pH-Dependent Chirality of L-Proline Studied by Raman Optical Activity and Density Functional Theory Calculation

	pH-Dependent Chirality of L-Proline Studied by Raman Optical Activity and Density Functional Theory Calculation
	Qiu, Shi 1,2; Li, Guanna 1,2; Wang, Peng 1,2; Zhou, Jun 1,2; Feng, Zhaochi 1; Li, Can 1
刊名	journal of physical chemistry a
	2011-03-03
卷号	115 期号:8 页码:1340-1349
ISSN号	待补充
通讯作者	冯兆池 ; 李灿
产权排序	1,1
中文摘要	ph-dependent chirality of l-proline studied by raman optical activity and density functional theory calculation
英文摘要	the characteristic pyrrolidine ring structure of proline (pro) and its conformational flexibility are important to its biological function in peptides and proteins properties of pro in aqueous solution vary with the acid base conditions. in this work, raman optical activity (roa) spectroscopy is used to carefully study the chirality of l-pro in aqueous solution with different ph values. raman shifts and roa intensities are found to be directly correlated with the acidic or basic environment. pyrrolidine ring torsions and carbonyl group twists differ in cation, zwitterion, and anion forms (denoted as proca, prozw, and proan, respectively), as confirmed by the agreement between the experimental results and density functional theory (dft) calculation. from analysis of vibrational modes and group couple matrices (gcms), the local carbonyl group stretching modes may reflect electronic structure changes, and the couplings between the three ch(2) group with others mainly contribute to the roa intensities in the low wavenumber region (1400-700 cm(-1)). the dramatic changes of the distributions and dispersion of the roa intensities indicate that an acidic or basic environment not only leads to the simple abstraction or addition of a proton, but also changes. the electron delocalization throughout the molecule. isolation of the two symmetric anisotropic invariants shows the predominant contributions of the electric dipole-magnetic dipole invariant to the roa signals in l-pro. these results will be useful for interpreting the roa spectra of proteins and at least proline-rich peptides.
学科主题	物理化学
WOS标题词	science & technology ; physical sciences
类目[WOS]	chemistry, physical ; physics, atomic, molecular & chemical
研究领域[WOS]	chemistry ; physics
关键词[WOS]	correlated molecular calculations ; gaussian-basis sets ; vibrational circular-dichroism ; activity spectra ; conformational preferences ; aqueous-solution ; amino-acids ; l-alanine ; proteins ; residues
收录类别	SCI
语种	英语
WOS记录号	WOS:000287636400005
公开日期	2012-07-09
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/115719]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China 2.Chinese Acad Sci, Grad Univ, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Qiu, Shi,Li, Guanna,Wang, Peng,et al. pH-Dependent Chirality of L-Proline Studied by Raman Optical Activity and Density Functional Theory Calculation[J]. journal of physical chemistry a,2011,115(8):1340-1349.
APA	Qiu, Shi,Li, Guanna,Wang, Peng,Zhou, Jun,Feng, Zhaochi,&Li, Can.(2011).pH-Dependent Chirality of L-Proline Studied by Raman Optical Activity and Density Functional Theory Calculation.journal of physical chemistry a,115(8),1340-1349.
MLA	Qiu, Shi,et al."pH-Dependent Chirality of L-Proline Studied by Raman Optical Activity and Density Functional Theory Calculation".journal of physical chemistry a 115.8(2011):1340-1349.