Objective To identify the bacteria tolerating chlorinated anilines and to study the biodegradability of o-chloroaniline and its coexistent compounds. Methods Microbial community of complex bacteria was identified by p...Objective To identify the bacteria tolerating chlorinated anilines and to study the biodegradability of o-chloroaniline and its coexistent compounds. Methods Microbial community of complex bacteria was identified by plate culture observation techniques and Gram stain method. Bacterial growth inhibition test was used to determine the tolerance of complex bacteria to toxicant. Biodegradability of chlorinated anilines was determined using domesticated complex bacteria as an inoculum by shaking-flask test. Results The complex bacteria were identified, consisting of Xanthomonas, Bacillus alcaligenes, Acinetobacter, Pseudomonas, and Actinomycetaceae nocardia. The obtained complex bacteria were more tolerant to o-chloroaniline than mixture bacteria in natural river waters. The effects of exposure concentration and inoculum size on the biodegradability of o-chloroaniline were analyzed, and the biodegradation characteristics of single o-chloroaniline and 2, 4-dichloroaniline were compared with the coexistent compounds. Conclusion The biodegradation rates can be improved by decreasing concentration of compounds and increasing inoculum size of complex bacteria. When o-chloroaniline coexists with aniline, the latter is biodegraded prior to the former, and as a consequence the metabolic efficiency of o-chloroaniline is improved with the increase of aniline concentration. Meanwhile, when o-chloroaniline coexists with 2,4-dichloroaniline, the metabolic efficiency of 2,4-dichloroaniline is markedly improved.展开更多
Using galvinoxyl as catalyst, the phase transfer catalyzed method of oxidation of primary amines to symmetrical azobenzenes with a saturated solution of potassium ferricyanide in 2 mom aqueous potassium hydroxide and ...Using galvinoxyl as catalyst, the phase transfer catalyzed method of oxidation of primary amines to symmetrical azobenzenes with a saturated solution of potassium ferricyanide in 2 mom aqueous potassium hydroxide and dichloromethane is described. The reaction has intimate relation with Hammett substituent constants. This report offers an efficient and rapid method to prepare azobenzenes and a possible mechanism is also suggested.展开更多
Octanol/water partition coefficient (Kow) is a crucial property for evaluating the environmental behavior and fate of organic compound. Herein, some quantitative structure-property relationship (QSPR) studies were...Octanol/water partition coefficient (Kow) is a crucial property for evaluating the environmental behavior and fate of organic compound. Herein, some quantitative structure-property relationship (QSPR) studies were performed to estimate and predict the lgK ow of substituted anilines. 2D method (multiple linear regression, MLR) and 3D method (comparative molecular field analysis, CoMFA) were applied in this study. Successful 2D and 3D models yielded the correlation coefficient (R2) values of 0.981 and 0.966 and the Leave-One-Out (LOO) cross-validated correlation coefficient (q2) values of 0.933 and 0.820, respectively. The developed models have a highly predictive ability in both internal and external validation. In addition, the results were interpreted in terms of physical and chemical meanings of descriptors and field contribution maps. It showed that the steric and electrostatic properties are the primary factors that govern the lgK ow of substituted anilines. The information obtained from the QSPR models would be helpful to the interpretation of structural features pertinent to the lgK ow of substituted anilines, which may be helpful in estimating the organic compounds' potential harm to the environment.展开更多
We report a one-pot three-component synthesis of N-arylmethyl-4-(7-cyclohepta-1,3,5-trienyl)anilines by using various aromatic imines, tropylium tetrafluoroborate, and sodium tetrahydroborate in the presence of imidaz...We report a one-pot three-component synthesis of N-arylmethyl-4-(7-cyclohepta-1,3,5-trienyl)anilines by using various aromatic imines, tropylium tetrafluoroborate, and sodium tetrahydroborate in the presence of imidazole as activator.展开更多
While Raman spectroscopy is a useful method for analyzing many organic compounds, it is limited by relatively low sensitivity. Therefore, Surface Enhanced Raman Spectroscopy (SERS) based on the adsorption of organic a...While Raman spectroscopy is a useful method for analyzing many organic compounds, it is limited by relatively low sensitivity. Therefore, Surface Enhanced Raman Spectroscopy (SERS) based on the adsorption of organic analytes onto gold or silver nanostructures has been used to enhance the signal of chemicals presented at very low concentrations. Although the plasmonic effect of SERS has been shown to play a large role in signal enhancement, the significance of the chemical effect due to the analyte chemisorption on the gold or silver surface is less well understood. In this study, the role of aniline substituents is examined by probing the SERS intensities of various anilines in silver and gold colloids using a Raman spectrometer with an excitation wavelength of 785 nm. The SERS enhancement factors and detection limits for aniline and its mono- and di-substituted ortho derivatives are determined and compared. Both the steric requirements of chemisorption and the inductive effects of electron-withdrawal due to the substituents affect the signal intensities of various vibrational modes of the amino group and the aromatic ring. The degree of enhancement is also related to the methods for preparing the silver and gold colloids, which are characterized by probing the nanoparticle morphology and its degree of aggregation using transmission electron microscopy (TEM).展开更多
