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  • 2020-2024
  • 2015-2019
  • 1995-1999  (132)
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  • 101
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 300-302 
    ISSN: 0935-6304
    Schlagwort(e): Supercritical-fluid-extraction ; supercritical-fluid-chromatography ; vitamin E ; pharmaceuticals ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: No abstract
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 102
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 315-321 
    ISSN: 0935-6304
    Schlagwort(e): Glycopeptide antibiotics ; chiral selectors ; Teicoplanin ; enantioseparations ; CZE ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Baseline separation of the enantiomers of a number of negatively charged amino and mandelic acid derivatives was achieved in less than 10 min by capillary electrophoresis in a polyacrylamide coated capillary, using the “partial filling method” (PFM) with submillimolar concentration of Teicoplanin (TE) as the chiral selector. The influence of the charge and concentration of TE, electrolyte solution composition and pH, on the enantioresolution was examined. Further proofs were brought to corroborate the hypothesis that the enantiorecognition takes place at the D-Ala-D-Ala binding site, whose blockade is responsible for the antibacterial activity of glycopeptide antibiotics. While the dependence of the chiral recognition capabilities of TE on electrolyte solution composition and pH could limit its applicability, improved sensitivity, reduction of TE wall adsorption, resulting in a good efficiency, and high cost reduction, due to the very small amount of chiral selector required, were shown as advantages of the PFM adopted in this study.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 103
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 327-334 
    ISSN: 0935-6304
    Schlagwort(e): Large volume on-column injection ; partially concurrent solvent evaporation ; solvent trapping ; retaining precolumn ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---When 0.53 mm i.d. uncoated precolumns connected to a solvent vapor exit are used for sample introduction with partially concurrent solvent evaporation, substantial losses of volatile solutes are often observed. They were found to be the consequence of solute accumulation at the front end of the flooded zone, which in turn is the result of a strong pressure drop over the flooded zone owing to the formation of plugs of sample liquid. The pressure drop causes significant solvent evaporation at the front, which enriches the solute material there and causes its loss. The use of 0.32 mm i.d. restrictions between the uncoated precolumn and the vapor exit greatly reduced this problem.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 104
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 339-342 
    ISSN: 0935-6304
    Schlagwort(e): Chlorophyll ; SFC ; supercritical fluid chromatography ; vegetables ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Complex mixtures of chlorophyll degradation products may arise during processing and storage of vegetable oil and green plant materials like broccoli and spinach. Determination of these compounds is important in the area of food chemistry. Therefore a method using packed column supercritical fluid chromatography (SFC) has been developed. The method comprises chromatography using a simple gradient of methanol in carbon dioxide at constant column back pressure of 30 MPa and a column temperature of 40°C. Effects of pressure and mobile phase composition showed the importance of applying a modifier gradient for optimal separation of the chlorophyll products. The method permits separation of 15 chlorophyll derivatives including chlorophyll a and b, pheophytins, and pyropheophytins on a C18 column in about 20 minutes. Identifications of the individual peaks were based on reference compounds, the retention order of the compounds, and their absorption spectra.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 105
    ISSN: 0935-6304
    Schlagwort(e): Capillary gas chromatography ; gas chromatography-mass spectrometry ; essential oil analysis ; Lepechinia schiedeana ; antioxidant activity ; lipid peroxidation ; Ledol; Ledol HMQC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Steam distillation (SD), simultaneous distillation-solvent extraction (SDE), microwave-assisted solvent extraction (MWE), and supercritical (CO2) extraction (SFE) were used to isolate secondary metabolites from Lepechinia schiedeana. The various extracts were analyzed by capillary gas-chromatography, on poly (dimethylsiloxane) (DB-1) and poly(ethyleneglycol) (INNOWAX), 60 m columns, using FID or MSD (EI, 70 eV). Kováts indexes, mass spectra, or standard compounds were employed for compound identification. 43, 61, 67, and 79 compounds at concentrations above 0.01% were detected in the SD, SDE, MWE, and SFE extracts, respectively. Ledol, C15H26O, was the major constituent (20.04-36.87%) in all extracts. Oxygenated sesquiterpenes (24.36-43.14%), C10H16, monoterpenes (27.70-39.87%), and C15H24, sesquiterpenes (10.04-22.22%) were the main groups of compounds present in SD, SDE, MWE, and SFE extracts. Heavy hydrocarbons (Cn 〉 15), diterpenoids, and phytosterols were found only in MWE and SFE extracts. The antioxidant activity of Lepechinia schiedeana was measured by the HRGC quantification of the volatile carbonyl compounds, final products of lipoxidation, released in a model lipid system (sunflower oil) by the effect of the Fenton reagent. The concentration of volatile carbonyl compounds decreased by 65% when lipid oxidation was induced in the presence of macerated Lepechinia plant. The protection of polyunsaturated acids in sunflower oil was also studied by measuring their concentrations after heating of the oil (180°C, 2 h) with and without macerated Lepechinia plant.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 106
    ISSN: 0935-6304
    Schlagwort(e): Silver ion HPLC ; long chain polyunsaturated fatty acid ; isopropanol ; separation of positional isomers ; degree of unsaturation ; normal phase retention effect ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A high resolution approach to silver ion HPLC was studied for the separation of positional isomers of triacylglycerols (TAGs) containing long chain polyunsaturated fatty acids (PUFA) such as eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and docosapentaenoic acid (DPA) in enzymatically synthesized structured TAGs. Isopropanol was used as a novel modifier in a hexane-acetonitrile based mobile phase for silver ion HPLC. Peak identification was based on HPLC-mass spectroscopy and selectivities of lipases. Positional isomers of TAGs containing one molecule of EPA, DHA, or DPA with saturated fatty acids (FAs) such as caprylic acid and palmitic acid were separated within 13 min using a gradient of hexane-isopropanol-acetonitrile as mobile phase. TAGs containing two or more EPA, DHA, or DPA were also separated from each other within 25 min, but their positional isomers were unresolved. The retention characteristics of the TAG were found to be related to the number of carbon atoms in the FAs present in addition to the number of double bonds and their isomeric configuration. One isomer with an unsaturated FA in the sn-2 position eluted faster than the other with the unsaturated FA in the sn-1 or 3 position. Species with longer chain FAs attached to TAGs with the same degree of unsaturation eluted faster than those that have shorter chain FAs. For example, docosapentaenoylhexadecanoyloctanoin (DPA/C16/C8) was eluted faster than dioctanoyldocosapentaenoin (DPA/C8/C8).
