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91.
The determination of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-(2,4,5-trichlorophenoxy) propionic acid (Silvex) in water at the μg l-1 level is based on liquid/ liquid extraction and high-performance liquid chromatography. Sample preparation for water samples is simplified. The ranges of linear response are 50 ng to 60 μg for 2,4-D and 30 ng to 60 μg for Silvex. The average recoveries of 2,4-D at the 10 μg l-1 and 1 μg l-1 levels are 91% and 120%, respectively, while the average recoveries of Silvex at the 10 μg l-1 and 1 μg l-1 levels are 85% and 110%, respectively. 相似文献
92.
A new and easy method for preparing blue sodalite pigments which involves high-temperature calcination of sodalite samples synthesized with aluminum sulfate and an organic template, is presented. Calcination generated the S(3)(-) and S(2)(-) radicals, and the effects of the Al/Si ratio and the calcination temperature on the nature and amounts of the radicals were examined. The radicals were characterized in detail by continuous wave and pulsed EPR at X- and W-band frequencies (approximately 9 and 95 GHz, respectively) complemented by UV-vis measurements. The high-field electron-paramagnetic resonance (EPR) measurements allowed us to clearly resolve the g anisotropy of S(3)(-) and W-band electron nuclear double resonance (ENDOR) measurements detected strong coupling with extra-framework (23)Na cations and weak coupling with framework (27)Al. On the basis of the spectroscopic results and density functional theory (DFT) calculations of the g-tensors of S(3)(-) and S(2)(-) radicals, the EPR signals were attributed to three different radicals, all with the open structure C(2v), that are located within the sodalite beta cages. While two of these radicals are well isolated, the third one is associated with an exchange-narrowed signal originating from S(3)(-) radicals in nearby sodalite cages. 相似文献
93.
Potter WR Henderson BW Bellnier DA Pandey RK Vaughan LA Weishaupt KR Dougherty TJ 《Photochemistry and photobiology》1999,70(5):781-788
An open three-compartment pharmacokinetic model was applied to the in vivo quantitative structure-activity relationship (QSAR) data of a homologous series of pyropheophorbide photosensitizers for photodynamic therapy (PDT). The physical model was a lipid compartment sandwiched between two identical aqueous compartments. The first compartment was assumed to clear irreversibly at a rate K0. The measured octanol-water partition coefficients, P(i) (where i is the number of carbons in the alkyl chain) and the clearance rate K0 determined the clearance kinetics of the drugs. Solving the coupled differential equations of the three-compartment model produced clearance kinetics for each of the sensitizers in each of the compartments. The third compartment was found to contain the target of PDT. This series of compounds is quite lipophilic. Therefore these drugs are found mainly in the second compartment. The drug level in the third compartment represents a small fraction of the tissue level and is thus not accessible to direct measurement by extraction. The second compartment of the model accurately predicted the clearance from the serum of mice of the hexyl ether of pyropheophorbide a, one member of this series of compounds. The diffusion and clearance rate constants were those found by fitting the pharmacokinetics of the third compartment to the QSAR data. This result validated the magnitude and mechanistic significance of the rate constants used to model the QSAR data. The PDT response to dose theory was applied to the kinetic behavior of the target compartment drug concentration. This produced a pharmacokinetic-based function connecting PDT response to dose as a function of time postinjection. This mechanistic dose-response function was fitted to published, single time point QSAR data for the pheophorbides. As a result, the PDT target threshold dose together with the predicted QSAR as a function of time postinjection was found. 相似文献
94.
Effect of sampler and skimmer orifice size on analyte and analyte oxide signals in inductively coupled plasma-mass spectrometry 总被引:2,自引:0,他引:2
The size of the orifice in the sampling cone of the interface in an inductively coupled plasma-mass spectrometer (ICP-MS) has a major impact on signal characteristics. In particular, for oxide forming elements, the MO+/M+ ratio is very dependent on orifice size. This is illustrated for a range of elements (La, Ho and Yb) as a function of nebulizer gas flow and for sampling cone orifice sizes ranging from 0.51 to 0.94 mm. In addition the size of the sampling orifice changes the shape of the signal vs nebulizer flow rate plot and this is illustrated. A curious and important observation is that the signal dependence on nebulizer flow rate is essentially identical for all analytes at any one orifice size if the analyte and analyte oxide (when observed) responses are summed. This indicates that the sampling orifice is the primary location of oxide formation in ICP-MS. Finally the effect of the skimmer orifice diameter on analyte signals is also illustrated for orifice diameters of 0.76, 0.89 and 1.0 mm in conjunction with sampling orifice sizes ranging from 0.51 to 0.94 mm. 相似文献
95.
We show room temperature plasticity in several ZrCu-based bulk metallic glasses (BMG) after dispersions of crystalline nanoparticles were generated prior to mechanical testing. BMGs are heated in synchrotron light in transmission such that annealing can be interrupted at the very first detection of nucleation of the crystallites. Effect of embedded nanocrystals on the mechanical properties of BMG-Composites was investigated by compressive testing. When nanocrystal dispersions were generated, zirconium-copper-based BMGs that initially showed no plastic deformation prior to fracture, exhibited ductile behavior in compression with about 10% deformation. 相似文献
96.
