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  • 1995-1999  (4.837)
  • 1965-1969  (564)
  • Analytical Chemistry and Spectroscopy  (2.605)
  • Theoretical, Physical and Computational Chemistry  (1.576)
  • Computational Chemistry and Molecular Modeling  (1.219)
  • Nuclear reactions
Materialart
Erscheinungszeitraum
Jahr
Schlagwörter
  • 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
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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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
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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
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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
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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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
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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
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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.
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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.
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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
    Digitale Medien
    Digitale Medien
    Springer
    Space science reviews 84 (1998), S. 199-206 
    ISSN: 1572-9672
    Schlagwort(e): Nuclear reactions ; Nucleosynthesis ; Abundances ; Stars:Evolution ; Interior ; Rotation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract We first recall the observational and theoretical facts that constitute the so-called 3He problem. We then review the chemical anomalies that could be related to the destruction of 3He in red giants stars. We show how a simple consistent mechanism can lead to the destruction of 3He in low mass stars and simultaneously account for the low 12C/13C ratios and low lithium abundances observed in giant stars of different populations. This process should both naturally account for the recent measurements of 3He/H in galactic HII regions and allow for high values of 3He observed in some planetary nebulae. We propose a simple statistical estimation of the fraction of stars that may be affected by this process.
    Materialart: Digitale Medien
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  • 134
    ISSN: 0894-3230
    Schlagwort(e): Menschutkin reaction ; duality of SN1, SN2 mechanisms ; benzyl tosylates ; Yukawa-Tsuno equation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The rate data for the Menschutkin reaction between strongly activated Z-substituted benzyl p-toluenesulfonates and Y-substituted N,N-dimethylanilines in acetonitrile at 35 °C fit the equation, kobs  =  k1 + k2 [DMA], which is consistent with concurrent first- and second-order processes. The k1 and k2 values for each substrate were separated based on the above equation. The SN1 rate constant, k1, is unaffected by the nature of the nucleophile, whereas the SN2 rate constant, k2, increased with the electron-donating substituent of the N,N-dimethylaniline. The substituent effect on the k1 values is linearly correlated by the Yukawa-Tsuno equation with ρ  =  -5.2 and r  =  1.3. The unimolecular reaction can be regarded as a classical SN1 mechanism. In contrast, that on the k2 values shows an upward curvature when analyzed by the Brown σ+ treatment. These results are ascribed to the simultaneous and independent occurrence of SN1 and SN2 mechanisms in the present Menschutkin reaction. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 135
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 231-231 
    ISSN: 0894-3230
    Schlagwort(e): Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: No Abstract
    Materialart: Digitale Medien
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  • 136
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 283-289 
    ISSN: 0894-3230
    Schlagwort(e): calorimetry ; IR spectra ; ketones ; solvation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Solution enthalpies of n-hexane, acetone, butan-2-one and octan-2-one in a series of tetrachloromethane-acetonitrile mixtures and the carbonyl stretching absorption frequencies in the IR spectra of these ketones were determined. It was found that over the whole range of concentrations (varying from neat tetrachloromethane up to neat acetonitrile) the solvation enthalpy of these compounds can be obtained additively from the contributions of the alkyl and carbonyl fragments. The solvent effect on the solvation enthalpy of the carbonyl group was found to be satisfactorily correlated with the corresponding IR frequency shifts of the C=O group. It was also found that the sensitivities of the carbonyl IR frequencies to the solvent composition are different for various ketones. From both IR and calorimetric data, the preferential solvation parameters were evaluated. The differences between the IR spectroscopic and calorimetric data are discussed. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
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  • 137
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 261-272 
    ISSN: 0894-3230
    Schlagwort(e): 1-substituted 2-pyrrolidinones ; C=O stretching frequencies ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: In an effort to model solute-solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational) parameter set. While an empirical parameter set gave the best correlation equations, the theoretical parameter equations are physically and statistically significant. Solvent volume, polarizability and hydrogen bond donor acidity (capacity) terms are significant in the correlation equations. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 14 Tab.
    Materialart: Digitale Medien
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  • 138
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 232-240 
    ISSN: 0894-3230
    Schlagwort(e): P - S bond cleavage ; hydroperoxidolysis ; nerve agent VX ; molecular orbital calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The P - S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P - S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol-1, respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 139
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 407-410 
    ISSN: 0894-3230
    Schlagwort(e): gas-phase thermolysis ; N-methyl-N-phenyl-tert-butylsulfenamide ; morpholinyl-tert-butylsulfenamide ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: N-Methyl-N-phenyl-tert-butylsulfenamide (MPSA) and morpholinyl-tert-butylsulfenamide (MOSA) were thermolyzed in a stirred-flow reactor at temperatures of 340-390 °C and pressures of 7-13 Torr, using toluene as carrier gas, at residence times of 0.3-1.3 s. Isobutene was formed in 99% yield through first-order reactions having the following Arrhenius parameters (A,s-1, Ea, kJ mol-1): MPSA, log A  =  12.41 ± 0.02, Ea  =  158.8 ± 0.2; MOSA, log A  =  12.91 ± 0.22, Ea  =  159 ± 3. It is proposed that the elimination of isobutene takes place by unimolecular reaction mechanisms involving polar, four-center cyclic transition states, forming S-unsubstituted thiohydroxylamines as co-products. Thermochemical parameters, estimated by semiempirical AM1 calculations, are reported for the latter and for the parent molecules. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 140
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 411-418 
    ISSN: 0894-3230
    Schlagwort(e): 2,2′-bisbenzimidazolyl ; tautomerism ; NMR ; semi-empirical calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A dynamic NMR study of the tautomerism of 2,2′-bisbenzimidazolyl in DMSO-d6 and a mechanistic interpretation of the process, based on a stepwise, single-proton transfer and formation of a zwitterionic intermediate, are presented. This interpretation is substantiated by semi-empirical calculations of the postulated intermediate and transition state, that yield results which are compared with previous studies on related aliphatic systems. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 5 Ill.
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  • 141
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 397-406 
    ISSN: 0894-3230
    Schlagwort(e): bond dissociation energy ; acidity ; phenylsulfenylamides ; phenylsulfenylanilides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Acidities and bond dissociation energies (BDEs) of the N-H bond in two phenylsulfenylamides, PhSNHBz and PhSNH-t-Bu, and four phenylsulfenylanilides, 4-GC6H4NHSPh, where G  =  MeO, H, Br and CN, were measured in order to compare the effects of substituents on acidities and BDEs of N - H bonds with those of C - H bonds. The effects of PhS groups on acidities and BDEs in a series of C - H acids were found to be comparable to those on acidities and BDEs of PhS in a similar series of N - H acids. Comparisons were also made of the effects of changing the oxidation state of sulfur in the series PhS, PhSO and PhSO2 on the acidities and BDEs of adjacent N - H and C - H bonds in weak acids. Hammett-type plots of pKHA values for phenyl benzyl sulfones (4-GC6H4CH2SO2Ph) and phenylsulfenylanilides (4-GC6H4NHSPh) were linear vs σp- values. A linear plot was obtained and explained for a plot of BDE of the N - H bonds in remotely substituted phenylsulfonylanilides with σ+ values. Plots of BDEs vs Eox(A-) were also linear for 4-substituted phenylsulfenylanilides (4-GC6H4NHSPh), phenylsulfonylanilides (4-GC6H4NHSO2Ph) and phenyl benzyl sulfones (4-GC6H4CH2SO2Ph). © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 7 Tab.