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 107
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 373-378 
    ISSN: 0935-6304
    Schlagwort(e): Electrophoresis ; electrophoretic mobilities ; CZE ; MEKC ; peptides ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A computer model is presented for the prediction of the electrophoretic mobilities of peptides from physical constants derived from their amino acid sequences. The model assumes that the electrophoretic mobility can be represented by a product of four functions according to the relation:  lcomp= l(L)w(W)q(Q)c(CC), where L (a length parameter) is represented by the number of amino acid residues of the peptide, W (a width parameter) is represented by the average residue mass, Q = the charge of the peptide, and CC = the position of the center of charge relative to the center of mass. The model was used to calculate the electrophoretic mobilities of peptides in a 50 mM phosphate buffer at pH 2.5. Sixty-four test peptides ranging in size from 2 to 39 amino acid residues were used for this study. The calculated mobilities show excellent correlation with experimental measurements with a correlation coefficient greater than 0.98.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 108
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 386-390 
    ISSN: 0935-6304
    Schlagwort(e): Sulfur chemiluminescence detection ; sulfur simulated distillation ; boiling point distribution ; simultaneous FID/SCD analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A gas chromatographic system for the simultaneous acquisition of hydrocarbon and sulfur chromatograms was developed. Detection of sulfur compounds is achieved using a sulfur chemiluminescence detector (SCD) mounted in series with a flame ionization detector (FID). A constant fraction of the effluent of the FID is transferred to the SCD by means of a fixed restrictor. Unlike previous versions of this approach, the FID is not used to generate the chemiluminescent sulfur species. Rather, the FID is operated under optimum conditions for hydrocarbon analysis and a furnace is used to generate the chemiluminescent sulfur species. The system permits dual acquisition of the hydrocarbon and sulfur signals in a single analysis with a single column, since the detectors are operated in a serial fashion. The application of sulfur simulated distillation using this approach was examined, since this requires simultaneous universal and sulfur selective detection. Precision of absolute response of both the FID and SCD was typically less than 2% RSD for a standard reference material.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 109
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 391-394 
    ISSN: 0935-6304
    Schlagwort(e): REMPI-TOFMS ; laser mass spectrometry ; supersonic jet ; GC-MS ; interface ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---The laser-based methods Laser Induced Fluorescence (LIF) and Resonance-Enhanced Multi-Photon Ionization (REMPI) can be used as highly selective detection modes for gas chromatography (GC). One major prerequisite for successful application of these detection methods is the availability of appropriate and reliable interfaces between the GC effluent and the molecular beam inlet. When a pulsed supersonic molecular beam (jet) source is used, the analyte molecules are efficiently cooled, allowing maximum selectivity of the laser spectroscopic detection methods. However, several technical problems have to be solved for practical realization of a GC-supersonic jet valve hyphenation. The pulsed jet interface should not interfere with the GC properties and the supersonic molecular beam properties. Further a good working cycle for the conversion from the continuously flowing GC current to the pulsed jet gas flow should be attained. This paper presents a novel setup of a GC-pulsed jet interface. The construction allows temporal and spatial compression of the analyte molecules in jet gas pulse and thus an increase of the detection sensitivity. Moreover, the GC effluent comes into contact only with glass surfaces and not with valve parts like plungers and seals. This reduces memory effects and sample decomposition. The valve setup is tested with a REMPI-TOFMS instrument.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 110
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 414-416 
    ISSN: 0935-6304
    Schlagwort(e): Selenium ; water ; SPME ; GC/MS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A method for the selective determination of Se4+ and Se6+ using solid phase microextraction (SPME) and GC/MS analysis is presented. Se4+ is selectively derivatized by reaction with 4,5-dichloro-1,2-phenylenediamine to form the corresponding piazselenolo complex, extracted by the SPME fiber, and determined by GC/MS. The RSD at a 5 μg/L concentration was 9.88% and the theoretical detection limit 6 ng/L. The method was employed to test real matrices; tap and river water were analyzed before and after spiking giving a recovery rate of 102% in river water and 97% in tap water.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 111
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 565-588 
    ISSN: 0935-6304
    Schlagwort(e): Gas chromatography ; Kovats retention index ; vapor pressure ; boiling point ; Wilson activity coefficient ; binary phase diagrams ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Non-ideal mixing in a dimethylsilicone stationary phase is modeled according to the Wilson activity coefficient. Pure liquid vapor pressures of alkylated compound series are calculated from capillary GLC retention with the functional group heat of solution in a polymer solvent. The new method uses the Kovats index, molar mass, and functional group to determine the bubble line of a compound. Boiling points at reduced and normal pressure are compared to literature values of 194 gasoline components. An unlike molecular pair interaction parameter is derived, using only bubble line data of the pure liquids. Binary phase diagrams are constructed and compared to vapor liquid equilibrium data.
    Zusätzliches Material: 22 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 112
    ISSN: 0935-6304
    Schlagwort(e): Computer modeling of GC ; computer simulation of GC ; computer-assisted GC analysis ; GC multicolumn analysis ; heart cutting GC analysis ; computer-assisted column design ; computer-assisted selectivity tuning ; retention index mapping ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---The analysis of four components in a mixture containing many possible interferents is simplified by heart-cutting serially connected columns containing stationary phases of widely different polarities. The design of the proper lengths of the two columns and timing the heart-cuts is accomplished with the aid of a computer simulation of the problem. The computer program calculates the proper lengths of column to produce the shortest analysis time and also outputs the predicted chromatograms from both columns. The chromatogram from the first column is used to construct the timing gates for the heart-cuts and the chromatogram from the second or analytical column is used to set integration gates for the selected compounds of interest.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 113
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 609-612 
    ISSN: 0935-6304
    Schlagwort(e): Cyclodextrins ; 2-p-toluidinyl-6-naphthalenesulfonate ; indirect fluorimetric detection ; liquid chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Cyclodextrins (CD's) were visualized by postcolumn mixing with 2-p-toluidinylnaphthalene sulfonate (TNS) in liquid chromatography. The indirect detection is based on fluorescence enhancement due to the formation of an inclusion complex between TNS and CD's. β-CD gave larger signal intensity than α- and γ-CD. Different selectivities were observed for alkyl-bonded silica stationary phases with different chain length.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 114
    ISSN: 0935-6304
    Schlagwort(e): Enantioselective multidimensional gas chromatography-mass spectrometry (enantio-MDGC-MS) ; methylcitric acid (MCA) ; inherited metabolic disease ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Methylcitric acid (2-hydroxybutane-1,2,3-tricarboxylic acid-MCA) is a structural analogue of citric acid, but due to an additional methyl group it is a chiral molecule with two stereogenic centers and thus four stereoisomers are conceivable. MCA occurs naturally as prominent metabolite in body fluids of patients with inherited metabolic diseases such as propionic acidemia, methylmalonic aciduria, or holocarboxylase synthetase deficiency. Therefore methylcitric acid is considered to be an important diagnostic marker for these diseases. MCA is most likely produced from accumulated propionyl-CoA in these diseases by the enzyme si-citrate synthase from the citric acid cycle; however, there are other enzymes known which could catalyze the same reaction with different stereoselectivity, such as re-citrate synthase or the more specific enzyme methylcitrate synthase, found in microorganisms. Almost all methods dealing with MCA in the literature are non-enantioselective. For that reason there is no information about occurrence of MCA enantiomers in healthy people, patients with propionic acidemia, methylmalonic aciduria, or holocarboxylase synthetase deficiency and about value of enantiomeric distribution for diagnosis and long-term treatment. The enantioselective analysis of MCA as corresponding trimethyl ester was achieved by enantioselective multidimensional gas chromatography coupled with mass spectrometry using heptakis-(2,3-di-O-methyl-6-O-tert-butyl-dimethylsilyl)-β-cyclodextrin as chiral stationary phase. The described method allows a reliable screening of MCA in complex matrices like urine without time consuming sample preparation and with mass selective detection. During this investigation urine samples from various patients and healthy controls were analyzed. As concluded, MCA is a good diagnostic marker and can be easily measured by the method presented. Only the two stereoisomers (2S,3R) and (2S,3S) were detectable in patients and healthy controls. The varying ratios of these stereoisomers cannot presently be correlated with the health status of patients, although there are some indications that this might be possible. However, the quantitative levels of MCA, determined as the ratio of MCA absolute peak area divided by 1,000 to the creatinine contents of urine samples in this investigation, showed a dependence on the state of health and MCA would thus also be a possible marker for long-term treatment. Such a substance is of major interest nowadays since there are different studies searching for such a long-term marker in propionic acidemia or methylmalonic aciduria.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 115
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 623-627 
    ISSN: 0935-6304
    Schlagwort(e): Supercritical fluid extraction ; hydrocarbons ; high temperature ; thermal desorption ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The extraction of n-alkanes, polyaromatic hydrocarbons (naphthalene, methylated naphthalenes, phenanthrene, methylated phenanthrenes, anthracene, and methylated anthracenes) and biomarkers (hopanes) from Posidonia shale by high temperature supercritical fluid (HT-SFE) carbon dioxide extraction has been evaluated, including the relative contributions from thermal desorption and relative comparisons to conventional Soxhlet extraction. These current results confirm those of previous studies indicating a widely differing extractability of strongly and weakly associated hydrocarbons in ancient sediments and the significantly higher recoveries possible using HT-SFE compared to conventional Soxhlet extraction. The present study also demonstrates that these high HT-SFE recoveries are due to true extraction rather than simple thermal desorption and that this procedure is a useful tool to study speciation as well as total extractable hydrocarbons from sediments.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 116
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 631-634 
    ISSN: 0935-6304
    Schlagwort(e): Dill ether ; stereoselective synthesis ; dill ether stereoisomers ; enantioselective multidimensional gas chromatography-mass spectrometry (enantio-MDGC/MS) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---No abstract
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 117
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 639-643 
    ISSN: 0935-6304
    Schlagwort(e): Cyclodextrin ; Halowax ; hexachloronaphthalene ; PCN ; polychlorinated naphthalenes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---No abstract
