结合模块化连接和超分子自组装用于星形大分子的构建。

Combining modular ligation and supramolecular self-assembly for the construction of star-shaped macromolecules.

作者信息

Altintas Ozcan, Muller Thierry, Lejeune Elise, Plietzsch Oliver, Bräse Stefan, Barner-Kowollik Christopher

机构信息

Preparative Macromolecular Chemistry, Center for Functional Nanostructures (CFN), Karlsruhe Institute of Technology (KIT), Engesserstr. 18, 76128 Karlsruhe, Germany.

出版信息

Macromol Rapid Commun. 2012 Jun 14;33(11):977-83. doi: 10.1002/marc.201200019. Epub 2012 Apr 17.

DOI:10.1002/marc.201200019

PMID:22508499

Abstract

A well-defined random copolymer of styrene (S) and chloromethylstyrene (CMS) featuring lateral chlorine moieties with an alkyne terminal group is prepared (P(S-co-CMS), M(n) = 5500 Da, PDI = 1.13). The chloromethyl groups are converted into Hamilton wedge (HW) entities (P(S-co-HWS), M(n) = 6200 Da, PDI = 1.13). The P(S-co-HWS) polymer is subsequently ligated with tetrakis(4-azidophenyl)methane to give HW-functional star-shaped macromolecules (P(S-co-HWS))(4), M(n) = 25,100 Da, PDI = 1.08). Supramolecular star-shaped copolymers are then prepared via self-assembly between the HW-functionalized four-arm star-shaped macromolecules (P(S-co-HW))(4) and cyanuric acid (CA) end-functionalized PS (PS-CA, M(n) = 3700 Da, PDI = 1.04), CA end-functionalized poly(methyl methacrylate) (PMMA-CA, M(n) = 8500 Da, PDI = 1.13) and CA end-functionalized polyethylene glycol (PEG-CA, M(n) = 1700 Da, PDI = 1.05). The self-assembly is monitored by (1)H NMR spectroscopy and light scattering analyses.

摘要

制备了一种结构明确的苯乙烯（S）和氯甲基苯乙烯（CMS）的无规共聚物，其具有带有炔端基的侧链氯部分（P（S-co-CMS），M(n)=5500 Da，PDI = 1.13）。氯甲基基团被转化为汉密尔顿楔（HW）实体（P（S-co-HWS），M(n)=6200 Da，PDI = 1.13）。随后将P（S-co-HWS）聚合物与四（4-叠氮基苯基）甲烷连接，得到HW功能化的星形大分子（P（S-co-HWS））₄，M(n)=25,100 Da，PDI = 1.08。然后通过HW功能化的四臂星形大分子（P（S-co-HW））₄与氰尿酸（CA）端功能化的聚苯乙烯（PS-CA，M(n)=3700 Da，PDI = 1.04）、CA端功能化的聚甲基丙烯酸甲酯（PMMA-CA，M(n)=8500 Da，PDI = 1.13）和CA端功能化的聚乙二醇（PEG-CA，M(n)=1700 Da，PDI = 1.05）之间的自组装制备超分子星形共聚物。通过¹H NMR光谱和光散射分析监测自组装过程。