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51.
52.
G. R. van der Hoff R. Hoogerbrugge R. A. Baumann U. A. Th. Brinkman P. van Zoonen 《Chromatographia》2000,52(7-8):433-438
Summary Normal-phase LC (NPLC) is a powerful method for the clean-up of fatty samples in the determination of organochlorine pesticides
(OCPs). The injected sample deactivates the stationary phase and the triglyceride matrix therefore serves as a polarity modifier
in the NPLC separation. Thus, the amount of sample injected is the key to both selectivity and sensitivity in matrixmodified
LC coupled to capillary GC.
In coupled LC-GC the NPLC separation becomes particularly critical because only a limited amount of the LC eluent can be transferred
to the GC and the triglyceride matrix must be prevented from entering the GC, because it degrades the performance of the injector
and the column. In previous applications method development was seriously hampered by these boundary conditions and tedious
and lengthy trial-and-error experiments were required to determine suitable experimental conditions. In this study an empirical
model was developed that describes the NPLC separation process in terms of column dimensions and fat loadability. The output
is given as the probability of achieving successful LC-GC analysis of a particular set of analytes, thus furnishing a useful
tool for the development of new applications in the field of exposure assessment and analysis of residues of apolar compounds
in fatty samples. The limitations of current procedures—maximum transfer volumes and minimal separation—are also discussed. 相似文献
53.
We study the propagation of singularities in solutions of the Navier–Stokes equations of compressible, barotropic fluid flow in two and three space dimensions. The solutions considered are in a fairly broad regularity class for which initial densities are nonnegative and essentially bounded, initial energies are small, and initial velocities are in certain fractional Sobolev spaces. We show that, if the initial density is bounded below away from zero in an open set V, then each point of V determines a unique integral curve of the velocity field and that this system of integral curves defines a locally bi-Hölder homeomorphism of V onto its image at each positive time. This “Lagrangean structure” is then applied to show that, if the initial density has a limit at a point of such a set V from a given side of a continuous hypersurface in V, then at each later time both the density and the divergence of the velocity have limits at the transported point from the corresponding side of the transported hypersurface, which is also a continuous manifold. If the limits from both sides exist, then the Rankine–Hugoniot conditions hold in a strict pointwise sense, showing that the jump in the divergence of the velocity is proportional to the jump in the pressure. This leads to a derivation of an explicit representation for the strength of the jump in the logarithm of the density, from which it follows that discontinuities persist for all time, convecting along fluid particle paths, and in the case that the pressure is strictly increasing in density, having strengths which decay exponentially in time. 相似文献
54.
S.A. Dzuba I.V. Borovykh A.J. Hoff 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1998,133(2):286-290
A microwave two-pulse sequence with a weak and long 180° first pulse and a hard 90° second pulse is employed to detect nuclear coherences in pulsed EPR. The coherences created by the first pulse are transferred after an evolution periodTinto an observable FID by the second pulse. The free induction is measured at some fixed delay after the second pulse; it is modulated whenTis varied. As the second pulse may be switched on immediately after the first pulse, the nuclear coherences may be detected immediately as they start to freely oscillate, without loss of information within the instrumental dead time. The method is demonstrated for a sample of the radical cation of15N-labeled bacteriochlorophylla. 相似文献
55.
P. Hoff B. Ekström B. Fogelberg J. P. Omtvedt 《Zeitschrift für Physik A Hadrons and Nuclei》1991,338(3):285-289
The decay properties of84As have been investigated with mass separated sources. Only one β-decaying state is seen, contradictory to previous observations. The halflife is found to be 4.5±0.2 s. A detailed decay scheme has been constructed, and 33 excited states in84Se have been determined. 相似文献
56.
E. Bodenstedt B. Hamer P. Herzog J. van den Hoff H. Münning S. Piel J. Prinz R. Sajok 《Zeitschrift für Physik A Hadrons and Nuclei》1992,342(3):249-256
Theg-factor of the 21 + state of192Pt has been measured by the IPAC technique in an external magnetic field as:g(21 +,192Pt)=+0.287(17). An additional IPAC experiment with an192IrFe sample was performed with the same level in order to investigate the hyperfine field. The result:ω L τ(21 +,192PtFe)=0.1115(9) gives the hyperfine field:B hf 4.2k (PtFe)=126.8(71) T. The result of an LTNO experiment with the same level is compatible with the assumption that 100% of the192Ir atoms were on unique sites. 相似文献
57.
A computer programme for determination of equilibrium constant (K) and enantiomer ratio (E) in biocatalytic resolutions has been developed. The programme utilises experimental data, ees and eep measured at more than one conversion, and determines both K and E no matter whether the reaction is irreversible (K=0) or reversible (K>0). An estimation of errors in the calculations indicates that errors in E does not show a Gaussian distribution, while errors in K does. The usefulness of the programme has been tested in a lipase-catalysed transesterification of 1-phenoxy-2-propanol at various concentrations of acyl donor, with different solvents and at different water activities. 相似文献
58.
