Rapid Synthesis of Functional Polymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization of an Acidic Monomer
Rapid Synthesis of Functional Polymer Brushes by Surface-Initiated Atom Transfer Radical Polymerization of an Acidic Monomer
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DOI：
10.1021/ma801297p
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发表时间：
2008-11-25
期刊：
影响因子：
5.5
通讯作者：
Bruening, Merlin L.
中科院分区：
文献类型：
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作者：
Jain, Parul;Dai, Jinhua;Bruening, Merlin L.
高反应性单体琥珀酸2-（甲基丙烯酰氧基）乙酯（MES）和活性催化剂体系（例如，与1，1，4，7，10，10-六甲基三亚乙基四胺（HMTETA）络合的Cu（I）允许通过原子转移自由基聚合（ATRP）从表面快速形成聚（羧酸）刷。ATRP从引发剂固定在Au涂层的Si晶片产生膜的椭圆厚度为120 nm，在不到15分钟。据我们所知，这是第一个例子的质子化酸性单体，能够产生这样的厚膜直接ATRP，MES聚合更迅速比甲基丙烯酸在溶液中和表面上。MES膜对于许多应用是有吸引力的，包括蛋白质的固定化。假设溶菌酶单层具有2nm的厚度，55 nm的聚（MES）刷通过离子交换相互作用结合类似于70个溶菌酶单层。此外，当用氨三乙酸-Cu 2+络合物衍生化时，聚（MES）膜通过金属离子亲和相互作用结合类似于34个BSA单层（假设BSA单层厚度为4 nm）。这些结合能力与通过丙烯酸叔丁酯聚合和随后水解制备的聚（丙烯酸）刷的结合能力相似，但聚（MES）合成是一步水溶液过程。
The combination of a highly reactive monomer, 2-(methacryloyloxy)ethyl succinate (MES), and active catalyst systems, e.g., Cu(I) complexed with 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), allows rapid formation of poly(carboxylic acid) brushes by atom transfer radical polymerization (ATRP) from a surface. ATRP from initiators immobilized on Au-coated Si wafers yields films with an ellipsometric thickness of 120 nm in less than 15 min. To the best of our knowledge, this is the first example of direct ATRP of protonated acidic monomers that is capable of yielding such thick films, and MES polymerizes much more rapidly than methacrylic acid both in solution and on a surface. The MES films are attractive for a number of applications, including immobilization of proteins. Assuming that a lysozyme monolayer has a thickness of 2 nm, a 55 nm poly(MES) brush binds similar to 70 monolayers of lysozyme via ion-exchange interactions. Additionally, when derivatized with nitrilotriacetate-Cu2+ complexes, poly(MES) films bind similar to 34 monolayers of BSA through metal-ion affinity interactions (assuming a BSA monolayer thickness of 4 nm). These binding capacities are similar to those of poly(acrylic acid) brushes prepared by polymerization of tert-butyl acrylate and subsequent hydrolysis, but the poly(MES) synthesis is a one-step, aqueous process.