Kishi Ryujiro, Nishitani Shoichi, Kudo Hiroyuki, Sakata Toshiya
Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Department of Electronics and Bioinformatics, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571, Japan.
ACS Omega. 2024 Dec 9;9(50):49368-49376. doi: 10.1021/acsomega.4c06671. eCollection 2024 Dec 17.
In this study, we realized a real-time and enzyme-free measurement of lactate in sweat in the same way as an enzyme-based amperometric method. A conductive polymer, which is based on polyaniline (PANI), was strongly coated on a glassy carbon electrode as a poly -aminophenylboronic acid (PANI-PBA) membrane by drop-casting, which is a convenient method, owing to adhesive phytic acid (PA) molecules with negative charges included as a dopant. This polymer membrane had a functional structure with PBA in the PANI main chain, which expectedly induced electrical charges upon diol binding to lactate, owing to the formation of deprotonated boronate esters with negative charges. This indicates that PBA served as the self-dopant and as the site of binding to lactate. On the basis of the fundamental electrochemical characteristics such as the membrane resistance, the change in the current density of the PA-doped PANI-PBA electrode was quantitatively monitored with the change in lactate concentration from 1 to 300 mM under acidic conditions in real time, considering pH and interfering substances in sweat. Moreover, the sweat lactate concentration was determined to be ca. 60 mM using the PA-doped PANI-PBA electrode in a microfluidic system in measurements using sweat samples collected during exercise load. A change in current density induced a change in the density of charges in the capacitive PA-doped PANI-PBA membrane. This means that the detection mechanism for the change in the lactate concentration in sweat was based on repeated charging and discharging in the PA-doped PANI-PBA electrode.
在本研究中,我们采用了一种基于酶的安培法,实现了汗液中乳酸的实时无酶检测。通过滴铸法将基于聚苯胺(PANI)的导电聚合物作为聚氨基苯硼酸(PANI-PBA)膜牢固地涂覆在玻碳电极上,由于掺杂了带负电荷的植酸(PA)分子,这种方法很方便。该聚合物膜在PANI主链中具有含PBA的功能结构,由于与乳酸结合的二醇形成带负电荷的去质子化硼酸酯,预计会在二醇与乳酸结合时感应出电荷。这表明PBA既作为自掺杂剂,又作为与乳酸结合的位点。基于诸如膜电阻等基本电化学特性,在考虑汗液中的pH值和干扰物质的情况下,在酸性条件下实时定量监测了PA掺杂的PANI-PBA电极的电流密度随乳酸浓度从1 mM到300 mM的变化。此外,在使用运动负荷期间收集的汗液样本进行的测量中,在微流控系统中使用PA掺杂的PANI-PBA电极测定出汗液乳酸浓度约为60 mM。电流密度的变化引起了电容性PA掺杂的PANI-PBA膜中电荷密度的变化。这意味着汗液中乳酸浓度变化的检测机制是基于PA掺杂的PANI-PBA电极中的反复充电和放电。