    Materialart: Digitale Medien
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  • 142
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 387-391 
    ISSN: 0894-3230
    Schlagwort(e): α-diamides ; 17O NMR ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 17O NMR spectra of several α-diamides were obtained at natural isotopic abundance in acetonitrile solution in order to study the conformations of these compounds in solution. The 17O NMR shifts vary with the intercarbonyl dihedral angle α in a sense opposite to that observed for α-diketones. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 143
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 392-396 
    ISSN: 0894-3230
    Schlagwort(e): 8-azaadenine ; tautomerism ; theoretical study ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The prototropic tautomerism of 8-azaadenine (azaade) was studied theoretically by means of ab initio methods, in both the gas phase and aqueous solution. A number of tautomeric forms were not included in the calculations after applying a stepwise elimination procedure based on both AM1 and HF/6-31G* energy values. The tautomers 9H-azaade, 8H-azaade and 7H-azaade survived to this elimination and their optimized geometries and energies were calculated at the MP2/6-31*//HF/6-31G* level. To include the solvent effects, two self-consistent reaction field method were used: (1) Onsager's SCRF with multipolar expansion up to the hexadecapolar term and (2) the isodensity polarizable continuum method (IPCM). Both methods produce similar results, although the latter represents better the situation in aqueous solution. The stability order in solution, 8H- 〉 9H- 〉 7H-azaade, differs slightly from that found in the gas phase, implying that in general the electrostatic effects in solution are important, but the intrinsic stability of these species in the gas phase overcomes the solvent effect. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 1 Ill.
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  • 144
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 377-377 
    ISSN: 0894-3230
    Schlagwort(e): Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: No abstract.
    Materialart: Digitale Medien
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  • 145
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 419-425 
    ISSN: 0894-3230
    Schlagwort(e): 5-nitro-5′-dimethylamino-2,2′-bisthiophene ; π* probe dye ; cyclic voltammetry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Cyclic voltamograms of the solvatochromic dye 5-nitro-5′-dimethylamino-2,2′-bisthiophene (1), introduced recently as a sensitive π* probe, were recorded in different solvents. An EPR spectrum of the anionic radical of 1 in DMSO was obtained and compared with other spectra of analogous substituted bisthiophene radicals. It was found that the presence of a donor- acceptor pair of substituents in 1-⋅ reduces significantly the rotational barrier of the radical compared with the unsubstituted bithienyl radical anion 2-⋅. This is the result of an electronic repulsion between the donor ring fragment and the added electron in the coplanar radical, which does not exist in 2-⋅. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 3 Ill.
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  • 146
    ISSN: 0894-3230
    Schlagwort(e): calix[4]resorcinarenes ; organophosphorus compounds ; solvatophobic interactions ; host-guest complexation ; high-performance liquid chromatography ; x-ray analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Reversed-phase high-performance liquid chromatography [LiChrosorb RP-18,UV detection at 254 nm and acetonitrile-water (86:14,v/v) as mobile phase] was applied to studies of the host-guest complexation of tetraalkylcalix[4]resorcinareneoctols and their upper rim phosphoryl, sulfonyl and dialkylaminomethyl derivatives with some aromatic guests in the mobile phase. It was shown that the formation of the inclusion complexes results in changes in the retention of aromatic guests and improves their separation. Stability constants of the complexes were calculated from the dependences of the l/k′ values of the aromatic guest on the concentration of the calix[4]resorcinarene in the mobile phase. The molecular structure of 4,6,16,18-tetrahydroxy-10,12,22,24-tetrakis(dipropoxyphosphoryloxy)-2,8,14,20-tetramethylcalix[4]resorcinarene (12) was determined. Crystal data for 12 are P21/n, a  =  16.708(9) Å, b  =  18.683(6) Å, c  =  20.243(5) Å, β  =  95.75(3)°, V  =  6287(4) Å3 and Z  =  4. Compound 12 exists in a boat conformation, in which two opposite unsubstituted resorcinol rings of the macrocyclic skeleton lie in the plane formed by four methine bridges and two diphosphorylated rings are perpendicular to the plane. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 7 Ill.
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  • 147
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 378-386 
    ISSN: 0894-3230
    Schlagwort(e): alkylboronic acids ; arylboronic acids ; ab initio ; MM3 ; molecular mechanics ; force field parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The boronic acid functional group has been incorporated into various biologically important compounds. In order to study this class of compounds better with molecular mechanics, five alkyl- and arylboronic acids were calculated using ab initio methods (Spartan) at the RHF/6-31G* level. MM3 force field parameters were developed based on the theoretically calculated geometries, vibrational spectra, and torsional profiles. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 3 Ill.
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  • 148
    ISSN: 0894-3230
    Schlagwort(e): γ-lactones ; base-catalysed hydrolysis ; reactivity-structure correlations ; isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Rate coefficients were measured for the base-catalysed hydrolysis of a series of substituted 3-(phenoxy- or thiophenoxymethylene)-(Z)-1(3H)-isobenzfuranones (3-phenoxy- or thiophenoxymethylenephthalides) in 70% (v/v) aqueous dioxane at 30.0 °C, in addition to the carbonyl stretching frequencies in chloroform and tetrachloromethane following deconvolution and band separation, when required. The Hammett reaction constants for the alkaline hydrolysis of the 3-/4-substituted phenoxy and thiophenoxy series are ca 0.75 and 1.10, respectively. These results are related to electrostatic field and resonance effects. Successful correlations between the carbonyl stretching frequencies and substituent constants and the rates of alkaline hydrolysis were found. Computational studies using the semi-empirical AM1 method correctly model both the details of the mechanistic pathway and the substituent effects. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
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  • 149
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 437-447 
    ISSN: 0894-3230
    Schlagwort(e): inductive constants ; theoretical estimation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A new model of the inductive effect is proposed, allowing highly accurate theoretical calculations of inductive constants for a diversity of substituents, using a simple and readily available system of mathematics. According to this approach, the inductive effect of a substituent is considered in terms of the additive influence of its constituent atoms. A constant inherent capacity for inductive interaction with a reactive center (with a four-coordinate carbon atom chosen for such a center), represented by an atomic constant σA, is ascribed to each atom. Values of σA for a wide variety of atoms are determined, and their physical meaning is revealed to elucidate to a certain extent the physical nature of the inductive effect. In addition, the proposed model permits the convenient use in calculations of group constants σG characterizing the inductive power of groups. Values of σG are determined for molecular fragments that are most widely dealt with in organic chemistry, and the use of σA or σG constants and of their superposition is shown to have, in most cases, little or no effect on the accuracy and reproducibility of the results obtained. It is also shown that, in terms of the developed approach, the inductive effect of a substituent is closely associated with its conformation. Theoretical inductive constants were calculated for 427 organic, aromatic, organometallic and charged substituents, and they showed perfect correlation with the corresponding experimental values. © 1998 John Wiley & Sons, Ltd.
