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生物氧化剂与硒脲的反应:氧化还原活性纳米硒的形成。

Reactions of biological oxidants with selenourea: formation of redox active nanoselenium.

作者信息

Mishra B, Hassan P A, Priyadarsini K I, Mohan Hari

机构信息

Radiation Chemistry and Chemical Dynamics Division and Novel Materials and Structural Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India.

出版信息

J Phys Chem B. 2005 Jul 7;109(26):12718-23. doi: 10.1021/jp051328n.

Abstract

Reactions of biological oxidizing agents, such as hydroxyl radicals (()OH), singlet oxygen ((1)O(2)), hydrogen peroxide (H(2)O(2)), and peroxynitrite (ONOO(-)) with selenourea were studied. The kinetics of the reactions was followed using time-resolved techniques, and the bimolecular rate constants were determined. In all these reactions, under aerated conditions, elemental red selenium was produced as one of the reaction products. The average size of the selenium particles could be controlled and stabilized in the range of 20-100 nm with the addition of bovine serum albumin (BSA) or sodium dodecyl sulfate (SDS). The particles were characterized by dynamic light scattering studies (DLS), which revealed that the size and distribution of the particles depended mainly on the amount of selenourea undergoing oxidation. Other factors such as the nature of the oxidant and the concentration of the stabilizer also are important in stabilizing the particles. Nanoselenium-reduced ABTS(-) to colorless ABTS(2-) (ABTS = 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) and oxidized dichlorodihydrofluoresecein diacetate (DCFA) to fluorescent dichlorofluorescein (DCF) indicating its ability to participate in redox and free radical reactions. The reactivity of selenium nanoparticles with these systems varied linearly with the surface area of the particles. The studies demonstrate that selenourea undergoes oxidation with both one-electron and two-electron oxidants to produce elemental selenium, which, on stabilization to nanometer size, exhibits size-dependent redox activity.

摘要

研究了生物氧化剂如羟基自由基(·OH)、单线态氧(¹O₂)、过氧化氢(H₂O₂)和过氧亚硝酸盐(ONOO⁻)与硒脲的反应。采用时间分辨技术跟踪反应动力学,并测定了双分子速率常数。在所有这些反应中,在曝气条件下,元素态红色硒作为反应产物之一生成。通过添加牛血清白蛋白(BSA)或十二烷基硫酸钠(SDS),可以将硒颗粒的平均尺寸控制并稳定在20 - 100 nm范围内。通过动态光散射研究(DLS)对颗粒进行了表征,结果表明颗粒的尺寸和分布主要取决于发生氧化的硒脲的量。其他因素如氧化剂的性质和稳定剂的浓度在稳定颗粒方面也很重要。纳米硒将ABTS⁻还原为无色的ABTS²⁻(ABTS = 2,2'-偶氮双(3-乙基苯并噻唑啉-6-磺酸盐)),并将二氯二氢荧光素二乙酸酯(DCFA)氧化为荧光二氯荧光素(DCF),表明其参与氧化还原和自由基反应的能力。硒纳米颗粒与这些体系的反应活性与颗粒的表面积呈线性变化。研究表明,硒脲与单电子和双电子氧化剂均发生氧化反应生成元素硒,当稳定到纳米尺寸时,表现出尺寸依赖性的氧化还原活性。

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