Water T2 relaxation in sugar solutions

被引:35
作者
Fabri, D [1 ]
Williams, MAK [1 ]
Halstead, TK [1 ]
机构
[1] Univ York, Dept Chem, York YO19 6AL, N Yorkshire, England
关键词
polyols; methyl glycosides of monosaccharides; sucrose; trehalose; oligosaccharides; H-1 NMR CPMG relaxation dispersion; proton exchange;
D O I
10.1016/j.carres.2005.01.034
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
H-1 spin-spin relaxation times of water were measured with the CPMG sequence in dilute aqueous solutions of glucitol, mannitol, glycerol, glycol, the methyl D-pyranosides of alpha-glucose, beta-glucose, alpha-galactose, beta-galactose, alpha-xylose, beta-xylose, beta-arabinose and sucrose, alpha,alpha-trehalose, beta-maltose, maltotriose and maltoheptaose. The relaxation-time dispersion was measured by varying the CPMG pulse spacing, tau. These data were interpreted by means of the Carver-Richards model in which exchange between water protons and labile solute hydroxyl protons provides a significant contribution to the relaxation. From the dependences on temperature and T-2 parameters characteristic of the pool of hydroxyls belonging to a given solute were extracted by nonlinear regression, including: the fraction of exchangeable protons, P, the chemical-shift difference between water protons and hydroxyl protons, delta omega, the intrinsic spin-spin relaxation time, T-2, and the chemical exchange rate, k. These solute-specific parameters are related, respectively, to the concentration, identity, mobility and exchange life-time of the hydroxyl site. At 298 K, values of delta omega, T-2 and k were found to be of the order of 1 ppm, 100 ms and 1000 s(-1), respectively. Effects of molecular size, conformation and solute concentration were investigated. The exchange mechanism was characterised by Eyring activation enthalpies and entropies with values in the ranges 50-70 kJ mol(-1) and -10 to 60 J K-1 mol(-1), respectively. (c) 2005 Elsevier Ltd. All rights reserved.
引用
收藏
页码:889 / 905
页数:17
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