Understanding behaviour of vitamin-C guest binding with the cucurbit[6]uril host
TL;DR: In this paper, non-covalent interaction and complexation behavior of sodium ascorbate (SA) with cucurbit[6]uril (CB[6]) at neutral pH in aqueous Na2SO4 solution was investigated using various analytical techniques like NMR, UV-Vis, fluorescence, TGA and DRS.
Abstract: The present study describes non-covalent interaction and complexation behaviour of sodium ascorbate (SA) with cucurbit[6]uril (CB[6]) at neutral pH in aqueous Na2SO4 solution. The interaction behaviour is investigated using various analytical techniques like NMR, UV–Vis, fluorescence, TGA and DRS. The substantial increase in the intensity of emission and absorption spectra of sodium ascorbate is observed. The Benesi–Hildebrand evaluation method is used to determine the stoichiometry and equilibrium constant of the cucurbit[6]uril–sodium ascorbate complex, which suggested the 1:1 complex. Time-dependent 1H NMR, 13C CP MAS and CD studies also echoed non-covalent interaction between SA with CB[6].
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55 citations
TL;DR: In this article, a review provides an overview of related advances and achievements involving such a combination of Q[n]-based host-guest chemistry and Q[ n]-based coordination chemistry.
Abstract: Cucurbit[n]urils (Q[n]s), a relatively new class of macrocyclic hosts with a rigid hydrophobic cavity and two identical carbonyl-fringed portals, have attracted much attention since the first member of the Q[n]-family, cucurbit[6]uril (Q[6]), was structurally identified in 1981 by Mock and co-workers. The interactions of the rigid cavities and negative portals of Q[n]s have resulted in the development of two almost mutually exclusive areas of study, namely Q[n]-based host–guest chemistry and Q[n]-based coordination chemistry. However, researches has revealed that Q[n]-based host–guest inclusion interactions may be influenced by metal ion coordination at the Q[n] portals, and in turn, coordination of metal ions at the Q[n] portals could be promoted by the formation of Q[n]-based inclusion host–guest complexes. Thus, this review provides an overview of related advances and achievements involving such a combination of Q[n]-based host–guest chemistry and Q[n]-based coordination chemistry, which could become an emerging branch, that is, Q[n]-based host–guest-metal ion chemistry. In particular, it could be useful in the treatment of wastewater, kinetic studies, drug delivery, the construction of novel supramolecular frameworks, metal-catalyzed reactions, recognition or response to metal cations, and so on.
22 citations
Cites background from "Understanding behaviour of vitamin-..."
...Significant increases in the intensities of the emission and absorption spectra of SA were observed, probably due to its restricted motion in the cavity of Q[6] by the coordinated Na+ cation [86]....
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TL;DR: This review will present examples from three directions of induction of chirality in or by cucurbituril-type hosts: first, through the incorporation of stereogenic elements into host molecules; second, through complexation with achiral guests, which leads to axial supramolecular chiralities and helical structures; and third,Through the formation of complexes with chiral guests in multi-molecule complexes and induction of supramolescular chorality.
Abstract: Cucurbituril-type hosts are highly symmetric, but there are means to break their symmetry. This review will present examples from three directions of induction of chirality in or by cucurbituril-type hosts: first, through the incorporation of stereogenic elements into host molecules; second, through complexation with achiral guests, which leads to axial supramolecular chirality and helical structures; third, through the formation of complexes with chiral guests in multi-molecule complexes and induction of supramolecular chirality. In addition, a list of chiral guests used in binding studies with cucurbiturils is collected. We would envision that encouraged by the outlined examples of outstanding applications of chiral cucurbituril-supramolecular systems, the boundaries of chiral applications of cucurbiturils would be widened.
12 citations
Cites background from "Understanding behaviour of vitamin-..."
...[82] [83] [84] G Symmetry 2018, 10, x FOR PEER REVIEW 18 of 26 CB[7] CB[6] Ref....
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TL;DR: In this article, the potential of cucurbit[5]uril to be used as inverse phase transfer catalyst in electrocatalytic hydrogenation of α,β-unsaturated ketones is illustrated.
Abstract: The potential of cucurbit[5]uril to be used as inverse phase transfer catalyst in electrocatalytic hydrogenation of α,β-unsaturated ketones is illustrated. The interaction behavior among isophorone and cucurbit[5]uril was also investigated using cyclic voltammetry and UV/vis absorption spectroscopy. The results concerning to both techniques revealed an enhancement in the intensity of the absorption peak and also in the current cathodic peak of isophorone in presence of cucurbit[5]uril. This achievement is related to the increase of the isophorone solubility in the medium being an indicative of a host-guest complex formation. The electrochemical hydrogenation of isophorone using cucurbit[5]uril was more efficient than others well-stablish methodologies. Regarding to (R)-(+)-pulegone and (S)-(+)-carvone, the use of cucurbit[5]uril leads to an increase of 17% and 9%, on average, respectively, in the yields when compared to the control reaction. The efficiency of selective C=O bond hydrogenation of 1-acetyl-1-cyclohexene was evaluated. The presence of cucurbit[5]uril increased by 12% the hydrogenations yields of 1-acetyl-1-cyclohexene when compared to the control reaction. In this sense, these results open up an opportunity to carry out electrocatalytic reactions within the cucurbit[5]uril environment.
