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  • Analytical Chemistry and Spectroscopy  (6,520)
  • 1995-1999  (2,202)
  • 1980-1984  (4,318)
  • 1925-1929
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  • 101
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    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 71-74 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The 70 eV mass spectra of dicyanoquinonediimine and several derivatives have been studied by accurate mass measurements and metastable-ion analysis. Characteristic fragmentations of quinone structures and cleavages involving cyanide rearrangement are responsible for most of the total ion current.
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  • 102
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    Rapid Communications in Mass Spectrometry 9 (1995) 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 103
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1330-1330 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 104
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1331-1334 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Oak and chestnut cask staves were planed to a depth of one centimeter, collecting a sample every millimeter. The samples were ground and subjected to pyrolysis/gas chromatography/mass spectrometry in order to determine their composition. Thirty-six compounds were identified, including a series of typical lignin phenolics commonly considered responsible for wine taste. All ions found in a previous pyrolysis/mass spectrometry study of oak wood and related to good quality whisky were confirmed in the mass spectra of the pyrolysis fragments specific for polysaccharides and lignin recorded in the present work. Compared to chestnut wood, oak wood showed significantly higher lignin and syringyl unit content and less variability as to lignin composition with depth.
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  • 105
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 107-113 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Mass spectral ‘ghost peaks’ are generated with the ion trap by the superposition of higher order multipole fields which originate through deviations from the pure quadrupole field. In data acquisition, when the amplitude of the RF voltage is ramping though a non-linear resonance point (q*) on the Mathieu stability diagram, some ions (m0) are ejected by the non-linear field rather than by the quadrupole field at qz=0.908 on the βz=1 boundary. The prematurely ejected ions will be seen as a peak at m1=(q*/0.908)m0, which we have termed a ‘ghost peak’.
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  • 106
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 358-362 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A new time-dependent wavepacket approach has been applied to illustrate a rigorous method of calculating the transition function for bound-to-continuum transitions in translational energy spectrometric experiments. The method is numerically exact and fully quantal, and is devoid of any classical or semi-classical approximations. The validity of the hitherto-applied reflection approximation is investigated in a comparative study. The method has been applied to two different translational energy spectrometry experiments: collision-induced dissociation of CO+ and collisional excitation of H2.
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  • 107
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    Rapid Communications in Mass Spectrometry 9 (1995) 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 108
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 143-149 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A rapid and simple method for deconvolution of partially resolved spectra has been developed. The algorithm is simple, extremely fast, and capable of deconvolving whole spectra in real time on a fast personal computer. The technique has been evaluated using known test spectra whose resolution has been purposely degraded. The original spectra were reproduced accurately, both in the positions and the intensities of the individual peaks they contained. The method was initially developed for translational energy spectroscopy (TES), where there is little a priori information on the spacing and widths of individual peaks in a spectrum. Examples are given for actual experimental TES spectra of varying complexity and signal-to-noise ratios. Four key variables are required as input before the programme can be executed; these have been parameterized for a range of conditions and typical values have been established. The procedure may be well suited as a rapid pre-screening process before more elaborate techniques are used and it can be applied widely, for example to deconvolute electrospray mass spectra.
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  • 109
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1395-1399 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method has been developed using reliable GC derivatization techniques interfaced with a high resolution mass spectrometer. The method has proved successful for the detection of low levels (less than 1 ppm) of clenbuterol in complex biological matrices. Selected ion recording of two characteristic isotopic fragment ions provides a specific mode of detection by verifying the GC retention time of these ions and also by comparing their relative abundance. Analysis of urine samples demands higher mass spectrometric resolution, and 40000 (10% valley) was found to be a prerequisite for accurate integration of the drug-related chromatographic peaks. The method developed is suitable for adaptation to a completely unattended automated routine incorporating sample injection, storage and retrieval of source tuning parameters, and data processing.
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  • 110
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1400-1401 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A fully automated sample preparation-mass spectrometry system has been described which prepares samples prior to electrospray mass spectrometry analysis, injects the samples, and acquires and processes the data. Fifty samples can be analysed without operator intervention within 8 hours. This type of system ensures optimum use of both the mass spectrometer, which can be in operation 24 hours per day, and the mass spectroscopist, who can concentrate on more challenging samples and spectral interpretation. The laboratory robot system used can be easily adapted for different types of sample preparation and other methods of analysis. For example, in addition to a spectrum exhibiting mainly protonated or deprotonated molecular ions, data could be acquired concurrently with a higher cone voltage, or under tandem mass spectrometry conditions, to generate structurally informative fragment ions. This sample preparation method has been adapted to encompass a variety of samples such as proteins and nucleic acids.
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  • 111
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A gas chromatographic/mass spectrometric method was developed for the simultaneous determination of five synthetic pyrethroid insecticides in soil, moss and fish tissue. These pyrethroids were extracted with hexane-dichloromethane by ultrasonication and cleaned up on Florisil (soil and moss) and mixed acid/base alumina (fish) columns prior to determination by gas chromatography/negative-ion chemical ionization mass spectrometry in selected ion monitoring mode. All the pyrethroids were analyzed simultaneously in a single run on a DB5-MS 15 m capillary column. Recoveries of the pyrethroids from the three matrices at fortification levels of 10, 50 and 100 μg/kg ranged from 80 to 117%. Four determinations were made at each concentration level for each matrix. The practical determination limit of the method was in the range 0.5 to 5 μg/kg depending on the compound. This method was also applied to samples obtained from a contaminated ecosystem.
