Solvent effect on hydrogen bonded Tyr⋯Asp⋯Arg triads: Enzymatic catalyzed model system.
The hydrogen bond plays a vital role in structural arrangement, intermediate state stabilization, materials function, and biological activity of certain enzymatic reactions. The solvent and electronic effects on hydrogen bonds are illustrated employing the polarizable contimuum model at B3LYP/6-311++G(d,p) level. Geometry optimizations reflect the significant solvent and electronic effect. The proton departs spontaneously upon oxidation from the hydroxyl group of tyrosyl in hydrogen bonded Tyr⋯Asp⋯Arg triads in both gas phase and solvents. The electron transfer isomers are observed for anionic triads, no matter what the solvent is. The difference of distance between two hydrogen bonds is enlarged in solvent as compared to that in gas phase. The electronic effect on IR spectra is distinctive. The tyrosyl fragment tends to be oxidized and the arginine moiety is easier to bind an excess electron. The variations of chemical shift and spin-spin coupling constant are more significant upon electron transfer than upon solvent dielectric constant. The augmentation of solvent dielectric constant stabilizes the system, enhances the difference of isomers, and increases the vertical ionization potential and vertical electron affinity values.
College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao, 266109, China. Electronic address: yansh@qibebt.ac.cn.
Shihai
S
Yan
Laboratory of Biofuels, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266061, China. Electronic address: yaols@qibebt.ac.cn.
Lishan
L
Yao
School of Chemistry and Chemical Engineering, University of Jinan, Jinan, 250022, China. Electronic address: chm_kangbt@ujn.edu.cn.
Baotao
B
Kang
Department of Chemistry, Sungkyunkwan University, Suwon, 440746, Republic of Korea, Republic of Korea. Electronic address: jinylee@skku.edu.
Jin Yong
JY
Lee
D001120:Arginine / Q000737:chemistry*; D001224:Aspartic Acid / Q000737:chemistry*; D002384:Catalysis; D004798:Enzymes / Q000378:metabolism*; D006860:Hydrogen Bonding; D012997:Solvents / Q000737:chemistry*; D013057:Spectrum Analysis; D013816:Thermodynamics; D014443:Tyrosine / Q000737:chemistry*
D004798:Enzymes; D012997:Solvents; D001224:Aspartic Acid; D014443:Tyrosine; D001120:Arginine
Electron transfer; Electronic effect; Proton transfer; Solvent effect; Spin-spin coupling constant