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991.
A. B. Deshpande S. M. Kale S. L. Kapur 《Journal of polymer science. Part A, Polymer chemistry》1973,11(6):1307-1315
Polymerization of methyl methacrylate has been studied with the chromium acetylacetonate–triisobutyl aluminum catalyst system in benzene medium at 40°C. These studies have been carried out at an Al/Cr ratio of 12 to compare the behavior with the previously studied chromium acetyl acetonate–triethyl aluminum catalyst system. The enhanced yield and gelling of polymer suggests a free-radical mechanism of polymerization. Further, the kinetics of polymerization and the heterotactic structure of polymer as determined by NMR examination have led to confirmation of the freeradical mechanism of polymerization of methyl methacrylate by an excess of triisobutylaluminum in the presence of catalyst complex. 相似文献
992.
M S Patterson S J Madsen B C Wilson 《Journal of photochemistry and photobiology. B, Biology》1990,5(1):69-84
Singlet oxygen (1O2) is thought to be the cytotoxic agent in photodynamic therapy (PDT) with current photosensitizers. Direct monitoring of 1O2 concentration in vivo would be a valuable tool in studying biological response. Attempts were made to measure 1O2 IR luminescence during PDT of cell suspensions and two murine tumour models using the photosensitizers Photofrin II and aluminium chlorosulphonated phthalocyanine. Instrumentation was virtually identical to that devised by Parker in the one positive report of in vivo luminescence detection in the literature. Despite the fact that our treatments caused cell killing and tissue necrosis, we were unable to observe 1O2 emission under any conditions. We attribute this negative result to a reduction in 1O2 lifetime in the cellular environment. Quantitative calibration of our system allowed us to estimate that the singlet oxygen lifetime in tissue is less than 0.5 microsecond. Some technical improvements are suggested which would improve detector performance and perhaps make such measurements feasible. 相似文献
993.
B. Laszkiewicz 《Journal of Thermal Analysis and Calorimetry》1985,30(4):889-894
The thermal properties of chitin ammonosphosphate complexes with methanol are discussed. The endothermic effect of chitin ammonophosphate decomposition is dependent on the substitution degree. The chitin ammonophosphates have a lower ability to form complexes with methanol than chitin itself. The bonding energy of methanol with chitin ammonophosphates is dependent on the substitution degree of the ammonophosphate group. As the substitution degree increases, the quantity of methanol bonded to the chitin ammonophosphate decreases, as does the bonding energy of the methanol; this is manifested in a lower endothermic effect and a lower temperature of the maximum of this effect. 相似文献
994.
2-Deoxy-2-[18F]fluoro-D-glucose ([18F] FDG), the most popular positron emitting radiopharmaceutical, may oxidise by autoradiolysis in aqueous solution. The aim of this work was to use LC-MS for determination of the oxidation products of fluorodeoxyglucose and glucose (Glc) obtained by oxidation with Fenton's reagent. Asahipak NH2P-50 polyamide silica column and acetonitrile-0.025% aqueous ammonium formate (80:20 (v/v)) eluent were utilised with an Agilent 1100 HPLC-MS instrument. Ten major oxidation products of FDG and Glc were separated and identified by mass spectrometry: 2-fluorogluconic acid, 2-fluoroglucuronic acid, 2-oxoerythronic acid, arabinose, arabonic acid, araburonic acid, erythrose, erythrulose, gluconic acid, and glucuronic acid. The most intensive electrospray ionisation signals were found in the negative ion spectra and were due to HCOO- adducts, the other acids being in their lactone forms. 相似文献
995.
[reaction: see text] A simple and efficient method for the synthesis of unsymmetrical diaryl sulfones using the palladium-catalyzed coupling of aryl boronic acids and arylsulfonyl chlorides has been developed. High product yields, a short reaction time, and mild reaction conditions are important features of this method. 相似文献
996.
