STUDIES ON THE INITIATION MECHANISM OF ORGANIC PEROXIDE AND N-METHACRYLOYLOXYETHYL-N-METHYL ANILINE IN METHYL METHACRYLATE POLYMERIZATION

The initiation mechanism of methyl methacrylate (MMA) polymerization by organic peroxide and polymerizable aromatic tertiary amine such as N-methacryloyloxyethyl-N-methyl aniline (MEMA) binary system has been studied. The kinetics of polymerization of MMA and the ESR spectra of organic peroxide/MEMA system were determined. Based on the ESR study and the end-group analysis by UV spectra of the polymer formed, the initiation mechanism is proposed.

Can the Prediction of Intrauterine Insemination Results by Used Aniline Blue Stain (ABS) and Sperm Chromatin Dispersion (SCD) Levels?

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.

An internal circulation iron-carbon micro-electrolysis reactor for aniline wastewater treatment:Parameter optimization,degradation pathways and mechanism

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.

A novel and complete gene cluster involved in the degradation of aniline by Delftia sp. AN3

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.

In situ chemical oxidation of aniline by persulfate with iron(Ⅱ) activation at ambient temperature

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.

Comparison Between Performances of PbO_2 and F^--doped PbO_2 Anodes for Electrochemical Degradation of Aniline

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.

Determination of aniline in environmental water samples by alternating-current oscillopolarographic titration

A new method for the determination of aniline in environmental water based on oscillopolarographic titration was presented in this paper. Several factors including the kind, concentration, and volume of acid, the dosage of potassium bromide, the temperature and concentration of concomitant substances were investigated in detail. The experimental results indicated that this method was simple, rapid, and sensitive. The linear range was 8.367 × 10(?4) to 2.789 × 10(?2) mol L(?1), the relative standard deviation (R.S.D.) was lower than 0.96%, and the spiked recoveries of aniline in environmental water samples were in the range of 99.4–106.9% under the optimal conditions. The results indicated that the present method could be used as an alternative method for aniline determination in realworld water samples.

Kinetics of aniline oxidation with chlorine dioxide

For the first time, kinetics of aniline oxidation with chlorine dioxide(ClO 2) were investigated systematically by detecting concentration of aniline with HPLC at regular intervals. Results showed that the reaction was first-order both in ClO 2 and in aniline, and the oxidation reaction could be described as second-order reaction. Stoichiometric factor η was experimentally determined to be 2 44. The second-order-reaction rate constant k was 0 11 L/(mol·s) under condition of pH 6 86 and water temperature(T w) 287K. Reaction activation energy was 72 31 kJ/mol, indicating that the reaction could take place under usual water treatment conditions. The reaction rate constants in acidic and alkali media were greater than that in neutral medium. Chlorite ion could slightly increase reaction rate in acidic medium. p-aminophenol and azobenzene were detected by GC-MS as intermediates.

Recovery of Aniline from Wastewater by Nitrobenzene Extraction Enhanced with Salting-Out Effect

Objective Nitrobenzene extraction enhanced by salting-out effect was employed to recover aniline from wastewater at 25 ℃. Method Batchwise experiments were conducted to elucidate the influence of various operating variables on the extracting performance, including acidity of wastewater, initial aniline concentration, ratios of solvent to wastewater, extraction stages, concentrations and different types of inorganic salts, such as NaCl, KCI, Na2SO4, CaCl2 and K29O4. Results Nitrobenzene with a concentration of 20% and a pH value of 9.1 at the temperature of 25 ℃ together with NaCl of a concentration of 14 wt.% realized nearly 100% aniline recovery at the fifth stage of wastewater treatment. Conclusions High pH values and volume ratios of nitrobenzene/wastewater are more suitable for recovery of aniline. In addition, recovery of aniline is significantly elevated with increase of the concentration of salts, whose promoting effects are in the following order: NaCI〉Na2SO4〉K2SO4〉CaC12〉KCI on the weight basis of wastewater. Furthermore, aniline in wastewater can be almost completely recovered by five-stage sequential nitrobenzene extraction, which is promoted continuously by the salting-out effect.

Selective N-Methylation of N-Methylaniline with CO_(2) and H_(2) over Cu/In_(2)O_(3) Catalyst

N-Methylation of amines with CO_(2) and H2 is a potential approach for CO_(2) utilization because N-methylated amines can be used as solvents and organic intermediates. In_(2)O_(3)-supported Cu (Cu/In_(2)O_(3)) acts as an effective heterogeneous catalyst for N-methylation reaction of N-methylaniline (MA) with CO_(2) and H_(2),showing higher N,N-dimethylaniline (DMA) selectivity than other supported Cu catalysts. On one hand,the dispersion of Cu can be improved by the defective In_(2)O_(3) support. On the other hand,In_(2)O_(3) support is active in the dissociative adsorption of CO_(2) through C—O bond breaking. In addition,the H_(2) dissociation ability of In_(2)O_(3) can also be enhanced by Cu. The combination of Cu and In_(2)O_(3) is effective in the activation of CO_(2),the adsorption of intermediate N-methylformanilide (MFA),the hydrogenation of MFA to DMA and the prohibition of C—N bond cleavage side reactions,thereby enhancing the reaction rate of MA conversion and the selectivity to DMA.

