Novel Nano-/Micro-Biocatalyst: Soybean Epoxide Hydrolase Immobilized on UiO-66-NH2 MOF for Efficient Biosynthesis of Enantiopure (R)-1, 2-Octanediol in Deep Eutectic Solvents
Novel Nano-/Micro-Biocatalyst: Soybean Epoxide Hydrolase Immobilized on UiO-66-NH2 MOF for Efficient Biosynthesis of Enantiopure (R)-1, 2-Octanediol in Deep Eutectic Solvents
复制标题
新型纳米/微生物催化剂：固定在 UiO-66-NH2 MOF 上的大豆环氧化物水解酶，用于在低共熔溶剂中高效生物合成对映体纯 (R)-1, 2-辛二醇
DOI：
10.1021/acssuschemeng.6b00777
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发表时间：
2016-06-01
影响因子：
8.4
通讯作者：
Lou, Wen-Yong
中科院分区：
文献类型：
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作者：
Cao, Shi-Lin;Yue, Dong-Mei;Lou, Wen-Yong
成功地制备了具有约350-400 nm的均匀尺寸的纳米/微米级U1 O-66-NH 2金属有机框架（MOF）材料，并对其结构进行了表征。大豆环氧化物水解酶（SEH）是一种合成邻二醇的有用水解酶，首次被有效地固定到所制备的UiO-66-NH_2 MOF上。所得的新型纳米/微生物催化剂SEH@UiO-66 NH（2）表现出高SEH负载（87.3mg/g）和酶活性回收率（88.0%）。新型SEH@U1O-66-NH 2在pH稳定性、热稳定性和对有机溶剂的耐受性方面大大超过游离SEH。在45 ° C下孵育2小时后，SEH@U10 -66-NH 2保留超过17.6U的活性，而游离SEH在相同条件下保持约10.1U的活性。在4 ℃下储存4周后，制备的SEH@U10 -66-NH 2仍保留其初始活性的约97.5%。SEH@UiO-66-NH 2的二级结构分析表明，该酶的结构刚性增加，从而使酶活力显著提高。SEH@UiO-66-NH_2的最适pH和最适温度均显著上级优于其游离对应物。此外，与游离SEH相比，SEH@U10 -66-NH 2表现出显著增强的酶-底物亲和力和催化效率，这分别由较低的表观Km值（6.5对19.2 mM）和增加的V-max/K-min值（8.0 x 10 - 3对5.8 x 10-3 min（-1））支持。此外，在新型低共熔溶剂（DES）中，SEH@UiO-66-NH 2首次被成功应用于1，2-环氧辛烷不对称水解合成（R）-1，2-辛烷，产率约为41.4%，产物e.e.值为81.2%。值得注意的是，纳米/微米级的UiO-66-NH 2 MOFs作为新型的酶载体材料是有希望的酶固定化，并且所制备的SEH@UiO-66-NH 2在高效生物合成对映体纯的（R）-1，2-辛内酯方面显示出巨大的潜力。
The nano-/microscale UiO-66-NH2 metal-organic framework (MOF) materials were successfully prepared with a uniform size of about 350-400 nm and structurally characterized. Soybean epoxide hydrolase (SEH), a useful hydrolase for synthesis of valuable vicinal diols, was for the first time efficiently immobilized onto the prepared UiO-66-NH2 MOF. The resulting novel nano-/microbiocatalyst SEH@UiO-66NH(2) manifested high SEH loading (87.3 mg/g) and enzyme activity recovery (88.0%). The novel SEH@UiO-66-NH2 greatly surpassed the free SEH with resepct to pH stability, thermostability, and tolerance to organic solvents. SEH@UiO-66-NH2 retained more than 17.6 U activity after 2 h of incubation at 45 degrees C, whereas free SEH maintained around 10.1 U activity under the same conditions. After storage at 4 degrees C for 4 weeks, the prepared SEH@UiO-66-NH2 still retained around 97.5% of its initial activity. The significant enhancements resulted from the increase of structural rigidity of SEH@UiO-66-NH2, which was demonstrated by the secondary structure analysis of the enzyme. The optimun pH and tempearture of SEH@UiO-66-NH2 were significantly superior to the corresponding levels of its free counterpart. Also, SEH@UiO-66-NH2 manifested markedly enhanced enzyme-substrate affinity and catalytic efficiency compared to free SEH, as supported by a lower apparent Km value (6.5 vs 19.2 mM) and an increased V-max/K-m,, value (8.0 x 10(-3) vs 5.8 x 10-3 min(-1)), respectively. Furthermore, the as-prepared SEH@UiO-66-NH2, for the first time, was successfully applied as an efficient biocatalyst for the asymmetric hydrolysis of 1,2-epoxyoctane to (R)-1,2-octanediol in a novel deep eutectic solvent (DES) with a yield of around 41.4% and a product e.e. value of 81.2%. Remarkably, the nano-/microscale UiO-66-NH2 MOFs as novel enzyme support materials are promising for enzyme immobilization, and the prepared SEH@UiO-66-NH2 exhibited great potential for efficient biosynthesis of enantipure (R)-1,2-octanediol.