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101.
102.
103.
For a restricted class of problems a mathematical model of microscopic degradation processes, statistical kinetics, is developed and linked throughacceleration transforms to the information which can be obtained from a system in which the only observable sign of degradation is sudden and catastrophic failure. The acceleration transforms were developed in accelerated life testing applications as a tool for extrapolating from the observable results of an accelerated life test to the dynamics of the underlying degradation processes. A particular concern of a physicist attempting to interpreted the results of an analysis based on acceleration transforms is determining the physical species involved in the degradation process. These species may be (a) relatively abundant or (b) relatively rare. The main results of this paper are a theorem showing that for an important subclass of statistical kinetic models, acceleration transforms cannot be used to distinguish between cases a and b, and an example showing that in some cases falling outside the restrictions of the theorem, cases a and b can be distinguished by their acceleration transforms. 相似文献
104.
Matoušek T Hernández-Zavala A Svoboda M Langrová L Adair BM Drobná Z Thomas DJ Stýblo M Dědina J 《Spectrochimica Acta Part B: Atomic Spectroscopy》2008,63(3):396-406
An automated system for hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l(-1). Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of L-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the L-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. 相似文献
105.
Pavel Svoboda Pavel Javorský Fuminori Honda Vladimír Sechovský Alois A. Menovsky 《Central European Journal of Physics》2004,2(2):397-418
The tetragonal compound UNi2Si2 exhibits in zero magnetic field three different antiferromagnetic phases belowT
N
=124 K. They are formed by ferromagnetic basal planes, which are antiferromagnetically coupled along thec-axis with the propagation vectorq=(0, 0, q
z
). Two additional order-order magnetic phase transitions are observed below T
N
, namely atT
1=108 K and T
2=40 K in zero magnetic field. All three phases exhibit strong uniaxial anisotropy confining the U moments to a direction parallel
to the c-axis. UNi2Si2 single crystals were studied in detail by measuring bulk thermodynamic properties, such as thermal expansion, resistivity,
susceptibility, and specific heat. A microscopic study using neutron diffraction was performed in magnetic fields up to 14.5
T parallel to the c-axis, and a complex magnetic phase diagram has been determined. Here, we present the analysis of specific-heat data measured
in magnetic fields up to 14 T compared with the results of the neutron-diffraction study and with other thermodynamic properties
of UNi2Si2. 相似文献
106.
M. Aksu S. Durmu M. Sari K. C. Emregül I. Svoboda H. Fuess O. Atakol 《Journal of Thermal Analysis and Calorimetry》2007,90(2):541-547
N,N′-bis(salicylidene)-1,3-propanediamine (LH2), N,N′-bis(salicylidene)-2,2′-dimethyl-1,3-propanediamine (LDMH2), N,N′-bis(salicylidene)-2-hydroxy-1,3-propanediamine (LOH3), N,N′-bis(2-hydroxyacetophenylidene)-1,3-propanediamine (LACH2) and N,N′-bis(2-hydroxyacetophenone)-2,2′-dimethyl-1,3-propanediamine (LACDMH2) were synthesized and reduced to their phenol-amine form in alcoholic media using NaBH4 (LHH2, LDMHH2, LOHHH2, LACHH2 and LACDMHH2). Heterodinuclear complexes were synthesized using Ni(II), Zn(II) and Cd(II) salts, according to the template method in DMF
media.
The complex structures were analyzed using elemental analysis, IR spectroscopy, and thermogravimetry. Suitable crystals of
only one complex were obtained and its structure determined using X-ray diffraction, NiLACH·CdBr2·DMF2, space group orthorhombic, Pbca, a=20.249, b=14.881, c=20.565 ? and Z=8. The heterodinuclear complexes were seen to be of [Ni·ligand·MX2·DMF2] structure (ligand=LH2−, LDMH2−, LOHH2−, LACH2−, LACDMH2−, M=ZnII, CdII, X=Br−, I−). Thermogravimetric analysis showed irreversible bond breakage of the coordinatively bonded DMF molecules followed by decomposition
at this temperature. 相似文献
107.
