Abstract In this work, carbon paste electrode (CPE) and carbon paste electrode modified with gold nanoparticles (AuNPs/CPE) were employed with rapid direct anodic square wave voltammetry (SWV) for macrolide antibiotics erythromycin ethylsuccinate (EES), azithromycin (AZI), clarithromycin (CLA) and roxithromycin (ROX) determination. The surface of working electrodes was morphologically characterized by scanning electron microscopic (SEM) measurements whereby the presence of randomly distributed AuNPs of 10 nm diameter size on CPE surface was confirmed by energy dispersive spectrometer (EDS). SWV determination of four macrolide antibiotics using CPE was performed in aqueous Britton-Robinson buffer solutions (pH 2.0 to 11.98) showing that oxidation signals strongly depend upon pH (at pH ≥ 6) and exhibited the most favorable characteristics at pH 8.0 in the case of EES and pH 11.98 in the case of AZI, CLA and ROX. Under optimized conditions, the SWV method using CPE enables determination of all investigated macrolide antibiotics in low μg mL−1 concentration ranges with relative standard deviations (RSDs) lower than 6% and achieved detection limits (LODs) as 0.18, 0.045, 1.43 and 0.30 μg mL−1 for EES, AZI, CLA and ROX, respectively. In the case of AZI and ROX, it was demonstrated that the use of AuNPs/CPE as working electrode could additionally improve the results obtained with the SWV method concerning exhibited sensitivity, reproducibility and linear concentration range, due to the electrocatalytic properties of synthesized AuNPs. The optimized experimental parameters with the use of SWV method and CPE or AuNPs/CPE were successfully applied for determination of ROX and AZI in their pharmaceutical preparations Runac® and Hemomycin®, respectively. The reliability of the elaborated procedures and thus the accuracy of the obtained results were validated by comparing them with those obtained by means of HPLC-DAD measurements.

中文翻译：

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使用碳糊电极和金纳米粒子修饰作为标准和药物制剂中选定的大环内酯类抗生素测定

摘要 在这项工作中，采用快速直接阳极方波伏安法 (SWV) 对大环内酯类抗生素乙基琥珀酸红霉素 (EES)、阿奇霉素 (AZI)、克拉霉素（CLA）和罗红霉素（ROX）的测定。通过扫描电子显微镜 (SEM) 测量对工作电极的表面进行形态学表征，由此通过能谱仪 (EDS) 确认 CPE 表面上存在随机分布的直径为 10 nm 的 AuNP。在 Britton-Robinson 缓冲溶液（pH 2.0 至 11.98）中使用 CPE 测定四种大环内酯抗生素的 SWV，表明氧化信号强烈依赖于 pH（pH ≥ 6），并在 pH 8 时表现出最有利的特性。EES 为 0，AZI、CLA 和 ROX 的 pH 值为 11.98。在优化条件下，使用 CPE 的 SWV 方法能够测定低 μg mL-1 浓度范围内所有研究的大环内酯类抗生素，相对标准偏差 (RSD) 低于 6%，检测限 (LOD) 为 0.18、0.045、1.43 和 0.30 EES、AZI、CLA 和 ROX 分别为 μg mL-1。在 AZI 和 ROX 的情况下，由于合成的 AuNPs 的电催化性能，证明使用 AuNPs/CPE 作为工作电极可以进一步改善 SWV 方法获得的结果，包括显示的灵敏度、重现性和线性浓度范围。使用 SWV 方法和 CPE 或 AuNPs/CPE 优化的实验参数分别成功应用于测定其药物制剂 Runac® 和 Hemomycin® 中的 ROX 和 AZI。通过将它们与通过 HPLC-DAD 测量获得的结果进行比较，验证了详细程序的可靠性以及所获得结果的准确性。