Neutron Inelastic Scattering and X-Ray Studies of Aqueous Solutions of Dimethylsulphoxide and Dimethylsulphone

Safford, G. J.; Schaffer, Paul; Leung, PingSun; Doebbler, G. F.; Brady, George W.; Lyden, E. F. X.

doi:10.1063/1.1671344

Cited by 145 publications

(41 citation statements)

References 37 publications

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“…Extrema in excess thermodynamic functions of mixing (38), in viscosities (40) and in Waldeii product (40) occur in the water-rich dioxane-water mixtures, but these are not thought to result from enhancement of the long-range order. On the other hand, aqueous DMSO mixtures also show extrerna in excess thermodynamic functions of mixing and in viscosity (41), and neutron inelastic scattering studies indicate that this solvent does increase the long-range order, with a maximum effect at x, = 0.33 (42).…”

Section: Resultsmentioning

confidence: 99%

Analysis of the Visual Spectrum of Methyl Orange in Solvents and in Hydrophobic Binding Sites

Reeves¹,

Kaiser²,

Maggio³

et al. 1973

Can. J. Chem.

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The absorption curves of methyl orange (MO) and analogous p-aminophenylazobenzenes in organic and aqueous organic solvents are shown to consist of two severely overlapping bands. The curves have been resolved into two skewed component bands using a regression method. The blue shift of the absorption maximum obtained when organic solvents are added to aqueous solutions of MO, or when MO is bound to bovine serum albumin or a surfactant micelle, is the result of a change in relative intensities of the component bands. The low-frequency component is assigned to a n, -. nlx transition of a solvate in which there is specific hydrogen-bonding interaction between solvent and the azo nitrogens, and the high-frequency component to a n1 + nl* transition of a solvate in which the interaction is absent. The low-frequency component is favored by aqueous solvent compositions and by low temperatures. The free energies of interconversion of the species in various hydrogen-bonding solvents are correlated by the solvent surface tension but not by the dielectric constant. The results show that the shift in absorption maximum accompanying binding to a protein or micelle should be interpreted as a shift in an equilibrium rather than as a shift in transition energy.Les courbes d'absorption du methylorange (MO) et des p-aminophCnylazobenzenes analogues, en solvants organiques et organiques aqueux, comprennent deux bandes fortement enchevktrees. La resolution de ces courbes en deux bandes gauches elementaires a ete faite par la methode de regression. Le d6placement vers le bleu du nlaxilnuin d'absorption, obtenu par addition de solvants organiques aux solutions aqueuses de MO ou lorsque le MO est lie a l'albumine du serum bovin ou a une micelle surfactive, est le resultat du changement des intensites relatives des bandes composantes. La bande a basse frequence est attribue a la transition n, + nl*, d'un produit de solvatation dans lequel il y a interaction specifique par liaison hydrogene entre le solvant et les azotes de l'azo; la bande a haute frequence correspond a la transition nl + n," du produit de solvatation sans interaction. La bande a basse frequence est favorisee par la composition en eau des solvants et aux basses temperatures. Les energies libres de l'interconversion des diverses especes dans differents solvants a liaison hydrogene, ont ete reliies a la tension superficielle du solvant et non a la constante dielectrique. Les rtsultats montrent que le deplacement du maximum d'absorption consecutif a une liaison a une protkine ou ~nicelle devraient &tre interpretes pluttit comme un deplacement d'equilibre qu'un diplacement de 1'Cnergie de transition.[Traduit par le journal]Can. J. Chem.. 51. 628 (1973) Methyl orange (MO, 1) has been used as a probe for studying the interaction of organic anions with proteins (1-9), synthetic polymers (10, 1 I), polyelectrolytes (12), and surfactants (12-14) in aqueous solution. The interaction is usually accompanied by spectral changes that are not associated with the acid-base indicator p...

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Section: Resultsmentioning

confidence: 99%

Analysis of the Visual Spectrum of Methyl Orange in Solvents and in Hydrophobic Binding Sites

Reeves¹,

Kaiser²,

Maggio³

et al. 1973

Can. J. Chem.

