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
相关论文
共 77 条
[11]   PROTON-EXCHANGE IN AQUEOUS-SOLUTIONS OF GLUCOSE - HYDRATION OF CARBOHYDRATES [J].
BOCIEK, S ;
FRANKS, F .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS I, 1979, 75 :262-270
[13]   INFRARED STUDY OF INTRAMOLECULAR HYDROGEN-BONDING IN ALPHA, OMEGA DIOLS [J].
BUSFIELD, WK ;
ENNIS, MP ;
MCEWEN, IJ .
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 1973, A 29 (07) :1259-1264
[14]   GENERAL 2-SITE SOLUTION FOR CHEMICAL EXCHANGE PRODUCED DEPENDENCE OF T2 UPON CARR-PURCELL PULSE SEPARATION [J].
CARVER, JP ;
RICHARDS, RE .
JOURNAL OF MAGNETIC RESONANCE, 1972, 6 (01) :89-&
[15]   Hydration studies of carbohydrates .4. NMR studies of carbohydrate hydration [J].
Cheetham, NWH ;
Lam, K .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1996, 49 (03) :365-369
[16]   Molecular dynamics simulations of glycosides in aqueous solution [J].
Cheetham, NWH ;
Lam, K .
CARBOHYDRATE RESEARCH, 1996, 282 (01) :13-23
[17]   CONFORMATION OF ETHYLENE-GLYCOL DISSOLVED IN A NEMATIC-LYOTROPIC SOLUTION - AN NMR ANALYSIS [J].
CHIDICHIMO, G ;
IMBARDELLI, D ;
LONGERI, M ;
SAUPE, A .
MOLECULAR PHYSICS, 1988, 65 (05) :1143-1151
[18]   DIRECT MEASUREMENTS OF THE DISSOCIATION-RATE CONSTANT FOR INHIBITOR-ENZYME COMPLEXES VIA THE T-1-RHO AND T-2 (CPMG) METHODS [J].
DAVIS, DG ;
PERLMAN, ME ;
LONDON, RE .
JOURNAL OF MAGNETIC RESONANCE SERIES B, 1994, 104 (03) :266-275
[19]   TREHALOSE CONFORMATION IN AQUEOUS-SOLUTION FROM OPTICAL-ROTATION [J].
DUDA, CA ;
STEVENS, ES .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (20) :7406-7407
[20]   Carbohydrate structural determination by NMR spectroscopy: Modern methods and limitations [J].
Duus, JO ;
Gotfredsen, CH ;
Bock, K .
CHEMICAL REVIEWS, 2000, 100 (12) :4589-+