccharification of cellulosic biomass to produce biofuels and chemicals is one of the most promising industries for gree n-power production and sustainable development.Cellulase is the core component in the saccharification process.Simple and efficient assay method to determine cellulase activity in saccharification is thus highly required.In this work,a boronate-affinity surface based renewable and ultrasensitive electrochemical sensor for cellulase activity determination has been fabricated.Through bo ronate-sugar interaction,celluloses are attached to the electrode surface,forming the cellulose na nonetwork at the sensing interface.Cellulase degradation can lead to the variation of electrochemical impedance.Thus,electrochemical impedance signal can reflect the cellulase activity.Importantly,via fully utilizing the boronate-affinity chemistry that enables reversible fabrication of cellulose nanonetwork,a renewable sensing surface has been firstly constructed for cellulase activity assay.Thanks to interfacial diffusion process of electrochemical sensor,the product inhibitory effect in the cellulase activity assays can be circumvented.The proposed electrochemical sensor is ultrasensitive for label-free cellulase activity detection with a very simple fabrication process,showing great potential for activity screen of new enzymes in saccharification conversion.

Component reconstitution-driven photoelectrochemical sensor for sensitive detection of Cu2+ based on advanced CuS/CdS p-n junction

The rational design of robust photoactive material and artful sensing strategy are vital for the construction of an ultrasensitive photoelectrochemical（PEC） sensor. Although great progress has been made in PEC sensing, the resultant detection performances and adoptable sensing strategies are still limited. Herein, through the design of a subtle component reconstitution strategy, an ultrasensitive PEC sensor is developed for the detection of Cu2+ based on advanced Cu S/Cd S nanohybrids（NHs）.This proposed sensor shows superior sensing performances with a low detection limit of 0.1 n M and a wide detection range from0.2 n M to 60 μM due to the formation of p-n junction between Cu S and Cd S and the component transformation of Cd S to CuxS（x=1,2）. Moreover, such PEC sensor also displays goodish results for monitoring the Cu2+released from apoptotic He La cells in vitro. This idea of component reconstitution provides a new paradigm for the design of advanced PEC sensors.

A follow up study of cycle threshold values of SARS-CoV-2 in Hunan Province,China

Since the epidemic of the severe acute respiratory syndrome coronavirus 2(SARS-COV-2),many governments have used reverse transcription polymerase chain reaction(RT-PCR)to detect the virus.However,there are fewer measures of CT values information based on RT-PCR results,and the relationship between CT values and factors from consecutive tests is not clear enough.So in this study,we analyzed the connection between CT values and the factors based on cohort data from Delta variant of SARS-CoV-2 in Hunan Province.Previous studies have showed that the mean age of the cases was 33.34 years(±18.72 years),with a female predominance(55.03%,n=71),and the greatest proportion of clinical symptoms were of the common type(60.47%,n=78).There were statistical differences between the N and ORF1ab genes in the CT values for the cases.Based on the analysis of the association between CT values and the factors,the lowest CT values were obtained for the unvaccinated,older and clinically symptomatic group at 3e10 days,the maximum peak of viral load occurred.Therefore,it is recommended to use patient information to focus on older,clinically symptomatic,unvaccinated patients and to intervene promptly upon admission.

Integrated Rabies Surveillance-Hunan Province,China,2020

Introduction:The objective of this paper was to assess the epidemiology of rabies in Hunan Province,analyze the associated factors,understand the status of prevention and treatment after rabies exposure,evaluate the effectiveness of prevention and treatment,and provide a scientific basis for formulating effective prevention and control measures.Methods:The surveillance data of rabies in Hunan Province in 2020 were collected and analyzed by descriptive epidemiological method.Results:In 2020,a total of 59 cases of rabies were reported in Hunan Province,with an incidence rate of 0.09/100,000.Overall,42 cases(71.19%)were due to animal bites and 43 cases(72.88%)were of grade III.The proportion of hand and combined injury of hand was the highest(40.68%).A total of 603,261 cases of rabies exposure were reported from the rabies post-exposure prophylaxis(PEP)clinic in Hunan Province.Dogs were the main animal causing injuries,accounting for 74.21%.Only 83,418(13.84%)of the animals had a clear immune history,and a total of 11 dog attacks were reported in Hunan Province.The average immunity rate of dogs in the whole province was 30.98%.In 2020,554 dogs were sampled in the whole province;20 of them were positive for a positivity rate of 3.61%.Conclusions:Rabies in Hunan Province in 2020 had a relatively low prevalence.Failure to treat wounds,immunoglobulin injections,and vaccination after exposure were the main causes of rabies.Therefore,post-exposure management of rabies should be further strengthened to reduce the risk of rabies for high-risk populations.

