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质子化过程是大多数酸碱理论的核心,也发生在许多生命过程中.因此,研究限域环境中分子或官能团的质子化过程将为进一步认识酸碱理论和阐述限域环境中生物分子的基本行为提供理论依据.本文提出了一种以荷电电化学探针检测多孔氧化铝阵列纳米通道内表面官能团质子化过程的新方法.该方法利用纳米通道表面官能团的质子化过程改变表面荷电性质,从而调控荷电电化学探针在纳米通道中的传输行为.实验中以喷涂在阵列氧化铝纳米通道膜一侧的薄金膜为工作电极,检测通过阵列纳米通道荷电电化学探针的流量,以此获得纳米通道限域条件下的质子化过程.同时以多孔氧化铝阵列纳米通道为限域空腔,利用硅烷化反应将氨基修饰在纳米通道的内表面,通过不同pH值条件下检测Fe(CN)63-离子在纳米通道中流量的变化,获得了纳米通道限域条件下氨基质子化滴定曲线.结果表明,纳米通道限域条件下氨基官能团发生一步质子化,其pK1/2值为5.9.本文提出的方法也适用于研究纳米通道限域条件下其它官能团或生物分子的质子化过程.
Protonation is the core of most acid-base theories and occurs in many life processes. Therefore, studying the protonation process of molecules or functional groups in localized environments will provide a theoretical basis for further understanding of acid-base theory and elucidation of biomolecules in localized environments The basic behavior of which provides a theoretical basis.This paper presents a new method to detect protonation of functional groups on the inner surface of porous alumina array nanochannel by charge electrochemical probe.The method uses the protonation process of the surface functional groups of the nanochannel to change the surface charge Properties of the charged electrochemical probe to control the transmission behavior of the charged electrochemical probe in the nanochannel.In the experiment, a thin gold film sprayed on the side of the array alumina nano channel membrane is used as a working electrode to detect charges transmitted through the array nanochannels, , So as to obtain the protonation process under the confinement of nanochannels.At the same time, porous alumina array nanochannels were used as cavities, and the amino groups were modified on the inner surface of nanochannels by silylation reaction, Under the condition of nanochannels, the protonation titration curve of amino protonation The results show that the amino functional group at the nanochannel confinement condition occurs step by protonation of pK1 / 2 value of 5.9. The proposed method is also applicable to protonation other functional groups or biomolecules under study nanochannel confinement conditions.