Tuning selectivity in macrotricyclic carbohydrate receptors; CH ? N mutations in aromatic spacersElectronic supplementary information (ESI) available: experimental details for the synthesis of receptors 3 and 4, binding studies of receptors 3 and 4 with monosaccharide 2, and extraction experiments. See http://www.rsc.org/suppdata/ob/b3/b315447e/

Velasco, Trinidad; Lecollinet, Grégory; Ryan, Theo; Davis, Anthony P.

doi:10.1039/b315447e

Cited by 35 publications

(12 citation statements)

References 14 publications

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“…As mentioned by Davis et al, the extractions of substrates from water into nonpolar solvents "allow straightforward comparisons between receptors under conditions which mimic, to some extent, the cytosol-membrane interface in biology". 12 Studies of the extraction of methyl glycosides, such as βglucoside 36, β-galactoside 37, α-glucoside 38, and α-galactoside 39, from aqueous solution into chloroform (see Table 2) revealed a binding preference for β-glucoside, i.e., for a substrate with all-equatorial substitution pattern (similar to the receptors reported by Davis et al 8 ). Compared to 1 and 2, compounds 11 and 13 showed increased affinity to the tested carbohydrates, but similar binding preferences; the extractability decreased in the sequence β-glucoside 36 > β-galactoside 37 > α-glucoside 38 > α-galactoside 39.…”

Section: ■ Introductionsupporting

confidence: 71%

Carbohydrate Receptors Combining Both a Macrocyclic Building Block and Flexible Side Arms as Recognition Units: Design, Syntheses, and Binding Studies

Lippe

Mazik

2015

J. Org. Chem.

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Carbohydrate receptors combining a macrocyclic building block and two flexible side arms were designed on the base of the analysis of the binding motifs found in the crystal structures of the complexes formed between artificial receptors and monosaccharides, reported previously by our group. Binding studies in two-phase systems, such as extractions of sugars from water into organic phase, as well as in homogeneous organic media, using (1)H NMR and fluorescence spectroscopic titrations, confirmed the suitability of the designed compounds to act as highly effective and selective carbohydrate receptors. Depending on the nature of the bridges and side arms used as the building blocks, various receptors with different binding properties could be developed. The obtained results confirmed the validity of the receptor design and revealed that crystalline receptor-sugar complexes are particularly a valuable basis for the design of new effective receptor systems.

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Section: ■ Introductionsupporting

confidence: 71%

Carbohydrate Receptors Combining Both a Macrocyclic Building Block and Flexible Side Arms as Recognition Units: Design, Syntheses, and Binding Studies

Lippe

Mazik

2015

J. Org. Chem.

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“…To study the extraction by 1 of monosaccharides from water into CHCl 3 , aqueous sugar solutions were equilibrated with 1 in CHCl 3 (1 m M ) at 25 °C. Solutions of receptor in chloroform were then shaken vigorously with aqueous carbohydrate, the phases were separated, and the organic phase was passed through hydrophobic filter paper to remove residual aqueous solution (similar to the procedure used by Davis et al 6g. n).…”

Section: Resultsmentioning

confidence: 99%

Highly Effective Recognition of Carbohydrates by Phenanthroline‐Based Receptors: α‐ versus β‐Anomer Binding Preference

Mazik

Hartmann

Jones

2009

Chemistry A European J

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(1)H NMR spectroscopic titrations in competitive and non-competitive media, as well as binding studies in two-phase systems, such as phase transfer of sugars from aqueous into organic solvents and dissolution of solid carbohydrates in apolar media revealed both highly effective recognition of neutral carbohydrates and interesting binding preferences of an acyclic phenanthroline-based receptor 1. Compared to the previously described acyclic receptors, compound 1 displays significantly higher binding affinities, the rare capability to extract sugars from water into non-polar organic solutions and alpha- versus beta-anomer binding preference in the recognition of glycosides, which differs from those observed for other receptor systems. X-ray crystallographic investigations revealed the presence of water molecules in the binding pocket of 1 that are engaged in the formation of hydrogen-bonding motifs similar to those suggested by molecular modelling for the sugar OH groups in the receptor-sugar complexes. The molecular modelling calculations, synthesis, crystal structure and binding properties of 1 are described and compared with those of the previously described receptors.

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“…On the contrary, the isophthalamide moiety, lacking such ordering interactions, is often perceived as having preference towards syn – anti conformation of its amide groups (Figure 1). 30 This conformation does not allow two convergent hydrogen bonds to be formed and is therefore unsuitable for anion binding. Such a view was gained from numerous crystal structures of syn – anti isophthalamides and reinforced by calculations of Hunter and Purvis 28.…”

Section: Synthesismentioning

confidence: 99%

Anion Binding versus Intramolecular Hydrogen Bonding in Neutral Macrocyclic Amides

Chmielewski

Jurczak

2006

Chemistry A European J

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Although amide groups are important hydrogen-bond donors in natural and synthetic anion receptors, studies on structure-affinity relationships of amide-based macrocyclic receptors are still very limited. Therefore, we synthesized a series of macrocyclic tetraamides 5-8 derived from 1,3-benzenedicarboxylic (isophthalic) acid and aliphatic alpha,omega-diamines of different lengths. (1)H NMR titrations in DMSO solution show that the anion affinity of these receptors decreases with increasing size of the macrocycle irrespective of the anion, and this suggests a minor role of geometric complementarity. Comparison with their previously studied pyridine congeners reveals that the isophthalic acid based macrocycles are less potent, in contrast to what was found for simple model diamides. Combined theoretical and experimental structural studies were carried out to determine the reasons behind this behaviour. The results show that the unexpectedly low anion binding ability of the isophthalic acid-based receptors is due to the self-complementary nature of the isophthalic bis-amide fragments: when two such moieties are present within a sufficiently flexible macrocycle, they adopt syn-anti conformations and bind each other by two strong intramolecular hydrogen bonds that close the macrocyclic cavity. Nevertheless, anion binding is able to break these hydrogen bonds and switch a macrocycle into a convergent all-syn conformation. Despite the ill-preorganized conformation, 20-membered receptor 6 is better than either its open-chain analogue (macrocyclic effect) and/or its isomer having differently placed carbonyl groups. The crystal structures of four anion complexes of the macrocyclic receptors are reported. X-ray studies and solution NMR data confirmed the inclusive nature of the complexes and pointed to strong involvement of aromatic CH hydrogen atoms in anion binding.

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Abstract: Dipicolinoyl spacer groups are used to control the conformational and H-bonding properties of tricyclic carbohydrate receptors 3 and 4. Binding selectivities are changed in relation to all-isophthaloyl system 1b.

Cited by 35 publications

References 14 publications

Carbohydrate Receptors Combining Both a Macrocyclic Building Block and Flexible Side Arms as Recognition Units: Design, Syntheses, and Binding Studies

Carbohydrate Receptors Combining Both a Macrocyclic Building Block and Flexible Side Arms as Recognition Units: Design, Syntheses, and Binding Studies

Highly Effective Recognition of Carbohydrates by Phenanthroline‐Based Receptors: α‐ versus β‐Anomer Binding Preference

Anion Binding versus Intramolecular Hydrogen Bonding in Neutral Macrocyclic Amides

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