Recognition Properties of Flavin Analogues with Bile Acid-Based Receptors: Role of Steric Effects in Hydrogen Bond Based Molecular Recognition

Chattopadhyay, Prosenjit; Nagpal, Rekha; Pandey, Pramod

doi:10.1071/ch07342

Cited by 9 publications

(4 citation statements)

References 11 publications

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“…The main chain of the polymer is not fully π-conjugated because of the methylene linkers, and therefore, this fluorescence quenching phenomenon may indicate a possible intermolecular energy transfer between the pendant fluorescent flavin residues of different polymer chains. These results suggest that the poly- 1 may form chiral aggregates in solution, although the exact structure remains unclear, but the chirality of the optically active ribityl pendants appears to be transferred to induce such a supramolecular chirality. , …”

Section: Resultsmentioning

confidence: 93%

Main-Chain Optically Active Riboflavin Polymer for Asymmetric Catalysis and Its Vapochromic Behavior

et al. 2012

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A novel optically active polymer consisting of riboflavin units as the main chain (poly-1) was prepared from naturally occurring riboflavin (vitamin B(2)) in three steps. The riboflavin residues of poly-1 were converted to 5-ethylriboflavinium cations (giving poly-2), which could be reversibly transformed into the corresponding 4a-hydroxyriboflavins (giving poly-2OH) through hydroxylation/dehydroxylation reactions. This reversible structural change was accompanied by a visible color change along with significant changes in the absorption and circular dichroism (CD) spectra. The nuclear Overhauser effect spectroscopy (NOESY) and CD spectra of poly-2 revealed a supramolecularly twisted helical structure with excess one-handedness through face-to-face stacking of the intermolecular riboflavinium units, as evidenced by the apparent NOE correlations between the interstrand riboflavin units and intense Cotton effects induced in the flavinium chromophore regions. The hydroxylation of poly-2 at the 4a-position proceeded in a diastereoselective fashion via chirality transfer from the induced supramolecular helical chirality assisted by the ribityl pendants, resulting in a 83:17 diastereomeric mixture of poly-2OH. The diastereoselectivity of poly-2 was remarkably higher than that of the corresponding monomeric model (64.5:35.5), indicating amplification of the chirality resulting from the supramolecular chirality induced in the stacked poly-2 backbones. The optically active poly-2 efficiently catalyzed the asymmetric organocatalytic oxidation of sulfides with hydrogen peroxide, yielding optically active sulfoxides with up to 60% enantiomeric excess (ee), whose enantioselectivity was higher than that catalyzed by the monomeric counterpart (30% ee). In addition, upon exposure to primary and secondary amines, poly-2 exhibited unique high-speed vapochromic behavior arising from the formation of 4a-amine adducts in the film.

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Section: Resultsmentioning

confidence: 93%

Main-Chain Optically Active Riboflavin Polymer for Asymmetric Catalysis and Its Vapochromic Behavior

et al. 2012

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“…3,4-Dimethylbenzene-1,2-diamine was synthesized from 3,4-dimethylaniline (synthetic procedure can be found in Supporting Information). 71 Complex 3a was synthesized by the reported procedure 48 and 4 was synthesized from 3a by metathesis with KBr in acetone. 72 C, H, and N elemental analyses were carried out on a Euro EA 3028HT CHNS/O analyzer.…”

Section: Methodsmentioning

confidence: 99%

H₂C(X)–X···X^–(X = Cl, Br) Halogen Bonding of Dihalomethanes

Ivanov

Kinzhalov

Novikov

et al. 2017

Crystal Growth & Design

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The dihalomethane-halide H 2 C(X)-X•••X -(X = Cl, Br) halogen bonding was detected in a series of the cis-[PdX(CNCy){C(NHCy)=NHC 6 H 2 Me 2 NH 2 }]X•CH 2 X 2 (X = Cl, Br) associates by single-crystal XRD followed by DFT calculations. Although ESP calculations demonstrated that the σ-hole of dichloromethane is the smallest among all halomethane solvents (the maximum electrostatic potential is only 2.6 kcal/mol), the theoretical DFT calculations followed

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“…Bile acid-based receptors containing 2,6-diaminopyridine and the dioctylamide of 2,6-diaminopyridine were also used to bind 7,8-dimethyl flavin analogues. The association constants increased with increasing electron-donating capacity of the substituents at the 7 and 8 positions of the flavin analogues [22].…”

Section: Steroid-based Molecular Clefts/tweezersmentioning

confidence: 96%

Steroid-Based Supramolecular Systems and their Biomedical Applications: Biomolecular Recognition and Transportation

Sheng¹

2020

Chemistry and Biological Activity of Steroids

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In this chapter, the biomedical application of steroid-based compounds at "beyond the molecule"-supramolecular level-is reviewed. The renewable and economic natural steroid compounds could be employed as building blocks in the design and construction of steroid-based supramolecular systems. The specific physicochemical features (size, shape, topology, hydrophobicity, chemical modifiability, etc.) and biological properties (biocompatibility, biodegradability, bioaffinity, etc.) could be integrated into functional supramolecular systems by chemical synthesis, modification and intermolecular interactions (such as hydrogen bonding, π-π stacking, van der Waals forces, inclusion interactions, chiral interactions, electrostatic interactions, and so on). The steroid-based (supra)molecules could be employed for molecular recognition and/or be self-assembled into various functional supramolecular assemblies for biomedical applications. The specific physicochemical and biological properties, good biocompatibility, and biological activity endow the steroid-based supramolecular systems good feasibility to be employed in biomolecular recognition/sensing and biomolecular transportation (gene/drug delivery). The examples in this chapter are exemplificative of the transformation of natural steroid-based compounds into functional steroid-based supramolecular systems through molecular and supramolecular engineering technology, moreover, which may inspire the systematic study of natural product-based supramolecular (nano)materials toward future pharmaceutical and biomedical industry.

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Recognition Properties of Flavin Analogues with Bile Acid-Based Receptors: Role of Steric Effects in Hydrogen Bond Based Molecular Recognition

Cited by 9 publications

References 11 publications

Main-Chain Optically Active Riboflavin Polymer for Asymmetric Catalysis and Its Vapochromic Behavior

Main-Chain Optically Active Riboflavin Polymer for Asymmetric Catalysis and Its Vapochromic Behavior

H₂C(X)–X···X^–(X = Cl, Br) Halogen Bonding of Dihalomethanes

Steroid-Based Supramolecular Systems and their Biomedical Applications: Biomolecular Recognition and Transportation

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Recognition Properties of Flavin Analogues with Bile Acid-Based Receptors: Role of Steric Effects in Hydrogen Bond Based Molecular Recognition

Cited by 9 publications

References 11 publications

Main-Chain Optically Active Riboflavin Polymer for Asymmetric Catalysis and Its Vapochromic Behavior

Main-Chain Optically Active Riboflavin Polymer for Asymmetric Catalysis and Its Vapochromic Behavior

H2C(X)–X···X–(X = Cl, Br) Halogen Bonding of Dihalomethanes

Steroid-Based Supramolecular Systems and their Biomedical Applications: Biomolecular Recognition and Transportation

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Product

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H₂C(X)–X···X^–(X = Cl, Br) Halogen Bonding of Dihalomethanes