基于Pt-Au-MoS2-ITO传感器对于H2O2的还原检测

实验探究了二硫化钼（MoS₂）作为一种新型材料与贵金属纳米粒子金（Au）、铂（Pt）的复合基底对于过氧化氢（H₂O₂）的还原性检测,采用氧化铟锡导电玻璃（ITO）作为电极,制备出了基于Pt-Au-MoS₂-ITO的生物传感器,为H₂O₂还原性检测的便携性操作打下了基础.实验采用电化学沉积的方法制备材料,同时使用循环伏安（CV）法、计时电流法等传统电化学手段表征了传感器电化学性能,采用场发射扫描电子显微镜（FE-SEM）来表征传感器表面形貌.建立了用于H₂O₂还原检测的、具有高检测限、高灵敏度和宽检测范围的传感器.     

Resistless photochemical etching of a silicon wafer by UV laser with an H<Superscript>2</Superscript>O<Superscript>2</Superscript> and HF aqueous solution

A new resistless etching method has been developed for Silicon wafers. This new method uses an aqueous solution consisting of hydrogen peroxide (H₂O₂) and hydrogen fluoride (HF) as the activating etchants. A 193 nm ArF excimer laser and a 266 nm fourth harmonic generation Nd: YAG laser were used as the photon sources. Results showed that pattern etching has been achieved without any photoresist film. In the case of the 193 nm laser, the optimal etching appeared at a 1.3 H₂O₂÷HF ratio, where an etch depth of 210 nm was achieved with a fluence of 29 mJ/cm² and shot number of 10000. At the same conditions, the etch depth with H₂O₂ and HF solution was three times of that by using H₂O and HF mixture. In the case of the 266 nm Nd: YAG laser, the optimal etching appeared at twice ratio of H₂O₂/HF, where the etch depth of 420 nm was achieved with a fluence of 12 mJ/cm² and shot number of 30000. Results showed that the etch effect of the 266 nm Nd: YAG laser was more desirable than that of the 193 nm ArF excimer laser.     

基于植酸锆/普鲁士蓝复合膜的电催化行为研究

通过层层自组装技术,构建植酸锆/普鲁士蓝(Zr-IP_6/PB)多层结构膜.基于普鲁士蓝(PB)对双氧水(H_2O_2)有很高的电催化性能,加之5层植酸锆/普鲁士蓝膜多孔结构有利于传质过程,该H_2O_2传感器具有高灵敏度和高选择性.实验结果显示:修饰电极对H_2O_2响应的物质的量浓度范围为2.00×10~(-5)～1.76×10~(-3) mol·L~(-1),线性相关系数R=0.998 9.     

铂微粒修饰固体石蜡碳糊电极对过氧化氢的电催化特征及分析应用

研究铂微粒修饰的固体石蜡碳糊电极(Pt-SCPE)对H2O2的电催化行为。在pH值4.6的柠檬酸盐-0.03 mol/L硝酸钾溶液中,用该电极H2O2在+0.18V(vs．SCE)可产生灵敏的还原电流,线性范围为1.0×10-1 mol/L～3.0×10-7 mol/L,检出限为7.5×10-8 mol/L。Pt-SCPE与液体石蜡碳糊电极比较,在峰电位、线性响应范围、检出限方面有更好的结果。用该电极测定样品中的过氧化氢,获得满意结果。     

Electrocatalytic oxidation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> at a carbon paste electrode modified with a nickel (II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(Diethylcarbamoylmethoxy) calix[4] arene complex and its application

Electrochemical behavior of a carbon paste electrode (CPE) modified with nickel(II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(diethylcarbamoylmethoxy) calix[4]arene (Ni (II)-L) complex and its electrocatalytic activity towards the oxidation of hydrogen peroxide were investigated by cyclic voltammetric technique in a 5.0×10⁻² mol/L NaClO₄+1.0×10⁻³ mol/L NaOH solution. It was found that Ni(II)-L acts as an effective catalyst for the oxidation of hydrogen peroxide. The modified electrode exhibited a linear response over a hydrogen peroxide concentrations in the range of 2.0×10⁻⁵−1.0×10⁻⁴ mol/L with a detection limit as low as 1.0×10⁻⁶ mol/L. The relative standard deviation was 3.5% for 5 successive determinations of H₂O₂ at 1.0×10⁻⁵ mol/L. The modified electrode was used successfully in rainwater analysis. Foundation item: Supported by the Natural Science Foundation of Hubei Province (98J040). Biography: Li Chun ya(1972-), Ph. D. candidate, research direction: electroanalysis and electrosynthesis.     

