Department of Chemistry, Faculty of Sciences and Technology, University of Coimbra, 3004-535, Coimbra, Portugal.
Anal Bioanal Chem. 2020 Sep;412(24):6381-6389. doi: 10.1007/s00216-020-02591-y. Epub 2020 Apr 8.
Lercanidipine, a third-generation dihydropyridine calcium L-type channel blocker, redox behavior at different carbon electrode materials, in a wide pH range, using cyclic, square-wave, and differential pulse voltammetry, was studied. A comparison was made between unmodified glassy carbon electrode (GCE) and boron-doped diamond electrode (BDDE), and GCE and BDDE modified with a carbon black (CB) nanoparticle embedded within a dihexadecylphosphate (DHP) nanostructured film (CB-DHP/GCE and CB-DHP/BDDE). Lercanidipine oxidation, for 3.4 < pH < 9.5, is an irreversible, diffusion-controlled, pH-dependent process that occurs in two consecutive steps, with the transfer of one electron and one proton, at the N1 and C4 positions in the 1,4-dihydropyridine ring. For pH > 9.5, both oxidation processes are pH-independent and a pKa = 9.40 was determined. Lercanidipine reduction at pH = 7.0 is an irreversible process, and the lercanidipine reduction products are electroactive and follow a reversible electron transfer reaction. Lercanidipine electroanalytical determination, at a nanostructured GCE modified with a CB-DHP film (CB-DHP/GCE), with no need for N2 purging, with a detection limit of 0.058 μM (3.58 × 10 g L) and a quantification limit of 0.176 μM (1.08 × 10 g L), was achieved. Graphical abstract.
乐卡地平是第三代二氢吡啶钙 L 型通道阻滞剂,在不同碳电极材料、宽 pH 范围内,使用循环伏安法、方波伏安法和差分脉冲伏安法研究了其氧化还原行为。比较了未修饰的玻碳电极(GCE)和掺硼金刚石电极(BDDE)、以及修饰有嵌入二己基磷酸(DHP)纳米结构膜中的碳黑(CB)纳米颗粒的 GCE 和 BDDE(CB-DHP/GCE 和 CB-DHP/BDDE)。3.4 < pH < 9.5 时,乐卡地平氧化是一个不可逆的、扩散控制的、依赖于 pH 的过程,发生在 1,4-二氢吡啶环的 N1 和 C4 位置,经历两个连续步骤,转移一个电子和一个质子。对于 pH > 9.5,两个氧化过程都与 pH 无关,确定了 pKa = 9.40。在 pH = 7.0 时,乐卡地平还原是一个不可逆过程,乐卡地平还原产物是电活性的,遵循可逆的电子转移反应。在未进行 N2 吹扫的情况下,使用修饰有 CB-DHP 膜的纳米结构化 GCE(CB-DHP/GCE)进行乐卡地平电分析测定,检测限为 0.058 μM(3.58 × 10 -6 g L -1),定量限为 0.176 μM(1.08 × 10 -6 g L -1)。