QSAR Study of Nitrobenzenes’ Toxicity to Tetrahymena Pyriformis Using Semi-empirical Quantum Chemical Methods

The molecular geometries and electronic structures of 30 nitrobenzenes have been calculated by using semi-empirical MO AM1 and PM3 methods. EHOMO, ELUMO, ENHOMO, ENLUMO, AE, QNO2, Qc and V were selected as the structural descriptors. The acute toxicity （-log/C50） of nitrobenzenes to tetrahymena pyriformis along with the above eight structural parameters was used to establish the quantitative structure-activity relationships （QSARs）. The results indicate that the established model based on AM I method is superior to that on PM3 method not only for the stability but also for the predictive powers of the model. Based on AM1 parameters, a further classifying discussion was presented for the study of nitrobenzene toxic mechanism. The results show that the substituents, nitro group and halogen substituents on the aromatic ring are crucial to the chemicals＇ toxicity. For nitrobenzenes without halogen or other substituent, the reduction of nitro group is the main route. However, for those with halogen substituents, their next lowest unoccupied molecular orbital may take part in the toxic action betweeen the chemicals and macromolecules, and ENLUMO has the most important effect on these chemicals＇ toxicity.

A DFT-based Quantum Theoretic QSAR Study of Nitrobenzenes' Toxicity to Tetrahymena Pyriformis

In this study,DFT-B3LYP level of theory with the 6-311G basis set was used to calculate a set of molecular descriptors of 36 nitrobenzenes.Quantitative structure-activity relationship（QSAR） models of the toxicity（pIGC50） of 36 nitrobenzenes were established using some of the following calculated descriptors：HOMO energy（EHOMO）,LUMO energy（ELUMO）,the difference between LUMO and HOMO energy values（ΔE=ELUMO–EHOMO）,average polarizability（P）,dipole moment（μ）,molecular volume（V） and the charge of nitro group（Q-NO2）.The QSAR models obtained by employing stepwise multiple regression techniques are aimed at correlating the structures with their reported experimental toxicity values. Among the models presented in this study, statistically the most significant one is a two-parameter linear equation with the correlation coefficient （R2） of 0.896 and cross-validated correlation coefficient （R2cv） of 0.878. To further validate the predictive ability of the resulting model, external validation was carried out with R2~xt and Q^2,ext values of 0.894, 0.900, 0.909, 0.874, 0.885 and 0.903, respectively. This study also reconstructed the obtained models using AMl-based calculated descriptors to demonstrate the superiority of DFT over AM1 for quantum calculations of mechanical descriptors. The results were discussed in the light of the main factors that influence the toxicity of nitrobenznenes.

Genotoxicity of substituted nitrobenzenes and the quantitative structure－activity relationship

The genotoxicity of 22 substituted nitrobenzenes were evaluated by the chromosome aberrations test in in vitro human peripheral lymphocytes.18 of 22 compounds exhibit genotoxic activities.Quantitative structure-activity relationship model was established to correlate the genotoxicity of substituted nitrobenzenes with the characteristics of the substituents on benzene ring.

Nucleophilic Aromatic Substitution of Nitrobenzenes with Nitrite Ion

It is experimentally found that different renction courses exist when mtrite ion reacts with nitrobenzenes with different electron withdrawing groups. when it is substituted with strong electron withdrawing groups. self-condensation in aprotic polar solvent occurs to give symmnetrical disubstituted diphenyl ethers. However. when it is substituted with moderate electron withdrawing groups, no diphenyl ethers are obtained under the same conditions, instead, corresponding carboxylates are yielded. As a result. the applicability of this reaction is distinctly clarified

QSAR Studies on the Toxicity of Nitrobenzenes to Population Growth of Tetrahymena Pyriformis

