DISACCHARIDE SOLUTION STEREOCHEMISTRY FROM VIBRATIONAL RAMAN OPTICAL-ACTIVITY
DISACCHARIDE SOLUTION STEREOCHEMISTRY FROM VIBRATIONAL RAMAN OPTICAL-ACTIVITY
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DOI：
10.1021/ja00091a019
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发表时间：
1994-06-15
影响因子：
15
通讯作者：
BARRON, LD
中科院分区：
文献类型：
--
作者：
BELL, AF;HECHT, L;BARRON, LD
本文报道了D-麦芽糖、D-麦芽糖-O-d（8）、D-纤维二糖、D-异麦芽糖、D-龙胆二糖、D-海藻糖和α-D-环糊精在水溶液中的振动拉曼旋光（罗阿）谱，其背散射波长在350 ~ 1500 cm（-1）之间，表明罗阿是一种新的二糖立体化学探针。指纹区域中的一些罗阿信号和两个罗阿对在类似于430+/-10和类似于917 cm（-1）处已被鉴定为表现出来自糖苷键的振动坐标的贡献。前对联的符号被发现取决于链接的配置，其宽度被发现取决于特定的链接类型。第二个罗阿对联只存在于D-麦芽糖和D-异麦芽糖的罗阿光谱中，并归因于氘代，研究涉及糖苷C-O-C伸缩坐标和C-O-H变形的模式。在D-麦芽糖和D-异麦芽糖中，这种偶合剂的相反符号可能反映了CH 2基团参与连接或构象变化。指纹区域中类似于950-1200 cm（-1）的罗阿信号的符号、强度和位置似乎是特定二糖单元的特征。在类似于1200-1500 cm（-1）的CH 2和COH变形区域中获得互补信息，其中二糖罗阿光谱被证明是组成单糖的相应罗阿光谱的叠加。同样在该区域中，在类似于1260 cm（-1）处的正罗阿带被指定为β-异头形式，并用于估计某些二糖的还原残基中的异头群体。
The vibrational Raman optical activity (ROA) spectra of D-maltose, D-maltose-O-d(8), D-cellobiose, D-isomaltose, D-gentiobiose, D-trehalose, and alpha-D-cyclodextrin in aqueous solution between similar to 350 and 1500 cm(-1) measured in backscattering are reported, which show that ROA is an incisive new probe of disaccharide stereochemistry. Some of the ROA signals in the fingerprint region and two ROA couplets at similar to 430+/-10 and similar to 917 cm(-1) have been identified to exhibit contributions from vibrational coordinates of the glycosidic link. The sign of the former couplet was found to depend on the configuration of the link, and its width was found to depend on the particular linkage type. The second ROA couplet was present only in the ROA spectra of D-maltose and D-isomaltose and was attributed from deuteration, studies to a mode involving glycosidic C-O-C stretching coordinates and C-O-H deformations. Opposite signs for this coupler in D-maltose and D-isomaltose may reflect either the involvement of the CH2 group in the linkage or conformational changes. Sign, intensity, and position of the ROA signals in the fingerprint region similar to 950-1200 cm(-1) appear to be characteristic for a particular disaccharide unit. Complementary information is obtained in the CH2 and COH deformations region similar to 1200-1500 cm(-1),where the disaccharide ROA spectra were demonstrated to be superpositions of the corresponding ROA spectra of the constituent monosaccharides. Also in this region a positive ROA band at similar to 1260 cm(-1) was assigned to the beta-anomeric form and used to estimate the anomeric populations in the reducing residues of some disaccharides.