1 citations
TL;DR: Theoretical methods were used to investigate the encapsulation of two vitamin E isoforms into the macrocycle cucurbit[7]uril (CB[7]). The [email protected][7] complexes were stable along 100 ns molecular dynamics simulation with similar conformation as mentioned in this paper .
Abstract: Theoretical methods were used to investigate the encapsulation of two vitamin E isoforms, α-tocopherol (α-TOC) and α-tocotrienol (α-TCT), into the macrocycle cucurbit[7]uril (CB[7]). The [email protected][7] complexes were stable along 100 ns molecular dynamics simulation with similar conformation. The binding free energy obtained from the MM/PBSA method is ∼ –25 kcal.mol−1 for both complexes. Also, DFT-D3/B3LYP/6-31G(d,p) calculations indicate a favorable encapsulation process with bind energies of –58.25 (α[email protected][7]) and –61.08 kcal.mol−1 (α[email protected][7]). Moreover, the calculated solvation enthalpies show a solubility enhancement of complexed vitamins compared to their free forms. Finally, CB[7] may be a promising macrocyclic host for encapsulating vitamins E.
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TL;DR: The fundamental properties of CBn homologues and their cyclic derivatives are discussed with a focus on their synthesis and their applications in catalysis.
Abstract: In the wide area of supramolecular chemistry, cucurbit[n]urils (CBn) present themselves as a young family of molecular containers, able to form stable complexes with various guests, including drug molecules, amino acids and peptides, saccharides, dyes, hydrocarbons, perfluorinated hydrocarbons, and even high molecular weight guests such as proteins (e.g., human insulin). Since the discovery of the first CBn, CB6, the field has seen tremendous growth with respect to the synthesis of new homologues and derivatives, the discovery of record binding affinities of guest molecules in their hydrophobic cavity, and associated applications ranging from sensing to drug delivery. In this review, we discuss in detail the fundamental properties of CBn homologues and their cyclic derivatives with a focus on their synthesis and their applications in catalysis.
960 citations
TL;DR: A wide range of reaction conditions are examined that include the effects of acid type, acid concentration, reactant concentrations, and temperature to both probe the mechanism and optimize the yields of isolated cucurbit[n]urils, where n = 5-10.
Abstract: The acid-catalyzed synthesis of cucurbit[n]urils from formaldehyde and glycoluril is poorly understood. In this paper, we examine a wide range of reaction conditions that include the effects of acid type, acid concentration, reactant concentrations, and temperature to both probe the mechanism and optimize the yields of isolated cucurbit[n]urils, where n = 5−10. A mechanism for the formation of these cucurbit[n]urils is presented. Individual cucurbit[n]urils were unambiguously identified in reaction mixtures using ESMS and 13C NMR.
860 citations
TL;DR: The combined results indicate a sufficiently low toxicity of cucurbit[n] as additives for medicinal and pharmaceutical use, and the bioadaptability of the compounds was further examined through in vivo studies on mice.
Abstract: Cucurbit[n]urils (CB[n]) are potential stabilizing, solubilizing, activating, and delivering agents for drugs. The toxicity of the macrocyclic host molecules cucurbit[7]uril (CB[7]), the most water-soluble homologue, as well as cucurbit[8]uril (CB[8]) has been evaluated. In vitro studies on cell cultures revealed an IC50 value of 0.53 ± 0.02 mM for CB[7], corresponding to around 620 mg of CB[7] per kg of cell material. Live-cell imaging studies performed on cells treated with subtoxic amounts of CB[7] showed no detrimental effects on the cellular integrity as assessed by mitochondrial activity. For CB[8], no significant cytotoxicity was observed within its solubility range. The bioadaptability of the compounds was further examined through in vivo studies on mice, where intravenous administration of CB[7] showed a maximum tolerated dosage of 250 mg kg−1, while oral administration of a CB[7]/CB[8] mixture showed a tolerance of up to 600 mg kg−1. The combined results indicate a sufficiently low toxicity to encourage further exploration of CB[n] as additives for medicinal and pharmaceutical use.
329 citations
TL;DR: Constantes de dissociation du cucurbiturile avec divers alkylammoniums and polymethylene bis-ammonium as discussed by the authors, i.e.
Abstract: Constantes de dissociation du cucurbiturile avec divers alkylammoniums et polymethylene bis-ammonium
204 citations