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  • Biochemistry  (23)
  • Analytical Chemistry and Spectroscopy  (18)
  • Theoretical, Physical and Computational Chemistry  (5)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 7 (1993), S. 543-550 
    ISSN: 0886-9383
    Keywords: Fragment occurrence data ; Molecular similarity ; Similarity searching ; Standardization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Substructural fragment occurrence data are widely used as the basis for measures of inter-molecular structural similarity. This paper investigates the effect of standardization on the effectiveness of such measures using eight data sets for which both structural and biological activity data are available. Eight different standardization methods are studied and it is shown that there is no significant difference in the effectivenesses of the various methods; accordingly, any of them can be used for the calculation of intermolecular structural similarity.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0935-6304
    Keywords: GC-AED ; Sulfur ; FCC gasoline ; Compound-independent calibration ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The identification and quantification of sulfur-containing compounds in gasoline has become an area of interest because of impending legislation regulating total sulfur levels in these fuels. To study the effects of catalyst type and catalytic conditions on gasoline sulfur distribution, a method has been developed employing both the compound-independent and element-specific response of the atomic emission detector (AED). Calibration and quantification can be accomplished even where standards are not available, owing to the nature of the AED response.Compounds were separated on a thick film polydimethylsiloxane column. An external calibration curve was applied to the area responses of individual sulfur components in the sulfur chromatogram, and the concentrations of each were calculated. Summation of these sulfur concentrations over the gasoline range yields the total sulfur content of the gasoline.The method is applicable to the determination of these compounds in raw crude oils, finished gasolines, fluid cracking catalyst (FCC) unit gasolines, and fluid catalytic cracking “model” compound studies. A prefractionating column was employed to remove heavy (〉C13) materials; prefractionation is not, however, necessary for distilled or commercial gasoline samples. Detection limits, linearity, detector stability, and accuracy are discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0894-3230
    Keywords: n-Butyllithium ; benzoic acid ; nucleophilic addition ; deprotonation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---An evaluation of a branching vs sequential mechanism for the reaction of benzoic acid with n-butyllithium favors the latter. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1141-1147 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Most matrices used in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) have been selected for their sound performance in the detection of proteins. We evaluated a series of new matrices for the analysis of synthetic polymers and compared their performance to that of conventional ones. Among substituted polycyclic aromatic hydrocarbons 1,4-dihydroxy-2-naphthoic acid, 9-anthracenecarboxylic acid (9-ACA), and its mixtures with 5-methoxysalicylic-acid (‘super’ 9-ACA) offered better signal quality for analysis of synthetic polymers. To test the performance of these new matrices, authentic standards of poly(ethylene glycol), poly(propylene glycol), Jeffamine, polybutadiene, poly(methyl methacrylate), poly(dimethyl siloxane), and some of their mixtures were analyzed. By generating mainly [M + Na]+ ions, 9-ACA showed superior performance to most conventional matrices and provided higher effective mass resolution. The ‘super’ 9-ACA composite matrix was found to be more suitable for larger polymer molecules (〉8000 Da).Broader acceptance of MALDI-MS for synthetic polymer analysis has been delayed by systematic differences observed between MALDI-MS and gel permeation chromatography (GPC) in terms of oligomer size distributions (R. S. Lehrle and D. S. Sarson, Rapid Commun. Mass Spectrom.), Vol. 9, p. 91 (1995). We found that part of the discrepancy can be explained by the profound dependence of mass distributions on the accelerating voltage of the time-of-flight mass spectrometer. With decreasing accelerating voltage both the ion intensity and the mass resolution decreased, and the high-mass end of the mass spectrum became truncated. For example, when the accelerating voltage was changed from 30 kV to 18 kV the center of the peak area distribution for poly(methyl-methacrylate) (PMMA) 6000 shifted to lower values by about 210 Da. At the same time, the skewness of the distribution increased tenfold indicating serious discrimination phenomena. These detrimental effects of lower accelerating voltage were particularly strong for relatively large synthetic polymer molecules.