Effect of Excited-state Substituent Constant on the UV Spectra of 1,4-disubstituted Benzenes

A correlation equation between the UV absorption wavenumbers of 1,4-disubstituted benzenes and the excited-state substituent constant was obtained. For 80 sorts of 1,4- disubstituted benzenes, the correlation coefficient was 0.9805, and the standard deviation was only 672.27 cm^-1. The results imply that the excited-state substituent constant can be used productively for research on UV energy of 1,4-disubstituted benzenes. The present method provides a new avenue to study the UV absorption spectra of aromatic systems with the excited-state substituent constant, and it is helpful to understand the effect of substituent electrostatic effects on the chemical and physical properties of conjugated compounds with multiple substituents in excited state.

QSTR Study on the Freshwater Photobacteria Toxicity of Substituted Benzenes

Using a novel freshwater photobacteria — Q67 as an indication organism and the VeritasTM luminometer with 96-well microplate as the testing equipment to determine luminous intensity of photobacteria,the familiar 29 substituted benzenes of the median inhibition toxicities（pEC50）were determined,respectively.The quantum chemical parameters of 29 substituted benzenes in the ideal gas state at 298.15 K and 1.013×105 Pa have been calculated at the B3LYP/6-31G＊ level using Gaussian 03 program.The Quantitative linear relationship（N1）between the pEC50 and two descriptors of 29 substituted benzenes was developed using the variable selection and modeling based on prediction（VSMP）.Model N1 showed good estimation ability and stability（r = 0.8777,q = 0.8482）,which exhibited the difference between empirical and predicted values of 2,3-dimethylphenol was greater（0.5）,so it was given up.Using VSMP to select the optimal descriptors,a 2-variable multiple linear regression model（called model N2）was developed for the pEC50 of substituted benzenes.The r and q for model N2 based on 28 substituted benzenes are 0.8991 and 0.8735,respectively.In order to validate the model,28 substituted benzenes were divided into a training set consisting of 20 compounds and a test set with 8 compounds.The result showed that some main structural factors influencing the pEC50 of substituted benzenes are the lowest unoccupied orbital（ELUMO）and total energy（EHF）.

TOXICITY OF CHLORINATED BENZENES TO MARINE ALGAE

Growth of Chlorella marine, Nannochloropsis oculata, Pyramidomonas sp, Platymonas subcordiformis and Phaeodactylum tricornutum exposed to monochlorobezene (MCB), 1, 2-dichlorobenzene (1, 2-DCB), 1, 2, 3, 4-tetrachlorobenzene (1, 2, 3, 4-TeCB) and pentachlorobenzene (PeCB) was tested. Tests of 72 h-EC50 values showed that the toxicity ranged in the order: MCB<1,2-DCB<1,2,3,4-TeCB<PeCB,and that toxjcity of chlorinated benzene (CB) alone to marine algae was almost in the order: Pyramidomonas sp.< Platymonas subcordiformis<Nannochloropsis oculata < Chlorella marine< Phaeodactylum tricomutum. Study of the QSAR (Quantitative Structure-Activity Relationship) between Kow and toxicity of CBs to marine algae showed good relationships between-logEC50 and logKow.

Calculations of Hyperpolarizabilities for Para-disubstituted Benzeneswith the QSPR

A quantitative structure-property relationship (QSPR) was made for the prediction of the hyperpolarizabilities(β) ofpara-disubstituted benzenes with the nonlinear optical properties, and the βca12 calculated by this model accorded better with the experimental values (βexpt) compared with theβcall calculated at the CPHF/6-31G*//HF/STO-3G level of theory, especially whenβ was big.

A Model Describing the Time Course and Variability in Toxicity of Hydrophobic Chemicals to Aquatic Organisms-Toxicity of chlorinated benzenes to marine algae

The growth of Chlorella marine, Nannochloris oculate, Pyramimonaos sp., Platymonas subcordiformis and Phaeodactylum tricornutum exposed to chlorobenzene, 1,2-dichlorobenzene, 1,2,3,4-tetrachlorobenzene and pentach-lorobenzene was tested. The Boltzman equation was used to describe organism growth. The time course for uptake of hydrophobic organic chemicals (HOCs) by aquatic organisms was expressed by incorporating growth and, if desired, the effect of metabolism into the HOC bioconcentration process. The probability of any given concentration of HOCs in the organisms causing a specified toxic endpoint was expressed with a modified Weibull distribution function. The combined bioconcentration and probability equations were tested with data for time course of incubation of algae exposed to chlorinated benzenes (CBs). A set of parameters, including the uptake rate constant k 1, the elimination rate constant k 2 and thereafter the bioconcentration factor on a dry weight basis, BCF D, the critical HOC concentration in the organism resulting in a specified toxic endpoint, C* A, and the spread factor, S, could be obtained by fitting only experimental data for percent growth inhibition(%)-time-CB exposure concentration. The average coefficients of variation within CBs were 15.2% for BCF D, 21.0% for k 1, 18.3% for k 2, 8.1% for C* A and 9.7% for S. The variability in toxicity (such as EC 10, EC 50, EC 90) derived from the model equations agreed well with those experimentally observed.

