Phillips Daniel J, Congdon Thomas R, Gibson Matthew I
Department of Chemistry and Warwick Medical School, University of Warwick, Coventry, UK, CV4 7AL.
Polym Chem. 2016 Mar 7;7(9):1701-1704. doi: 10.1039/C5PY01948F.
Antifreeze (glyco)proteins (AF(G)Ps) have potent ice recrystallisation inhibition (IRI) activity - a desirable phenomenon in applications such as cryopreservation, frozen food and more. In Nature AF(G)P activity is regulated by protein expression levels in response to an environmental stimulus; temperature. However, this level of regulation is not possible in synthetic systems. Here, a synthetic macromolecular mimic is introduced, using supramolecular assembly to regulate activity. Catechol-terminated poly(vinyl alcohol) was synthesised by RAFT polymerization. Upon addition of Fe, larger supramolecular star polymers form by assembly with two or three catechols. This increase in molecular weight effectively 'switches on' the IRI activity and is the first example of external control over the function of AFP mimetics. This provides a simple but elegant solution to the challenge of external control of AFP-mimetic function.
抗冻(糖)蛋白(AF(G)Ps)具有强大的抑制冰重结晶(IRI)活性——这在诸如冷冻保存、冷冻食品等应用中是一种理想的现象。在自然界中,AF(G)P活性通过蛋白质表达水平响应环境刺激(温度)进行调节。然而,在合成系统中无法实现这种调节水平。在此,引入了一种合成大分子模拟物,利用超分子组装来调节活性。通过可逆加成-断裂链转移(RAFT)聚合合成了儿茶酚封端的聚乙烯醇。加入铁后,通过与两个或三个儿茶酚组装形成更大的超分子星形聚合物。分子量的这种增加有效地“开启”了IRI活性,这是对AFP模拟物功能进行外部控制的首个实例。这为AFP模拟物功能的外部控制挑战提供了一个简单而巧妙的解决方案。