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 118
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 501-508 
    ISSN: 0935-6304
    Schlagwort(e): Fast GC ; film inefficiency factor ; high pressure drop ; thick film columns ; thin film columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The negative effect of the liquid stationary phase film thickness on the column efficiency is strongest for peaks with retention factors, k, in the vicinity of k = 0.3-0.4 and rapidly diminishes with the departure of k from that region. Additionally, at the high pressure drop required for fast analysis of complex mixtures, the negative effect of the same film thickness diminishes with the increase in column length, regardless of the k values. In practice, it is recommended to ignore the film thickness and optimize the columns as thin film ones regardless of their actual film thickness. Accounting for the film thickness results only in a modest improvement in the resolution for a few affected peaks - those with k = 0.3-0.4. However, this improvement comes at the cost of a substantial increase in analysis time, and should be used only as the action of the last resort.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 119
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 514-520 
    ISSN: 0935-6304
    Schlagwort(e): Solid-phase extraction ; high temperature - gas chromatography ; gas chromatography - mass spectrometry ; wax esters fennel seed oil ; caraway seed oil ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A rapid method for the isolation and quantitative determination of wax esters in vegetable oils was developed. For the first time wax esters in oils were separated from the triglyceride matrix by means of solid-phase extraction, which allows rapid sample preparation in parallel and therefore a high sample throughput. The thus obtained wax ester fractions of fennel and caraway seed oils were analyzed by high temperature gas chromatography. GC-MS analyses were carried out using electron impact ionization in order to characterize the wax ester fraction. With respect to the results of the GC-MS analyses different isomers of saturated wax esters with the same carbon number were observed. Additional monounsaturated wax esters with an unsaturated fatty acid moiety were identified.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 120
    ISSN: 0935-6304
    Schlagwort(e): Clusia criuva Cambess ; counter-current chromatography ; flavonoids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---The family Guttiferae belongs to the superorder Theiflorae, order Theales and according to Dahlgren's system of classification, it is equivalent to Hypericaceae (=Clusiaceae) [1]. This family consists of 49 genera encompassing over 1000 species of wide distribution in the tropics as shrubs and trees [2]. Plants of the genus Clusia have been used in folk medicine for the treatment of different kind of illness such as: febrifuge, anti rheumatic, purgative, for stomach problems and, in Brazil, they are very commonly used to heal wounds [3]. The key of any study of material from natural sources is the availability of suitable separation methods for the isolation of pure products [4-6]. Tentatives for separations using chomatography on solid support phases were not very efficients in the fractionation of Clusia criuva Cambess methanolic/ethyl acetate extracts. However, the use of counter-current chromatography, an all liquid technique, showed advantages in comparison with the more traditional liquid-solid separation methods and even with HPLC. In this sense it was possible to isolate flavonoid glycosides from ethyl acetate extract of Clusia criuva, in a very short operation time.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 121
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 541-546 
    ISSN: 0935-6304
    Schlagwort(e): Solvating gas chromatography ; gas chromatography ; fast separation ; pesticides ; herbicides ; aldehydes ; packed capillary columns ; polymer-encapsulated silica ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Rapid separations of selected environmentally important polar compounds using polymer-encapsulated silica stationary phases and a carbon dioxide mobile phase under solvating gas chromatography (SGC) conditions are reported. Ten underivatized short chain aldehydes and ten nitrogen-containing herbicides were separated within 1 min and 5 min, respectively, using a 30 cm×250 μm i. d. column packed with diol-bonded, polyethylenimine (PEI)-coated, and hexamethyldisilazane (HMDS)-end-capped silica particles (5 μm, 120 Å). Seven organophosphorus pesticides were resolved in less than 5 min using a 30 cm×250 μm i. d. column packed with polymethylhydrosiloxane-deactivated and SE-54 encapsulated silica particles. Separation numbers per unit time increased with pressure and temperature ramps. Both rapid pressure and temperature programming can be used to increase the speed of SGC. The effects of pressure and temperature on apparent retention factors of solutes with various polarities were investigated using diol-PEI-HMDS silica particles in SGC.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 122
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 559-564 
    ISSN: 0935-6304
    Schlagwort(e): Liquid chromatography ; dead time ; multiparametric least-squares adjustment ; homologous series ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---In reversed phase liquid chromatography (RP-HPLC), the validity of a multiparametric non-linear least-squares regression iterative method for the determination of the column dead time tM and the regression parameter (slope b), based on the use of alkan-2-ones, alkyl aryl ketones, and 1-nitroalkanes has been evaluated. The determination of tM and b has been extensively studied for two mobile phase systems acetonitrile-water and methanol-water on seven octadecyl-C18 and one octyl C8 analytical columns. The calculated tM and b values were compared with those obtained by Guardino's and Grobler's methods. The influence exerted thereon by the nature of the homologous series, the mobile phase composition, and the packing materials were investigated.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
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  • 123
    ISSN: 0935-6304
    Schlagwort(e): SFE ; experimental design ; additives ; recycling ; polyolefins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---The performance and feasibility of supercritical fluid extraction (SFE) applied to the extraction of some antioxidants (Irganox 1076, Irgafos 168) and one UV-stabilizer (Chimassorb 81) from both virgin and recycled low density polyethylene (LDPE), and virgin high density polyethylene (HDPE) are studied. Due to the high number of variables a full-factorial design has been applied to minimize the number of experiments required to reach the optimum extraction conditions. Further analysis has been carried out off-line by reversed-phase HPLC. Modification of the physical properties of the polymeric matrix and increased number of recycling cycles as well as the influence of physical properties on the efficiency of SFE are also discussed.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 124
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 595-598 
    ISSN: 0935-6304
    Schlagwort(e): Xylitol ; samarium ; weak association ; equilibrium constant ; capillary electrophoresis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---No abstract
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 125
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 599-603 
    ISSN: 0935-6304
    Schlagwort(e): Capillary electrochromatography ; retention ; mixed stationary phases ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Most commercially available instruments for capillary electrochromatography (CEC) have a fixed configuration and lack the flexibility to use shorter columns. Applying a blended stationary phase (a phase consisting of a given ratio of bare silica and reversed phase material) can simulate columns of different length in CEC. The goal of this work was to examine the effect of the degree of blending of reversed-phase columns (with bare silica) on the speed of the separation of neutral compounds in CEC. Optimum column packing mixture was determined from the variation of the solute retention factors as a function of the ratios of blending of reversed-phase and bare silica. By adjusting the column composition, solute retention factors and the analysis run time were halved when compared to a pure reversed-phase column of the same length. Stationary phase blending can be considered as an additional parameter to mobile phase variation, column temperature and applied electric field for the optimization of selectivity and analysis time. By adjusting the stationary phase composition, mobile phase composition, column temperature and applied electric field, the analysis run time of neutral components was decreased more than 75% when compared to a separation obtained on neat reversed-phase column of the same dimensions. The linear dependence of the retention factors as a function of the blend ratio (reversed phase/bare silica) offers a framework for designing a “blended” packed capillary column for CEC separations.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 126
    ISSN: 0935-6304
    Schlagwort(e): Liquid chromatography ; retention index ; multiparametric least-squares adjustment ; homologous series ; nitramines ; nitroaromatics ; aminoaromatics and nitrophenols ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---In reversed phase liquid chromatography, the retention indices of some neutral and acidic explosives and related compounds (nitramines, nitroaromatics, aminoaromatics, and nitrophenols) based on the alkan-2-one, alkyl aryl ketone, and 1-nitroalkane retention index standards have been determined by the application of a new mathematical adaptation method, viz. a multiparametric least-squares regression iterative method. This method was applied to two types of columns. The first group includes six octadecyl-C18 columns with different packing materials and obtained from different manufacturers, while the second group comprises one octyl-C8 column. The retention indices have been extensively studied using either methanol-water or methanol-phosphate buffer mobile phase systems. The calculated multiparametric retention indices values were compared with those obtained by Guardino's, Grobler's, and Kovàts' methods. The influences of the concentration of the organic modifier in the mobile phase, aqueous mobile phase pH, and the column packing material on the retention indices of the explosives were also investigated. Good agreement was observed between the retention indices calculated by the use of the four mathematical methods for both neutral and acidic explosives.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 127
    ISSN: 0935-6304
    Schlagwort(e): Organochlorine compounds ; pesticides ; food analysis ; tomatoes ; GLC-ECD ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A method is described for the simultaneous extraction and determination of twenty organochlorine pesticides residues [hexachlorocyclohexane (HCH) isomers (α, β, γ, δ), aldrin, dieldrin, endrin, heptachlor and its epoxide (HE), hexachlorobenzene (HCB), α-endosulfan, o,p′-DDD, p,p′-DDD, o,p′-DDE, p,p′-DDE, o,p′-DDT, p,p′-DDT, dicofol, methoxychlor, and mirex] that were spiked in tomatoes. Samples were extracted with ethyl acetate, and the extract was subjected to a rapid clean-up using a Florisil column. The residues were determined by GLC-ECD using two columns of different polarity. The calibration graph correlation coefficient ranged from 0.9903 to 0.9990. The recoveries ranged from 95 to 99% with relative standard deviation ranging from 0.5 to 14.7% in the concentration range 0.005 to 0.2 μg/g. The limits of detection ranged from 0.004 to 0.05 μg/g and the limits of quantification ranged from 0.005 to 0.174 μg/g.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 128
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 628-630 
    ISSN: 0935-6304
    Schlagwort(e): p-Nitrophenol ; urine ; SPME ; GC/MS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---No abstract
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 129
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 635-638 
    ISSN: 0935-6304
    Schlagwort(e): High resolution gas chromatography ; thermal desorption ; archeological cosmetic powders ; PTV injector ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---No abstract
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 130
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 666-670 
    ISSN: 0935-6304
