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51.
Summary Micromolar analyses of the nitrogen species NH3, NO
2
–
, and NO
3
–
in soil and other samples are usually accomplished by extracting several samples and testing each for a different species. This procedure is not viable when the quantity of the initial sample is limited. An improved method of separating and analysing for ammonia NH3(aq), nitrite NO
2
–
(aq), and nitrate NO
3
–
(aq) from a single small sample with concentrations of 0–50 mol/l is reported. No interferences or carryovers among the three nitrogen containing species were found. Uncertainties were ±2–5 mol/l and accuracies with respect to standards were ±3 mol/l. 相似文献
52.
Oxide ceramic masses react to simple shearing with hardening (peptisation: increase in the shear stress with the shear deformation).
In the present study the correlation between the increase in the shear stress and the porosity, agglomeration processes and
the type of flow are analysed. For this purpose oxide ceramic masses are tested in a shear device especially developed for
pastes and analysed by rheometric experiments, NMR methods and particle size analysis. The results support the hypothesis
that structural changes (hardening, increase in the mean porosity) of the material during the peptisation mainly depend on
the magnitude and not on the kind of the energy input and thus of the type of flow. The fraction of bound (more generally,
the immobilised) water increases with the shear displacement. Also crushing of primary particles could be observed. Both the
crushing of solid particles causing an increased solid surface and the formation of a three-dimensional gel structure are
microscopic effects capable of resulting in the binding or retaining water. On a macroscopic scale these phenomena cause hardening.
Magnetic resonance imaging visualises flow-induced agglomerates, which form owing to the shear flow and increase the porosity
averaged over the whole sample. After the shear experiment rolls of paste can be seen which indicate that the general assumption
of a plane shear flow in the shear device is not warrantable.
Received: 19 July 2001 Accepted: 25 October 2001 相似文献
53.
Irradiation (λ = 254 nm) of N-(4,4,6,6-tetramethyl-2-cyclohexen-1-ylidene)-1,1,3,3-tetramethyl-2-cyclohexen-1-ylidene-1,1,3,3-tetramethylbutylamine (7d) , which in turn is photodecomposed by light of the same wavelength, but at a four times slower rate than it is formed. The rate of formation of photoproduct 7d is a function of the concentration of starting material 1d , suggesting the involvement of a bimolecular ( 1d * + 1d ) step. The structure of 7d was established by spectroscopy and by its hydrolysis to 3-cyclohexyl-4,4,6,6-tetramethyl-2-cyclohexenone ( 8 ). The previously made assumption that N-(2-cyclohexen-1-ylidene)cyclohexylamine ( 1a ) and 2,3,4,4a,5,6-hexahydroquinolines 2 photorearrange to N-cyclohexylidenecyclohexanamine 3a and 3,4,4a,5,6,8a-hexahydroquinolines 4 , respectively, via a light-induced 1,3-hydrogen shift proves incorrect. 相似文献
54.
The bimolecular electron transfer from secondary aromatic amines to parent radical cations of nonpolar solvents such as alkanes and alkyl chlorides results in the synchronous formation of amine radical cations as well as aminyl radicals, in comparable amounts. If as for cyclic aromatic amines (c-Ar(2)NH) the intramolecular bending motion around the amine group is restricted in varying degrees (acridane, phenothiazine) or completely prevented (carbazole), then this picture is modified. In the free electron transfer, the completely rigid carbazole yields exclusively amine radical cations. Acridane exhibits preferred radical cations, but phenothiazine with the more flexible six-membered ring involving sulfur as a further heteroatom follows the common two-product rule; see above. The phenomenon is reasoned by a peculiarity in the bimolecular free electron transfer where after diffusional approach the actual electron jump proceeds in the ultrashort time range. Therefore, it reflects femtosecond molecular motions which, in the case of free mobility, continuously pass through different molecule conformers, combined with fluctuation of the electrons of the responsible molecular n-orbitals. The rigid systems, however, do not show this effect because of a nonexistent bending motion. 相似文献
55.
The Molecule S?GeCl2. Matrix IR Investigation and Ab initio SCF Calculation Molecular S?GeCl2 is found in a matrix reaction between the high-temperature molecule Ge?S and Cl2. A structure analog to that of phosgene can be derived from the isotopical shifts (70Ge/72Ge/73Ge/74Ge/76Ge and 35Cl/37Cl) within the IR spectra. The normal coordinate analysis results for the Ge?S force constant a value of 4.21 mdyn/Å. The spectroscopic results are confirmed by ab initio SCF calculations. 相似文献
56.
