环境友好氧化剂催化氧化合成己二酸研究进展

综述了以环境友好的氧气(或空气)和过氧化氢为氧化剂催化氧化法合成己二酸的研究进展,并介绍了目前正在开发的生物催化法合成己二酸的新工艺。

DNA加合物8-羟基脱氧鸟苷特性研究

作为DNA氧化损伤的生物学标志物,8-羟基脱氧鸟苷(8-OH-dG)的特性研究,对稳定、灵敏、准确地定量8-OH-dG,进而研究有毒化学物质对生物体内的氧化损伤很重要。该文研究了氧化损伤后DNA中8-OH-dG的分析、水解、储存、稳定性等方面的问题。采用Fenton型产羟自由基系统如螯合剂Fe2+-H2O2为氧化源,与脱氧鸟苷和小牛胸腺DNA反应,生成的8-OH-dG用高压液相色谱-电化学法检测,并对8-OH-dG的分析条件进行优化。该法最低检出限为32fmol,比光学吸收法高2～3个数量级,线性范围可高达4个数量级,从0.32pmol到3.2nmol,相关系数0.9996。并对酶水解DNA的条件、储存酸度、介质环境及其稳定性等进行了探讨,结果表明8-OH-dG储存在中性偏酸的缓冲溶液中损失较少,其形成与所处介质环境有关,在氧化源存在或有氧环境中一定时间内有累积作用,添加抗氧化剂等干预措施后,能灵敏而稳定地对DNA中的8-OH-dG进行测定。

Degradation of chlorophenol by in－situ electrochemically generated oxidant

A novel in-situ electrochemical oxidation method was applied to the degradation of wastewater containing chlorophenol. Under oxygen sparging, the strong oxidant, hydrogen dioxide, could be in-situ generated through the reduction of oxygen on the surface of the cathode. The removal rate ofchlorophenol could be increased 149% when oxygen was induced in the electrochemical cell. The promotion factor was estimated to be about 82.63% according to the pseudo-first-order reaction rate constant (min^-1). Important operating parameters such as current density, sparged oxygen rate were investigated. Higher sparged oxygen rate could improve the degradation of chlorophenol. To make full use of oxygen, however, sparged oxygen rate of 0.05 m3/h was adopted in this work. Oxidation-reduction potential could remarkably affect the generation of hydrogen peroxide. It was found that the removal rate of chlorophenol was not in direct proportion to the applied current density. The optimum current density was 3.5 mA/cm^2 when initial chlorophenol concentration was 100 mg/L and sparged oxygen rate was 0.05 m^3/h.

Commercial indium-tin oxide glass:A catalyst electrode for efficient N_(2)reduction at ambient conditions

The typical Haber technical process for industrial NH_(3)production involves plenty of energy-consumption and large quantities of greenhouse gas emission.In contrast,electrochemical N_(2)reduction proffers environment-friendly and energy-efficient avenues to synthesize NH_(3)at mild conditions but demands efficient electrocatalysts for the N_(2)reduction reaction(NRR).Herein we report for the first time that commercial indium-tin oxide glass(ITO/G)can be used as a catalyst electrode toward artificial N_(2)fixation,as it demonstrates excellent selectivity at mild conditions.Such ITO/G delivers excellent NRR performance with a NH_(3)yield of 1.06×10^(-10) mol s^(-1) cm^(-2) and a faradaic efficiency of 6.17%at-0.40 V versus the reversible hydrogen electrode(RHE)in 0.5 M LiClO4.Furthermore,the ITO/G also possesses good electrochemical stability and durability.Finally,the possible reaction mechanism for the NRR on the ITO catalysts was explored using first-principles calculations.

Redox physiology in animal function:The struggle of living in an oxidant environment

A strong focus of ecological research for several decades has been to understand the factors underlying the variation in animal life-histories. In recent times, ecological studies have begun to show that oxidative stress may represent another important modulator of competitive trade-offs among fitness traits or of positively integrated patterns of traits. Therefore, incorporating mechanisms underlying oxidative physiology into evolutionary ecology has the potential to help understand variation in life-history strategies. In this review, I provide a general overview of oxidative stress physiology, and subsequently focus on topics that have been neglected in previous ecological reviews on oxidative stress. Specifically, I introduce and discuss the adaptations that animals have evolved to cope with oxidative stress; the environmental stressors that can generate changes in oxidative balance; the role of reactive species in transduction of environmental stimuli and cell signaling; and the range of hormetic responses to oxidative stress [Current Zoology 56 （6）： 687-702, 2010].

