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  • Analytical Chemistry and Spectroscopy  (35)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 5 (1991), S. 238-239 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Measurements of the translational energy loss accompanying the charge-stripping reactions M++N→M2++N+e- and M2++N→M3++N+e- have been performed for C60+, C70+ and C602+, C702+ respectively. The energy nesessary to remove the second electron from Buckminsterfullerene was determined, QminI=IE(C60+→C602+=12.25±0.5 eV.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 7 (1993), S. 225-228 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The suitability of the hydrochloride salt of tris(2-carboxyethyl)phosphine (TCEP) for in situ reduction with matrix-assisted laser desorption/ionization (MALDI) and liquid secondary ionization (LSI) mass spectrometry is evaluated. TCEP can be used to irreversibly reduce organic disulfldes to thiols in water and is active at an acidic pH. We found that TCEP was suitable for partial reduction of bovine insulin deposited on the target and mixed with either sinapinic acid in MALDI or glycerol and m-nitrobenzyl alcohol in LSIMS. When TCEP was added to insulin deposited on the target without prior mixing of sinapinic acid the in situ MALDI protocol resulted in almost complete reduction.
    Additional Material: 5 Ill.
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  • 3
    ISSN: 0306-042X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method employing selected ion monitoring for the analysis of glutethimide and six of its metabolites has been developed. Hydroxylated metabolites analyzed as trifluoroacetates, included 4-hydroxyglutethimide, (1-hydroxyethyl)glutethimide and p-hydroxyglutethimide. The unchanged drug, 3-dehydroglutethimide, desethylglutethimide and the internal standard, [2H5]glutethimide, were chromatographed underivatized on OV-225. The assay was used to measure drug and metabolites in the plasma and urine of patients intoxicated with glutethimide. High levels (e.g. 20-35 μg ml-1) of unconjugated 4-hydroxyglutethimide, an active metabolite, were found in all patients at a time when levels of unchanged drug were lower and declining. Other unconjugated and conjugated metabolites were found in relatively low concentrations in the plasma (i.e. 〈 4 μg ml-1). The major urinary metabolites were conjugates of 4-hydroxyglutethimide and (1-hydroxyethyl)glutethimide. The unchanged drug and other conjugated and unconjugated metabolites were found in lower amounts in the urine. Normal plasma half-lives of glutethimide and the relatively small amounts in urine of unchanged drug and unconjugated metabolites indicated that drug elimination was not markedly impaired in the intoxicated patients.
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  • 4
    ISSN: 0306-042X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-pressure liquid chromatography in combination with field desorption mass spectrometry as techniques of high specificity and sensitivity have been applied to the identification and quantitation of the anticancer drug methotrexate and its metabolites which occur in clinical high-dose therapy. Field desorption mass spectra of methotrexate and several methotrexate and folic acid derivatives, when investigated as free acids or ammonium salts, yield abundant protonated molecular ions and a consistent pattern of structurally significant fragments. High-pressure liquid chromatographic separation of methotrexate metabolites was performed on reverse-phase, C-18 columns using a volatile, ammonium bicarbonate/acetate containing mobile phase that was especially suited for the field desorption mass spectral analysis of isolated metabolites, and provided the definite identification of 7-hydroxymethotrexate and 4-[[2,4-diamino-6-pteridinyl]methylmethylamino]-benzoic acid in serum and urine of patients treated with high-dose methotrexate. The high intensity and stability of the [MH]+ ions was found suitable for the quantitation of methotrexate and related folate analogues by field desorption mass spectrometry. A synthetic methotrexate derivative, methotrexate-γ-(2-hydroxy)ethylamide was used as internal standard for the quantitative determination of methotrexate in serum and urine. In a study to comparatively assess the potential of specific quantitation methods, serum and urine levels of methotrexate and its major metabolite, 7-hydroxymethotrexate were determined by (i) an enzyme immunoassay, (ii) reverse phase high-pressure liquid chromatography and (iii) field desorption mass spectrometry. Results obtained from four patients with osteogenic sarcoma receiving high-dose methotrexate/leucovorin rescue therapy consistently show the sustained elimination of 7-hydroxymethotrexate over several days, thus indicating the utility of specifically monitoring this nephrotoxic metabolite, at massive methotrexate doses.
