Saccharide Recognition and Helix Formation in Water with an Amphiphilic Pyridine–Phenol Alternating Oligomer

Ohishi, Yuki; Abe, Hajime; Inoûye, Masahiko

doi:10.1002/ejoc.201701522

Cited by 20 publications

(7 citation statements)

References 67 publications

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“…A series of scaffolds, including mono-, , bi-, − and tricyclic systems, as well as podand-like − and foldameric − receptors, have exhibited remarkable binding affinities for glucose and its derivatives in organic solvents. By contrast, linear oligomeric, acyclic, , monocyclic, − multicyclic, − and capsule-like receptors, exhibiting increasing performance in the recognition of carbohydrates in water, have all emerged over the past two decades. Among these receptors, one of the most successful strategies for recognizing glucose in water is based on the temple-like receptors developed by Davis − at the University of Bristol in the United Kingdom.…”

Section: Introductionmentioning

confidence: 99%

PCage: Fluorescent Molecular Temples for Binding Sugars in Water

et al. 2021

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The development of synthetic receptors that recognize carbohydrates in water with high selectivity and specificity is challenging on account of their structural complexity and strong hydrophilicity. Here, we report on the design and synthesis of two pyrene-based, temple-shaped receptors for the recognition of a range of common sugars in water. These receptors rely on the use of two parallel pyrene panels, which serve as roofs and floors, capable of forming multiple [C−H•••π] interactions with the axially oriented C−H bonds on glycopyranosyl rings in the carbohydratebased substrates. In addition, eight polarized pyridinium C−H bonds, projecting from the roofs and floors of the temple receptors toward the binding cavities, form [C−H•••O] hydrogen bonds, with the equatorially oriented OH groups on the sugars located inside the hydrophobic cavities. Four para-xylylene pillars play a crucial role in controlling the distance between the roof and floor. These temple receptors are highly selective for the binding of glucose and its derivatives. Furthermore, they show enhanced fluorescence upon binding with glucose in water, a property which is useful for glucose-sensing in aqueous solution.

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Section: Introductionmentioning

confidence: 99%

PCage: Fluorescent Molecular Temples for Binding Sugars in Water

et al. 2021

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“…45 The phenolpyridine oligomer 62, an acyclic water-soluble relative of 23, showed evidence of very weak binding to glucose, but was more successful with aminosugars; its affinity for glucosamine 34 was measured as Ka = 2000 M -1 . 46 Both 61 and 62 are composed of rigid units so that conformational freedom is limited. It may be difficult to predict exactly how they will fold, but the ch ances of clefts or cavities may be relatively high.…”

Section: Alternative Solutionsplatforms Strands and Toroidsmentioning

confidence: 99%

Biomimetic carbohydrate recognition

2020

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“…21 Our research efforts, aimed at exploiting a highly directional noncovalent network to select saccharides, have been applied herein to their amino derivatives. Recently, an amphiphilic oligomer was found to form very stable complexes with D-glucosamine, 22 but so far cucurbit [7]uril (CB [7]) has been shown to be the best-suited receptor to discriminate between D-glucosamine and D-galactosamine by selectively trapping their α-anomers. 23 This very specific ability of CB [7] has been further investigated for analytical purposes by ESI-mass spectrometry, 24 whose speed and sensitivity are its most remarkable advantages.…”

Section: ■ Introductionmentioning

confidence: 99%

Unprotected Galactosamine as a Dynamic Key for a Cyclochiral Lock

Fraschetti

Letzel

Paletta

et al. 2021

J. Am. Soc. Mass Spectrom.

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The discrimination of d -galactosamine ( G ), representative of the amino-sugar class of compounds, has been probed through nano-ESI-FT-ICR mass spectrometry by isolating the relevant [ C ·H· G ] + proton-bound complexes with the enantiomers of the cyclochiral resorcin[4]arene C and allowing them to react toward three primary amines ( B = EtNH 2 , i PrNH 2 , and ( R )- and ( S )- s BuNH 2 ). The system under investigation presents several features that help to unveil the behavior of unprotected G in such a supramolecular architecture: (i) the hydrophobic derivatization of the C convex side forces the polar guest G to be coordinated by the cyclochiral concave region; (ii) protonated d -galactosamine exists as an anomeric mixture, dynamically interconverting throughout the experimental time-window; and (iii) different basicities of B allow the experiment to subtly tune the reactivity of the [ C ·H· G ] + complexes. Three [ C ·H· G ] + aggregate-types were found to exist, differing in both their origin and reactivity. The most reactive adducts ([ C ·H· G ] ESI + ), generated in the electrospray environment, undergo a G -to- B ligand exchange in competition with a partial isomerization to the unreactive [ C ·H· G ] GAS + -type complexes. Finally, the poorly reactive [ C ·H· G ] SOL + aggregates are formed in solution over an hours-long time scale. A cyclochirality effect on the reactivity was found to depend on the considered [ C ·H· G ] + aggregate-type.

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Saccharide Recognition and Helix Formation in Water with an Amphiphilic Pyridine–Phenol Alternating Oligomer

Cited by 20 publications

References 67 publications

PCage: Fluorescent Molecular Temples for Binding Sugars in Water

PCage: Fluorescent Molecular Temples for Binding Sugars in Water

Biomimetic carbohydrate recognition

Unprotected Galactosamine as a Dynamic Key for a Cyclochiral Lock

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