Nitroanilines are important building blocks in pharmaceuticals,materials and dyes.Nitration methods for anilines under mild conditions are highly desired.Herein,we report a photochemical method for the nitration of an...Nitroanilines are important building blocks in pharmaceuticals,materials and dyes.Nitration methods for anilines under mild conditions are highly desired.Herein,we report a photochemical method for the nitration of anilines bearing various protecting groups by 5-methyl-1,4-dinitroimidazole as a new type of nitro source.This method is light-controlled and proceeds under mild reaction conditions with high efficiency.Fmoc-,Ts-and alkyl-protected anilines are all well nitrated with good functional group tolerance.展开更多
This article describes the preparation and liquid crystalline properties of a new homologous series of 4-(4-bromopropyloxy)-4'- (4-alkyloxybenzylidene)anilines in which the phenyl ring is armed by a bromopropylox...This article describes the preparation and liquid crystalline properties of a new homologous series of 4-(4-bromopropyloxy)-4'- (4-alkyloxybenzylidene)anilines in which the phenyl ring is armed by a bromopropyloxy chain.The thermal behavior and mesomorphic properties of the synthesized compounds were studied with particular attention given to the correlation between their phase transition temperatures and anisotropic change influenced by molecular structure.All the members displayed enantiotropic smectic phase except for the homologue with the longest alkyloxy chain(R = C_(18)H_(37)),exhibiting only monotropic characteristic. The presence of bromine atom from the propyloxy side chain is found to be capable of altering and influencing the mesomorphic properties.展开更多
Amines are among the most fundamental motifs in chemical synthesis,and the introduction of amine building blocks via selective C-C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons t...Amines are among the most fundamental motifs in chemical synthesis,and the introduction of amine building blocks via selective C-C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification.Herein,we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents,which are easily prepared from hydroxylamine.Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions.Good compatibility and valuable applications of the transformation were also displayed.展开更多
Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides....Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.展开更多
Rhodium-catalysed regioselective redox-neutral[3+3]-cycloaddition of anilines with CF_(3)-ynones was achieved via a traceless directing group strategy.A variety of substituted 2-trifluromethylquinoline compounds were ...Rhodium-catalysed regioselective redox-neutral[3+3]-cycloaddition of anilines with CF_(3)-ynones was achieved via a traceless directing group strategy.A variety of substituted 2-trifluromethylquinoline compounds were obtained in good to excellent yields,which exhibited favorable blue emission properties.展开更多
Aniline is a vital industrial raw material.However,highly-toxic aniline wastewater usually deteriorated effluent quality,posed a threat to human health and ecosystem safety.Therefore,this study reported a novel intern...Aniline is a vital industrial raw material.However,highly-toxic aniline wastewater usually deteriorated effluent quality,posed a threat to human health and ecosystem safety.Therefore,this study reported a novel internal circulation iron-carbon micro-electrolysis(ICE)reactor to treat aniline wastewater.The effects of reaction time,pH,aeration rate and iron-carbon(Fe/C)ratio on the removal rate of aniline and the chemical oxygen demand were investigated using single-factor experiments.This process exhibited high aniline degradation performance of approximately 99.86% under optimal operating conditions(reaction time=20 min,pH=3,aeration rate=0.5 m3·h^(-1),and Fe/C=1:2).Based on the experimental results,the response surface method was applied to optimize the aniline removal rate.The Box–Behnken method was used to obtain the interaction effects of three main factors.The result showed that the reaction time had a dominant effect on the removal rate of aniline.The highest aniline removal rate was obtained at pH of 2,aeration rate of 0.5 m^(3)·h^(-1)and reaction time of 30 min.Under optional experimental conditions,the aniline content of effluent was reduced to 3 mg·L^(-1)and the removal rate was as high as 98.24%,within the 95% confidence interval(97.84%-99.32%)of the predicted values.The solution was treated and the reaction intermediates were identified by high-performance liquid chromatography,ultraviolet-visible spectroscopy,Fourier-transform infrared spectroscopy,gas chromatography-mass spectrometry,and ion chromatography.The main intermediates were phenol,benzoquinone,and carboxylic acid.These were used to propose the potential mechanism of aniline degradation in the ICE reactor.The results obtained in this study provide optimized conditions for the treatment of industrial wastewater containing aniline and can strengthen the understanding of the degradation mechanism of iron-carbon micro-electrolysis.展开更多