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  • 112
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1437-1440 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has been used to analyse the results of solid-phase combinatorial chemistry on a single bead. A single component from a five-membered combinatorial library was positively identified using the method outlined in this paper.
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  • 113
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A high performance liquid chromatographic/atmospheric pressure chemical ionization-mass spectrometric (HPLC/APCI-MS) method has been developed for the determination of the pesticides diflubenzuron (1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea) and clofentezine (3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine) in plums, strawberries and blackcurrant-based fruit drinks. Samples were homogenized with acetone, extracted into dichloromethane + cyclohexane and cleaned-up by high performance gel permeation chromatography. HPLC was performed on an ODS column with methanol + water at 1 mL/min. Detection was by negative-ion selected-ion monitoring APCI-MS. Comparison of response with solvent and matrix-matched standards showed some ehancement of response for the latter, and these standards were consequently used for quantification. The calibration was linear over the range 0.05-0.50 ng/μL in all three matrices. The mean overall recovery of diflubenzuron and clofentezine from spiked extracts (0.086 mg/kg) in all three matrices was 76% and 70% respectively with relative standard deviations of 15% and 12% respectively (n = 12). The limit of detection was both compound and commodity dependent and ranged from 0.01-0.05 ng/μL, equivalent to 0.003-0.014 mg/kg in the crop.
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  • 114
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1465-1469 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A method has been developed for the study of samples adsorbed on solid substrates using matrix-assisted laser desorption/ionization combined with quadrupole ion-trap mass spectrometry. The introduction of ions generated externally to the ion trap facilitates the direct analysis of molecules contained on substrates without the need for a lengthy extraction procedure. The method is demonstrated for the analysis of colour coupler compounds separated by thin-layer chromatography and present on a photographic substrate.
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  • 115
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1473-1473 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 116
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    Rapid Communications in Mass Spectrometry 9 (1995) 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 117
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: We report here on the first analysis of polymerase chain reaction (PCR) products amplified from a small amount of human blood DNA by electrospray ionization mass spectrometry (ESI-MS). Adenomatous polyposis coli (APC) gene fragment of about 50 base pairs (bp) with a relative molecular mass (Mr) of approximately 15 000 u was amplified from human blood DNA by PCR. The accurate molecular mass of the PCR products was determined with an accuracy of ∼0.005% by ESI-MS. The amount of DNA used was only 100 ng (∼ 50 zmol; the theoretically required amount of blood is therefore less than 1 μL for PCR). The ESI-MS measurement of the PCR products proved to be a new accurate, sensitive and fast tool for gene diagnosis.
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  • 118
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1507-1511 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: i-Butylvinylether and diethyleneglycol-n-butyl ether (Dowanol-DBTrade name of The Dow Chemical Company.) were reacted under mild acidic conditions to yield acetals. This report deals with the identification of the reaction products by means of gas chromatographic separation followed by mass spectrometric analysis in both electron impact and chemical ionization modes. Consultation of the standard NIST library (50k spectra) revealed that none of the spectra of the acetals in this study were present. A more elaborate study of fragmentation patterns was therefore initiated. The fragmentation patterns of the reaction products in electron impact ionization mode are discussed in detail. During ammonia chemical ionization, typical [M+NH4+26]+ ions are observed for 4,6-dioxa-2,5,8-trimethylnonane. A hypothesis for this phenomenon is presented.
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  • 119
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Resonance-enhanced multiphoton ionization spectrometry (REMPI), using time-of-flight mass spectrometers and tuned lasers, has proved an important ultra-sensitive analytical technique. Nevertheless, conventional nanosecond REMPI suffers from a number of shortcomings: most importantly, REMPI often fails through rapidly (pre)dissociating states. In the case of thermally labile molecules, which include the nitro-molecules, either no or very small parent or high/mass fragment ion peaks exist, making the interpretation of the mass spectra ambiguous at best and often impossible. Femtosecond laser mass spectrometry (FLMS) can often ‘defeat’ these dissociative states, resulting in large parent or high-mass fragment ion peaks which make the interpretation less ambiguous. In the present paper, nanosecond and femtosecond multiphoton ionization and fragmentation are compared using time-of-flight mass spectrometry for NO2 gas and a number of different nitro-molecules: nitromethane, nitrobenzene, m-nitrotoluene, dinitrotoluene and trinitrotoluene.
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  • 120
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1528-1538 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: We present results obtained with a novel mass spectrometer capable of determining the mass of multiply charged electrospray ions generated from samples of macromolecules in the megadalton (MDa) size range. The instrument utilizes a sensitive amplifier which can detect the charge on a single ion as it passes through a tube detector. A velocity measurement of an ion with known electrostatic energy provides the ion's mass-to-charge ratio. Simultaneous detection of the ion charge permits a mass assignment to be made for each ion. Electrospray ions of DNA and polymer molecules with masses greater than 1 × 106 Da and charge numbers (z) in excess of 425 e- are readily detected in this mass spectrometer. The weights of small particles were also measured. The on-axis single-ion detection configuration provides a duty cycle of nearly 100% and extends the practical application of electrospray mass spectrometry to the analysis of very large molecules with relatively inexpensive instrumentation.
