Faculty of Science and Engineering, Waseda University, Tokyo 169-8555, Japan.
Institute of Materials and Systems for Sustainability, Nagoya University, Furo-Cho, Chikusa-ku, Nagoya 464-8603, Japan.
Sensors (Basel). 2018 Jul 6;18(7):2178. doi: 10.3390/s18072178.
In this paper, we report on the effect of carboxyl- and amine terminations on a boron-doped diamond surface (BDD) in relation to pH sensitivity. Carboxyl termination was achieved by anodization oxidation in Carmody buffer solution (pH 7). The carboxyl-terminated diamond surface was exposed to nitrogen radicals to generate an amine-terminated surface. The pH sensitivity of the carboxyl- and amine-terminated surfaces was measured from pH 2 to pH 12. The pH sensitivities of the carboxyl-terminated surface at low and high pH are 45 and 3 mV/pH, respectively. The pH sensitivity after amine termination is significantly higher—the pH sensitivities at low and high pH are 65 and 24 mV/pH, respectively. We find that the negatively-charged surface properties of the carboxyl-terminated surface due to ionization of ⁻COOH causes very low pH detection in the high pH region (pH 7⁻12). In the case of the amine-terminated surface, the surface properties are interchangeable in both acidic and basic solutions; therefore, we observed pH detection at both low and high pH regions. The results presented here may provide molecular-level understanding of surface properties with charged ions in pH solutions. The understanding of these surface terminations on BDD substrate may be useful to design diamond-based biosensors.
本文报告了羧基和氨基末端对掺硼金刚石表面(BDD)与 pH 值敏感性的关系的影响。羧基末端是通过在 Carmody 缓冲溶液(pH 7)中阳极氧化实现的。将羧基化的金刚石表面暴露于氮自由基中以生成胺末端表面。测量了羧基和胺末端表面在 pH 2 至 pH 12 之间的 pH 值敏感性。低 pH 值和高 pH 值下羧基末端表面的 pH 值敏感性分别为 45 和 3 mV/pH。胺末端化后的 pH 值敏感性显著更高——低 pH 值和高 pH 值下的 pH 值敏感性分别为 65 和 24 mV/pH。我们发现,由于 ⁻COOH 的离子化,带负电荷的羧基末端表面特性导致在高 pH 区域(pH 7-12)中检测到非常低的 pH 值。在胺末端化表面的情况下,表面特性在酸性和碱性溶液中是可互换的;因此,我们在低 pH 值和高 pH 值区域都观察到了 pH 值检测。这里呈现的结果可能为 pH 溶液中带电荷离子的表面特性提供了分子水平的理解。对 BDD 衬底上这些表面末端的理解可能对设计基于金刚石的生物传感器有用。