Synthetic Receptors for the High‐Affinity Recognition of O‐GlcNAc Derivatives

Ríos, Pablo; Carter, Tom S.; Mooibroek, Tiddo J.; Crump, Matthew P.; Lisbjerg, Micke; Pittelkow, Michael; Supekar, Nitin T.; Boons, Geert‐Jan; Davis, Anthony P.

doi:10.1002/anie.201510611

Cited by 85 publications

(92 citation statements)

References 34 publications

(8 reference statements)

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“…Such an analysis can indeed be informative, as it has been often reported that carbohydrate binding in water with inflexible cages is driven substantially by entropy. [17,18] For the specific case of amino saccharides with CB [7], our earlier experiment [25] suggested that entropy participated importantly (ÀTDS/DG % 35 %) in the binding of GalN and GluN, for which the anomer discrimination is more dramatic than for ManN. This substantial entropic contribution is also consistent with recent experimental binding data for polysaccharides with synthetic lectins, [18] for which it was reported that entropy sometimes contributed more to the binding than enthalpy.…”

Section: Decomposition Of Binding Free Energiessupporting

confidence: 82%

How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?

Wang

Jang

Khedkar

et al. 2016

Chemistry A European J

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Cucurbit[7]uril (CB[7]) is known to bind strongly to hydrophilic amino saccharide guests with exceptional α-anomer selectivities under aqueous conditions. Single-crystal X-ray crystallography and computational methods were used to elucidate the reason behind this interesting phenomenon. The crystal structures of protonated galactosamine (GalN) and glucosamine (GluN) complexes confirm the inclusion of α anomers inside CB[7] and disclose the details of the host-guest binding. Whereas computed gas-phase structures agree with these crystal structures, gas-phase binding free energies show preferences for the β-anomer complexes over their α counterparts, in striking contrast to the experimental results under aqueous conditions. However, when the solvation effect is considered, the binding structures drastically change and the preference for the α anomers is recovered. The α anomers also tend to bind more tightly and leave less space in the CB[7] cavity toward inclusion of only one water molecule, whereas loosely bound β anomers leave more space toward accommodating two water molecules, with markedly different hydrogen-bonding natures. Surprisingly, entropy seems to contribute significantly to both anomeric discrimination and binding. This suggests that of all the driving factors for the strong complexation of the hydrophilic amino saccharide guests, water mediation plays a crucial role in the anomer discrimination.

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Section: Decomposition Of Binding Free Energiessupporting

confidence: 82%

How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?

Wang

Jang

Khedkar

et al. 2016

Chemistry A European J

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“…[7] Synthesis 2,4,:T oam ixture of Pd(OAc) 2 (90 mg, 0.40 mmol) and SPhos (330 mg, 0.80 mmol) in toluene (200 mL) were added K 3 PO 4 (13 g, 80 mmol), 4-methoxybenzeneboronic acid (5,9 .1 g, 60 mmol), and 2-bromo-1,3,5-triisopropylbenzene (11g,4 0mmol 1, 147.7, 146.9, 136.7, 132.9, 130.7, 120.5, 113.3, 55.2, 34.2, 30.2, 24.2, 24 (7):B Br 3 (19 g, 77 mmol) was added to as olution of 6 (12 g, 39 mmol) in CH 2 Cl 2 (75 mL) at À80 8C. ESI-HRMS analyses were carried out on aJ EOL JMS-T100LC mass spectrometer by using MeOH solutions of the analytes.…”

Section: Methodsmentioning

confidence: 99%

D_3h‐Symmetrical Shape‐Persistent Macrocycles Consisting of Pyridine–Acetylene–Phenol Conjugates as an Efficient Host Architecture for Saccharide Recognition

Abe

Yoneda

Ohishi

et al. 2016

Chemistry A European J

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Hexagonal shape-persistent macrocycles (SPMs) consisting of three pyridine and three phenol rings linked with acetylene bonds were developed as a preorganized host for saccharide recognition by push-pull-type hydrogen bonding. Three tert-butyl or 2,4,6-triisopropylphenyl substituents were introduced on the host to suppress self-aggregation by steric hindrance. In spite of the simple architecture, association constants K of the host with alkyl glycoside guests reached the order of 10 m on the basis of UV/Vis titration experiments. This glycoside recognition was much stronger than that in the cases of acyclic equivalent hosts because of the entropic advantage brought by preorganization of the hydrogen-bonding sites. Solid-liquid extraction and liquid-liquid transport through a liquid membrane were demonstrated by using native saccharides, and much preference to mannose was observed.

