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21.
Helmut Sengstschmid Heinz Sterk Ray Freeman 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1998,131(2):315-326
An automated scheme is described which locates the centers of cross peaks in two-dimensional correlation spectra, even under conditions of severe overlap. Double-quantum-filtered correlation (DQ-COSY) spectra have been investigated, but the method is also applicable to TOCSY and NOESY spectra. The search criterion is the intrinsic symmetry (or antisymmetry) of cross-peak multiplets. An initial global search provides the preliminary information to build up a two-dimensional “chemical shift grid.” All genuine cross peaks must be centered at intersections of this grid, a fact that reduces the extent of the subsequent search program enormously. The program recognizes cross peaks by examining the symmetry of signals in a test zone centered at a grid intersection. This “symmetry filter” employs a “lowest value algorithm” to discriminate against overlapping responses from adjacent multiplets. A progressive multiplet subtraction scheme provides further suppression of overlap effects. The processed two-dimensional correlation spectrum represents cross peaks as points at the chemical shift coordinates, with some indication of their relative intensities. Alternatively, the information is presented in the form of a correlation table. The authenticity of a given cross peak is judged by a set of “confidence criteria” expressed as numerical parameters. Experimental results are presented for the 400-MHz double-quantum-filtered COSY spectrum of 4-androsten-3,17-dione, a case where there is severe overlap. 相似文献
22.
23.
KlÁra GÁll-IstÓk Lili Sterk GÁbor TÓth Gyula Deák 《Journal of heterocyclic chemistry》1984,21(4):1045-1048
1-(2′-Chloroacetylamino)-4,4-dimethyl-1,4-dihydro-3(2H)-isoquinolinone ( 3 ) was cyclised by treatment with sodium hydride in dimethyl sulphoxide containing 0.1 % of water to give 10,10-dimethyl-6,7,9,10-tetrahydro-5H,14bH-isoquino[2,1-d][1,4]benzodiazepine-6,9-dione ( 4 ) in a yield of 80%. In anhydrous dimethyl sulphoxide the main product of the reaction was 5-N-(4,4-dimethyl-1-phenyl-1,4-dihydro-3(2H)-isoquinolinon-1′-yl)isoquino[2,1-d][1,4]benzodiazepine-6,9-dione ( 5 ), which was also prepared by the reaction of 3 with 4 . 相似文献
24.
Zusammenfassung Die Fragmentation von -Lactamen ergibt massenspektroskopisch sowie thermisch entweder die Ausgangsverbindungen Keten und Azomethin oder bevorzugt Äthylene und Isocyanate. Dabei brechen jeweils zwei gegenüberliegende Bindungen. Eine Berechnung der Überlappungsenergien im Ring mittels der EHT-Methode zeigt, daß der induktive Einfluß der Substituenten die Richtung des Zerfalls bestimmt. Es kann auch bei anderen Vierring-Ketonen eine bevorzugte Fragmentation des Ketenbestandteiles nachgewiesen werden.
Mit 4 Abbildungen
Herrn Prof. Dr. techn. Dr. h. c.O. Kratky, Vorstand des Institutes für Physikalische Chemie der Universität Graz, zum 70. Geburtstag gewidmet. 相似文献
An attempt to calculate the fragmentation of -lactams by the EHT method
Both mass spectroscopic and thermal fragmentation of -lactams yield either the reactants (ketenes and azomethines), or preferentially ethylenes and isocyanates. In each case two opposite bonds are broken. Calculation of the overlap energies in the ring by the EHT method shows that the direction of fragmentation is determined by the inductive influence of the substituents. Preferential fragmentation of the ketene constituent can also be demonstrated in other four-membered ring ketones.
Mit 4 Abbildungen
Herrn Prof. Dr. techn. Dr. h. c.O. Kratky, Vorstand des Institutes für Physikalische Chemie der Universität Graz, zum 70. Geburtstag gewidmet. 相似文献
25.
This work is concerned with the relationship between chemical shifts (δ) of protons and their charge densities (q). It can be shown that the relation δH = a + bqH + cqC (qC = charge density at the corresponding C-atom) fits best for a prediction of δ-values from calculated charge densities. The smallest standard error for the prediction of δ-values is obtained if the charge densities are calculated by the CNDO- or INDO-method. 相似文献
26.
Blokland MH Sterk SS Stephany RW Launay FM Kennedy DG van Ginkel LA 《Analytical and bioanalytical chemistry》2006,384(5):1221-1227
An EU project, FAIR5-CT-1997-3443, has been undertaken to distinguish illegal use of zeranol from consumption of food contaminated
with Fusarium spp. toxin. One of the tasks was development of screening and confirmatory methods of analysis. This paper describes a new method
based on two-step clean-up and GC–MS analysis. The first clean-up step is matrix-dependant; the second is applicable to both
urine and meat. The MS is operated in negative chemical ionisation mode. The method is quantitative for zeranol and taleranol,
α- and β-zearalenol, and zearalenone and qualitative for zearalanone. Validation was performed according to the latest EU
performance criteria (Commission Decision 2002/657). For analysis of urine and for the method (μg L−1) were 0.06–0.11 for zeranol, 0.07–0.12 for taleranol, 0.07–0.11 for α-zearalenol, 0.21–0.36 for β-zearalenol, 0.35–0.60 for
zearalenone, and 0.19–0.33 zearalanone. Within-laboratory reproducibility was 16.2, 11.2, 31.9, 30.1, 26.6, and 54.2% for
zeranol, taleranol, α-zearalenol, β-zearalenol, zearalenone, and zearalanone, respectively. It was found that all the compounds
are stable in urine at −20°C for at least a year. Part of the validation program was organisation of a small proficiency study
(ringtest) and a correlation study with an LC–MS–MS method developed by the Veterinary Science Division (VSD; Belfast, UK-NI).