Near-infrared to visible up-conversion emissions of Er^3＋ doped Al2O3 powders derived from the sol-gel method

The Er3 doped Al2O3 powders were prepared by the sol-gel method using the aluminium isopropoxide [Al(OC3H7)3]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)3.5H2O]. The different phase structure, including three crystalline types of (Al,Er)2O3 phases, γ, θ, α, and two Er-Al-O phases, ErAlO3 and Al10Er6O24, was obtained with the 1 mol% Er3 doped Al2O3 powders at the different sintering temperatures of 600―1200℃. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the 2H11/2, 4S3/2→4I15/2 and 4F9/2→4I15/2 transitions of Er3 , were detected by a 978 nm semiconductor laser diodes excitation. The phase structure and OH content had evident influence on the up-conversion emissions intensity. The maximum intensities of both the green and red emissions were obtained respectively for the Er3 doped Al2O3 powders sintered at 1200 ℃, which was composed mainly of α-(Al,Er)2O3, less of ErAlO3 and Al10Er6O24 phases, and with the least OH content. The two-photon absorption up-conversion process was involved in the green and red up-conversion emissions of the Er3 doped Al2O3 powders.     

Li3O+超碱团簇的结构及储氢性能的理论研究

采用杂化密度泛函理论(DFT)的B3LYP方法,在6-311++G (d, p)基组水平上对Li₃O ^{0, +}超碱团簇的几何结构和稳定性进行理论计算,并研究了Li₃O⁺团簇的储氢性能。结果表明,Li₃O⁺团簇结构相比中性Li₃O团簇结构的动力学稳定性要高。氢分子在Li₃O⁺团簇表面能以介于物理吸附与化学吸附之间的形式吸附,每个Li原子最多可以有效吸附三个H₂,储氢质量分数可达33.01 wt%。H₂分子在Li₃O⁺团簇表面的平均吸附能范围为1.959~3.591 kCal/mol,该吸附能满足在近室温条件下可逆吸放氢反应的热力学要求。     

Mechanism of oxidative damage to DNA by Fe-loaded MCM-41 irradiated with visible light

The mechanism of oxidative damage to deoxyribonucleic acid (DNA) by iron-containing mesoporous molecular sieves (MCM-41) irradiated with visible light was elucidated. Fe-loaded MCM-41 (Fe/MCM-41) was used as a photocatalyst and the damage to calf thymus DNA caused by hydrogen peroxide (H2O2) was studied. The damage and extent of oxidation of DNA were measured by high-performance liquid chromatography (HPLC) and intermediate products were detected by HPLC/electrospray ionization tandem mass spectrometry. Electron spin resonance was used to detect changes in reactive oxygen species and peroxidase catalytic spectrophotometry was used to determine the concentration of H2O2. The results indicated that Fe/MCM-41 efficiently activated H2O2 in solution at pH 4.0-8.0 under irradiation with visible light. The photocatalytic system degraded DNA most effectively at pH 5.0-6.0 but also operated at pH 8.0. At pH 4.2, the degree of DNA damage reached 25.65% after 5 h and the kinetic constant was 5.89×10 2 min 1. Damage to DNA was predominantly caused by hydroxyl radicals generated in the system. The mechanism of DNA damage is of potential concern to human health because it can occur in neutral solutions irradiated by visible light.     

