物理化学学报 >> 1997, Vol. 13 >> Issue (06): 515-524.doi: 10.3866/PKU.WHXB19970608

研究论文 上一篇    下一篇

含酰胺结构的巯基自组装膜的设计与结构表征

张浩力,张锦,赵江,王永强,佘劲,于化忠,力虎林,刘忠范   

  1. 北京大学化学与分子工程学院，智能材料研究中心，北京 100871|兰州大学化学系，兰州 730000
  • 收稿日期:1996-10-22 修回日期:1996-12-30 发布日期:1997-06-15
  • 通讯作者: 刘忠范

New Approach on the Synthesis of Functionalized Alkanethiols and the Structural Characterization of Their Self-Assembled Monolayers

Zhang Hao-Li,Zhang Jin,Zhao Jiang,Wang Yong-Qiang,She Jin,Yu Hua-Zhong,Li Hu-Lin,Liu Zhong-Fan   

  1. Center for Intelligent Materials Research(CIMR),College of Chemistry and Molecular Engineering,Peking University,Beijing 100871|Chemistry Department of Lanzhou University,Lanzhou 730000
  • Received:1996-10-22 Revised:1996-12-30 Published:1997-06-15
  • Contact: Liu Zhong-Fan

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摘要：

提出了一种简便通用的合成巯基化合物的途径，以分子中的羧基CO2H为起始基团，与2-巯基乙胺的氨基选择性缩合；合成了一系列具有RC（O）NHCH2CH2SH（R分别为偶氯苯衍生物，双炔衍生物及直链烷基）结构的化合物. 并用接触角测量，电化学和掠角反射红外光谱（GIR-IR）等手段对这些化合物在金表面形成的自组装单分子膜进行了表征. 发现4-（N－（2’-巯基已基））酰胺偶氮苯的自组装膜表现出良好的电活性，电化学测定表面浓度为4.21×10(－10)mol•cm(-2). 当R为烷基链时，随烷基链的增长，膜的致密度与有序度增加. GIR-IR证明在自组装膜中CH3（CH2）6C（O）NHCH2CH2SH的C＝O和N－H键与Au表面平行，分子轴线与Au表面近似垂直.

关键词: 自组装膜, 巯基化合物, 偶氮苯衍生物, 双炔衍生物, 接触角测量, 电化学, 掠角反射红外光谱

Abstract:

A simple and general method for synthesizing functionalized alkanethiols is reported. The synthesis started from carboxylic acid, RCOOH, which was selectively condensed with the amino group of 2-aminoethanethiol, thus giving the targetting thiol compounds. A series of thiol compounds having a structure of RC(O)NHCH2CH2SH, where R was azobenzene derivatives, dicetylene derivatives and n-akanes, respectively, have been synthesized using this method. The self-assembled monolayers(SAMs) of these species were characterized by wettability measurement, electrochemistry and grazing incidence refletance infrared spectroscopy(GIR-IR). The SAM from 4((N-(2’-mercaptrvethyl)amino)carbonyl) azobenzene showed clearcut electrochemical reactivity in aqueous solution, in which the surface coverage was evaluated to be 4.21×10-10mol•cm-2. On the other hand, for the thiols of R being n-alkanes, the packing structures became gradually improved with increasing the alkyl chain length. For CH3(CH2)6C(O)NHCH2CH2SH SAM, GIR-IR data indicate that the C=O and N-H groups are parallel with the substrate surface while the whole molecular axis is perpendicular to the surface.

Key words: Self-assembled monolayers(SAMs), Thiols, Azobenzene derivative, Diacetylene derivative, Contact angle measurement;Electrochemistry, Grazing incidence reflectance infrared spectroscopy(GIR-IR)