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  • 150
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 448-454 
    ISSN: 0894-3230
    Schlagwort(e): mandelic acid ; alkaline permanganate ; oxidation ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of the oxidation of mandelic acid (MA) by permanganate in aqueous alkaline medium at a constant ionic strength of 1.0 mol dm-3 were studied spectrophotometrically. The reaction shows first-order kinetics in [permanganate ion] and fractional order dependences in [MA] and [alkali]. Addition of products, manganate and aldehyde have no significant effect on the reaction rate. An increase in ionic strength and a decrease in dielectric constant of the medium increase the rate. The oxidation process in alkaline medium under the conditions employed in the present investigation proceeds first by formation of an alkali permanganate complex, which combines with mandelic acid to form another complex. The latter decomposes slowly followed by a fast reaction between the free radical of mandelic acid and another molecule of permanganate to give products. The reaction constants involved in the mechanism were derived. There is good agreement between the observed and calculated rate constants under different experimental conditions. The reaction was studied at different temperatures and activation parameters were computed with respect to the slow step of the proposed mechanism. © 1998 John Wiley & Sons, Ltd.
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  • 151
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 478-484 
    ISSN: 0894-3230
    Schlagwort(e): Selective arylation ; exocyclic N-position ; 2-pyrimidylnitrenium ion ; tetrazolo[1,5a]pyrimidine ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Photo-reactions of tetrazolo[1,5-a]pyrimidine (1) with benzene (2a) and substituted benzenes (2b-f) in the presence of trifluoroacetic acid (TFA) gave 2-(2-, 3- and 4-substituted anilino)pyrimidines (3-5) together with 2-aminopyridine (6) and biphenyl (7) or diarylmethanes (8b, 8c and 8e). From the effect of heavy-atom solvent on the reactions, it is reasonable to assume that 3-5 are formed via a singlet species, but 6-8 via a triplet species. The intermediacy of 2-pyrimidylnitrenium ion is consistent with the evidence derived by the above effect, by a Hammett plot with ρ = -2.9 and by effects of solvent nucleophilicity and counter-anions. The selective exocyclic N-arylation giving 3-5 is discussed. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 2 Ill.
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  • 152
    ISSN: 0894-3230
    Schlagwort(e): 3-methyl-2, 4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol esters ; analgesics ; synthesis ; structure ; conformation ; pharmacological assays ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A series of esters derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol (1) was synthesized and studied by 1H and 13C NMR spectroscopy, and the crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dimethylbenzoyloxy)-3-azabicyclo[3.3.1]nonane (2) was determined by x-ray diffraction. The compounds studied display in CDCl3 a preferred flattened chair-chair conformation. This bicycle conformation is similar to that found for 2 in the crystal state. Pharmacological assays on mice were performed to evaluate drug-induced behavioral alteration, peripheral or central acute toxicity and analgesic activity. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 3 Ill.
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  • 153
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 101-108 
    ISSN: 0894-3230
    Schlagwort(e): encounter complexes ; 1-cyanonaphthalene ; norbornadiene ; stereospecific ; nucleophilic trapping ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Photo-induced electron donor-acceptor reactions between 1-cyanonaphthalene (CNN) and norbornadiene (N) generate products of several structure types. Methanol adducts (1-3) formed in polar solvents are rationalized via the radical cation, N+·, and stereospecific (exo-) nucleophilic attack by methanol. In less polar solvents, CNN and N form [2 + 2]-cycloadducts, exclusively on the exo-face of N. In non-polar solvents containing methanol, CNN, N and methanol combine to form 1:1:1 adducts, containing the sensitizer on the endo- and the methoxy groups on the exo-face. The formation of these products is rationalized via the trapping of encounter complexes of different geometries. Any rearrangement of the norbornenyl system can be eliminated, since neither tricyclyl nor 7-methoxynorbornenyl structures are formed. Apparently, the alcohol captures an endo-encounter complex of CNN and N by attack from the exo-face, similar to the attack of methanol on N+·. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 2 Ill.
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  • 154
    ISSN: 0894-3230
    Schlagwort(e): aromaticity ; Diels-Alder transition states ; Diels-Alder adducts ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Semiempirical, ab initio and DFT investigations on the mechanism of the Diels-Alder reactions of a set of masked dienes (ring-fused dienes), viz. o-quinodimethane, anthracene and α-vinylnaphthalene, with ethylene, and reactions of α-vinylnaphthalene with maleic anhydride and p-benzoquinone were performed with a view to understanding the role of masking factors on the activation and reaction energies. The reactions were found to occur in a concerted fashion through synchronous transition states (TSs) in the first two reactions and through asynchronous TS in the other case. Of the compounds studied, o-quinodimethane is the most reactive diene both in a kinetic and a thermodynamic sense. α-Vinylnaphthalene reacts faster with maleic anhydride than p-benzoquinone, as expected, and two possible stereoselective TSs, one endo and the other exo, have been located for the reactions of α-vinylnaphthalene with the above dienophiles. Calculations show that the relative gain or loss of aromatic stabilization of the benzonoid ring in the transition state and in the product seems to play a major role in the kinetic and thermodynamic control of these reactions. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 2 Ill.
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  • 155
    ISSN: 0894-3230
    Schlagwort(e): methylbenzoic acids ; infrared spectra ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Infrared spectra of all isomers of polymethyl-substituted benzoic acids were recorded in the carbonyl and hydroxyl regions in tetrachloromethane at various concentrations and interpreted in terms of conformation. According to a plot of ν(C=O) of the monomeric form vs Hammett substituent constants σ, these compounds may be classified into two classes. Derivatives with none or only one methyl group in the ortho position are concluded to exist in an equilibrium of two planar conformations, unless the equilibrium is degenerate. Derivatives with two ortho-situated methyl groups are concluded to take up one non-planar conformation. These findings are supported by the shape of the hydroxyl and carbonyl bands, which are unsymmetrical in the former class, although they could not be reliably separated into bands pertinent to the individual conformers. This conclusion is at variance with the common interpretation which has invariably ascribed to these and similar ortho derivatives non-planar conformations with a variable torsional angle. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 6 Ill.