The IGC 50 (50% inhibitory growth concentration) values of 27 nitrobenzenes were determined for the population growth endpoint of Tetrahymena pyriformis . The toxicity order of the observed compounds was found to be as follows: dinitro compounds>mononitro compounds, dichloronitrobenzenes>monochloronitrobenzenes, meta substituted nitrobenzenes>ortho /para substituted nitrobenzenes(NT, NPh, NAnis) except for the dinitrobenzenes and nitroanilines(DNB, NAn). Quantitative structure activity relationships(QSARs) were developed with the logarithm of the reciprocal of IGC 50 [lg(IGC 50 ) -1 ] in mole liter as dependent variable and six molecular descriptors lg P , 1 X Ⅴ, I, 1K a, ∑σ - and E LUMO as independent variables. Via multiple regression analysis, one best equation was obtained: lg(IGC 50 ) -1 =3.029+0.860∑ σ -+0.341I n=27, r=0.924, r 2=0.854, s=0.265, f=70.44 , Pr> f =0.000 1 The equation was used to estimate IGC 50 for five analogues.

The promoting role of minor amount of water in solvent-free hydrogenation of halogenated nitrobenzenes

This study shows that minor amount of water plays a very important role in solvent-free hydrogenation of halogenated nitrobenzenes. For dried sponge Pd, the reaction cannot occur in the absence of water. For Pd/C catalyst, minor amount of water reduces the induction time, increases the reaction rate and reaction TOFs. Water might enhance the diffusion, adsorption and dissociation of H2 on Pd catalysts.

Electrosynthesis of Azobenzenes Directly from Nitrobenzenes

The electrochemical reduction strategy of nitrobenzenes is developed.The chemistry occurs under ambient conditions.The protocol uses inert electrodes and the solvent,DMSO,plays a dual role as a reducing agent.Its synthetic value has been demonstrated by the highly efficient synthesis of symmetric,unsymmetric and cyclic azo compounds.

Room-temperature hydrogenation of halogenated nitrobenzenes over metal-organic-framework-derived ultra-dispersed Ni stabilized by N-doped carbon nanoneedles

Ultra-dispersed Ni nanoparticles(7.5 nm)on nitrogen-doped carbon nanoneedles(Ni@NCNs)were prepared by simple pyrolysis of Ni-based metal–organic-framework for selective hydrogenation of halogenated nitrobenzenes to corresponding anilines.Two different crystallization methods(stirring and static)were compared and the optimal pyrolysis temperature was explored.Ni@NCNs were systematically characterized by wide analytical techniques.In the hydrogenation of p-chloronitrobenzene,Ni@NCNs-600(pyrolyzed at 600°C)exhibited extraordinarily high performance with 77.9 h^(–1)catalytic productivity and>99%p-chloroaniline selectivity at full p-chloronitrobenzene conversion under mild conditions(90°C,1.5 MPa H2),showing obvious superiority compared with reported Ni-based catalysts.Notably,the reaction smoothly proceeded at room temperature with full conversion and>99%selectivity.Moreover,Ni@NCNs-600 afforded good tolerance to various nitroarenes substituted by sensitive groups(halogen,nitrile,keto,carboxylic,etc.),and could be easily recycled by magnetic separation and reused for 5 times without deactivation.The adsorption tests showed that the preferential adsorption of–NO2 on the catalyst can restrain the dehalogenation of p-chloronitrobenzene,thus achieving high p-chloroaniline selectivity.While the high activity can be attributed to high Ni dispersion,special morphology,and rich pore structure of the catalyst.

One-pot synthesis of 1,4-disubstituted 1,2,3-triazoles from nitrobenzenes

A facile synthesis of 1,4-disubstituted 1,2,3-triazoles was achieved from nitrobenzenes and terminal alkynes under mild conditions. The reactions were successful for nitrobenzenes and terminal alkynes bearing various functionalities, from which the 1,2,3-triazole derivatives were smoothly synthesized through a four-step one-pot sequence.