Michael R. J. Dorrity Ann Lavery John F. Malone Christopher P. Morley Richard R. Vaughan 《Heteroatom Chemistry》1992,3(2):87-91
Cycloocteno-1,2,3-selenadiazole ( 1 ) and cyclopenta-dienyldicarbonylcobalt ( 2 ) react in the presence of an excess of elemental sulfur to yield the dithiolene cyclopentadienyl(1,2-cyclooctenedithiolato)cobalt ( 3 ). Available evidence indicates that this reaction involves the intermediacy of a cobalt–alkyne complex. Compound 3 is the first example of a cyclopentadienylcobalt dithiolene bearing aliphatic substituents. Analogous reactions performed using only catalytic quantities of 2 provide high-yield syntheses of bis(cycloocteno)-1,4-dithiin ( 6 ) and bis(cycloocteno)-1,4-diselenin ( 7 ), whose structures have been determined by X-ray diffraction. 相似文献
97.
IL-10 does not play a role in cutaneous Photofrin photodynamic therapy-induced suppression of the contact hypersensitivity response. 总被引:2,自引:0,他引:2
S O Gollnick D A Musser A R Oseroff L Vaughan B Owczarczak B W Henderson 《Photochemistry and photobiology》2001,74(6):811-816
Photodynamic therapy (PDT) treatment of both malignant and benign skin diseases has proven to be effective, and its use is increasing worldwide. However, preclinical studies using murine models have shown that PDT of the skin inhibits cell-mediated immune reactions, as measured by the suppression of the contact hypersensitivity (CHS) reaction. We have previously demonstrated that PDT enhances IL-10 expression in treated skin, and that the kinetics of induction of IL-10 is similar to the kinetics of suppression of systemic CHS reactions by cutaneous PDT. In the following report we have expanded upon these studies to demonstrate that cutaneous PDT, using Photofrin, induces elevated levels of systemic IL-10 that persist for at least 28 days following treatment. The increase in systemic IL-10 correlates to a prolonged suppression of CHS of at least 28 days following cutaneous PDT. IL-10 has been implicated as the causative agent in the suppression of cell-mediated immune reactions by UVB and transdermal PDT. However, in the studies reported here we demonstrate that the suppression of CHS by cutaneous PDT occurs via an IL-10 independent mechanism, as administration of anti-IL-10 antibodies had no effect on the ability of PDT to induce CHS suppression. These results were further confirmed using IL-10 knockout (KO) mice. Cutaneous PDT of IL-10 KO mice resulted in CHS suppression that was not significantly different from suppression induced in wild-type mice. Thus, it appears as though IL-10 does not play a role in CHS suppression by cutaneous PDT. Suppression of cell-mediated immune reactions by UVB and transdermal PDT is reversible by IL-12, which is critical for the development of these reactions. We show that administration of exogenous IL-12 is also able to reverse CHS suppression induced by cutaneous PDT, suggesting that whereas suppression of cell-mediated immune reactions by UVB, transdermal PDT and cutaneous PDT occurs via different mechanisms, a common regulatory point exists. 相似文献
98.
I. L. Hosier A. S. Vaughan S. G. Swingler 《Journal of Polymer Science.Polymer Physics》2000,38(17):2309-2322
The effects of morphology and molecular composition on the electrical strength of blends of linear and branched polyethylenes were investigated. A range of blend systems were considered, in which both the molecular mass of the linear polymer and the comonomer in the branched component were varied. All the blends contained 10% linear polyethylene and 90% branched polymer and, in each system, three crystallization procedures were employed to modify the morphology. Isothermal crystallization at 124 °C generally resulted in compact linear inclusions within a branched matrix; isothermal crystallization at 115 °C produced a space‐filling network of open, spherulitic structures; and quenching gave a banded spherulitic morphology. In these systems, the electrical strength, as measured by ramp testing, was dependent on the morphology of the material but was not influenced per se by significant changes in the molecular composition of the blend. The effect of crosslinking was also examined; the inclusion of a network did not, in itself, affect the breakdown strength or the morphology. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2309–2322, 2000 相似文献
99.
Stuart R. Gooding Peter J. Winn Richard I. Maurer Gyrgy G. Ferenczy John R. Miller Jayne E. Harris D. Vaughan Griffiths Christopher A. Reynolds 《Journal of computational chemistry》2000,21(6):478-482
The compound dimethyl‐2‐iodobenzoylphosphonate is unusual in that it forms well‐ordered crystals that clearly show short iodine‐oxygen interactions in which both the iodine and the oxygen are in their normal oxidation states. These interactions were studied using a new hybrid quantum mechanical–molecular mechanical approach that employs a polarizable molecular mechanics component. The electric field at the molecular mechanics atoms was calculated from a distributed multipole expansion of the wave function; this induced dipoles on the molecular mechanics atoms. The electrostatic potential in a spherical shell around the induced dipoles was reproduced through induced charges on the atomic center and those bonded to it using an analytical (rather than numerical) procedure. The new atomic charges (induced charges plus permanent charges) were then able to interact with the quantum mechanical entity and polarize the wave function. The procedure was iterated to convergence. The calculations show that the iodine atom becomes more positive in the crystal environment (modeled by a chain of three molecules of dimethyl‐2‐iodobenzoylphosphonate). Thus, while the cooperative effects of the crystal environment may not be the only feature stabilizing this unusual interaction, they do play a significant role in reducing the otherwise unfavourable iodine–oxygen monopole–monopole interaction. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 478–482, 2000 相似文献
100.
K. E. R. England C. M. B. Henderson J. Charnock D. J. Vaughan 《Hyperfine Interactions》1994,91(1):709-714
Synthetic iron-containing leucite-type phases have been studied using57Fe Mössbauer spectroscopy in combination with X-ray absorption spectroscopy (XAFS and XANES). The Mössbauer and XAS data confirm that both Fe2+ and Fe3+ occupy tetrahedrally coordinated framework sites in the synthetic phases. In addition, information on Fe2+/Fe3+ ratios, cation site occupancies and first shell bond lengths has also been obtained. 相似文献