    Schlagwort(e): Capillary electrochromatography ; mixed packing technique ; electroosmotic flow ; retention mechanism ; fast analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Mixed packing capillary electrochromatography (MP CEC) with the stationary phase comprising a physical mixture of strong cation exchange (SCX) phase and octadecysilyl (ODS) phase was developed. With the existence of a sulfonic acid group on the surface of SCX, not only could the electroosmotic flow (EOF) remain high at low pH, but also the hydrophilicity of the stationary phase was increased greatly, leading to broad adaptable ranges of both pH and organic modifier concentration in the mobile phase. At the same time, with the coexistence of C18 on the surface of ODS, both the retention and the resolution of samples were improved. Accordingly, MP CEC combined the advantages of both SCX and ODS columns. Effects of operation parameters on EOF and the capacity factors of solutes as well as the retention mechanism of such a column were studied systematically. In addition, MP CEC columns were used in the analysis of strong polar solutes as well as for the high speed separation of acidic, basic, and neutral compounds in a single run.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 131
    ISSN: 0935-6304
    Schlagwort(e): Enantioselective capillary gas chromatography ; chiral stationary phase ; chiral recognition mechanism ; cholic acid ; cyclocholates ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---The suitability of cyclocholates as chiral selectors in gas chromatography has been evaluated. We present the synthesis and characterization of two cyclocholates, viz. 3α,7α-diacetoxycyclo[3]cholate and 3α,7α-diacetoxycylo[4]cholate. Mixtures of these new selectors with polysiloxanes were tested as chiral stationary phases in capillary gas chromatography. Several enantiomer separations of common racemates were achieved with the 3α,7α-diacetoxycyclo[3]cholate at 10% in OV-1701 (w/w). It was shown that column efficiency was strongly dependent on temperature and that enantioselectivity was very sensitive to column conditioning. This chromatographic behavior suggested that cyclocholates were only dispersed in polysiloxane. Thus, it was assumed that chiral discrimination occurred via enantioselective adsorption interactions of enantiomers at the surface of the solid chiral selector dispersed in the polysiloxane matrix OV-1701.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 132
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 683-686 
    ISSN: 0935-6304
    Schlagwort(e): Vacuum gas oils ; packed column chromatography ; n-paraffins ; carbon number distribution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Gas chromatographic methods are of widespread use in the petroleum industry for assessing petroleum and derivatives quality. The feedstocks for catcracking processes are very sensitive to the n-paraffin contents, which can be accurately determined using capillary column chromatography. Nevertheless, packed column chromatography does have potential advantages, viz. sometimes shorter analysis times, lower costs, higher column capacity, for vacuum gas oil analysis. This paper presents a method for such a determination using a Dexsil-300 packed column. The results obtained (n-alkane contents, carbon number distribution) agree fairly well with those obtained on a 30 m × 0.25 mm DB-1 fused silica capillary column.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 133
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The temperature dependence of NQR frequencies and spin-lattice relaxation times in Menshutkin's complexes, prepared on the basis of AsCl3 and AsBr3 have been investigated.The rotational oscillation frequencies νt and the average life times τa of rotational oscillation quanta have been calculated by both the Bayer and Woessner-Gutowsky theories.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 134
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 527-531 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: PMR spectra of thirty-eight chloromethylthiophene and seven dithienylmethane derivatives were observed at 60 or 40 MHz. The chemical shifts of methylene protons were 4·63 to 5·25 ppm for monosubstituted 2-chloromethylthiophenes and 4·37 to 4·56 ppm for monosubstituted 3-chloromethylthiophenes, respectively, with reference to TMS. Those for 2,2′ -dithienylmethanes, which have one substituent in each ring, were 4·12 to 4·34 ppm. These shifs are useful for determination of the positions of the methylene groups in the related compounds. The long-range coupling constants observed for methylene proton signals are also useful for the determination of the positions of substituents.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 135
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 533-537 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: The NMR spectrum of acetone oriented in the nematic phase of butyl-p-(p′-ethoxyphenyloxycarbonyl) phenyl carbonate has been studied in the 48° to 58°C temperature range. The determination of direct coupling constants allows the computation of orientation parameters; these values lead us to emphasize the intervention of polarizability in orientation phenomena.
    Notizen: Le spectre RMN de l'acétone orientée dans le p-(p′ ethoxyphenyloxycarbonyl)phényl carbonate de butyle est étudié dans l' intervalle de température 48° à 58°C. La mesure des constantes de couplage direct permet de calculer les facteurs d' orientation moléculaires; ceux-ci permettent de mettre en évidence ici l' intervention de la polarisabilité dans le phénoméne d' orientation.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 136
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The proton magnetic resonance spectra of the three title carbanions have been observed in THF with potassium as a counter ion. The ortho-protons in the α-methylbenzyl carbanion are nonequivalent at room temperature. This shows that the α-carbon in this carbanion is in the near-sp2 configuration. The aromatic proton chemical shifts of the benzylpotassium obtained here are at higher shielding than those of benzyllithium reported previously by Sandel and Freedman. This seems to arise from the different ionic nature of the bonds between carbon and metal in the carbanions.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 137
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: The NMR-spectra of cis- and trans-isomers of proline-containing diketopiperazines were investigated. It was demonstrated that the differences in the spectra are connected to the different position (pseudoaxial or pseudoequatorial) of the substituent (α-hydrogen atom, α-methyl-group, α-isopropyl-group).
    Notizen: Bei NMR-Untersuchungen der cis- und trans-Reihe Prolin-enthaltender Diketopiperazine konnten Unterschiede zwischen den Signalen pseudoaxialer und pseudoäquatorialer Substituenten (α-Proton, α-Methylgruppe, α-iso-Propylgruppe) festgestellt werden.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 138
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rotational barriers about the C—N bond of eight m- and p-substituted N, N-dimethyl cinnamamides have been determined by the iterative total line shape NMR method. The ΔG298·2-≠ values have been correlated with the substituent constants σ, σn and σ+. By comparison of the results with literature data, some conclusions about the accuracy of the barrier determination as well as the transmittance of polar effects in conjugated amides have been drawn.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 139
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 567-573 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 13C shielding constants have been calculated for a series of alkanes, methane to pentane. The quantities σd and σp have been obtained, using an average excitation energy approximation and the extended Hückel MO wave functions in terms of the Pople method. The results fit the experimental data and the VB results of Grant et al. fairly well. The quantity σd varies within a wide range for carbon atoms of various degrees of substitution. Two conformations of the hydrocarbons studied have been calculated. The results show that the 13C chemical shifts may be used for conformational analysis.
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  • 140
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 575-582 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Tris(dipivaloylmethanato)europium [Eu(DPM)3]induced shifts of the proton resonances of pyridine and its 2-methyl, 3-methyl, 2,3-dimethyl and 2,5-dimethyl derivatives, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, 1,6-, 1,7- and 1,8-naphthyridine, cinnoline, phthalazine, quinazoline, quinoxaline, 1,4,5- and 1,4,6-triazanaphthalene, pteridine, acridine, phenanthridine and 1, 10-phenanthroline, have been measured for solutions containing 0·1, 0·3 and 0·5 molar equivalents of Eu(DPM)3. Differences in the behaviour of these heterocycles are discussed in terms of the steric relationship between the heterocycle and the complex. The 3 cos2 φ term, present in the expression for calculating pseudo-contact shifts, is shown to be important. The order of basicity of these heterocycles, as measured by their pKa values, cannot be used to predict the order of Eu(DPM)3 induced chemical shifts.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 141
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 557-565 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A simple procedure is provided for the quantitative analysis of Diels-Alder adduct prepared from commercial methylcyclopentadiene and maleic anhydride by NMR spectra without further separation of its components. The adduct is considered as a mixture of endo norbornene derivatives (Cn), (Dn), (E) and (Fn) which are obtained from 1-, 2- and 5-methylcyclopentadiene and cyclopentadiene, respectively.The quantitative analysis of the adduct can be made on a basis of the ratio of the signal intensities of the olefinic protons in the adduct. The result shows that the adduct prepared under mild conditions mainly consists of three norbornene derivatives (Cn), (Dn) and (Fn), with a negligibly small amount of (E). When the adduct prepared under mild conditions is heated, it contains the exo isomers (Cx), (Dx) and (Fx). The ratio of the endo and the exo norbornene derivatives, i.e. ((Cn) + (Dn) + (Fn)):((Cx) + (Dx) + (Fx)), may be estimated from the signal intensities of the 5- and 6-protons.As the result of the analyses of the adducts which are obtained by heating at different temperatures the adduct prepared under mild conditions, the mole fraction of 2-methyl isomers (Dn) and (Dx), which is found to be 58 % in the adduct prepared at - 15°C, keeps on increasing with rising temperature and shows almost the same value, ∼86%, when heated above 150°C. Therefore, the equilibrium between 1-methyl and 2-methyl isomers does not change above 150°C. On the other hand, the isomerization from endo to exo isomers is not found below 110°C, and then exo isomers keep on increasing above 140°C.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 142
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 583-587 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The PMR spectrum of thiophen dissolved in a nematic phase is reported. This spectrum has been analysed iteratively. The ratios of the various inter-proton distances determined in this study are in good agreement with those previously reported.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 143
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 589-594 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The 14N chemical shifts were measured for a series of quaternary ammonium salts of enamino ketones. An upfield shift of the 14N resonance signals upon quaternization has been observed. The interpretation in terms of the approximate theory of nuclear magnetic shielding is given. The calculations for some model systems result in a general agreement with the experimental data.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 144
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 599-604 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The complete analysis of the spectrum of 2,2,4,4,4-pentafluoro-n-butane is reported. From the sum of the vicinal proton-fluorine coupling constants an estimate of the conformational energy has been obtained and successively the long-range coupling of the individual conformers has been calculated.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 145
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: The effects produced by four shift reagents on the proton magnetic resonance spectra of 1-methylimidazole and seven pyrazole derivatives have been determined. These results are discussed in the light of their usefulness in differentiating between structural isomers.
