Glutaraldehyde-crosslinked Rhizopus oryzae whole cells show improved catalytic performance in alkene epoxidation.
Glutaraldehyde-crosslinked Rhizopus oryzae whole cells show improved catalytic performance in alkene epoxidation.
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DOI：
10.1186/s12934-023-02026-0
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发表时间：
2023-02-22
影响因子：
6.4
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中科院分区：
文献类型：
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现有的烯烃环氧化方法是基于脂肪酶催化的过水解法。然而，昂贵的脂肪酶的失活对于大规模的酶促环氧化是有问题的，因为在反应中使用了高浓度的过氧化氢和过氧酸。整个细胞的固定化似乎是缓解这一问题的一种有前途的方法。以过氧化氢、酰基供体Na3C6H5O7和戊二醛(GA)为交联剂，开发了一种绿色氧化体系用于烯烃的环氧化。采用GA交联的米根霉细胞作为环氧化反应的生物催化剂。用该体系氧化了多种烯烃，相应环氧化物的分析产率为56-95%。与未处理细胞相比，交联处理细胞的催化性能有了很大的提高，初始反应速率从126.71提高到234.72 mmo1/L/h，即使在四批反应后仍保持了83%的产率。加入3.5 mg/L的Na3C6H5O7不仅起到了捕酸剂的作用，消除了羧酸对环氧化烯烃的负面影响，而且与水相形成饱和盐溶液，影响三相中H_2O_2的浓度，从而影响环氧化反应的进行。LogP值为 >； 为0.68的有机溶剂有利于羟基过氧酸的生成，但该方法仅适用于两液相氧化。与其他脂肪酶生物催化剂相比，GA-交联型全细胞生物催化剂具有价格低廉、易得、稳定性高等优点。因此，它可以被认为是很有工业应用前景的。网上版载有补充材料，可在10.1186/s12934-023-02026-0查阅。
Existing methods for alkene epoxidation are based on lipase-catalysed perhydrolysis. However, the inactivation of the expensive lipase enzyme is problematic for enzymatic epoxidation at large scales due to the use of hydrogen peroxide and peracids at high concentrations in the reaction. The immobilisation of whole cells appears to be a promising approach to alleviate this problem. A green oxidation system containing hydrogen peroxide, Na3C6H5O7, an acyl donor, and glutaraldehyde (GA)-crosslinked cells of Rhizopus oryzae was developed for the epoxidation of alkenes. GA-crosslinked cells of Rhizopus oryzae were adopted as a biocatalyst into the epoxidation system. A variety of alkenes were oxidised with this system, with a 56–95% analytical yield of the corresponding epoxides. The catalytic performance of the crosslinked treated cells was substantially improved compared to that of the untreated cells and the initial reaction rate increased from 126.71 to 234.72 mmol/L/h, retaining 83% yields even after four batches of reactions. The addition of 3.5 mmol Na3C6H5O7 not only acts as an acid-trapping reagent to eliminate the negative effect of the carboxylic acid on the alkene oxide but also forms a saturated salt solution with the aqueous phase, affecting the concentration of H2O2 in the three phases and thus the epoxidation reaction. Organic solvents with a logP value > 0.68 were good at producing hydroxy peracids; however, this method is only suitable for oxidation in a two-liquid phase. Compared with other lipase biocatalysts, the GA-crosslinked whole-cell biocatalyst is inexpensive, readily available, and highly stable. Therefore, it can be considered promising for industrial applications. The online version contains supplementary material available at 10.1186/s12934-023-02026-0.
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影响因子：
2.1
作者：
BJORKLING, F;FRYKMAN, H;KIRK, O
通讯作者：
KIRK, O
影响因子：
2.8
作者：
Hama, Shinji;Tamalampudi, Sriappareddy;Fukuda, Hideki
通讯作者：
Fukuda, Hideki
影响因子：
5.6
作者：
Hofmann, B;Tölzer, S;Hecht, HJ
通讯作者：
Hecht, HJ
影响因子：
3.3
作者：
Morozov, Alexander N.;Pardillo, Armando D.;Chatfield, David C.
通讯作者：
Chatfield, David C.
影响因子：
--
作者：
Klaas, MRG;Warwel, S
通讯作者：
Warwel, S