Pyrrolic tripodal receptors effectively recognizing monosaccharides. Affinity assessment through a generalized binding descriptor

被引:86
作者
Nativi, Cristina
Cacciarini, Martina
Francesconi, Oscar
Vacca, Alberto
Moneti, Gloriano
Ienco, Andrea
Roelens, Stefano
机构
[1] CNR, IMC, I-50019 Florence, Italy
[2] CNR, ICCOM, I-50019 Florence, Italy
[3] Univ Florence, Dipartimento Chim Organ, I-50121 Florence, Italy
[4] Univ Florence, Dipartimento Chim, CERM, I-50121 Florence, Italy
[5] Univ Florence, CISM, I-50121 Florence, Italy
关键词
MOLECULAR RECOGNITION; CARBOHYDRATE-RECOGNITION; WATER;
D O I
10.1021/ja068754m
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Pyrrolic and imino (3) or amino (4) H-bonding ligands were incorporated into a benzene-based tripodal scaffold to develop a new generation of receptors for molecular recognition of carbohydrates. Receptors 3 and 4 effectively bound a set of octylglycosides of biologically relevant monosaccharides, including glucose (Glc), galactose (Gal), mannose (Man), and N-acetyl-glucosamine (GlcNAc), showing micromolar affinities in CDCl3 and millimolar affinities in CD3CN by NMR titrations. Both receptors selectively recognized Glc among the investigated monosaccharides, with 3 generally less effective than 4 but showing selectivities for the all-equatorial beta-glycosides of Glc and GlcNAc among the largest reported for H-bonding synthetic receptors. Selectivities in CDCl3 spanned a range of nearly 250-fold for 3 and over 30-fold for 4. Affinities and selectivities were univocally assessed through the BC50 descriptor, for which a generalized treatment is described that extends the scope of the descriptor to include any two-reagent host-guest system featuring any number of binding constants. ITC titrations of beta Glc in acetonitrile evidenced, for both receptors, a strong enthalpic contribution to the binding interaction, suggesting multiple H bonding. Selectivity trends toward alpha Glc and beta Glc analogous to those obtained in solution were also observed in the gas phase for 3 and 4 by collision-induced dissociation experiments. From comparison with appropriate reference compounds, a substantial contribution to carbohydrate binding emerged for both the imino/amino and the pyrrolic H-bonding groups but not for the amidic group. This previously undocumented behavior, supported by crystallographic evidence, has been discussed in terms of geometric, functional, and coordinative complementarity between H-bonding groups and glycosidic hydroxyls and opens the way to a new designer strategy of H-bonding receptors for carbohydrates.
引用
收藏
页码:4377 / 4385
页数:9
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