Matsuzaka Naoki, Takahashi Hironobu, Nakayama Masamichi, Kikuchi Akihiko, Okano Teruo
a Department of Materials Science and Technology , Graduate School of Industrial Science and Technology, Tokyo University of Science , 2641 Yamazaki , Noda , Chiba , 278-8510 , Japan.
J Biomater Sci Polym Ed. 2012;23(10):1301-14. doi: 10.1163/092050611X580454. Epub 2012 May 11.
Thermoresponsive poly(benzyl methacrylate)-b-poly(N-isopropylacrylamide) (PBzMA-b-PIPAAm) block co-polymer brush surfaces were prepared by surface-initiated two-step reversible addition-fragmentation chain transfer radical (RAFT) polymerization. PBzMA brushes were fabricated on azoinitiator-immobilized glass substrates in the presence of dithiobenzoate (DTB) compound as a RAFT agent. The amount of grafted polymer was regulated by initial monomer concentrations. The second thermoresponsive blocks were added to the RAFT-related DTB groups located at PBzMA termini through the propagation of PIPAAm chains, resulting in formation of PBzMA-b-PIPAAm brushes. Surface characteristics of the block co-polymer brushes and its influence on thermally regulated cellular behavior were investigated using bovine carotid artery endothelial cells (BAECs), compared with PIPAAm brush surfaces. Cell adhesion/detachment behavior on thermoresponsive polymer brush surfaces significantly depended on their individual polymer architectures and chemical compositions of grafted polymers. Low-temperature treatment at 20°C, below the phase-transition temperature of PIPAAm, induced the spontaneous detachment of adhering cells from the PBzMA-b-PIPAAm brush surfaces with a higher rate than that from PIPAAm brush surfaces. In addition, the cell-repellent effect of the hydrophobic basal layer successfully accelerated for harvesting BAEC sheets from the block co-polymer brush surfaces. Unique features of thermoresponsive block co-polymer brush architectures can be applied to control cell-adhesion strength for enhancing cell adhesion or accelerating cell detachment.
通过表面引发的两步可逆加成-断裂链转移自由基(RAFT)聚合制备了热响应性聚(甲基丙烯酸苄酯)-b-聚(N-异丙基丙烯酰胺)(PBzMA-b-PIPAAm)嵌段共聚物刷表面。在作为RAFT剂的二硫代苯甲酸酯(DTB)化合物存在下,在固定有偶氮引发剂的玻璃基板上制备PBzMA刷。接枝聚合物的量通过初始单体浓度来调节。通过PIPAAm链的增长,将第二个热响应性嵌段添加到位于PBzMA末端的与RAFT相关的DTB基团上,从而形成PBzMA-b-PIPAAm刷。与PIPAAm刷表面相比,使用牛颈动脉内皮细胞(BAECs)研究了嵌段共聚物刷的表面特性及其对热调节细胞行为的影响。热响应性聚合物刷表面上的细胞粘附/脱离行为显著取决于其各自的聚合物结构和接枝聚合物的化学组成。在低于PIPAAm的相转变温度的20°C下进行低温处理,导致粘附细胞从PBzMA-b-PIPAAm刷表面自发脱离的速率高于从PIPAAm刷表面脱离的速率。此外,疏水基层的细胞排斥作用成功加速了从嵌段共聚物刷表面收获BAEC片层的过程。热响应性嵌段共聚物刷结构的独特特征可应用于控制细胞粘附强度,以增强细胞粘附或加速细胞脱离。