Preferential Solvation of 4-Carboxyl-2, 6-Dinitrophenylazohydroxynaphthalenes in Mixed Hydroxylic Solvents

Background: The applications of a group of 4-carboxyl-2,6-dintrophenylazohydroxynaphathalenes, AZ-01 to 04, as colourants, chemosensors or synthetic intermediates have been limited by their solubility.Aim: To investigate the effect of solvent mixture composition on the solubility, solution thermodynamics and position of equilibrium processes of the dyes.Method: The UV-visible spectral patterns of the dyes in binary mixtures including Methanol:Water, Ethanol:Water, Methanol:Ethanol, Methanol:Propan-1-ol, Methanol:Propan-2-ol, Propan-1-ol:Water and Propan-2-ol:Water were acquired. The type and quantitative estimation of solute-solvent interactions at play were determined by fitting spectral patterns to solvent parameters using multilinear regression.Results: Preferential solvation was detected by the non-ideality of the plots of E12 as against the mole fractions of co-solvent in all binary mixtures. In pure solvents, the spectral shifts of AZ-01, 03 and 04, which exist predominantly in the hydrazone form, were affected by polarity of solvent milieu while solvent basicity and acidity, in that order, were the significant parameters for AZ-02. In aqueous alcoholic mixtures, solvent polarity was contributory, although to different degrees, to the observed spectral data of the four dyes. However, solvent acidity and basicity were the primary determinants of spectral shifts observed with AZ-04 and AZ-03 respectively. Spectra-structure relationships identified the formation of the charged hydrazone tautomer which requires stabilisation by polar solvent milieu as responsible for the observed trend. In addition, interactions between new aggregated solvent-solvent species and the propionic acid substituent present in AZ-03 contributed to its spectral shifts.Conclusion: The solvatochromic properties of the phenylazonaphthalene series in binary mixtures have been successfully studied.

Download Full-text

Solvatochromism in some cosolvent mixtures of sulfolane and aliphatic alcohols: a tool to predict preferential solvation

Canadian Journal of Chemistry ◽

10.1139/cjc-2019-0369 ◽

2020 ◽

Vol 98 (3) ◽

pp. 134-144 ◽

Cited By ~ 1

Author(s):

Mohsen Sarijloo ◽

Morteza Jabbari ◽

Ali Farajtabar

Keyword(s):

Binary Mixtures ◽

Preferential Solvation ◽

Solvation Shell ◽

Solvent Exchange ◽

Solvent Interactions ◽

Spectral Shifts ◽

Fraction Distribution ◽

Solvation Parameters ◽

Absorption Measurements ◽

Solvent Solvent

The phenomenon of solvatochromism for three indicator solutes, namely para-nitroaniline, N,N-dimethyl-p-nitroaniline, and the betaine dye 4-(2,4,6-triphenylpyridinium-1-yl)-2,6-diphenylphenolate, was studied at 303.15 ± 0.1 K by means of UV–vis absorption measurements. The spectral shifts of these dyes in different mole fractions (0.0–1.0) of binary mixtures of sulfolane with eight alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, tert-butanol) were analyzed to investigate preferential solvation of them in terms of both the solute–solvent and the solvent–solvent interactions. A modified theoretical model (solvent exchange model) was successfully employed to calculate preferential solvation parameters and to obtain information into the contribution of intermolecular interactions to the local and bulk mole fraction distribution of solvation species. It was found that the solvation shell of the dyes is mainly affected by the solvent–solvent interactions, and in all binary mixtures, the studied solvation behavior was non-ideal.

