Kim Gyeongho, Park Soo Eun, Lee Woohyeong, Joo Jung Min, Yang Haesik
Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan 46241, Korea.
Department of Chemistry, College of Sciences, Kyung Hee University, Seoul 02447, Korea.
ACS Sens. 2024 Dec 27;9(12):6450-6459. doi: 10.1021/acssensors.4c01773. Epub 2024 Dec 3.
This study explores the potential of seven ferrocenyl (Fc) compounds with cross-linking groups as alternative redox labels to methylene blue (MB) for electrochemical aptamer-based (E-AB) sensors. The cross-linking efficiency, formal potential ('), and electrochemical durability of these compounds were evaluated. Compound exhibited superior performance, characterized by efficient cross-linking, a moderate and pH-insensitive ', and enhanced durability during repeated potential scans. The attachment of , which includes a 3-carbon chain spacer and an -hydroxysuccinimide-ester cross-linking group, to an amine-terminated monolayer on a Au electrode demonstrated high cross-linking efficiency, which is critical for achieving high sensitivity. The ' of attached to the aptamer monolayer was 0.14 V, which is within the optimal range of -0.2 to 0.2 V vs Ag/AgCl. Square wave voltammetry showed that the peak potential and current of are pH-insensitive, which is critical for versatile use. In serum, maintained stable peak current levels without a gradual decrease after an initial rapid decrease during the first 2 h with considerably less reduction over 12 h compared to MB. Using as the redox label, an E-AB sensor effectively detected doxorubicin in serum, covering the clinical range. These findings suggest as a promising candidate for developing robust, versatile, and sensitive E-AB sensors.
本研究探索了七种带有交联基团的二茂铁(Fc)化合物作为亚甲基蓝(MB)的替代氧化还原标记物用于基于电化学适配体(E-AB)传感器的潜力。评估了这些化合物的交联效率、形式电位(')和电化学耐久性。化合物表现出优异的性能,其特征在于交联效率高、'适中且对pH不敏感,以及在重复电位扫描期间耐久性增强。包含3碳链间隔基和N-羟基琥珀酰亚胺酯交联基团的化合物连接到金电极上的胺端单层上显示出高交联效率,这对于实现高灵敏度至关重要。连接到适配体单层上的化合物的'为0.14 V,相对于Ag/AgCl在-0.2至0.2 V的最佳范围内。方波伏安法表明化合物的峰值电位和电流对pH不敏感,这对于通用用途至关重要。在血清中,化合物在前2小时内最初快速下降后,保持稳定的峰值电流水平,没有逐渐降低,与MB相比,在12小时内还原程度要小得多。使用化合物作为氧化还原标记物,E-AB传感器有效地检测了血清中的阿霉素,涵盖了临床范围。这些发现表明化合物是开发强大、通用且灵敏的E-AB传感器的有前景的候选物。