Enhanced sugar-binding ability of deprotonated calix[4]resorcarene in water: Balance of CH-π interaction and hydrophobic effect

The importance of carbohydrate recognition in biology, and the unusual challenges involved, have lead to great interest in mimicking saccharide-binding proteins such as lectins. In this review, we discuss the design of artificial carbohydrate receptors, focusing on those which work under natural (i.e. aqueous) conditions. The problem is intrinsically difficult because of the similarity between substrate (carbohydrate) and solvent (water) and, accordingly, progress has been slow. However, recent developments suggest that solutions can be found. In particular, the "temple" family of carbohydrate receptors show good affinities and excellent selectivities for certain all-equatorial substrates. One example is selective for O-linked beta-N-acetylglucosamine (GlcNAc, as in the O-GlcNAc protein modification), while another is specific for beta-cellobiosyl and closely related disaccharides. Both show roughly millimolar affinities, matching the strength of some lectin-carbohydrate interactions.

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“…/4H ? ) [63] considerably improved saccharide binding, most likely through enhanced CH-p stacking interactions.…”

Section: Calixarenes and Other Oligoaromatic Hostsmentioning

confidence: 99%

Progress in biomimetic carbohydrate recognition

Walker

Joshi

Davis

2009

Cell. Mol. Life Sci.

109

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“…[1][2][3] In addition, synthetic carbohydrate receptors have contributed significantly to our current understanding of the factors that control affinity as well as selectivity in carbohydrate recognition. [4] In spite of the significant progress that has undoubtedly been made in the development of artificial carbohydrate receptors, including the first systems active in aqueous solution, [5][6][7][8][9] practical applications for such receptors, for example as chemosensors to detect the presence and concentration of biologically important sugars in aqueous solution, are not yet in sight. These applications, examples of which are monitoring the glucose level in blood or the sugar concentration during fermentation processes, require a receptor to bind to a given substrate and signal complex formation in water, yet most while D-fructose, D-ribose, and D-xylose cannot be bound by cooperative action of both boronic acid binding sites.…”

Section: Introductionmentioning

confidence: 99%

An Enantioselective Fluorescence Sensor for Glucose Based on a Cyclic Tetrapeptide Containing Two Boronic Acid Binding Sites

2006

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The synthesis and binding properties of carbohydrate receptor 1d, which contains two boronic acid binding sites facing each other at opposing sides of a cyclotetrapeptide cavity, are presented. According to electrospray mass spectrometry, 1H NMR spectroscopy, and fluorescence spectroscopy, this receptor forms stable 1:1 complexes with D‐glucose (Ka = 24800 ± 1200 M–1) and L‐glucose (Ka = 11900 ± 1600 M–1) in water/methanol (1:1) at pH = 11.7. Complexes with D‐galactose, D‐mannose, and D‐allose are significantly less stable, while D‐fructose, D‐ribose, and D‐xylose cannot be bound by cooperative action of both boronic acid binding sites. Thus, 1d possesses high affinity and selectivity in glucose recognition combined with good enantioselectivity. Moreover, fluorescence of 1d is quenched upon substrate binding, which allows the use of this receptor as an optical sensor for glucose in aqueous solution. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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“…[12] Therefore, the ability of deprotonated resorcinarenes to complex six different monosaccharides, one disaccharide, and four oligosaccharides (Scheme 1) was studied. Initially, it was our intention to also study tetraethyl pyrogallarene, but the deprotonation of pyrogallarane proved so difficult that this goal had to be reconsidered.…”

Section: Introductionmentioning

confidence: 99%

Size‐ and Structure‐Selective Noncovalent Recognition of Saccharides by Tetraethyl and Tetraphenyl Resorcinarenes in the Gas Phase

Kalenius

Kekäläinen

Neitola

et al. 2008

Chemistry A European J

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The noncovalent complexation of tetraethyl and tetraphenyl resorcinarenes with mono-, di-, and oligosaccharides was studied with negative-polarization electrospray ionization quadrupole ion trap and electrospray ionization Fourier-transform ion cyclotron resonance mass-spectrometric analysis. The saccharides formed 1:1 complexes with deprotonated resorcinarenes, which exhibited clear size and structure selectivity in their complexation. In the case of the monosaccharides, hexoses formed much more abundant and kinetically stable complexes than pentoses or deoxyhexoses. A comparison of the mono-, di-, and oligosaccharides revealed that both the relative abundance and stability of the complexes increase up to biose and triose, but start to decrease after that point, as the length of the oligosaccharide is increased. This behavior was rationalized by comparing the lowest-energy conformations of the complexes formed between the resorcinarene and oligosaccharides. This comparison was achieved by using theoretical calculations and X-ray crystal studies.

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Enhanced sugar-binding ability of deprotonated calix[4]resorcarene in water: Balance of CH-π interaction and hydrophobic effect

Cited by 42 publications

References 9 publications

Progress in biomimetic carbohydrate recognition

Progress in biomimetic carbohydrate recognition

An Enantioselective Fluorescence Sensor for Glucose Based on a Cyclic Tetrapeptide Containing Two Boronic Acid Binding Sites

Size‐ and Structure‐Selective Noncovalent Recognition of Saccharides by Tetraethyl and Tetraphenyl Resorcinarenes in the Gas Phase

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