Gamini Rajapakse R M, Horrocks Benjamin R, Gunarathna H M N P, Malikaramage A U, Egodawele M G S A M E W D D K, Herath W H M R N K, Sandakelum Lahiru, Bandara V M Y S U, Bowatta W V N S, Susanthi Jayasinghe J M, Seneviratne V N, Ranatunga Udayana, Perera L L K, Dassanayake S M, Udawatte Chandana P
Department of Chemistry, University of Peradeniya, Peradeniya, 20400, Sri Lanka.
School of Natural and Environmental Sciences, Newcastle University, Newcastle Upon Tyne, NE1 7RU, UK.
Sci Rep. 2023 Nov 18;13(1):20186. doi: 10.1038/s41598-023-47541-7.
The donor-acceptor (D-A) type of conjugated polymers has emerged as the paradigm of the third generation of electronically conducting polymers demonstrating improved infrared activity and intrinsic electronic conductivity. Judicious selection of donor (D) and acceptor (A) monomers for copolymerization can further fine-tune these properties. Notably, for such refinement, natural compounds provide many conjugated molecules with various functional groups. Berberine cation (Ber) found in Coscinium fenestratum has extensive conjugation and contains both an electron deficient isoquinolium A moiety and electron-rich D-type methylenedioxy and methoxy groups. The incorporation of natural products in electronic materials is a novel area of research which opens a wide scope for future electronic and optoelectronic devices. Investigation of their fundamental properties via computer simulations is therefore important. In this study, quantum chemical calculations are performed using density functional theory (DFT) to investigate the electronic and optical properties of oligomers of Ber and 3,4-ethylenedioxythiophene (EDOT) and to explore the possibilities for homo-polymerization of Ber and its copolymerization with EDOT. It has been revealed that homo-polymerization is not favoured but copolymerization with EDOT is possible. As such, Ber was copolymerized with EDOT and the copolymers formed by electro-polymerization are extensively characterised and the D-A behaviour of the copolymers verified. Furthermore, the theoretical predictions have been compared with the experimental data.
供体-受体（D-A）型共轭聚合物已成为第三代导电聚合物的典范，展现出改善的红外活性和固有电子导电性。明智地选择用于共聚的供体（D）和受体（A）单体可以进一步微调这些性质。值得注意的是，对于这种优化，天然化合物提供了许多带有各种官能团的共轭分子。在藤黄连中发现的小檗碱阳离子（Ber）具有广泛的共轭结构，并且既含有缺电子的异喹啉鎓A部分，又含有富电子的D型亚甲二氧基和甲氧基。将天然产物纳入电子材料是一个新的研究领域，为未来的电子和光电器件开辟了广阔的前景。因此，通过计算机模拟研究它们的基本性质很重要。在本研究中，使用密度泛函理论（DFT）进行量子化学计算，以研究Ber和3,4-亚乙基二氧噻吩（EDOT）低聚物的电子和光学性质，并探索Ber的均聚及其与EDOT共聚的可能性。结果表明，Ber的均聚不受青睐，但与EDOT共聚是可能的。因此，将Ber与EDOT共聚，并对通过电聚合形成的共聚物进行了广泛表征，并验证了共聚物的D-A行为。此外，还将理论预测与实验数据进行了比较。