Introduction: This study aimed to perform routine seminal fluid analysis, sperm DNA fragmentation, and sperm function tests at the chromatin maturation level and evaluate pregnancy in the patients passing intrauterine...Introduction: This study aimed to perform routine seminal fluid analysis, sperm DNA fragmentation, and sperm function tests at the chromatin maturation level and evaluate pregnancy in the patients passing intrauterine insemination before starting Intrauterine Insemination (IUI) method. Materials and Methods: In this prospective study, 111 couples who underwent Intrauterine Insemination (IUI) in unexplained infertility patients were admitted to Al-Farah IVF and assisted reproductive center in Baghdad, Iraq between November 2020 and February 2021 were evaluated. Semen fluid analysis was performed based on (WHO 4th) guiding rules. In addition, Sperm Chromatin Dispersion (halo test) and sperm maturation were performed with Aniline Blue Stain (ABS). Results: Sperm Chromatin Dispersion (SCD) groups were compared in terms of pregnancy outcome;the positive pregnancy rate was found to be above in the normal SCD groups (p = 0.0005). In addition, Aniline Blue Stain (ABS) groups were compared in the terms of pregnancy outcome;the positive pregnancy rate was found to be higher in the normal ABS group (p = 0.017). Conclusion: Our study showed that the use of DNA fragmentation (SCD) and sperm maturation tests (ABS) together with routine semen analysis in intrauterine insemination cases will make a significant contribution to the prediction of Intrauterine Insemination (IUI) increased results. So, these results indicate a defect in the effect of DNA fragmentation on the outcome of intrauterine insemination.展开更多
The tetrahydroquinoline moiety is a structural feature of many natural products. By using a domino reaction of aromatic amines and cyclic enol ethers catalyzed by zirconyl chloride in water, various tetrahydroquinolin...The tetrahydroquinoline moiety is a structural feature of many natural products. By using a domino reaction of aromatic amines and cyclic enol ethers catalyzed by zirconyl chloride in water, various tetrahydroquinoline derivatives were synthesized efficiently. Most cyclized products showed cis selectivity. The cis selectivity was tentatively rationalized due to chelation control in water.展开更多
Among the inherent drawbacks of conducting polymers are the limited processibility, uneven polydispersity inmolecular weigh and the existence of structure defects, which become the obstacles for many electronic, optic...Among the inherent drawbacks of conducting polymers are the limited processibility, uneven polydispersity inmolecular weigh and the existence of structure defects, which become the obstacles for many electronic, optical andbiological applications that demand the materials to have well-defined structures and high chemical purity. To solve theseproblems, our research in the last decade or so has focused on the synthesis of electroactive oligomers of well-definedstructures, controllable molecular weighs, narrow or uniform polydispersity. We have developed a general strategy for thesynthesis of such oligomers based on the theory of non-classical or reactivation chain polymerization. The aniline oligomerswith minimum 4 nitrogen atoms and 3 phenylene rings exhibit similar characteristic redox behavior and electroactivity aspolyaniline. Electronic conductivity of the oligomers of 7 or 8 aniline units approaches that of polyaniline. Solubility of theoligomers is much improved over that of conventional polyaniline. Various functional groups can be introduced into theoligomers either by proper selection of starting materials or by post-synthesis modifications via common organic reactions.The functionalized oligomers undergo further polymerizations to afford a variety of new electroactive materials, includingpolyamides, polyimides, polyureas, polyurethanes, polyacrylamides and epoxy polymers. Numerous potential applications,particularly as anticorrosion materials, are discussed for the oligomers and their polymeric derivatives.展开更多
Chiral 4-[(2-isopropyl-5-methylcyclohexyl)oxo]-4-oxobutanoic acid reacts with substituted anilines to produce amides 1-6 in high yields. Resulted amides 1-6 were investigated for their antifungal and antibacterial act...Chiral 4-[(2-isopropyl-5-methylcyclohexyl)oxo]-4-oxobutanoic acid reacts with substituted anilines to produce amides 1-6 in high yields. Resulted amides 1-6 were investigated for their antifungal and antibacterial activities. Compounds 2 (96.5%) against Aspergillus fumigatus and 6 (93.7%) against Helminthosporium sativum demonstrated excellent activities. However, compounds 3 (37.6%) against Bacillus subtilis, 4 (33.2%) against Pseudomonas aurignosa, 5 against Klebsiella pneumonia demonstrated excellent growth inhibition potential.展开更多
