Mustafa Mohd, Jan Tabee, Rohullah Mehdi, Masoodi Mubashir Hussain, Din Reshi Noor U, Rizvi Masood Ahmad
Department of Chemistry, University of Kashmir Hazratbal Srinagar 190006 J&K India
School of Chemistry, University of Hyderabad Gachibowli Hyderabad-500046 India.
RSC Adv. 2025 Mar 4;15(9):7004-7017. doi: 10.1039/d4ra07773c. eCollection 2025 Feb 26.
Homogenous electrochemical sensing using unmodified electrodes remove electrode fabrication challenges and prove effective for detecting sensitive bio-analytes without chances of surface degradation. This work envisages design and optimization of a ruthenium(ii) half-sandwich complex as supradecorated homogeneous electrochemical sensor for simultaneous detection of rifampicin (RIF) and isoniazid (INH) as first-line anti-tuberculosis drugs in aqueous environments. The electrochemical profile of GCE/ruthenium(ii) half-sandwich complex sensor was analyzed using cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy (EIS). The results indicate significant electrochemical parameters corroborating enhanced sensing propensity of GCE/ruthenium(ii) half-sandwich complex over bare GCE for simultaneous estimation of RIF and INH binary mixture. The RIF and INZ analytical figure of merit has been corroborated with their relative supra interactional propensity. Supra interactional propensity has also been predicted to be the plausible mechanism of RIF and INZ electrochemical sensing. Under optimized conditions GCE/ruthenium(ii) half-sandwich complex sensor depicted INH detection limits of 1.2 μM, and RIF detection limit of 32 nM. The comparative study of RIF and INZ analytes individually depicted high sensitivity of 24.57 μA μM cm and 1.69 μA μM cm under a linear response in the range of 0.29-3.72 μM and 4.9-82.22 μM for RIF and INH respectively. The analytical figure of merit of homogenous sensor has been compared to other GCE modified electrodes for RIF and INZ analytes. A significant antibiotic contaminant recovery of RIF and INZ drugs in pharmaceutical formulations, municipal water supplies and Dal lake water under spiked as well as unspiked conditions was observed portraying real time sensing application propensity. The homogenous GCE/ruthenium(ii) half-sandwich complex expresses excellent stability and reproducibility. The GCE/ruthenium(ii) half-sandwich complex in the presence of potential redox active biological interfering agents confirmed selectivity towards RIF and INZ analytes.
使用未修饰电极的均相电化学传感消除了电极制造方面的挑战，并被证明对于检测敏感生物分析物有效，且不存在表面降解的风险。这项工作设想设计和优化一种钌（II）半夹心配合物，作为超修饰的均相电化学传感器，用于在水性环境中同时检测作为一线抗结核药物的利福平（RIF）和异烟肼（INH）。使用循环伏安法、差分脉冲伏安法和电化学阻抗谱（EIS）分析了玻碳电极/钌（II）半夹心配合物传感器的电化学特征。结果表明，显著的电化学参数证实了玻碳电极/钌（II）半夹心配合物相对于裸玻碳电极在同时测定RIF和INH二元混合物方面增强的传感倾向。RIF和INZ的分析优值已通过它们相对的超相互作用倾向得到证实。超相互作用倾向也被预测为RIF和INZ电化学传感的合理机制。在优化条件下，玻碳电极/钌（II）半夹心配合物传感器对INH的检测限为1.2 μM，对RIF的检测限为32 nM。对RIF和INZ分析物的单独比较研究表明，在分别为0.29 - 3.72 μM和4.9 - 82.22 μM的线性响应范围内，RIF和INH的灵敏度分别高达24.57 μA μM cm和1.69 μA μM cm。已将均相传感器的分析优值与用于RIF和INZ分析物的其他玻碳电极修饰电极进行了比较。观察到在加标和未加标条件下，药物制剂、市政供水和达尔湖水中RIF和INZ药物的抗生素污染物回收率显著，显示出实时传感应用倾向。均相玻碳电极/钌（II）半夹心配合物表现出优异的稳定性和重现性。在存在潜在氧化还原活性生物干扰剂的情况下，玻碳电极/钌（II）半夹心配合物证实了对RIF和INZ分析物的选择性。