Synthesis and Characterization of Fluorodinitrobenzenes with Tunable Melting Point:Potential Low Sensitive Energetic Plasticizer and Melt-Cast Carrier

of main observation and conclusion In order to explore the effects of fluoro substituents on the energy and safety of energetic compounds,a series of fluorodinitrobenzenes including l,3-difluoro-2,4-dinitrobenzene(1),1,5-difluoro-2,4-dinitrobenzene(2),1,2,3-trifluoro-4,6-dinitrobenzne(3)and 1,3,5-trifluoro-2,4-dinitrobenzene(4)were prepared.All the compounds were fully characterized.The structures of 2 and 3 were further confirmed by single crystal X-ray diffraction analysis.The results show that these compounds exhibit comparable detonation properties(D=6703-6978 m s^-1,and p=21.3-23.76Pa)to those of 2,4,6-trinitrotoluene(TNT)due to the significantly increased density of fluorine introduced.Low sensitivity(IS>40 J,and FS>360 N)of these compounds along with different melting points make them potential candidates for different allocation.Among them,1 and 4 with the melting point of 42.5℃and 55.2℃,respectively,show promise for application in the field of energetic plasticizer.Compounds 2 and 3 are potential low sensitive melt-cast carrier due to their similar melting point and superior detonation performance to that of TNT.

Pt-Ni core-shell structure with Pt-skin and electronic effect on catalytic performance

In order to improve the catalytic performance of the nitrobenzene hydrogenation rearrangement to prepare p-aminophenol,a bimetallic Pt-Ni/C(PNC)catalyst was synthesized.Taking advantage of the synergistic effect of Ni and Pt to enhance product selectivity and catalytic performance stability,the electrons in Ni are moved to Pt by the electron effect,which affects the catalyst’s ability to activate H_(2)as well as the amount of hydrogen activated.Furthermore,due to the strong Pt(5d)-Ni(3d)coupling effect,Ni can effectively maintain Pt stability in the acidic system and reduce Pt dissolution.The stability of the PNC can be found to be greatly enhanced compared to the Pt/C(PC)catalyst,and p-aminophenol selectivity is greatly enhanced,showing excellent catalytic performance.

Prediction of the environmental fate and aquatic ecological impact of nitrobenzene in the Songhua River using the modified AQUATOX model

An accidental discharge of nitrobenzene happened in November 2005 in the Songhua River,China.The AQUATOX model was modified and adapted to simulate the time-dependent nitrobenzene distribution in this multimedia aquatic system and its potential ecological impacts.Nitrobenzene concentrations in flowing water,sediment,and biota were predicted.Based on the initial concentrations of nitrobenzene observed in the field during the accidental discharge,that is,0.167-1.47 mg/L at different river segments, the predic...

Nitrobenzene biodegradation ability of microbial communities in water and sediments along the Songhua River after a nitrobenzene pollution event

More than 100 t of nitrobenzene (NB) and related compounds were discharged into the Songhua River,the fourth longest river in China,because of the world-shaking explosion of an aniline production factory located in Jilin City on November 13,2005.As one of the efforts to predict the fate of residual NB in the river,NB biodegradation abilities by microbes in the water and sediments from different river sections were evaluated systematically.The results indicated that microbial communities from any section of ...

Characterization of the Songhua River sediments and evaluation of their adsorption behavior for nitrobenzene

The explosion at a plant of the Jilin Petrochemical Corporation on 13 November,2005,and the spill of an estimated 100 t of toxic substances (nitrobenzene as the main component) into the Songhua River received worldwide attention.This study has focused on the adsorption behavior of nitrobenzene that spilled onto sediments along the Songhua River,which was one of the efforts to evaluate the fate of nitrobenzene after the spillage event.The organic carbon contents of these sediments along the Songhua River var...