Luo Y Uboh CE Soma LR Guan FY Rudy JA Tsang DS 《Rapid communications in mass spectrometry : RCM》2005,19(10):1245-1256
A method for the simultaneous separation, identification, quantification and confirmation of the presence of 21 glucocorticoids (GCC) in equine plasma by liquid chromatography coupled with triple stage quadrupole tandem mass spectrometry (LC/TSQ-MS/MS) is described. Plasma sample augmented with the 21 GCC was extracted with methyl tert-butyl ether (MTBE) and analyzed by positive electrospray ionization. Desoxymetasone or dichlorisone acetate was used as the internal standard (IS). Quantification was performed by IS calibration. For each drug, one major product ion was chosen and used for screening for that drug. Analyte confirmation was performed by using the three most intense product ions formed from the precursor ion and the corresponding mass ratios. The recovery of the 21 GCC when spiked into blank plasma at 5 ng/mL was 45-200% with coefficient of variation (CV) from 0.3-18%. The limit of detection (LOD) and that of quantification (LOQ) for most of the analytes were 50-100 pg/mL and 1 ng/mL, respectively, whereas that of confirmation (LOC) was 100-300 pg/mL depending on the analyte. Intra- and inter-day precisions expressed as CV for quantification of 1 and 10 ng/mL was 1.0-17%, and 0.51-19%, respectively, and the accuracy was from 84-110%. The linear concentration range for quantification was 0.1-100 ng/mL (r(2) > 0.997). Estimated measurement uncertainty was from 11-37%. This study was undertaken to develop a method for simultaneous screening, identification, quantification and confirmation of these agents in post-race equine plasma samples. The method has been successfully applied to screening of a large number of plasma samples obtained from racehorses in competition and in pharmacokinetic studies of dexamethasone in the horse and concurrent changes in endogenous GCC, hydrocortisone and cortisone. The method is simple, sensitive, selective and reliably reproducible. 相似文献
108.
Zusammenfassung Der Aufbau des Dreistoffes: Hf–Ta–C wird für 1850°C mittels druckgesinterter und vakuum-geglühter Proben bestimmt. Die lückenlose Mischbarkeit der Monocarbide wird erneut bestätigt. Ta2C löst etwas mehr als 10 Mol% Hafniumcarbid. Die -Phase (Ta3C2) wird bereits bei geringen Hf-Konzentrationen unterdrückt. Das Dreiphasenfeld: (Hf, Ta)-Mischkristall+(Hf, Ta)C1-x+(Ta, Hf)2C charakterisiert den Schnitt. Hafnium reichert sich in der Carbidphase an. Die Gleichgewichte werden unter vereinfachenden Annahmen thermodynamisch ausgewertet und folgende Differenzen für freie Bildungsenergien (1850°C) errechnet: G
HfC–G
TaC=–8500 cal/Mol, G(Hf2C)—G
Ta
2C=–5000 cal/Mol. Ein zu Ta2C analoges Hafniumcarbid (Hf2C) ist jedoch um 10 000 cal/Mol weniger stabil als ein Gemenge: HfC1–x+Hafnium. Es besteht gute Übereinstimmung zwischen den gerechneten und den experimentell ermittelten Konoden. Aussagen über das verwandte System: Hf–Nb–C werden gemacht.Mit 5 Abbildungen 相似文献
109.
J. Leitner M. Hampl K. Ri
ka D. Sedmidubský P. Svoboda J. Vejpravov 《Thermochimica Acta》2006,450(1-2):105-109
The heat capacities and enthalpy increments of strontium bismuth niobate SrBi2Nb2O9 (SBN) and strontium bismuth tantalate SrBi2Ta2O9 (SBT) were measured by the relaxation method (2–150 K), Calvet-type heat-conduction calorimetry (305–570 K) and drop calorimetry (773–1373 K). The temperature dependences of non-transition heat capacities in the form Cpm = 324.47 + 0.06371T − 5.0755 × 106/T2 J K−1 mol−1 (298–1400 K) and Cpm = 320.22 + 0.06451T − 4.7001 × 106/T2 J K−1 mol−1 (298–1400 K) were derived for SBN and SBT, respectively, by the least-squares method from the experimental data. Furthermore, the standard molar entropies at 298.15 K Sm°(SBN)=327.15±0.80 and Sm°(SBT)=339.23±0.72 J K−1 mol−1 were evaluated from the low-temperature heat capacity measurements. 相似文献
110.
Nobilis M Kopecký J Kvetina J Chládek J Svoboda Z Vorísek V Perlík F Pour M Kunes J 《Journal of chromatography. A》2002,949(1-2):11-22
Simultaneous HPLC determination of the analgetic agent tramadol, its major pharmacodynamically active metabolite (O-desmethyltramadol) in human plasma is described. Simple methods for the preparation of the standard of the above-mentioned tramadol metabolite and N1,N1-dimethylsulfanilamide (used as the internal standard) are also presented. The analytical procedure involved a simple liquid-liquid extraction of the analytes from the plasma under the conditions described previously. HPLC analysis was performed on a 250x4 mm chromatographic column with LiChrospher 60 RP-selectB 5-microm (Merck) and consists of an analytical period where the mobile phase acetonitrile-0.01 M phosphate buffer, pH 2.8 (3:7, v/v) was used, and of a subsequent wash-out period where the plasmatic ballast compounds were eluted from the column using acetonitrile-ultra-high-quality water (8:2, v/v). The whole analysis, including the equilibration preceding the initial analytical conditions lasted 19 min. Fluorescence detection (lambda(ex) 202 nm/lambda(em) 296 nm for tramadol and its metabolite, lambda(ex) 264 nm/lambda(em) 344 nm for N1,N1-dimethylsulfanilamide) was used. The validated analytical method was applied to pharmacokinetic studies of tramadol in human volunteers. 相似文献