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Catalytic Degradation of Organophosphate Esters Using Gold Nanoparticles, Supported Copper(II) Bipyridine Complexes and Plasmonics.

机译:使用金纳米粒子,负载的铜(II)联吡啶配合物和等离子的催化降解有机磷酸酯。

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摘要

Weapons of mass destruction are often comprised of various types of phosphate esters that mimic critical endogenous biological molecules, thereby blocking essential functions, such as heartbeat. It is, therefore, of utmost importance to design systems that degrade phosphate esters as countermeasure for such chemical and biological weapons. An investigation into the unique properties of gold nanoparticles (AuNPs) has shown that gold surfaces can be used for control of the catalytic hydrolysis of phosphate esters under low-power laser irradiation. Using Michaelis-Menten formalism to determine catalytic rate constants, citrate stabilized gold nanoparticles catalyze the hydrolysis of methyl parathion (MeP) with kcat = 1.8 +/- 0.2 x 10-4 s -1 at pH 8.1. Additionally, the AuNP supported copper(II) complex Cu[(N-(6-mercaptohexyl)-2,2'-bipyridinyl-5-carboxamide)]Cl 2 (1) enhances the activity of MeP by 90-fold ( kcat = 1.2 +/- 0.3 x 10-5 s -1) compared to the unattached Cu(II) bipyridine complex. Laser irradiation (300 mW, 532 nm) of 1/AuNPs results in a 12-fold enhancement for MeP hydrolysis (kcat = 4.3 +/- 2 x 10 -4) and a 1000-fold enhancement for BNPP hydrolysis (k cat = 1.3 +/- 0.06 x 10-4). The ability to influence homogeneous catalytic reactions using plasmonics is an important step towards the development of new catalytic reactions.
机译:大规模杀伤性武器通常由各种类型的磷酸酯组成,这些磷酸酯模拟关键的内源性生物分子,从而阻碍了诸如心跳等基本功能。因此,设计降解磷酸酯的系统作为此类化学和生物武器的对策至关重要。对金纳米颗粒(AuNPs)独特性能的研究表明,金表面可用于控制低功率激光辐照下磷酸酯的催化水解。使用Michaelis-Menten形式主义确定催化速率常数,柠檬酸盐稳定的金纳米颗粒在pH 8.1时kcat = 1.8 +/- 0.2 x 10-4 s -1催化甲基对硫磷(MeP)的水解。此外,AuNP负载的铜(II)络合物Cu [(N-(6-巯基己基)-2,2'-联吡啶基-5-羧酰胺)] Cl 2(1)将MeP的活性提高90倍(kcat =与未连接的Cu(II)联吡啶配合物相比,可达到1.2 +/- 0.3 x 10-5 s -1)。 1 / AuNPs的激光照射(300 mW,532 nm)导致MeP水解增强12倍(kcat = 4.3 +/- 2 x 10 -4)和BNPP水解增强1000倍(k cat = 1.3 +/- 0.06 x 10-4)。使用等离激元影响均相催化反应的能力是开发新催化反应的重要一步。

著录项

  • 作者

    Nita, Rafaela.;

  • 作者单位

    Florida Institute of Technology.;

  • 授予单位 Florida Institute of Technology.;
  • 学科 Chemistry.
  • 学位 Ph.D.
  • 年度 2016
  • 页码 187 p.
  • 总页数 187
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 农学(农艺学);
  • 关键词

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