Qualitative analysis of aromatic compounds via 1D TOCSY techniques

The aromatic compounds,including o-xylene,m-xylene,p-xylene,and ethylbenzene,primarily originate from the catalytic reforming of crude oil,and have a wide variety of applications.However,because of similar physical and chemical properties,these compounds are difficult to be identified by gas chromatography(GC)without standard samples.With the development of modern nuclear magnetic resonance(NMR)techniques,NMR has emerged as a powerful and efficient tool for the rapid analysis of complex and crude mixtures without purification.In this study,the parameters of one-dimensional(1D)total correlation spectroscopy(TOCSY)NMR techniques,including 1D selective gradient TOCSY and 1D chemicalshift-selective filtration(CSSF)with TOCSY,were optimized to obtain comprehensive molecular structure information.The results indicate that the overlapped signals in NMR spectra of nonpolar aromatic compounds(including o-xylene,m-xylene,p-xylene and ethylbenzene),polar aromatic compounds(benzyl alcohol,benzaldehyde,benzoic acid),and aromatic compounds with additional conjugated bonds(styrene)can be resolved in 1D TOCSY.More importantly,full molecular structures can be clearly distinguished by setting appropriate mixing time in 1D TOCSY.This approach simplifies the NMR spectra,provides structural information of entire molecules,and can be applied for the analysis of other structural isomers.

Aromatic Compounds Production from Sorbitol by Aqueous Catalytic Reforming

The rules on regulating aromatic compounds production was investigated by aqueous cat- alytic reforming of sorbitol. It was found that aromatics, ketones, furans, organic acids were main compounds in organic phase. The obvious effect of metal content showed that the highest carbon selectivity of aromatics was 34.36% when 3wt% Ni content was loaded on HZSM-5 zeolite modified by MCM-41. However, it was decreased only to 4.82% when Ni content was improved to 20wt%. Meanwhile, different reaction parameters also displayed important impacts on carbon selectivity. It was improved with the increase of temperature, while it was decreased as liquid hourly space velocity and hydrogen pressure was increased. The results showed that appropriate higher temperature, longer contact time and lower hy- drogen pressure were in favor of aromatics information, which suggested a feasible process to solve energy crisis.

Simultaneous biodegradation of nitrogen-containing aromatic compounds in a sequencing batch bioreactor

Many nitrogen-containing aromatic compounds （NACs）, such as nitrobenzene （NB）, 4-nitrophenol （4-NP）, aniline （AN）, and 2,4-dinitrophenol （2,4-DNP）, are environmentally hazardous, and their removal from contaminated water is one of the main challenges facing wastewater treatment plants. In this study, synthetic wastewater containing NB, 4-NP, 2,4-DNP, and AN at concentrations ranging from 50 to 180 mg/L was fed into a sequencing batch reactor （SBR）. Analyses of the SBR system indicated that it simultaneously removed more than 99% of the NACs at loading rates of 0.36 kg NB/（m^3·d）, 0.3 kg 4-NP/（m^3·d）, 0.25 kg AN/（m^3·d）, and 0.1 kg 2,4-DNP/（m^3·d）. Bacterial groups of Bacteriodetes, Candidate division TM7, α-Proteobacteria, and β-Proteobacteria were dominant in the clone libraries of 16S rRNA genes retrieved from the microbial communities in the SBR system. ＂Cycle tests＂ designed to alter feeding and aeration parameters of the SBR system demonstrated that the resident microbial biome of the SBR system responded rapidly to changing conditions. Consumption of O2 was concomitant with the apparent mineralization of NACs. Aromatic ring-cleaving dioxygenase activities suggested that （1） AN and NB were degraded via catechol 2,3-dioxygenase; （2） 4-NP was degraded via 1,2,4-benzentriol 1,2-dioxygenase; and （3） 2,4-DNP was degraded via an unresolved pathway.

Adsorption thermodynamics and kinetic investigation of aromatic amphoteric compounds onto different polymeric adsorbents

The adsorption behavior ofp-aminobenzoic acid and o-aminobenzoic acid onto the different polymeric adsorbents was systematically investigated as a function of the solution concentration and temperature. Experimental results indicated that the equilibrium adsorption data of the four polymeric adsorbents fitted well in the Freundlich isotherm. The adsorption capacity of multi-functional polymeric adsorbent NJ-99 was the highest, which might be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of aminobenzoic acid. The adsorption capacity of o-aminobenzoic acid onto any adsorbent was higher than p-aminobenzoic acid. Thermodynamic studies suggested the exothermic, spontaneous physical adsorption process. Adsorption kinetics results showed that the adsorption followed the pseudo-second-order kinetics model and the intraparticle mass transfer process was the rate-controlling step.