Site-selection experiments have been performed on pheophytin-a and chlorophyll-a in n-octane at 4.2 K. Single-site absorption spectra of both compounds were recorded, but single-site emission spectra could not be obtained. The absorption spectra show sharp lines and vibrational frequencies of the lowest excited singlet state correspond with resonance Raman frequencies. A remarkable feature of the emission is the presence of a strong 0-0 transition but extremely weak vibronic transitions. 相似文献
59.
Vladimira Jirsakova Françoise Reiss-Husson Bas van Dijk Gabrielle Owen Arnold J. Hoff 《Photochemistry and photobiology》1996,64(2):363-368
The carotenoid triplet states in the light-harvesting complex B800–850from purple bacterium Rubrivivax gelatinosus were characterized by absorption-detected magnetic resonance in zero magnetic field (ADMR) spectroscopy. Detailed HPLC analysis of carotenoids from B800–850demonstrated the presence of several carotenoids bound to the complex: the major ones are hydroxyspheroidene and spheroidene (together 80%), followed by neurosporene and hydroxyneurosporene (7%), spheroidenone and hydroxyspheroidenone (7.5%) and two other minor carotenoids that could be 3,4-dihydrospheroidenone and 3,4-dihydrohydroxyspheroidenone (5.5%). Three triplet states originating from carotenoids present in the B800–850were observed. The identical T-S spectra recorded at selectively chosen 2|E| transitions of carotenoids indicated that all these triplet states can be attributed to three different populations of one carotenoid family, probably to spheroidene and to hydroxyspheroidene, with different out-of-plane distortions of their polyene chain due to a different protein environment. Triplet states of the neurosporene and the spheroidenone families are probably not observed because of the low signal amplitude. 相似文献
60.
Sukcharoenphon K Moran D Schleyer Pv McDonough JE Abboud KA Hoff CD 《Inorganic chemistry》2003,42(25):8494-8503
2-pyridinethione (2-mercaptopyridine, H-2mp) undergoes rapid oxidative addition with 2 mol of the 17-electron organometallic radical *Cr(CO)3Cp (where Cp*=C5Me5), yielding hydride H-Cr(CO)3Cp* and thiolate (eta1-2mp)Cr(CO)3Cp*. In a slower secondary reaction, (eta1-2mp)Cr(CO)3Cp* loses CO generating the N,S-chelate complex (eta2-2mp)Cr(CO)2Cp* for which the crystal structure is reported. The rate of 2-pyridine thione oxidative addition with *Cr(CO)3Cp* (abbreviated *Cr) in toluene best fits rate=kobs[H-2mp][*Cr]; kobs(288 K)=22 +/- 4 M(-1) s(-1); DeltaH++=4 +/- 1 kcal/mol; DeltaS++=- 40 +/- 5 cal/mol K. The rate of reaction is the same under CO or Ar, and the reaction of deuterated 2-pyridine thione (D-2mp) shows a negligible (inverse) kinetic isotope effect (kD/kH=1.06 +/- 0.10). The rate of decarbonylation of (eta1-2mp)Cr(CO)3Cp* forming (eta2-2mp)Cr(CO)2Cp* obeys simple first-order kinetics with kobs (288 K)=3.1x10(-4) s(-1), DeltaH++=23 +/- 1 kcal/mol, and DeltaS++=+ 5.0 +/- 2 cal/mol K. Reaction of 4-pyridine thione (4-mercaptopyridine, H-4mp) with *Cr(CO)3Cp* in THF and CH2Cl2 also follows second-order kinetics and is approximately 2-5 times faster than H-2mp in the same solvents. The relatively rapid nature of the thione versus thiol reactions is attributed to differences in the proposed 19-electron intermediate complexes, [*(S=C5H4N-H)Cr(CO)3Cp*] versus [*(H-S-C6H5)Cr(CO)3Cp*]. In comparison, reactions of pyridyl disulfides occur by a mechanism similar to that followed by aryl disulfides involving direct attack of the sulfur-sulfur bond by the metal radical. Calorimetric data indicate Cr-SR bond strengths for aryl and pyridyl derivatives are similar. The experimental conclusions are supported by B3LYP/6-311+G(3df,2p) calculations, which also provide additional insight into the reaction pathways open to the thione/thiol tautomers. For example, the reaction between H* radical and the 2-pyridine thione S atom yielding a thionyl radical is exothermic by approximately 30 kcal/mol. In contrast, the thiuranyl radical formed from the addition of H* to the 2-pyridine thiol S atom is predicted to be unstable, eliminating either H* or HS* without barrier. 相似文献