Experimental and QSPR Studies on n-Octanol/water Partition Coefficient (lgK_(ow)) of Substituted Aniline

The n-octanol/water partition coefficients （lgKow） of 18 substituted anilines were determined at 25 ℃ by shake-flask method. The geometrical optimization of substituted anilines has been performed at B3LYP/6-311G^＊＊ level with Gaussian98 program, and the molecular surface areas of substituted anilines were calculated using ChemOffice 2004 program. The calculated structural parameters of substituted anilines were used as theoretical descriptors and the two-parameter （molecular surface area （MA） and the energy of the highest occupied molecular orbital （EaoMo）） quantitative structure-property relationship （QSPR） model of lgKow for substituted aniline with molecular structural parameters was developed by multi-linear regression method. The regression coefficient square （r^2） is 0.990 and the standard deviation SE 0.109. The model was validated by variance inflation factors （VIF） and t-test, and the results show that there exists small self-correlation between variables of the model with perfect stability. The model gives results in good qualitative agreement with experimental data. At last, the model was applied to predict lgKow values of five substituted anilines whose lgKow values have not been determined experimentally.

Degradation of Aniline Wastewater Using Dielectric Barrier Discharges at Atmospheric Pressure

Aniline is a toxic water pollutant detected in drinking water and surface water, and this chemical is harmful to both human and aquatic life. A dielectric barrier discharge （DBD） reactor was designed in this study to investigate the treatment of aniline in aqueous solution. Discharge characteristics were assessed by measuring voltage and current waveforms, capturing light emission images, and obtaining optical emission spectra. The effects of several parameters were analyzed, including treatment distance, discharge power, DBD treatment time, initial pH of aniline solutions, and addition of sodium carbonate and hydrogen peroxide to the treatment. Aniline degradation increased with increasing discharge power. Under the same conditions, higher degradation was obtained at a treatment distance of 0 mm than at other treatment distances. At a discharge power of 21.5 W, 84.32% of aniline was removed after 10 rain of DBD treatment. Initial pH significantly influenced aniline degradation. Adding a certain dosage of sodium carbonate and hydrogen peroxide to the wastewater can accelerate the degradation rate of aniline. Possible degradation pathways of aniline by DBD plasmas were proposed based on the analytical data of GC/MS and TOC.

Biodegradability of Chlorinated Anilines in Waters

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.

Preparation and Electrocatalytic Activity of Polyaniline-poly (Propylene Oxide) Modified by Pt Nanoparticles

The preparation and electrocatalytic activity of polyaniline-poly （ propylene oxide ） （ PAN-PPO ） modified by Pt particles （ Pt/ PAN-PPO ） were investigated. Pt/ PAN-PPO was characterized by scanning electron microscopy （SEM） and energy dispersive spectroscopy （ EDS ）. Pt particles on PAN-PPO were in the nanometer range, and dispersed in a three-dimensional distribution on the surface of PAN-PPO film. Compared with polyaniline and glassy carbon modified with Pt particles under the same conditions, Pt/PAN-PPO exhibited a high electrocatalytic activity for lysine oxidation.

Degradation of aniline by Fe^(2+)-activated persulfate oxidation at ambient temperature

The aniline degradation by persulfate activated with ferrous ion (Fe2+ ) was investigated in batch reactor at ambient temperature. The experimental factors in aqueous solutions including persulfate concentration, Fe2+ concentration, pH and ionic strength level were discussed. It is demonstrated that, aniline degradation rate increases with increasing persulfate concentration, but much more ferrous ion inhibits the aniline degradation. When the aniline concentration is 0.10 mmol/L, the maximum aniline degradation occurs at the S2O82- to Fe2+ molar ratio of 250/5 at pH 7.0. In the pH range of 5.0-8.5, increasing pH causes higher aniline degradation. What's more, the increase of ionic strength in solution causes inhibiting in the reaction. Produced intermediates during the oxidation process were identified using gas chromatography-mass spectrometry (GC-MS) technology. And degradation pathways of aniline were also tentatively proposed.

