Linear QSAR Regression Models for the Prediction of Bioconcentration Factors of Chloroanilines in Fish by Density Functional Theory

Density functional theory（DFT）-B3LYP level with the 6-311G＊＊（d,p） basis set was used to calculate a set of molecular quantum chemical descriptors of 12 chloroanilines. Quantitative structure-activity relationship（QSAR） models of the bioconcentration factors（BCF） of the anilines in fish were established using some of the following calculated descriptors： EHOMO, ENHOMO, ELUMO, ENLUMO, ΔE1（= ELUMO- EHOMO）, ΔE2（= ENLUMO- ENHOMO）, dipole moment（μ）, molecular volume（V）, vibrational energy of 0 K（Ev）, thermodynamic energy（E）, heat capacity（Cv）, entropy（Sm） and the charge of benzene ring（Qph）. Using the variable selection and leaps-and-bounds regression, the quantum chemical descriptors derived directly from the molecular structures were employed to develop a linear QSAR model between the bioconcentration factors（BCF） and two descriptors（Sm, ENHOMO） of 12 chloroanilines. Statistically, the most significant one is a two-parameter linear equation with the correlation coefficient（R^2） of 0.981 and cross-validated correlation coefficient（Rcv^2） of 0.967. The established QSAR model has good stability and predictability based on the results from Rcv2 of leave-one-out cross-validation, AIC, FIT and tα/2. The quantum chemical analyses were performed from two aspects of frontier molecular orbital and entropy. The results show that two structural describers are crucial to the bioconcentration activity of chloroanilines.

Degradation of Chloroanilines in Aqueous Solution by Contact Glow Discharge Electrolysis

Contact glow discharge electrolysis of some chloroanilines in sodium sulfate was investigated in different initial concentrations. Each of them underwent the dechlorination, deam-ination through oxidative degradation, and were eventually decomposed into hydrogen carbonate and carbon dioxide. It was testified that the chlorine atom and amidogen could be transformed into chloride ion and nitrite ion, respectively. Fe2+ has a remarkable catalytic effect on the degradation of them. On the basis of the detailed analysis of the intermediate products and kinetic behaviors, the reaction pathway was proposed, in which the attack of hydroxyl radical on the benzene ring of starting material might be a key step.

Rapid HPLC Method for Determination of Parachloroaniline in Chlorhexidine Antiseptic Agent in Mouthrinses, Ophthalmic and Skin Solution

We described a simple and rapid method to quantify simultaneously chlorhexidine (CHD) and its major metabolite, para Chloroaniline (pCA) by HPLC with UV detection without the additional need of mobile-phase amine modifiers or ion-pairing reagents, with good resolution between pCA and CHD, symmetry peak of the compound and short run time. HPLC-UV analyses were performed using a Dionex? Summit liquid chromatograph (Dionex Corp, Sunnyvale, CA, USA). Chromatographic separations were carried out on a Luna? 150 mm×3 mm i.d. column packed with 3 μm CN (cyano) particles (Phenomenex?), guarded by an on-line filter. Mobile phase consist of methanol:water with sodium chloride with 0.02% of formic acid (55:45). Wavelengths for pCA and for CHD are 238 and 255 nm respectively. Influence of methanol and of sodium chloride content in the eluant has been studied. Linearity of CHD is very good, from 0.5 up to 21.2 μg/l while linearity of pCA is in the range of 0.05 to 10 μg/l with correlation coefficients above 0.999. Resolution between the components is above 4, asymmetry is about 1.3 and 1.7 for pCA and CHD respectively and the run time is less than 5 minutes. This method has been applied to CHD solution of different medical devices. No interference has been reported, and the analysis of direct injection of solution, without any treatment is achieved in less than five minutes.In conclusion, we present a validated method for dosage of CHD and its major impurity pCA, known to be carcinogen, available into medical products or medicinal device for in-vitro diagnostic.

Effect of rare earths on selective hydrogenation of p-chloronitrobenzene over PtMOx/CNTs catalysts

The effect of rare earths （Sm, Pr, Ce, Nd and La） on the hydrogenation properties ofp-chloronitrobenzene （CNB） over Pt/CNTs catalyst was studied in ethanol at 303 K and normal pressure. The results exhibited that the hydrogenation of p-CNB could be carried out over PtMOx/CNTs catalysts. Both catalytic activities and yields ofp-chloroaniline （CAN） were all improved. PtCeOx/ CNTs catalyst exhibited the best catalytic activity （TOF was 0.47 s^-1） and the highest yield of p-CAN （97.5 mol%）. PtCeOx/CNTs （1.0 wt%） catalyst exhibited good stability on the hydrogenation of p-CNB.

Liquid Phase Hydrogenation of <i>p</i>-Chloronitrobenzene on Au-Pd/TiO₂Catalysts: Effects of Reduction Methods

The effects of palladium addition and the reduction methods on Au/TiO2 were investigated. Pd was loaded on TiO2 firstly by incipient-wetness impregnation, Au was then loaded by deposition-precipitation method. The nominal loadings of Au and Pd were 1 wt% and 0.01 wt%. The bimetallic catalysts were reduced by heating at 453 K, by flowing H2 at 423 K, or by NaBH4 at 298 K. The catalysts were characterized by ICP, XRD, TEM, HRTEM, TPR and XPS. Hydrogenation of p-chloronitrobenzene was carried out at 1.2 MPa H2 pressure and 353 K. The results showed that even adding very small amount of Pd could enhance activity and selectivity of p-chloroaniline significantly. Pd and Au formed alloy and Pd could donate partial electron to Au. Pd metal on the surface of alloy could adsorb hydrogen and enhanced the activity. The pretreatment methods did not change particle size significantly, all were below 4 nm. The sample reduced by NaBH4 could have higher concentration of Au0 and sustain small Au particle size, resulting in high activity.