大枣多糖的提取与抗活性氧研究

为了分析大枣多糖对各类活性氧的清除能力,建立了热水提取-乙醇沉淀-氯仿、正丁醇去蛋白的工艺以提取大枣多糖(JPS),并作了糖的含量测定.用化学发光分析法分别测定提取的JPS对全血化学发光法中的全血白细胞呼吸爆发中产生的活性氧(H2O2、O2(-·)、·OH)、连苯三酚自氧化法产生的O2(-·)(超氧阴离子自由基)、抗坏血酸-Cu2+-H2O2体系产生的·OH(羟氧自由基)以及H2O2-鲁米诺发光体系中的H2O2的清除作用.结果:大枣多糖的得率为0.848%,总糖含量为37.7% .测定JPS清除·OH、O2(-·)、H2O2、白细胞呼吸爆发中产生的氧自由基活性的AOV值分别为109.48、9057.9 、312.01、5.204.结论:JPS具有清除氧自由基的作用,其活性大小与多糖的用量呈正相关.在全血生理环境下,对全血化学发光中活性氧的清除能力最强.     

Myoglobin as Mimetic Enzyme and Its Analytical Application in Determination of H2O2

0 IntroductionSltougdiiceasl csoynstceermnsin gharveeac btieveen o txhyeg ei nm psopretcaienst ( oRbjOecSt) iinn bbiioo--medicine and analytical chemistry in recent years[1-4]. Manyi mportant life phenomena and diseases are relatedtotheinter-mediates of ROS[5-7].ROS have beeni mplicated as ani mpor-tant causative factor in cell damage,including apoptosis andnecrosis . Their proposed actions comprise lipid peroxidation,DNAdamage,the mitochondrial respiratory chain destructionand protein mo…     

腐殖酸包覆Fe_3O_4纳米粒子类Fenton催化降解亚甲基蓝

采用共沉淀法制备腐殖酸包覆的磁性四氧化三铁纳米粒子(HA@Fe_3O_4)并将其用于类Fenton体系催化降解亚甲基蓝(MB).通过透射电子显微镜(TEM)、动态光散射(DLS)、X射线衍射仪(XRD)、傅里叶变换红外光谱(FT-IR)对样品的形貌、结构及成分进行表征.比较HA包覆前后Fe_3O_4纳米粒子的催化效果,考察HA@Fe_3O_4催化剂用量、H_2O_2浓度等因素对降解效率的影响.结果表明HA的包覆可以显著提高MB的降解效率.     

Supramolecular self-assembly of nickel (Ⅱ)-substituted α-Keggin-type polyoxometalate and polyaniline coated Fe2O3 hollow nanospindle for microwave absorption application

A general strategy has been developed here to supramolecular self-assembly of nickel (Ⅱ)-substituted α-Keggin-type polyoxometalate and polyaniline coated Fe₂O₃ hollow nanospindle (Fe₂O₃ hollow nanospindle@PANI/α-SiW₁₁Ni composites) via electrostatic attraction and hydrothermal method. Fe³⁺ was first hydrolyzed and polymerized into Fe₂O₃, then dissolved into [Fe(H₂PO₄)_x]^3?x, resulting in hollow structure. The polyoxometalate existed in polyaniline as a proton-doped counter-ion form, rather than as a separate crystalline state. The protons and anions entered the PANI main chain and combined with N atoms of amines and imines on the PANI chain ((-NH^?+ ?= ?)/α-[SiW₁₁Ni(H₂O)O₃₉]^6-) to form poles and bipolar delocalization into π bonds of the whole polyaniline molecular chain, which leaded to conductance and polarization. The Fe₂O₃ hollow nanospindle@PANI/α-SiW₁₁Ni composites were proven to be excellent microwave absorber in terms of reflection loss (R_L) and bandwidth. The maximum R_L value was up to ?53.6 ?dB at 3.5 ?mm and 6.9 ?GHz. The broadest absorption bandwidth exceeding ?10 dB was 6.3 ?GHz at a thickness of only 1.9 ?mm. Moreover, the ternary composites presented obvious multi-band absorption with the matching thickness range of 1.5–5 ?mm. The absorption peaks bandwidth reached as wide as 14.3 ?GHz, which included all C-Ku bands. The hollow and core-shell structures could provide non-uniform interface for the induced polarization loss and space for the reflecting and scattering of microwave. The carrier, pair-ion carrier and hydrogen bond network could lead to conduction loss. The magnetic losses were caused by eddy current effect and natural resonance. This work can lay a theoretical foundation for the design and performance regulation of new absorbing materials.     