Accelerated degradation of a variety of aromatic compounds by Spirodela polyrrhiza-bacterial associations and contribution of root exudates released from S. polyrrhiza

Removal experiments of phenol, aniline, 2,4-dichlorophenol, nonylphenol and bisphenol A （BPA） using Spirodela polyrrhiza- bacterial associations revealed that all compounds but BPA underwent accelerated removal. The mechanisms differed depending on the substrates. It was found that S. polyrrhiza has a great ability to release phenolic compound-rich root exudates, and the exudates seem to stimulate bacterial degradation of a variety of aromatic compounds.

Screening and Phylogenetic Analysis of Deep-Sea Bacteria Capable of Metabolizing Lignin-Derived Aromatic Compounds

Lignin is one of the most abundant biomasses in nature. It is composed of aromatic moieties and has great potential for use in the production of chemical alternatives to petroleum products. Because of increasing interest in biocatalysis, the potential for industrial application of microbial metabolism of lignin-derived compounds has gained considerable recent attention. Functional screenings of culturable bacteria isolated from sediments and sunken wood collected from the deep sea revealed the existence of a number of previously unidentified bacteria capable of metabolizing lignin-related aromatic compounds. Of the 510 isolates obtained in the present study, 208 completely or partially metabolized these compounds. The 208 isolates were classified into diverse phyla, including Firmicutes, Actinobacteria, Bacteroidetes, and Proteobacteria. Among the 208 isolates, 61 unique 16S rRNA gene sequences were detected including previously unidentified marine lineage isolates. The metabolites of the isolates were analysed using liquid chromatography/mass spectrometry (LC/MS) or gas chromatography/mass spectrometry (GC/MS). Most of the representative 61 isolates non-oxidatively decarboxylated the substrates to produce the corresponding aromatic vinyl monomers, which are used as feed stocks for bio-based plastics production. Oxidative metabolism of the lignin-related compounds for assimilation was frequently observed. Our study showed that the deep-sea environment contains an abundance of microorganisms capable of both non-oxidative and oxidative bioconversion of lignin-derived aromatic compounds. The ability for bio-conversion of aromatic compounds found in this study will facilitate the development of future biotechnological applications.

The Condensation of Aromatic Aldehydes with Acidic Methylene Compounds in Water

The condensation of aromatic aldehydes with acidic methylene compounds such as malononitrile, methyl cyanoacetate, cyanoacetamide, 5,5-dimethyl-1,3-cyclohexanedione, bartbituric acid and 2-thiobarbituric acid proceeded very efficiently in water in the presence of triethylbenzylammonium chloride (TEBA) and the products were isolated simply by filtration.

Component characteristics of polycyclic aromatic compounds in sediments of the South Mid-Atlantic Ridge

10 samples of sediments obtained from the South Mid-Atlantic Ridge were measured for the abundances and distributions of polycyclic aromatic compounds（PAHs）. The total concentrations of PAHs（∑PAHs） ranged from 2.768 to 9.826 μg/g dry sediment. The ∑PAHs was higher in sample 22V-TVG10 and sample 26V-TVG05 which were close to hydrothermal fields, with the lowest value in sample 22V-TVG14 which was farthest from hydrothermal fields, suggesting a probable hydrothermal origin of ∑PAHs of samples. Approximately nine kinds of PAHs were identified, and low molecular mass tricyclic and tetracyclic aromatic compounds were predominant in the samples. The concentrations of fluoranthene which were typical as hydrothermal alteration compounds were the highest among PAHs with dry weight between 0.913–3.157 μg/g. The phenanthrene homologue was most abundant in the samples, and the ratios between parent phenanthrene and methylphenanthrene which probably reflected the degree of hydrothermal alteration ranged from 0.097 to 1.602. The sample 22V-TVG10 possessing a maximum ratio value showed the intense influence of the hydrothermal alteration on this sample, which might further imply that PAHs in sediments were mainly derived from the hydrothermal alteration.

Blanc Reaction of Aromatic Compounds Catalyzed by Ionic Liquids

Ionic liquids have been used as catalysts for Blanc reaction of toluene. The effects of reaction temperature, reaction time and dosage of the ionic liquid catalyst have been investigated, and the catalytic performance of different ionic liquid catalysts for toluene chloromethylation was also studied. The reaction was found to proceed under mild conditions with excellent conversion （up to 90%） in the absence of Lewis acids. The ionic liquids could be recycled and reused without loss of their catalytic activities.

