Surface modification using thiol-acrylate conjugate addition reactions
Surface modification using thiol-acrylate conjugate addition reactions
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DOI：
10.1021/ma070146j
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发表时间：
2007-08-07
期刊：
影响因子：
5.5
通讯作者：
Bowman, Christopher N.
中科院分区：
文献类型：
--
作者：
Khire, Vaibhav S.;Lee, Tai Yeon;Bowman, Christopher N.
研究了一种使用胺催化的硫醇-丙烯酸酯反应形成表面结合聚合物膜的新方法。在胺催化剂存在下，用硫醇封端的自组装单分子膜(SAM)修饰表面，并用丙烯酸酯单体进行处理。在表面发生共轭加成反应，将丙烯酸酯分子附着到表面。反应时间控制了丙烯酸酯在表面的含量，形成了丙烯酸酯表面密度的梯度，丙烯酸酯在表面的含量从0变化到0.6。在同一表面上还获得了由相同的丙烯酸酯官能团或多个官能团组成的正交梯度。该技术被进一步改进，以在聚合物表面产生丙烯酸酯表面密度梯度。通过在端硫醇表面聚合二硫醇-二丙烯酸酯混合物，通过改变硫醇-丙烯酸酯的化学计量比和反应程度，以控制的方式生长出更厚的薄膜，薄膜的厚度可控制在0.1~6 nm之间。在这两种情况下，都从理论上计算了连接链的表面密度，并提出了预测它们的模型。
A novel method for forming surface-bound polymer films using amine-catalyzed thiol-acrylate reactions is investigated. The surface is modified with a thiol-terminated self-assembled monolayer (SAM) and treated with acrylate monomer in the presence of an amine catalyst. A conjugate addition reaction takes place at the surface, attaching an acrylate molecule to the surface. The fraction of attached acrylate on the surface was controlled by the reaction time, forming a gradient of acrylate surface density, and the acrylate fraction of the surface was changed from 0 to 0.6. An orthogonal gradient comprised of either the same acrylate functionality or multiple functionalities was also obtained on the same surface. The technique was further modified to yield acrylate surface density gradient on a polymer surface. Thicker films were grown in a controlled manner by polymerizing a dithiol-diacrylate mixture on a thiol-terminated surface, and the thicknesses of the films were controlled from 0.1 to 6 nm by changing the thiol-acrylate stoichiometry and the extent of reaction. In both cases the surface densities of the attached chains were theoretically calculated, and a model to predict them was proposed.