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71.
Metastable ion peak shapes, dimensions and relative abundances have been measured for the three fragmentations [C3H6]+· → [C3H4]+· + H2, [C3H6]+· → [C3H5]+ + H· and [C3H6]+· → [C3H3]+ + H2 + H·. [C3H6]+· ions were derived from propene, cyclopropane, tetrahydrofuran, cyclohexanone, 2-methyl but-1-ene and cis-pent-2-ene. Activation energies for these fragmentations have been evaluated. Three daughter ion dissociations ([C3H5]+ → [C3H3]+ + H2, [C3H5]+ → [C3H4]+· + H· and [C3H4]+· → [C3H3]+ + H·) have been similarly examined. Ion structures have been determined and the metastable energy releases have been correlated with the thermochemical data. It is concluded that the molecular ions of propene and cyclopropane become structurally indistinguishable prior to fragmentation and that differences in their metastable ion characteristics can be ascribed wholly to internal energy differences; the latter can be correlated with the photoelectron spectra of the isomers. The pathway for the consecutive fragmentation which generates the metastable ion peak (m/e 42 → m/e.39) has been shown to be It is likewise concluded that fragmentating [C3H6]+· ions generated from the various precursor molecules are also structurally indistinguishable and cannot be classified with either molecular ion of the isomeric C3H6 hydrocarbons. 相似文献
72.
PRIMARY DNA DAMAGE, HPRT MUTATION AND CELL INACTIVATION PHOTOINDUCED WITH VARIOUS SENSITIZERS IN V79 CELLS 总被引:1,自引:0,他引:1
Barbara B. Noodt Egil Kvam Harald B. Steen Johan Moan 《Photochemistry and photobiology》1993,58(4):541-547
DNA strand breaks and hypoxanthine guanine phosphoribosyl transferase (HPRT) mutants were measured in parallel in photochemically treated (PCT) cells and compared at the same level of cell survival. Chinese hamster fibroblasts (V79 cells) were either incubated with the lipophilic dyes tetra(3—hydroxyphenyl)porphyrin (3THPP) and Photofrin II (PII), the anionic dye meso -tetra(4—sulfonatophenyl)porphine (TPPS4 ) or the cationic dye meso -tetra( N -methyl-4-pyridyl)porphine ( p -TMPyPH2 before light exposure. In the cells, the lipophilic dyes were localized in membranes, including the nuclear membrane, while the hydrophilic dyes were taken up primarily into spots in the cytoplasm. In addition, the hydrophilic TPPS4 was distributed homogeneously throughout the whole cytoplasm and nucleoplasm. According to the HPRT mutation test, the mutagenicity of light doses survived by 10% of the cells was a factor of six higher in the presence of 3THPP than of PII, whereas for X-rays it was a factor of three higher than for PCT with 3THPP. Light exposure in the presence of the hydrophilic dyes TPPS4 and p -TMPyPH2 was not significantly mutagenic. There was no correlation between the induced rates of HPRT mutants and of DNA strand breaks. Thus, TPPS4 was the most efficient sensitizer with regard to DNA strand breaks when compared at the same level of cell survival, followed by 3THPP, PII and p -TMPyPH2 . Hence, the rate of DNA strand breaks cannot be used to predict the mutagenicity of PCT. 相似文献
73.