A recombinant strain, Escherichia coli JM109-AN1, was obtained by constructing of a genomic library of the total DNA of Delftia sp. AN3 in E. coli JM109 and screening for catechol 2,3-dioxygenase activity. This recomb...A recombinant strain, Escherichia coli JM109-AN1, was obtained by constructing of a genomic library of the total DNA of Delftia sp. AN3 in E. coli JM109 and screening for catechol 2,3-dioxygenase activity. This recombinant strain could grow on aniline as sole carbon, nitrogen and energy source. Enzymatic assays revealed that the exogenous genes including aniline dioxygenase (AD) and catechol 2,3-dioxygenase (C230) genes could well express in the recombinant strain with the activities of AD and C230 up to 0.31 U/mg wet cell and 1.92 U/mg crude proteins, respectively. The AD or C23O of strain AN3 could only catalyze aniline or catechol but not any other substituted substrates. This recombinant strain contained a recombinant plasmid, pKC505-AN1, in which a 29.7-kb DNA fragment from Delftia sp. AN3 was inserted. Sequencing and open reading frame (orfs) analysis of this 29.7 kb fragment revealed that it contained at least 27 orfs, among them a gene cluster (consisting of at least 16 genes, named danQTA1A2BRDCEFG1HIJKG2) was responsible for the complete metabolism of aniline to TCA-cycle intermediates. This gene cluster could be divided into two main parts, the upper sequences consisted of 7 genes (danQTA1A2BRD) were predicted to encode a multi-component aniline dioxygenase and a LysR-type regulator, and the central genes (danCEFG1HIJKG2) were expected to encode meta-cleavage pathway enzymes for catechol degradation to TCA-cycle intermediates. Unlike clusters tad from Delftia tsuruhatensis AD9 and tdn from Pseudomonas putida UCC22, in this gene cluster, all the genes were in the same transcriptional direction. There was only one set of C230 gene (danC) and ferredoxin-like protein gene (danD). The presence of only one set of these two genes and specificity of AD and C230 might be the reason for strain AN3 could only degrade aniline. The products of danQTA1A2BRDC showed 99%-100% identity to those from Delftia acidovorans 7N, and 50%-85% identity to those of tad cluster from D. tsuruhatensis AD9 in amino acid residues. Besides this dan cluster, the 29.7 kb fragment also contained genes encoding the trans-membrane transporter and transposases which might be needed for transposition of the gene cluster. Pulsed-field gel electrophoresis (PFGE) and plasmid curing experiments suggested that the dan cluster might be encoded on the chromosome of strain AN3. The GenBank accession number for the dan cluster of Delftia sp. AN3 is DQ661649.展开更多
The kinetics of aniline degradation by persulfate processes with iron(Ⅱ) activation at ambient temperature was investigated in this study.With iron(Ⅱ) as initiator,the oxidation reactions were found to follow a ...The kinetics of aniline degradation by persulfate processes with iron(Ⅱ) activation at ambient temperature was investigated in this study.With iron(Ⅱ) as initiator,the oxidation reactions were found to follow a biphasic rate phenomenon:a rapid transformation followed by a slow but sustained oxidation process.In the first 30 s,the reaction mainly relies on the persulfate-Fe^(2+) reaction in which aniline is oxidized rapidly.After 30 s,the aniline was still oxidized but the rate of reaction tended to be slower and the rates were clearly linear-proportional.After the initial fast oxidation,the reactions appeared to follow a pseudo-first-order model.展开更多
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 ...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.展开更多
The paper deals with the influence of anode material on the efficiency of degradation for organic pollutants in water system.The electrochemical performance of fluorine ion doped lead dioxide(F--PbO2) electrode for ...The paper deals with the influence of anode material on the efficiency of degradation for organic pollutants in water system.The electrochemical performance of fluorine ion doped lead dioxide(F--PbO2) electrode for the degradation of aniline was compared with that of undoped lead dioxide(PbO2) electrode by ultraviolet-visible(UV-Vis) spectroscopy,linear voltammetry and other analytical methods,such as the measurement by chemical oxygen demand analyzer,high performance liquid chromatography and scanning electron micrography.It was shown that both PbO2 electrode and F--PbO2 electrode could make aniline be mineralized completely and have the same degradation course,but F--PbO2 electrode has much higher electrocatalytic activity than undoped PbO2 electrode for the electrochemical degradation of aniline.The experimental results confirm that F--PbO2 electrode has much higher potential for oxygen evolution than undoped PbO2 electrode.展开更多
基金This work was supported by the National Natural Science Foundation of China (No. 50379012)Program for New Century Excellent Talents in University (No. 05-0481).
