A computational perspective of vibrational and electronic analysis of potential photosensitizer 2-chlorothioxanthone

Ali, Nawazish; Mansha, Asim; Asim, Sadia; Zahoor, Ameer Fawad; Ghafoor, Sidra; Akbar, Muhammad Usman

doi:10.1016/j.molstruc.2017.12.015

Cited by 20 publications

(5 citation statements)

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“…In the present work, azo direct dye, named p-(dimethylamino)azobenzene (DMAB), was studied theoretically in the gas phase as well as in different solvents and its vibrational and structural properties have been reported in comparison with some experimental data. Multidisciplinary studies involving experimental as well as theoretical methods proved to be very useful for understanding the chemistry of the title compound and provide insight into molecular analysis [14,15]. This manuscript mainly deals with the structural and spectroscopic (IR, Raman, and UV-Vis absorption spectra) properties, NBO analysis, and transition states of the title compound and its behavior in different solvents.…”

Section: Introductionmentioning

confidence: 99%

DFT Study for the Spectroscopic and Structural Analysis of p-Dimethylaminoazobenzene

Ali

Mansha

Asim

et al. 2018

Journal of Spectroscopy

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The study under consideration represents the computational calculations of Azo-based direct dye named p-(dimethylamino)azobenzene (DMAB) under the effect of solvents with different relative permittivities. A density functional theory (DFT) method at the B3LYP level with 6-311G++ was applied for the spectroscopic and structural analysis of the title compound. Calculations of geometric parameters (bond orders, bond lengths, and dihedral angles), electron densities, thermodynamic parameters, and orbital energies were performed for the title compound. Mulliken population analysis (MPA) as well as natural population analysis (NPA) was also performed at the B3LYP level with different solvents for finding solvent effects. In order to predict the reactivity of DMAB, molecular electrostatic potential (MESP) calculations were carried out for it. For vibrational analysis, the infrared (IR) spectra were computed for the title compound at the B3LYP/6-311G++ level in the gas phase and in different solvents with good agreement to the experimental FT-IR spectrum. The different modes of vibrations were assigned using potential energy distribution (PED). The computed Raman spectra also showed appreciable agreement with the experimental recorded Raman spectrum. The electronic absorption spectra of the title compound have been computed employing DFT/B3LYP with the 6-311G++ basis set in the gas phase and in four different solvents, that is, DMSO, ethanol, acetonitrile, and water which were compared with the experimental spectra with appreciable agreement. NBO analysis was carried out for understanding the intramolecular and intermolecular bonding of the compound and the density transfer from completely filled to unfilled orbital was found. The HOMO-LUMO energies were determined for analyzing the mechanism of intramolecular charge transfer.

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Section: Introductionmentioning

confidence: 99%

DFT Study for the Spectroscopic and Structural Analysis of p-Dimethylaminoazobenzene

Ali

Mansha

Asim

et al. 2018

Journal of Spectroscopy

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“…In the present study using one of the most widely used TX-based commercial photoinitiators, , we investigated the metabolic susceptibility of 2-Chlorothioxanthone (2-Cl-TX) (Figure S1 of the Supporting Information, SI) and its effect on the enzymatic activities, mRNA, and protein expression of human CYP1A2 and CYP3A4. The in vitro biotransformation of 2-Cl-TX by CYP1A2 and CYP3A4 was probed for the first time by in vitro incubation with CYP1A2 and CYP3A4, and the metabolites were proposed by quadrupole-time-of-flight (Q-TOF) tandem mass spectrometry and in silico prediction.…”

Section: Introductionmentioning

confidence: 99%

Metabolic Susceptibility of 2-Chlorothioxanthone and Its Toxic Effects on mRNA and Protein Expression and Activities of Human CYP1A2 and CYP3A4 Enzymes

Zhan

Pan

Liu

et al. 2018

Environ. Sci. Technol.