Reduction of Sulphur-containing Aromatic Nitro Compounds with Hydrazine Hydrate over Iron(III) Oxide-MgO Catalyst

Sulphur-containing aromatic amines were prepared efficiently in good to excellent yields by reduction of the corresponding sulphur-containing aromatic nitro compounds with hydrazine hydrate in the presence of iron（Ⅲ） oxide-MgO catalyst. The catalyst exhibited high activity and stability for the reduction of sulphur-containing aromatic nitro compounds. The yields of sulphur-containing aromatic amines were up to 91-99 % at 355 K after reduction for 1-4 h over this catalyst.

Quantitative Structure-activity Relationship(QSAR) Study of Toxicity of Substituted Aromatic Compounds to Photobacterium Phosphoreum

With the artificial neural network（ANN） method combined with the multiple linear regression（MLR）,based on a series of quantum chemical descriptors and molecular connectivity indexes,quantitative structure-activity relationship（QSAR） models to predict the acute toxicity（-lgEC50） of substituted aromatic compounds to Photobacterium phosphoreum were established.Four molecular descriptors that appear in the MLR model,namely,the second order valence molecular connectivity index（2XV）,the energy of the highest occupied molecular orbital（EHOMO）,the logarithm of n-octyl alcohol/water partition coefficient（logKow） and the Connolly molecular area（MA）,were inputs of the ANN model.The root-mean-square error（RMSE） of the training and validation sets of the ANN model are 0.1359 and 0.2523,and the correlation coefficient（R） is 0.9810 and 0.8681,respectively.The leave-one-out（LOO） cross validated correlation coefficient（Q L2OO） of the MLR and ANN models is 0.6954 and 0.6708,respectively.The result showed that the two methods are complementary in the calculations.The regression method gave support to the neural network with physical explanation,and the neural network method gave a more accurate model for QSAR.In addition,some insights into the structural factors affecting the acute toxicity and toxicity mechanism of substituted aromatic compounds were discussed.

Comparative study of four QSAR models of aromatic compounds to aquatic organisms

Quantitative structure activity relationships(QSARs)were developed for 43 aromatic compounds toxicity to Photobacterium phosphoreum and Daphnia magna based on four methods: octanol/water partition coefficient, linear solvation energy relationship, molecular connectivity index and group contribution. Through the evaluation of four QSAR methods, LSER was proved to be the best. And it applied to the widest range of chemicals with the greatest accuracy.

A mild,efficient and selective iodination of aromatic compounds using iodine and 1,4-bis(triphenylphosphonium)-2-butene peroxodisulfate

A simple and efficient method for the iodination of aromatic compounds has been achieved in the presence of iodine and 1,4- bis（triphenylphosphonium）-2-butene peroxodisulfate.

Preparation of Sulphur-containing Aromatic Amines by Reduction of the Corresponding Aromatic Nitro Compounds with Hydrazine Hydrate over Iron Oxide Hydroxide Catalyst

Sulphur-containing aromatic nitro compounds were rapidly reduced to the corresponding amines in high yields by employing hydrazine hydrate as a hydrogen donor in the presence of iron oxide hydroxide catalyst. It was worth noting that the catalyst exhibited extremely high activity. The reduction could be completed within 20-50 min and the yields were up to 97-99 %.

Preparation of Polymeric Monolithic Column and Application to the Resolution of Aromatic Compounds in Capillary Electrochromatography

Polymeric monolithic capillary column-poly(GMA-co-EDMA-co-AMPS) was prepared andused for resolution of aromatic compounds (benzalcohol, 2-phenylethanol, toluene, ethylbenzene).

Development of QSAR Model for Predicting the Mutagenicity of Aromatic Compounds

Quantitative structure-activity relationship （QSAR） model was developed for pre- dicting the mutagenicity of aromatic compounds. The log revertants data of S. typhimurium TA98 strain from Ames test have been collected. 225 aromatic compounds were randomly divided into the training set with 186 molecules and test set with 39 molecules. Multiple linear regression （MLR） analysis was used to select six descriptors from thousands of descriptors calculated by semi- empirical AM l and E-dragon methods. The final QSAR model with six descriptors was internal and external validated. In addition, to validate the utility of our QSAR model for the chemical evaluation, three aromatic compounds were taken to test the predictive ability and reliability of the model experimentally. The compounds selected for testing were not based on the predictions, thus spanning the range of predicted probabilities. The subsequently generated results of the Ames test were in good correspondence with the predictions and confirmed this approach as a useful means of predicting likely mutagenic risk of aromatic compounds.