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“…Experimentally, the excess mixing properties of the DMSO-water system were explored in [10,14,15]. The self-diffusion coefficients of DMSO and water species, together with some other relevant data, for mixtures of various compositions were given in [16,17,18]. Due to methodological issues, samples containing deuterated species of either DMSO or water were used.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…A distinct feature of the two latter articles is that experimental data were augmented by MD computer simulation results, explicitly demonstrating cross-feedback between the two techniques; the experimental data were useful for the design of the force fields whereas the simulation results were necessary and important for a better interpretation of the observed structural features. For DMSO-water mixtures of different compositions inelastic neutron scattering and X-ray diffraction experiments were carried out to explore the microscopic structure in [18]. Soper and Luzar performed neutron diffraction experiments using isotope substitution on two mixtures and provided partial structure factors and partial correlation functions involving water hydrogen atoms [29].…”

Section: Accepted Manuscriptmentioning

confidence: 99%

On the composition dependence of thermodynamic, dynamic and dielectric properties of water-dimethyl sulfoxide model mixtures. NPT molecular dynamics simulation results

Gujt

Vargas

Pusztai

et al. 2017

Journal of Molecular Liquids

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“…In a study (8) of the low frequency vibrational spectrum, a single band was assigned to methyl torsion. Two bands were assigned to methyl torsion in an inelastic neutron scattering study (9), although the assignment may be somewhat in doubt (8). Two minima in the 'H relaxation time vs. temperature plot were interpreted in terms of dynamically inequivalent methyl groups in a pulsed nmr study (10).…”

Section: Dimethyl Sulphoxidementioning

confidence: 99%

Methyl group inequivalence and rotational barrier heights from ¹H nmr lineshapes: dimethylsulphoxide and trimethylsulphoxonium iodide

Ripmeester¹

1981

Can. J. Chem.

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The 1H nmr lineshapes obtained for a solid solution of DMSO-d3 in DMSO-d6 and for CH3(CD3)2SO+I− indicated the presence of inequivalent methyl groups in each solid. The effect of methyl group tunnelling on the lineshapes at low temperatures was used to derive barrier heights of 4.15 and 5.0 kcal/mol of a DMSO and 3.70 and 3.85 kcal/mol for CH3(CD3)2SO+I−. Using 1H nmr lineshapes, including temperature dependent effects, may well be one of the more sensitive techniques to detect inequivalent methyl groups.

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Neutron Inelastic Scattering and X-Ray Studies of Aqueous Solutions of Dimethylsulphoxide and Dimethylsulphone

Cited by 145 publications

References 37 publications

Analysis of the Visual Spectrum of Methyl Orange in Solvents and in Hydrophobic Binding Sites

Analysis of the Visual Spectrum of Methyl Orange in Solvents and in Hydrophobic Binding Sites

On the composition dependence of thermodynamic, dynamic and dielectric properties of water-dimethyl sulfoxide model mixtures. NPT molecular dynamics simulation results

Methyl group inequivalence and rotational barrier heights from ¹H nmr lineshapes: dimethylsulphoxide and trimethylsulphoxonium iodide

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Neutron Inelastic Scattering and X-Ray Studies of Aqueous Solutions of Dimethylsulphoxide and Dimethylsulphone

Cited by 145 publications

References 37 publications

Analysis of the Visual Spectrum of Methyl Orange in Solvents and in Hydrophobic Binding Sites

Analysis of the Visual Spectrum of Methyl Orange in Solvents and in Hydrophobic Binding Sites

On the composition dependence of thermodynamic, dynamic and dielectric properties of water-dimethyl sulfoxide model mixtures. NPT molecular dynamics simulation results

Methyl group inequivalence and rotational barrier heights from 1H nmr lineshapes: dimethylsulphoxide and trimethylsulphoxonium iodide

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Methyl group inequivalence and rotational barrier heights from ¹H nmr lineshapes: dimethylsulphoxide and trimethylsulphoxonium iodide