Research on Thermodynamic Properties of Polybrominated Diphenylamine by Neural Network

Based on the location of bromine substituents and conjugation matrix, a new substituent po- sition index ~X not only was defined, but also molecular shape indexes Km and electronega- tivity distance vectors Mm of diphenylamine and 209 kinds of polybrominated diphenylamine （PBDPA） molecules were calculated. Then the quantitative structure-property relationships （QSPR） among the thermodynamic properties of 210 organic pollutants and 0X, K3, M29, M36 were founded by Leaps-and-Bounds regression. Using the four structural parameters as input neurons of the artificial neural network, three satisfactory QSPR models with network structures of 4：21：1, 4：24：1, and 4：24：1 respectively, were achieved by the back-propagation algorithm. The total correlation coefficients R were 0.9999, 0.9997, and 0.9995 respectively and the standard errors S were 1.036, 1.469, and 1.510 respectively. The relative mean deviation between the predicted value and the experimental value of Sθ, AfHe and △fGθ- were 0.11%, 0.34% and 0.24% respectively, which indicated that the QSPR models had good stability and superior predictive ability. The results showed that there were good nonlinear correlations between the thermodynamic properties of PBDPAs and the four structural pa- rameters. Thus, it was concluded that the ANN models established by the new substituent position index were fully applicable to predict properties of PBDPAs.

<i>In Situ</i>UV–Vis Spectroelectrochemical Studies on the Copolymerization of Diphenylamine and <i>o</i>-Phenylenediamine

The in situ ultraviolet-visible (UV-Vis) spectroelectrochemical study on the copolymerization of diphenylamine (DPA) and o-phenylenediamine (OPD) has been performed at a constant potential of 0.8 V using indium tin oxide (ITO)-coated glass electrodes as working electrode. And also, as a comparison, the electrochemical homopolymerizations of DPA and OPD have been investigated by using the in situ spectroelectrochemical technique. The intermediate species generated during the electrochemical homopoly-merization of DPA and OPD, and the copolymerization of DPA with OPD have been identified by using the in situ spectroelectrochemical procedure. The results reveal the formation of an intermediate in the initial stage of copolymerization through the cross-reaction of the cation radicals of DPA and OPD, and the absorption peak located at 538 nm in the UV–Vis spectra is assigned to this intermediate. To further investigate the copolymerization of DPA with OPD, cyclic voltammetry (CV) has been used to study the electrochemical homopolymerization of DPA and OPD and also the copolymerization of DPA and OPD with different concentration ratios in solution. The different voltammetric characteristics between the homopolymerization and copolymerization processes exhibit the occurrence of the copolymerization, and the difference between the copolymerization of DPA and OPD with different concentration ratios shows the dependence of the copoly-merization on the concentrations of DPA and OPD. The copolymer has also been characterized by Fourier transform infrared spectroscopy (FT-IR).

A POLAROGRAPHIC CATALYTIC WAVE OF OXYGEN INDUCED BY DIPHENYLAMINE COMPOUNDS

It is reported in this paper a polarographic catalytic double wave of oxygen reduction caused by diphenylamine compounds(diphs).The electrochemical process of the wave includes the polarographic generation of the superoxide anion O_2^- and the dismutation of O_2^- catalyzed by diphs with redox pseudoreversibility.

Formation and cytotoxicity of a new disinfection by-product (DBP) phenazine by chloramination of water containing diphenylamine

Disinfection by-products （DBPs） in drinking water have caused worldwide concern due to their potential carcinogenic effects. The formation of phenazine from diphenylamine （DPhA） chloramination was studied and its cytotoxicities for two human cancer cells were also investigated. Phenazine was detected synchronously with the consumption of DPhA by chloramination, which further confirmed that the new DBP phenazine can be produced along with N-nitrosodiphenylamine （NDPhA） from DPhA chloramination. The formation of phenazine had a maximum molar yield with solution pH increasing from 5.0 to 9.0, with phenazine as the main product for DPhA chloramination at lower pH, but higher pH favored the formation of NDPhA. Thus, solution pH is the key factor in controlling the formation of phenazine and NDPhA. Both the initial DPhA and chloramine concentrations did not show a significant effect on the molar yields of phenazine, although increasing the chloramine concentration could speed up the reaction rate of DPhA with chloramines. The cytotoxicity assays showed that phenazine had significant cell-specific toxicity towards T24 （bladder cancer cell lines） and HepG2 （hepatic tumor cell lines） cells with IC50 values of 0.50 and 2.04 mmol/L, respectively, and T24 cells being more sensitive to phenazine than HepG2 cells. The ICs0 values of phenazine, DPhA, and NDPhA for T24 cells were of the same order of magnitude and the cytotoxicity of phenazine for T24 cells was slightly lower than that of NDPhA （IC50, 0.16 mmol/L）, suggesting that phenazine in drinking water may have an adverse effect on human health.

