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71.
72.
A high performance liquid chromatography (HPLC) method with fluorescence detection including an on-line purification was established for determination of catecholamines in human urine. The method was evaluated using samples of pooled urine spiked with catecholamines and validated for measurements of catecholamines in urine of healthy individuals in a field study. The laboratory method evaluation study showed that the recovery of the method was 0.82 (confidence interval (CI): 0.79-0.86) and 0.92 (CI: 0.89-0.95) for noradrenaline and adrenaline, respectively. Thus, correction factors of 0.82(-1) and 0.92(-1) were applied to correct the measurement results for this systematic effect. Furthermore, an uncertainty budget was generated for the analytical method using the BIPM-approach recommended by the International Organization for Standardization. The relative uncertainty of the method was estimated to be 10-12%, which was consistent with the observed relative variability found in the method evaluation. The method was evaluated in accordance with EURACHEM Guidance Document No 1 concerning accreditation for chemical laboratories with respect to accuracy and precision. The field study showed that the standard deviation of the method was sufficiently low to distinguish between persons working with two different processes of garbage collection, i.e. collection using four wheeled containers versus collection using bins. 相似文献
73.
Cahn's phenomenological theory of wetting of a solid substrate by a saturated vapor is generalized to the case where the substrate is charged and the wetting film contains counterions, with or without added salt. The electrostatic contribution to the grand potential associated with these ions is calculated within a nonlinear Poisson-Boltzmann theory. In the salt-free case, when the wetting film includes only counterions released by the substrate, the wetting transition is always first order, regardless of its nature in a neutral system. When salt is present, other wetting scenarios may arise, depending on the salt concentration and substrate surface charge. Over a restricted range of salt concentrations, a wetting scenario similar to that of prewetting, is predicted to occur along the liquid-vapor coexistence line. This scenario includes a discontinuous wetting transition between microscopic and mesoscopic film thicknesses, followed by a continuous divergence of the film thickness at higher temperatures. 相似文献
74.
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76.
H. E. Hansen R. Talja H. Rajainmäki H. K. Nielsen B. Nielsen R. M. Nieminen 《Applied Physics A: Materials Science & Processing》1985,36(2):81-92
Molybdenum single crystals are irradiated at 20 K with 6 MeV protons. The radiation damage and lattice defect annealing is studied by positron lifetime spectroscopy in the temperature range from 15 to 720 K. Loss of vacancies due to recombination with mobile interstitials is observed at 40 K (Stage I) in agreement with resistivity measurements. This is the first time Stage I is observed by positrons below 77 K. The implanted hydrogen decorates the vacancies around 100 K, which is consistent with a hydrogen migration energy in molybdenum:E
M
H
= 0.3–0.4 eV. Clustering of spatially correlated vacancies takes place in a wide temperature region below the usual vacancy clustering stage (Stage III). Stage III is observed at rather low temperatures (400–480 K) due to the very high vacancy concentration. Hydrogen bound to vacancies and vacancy clusters is released above 540 K, which puts an upper limit to the hydrogen binding energy:E
B
H
1.4 eV. The present work emphasizes the advantage of employing a vacancy sensitive technique to study hydrogen in metals, where its intrinsic solubility is low. In such metals (as molybdenum) both the effective solubility and the effective mobility of hydrogen are strongly influenced by the presence of vacancies. 相似文献
77.
The acid catalysed dienone-phenol rearrangement of methyl substituted o-propargyl-cyclohexadienones (scheme 3) was investigated. The rearrangements were carried out in acetic anhydride containing about 10/00 sulfuric acid. Under these conditions acetoxy benzenium ions are formed as intermediates. These then undergo charge-controlled [3s, 4s]- and [1s, 2s]-sigmatropic rearrangements. Thus, the [3s, 4s]-process leads to the formation of the corresponding allenyl-phenol acetates ( 19 , 21 , 23 , 25 , 28 , 30 ) whereas the [1s, 2s]-process yields propargyl-phenol acetates ( 20 , 22 , 24 , 26 , 29 ), respectively (cf. scheme 4). 相似文献
78.
