Freeman A, Sokolovsky M, Goldstein L
Biochim Biophys Acta. 1979 Nov 9;571(1):127-36. doi: 10.1016/0005-2744(79)90233-x.
A method for the introduction of side chains containing isonitrile (isocyanide, functional group) on the backbone of polysaccharides and other hydroxylic polymers was developed. The method was based on (a) ionization of some of the hydroxyl groups on the polymer by treatment with a strong base (tert-butoxide) in a polar aprotic solvent (dimethylsulfoxide), and (b) introduction of side chains containing isonitrile groups by nucleophilic attack of the polymeric alkoxide ions on a low molecular weight isonitrile containing a good leaving group in the omega-position, (1-tosyl-3-isocyanopropane). By this method, the side chains containing the-NC functional groups are attached to the polymeric backbone via stable ether bonds. The isonitrile derivatives of cellulose, linear and cross-linked dextran and cross-linked agarose utilized for the covalent fixation of high and low molecular weight ligands by four-component reactions carried out in aqueous medium, at neutral pH.
开发了一种在多糖和其他含羟基聚合物主链上引入含异腈(异氰化物,官能团)侧链的方法。该方法基于:(a)在极性非质子溶剂(二甲基亚砜)中用强碱(叔丁醇盐)处理聚合物上的一些羟基使其离子化;(b)聚合物醇盐离子对在ω-位含有良好离去基团的低分子量异腈(1-甲苯磺酰基-3-异氰基丙烷)进行亲核进攻,从而引入含异腈基团的侧链。通过这种方法,含-NC官能团的侧链通过稳定的醚键连接到聚合物主链上。纤维素、线性和交联葡聚糖以及交联琼脂糖的异腈衍生物用于在中性pH的水性介质中通过四组分反应共价固定高分子量和低分子量配体。