The molecular structure of Ph3CSSC(S)SCPh3 · CS2 has been determined by X-ray structural analysis. The substance crystallizes in the triclinic crystal system [a = 884.9(2) pm, b = 1 039.5(2) pm, c = 2 064.6(3) pm, α = 75.86(1)°, β = 79.83(2)°, γ = 77.31(5)°, Z = 2, space group P1 ]. The CS3 group is planar; the S? S-bond (201.4 pm) forms an angle of 5.7° with the CS3 plane. The torsional angle CSSC equals 96.3°. (Ph3C)2CS4 was obtained by reaction of TosNSCl2 (Tos = p-MeC6H4SO2) with Ph3CSH in CS2 in the presence of triethylamine. The reaction mechanism is discussed. 相似文献
57.
Investigation of the pharmacokinetics of celecoxib by liquid chromatography-mass spectrometry 总被引:4,自引:0,他引:4
Werner U Werner D Pahl A Mundkowski R Gillich M Brune K 《Biomedical chromatography : BMC》2002,16(1):56-60
A new method for the quantification of celecoxib in human plasma based on reversed-phase high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) after liquid-liquid extraction is presented. The method is rapid, sensitive and highly selective. The retention time of celecoxib was 2.3 min. The limit of quantification was 5 microg/L. Rofecoxib was used as internal standard. After validation, the method was used to study the pharmacokinetic profile of celecoxib following administration of a single oral dose (200 mg) in 12 healthy volunteers. Since celecoxib should be metabolized primarily by cytochrome 2C9 (CYP2C9), a poor metabolizer (PM) for this cytochrome P450 enzyme was included in the study. Pharmacokinetic characteristics (mean +/- SD) of extensive metabolizers (EM) were t(max) 2.9+/-1.2h, c(max) 842+/-280 microg/L, AUC(infinity) 6246+/-2147 microg h/L and t(1/2) 7.8+/-2.7h. The area under the curve (AUC(infinity)) for the PM was 12561 microg h/L. However, we found no noticeable increase in half life in the PM (11.5 h) after a single dose of celecoxib. 相似文献
58.
[reaction: see text] A sequential solid-phase peptide synthesis was developed using both photolabile linker and protecting groups. The chromatic sequential lability between a tert-butyl ketone-derived linker (sensitive to irradiation at 305 nm) and a nitroveratryloxycarbonyl (NVOC) group (sensitive at 360 nm) was exploited to prepare Leu-Enkephalin in a 55% overall yield. This new strategy allows the preparation of peptides in essentially neutral medium, by avoiding the use of common deprotection reagents such as trifluoroacetic acid or piperidine. 相似文献
59.
Pierre-Anton Aichinger Martin Michel Colin Servais Marie-Lise Dillmann Martine Rouvet Nicola D''Amico Ralf Zink Henning Klostermeyer David S. Horne 《Colloids and surfaces. B, Biointerfaces》2003,31(1-4):243-255
Fermentation of a reconstituted skim milk concentrate (8% protein) was investigated to elucidate the effects of various fermentation parameters on the structural, rheological and visual (wheying-off) properties of the resulting gels (pH 4.60). Fermentation trials were performed with non-exocellular polysaccharide-producing strains of Streptococcus thermophilus at various fermentation temperatures and at various chymosin levels. Oscillatory vane rheometry carried out on the intact gels (at 4 °C) showed that the level of chymosin had a significant impact on the gel strength (storage modulus G′). This can be explained by the arrangement of casein micelles into more compact aggregates and the enhanced fusion of aggregated casein micelles as revealed by transmission electron microscopy for the gels fermented with chymosin. Wheying-off of the stirred gels as measured by a centrifugation test (at 4 °C) and pore size of the intact gel structures investigated by scanning electron microscopy both increased with increasing level of chymosin and increasing fermentation temperature (resulting in an increase in acidification rate). A higher level of syneresis (wheying-off) is explained by the larger pore size, since larger pores present a lower resistance to the outflow of whey from the gel. 相似文献
60.