Menaquinone-7 production from maize meal hydrolysate by Bacillus isolates with diphenylamine and analogue resistance

A menaquinone-7（MK-7） high-producing strain needs to be isolated to increase MK-7 production, in order to meet a requirement of MK-7 given the low MK-7 content in food products. This article focuses on developing MK-7 high-producing strains via screening and mutagenesis by an atmospheric and room temperature plasma（ARTP） mutation breeding system. We isolated an MK-7-producing strain Y-2 and identified it as Bacillus amyloliquefaciens, which produced（7.1±0.5） mg/L of MK-7 with maize meal hydrolysate as carbon source. Then, an MK-7 highproducing strain B. amyloliquefaciens H.β.D.R.-5 with resistance to 1-hydroxy-2-naphthoic acid, β-2-thienylalanine, and diphenylamine was obtained from the mutation of the strain Y-2 using an ARTP mutation breeding system. Using strain H.β.D.R.-5, efficient production of MK-7 was achieved（（30.2±2.7） mg/L）. In addition, the effects of nitrogen sources, prenyl alcohols, and MgSO_4 on MK-7 production were investigated, suggesting that soymeal extract combined with yeast extract, isopentenol, and MgSO4 was beneficial. Under the optimized condition, the MK-7 production and biomass-specific yield reached（61.3±5.2） mg/L and 2.59 mg/L per OD600 unit respectively in a 7-L fermenter. These results demonstrated that strain H.β.D.R.-5 has the capacity to produce MK-7 from maize meal hydrolysate, which could reduce the substrate cost.

Determination of Diphenylamine in Gunshot Residue by HPLC‑MS/MS

A high performance liquid chromatography tandem mass spectrometry/mass spectrometry(HPLC-MS/MS)protocol was developed for the determination of diphenylamine(DPA).Four productions of DPA were selected for qualitative assay and the peak area of the main product ion for quantitation.By means of separation using an Agilent Extend-C18 column(CA,USA)(150 mm×4.6 mm,5μm)with methanol‑water(90:10)as the mobile phase,DPA was detected by electrospray ionization(ESI)tandem mass spectrometry in positive mode.The linearity of the peak area versus concentration ranged 5‑500 ng/mL,r^(2)=0.9978.The limit of detection(S/N=3)of this method was 0.3 ng/mL.This method is applicable for the determination of DPA in gunshot residue.

The effect of diphenylamine on the electronic,optical,and charge transport properties of BTD-based derivative:Insights from theory

Theoretical investigations have been performed to explore the variation in electronic,optical,and charge transport properties upon the change of the chemical composition along the backbone in 2,1,3-benzothiadiazole（BTD）-based derivative.Narrow difference between hole and electron transportations with the charge hopping model indicates studied BTD-based derivative can be used as good ambipolar transport material in organic light-emitting diodes.

Inhibitory Effects of 1-MCP and DPA on Superficial Scald of Dangshansuli Pear

Dangshansuli pear is one of crisp pears and has a non-climacteric respiratory pattern. Dangshansuli pear fruits were treated with 1 000 or 2 000 μL L-1 diphenylamine （DPA） for 1 min, or with 0.5 μL L-1 1-methylcyclopropene （l-MCP） for 12 h before cold storage at （2±0.5）℃ for up to 210 d. Incidences of superficial scald and related physiological indexes were investigated during storage. The results showed that superficial scald occurred in control fruit with a rate of over 90% after 210 d at cold storage plus 10 d at room temperature. Treatments with 1 000 and 2 000 μL L-1 DPA and 0.5 μL L-1 l-MCP inhibited the accumulation of a-farnesene, conjugated trienes, total phenolic contents, and malondialdehyde （MDA） during storage. The treatments also decreased leakage of cell membrane and the activity of polyphenol oxidase （PPO） in the peel. These results indicate that 1-MCP and DPA treatments inhibit and postpone the occurrence of superficial scald of Dangshansuli pears remarkably in cold storage and post-storage shelf life, respectively, while the mechanisms were different. The results above may provide a theoretical evidence for the agriculture production.