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  • 121
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1552-1555 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An entire series of Starburst polyamidoamine (PAMAM) dendrimers consisting of generations 1 through 10 (G1-10) have been studied by positive-ion electrospray ionization mass spectrometry (ESI-MS) using an extended m/z range quadrupole mass spectrometer. Charge-state distributions were detected as high as m/z 12 000 for the generation 10 dendrimer, having a theoretical molecular weight of 1 megadalton and containing approximately 93 maximum positive charges on the molecule. Accurate molecular weight determinations of the smaller generation dendrimers (G1-3, Mr ∼ 1.4kDa to 6.9kDa) were obtained using a commercial triple quadrupole instrument. The unit resolution ESI mass spectra provide information on the number of incomplete reactions which may occur during polymer synthesis. The extent of gas-phase charging observed by ESI-MS on the entire series of macromolecules was found to exhibit a linear relationship to Mr2/3, consistent with theoretical models prediciting a spherical ion structure with maximum charging controlled by Coulombic effects.
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  • 122
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1562-1564 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Molecular weight parameters for synthetic polymers are defined and their determination by matrix-assisted laser desorption/ionization (MALDI) is described. In particular, details of matrix materials that are suitable for this type of measurement are provided. The availability of increased instrumental resolution provides a simple means of endgroup identification for some synthetic polymers.
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  • 123
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1580-1583 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: N+ ions were stored in a home-made ion trap. The apparatus allows the systematic characterization of ion motion in the presence of anharmonicities due to geometric defects, or to a smaller degree, due to the space charge. Enrichment of the spectrum of the motion frequencies and drastic reduction of the storage capability occur due to radial-axial couplings. The paper presents experimental observations of these effects.
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  • 124
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 532-536 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Tandem mass spectrometric (MS/MS) collision-induced dissociation (CID) mass spectra of the molecular ion and main fragment ions in electron ionization of a series of pesticides were recorded using a triple quadrupole mass spectrometer. The fragmentation pathway map of simazine was deduced from the CID mass spectra. The utility of these CID fragmentation ions is demonstrated in the gas chromatography/MS/MS spectrum of carbofuran.
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  • 125
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Oligodeoxynucleotides which contain 7-deaza analogues of the normal purine nucleotides have been synthesized both enzymatically and chemically. When subjected to matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) analysis, the modified samples offer both higher stability and increased sensitivity compared to otherwise identical unmodified Oligodeoxynucleotides. In view of these observations, models for the fragmentation of oligodeoxynucleotides in MALDI-MS with positive ion detection mode are presented. Additionally, the potential use of 7-deaza purine nucleotides in the MALDI-MS analysis of DNA sequencing reactions is discussed.
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  • 126
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 405-407 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Positive-ion chemical ionization (CI) mass fragmentations were studied in the case of different 1,3-dioxolanes. The formation in methane CI mass spectra of interesting fragment ions allowing the characterization of their parent carbonyl compounds and diols is discussed and some mechanisms (supported by D2O CI analyses) are proposed in order to explain these fragmentations.
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  • 127
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The process of the detoxification of A-destruxin into a polar linear peptide in vivo in Locusta migratoria has been demonstrated using both high performance liquid chromatography and negative-ion fast-atom bombardment mass spectrometry. The final structure of the metabolite, after synthesis and comparison of retention time with the component in the crude biological mixture, was elucidated by positive-ion fast-atom bombardment linked-scan mass spectrometry. Diagnostic fragment ions produced by collision-induced dissociation are discussed.
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  • 128
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 437-452 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: High-resolution translational energy spectroscopy is an effective means of obtaining detailed state-selective information, permitting systematic investigation of spin conservation in collisional processes. In this paper, we examine collisional excitation of one selected singlet (N2) and one non-singlet (O2) target by a variety of projectile ions, providing a kaleidoscope of assorted effects.
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  • 129
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    Rapid Communications in Mass Spectrometry 9 (1995), S. i 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 130
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) allows the detection of large molecules such as those present in synthetic and natural macromolecules. Synthetic polymers may show a wide range of molecular weight distributions (MWD), according to the synthetic method used in their preparation. We have studied several poly(methylmethacrylate) (PMMA), poly(styrene) (PS) and poly(ethyleneglycol) (PEG) samples with varying MWD, and also a number of condensation polymers such as Nylon-6, poly(carbonate) and poly(ester). Measurements of MALDI-TOF spectra in the linear mode were used in our work to estimate the molecular weight (MW) and MWD of the polymer samples. Our results show that the molecular weight estimates provided by MALDI-TOF measurements agree with the values obtained by conventional techniques, such as gel-permeation chromatography (GPC), only in the case of polymer samples with very narrow molecular weight distribution. However, when the polydispersity reaches values around 1.10 the difference between the MW measured by GPC and measured by MALDI may amount to up to about 20%. At higher dispersions, the MALDI spectra fail to yield reliable MW values.
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  • 131
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 767-771 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A multiresidue method was developed for the trace level determination of sulfonylurea herbicides in aqueous samples. The method employs on-line solid-phase extraction and electrospray and thermospray reversed-phase liquid chromatography mass spectrometry. In combination with time-scheduled selected-ion monitoring, the method permits the detection of the sulfonylureas down to the 50-100 ng/L level with excellent recoveries of 〉 90% and reproducibilities between 2 and 8.5% for almost all of the investigated compounds. This improved method is superior to existing techniques because no special clean-up step is necessary, and owing to the fast online preconcentration step, the technique can be used as a rapid screening and confirmatory method. The method can be used with either thermospray cr electrospray mass spectrometry, both of which provided mass spectra with at least three structure-signficant ions necessary for an unambiguous identification in environmental samples.