    Additional Material: 10 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 11 (1984), S. 539-544 
    ISSN: 0306-042X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a number of N-acyl-5-aminosalicylic acids and their derivatives is described. These compounds allow the sensitive and specific mass spectrometric determination of unlabelled or deuterium-labelled N-acetyl-5-aminosalicylic acid in biological samples. An in vivo study shows that the labelled compound, administered to rats, is excreted isotopically unchanged to at least 97%, and that no significant deacety lation/acetylation mechanism exists for this metabolite N-acetyl-5-aminosalicylic acid of salicylazosulphapyridine.
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  • 6
    ISSN: 0306-042X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quantification of prostaglandin PGE2 by gas chromatography mass spectrometry in the form of an easily prepared derivative is described. After extraction and purification of biological samples the compound was derivatized in two steps to 9-enol-PGE2-methylester-trimethylsilylether, 9-enol-PGE2 -Me-TMS3. The molecular ion at m/z 582 with 40% relative abundance and the fragment ion at m/z 492 with 100% relative abundance permit a specific and sensitive evaluation in the selected ion monitoring mode. The high masses selected lie above the biological background. The calibration curve produced by adding known amounts (10-200 ng) of PGE2 to blank human urine and with (2H4)-deuterated PGE2 as internal standard gave a linear correlation. The separation from biological impurities was obtained on a 50 m glass capillary column and resulted in sharp and symmetrical peaks.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 28 (1993), S. 303-304 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 8
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electron-capture negative ion chemical ionization (EC-NICI) and field desorption (FD) mass spectrometric techniques were utilized to examine polyfluorinated C60. Two different samples from the same preparation, one prior to sublimation and the other sublimed material, were investigated. From the raw non-sublimed product in EC-NCI six series of ions corresponding to different numbers of attached oxygen atoms were obtained, which are represented by the formula [C60F2nOm]-, where n ranged from 0 to 30 and m from 0 to 5. The sublimed material in EC-NICI produced the same six series of ions with up to 48 fluorine atoms attached to C60. The field desorption of the same sample produced similar results, but the signal-to-noise ratios of the spectra were low. Both samples, in the two different techniques examined, yielded C60F60 ions with only an even number of fluorine atoms attached. The present investigation, for the first time, provides direct experimental evidence for the existence of higher fluorinated C60 up to C60F60 and multiple oxides of polyfluoro-C60 with up to five oxygen atoms attached.
    Additional Material: 7 Ill.
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  • 9
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fragmentation of 2,7-octanedione, induced by chemical ionization with methane as a reagent gas (CI (CH4)), is shown to be extensively governed by the interaction of the two carbonyl groups. Tandem mass spectrometry reveals that a sequential loss of H2O and C2H4O from the [M + H]+ ion competes with sequential loss of H2O and C6H10, and that both processes occur via the same [MH - H2O]+ intermediate. This intermediate is likely to be formed via intramolecular gas-phase aldol condensation and subsequent dehydration. The resulting C(1) protonated 1-acetyl-2-methylcyclopentene structure readily accounts for the observed further decomposition to CH3C≡O+ and 1-methylcyclopentene (C6H10) or, alternatively, to [C6H9]+ (e. g. 1-methylcyclopentenylium) ions and acetaldehyde (C2H4O). Support for this mechanistic rationale is derived from deuterium isotope labelling and low-energy collision-induced dissociation (CID) of the [MH - H2O]+ ion. The common intermediate shows a CID behaviour indistinguishable by these techniques from that of reference ions, which are produced by gas-phase protonation of the authentic cyclic aldol or by gas-phase addition of an acetyl cation to 1-methylcyclopentene in a CI (CH3COOCH3) experiment.
    Additional Material: 7 Ill.
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  • 10
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The investigation of suitable model compounds shows that it is impossible to generalise about the mechanisms of the electron-impact-induced ‘Retro-Diels-Alder’ reaction on the basis of stereochemical effects.
    Notes: Durch die Untersuchung geeigneter Modellverbindungen wird belgt, daß eine Generalisierung der Mechanismen der elektronenstoßinduzierten ‘Retro-Diels-Alder’-Reaktion aufgrund sterischer Effekte unmöglich ist.
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