Sun Yuhuan, Zhao Chuanqi, Gao Nan, Ren Jinsong, Qu Xiaogang
Laboratory of Chemical Biology, State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin, 130022, China.
University of Science and Technology of China, Hefei, Anhui, 230026, China.
Chemistry. 2017 Dec 22;23(72):18146-18150. doi: 10.1002/chem.201704579. Epub 2017 Dec 4.
Stereoselectivity towards substrates is one of the most important characteristics of enzymes. Amino acids, as cofactors of many enzymes, play important roles in stereochemistry. Herein, chiral nanozymes were constructed by grafting a series of d- or l-amino acids onto the surfaces of ceria (cerium oxide) nanoparticles. We selected the most commonly used drug for combating Parkinson's disease, that is, 3,4-dihydroxyphenylalanine (DOPA) enantiomers, as examples for chiral catalysis. Through detailed kinetic studies of cerium oxide nanoparticles (CeNPs) modified with different eight amino acids, we found that phenylalanine-modified CeNP was optimal for the DOPA oxidation reaction and showed excellent stereoselectivity towards its enantiomers. l-Phenylalanine-modified CeNPs showed higher catalytic ability for oxidation of d-DOPA, while d-phenylalanine-modified CeNPs were more effective towards l-DOPA. Taken together, the results indicated that stereoselective nanozyme can be constructed by grafting nanoparticles with chiral molecules. This work may inspire better design of chiral nanozymes.
对底物的立体选择性是酶最重要的特性之一。氨基酸作为许多酶的辅助因子,在立体化学中发挥着重要作用。在此,通过将一系列d-或l-氨基酸接枝到二氧化铈(氧化铈)纳米颗粒表面构建了手性纳米酶。我们选择了治疗帕金森病最常用的药物,即3,4-二羟基苯丙氨酸(DOPA)对映体,作为手性催化的实例。通过对用不同的八种氨基酸修饰的氧化铈纳米颗粒(CeNPs)进行详细的动力学研究,我们发现苯丙氨酸修饰的CeNP对DOPA氧化反应是最优的,并且对其对映体表现出优异的立体选择性。l-苯丙氨酸修饰的CeNPs对d-DOPA的氧化具有更高的催化能力,而d-苯丙氨酸修饰的CeNPs对l-DOPA更有效。综上所述,结果表明通过用手性分子接枝纳米颗粒可以构建立体选择性纳米酶。这项工作可能会激发对手性纳米酶的更好设计。