Copper(II) Complexes Derived from Schiff Bases Containing 4-Methylbenzylamine as a Core Unit: Cytotoxicity, pBR322-DNA Studies, Biological Assays, and Quantum Chemical Parameters.

Bivalent copper complexes, [Cu(SB1 )2 ] 1 (SB1 =(2-(4-methylbenzylimino)methyl)-5-methylphenol, [Cu(SB2 )2 ] 2 (SB2 =(2-(4-methylbenzylimino)methyl)-4-bromolphenol), and [Cu(SB3 )2 ] 3 (SB3 =(2-(4-methylbenzylimino)methyl)-4,6-dibromophenol) were synthesized using the Schiff bases prepared from 4-methylbenzylamine (p-tolylmethanamine). These were characterized using a variety of spectro-analytical methods. For all copper complexes, a square planar geometry was determined through spectral analyses. Utilizing molecular orbital energies, the stability of the copper complexes was calculated from quantum chemical characteristics. The kinetic and thermal degradation parameters were calculated from the thermograms. Studies on DNA binding interactions, such as UV absorption and emission, have shown that the manner of DNA binding is intercalative, and the binding constant (Kb ) order is 3>2>1. Under oxidative and photolytic techniques, the copper complexes outperform the parent Schiff bases in their ability to cleave double-stranded pBR322 DNA. When tested for cytotoxicity on the KB3 and MCF7 cell lines, complexes displayed greater activity than their parent ligands. Studies on the complexes' in-vitro antibacterial and antioxidant activity showed that they are significantly more powerful than the parent ligands.

Predicting the rate constants of volatile organic compounds (VOCs) with ozone reaction at different temperatures.

Based on the bond order, fukui indices and other related descriptors, as well as temperature, a new QSAR model was established to predict the rate constant (kO3) of VOCs degradation by O3. 302 logkO3 values (178-409 K) of 149 VOCs were divided into training set (242 logkO3) and test set (60 logkO3), respectively, which were used to construct and verify the QSAR model. The optimal model (R2 = 0.83, q2 = 0.82, Qext2 = 0.72) shows that EHOMO, BOx and q(C-)n have a greater influence on the value of logkO3. In addition, fukui indices and logkO3 are well correlated. The applicability domains of the current models can be used to predict kO3 of a wide range of VOCs at different temperatures.

Two new predictors combined with quantum chemical parameters for the selection of oxidants and degradation of organic contaminants: A QSAR modeling study.

Oxidation is an attractive treatment method to effectively remove organic contaminants in water. In this study, degradation of 30 organic compounds in different oxidation systems was evaluated, including oxygen (O2), hydrogen peroxide (H2O2), ozone (O3) and hydroxyl radical (HO). First, a quantitative structure-activity relationship (QSAR) model for oxidation-reduction potentials (ORPs) of organics was developed and exhibited a good performance to predict ORP values of organics with evaluation indices of squared correlation coefficient (R2) = 0.866, internal validation (q2) = 0.811 and external validation (Qext2) = 0.669. Four quantum parameters, including f(+)n, f(-)n, EHOMO and EB3LYP dominate the ORP values. Subsequently, a relationship between reaction rates (k) and the difference of ORP for oxidants and organics (ΔEoxi-org) was established, however, which was limited (R2= 0.697). Therefore, two new predictors (slopes and intercepts) are proposed based on the linear relationships between k values and ORPs of oxidants. These new predictors can be applied to estimate the reaction rates and minimum oxidation potential for organic compounds. Afterwards, to express the two predictors, QSAR models were established. The two optimal QSAR models fitted very well with experimental values and were demonstrated to be stable and accurate based on R2 (0.982 and 0.965), q2 (0.950 and 0.950) and Qext2 (0.985 and 0.989). BOx, q(H)+ and q(C)x were main factors influencing the slopes and intercepts. This study developed methods to predict ORPs of organics and established two new predictors to estimate the reaction rates undergoing different oxidation processes, offering new insights into the oxidant selection.

Cytotoxicity and Pro-inflammatory Properties of Aliphatic Alpha, Beta-unsaturated Acid and Ester Monomers in RAW264.7 Cells and Their Chemical Reactivity.