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  • 156
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 149-154 
    ISSN: 0894-3230
    Schlagwort(e): P - C bond cleavage ; phosphoranyl radicals ; organophosphonate biodegradation ; ab initio calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Barrier heights for P - C bond homolysis in P-hydroxy-P-methyl-P,P-dioxophosphoranyl and P,P,P-trihydroxy-P-methylphosphoranyl were calculated using well correlated levels of electronic structure theory. The best estimate for the difference in barriers between the two indicates that homolysis is more facile for P,P,P-trihydroxy-P-methylphosphoranyl by roughly 9 kcal mol-1. This result suggests that bacterial pathways leading to P - C bond cleavage in organophosphonate derivatives will preferentially proceed via initial one-electron reduction of substrates rather than oxidation. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
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  • 157
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 201-208 
    ISSN: 0894-3230
    Schlagwort(e): indolizines ; cycloaddition ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The peculiarities of [8+2] cycloaddition reactions of indolizines with dienophiles are reviewed. Quantum chemical SINDO1, AM1 and ab initio calculations of transition states were performed for [8+2] cycloaddition reactions of indolizine and 6-nitroindolizine with a series of alkenes with donor and acceptor groups. The calculations predict a dipolar cycloaddition mechanism (electrophilic addition and ring closure) for reactions of indolizine and 6-nitroindolizine with nitroethylene. For the reaction of 6-nitroindolizine with N,N-dimethylaminoethylene, the predicted mechanism corresponds to a previously unknown ‘inverse’ dipolar cycloaddition (nucleophilic addition and ring closure). © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 5 Ill.
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  • 158
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 115-124 
    ISSN: 0894-3230
    Schlagwort(e): cross-interaction constants ; gas-phase nucleophilic substitution reactions ; PM3 MO ; benzyl chlorides ; phenoxides ; thiophenoxides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Gas-phase nucleophilic substitution reactions of Y-benzyl chlorides with X-phenoxide and X-thiophenoxide nucleophiles were investigated theoretically using the PM3 semi-empirical MO method. The Leffler-Grunwald rate-equilibrium and Brønsted correlations predict that the degree of bond formation in the transition state (TS) is approximately 45 and 40% on the reaction coordinate for the phenoxides and thiophenoxides, respectively. For a weaker nucleophile, a later TS is obtained with an increased bond making and breaking. The variation of the TS structure with substituents in the nucleophile is thermodynamically controlled and is well correlated by rate-equilibrium relationships. In contrast, the TS variation (a tighter TS) with substituent (for a stronger acceptor Y) in the substrate is dependent only on variations of the intrinsic barrier and so cannot be correlated by such thermodynamically based rate-equilibrium relationships. The gas phase ρX and ρY values are much greater in magnitude than those in solution. A similar gas-phase theoretical cross-interaction constant, ρXY (ca -0.60), is obtained for both phenoxides and thiophenoxides, which is in good agreement with the experimental value (-0.62) for the thiophenoxide reactions in MeOH at 20.0 °C. The oxy and sulfur anion bases lead to a similar TS structure, but a lower reactivity for the former is due to a greater endothermicity of the reaction. A relatively wide range variation of the reaction energies, ΔG°, can be ascribed to the loss of resonance stabilization of anion nucleophiles upon product formation. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 3 Ill.
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  • 159
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 171-176 
    ISSN: 0894-3230
    Schlagwort(e): acetaldehyde ; oxidation ; periodate ; osmium (VIII) catalysis ; ruthenium (III) catalysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Os(VIII) and Ru(III) catalysis of the periodate oxidation of acetaldehyde in aqueous alkaline medium was investigated. The catalytic efficiency is Ru(III)〈Os(VIII). The product of oxidation in both cases is acetate and IO3-. The stoichiometry is the same in both catalyzed reactions, i.e. [IO4-]:[CH3CHO] = 1:1. Probable mechanisms are proposed and discussed. The reaction constants involved in the mechanisms are derived. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 2 Ill.
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  • 160
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 223-229 
    ISSN: 0894-3230
    Schlagwort(e): Solvolysis ; Grunwald-Winstein-type analysis ; Hammett-type analysis ; YxBnCl scale ; 1-aryl-1-phenylmethyl cations ; Mulliken population analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Rate constants of solvolysis of α-tert-butyl(2-naphthyl)methyl chloride (1), 9-fluorenyl chloride (2) and a series of monosubstituted benzhydryl chlorides (3) in a wide range of solvents were measured. Grunwald-Winstein-type correlation analysis of log k for 2 and 3 against YBnCl, with or without nucleophilicity N, yielded less satisfactory linear correlations than that against log k(1). A new scale of solvent ionizing power, YxBnCl, for the correlation of solvolytic reactivities of benzylic chlorides with extended charge delocalization based on log k(1) was developed. Application to the mechanistic study suggested the solvolysis of 2 and 4-nitrobenzhydryl chloride were non-limiting. Hammett plots against σ+ constants exhibited more negative ρ values in less nucleophilic solvents. In a benzhydryl chloride containing a strong deactivating substituent, such as 4-nitro, the positive charge delocalizes mainly over the unsubstituted ring in the cationic transition state. The uneven charge distribution was also confirmed by Mulliken population analysis at the level of the RHF/6-31G*//RHF/3-21G(*) basis set for cations. Comparison of the results of correlation analysis using the equation log(k/k0) = mY vs the equation log(k/k0) = mY+hI, and using the equation log(k/k0) = mY+lN vs the equation log(k/k0) = mY+lN+hI indicated the use of YBnCl or YxBnCl could give a better understanding of solvolytic mechanisms than the combinatorial use of YCl and I. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 3 Ill.
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  • 161
    ISSN: 0894-3230
    Schlagwort(e): Solvent-solute interactions ; β-carotene ; electronic absorption spectrum ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Solvent effects on the wavenumber of the maximum of the longest wavelength electronic absorption band of all-trans-β-carotene were determined in 34 solvents. Together with results from previous studies, a data set for 51 solvents, mostly non-hydrogen bond donors, was constructed. This information was analyzed in terms of reaction field models and also showed its value for correlation purposes when used either alone or in combination with standard empirical solvent polarity-polarizability scales. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
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  • 162
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 177-184 
    ISSN: 0894-3230
    Schlagwort(e): nitro derivatives of phenols ; pyrolysis initiation reactions ; impact sensitivity ; UHF-SCF-AM1 MO method ; activation energy. ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The UHF-SCF-AM1 MO method was applied to the study of two kinds of pyrolysis reactions of six nitro derivatives of phenols (homolysis reaction by rupture of the C - NO2 bond into radicals and isomerization reaction involving phenolic hydrogen transferring to oxygen on the NO2 group). The molecular geometries of reactants, transition states and products were fully optimized. The potential energy curves and activation energies were first obtained. The results show that this category of compounds is more easily initiated via isomerization reactions than by homolysis reactions. The parallel relationship among the Wiberg bond order of the pyrolysis-initiation H - O bond in the molecule of a reactant, the activation energy of the isomerization reaction breaking the H - O bond and impact sensitivity of the reactant gives ‘the principle of the smallest bond order’ (PSBO) powerful support. The sensitizing effect of a phenol group was elucidated based on calculation results. The different influences of OH and NO2 groups on the heat of formation of a molecule are discussed. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 3 Ill.