Degradation of nitrobenzene in aqueous solution by ozone-ceramic honeycomb

The degradation of nitrobenzene by ceramic-honeycomb catalyzed ozonation was investigated. The results showed that the presence of ceramic honeycombs significantly increased the oxidation rate of nitrobenzene by ozone compared to the case of ozone oxidation alone. In this paper, the effects of various factors on the catalytic oxidation were investigated, such as the amount of catalysts, the ozone dosage, the temperature, the pH value and the presence of tert-butanol. With the addition of tert-butanol the removal of nitrobenzene decreased sharply, which appeared to support that, the degradation of nitrobenzene by ozonation followed a radical type mechanism. The EPR experiments verified that higher nitrobenzene removal rate was attributed to more OH radicals generated in the catalyzed ozonation than ozonation alone.

Location and PCR analysis of catabolic genes in a novel Streptomyces sp. DUT_AHX capable of degrading nitrobenzene

A novel strain of Streptomyces sp.DUT_AHX was isolated from sludge contaminated with nitrobenzene and identified on the basis of physiological and biochemical tests and 16S ribosomal DNA (rDNA) sequence analysis.The optimal degradation conditions were as follows:temperature 30℃,pH 7.0-8.0,shaking speed 150-180 r/min,and inocula 10%(V/V).The strain,which possessed a partial reductive pathway with the release of ammonia,was also able to grow on mineral salts basal (MSB) medium plates with 2-aminophenol, pheno...

Concentration level and geographical distribution of nitrobenzene in Chinese surface waters

Nitrobenzene was reported to occur at relatively high concentrations in some Chinese surface water and to cause an environmental pollution event in 2005.To map the distribution of nitrobenzene in the Chinese surface water throughout China,surface water samples were collected from over 600 sites in the 7 major watersheds and three drainage areas.The samples were analyzed for concentration of nitrobenzene.Overall,nitrobenzene was more frequently detected at higher concentrations in the rivers of North China,i...

TiO_2担载镍催化剂上硝基苯液相加氢(英文)

The catalytic hydrogenation of nitrobenzene to aniline employing nickel impregnated on rutile,anatase,and high surface area titania supports has been investigated.The nickel is present in elemental state as fcc phase on the catalyst as evidenced by X-ray diffraction results.The Ni crystallite size was found to be greater for Ni/anatase.The temperature-programmed reduction results suggest a greater metal-support interaction for Ni/rutile.The observed order of catalytic activity for the hydrogenation of nitrobenzene is Ni/rutile > Ni/anatase > Ni/TiO2.A conversion of 99% was observed for Ni/rutile at 140 oC and hydrogen pressure of 1.96 MPa.Interestingly,aniline is the only product formed which demonstrates the catalytic hydrogenation of nitrobenzene proceeds with atom economy.Both Ni/rutile and Ni/anatase exhibited a better stability than Ni/TiO2.The hydrogenation proceeds with the preferential adsorption of hydrogen on nickel present in the catalyst surface,possibly assisted by TiOx species.

Reduction of nitrobenzene by the catalyzed Fe/Cu process

The polarization behavior of the couple Fe/Cu in 100 mg/L nitrobenzene aqueous solution was studied using Evans coupling diagrams.The results indicated that the iron corrosion was limited by both anodic and cathodic half-cell reactions under the neutral conditions,and cathodically controlled under the alkaline conditions.Batch experiments were performed to study the effect of solution pH,reaction duration,concentration,type of electrolyte,and dissolved oxygen(DO)on the reduction of nitrobenzene by the catal...

Phototransformation of nitrobenzene in the Songhua River:Kinetics and photoproduct analysis

Nitrobenzene (NB) pollution of the Songhua River caused by an explosion at a petrochemical plant in Jilin City,Jilin Province, China,attracted public concern over the fate of NB in the river.As one of the efforts to predict the fate of residual NB in the river,the kinetics and mechanism of phototransformation of NB in natural water from four sections of the Songhua River were investigated.It was found that photodegradation of NB in water proceeded via pseudo-first-order reaction kinetics under simulated sol...