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  • 1
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Mixtures of a specific group of proteins, the major urinary proteins (MUPs), believed to have a role in odorant binding, have been analysed by electrospray ionization mass spectrometry. The data obtained from conventional transformed electrospray data confirm that the molecular weights of the protein mixtures, deduced from published sequences, lie in the molecular weight range 18600 to 19 000 Da. Application of maximum-entropy analysis to the raw electrospray data has confirmed a heterogeneity in MUP composition, consistent with allelic similarities (and differences) between the different mouse strains. This work demonstrates the use of maximum entropy in the assessment of protein content and in the subsequent resolution enhancement of naturally occurring protein mixtures containing components of closely similar molecular mass.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Metastable ions arising from pseudomolecular [M — H]- ions produced by fast-atom bombardment negative-ion mass spectrometry of a range of free ecdysteroids, ecdysteroid conjugates and polar metabolites were investigated by means of linked scanning at constant B/E. Free ecdysteroids displayed daughter-ion spectra which allow 20-hydroxyecdysteroids and ecdysteroids lacking C-20 hydroxylation to be readily distinguished. The ejection of acetic acid from acetylated ecdysteroids was also readily detectable. Characteristic metastable-ion decomposition of ecdysteroid acids was not observed, presumably as a result of charge localization. High-mass daughter ions were also lacking in the case of phosphate conjugates.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 7 (1993), S. 477-481 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: High-performance liquid chromatography/mass spectrometry (HPLC/MS) with thermospray ionization has been applied to the analysis of free ecdysteroids (polyhydroxylated steroids that serve as arthropod moulting hormones). Of a range of analytical conditions that were tested, optimum results were obtained by the use of re versed-phase HPLC using a methanol + water mixture containing 0.1 M ammonium acetate. The positive-ion spectra of ecdysteroids showed pseudo-molecular ions, [M + H]+, and fragment ions corresponding to the sequential losses of hydroxyl groups. The [M + H - H2O]+ and [M + H - H2O]+ ions were the most abundant for all the compounds tested. Ecdysteroids bearing a C-20 hydroxyl group (e.g. 20-hydroxyecdysone) showed ions characteristic of cleavage of the side-chain from the steroid nucleus. This mode of fragmentation was much less obvious in the case of ecdysteroids lacking C-20 hydroxylation (e.g. ecdysone). Full-scan mass spectra were readily obtained from 1 μg of free ecdysteroids, while a limit of detection of 5 ng (signal-to-noise ratio 3) was attained in the selected-ion monitoring mode. The application of HPLC/MS to the study of ecdysteroids in biological materials is demonstrated by the analysis of extracts of newly laid eggs of the desert locust (Schistocerca gregaria) and pupae of the cotton leafworm (Spodoptera litoralis).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Nucleic acid extracts from 1400-year-old radish seeds recovered from excavations at Qasr Ibrim, Upper Egypt, have been analysed by gas chromatography/mass spectrometry and gas chromatography/mass spectrometry/mass spectrometry. tert-Butyldimethyisilyl derivatives of the purine and pyrimidine bases were prepared, after treatment of the nucleic acid extracts with concentrated formic acid. Under electron ionization these derivatives yield prominent [M-57]+ ions that were found to be of value for use in analyses employing selected-ion monitoring and product-ion studies. These two techniques were used in the sensitive and selective detection of nucieotide bases in crude extracts of ancient seeds. The results obtained were supported by complementary analyses of hydrolysates of ancient nucleic acids and authentic bases by means of retention time and spectral comparisons. This work demonstrates for the first time that mass spectrometry can be used in the direct chemical examination of nucleotide bases in ancient materials. This analytical approach is currently being used to address questions regarding the possible chemical (diagenetic) changes occurring in the nucleic acids of ancient biological material.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acetylacetone (Hacac) admitted as a gas to an ion source containing CoCl2 adsorbed on a field ionization/field desorption emitter produces the ion [Co(acac)Cl]+. Similar ions arising from interaction of adsorbed salt and a ligand admitted as a gas were found for CoCl2 and trifluoroacetyl acetone, and for FeCl2 and acetylacetone. The chelation process represents a new kind of reaction of chemisorbed species in field ionization mass spectrometry.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 3 (1970), S. 387-393 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A probability distribution of internal energies is derived for aromatic molecular ions which can decompose to give only a single product whose relative intensity and appearance potential are each a function of Hammett sigma constants, with certain simplifying assumptions.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 20 (1985), S. 445-453 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrogen chemical ionization (H2 CI) mass spectra of a range of metal(II) (Ni, Cu, Co, Pt), metal (III) (Al, Mn, Ga, Fe (bearing a single axial ligand)) and metal(IV) (Si, Ge, Sn (bearing two axial ligands) and V (as V=O2+)) porphyrins have been determined, The spectra are highly dependent on the coordinated metal, rather than the axial ligand(s) (where present). Ni(II), Cu(II), Mn(II or III), Ga(III), Ge(IV), Fe(III) and Sn(IV) porphyrins fragment via hydrogenation and demetallation, followed by cleavage of the resulting porphyrinogens at the meso(bridge) positions to give mono- and di-pyrrolic fragments. Tripyrrolic fragments are also observed in the case of Ni(II), Cu(II) and Sn(IV). Fragmentations of this type are similar to those observed for free-base porphyrins. In the case of Pt(II), Co(II), Al(III), Si(IV) and V(IV) (as vanadyl), the dipyrrolic fragment ions are either very weak or completely absent; hence their H2CI spectra contain limited structural information. This variable CI behaviour may be related to the relative stabilities of the metalloporphyrins together with the multiple stable valency states exhibited by several metals.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 14 (1987), S. 131-140 
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of both synthetic and naturally occurring (human plasma) cholesteryl esters have been examined by capillary gas chromatography/mass spectrometry (GC/MS). A magnetic sector mass spectrometer was used and a variety of ionization modes were assessed with a view to obtaining structural information on intact cholesteryl esters. By employing ammonia as reagent gas, with negative ion scanning, spectra were produced from which the nature of steryl and fatty acyl moieties could be readily deduced. Analyses were performed at an ion source temperature of 300°C in order to maintain the integrity of the gas chromatographic profile. The technique described is of general use for the GC/MS analysis of steryl esters, particularly in conjunction with magnetic sector instruments.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 4 (1977), S. 52-54 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Details for the construction of a novel, inexpensive device for the electrochemical generation of metallic emitters for field desorption mass spectrometry are described. Use of the device for the generation of cobalt and nickel emitters is demonstrated.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1974), S. 269-273 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An azurin, a small respiratory copper protein from the bacterium Pseudomonas fluorescens biotype G, has been studied by mass spectrometry to determine sequence information. The study of homologously related proteins by mass spectiometry is particularly attractive, since the correct nature of major parts of the deduced sequences can be confirmed by comparison with the sequences of the protein from related organisms. An oxidized tryptohan residue has been identified amongst the products from a cyanogen bromide digest of this wild type azurin. In the same digest, a product is also found to arise from cleavage of the peptide chain at the C-terminal side of the same tryptophan residue. These results are rationalized.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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