文摘Objective To identify the bacteria tolerating chlorinated anilines and to study the biodegradability of o-chloroaniline and its coexistent compounds. Methods Microbial community of complex bacteria was identified by plate culture observation techniques and Gram stain method. Bacterial growth inhibition test was used to determine the tolerance of complex bacteria to toxicant. Biodegradability of chlorinated anilines was determined using domesticated complex bacteria as an inoculum by shaking-flask test. Results The complex bacteria were identified, consisting of Xanthomonas, Bacillus alcaligenes, Acinetobacter, Pseudomonas, and Actinomycetaceae nocardia. The obtained complex bacteria were more tolerant to o-chloroaniline than mixture bacteria in natural river waters. The effects of exposure concentration and inoculum size on the biodegradability of o-chloroaniline were analyzed, and the biodegradation characteristics of single o-chloroaniline and 2, 4-dichloroaniline were compared with the coexistent compounds. Conclusion The biodegradation rates can be improved by decreasing concentration of compounds and increasing inoculum size of complex bacteria. When o-chloroaniline coexists with aniline, the latter is biodegraded prior to the former, and as a consequence the metabolic efficiency of o-chloroaniline is improved with the increase of aniline concentration. Meanwhile, when o-chloroaniline coexists with 2,4-dichloroaniline, the metabolic efficiency of 2,4-dichloroaniline is markedly improved.
文摘Using galvinoxyl as catalyst, the phase transfer catalyzed method of oxidation of primary amines to symmetrical azobenzenes with a saturated solution of potassium ferricyanide in 2 mom aqueous potassium hydroxide and dichloromethane is described. The reaction has intimate relation with Hammett substituent constants. This report offers an efficient and rapid method to prepare azobenzenes and a possible mechanism is also suggested.
基金Supported by the NNSF of China (No. 20737001)Program for Environment Protection in Jiangsu Province (201140)
文摘Octanol/water partition coefficient (Kow) is a crucial property for evaluating the environmental behavior and fate of organic compound. Herein, some quantitative structure-property relationship (QSPR) studies were performed to estimate and predict the lgK ow of substituted anilines. 2D method (multiple linear regression, MLR) and 3D method (comparative molecular field analysis, CoMFA) were applied in this study. Successful 2D and 3D models yielded the correlation coefficient (R2) values of 0.981 and 0.966 and the Leave-One-Out (LOO) cross-validated correlation coefficient (q2) values of 0.933 and 0.820, respectively. The developed models have a highly predictive ability in both internal and external validation. In addition, the results were interpreted in terms of physical and chemical meanings of descriptors and field contribution maps. It showed that the steric and electrostatic properties are the primary factors that govern the lgK ow of substituted anilines. The information obtained from the QSPR models would be helpful to the interpretation of structural features pertinent to the lgK ow of substituted anilines, which may be helpful in estimating the organic compounds' potential harm to the environment.
文摘We report a one-pot three-component synthesis of N-arylmethyl-4-(7-cyclohepta-1,3,5-trienyl)anilines by using various aromatic imines, tropylium tetrafluoroborate, and sodium tetrahydroborate in the presence of imidazole as activator.