Download Full-text

Probing solvent–solvent and solute–solvent interactions in surfactant binary mixtures: solvatochromic parameters, preferential solvation, and quantum theory of atoms in molecules analysis

RSC Advances ◽

10.1039/c5ra23942g ◽

2016 ◽

Vol 6 (22) ◽

pp. 18515-18524 ◽

Cited By ~ 9

Author(s):

Mona Kohantorabi ◽

Mostafa Fakhraee ◽

Hadi Salari ◽

Mohammad Reza Gholami

Keyword(s):

Quantum Theory ◽

Binary Mixtures ◽

Organic Solvents ◽

Preferential Solvation ◽

Atoms In Molecules ◽

Solvatochromic Parameters ◽

Solvent Interactions ◽

Solvent Solvent

The behaviour of solvatochromic absorbance probes within binary mixtures of TX-100/organic solvents.

Download Full-text

Delineating Solute−Solvent Interactions in Binary Mixtures of Ionic Liquids in Molecular Solvents and Preferential Solvation Approach

The Journal of Physical Chemistry B ◽

10.1021/jp110040a ◽

2011 ◽

Vol 115 (4) ◽

pp. 711-718 ◽

Cited By ~ 70

Author(s):

Nageshwar D. Khupse ◽

Anil Kumar

Keyword(s):

Ionic Liquids ◽

Binary Mixtures ◽

Preferential Solvation ◽

Solvent Interactions ◽

Molecular Solvents

Download Full-text

Preferential solvation of quercetin in aqueous aprotic solvent mixtures

Journal of the Serbian Chemical Society ◽

10.2298/jsc190408037f ◽

2020 ◽

Vol 85 (2) ◽

pp. 227-236

Author(s):

Mohammad Faraji ◽

Ali Farajtabar

Keyword(s):

Aprotic Solvent ◽

Linear Trend ◽

Bulk Composition ◽

Preferential Solvation ◽

Great Influence ◽

Solvation Shell ◽

Solvent Mixtures ◽

Solvent Interactions ◽

Spectral Shifts ◽

Solvent Solvent

Solvatochromism of quercetin was studied in binary mixtures of water with dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide at 25 ?C by UV?Vis measurements. For all mixtures, a non-linear trend was observed in spectral shifts plotted against the bulk mole fractions. Deviation from ideal behaviour indicates that the solvation shell of quercetin differs in composition from the bulk because of preferential solvation. The solvent exchange model was applied in the analysis of solvatochromic data in order to quantify the extent of preferential solvation in the case of solute?solvent and solvent?solvent intermolecular interactions. The results show that the solvation shell of quercetin is enriched in aprotic solvent and the complex that was formed by the interaction between water and an aprotic solvent, over the whole composition range. The distribution of the solvent species in the solvation cage was obtained from the calculation of the local mole fractions as a function the bulk composition. It shows that the solvent?solvent interactions have great influence on the solvation behaviour of quercetin in aqueous aprotic solvent mixtures.

Download Full-text

Solvatochromism of naringenin in aqueous alcoholic mixtures

Journal of the Serbian Chemical Society ◽

10.2298/jsc160327060f ◽

2016 ◽

Vol 81 (10) ◽

pp. 1161-1169

Author(s):

Mohammad Faraji ◽

Ali Farajtabar

Keyword(s):

Nonlinear Response ◽

Preferential Solvation ◽

Electron Transition ◽

Solvent Interactions ◽

Fraction Distribution ◽

Energy Relationships ◽

Linear Solvation Energy ◽

Alcoholic Mixtures ◽

Maximum Absorption Wavelength ◽

Solvent Solvent

The spectral change of naringenin was studied by Uv-vis spectrophotometric method in binary mixtures of water with methanol, ethanol and 1-propanol at 25?C. The effect of solvent was investigated by analysis of electron transition energy at the maximum absorption wavelength as a function of Kamlet and Taft parameters of mixtures by means of linear solvation energy relationships. The nonlinear response of solvatochromism was explained based on solute-solvent and solvent-solvent interactions. The possible preferential solvation of naringenin by each of solvents was studied through a modified preferential solvation model which considers the hydrogen bonding interactions between the prior solvents due to solvent-solvent interactions. The preferential solvation parameters and local mole fraction distribution around the solute were calculated. Results indicate that naringenin prefers to be more solvated by the complex solvating species and organic solvents than water.

Download Full-text