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771.
Observation that rates of dehydrobromination of trans-β-bromostyrene (1) and the Hofmann degradation of tetrabutyl ammonium cation depend on strength of base in different ways and that treatment of 1 with base results in fast abstraction of the β-proton imply the possibility that the dehydrobromination of 1 could proceed via α-elimination and Ph migration. In order to clarify this question, β-13C-labeled 1 was obtained and subjected to PTC dehydrobromination which proceeds without migration of Ph. The obtained results are consistent with an irreversible E1cB mechanism. 相似文献
772.
Le Ngoc Xuyen Hoang Dang Lanh Ho Si Thoang J. V?lter 《Reaction Kinetics and Catalysis Letters》1989,39(2):293-298
Pt–Ni/-Al2O3 catalysts have been prepared and studied in n-hexane dehydrocyclization. The selectivity for benzene and toluene, a chain lengthening product formation was improved by Ni and correlated with its content.
Pt–Ni/-Al2O3 -. Ni . Ni , .相似文献
773.
Livio Racanè Vesna Trali?-Kulenovi? Richard P. Kitson Grace Karminski-Zamola 《Monatshefte für Chemie / Chemical Monthly》2006,18(1):1571-1577
Series of cyano, dicyano, amidino, and diamidino substituted 2-phenylbenzothiazoles were prepared. Mono- and dicyano substituted
benzothiazoles were obtained by condensation of appropriate substituted benzaldehydes with 2-aminothiophenol or 4-amino-3-mercaptobenzonitrile.
The appropriate amidines or diamidines were prepared by Pinner reaction. The compounds were tested against breast, prostate, and lung cancer cell lines in a 72 h cytotoxicity assay. Many
of the compounds had at 10 μM activity equivalent to 2-(4-aminophenyl)benzothiazole, while four compounds had significantly better activity, particularly
in the breast cancer model. 相似文献
774.
Mieczys?aw Makosza Tadeusz Lemek Andrzej Kwast Fran?ois Terrier 《The Journal of organic chemistry》2002,67(2):394-400
Relations of rates of the vicarious nucleophilic substitution of hydrogen (VNS) and S(N)Ar substitution of fluorine in 2-fluoronitrobenzenes with chloroalkyl aryl sulfone carbanions were determined from competitive experiments carried out at various concentrations of base. The observed dependence of the VNS/S(N)Ar rate ratio on the base concentration confirmed the two-step mechanism of the VNS, which consists of reversible formation of sigma(H) adducts of the alpha-chlorocarbanion to nitroarene, followed by base-induced beta-elimination of HCl. It was also evidenced that both of these processes can be the rate-limiting steps: the beta-elimination at low base concentration and the nucleophilic addition at high base concentration. Consistent with that conclusion is the finding that the kinetic isotope effect in the VNS reaction decreases from 4.2 (a value typical of a primary KIE) to 0.8 (a value typical of a secondary KIE) with increasing base concentration. Also reported is our discovery that the S(N)Ar substitution of the 2-fluoronitrobenzenes studied in this work was subject to base catalysis under some of the experimental conditions employed in our competitive experiments. 相似文献
775.
Decomposition of Toluene and Acetone in Packed Dielectric Barrier Discharge Reactors 总被引:2,自引:0,他引:2
Chung-Liang?ChangEmail author Tser-Sheng?Lin 《Plasma Chemistry and Plasma Processing》2005,25(3):227-243
The influences of TiO2 catalytic material and glass pellet packing on the decomposition efficiency of toluene and acetone in air by dielectric barrier discharge (DBD) reactors were experimentally investigated in this study. The effects of both packing materials on the formation of byproducts such as CO and CO2 were also evaluated. Experimental results indicate that the introduction of glass materials into the plasma zone of a wire-tube reactor would improve the decomposition efficiency of toluene and acetone compared to a nonpacked reactor. The apparent decomposition rate constant of a glass packed-bed reactor was 4.5–4.8 times greater than that of a nonpacked reactor. The results also indicate that the decomposition rate constant of toluene was approximately 2.6 times higher than that of acetone no matter which type reactor was utilized. The application of TiO2 coated pellets in DBD reactors will enforce the hydrocarbon byproducts to further be oxidized to CO2, notwithstanding, it will not significantly improve the performance of the reactors in the decomposition of toluene and acetone, and in the formation of CO. The results show that the best selectivity of CO2 for acetone decomposition in a TiO2 coated pellets packed-bed reactor was approximately 40% higher than that in a glass packed-bed reactor. 相似文献
776.