    Notizen: On a déterminé l'effet produit par quatre réactifs de déplacement sur les signaux de sept derivés du pyrazole et sur ceux du methyl- 1 imidazole. Ces effets sont discutés en fonction de leur utilité pour différencier des structures isomères.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 146
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Amide-rotational barriers of a series of para-substituted N,N-dimethylbenzamides and -cinnamamides have been obtained by both the intensity ratio method, according to Rogers and Woodbrey,2 and an iterative total line shape analysis.From a comparison of the results, it is concluded that a discussion of rotational barriers obtained with the intensity ratio method should preferably be based on ΔGTC
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 147
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Amide-rotational barriers obtained with a total line shape analysis of a series of para-substituted N,N-dimethylbenzamides and -cinnamamides are correlated with the result of an H. M. O. (Ω = 1·4) calculation. There is no difference in the activation parameters at a concentration of 0·25 M and 1 M in CDCI3 as a solvent.Despite the lower solvent polarity of chloroform (ε = 4·7) compared with acetonitrile (ε = 37·5) the rotational barriers in both solvents are about equal, probably due to hydrogen bonding in chloroform.The amide rotation rate appears to be very sensitive to traces of hydrochloric acid in a non-basic solvent like chloroform.
    Zusätzliches Material: 2 Ill.
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  • 148
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 635-635 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 149
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 679-687 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The carbon-13 chemical shifts of monosubstituted cyclohexane derivatives are compared with those of aliphatic compounds. The polar substituents exert a similar influence on the α-, β- and γ-carbons in both series of compounds. The δ-effect is shown to be characteristic mainly to the cyclic compounds, however. The appearance of a δ-effect is discussed as a possible consequence of electron delocalization in alicyclic molecules. A correlation of these δ-effects with inductive parameters of the substituents is presented.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 150
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 689-691 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The structure elucidation of some isomeric imidazo(1,2-a)pyrimidones by NMR spectroscopy is described. The tautomerism of the compounds with non-substituted nitrogen is also discussed.
    Zusätzliches Material: 3 Tab.
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  • 151
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 693-701 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A PMR study of the 1,4:3,6-dianhydroglucitol mononitrates allows the easy attribution of the 2-exo- or 5-endo nitrate configuration to each of the isomers. Coupling data obtained in chloroform and in pyridine provide insight into their conformations. The solvent shifts indicate a hydrogen bridged solute-solvent complex in the exo-compound, but a random solvation for the endo-nitrate.
    Zusätzliches Material: 2 Ill.
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  • 152
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 713-720 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: meso and dl Dimers (ArCHOR)2 where R is Me, Et, iPr, tBu, cyclohexyl and 1-adamantyl may readily be differentiated by their NMR spectra; the benzylic protons of the meso isomer always absorb at a slightly higher field than those of the dl isomer in each of the solvents used. Differences in chemical shift are discussed in terms of preferences in conformer distribution. The formation of equal amounts of both dimers from the corresponding radical ArCHOR shows that steric and polar factors are not important in influencing the dimerization. Magnetic non-equivalence due to the presence of asymmetric centres was found in some of the compounds discussed above.
    Zusätzliches Material: 6 Tab.
    Materialart: Digitale Medien
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  • 153
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 721-723 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The temperature or the nature of the solvent selectively affects the NMR equivalence of the protons at C-2 and C-4 in 1.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 154
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 725-732 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The complete analysis of the NMR spectrum of CH2Cl.CFBr.CH3 in CCl4 and acetone is given. The long range 4JHH couplings in this molecule differ considerably and surprisingly are both positive. An analysis of the solvent dependence of the couplings enables the rotamer couplings and energies to be obtained. The rotamer energies and their variation with solvent are in accord with quantitative predictions and results from similar halogenated ethanes. The values of the 4JHH couplings can be rationalised in terms of substituent electronegativity effects.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 155
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Evidence is presented which shows, contrary to the opinion expressed by Moriarty et al., that for electronic reasons internal rotation is substantially more hindered in thioamides than in amides.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 156
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 325-330 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: As is well known, the relative intensities of NMR hyperfinestructure-lines (spin-spin-coupling) under the influence of n neighbouring protons (I = ½) are given by the binomial coefficients and Pascal's triangle. For n equivalent neighbouring nuclei with I 〉 ½ a simple equation for the evaluation of intensities is not known. On the other hand the determination of the high values out of the possible arrangements of the spins is very circumstantial.Arranging the values in n lines, one obtains a kind of ‘Pascal's triangles of higher order’, which show the following qualities: (a) They are symmetric, (b) The sum of the values in the nth line is always (2I + 1)n, (c) Each value in one of the triangles is calculable as the sum of r values of the preceding line. Thereby it is r = 2I + 1.For the evaluation of the vth value in the nth line of any one of the triangles a recursion-formula is given.Furthermore it is shown, that a direct evaluation, without the knowledge of the values in the preceding line, is also possible up to any high values of n and I by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ x_r (n,\,v) = \sum\limits_{k = 0}^a {(- 1)^k} \left({\begin{array}{*{20}c} n \\ k \\\end{array}} \right)\left({\begin{array}{*{20}c} {n + r - kr - 2} \\ {n - 1} \\\end{array}} \right) $$\end{document} Thereby a is the greatest whole positive number ≦(v - 1)/r and ≦n.With the assumption, that the spin-spin-coupling J is small compared to the chemical shift Δv*, the intensity ratios of the lines can be calculated by the given equation in a simple way as is shown by some examples.
    Notizen: Die relativen Intensitäten der kernmagnetischen Hyperfeinstrukturlinien sind bei n aequivalenten, benachbarten Protonen (I = ½) bekanntlich durch die Binomialkoeffizienten und das Pascalsche Dreieck gegeben. Bei n aequivalenten, benachbarten Kernen mit I 〉 ½ ist eine einfache Berechnungsformel für die relativen Intensitäten nicht bekannt, andrerseits ist die Ermittlung der sehr großen Zahlen aus den Anordnungsmöglichkeiten der Spins sehr umständlich.Ordnet man die Zahlen wiederum in n Reihen an, so erhält man ‘Pascalsche Dreiecke höherer Ordnung’. Sie sing (a) symmetrisch, (b) Die Summe der Zahlen der n-ten Reihe ist stets (2I + 1)n und (c) Es ergibt sich jede Zahl in irgendeinem der Dreiecke als Summe der r darüberstehenden Zahlen, wobei r = 2I + 1 ist.Für die Berechung der v-ten Zahl in der n-ten Reihe eines beliebigen Dreiecks höherer Ordnung wird eine Rekursionsformel angegeben.Weitergehend wird gezeigt, daß auch eine direkte Berechnung, ohne Kenntnis der Zahlen der voraufgehenden Reihe, bei beliebig hohen Werten von n und I aus der Beziehung: \documentclass{article}\pagestyle{empty}\begin{document}$$ x_r (n,\,v) = \sum\limits_{k = 0}^a {(- 1)^k} \left({\begin{array}{*{20}c} n \\ k \\\end{array}} \right)\left({\begin{array}{*{20}c} {n + r - kr - 2} \\ {n - 1} \\\end{array}} \right) $$\end{document} möglich ist. Darin ist a die größte ganze, psotive Zahl ≦(v - 1)/r und ≦n.Unter der Voraussetzung, daß die Hyperfeinstruktur-Aufspaltung J klein gegenüber der chemischen Verschiebungsdifferenz Δν* ist, lassen sich die relativen Intensitäten der Hyperfeinstrukturlinien aus der Formel in sehr einfacher Weise berechnen, wie an einigen Beispielen gezeigt wird.