A Study on the Inclusion of α-Cyclodextrin with Mono-and 1,4-Disubstituted Benzenes by Neural Networks

The association constant (Ka) values were calculated by the function-strengthen ing neural networks (FNN) for the inclusion complexation of α-CD with mono- and 1,4-disubstituted benzenes. The lnKa predicted by FNN from Rm, π and σ constants of substituents are in great agreement with the experimental data.

Ligand Exchange Reaction of Ferrocene with Substituted Benzenes

Ligand exchange reaction is one of the typical reactions of ferrocene. In this paper, ligand exchange reactions were carried out between ferrocene and various substituted benzenes using aluminum chloride catalysis. The product yields of the reactions with alkanoyl- and alkoxybenzenes were low because of the coordination of aluminum chloride to the oxygens of the benzene substituents. Comparing the reactions using o- and p-dimethoxybenzene, the former was revealed to be less reactive;this is likely due to the deviation of the π-electrons of its benzene ring being larger.

Reactions of [60]Fullerene with Di(azidomethyl) benzenes

A diazafulleroid derivative with adjacent 5-6 junctions has been synthesized by the regioselective addition of 1,2-di(azidomethyl) benzene to [60]fullerene. Reaction of [60]fullerene with 1,4-di(azidomethyl) benzene in refluxing chlorobenzene gave a copolymer.

Determination of the Toxicities of 16 Halogenated Benzenes to Photobacterium Phosphoreum and 2D- and 3D-QSAR Studies

In this paper we take photobacterium phosphoreum （T3） as the experimental bacteria, and determine the half-inhibitory concentration （-1gEC50） against the photobacterium phosphoreum of 16 halogenated benzenes. Using B3LYP method of DFT in the Gaussian 03 program, we obtain the structural and thermodynamic descriptors of 16 halogenated benzenes by fully-optimized calculation at the 6-311G＊＊ level. Taking the structural and thermodynamic descriptors as theoretical descriptors, the 2D QSAR model （R2 = 0.983） was established, which can be utilized to predict -lgEC50 of halogenated benzene according to the corrected linear solvation energy theory based on the experimental data of-lgECs0. In addition, the relationship between the toxicity and 3D spatial structure of the compound is studied by comparing the molecular similarity index analysis （CoMSIA） of 3D-QSAR method. By cross validation, the correlation coefficient q2 of CoMSIA model is 0.687, and the conventional correlation coefficient R2 = 0.958. The model is stable and reliable with great predictive ability. The 3D-QSAR model shows that the toxicity of halogenated benzene compound is mainly affected by the characteristics of hydrophobie field of the substituted halogens.

MICELLIZATION STUDIES OF DODECYL BENZENESULFONIC ACID AND ITS INTERACTION WITH POLYVINYLPYRROLIDONE

Dodecyl benzenesulfonic acid(DBSA)surfactant was used in the present study to find the effect of concentrationon its electrical conductance in solution from 293-323 K above and below the critical micelle concentration(CMC).Themicellization parameters i.e.degree of counter ion binding(β),aggregation number(n)and number of counter ion micelle(m)were measured.The interaction of DBSA with polyvinylpyrrolidone(PVP)was also studied at 293 K throughconductance and surface tension measure ments.A number of important parameters i.e.critical aggregation concentration(CAC),Gibb's free energy(△G)and binding ratio(R)were determined and the effect of NaCl on the CAC and polymersaturation point(PSP)was also investigated.

A Topological Approach to the Correlation of Standard Formation Enthalpy with Path Index of Benzenes Derivatives

A mathematical model formulated as ΔfHθm(g)=a+sum from i=1 to 5bipi(i≠2) was constructed for the relationshipbetween standard formation enthalpy ΔfHθm(g) and path index Pi of substituted benzenes derivatives. An empiric equation for the calculation of ΔfHθm(g) was worked out. The calculated values of standard formation enthalpy based on this model are excellently consistent with those from experimental for 55 organic compounds. The model is shown to be simple and of practical usefulness, particularly when required experimental data are unavailable.