Raman imaging analysis of intracellular biothiols independent of the aggregation of sensing substrates

The content of biothiols in cells is highly associated with the occurrence and development of several diseases.However,due to their active chemical properties,thiol-contained molecules are normally volatile during the detection process,rendering precise analysis of intracellular biothiols challenging.In this study,5,5’-dithiobis-(2-nitrobenzoic acid)(DTNB)is covalently modified on the surface of gold nanorods(AuNRs),constructing sensing substrates for in situ Raman imaging analysis of biothiols in cells.Au NRs are able to serve as ideal surface-enhanced Raman scattering substrates,and thus Raman signals of DTNB are greatly amplified by AuNRs.Meanwhile,the disulfide bond of DTNB can be broken by thiols,thereby releasing part of DTNB from the surface of AuNRs.As a result,three kinds of main biothiols are sensitively quantified with DTNB-modified AuNRs according to the variation of Raman signals,and DTNB-modified Au NRs exhibit far better analytical performance than a commercial probe.In addition,the sensing substrates can be readily delivered to cytoplasm with the transmembrane of Au NRs,and are capable of responding to biothiols in cells.Notably,the Raman approach is established by the breaking of chemical bonds rather than the aggregation of substrates,which is more inclined to analyze intracellular biothiols with a desirable spatial resolution.Therefore,fluctuation of biothiols in glioma cells is evidently observed via Raman imaging.Overall,this work provides an alternative strategy for designing Raman sensors to visualize active molecules in cells.

Ultrasensitive determination of intracellular hydrogen peroxide by equipping quantum dots with a sensing layer via self-passivation

Abnormal expression of hydrogen peroxide(H_(2)O_(2))indicates the disorder of cell functions and is able to induce the occurrence and deterioration of numerous diseases.However,limited by its low concentration under pathophysiological conditions,intracellular H_(2)O_(2) is still difficult to be determined to date.Herein,to achieve sensitive quantification of H_(2)O_(2) in cells,CIS/ZnS/ZnS quantum dots(CIS/d-ZnS QDs)are retrofitted with ZnO shells via self-passivation.Different from the traditional self-passivation of QDs,self-passivation of CIS/d-ZnS QDs is realized facilely without the assistance of additional cation ions,which improves optical properties of QDs and equips the QDs with a sensing layer.As a result,the CIS/d-ZnS/ZnO QDs exhibit enhanced fluorescence emission and stability.Relying on the decomposition of ZnO and ZnS shells in the presence of H_(2)O_(2),aggregated QDs reveal exciton energy transfer effect,resulting in fluorescence quenching.On a basis of this principle,a fluorescence H_(2)O_(2) sensor is further established with the CIS/d-ZnS/ZnO QDs.To be noted,since the equipped ZnO shells are more susceptible to H2O2 than original ZnS shells,analytical performance of the fluorescence sensor is remarkably promoted by the self-passivation of QDs.Accordingly,H_(2)O_(2) can be measured in 5 orders of magnitude with a limit of detection(LOD)of 0.46 nM.Furthermore,because the ZnO shells improve H2O2-responsive selectivity and sensitivity,variation of H_(2)O_(2) in cells can also be quantified with the CIS/d-ZnS/ZnO QDs.In this work,sensitive detection of intracellular H_(2)O_(2) is enabled by equipping QDs with a sensing layer,which provides an alternative perspective of functionalizing nanomaterials for analytical applications.

A facile and sensitive colorimetric detection for RNase A activity based on target regulated protection effect on plasmonic gold nanoparticles aggregation

In this work,a facile and sensitive colorimetric detection method was firstly reported for RNase A activity detection based on target regulated protection effect of chimeric DNA probe on the salt-induced aggregation of plasmonic gold nanoparticles.Compared with previous works of RNase A activity detection,this colorimetric assay integrated the advantages of sensitive,low cost,facile operation,rapid response and low biological toxicity.