Involvement of NADPH oxidase NtrbohD in the rapid production of H2O2 induced by ABA in cultured tobacco cell line BY-2

The mechanisms for the production of hydrogen peroxide (H₂O₂) induced by abscisic acid (ABA) were investigated in suspension culture cells of tobacco BY-2 cells. The results showed that the immediate generation of H₂O₂, which was mainly derived from superoxide dismutase-catalyzed dismutation of superoxide radical, was significantly induced by ABA. Furthermore, treatment of the cultured tobacco cells with ABA resulted in a time-dependent quick increase in plasma membrane (PM) NADPH oxidase activity, which coincided on time and magnitude with the elevation in ABA-induced accumulation of H₂O₂. Moreover, these enhanced effects were pronouncedly inhibited by two NADPH oxidase inhibitor, diphenylene iodonium and imidazole, suggesting that PM NADPH oxidase is involved in the rapid accumulation of ₂O₂ in cultured tobacco cells. In addition, analysis of the expression level of NtrbohD, a PM NADPH oxidase gene in tobacco, by RT-PCR and protein gel blot revealed that the gene at both mRNA and protein levels was upregulated by ABA, indicating that NtrbohD participates in the ABA-stimulated rapid production of H₂O₂ in tobacco culture cells. Taken together, these findings suggest that ABA induces the rapid accumulation of reactive oxygen species via NADPH oxidase in suspension culture cells of tobacco, and that NADPH oxidase and H₂O₂ appear to be important components in ABA signal transduction pathway in plants.     

Involvement of NADPH oxidase NtrbohD in the rapid production of H2O2 induced by ABA in cultured tobacco cell line BY-2

The mechanisms for the production of hydrogen peroxide (H₂O₂) induced by abscisic acid (ABA) were investigated in suspension culture cells of tobacco BY-2 cells. The results showed that the immediate generation of H₂O₂, which was mainly derived from superoxide dismutase-catalyzed dismutation of superoxide radical, was significantly induced by ABA. Furthermore, treatment of the cultured tobacco cells with ABA resulted in a time-dependent quick increase in plasma membrane (PM) NADPH oxidase activity, which coincided on time and magnitude with the elevation in ABA-induced accumulation of H₂O₂. Moreover, these enhanced effects were pronouncedly inhibited by two NADPH oxidase inhibitor, diphenylene iodonium and imidazole, suggesting that PM NADPH oxidase is involved in the rapid accumulation of ₂O₂ in cultured tobacco cells. In addition, analysis of the expression level of NtrbohD, a PM NADPH oxidase gene in tobacco, by RT-PCR and protein gel blot revealed that the gene at both mRNA and protein levels was upregulated by ABA, indicating that NtrbohD participates in the ABA-stimulated rapid production of H₂O₂ in tobacco culture cells. Taken together, these findings suggest that ABA induces the rapid accumulation of reactive oxygen species via NADPH oxidase in suspension culture cells of tobacco, and that NADPH oxidase and H₂O₂ appear to be important components in ABA signal transduction pathway in plants.     

Use of ionic liquid in leaching process of brass wastes for copper and zinc recovery

Brass ash from the industrial brass manufacturer in Turkey was leached using the solutions of ionic liquid (IL) 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO₄) at ambient pressure in the presence of hydrogen peroxide (H₂O₂) and potassium peroxymonosulfate (oxone) as the oxidants. Parameters affecting leaching efficiency, such as dissolution time, IL concentration, and oxidizing agent addition, were investigated. The results show that [bmim]HSO₄ is an efficient IL for the brass ash leaching, providing the dissolution efficiencies of 99% for Zn and 24.82% for Cu at a concentration of 50vol% [bmim]HSO₄ in the aqueous solution without any oxidant. However, more than 99% of zinc and 82% of copper are leached by the addition of 50vol% H₂O₂ to the [bmim]HSO₄ solution. Nevertheless, the oxone does not show the promising oxidant behavior in leaching using [bmim]HSO₄.     