This study showed there was good correlation between results from both laboratories. The method can be used for quantitative
analysis discriminating illegal use of zeranol from consumption of zearalenone-contaminated food. 相似文献
27.
Blokland MH Zoontjes PW Sterk SS Stephany RW Zweigenbaum J van Ginkel LA 《Analytica chimica acta》2008,618(1):86-93
The use of accurate mass measurement as a confirmation tool is examined on a TOF-MS and compared with confirmation using a triple quadrupole mass spectrometer (QqQ-MS). Confirmation of the identity of a substance using mass-spectrometric detection has been described. However, the use of accurate mass measurement for confirmatory analysis has not been taken into account. In this study, criteria for confirmation with accurate mass are proposed and feasibility is demonstrated. Mass accuracy better than 3 ppm of the quasi-molecular ion and a fragment and their relative ratios determined with LC/TOF-MS are compared to the criteria of two transition ions and their ratio of LC/QqQ-MS. The results show that these criteria can be met for Trenbolone in samples of bovine urine and that single MS accurate mass measurement is comparable to nominal mass MS/MS for confirmation. The increase in popularity and availability of LC/TOF-MS instruments and the ease, of which exact masses can be measured, make it important to formulate criteria for this type of instrumentation. It is shown in this study that accurate mass measurement can be used for confirmatory analysis. However, more experiments need to be conducted to demonstrate the applicability of accurate mass measurement in general for residue analysis. 相似文献
28.
The method comprises the screening of two groups of anabolic compounds, the stilbenes and several steroids. All compounds, inclusive their metabolites when possible, for which gas chromatography-mass spectrometry (GC-MS) currently is the preferred analytical technique, are included. Two different derivatives are prepared. One group, including the stilbenes, is detected as HFB derivative (Method 1), the second group is detected as TMS derivative (Method 2). The method is used to perform a qualitative and semi-quantitative analysis of a minimum package of anabolic steroids to be included in National Residue Control Plans based on Council Directive 96/23 and complies with the current Minimum Required Performance Limits. The method has been validated according to Commission Decision 2002/657/EC. The CCalpha and CCbeta values are based on the detection of the most abundant ion. Results of validation experiments are presented. The method is flexible and due to the non-specific sample clean-up more and new anabolic compounds can be easily added in order to new monitoring requirements. 相似文献
29.
Mark P. HollandRenato Vitolo Pau RabassaAlef E. Sterk Henk W. Broer 《Physica D: Nonlinear Phenomena》2012,241(5):497-513
Extreme value theory for chaotic deterministic dynamical systems is a rapidly expanding area of research. Given a system and a real function (observable) defined on its phase space, extreme value theory studies the limit probabilistic laws obeyed by large values attained by the observable along orbits of the system. Based on this theory, the so-called block maximum method is often used in applications for statistical prediction of large value occurrences. In this method, one performs statistical inference for the parameters of the Generalised Extreme Value (GEV) distribution, using maxima over blocks of regularly sampled observable values along an orbit of the system. The observables studied so far in the theory are expressed as functions of the distance with respect to a point, which is assumed to be a density point of the system’s invariant measure. However, at least with respect to the ambient (usually Euclidean) metric, this is not the structure of the observables typically encountered in physical applications, such as windspeed or vorticity in atmospheric models. In this paper we consider extreme value limit laws for observables which are not expressed as functions of the distance (in the ambient metric) from a density point of the dynamical system. In such cases, the limit laws are no longer determined by the functional form of the observable and the dimension of the invariant measure: they also depend on the specific geometry of the underlying attractor and of the observable’s level sets. We present a collection of analytical and numerical results, starting with a toral hyperbolic automorphism as a simple template to illustrate the main ideas. We then formulate our main results for a uniformly hyperbolic system, the solenoid map. We also discuss non-uniformly hyperbolic examples of maps (Hénon and Lozi maps) and of flows (the Lorenz63 and Lorenz84 models). Our purpose is to outline the main ideas and to highlight several serious problems found in the numerical estimation of the limit laws. 相似文献
30.
Helga Wittmann H. Platzer H. Sterk A. K. Müller E. Ziegler 《Monatshefte für Chemie / Chemical Monthly》1972,103(5):1253-1261
o-Halogenated (o,o-dihalogenated) anilines react with phenalenetrione (PT) in boiling xylene or acetic acid to give 7H,8H-naphtho[1.8–bc]phenoxazin-7-one derivatives. The analogous reaction with 2.6-dimethyl-or 2.6-diethyl-aniline in xylene gives oxazepines, while in acetic acid preferential addition of the aniline with the para position to the NH2-group to the central C=O-group ofPT occurs. It can be shown, that the first step in the ring closure reaction is the formation of semiaminales.Es wird gezeigt, daß Aniline, die in 2-bzw. 2,6-Stellung halogensubstituiert sind, mit Phenalentrion (PT) in Xylol oder Eisessig zu den entsprechenden 7H,8H-Naphtho[1,8–bc]-phenoxazin-7-on-derivaten reagieren. Die analoge Umsetzung mit 2,6-Dimethyl-bzw. 2,6-Diäthyl-anilin in Xylol führt zu Oxazepinen, während in Eisessig bevorzugt Addition des zur NH2-Gruppe in p-Stellung befindlichen H-Atoms an die mittelständige C=O-Gruppe desPT stattfindet. Es wird experimentell bewiesen, daß diese Ringschlußreaktion über primär gebildete Halbaminale abläuft.
Herrn Prof. Dr.O. Kratky, Graz, mit besten Wünschen zum 70. Geburtstag gewidmet. 相似文献
Herrn Prof. Dr.O. Kratky, Graz, mit besten Wünschen zum 70. Geburtstag gewidmet. 相似文献