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51.
A non-linear least-squares program for the analysis of Mössbauer spectra is presented. The program is capable of resolving very complex spectra and can be used on a minicomputer system, with regard to both calculation time and memory requirements. The commonly used x2-minimization algorithm was slightly adapted, so as to broaden its working range. All possibilities for fixing or changing parameters are provided. Two new parameter limitation techniques, which greatly reduce the need for manual intervention during the fitting process, are discussed extensively. 相似文献
52.
First we introduce and analyze a convergent numerical method for a large class of nonlinear nonlocal possibly degenerate convection diffusion equations. Secondly we develop a new Kuznetsov type theory and obtain general and possibly optimal error estimates for our numerical methods—even when the principal derivatives have any fractional order between 1 and 2! The class of equations we consider includes equations with nonlinear and possibly degenerate fractional or general Levy diffusion. Special cases are conservation laws, fractional conservation laws, certain fractional porous medium equations, and new strongly degenerate equations. 相似文献
53.
54.
A two-valve sub-ambient temperature-promoted reversed-phase packed-capillary liquid-chromatography column-switching system has been tailored for sensitive determination of hydrophobic compounds. Such compounds are not easily dissolved in solvent mixtures of non-eluting properties that traditionally are used for solute enrichment in reversed-phase liquid chromatography. Enrichment-column solute focusing of large sample volumes was promoted by use of sub-ambient temperatures only, allowing the use of sample solvents that were stronger or equal to the mobile phase solvent strength. Subsequent column switching and enrichment-column temperature increment provided efficient low-dispersion back-flushed enrichment-column solute desorption onto the analytical column, where the solute was subjected to temperature-programmed gradient action. The antioxidant, Irganox 1076 (octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) extracted from low density polyethylene with 100% acetonitrile served as a hydrophobic model compound. The mobile phase consisted of acetonitrile containing 10 mM triethylamine and formic acid, and the 0.25 mm id enrichment-column and analytical column in lengths of 27 and 250 mm, respectively, were packed with 3.5 microm Kromasil C18 particles. Sample volumes of up to 500 microL were successfully focused on the enrichment column at 5 degrees C using loading flow rates of up to 40 microL min(-1) prior to temperature programming to 90 degrees C. The concentration limit of detection of Irganox 1076 was 6 ng mL(-1) when using an injection volume of 500 microL. The within-assay precision was in the range 3.5-6.8% (n = 6) while the between-day precision was 7.5% (n = 3) relative standard deviation. The method was linear within the investigated mass range 3-100 ng (R2 = 0.9993). 相似文献
55.
A 3D lattice Boltzmann model for two-phase flow with amphiphilic surfactant was used to investigate the evolution of emulsion morphology and shear stress in starting shear flow. The interfacial contributions were analyzed for low and high volume fractions and varying surfactant activity. A transient viscoelastic contribution to the emulsion rheology under constant strain rate conditions was attributed to the interfacial stress. For droplet volume fractions below 0.3 and an average capillary number of about 0.25, highly elliptical droplets formed. Consistent with affine deformation models, gradual elongation of the droplets increased the shear stress at early times and reduced it at later times. Lower interfacial tension with increased surfactant activity counterbalanced the effect of increased interfacial area, and the net shear stress did not change significantly. For higher volume fractions, co-continuous phases with a complex topology were formed. The surfactant decreased the interfacial shear stress due mainly to advection of surfactant to higher curvature areas. Our results are in qualitative agreement with experimental data for polymer blends in terms of transient interfacial stresses and limited enhancement of the emulsion viscosity at larger volume fractions where the phases are co-continuous. 相似文献
56.
Anthony Prandina Sylvie Radix Marc Le Borgne Lars Petter Jordheim Zineb Bousfiha Christopher Fröhlich Hanna-Kirsti S. Leiros Ørjan Samuelsen Espen Frøvold Pål Rongved Ove Alexander Høgmoen Åstrand 《Tetrahedron》2019,75(11):1525-1540
Antibiotics are key drugs in modern healthcare, especially in hospitals, where multiresistant bacteria resides and is a potential threat to human health. In the present work, a new series of adjuvants working synergistically with the carbapenem meropenem, in which a selective zinc-chelating agent was covalently linked to the small bacterial peptide D-Ala-D-Ala, was synthesized and tested against VIM-2 and NDM-1 metallo-β-lactamases (MBLs). The nature of the linker was modified in a structure-activity relationship study. Compound 1i, having an ethyl piperidine linker, lowered the MIC of meropenem from 32 to 64?mg/L to 2 and 1–2?mg/L against VIM-2- and NDM-1-producing clinical isolates, respectively. The IC50 value of 1i against VIM-2 was 9.8 and 2.2?μM after 5 and 20?min, respectively. Compound 1i also showed intrinsic toxicity against three eukaryotic human tumoral cell lines between 50 and 120?μM. 相似文献
57.
