College of Biology and the Environment, Nanjing Forestry University, Nanjing 210037, China.
School of Pharmacy, Changzhou University, Changzhou 213164, China.
Int J Biol Macromol. 2022 Dec 1;222(Pt A):1201-1210. doi: 10.1016/j.ijbiomac.2022.09.215. Epub 2022 Sep 27.
Recently, efficient synthesis of furan-based chemicals from biomacromolecule via chemoenzymatic approaches have been widely recognized. In this work, an efficient conversion of biomacromolecule (e.g., xylan in biomass) to furfurylamine (FLA) was developed in a tandem reaction by bridging with chemocatalysis and biocatalysis. Various biomasses (e.g., corncob, bagasse, bamboo shoot shell, corn stalk, rice straw stalk, reed, water bamboo and sunflower stalk) could produce different titer of furfural due to the diverse xylan content in biomass. After being catalyzed by shrimp shell-supported solid acid catalyst (Sn-DAT-SS) in deep eutectic solvent choline chloride:ethylene glycol (ChCl:EG) - water (10:90, v/v) at 170 °C after 30 min, corncob gave the highest furfural yield of 52.4 %. The potential catalytic mechanism for Sn-DAT-SS-catalyzing the conversion of biomass into furfural in ChCl:EG - water was proposed. It was found that by-products (formic acid, levulinic acid, 5-hydroxymethylfurfural) and soluble sugars (glucose, xylose, arabinose, cellobiose) produced during the conversion of biomass to furfural had certain inhibition effects on the biotransamination of furfural to FLA. Biomass-derived furfural (36.7-92.3 mM) could be fully aminated to FLA by E. coli CCZU-XLS160 cells harboring ω-transaminase after 24-72 h. The established chemoenzymatic strategy for converting biomacromolecules into valuable furan-based products was successfully developed in an eco-friendly system.
最近，通过化学酶法途径从生物大分子高效合成呋喃类化学品得到了广泛的认可。在这项工作中，通过化学催化和生物催化的桥接，在串联反应中开发了一种从生物大分子（例如生物质中的木聚糖）高效转化为糠胺（FLA）的方法。由于生物质中木聚糖的含量不同，各种生物质（例如玉米芯、甘蔗渣、竹笋壳、玉米秸秆、稻草秸秆、芦苇、水竹和向日葵秸秆）会产生不同含量的糠醛。在 170°C 下，在深共晶溶剂氯化胆碱：乙二醇（ChCl：EG）-水（10：90，v/v）中用虾壳负载固体酸催化剂（Sn-DAT-SS）催化 30 分钟后，玉米芯的糠醛得率最高，为 52.4%。提出了 Sn-DAT-SS 在 ChCl：EG-水体系中催化生物质转化为糠醛的潜在催化机制。研究发现，在生物质转化为糠醛的过程中产生的副产物（甲酸、乙酰丙酸、5-羟甲基糠醛）和可溶性糖（葡萄糖、木糖、阿拉伯糖、纤维二糖）对糠醛的生物转氨作用有一定的抑制作用。生物量衍生的糠醛（36.7-92.3mM）可以通过含有ω-转氨酶的大肠杆菌 CCZU-XLS160 细胞在 24-72 小时内完全氨化为 FLA。在环保体系中成功开发了将生物大分子转化为有价值的呋喃类产品的化学酶法策略。
