Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, Brazil.
Phys Chem Chem Phys. 2011 Jul 14;13(26):12155-62. doi: 10.1039/c1cp20432g. Epub 2011 Jun 3.
This paper presents studies about the molecular interactions and redox processes involved in the formation of palladium nanoparticles associated to glucose oxidase (GOx-PdNPs) in a supramolecular arrangement. The synthesis occurs in two steps, the Pd reduction and the formation of the 80 nm sized supramolecular aggregates containing multiples units of GOx associated to 3.5 nm sized PdNPs. During synthesis, GOx molecules interact with Pd salt leading to metal ion and FAD reduction probably via the thiol group of the cysteine 521 residue. For the growing of PdNPs, formic acid was necessary as a co-adjuvant reducing agent. Besides the contribution for the redox processes, GOx is also necessary for the NP stability preventing the formation of precipitates resulted from uncontrolled growing of NPs Cyclic voltammetry of the GOx-PdNPs demonstrated electroactivity of the bionanocomposite immobilized on ITO (indium-tin oxide) electrode surface and also the NP is partially blocked due to strong interaction GOx and the surface of PdNPs. Vibrational spectroscopy (FTIR) showed that significant structural changes occurred in GOx after the association to PdNP. These mechanistics and structural studies can contribute for modulation of bionanocomposites properties.
本文研究了在超分子排列中形成与葡萄糖氧化酶(GOx-PdNPs)结合的钯纳米粒子的分子相互作用和氧化还原过程。合成分两步进行,Pd 还原和形成包含多个与 3.5nm 大小的 PdNPs 结合的 GOx 单元的 80nm 大小的超分子聚集体。在合成过程中,GOx 分子与 Pd 盐相互作用,导致金属离子和 FAD 还原,可能通过半胱氨酸 521 残基的巯基。对于 PdNPs 的生长,需要甲酸作为共辅助还原剂。除了对氧化还原过程的贡献外,GOx 对于 NP 的稳定性也是必需的,防止由于 NPs 的不受控制的生长而形成沉淀。GOx-PdNPs 的循环伏安法证明了固定在 ITO(氧化铟锡)电极表面的生物纳米复合材料的电活性,并且由于 GOx 和 PdNPs 表面之间的强烈相互作用,NP 部分被阻断。振动光谱(FTIR)表明,GOx 在与 PdNP 结合后发生了显著的结构变化。这些机理和结构研究可以为生物纳米复合材料性能的调制做出贡献。