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1.
2.
The π? pe + e ? n and π+ ne + e ? p reaction cross sections are calculated below and in the vicinity of the vector-meson (?0,ω) production threshold. These processes are largely responsible for the emission of e +e? pairs in pion-nucleus reactions and contribute to the dilepton spectra observed in relativistic heavy ion collisions. They are dominated by the decay of low-lying baryon resonances into vector-meson-nucleon channels. The vector mesons materialize subsequently into e + e? pairs. Using πN→?0 N and πN→ωN, amplitudes calculated in the center of mass energy interval 1.4 < √s<1.8 GeV, we compute the π? pe + e ? n and π+ ne + e ? p reaction cross sections in these kinematics. Below the vector-meson production threshold, the π0?ω interference in the e + e? channel appears largely destructive for the π? pe + e ? n cross section and constructive for the π+ ne + e ? p cross section. The pion beam and the HADES detector at GSI offer a unique possibility to measure these effects. Such data would provide strong constraints on the coupling of vector-meson-nucleon channels to low-lying baryon resonances.  相似文献   
3.
Human glutathione (GSH) transferase (hGSTP1-1) processes with similar kinetic efficiencies the antitumor agents 2-crotonyloxymethyl-2-cyclohexenone (COMC-6), 2-crotonyloxymethyl-2-cycloheptenone (COMC-7), and 2-crotonyloxymethyl-2-cyclopentenone (COMC-5) to 2-glutathionylmethyl-2-cyclohexenone, 2-glutathionylmethyl-3-glutathionyl-2-cycloheptenone, and 2-glutathionylmethyl-2-cyclopentenone, respectively. This process likely involves initial enzyme-catalyzed Michael addition of GSH to the COMC derivative to give a glutathionylated enol(ate), which undergoes nonstereospecific ketonization, either while bound to the active site or free in solution, to a glutathionylated exocyclic enone. Free in solution, GSH reacts at the exomethylene carbon of the exocyclic enone, displacing the first GSH to give the final product. This mechanism is supported by the observation of multiphasic kinetics in the presence of high concentrations of hGSTP1-1 and the ability to trap kinetically competent exocyclic enones in aqueous acid using COMC-6 and COMC-7 as substrates. That the exocyclic enone is formed by nonstereospecific ketonization of an enol(ate) species is indicated by the observation that COMC-6 (chirally labeled with deuterium at the exomethylene carbon) gives stereorandomly labeled exocyclic enone. The isozymes hGSTP1-1, hGSTA1-1, hGSTA4-4, and hGSTM2-2 catalyze the conversion of COMC-6 to final product with similar efficiencies (K(m) = 0.08-0.34 mM, k(cat) = 1.5-6.1 s(-)(1)); no activity was detected with the rat rGSTT2-2 isozyme. Molecular docking studies indicate that in hGSTP1-1, the hydroxyl group of Tyr108 might serve as a general acid catalyst during substrate turnover. The possible significance of these observations with respect to the metabolism of COMC derivatives in multidrug resistant tumors is discussed.  相似文献   
4.
Ozonization reaction of ethene in neat film at 77 K was performed. Separation of ethene secondary ozonide from the other products of the reaction was performed by continuous pumping of the reactor. Only the products, which evaporated from the walls of the reactor at 185 K, were transferred to the gas cell. The high-resolution infrared absorption spectrum of gaseous ethene secondary ozonide (C(2)H(4)O(3)) in a static gas long-path absorption cell has been recorded in the 900-1100 cm(-1) spectral region at 185 K. The spectral resolution was 0.003 cm(-1). Analyses of the nu(7)(A) band at 1037.0 cm(-1), the nu(8)(A) band at 956.1 cm(-1), and the nu(18)(B) band at 1082.1 cm(-1) have been performed using the Watson Hamiltonian model (A, reduction; III(r), representation). A set of ground-state rotational and quartic centrifugal distortion constants have been obtained, and upper state spectroscopic constants have been determined for the bands investigated. A local resonance observed in nu(18) is explained as c-Coriolis interaction with nu(10) + nu(11).  相似文献   
5.