Jensen KM Christensen M Juhas P Tyrsted C Bøjesen ED Lock N Billinge SJ Iversen BB 《Journal of the American Chemical Society》2012,134(15):6785-6792
The formation and growth mechanisms in the hydrothermal synthesis of SnO(2) nanoparticles from aqueous solutions of SnCl(4)·5H(2)O have been elucidated by means of in situ X-ray total scattering (PDF) measurements. The analysis of the data reveals that when the tin(IV) chloride precursor is dissolved, chloride ions and water coordinate octahedrally to tin(IV), forming aquachlorotin(IV) complexes of the form [SnCl(x)(H(2)O)(6-x)]((4-x)+) as well as hexaaquatin(IV) complexes [Sn(H(2)O)(6-y)(OH)(y)]((4-y)+). Upon heating, ellipsoidal SnO(2) nanoparticles are formed uniquely from hexaaquatin(IV). The nanoparticle size and morphology (aspect ratio) are dependent on both the reaction temperature and the precursor concentration, and particles as small as ~2 nm can be synthesized. Analysis of the growth curves shows that Ostwald ripening only takes place above 200 °C, and in general the growth is limited by diffusion of precursor species to the growing particle. The c-parameter in the tetragonal lattice is observed to expand up to 0.5% for particle sizes down to 2-3 nm as compared to the bulk value. SnO(2) nanoparticles below 3-4 nm do not form in the bulk rutile structure, but as an orthorhombic structural modification, which previously has only been reported at pressures above 5 GPa. Thus, adjustment of the synthesis temperature and precursor concentration not only allows control over nanoparticle size and morphology but also the structure. 相似文献
58.
von der Recke R Mariussen E Berger U Götsch A Herzke D Vetter W 《Rapid communications in mass spectrometry : RCM》2005,19(24):3719-3723
Enantioselective determination of the atropisomers of 2,2',3,4',5',6-hexabromobiphenyl (PBB 149) in a purified sample from a bird egg was attempted in this work. By application of the classic method for PBB determination, i.e. gas chromatography coupled to electron capture negative ionization mass spectrometry (GC/ECNI-MS) using the bromide ions, the enantiomers interfered with another brominated compound. Subsequent measurements clarified that this interference did not occur in the mass chromatogram of the molecular ion of PBB 149. Therefore, a GC/ECNI tandem mass spectrometry (MS/MS) method was developed, based on the fragmentation of [M]-. A suitable precursor-product ion transition was found for m/z 627.5 --> 80 +/- 1.5, representing the most abundant ion trace of the molecular ion and the bromide ions. Optimization of the ion source temperature, the methane gas pressure, and the collision voltages resulted in a robust method that could solve the problem. Subsequent injections of a technical PBB product (Firemaster BP-6) resulted in the anticipated racemic proportion (enantiomer fraction (EF) = 0.50 +/- 0.02 (n = 8)). By contrast, the EF in the purified extract of a bird egg was found to be 0.42 +/- 0.02 (n = 10), indicative of a significant enantioenrichment of the second eluting atropisomer. Additional measurements were performed on a non-chiral column. These measurements allowed for the detection of 16 hexabromobiphenyls (hexa-BBs) in Firemaster BP-6. These comparisons verified that PBB 149 enantiomers did not interfere with an isomer that could falsify the enantiomer fraction in the sample. The novel method using GC/ECNI-MS/MS in the selected reaction monitoring (SRM) mode was eight times more sensitive than application of conventional GC/ECNI-MS selected ion monitoring (SIM) analysis of the molecular ion. 相似文献
59.
Stochastic Modelling of Temperature Variations with a View Towards Weather Derivatives 总被引:1,自引:0,他引:1
Daily average temperature variations are modelled with a mean‐reverting Ornstein–Uhlenbeck process driven by a generalized hyperbolic Lévy process and having seasonal mean and volatility. It is empirically demonstrated that the proposed dynamics fits Norwegian temperature data quite successfully, and in particular explains the seasonality, heavy tails and skewness observed in the data. The stability of mean‐reversion and the question of fractionality of the temperature data are discussed. The model is applied to derive explicit prices for some standardized futures contracts based on temperature indices and options on these traded on the Chicago Mercantile Exchange (CME). 相似文献
60.
A mean‐reverting model is proposed for the spot price dynamics of electricity which includes seasonality of the prices and spikes. The dynamics is a sum of non‐Gaussian Ornstein–Uhlenbeck processes with jump processes giving the normal variations and spike behaviour of the prices. The amplitude and frequency of jumps may be seasonally dependent. The proposed dynamics ensures that spot prices are positive, and that the dynamics is simple enough to allow for analytical pricing of electricity forward and futures contracts. Electricity forward and futures contracts have the distinctive feature of delivery over a period rather than at a fixed point in time, which leads to quite complicated expressions when using the more traditional multiplicative models for spot price dynamics. In a simulation example it is demonstrated that the model seems to be sufficiently flexible to capture the observed dynamics of electricity spot prices. The pricing of European call and put options written on electricity forward contracts is also discussed. 相似文献