Supramolecular Chemistry<i>In Silico</i>

Sheehan, Rosemary; Cragg, Peter J.

doi:10.1080/10610270701302465

Cited by 11 publications

(5 citation statements)

References 34 publications

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“…While it is possible to use gas phase simulations to describe supramolecular complexes in organic solvents (43,44), due to the extensive hydrogen bonding that could exist in the α-CD complexes an explicitly solvated approach was adopted. The simulation shows that the methyl 6) and are similar in magnitude to both modelled (45) and experimental intramolecular α-CD hydrogen bonds (46,47).…”

Section: Gb Inclusion In α-Cdmentioning

confidence: 99%

Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study

Sambrook

Gass

Cragg

2017

Supramolecular Chemistry

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A computational protocol to predict the infrared spectra of chemical warfare agents (CWAs) tabun (GA), sarin (GB), soman (GD) and cyclosarin (GF) has been developed. Sarin was used to benchmark the method through gas phase simulations. DFT calculations using the EDF2 functional and diffuse 6-311++G** basis set was found to give the closest match to experimental infrared spectra. Using the same functional the 6-31G (2df, 2p) basis set was found to be superior when hydrated sarin was modelled. GA, GB, GD and GF, together with 11 commonly used simulants, were modelled in the gas and hydrated states. Complexes of GB and a number of CWA mimics with α-cyclodextrin were modelled to give insight into their different modes of inclusion

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Section: Gb Inclusion In α-Cdmentioning

confidence: 99%

Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study

Sambrook

Gass

Cragg

2017

Supramolecular Chemistry

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“…To further investigate any possible complexation between hexahomotrioxacalix[3]arene ureas 1 and 2 and the NACs, they were subjected to computational analysis. The calixarenes, NAC guests and their complexes were built in Spartan 20 [ 26 ] and geometry optimised using molecular mechanics (MMFF) before gas phase semiempirical calculations (PM6) were undertaken using our previously published methods [ 27 , 28 ]. The resulting structures ( Figures S18 and S19 ) indicate the possibility of

interactions in some cases, so the thermodynamics of the systems were calculated.…”

Section: Resultsmentioning

confidence: 99%

Critical Analysis of Association Constants between Calixarenes and Nitroaromatic Compounds Obtained by Fluorescence. Implications for Explosives Sensing

Miranda

Marcos

Ascenso³

et al. 2023

Molecules

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The binding behaviour of two ureido-hexahomotrioxacalix[3]arene derivatives bearing naphthyl (1) and pyrenyl (2) fluorogenic units at the lower rim towards selected nitroaromatic compounds (NACs) was evaluated. Their affinity, or lack of it, was determined by UV-Vis absorption, fluorescence and NMR spectroscopy. Different computational methods were also used to further investigate any possible complexation between the calixarenes and the NACs. All the results show no significant interaction between calixarenes 1 and 2 and the NACs in either dichloromethane or acetonitrile solutions. Moreover, the fluorescence quenching observed is only apparent and merely results from the absorption of the NACs at the excitation wavelength (inner filter effect). This evidence is in stark contrast with reports in the literature for similar calixarenes. A naphthyl urea dihomooxacalix[4]arene (3) is also subject to the inner filter effect and is shown to form a stable complex with trinitrophenol; however, the equilibrium association constant is greatly overestimated if no correction is applied (9400 M−1 vs 3000 M−1), again stressing the importance of taking into account the inner filter effect in these systems.

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“…The latter calculations encountered problems upon refinement at semi-empirical level so discussion has been restricted to the gas phase results. We have previously shown that, at this level of theory, solution phase host–guest complexes are quite adequately represented by gas phase models [ 30 , 31 ].…”

Section: Resultsmentioning

confidence: 99%

Comparison of Binding Affinities of Water-Soluble Calixarenes with the Organophosphorus Nerve Agent Soman (GD) and Commonly-Used Nerve Agent Simulants

2018

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The formation of inclusion complexes of the water-soluble p-sulfonatocalix[n]arenes, where n = 4 or 6, with the Chemical Warfare Agent (CWA) GD, or Soman, and commonly used dialkyl methylphosphonate simulants has been studied by experimental solution NMR methods and by Molecular Mechanics (MMFF) and semi-empirical (PM6) calculations. Complex formation in non-buffered and buffered solutions is driven by the hydrophobic effect, and complex stoichiometry determined as 1:1 for all host:guest pairs. Low affinity complexes (Kassoc < 100 M−1) are observed for all guests, attributed to poor host–guest complementarity and the role of buffer cation species accounts for the low affinity of the complexes. Comparison of CWA and simulant behavior adds to understanding of CWA–simulant correlations and the challenges of simulant selection.

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Supramolecular ChemistryIn Silico

Cited by 11 publications

References 34 publications

Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study

Spectroscopic and inclusion properties of G-series chemical warfare agents and their simulants: a DFT study

Critical Analysis of Association Constants between Calixarenes and Nitroaromatic Compounds Obtained by Fluorescence. Implications for Explosives Sensing

Comparison of Binding Affinities of Water-Soluble Calixarenes with the Organophosphorus Nerve Agent Soman (GD) and Commonly-Used Nerve Agent Simulants

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