Brizuela Guerra Nayrim, Morais Lima João Victor, Nozella Natan Luis, Boratto Miguel Henrique, Paulin João Vitor, Graeff Carlos Frederico de Oliveira
Department of Physics and Meteorology, School of Sciences, São Paulo State University (UNESP), Bauru 17033-360, SP, Brazil.
ACS Appl Bio Mater. 2024 Apr 15;7(4):2186-2196. doi: 10.1021/acsabm.3c01166. Epub 2024 Mar 11.
Eumelanin is a natural pigment that can be particularly valuable for sustainable bioelectronic devices due to its inherent biocompatibility and hydration-dependent conductivity. However, the low conductivity of eumelanin limits its technological development. In this research, electrochemical doping was proposed as an alternative route to increase the electronic conductivity of synthetic eumelanin derivatives. Thin films of sulfonated eumelanin were deposited on platinum interdigitated electrodes and electrochemically treated by using cyclic voltammetry and chronoamperometry treatments. X-ray photoelectron spectroscopy analysis confirmed ion doping in sulfonated melanin. Current-voltage, current-time, and electrochemical impedance measurements were used to investigate the effect of different aqueous electrolytes (including KCl and LiClO) treatments on the charge transport of sulfonated eumelanin. We show that the conductivity depends on the type and size of the anion used and can reach 10 S·cm. Additionally, depending on the electrolyte, there is a change in charge transport from mixed ionic/electronic to a predominantly electronic-only conduction. Our results show that the chemical nature of the ion plays an important role in the electrochemical doping and, consequently, in the charge transport of eumelanin. These insights serve as inspiration to explore the use of alternative electrolytes with different compositions further and develop eumelanin-based devices with tunable conductivities.
真黑素是一种天然色素,由于其固有的生物相容性和与水合作用相关的导电性,对于可持续生物电子器件而言可能具有特别重要的价值。然而,真黑素的低导电性限制了其技术发展。在本研究中,提出了电化学掺杂作为提高合成真黑素衍生物电子导电性的替代途径。将磺化真黑素薄膜沉积在铂叉指电极上,并通过循环伏安法和计时电流法进行电化学处理。X射线光电子能谱分析证实了磺化黑素中的离子掺杂。使用电流-电压、电流-时间和电化学阻抗测量来研究不同水性电解质(包括KCl和LiClO)处理对磺化真黑素电荷传输的影响。我们表明,导电性取决于所使用阴离子的类型和大小,并且可以达到10 S·cm。此外,根据电解质的不同,电荷传输会从离子/电子混合传导转变为主要仅为电子传导。我们的结果表明,离子的化学性质在电化学掺杂中起着重要作用,因此在真黑素的电荷传输中也起着重要作用。这些见解为进一步探索使用具有不同组成的替代电解质以及开发具有可调导电性的基于真黑素的器件提供了灵感。