title: Spectroscopic and DFT study of solvent effects on the electronic absorption spectra of sulfamethoxazole in neat and binary solvent mixtures.
abstract: The solvatochromic behavior of sulfamethoxazole (SMX) was investigated using UV-vis spectroscopy and DFT methods in neat and binary solvent mixtures. The spectral shifts of this solute were correlated with the Kamlet and Taft parameters (α, β and π(*)). Multiple lineal regression analysis indicates that both specific hydrogen-bond interaction and non specific dipolar interaction play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra using TD-DFT methods were in good agreement with the experimental ones. Binary mixtures consist of cyclohexane (Cy)-ethanol (EtOH), acetonitrile (ACN)-dimethylsulfoxide (DMSO), ACN-dimethylformamide (DMF), and aqueous mixtures containing as co-solvents DMSO, ACN, EtOH and MeOH. Index of preferential solvation was calculated as a function of solvent composition and non-ideal characteristics are observed in all binary mixtures. In ACN-DMSO and ACN-DMF mixtures, the results show that the solvents with higher polarity and hydrogen bond donor ability interact preferentially with the solute. In binary mixtures containing water, the SMX molecules are solvated by the organic co-solvent (DMSO or EtOH) over the whole composition range. Synergistic effect is observed in the case of ACN-H2O and MeOH-H2O, indicating that at certain concentrations solvents interact to form association complexes, which should be more polar than the individual solvents of the mixture.
authors.affiliation: Área de Química Física, Facultad de Química Bioquímica y Farmacia, Instituto Multidisciplinario de Investigaciones Biológicas (IMIBIO-SL) CONICET, Universidad Nacional de San Luis, 5700 San Luis, Argentina.
authors.forename: M C
authors.initials: MC
authors.lastname: Almandoz
authors.forename: M I
authors.initials: MI
authors.lastname: Sancho
authors.forename: S E
authors.initials: SE
authors.lastname: Blanco
mesh_terms: D065966:Absorption, Physicochemical; D000097:Acetonitriles / Q000737:chemistry; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D004126:Dimethylformamide / Q000737:chemistry; D004583:Electrons; D000431:Ethanol / Q000737:chemistry; D008958:Models, Molecular; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013420:Sulfamethoxazole / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000097:Acetonitriles; D012997:Solvents; D000431:Ethanol; D004126:Dimethylformamide; D013420:Sulfamethoxazole; D004121:Dimethyl Sulfoxide; C032159:acetonitrile
keywords: LSER; Preferential solvation; Solvatochromism; Sulfamethoxazole; TD–DFT; UV–vis spectroscopy