Investigation of the Hydrogen Bonding Properties of a Series of Monosaccharides in Aqueous Media by 1H NMR and IR Spectroscopy

Abstract

A technique, based on 1 H NMR and IR experiments, to characterise intramolecular hydrogen bonds in aqueous medium in a series of amino, amido and ammonium sugar derivatives has been established. Three groups of molecules, representing amides (4, 5 and 6), amines (7 and 8) and ammonium salts (chlorides 9 and 10, and phosphates 11 and 12), with different relative configurations of their functional groups, have been investigated to assess the effect of the nature and the stereochemistry of these groups on the hydrogen-bonding features of the sugar. The deduced features in water solution are compared to those obtained previously in nonpolar solvents. The phosphate salts of amines 7 and 8 (11 and 12)

Conformation, dynamics, solvation and relative stabilities of selected β-hexopyranoses in water: a molecular dynamics study with the gromos 45A4 force field

“…However, although sometimes questioned, 143 the existence of stable intramolecular hydrogen-bonds for monosaccharide analogs in aqueous solution has been unambiguously evidenced by NMR and IR techniques. 110,[113][114][115]144,148 It is also supported by the results of numerous atomistic simulations of carbohydrate systems (see below). Finally, a number of studies have also underlined the importance of cooperativity effects in intramolecular hydrogen-bonding for this class of compounds.…”

Conformation, dynamics, solvation and relative stabilities of selected β-hexopyranoses in water: a molecular dynamics study with the gromos 45A4 force field

“…However, although sometimes questioned, 143 the existence of stable intramolecular hydrogen-bonds for monosaccharide analogs in aqueous solution has been unambiguously evidenced by NMR and IR techniques. 110,[113][114][115]144,148 It is also supported by the results of numerous atomistic simulations of carbohydrate systems (see below). Finally, a number of studies have also underlined the importance of cooperativity effects in intramolecular hydrogen-bonding for this class of compounds.…”

Glycopolymer-Wrapped Carbon Nanotubes Show Distinct Interaction of Carbohydrates With Lectins

“…This observation also suggests that the noncovalent system of Glyco-SWCNTs provides an advantage of studying the carbohydrate-protein interactions with improved sensitivity via the competitive binding of molecules, as a biologically active ligand-receptor pair may act as a competitor to displace the lower affinity glycopolymer-SWCNT interaction ( Antonik et al, 2016 ). Furthermore, the cooperative hydrogen-bond networks created by the intra- and inter-molecular hydrogen bonds with the hydroxyl groups of neighboring carbohydrates and the environment, such as water molecules, play a major role in stabilizing hydrated carbohydrate conformation as well as molecular recognition ( Hawley et al, 2002 ; Çarçabal et al, 2005 ). The strongly rigidified conformation of disaccharide Lact-homopolymers around the SWCNT surface may create a specific solvated state of the internal Glc groups with certain conformation that can potentially involve in the cooperative hydrogen bond recognition of Con A.…”

Intramolecular hydrogen-bonding in aqueous carbohydrates as a cause or consequence of conformational preferences: a molecular dynamics study of cellobiose stereoisomers

“…It may not be applicable to longer polymers and to other environments. For longer polymers, H-bonding cooperativity effect (Jeffrey 1990;Luque et al 1998;Hawley et al 2002;López de la Paz et al 2002;Ç arçabal et al 2005;Simons et al 2005;Dashnau et al 2005;Deshmukh et al 2008) may come into play. Furthermore, for extended chains or at finite concentrations, folding or intermolecular association (principally driven by the hydrophobic effect) lead to the occurrence of buried H-bonds.…”

Conformation, dynamics, solvation and relative stabilities of selected β-hexopyranoses in water: a molecular dynamics study with the gromos 45A4 force field

“…However, although sometimes questioned, 143 the existence of stable intramolecular hydrogen-bonds for monosaccharide analogs in aqueous solution has been unambiguously evidenced by NMR and IR techniques. 110,[113][114][115]144,148 It is also supported by the results of numerous atomistic simulations of carbohydrate systems (see below). Finally, a number of studies have also underlined the importance of cooperativity effects in intramolecular hydrogen-bonding for this class of compounds.…”

