Stereochemical aspects of hydration of carbohydrates in aqueous solutions. 3. Density and ultrasound measurements

Galema, Saskia A.; Høiland, Harald

doi:10.1021/j100166a073

Cited by 259 publications

(235 citation statements)

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“…The affinities for galactose 17 and mannose 18 are considerably smaller. The order of extractabilities (glucose Ͼ galactose Ͼ mannose) does not reflect the estimated degrees of hydration (mannose Ͻ glucose Ͻ galactose) (32,33), suggesting a stereospecific interaction with the receptor. Indeed, as initially proposed (25), the tricyclic core of 1 may be especially complementary to substrates with equatorial substituents.…”

Section: H Nmrmentioning

confidence: 93%

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Ryan

Lecollinet²,

Velasco³

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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We have previously shown that macrotricyclic host 1a is a powerful receptor for glucopyranosyl units in the nonpolar medium of chloroform. However, the solubility properties of 1a did not permit studies of the extraction of carbohydrates from aqueous solution. This paper describes the synthesis of the new variant 1b, furnished with a highly lipophilic exterior array of 12 benzyloxy substituents. In homogeneous solution, 1b behaves much as 1a, binding n-octyl ␤-D-glucoside with Ka ‫؍‬ 720 M ؊1 in CD3OH͞CDCl3 (8:92). In twophase experiments, the improved solubility of 1b allows carbohydrate extraction to be observed. Three hexoses (glucose, galactose, and mannose), two pentoses (ribose and xylose), and the two methyl glucosides are all extracted substantially into chloroform from 1 M aqueous solutions. Among the hexoses, 1b shows notable affinity and selectivity for glucose, extracting detectable amounts even from 0.1 M aqueous solutions. C arbohydrate recognition is an active area of supramolecular chemistry, motivated by the biological importance of saccharides and also by the unusual challenge represented by these complex substrates (1-13). On the one hand, carbohydrates must be recognized and processed during metabolism, whereas saccharide motifs are known to mediate cell-cell recognition, the infection of cells by pathogens, and many aspects of the immune response (14-17). On the other, carbohydrates possess structures that are fairly large, irregular, and multivalent, while being quite similar to clusters of water molecules. Even in nonpolar solvents, selective carbohydrate receptors require extended, sophisticated architectures (1, 3-6). In the presence of liquid water, the problem becomes yet more difficult. Recognition by means of boronate formation has been relatively successful (2, 7-10), but there are few effective systems for binding saccharides from water by using noncovalent bonds (1, 11-13).A receptor can be shown to discriminate between saccharide and water in one of two ways. Firstly (and most obviously), it can be studied in homogeneous aqueous solution. Secondly, it can be designed for solubility in nonpolar media and studied in a two-phase system, demonstrating the ability to extract or transport the carbohydrate (18)(19)(20)(21)(22)(23)(24). This latter approach is directly relevant to the transport of carbohydrates across biological membranes. Boron-based systems have again proved quite effective (22-24). However, for those receptors operating through noncovalent interactions, success has been limited thus far. Positive results have been obtained with the less hydrophilic saccharides at high aqueous concentrations (18, 20), but not in general with the more hydrophilic substrates such as glucose. § Recently we described the tricyclic tetraester 1a (Fig. 1), a novel receptor that showed an exceptional affinity for n-octyl ␤-D-glucoside, remarkable ␤ vs. ␣ selectivity, and the unusual ability to dissolve solid glucose in CHCl 3 (25). Although we hoped to demonstrate the extraction of glucose ...

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Section: H Nmrmentioning

confidence: 93%

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Ryan

Lecollinet²,

Velasco³

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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“…This is the first example where a glucopyranose derivative is significantly more IRI active than a galactopyranose derivative. It was also surprising that both b-PMP-Gal (5) and b-PMP-Man (7) exhibited identical IRI activities despite the difference in hydration between these two pyranose residues 23,43,44 . Unfortunately, hydration numbers or molar compressibilities of 5-7 have not been reported in the literature, thus a correlation between the hydration characteristics of these compounds and their IRI activity is not possible at this time.…”

Section: Resultsmentioning

confidence: 99%

Small molecule ice recrystallization inhibitors enable freezing of human red blood cells with reduced glycerol concentrations

Acker

Capicciotti

Kurach

et al. 2015

Transfusion Medicine Reviews

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“…3 Interestingly, the extent of interaction could be related to the hydration characteristics of the carbohydrates. 3,4 Furthermore, the pattern of interactions reflected the stereochemistry of the carbohydrates: a carbohydrate with a better fit into the three dimensional hydrogenbonded network of water has a greater apparent hydrophobicity as gauged from its interaction parameter. (2) As a vehicle for studying the reaction mechanism of selected reactions in aqueous solution; for example the mechanism of the neutral hydrolysis of p-nitrophenyl methylsulfonyl perchlorate could be further elucidated.…”

Section: Introductionmentioning

confidence: 99%

Quantitative comparison of the effect of methylD-glycopyranosides as cosolutes on the rates of base hydrolysis and aquation of some iron(II)-diimine Complexes

Milde

Blandamer

Burgess

et al. 1999

J. Phys. Org. Chem.

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Quantitative comparison of the effect of methyl D-glycopyranosides as cosolutes on the rates of base hydrolysis and aquation of some iron(II)-diimine complexes Milde, Siobhan P.; Blandamer, Michael J.; Burgess, John; Engberts, Jan B.F.N.; Galema, Saskia A.; Hubbard, Colin D. Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. ABSTRACT: The kinetics of base hydrolysis and of aquation of some iron(II)-diimine complexes in the presence of stereoisomeric carbohydrates were monitored spectrophotometrically at 25.0°C. In basic aqueous solution dissociation of both Fe(1,10-phenanthroline) 3 2 and Fe(2,2'-bipyridine) 3 2 is accelerated when methyl Dglycopyranosides are present. The aquation reaction of Fe(1,10-phenanthroline) 3 2 in an aqueous EDTA medium is also accelerated in the presence of carbohydrates, but that of Fe(5-nitro-1,10-phenanthroline) 3 2 is retarded. An equation obtained from a modification of the Savage-Wood additivity of groups principle applied to kinetics is used to quantify the kinetic medium effects observed. The magnitudes of these effects can be explained in terms of the hydration characteristics of the carbohydrates, which depend on their stereochemistry, and the change in the hydration environment of the iron(II)-diimine complexes during activation. Results and their interpretation for the aquation in acidic medium of the Fe(5-bromo-1,10-phenanthroline) 3 2 and Fe(4,7-dimethyl-1,10-phenanthroline) 3 2 complexes in highly aqueous methanol and ethanol solutions are also presented. The kinetic medium effects of the carbohydrates are consistent with those of simple alcohols.

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Stereochemical aspects of hydration of carbohydrates in aqueous solutions. 3. Density and ultrasound measurements

Cited by 259 publications

References 0 publications

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Small molecule ice recrystallization inhibitors enable freezing of human red blood cells with reduced glycerol concentrations

Quantitative comparison of the effect of methylD-glycopyranosides as cosolutes on the rates of base hydrolysis and aquation of some iron(II)-diimine Complexes

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