Synthesis and Characterization of Ferrocene Derivatives and Preliminarily Electrocatalytic Oxidation of L-Cysteine at Nafion-Ferrocene Derivatives Modified Glassy Carbon Electrode
Five new structural ferrocene derivatives (2a~2e) were firstly synthesized and characterized by 1H NMR, 13C NMR, ESI-MS, and XRD. Subsequently, the preliminarily electrocatalytic oxidation of L-cysteine (L-Cys) at nafion-ferrocene derivatives modified glassy carbon electrode (GCE) has also been investigated by cyclic voltammetry. The results showed that 2e can dramatically electrocatalyze the oxidation of L-cysteine at its modified GCE in 0.1？mol L？1 NaNO3 aqueous solution with a quasireversible process with ？mV. 1. Introduction Ferrocene derivatives have attracted considerable attention for their potential applications as nonlinear optical devices, functional materials in electrochemical sensor [1–4], and chiral catalysts [5–7]. In addition, ferrocene derivatives have also attracted wide interest for their considerably biological activities [8–15]. For example, the ferroquine (FQ, SSR97193, Figure 1) is about to complete phase II clinical trials as a treatment for uncomplicated malaria [16]. Figure 1 L-Cysteine (L-Cys) plays a crucial role in both bio- and environmental chemistry and can be applied in many biochemical processes and diagnosis of disease states. Especially, L-Cys provides a modality for the intramolecular crosslinking of proteins through disulfide bonds to support their secondary structures and functions. Therefore, it is very important to develop simple and effective methods to trace L-Cys detection. Many methods, such as spectrometric method [17], chromatography [18], and electrochemical method [19–23], have been used to detect the trace content of L-Cys. However, electrochemical method has attracted considerable attention for simple operation, fast response, and sensitive in situ detection. The oxidation of L-Cys at Hg, Au, Ag, Pt, and diamond electrodes has been reported [24–27]. However, the direct oxidation of L-Cys at GCE is very sluggish. Ferrocene derivatives have been used as the selective probes for detecting the trace ions, biomacromolecules [28–32]. Nafion is a special material, which possesses widespread applications in the field of electrochemistry analysis, chemical sensor, and nanomaterials [33, 34]. According to our survey, no electrocatalytic oxidation of L-Cys at the nafion-ferrocene derivatives modified GCE has been reported. In this work, five new structural ferrocene derivatives (2a~2e) (Scheme 1) were firstly synthesized and then confirmed by IR, 1H NMR, 13C NMR, MS, and XRD. Subsequently, their preliminarily electrocatalytic oxidation of L-Cys at the nafion-ferrocene derivatives modified GCE has also been
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