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A Hydrogen‐Bonding Receptor That Binds Cationic Monosaccharides with High Affinity in Methanol
Author(s) -
Tamaru Shunichi,
Yamamoto Masashi,
Shinkai Seiji,
Khasanov Alisher B.,
Bell Thomas W.
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20011217)7:24<5270::aid-chem5270>3.0.co;2-h
Subject(s) - chemistry , hydrogen bond , monosaccharide , cationic polymerization , carboxylate , non covalent interactions , circular dichroism , hydrophobic effect , solvent , crystallography , stereochemistry , molecule , organic chemistry
A dicarboxylate host ( 1 ) binds cationic monosaccharides such as D ‐glucosamine ⋅ HCl ( 2 ), D ‐galactosamine ⋅ HCl ( 3 ), and D ‐mannosamine ⋅ HCl ( 4 ) with high affinity ( K 1 =8.0×10 4 –−2.0×10 5 M −1 ) in methanol. In circular dichroism (CD) spectroscopy a positive exciton‐coupling band was observed near 290 nm; this indicates that the saccharides are recognized by multiple point interactions. Since the corresponding neutral monosaccharides are not significantly bound, one may conclude that complex formation is primarily due to the electrostatic interaction between NH 3 + in the guest and one carboxylate in the host and secondarily due to hydrogen‐bonding interactions of OH groups with the other carboxylate and/or nitrogen bases. Molar ratio plots and Job plots indicate that host 1 and cationic monosaccharide guests form CD‐active, pseudo‐cyclic 1:1 complexes at low guest concentration followed by the formation of CD‐silent, acyclic 1:2 1⋅ saccharide complexes at high guest concentration. The possible binding modes are discussed in detail on the basis of molecular mechanics calculations and chemical shift changes in 1 H NMR spectra. The results of competition experiments with several cationic reference compounds bearing fewer OH groups than 2 – 4 are consistent with the proposed binding model. Thus, the present study is a rare example of saccharide recognition in a protic solvent, where in general, hydrogen‐bonding interactions are rarely useful because of strong solvation energy. These are apparently the strongest saccharide complexes involving noncovalent interactions between host and guest. We believe that the findings are significant as a milestone toward development of new saccharide recognition systems ultimately useful in aqueous solution.