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  • 163
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 216-222 
    ISSN: 0894-3230
    Schlagwort(e): o-carboxybenzohydroxamic acid ; phthalic anhydride ; phthalic acid ; hydrolysis ; intramolecular acid catalysis ; kinetics ; activation parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Phthalic anhydride was detected spectrophotometrically in the hydrolysis of o-carboxybenzohydroxamic acid (OCBA) in CH3CN-H2O solvent containing 0.03 mol dm-3 HCl. Pseudo-first-order rate constants (k1) for hydrolysis of OCBA are almost independent of the change in CH3CN content from 10 to 80% (v/v) in mixed aqueous solvents. The rate constants k1 are more than 10-fold larger than the corresponding rate constants for hydrolysis of phthalamic acid. These observations are explained in terms of a mechanism slightly different from the mechanism for hydrolysis of phthalamic acid. The activation parameters, ΔH* and ΔS*, are not affected appreciably by an increase in CH3CN content from 10 to 80% in mixed aqueous solvents. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
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  • 164
    ISSN: 0894-3230
    Schlagwort(e): solute-solvent interactions ; solvent-solvent interactions ; binary solvents ; alcohol-water mixtures ; water structure ; solvatochromic indicators ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A preferential solvation model that takes into account the enhancement of the structure of water when small amounts of alcohol are added was applied to solvatochromic data for binary mixtures of water with 2-methylpropan-2-ol, propan-2-ol, ethanol and methanol. Application of the model allows the calculation of the effect of the enhancement of the water structure on solvatochromic solvent properties. It is demonstrated that the enhancement of water structure increases the solvent dipolarity/polarizability and hydrogen-bond donor acidity and decreases the solvent hydrogen-bond acceptor basicity. The effect decreases in the order 2-methylpropan-2-ol-water, propan-2-ol-water, ethanol-water and methanol-water. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 5 Ill.
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  • 165
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 157-170 
    ISSN: 0894-3230
    Schlagwort(e): heterolytic bond dissociation energy ; carbon-carbon σ bonds ; hydrocarbons ; structural dependence ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The coordination of a resonance-stabilized hydrocarbon cation and anion yielded a series of unprecedented hydrocarbons, which are susceptible to thermal heterolytic cleavage of carbon-carbon σ bonds in polar media, generating the original ions under reversible conditions. When the component ions were sufficiently stabilized, some ion pairs were even isolated as solids, thus providing the first examples of hydrocarbon salts. The direct observation of the heterolysis by means of spectroscopy permitted reliable thermodynamic treatments of the observed degree of ionic dissociation. Correlation of the free energy of heterolysis with solvent dielectric constants and parameters of ion stabilities such as pKHA, pKR+ and redox potentials revealed the importance of the thermodynamic stabilities of ions, the degree of solvation and steric congestion in the starting molecule as major controlling factors in the heterolysis. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 16 Ill.
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  • 166
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    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 273-276 
    ISSN: 0894-3230
    Schlagwort(e): N,N-diphenylcarbamoylpyridinium ion ; solvolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Solvolyses of the N,N-diphenylcarbamoylpyridinium ion are subject to specific and/or general base catalysis, which can be eliminated by addition of perchloric acid or increased, especially in fluoroalcohol-containing solvents, by addition of pyridine. The uncatalyzed solvolyses in aqueous methanol and aqueous ethanol involve a weakly nucleophilically assisted (l  =  0.22) heterolysis and the solvolyses in the pure alcohols are anomalously slow. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 2 Tab.
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  • 167
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 209-215 
    ISSN: 0894-3230
    Schlagwort(e): securinine ; cationic micelles ; anionic micelle ; non-ionic micelle ; alkaline hydrolysis ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The effects of micelles of cetyltrimethylammonium bromide (CTABr), tetradecyltrimethylammonium bromide (TTABr), sodium dodecyl sulfate (SDS) and polyoxyethylene 10 lauryl ether (C12E10) on the rates of alkaline hydrolysis of securinine were studied at a constant [-OH] (0.05 M). An increase in the total concentrations of CTABr, TTABr, SDS and C12E10 from 0.0 to 0.2 M causes a decrease in the observed pseudo-first-order rate constants (kobs) by factors of ca 2.5, 3, 7 and 4, respectively. The observed data are explained in terms of pseudophase and pseudophase ion-exchange (PIE) models of micelle. The binding constants, KS, of securinine with SDS, C12E10, CTABr and TTABr micelles are 32.4, 14.8, 22.1, and 9.1 M-1, respectively. The magnitudes of the second-order rate constants, kM, for the reactions in the micellar pseudophase are negligible compared with the corresponding rate constant, kW, for the reaction occurring in the aqueous pseudophase for CTABr, TTABr, SDS and C12E10. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 168
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 277-282 
    ISSN: 0894-3230
    Schlagwort(e): colloidal CdS-induced photochemical reactions ; photocatalytic reactions ; photooxidation ; 2-methylindole ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 2-Methylindole (2-MI) is adsorbed on the surface of colloidal CdS particles with an adsorption intensity of 0.6 × 103 dm3 mol-1. A new emission band at 530 nm is produced by forming an exciplex between excited CdS and 2-MI and the red emission due to CdS is simultaneously quenched. The emission maxima of green bands for different indoles increase in the order indole 〈 tryptophan 〈 2-MI 〈 3-MI and are observed at 508, 520, 530 and 540 nm, respectively. The shift in emission maxima is related to the oxidation potential of these substrates. The irradiation of an aerated reaction mixture containing CdS and 2-MI with visible light induces the oxidation of adsorbed 2-MI by photogenerated holes to produce 2-methyl-3-indolinone and 2-acetamidobenzaldehyde. The latter product is formed due to oxidative C - C bond cleavage of the pyrrole ring. The reactivity of trapped holes towards the adsorbed 2-MI is evidenced by a decrease in the lifetime of the red emission of CdS in the presence of 2-MI. In this reaction the possibility of the participation of singlet oxygen is ruled out. A general mechanism of CdS-induced oxidation of indoles is discussed. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
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  • 169
    ISSN: 0894-3230
    Schlagwort(e): crown dithioether ; conformational analysis ; multicomponent equilibrium ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The solid-state molecular structure and the conformational behaviour in solution of the 12-membered crown dithioether 8-methyl-1,4-dioxa-7,10-dithiacyclododecane-5,12-dione were studied by x-ray crystallography, 1H and 13C NMR spectroscopy and molecular mechanics. The conformational rigidity of some constituent structural fragments allowed a detailed analysis of the structure and distribution of the conformers. A protocol for studies of multiconformational equilibrium was developed by means of the combined use of structure calculations and dynamic NMR measurements. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 170
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 321-333 
    ISSN: 0894-3230
    Schlagwort(e): metal-catalyzed carbenoid reactions ; iodonium ylides ; sulfonium ylides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Transition metal-catalyzed decomposition of phenyliodonium and diphenylsulfonium ylides was investigated with regard to application in asymmetric carbenoid reactions. Phenyliodonium ylides react in the presence of Rh(II) catalysts with the same selectivity in inter- and intramolecular cyclopropanations as the corresponding diazo compounds, and intramolecular CH insertions proceed with identical enantioselectivities. With diphenylsulfonium ethoxycarbonylmethylide the Cu(I)-catalyzed cyclopropanation of olefins affords trans/cis ratios and asymmetric inductions identical with those of diazo compounds, but with Rh(II) catalysts some small, although significant, selectivity variations occur, which are ascribed to coordination of diphenyl sulfide to one of the coordination sites of the catalyst. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 2 Ill.