    Zusätzliches Material: 1 Tab.
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  • 157
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 373-377 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: High resolution fluorine magnetic resonance spectra have been obtained for poly(vinyl fluoride) at elevated temperature. Proton noise-decoupling and time-averaging techniques have given new tacticity and sequence information.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 158
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 379-381 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Chemical polarization of protons was observed in methyl benzoate formed during the thermal decomposition of dimethyl ester of peroxydiphthalic acid. The polarization pattern of methyl benzoate aromatic protons was very different in this case from that observed during the thermal decomposition of acetyl benzoyl peroxide. The unpolarized products formed from the methoxy radical, CH2O and CH3OH, were found in the mixture of decomposition products of this peroxide and were identified by means of PMR spectroscopy.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 159
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: The NMR study of the reaction of methoxide ions on several substituted 2-X-4,6-dinitroanisoles (X = F, Cl, CF3, CN) permitted the identification of various Meisenheimer complexes formed by the attack of CH3O- ions on the non-substituted 5- and 3-carbons. The shortlived 1,5- and 1,3-complexes undergo a fast conversion to the stable 1,1-complexes.The chemical shifts of anisoles and complexes are dependent on electronic and steric effects of the X-substituent. The influence of the negative charge held by the ring and the geometrical changes of the skeleton are shown by a comparison between the NMR parameters of anisoles and the corresponding complexes.When X = F, a study of the relative signs of the coupling constants shows that 3J(F—H) and 5J(F—H) are of opposite signs for the anisole and the 1,1-complex.
    Notizen: L'étude RMN de l'interaction des ions CH3O- avec les dinitro-4,6 anisoles X-2 substitués (X = CN, CF3, Cl, F) a permis d'identifier divers complexes de Meisenheimer résultant de l'attaque des ions CH3O- sur les carbones -5 et -3 non substitués. Ces complexes -1,5 et -1,3, dont la durée de vie est très courte, se transforment rapidement au profit des complexes stables -1,1. Les déplacements chimiques des anisoles et des différents complexes reflètent les effets électroniques et stériques des substituants X. L'influence de la charge négative portée par le cycle et les modifications géométriques du squelette sont mises en évidence en comparant les paramètres RMN des anisoles et des complexes correspondants. Lorsque X = F, l'étude des signes des constantes de couplage montre que 3J(F—H) et 5J(F—H) sont de signes contraires dans l'anisole et dans le complexe -1,1.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 160
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 389-403 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The NMR spectra of the nonaromatic protons in several benzo-substituted five- and six-membered rings have been analyzed at 60- and 90-MHz. The vicinal coupling constants from the—CH2—CH2—fragments give a quantitative assessment of the degree of ring flattening. The distortions are discussed in terms of the structural components of the molecules.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 161
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 405-416 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Infinite dilution data for six sulphur heterocycles have been obtained from second order analyses of their NMR spectra in CS2, CDCl3, CD3COCD3, or C6D6. Use of LAOCOON3 leads to accurate chemical shifts, but substantial errors remain in some of the coupling constants. Evidence is presented of specific association of chloroform with the sulphur heterocycles and of the interaction of acetone with the sulphur atom. An apparently anomalous geometry for the complex of benzene with thiophen and with other solutes is discussed. Dilution effects are considered in relation to the formation of solute dimers.
    Zusätzliches Material: 4 Tab.
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  • 162
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Proton spin-spin coupling values measured for a wide range of tetrasubstituted tetrahydropyran ring-systems obtained from aldopentopyranose sugars have been correlated with values calculated from a generalized version of the Karplus equation which takes into account the electronegativities of the various atoms in the molecule and the configurations of these substituents. Minor discrepancies between observed and calculated values can be attributed to slight flattening of the tetrahydropyran ring as a result of steric interactions of the substituents. The magnitude of the geminal coupling J5e,5a of these aldopentopyranose derivatives provides a rough measure of the conformational population; when H-4 is axial [Cl(D) or 1C(L) conformation] J5e,5a is ∼10.9 Hz, and is ∼13.4 Hz when H-4 is equatorial [1C(D) or Cl(L) conformation].
    Zusätzliches Material: 3 Tab.
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  • 163
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 37-43 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The preparation of 4-phenyl-1, 3-oxathian, 6-methyl-1, 3-oxathian, and some of their 2-substituted derivatives is described. Significant features of their NMR spectra are discussed with particular reference to the influence of the heteroatoms on the coupling constants of adjacent protons.
    Zusätzliches Material: 3 Tab.
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  • 164
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 45-74 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: We have studied the temperature dependence of NMR spectra of six spirophosphoranes of the general formula: Experimental data show intramolecular isomerism which was explained by pseudo-rotation mechanism (Berry, Lit. 1).In all cases except one we also observed tautomerism between spirophosphorane and phosphite forms.
    Notizen: Nous avons étudié la variation, en fonction de la température, des spectres de RMN de six spirophosphoranes des types: Les résultats expérimentaux indiquent l'existence d'une isomérie intramoléculaire que nous avons interprétée en adoptant le mécanisme de pseudo-rotation proposé par Berry.1Dans tous les cas, sauf un, le déplacement de l'équilibre tautomère spirophosphorane ⇌ phosphite s'ajoute an phénomène d'isomérie observé.
    Zusätzliches Material: 15 Ill.
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  • 165
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 83-99 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The AA′BB′ and AA′BB′MX nuclear magnetic resonance spin systems for I = ½ nuclei have been analysed. Expressions for the transition frequencies and intensities have been obtained which have the maximum accuracy consistent with practicable use. The analyses have been applied respectively to a hypothetical AA′BB′ nuclear spin system and to the two molecules para- fluoro-phenyldichlorophosphine and tris-para-fluorophenylphosphine. Inconsistencies in earlier treatments of the AA′BB′ system have been clarified.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 166
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 193-200 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Double and triple nuclear magnetic resonance experiments performed at 100 MHz demonstrate the existence of long range 1H - 1H couplings through epoxides. In a series of epoxycontaining sesquiterpenoids, interactions between protons separated by up to six sigma bonds were detected. These interactions may have origins similar to the well-known allylic and homoallylic couplings found in carbon-carbon double bonded compounds, although they are much smaller in the epoxy systems. We propose to name them as ‘epoallylic’ and ‘epohomoallylic’ interactions. Some couplings are observed directly, whereas in other cases only an improvement in resolution is seen during multiple irradiation experiments. Even in these latter cases the areas of the observed peak do not change upon multiple irradiation which demonstrates the absence of nuclear Overhauser effects. The stereochemistry of some asymmetric centers of the compounds studied is deduced from the spectra.
    Zusätzliches Material: 1 Ill.
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  • 167
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 217-220 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The benzene-induced solvent effects upon the proton chemical shifts of various pyrazines, pyrimidines and their N-oxides are described. Larger chemical shift effects, implying closer benzeneheterocycle association, are noted in the N-oxides as compared to the non-oxidized heterocycles.The solvent-induced chemical shift changes can be used to establish the site of N-oxidation in those instances where different isomers can be formed.
    Zusätzliches Material: 1 Tab.
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  • 168
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 3 (1971), S. 243-248 
    ISSN: 0030-4921
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The NMR spectrum of benzaldehyde oriented in the nematic phase of a mixture of p-(p-ethoxyphenylazo)phenylheptanoate and p-(p-ethoxyphenylazo)phenylundecylenate is analysed. It is demonstrated that the data are inconsistent with models in which the aldehyde group freely rotates or has minimum energy when it is perpendicular to the ring plane. The barrier height to rotation, however, cannot be obtained, nor is it possible to discriminate between the two possible solutions in which the averaging planar forms do or do not reorient in the liquid crystal between successive internal rotations.
    Zusätzliches Material: 2 Ill.
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  • 169
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 19-31 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The chemical ionization mass spectra of a series of simple peptides containing six or fewer amino acids have been studied. Using methane as the reactant gas we found cleavage of the peptide bond occurs in two ways, yielding either the acyl carbonium ion or the complementary ammonium ion. The observation of both types of fragments permits the determination of the amino acid sequence of the peptide. The ammonium ions provide an additional sequence determining route compared to that available from electron-impact spectra. ‘Sequence-determing ions,’ especially the quasimolecular ion at m/e [M+1] are usually more intense than in the electron-impact mass spectra.