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  • 132
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 778-780 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The electron impact mass spectra of some 2-methyl-3-furancarboxanilides and 2-methyl-3-furancarbothioanilides are discussed. Dominant peaks are formed by simple cleavage of a C—N bond in the anilides as well as in the thioanilides. Thioanilides show some additional fragmentation pathways recently reported which are not seen in the anilides. (T. Jagodzinski and M. Stobiecki, Org. Mass Spectrom., Vol. 25, p. 333 (1990)).
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  • 133
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 804-808 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Phenytoin is one of the most widely employed anticonvulsant drugs in the world. Because this drug has several side effects, an exhaustive structure-toxicity study is needed. To find an easy and cost-effective way to monitor phenytoin in metabolism and toxicity studies, 18 phenytoin derivatives were synthesized and analysed by fast-atom bombardment tandem mass spectrometry.
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  • 134
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The use of pyrolysis/gas chromatography/mass spectrometry (PY/GC/MS) to determine the molecular composition of lignocellulose is reviewed and the technique illustrated with applications on some novel systems. Constituents and structural arrangement of lignocellulosic polymers in plant cell wall are briefly described. The basic principles of pyrolysis and the main advantages and disadvantages of PY/GC/MS are discussed. PY/GC/MS analyses of (a) paper industry effluents, (b) agricultural by-products subjected to biological processes of delignification and (c) recycled paper are presented as examples of the amount of information that PY/GC/MS can provide on lignin classification and monitoring of delignification treatments as well as on the fingerprinting of lignocellulosic materials. The ion trap detector mass spectra of 56 pyrolysis products of lignocellulose, including compounds of phenolic, furanic and pyranic nature, are shown.
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  • 135
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 829-836 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Rate constants for the unimolecular decomposition of peptide monomer and dimer ions by thermal and surface-induced dissociation (SID) are measured and compared. Rate constants for thermal dissociation are measured in a heated wide-bore capillary flow reactor attached in front of the capillary leading into the mass spectrometer. Thermal decomposition of the leucine enkephalin ion (YGGFL)H+ is observed between 600 and 680 K with rate constants of 20-200 s-1, and yields many of the same fragments as SID at 35 eV, although with different relative intensities. The thermal decomposition yields the Arrhenius parameters Ea = 38.3 kcal/mol, log A = 15.7. The decomposition of the monomer and dimer ions are also observed by using SID on C18 and fluorinated hydrocarbon surfaces, with rate constants of 2 × 104 to 40 × 104 s-1. The SID activated monomer ions are assigned equivalent temperatures of 710-840 K by extrapolation of the thermal activation parameters. The protonated dimer ion (YGGFL)2 H+ decomposes thermally at 500-540 K to yield the monomer ion. The dimer also decomposes by SID at low collision energies 10-20 eV on both surfaces to yield the monomer ion, and at much higher energies of 60-80 eV to yield fragments identical to the decomposition of the monomer. The large energy requirement for fragmentation from the dimer is due to energy deposition into more degrees of freedom plus the additional energy required for dissociation of the dimer to the monomer. It is assumed that the energy deposition is linear with collision energy up to 80 eV, and that the energy becomes randomized throughout the dimer, including energy flow through the hydrogen bond(s). These mechanistic assumptions are supported quantitatively by the SID energy relations between monomer and dimer fragmentation. Thermal decomposition of the larger, multiply protonated melittin ion [M + 3H]3+ occurs at substantially higher temperatures, between 810-840 K, than those required for thermal decomposition of (YGGFL)H+, to yield many of the same sequence ions as produced by SID at 135 eV on a fluorinated surface.
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  • 136
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 854-855 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Mass spectrometry was used to study the main fragmentation routes of some 3-alkyl-5-substituted-6-methyl uracils. Differences in fragmentation were caused by changes in the structure of the alkyl group in position 3 of the uracil ring, with the same substituent in position 5, and by differences in the substituent in position 5.
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  • 137
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    Rapid Communications in Mass Spectrometry 9 (1995), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 138
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1266-1269 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Electron impact (EI) mass spectra of ten derivatives of dicyclopentadienyltitanium (IV) dichloride were studied. Fragmentation pathways were constructed and confirmed using daughter-ion, parent-ion and neutral-species loss scan modes of MS/MS.
