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11.
12.
A Study of the Uptake of Toluidine Blue O by Porphyromonas gingivalis and the Mechanism of Lethal Photosensitization 总被引:2,自引:1,他引:2
Manpreet Bhatti Alexander MacRobert Sajeda Meghji Brian Henderson Michael Wilson 《Photochemistry and photobiology》1998,68(3):370-376
The purpose of the study was to determine the distribution of the photosensitizer toluidine blue O (TBO) within Porphyromonas gingivalis and the possible mechanism(s) involved in the lethal photosensitization of this organism. The distribution of TBO was determined by incubating P. gingivalis with tritiated TBO (3H-TBO) and fractionating the cells into outer membrane (OM), plasma membrane (PM), cytoplasmic proteins, other cytoplasmic constituents and DNA. The percentage of TBO in each of the fractions was found to be, 86.7, 5.4, 1.9, 5.7 and 0.3%, respectively. The involvement of cytotoxic species in the lethal photosensitization induced by light from a helium-neon (HeNe) laser and TBO was investigated by using deuterium oxide (D2O), which prolongs the lifetime of singlet oxygen, and the free radical and singlet oxygen scavenger L-tryptophan. There were 9.0 log10 and 2 log10 reductions in the presence of D2O and H2O (saline solutions), respectively, at a light dose of 0.44 J (energy density = 0.22 J/cm2), suggesting the involvement of singlet oxygen. Decreased kills were attained in the presence of increasing concentrations of L-tryptophan. The effect of lethal photosensitization on whole cell proteins was determined by measuring tryptophan fluorescence, which decreased by 30% using 4.3 J (energy density = 4.3 J/ cm2) of light. Effects on the OM and PM proteins were determined by sodium dodecyl sulfate polyacrylamide gel electrophoresis. There was evidence of change in the molecular masses of several PM proteins and OM proteins compared to controls. There was evidence of damage to the DNA obtained from irradiated cells. Scanning electron microscopic studies showed that there was coaggre-gation of P. gingivalis cells when sensitized and then exposed to laser light. These results suggest that lethal photosensitization of P. gingivalis may involve changes in OM and/or PM proteins and DNA damage mediated by singlet oxygen. 相似文献
13.
Alan R. Katritzky Scott A. Henderson Baozhen Yang 《Journal of heterocyclic chemistry》1998,35(5):1123-1159
Applications of benzotriazole methodology for the preparation of heterocyclic compounds are reviewed. The characteristic advantages of benzotriazole as a synthetic auxiliary are first briefly considered. This is followed by a summary of its use in ring synthesis in which the construction of small; five-membered; six-membered; and larger heterocyclic rings using benzotriazole methodology are each examined separately. Finally, consideration of the use of benzotriazole in the ring annulation - particularly benzannulation - of heterocycles. Subsequent sections deal with the introduction of substituents into aromatic heterocycles; the ring substitution of saturated heterocycles; and benzotriazole assisted modification of heterocyclic substituents. The present review supplements a recent comprehensive review of benzotriazole chemistry [1] which covers the literature through 1996. 相似文献
14.
Bonvin Y Callens E Larrosa I Henderson DA Oldham J Burton AJ Barrett AG 《Organic letters》2005,7(21):4549-4552
[reaction: see text] Oxidation of alkyl and cycloalkyl arenes with tert-butyl hydroperoxide catalyzed by bismuth and picolinic acid in pyridine and acetic acid gave the corresponding benzylic ketones (48-99%). Alternatively, oxidation of methyl arenes gave the corresponding substituted benzoic acids (50-95%). Preliminary mechanistic studies were consistent with a radical mechanism rather than a bismuth(III)-bismuth(V) cycle. 相似文献
15.