Effect of chelating agent on oxidation rate of aniline in ferrous ion activated persulfate system at neutral pH

In the interest of accelerating aniline degradation, Fe2+ and chelated Fe2+ activated persulfate oxidations were investigated in neutral pH condition. Three kinds of chelating agents were selected including citric acid, oxalic acid and ethylenediamine tetraaceatate(EDTA) to maintain available Fe2+. The results indicate that the concentration of chelating agent and ferrous ion didn't follow a linear relationship with the degradation rate of aniline. A 1/1 ratio of chelating agent/Fe2+ results in a higher degradation rate compared to the results by other ratios. The oxidation enhancement factor using oxalic acid was found to be relatively low. In contrast, citric acid is more suitable chelating agent in the ferrous iron activated persulfate system and aniline exhibits a highest degradation with a persulfate/Fe2+/citric acid/aniline molar ratio of 50/25/25/1 compared to other molar ratios.

Rapid Quantification of Bioactive Lentinan with an Aniline Blue Fluorescent Method

Lentinan is a clinically approved immune modulator and its anticancer and immunomodulatory bioactivity is found to be dependent on its triple helical conformation. Therefore, the development of rapid and convenient method for determination of bioactive lentinan with triple helical conformation holds great promise for the quality control of lentinan healthy products. In this work, an aniline blue fluorescent method was optimized and established to accurately and rapidly detect bioactive lentinan. In the presence of lentinan, the fluorescence intensity of aniline blue with 404 nm excitation and 492 nm emission dramatically enhanced within 15 min in pH 10 glycine-NaOH buffer solution, which allowed the analysis of lentinan in a very simple and fast manner. The method allowed for the sensitive determination of lentinan in the range of 1 to 60 μg/mL with a detection limit of 0.25 μg/mL. Notably, the protocol exhibited excellent selectivity for the determination of triple helical lentinan over other saccharides. The method was successfully applied to the detection of bioactive lentinan in health tonic solution, which demonstrated the method had great potential for quality control of lentinan contained products.

Study on degradation mechanism of aniline solution by potassium ferrate

研究了高铁酸钾投加量、初始pH及苯胺初始浓度对苯胺降解效果的影响。结果表明，苯胺废水的COD去除率照高铁酸钾投加量和苯胺初始浓度的增大而升高，而初始pH对COD去除率影响不明显。对高铁酸钾降解苯胺废水后的产物进行了气相色谱／质谱（GC／MS）分析，在此基础上详细探讨了高铁酸钾降解苯胺的机制。

Degradation and mineralization of aniline by O_3/Fenton process enhanced using high-gravity technology

The degradation and mineralization of aniline(AN) using ozone combined with Fenton reagent(O_3/Fenton) in a rotating packed bed(RPB) was proposed in this study, and the process(RPB-O_3/Fenton) was compared with conventional O_3/Fenton in a stirred tank reactor(STR-O_3/Fenton) or single ozonation in an RPB(RPB-O_3). Effects of high gravity factor, H_2O_2 dosage, H_2O_2 dosing method and initial p H on the AN mineralization efficiency were investigated in the RPB-O_3/Fenton process. In addition, the behavior of Fe(II) was monitored at different H2 O2 dosing methods and p H values. Finally, the optimal operation conditions were determined with high gravity factor of100, initial pH of 5, Fe(II) concentration of 0.8 mmol·L^(-1) and H_2O_2 dosage of 2.5 ml. Under these conditions, for aniline wastewater at the volume of 1 L and concentration of 200 mg·L^(-1), a fast and thorough decay of AN was conducted in 10 min, and the TOC removal efficiency reached 89% in 60 min. The main intermediates of p-benzoquinone, nitrobenzene, maleic acid and oxalic acid were identified by liquid chromatography/mass spectroscopy(LC/MS), and the degradation pathways of AN in RPB-O_3/Fenton system were proposed based on experimental evidence. It could be envisioned that high-gravity technology combined with O_3/Fenton processes would be promising in the rapid and efficient mineralization of wastewater.

Catalytic Hydrogenation of Nitrobenzene to Aniline by Ag/γ-Fe_2O_3

The Ag/γ-Fe_2O_3 nanocomposite was synthesized by solvothermal reduction method via using ferric nitrate and silver nitrate as raw materials, and ethylene glycol as the reducing agent. The composite was characterized by X-ray powder diffraction, scanning electron microscope, transmission electron microscope, and energy dispersive X-ray. The prepared Ag/γ-Fe_2O_3 was used for the catalytic hydrogenation of nitrobenzene to aniline by hydrazine hydrate. The factors such as the silver content in the catalyst, reaction time, reaction temperature and the regeneration of catalyst were investigated. The results showed that the yield of aniline reached 100% by utilizing the 1%wt（nitrobenzene） Ag/γ-Fe_2O_3 for the catalytic hydrogenation of nitrobenzene for 3 h to obtain aniline at 78 ℃, hydrazine hydrate as the hydrogen source, while the silver content in the catalyst was 3%mol.