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 7 (1980), S. 201-204 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The field desorption mass spectra of several underivatized cyanogenic glycosides exhibit molecular ions or ions derived from the parent compound by protonation and alkali metal cationization. Abundant fragment ions are present and can be readily related to structure. Significant deviations from established fragmentation pathways are observed due to the nature of the aglycone. The ability to successfully determine the presence of cyanogenic glycosides by field desorption is demonstrated in crude extracts isolated from Vicia sativa, a food-contaminating plant material.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 8 (1981), S. 270-277 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electron impact mass spectral studies on the mono-and di-N-oxides of metyrapone and metyrapol revealed that the technique readily differentiates between the mono-N-oxides of metyrapol, but not of metyrapone. The unequivocal mass spectral differentiation between the isomeric N-oxide metabolites of metyrapone was achieved by the selective and rapid reduction of the keto group in these compounds, with sodium borohydride, to yield the correspoding metyrapol-N-oxides. Chromatographic methods (thin-layer chromatography, gas-liquid chromatography and high-performance liquid chromatography) have been developed for the separation and identification of potential in vitro metabolites of metyrapone. Incubation of metyrapone, under oxidative conditions, with rat or mouse hepatic microsomal preparations, afforded metyrapol (keto reduction) and the isomeric mono-N-oxides of metyrapone. Similar incubation with the hepatic soluble fraction yielded, in addition to metyrapol, an α-pyridone metabolite.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 23 (2000), S. 245-252 
    ISSN: 0935-6304
    Keywords: LMCS ; cryogenic modulation ; comprehensive gas chromatography ; GC×GC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Comprehensive gas chromatography is the realization of true continuous multidimensional (dual column) gas chromatography. The key requirement in the comprehensive GC experiment is that the second dimension analysis is completed in a rapid time-frame compared to the elution of components in the first dimension, and that the two coupled dimensions represent ‘orthogonal’ analyses towards the analytes to be separated. The former normally necessitates pulsing of contiguous segments of each chromatographic band from the first to the second dimensions. The two dimensions should be in fluid communication. The comprehensive GC×GC experiment passes all the column flow from the first column to the second column, leading to no sample loss, but this also requires a suitable method for time- or zone-compression of the band to be pulsed to the second column. The final pulse should be narrow, and should be delivered to the second column quickly. A simple procedure can achieve this using the cryogenic modulator that has been recently described by this group. The system uses a cryogenic trap which can be moved away from the cooled zone of the column faster than 10 ms. A fast-acting pneumatic ram achieves this performance. The cooled column heats up to the prevailing oven temperature within 10-15 ms. Molecules as volatile as C5 alkanes or small aromatics will be fully retained by the trap within the period of modulation used for GC×GC. The technique is simple to implement and requires no special column connections. Using a gas chromatograph which allows control of external events and can acquire from a detector at 50 Hz or faster, and a timing controller for modulation, the comprehensive result can easily and effectively be achieved.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 15 (1986), S. 287-288 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method for improving the determination of cobalt as a minor element in steel specimens is reported. A line overlap correction for the contribution of the Fe Kβ background on the Co Kα peak plus inter-element matrix corrections is necessary in the determination of Co when standards of varying matrix compositions are used. Co was determined in several NBS SRM steels and values were found that agreed with the certificate values to within 5% relative error in the range 0.005-0.40 wt-% cobalt.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 23 (1994), S. 169-172 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Geometrical effects occur when primary x-rays irradiate a mineral inclusion which lies close to the boundary between it and a surrounding mineral having a different chemical composition. An investigation of two types of near-edge effects was performed in the case when x-ray microfluorescence is applied for analysis. For zinc sulfide in calcium carbonate and for arsenopyrite in serpentine, the increase in measured characteristic x-ray intensity near the boundary is 15-25%. Analytical mathematical expressions were developed to correct for such effects and the calculated results are in good agreement with measured values.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    X-Ray Spectrometry 23 (1994), S. 242-242 
    ISSN: 0049-8246
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Type of Medium: Electronic Resource
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