Carçabal Pierre, Jockusch Rebecca A, Hünig Isabel, Snoek Lavina C, Kroemer Romano T, Davis Benjamin G, Gamblin David P, Compagnon Isabelle, Oomens Jos, Simons John P
Chemistry Department, Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QZ United Kingdom.
J Am Chem Soc. 2005 Aug 17;127(32):11414-25. doi: 10.1021/ja0518575.
The conformation of phenyl-substituted monosaccharides (mannose, galactose, and glucose) and their singly hydrated complexes has been investigated in the gas phase by means of a combination of mass selected, conformer specific ultraviolet and infrared double resonance hole burning spectroscopy experiments, and ab initio quantum chemistry calculations. In each case, the water molecule inserts into the carbohydrate at a position where it can replace a weak intramolecular interaction by two stronger intermolecular hydrogen bonds. The insertion can produce significant changes in the conformational preferences of the carbohydrates, and there is a clear preference for structures where cooperative effects enhance the stability of the monosaccharide conformers to which the water molecule chooses to bind. The conclusions drawn from the study of monosaccharide-water complexes are extended to the disaccharide lactose and discussed in the light of the underlying mechanisms that may be involved in the binding of carbohydrate assemblies to proteins and the involvement, or not, of key structural water molecules.
通过质量选择、构象特异性紫外和红外双共振空穴烧蚀光谱实验以及从头算量子化学计算相结合的方法，在气相中研究了苯基取代的单糖（甘露糖、半乳糖和葡萄糖）及其单水合物配合物的构象。在每种情况下，水分子都插入到碳水化合物的某个位置，在该位置它可以通过两个更强的分子间氢键取代一个弱的分子内相互作用。这种插入会使碳水化合物的构象偏好产生显著变化，并且明显偏好那些协同效应增强水分子选择结合的单糖构象稳定性的结构。从单糖 - 水配合物研究中得出的结论扩展到二糖乳糖，并根据碳水化合物组装体与蛋白质结合可能涉及的潜在机制以及关键结构水分子是否参与进行了讨论。
