Kinetics and mechanism of gas‐phase pyrolysis of N‐aryl‐3‐oxobutanamide ketoanilides,their 2‐arylhydrazono derivatives,and related compounds

Rates and products of reaction and Arrhenius activation parameters were determined for the gas‐phase thermolysis of 14 substrates of the title compounds using sealed pyrex reactor tubes and HPLC/UV‐VIS to monitor substrate pyrolysis. The 14 compounds under study are N‐phenyl‐3‐oxo‐ ( 1 ), N‐(p‐chlorophenyl)‐3‐oxo‐ ( 2 ), N‐(p‐methylphenyl)‐3‐oxo‐ ( 3 ), and N‐(p‐methoxyphenyl)‐3‐oxobutanamide ( 4 ), in addition to (i) four substrates ( 5–8 ) obtained by the replacement of the pairs of methylene hydrogens at the 2‐position of compounds ( 1–4 ), each pair by a phenylhydrazono group; (ii) three arylhydrazono derivatives ( 9–11 ) in which Cl, CH₃, or OCH₃ groups are substituted at the para position of the phenylhydrazono moiety of compound 5 ; (iii) 3‐oxobutanamide (acetoacetamide, 12 ), N‐phenyl‐3‐oxo‐3‐phenylpropanamide ( 13 ), and N,N′‐diphenylpropanediamide ( 14 ). The reactions were conducted over 374–546 K temperature range, and the values of the Arrhenius log A(s^?1) and E_a(kJ mol^?1) of these reactions were, respectively, 12.0 ± 2.0 and 119.2 ± 17.0 for the ketoanilides ( 1–4, 12–14 ), and 13.0 ± 0.7 and 157.5 ± 8.6 for the arylhyrazono compounds ( 5–11 ). Kinetically, the arylhydrazono derivatives were found to be ca. 1.4 × 10³ to 5.7 × 10³ times less reactive than the parent ketoanilides. A mechanism is proposed to account for reaction products and to rationalize molecular reactivities. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 82–91, 2007     

Nucleon currents between highly excited nuclei: (II). Influence of the relative motion

A finite-temperature Thomas-Fermi method has been used to study the nucleon flux between two hot semi-infinite slabs of nuclear matter in arbitrary relative motion. As an application, we estimate the imaginary part of the optical potential associated with nucléon transfer at the strong absorption radius. Analytical fits to the exact results are given for head-on and tangential collisions at zero temperature.     

The complexometric determination of Ca based on the concentration-dependent distribution using90Sr and a cation exchanger

The method described enables the determination of about 8·10^?5 Ca which compares favourably with published data obtained by other radiometric methods. In 3 ml solution 0.1 mg of Ca can be determined with a precision of ±1.5%. Iron does not interfere in moderate concentrations. The method can also be used for the determination of water hardness in the case of very low hardness values or in turbid or coloured solutions.     

KLL Auger and x-ray photoelectron spectra of phosphine,some phosphorus halides and the other hydrides isoelectronic with argon

KL₂L₃(¹D₂) Auger and 1s photoelectron energies have been measured for molecular hydrides isoelectronic with Argon (HCl, H₂S, PH₃ and SiH₄). In addition a detailed comparison of Auger and photoelectron shifts in a series of phosphorus halides (vs phosphine) has been undertaken using additional P_2p binding energies. The potential model is better able to predict 1s binding energy shifts with either ground state or relaxation corrected models than the 2p shifts. These latter values seem also to be reduced by shielding effects. In general, fluorides are better predicted than chlorides. Auger shifts correlate linearly(but not in a 1:1 relationship) with 1s photoelectron shifts throughout the isoelectronic series and also in the case of the phosphorus fluorides and phosphine. The two potential models, however, provide poor prediction of Auger shifts.     