BACKGROUND/AIM: α,ß-Unsaturated ester monomers such as methyl methacrylates (MMA), 2-hydroxyethyl methacrylates (2-HEMA), ethyleneglycol dimethacrylate (EGDMA) and triethyleneglycol dimetacrylate (TEGDMA) have been widely used in dentistry as dental materials. The present study was designed to clarify the proinflammatory activity of monomers. MATERIALS AND METHODS: The cytotoxicity of the monomers and their effects on the expression of cyclooxygenase-2 (Cox2), nitric oxide synthase 2 (Nos2) and heme oxygenase 1 (Ho-1) mRNAs in RAW264.7 cells were determined using a cell counting kit and real-time reverse transcriptase-polymerase chain reaction, respectively. RESULTS: The cytotoxicity declined in the order n-butyl acrylate (nBA) > acrylic acid > TEGDMA > EGDMA > methacrylic acid ≈ 2-HEMA > lauryl methacrylate > nBMA > MMA. nBA and EGDMA at 1 mM up-regulated the expression of Cox2 mRNA. In contrast, 1 mM nBA and 10 mM 2-HEMA up-regulated the expression of Nos2 mRNA. Up-regulation of Ho-1 mRNA expression was found for 0.1 mM nBA, 1 mM EGDMA and 2 mM TEGDMA. The electrophilicity, ω was calculated on the basis of the density function theory BLYP/6-31G*. CONCLUSION: nBA and EGDMA with high ω values exerted potent pro-inflammatory activities. nBA, EGDMA and TEGDMA upregulated Ho-1 gene expression. Ho-1 gene activation of monomers may promote resistance of chemical carcinogenesis in biological systems.

Synthesis, characterization, DNA binding and catalytic applications of Ru(III) complexes.

A new series of azodye ligands 5-chloro-3-hydroxy-4-(aryldiazenyl)pyridin-2(1H)-one (HLn) were synthesized by coupling of 5-chloro-3-hydroxypyridin-2(1H)-one with aniline and its p-derivatives. These ligands and their Ru(III) complexes of the type trans-[Ru(Ln)2(AsPh3)2]Cl were characterized by elemental analyses, IR, (1)H NMR and UV-Visible spectra as well as magnetic and thermal measurements. The molar conductance measurements proved that all the complexes are electrolytes. IR spectra show that the ligands (HLn) acts as a monobasic bidentate ligand by coordinating via the nitrogen atom of the azo group (NN) and oxygen atom of the deprotonated phenolic OH group, thereby forming a six-membered chelating ring and concomitant formation of an intramolecular hydrogen bond. The molecular and electronic structures of the investigated compounds (HLn) were also studied using quantum chemical calculations. The calf thymus DNA binding activity of the ligands (HLn) and their Ru(III) complexes were studied by absorption spectra and viscosity measurements. The mechanism and the catalytic oxidation of benzyl alcohol by trans-[Ru(Ln)2(AsPh3)2]Cl with hydrogen peroxide as co-oxidant were described.

Polymer complexes. LX. Supramolecular coordination and structures of N(4-(acrylamido)-2-hydroxybenzoic acid) polymer complexes.

A number of novel polymer complexes of various anions of copper(II), cobalt(II), nickel(II) and uranyl(II) with N(4-(acrylamido)-2-hydroxy benzoic acid) (ABH) have been synthesized and characterized by elemental analysis, IR, 1H NMR, magnetic susceptibility measurements, electronic spin resonance, vibrational spectra and thermal analysis. The molecular structures of the ligand are optimized theoretically and the quantum chemical parameters are calculated. Tentative structures for the polymeric metal complexes due to their potential application are also suggested. The IR data exhibit the coordination of ONO2/OAc/SO4 with the metal ions in the polymeric metal complex. Vibrational spectra indicate coordination of carboxylate oxygen and phenolic OH of the ligand giving a MO4 square planar chromophore. Ligand field ESR spectra support square planar geometry around Cu(II). The thermal decomposition of the polymer complexes were discussed in relation to structure, and the thermodynamic parameters of the decomposition stages were evaluated applying Coast-Redfern and Horowitz-Metzger methods.