Medical Scientist Training Program, Baylor College of Medicine , Houston, Texas 77030, United States.
Department of Infectious Diseases, The University of Texas MD Anderson Cancer Center , Houston, Texas 77030, United States.
Biomacromolecules. 2017 Jun 12;18(6):1724-1735. doi: 10.1021/acs.biomac.7b00044. Epub 2017 May 17.
In this work, we describe the synthesis and characterization of variants of poly(diol fumarate) and poly(diol fumarate-co-succinate). Through a Fischer esterification, α,ω-diols and dicarboxylic acids were polymerized to form aliphatic polyester comacromers. Because of the carbon-carbon double bond of fumaric acid, incorporating it into the macromer backbone structure resulted in unsaturated chains. By choosing α,ω-diols of different lengths (1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol) and controlling the amount of fumaric acid in the dicarboxylic acid monomer feed (33, 50, and 100 mol %), nine diol-based macromer variants were synthesized and characterized for molecular weight, number of unsaturated bonds per chain, and thermal properties. Degradation and in vitro cytotoxicity were also measured in a subset of macromers. As proof-of-principle, macromer networks were photo-cross-linked to demonstrate the ability to perform free radical addition using the unsaturated macromer backbone. Cross-linked macromer networks were also characterized for physicochemical properties (swelling, sol fraction, compressive modulus) based on diol length and amount of unsaturated bonds. A statistical model was built using data generated from these diol-based macromers and macromer networks to evaluate the impact of monomer inputs on final macromer and macromer network properties. With the ability to be modified by free radical addition, biodegradable unsaturated polyesters serve as important macromers in the design of devices such as drug delivery vehicles and tissue scaffolds. Given the ability to extensively control final macromer properties based on monomer input parameters, poly(diol fumarate) and poly(diol fumarate-co-succinate) represent an exciting new class of macromers.
在这项工作中，我们描述了聚（延胡索酸二醇）和聚（延胡索酸二醇-共琥珀酸）变体的合成和表征。通过 Fischer 酯化反应，将α，ω-二醇和二酸聚合形成脂肪族聚酯大分子单体。由于富马酸的碳-碳双键，将其引入大分子单体的主链结构中会导致不饱和链。通过选择不同长度的α，ω-二醇（1,6-己二醇、1,8-辛二醇和 1,10-癸二醇）和控制二酸单体进料中的富马酸含量（33、50 和 100 mol%），合成并表征了 9 种基于二醇的大分子单体变体，以测定分子量、每链不饱和键数和热性能。还测量了降解和体外细胞毒性的一小部分大分子单体。作为原理验证，大分子单体网络通过光交联进行了证明，以展示使用不饱和大分子单体主链进行自由基加成的能力。根据二醇长度和不饱和键数量，对交联大分子单体网络的理化性质（溶胀、溶胶分数、压缩模量）进行了表征。使用这些基于二醇的大分子单体和大分子单体网络生成的数据构建了一个统计模型，以评估单体输入对最终大分子单体和大分子单体网络性质的影响。具有通过自由基加成进行修饰的能力，可生物降解的不饱和聚酯可用作药物输送载体和组织支架等装置设计中的重要大分子单体。鉴于能够根据单体输入参数广泛控制最终大分子单体性质，聚（延胡索酸二醇）和聚（延胡索酸二醇-共琥珀酸）代表了一类令人兴奋的新型大分子单体。