?ystein?BrandalEmail author Ann-Mari?Dahl?Hanneseth Johan?Sj?blom 《Colloid and polymer science》2005,284(2):124-133
Interactions between naphthenic acids and divalent metal cations across model oil–alkaline water interfaces were investigated by correlating changes in dynamic interfacial tension (IFT), to plausible reaction mechanisms. The measurements were carried out by using a CAM 200 optical instrument, which is based on the pendant drop technique. The naphthenic acids used were synthesised model compounds as well as commercial acid mixtures from crude distillation and extracted acid fractions from a North Sea crude oil. The divalent cations involved Ca2+, Mg2+, Sr2+, and Ba2+, which are all common in co-produced formation water and naphthenate deposits. The results show that the dynamic IFT strongly depends on naphthenic acid structure, type of divalent cation, and the concentration of the compounds as well as the pH of the aqueous phase. Introducing divalent cations to systems involving saturated naphthenic acids caused mostly a permanent lowering of the IFT. The decline in IFT is due to electrostatic attraction forces across the interface between the cations in the aqueous phase and the carboxylic-groups at the o/w interface, which cause a higher interfacial density of naphthenic acid monomers. The permanent lowering in IFT is likely due to formation of positively charged monoacid complexes, which possess high interfacial activity. On the other hand, in the case of the aromatic model compounds, the cations affected the IFT differently. This is mainly discussed in light of degree of cation hydration and steric conditions. Various oil-soluble non-ionic surfactant mixtures were also introduced to systems involving a model naphthenic acid and Ca2+ in order to investigate how the interfacial competition affected the local interactions. Based on the behaviour of dynamic IFT, probable inhibition mechanisms are discussed.Electronic Supplementary Material Supplementary material is available for this article at 相似文献
74.
A modification of a variation principle due to Delves, is derived which permits the direct calculation of energy differences between states of two different Hamiltonians: [Δ ??] = 〈X0| ??x – Wx|X1〉 – 〈Y0|??y – Wy|y1〉 + 〈X0| Δ ??|Y0〉 · 〈X0| Y0〉?1. Δ ?? = ??y – ??x, |X0〉 and |Y0〉 are the wave functions for the X and Y states and |X1〉 and |Y1〉 are functions defined in the text. The principle is applied to a few simple examples. 相似文献
75.
Johan Wouters Bernadette Norberg Salvatore Guccione 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):o69-o71
The crystal structures of 4‐methyl‐2‐[N‐(3,4‐methylenedioxybenzylidene)hydrazino]thiazole, C12H11N3O2S, and its reduction product 4‐methyl‐2‐[N‐(3,4‐methylenedioxybenzylidene)hydrazono]‐4,5‐dihydrothiazole, C12H13N3O2S, have been determined and compared. In the reduction product, the tautomer observed bears an H atom on the exocyclic N atom. Both compounds form hydrogen‐bonded dimers over centers of inversion. 相似文献
76.
Olofsson J Wilhelmsson LM Lincoln P 《Journal of the American Chemical Society》2004,126(47):15458-15465
Methyl substituents on the distant benzene ring of the dppz ligand in the "light switch" complex [Ru(phen)(2)dppz](2+) have profound effects on the photophysics of the complexes in water as well as in the polyol solvents ethylene glycol, glycerol, and 1,2- and 1,3-propanediol. Whereas 11,12-dimethyl substitution decreases the rate of quenching by diminishing hydrogen bonding by solvent, the 10-methyl substituent in addition also decreases both the radiative and the nonradiative rate constant for decay to the ground state of the non-hydrogen-bonded excited state species. For both the 10-methyl and the 11,12-dimethyl derivatives, the effect of methyl substitution on the equilibrium of solvent hydrogen bonding to the excited state is due to changes in the entropy terms, rather than in the enthalpy, indicating that the effect is a steric perturbation of the solvent cage around the molecule. When intercalated into DNA, the effects of methyl substitution is smaller than those in polyol solvent or water, suggesting that the water molecules that quench the excited state by hydrogen bonding to the phenazine aza nitrogens mainly access them from the same groove as in which the Ru(II) ion resides. Since the Delta-enantiomer of [Ru(phen)(2)10-methyl-dppz](2+) has an absolute quantum yield of up to 0.23 when bound to DNA, a value 7000 times higher than in pure water solution, it is promising as a new luminescent DNA probe. 相似文献
77.
78.