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  • 171
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 299-304 
    ISSN: 0894-3230
    Schlagwort(e): molecular architecture ; molecule-based magnets ; biopolymers ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Application of the principles of physical organic chemistry to the construction of molecule-based magnets is discussed. Not only the magnetic structures of conventional magnets but also secondary and tertiary structures of biopolymers are instrumental in the molecular design. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
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  • 172
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 350-355 
    ISSN: 0894-3230
    Schlagwort(e): 1,3-dipoles ; cumulenes ; infrared spectroscopy ; mass spectrometry ; flash vacuum thermolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: In the direct investigation of reactive intermediates it is particularly valuable to use a combination of several spectroscopic techniques. This commentary highlights recent examples, using primarily flash vacuum thermolysis for the generation of the intermediates, and matrix IR spectroscopy in conjunction with gas-phase mass spectrometric methods for their identification. The examples include nitrile imines, nitrile ylides, nitrile sulfides and selenides, dinitrogen sulfide and several novel cumulenes (X=C=C=Y, RN=C=C=C=X). © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 10 Ill.
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  • 173
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 305-320 
    ISSN: 0894-3230
    Schlagwort(e): poly(alkylmethyldiallylammonium halides) ; aggregation behavior ; polyelectrolytes ; polysoaps ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Hydrophobically modified polyelectrolytes (polysoaps) are a unique class of water-soluble polymers containing distinct hydrophobic and hydrophilic regions. Above a certain concentration, polysoaps form intramolecular and intermolecular aggregates in aqueous solution. They have attracted much attention not only for their ability to mimic some functions demonstrated by biopolymers but also for their important industrial applications. This review highlights some interesting features of novel non-cross-linked and cross-linked poly(alkylmethyldiallylammonium halides) that have been described in recent years. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 10 Ill.
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  • 174
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 334-340 
    ISSN: 0894-3230
    Schlagwort(e): brain chemistry ; membrane proteins ; molecular neurobiology ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Efforts to developed detailed insights into the structure and function of the molecules of memory, thought and sensory perception - physical organic chemistry on the brain - are described. By combining more conventional chemical tools with a number of techniques adapted from modern biology, it is now possible to perform systematic structure-function studies on the integral membrane proteins that play a central role in molecular neurobiology. There are substantial challenges associated with such studies, but we believe the potential payoff is considerable. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 3 Ill.
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  • 175
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 341-349 
    ISSN: 0894-3230
    Schlagwort(e): vicarious nucleophilic substitution ; hydrogen ; mechanism ; orientation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Hydrogens located at activated positions in electrophilic arenes, e.g. ortho and para hydrogens in nitrobenzenes, can be replaced with a nucleophile moiety provided there is at least one nucleofuge X connected to the nucleophilic centre. As the group really leaving in this hydrogen substitution process is not the hydride anion but X, the reaction has been named vicarious nucleophilic substitution of hydrogen (VNS). The concepts on the mechanism of the reaction and their experimental background are presented. Reactivity and orientation - the fundamental questions concerning synthetical applications of VNS - are discussed in light of the supposed mechanistic picture.
    Zusätzliches Material: 8 Ill.
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  • 176
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 291-291 
    ISSN: 0894-3230
    Schlagwort(e): Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: No Abstract
    Materialart: Digitale Medien
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  • 177
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 362-376 
    ISSN: 0894-3230
    Schlagwort(e): highly strained cyclophanes ; reactivity ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: An essential feature of the concept of aromaticity has been the stability and lack of reactivity of aromatics relative to that of other unsaturated compounds. Contrary to this general experience, high and unusual reactivity is encountered when simple, monocyclic benzene rings are bent by short bridges into a boat-shaped conformation, as is the case in small [n] paracyclophanes (n ≤ 8) and [n]metacyclophanes (n ≤ 7). This is illustrated, mostly with examples taken from the authors' own work, for thermal and photochemical behavior and reactions with electrophiles, nucleophiles and dienophiles. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 22 Ill.
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  • 178
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 356-361 
    ISSN: 0894-3230
    Schlagwort(e): heterogeneous catalysis ; organic reactions ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A decade's worth of work is reviewed: building on the demonstrated prowess of heterogeneous catalysis in industrial organic chemistry, the author's laboratory devised efficient catalysts for a number of organic reactions, based on aluminosilicates such as clays and zeolites. This review also spells out, at a time when creative research is overshadowed by imitative research, some of the methodological musts that also happen to characterize physical organic chemistry: the devising of experiments so that accurate numerical data can be obtained; the importance of remote, interdisciplinary connections; the need for estrangement from stereotypic preconceptions that may obscure the true explanations for the phenomena; and the over-riding need for concerning oneself only, or at least predominantly, with the important facts that nature tells, if one cares to listen. © 1998 John Wiley & Sons, Ltd.
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  • 179
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 292-298 
    ISSN: 0894-3230
    Schlagwort(e): flash-photolysis ; short-lived reaction intermediates ; mandelic acid ; keto-enol tautomers ; enzyme-catalyzed racemization ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The advantage of adding more structure-diagnostic information to the simple detection of flash photolytically generated transient species by changes in UV-visible light absorbance is illustrated by a case study involving the mandelic acid keto-enol system. An early report based on preliminary evidence proposed that flash photolysis of phenyldiazoacetic acid produces the enol of mandelic acid by hydration of phenylhydroxyketene, itself generated by a photo-Wolff reaction of the diazo acid. Further examination, however, shows that this is only a minor route, and that the major pathway is a new enol-forming reaction involving what appears to be hydration of a carboxycarbene formed by dediazotization of the diazo compound. Hydration of phenylhydroxyketene is nevertheless the reaction by which mandelic acid enol is generated when esters of benzoylformic acid are the flash photolysis substrates. These mechanisms, and also identification of the enol as a tranisent species, are supported by detailed arguments involving acid-base catalysis, solvent isotope effects, and the use of oxygen-18 as a tracer. The work produces a keto-enol equilibrium constant for the mandelic acid system, pKE  =  16.19, and also acidity constants of the enol ionizing as an oxygen acid, pKEa  =  6.39, and the keto isomer ionizing as a carbon acid, pKKa  =  22.57. The bearing of these results on the enzyme-catalyzed racemization of mandelic acid is discussed. © 1998 John Wiley & Sons, Ltd.
    Zusätzliches Material: 4 Ill.
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  • 180
    ISSN: 0935-6304
    Schlagwort(e): Epoxytriacylglycerols ; high temperature gas chromatography ; hydroxytriacylglycerols ; ketotriacylglycerols ; lipids ; negative chemical ionization mass spectrometry ; SOP-50 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Five seed oils consisting of unusual triacylglycerols have been examined by high temperature gas chromatography using glass capillary columns coated with the stationary phase SOP-50 (50%-diphenyl-50%-dimethylpolysiloxane, methoxy-terminated). The investigated hydroxy, epoxy, and ketokonjuene triacylglycerols were first derivatized in order to permit analysis by high temperature gas chromatography. Structural elucidation of the intact triacylglycerols was performed with high temperature gas chromatography/negative chemical ionization-mass spectrometry using NH3 as a reagent gas. Individual derivatized lipid species with a molecular weight up to 1176 g/mol could be identified.