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  • 139
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1270-1274 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Electrospray ioniztion (ESI) high-performance liquid chromatography/mass spectrometry (LC/MS) has been utilized for the characterization of the active ingredients in over-the-counter (OTC) cough and cold medications. The use of in-source collision-induced dissociation (CID) on a single quadrupole instrument produced spectra with characteristic fragment ions. The in-source CID potential was rotated through different energies on alternate scans throughout the chromatographic run. The spectra across a given chromatographic peak were summed and averaged to give composite spectra which displayed molecular ions in addition to fragment ions, producing library searchable spectra of analytes with varying collisional stabilities, within a single chromatographic run. These spectra were then saved into a library which was created with the following OTC drugs, phenylpropanolamine, doxvlamine, pyrilamine, chlorpheniramine, brompheniramine, dextromethorphan, cyclizine, and clemastine. The active ingredients in commercial OTC remedies were detected and characterized using this created library. The method requires no derivatization and minimal sample preparation, is applicable to a range of analytes, and can be fully automated for multiple sample analyses.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1275-1282 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Single-frequency collisional activation of multiply charged peptides has been studied via electrospray ionization in an ion trap storage/reflectron time-of-flight device (IT/reTOF). Several peptides with molecular weights ranging from 600 to 1700 were used to demonstrate that sequence information can be obtained with this hybrid instrument with a sensitivity in the low picomole level. Further, a resolution of nearly 1000 can be obtained for the fragment products, due to the cooling effects of the buffer gas in the trap before analysis by the reTOF. The influence of the primary structure of the peptides on the observed collision-induced fragmentation patterns is discussed. Although the current study is limited by the electronics, in terms of its ion isolation capabilities, it is demonstrated that the device has the potential for obtaining sequence information for peptides with excellent sensitivity and relatively high resolution.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1293-1296 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A detector has been developed, which collects and amplifies the electric charge of an incoming bunch of ions, for use in matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry. The detector has a time-of-flight resolution of about 50 ns and a noise level of 750 electrons rms. It has been tested in a Finnigan LaserMAT spectrometer with a number of samples which Were expected to give reliable results in MALDI time-of-flight mass spectrometry. Clear mass peaks have been observed from samples with masses above 300 kDa.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 937-941 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In this paper we report matrix-assisted laser desorption/ionization (MALDI) mass spectra of dextrans up to 100 000 Da molecular weight and compare these measurements with those obtained by conventional size-exclusion chromatography with low-angle laser light scattering (SEC/LALLS). These results extend the usefulness of MALDI-MS to higher molecular weight polysaccharides and give some insights into the MALDI process.
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  • 143
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Notes: The electron-ionization induced mass spectra of some N-monosubstituted fluoroacetamides of the general formula FCH2—CONH—R, in which the substituent R is (C3—C7) cycloalkyl, phenyl, 4-methylphenyl, 4-carbo-methoxyphenyl, 4-nitrophenyl and 4-diethylaminophenyl, were recorded and their fragmentation patterns were studied by metastable-ion analyses.
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    Rapid Communications in Mass Spectrometry 9 (1995) 
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 985-997 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Time-of-flight mass spectrometers are able to cover mass ranges to around a half a million Da. The mass resolution of these instruments has been improved drastically by incorporation of electrostatic mirrors. The ion-optical solutions enabling these achievements and other promising features are discussed in terms of: First- and second-order space focusing in time for linear drift time-of-flight mass spectrometers; velocity focusing by time lag; ion-packet bunching in post-source impulse focusing; first- and second-order energy focusing in time, in single- and double-stage homogeneous electrostatic mirrors with normal and oblique ion incidence; gridless designs; perfect time focusing in parabolic potential and axial symmetry; cylindrical ion mirrors and toroidal electrostatic deflectors as time-of-flight mass analyzers; three electrostatic sector geometry applied in secondary ion microscopy and four toroidal sector systems for tandem mass spectrometry; poloidal electrostatic sectors. Estimation of time-of-flight mass spectrometer performance limits is discussed and the stable as well as the metastable peak shapes found in time-of-flight mass spectra.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1007-1011 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: We evaluated the precision, accuracy and linearity of three commercial gas chromatography/combustion isotope ratio mass spectrometry (GC/C-IRMS) instruments in regard to stable carbon isotope ratio measurements of fatty acids with 13C enrichment levels ranging from natural abundance to 924‰, in comparison to measurements by conventional gas isotope ratio mass spectrometry (GIRMS). Memory effect was also evaluated with a fatty acid mixture containing methyl myristate and methyl stearate at natural abundance levels of 13C but methyl palmitate at 13C enrichment levels of 460 or 924‰. At natural abundance, the δ13C values of fatty acids measured by the GC/C-IRMS instruments were reproducible to within 0.34‰ (range: 0.11‰ to 0.32‰) and accurate to -0.38±0.40‰ (mean difference ± standard deviation; range: -0.03±0.25‰ to -0.84±0.39‰). At enrichment levels of 13C (23 to 924‰), the δ13C values were reproducible to within 1.48‰ (range 0.20‰ to 1.00‰) and accurate to -1.11±3.16‰ (range: -1.02±3.23‰ to +4.56±13.42‰). Stable carbon isotope ratio measurements by all three GC/C-IRMS instruments were found to be linear from -30 to 924‰ (r2 〉 0.9999; p ≤ 0.004) in comparison to those measured by GIRMS. Significant memory effect was found in only one system. Based on our data, the GC/C-IRMS instruments can provide linear, precise and accurate stable carbon isotope ratio measurements and require only pico-and nanogram quantities of samples.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1335-1341 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The behavior of peptides containing multiple tyrosine-O-sulfates in liquid secondary-ion mass spectrometry (LSIMS) has been investigated. In the positive-ion spectra of the peptides containing two tyrosine-O-sulfates, Cionin and CCK-associated C-terminal nonapeptide (CAP-9), the completely desulfated [M+H-2SO3]+ ions formed the base peaks, accompanying the significantly less-intense [M+H]+ and [M+H-SO3]+ ions. In the negative-ion spectra of these peptides, the [M-H]- and [M-H-SO3]- ions gave prominent peaks with significantly weaker [M-H-2SO3]- ions. In the case of a peptide containing three tyrosine-O-sulfates, [Tyr(SO3H)1]CAP-9, the completely desulfated [M+H-3SO3]+ ion again formed the base peak in the positive-ion spectrum. On the other hand, the sulfated tyrosine-containing [M+H]+, [M+H-SO3]+, and [M+H-2SO3]+ ions were of negligible abundance compared to the spectra of peptides containing two tyrosine-O-sulfates. We observed an intriguing ‘ladder fragmentation pattern’ in the negative-ion spectrum of this triply-sulfated peptide. The ladder consisted of the [M-H]-, [M-H-SO3]-, and [M-H-2SO3]- ions, but without the completely desulfated [M-H-3SO3]- ion. These characteristic fragmentation patterns of sulfated tyrosine-containing peptides were considered to bear a close correlation with the inherent acid-lability of a tyrosine-O-sulfate in solution. A possible mechanism has been proposed to explain the fragmentation patterns in the gaseous phase, in which a proton plays a decisive role.