文摘While Raman spectroscopy is a useful method for analyzing many organic compounds, it is limited by relatively low sensitivity. Therefore, Surface Enhanced Raman Spectroscopy (SERS) based on the adsorption of organic analytes onto gold or silver nanostructures has been used to enhance the signal of chemicals presented at very low concentrations. Although the plasmonic effect of SERS has been shown to play a large role in signal enhancement, the significance of the chemical effect due to the analyte chemisorption on the gold or silver surface is less well understood. In this study, the role of aniline substituents is examined by probing the SERS intensities of various anilines in silver and gold colloids using a Raman spectrometer with an excitation wavelength of 785 nm. The SERS enhancement factors and detection limits for aniline and its mono- and di-substituted ortho derivatives are determined and compared. Both the steric requirements of chemisorption and the inductive effects of electron-withdrawal due to the substituents affect the signal intensities of various vibrational modes of the amino group and the aromatic ring. The degree of enhancement is also related to the methods for preparing the silver and gold colloids, which are characterized by probing the nanoparticle morphology and its degree of aggregation using transmission electron microscopy (TEM).
基金supported by NSF of China(Grant 21922703 and 91953112 to H.W.)the Natural Science Foundation of Jiangsu Province(Grant BK20190004 and BK20202004)National Key R&D Program of China(2019YFA0905800).
文摘Nitroanilines are important building blocks in pharmaceuticals,materials and dyes.Nitration methods for anilines under mild conditions are highly desired.Herein,we report a photochemical method for the nitration of anilines bearing various protecting groups by 5-methyl-1,4-dinitroimidazole as a new type of nitro source.This method is light-controlled and proceeds under mild reaction conditions with high efficiency.Fmoc-,Ts-and alkyl-protected anilines are all well nitrated with good functional group tolerance.
基金Universiti Sains Malaysia for USM RU(No.1001/PKIMIA/811159) and the research facilities
文摘This article describes the preparation and liquid crystalline properties of a new homologous series of 4-(4-bromopropyloxy)-4'- (4-alkyloxybenzylidene)anilines in which the phenyl ring is armed by a bromopropyloxy chain.The thermal behavior and mesomorphic properties of the synthesized compounds were studied with particular attention given to the correlation between their phase transition temperatures and anisotropic change influenced by molecular structure.All the members displayed enantiotropic smectic phase except for the homologue with the longest alkyloxy chain(R = C_(18)H_(37)),exhibiting only monotropic characteristic. The presence of bromine atom from the propyloxy side chain is found to be capable of altering and influencing the mesomorphic properties.
基金Financial support from the National Natural Science Foundation of China(Nos.21772002,21901010,and 21901012)the Open Research Fund of State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)is greatly appreciated.
文摘Amines are among the most fundamental motifs in chemical synthesis,and the introduction of amine building blocks via selective C-C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification.Herein,we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents,which are easily prepared from hydroxylamine.Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions.Good compatibility and valuable applications of the transformation were also displayed.
基金partial financial support from the Ministry of Science and Technology of China (No. 2016YFE0132600)Zhengzhou University
文摘Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.
基金supported by NSF of China(no.21602064 and 22004041)the Science and Technology Project of Quanzhou City(2018C073R)the Instrumental Analysis Center of Huaqiao University.
文摘Rhodium-catalysed regioselective redox-neutral[3+3]-cycloaddition of anilines with CF_(3)-ynones was achieved via a traceless directing group strategy.A variety of substituted 2-trifluromethylquinoline compounds were obtained in good to excellent yields,which exhibited favorable blue emission properties.
基金supported by the National Natural Science Foundation of China(21677018)the Joint Fund of the Beijing Municipal Natural Science Foundation and Beijing Municipal Education Commission(KZ201810017024)the Cross-Disciplinary Science Foundation from Beijing Institute of Petrochemical Technology(BIPTCSF–22032205003/014)。
文摘Aniline is a vital industrial raw material.However,highly-toxic aniline wastewater usually deteriorated effluent quality,posed a threat to human health and ecosystem safety.Therefore,this study reported a novel internal circulation iron-carbon micro-electrolysis(ICE)reactor to treat aniline wastewater.The effects of reaction time,pH,aeration rate and iron-carbon(Fe/C)ratio on the removal rate of aniline and the chemical oxygen demand were investigated using single-factor experiments.This process exhibited high aniline degradation performance of approximately 99.86% under optimal operating conditions(reaction time=20 min,pH=3,aeration rate=0.5 m3·h^(-1),and Fe/C=1:2).Based on the experimental results,the response surface method was applied to optimize the aniline removal rate.The Box–Behnken method was used to obtain the interaction effects of three main factors.The result showed that the reaction time had a dominant effect on the removal rate of aniline.The highest aniline removal rate was obtained at pH of 2,aeration rate of 0.5 m^(3)·h^(-1)and reaction time of 30 min.Under optional experimental conditions,the aniline content of effluent was reduced to 3 mg·L^(-1)and the removal rate was as high as 98.24%,within the 95% confidence interval(97.84%-99.32%)of the predicted values.The solution was treated and the reaction intermediates were identified by high-performance liquid chromatography,ultraviolet-visible spectroscopy,Fourier-transform infrared spectroscopy,gas chromatography-mass spectrometry,and ion chromatography.The main intermediates were phenol,benzoquinone,and carboxylic acid.These were used to propose the potential mechanism of aniline degradation in the ICE reactor.The results obtained in this study provide optimized conditions for the treatment of industrial wastewater containing aniline and can strengthen the understanding of the degradation mechanism of iron-carbon micro-electrolysis.
