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多糖衍生的具有模块化设计的冰重结晶抑制剂:以葡聚糖接枝聚合物为例。

Polysaccharide-Derived Ice Recrystallization Inhibitors with a Modular Design: The Case of Dextran-Based Graft Polymers.

出版信息

Langmuir. 2022 Nov 22;38(46):14097-14108. doi: 10.1021/acs.langmuir.2c02032. Epub 2022 Nov 7.

Abstract

Ice recrystallization inhibitors inspired from antifreeze proteins (AFPs) are receiving increasing interest for cryobiology and other extreme environment applications. Here, we present a modular strategy to develop polysaccharide-derived biomimetics, and detailed studies were performed in the case of dextran. Poly(vinyl alcohol) (PVA) which has been termed as one of the most potent biomimetics of AFPs was grafted onto dextran via thiol-ene click chemistry (Dex--PVA). This demonstrated that Dex--PVA is effective in IRI and its activity increases with the degree of polymerization (DP) (sizes of ice crystals were 18.846 ± 1.759 and 9.700 ± 1.920 μm with DPs of 30 and 80, respectively) and fraction of PVA. By means of the dynamic ice shaping (DIS) assay, Dex--PVA is found to engage on the ice crystal surfaces, thus the ice affinity accounts for their IRI activity. In addition, Dex- -PVA displayed enhanced IRI activity compared to that of equivalent PVA alone. We speculate that the hydrophilic nature of dextran would derive PVA in a stretch conformation that favors ice binding. The modular design can not only offer polysaccharides IRI activity but also favor the ice-binding behavior of PVA.

摘要

受抗冻蛋白 (AFP) 启发的冰晶再结晶抑制剂在低温生物学和其他极端环境应用中受到越来越多的关注。在这里,我们提出了一种开发多糖衍生仿生物的模块化策略,并详细研究了葡聚糖的情况。 已被称为 AFP 最有效仿生物之一的聚乙烯醇 (PVA) 通过硫醇-烯点击化学 (Dex--PVA) 接枝到葡聚糖上。 这表明 Dex--PVA 对 IRI 有效,其活性随聚合度 (DP) 增加 (DP 为 30 和 80 时,冰晶的大小分别为 18.846±1.759 和 9.700±1.920μm) 和 PVA 分数增加。 通过动态冰成型 (DIS) 测定,发现 Dex--PVA 与冰晶表面结合,因此冰亲和力是其 IRI 活性的原因。 此外,与单独使用等效 PVA 相比,Dex- -PVA 显示出增强的 IRI 活性。 我们推测葡聚糖的亲水性会使 PVA 处于伸展构象,从而有利于与冰结合。 模块化设计不仅可以为多糖提供 IRI 活性,还可以促进 PVA 的冰结合行为。

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