Department of Chemistry and Biochemistry, University of South Carolina , 631 Sumter Street, Columbia, South Carolina 29208, United States.
Department of Chemistry, Wayne State University , 5101 Cass Avenue, Detroit, Michigan 48202, United States.
Anal Chem. 2016 Aug 2;88(15):7603-8. doi: 10.1021/acs.analchem.6b01312. Epub 2016 Jul 18.
Aqueous metal behavior is strongly regulated by speciation, which in turn is highly dependent on complexation. Trace metal complexation is difficult to characterize in dynamically changing systems due to a lack of analytical methods that can rapidly report free-metal concentrations. In this paper, we perform proof-of-principle experiments that demonstrate the utility of fast-scan cyclic voltammetry (FSCV) for providing speciation information in real-time by characterizing dynamic Cu(II) binding. We study Cu(II) FSCV responses in 3-(N-morpholino)propanesulfonic acid (MOPS) buffer and characterize the hydrodynamic aspects of our experimental setup (continuously stirred tank reactor). We observe Cu(II) complexation in real-time using five ligands with differing formation constants of Cu(II) complexation. Finally, we utilize geochemical models to fit our real-time experimental Cu(II)-binding curves. Our proof-of-principle experiments show that FSCV is a powerful tool for studying real-time Cu(II) complexation, which is essential speciation information for better interpretation of Cu(II) behavior in dynamically changing systems, such as those encountered in biology or the environment.
水相金属行为受形态(speciation)强烈调控,而形态又高度依赖于配位作用。痕量金属的配位作用在动态变化的系统中很难被描述,因为缺乏能够快速报告游离金属浓度的分析方法。在本文中,我们进行了原理验证实验,通过对动态 Cu(II) 结合作用的特征描述,展示了快速扫描循环伏安法(FSCV)实时提供形态信息的实用性。我们在 3-(N-吗啉基)丙磺酸(MOPS)缓冲液中研究了 Cu(II) 的 FSCV 响应,并对我们的实验装置(连续搅拌釜式反应器)的流体动力学方面进行了特征描述。我们使用五个具有不同 Cu(II) 配位形成常数的配体,实时观察 Cu(II) 的配位作用。最后,我们利用地球化学模型拟合我们的实时实验 Cu(II)-结合曲线。我们的原理验证实验表明,FSCV 是研究实时 Cu(II) 配位作用的有力工具,这是更好地解释动态变化系统中 Cu(II) 行为所必需的形态信息,这些系统在生物学或环境中经常遇到。