Laboratory for Polymer Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
ACS Appl Mater Interfaces. 2011 Jul;3(7):2487-95. doi: 10.1021/am200371c. Epub 2011 Jul 6.
Recently, fabrication of functional porous polymer films with patterned surface structures at the scale from nanometer to micrometer has been attracting increasing interests in material science and nanobiotechnology. In this work, we present new preparation of two series of multifunctional amphiphilic copolymers and preparation of their microporous thin films on solid substrates. First, diblock dendritic poly(l-lysine)-b-poly(l-lactide)s and triblock dendritic poly(l-lysine)-b-poly(l-lactide)-b-dendritic poly(l-lysine)s (C1-C6) were synthesized through 4-dimethylaminopyridine (DMAP)-catalyzed living ring-opening polymerization of (l-)-lactide with (l-)-lysine dendron initiators, and their structures were characterized by nuclear magnetic resonance spectrometer (NMR), gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization Fourier-transformed mass spectra (MALDI-FTMS). Employing the breath-figure (BF) fabrication strategy, thin films of the synthesized amphiphiles (C1-C6) were drop-cast, and their surface topologies were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM), and the effects of new amphiphile structure and drop-casting parameters of amphiphile concentration, humidity and temperature on self-assembly of ordered porous surface were studied. Furthermore, the influence of surface energy of drop-casting substrates was additionally investigated. With a human cervical epithelial carcinoma cell line (HeLa), cytotoxicity of the prepared honeycomb-structured films by new amphiphile C6 was evaluated by thiazoyl-blue-tetrazolium-bromide (MTT) assay, and HeLa cell growth behavior with microporous amphiphile films as the scaffolds was also examined. It was found that tunable micropore diameter sizes and well ordered surface topologies of BF films could be achieved for the new prepared amphiphiles, and utilization of the honeycomb-like microporous films as scaffolds indicated favorable enhancement in cell proliferation. Therefore, the honeycomb-structured films by these biocompatible multifunctional amphiphiles may provide new materials as 3D-scaffold materials for potential application in tissue engineering and regeneration.
最近，在纳米到微米尺度上具有图案化表面结构的功能多孔聚合物薄膜的制备在材料科学和纳米生物技术领域引起了越来越多的关注。在这项工作中，我们提出了两种系列多功能两亲嵌段共聚物的新制备方法，并在固体基底上制备了它们的微孔薄膜。首先，通过 4-二甲氨基吡啶（DMAP）催化的（L）-丙交酯与（L）-赖氨酸树枝状引发剂的活性开环聚合，合成了两亲性嵌段树枝状聚（L-赖氨酸）-b-聚（L-丙交酯）和三嵌段树枝状聚（L-赖氨酸）-b-聚（L-丙交酯）-b-树枝状聚（L-赖氨酸）（C1-C6），并通过核磁共振光谱仪（NMR）、凝胶渗透色谱（GPC）和基质辅助激光解吸/电离傅里叶变换质谱（MALDI-FTMS）对其结构进行了表征。采用呼吸图案（BF）制备策略，将合成的两亲性（C1-C6）薄膜滴铸，通过扫描电子显微镜（SEM）和原子力显微镜（AFM）对其表面形貌进行了研究，并研究了新两亲性结构和滴铸参数（两亲性浓度、湿度和温度）对有序多孔表面自组装的影响。此外，还研究了滴铸基底表面能的影响。通过噻唑蓝-溴化四唑（MTT）测定法，用人宫颈上皮癌细胞系（HeLa）评估了新型两亲性 C6 制备的蜂窝状薄膜的细胞毒性，还研究了微孔两亲性薄膜作为支架时 HeLa 细胞的生长行为。结果表明，新制备的两亲性聚合物可以实现可调的微孔直径和良好的 BF 薄膜有序表面形貌，并且利用类似蜂窝状的微孔薄膜作为支架可以显著促进细胞增殖。因此，这些生物相容性多功能两亲性聚合物的蜂窝状薄膜可为组织工程和再生的潜在应用提供 3D 支架材料的新材料。
