Yongping Cui, Jing Ai, Yingying Duan, Menghui Jia, Tianwei Ouyang, Aokun Liu, Lu Yu, Junhong Liu, Xi Liu, Chaoyang Chu, Yuanbo Li, Yanhang Ma, Liwei Chen, Lu Han, Jinquan Chen, Changlin Tian, Shunai Che, Yuxi Fang
{"title":"Enantioselective synthesis of amino acids by photocatalytic reduction of CO2 on chiral mesostructured ZnS","authors":"Yongping Cui, Jing Ai, Yingying Duan, Menghui Jia, Tianwei Ouyang, Aokun Liu, Lu Yu, Junhong Liu, Xi Liu, Chaoyang Chu, Yuanbo Li, Yanhang Ma, Liwei Chen, Lu Han, Jinquan Chen, Changlin Tian, Shunai Che, Yuxi Fang","doi":"10.1016/j.chempr.2024.102390","DOIUrl":null,"url":null,"abstract":"Reduction and fixation of CO<sub>2</sub> in natural systems via solar energy generate diverse products, ranging from small molecules to biomolecules. To date, only a few multicarbon species have been obtained by artificial CO<sub>2</sub> photoreduction, especially abiotic photosynthesis of biomolecules with various functional groups, which is a challenging issue. Herein, we report the photocatalytic synthesis of amino acids from CO<sub>2</sub> and NH<sub>3</sub> on a chiral mesostructured ZnS (CMZ). Serine is the main component of various amino acids, with an enantiomeric excess (<em>ee</em>) greater than 96% and a total yield of over 30 μmol g<sub>cat</sub><sup>−1</sup>. We propose that the chirality-induced spin polarization of CMZ boosts the creation of triplet OCCO by aligning its parallel electron spins, and the helical lattice distortion reduces the free energy of <sup>∗</sup>OCCO. Enantiospecific activation energies of reactions driven by the spin-polarized electrons in CMZ lead to the formation of enantiomeric amino acids.","PeriodicalId":268,"journal":{"name":"Chem","volume":"5 1","pages":""},"PeriodicalIF":19.1000,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/j.chempr.2024.102390","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Reduction and fixation of CO2 in natural systems via solar energy generate diverse products, ranging from small molecules to biomolecules. To date, only a few multicarbon species have been obtained by artificial CO2 photoreduction, especially abiotic photosynthesis of biomolecules with various functional groups, which is a challenging issue. Herein, we report the photocatalytic synthesis of amino acids from CO2 and NH3 on a chiral mesostructured ZnS (CMZ). Serine is the main component of various amino acids, with an enantiomeric excess (ee) greater than 96% and a total yield of over 30 μmol gcat−1. We propose that the chirality-induced spin polarization of CMZ boosts the creation of triplet OCCO by aligning its parallel electron spins, and the helical lattice distortion reduces the free energy of ∗OCCO. Enantiospecific activation energies of reactions driven by the spin-polarized electrons in CMZ lead to the formation of enantiomeric amino acids.
期刊介绍:
Chem, affiliated with Cell as its sister journal, serves as a platform for groundbreaking research and illustrates how fundamental inquiries in chemistry and its related fields can contribute to addressing future global challenges. It was established in 2016, and is currently edited by Robert Eagling.