Svyatoslav V. Katyurin Oleg B. Glinkin 《International journal of quantum chemistry》1992,43(2):251-258
A quantum chemical study of the two low-lying quartet states of seven model compound I iron–porphyrin complexes with varying axial ligands has been carried out using the INDO method. The varying axial ligands included in this study are five that are models for those in the intact enzymes: imidazole and imidazolate (model peroxidase HRP and CCP), CH3CONH2 (Gln175 mutant of CCP), PhO?1 (catalase), CH3S?1 (P450), and two that have been used in biomimetics of these enzymes: Cl?1 (hemin) and PhS?1 (model P450s). The purpose of these studies was to determine the role of the axial ligands in determining (i) the relative energies of the two nearly degenerate quartet electronic states of compound I, involved either as an a1u or a2u porphyrin π cation radical and (ii) the electron and spin distributions in the a1u and a2u radical cations of compound I. For most of the model complexes, including both HRP-I and CAT-I, a moderate effect of the axial ligand on the relative energy of these two states was observed and the a1u radical cation was found to be the ground state. The energy order of these two radical cations, however, was reversed in the P450-I model complexes, indicating an association of the unique property of the Fe?O bond breaking with an a2u radical cation. The symmetry-allowed overlap between the Fe?O and 3a2u orbitals may lower the activation energy for the Fe?O bond cleavage in P450-I. However, the calculated electronic and spin properties, including the unpaired spin and net charge on the oxygen and the Fe?O bond overlap density, important determinants of the reactivity of this complex in the ligand–Fe?O region, are very similar for all complexes and in both cation states. © 1992 John Wiley & Sons, Inc. 相似文献
997.
The reaction of Cp'ReCl(2)S(3) (Cp' = Me(4)EtC(5)) with slightly less than 2 equiv of a phosphine reagent results in the formation of [Cp'Re(Cl)(2)(mu-S)](2), 2, which has been characterized by an X-ray diffraction study. Reactions of 2 with nucleophiles did not lead to monomeric derivatives of the type Cp'ReS(Cl)(2)(Nuc). The reaction of Cp'ReCl(2)(SC(2)H(4)S) with (Me(3)Si)(2)S resulted in the formation of three new products: Cp'ReS(SC(2)H(4)S), 4; Cp'Re(S(3))(SC(2)H(4)S), 5; and a tetranuclear derivative, [(Cp'Re)(2)(mu-S)(mu,eta(2)-SC(2)H(4)S)(mu,eta(1)-SC(2)H(4)S](2)Cl(2), 6. Complexes 4 and 6 have been characterized by X-ray diffraction studies. The electrochemical properties of the mononuclear Re=S derivative, 4, are compared with those of Re=O and Re=NR analogues. 相似文献
998.
Kanney JA Noll BC Rakowski DuBois M 《Journal of the American Chemical Society》2002,124(33):9878-9886
The thermal reactions of the Re(V) dithiolate complex Cp'ReCl2(SCH2CH2S), 1 (where Cp' = EtMe4C5), and related derivatives have been studied. When 1 is heated in toluene in a sealed evacuated tube at 100 degrees C, a dehydrogenation reaction occurs to form a new rhenium complex with a dithiolene ligand, Cp'ReCl2(SCHCHS), 6, in ca. 40% yield. The structure of 6 has been confirmed by an X-ray diffraction study. Under the thermal conditions studied, 1 also undergoes an olefin extrusion reaction. Free ethene is detected in the NMR spectrum of the products, and insoluble rhenium products are also formed. When 1 is reacted with excess ethene under mild conditions, a new organic product, 1,4-dithiane, is formed. Complex 1 is also found to react with oxidants, such as O2 and S8, under mild conditions to form the dehydrogenation product 6. Kinetic studies of the thermal reaction of 1 and related derivatives have been completed, and possible mechanisms for the thermally induced dehydrogenation reaction are discussed. 相似文献
999.
Determination of four nitroimidazole residues in poultry meat by liquid chromatography-mass spectrometry 总被引:8,自引:0,他引:8
A multi-residue liquid chromatography-mass spectrometry (LC-MS) assay method is described for the determination of four nitroimidazoles in poultry muscle. The extraction procedure is based on liquid-liquid extraction with ethyl acetate followed by an evaporation step. A deuterated internal standard is used. The LC separation was made on a C18 bonded silica column with an aqueous formic acid (0.2%) solution-methanol-acetonitrile (81:13:6) mobile phase. Following electrospray ionization, the protonated molecular ion [M+H]+ is obtained for each compound. Monitoring several ions for each nitroimidazole provides the specificity required for confirmatory assay. Validation of the method was performed to estimate linearity, intra-day and inter-day repeatability, accuracy and detection limit. The present method is capable of identifying nitroimidazole residues in muscle at levels below 5 microg/kg. 相似文献
1000.
O. B. Mokhodoeva G. V. Myasoedova I. V. Kubrakova 《Journal of Analytical Chemistry》2007,62(7):607-622
Combined methods for the determination of noble metals with the use of sorption preconcentration with complexing, anion-exchange, and other sorbents are reviewed. Characteristics of sorbents, techniques of sorption preconcentration, and techniques for the preparation of a concentrate for determination are considered. Features of instrumental methods for the determination of noble metals in the analysis of different materials are discussed. Examples of the use of sorption preconcentration in combined methods for the determination of noble metals are given from publications between 1996–2005. 相似文献