CNa42+团簇的结构及其储氢性能研究

氢是一种理想的二次能源,它将成为化石燃料最有希望的替代能源之一,也是亟待开发的重要能源。而氢能的储存成本高,危险性大是急需解决的问题。理论上预测CNa_4~(2+)的储氢性能,通过理论分析,发现了每个CNa_4~(2+)团簇最多可与16个H2分子有效结合,获得23.5%的质量储氢密度。在B3LYP理论水平上,H2分子与CNa_4~(2+)团簇的平均相互作用能在2.107～4.948Kcal/mol之间。由于CNa_4~(2+)的质量储氢密度在7.1～23.7wt%之间,符合美国能源部的要求目标(5.5 wt%)。研究结果表明,CNa_4~(2+)在一定环境条件下可逆吸放氢性能良好,可作为潜在的理想高容量储氢材料。     

基于化学动力学疗法的联合治疗在肿瘤中的研究进展

由于肿瘤微环境(TME)的复杂性,单一的治疗策略难以有效地消除肿瘤,因此需要多种方法以克服单一治疗策略的缺陷.化学动力学疗法(CDT)是一种新兴的癌症治疗策略,通过芬顿或类芬顿反应,将内源性过氧化氢(H₂O₂)转化为羟基自由基(·OH)杀死癌细胞.该治疗方法因其侵袭性小、肿瘤特异性高而受到广泛研究.但是,温和的酸性pH值、低H₂O₂含量,以及TME中过表达的还原物质严重抑制了CDT效率.因此,基于CDT的联合治疗策略得到了广泛的发展.文章对近年来CDT联合治疗策略进行了概述,并对其进行了展望.     

铜基纳米材料在增强化学动力学治疗上的应用研究

和传统治疗相比,化学动力学治疗(CDT)被认为是一种低副作用且无创的治疗方法,在众多的治疗方法中脱颖而出.CDT通过金属离子介导的芬顿反应或类芬顿反应,将肿瘤中过表达的过氧化氢(H2O2)分解为剧毒的羟基自由基(·OH),从而杀死肿瘤细胞.近年来,铜基纳米材料在CDT中蓬勃发展,极大地提高了CDT的效率.因此,基于铜基...     

微波辅助H2O2复配体系脱除煤中硫分研究

为研究微波辅助H₂O₂复配体系脱除煤中硫分的效果,选取宁夏宁东地区鸳鸯湖煤样作为研究对象。分别用柠檬酸和氢氧化钠与过氧化氢复配作用于煤样,通过微波辐照处理,微波辐照功率为900 W,辐照时间为5 min。结果表明：单独过氧化氢处理后脱硫率为34.29%,过氧化氢–柠檬酸和过氧化氢–氢氧化钠复配体系最大脱硫率分别高达43.67%和45.31%,且脱硫过程大部分硫铁矿硫被脱除,煤中硫形态逐渐向高价态转化,原煤中的噻吩被部分转化为亚砜、砜和硫酸盐硫;微波辅助复配助剂处理后可以增大煤样与助剂的接触面积,提高羟基自由基与煤中含硫基团接触的可能性,从而提高脱硫率。     

氯过氧化物酶与苯酚降解菌株的协同降解动力学研究

氯过氧化物酶(CPO)催化苯酚与H_2O_2发生过氧化反应生成邻苯二酚,能减轻苯酚对降解菌株的抑制作用,加快降解菌株对苯酚的生物降解.实验结果表明:在2 h内适量的H2O2存在时10 U/L的CPO可以使300 mg/L苯酚降解率达到67.85%,而CPO与降解菌株协同作用下苯酚降解率则可达到70.72%,比单一菌株降解率8.52%提高了62.2%.在降解体系中补充邻苯二酚进一步揭示了CPO氧化苯酚的中间产物有利于菌体细胞形成共基质效应,提高细胞的苯酚生物降解效率.降解动力学分析显示:在苯酚质量浓度为100~1 200 mg/L时,CPO与菌株协同降解体系的最大比降解速率qmax=0.000195 h-1,基质饱和常数Ks=1.0501 mg/L,基质抑制常数KI=5.1272 mg/L.