文摘Introduction: This study aimed to perform routine seminal fluid analysis, sperm DNA fragmentation, and sperm function tests at the chromatin maturation level and evaluate pregnancy in the patients passing intrauterine insemination before starting Intrauterine Insemination (IUI) method. Materials and Methods: In this prospective study, 111 couples who underwent Intrauterine Insemination (IUI) in unexplained infertility patients were admitted to Al-Farah IVF and assisted reproductive center in Baghdad, Iraq between November 2020 and February 2021 were evaluated. Semen fluid analysis was performed based on (WHO 4th) guiding rules. In addition, Sperm Chromatin Dispersion (halo test) and sperm maturation were performed with Aniline Blue Stain (ABS). Results: Sperm Chromatin Dispersion (SCD) groups were compared in terms of pregnancy outcome;the positive pregnancy rate was found to be above in the normal SCD groups (p = 0.0005). In addition, Aniline Blue Stain (ABS) groups were compared in the terms of pregnancy outcome;the positive pregnancy rate was found to be higher in the normal ABS group (p = 0.017). Conclusion: Our study showed that the use of DNA fragmentation (SCD) and sperm maturation tests (ABS) together with routine semen analysis in intrauterine insemination cases will make a significant contribution to the prediction of Intrauterine Insemination (IUI) increased results. So, these results indicate a defect in the effect of DNA fragmentation on the outcome of intrauterine insemination.
文摘The tetrahydroquinoline moiety is a structural feature of many natural products. By using a domino reaction of aromatic amines and cyclic enol ethers catalyzed by zirconyl chloride in water, various tetrahydroquinoline derivatives were synthesized efficiently. Most cyclized products showed cis selectivity. The cis selectivity was tentatively rationalized due to chelation control in water.
文摘Among the inherent drawbacks of conducting polymers are the limited processibility, uneven polydispersity inmolecular weigh and the existence of structure defects, which become the obstacles for many electronic, optical andbiological applications that demand the materials to have well-defined structures and high chemical purity. To solve theseproblems, our research in the last decade or so has focused on the synthesis of electroactive oligomers of well-definedstructures, controllable molecular weighs, narrow or uniform polydispersity. We have developed a general strategy for thesynthesis of such oligomers based on the theory of non-classical or reactivation chain polymerization. The aniline oligomerswith minimum 4 nitrogen atoms and 3 phenylene rings exhibit similar characteristic redox behavior and electroactivity aspolyaniline. Electronic conductivity of the oligomers of 7 or 8 aniline units approaches that of polyaniline. Solubility of theoligomers is much improved over that of conventional polyaniline. Various functional groups can be introduced into theoligomers either by proper selection of starting materials or by post-synthesis modifications via common organic reactions.The functionalized oligomers undergo further polymerizations to afford a variety of new electroactive materials, includingpolyamides, polyimides, polyureas, polyurethanes, polyacrylamides and epoxy polymers. Numerous potential applications,particularly as anticorrosion materials, are discussed for the oligomers and their polymeric derivatives.
文摘Chiral 4-[(2-isopropyl-5-methylcyclohexyl)oxo]-4-oxobutanoic acid reacts with substituted anilines to produce amides 1-6 in high yields. Resulted amides 1-6 were investigated for their antifungal and antibacterial activities. Compounds 2 (96.5%) against Aspergillus fumigatus and 6 (93.7%) against Helminthosporium sativum demonstrated excellent activities. However, compounds 3 (37.6%) against Bacillus subtilis, 4 (33.2%) against Pseudomonas aurignosa, 5 against Klebsiella pneumonia demonstrated excellent growth inhibition potential.