    Zusätzliches Material: 4 Ill.
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  • 170
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 61-71 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mass spectral fragmentation behaviour of N-acyliminopyridinium and isoquinolinium betaines has been investigated. Major fragmentations of the pyridinium betaines can be rationalized in terms of charge localization on the pyridinium nitrogen. The most prominent process is α-cleavage followed by loss of NCO to furnish a pyridine ion. The electron-impact induced fragmentation of N-benzoyliminopyridinium betaine (I) was compared with that of thermolysis. The completely analogous behaviour has been observed in the corresponding isoquinolinium betaines.
    Zusätzliches Material: 7 Ill.
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  • 171
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    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 95-97 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 172
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 99-101 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 173
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electron-impact induced fragmentation of twenty 3-alkyl-1-phenyl-Δ2-1,2,4-triazolin-5-ones, three 1-phenyl-1,2,4-triazolin-3,5-diones and ten 2-alkyl-4-phenyloxadiazolin-5-ones has been studied by conventional mass spectrometry. The major cleavages take place in the 1-phenyl-Δ2-1,2,4-triazolin-5-one nucleus, producing three major fragment ions. 4-Phenyloxadiazolin-5-ones exhibit a similar fragmentation pattern to 1-phenyl-Δ2-1,2,4-triazolin-5-ones. Furthermore, several additional fragmentation processes are observed in the case of specific 1,2,4-triasolines.
    Zusätzliches Material: 1 Tab.
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  • 174
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 187-195 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Some of the fragmentation modes operating in a few furanosesquiterpenes have been established from accurate mass measurements and metastable data.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 175
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The principal mode of fragmentation, at both 70 and 15 eV, of pyrilium iodides (I to V) which are substituted by at least one methyl group is the elimination of hydrogen iodide from the non-detectable molecular ion. In contrast the mass spectrum (Fig. 6) of 2,4,6-triphenyl pyrilium iodide (VI) shows its dominant fragmentation to be due to the loss of an iodine atom from the molecular ion. The mass spectra (for example Figs. 6 and 7) of 2,4,6-triphenyl pyrilium iodide, bromide and tetrafluoroborate (VI, VII and VIII) are virtually identical except for the peaks corresponding to a molecule of iodine (m/e 254), hydrogen iodide (m/e 128) and iodine (m/e 127) in the mass spectrum (Fig. 6) of the iodide. Other fragmentation routes common to these pyrilium salts are described.
    Zusätzliches Material: 7 Ill.
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  • 176
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971) 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 177
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 135-146 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The molecular ions of phenyl benzoate, methyl benzoate, t-butylbenzene, phthalic anhydride, p-dimethoxybenzene, o-dimethoxybenzene and acetophenone each undergo two consecutive reactions ([M]+.→[A]+→[B]+). These unimolecular reactions are treated within the framework of the quasi-equilibrium theory (QET); a simple modification of the original equation relating the rate constant (k) with the internal energy (E) was used to calculate mass spectra of the above compounds from 12 to 20 eV. Good agreement between calculated and observed spectra is obtained.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 178
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: The presence of a hydroxyl group in steroidal amines, amides and imines, may profoundly influence their fragmentation in the mass spectrometer. This fragmentation is initiated by the rearrangement of the hydroxylic hydrogen on the nitrogen containing groups and products ions characteristic of the OH site in the molecule. Sometimes this may occur even when the two groups are situated at remote positions.
    Notizen: La prtsénce d'un groupement hydroxyle dans les molécules de certaines amines, amides et imines stéroídiques joue un grand rôe dans la fragmentation de celles-ci en spectrométrie de masse. Cette fragmentation est initiée par le transfert, parfois à longue distance, de l'hydrogéne hydroxylique sur les groupements azotés et donne naissance à des ions caractéristiques de la place de l'hydroxyle.
    Zusätzliches Material: 17 Ill.
    Materialart: Digitale Medien
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  • 179
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Mass spectral studies on costunolide and lactones derived therefrom, have revealed some general fragmentation modes involving the losses of 44, 55, 57, 59, 71, 73 and 83 mass units from the molecular ion. The probable genesis of these ions is established by high resolution, metastable transitions and deuterium labelling studies. Comparison has been made with the mass spectra of some C6- desoxy esters.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 180
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The low resolution 70 eV mass spectra of the TMS (Trimethylsilyl) derivatives of eight naturally occurring hydroxy- and/or methoxycinnamic acids are presented in detail. The TMS derivatives studied are I, of o-coumaric acid; II, of m-coumaric acid; III, of p-coumaric acid; IV, of isoferulic acid; V, of ferulic acid; VI, of 3,4-dimethoxycinnamic acid; VII, of sinapic acid; VIII, of caffeic acid; Ia to Va, VIIa, of the corresponding methyl esters; and VIa, methyl 3,4-dimethoxycinnamate.The derivatives studied show a high degree of stability under conditions of electron-impact. The major fragmentation processes for the free acid TMS derivatives begin with methyl radical loss from either the ester or ring TMS group. The spectra of the methyl ester TMS derivatives have enabled the site of initial methyl loss to be determined. Accurate mass measurements and analysis of the second field-free region metastable peaks provide support for suggested fragmentation schemes. The spectra are sufficiently different to permit identification except between compounds IV and V (and IVa and Va) where the major fragmentation process involves a common ion, thought to be the silicon analogue of an acetonide.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 181
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A study on the behavior of a large number of monomeric and dimeric coumarins in the mass spectrometer is reported and discussed. The results illustrate that the observed characteristic fragmentation patterns are of considerable utility in the application of mass spectrometry to structure elucidation in this series.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 182
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 289-295 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mass spectra of 1,2-dichloro-3,4-bis(dichloromethylene)cyclobutene (IV) and of hexachloropentafulvene (II) have been studied. Compound IV cannot be an intermediate in the formation of II from octachloro-1,2-dimethylenecyclobutane (III) under electron-impact, as previously suggested. In the mass spectra of II and IV the species [C6]+ and [C5]+ occur, obviously through cleavage of the semicyclic C-C bond.The mass spectrum of pentachlorofulvalene (VI) shows strikingly that successive elimination of an even number of CI atoms is preferred over that of an odd number of CI atoms; probably corresponding C-CI bonds in the two rings are broken simultaneously. Amongst the fragments, the species [C10]+ and [C7]+ and possibly also [C8]+ and [C9]+ have been observed.
    Zusätzliches Material: 3 Tab.
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  • 183
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 651-662 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A study of the low and high-resolution mass spectra of caprolactam (I), 1-methylcaprolactam (II), 3-methylcaprolactam (III), 4-methylcaprolactam (IV), 5-methylcaprolactam (V), 6-methylcaprolactam (VI), 7-methylcaprolactam (VII) and deuterium labelled compounds has facilitated the proposal of some principal fragmentation mechanisms of ionized molecules of these compounds.The base peaks in the spectra of all compounds studied (except 3-methylcaprolactam) are the ions m/e 30 and m/e 44 respectively formed through the cleavage of the C6-C7 bond and the C2-N bond with simultaneous transfer of a hydrogen atom.It has been proved that the fragmentation of molecular ions leading to ions with the structure of cyclopentanone 2-methylcyclopentanone and 3-methylcyclopentanone respectively (according to the position of methyl group) is the general feature of the fragmentation of caprolactam and its methyl derivatives.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 184
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 713-724 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: A series of 24 fluorinated steroidal ketones was studied by mass spectrometry. The different locations of the keto group or fluorine atom, permitted of fragmentation patterns to be derived.
    Notizen: Une série de 24 cétones stéroïdes fluorées a été étudiée enspectrométrie de masse. Les différentes positions de la fonction cétone et de l'atome de fluor ont permis de mettre en évidence des fragmentations intéressantes.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 185
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: From the mass spectra of site-specifically deuterated analogues of isonicotinic acid it appears that the molecular ion eliminates hydroxyl and water after an exchange between the hydroxylic and β-hydrogens. The percentage of exchange in these reactions depends on the internal energy of the molecular ion and is shown to be 53 to 57% in the ion source, 92 to 97% in the first and ∽ 100% in the second field free regions.Furthermore, the isotope effect i, operative in the loss of water, increases with decreasing internal energy of the molecular ion, being 1.6, 2.0 and 2.3 in the ion source, first- and second field free regions, respectively.In the molecular ions, losing successively hydroxyl and carbon monoxide as deduced from diffuse peaks in the first-and second field free regions, a substantially lower percentage of exchange (ca. 20%) is found, which is due to the higher internal energy of these molecular ions.In the molecular ion of nicotinic acid only one of the ortho hydrogens (α) is involved in the exchange of hydrogen. The percentage of exchange for loss of hydroxyl in the ion source is 66%. Molecular ions, which successively eliminate hydroxyl and carbon monoxide, show a 45% exchange of hydrogen as calculated from diffuse peaks in the first- and second field free regions.
