Poly(vinyl alcohol) Molecular Bottlebrushes Nucleate Ice.
Poly(vinyl alcohol) Molecular Bottlebrushes Nucleate Ice.
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DOI：
10.1021/acs.biomac.2c01097
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发表时间：
2022-12-12
影响因子：
6.2
通讯作者：
Gibson, Matthew I.
中科院分区：
文献类型：
--
作者：
Georgiou, Panagiotis G.;Kinney, Nina L. H.;Kontopoulou, Ioanna;Baker, Alexander N.;Hindmarsh, Steven A.;Bissoyi, Akalabya;Congdon, Thomas R.;Whale, Thomas F.;Gibson, Matthew I.
冰结合蛋白（IBP）已经进化到限制冰的生长，但也通过冰成核蛋白（INPs）促进冰的形成。调节这些看似不同的过程的IBP通常具有高序列相似性，并且分子大小/组装被假设为是关键的决定因素。只有少数合成材料再现INP功能，并且由于冰结合机制的突出问题，尚未实现冰成核剂的合理设计。聚（乙烯醇）（PVA）是一种水溶性合成聚合物，众所周知，通过结合到冰上，可以有效地阻止冰的重结晶。在这里，我们报告的聚合物冰成核剂，它模仿的IBPs的密集组装，使用限制冰结合聚合物在一个高摩尔质量的分子bottlebrush的合成。采用开环易位聚合（ROMP）和可逆加成-断裂链转移（RAFT）聚合相结合的方法，采用“接枝到”和“接枝通过”的方法，合成了具有不同侧链密度的聚乙烯醇基分子瓶刷。PVA瓶刷的简易制备通过选择性水解PVAc瓶刷前体的聚（乙酸乙烯酯）（PVAc）侧链的乙酸酯来进行。冰结合聚合物侧链密度被证明是至关重要的成核活性，与较低的密度刷导致冷的成核比密度刷。这种受生物启发的方法提供了一个用于探测非均质冰成核的合成框架，并为生物技术应用提供了一条确定合成成核剂的途径。
Ice binding proteins (IBP) have evolved to limit the growth of ice but also to promote ice formation by ice-nucleating proteins (INPs). IBPs, which modulate these seemingly distinct processes, often have high sequence similarities, and molecular size/assembly is hypothesized to be a crucial determinant. There are only a few synthetic materials that reproduce INP function, and rational design of ice nucleators has not been achieved due to outstanding questions about the mechanisms of ice binding. Poly(vinyl alcohol) (PVA) is a water-soluble synthetic polymer well known to effectively block ice recrystallization, by binding to ice. Here, we report the synthesis of a polymeric ice nucleator, which mimics the dense assembly of IBPs, using confined ice-binding polymers in a high-molar-mass molecular bottlebrush. Poly(vinyl alcohol)-based molecular bottlebrushes with different side-chain densities were synthesized via a combination of ring-opening metathesis polymerization (ROMP) and reversible addition–fragmentation chain-transfer (RAFT) polymerization, using “grafting-to” and “grafting-through” approaches. The facile preparation of the PVA bottlebrushes was performed via selective hydrolysis of the acetate of the poly(vinyl acetate) (PVAc) side chains of the PVAc bottlebrush precursors. Ice-binding polymer side-chain density was shown to be crucial for nucleation activity, with less dense brushes resulting in colder nucleation than denser brushes. This bio-inspired approach provides a synthetic framework for probing heterogeneous ice nucleation and a route toward defined synthetic nucleators for biotechnological applications.
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影响因子：
16.6
作者：
Biggs CI;Bailey TL;Ben Graham;Stubbs C;Fayter A;Gibson MI
通讯作者：
Gibson MI
DOI：
10.1073/pnas.1100429108
发表时间：
2011-05-03
影响因子：
11.1
作者：
Garnham, Christopher P.;Campbell, Robert L.;Davies, Peter L.
通讯作者：
Davies, Peter L.
用氧化石墨烯纳米片探测冰形成的临界核尺寸
影响因子：
64.8
作者：
Bai, Guoying;Gao, Dong;Wang, Jianjun
通讯作者：
Wang, Jianjun
影响因子：
16.6
作者：
Bachtiger F;Congdon TR;Stubbs C;Gibson MI;Sosso GC
通讯作者：
Sosso GC
影响因子：
15
作者：
Graham B;Fayter AER;Houston JE;Evans RC;Gibson MI
通讯作者：
Gibson MI