Molekulare Erkennung von Kohlenhydraten durch künstliche Polypyridin- und Polypyrimidinrezeptoren

Mazik, Monika; Bandmann, Hans‐Jürgen; Sicking, Willi

doi:10.1002/(sici)1521-3757(20000204)112:3<562::aid-ange562>3.0.co;2-n

Cited by 23 publications

(6 citation statements)

References 32 publications

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“…The peak shifts are attributed to the change in chemical environment as a result of reversible supramolecular association between the glycan and the SCR that is occurring in the fast exchange regime. When involved in C−H⋅⋅⋅π interactions with aryl rings of SCRs, protons shift upfield,–– so these results suggest that these Hs do not form C−H⋅⋅⋅π interactions with SCR019 . In contrast, the peaks corresponding to H 1 and H 5 of β‐Man both shift upfield 0.04 ppm, upon association, suggesting the formation of C−H⋅⋅⋅π interactions with the aromatic rings of SCR019 , which is corroborated by molecular modeling (Figure S80).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Binding of Mannose‐Specific Synthetic Carbohydrate Receptors

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Palanichamy

Shlain

et al. 2020

Chemistry A European J

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Synthetic carbohydrate receptors (SCRs) that selectively recognize cell‐surface glycans could be used for detection, drug delivery, or as therapeutics. Here we report the synthesis of seven new C2h symmetric tetrapodal SCRs. The structures of these SCRs possess a conserved biaryl core, and they vary in the four heterocyclic binding groups that are linked to the biaryl core via secondary amines. Supramolecular association between these SCRs and five biologically relevant C1‐O‐octyloxy glycans, α/β‐glucoside (α/β‐Glc), α/β‐mannoside (α/β‐Man), and β‐galactoside (β‐Gal), was studied by mass spectrometry, 1H NMR titrations, and molecular modeling. These studies revealed that selectivity can be achieved in these tetrapodal SCRs by varying the heterocyclic binding group. We found that SCR017 (3‐pyrrole), SCR021 (3‐pyridine), and SCR022 (2‐phenol) bind only to β‐Glc. SCR019 (3‐indole) binds only to β‐Man. SCR020 (2‐pyridine) binds β‐Man and α‐Man with a preference to the latter. SCR018 (2‐indole) binds α‐Man and β‐Gal with a preference to the former. The glycan guests bound within their SCR hosts in one of three supramolecular geometries: center‐parallel, center‐perpendicular, and off‐center. Many host–guest combinations formed higher stoichiometry complexes, 2:1 glycan⋅SCR or 1:2 glycan⋅SCR, where the former are driven by positive allosteric cooperativity induced by glycan–glycan contacts.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Binding of Mannose‐Specific Synthetic Carbohydrate Receptors

Bravo

Palanichamy

Shlain

et al. 2020

Chemistry A European J

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“…For α‐Man, the largest Δ δ occurred with the peak corresponding to H 7’ , with Δ δ =0.66 ppm upfield, and the second‐largest shift was for the peak corresponding to H 1 , with Δ δ =0.59 ppm upfield. When involved in C−H⋅⋅⋅π interactions with aryl rings of SCRs, protons shift upfield, [21c,31,32i,j,33a–i,34a,43b–o] suggesting the formation of C−H⋅⋅⋅π interactions between these protons and with the aromatic rings of SCR032 . 1 H NMR of the indole‐based SCRs in all the titrations presented significant downfield shifts.…”

Section: Resultsmentioning

confidence: 99%

Regiochemical Effects on the Carbohydrate Binding and Selectivity of Flexible Synthetic Carbohydrate Receptors with Indole and Quinoline Heterocyclic Groups

et al. 2021

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Synthetic carbohydrate receptors (SCRs) that bind cell‐surface carbohydrates could be used for disease detection, drug‐delivery, and therapeutics, or for the site‐selective modification of complex carbohydrates, but their potential has not been realized because of remaining challenges associated with binding affinity and substrate selectivity. We have reported recently a series of flexible SCRs based upon a biaryl core with four pendant heterocyclic groups that bind glycans selectively through noncovalent interactions. Here we continue to explore the role of heterocycles on substrate selectivity by expanding our library to include a series of indole and quinoline heterocycles that vary in their regiochemistry of attachment to the biaryl core. The binding of these SCRs to a series of biologically‐relevant carbohydrates was studied by 1H NMR titrations in CD2Cl2 and density‐functional theory calculations. We find SCR030, SCR034 and SCR037 are selective, SCR031, SCR032, and SCR039 are strong binders, and SCR033, SCR035, SCR036, and SCR038 are promiscuous and bind weakly. Computational analysis reveals the importance of C−H⋅⋅⋅π and H‐bonding interactions in defining the binding properties of these new receptors. By combining these data with those obtained from our previous studies on this class of flexible SCRs, we develop a series of design rules that account for the binding of all SCRs of this class, and anticipate the binding of future, not‐yet imagined tetrapodal SCRs.

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“…[8] This fact showed once again that the hydrogen-bonding interactions with naphthyridine-amide units are more favorable than with pyridine-amide moieties and revealed the suitability of the naphthyridine-amide unit as a recognition motif for carbohydrates.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we have found that receptors 1 and 2, which incorporate three pyridine-amide or pyrimidine-amide moieties linked by a phenyl spacer, are effective host molecules for recognition of pyranosides in chloroform solution. [8] The binding properties of 1 and 2 have demonstrated the adjustability of the pyridine-amide and pyrimidine-amide subunits as hydrogen bonding motifs for carbohydrates.…”

Section: Introductionmentioning

confidence: 95%

Molecular Recognition of Carbohydrates by Artificial Receptors: Systematic Studies towards Recognition Motifs for Carbohydrates

Mazik

Sicking

2001

Chem. Eur. J.

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The synthesis and binding properties for carbohydrates of several artificial, acyclic receptors containing two or three heterocyclic recognition units covalently attached to a phenyl spacer is described. These host molecules having uncharged hydrogen-bonding sites were used in a systematic study towards the evaluation of recognition motifs for carbohydrates. A novel effective, acyclic hydrogen-bonding receptor possessing naphthyridine-amide moieties as heterocyclic recognition units has been developed.

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Molekulare Erkennung von Kohlenhydraten durch künstliche Polypyridin- und Polypyrimidinrezeptoren

Cited by 23 publications

References 32 publications

Synthesis and Binding of Mannose‐Specific Synthetic Carbohydrate Receptors

Synthesis and Binding of Mannose‐Specific Synthetic Carbohydrate Receptors

Regiochemical Effects on the Carbohydrate Binding and Selectivity of Flexible Synthetic Carbohydrate Receptors with Indole and Quinoline Heterocyclic Groups

Molecular Recognition of Carbohydrates by Artificial Receptors: Systematic Studies towards Recognition Motifs for Carbohydrates

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