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  • 148
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    Notes: The conformational properties of Rhodobacter capsulatus cytochrome c2 wild-type and two site-directed mutants (glycine 34 replaced by serine and proline 35 replaced by alanine) were characterized by their charge state distributions and hydrogen/deuterium (H/D) exchange properties monitored by electrospray ionization mass spectrometry. The results suggest the presence of structural perturbations in the mutated cytochromes, an observation that is in agreement with their decreased conformational stabilities. In addition, a fast enzymatic procedure was developed to identify regions for which the H-bonding or solvent accessibility properties were perturbed by the mutations. In this procedure, deuterated peptides were separated and analysed by using liquid chromatography directly coupled to the electrospray ionization source in order to minimize the occurrence of back-exchange during analysis. In the case of G34S, mutational effects were found for peptides 1-26, 38-51, 52-59 and 109-116, which in the Rb. capsulatus cytochrome c2 structure correspond to extensive regions on the same side of the molecule as the proximal histidine, as well as part of the C-terminal helix. In the case of P35A, mutational effects were found for peptides 1-26, 27-37, 38-51 and 52-59, which in the Rb. capsulatus cytochrome c2 stucture correspond to extensive regions on the same side of the molecule as the proximal histidine. We show that the present set of mass spectrometric experiments is useful as an initial characterization of mutant conformational properties because the analyses require only nanomole quantities of protein and can be performed rapidly.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1141-1147 
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    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.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1499-1501 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Addition of carbon or graphite powder, to either the matrix or the sample if no matrix is used, facilitates the formation of sample ions. For most of the compounds investigated, [M + H]+ ions are observed. For long-chain alcohols, [M - 1]+ ions are formed. This new analysis method allows mass spectra of compounds, that hitherto were difficult or impossible to ionize, using liquid secondary mass spectrometry to be obtained and enhances the signal intensity of poorly ionizable compounds. Using this technique in the negative ion mode, a spectrum of Fomblin® can be obtained which is suitable for calibration purpose over a mass range of 1400 u. The observed effect is possibly due to enhancement of the field strength at the sample surface in the presence of carbon powder. No evidence of contamination of the ion source was visible after four weeks of intensive use of this technique.
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    Notes: A systematic pathway of fragmentation for several protonated cyclohexadepsipeptides is demonstrated by positive-ion fast-atom bombardment linked-scan mass spectrometry. It involves classical sequential acylium and immonium ions, but also, unusual fragment ions characteristic of this family of compounds.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1565-1565 
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1572-1575 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Linear oligogalacturonic acids (1,4-linked α-D-galacturonic acid oligomers), obtained by partial acid hydrolysis of orange polygalacturonides, were studied by negative-ion electrospray ionization mass spectrometry, without prior sample derivatization. After preparative separation using high-resolution anion-exchange chromatography, some fractions enriched in uronic acids were desalted, transferred into a methanol+water solution adjusted to pH 10, and directly submitted to electrospray ionization mass spectrometry in the negative-ion recording mode. Clear molecular mass assignments of the oligomers, covering a degree of polymerization between 4 and 7, were obtained.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1201-1209 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The gas-phase reactions of W(CO)x+ (x=1-4) with methane, ethane, propane, ethene and propene have been studied in a Fourier transform ion cyclotron resonance mass spectrometer. Virtually all reactions observed involve hydrocarbon dehydrogenation, either single or double, a reactivity similar in type to what is observed with bare W+. The most reactive ion is W(CO)2+ except for this ion, reactivity tends to diminish with increasing number of carbonyl ligands. Whenever there is sufficient internal energy available, CO detachment competes with H2 loss. This is the case for ethene and propene, and in some cases with propane. However, this is strongly dependent upon the number of carbonyl ligands in the reacting ion. In most cases, product ions are themselves reactive with the neutral, leading to reaction sequences of various lengths. These sequences end either because the metal no longer has the appropriate number of non-bonding electrons for inserting into a C—H bond with low activation energy, or because of saturation of the coordination shell around the metal.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1225-1225 
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1238-1240 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The time-of-flight properties of magnetic wedge-field sectors have been derived in a second-order approximation. The following quantities were included: source slit width, radial and axial opening angles of the ion beam and relative energy spread. The transfer matrix elements of the time-of-flight (longitudinal) row were derived in terms of the initial and final angles and of K-parameter dependence on the ion momentum and magnetic field. The longitudinal mass dispersion coefficient required in the time resolution formula was derived. The time-of-flight ion optical properties of a 60° symmetric, homogeneous magnetic sector mass spectrometer, already employed for time-resolved ion momentum spectrometry studies, were compared with those of a wedge-field, 180° deflecting stigmatic arrangement with K=0.7423. The time-of-flight aberrations were calculated from transfer matrix multiplications. The advantages of the wedge-field geometry are: independence, up to second order, of the ion packet length upon the ion source slit width, independence to first order of the ion energy spread and stigmatic focusing in space. These factors ensure both improved sensitivity and time resolution.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 583-584 
