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"Yolk-shell"结构中高效双酶级联催化体系的构筑

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合成了一种生物-无机杂化材料ZIF-8@GOx-CPO@ZIF-8,该材料以具有"蛋黄-壳(Yolk-shell)"结构的金属有机框架(MOF)为载体,将葡萄糖氧化酶(GOx)和氯过氧化物酶(CPO)封装在不同隔离空间中构建了双酶纳米反应器."Yolk-shell"结构可为封装的酶提供纳米邻近效应,GOx催化底物原位生成的H2O2可启动相邻的CPO催化反应,有效减少了反应物的扩散阻力和H2O2的分解和逃逸,同时避免了两种酶催化反应的相互影响.与均相缓冲液中的游离酶相比,ZIF-8@GOx-CPO@ZIF-8的级联催化效率更高.由于MOF的屏蔽效应,酶的热稳定性和有机溶剂耐受性显著提高."Yolk-shell"结构还可有效抑制材料重复使用过程中酶分子的泄漏,经过20次重复使用后,ZIF-8@GOx-CPO@ZIF-8仍可保持初始级联催化效率的72%.将ZIF-8@GOx-CPO@ZIF-8双酶级联反应生成的HC1O应用于偶氮染料的高效脱色和水果保鲜.在1 mg/mLZIF-8@GOx-CPO@ZIF-8水溶液中,橙黄G(0.3 mmol/L)在15 min内可完成脱色(脱色率>98%).在新鲜草莓的杀菌保鲜实验中,ZIF-8@GOx-CPO@ZIF-8也显示出良好效果.ZIF-8@GOx-CPO@ZIF-8双酶级联催化体系具有高效、稳定、温和及绿色的特点,极具应用潜力.
Construction of Efficient Bienzyme Cascade Catalytic System by"Yolk-shell"Structure
This work proposes a bio-composite,ZIF-8@GOx-CPO@ZIF-8,which is constructed by"Yolk-shell"characteristic metal-organic framework(MOF)for specific division of glucose oxidase(GOx)and chloroperoxidase(CPO)by encapsulating them at different compartments.The structure of"Yolk-shell"can provide nano-proximity effect for encapsulated enzymes.H12O2 generated in situ by GOx immediately starts the enzymatic reaction of adjacent CPO,effectively reducing the diffusion resistance of reactants and the decomposition and escape of H2O2,and avoiding the interaction of the two enzymes during reuse.Compared with the free enzymes in the homogeneous buffer,the cascade catalytic efficiency of ZIF-8@GOx-CPO@ZIF-8 is improved.Owing to the shielding effect provided by the MOF,the thermal stability and organic solvent tolerance of the enzyme is also greatly improved.The"Yolk-shell"structure also effectively inhibits the leakage of enzyme molecules during the reuse process of the material.After 20 reuses,the bio-composite ZIF-8@GOx-CPO@ZIF-8 can keep 72%of the initial cascade efficiency.The cascade reaction of GOx-CPO can generate HC1O,which is applied in efficient decolorization of azo dye and fresh-keeping of fruit.The decolorization of azo dye orange G(0.3 mmol/L)was almost completed in only 15 min with 98%decolorization efficiency by 1 mg/L of ZIF-8@GOx-CPO@ZIF-8.ZIF-8@GOx-CPO@ZIF-8 bienzyme cascade catalytic system is efficient,stable,mild and green with great application potential.

"Yolk-shell"structureChloroperoxidaseGlucose oxidaseBienzymatic cascade catalysis

蒋佳祺、杨红霞、闫梦飞、史馨瑶、李佳琪、蒋育澄

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陕西师范大学化学化工学院,西安 710119

陕西师范大学陕西省大分子科学重点实验室,西安 710119

"Yolk-shell"结构 氯过氧化物酶 葡萄糖过氧化物酶 双酶级联催化

国家自然科学基金

22273056

2024

高等学校化学学报
中华人民共和国教育部委托 吉林大学和南开大学

高等学校化学学报

CSTPCD北大核心
影响因子:1.067
ISSN:0251-0790
年,卷(期):2024.45(10)