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正交链端脱保护与巯基-马来酰亚胺迈克尔加成结合:通过迭代增长策略构建离散低聚物。

Combining Orthogonal Chain-End Deprotections and Thiol-Maleimide Michael Coupling: Engineering Discrete Oligomers by an Iterative Growth Strategy.

机构信息

State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.

Department of Chemistry, University of South Florida, Tampa, Florida, 33620, USA.

出版信息

Angew Chem Int Ed Engl. 2017 Oct 23;56(44):13612-13617. doi: 10.1002/anie.201706522. Epub 2017 Sep 27.

DOI:10.1002/anie.201706522
PMID:28872744
Abstract

Orthogonal maleimide and thiol deprotections were combined with thiol-maleimide coupling to synthesize discrete oligomers/macromolecules on a gram scale with molecular weights up to 27.4 kDa (128mer, 7.9 g) using an iterative exponential growth strategy with a degree of polymerization (DP) of 2 -1. Using the same chemistry, a "readable" sequence-defined oligomer and a discrete cyclic topology were also created. Furthermore, uniform dendrons were fabricated using sequential growth (DP=2 -1) or double exponential dendrimer growth approaches (DP=22n -1) with significantly accelerated growth rates. A versatile, efficient, and metal-free method for construction of discrete oligomers with tailored structures and a high growth rate would greatly facilitate research into the structure-property relationships of sophisticated polymeric materials.

摘要

正交马来酰亚胺和巯基脱保护与巯基-马来酰亚胺偶联相结合,使用聚合度为 2-1 的迭代指数增长策略,在克级规模上合成了离散的低聚物/高分子,分子量高达 27.4 kDa(128 -mer,7.9 g)。使用相同的化学方法,还创建了一个“可读”的序列定义的低聚物和离散的环状拓扑结构。此外,使用顺序生长(DP=2-1)或双指数树状大分子生长方法(DP=22n-1),可以制备均匀的树突,其生长速率明显加快。具有定制结构和高生长速率的离散低聚物的通用、高效、无金属构建方法将极大地促进对复杂聚合物材料结构-性能关系的研究。

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