Faculty of Science, Department of Chemistry, Middle East Technical University, Ankara 06800, Turkey.
METU Center for Solar Energy Research and Applications (ODTU-GUNAM), Ankara 06800, Turkey.
Biosensors (Basel). 2023 Jun 25;13(7):677. doi: 10.3390/bios13070677.
The molecular engineering of conjugated systems has proven to be an effective method for understanding structure-property relationships toward the advancement of optoelectronic properties and biosensing characteristics. Herein, a series of three thieno[3,4-]pyrrole-4,6-dione (TPD)-based conjugated monomers, modified with electron-rich selenophene, 3,4-ethylenedioxythiophene (EDOT), or both building blocks (, , and ), were synthesized using Stille cross-coupling and electrochemically polymerized, and their electrochromic properties and applications in a glucose biosensing platform were explored. The influence of structural modification on electrochemical, electronic, optical, and biosensing properties was systematically investigated. The results showed that the cyclic voltammograms of EDOT-containing materials displayed a high charge capacity over a wide range of scan rates representing a quick charge propagation, making them appropriate materials for high-performance supercapacitor devices. UV-Vis studies revealed that EDOT-based materials presented wide-range absorptions, and thus low optical band gaps. These two EDOT-modified materials also exhibited superior optical contrasts and fast switching times, and further displayed multi-color properties in their neutral and fully oxidized states, enabling them to be promising materials for constructing advanced electrochromic devices. In the context of biosensing applications, a selenophene-containing polymer showed markedly lower performance, specifically in signal intensity and stability, which was attributed to the improper localization of biomolecules on the polymer surface. Overall, we demonstrated that relatively small changes in the structure had a significant impact on both optoelectronic and biosensing properties for TPD-based donor-acceptor polymers.
共轭体系的分子工程已被证明是一种有效的方法,可以理解结构-性质关系,从而推进光电性能和生物传感特性的发展。在此,通过 Stille 交叉偶联合成了一系列三种基于噻吩并[3,4-b]吡咯-4,6-二酮(TPD)的共轭单体,并用富电子硒吩、3,4-亚乙基二氧噻吩(EDOT)或这两个构筑块(、和)进行了修饰,然后通过电化学聚合得到了这些单体,并探索了它们的电致变色性能及其在葡萄糖生物传感平台中的应用。系统研究了结构修饰对电化学、电子、光学和生物传感性能的影响。结果表明,含 EDOT 的材料的循环伏安曲线在很宽的扫描速率范围内表现出高电荷容量,这代表了快速的电荷传递,使它们成为高性能超级电容器器件的合适材料。紫外-可见研究表明,基于 EDOT 的材料具有宽范围的吸收,因此具有较低的光学带隙。这两种 EDOT 修饰的材料还表现出优异的光学对比度和快速的开关时间,并且在中性和完全氧化状态下进一步显示出多色特性,使它们成为构建先进电致变色器件的有前途的材料。在生物传感应用方面,含硒吩的聚合物表现出明显较差的性能,特别是在信号强度和稳定性方面,这归因于生物分子在聚合物表面的定位不当。总的来说,我们证明了结构的微小变化对 TPD 基给体-受体聚合物的光电和生物传感性能有重大影响。