Theoretical insight into methanol steam reforming on indium oxide with different coordination environments

Indium oxide(In_2O_3) has demonstrated to be an effective non-noble metal catalyst for methanol steam reforming reaction(MSR).However, the reaction mechanism of MSR and crucial structure-activity relations determining the catalytic performance of In_2O_3 are still not fully understood yet. Using density functional theory(DFT) calculation, we systematically investigate the MSR process over a high-index In_2O_3(211) and a favoured catalytic cycle of MSR is determined. The results show that In_2O_3(211) possesses excellent dehydrogenation and oxidizing ability, on which CH_3 OH can readily adsorb on the In4 c site and be easily activated by the reactive lattice oxygens, resulting in a total oxidation into CO_2 rather than CO, while the H_2 formation through surface H–H coupling limits the overall MSR activity because of the strong H adsorption on the two-coordinated lattice O(O_(2c)). Our analyses show that the relatively inert three-coordinated lattice O(O_(3c)) could play an important catalytic role. To uncover the influence of the local coordination of surface In atoms and lattice O on the catalytic activity, we evaluate the activity trend of several types of In_2O_3 surfaces including(211),(111), and(100) by examining the rate-limiting, which reveals the following activity order:(211)>(111)>(100). These findings provide an in-depth understanding on the MSR reaction mechanism over In_2O_3 catalysts and some basic structure-activity relations at the atomic scale, could facilitate the rational design of In_2O_3-based catalysts for MSR by controlling the local coordination environment of surface active sites.

Meta-analysis reveals that reproductive strategies are associated with sexual differences in oxidative balance across vertebrates

Oxidative stress is a key physiological mechanism underlying life-history tradeoffs. Here, I use meta-analytic techniques to test whether sexual differences in oxidative balance are common in vertebrates and to identify which factors are associated with such differences. The dataset included 732 effect size estimates from 100 articles （82 species）. Larger unsigned effect size （meaning larger sexual differences in a given marker） occurred in： reptiles and fish; those species that do not pro- vide parental care; and oviparous species. Estimates of signed effect size （positive values meaning higher oxidative stress in males） indicated that females were less resistant to oxidative stress than males in： reptiles while males and females were similar in fish, birds, and mammals; those species that do not provide parental care; and oviparous species. There was no evidence for a significant sexual differentiation in oxidative balance in fish, birds, and mammals. Effect size was not associ- ated with： the number of offspring; whether the experimental animals were reproducing or not; biomarker （oxidative damage, non-enzymatic, or enzymatic antioxidant）, the species body mass; the strain （wild vs. domestic）; or the study environment （wild vs. captivity）. Oxidative stress tended to be higher in females than males across most of the tissues analyzed. Levels of residual heterogeneity were high in all models tested. The findings of this meta-analysis indicate that diversification of reproductive strategies might be associated with sexual differences in oxidative balance. This explorative meta-analysis offers a starting platform for future research to investigate the rela-tionship between sex and oxidative balance further.

Recent advances on silica-based nanostructures in photocatalysis

Development of highly efficient photocatalysts has emerged as a research hotspot because of their crucial role in affecting the conversion efficiency of solar energy for applications in resource exploitation and environmental purification.The photocatalytic performance of the photocatalysts basically depends on the behaviors of light absorption,charge generation and separation,surface property and structural stability.Owing to its unique advantages(high surface area,tunable porosity,modifiable surface),porous silica provides an interesting platform to construct well-defined nanostructures such as core-shell,yolk-shell and other specific structures which effectively improved one or more of the above behaviors for photocatalysis.Typically,the structure with hollow morphology favors the light scattering and enlargement of surface area,while coating or binding with silica can modify the surface property of a photocatalyst to enhance the surface adsorption of reactants and physicochemical stability of catalysts.This review discusses the recent advances in the design,synthesis,formation mechanism of well-defined silica-based nanostructures,and the achievements of desired physicochemical properties for regulating the photocatalytic performance.

The dual role of hydrogen peroxide in fuel cells

Clean and highly efficient energy production has long been sought after, as a way to solve global energy and environmental problems. Fuel cells, which convert the chemical energy stored in fuel directly into electricity, are expected to be a key enabling technology for the pressing energy issues that plague our planet. Fuel cells require oxygen as an oxidant and require oxygen tank containers when used in air-free environments such as outer space and underwater. Hydrogen peroxide has been extensively uti- lized as an alternative liquid oxidant in place of gaseous oxygen. In addition to being an oxidant, hydrogen peroxide can donate electrons in the oxidation reaction to act as a fuel. This article provides an overview of the dual role of hydrogen peroxide in fuel-cell applications, including working principle, system design, and cell performance. Recent innovations and future perspectives of fuel cells that use hydrogen peroxide are particularly emphasized.