SYNTHESIS OF POLYISOBUTYLENE WITH SEC-ARYLAMINO TERMINAL GROUP BY COMBINATION OF CATIONIC POLYMERIZATION WITH ALKYLATION

The highly reactive polyisobutylenes(PIBs) withα-double bonds(87.5 mol%) or tert-chloro(tert-Cl) groups(95 mol%) could be prepared via the cationic polymerization of isobutylene(IB) coinitiated by BF_3 or TiCl_4 respectively.The Friedel-Crafts alkylation of diphenylamine(DPA) with the highly reactive PIB withα-double bonds was further conducted under different conditions,such as at different alkylation temperature,in the mixed solvents of CH_2Cl_2/n-hexane with different solvent polarity and at DPA concentr...

铂基双金属催化剂上二苯胺脱氢环化生成咔唑(英文)

Gas phase dehydrocyclization of diphenylamine (DPA) to carbazole over monometallic and bimetallic 0.4 wt% Pt-based catalysts in a fixed bed reactor was studied in the presence of hydrogen at a temperature of 550 oC. Alumina and carbon supported Pt catalysts showed very high initial activity (> 95%). The selectivity for carbazole over carbon supported Pt catalysts was slightly lower. Doping of the catalyst with potassium led to an increase in the selectivity for carbazole by 15%. Bimetallic Pt-Sn catalysts prepared by co-impregnation were less selective than catalysts prepared by successive impregnation. The selectivity for carbazole over bimetallic Pt-Sn catalysts prepared by successive impregnation was 75%,but their activity decreased with increased Sn loading. Highly active and reasonably selective catalysts were Ir-doped bimetallic Pt-based catalysts. The conversion of diphenylamine over Pt-Ir catalysts was above 98% and the selectivity for carbazole was nearly 55%,while the lifetime was much longer.

Synthesis and Crystal Structure of Methyl 2-(Diphenylamino)-4-phenyl-1,3-thiazole-5-carboxylate

The title compound, methyl 2-（diphenylamino）-4-phenyl-1,3-thiazole-5-carboxylate, was synthesized and studied by single-crystal X-ray diffraction method. The structure of the product was confirmed by IR, 1H- and 13C-NMR spectroscopy and elemental analysis. These experimental studies were supported by quantum mechanical calculations. The structure was solved in monoclinic, space group P21/c with a = 9.573（3）, b = 19.533（7）, c = 9.876（3）, β = 92.35（4）°, V = 1845.2（10）3, T = 85（2） K, Z = 4, R = 0.040 and wR = 0.089 for 6424 observed reflections with I2σ（I）.

气相色谱法测定烟火药剂中二苯胺含量

二苯胺(Diphenylamine)是一种重要的工业原料。二苯胺作为橡胶抗氧剂、染料、杀菌剂和医药中间体有广泛的应用。在军工行业中,二苯胺由于能够结合炸药药剂的降解物从而延缓炸药的分解,作为炸药的安定剂和钝化剂。

PHOTOPHYSICS STUDIES OF ORGANIC COMPOUNDS——NANOSECOND LASER PHOTOLYSIS AND TRANSIENT ABSORPTION SPECTRA STUDIES OF PYRENE-AROMATIC AMINES

Nanosecond time-resolved transient absorption spectra of pyrene-triphenylamine, pyrenediphenylamine, pyrene-N, N-dibenzylaniline systems in various solvents have been investigated. In nonpolar solvent, pyrene-triphenylamine exciplex and pyrene-N, N-dibenzylaniline exciplex were observed directly. In acetonitrile, the pyrene anion radical, triphenylamine and diphenylamine cation radicals were detected. On the basis of the present experimental facts, the mechanism of fluorescence quenching processes of pyrene in polar and nonpolar solvents has been established.