Biomedical subjects

Sundaram Arulmozhiraja

Publications and source records attributed to Sundaram Arulmozhiraja.

6 recordsLinked to original sources

PubMed2006

C4Cl: bent or linear?

The ground state structure for the CCCCCl radical was computed by using symmetry-adapted cluster configuration-interaction (SAC-CI) theory along with density functional theory to overcome the differences raised in the recently published paper [Y. Sumiyoshi et al., Chem. Phys. Lett. 414, 82 (2005)] between the theory and the experiment. SAC-CI results clearly support the earlier experimental conclusion that the radical has the bent ground state structure corresponding to 2Pi symmetry. Contrarily, probably due to spin contamination, mixing of a bent doublet ground state with the quartet components of a linear structure, coupled-cluster singles and doubles (CCSD) calculations were unable to provide reliable results. Results obtained using density functional theory also show that the radical has a bent structure. Some low-lying doublet excited states were also studied using the SAC-CI theory. The energy difference between the ground Pi state and the nearby Sigma state is around 0.2 eV. The excitation energy for the transition with the largest oscillator strength agrees with the strongest absorption peak.

Journal Article↗

PubMed2006

Electronic spectra and photodissociation of vinyl chloride: a symmetry-adapted cluster configuration interaction study.

The vertical absorption spectrum and photodissociation mechanism of vinyl chloride (VC) were studied by using symmetry-adapted cluster configuration interaction theory. The important vertical pi --> pi* excitation was intensively examined with various basis sets up to aug-cc-pVTZ augmented with appropriate Rydberg functions. The excitation energy for pi --> pi* transition obtained in the present study, 6.96 eV, agrees well with the experimental value, 6.7-6.9 eV. Calculated excitation energies along with the oscillator strengths clarify that the main excitation in VC is the pi --> pi* excitation. Contrary to the earlier theoretical reports, the results obtained here support that the C-Cl bond dissociation takes place through the n(Cl-)sigma(C-Cl)* state.

Journal Article↗

PubMed2004

Structural requirements for the interaction of 91 hydroxylated polychlorinated biphenyls with estrogen and thyroid hormone receptors.

Estrogenic and thyroid activities of 91 monohydroxylated PCBs were measured with two-hybrid assays using yeast cells containing the human estrogen receptor ERalpha or human thyroid receptor TRalpha. Estrogenic activity of 30 of the 91 compounds, including all compounds active in the yeast two-hybrid assay, were also measured by a reporter gene assay employing Chinese hamster ovary cells. The mammalian cell assay was more sensitive than the yeast assay but the rank order of estrogenicities of the compounds were in broad agreement for the two assays. Results for estrogenicity and thyroid activity were analyzed by inspection and those for estrogenicity by a theoretical treatment. Inspection indicated para-hydroxyl was more likely to be estrogenically active than meta-, which was more likely to be active than ortho-; one ortho-chlorine was important for activity but additional ortho-chlorines did not increase activity; and 2 lateral chlorines or 2,4,6-chloro- substitution of the non-phenol ring were favorable. In contrast, thyroid activity appeared not to depend strongly on the position of the hydroxyl group although ortho-hydroxyls occurred in the most active compounds. Activity was usually associated with at least one ortho-chlorine, with 2 chlorines in the phenolic ring and, importantly, two chlorines in the non-phenolic ring, and with 1 or 2 chlorines ortho to the hydroxyl group. Examination of the torsion angle between the rings, in the theoretical examination of estrogenicity, suggested that perpendicular orientation (i.e., rigidity) was not essential for activity. Intramolecular hydrogen bonding of the phenolic groups to adjacent chlorines or to the pi-electron cloud of the non-phenol ring possibly decreased activity--the hydroxyl should be free of intramolecular interactions for maximum activity. It was difficult to predict the estrogenic activity of a congener from its obtained potential energy curve (PEC). In general, estrogenically active congeners had large values for the sum of the atomic charges on the carbon atoms of the hydroxylated ring, and on the oxygen atom. Hydroxyl substitution at the para-position allowed the compounds to become more polarizable in the x-axis (molecular axis), whereas OH substitution at the ortho-position made the congeners less polarizable in the same direction. However, no general statement about polarizability and estrogenic activity was possible.