Heavy-ion optical potentials at finite temperature calculated using a complex effective interaction derived from a realistic force

Hot density distributions of heavy ions generated by a modified Thomas-Fermi calculation at finite temperature are used to calculate the optical potential using the double-folding method and a complex effective energy and density-dependent interaction deduced from a realistic NN (Reid soft-core) force in nuclear matter. The real and the imaginary part of the optical potential become more attractive when the temperature increases.     

Phytochemical study and cytotoxicity evaluation of Colchicum stevenii Kunth (Colchicaceae): a Jordanian meadow saffron

Isolation, characterization, and biological evaluation of active components of Colchicum stevenii Kunth (Colchicaceae) are described. Colchicum stevenii is an unexplored Jordanian specie with toxic reputation. Directed by brine shrimp lethality test (BST), methanolic extraction, liquid-liquid partition, preparative TLC, and semi-preparative HPLC, it resulted in the isolation of six cytotoxic compounds. The compounds, reported for the first time from this specie, are: (-)-colchicine (1), 2-demethyl-(-)-colchicine (2), (-)-cornigerine (3), beta-lumicolchicine (4), (-)-isoandrocymbine (5) and (-)-O-methylandrocymbine (6). A new, in-house developed, acidic-based reverse-phase gradient semi-preparative HPLC method for the separation of colchisides is presented here. Structural elucidation was based on spectroscopic techniques principally; 1H-NMR and low resolution EIMS. Based on BST results, reported as LC50 values in microg mL(-1) (ppm) with 95% confidence intervals, (-)-colchicine (2.5 ppm) and (-)-cornigerine (2.7 ppm) were the most potent.     

A chemiluminescence method for the detection of electrochemically generated H2O2 and ferryl porphyrin

Electrochemical formation of H2O2 and the subsequent ferryl porphyrin were examined by measuring luminol chemiluminescence and absorption spectrum using flow-injection method. Emission was observed under the cathodic potential (0.05 V at pH 2.0 and -0.3 V at pH 11.0) by the electrochemical reduction of buffer electrolytes solution but no emission was observed at anodic potentials. Fe(III)TMPyP solution was added at the down stream of the working electrode and was essential for the emission. Removal of dissolved O2 resulted in the decrease of emission intensity by more than 70%. In order to examine the lifetime of reduced active species, delay tubes were used in between working electrode and Fe(III)TMPyP inlet. Experimental results suggested the active species were stable for quite long. The emission was quenched considerably (>90%) when hydroperoxy catalase was added at the down stream of the working electrode whereas SOD had little effect. Significant inhibition of the emission by the addition of alkene at the down stream of the Fe(III)TMPyP inlet was considered as evidence of oxo-ferryl formation. The spectra at reduction potential under aerated condition were shifted to the longer wavelength (>430 nm) compared to the original spectrum of Fe(III)TMPyP (422 nm). All the spectra were perfectly reproduced by a combination of Fe(III)TMPyP and O=Fe(IV)TMPyP (438 nm) spectra. These observations lead to the conclusion that H2O2 was produced first by electrochemical reduction of O2, which then converted Fe(III)TMPyP into O=Fe(IV)TMPyP to activate luminol. The current efficiencies for the formation of H2O2 were estimated as about 30-65% in all over the pH.     

Transition-metal complexes of boron-new insights and novel coordination modes

Since the publication of the last review in 1998, the transition-metal chemistry of boron has continued to raise unceasing interest. Boryl complexes, representing the most extensive subclass, have remained a focus of intense research, particularly for their implication in the metal-mediated functionalization of organic substrates. Absolute novelties such as borane complexes and terminal borylene complexes have been structurally authenticated. Upon further elaboration of these compounds, the known coordination modes of boron-based ligands have grown considerably. Combined structural and theoretical investigations have contributed to elucidate the fundamental electronic characteristics of the transition-metal-boron bond and are leading to applications of these compounds. The most useful synthetic strategies for the generation of transition-metal-boron bonds are highlighted here, and the most recent and intriguing compounds that have been reported are outlined and discussed.