Alkaline earth metal-based minerals/wastes-catalyzed pyrolysis of poly(ethylene terephthalate)/poly(butylene terephthalate)for benzenes-enriched oil production

The pyrolysis of poly(ethylene terephthalate)(PET)/poly(butylene terephthalate)(PBT)catalyzed by five alkaline earth metal-based minerals/wastes,namely calcined dolomite,calcite,magnesite,calcium carbide slag(CCS),and ophicalcitum,was conducted by a pyrolyzer-gas chromatography-mass spectrometer(Py-GC-MS)with the objective of recovering benzenes-enriched oil.Compared with magnesium-based catalysts and pure CaO,the calcium-based catalysts with calcium hydroxide as the main component performed better catalytic effect,which could simultaneously promote the hydrolysis of ester products and the decarboxylation of aromatic acids after hydrolysis.For PET,the addition of solid base catalysts at 600℃promoted the complete degradation of aromatic acids and aryl esters,which accounted for 32.6%and 30.7%of the pyrolysis oil,respectively.The content of benzene in oil increased from 8.8%to 31.7%–78.8%.For PBT,the addition of solid base catalysts at 600℃completely decomposed the aromatic acids,which accounted for 67.1%of the pyrolysis oil,and the content of benzene in oil increased from 12.3%to 34.5%–81.0%.During the deoxygenation of polyester pyrolysis products,increasing temperature was more effective for the decomposition/conversion of acetone and tetrahydrofuran,while increasing the alkalinity of the reaction environment contributed to the rapid decrease in acetaldehyde and aryl ketone contents.

Fate Processes of Chlorobenzenes in Soil and Potential Remediation Strategies: A Review

Chlorobenzenes （CBs） are a group of organic pollutants that pose a high environmental risk due to their toxicity, persistence and possible transfer in the food chain. Available data in literature show that CBs axe detected in different environmental compartments such as soil, water, air and sediment. The widespread presence of CBs in the environment is related to their former extensive use in agriculture and industry. Some CBs are ranked in the list of priority pollutants by the Stockholm Convention, and their reduction or elimination from the environment is therefore of high importance. Environmental risk assessment of CBs requires knowledge on the role and importance of the main environmental fate processes, especially in soil. Furthermore, development of remediation strategies for reduction or elimination of CBs from the environment is related to the enhancement of fate processes that increase their dissipation in various environmental compartments. The main objectives of the current review were to present up-to-date data on fate processes of CBs in the soil environment and to explore possible remediation strategies for soils contaminated with CBs. Dechlorination of highly-chlorinated benzenes is the main degradation pathway under anaerobic conditions, leading to the formation of lower-chlorinated benzenes. Biodegradation of lower-chlorinated benzenes is well documented, especially by strains of adapted or specialized microorganisms. Development of techniques that combine dechlorination of highly-chlorinated benzehes with biodegradation or biomineralization of lower-chlorinated benzenes can result in useful tools for remediation of soils contaminated with CBs. In addition, immobilization of CBs in soil by use of different amendments is a useful method for reducing the environmental risk of CBs.

Kinetics and mechanisms of reactions for hydrated electron with chlorinated benzenes in aqueous solution

The reactions between chlorinated benzenes （CBzs） and hydrated electron （eaq^-） were investigated by the electron beam （EB） and laser flash photolysis （LFP） experiments. Under the EB irradiation, the effects of irradiation dose, initial concentration and the number of Cl atoms on the removal efficiencies were further examined. At 10 kGy, the removal efficiencies of mono-CB, 1,3-diCB, 1,2-diCB and 1,4-diCB were 41.2%, 87.2%, 84.0%, and 84.1%, respectively. While irradiation dose was 50 kGy, the removal efficiencies increased to 47.4%, 95.8%, 95.0%, and 95.2%, respectively. Irradiation of CBzs solutions has shown that the higher the initial concentration, the lower the percentage of CBzs removal. In addition to this, the dechlorination efficiencies of 1,2-dichlorobenzene （1,2-diCB）, 1,3-dichlorobenzene （1,3-diCB） and 1,4-dichlorobenzene （1,4-diCB） were much higher than that of chlorobenzene （mono-CB）. The kinetics of the reactions was achieved with nanosecond LFP. The rate constants of second-order reaction between eaq^- with mono-CB, 1,2-diCB, 1,3-diCB and 1,4-diCB were （5.3±0.4） × 10^8, （4.76±0.1） × 10^9, （1.01±0.1） × 1010 and （3.29±0.2） × 10^9 L·mol^-1·s^-1, respectively. Density functional theory （DFT） calculations were performed to determine the optical properties of unstable CBzs anion radicals, and the main absorption peaks lied in the range of 300–550 nm. The primary reaction pathway of CBzs with eaq^- was gradual dechlorination, and the major products were Cl^- and benzene （CBzs（-Cl^-））. Furthermore, biphenyl （or chlorobiphenyl） was observed during the LFP, which was probably formed by recombination of benzene radicals.