    Zusätzliches Material: 7 Tab.
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  • 186
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The methylene groups in 2-(1-azulyl)ethyl tosylate are largely scrambled prior to formation of fragment ions in the mass spectrometer. This process also occurs in the 3-nitro analog, where it is dependent on sample residence time in the source and independent of electron energy. It could not be observed with the isomeric 6-substituted tosylates, the 1-substituted acetates or alcohols, or with 2-(p-anisyl)ethyl tosylate. Scrambling occurs in the neutral molecule prior to ionization and a mechanism involving absorption onto the metal surface and formation of a complexed ethylenazulonium ion is suggested.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 187
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: The molecular ions generated by electron-impact from olefins of the general structure I, II and III fragment mainly via the McLafferty rearrangement. Even under mild ionization conditions, however, they undergo isomerization before fragmentation takes place.The origin and mode of formation of an ion generated simultaneously by decay of the molecular ion and the McLafferty ion were investigated by means of 13C- and D-labelling.The influence of branching at the γ-, ω-, or ∊-positions of the double bond in type I-olefins was studied.
    Notizen: Bei Olefinen der allgemeinen Struktur I, II und III erleidet das unter Elektronenbeschuss erzeugte Molekülion neben der als Hauptreaktion ablaufenden McLafferty-Umlagerung auch bei milden Anregungsbedingungen eine vor der Fragmentierung eintretende Isomerisierung.Es wurde versucht, Herkunft und Entstehungsweg eines sowohl beim Abbau des Molekülions als auch des McLafferty-Ions gebildeten gemeinsamen Bruchstückes mit Hilfe von 13C- und D-Markierung zu klären.Der Einfluss einer Verzweigungstelle in γ-, ω- oder ∊-Position zur Doppelbindung bei Olefinen vom Typ I auf deren Verhalten im Massenspektrometer wurde untersucht.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 188
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 845-850 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Ionization potentials and fine structure in ionization efficiency curves have been determined for nine cyano-1 diphenyl-1,2 cyclopropanes. It is shown that derivatives which include dimethylamino group have the lowest ionization potential, the first break of the fine structure and Hammett constants. For compounds containing the nitro substituent we have a constant value of the first break after the ionization potential, which shows the primary role of the nitro group in the excited state of the molecular ions.
    Notizen: Rües potentiels d'ionisation, les courbes d'efficacité d'ionisation différentielle ont été déterminées par la méthode EDDEDD: Energy Difference Distribution (voir R. E. Winters).6 pour 9 cyano-1 diphényl-l,2 cyclopropanes. II est montrk que les composés comprenant le groupement diméthylamino possedent les potentiels d'ionisation les plus bas. Pour ces cornposés, on peut établir une corrélation qualitative entre le potentiel d'ionisation, la première cassure dans la courbe d'efficacité d'ionisation différentielle et la constante de Hammett. Pour les composés comprenant le groupement nitro, la valeur constante de la première cassure au dessus du potentiel d'ionisation nous permet de penser que ce substituant a un rǒe primordial dans l'état excité des ions moléculaires.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 189
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 851-855 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The pyrolysis of perfluoroalkylene-linked polyimides in an inert atmosphere has been studied using a pyrolysis-gas chromatographic-mass spectrometric method. The major primary gaseous degradation products were carbon monoxide and carbon dioxide. In addition large amounts of silicon tetrafluoride were produced by secondary reactions.Results obtained with 1,3-di-(3-phthalimidophenyl)hexafluo0ropropane and bis[N-phenyl-1,3-dioxo-isoindolyl(5,5′)]hexafluoropropane suggest that the perfluoroalkylene groups have a greater influence on the electron-impact induced fragmentation of the imide ring than on its thermal breakdown.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 190
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 891-892 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: An isotope seperator has been modified so that work can be carried out on organic compounds. Analysis of the collector by mass spectrometry showed a weighable deposit of organic fragments.
    Notizen: Après modification, nous avons pu déposer une quantité pondérable de matière organique sur le collecteur d'un séparateur d'isotopes.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 191
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 935-938 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mass spectra of N-iminopyridinium betaines, which have been generated within the ion source by pyrolysis of the corresponding hydrochlorides, have been compared with those of pyridine N-oxides.
    Zusätzliches Material: 1 Tab.
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  • 192
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 967-975 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of alkylphenylketones has been examined. Whenever the alkyl chain is three or more carbon atoms long, the well-known McLafferty rearrangement occurs with elimination of the elements of a neutral olefin. The further fragmentation of the ion formed in this rearrangement reaction has been studied using the technique of ion kinetic energy (IKE) spectroscopy. The measured release of kinetic energy has been used to show that the rearrangement ion has an enolic type structure.
    Zusätzliches Material: 2 Ill.
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  • 193
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 983-991 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Mass analysis of mono- and oligosaccharides was carried out by the field ionization (FI) method. Unsubstituted monosaccharides exhibit an intense peak at [M + 1]+ in the FI spectra, but are not so suited to structural analysis because of their thermal instability. Permethylation is the most suitable method of obtaining good FI mass spectra of oligosaccharides. Permethylated disaccharides which are linked via C-1 - C-4 or C-1 - C-6, respectively, exhibited characteristic differences in the fragment ion intensities. It is not possible, however, to derive all of the different modes of linkage from the FI mass spectrum of permethylated raffinose. The field desorption method is more suitable for further studies of thermally instable compounds than the method of sample evaporation from an oven with subsequent field ionization.
    Notizen: Mit Hilfe der Feldionisation wurde die Massenanalyse von Mono- und Oligosacchariden durchgeführt. Die FI-SpektrenFI wird als Abkürzung für Feldionisation und ES für Elektronenstoß-Ionisation benutzt.unsubstituierter Monosaccharide zeigtren zwar alle einen intensiven Peak auf der MZ [M + 1], eignen sich aber wegen der thermischen Labilität nur schlecht für Strukturanalysen. Im Hinblick auf Oligosaccharide ist eine Permethylierung für die Aufnahme von FI-Massenspektren vorteilhaft. Permethylierte Disaccharide, die über C-1 - C-4 bzw. über C-1 - C-6 verknüpft sind, zeigten charakteristische Unterschiede in den Fragment-Ionenintensitäten. Dagegen lassen sich aus dem FI-Spektrum der permethylierten Raffinose nicht alle Verknüpfungsarten entnehmen. Für zukünftige Untersuchungen thermisch labiler Substanzen eignet sich die Felddesorptionsmethode besser als die Methode der Probenverdampfung aus einem Ofen mit anschließender Feldionisation.
    Zusätzliches Material: 5 Ill.
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  • 194
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 1027-1027 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 195
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 1029-1041 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mass spectra of quinuclidone-3, benzquinuclidone-3, 2-azaquinuclidone-3, 2-azabenzquinuclidone-3 and some of their functional substituted derivatives have been investigated. Fragmentation of the compounds investigated has been shown to proceed through the open form of the molecular ion with cleavage of a bridgehead bond containing the carbonyl group and subsequent elimination of carbon monoxide.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 196
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 1081-1084 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A complex rearrangement on electron-impact for β-aroyl-α-methylpropionic acids, involving both hydrogen and hydroxy migration followed by loss of carbon monoxide and allyl radical, is described and discussed. The rearrangement process, resulting in an ion [ArCOOH2]+, is favoured by electron-withdrawing substituents in the aromatic ring.
    Zusätzliches Material: 2 Tab.
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  • 197
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 1101-1105 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The mass spectra of deuterated pyrazoles show that loss of H. and of HCN from the molecular ion occurs with a very high specificity from the 3(5)-position. For the two processes isotope effects and preference factors have been determined. Metastable ion decompositions involving the loss of HCN from the [M - H] -fragment indicate that the identity of the hydrogen atoms in this fragment is lost to a large extent.
    Zusätzliches Material: 5 Tab.
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  • 198
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 1123-1125 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 199
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971) 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 200
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 5 (1971), S. 1345-1346 
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Elimination of CO gives rise to prominent peaks in the mass spectra of cis-1,2,3,6-tetrahydrophthalic anhydride (Ia) and its 4,5-dimethyl analogue which are almost absent in the corresponding trans-isomers. The striking difference in the fragmentation of the isomers shows that practically no rearrangement in the molecular ion occurs prior to this fragmentation. In this case a high degree of stereospecificity is observed, although hydrogen migration is apparently not involved in the process.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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