Previously, it has been shown that proteins and some polysaccharides (PSs) catalyse hydrogen evolution, producing electrochemical signals on mercury electrodes. The catalytic hydrogen evolution reaction (CHER) of the above-mentioned biomacromolecules was studied by voltammetric and chronopotentiometric stripping (CPS) methods. To obtain more information about electrode processes involving CHER, here we used protein such as BSA, and chitosan as a PS; in addition, we investigated dextran as a control PS not involved in CHER. We studied biomacromolecules by phase-sensitive alternating current (AC) voltammetry. Using phase-in AC voltammetry, for CHER-involved biomacromolecules we observed a CHER peak at highly negative potentials, similar to that observed with other voltammetric and CPS methods. On the other hand, by means of the adsorption/desorption processes studied in phase-out AC voltammetry, we uncovered a sharp and narrow decrease of capacitive current in the potential range of the CHER peak, denominated as the tensammetric minimum. This minimum was closely related to the CHER peak, as demonstrated by similar dependences on specific conditions affecting the CHER peak such as buffer capacity and pH. A tensammetric minimum was not observed for dextran. Our results suggest specific organization of biopolymer layers at negative potentials observed only in biomacromolecules involved in CHER.

以前，已经证明蛋白质和某些多糖（PSs）催化氢的释放，从而在汞电极上产生电化学信号。通过伏安和计时电位溶出（CPS）方法研究了上述生物大分子的催化氢释放反应（CHER）。为了获得有关涉及CHER的电极过程的更多信息，在这里我们使用蛋白质（例如BSA）和壳聚糖作为PS。此外，我们研究了葡聚糖作为不参与CHER的对照PS。我们通过相敏交流电（AC）伏安法研究了生物大分子。使用阶段-中交流伏安法，对于涉及CHER的生物大分子，我们在高度负电势下观察到一个CHER峰，与其他伏安法和CPS方法观察到的相似。在另一方面，通过在所研究的吸附/解吸过程的手段相-出交流伏安法，我们发现了电容性电流在CHER峰的电势范围内的尖锐和狭窄减少，命名为tensammetric最小。该最小值与CHER峰密切相关，这通过对影响CHER峰的特定条件（例如缓冲液容量和pH）的类似依赖性证明。没有观察到右旋糖酐的最小张力。我们的结果表明，只有在参与CHER的生物大分子中才能观察到负电位下生物聚合物层的特定组织。