Study on the Effectiveness of Circulation Well for Remediation of Benzene and Toluene Contaminated Silt Sand Aquifer

In order to investigate the remediation effect of groundwater circulation well on benzene and toluene contaminated silt sand aquifer,a simulation remediation experiment was conducted in the laboratory using a two-dimensional simulation tank.The results showed that in the silt sand aquifer,the concentrations of benzene and toluene decreased from 179.210 mg/L and 327.520 mg/L to below the detection limit after 24 h of operation of the circulation well.The closer to the circulation well in the horizontal direction,the faster the removal efficiency of benzene and toluene.The study has shown that circulating wells have good remediation effects on both benzene-and toluene-contaminated chalk sand aquifers.

Benzoylation of benzene and substituted benzenes catalyzed by superacid ZrO_2:H_2SO_4

Superacid ZrO_2:H_2SO_4 showed high activity in Friedel-Crafts benzoylation of benzene and substituted benzenes such an chlorobenzene,toluene and 1,3,5-trimethylbenzene.Benzophenones in 90-100% yields were obtained with catalytic amount of superacid ZrO_2:H_2SO_4.The calcination temperature greatly influenced the acid strength and activity of the superacid ZrO_2:H_2SO_4.The superacid has both Lewis and Bronsted acid sites.The reversibility of Friedel-Crafts benzoylation and transacylation were observed over the superacid.The used superacid could be readily regenerated and showed identical benzoylation activity to toluene.

Construction of Multi-Substituted Benzenes via NHC-Catalyzed Reactions of Carboxylic Esters

A carbene-catalyzed ester activation reaction for the synthesis of multi-substituted benzenes is developed. Tetra-substituted benzene com- pounds are efficiently synthesized through this methodology. Compared with aldehyde substrates used in previous reports, the ester substrates used here are much more readily available and inexpensive. In addition, the TEMPO oxidant used here is more inexpensive than the quinones commonly used in related carbene-catalyzed reactions.

Zirconium-mediated Selective Synthesis of 1,4-Dialkyl（aryl）-hexa-substituted Benzenes from Two Silyl-substituted Alkynes and One Internal Alkyne

Based on the formation of 2,5-bis（trimethylsilyl）-zirconacyclopentadienes from two silylalkynes with CpEZrBu2 and the Cu-mediated formation of 1,4-disilylbenzene via the cycloaddition of zirconacyclopentadienes to disubstituted alkynes, a selective synthesis of 1,4-dialkyl（aryl）-hexa-substituted benzenes was achieved followed by iodination and coupling reaction. The coupling reactions were carried out with either organolithium reagent or orga- nozinc reagent（Negishi coupling）, depending on the electrophilic species.

Numerical simulation for symmetric diffraction patterns of 8-hydroxyquinolin-1-ium 4-aminobenzenesulfonate

We reported the formation of diffraction ring patterns induced by transmitted Gaussian laser beam through 8-hydroxyquinolin-1-ium 4-aminobenzenesulfonate(8 HQABS) solution as absorbing medium. Theoretical model depending on the Fresnel-Kirchhoff diffraction(FKD) theory was used to generate diffraction rings with respect to the sample position. Analysis of the generated diffraction rings shows a reasonable agreement between the features of the experimental and numerical diffraction rings. Our results are considered to be useful to understand the way of propagation and interaction of laser beam with liquid absorbing medium.

Process analysis of temperature swing adsorption and temperature vacuum swing adsorption in VOCs recovery from activated carbon

In order to better guide the design of industrial process for purification and recovery of VOCs,temperature swing adsorption(TSA)and temperature vacuum swing adsorption(TVSA)process for VOCs purification and recovery were studied systematically with activated carbon adsorbent.The adsorption and desorption behaviors of benzene on activated carbon in above two processes were investigated systematically.Effects of operating parameters on process performances were further analyzed,including as regeneration temperature,purging feed ratio and hot–cold purging ratio.The results showed that the increase of hot–cold purging ratio(HP/CP)could obtain the same regeneration effect as the increase of desorption temperature.Increasing the feed purge ratio without increasing the hot–cold purging ratio is not conducive to bed regeneration,because a large number of cold purge gases cannot utilize the residual heat of temperature wave,thus reducing the desorption effect of the cooling step on the bed.In addition,the vacuum step can enhance the regeneration ability of hot nitrogen to the bed at the same regeneration temperature,making the bed regeneration of TVSA process more thorough.Temperature in the middle and lower part of the bed in TVSA process was higher and the regeneration was more thorough.In conclusion,TVSA has more obvious advantages than TSA in terms of energy consumption,hot or cold purge volume and bed regeneration.