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An ion microprobe unit was used to study silver isotope ratios in gold-bearing ores. It was found that for ores formed under high-temperature conditions the light isotope 107Ag is enriched. Low-temperature deposits are enriched in the heavy isotope 109Ag.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. i 
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1095-1100 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A matrix-assisted laser desorption/ionization (MALDI) mass spectrometric mapping strategy for the identification and characterization of isolated and purified proteins is described. The method, which employs the combined usage of a new site-specific enzyme Asparaginyl endopeptidase (Asn-EP) for proteolysis, and MALDI for subsequent mass analysis, is capable of rapidly and sensitively examining the components of complex mixtures without any chromatographic or electrophoretic separation steps. Subpicomole sample quantities typically suffice to permit the confirmation of deduced primary structures and/or the identification of possible post-translational modifications. The data obtained should also prove useful for mass matching and sequence homology searching of computerised protein sequence data bases of known proteins.
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    Notes: Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) allows detection of large molecules such as those present in synthetic and natural macromolecules. Until recently, it was reported that MALDI-TOF measurements can provide correct molecular weight (MW) estimates only for nearly monodisperse polymer samples. We have now developed a methodology for polydisperse samples. We recorded the gel-permeation chromatography (GPC) trace of a polydisperse polymeric sample of poly(dimethylsiloxane) (PDMS), collecting 42 fractions. Selected fractions were analyzed by MALDI-TOF and the average MW of each fraction was determined, allowing a calibration of GPC curves against absolute MW. The calibrated GPC trace was then used to compute average MW and molecular-weight distribution (MWD) of the unfractionated poly(dimethylsiloxane) sample. In the spectra of low molecular-weight fractions, the resolution is high enough to resolve the contributions of the various PDMS oligomers as separate signals.
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  • 163
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1184-1184 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 164
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The qualitative and quantitative determination of cholesterol and 7-dehydrocholesterol (7-DHC) in plasma as a biochemical diagnostic marker for the Smith-Lemli-Opitz syndrome by liquid chromatography/particle beam interface-mass Spectrometry (LC/PB-MS) is presented. Baseline separation of cholesterol arid 7-DHC is achieved on a silica column with hexane + ethanol (99:1 v/v) as mobile phase within a 10 min analysis. Recoveries of cholesterol and 7-DHC in a simple two-phase extraction system are nearly 100%. The absolute limit of detection using LC/PB-MS is ≈10 ng. The method presented allows extraction, analysis and quantification of cholesterol and 7-DHC within 15 min without the necessity of sample derivatization.
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  • 165
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1297-1301 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Tilmicosin is a semisynthetic macrolide antibiotic used in the treatment of respiratory disease in cattle and swine. The technique of liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (LC/APCI-MS) was employed in an on-line capacity for the analysis of tilmicosin in extracts from spiked swine liver. Increasing the potential in the cone/skimmer region of the ion source resulted in an increased abundance of unique structurally indicating fragment ions of tilmicosin. Three ions, [M + H]+ and two diagnostic fragment ions were chosen for confirmation of the presence of tilmicosin in swine liver tissue extracts using the mass spectrometer in selected-ion monitoring mode. The ion abundance ratios arising from any given combination of ions in data acquired from extracts of swine liver tissue spiked with tilmicosin at 5 and 10 ppm were within 〈10% of the corresponding mean standard abundance ratio, and duplicate sample analyses exhibited 〈 10% relative standard deviation. These results suggest the potential for the application of LC/APCI-MS as a confirmatory technique for tilmicosin in swine liver.
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  • 166
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 82-90 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The attachment of metal ions to non-polar polymers is shown to be readily achieved using 337 nm laser desorption and ionization, with time-of-flight mass analysis, and could thus prove useful for the analysis of such polymers using commercially available matrix-assisted laser desorption/ionization instruments. Attachment of Cr+, Cu+ and Ag+ has been used successfully to increase the ion yield of polystyrene and polybutadiene during laser desorption/ionization. The metal ion used may originate from the metal sample holder substrate on which the polystyrene is placed, or from metal salts mixed with the polystyrene either prior to placement on the sample holder or in situ. Results have been obtained which illustrate metal-ion attachment to the polystyrene from the substrate and from a dopant salt simultaneously and the roles of each of these will be discussed.
