Department of Biomolecular Systems, Max-Planck-Institute of Colloids and Interfaces, Am Mühlenberg 1, 14476, Potsdam, Germany.
Department of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195, Berlin, Germany.
Angew Chem Int Ed Engl. 2019 Sep 9;58(37):13127-13132. doi: 10.1002/anie.201906577. Epub 2019 Aug 19.
A dense hydrogen-bond network is responsible for the mechanical and structural properties of polysaccharides. Random derivatization alters the properties of the bulk material by disrupting the hydrogen bonds, but obstructs detailed structure-function correlations. We have prepared well-defined unnatural oligosaccharides including methylated, deoxygenated, deoxyfluorinated, as well as carboxymethylated cellulose and chitin analogues with full control over the degree and pattern of substitution. Molecular dynamics simulations and crystallographic analysis show how distinct hydrogen-bond modifications drastically affect the solubility, aggregation behavior, and crystallinity of carbohydrate materials. This systematic approach to establishing detailed structure-property correlations will guide the synthesis of novel, tailor-made carbohydrate materials.
密集的氢键网络是多糖机械和结构性能的决定因素。随机衍生化通过破坏氢键改变了大块材料的性质，但阻碍了详细的结构-功能相关性。我们已经制备了具有完全取代度和取代模式可控性的定义明确的非天然寡糖，包括甲基化、脱氧、脱氧氟化以及羧甲基化纤维素和壳聚糖类似物。分子动力学模拟和晶体学分析表明，氢键的不同修饰如何显著影响碳水化合物材料的溶解度、聚集行为和结晶度。这种建立详细结构-性能相关性的系统方法将指导新型定制碳水化合物材料的合成。