Explanation for peat-forming environments of coal seam 2 and 9^(-2)based on the maceral composition and aromatic compounds in the Xingtai coalfield,China

Maceral composition and aromatic compounds were determined on columnsamples to study the peat-forming environments of Permian coal seam 2 and Carboniferouscoal seam 9^(-2) from the Xingtai coalfield,China.The macerals were dominated by inertinitein seam 2 and by vitrinite in seam 9^(-2).Three maceral groups were selected as indicatorsof peat-forming environments.Two triangle diagrams were drawn based on the indicatorsto explicate the peat-forming environments of permian seam 2 and Carboniferousseam 9^(-2).The results indicate that the peat of carboniferous seam 9^(-2) formed dominantlyin wet swamps,whereas the peat of Permian seam 2 formed dominantly in dry swampsand open moor environments.

Quantitative Structure-biodegradability Relationship Study about the Aerobic Biodegradation of Some Aromatic Compounds

10 quantum chemical descriptors of 21 aromatic compounds have been calculated by the semi-empirical quantum chemical method AM1. The Quantitative Structure-Biodegradability Relationships （QSBR） studies were performed by the multiple linear regression （MLR）, principal component regression （PCR） and back propagation artificial neural network （BP-ANN）, respectively. The root mean square error （RMSE） of the training and validation sets of the BP-ANN model are 0.1363 and 0.0244, the mean absolute percentage errors （MAPE） are 0.1638 and 0.0326, the squared correlation coefficients （R^2） are 0.9853 and 0.9996, respectively. The results show that the BP-ANN model achieved a better prediction result than those of MLR and PCR. In addition, some insights into the structural factors affecting the aerobic biodegradation mechanism were discussed in detail.

Accumulation of Polyphenolic Compounds and Osmolytes under Dehydration Stress and Their Implication in Redox Regulation in Four Indigenous Aromatic Rice Cultivars

Present work was undertaken to screen some drought tolerant indigenous aromatic rice cultivars(IARCs),commonly cultivated in West Bengal,India,based on their capacity to produce osmolytes,redox-sensitive phenolic acids and flavonoids,as contrivances for redox-regulation under drought stress.Polyethylene glycol induced post imbibitional dehydration stress mediated changes in redox regulatory properties of the germinating seeds of the four IARCs(Jamainadu,Tulaipanji,Sitabhog,Badshabhog),which were assessed in terms of changes in prooxidant accumulation(in-situ localization of reactive oxygen species(ROS)by confocal microscopy,DCFDA(2′,7′-dichlorofluorescin diacetate)oxidation,O2-and H2O2 accumulation),cumulative antioxidative defense(radical scavenging property and total thiol content),ROS scavenging phenolic acids(gallic acid,protocatechuic acid,gentisic acid,para-hydroxy benzoic acid,chlorogenic acid,caffeic acid,syringic acid,salicylic acid,sinapic acid and p-coumaric acid)and flavonoids(catechin,naringin,rutin,quercetin,kaempferol,myricetin and apigenin).The capability of germinating seeds to accumulate osmolytes(like glycinebetaine,proline,soluble carbohydrates and K+ion)and polyphenolic compounds was also correlated with their corresponding redox status and redox biomarkers(conjugated diene,hydroperoxide,thiobarbituric acid reactive substances and free carbonyl content)produced under the same conditions.The results in general showed that accumulation of osmolytes along with the redox-sensitive phenolics and flavonoids conferred the ability to maintain the redox homeostasis under drought stress for the tolerant IARCs(Badshabhog and Tulaipanji).

RELATIONSHIP OF POLYCYCLIC AROMATIC SULFUR COMPOUNDS AND GOLD ENRICHMENT IN THE KUPFERSCHIEFER FROM POLAND AND GERMANY

The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only observed in samples with higher PASC contents. At the same time, all the samples with gold enrichment originated from areas close to the redox boundary (the front section of Rote Fule) that was formed by oxidizing brines in contact with the reducing Kupferschiefer. It is proposed that the gold-bearing solutions encountered PASCs in the Kupferschiefer. PASCs could easily displace chloride ions from aurous chloride complexes to form stable gold S-chelates. Subsequent oxidation of these gold organic compounds could destroy the organic components and lead to the formation of metallic gold.