Template Polymerization Using Artificial Double Strands
Template Polymerization Using Artificial Double Strands
复制标题
使用人工双链的模板聚合
DOI：
10.1021/ma050963o
复制
发表时间：
2005
期刊：
影响因子：
5.5
通讯作者：
M. Akashi
中科院分区：
文献类型：
--
作者：
K. Hamada;T. Serizawa;M. Akashi
合成聚合物的模板合成是精确聚合的有趣目标。全同立构（it）和间同立构（st）聚甲基丙烯酸甲酯（PMMAs）在极性有机溶剂中，根据货车的范德华相互作用1的结构拟合，人工合成了双链螺旋立体复合物，其中复合物it-PMMAs被两倍长度的st-PMMAs包围。2聚合物化学家对这种双链部分非常感兴趣，因为它是一种适当的组装系统，可以在单一PMMA存在下原位自由基模板合成有规立构的PMMA。虽然这种复合物的化学计量与核酸的不同，但模板聚合受到温和生理条件下核酸和蛋白质的模板合成的启发。5然而，迄今为止，通过这种方法合成的模板到聚合物的结构转录是不够的。聚合反应已被证明在限制性条件下（低转化率，低温，和高分子量的模板）。3由于生物体系同时利用适当的酶形成的复杂纳米空间以及模板效应，具有随机和动态构象的溶剂化聚合物不是合适的聚合模板。为了克服这个问题，我们提出了聚合物模板作为多孔膜形成的纳米空间内的聚合，并实现了有规立构的甲基丙烯酸酯聚合物的高效模板合成。6聚合反应沿着进行，在它-PMMA和st-聚甲基丙烯酸（PMAA）之间形成货车范德华力接触，形成1：1（长度/长度）化学计量比的立体复合物。合成的甲基丙烯酸酯聚合物的分子量与模板聚合物的分子量几乎相同，这表明长度信息被转移到合成的聚合物。然而，由于我们对1：1立体复合物的组装结构的信息不足，7结构信息的绝对转移并不令人信服。因此，期望的是针对用于模板聚合的其他重要组件的应用。在此，我们报告了使用自由基引发剂在模板纳米空间中的有规立构模板聚合，基于它与模板纳米空间之间形成的双链螺旋立体复合物。
Template syntheses of synthetic polymers are interesting targets for precision polymerization. Isotactic (it) and syndiotactic (st) poly (methyl methacrylate) s (PMMAs) artificially form double-stranded helical stereocomplexes in polar organic solvents on the basis of structural fitting with van der Waals interactions, 1 in which complex it-PMMAs are surrounded by twice length of st-PMMAs. 2 Polymer chemists are strongly interested in this double-stranded moiety as an adequate assembly system to perform in situ free radical template syntheses of stereoregular PMMAs in the presence of a single PMMA. 3, 4 Although the stoichiometry of this complex is different from that of nucleic acids, template polymerization is inspired by template syntheses of nucleic acids and proteins under mild physiological conditions. 5 However, the structural transcription of templates to polymers synthesized by this method has thus far been insufficient. Polymerization has been demonstrated under restrictive conditions (low conversions, low temperatures, and high molecular weights of templates). 3Since biological systems synchronously utilize sophisticated nanospaces formed by proper enzymes as well as template effects, solvated polymers with random and dynamic conformations are not suitable polymerization templates. To overcome this problem, we proposed polymerization within nanospaces formed by polymer templates as porous ultrathin films and realized highly efficient template synthesis of stereoregular methacrylate polymers. 6 Polymerization proceeded along with stereocomplexes formed with van der Waals contacts between it-PMMA and st-poly (methacrylic acid)(PMAA) with 1: 1 (length/length) stoichiometry. The molecular weights of methacrylate polymers synthesized were almost the same as those of template polymers, suggesting that length information was transferred to synthesized polymers. However, since we have insufficient information for the assembly structure of 1: 1 stereocomplexes, 7 the absolute transfer of structural information was not convincing. It is therefore desirable to aim for applications with other significant assemblies for template polymerization. Herein, we report the stereoregular template polymerization in template nanospaces using free radical initiators, based on doublestranded helical stereocomplexes formed between it-