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  • Analytical Chemistry and Spectroscopy  (17)
  • Capillary electrophoresis  (4)
  • 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
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electroanalysis 9 (1997), S. 1145-1151 
    ISSN: 1040-0397
    Keywords: Copper electrode ; Antibiotics ; Capillary electrophoresis ; Aminoglycosides ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aminoglycoside antibiotics including gentamicin, bekanamycin, tobramycin, lincomycin, neomycin, kanamycin, and ribostamycin have been determined by CE-EC with copper clectrodes. Both copper wall-jet electrodes (WJEs) and copper on-capillary electrodes (OCEs) were evaluated. The OCEs provided μM detection limits, superior stability and reproducibility (2-3% relative standard deviation in oxidation current), and a simple instrumental set-up without the need for capillary/electrode alignment. The analytical capabilities of the Cu-OCE were examined, following the optimization of CE conditions, for the seven aminoglycosides above; and the practical utility of this approach was demonstrated through the determination of aminoglycoside antibiotics in three pharmaceutical preparations.
    Additional Material: 6 Ill.
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  • 6
    ISSN: 0173-0835
    Keywords: Capillary electrophoresis ; Polysaccharides ; Electrochemical detection ; Cu electrode ; Carbohydrates ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Complex polysaccharide mixtures were analyzed directly without derivatization by capillary zone electrophoresis in strongly alkaline solutions and electrochemical detection at a Cu electrode. The positively charged surfactant cetyltrimethylammonium bromide was included in the electrophoresis medium in order to reverse the electroosmotic flow and permit elution to be in order of increasing polysaccharide size. Carbohydrate samples analyzed by this approach included linear maltoses, enzymatically hydrolyzed starch, and commercially available dextrans of up to an average molecular weight of 18 300. Detection by constant-potential oxidation at a Cu electrode was very sensitive, with detection limits for individual carbohydrates generally below the femtomole level.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electrophoresis 19 (1998), S. 2226-2232 
    ISSN: 0173-0835
    Keywords: Electrochemical detection ; Capillary electrophoresis ; Dual-parallel electrodes ; On-capillary electrodes ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: A new approach for dual electrode electrochemical detection in capillary electrophoresis (CEEC) is described. In this approach, two identical capillaries, each containing an on-capillary electrode incorporated permanently onto its tip, were paired together for simultaneous sample injection and detection. This procedure permitted dual-parallel detection to be performed without the need for painstaking alignment of the electrodes with respect to one another and to the capillary outlet as is required for the off-capillary microelectrode systems usually employed in CEEC. As a result, independent detection at two electrodes held at different potentials or at two electrodes of different composition or structure could be performed simply and with wide flexibility. Fabrication of on-capillary electrodes was carried out by sputter-coating the exit end of the capillaries with a thin layer of Au or Pt. Dual electrode system performance was demonstrated by separation and analysis of phenol and catechol samples. In addition, the detection system was coupled with glucose oxidase for the selective detection of glucose.
    Additional Material: 5 Ill.
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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: 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.
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  • 9
    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.
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  • 10
    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.
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