The conformations and dynamic processes in two bicyclophanes have been analysed on the basis of temperature-dependent 1H NMR spectra. Both bicyclophanes are suggested to have a lowest-energy conformation of D3 symmetry in which the substituents at all ethylene bridges are gauche+ (or gauche?) oriented. The interconversion of the mirror image conformers of each bicyclophane equilibrates the two hydrogens in each methylene group, the barriers being ca 36 and 37 kJ mol?1, respectively, as determined by line-shape analysis.  相似文献   
6.
Anionic polymerization of vinyl chloride has been studied. Of the organometallic compounds tested as initiators, only butyllithium was found to initiate polymerization. Polymerization in bulk at 0°C and with tert-butyllithium as initiator gave poly(vinyl chloride) in a yield of 38% with M n = 55,000. Tacticity of the anionic PVC was similar to that of conventional PVC prepared at similar temperatures. Anionic PVC was found to be less branched and more heat-stable than the conventional polymer.  相似文献   
7.
Detergent sequestration using micelles as a hydrophobic sink for dissociated drug molecules is an established technique for determination of dissociation rates. The anionic surfactant molecules are generally assumed not to interact with the anionic DNA and thereby not to affect the rate of dissociation. By contrast, we here demonstrate that the surfactant molecules sodium dodecyl sulfate (SDS), sodium decyl sulfate, and sodium octyl sulfate all induce substantial rate enhancements of the dissociation of intercalators from DNA. Four different cationic DNA intercalators are studied with respect to surfactant-induced dissociation. Except for the smallest intercalator, ethidium, the dissociation rate constants increase monotonically with surfactant concentration both below cmc and (more strongly) above cmc, much more than expected from electrostatic effects of increased counterion concentration. The rate enhancement, most pronounced for the bulky, multicationic, hydrophobic DNA ligands in this study, indicates a reduction of the activation energy for the ligand to pass out from a deeply penetrating intercalation site of DNA. The discovery that surfactants enhance the rate of dissociation of cationic DNA-intercalators implies that rate constants previously determined by micelle-sequestered dissociation may have been overestimated. As an alternative, more reliable method, we suggest instead the addition of excess of dummy DNA as an absorbent for dissociated ligand.  相似文献   
8.
Tetracyanoethylene (TCNE) reacts with indolizines ( 1a-c ) to give mixtures of 1- and 3-sub-stituted tricyanovinylindolizines, respectively. The isomers are identified by nmr spectroscopy. The occurrence of intramolecular charge-transfer bands in the visible spectra is discussed.  相似文献   
9.
A new mechanism has been proposed for the photooxidation of polystyrene as film and in benzene. The initial stage of the photooxidative degradation may involve reactions of singlet oxygen with polystyrene molecules. Singlet oxygen may be formed in the reaction between excited benzene ring in polystyrene molecule and molecular oxygen. The addition of singlet oxygen quenchers such as 1,3-cyclohexadiene or β-carotene reduces the rate of polymer degradation in benzene solution. The mechanisms of the photolysis of polystyrene as film and in benzene solution, in vacuo and in the presence of oxygen, are discussed and interpretations proposed. The pronounced yellowing of polystyrene during the photooxidation process is interpreted as a reaction involving benzene ring-opening photooxidation in polystyrene molecule. These results were obtained by comparing ultraviolet and infrared spectra in experiments of photooxidation of pure liquid benzene and polystyrene film.  相似文献   
10.
Photoinitiated radical carbonylation with [(11)C]carbon monoxide at low concentration was employed in syntheses of carbonyl-(11)C-labeled amides using alkyl iodides and amines as precursors. Eleven (11)C-amides were synthesized in up to 74% decay-corrected radiochemical yields with reaction times of 400 s and with up to 95% conversion of carbon monoxide. Starting with 26.3 GBq of [(11)C]carbon monoxide, 10.6 GBq of 1-cyclohexane [(11)C]carbonyl-4-phenyl-piperazine (15) was obtained within 35 min from the end of bombardment (33 microA) and with a specific radioactivity of 192 GBq/micromol at the same time point. The influence of solvents was investigated. The described procedure extends the range of accessible labeling methods. The method may also be useful for preparation of (13)C- and (14)C-substituted compounds.  相似文献   
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