CHEMICAL FUNCTIONALITY IN SELF-ASSEMBLED MONOLAYERS - STRUCTURAL AND ELECTROCHEMICAL PROPERTIES
CHEMICAL FUNCTIONALITY IN SELF-ASSEMBLED MONOLAYERS - STRUCTURAL AND ELECTROCHEMICAL PROPERTIES
复制标题
DOI：
10.1021/la00093a026
复制
发表时间：
1990-03-01
期刊：
影响因子：
3.9
通讯作者：
LOIACONO, DN
中科院分区：
文献类型：
--
作者：
CHIDSEY, CED;LOIACONO, DN
我们研究的缺陷和渗透性的单层的长链有机分子绑定到金电极通过硫附件。被选择以在单层的外表面处呈现一系列化学基团的吸附物是氟化的烷硫醇（CF 3（CF2）7-（CH 2）2SH）、未取代的烷硫醇（CH 3（CH 2）9 SH）、醇-硫醇（HOCH 2（CH 2）10 SH）、腈-硫醇（NC（CH 2）10 SH）和羧酸-硫醇（HO 2C（CH 2）10 SH）。通过电子转移到接触水溶液中的受体确定的单分子膜的缺陷性和通过电化学电容测量确定的单分子膜对水离子的渗透性两者与通过红外光谱确定的碳链的堆积质量相当好地相关，以及与被吸附物的其它部分相比的链的相对横截面积。另一方面，无论是渗透性，也没有缺陷的单分子膜相关以及与它们的表面的润湿性。因此，具有较大面积链的氟化烷基硫醇单层渗透性最低且缺陷最少，依次是疏水性烷基硫醇单层、亲水性醇-硫醇单层、疏水性腈-硫醇单层，最后是亲水性酸-硫醇单层。
We examine the defectiveness and permeability of monolayers of long-chainorganic molecules bound to gold electrodes via a sulfur attachment. The adsorbates, which were chosen to present a range of chemical groups at the outer surface of the monolayer, are a fluorinated alkanethiol (CF3 (CF2) 7-(CH2) 2SH), an unsubstituted alkanethiol (CH3 (CH2) 9SH), an alcohol-thiol (HOCH2 (CH2) 10SH), a nitrile-thiol (NC (CH2) 10SH), and a carboxylic acid-thiol (H02C (CH2) 10SH). Both the defectiveness of the monolayers, as determined by electron transfer to acceptors in a contacting aqueous solution, and the permeability of the monolayers to aqueous ions, as determined by electrochemical capacitance measure-ments, correlate reasonably well with the quality of the packing of the carbon chains, which was determined by infrared spectroscopy, and with the relative cross sectional area of the chains compared to the other parts of the adsorbate. On the other hand, neither the permeability nor the defectiveness of the monolayers correlates well with the wettability of their surfaces. Thus, the fluorinated alkanethiol mono-layer, with larger area chains, is the least permeable and the least defective, followedin order by the hydrophobic alkanethiol monolayer, the hydrophilic alcohol-thiol monolayer, the hydrophobic nitrile-thiol monolayer, and finally by the hydrophilic acid-thiol monolayer.