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Thioxanthones (TXs) are photoinitiators widely used in UV curable resins and food packaging, and their residues have been frequently detected in human bodies. Our current understanding of the susceptibility of residual TXs to metabolism and their effects on human health is very limited. The in vitro metabolism of TXs and its toxic effects on cytochrome P450 (CYP) (the key xenobiotic metabolizing enzymes) were examined in this study. 2-Chlorothioxanthone (2-Cl-TX) significantly inhibited the enzymatic activities of CYP1A2 and CYP3A4 with IC 50 of 8.36 and 0.86 μM, respectively. The exposure to 2-Cl-TX at 2.5 μM up-regulated the mRNA expression of CYP1A2 and CYP3A4 in human hepatocellular carcinoma cells to 3.03-fold and 2.02-fold, respectively. 2-Cl-TX at 2.5 μM caused 2.19-fold and 1.98-fold overexpression of CYP1A2 and CYP3A4, respectively. In vitro studies revealed that 2-Cl-TX was biotransformed into two metabolites through the sulfoxidation of the sulfur atom, or via the hydroxylation of aromatic carbon. Results from this study, including the metabolic susceptibility of residual 2-Cl-TX, the proposed metabolites and the significant toxic effect on the activities, mRNA, and protein expression of CYP1A2 and CYP3A4, are vital to the human health and safety risk assessment from this ubiquitous xenobiotic.

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“…Compound ( I ) with 14 number of atoms possess 36 vibrational modes, while compound ( II ) containing 21 atoms will indicate 57 fundamental vibrational modes. Compound ( III ) containing 18 atoms has shown 48 vibrations, and compound ( IV ) with 15 atoms has shown 39 IR-vibrational frequencies according to the 3N-6 rule . The IR spectra of these polyphenols taken by DFT with different solvents have been compared (Figure ), and the calculated frequencies were compared with their respective experimental values (from the literature).…”

Section: Resultsmentioning

confidence: 99%

Combined Experimental and Theoretical Insights: Spectroscopic and Molecular Investigation of Polyphenols from Fagonia indica via DFT, UV–vis, and FT-IR Approaches

Riaz,

Parveen,

Rashid

et al. 2023

ACS Omega

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This review deals with computational study of polyphenolic compounds of medicinal importance and interest for drug development. Herein, four polyphenolic compounds comprising catechol (1), caffeic acid (II), gallic acid (III), and pyrogallol (IV) have been isolated from a medicinal specie, Fagonia indica, by applying silica gel column chromatography. These compounds were identified by using gas chromatography−mass spectrometry (GC−MS) analysis and confirmed by geometric computational analysis. According to computational results, caffeic acid has shown the highest biological activation due to higher chemical softness, electronegativity (χ (eV) = −648.644), and electrostatic potential value (−8.424 × 10 −2 to +8.424 × 10 −2 ), while smaller values of chemical potential (−0.269), E LUMO (−0.080), and energy gap (ΔE = 0.149). The Mulliken atomic charges were calculated by using DFT/B3LYP with basis set 6-311G for the determination of active sites. The oxygen atom of catechol showed highest nucleophilic characteristic with a more negative charge (08 = −0.695), and pyrogallol indicated a strong electrophilic center at C14 = 0.415 with a higher positive charge. Moreover, UV−visible absorption spectra and a detailed study of vibrational frequencies for all phenolic compounds by employing the DFT approach with 3-21G, 6-31G, and 6-311G basis sets at the ground-state level showed the great agreement with experimental results. ANOVA has been applied to validate the theoretical data. Results suggest that compounds I− IV are suitable in diverse fields.

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A computational perspective of vibrational and electronic analysis of potential photosensitizer 2-chlorothioxanthone

Cited by 20 publications

References 58 publications

DFT Study for the Spectroscopic and Structural Analysis of p-Dimethylaminoazobenzene

DFT Study for the Spectroscopic and Structural Analysis of p-Dimethylaminoazobenzene

Metabolic Susceptibility of 2-Chlorothioxanthone and Its Toxic Effects on mRNA and Protein Expression and Activities of Human CYP1A2 and CYP3A4 Enzymes

Combined Experimental and Theoretical Insights: Spectroscopic and Molecular Investigation of Polyphenols from Fagonia indica via DFT, UV–vis, and FT-IR Approaches

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