Development and application of a simple routine method for the determination of selenium in serum by octopole reaction system ICPMS 总被引:1,自引:0,他引:1
The aim of the study was to develop an inductively coupled plasma mass spectrometry (ICPMS) method for robust and simple routine determination of selenium in serum. Polyatomic interferences on 76Se, 77Se, and 78Se were removed by applying an octopole reaction system ICPMS with the reaction cell pressurized with H2 gas. We developed a novel simple optimization routine for the H2 gas flow based on a signal-to-noise ratio (SNR) calculation of the selenium signal measured in a single selenium standard. The optimum H2 flow was 2.9 mL min–1. The selenium content in serum was determined after a 50-fold dilution with 0.16 M HNO3 and quantified by using addition calibration and gallium as an internal standard. The method detection limit was 0.10 g L–1 for 76Se and 78Se and 0.13 g L–1 for 77Se. Human serum samples from a case-control study investigating if selenium was associated with risk of colorectal adenoma were analyzed. The average selenium concentration for the control group (n=768) was 137.1 g L–1 and the range was 73.4–305.5 g L–1. The within-batch repeatability (a batch is ten samples) estimated from 182 replicate analyses was 6.3% coefficient of variation (CV), whereas the between-batch repeatability was 7.4% CV estimated from 361 replicates between batches. The method accuracy was evaluated by analysis of a human serum certified reference material (Seronorm Serum level II, Sero A/S, Norway). There was a fairly good agreement between the measured average of 145±3 g L–1 (n=36) and the certified value of 136±9 g L–1. In addition the method was successfully applied for analysis of zinc serum concentrations without further optimization. For the Seronorm certified reference material a value of 911±75 g L–1 (n=31) for zinc was obtained, which corresponds well to the certified zinc value of 920±60 g L–1. 相似文献
777.
In this work, 1,10-phenanthroline was used as a complexing agent for the separation and preconcentration of Cd(II), Co(II), Ni(II), Cu(II) and Pb(II) on activated carbon. The metals were adsorbed on activated carbon by two methods: static (1) and dynamic (2). The optimal condition for separation and quantitative preconcentration of metal ions with activated carbon for the proposed methods was for (1) in the static methods in the pH range 7-9. The desorption was found quantitative with 8 mol dm−3 HNO3 for Cd(II) (92.6%), Co(II) (95.6%), Pb(II) (91.0%), and with 3 mol dm−3 HNO3 for Cd(II) (95.4%), Pb(II) (100.2%). The preconcentration factor was 100 with R.S.D. values between 1.0 and 2.9%. For (2), the dynamic method (SPE), the pH range for the quantitative sorption was 7-9. The desorption was found quantitative with 8 mol dm−3 HNO3 for Cd(II) (100.6%), Pb(II) (94.4%), and reasonably high recovery for Co(II) (83%), Cu(II) (88%). The optimum flow rate of metal ions solution for quantitative sorption of metals with 1,10-phenanthroline was 1-2 cm3 min−1 whereas for desorption it was 1 cm3 min−1. The preconcentration factor was 50 for all the ions of the metals with R.S.D. values between 2.9 and 9.8%.The samples of the activated carbon with the adsorbed trace metals can be determined by ICP-OES after mineralization by means of a high-pressure microwave mineralizer. The proposed method provides recovery for Cd (100.8%), Co (97.2%), Cu (94.6%), Ni (99.6%) and Pb (100.0%) with R.S.D. values between 1.2 and 3.2%.The preconcentration procedure showed a linear calibration curve within the concentration range 0.1-1.5 μg cm−3. The limits of detection values (defined as “blank + 3s” where s is standard deviation of the blank determination) are 5.8, 70.8, 6.7, 24.6, and 10.8 μg dm−3 for Cd(II), Pb(II), Co(II), Ni(II) and Cu(II), respectively, and corresponding limit of quantification (blank + 10s) values were 13.5, 151.3, 20.0, 58.9 and 33.2 μg dm−3, respectively.As a result, these simple methods were applied for the determination of the above-mentioned metals in reference materials and in samples of plant material. 相似文献
778.
The elucidation of structures of glutathione (GSH) complexes play an important role in the fundamental understanding of biochemical pathways of metal ion deactivation in plants. This article attempts to feature key studies for stoichiometry of metal complexes with glutathione and its constituent amino acids to obtain a better understanding of the different metal affinities of the complexation sites of glutathione. The SEC-ICP-MS experiments have indicated that oxidation process of glutathione was accelerated by metal ion presence in following order Cu+, Pb2+ and Cd2+. The redox activity of metal ions was confirmed by ESI-MS experiments, which allowed to observe formation of glutathione disulphide (GSSG) in time. The stoichiometry of Cd2+, Cu+ and Pb2+ complexes with GSH was defined by observing the isotope pattern of investigated metals and hydrogen loss or transfer during binding. The complexes with metal bound to sulphur of 1:1 and 1:2 stoichiometry were found in case of cadmium and lead. The number of hydrogen atoms lost during metal binding and the SEC-ESI-MS results allowed to elucidate that copper is bound by GSSG in ratio 1:1 and 1:2. Additionally, size exclusion chromatography coupled to electrospray MS allowed to differentiate more stable complexes from weak ones that could be created in the gas phase. 相似文献
779.
780.
HO. radical is an aggressive reagent to abstract hydrogen from diverse substitutes and lead them to degradation, however, in
reaction of active oxygen species with lignins, complex phenolic polymers, in dispersed lignocellulose such as pulp for environment-benign
delignification, HO. radicals should be eliminated as more as possible to prevent cellulose from unfavorably concomitant degradation. A reaction
system of O3 is constructed under UV laser flash irradiation, and HO. radicals are controlled efficiently by it. A new mechanism is proposed, for the first time, that O. radicals generated from reaction of O3 with UV laser flash irradiation might be the contributor to scavenge HO. radicals. 相似文献