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“…[39] The chemistry of saccharides and related molecules is involved in the metabolic pathways of living organisms. Due to the high number of hydroxyl groups in their structure, saccharides have high solvation enthalpies, [43,44] and are also hard to distinguish from an aqueous solvent. An obvious example is monitoring of blood glucose levels, which is of paramount importance because the breakdown of glucose transport has been correlated with diseases such as diabetes, cystic fibrosis, and cancer.…”

Section: Detection Of Saccharidesmentioning

confidence: 99%

Plasmonic Detection of Carbohydrate‐Mediated Biological Events

Garcı́a

Mosquera

Plou

et al. 2018

Advanced Optical Materials

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regulation of a variety of physiological and pathological processes, such as proliferation and adhesion, immune response, and cell differentiation. [8] The biological roles of carbohydrates as signaling effectors and recognition markers are associated to specific molecular recognition events in which proteins [9] or other carbohydrates [10] are involved. However, individual carbohydrate-based molecular interactions have been shown to be generally weak and, therefore, biomolecules usually present clusters of carbohydrates that interact cooperatively with their natural ligands (multivalent effect), thereby increasing the binding strength. [11] Interestingly, the multivalent carbohydrate presentation can be mimicked by man-made multivalent systems, which involve multiple synthetic oligosaccharides, [12][13][14][15][16][17] and have been used to address basic studies, but also as probe molecules and drugs. Mammalian cells are covered by a dense array of carbohydrates known as glycocalyx. The glycocalyx composition depends on the specific cellular state, and therefore it can provide information about diseases. For example, an increase of α-2,6-sialylation, fucosylation, and/or other tumor-associated carbohydrate antigens on the cellular membrane is considered as a biomarker of cancer progression, with diagnostic value. [18,19] In addition, oligosaccharides can be used as disease biomarkers for targeted therapy, and therefore the analysis and characterization of the composition of cellular glycans provide information of relevance to the diagnosis of several diseases. [20] Different strategies can be used to label glycans, including the use of covalent recognizing ligands (e.g., boronic acid), using specific carbohydrate-binding proteins, and via metabolic labeling.Plasmonics is based on the excitation of surface plasmons, that is, coherent oscillations of electrons induced by an electromagnetic radiation at metal-dielectric interfaces. [21] When the dimensions of plasmonic nanostructures are smaller than the wavelength of the incident light, the interaction between the electromagnetic field and surface charges results in nonpropagating oscillations denoted as localized surface plasmon resonances (LSPR). [22] LSPR frequencies in metal nanoparticles depend on their size, shape, organization, interparticle distance, and dielectric environment, ranging from the visible through the near-infrared (NIR). [23,24] A large volume of research has been devoted to the development of reliable methods for the preparation of plasmonic nanostructures with well-defined shape, size, and/or interparticle spacing, as basic components of various analytical applications. [25,26] Another important element, the surface chemistry of plasmonic The incorporation of nanomaterials in glycoscience research enables the design of highly selective and sensitive bioanalytical devices for the detection of disease-associated biomarkers. In particular, localized surface plasmon resonance (LSPR) and surface enhanced Raman scattering (SERS) spectroscopies ar...

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Synthetic Receptors for the High‐Affinity Recognition of O‐GlcNAc Derivatives

Cited by 85 publications

References 34 publications

How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?

How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?

D_3h‐Symmetrical Shape‐Persistent Macrocycles Consisting of Pyridine–Acetylene–Phenol Conjugates as an Efficient Host Architecture for Saccharide Recognition

Plasmonic Detection of Carbohydrate‐Mediated Biological Events

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Synthetic Receptors for the High‐Affinity Recognition of O‐GlcNAc Derivatives

Cited by 85 publications

References 34 publications

How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?

How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?

D3h‐Symmetrical Shape‐Persistent Macrocycles Consisting of Pyridine–Acetylene–Phenol Conjugates as an Efficient Host Architecture for Saccharide Recognition

Plasmonic Detection of Carbohydrate‐Mediated Biological Events

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Product

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D_3h‐Symmetrical Shape‐Persistent Macrocycles Consisting of Pyridine–Acetylene–Phenol Conjugates as an Efficient Host Architecture for Saccharide Recognition