Animals↗

PubMed2004

Structure-activity relationships for the toxicity of polychlorinated dibenzofurans: approach through density functional theory-based descriptors.

The applicability of various density functional theory (DFT)-based descriptors--chemical softness, electronegativity, and electrophilicity index--for quantitative structure--activity relationships (QSARs) was investigated for polychlorinated dibenzofurans (PCDFs). The DFT descriptors were obtained by using the three parameter hybrid density functional, B3LYP, with the 6-311G(d,p) basis set. QSARs were developed relating aryl hydrocarbon receptor (AhR) binding affinities, aryl hydrocarbon hydroxylase and ethoxyresorufin O-deethylase induction potencies of PCDFs with DFT descriptors, hydrophobicity, and steric parameters. These QSARs explain around 75% of variation in AhR binding affinities of PCDFs. Congeners with higher toxicity values had larger softness values. Studies also showed that the most toxic isomer of tetrachlorodibenzofurans (TCDFs) and dibenzo-p-dioxins (TCDDs), respectively, had the largest chemical softness value in its respective group. The results show that DFT descriptors could be used as useful electronic descriptors in QSARs for the prediction of toxicity of PCDFs. Overall, 85 congeners of PCDFs and TCDDs were considered in this study.

Air Pollutants, Occupational↗

PubMed2003

Substituent effects on benzdiyne: a density functional theory study.

Density functional theory (DFT) studies were performed to investigate the effect of substituents on the properties of benzdiyne derivatives. Twelve substituted benzdiynes-C(6)X(2), where X = F, Cl, Br, Me, CF(3), CN, OH, NO(2), NH(2), OMe, NMe(2), and Ph-were considered along with the unsubstituted 1,4-benzdiyne. The structures, vibrational frequencies, and IR intensities of these benzdiynes were studied with a popular three-parameter hybrid density functional (B3LYP) combined with the split-valence 6-31G(d) basis set and Dunning's correlation-consistent polarized triple-zeta (cc-pVTZ) basis set. The relative stabilities of the substituted benzdiynes were studied with the help of reaction energies of isodesmic reactions, which showed that the electron-withdrawing groups destabilized the benzdiynes more than they did the corresponding benzenes, whereas the electron-donating groups stabilized the benzdiynes more than they did their benzene counterparts. Correlation analyses revealed that field/inductive effects played a more important role than did resonance effects. The changes in atomic charges and spin populations due to the substituents were also studied. The asymmetric nu(Ctbd1;C) stretching modes obtained were close to the 1500-cm(-)(1) mark. Reinvestigation of the experimental results supported these results; a weak IR band at 1486 cm(-)(1) was assigned to this asymmetric stretching mode in C(6)(CF(3))(2) F. Some other benzdiynes also had large IR intensity values for their asymmetric nu(Ctbd1;C) vibrational modes due to the coupling with other vibrational modes. Heats of formation for the substituted benzdiynes were obtained from the reaction energies calculated at the B3LYP/cc-pVTZ level of theory.

Journal Article↗

PubMed2002

Benzdiynes (1,2,4,5-tetradehydrobenzenes): direct observation by wavelength-selective photolyses of benzenetetracarboxylic dianhydrides in low-temperature nitrogen matrixes.

Toward direct observation of benzdiynes, we investigated the wavelength-selective photolyses of five kinds of benzenetetracarboxylic dianhydride derivatives in nitrogen matrixes at 13 K. In the first step of the photolyses, all dianhydrides were converted into benzynedicarboxylic anhydrides with loss of CO and CO2 upon irradiation at 308 nm. In the second step, the benzyne intermediates were photolyzed at 266 nm. In these photolyses, the generation of two kinds of benzdiynes, 3,6-difluoro-1,4-benzdiyne and 3,6-bis(trifluoromethyl)-1,4-benzdiyne, was confirmed by good correspondence between observed and calculated IR spectra. These benzdiynes were converted into the corresponding hexatriynes upon further irradiation at 266 nm. Benzdiynes were not observed in the photolyses of the other three dianhydrides: only hexatriynes were observed as major photoproducts. These results suggested that benzdiynes were generated first and then converted into hexatriynes and that the efficiency of the decomposition of benzdiynes depended on the substituents. The dynamics of the generation and decomposition of benzdiynes in the matrixes was analyzed by using a successive reaction scheme.

Journal Article↗