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通过原位傅里叶变换红外光谱和石英晶体微天平耗散技术研究L-半胱氨酸在铂上吸附的动力学、组装及构象控制

Kinetics, Assembling, and Conformation Control of L-Cysteine Adsorption on Pt Investigated by in situ FTIR Spectroscopy and QCM-D.

作者信息

Dourado André H B, Silva Rubens A, Torresi Roberto M, Sumodjo Paulo T A, Arenz Matthias, Cordoba de Torresi Susana I

机构信息

Depto. Química Fundamental, Instituto de Química, Universidade de São Paulo, Av. Prof. Lineu Prestes, 05508-080, São Paulo - SP, Brazil.

Chemistry Department, København Universitet, Universistetsparken 5, 2100, Copenhagen, Denmark.

出版信息

Chemphyschem. 2018 Sep 18;19(18):2340-2348. doi: 10.1002/cphc.201800380. Epub 2018 Jun 20.

Abstract

A quartz crystal microbalance method with dissipation (QCM-D) and attenuated total reflection Fourier-transform infrared (ATR-FTIRS) spectroscopy were used to study the adsorption of L-cysteine (L-Cys) on Pt. Through QCM-D, it was possible to verify that the viscoelastic properties of the adsorbed species play an important role in the adsorption, rendering Sauerbrey's equation inapplicable. The modelling of QCM-D data exposed two different processes for the adsorption reaction. The first one had an activation time and is fast, whereas the second is slow. These processes were also resolved by ATR-FTIRS and identified to be water and anion adsorption preceded by L-Cys adsorption. Both techniques reveal that the degree of surface coverage is pH dependent. Spectroscopic data indicate that the conformation of L-Cys changes with pH and that the structures do not fully agree with those proposed in literature for other metallic surfaces. The assembling of the adsorbed monolayer appeared to be very fast, and it was not possible to determine or quantify this kinetics. The conformation is also controlled by applied potential, and the anion adsorption and interfacial water depends on the conformation of the adsorbed molecules.

摘要

采用带耗散监测的石英晶体微天平方法(QCM-D)和衰减全反射傅里叶变换红外光谱法(ATR-FTIRS)研究了L-半胱氨酸(L-Cys)在铂上的吸附。通过QCM-D,可以证实吸附物种的粘弹性性质在吸附过程中起着重要作用,使得绍尔布雷方程不再适用。对QCM-D数据的建模揭示了吸附反应的两个不同过程。第一个过程有一个活化时间且很快,而第二个过程较慢。这些过程也通过ATR-FTIRS得到了解析,并确定为在L-Cys吸附之前先发生水和阴离子吸附。两种技术都表明表面覆盖度与pH值有关。光谱数据表明,L-Cys的构象随pH值变化,且其结构与文献中针对其他金属表面所提出的结构并不完全一致。吸附单层的组装似乎非常快,无法确定或量化这种动力学。构象也受外加电势控制,阴离子吸附和界面水取决于吸附分子的构象。

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