Glycopolymer-Wrapped Carbon Nanotubes Show Distinct Interaction of Carbohydrates With Lectins

“…This observation also suggests that the noncovalent system of Glyco-SWCNTs provides an advantage of studying the carbohydrate-protein interactions with improved sensitivity via the competitive binding of molecules, as a biologically active ligand-receptor pair may act as a competitor to displace the lower affinity glycopolymer-SWCNT interaction ( Antonik et al, 2016 ). Furthermore, the cooperative hydrogen-bond networks created by the intra- and inter-molecular hydrogen bonds with the hydroxyl groups of neighboring carbohydrates and the environment, such as water molecules, play a major role in stabilizing hydrated carbohydrate conformation as well as molecular recognition ( Hawley et al, 2002 ; Çarçabal et al, 2005 ). The strongly rigidified conformation of disaccharide Lact-homopolymers around the SWCNT surface may create a specific solvated state of the internal Glc groups with certain conformation that can potentially involve in the cooperative hydrogen bond recognition of Con A.…”

Intramolecular hydrogen-bonding in aqueous carbohydrates as a cause or consequence of conformational preferences: a molecular dynamics study of cellobiose stereoisomers

“…It may not be applicable to longer polymers and to other environments. For longer polymers, H-bonding cooperativity effect (Jeffrey 1990;Luque et al 1998;Hawley et al 2002;López de la Paz et al 2002;Ç arçabal et al 2005;Simons et al 2005;Dashnau et al 2005;Deshmukh et al 2008) may come into play. Furthermore, for extended chains or at finite concentrations, folding or intermolecular association (principally driven by the hydrophobic effect) lead to the occurrence of buried H-bonds.…”

Conformation, dynamics, solvation and relative stabilities of selected β-hexopyranoses in water: a molecular dynamics study with the gromos 45A4 force field

“…However, although sometimes questioned, 143 the existence of stable intramolecular hydrogen-bonds for monosaccharide analogs in aqueous solution has been unambiguously evidenced by NMR and IR techniques. 110,[113][114][115]144,148 It is also supported by the results of numerous atomistic simulations of carbohydrate systems (see below). Finally, a number of studies have also underlined the importance of cooperativity effects in intramolecular hydrogen-bonding for this class of compounds.…”

Glycopolymer-Wrapped Carbon Nanotubes Show Distinct Interaction of Carbohydrates With Lectins

“…This observation also suggests that the noncovalent system of Glyco-SWCNTs provides an advantage of studying the carbohydrate-protein interactions with improved sensitivity via the competitive binding of molecules, as a biologically active ligand-receptor pair may act as a competitor to displace the lower affinity glycopolymer-SWCNT interaction ( Antonik et al, 2016 ). Furthermore, the cooperative hydrogen-bond networks created by the intra- and inter-molecular hydrogen bonds with the hydroxyl groups of neighboring carbohydrates and the environment, such as water molecules, play a major role in stabilizing hydrated carbohydrate conformation as well as molecular recognition ( Hawley et al, 2002 ; Çarçabal et al, 2005 ). The strongly rigidified conformation of disaccharide Lact-homopolymers around the SWCNT surface may create a specific solvated state of the internal Glc groups with certain conformation that can potentially involve in the cooperative hydrogen bond recognition of Con A.…”

Intramolecular hydrogen-bonding in aqueous carbohydrates as a cause or consequence of conformational preferences: a molecular dynamics study of cellobiose stereoisomers

“…It may not be applicable to longer polymers and to other environments. For longer polymers, H-bonding cooperativity effect (Jeffrey 1990;Luque et al 1998;Hawley et al 2002;López de la Paz et al 2002;Ç arçabal et al 2005;Simons et al 2005;Dashnau et al 2005;Deshmukh et al 2008) may come into play. Furthermore, for extended chains or at finite concentrations, folding or intermolecular association (principally driven by the hydrophobic effect) lead to the occurrence of buried H-bonds.…”