Bassil BS Nellutla S Kortz U Stowe AC van Tol J Dalal NS Keita B Nadjo L 《Inorganic chemistry》2005,44(8):2659-2665
The 15-cobalt-substituted polyoxotungstate [Co(6)(H(2)O)(30){Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}](5-) (1) has been characterized by single-crystal XRD, elemental analysis, IR, electrochemistry, magnetic measurements, and EPR. Single-crystal X-ray analysis was carried out on Na(5)[Co(6)(H(2)O)(30){Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}].37H(2)O, which crystallizes in the hexagonal system, space group P6(3)/m, with a = 19.8754(17) A, b = 19.8754(17) A, c = 22.344(4) A, alpha= 90 degrees, beta = 90 degrees, gamma = 120 degrees, and Z = 2. The trimeric polyanion 1 has a core of nine Co(II) ions encapsulated by three unprecedented (beta-SiW(8)O(31)) fragments and two Cl(-) ligands. This central assembly {Co(9)Cl(2)(OH)(3)(H(2)O)(9)(beta-SiW(8)O(31))(3)}(17-) is surrounded by six antenna-like Co(II)(H(2)O)(5) groups resulting in the satellite-like structure 1. Synthesis of 1 is accomplished in a simple one-pot procedure by interaction of Co(II) ions with [gamma-SiW(10)O(36)](8-) in aqueous, acidic NaCl medium (pH 5.4). Polyanion 1 was studied by cyclic voltammetry as a function of pH. The current intensity of its Co(II) centers was compared with that of free Co(II) in solution. Our results suggest that 1 keeps its integrity in solution. Magnetic susceptibility results show the presence of both antiferro- and ferromagnetic coupling within the (Co(II))(9) core. A fully anisotropic Ising model has been employed to describe the exchange-coupling and yields g = 2.42 +/- 0.01, J(1) = 17.0 +/- 1.5 cm(-1), and J(2) = -13 +/- 1 cm(-(1). Variable frequency EPR studies reveal an anisotropic Kramer's doublet. 相似文献
79.
We present analytical results on the so-called end-evaporation kinetics in equilibrium polymeric systems following a temperature jump (T jump). A T jump prepares the system with a nonequilibrium length distribution, after which it relaxes back to its equilibrium state. Starting from a master equation, we develop a mean-field analytical theory based on a generating function approach, which allows explicit approximate expressions for the monomer and dimer concentrations to be derived in a discrete setting; the concentrations of the other chains as well as the average chain length were shown to be entirely expressible in terms of the monomer and dimer concentrations. We find that the calculated monomer and dimer concentrations as well as the average chain length are in good agreement with numerical simulation results and do not suffer from some of the defects of earlier continuum theories. Furthermore, the relaxation was shown to take place in three different stages. The first stage comprises the very fast relaxation of the monomers to almost their equilibrium concentration; the other polymer chains have hardly relaxed. During the second stage, which is highly nonlinear, a redistribution of material at practically constant monomer density takes place. Only in the final stage of the relaxation process the chain concentrations approach their true equilibrium values. In this stage there are only very small shifts in the concentrations of chains, which are governed by extremely slow "indirect" monomer-mediated processes. 相似文献
80.
Quantitative accuracy is of great importance in the analysis of bulk mixtures of solvents, particularly when the analysis is related to quality control of very large product volumes like in solvent recovery plants. Serious errors can be made if the effects of density differences between the pure solvents and volume contractions are not properly addressed. In earlier work, the use of an iterative process for correcting such errors has been suggested. However, in the case of volume contractions and mixtures of several solvents, this procedure is difficult to apply. In the present paper, we describe a simple procedure where calibration curves based on mass concentration are utilized. The densities of calibration mixtures of known compositions are determined with a density meter, in order to provide for correction factors caused by volume contractions. Model experiments with mixtures of water, ethanol, acetone and methanol showed a significant improvement in quantitative accuracy. when the suggested calibration strategy was applied. 相似文献