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81.
Kinetic and thermodynamic aspects of the axial base dissociation of solid Co(salen) (X-py) complexes, X = H (1), 3-Me (2), 4-Me (3), 3,4-Me2 (4), 3,5-Me2 (5), 3-NH2 (6), 3-Cl (7), 3-CN (8), 4-CN (9), have been investigated by means of TG-DSC and isothermal weight-loss measurements. These adducts endothermically dissociate the axial base giving rise to the oxygen-active Co(salen) complex. The axial base dissociation reactions fit the contracting disc equation and the kinetic compensation effect is observed for all the adducts excepting Adducts 4–6. For the remaining adducts the kinetic and thermodynamic stabilities of the Co-(X-py) bond are found to increase linearly with increasing Hammett's substitution constants of X except for Adducts 3 and 9. These results are discussed in terms of the σ and π interactions between cobalt(II) and substituted pyridine. Factors dominating the kinetic bond stability are briefly discussed.  相似文献   
82.
Kapurimycin A3 (kap A3, 1 ), an antitumour antibiotic, alkylates N7 of guanine2 (G2) and G4 of d(C1G2C3G4)2 to produce their covalent adducts 2 (64 %) and 3 (7.0 %), respectively. Heating at 90 °C for 5 min degraded both adducts to kap A3 - G adduct (5) with the concurrent release of their respective abasic-site containing oligomers 4 and 6.  相似文献   
83.
A novel lignan: sphaerophyside SC was isolated from ethanolic extract of the seeds of Sphaerophysa salsula (Pall.) DC. The structure of the compound was elucidated mainly on the basis of the 1D NMR and 2D NMR data.  相似文献   
84.
New proton exchange membranes (PEMs) were prepared by pre-irradiation induced grafting of α-methylstyrene (AMS)/styrene (STY)/divinylbenzene (DVB) into the crosslinked polytetrafluoroethylene (RX-PTFE) films and successively sulfonated. The new PEMs showed the improved glass transition temperature and chemical stability as compared with the PEMs prepared by pre-irradiation induced grafting of STY/DVB. The balance of the cost, grafting kinetic, thermal properties and the properties of the resulted proton exchange membrane is the key point of this work.  相似文献   
85.
The mechanisms of nitrosation of acetone through sodium enolate [CH3CO1CH2]-Na+ (1) or naked enolate [CH3CO1CH2]- (2) with methyl nitrite CH3O3NO2 (3), and the reactivity of the syn-form of 3 (syn-3) during the C-N bond formation process were investigated using ab initio molecular orbital (MO) methods. Our results have demonstrated the predominant formation of E-1-hydroxyimino-2-oxo-propane CH3COCH=NOH (4E) when the complex [CH3CO1CH2NO2(O3CH3)]-Na+ was produced kinetically via a metal-chelated pericyclic transition state (TS(CHELATED)), in which the O3 atom of syn-3 was coordinated to the Na+ atom of 1.  相似文献   
86.
A catalytic immuno-reactor for the determination of human serum albumin (HSA) was constructed by using immobilized antibody and an amperometric detector. A sandwich assay with hemin-labeled antibody to catalyze the decomposition of hydrogen peroxide was used, the catalytic activity of the hemin-antibody conjugate being determined by measuring the decrease in hydrogen peroxide concentration. The reaction of hemin-labeled antibody with antigen was complete within 30 min and the current decrease was correlated with the HSA concentration. The relative standard deviation was about 9% at an HSA concentration of 1 mg ml?1.  相似文献   
87.
88.
Zero field positive muon spin rotation method ( +SR) is applied on La2–x Sr x CuO4 around forx=0.12 at which the high-T c superconductivity (SC) is suppressed. The magnetically ordered state of Cu-moments, which is not a spin glass state but an antiferromagnetic like state, appears below 15 K for 0.105x0.120. The magnetic phase boundary is very similar to the one of the La2–x Ba x CuO4 in which the structural transition from the low temperature orthorhombic (LTO) phase to the low temperature tetragonal (LTT) phase is observed aroundx=0.12. The present study suggests that there is no big difference of the electronic state of the CuO2 plane between the La-Ba system and the La-Sr system and that the magnetic ordering of Cu-moments plays an important role for the suppression of the high-T c SC aroundx=0.12 in both of the systems, although the LTO-LTT structural transition has not been observed yet in the La-Sr system.  相似文献   
89.
90.
The site diluted finite spin cluster system Rb2CO x Mg1–x F4 (x=0.15, 0.4, 0.5) has been investigated by the +SR technique. Muon spin relaxation was observed in these diluted magnetic systems in a weak longitudinal field of 100 G. By reducing temperature below 100 K, the experimental data show features of slowing down phenomena of the Co electron moments in the finite spin clusters.  相似文献   
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