文摘A recombinant strain, Escherichia coli JM109-AN1, was obtained by constructing of a genomic library of the total DNA of Delftia sp. AN3 in E. coli JM109 and screening for catechol 2,3-dioxygenase activity. This recombinant strain could grow on aniline as sole carbon, nitrogen and energy source. Enzymatic assays revealed that the exogenous genes including aniline dioxygenase (AD) and catechol 2,3-dioxygenase (C230) genes could well express in the recombinant strain with the activities of AD and C230 up to 0.31 U/mg wet cell and 1.92 U/mg crude proteins, respectively. The AD or C23O of strain AN3 could only catalyze aniline or catechol but not any other substituted substrates. This recombinant strain contained a recombinant plasmid, pKC505-AN1, in which a 29.7-kb DNA fragment from Delftia sp. AN3 was inserted. Sequencing and open reading frame (orfs) analysis of this 29.7 kb fragment revealed that it contained at least 27 orfs, among them a gene cluster (consisting of at least 16 genes, named danQTA1A2BRDCEFG1HIJKG2) was responsible for the complete metabolism of aniline to TCA-cycle intermediates. This gene cluster could be divided into two main parts, the upper sequences consisted of 7 genes (danQTA1A2BRD) were predicted to encode a multi-component aniline dioxygenase and a LysR-type regulator, and the central genes (danCEFG1HIJKG2) were expected to encode meta-cleavage pathway enzymes for catechol degradation to TCA-cycle intermediates. Unlike clusters tad from Delftia tsuruhatensis AD9 and tdn from Pseudomonas putida UCC22, in this gene cluster, all the genes were in the same transcriptional direction. There was only one set of C230 gene (danC) and ferredoxin-like protein gene (danD). The presence of only one set of these two genes and specificity of AD and C230 might be the reason for strain AN3 could only degrade aniline. The products of danQTA1A2BRDC showed 99%-100% identity to those from Delftia acidovorans 7N, and 50%-85% identity to those of tad cluster from D. tsuruhatensis AD9 in amino acid residues. Besides this dan cluster, the 29.7 kb fragment also contained genes encoding the trans-membrane transporter and transposases which might be needed for transposition of the gene cluster. Pulsed-field gel electrophoresis (PFGE) and plasmid curing experiments suggested that the dan cluster might be encoded on the chromosome of strain AN3. The GenBank accession number for the dan cluster of Delftia sp. AN3 is DQ661649.
基金supported by a grant from E.I.du Pont de Nemours and Company to Rutgers University.Partial funding wasalso provided by the Natural Science Foundation of Guangdong Province(No.9351064101000001)Science and Technology Planning Project of Guangdong Province(No.2007A020100001-13)the Key Laboratory of Environmental Protection and Eco-Remediation of Guangdong Higher Education Institutions(China)
文摘The kinetics of aniline degradation by persulfate processes with iron(Ⅱ) activation at ambient temperature was investigated in this study.With iron(Ⅱ) as initiator,the oxidation reactions were found to follow a biphasic rate phenomenon:a rapid transformation followed by a slow but sustained oxidation process.In the first 30 s,the reaction mainly relies on the persulfate-Fe^(2+) reaction in which aniline is oxidized rapidly.After 30 s,the aniline was still oxidized but the rate of reaction tended to be slower and the rates were clearly linear-proportional.After the initial fast oxidation,the reactions appeared to follow a pseudo-first-order model.
基金supported by Department of Science and Technology,Government of India
文摘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.
基金Supported by the National Natural Science Foundation of China(No.20873051)the High-tech Research and Development Program of China(No.2006AA06Z321)the Natural Science Foundation of Jiangsu Province,China(No.BK2008555)
文摘The paper deals with the influence of anode material on the efficiency of degradation for organic pollutants in water system.The electrochemical performance of fluorine ion doped lead dioxide(F--PbO2) electrode for the degradation of aniline was compared with that of undoped lead dioxide(PbO2) electrode by ultraviolet-visible(UV-Vis) spectroscopy,linear voltammetry and other analytical methods,such as the measurement by chemical oxygen demand analyzer,high performance liquid chromatography and scanning electron micrography.It was shown that both PbO2 electrode and F--PbO2 electrode could make aniline be mineralized completely and have the same degradation course,but F--PbO2 electrode has much higher electrocatalytic activity than undoped PbO2 electrode for the electrochemical degradation of aniline.The experimental results confirm that F--PbO2 electrode has much higher potential for oxygen evolution than undoped PbO2 electrode.