    Zusätzliches Material: 10 Ill.
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  • 181
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 169-174 
    ISSN: 0935-6304
    Schlagwort(e): CZE ; detection limit ; signal-to-noise ratio ; correlation chromatography ; reproducibility ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Poor signal-to-noise ratios and analytical reproducibility in capillary electrophoresis were improved by application of multiple injections of the same sample at (pseudo) randomly chosen time moments. One order of signal-to-noise ratio improvement was achieved in practice using an in-house developed computer-controlled pneumatic sampler. However, it is demonstrated here that better implementation of the capabilities of multiple input requires that the detector signal noise be “pre-whitened”, i.e. spikes, baseline drift, oscillations etc. must be removed from the detector signal before transforming it to the electropherogram in the common form. Such filtering of the detector signal was realized by implementing iterative, menu-driven software written in Matlab, a high-level programming language.
    Zusätzliches Material: 5 Ill.
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  • 182
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 181-184 
    ISSN: 0935-6304
    Schlagwort(e): Trace analysis, atmospheric ; digital signal processing ; signal to noise reduction ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 183
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 189-192 
    ISSN: 0935-6304
    Schlagwort(e): Chiral stationary phases ; pyrethroic acids ; enantiomer separation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 184
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 193-196 
    ISSN: 0935-6304
    Schlagwort(e): capillary electrophoresis ; dissolving solvent selection ; optimization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 185
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 201-208 
    ISSN: 0935-6304
    Schlagwort(e): PAN ; peroxyacetyl nitrate ; alkyl nitrate ; chlorinated hydrocarbons ; halocarbons ; capillary GC-ECD ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A cryogenic preconcentration/high-resolution gas chromatographic technique has been developed for the rapid, simultaneous quantitation of C1-C4 organic nitrates and halocarbons in ambient air. Whole-air samples are collected in TedlarTM bags by an evacuated-chamber method. Samples were stable in 0.010-cm-thick bags for 24 h if they were immediately stored in a freezer at -25°C. Analytes in a 50-cm3 air sample were efficiently preconcentrated on fused-silica beads at -180°C and thermally desorbed at 30°C. High-resolution gas chromatography with a cross-linked polydimethylsiloxane fused-silica capillary column and an electron-capture detector were used for separation and quantitation of the analytes. An analysis time of about 12 min was facilitated by sample cryofocusing at -180°C and oven temperature programming. Recoveries of the analytes by the evacuated-chamber method were better than 95%. The sensitivity of the technique for sample volumes of 50 cm3 is in the sub-parts-per-trillion by volume (ppt[v]) range for many of the analytes, with an average precision of about ±5% for analytes at levels of about 10 ppt(v).
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  • 186
    ISSN: 0935-6304
    Schlagwort(e): capillary electrophoresis ; enantiomer separation ; hydroxypropyl-β-cyclodextrin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Following an extended screening project, 86 racemic drugs were investigated by capillary zone electrophoresis in the presence of the chiral solvating agent (CSA) hydroxypropyl-β-cyclodextrin. A total of 42 drugs out of 86 tested was thereby separated into enantiomeric pairs. Statistical analysis of the numerous experiments performed un der identical conditions reveals a loose correlation of the migration separation factor (αm) with the migration retardation factor (Rm). For a subset of 23 drugs, a drop in the concentration of the CSA was also studied, showing the way to further optimization.
    Zusätzliches Material: 6 Ill.
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  • 187
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 253-257 
    ISSN: 0935-6304
    Schlagwort(e): Edible oils ; lipids in foods ; HPLC ; Polycyclic Aromatic Hydrocarbons (PAHs) ; off line LC-LC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 188
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 234-240 
    ISSN: 0935-6304
    Schlagwort(e): Micellar electrokinetic capillary chromatography ; electroosmotic migration ; electrophoretic migration of micelle ; retention mechanism ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---In the present work, four organic modifiers, viz. urea, dioxane, methanol, and tetrahydrofuran, were comparatively and systematically studied in terms of their effects on electrokinetic migration behavior and the retention mechanism of homologous solutes in MECC. The results showed that the electroosmotic mobility, μeo, and the electrophoretic mobility of a micelle, μep,mc, decrease linearly with increasing organic modifier concentration. The ability of organic modifiers to lower μeo is greater than their ability to lower μep,mc. The negative values of the slopes of these linear relationships, Deo and Dep,mc, increase along the series the order urea 〈 methanol 〈 dioxane 〈 tetrahydrofuran. The logarithm of the capacity factor (ln k′) of uncharged homologous solute, which is mainly determined by the hydrophobic interaction, decreases linearly with increasing organic modifier concentration, due not only to the decrease in the partition coefficient but also to the decrease in the phase ratio. A linear relationship was observed between the slope of the plot of ln k′ vs. organic modifier concentration and the carbon number of homologous compound. The slope of such a relationship can characterize the hydrophobicity of the organic modifier. The hydrophobicity of such organic modifiers is also found to increase along the series urea 〈 methanol 〈 dioxane 〈 tetrahydrofuran.
    Zusätzliches Material: 7 Ill.
