Preparation and Application of Zwitterion Modified Starch Catalyzed by HRP‐ACAC Binary System

Starch Pub Date : 2024-03-22 DOI:10.1002/star.202300225
Wenda Wang, Ning Zhang, Yifan Cui, Qiang Wang, Man Zhou, Ping Wang, Yuanyuan Yu
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Abstract

Enzymatic modification, compared with traditional starch (St) chemical modification methods, avoids using toxic solvents and toxic catalysts. The horseradish peroxidase (HRP), being the most commonly employed natural green initiator, has found extensive application in starch grafting modification as a substitute for chemical initiators. HRP‐catalyzed grafting of starch with vinyl zwitterionic monomers has not been reported. Here, modified starch (St‐PSBMA) is first synthesized by grafting zwitterionic sulfobetaine [2‐(Methacryloyloxy)ethyl]dimethyl‐(3‐sulfopropyl) (SBMA) onto starch by HRP/Acetylacetone(ACAC) binary initiation system catalyzed. The modified starch‐based hydrogel is then prepared by the repeated freeze‐thaw method. Compared with native starch‐based hydrogels, which bind water molecules only through hydrogen bonding, the ability of modified starch‐based hydrogels to bind water molecules is enhanced by ionic solvation. The modified starch hydrogels also have excellent antiprotein adsorption and antibacterial properties due to the presence of a strong hydration layer. The modified starch‐based hydrogel also has excellent sensitivity and stability when used as a sensor for detecting joint motion. The binary HRP initiating system, employed in this study instead of the traditional three‐component HRP initiating system, offers a novel and promising approach for grafting modification of starch without the need for strong oxidant hydrogen peroxide.

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在 HRP-ACAC 二元体系催化下制备和应用添加剂改性淀粉
与传统的淀粉(St)化学改性方法相比,酶改性可避免使用有毒溶剂和有毒催化剂。辣根过氧化物酶(HRP)是最常用的天然绿色引发剂,在淀粉接枝改性中作为化学引发剂的替代品得到了广泛应用。HRP 催化淀粉与乙烯基齐聚物单体的接枝尚未见报道。在此,首先通过 HRP/乙酰丙酮(ACAC)二元引发体系催化,在淀粉上接枝齐聚物磺基甜菜碱[2-(甲基丙烯酰氧基)乙基]二甲基-(3-磺丙基)(SBMA),从而合成改性淀粉(St-PSBMA)。然后通过反复冻融法制备改性淀粉基水凝胶。与仅通过氢键结合水分子的原生淀粉基水凝胶相比,改性淀粉基水凝胶通过离子溶解增强了结合水分子的能力。由于存在一个强大的水合层,改性淀粉水凝胶还具有出色的抗蛋白质吸附和抗菌性能。改性淀粉基水凝胶用作检测关节运动的传感器时,也具有极佳的灵敏度和稳定性。本研究中采用的二元 HRP 起始体系取代了传统的三元 HRP 起始体系,为淀粉的接枝改性提供了一种新颖且前景广阔的方法,而无需使用强氧化剂过氧化氢。
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