One-pot synthesis of enzyme@metal–organic material (MOM) biocomposites for enzyme biocatalysis
One-pot synthesis of enzyme@metal–organic material (MOM) biocomposites for enzyme biocatalysis
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DOI：
10.1039/d1gc00775k
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发表时间：
2021-06
期刊：
影响因子：
9.8
通讯作者：
Yanxiong Pan;Hui Li;Mary Lenertz;Yulun Han;A. Ugrinov;D. Kilin;Bingcan Chen;Zhongyu Yang
中科院分区：
文献类型：
--
作者：
Yanxiong Pan;Hui Li;Mary Lenertz;Yulun Han;A. Ugrinov;D. Kilin;Bingcan Chen;Zhongyu Yang
金属有机框架/材料（MOFs/MOMs）是先进的酶固定化平台，可改善生物催化，材料科学和蛋白质生物物理学。一种独特的方法是共结晶/共沉淀，它消除了对酶/底物大小的限制。到目前为止，大多数酶@MOF复合材料依赖于使用非可持续的化学品，在某些情况下，重金属，这不仅引起了对环境保护的担忧，而且限制了它们在营养和生物医学中的应用。在这里，我们表明，来自木质素的二聚化合物，5，5 ′-脱氢二香草酸酯（DDVA），与酶和低毒性金属，Ca 2+和Zn 2+共沉淀，并形成稳定的酶@Ca/Zn-Cu复合物。我们证明了这一战略的四种酶具有不同的等电点（IEPs），分子量和底物大小。此外，我们发现，所有的酶表现出略有不同，但合理的催化效率固定在钙DDVA和锌DDVA MOMs，以及合理的可重复使用性在这两种复合材料。然后，我们探讨了这种差异的结构基础，使用一种代表性的酶，并发现增强限制酶在锌DDVA比在钙DDVA，这可能导致的活性差异。据我们所知，这是木质素衍生的“绿色”酶@M0F/H2O平台的第一个水相一锅法合成，其可以宿主酶而对酶IEP、分子量和底物大小没有任何限制。由Ca-DDVA和Zn-DDVA MOMs形成的复合材料的不同形态和堆叠结构根据感兴趣的问题拓宽了它们的应用。我们的酶固定化方法不仅提高了几乎所有酶的可持续性/可重复使用性，而且还减少/消除了非可持续资源的使用。这种合成方法对环境的影响可以忽略不计，而产品对生物和环境无毒。生物相容性还使得通过我们的“绿色”生物复合材料进行营养或生物医学应用的酶递送/释放成为可能。
Metal–organic frameworks/materials (MOFs/MOMs) are advanced enzyme immobilization platforms that improve biocatalysis, materials science, and protein biophysics. A unique way to immobilize enzymes is co-crystallization/co-precipitation, which removes the limitation on enzyme/substrate size. Thus far, most enzyme@MOF composites rely on the use of non-sustainable chemicals and, in certain cases, heavy metals, which not only creates concerns regarding environmental conservation but also limits their applications in nutrition and biomedicine. Here, we show that a dimeric compound derived from lignin, 5,5′-dehydrodivanillate (DDVA), co-precipitates with enzymes and low-toxicity metals, Ca2+ and Zn2+, and forms stable enzyme@Ca/Zn–MOM composites. We demonstrated this strategy on four enzymes with different isoelectric points (IEPs), molecular weights, and substrate sizes. Furthermore, we found that all enzymes displayed slightly different but reasonable catalytic efficiencies upon immobilization in the Ca–DDVA and Zn–DDVA MOMs, as well as reasonable reusability in both composites. We then probed the structural basis of such differences using a representative enzyme and found enhanced restriction of enzymes in Zn–DDVA than in Ca–DDVA, which might have caused the activity difference. To the best of our knowledge, this is the first aqueous-phase, one-pot synthesis of a lignin-derived “green” enzyme@MOF/MOM platform that can host enzymes without any limitations on enzyme IEP, molecular weight, and substrate size. The different morphologies and crystallinities of the composites formed by Ca–DDVA and Zn–DDVA MOMs broaden their applications depending on the problem of interest. Our approach of enzyme immobilization not only improves the sustainability/reusability of almost all enzymes but also reduces/eliminates the use of non-sustainable resources. This synthesis method has a negligible environmental impact while the products are non-toxic to living things and the environment. The biocompatibility also makes it possible to carry out enzyme delivery/release for nutritional or biomedical applications via our “green” biocomposites.