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  • 189
    ISSN: 0935-6304
    Schlagwort(e): Fluoroquinolone ; ASTED ; HPLC fluorescence ; sarafloxacin ; flumequine ; oxolinic acid ; chicken liver ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A recently introduced programmable fluorescence detector was compared with a single wavelength fluorescence detector for quantification of fluoroquinolone (FQ) antibacterial agents, which have widely varying spectral characteristics. The two detectors were connected in parallel to an HPLC system to test their performance characteristics. With single wavelength detection, two FQs, flumequine and oxolinic acid could be detected at an emission wavelength of 368 nm in a single chromatogram while a third FQ, sarafloxacin, was not observed at that wavelength. Similarly, when the detector was optimized for sarafloxacin emission at 440 nm, the other two compounds were undetected. In contrast, all three FQs were quantified at their individual maxima in a single run using the programmable fluorescence detection. The applicability of an HPLC - programmable fluorescence detector, in combination with on-line microdialysis, also was evaluated using chicken liver fortified at low ppb levels with the three FQs. After on-line microdialysis sample clean up, the resultant HPLC chromatograms were free of background interference enabling the programmable detector to optimize the quantitation of the three analytes in a single run. The limit of quantification (LOQ) determined for each FQ was 1.0 ppb and the limit of detection (LOD) was 0.2 ppb, an order lower in magnitude than was obtainable with single wavelength detection.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 190
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 267-281 
    ISSN: 0935-6304
    Schlagwort(e): Chemically bonded phases, CBPs ; liquid chromatography, HPLC ; preparation; surface characterization ; column evaluation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---In order to increase chromatographic selectivity and to extend the analytical capability of reversed phase liquid chromatography (RP HPLC) many investigators have concentrated on the preparation of silica based column packings with chemically bonded phases (CBP). These phases have also been successfully used in sample preparation techniques, mainly in solid phase extraction (SPE). Although alkyl bonded phases (e.g., C2, C8, and C18) are the most widely used packings in RP HPLC and SPE, various specific applications require CBPs with polar functional groups (e.g., -NH2, -NO2, -CN, and/or -OH). The solution of problems with separation of complicated chiral compounds was attempted by applying stationary phases with chiral selectors (e.g., cyclodextrins, Pirkle phases, crown ethers, etc.). On the other hand, packings with pseudo-membrane or liquid crystal properties have been utilized for the separation of various substances of natural origin. Porous silica is commonly used as a support in the preparation of CBPs. Its physico-chemical characteristics, such as: type and structure of siliceous matrix, porosity, type and concentration of silanol groups, as well as surface purity, strongly influence the density and structure of chemically bonded phases. Recognition of these properties is helpful in optimizing separation processes based on RP HPLC elution and/or extraction of substances with polar character.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 191
    ISSN: 0935-6304
    Schlagwort(e): capillary gas chromatography ; microplasma mass spectrometry ; radio frequency plasma ; element-selective detection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Capillary gas chromatography was performed with mass spectrometric detection using a novel microplasma ion source for operation in an element-selective mode. The ion source was a 350 kHz radio frequency helium plasma, which was sustained inside the 4 cm end of a 0.32 mm i.d. fused silica capillary column, and located inside the high vacuum chamber of the quadrupole mass spectrometer. Due to the low volume of the ion source, a stable low pressure discharge was produced utilizing only the 2.25 mL min-1 of GC carrier gas (helium) for plasma support. Small amounts of oxygen (0.1-0.2% v/v) were added to the plasma gas in order to prevent carbon deposits and to enhance signal-to-noise ratios. Chlorine and bromine were selectively detected at the 5-20 pg s-1 level (S/N = 2), and both produced a response that was linear within 3 orders of magnitude.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 192
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 315-316 
    ISSN: 0935-6304
    Schlagwort(e): Tertiary amine ; ruthenium ; chemiluminescence ; photochemical oxidation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 193
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 303-307 
    ISSN: 0935-6304
    Schlagwort(e): gas chromatography ; modified silica gel ; gaseous standard mixtures ; FID calibration ; carbon monoxide and carbon dioxide ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Quartz rods coated with a thin layer of chemically modified silica gel have been used for the generation of a two-component gaseous standard mixture containing carbon monoxide and carbon dioxide. A new method based on thermal decomposition of immobilized compounds chemically bonded to the surface of silica gel has been used in the generation process. The oxalic acid moiety bonded to the glycydoxypropylsilylated surface of silica gel underwent decarbonylation and decarboxylation at 300°C, yielding carbon monoxide and carbon dioxide. On-line connection of a thermal desorber with the GC/FID enabled calibration of the detector following the process of methanization of CO and CO2. The following amounts of CO and CO2 were generated per unit length of the rod: 15.1 × 10-8 Mol cm-1 (RSD = 5.71%) for CO and 34.2 × 10-8 Mol cm-1(RSD = 5.16%) for CO2.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 194
    ISSN: 0935-6304
    Schlagwort(e): Large-volume on-column injection ; gas chromatography ; infrared spectrometry ; microcontaminants ; solid-phase extraction ; open-split interface ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A large-volume on-column GC-cryotrapping-IR system was developed for injections of up to 100 μl of organic extracts. Considerable reduction of the solvent-and-water background and enhanced analyte detectability was achieved by using an open-split interface between the GC column and the IR detector and improving the leak-tightness of the system. The system was combined with solid-phase extraction to yield on-line SPE-GC-IR. With this set-up, sample volumes of only 20 ml sufficed to detect, and identify, microcontaminants in tap and surface water at the 0.1-1 μg/L level. Detection limits were on the order of 15 ng/L for tap water when using appropriate functional-group chromatograms. Or, in other words, SPE-GC-IR is a suitable technique for the screening of environmental water samples for functional groups, i.e. classes of compounds, of interest.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 195
    ISSN: 0935-6304
    Schlagwort(e): Adsorption/thermal desorption sampling instrument ; capillary gas chromatography ; electrolytic conductivity detector ; photoionization detector ; environmental air monitoring ; hazardous air pollutants ; volatile organic compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 196
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 475-476 
    ISSN: 0935-6304
    Schlagwort(e): Scent glands ; defense substances ; n-alkanes ; furanones ; 2-alkenals ; 2-alkenyl acetates ; 2-decenols ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 197
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 491-497 
    ISSN: 0935-6304
    Schlagwort(e): Fast GC ; narrow-bore columns ; trace analysis ; splitless injection ; on-column injection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---The use of hot splitless, cold splitless, and on-column injections for trace analysis in narrow-bore capillary GC is evaluated. Despite the low flow rates for the columns used, the required splitless times for splitless injections can be surprisingly short if liners with a small inside diameter are used. On-column injection can be applied by using an appropriate normal-bore precolumn coupled to the narrow-bore analytical column using a specially designed low dead volume column connector. The effects of the experimental conditions such as sample volume, injection temperature, and initial oven temperature on peak focusing and the discrimination and degradation behavior of the analytes are discussed. The possibilities to obtain sensitive and fast separations are illustrated by various applications.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 198
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 505-508 
    ISSN: 0935-6304
    Schlagwort(e): capillary electrophoresis ; inorganic ions ; polyethyleneimine ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A capillary zone electrophoresis (CZE) method for the simultaneous assay of bromide, iodide, nitrite, nitrate, and thiocyanate using direct UV detection is reported. The method is based on the separation of anions in a capillary coated with a cationic polymer, polyethyleneimine (PEI). The minimum detection limits, reproducibility of peak areas, and migration times were determined at the optimal condition. The method was applied to the analysis of tap water and human urine. The changes in separation selectivity of the anions resulting from addition of the cationic polymer to the buffer were investigated.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 199
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 523-526 
    ISSN: 0935-6304
    Schlagwort(e): High-performance liquid chromatography ; gardenia constituent separation ; genipin gentiobioside ; geniposide ; crocin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 200
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 435-439 
    ISSN: 0935-6304
    Schlagwort(e): Micellar Electrokinetic Chromatography (MEKC) ; counter pressure moderated MEKC ; migration time window ; peak resolution and peak capacity in MEKC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---The influence of a hydrostatic counter pressure on basic mobility equations in MEKC was analyzed theoretically and investigated experimentally. Taking into account the influence of counter pressure, the modified mobility equations predict a decreased migration time ratio t0/tMC, which was confirmed by results obtained in SDS-MEKC separation of a homologous series of n-alkyl phenyl ketones. As a result, the migration time window could be enlarged in a simple way without having to change the chemistry of the system. Although counter pressures reduce peak efficiency in MEKC by disturbing the plug profile, the concomitant enlargement of the migration time window compensates for this effect. Especially for later migrating compounds, peak resolution could be enhanced at moderate counter pressures. The overall peak capacities within the whole migration window increases slightly when applying counter pressures up to 10 mbar.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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