Zhang Chengfeng, Liu Ziyuan, Wang Haiye, Feng Xiaofeng, He Chunju
College of Material Science and Engineering, Donghua University, Shanghai, 201620, P. R. China.
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai, 201620, P. R. China.
Macromol Biosci. 2017 Jul;17(7). doi: 10.1002/mabi.201600444. Epub 2017 Mar 2.
A unique l-cysteine conjugated antifouling amphiphilic conetwork (APCN) is synthesized through end-crosslinking of well-defined triblock copolymers poly(allyl methacrylate)-b-poly(ethylene glycol)-b-poly(allyl methacrylate) via a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and thiol-ene "click" chemistry. The synthesized poly(ethylene glycol) macro-RAFT agent initiates the polymerization of allyl methacrylate in a controlled manner. The vinyl pendant groups of the precursor partially conjugate with l-cysteine and the rest fully crosslink with mercaptopropyl-containing siloxane via thiol-ene click chemistry under UV irradiation into APCNs, which show distinguished properties, that is, excellent biocompatibility, more than 39.6% water content, 101 barrers oxygen permeability, optimized mechanical properties, and more than 93% visible light transmittance. What's more, the resultant APCNs exhibit eminent resistance to protein adsorption, where the bovine serum albumin and lysozyme adsorption are decreased to 12 and 21 µg cm , respectively. The outstanding properties of APCNs depend on the RAFT controlled method, which precisely designs the hydrophilic/hydrophobic segments and eventually greatly improves the crosslinking efficiency and homogeneity. Meantime, the l-cysteine monolayer can effectively reduce the surface hydrophobicity and prevent protein adsorption, which exhibits the viability for antifouling surface over and under ophthalmic devices, suggesting a promising soft contact lens.
通过可逆加成-断裂链转移（RAFT）聚合和硫醇-烯“点击”化学相结合的方法，对定义明确的三嵌段共聚物聚（甲基丙烯酸烯丙酯）-b-聚（乙二醇）-b-聚（甲基丙烯酸烯丙酯）进行端基交联，合成了一种独特的L-半胱氨酸共轭防污两亲性互穿网络（APCN）。合成的聚（乙二醇）大分子RAFT试剂以可控方式引发甲基丙烯酸烯丙酯的聚合反应。前驱体的乙烯基侧基部分与L-半胱氨酸共轭，其余部分在紫外线照射下通过硫醇-烯点击化学与含巯丙基的硅氧烷完全交联形成APCN，其具有卓越的性能，即优异的生物相容性、超过39.6%的含水量、101 Barrers的氧气透过率、优化的机械性能以及超过93%的可见光透过率。此外，所得的APCN对蛋白质吸附表现出显著的抗性，其中牛血清白蛋白和溶菌酶的吸附量分别降至12和21 μg/cm²。APCN的优异性能取决于RAFT控制方法，该方法精确设计了亲水/疏水链段，最终极大地提高了交联效率和均匀性。同时，L-半胱氨酸单分子层可有效降低表面疏水性并防止蛋白质吸附，这展示了其在眼科装置上下表面作为防污表面的可行性，表明其有望用于软性隐形眼镜。