Nanostructure and irreversible colloidal behavior of Ca(OH)2: implications in cultural heritage conservation 总被引:1,自引:0,他引:1
Rodriguez-Navarro C Ruiz-Agudo E Ortega-Huertas M Hansen E 《Langmuir : the ACS journal of surfaces and colloids》2005,21(24):10948-10957
Although Ca(OH)2 is one of the oldest art and building material used by mankind, little is known about its nanostructural and colloidal characteristics that play a crucial role in its ultimate performance as a binder in lime mortars and plasters. In particular, it is unknown why hydrated lime putty behaves as an irreversible colloid once dried. Such effect dramatically affects the reactivity and rheology of hydrated lime dispersions. Here we show that the irreversible colloidal behavior of Ca(OH)2 dispersions is the result of an oriented aggregation mechanism triggered by drying. Kinetic stability and particle size distribution analysis of oven-dried slaked lime or commercial dry hydrate dispersions exhibit a significant increase in settling speed and particle (cluster) size in comparison to slaked lime putty that has never been dried. Drying-related particle aggregation also leads to a significant reduction in surface area. Electron microscopy analyses show porous, randomly oriented, micron-sized clusters that are dominant in the dispersions both before and after drying. However, oriented aggregation of the primary Ca(OH)2 nanocrystals (approximately 60 nm in size) is also observed. Oriented aggregation occurs both before and during drying, and although limited before drying, it is extensive during drying. Nanocrystals self-assemble in a crystallographically oriented manner either along the 100 or equivalent 110 directions, or along the Ca(OH)2 basal planes, i.e., along [001]. While random aggregation appears to be reversible, oriented aggregation is not. The strong coherent bonding among oriented nanoparticles prevents disaggregation upon redispersion in water. The observed irreversible colloidal behavior associated with drying of Ca(OH)2 dispersions has important implications in heritage conservation, particularly considering that nowadays hydrated lime is often the preferred alternative to portland cement in architectural heritage conservation. Finally, our study demonstrates that, fortuitously, hydrated lime could be one of the first nanomaterials used by mankind. 相似文献
79.
Yevgen Posokhov Alexander Gorski Jens Spanget-Larsen Fritz Duus Poul Erik Hansen Jacek Waluk 《Chemphyschem》2004,5(4):495-502
Thioacetylacetone and its variously deuterated isotopomers have been investigated using electronic and vibrational spectroscopy combined with quantum chemical calculations. Thioacetylacetone is known for its photochromic properties, but the structures of the initial and final forms have been the subject of a long debate. Analysis of the IR spectra recorded in low-temperature argon and xenon matrices, room-temperature solutions, and in the gas phase has allowed us to establish the nature of the photochromic species and of its precursor. Similar to the case of another beta-thioxoketone, monothiodibenzoylmethane, the photo-product has been assigned to the nonchelated SH exo-rotamer of the (Z)-enethiol tautomeric form, whereas the dominant ground-state species corresponds to the chelated (Z)-enol tautomeric form. Detailed vibrational assignments have been proposed for both forms based on quantum chemical calculations and polarization experiments. In the case of the chelated (Z)-enol species prevailing in the ground state, a second-order perturbative anharmonic analysis at the B3LYP/cc-pVTZ level indicated strong anharmonic effects associated with the intramolecular hydrogen bond, leading to a shift of more than 600 cm-1 of the wavenumber of the OH-stretching vibration. A small fraction of the SH endo-rotameric chelated (Z)-enethiol form was also detected under unperturbed conditions. The (Z)-enethiol form can be converted into the (Z)-enol form by irradiation at 290 nm. 相似文献
80.
It has been shown, that in vitro incubation of Laminaria digitata extract (containing mainly As-sugar 1 (glycerol-arsenoribose) and As-sugar 3 (sulfonate-arsenoribose)) with liver cytosol, produced the same two arsenicals, as when L. digitata extract was treated with H(2)S. By parallel use of HPLC-ICP-MS and HPLC-ES-MS the compounds displayed mainly m/z 345 and m/z 409. A pure As-sugar 1 standard was obtained, and a standard of arsinothioyl-sugar 1 (m/z 345) was produced, by purging a solution of As-sugar 1 with gaseous H(2)S. The identity of arsinothioyl-sugar 1 was characterised by ES-MS, 1D and 2D NMR. Arsinothioyl-sugar 1 showed the same chromatographic behaviour and MS characteristics as one of the two arsenic-containing compounds (m/z 345) produced by incubation of L. digitata extracts with liver cytosol, and as the product of the incubation of As-sugar 1 with liver cytosol (HPLC-ICP-MS, HPLC-ES-MS). Assuming that As-sugar 3 reacts in a similar way to As-sugar 1 with H(2)S, it is most likely that the second unknown (m/z 409) is arsinothioyl-sugar 3. The degradation of As-sugar 1 in acidic solution (100 mM HCl) was followed by (1)H-NMR, and the relative slow degradation (t(1/2)= 17 h) suggests that arsenosugars are taken up from the stomach in their original chemical form, hence the study of arsenosugar incubation in tissue is highly relevant. The arsinothioyls are a new group of organoarsenicals, which have only recently been identified in nature. Here, arsinothioyl sugars are detected for the first time. The in vitro formation of arsinothioyl-sugars in liver cytosol suggests that arsinothioyls may be of large biochemical and toxicological importance. 相似文献