A theoretical analysis of a classic example of supramolecular catalysis

Carlqvist, Peter; Maseras, Feliu

doi:10.1039/b613434c

Cited by 58 publications

(61 citation statements)

References 19 publications

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“…1). Further, our calculated geometric parameters are consistent with the previously reported values using B3LYP functionals [16,20]. Our calculated energy gap of 6.58 eV (HOMO-LUMO) for CB- [6] is close to the values reported in earlier calculations [16].…”

Section: Resultssupporting

confidence: 93%

Elucidating the mechanism of binding of chromate to cucurbit[6]uril: a DFT study

Sundararajan

Ghosh

2011

J Incl Phenom Macrocycl Chem

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We report the binding of chromate, a toxic heavy metal ion to the macrocyclic host molecule, cucurbituril using density functional theory. Due to the anionic nature of the guest molecule and the portals of the host molecule, we propose that the binding mechanism should be assisted by cations. The calculated barrier for chromate binding to cucurbituril is found to be *17 kcal mol -1 . The large barrier can be attributed to portal opening of the host molecule, electrostatic repulsion between the guest molecule and the portals of the host molecule and the solvent re-organization around guest molecule.

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Section: Resultssupporting

confidence: 93%

Elucidating the mechanism of binding of chromate to cucurbit[6]uril: a DFT study

Sundararajan

Ghosh

2011

J Incl Phenom Macrocycl Chem

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“…Very recently, computational chemistry has been used to investigate the supramolecular catalytic cycloaddition [22]. An argument based on the calculated results showed that the slow reaction of the non-catalytic 1,3-dipole cycloaddition was caused by thermodynamic barriers (calc.…”

Section: Cucurbit[6]uril-induced Chemical Controlmentioning

confidence: 99%

“…The encapsulation, moreover, had no noticeable effect on the photochemical degradation of ranitidine dihydrochlride, the effective form for treatment of the disease, at pH 1.5; therefore it cannot prevent degradation of the drug excreted from human body. Lansoprazole (22 ) and Omeprazole (23), which are used to treat the classic disease of excessive secretion of gastric acid, have enhanced solubility in aqueous solutions and the acidic stability has been improved by 4 pH units via encapsulation within Q [7], allowing increased application of the drugs in a more extensive pH range [41]. The encapsulation of drug guests within Q[7] eliminated or decreased unwanted side effects, while the activation was preserved or allayed slightly with enhanced stability.…”

Section: Cucurbit[7]uril-induced Chemical Controlmentioning

confidence: 99%

Host-induced Chemical Control: Supramolecular Catalysis Based on the Host – Guest Interaction of Cucurbit[n]urils

Cong¹,

Tao

Xue³

et al. 2011

COC

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The controllable functional encapsulation of cucurbit[n]urils (Q[n]s) to form supramolecular catalysts is reviewed. The relationship of the supramolecular catalytic activity with the structure of included guests and cucurbit[n]urils is documented and discussed. The controllable functional encapsulation is attributed to overall interactions of hydrophobic, ion-dipole and size effects of the cucurbit[n]urils. The accelerated and stereochemical aspects of chemical reactions result from overcoming the hindrance of decreased entropy, the hydrophobic effect and the encapsulation model induced by hosts. The stability of drugs and chemical intermediates of the inclusion complexes depends on the environment within the hydrophobic cavity; the enhanced charge-transfer process of the included electron donor and acceptor guests depends on the compressed distance between guests, the electron donors, and acceptors within the limited space.

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“…By bringing in close contact reactive groups of one or more molecules, they may enhance the rate of a specific chemical reaction. [7][8][9] Sanders used a porphyrin trimer to catalyze a Diels-Alder reaction with up to a 1030-fold acceleration. A series of successful examples have been reported in the past several decades.…”

Section: Introductionmentioning

confidence: 99%

Computational Description of a Huisgen Cycloaddition Inside a Self‐Assembled Nanocapsule

2018

Self Cite

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Density functional theory calculations are applied to the study of a cycloaddition reaction between phenyl acetylene and phenyl azide taking place inside a self‐assembled nanoreactor derived from the coupling of two resorcinarene‐derived units. Calculations are applied to all steps in the reactivity of the system: self‐assembly, guest trapping, guest exchange, in‐core reaction, and product release. A reaction network is built, and the evolution of concentrations of a large variety of species over a range of time scales is obtained through the application of a kinetic model. The modeled behavior of the nanocapsule and its guests reproduces the experimental observations and completes our knowledge and understanding of this chemical system.

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A theoretical analysis of a classic example of supramolecular catalysis

Abstract: Computational chemistry is used to study a 1,3-dipolar cycloaddition between an azide and an alkyne inside the macrocycle cucurbit[6]uril, in order to elucidate the catalytic function of a highly efficient supramolecular catalyst.

Cited by 58 publications

References 19 publications

Elucidating the mechanism of binding of chromate to cucurbit[6]uril: a DFT study

Elucidating the mechanism of binding of chromate to cucurbit[6]uril: a DFT study

Host-induced Chemical Control: Supramolecular Catalysis Based on the Host – Guest Interaction of Cucurbit[n]urils

Computational Description of a Huisgen Cycloaddition Inside a Self‐Assembled Nanocapsule

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