Experimental measurement of carbohydrate-aromatic stacking in water by using a dangling-ended DNA model system.
Protein-carbohydrate recognition is of fundamental importance for a large number of biological processes; carbohydrate-aromatic stacking is a widespread, but poorly understood, structural motif in this recognition. We describe, for the first time, the measurement of carbohydrate-aromatic interactions from their contribution to the stability of a dangling-ended DNA model system. We observe clear differences in the energetics of the interactions of several monosaccharides with a benzene moiety depending on the number of hydroxy groups, the stereochemistry, and the presence of a methyl group in the pyranose ring. A fucose-benzene pair is the most stabilizing of the studied series (-0.4 Kcal mol(-1)) and this interaction can be placed in the same range as other more studied interactions with aromatic residues of proteins, such as Phe-Phe, Phe-Met, or Phe-His. The noncovalent forces involved seem to be dispersion forces and nonconventional hydrogen bonds, whereas hydrophobic effects do not seem to drive the interaction.
Morales
Juan C
JC
Department of Bioorganic Chemistry, Instituto de Investigaciones Químicas, CSIC-Universidad de Sevilla, Sevilla, Spain. jcmorales@iiq.csic.es
Reina
José J
JJ
Díaz
Irene
I
Aviñó
Anna
A
Nieto
Pedro M
PM
Eritja
Ramón
R
D002241:Carbohydrates / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008957:Models, Genetic; D009841:Oligonucleotides / Q000737:chemistry; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D002241:Carbohydrates; D009841:Oligonucleotides; D014867:Water; D004247:DNA