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91.
The mass spectrum of o-picolinotoluidide gives rise to three major fragments at m/z 184, m/z 169 and m/z 168, corresponding to the loss of CO from the molecular ion followed by the loss of ?H2 and ?H3 by independent pathways. It has been shown that the ortho methyl group and the nitrogen of the pyridine ring in the 2-position are involved in the formation of these three major fragments observed in the mass spectrum of o-picolinotoluidide. The mass spectrum of 2-(o-toluidino) pyridine, the molecular ion of which can resemble the [M? CO]+ ion in o-picolinotoluidide, also shows loss of CH3 and NH2 radicals from the molecular ions. Based on these observations coupled with the high resolution data, the mass analysed ion kinetic energy spectrometry and high voltage scans of these fragments in both the compounds, two mechanistic pathways have been proposed for the formation of these ions in o-picolinotoluidide. 相似文献
92.
The kinetic results of the oxidation of aminoacids by N-bromoacetamide in acid and alkaline media are presented. It is noticed that the order with respect to substrate is dependent on the nature of the medium, 0.30 – 0.80 in perchloric acid (except phenylalanine in which case the order is 1.0) and alkaline media and zero order in aqueous acetic acid. Irrespective of the medium, the reaction is first order in [oxidant]. The rate of oxidation increases with [OH-] and decreases with [H+]. The changes observed in the direction of the pH-rate profile correspond to the ionization constants of the aminoacids. The reaction is inhibited by the addition of acetamide in perchloric acid medium but, is independent of it in alkaline medium. The rate of oxidation is susceptible to changes in the composition of acetic acid and is maximum at 25% aqueous acetic acid. The oxidation of aminoacids by N-bromoacetamide is also catalysed by carboxylate anions. The catalytic constants of propionate, butyrate, acetate, chloropropionate and chloroacetate are measured and Brønsted coefficients (β) so evaluated are in the range 0.38 – 0.46. The proposed mechanism and the derived rate laws are consistent with the observed kinetics. 相似文献
93.
In this paper, a novel strategy for multicomponent analysis of two classes of pesticides such as triazines (atrazine and simazine) and phenoxyalkanoic acids (2,4-dichlorophenoxy acetic acid (2,4-D), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 4-chlorophenoxyacetic acid (CPOAc), phenoxyacetic acid (POAc)) employing immuno-arrays is demonstrated. The approach is based on cross-reactive arrays of specific antibody pairs coupled to chemometric pattern recognition. The monoclonal antibody pairs employed in this work (atrazine-simazine and 2,4-D) are specific towards a set of analytes and preclude a particular set of others present in the sample matrix. Antibody pairs of atrazine, simazine, and 2,4-D are used to discriminate and quantify analyte of interest. Atrazine was quantified in presence of trace concentration of simazine and that of 2,4-D. The combinatorial cross-reactivity of antibody pairs towards simazine, atrazine and 2,4-D is used to distinguish among different classes of analytes and their influence on the signal suppression in immuno-techniques. These sensors exclude recognition by carbamates such as carbaryl and carbofuran. 相似文献
94.
Kinetics of the reactions of propyl, propargyl and allyl bromides with anilines has been studied in methanol and dipolardmf. All reactions were found to be of second order. The values of the Bronsted slope (0–4) suggested that bond formation occurs
to a considerable extent in the transition state. Electron-donating substituents increased the rate, while electron-withdrawing
groups decreased the rate. The magnitudes of the negative values (≈1) indicate that the reaction rate depends on the availability
of electron-density on the nitrogen atom, which implies bond formation, suggesting that all the reactions are SN2 in nature, forming a loose transition state. Isokinetic temperature values calculated from the three methods for the reaction
of allyl bromide-anilines suggested that the reaction series indmf is entropy controlled while in a methanol medium hydrogen bonding is responsible for the solute-solvent interactions. 相似文献
95.
96.
In cation interactions with some organics: ab initio molecular orbital and density functional theory
Ab initio molecular orbital and density functional theory studies were undertaken to investigate the structural and energetic characteristics of complexes of In+ with several different organic molecules for the first time. HF, MP2, QCISD, and CCD levels of theory in ab initio MO as well as B3LYP, B3PW91 hybrid functionals in density functional theory were used. A valence TZ+P basis set with relativistic effective core potentials was used for the In atom while the 6-311++G(3d, 2p) basis set was utilized for all other atoms. Both closed-shell (H2O, CH4, CH3OH, and C6H6) and open-shell (CH3 and C2H3) molecules were considered for complexation with In+. In+ affinities of 21.5, 24.8, 28.6, 18.4, and 23.0 kcal/mol were obtained with the B3PW91 hybrid functional for H2O, CH3OH, C6H6, CH3, and C2H3, respectively. The large values for the calculated affinities indicate the validity of our recent experimental detection of In+ ion attachment to some organic molecules. 相似文献
97.
Sabir H. Mashraqui Tabrez Khan Subramanian Sundaram Shailesh Ghadigaonkar 《Tetrahedron letters》2008,49(23):3739-3743
Phenothiazine-pyridyl chalcone, a new internal charge transfer (ICT) probe, has been designed that allows naked eye detection and a reversible, ratiometric ‘on-off’ sensing capability for biologically and environmentally significant Cu2+ in CH3OH-H2O (4:1 v/v) under buffered conditions. The association constants determined using spectrophotometric and the fluorimetric techniques follow the order Cu2+ > Ni2+ > Co2+ > Zn2+ > Cd2+ > Mg2+ ≈ Ba2+ ≈ Ca2+ ≈ K+≈ Na+ ≈ Li+. 相似文献
98.
The method of DeFord and Hume for the study of complexes by polarography has been extended to the study of mixed complexes of copper-glycine-α-alanine and cadmium-ammonia-pyridine. 相似文献
99.
Solvent extraction of indium from malonic acid medium by Primene JM-T has been studied. The extraction has been studied as a function of pH and concentrations of malonic acid and sodium malonate. The nature of the acid-amine complex has been established by chemical analysis and by the application of the method of Hogfeldt and Fredlund. The equilibrium constant for the reaction has also been calculated. The nature of the indium complexes getting extracted has also been discussed. 相似文献
100.