Wen-Ping Wang Robert G. Parr Danny R. Murphy George A. Henderson 《Chemical physics letters》1976,43(3):409-412
It is demonstrated that the ground-state atomic kinetic energy functional T[?], where ? is the electron density, can be computed to surprising accuracy from the truncated gradient expansion: T[?] = + T2[?] + T4[?], with To[?] = (3π2) ∫ ? dτ, T2 [?] = ∫ (??)2??1 dτ, and T4 [?] given by the formula of Hodges. Calculations of T0, T2 and T4 are reported for He with ? both the Hartree—Fock and a very accurate density, and for Ne, Ar and Kr with ? the Hartree—Fock density. For Kr, T0 + T2 + T4 is within 0.3% of the exact Hartree—Fock T, with T2/T0 = 0.05, T4/T2 = 0.17. 相似文献
16.
Fred C Cantillana T Henderson AP Golding BT Törnqvist M 《Rapid communications in mass spectrometry : RCM》2004,18(18):2177-2184
Isoprene (2-methylbuta-1,3-diene) is a multi-site carcinogen in rodents. To evaluate the role of the diepoxide metabolite (1,2:3,4-diepoxy-2-methylbutane) in carcinogenesis, measurements of in vivo doses of the diepoxide are needed. The in vivo dose may be inferred from levels of reaction products with hemoglobin (Hb adducts). This report presents in vitro studies of the adduct formation by the diepoxide of isoprene with valinamide and oligopeptides as model compounds of N-terminal valines in hemoglobin (Hb). In the reaction with valinamide it was shown that isoprene diepoxide forms as the main product a ring-closed adduct, which is a pyrrolidine derivative [N,N-(2,3-dihydroxy-2-methyl-1,4-butadiyl)valinamide, MPyr-Val]. The analysis was performed by gas chromatography/mass spectrometry (GC/MS) (EI and PICI) after acetylation. The ring-closed adduct was also identified by liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) as the main product in the reaction between isoprene diepoxide and standard hepta- or (2H8)octapeptides, corresponding to the N-terminal peptides of the alpha-chains in mouse and rat Hb. These peptides, alkylated with isoprene diepoxide, to be used as internal standards and calibration standards for quantification of MPyr-adduct levels in vitro and in vivo, were analyzed with respect to the degree of MPyr-alkylation by two independent methods, amino acid analysis and HPLC-UV; similar results were obtained using these methods. A method for measurement of Hb adducts as modified peptides, used earlier to measure a similar adduct to N-terminal valines in Hb from the diepoxide of 1,3-butadiene, has in the present work been tested for application to isoprene diepoxide. The method is based on tryptic degradation of globin and LC/ESI-MS analysis of N-terminal Pyr-heptapeptides of the Hb alpha-chain enriched by HPLC. MPyr-adduct levels in isoprene diepoxide alkylated hemolysate from mouse erythrocytes incubated with different concentrations of isoprene diepoxide (2 and 10 mM) for 1 h were quantified. The adduct level was about 50 nmol/g alpha-chain Hb per mM x h. From the adduct levels the rate constant of isoprene diepoxide for reaction with N-terminal valine was calculated to be about 1.6 times faster than for diepoxybutane. 相似文献
17.
Eckhard Spohr Andrij Trokhymchuk Douglas Henderson 《Journal of Electroanalytical Chemistry》1998,450(2):211
We report molecular dynamics (MD) simulations on the adsorption of water in attractive and repulsive slit pores, where the slit and a bulk region are in contact with each other. Water structure, surface force and adsorption behavior are investigated as a function of the overall density in the bulk region. The gas–liquid transition in both types of pores occurs at similar densities of the bulk region. 相似文献
18.
