Clément Benoît, Trimaille Thomas, Alluin Olivier, Gigmes Didier, Mabrouk Kamel, Féron François, Decherchi Patrick, Marqueste Tanguy, Bertin Denis
Laboratoire Chimie Provence, UMR 6264, Universites d'Aix-Marseille I, II et III-CNRS, Equipe Chimie Radicalaire Organique et Polymeres de Specialite, Case 542, Marseille Cedex 20, France.
Biomacromolecules. 2009 Jun 8;10(6):1436-45. doi: 10.1021/bm900003f.
SG1-based poly(d,l-lactide) (PLA) or poly(epsilon-caprolactone) (PCL) macro-alkoxyamines were synthesized and further used as macroinitiators for nitroxide-mediated polymerization (NMP) of 2-hydroxyethyl (meth)acrylate (HE(M)A) to obtain the corresponding PLA- or PCL-PHE(M)A block copolymers. First, a PLA-SG1 macro-alkoxyamine was prepared by 1,2-intermolecular radical addition (IRA) of the MAMA-SG1 (BlocBuilder) alkoxyamine onto acrylate end-capped PLA previously prepared by ring-opening polymerization. The NMP of HEA monomer from the PLA-SG1 macro-alkoxyamine appeared to be well controlled in the presence of free SG1 nitroxide, contrary to that of HEMA. In the latter case, adjustable molecular weights could be obtained by varying the HEMA to macro-alkoxyamine ratio. The versatility of our approach was then further applied to the preparation of PHEMA-b-PCL-b-PHEMA copolymers from a alpha,omega-di-SG1 functionalized PCL macro-alkoxyamine previously obtained from a PCL diacrylate by IRA. Preliminary studies of neuroblast cultures on these PCL-based copolymer films showed acceptable cyto-compatibility, demonstrating their potential for nerve repair applications.
合成了基于SG1的聚（d，l-丙交酯）（PLA）或聚（ε-己内酯）（PCL）大分子烷氧基胺，并进一步将其用作2-羟乙基（甲基）丙烯酸酯（HE（M）A）的氮氧自由基介导聚合（NMP）的大分子引发剂，以获得相应的PLA-或PCL-PHE（M）A嵌段共聚物。首先，通过将MAMA-SG1（嵌段构建剂）烷氧基胺与先前通过开环聚合制备的丙烯酸酯封端的PLA进行1,2-分子间自由基加成（IRA），制备了PLA-SG1大分子烷氧基胺。与甲基丙烯酸羟乙酯（HEMA）的情况相反，在游离SG1氮氧自由基存在下，由PLA-SG1大分子烷氧基胺引发的HEA单体的NMP似乎得到了很好的控制。在后一种情况下，通过改变HEMA与大分子烷氧基胺的比例可以获得可调节的分子量。然后，我们的方法的通用性进一步应用于由先前通过IRA从PCL二丙烯酸酯获得的α，ω-二-SG1官能化PCL大分子烷氧基胺制备PHEMA-b-PCL-b-PHEMA共聚物。对这些基于PCL的共聚物薄膜上的神经母细胞培养物的初步研究表明其具有可接受的细胞相容性，证明了它们在神经修复应用中的潜力。
