电势诱导的<i>N</i>-异丁酰基-L-半胱氨酸分子在金（111）表面的相转变

引用本文: 陈爱喜, 汪宏, 段赛, 张海明, 徐昕, 迟力峰. 电势诱导的N-异丁酰基-L-半胱氨酸分子在金（111）表面的相转变[J]. 物理化学学报, 2017, 33(5): 1010-1016. doi: 10.3866/PKU.WHXB201702102 shu

Citation: CHEN Ai-Xi, WANG Hong, DUAN Sai, ZHANG Hai-Ming, XU Xin, CHI Li-Feng. Potential-Induced Phase Transition of N-Isobutyryl-L-cysteine Monolayers on Au(111) Surfaces[J]. Acta Physico-Chimica Sinica, 2017, 33(5): 1010-1016. doi: 10.3866/PKU.WHXB201702102 shu

电势诱导的N-异丁酰基-L-半胱氨酸分子在金（111）表面的相转变

陈爱喜 ^1, ,
汪宏 ^2, ,
段赛 ^3, ,
张海明 ^1, ,
徐昕 ^4, ,
迟力峰 ^1,

1.
苏州大学功能纳米与软物质研究院, 江苏省碳基功能材料与器件高技术研究重点实验室, 江苏苏州 215123;
2.
明斯特大学物理研究所, 威廉-克莱姆街10号, 明斯特 48149, 德国;
3.
皇家理工学院, 生物工程学院理论化学与生物系, 斯德哥尔摩S-106 91, 瑞典;
4.
复旦大学化学系, 上海 200433
基金项目:
国家自然科学基金（91227201，21527805）项目资助

摘要: 自组装单层膜修饰的功能性基底在生物传感，色谱分析，生物相容性材料等方面均具有潜在应用。本文利用原位电化学扫描隧道显微镜（EC-STM）研究了电势诱导的N-异丁酰基-L-半胱氨酸（L-NIBC）分子在Au（111）表面自组装结构的相转变。我们把Au（111）基底分别浸润在纯的NIBC水溶液和pH = 7（磷酸盐缓冲溶液调节）的NIBC溶液中，分别制备了NIBC的α 相和β 相两种不同的自组装结构。EC-STM观测显示，当改变金的电极电势时，α 相和β 相的NIBC自组装单层膜出现了多种不同的结构变化。当电压从0.7 V（相对于饱和甘汞电极而言）降低到0.2 V时，α 相由有序结构变为无序结构。而对于β 相的样品，当E < 0.3 V时，为无序结构；当电极电势增大到0.4 V < E < 0.5 V时，出现γ 相；继续增大到0.5 V < E < 0.7 V时，变为β 相。另外，EC-STM图像也证实存在β 相转变为α 相的可能。综合密度泛函理论计算的结果，我们提出，β 相转变为α 相的原因可以解释为电极电势的变化引起了Au―COO^－键的断裂，从而引发分子吸附构型变化而导致相变。

关键词:

English

Potential-Induced Phase Transition of N-Isobutyryl-L-cysteine Monolayers on Au(111) Surfaces

1.
Institute of Functional Nano&Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou 215123, Jiangsu Province, P. R. China;
2.
Physikalisches Institut, Universität Münster, Wilhelm-Klemm Strasse 10, 48149 Münster, Germany;
3.
Department of Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, S-106 91 Stockholm, Sweden;
4.
Department of Chemistry, Fudan University, Shanghai 200433, P. R. China
Received Date: 19 December 2016
Revised Date: 10 February 2017
Available Online: 10 February 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (91227201, 21527805).

Abstract: Functional solid substrates modified by self-assembled monolayers (SAMs) have potential applications in biosensors, chromatography, and biocompatible materials. The potential-induced phase transition of N-isobutyryl-L-cysteine (L-NIBC) SAMs on Au(111) surfaces was investigated by in-situ electrochemical scanning tunneling microscopy (EC-STM) in 0.1 mol·L^－1 H₂SO₄ solution. The NIBC SAMs with two distinct structures (α phase and β phase) can be prepared by immersing the Au(111) substrate in pure NIBC aqueous solution and NIBC solution controlled by phosphate buffer at pH 7, respectively. The as-prepared α phase and β phase of NIBC SAMs show various structural changes under the control of electrochemical potentials of the Au(111) in H₂SO₄ solution. The α phase NIBC SAMs exhibit structural changes from ordered to disordered structures with potential changes from 0.7 V (vs saturated calomel electrode, SCE) to 0.2 V. However, the β phase NIBC SAMs undergo structural changes from disordered structures (E < 0.3 V) to γ phase (0.4 V < E < 0.5 V) and finally to the β phase (0.5 V < E < 0.7 V). EC-STM images also indicate that the phase transition from the β phase NIBC SAMs to the α phase occurs at positive potential. Combined with density functional theory (DFT) calculations, the phase transition from the β phase to the α phase is explained by the potential-induced break of bonding interactions between ―COO^－ and the negatively charged gold surfaces.

Key words:

Self-assembly
/ Thiol
/ Phase transition
/ Potential-induced
/ Electrochemical scanning tunneling microscopy
/ Density functional theory

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沈阳化工大学材料科学与工程学院沈阳 110142

电势诱导的N-异丁酰基-L-半胱氨酸分子在金（111）表面的相转变

English

Potential-Induced Phase Transition of N-Isobutyryl-L-cysteine Monolayers on Au(111) Surfaces

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

电势诱导的N-异丁酰基-L-半胱氨酸分子在金（111）表面的相转变

English

Potential-Induced Phase Transition of N-Isobutyryl-L-cysteine Monolayers on Au(111) Surfaces

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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