Kinetic studies on the substitution reaction between [Fe(4)S(4)Cl(4)](2-) and Bu(t)NC or Et(2)NCS(2)(-) are reported. The binding of small molecules and ions to Fe-S clusters is a fundamental step in substitution reactions but can be difficult to follow directly because these reactions are rapid and often associated with small spectroscopic changes. A novel kinetic method is reported which allows the time course of molecule and ion binding to Fe-S clusters to be followed by monitoring the lability of the cluster. Using a stopped-flow, sequential-mix apparatus, [Fe(4)S(4)Cl(4)](2-) and L (L = Et(2)NCS(2)(-) or Bu(t)NC) are rapidly mixed, and after a known time (delta) the resulting solution is mixed with a solution of PhS(-). The thiolate substitutes for the chloro ligands on the cluster, in a reaction which is easy to follow because of the large change in the visible absorption spectrum. The rate of this substitution is extremely sensitive to whether L is bound to the cluster or not. By correlation of delta with the rate of the reaction with PhS(-), the time course of the reaction between [Fe(4)S(4)Cl(4)](2-) and L can be mapped out. In studies where L = Bu(t)NC this technique has allowed the detection of an intermediate ([Fe(4)S(4)Cl(4)(CNBu(t))](2-)) which cannot be detected spectrophotometrically. In further studies, the substitution reactions of [Fe(4)S(4)Cl(4)](2-) with PhS(-), Et(2)NCS(2)(-), or Bu(t)NC are all perturbed by the addition of Cl(-). In all cases a common pathway for substitution is evident, but with Et(2)NCS(2)(-) an additional, slower pathway becomes apparent under conditions where the common pathway is completely inhibited by Cl(-). 相似文献
19.
Gajewski JJ Bocian W Brichford NL Henderson JL 《The Journal of organic chemistry》2002,67(12):4236-4240
The competitive kinetics of additions of allyl to benzaldehyde-h and -d from allyltributyl tin, from diisopropyltartrylallyl boronate, and from allyl bromide and zinc dust in aqueous tetrahydrofuran have inverse secondary deuterium kinetic isotope effects, SDKIEs. These inverse SDKIEs are in contrast to the normal SDKIEs that were obtained with allyl lithium and allyl Grignard, suggesting rate-determining single-electron transfer in these cases. By various MO calculations the transition state for addition of allyl boronate occurs with substantial B-O bond formation and little C-C bond formation. The magnitudes of the SDKIEs with the other two allylating reagents, when compared with reasonable equilibrium isotope effects for the addition, suggest transition states with substantial C-C bond formation. 相似文献
20.
The alpha,alpha'-stabilized carbanion complexes [PhSO(2)CHCNNa.THF], 3, [t-BuSO(2)CHCNNa], 4, [PhSO(2)CHCNK], 5, [t-BuSO(2)CHCNK], 6, and [MeSO(2)CHCNLi.TMEDA], 7, have been synthesized via the metalation of the parent (organo)sulfonylacetonitriles by BuLi, BuNa, or BnK in THF solution (or THF/TMEDA in the case of 7). In addition, complexes 3 and 7 have been characterized by single-crystal X-ray analyses and have been found to adopt related structures in the solid state. Complex 7 is a molecular dimer containing a central 12-membered (OSCCNLi)(2) ring core, with each metal rendered tetracoordinate by binding to a chelating TMEDA molecule. As found in related complexes, no direct carbanion to lithium contacts are present in the structure of 7. Complex 3 forms a polymeric cage structure composed of associated "dimeric" (OSCCNNa)(2) rings, similar to those found in 7. The larger sodium cations, and the presence of only one THF molecule/metal, allow additional contacts with the anions, leading to hexacoordination at the metal centers. These contacts include long-range transannular Na-N interactions (2.8042(14) A) across the central dimeric ring and "interdimer" Na-C connections (2.8718(15) A). Dissolution of complexes 3-6 and their lithiated derivatives [PhSO(2)CHCNLi.TMEDA], 1, and [t-BuSO(2)CHCNLi.THF], 2, in DMSO-d(6) results in almost identical chemical shifts for each type of ligand. This suggests that charge-separated complexes of the form [RSO(2)CHCN](-)[M(DMSO-d(6))(n)()](+) are formed in highly polar solution. 相似文献