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  • 167
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1315-1320 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Matrix-assisted laser desorption/ionization (MALDI) was used for several small proteins (such as insulin) and for peptides. It was found that the detection efficiencies of MALDI for the insulin B chain and the insulin A chain are drastically different. Similar phenomena were also observed for various types of peptides. The positive-ion signal of MALDI in detecting proteins or peptides was found to be greatly enhanced by the presence of a basic amino acid in their chains. The experimental results indicate that this enhancement may arise from proton transfer in solution by an acid-base reaction between the protein/peptide and matrix molecule. This pre-protonated mechanism provides a low energy barrier for the ionization of peptides in a MALDI process, and greatly reduces the energy threshold of MALDI. Matrix effects on the ionization mechanism are discussed.
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  • 168
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1328-1328 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 169
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 114-118 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Dissociation of C60- ions induced in 30 keV collisions with atomic and molecular gases has been studied. The pattern of negativeion formation from C60- precursors is found to be distinctly different from that obtained for positive-ion fragments from C60+ precursors in that the collision-induced dissociation spectrum in the former case is dominated by small negative clusters, presumably of linear geometry, Simple arguments utilizing the relationship of electrostatic properties of different molecular structures to their electron affinities and ionization energies have been invoked to rationalize these observations. The difference in the dissociation dynamics of C60- and C60+ ions is discussed in terms of competition between different energy-coupling schemes involving either electronic degrees of freedom or nuclear (vibrational) degrees of freedom.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 119-127 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Two-step laser mass spectrometry (L2MS) was applied to study the chemical nature of adsorbates on aerosol particles which were collected from different sites, e.g. in the countryside, in an industrial zone, by a downtown road, and in a tunnel. The method combines infrared laser desorption from the particle surfaces followed by ultraviolet laser post-ionization of the desorbed neutral molecules. Because of the high sensitivity and optical selectivity of L2MS, virtually no sample preparation is needed, and mass spectra can be recorded in a very short time. Qualitative and quantitative comparisons of polycyclic aromatic hydrocarbons in different sampling areas were carried out. By scanning the ionization laser wavelength, two-dimensional UV/MS spectra can be generated for better identification of the adsorbed species.
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  • 171
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    Notes: We characterized the particle size distribution and the analyte transmission efficiency of a liquid chromatography/particle beam/mass spectrometry (LC/PB/MS) system as a function of experimental variations normally used to optimize the LC/PB/MS system. The particle size distribution was evaluated using an electrical differential mobility particle sizer (DMPS) and both the DMPS and the mass spectrometer were used to evaluate transmission. The latter results were correlated to provide evidence related to mechanisms which contribute to poor sample transmission. Addition of ammonium acetate buffer did not increase the aerosol particle riean diameter. However, it did lead to significant increases in caffeine transmission efficiency observed in both the DMPS and the mass spectrometer. Our results were interpreted to suggest a possible electrostatic cause for quantitative anomalies in LC/PB/MS rather than simple mass discrimination in the particle beam momentum separator.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 150-155 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: In this paper we report our studies of reduction phenomena in a high performance liquid chromatography/particle beam interface-mass spectrometer system (HPLC/PB-MS). It is shown that reduction takes place in the ion source of the mass spectrometer, but that the particle beam interface plays an important role in the reduction process since the HPLC mobile phase is involved in the reduction. HPLC flow rate and desolvation-chamber temperature have significant effects on the reduction extent, while ion-source temperature has only a minor effect. All the nitro compounds and sulfoxides tested in this work showed reduction in the system. There was no observed reduction for sulfones. 1,4-Naphthaquinone showed significant reduction, while no reduction was observed for anthraqunone.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 138-142 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An AC corona-discharge device was inserted upstream of a thermospray vaporizer tip in a liquid chromatography/particle beam mass spectrometer to neutralize static aerosol charging. Response of a test analyte was measured with or without discharge initiation. If the solvent contained no ammonium acetate buffer, increased analyte signal was associated with the discharge. However, in the presence of ammonium acetate the benefit of AC discharge neutralization was either not observed or was more subtle. This led to the conclusion that the previously observed ammonium acetate “carrier” effect is attributable, at least in part, to neutralization of static electric charges produced spontaneously during the solvent nebulization process. In a second experiment, the pattern of particles issuing from the system momentum separator was examined by aiming the particle beam at a cold target located within a mass spectrometer ion source. Variations in particle density were observed depending on (i) whether or not the aerosol had been neutralized and (ii) the proximity of electron-beam-collimating magnets to the particle beam trajectory. These results are consistent with a hypothesis that electrostatic charging occurs spontaneously during the nebulization process in which an aerosol is formed from the high performance liquid chromatography effluent. Such electrostatic charging introduces a factor likely to degrade system performance by at least two modes: through interactions of the charged aerosol particles (i) with the walls of the aerosol transmission pathway, and, after they are accelerated into a particle beam and introduced into the mass spectrometer, (ii) with the magnets used for electron beam collimation in many mass spectrometer ion sources.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 1391-1394 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Complex formation of the important nitramines, RDX, HMX and TNAZ with α-, β-, and γ-cyclodextrins (CDs) was studied using ion-spray mass spectrometry (IS-MS). Complexations between β-CD/TNAZ, β-CD/RDX, γ-CD/RDX, and γ-CD/HMX were detected in the gas phase by this technique. Control experiments using α-CD and TNAZ did not lead to a detectable molecular association, which is in accord with the previously reported NMR data. In addition, none of the nitramines showed any complex formation with the non-cyclic sugar, maltohexose. The IS-MS results are in agreement with the previously reported conclusions from proton nuclear magnetic resonance spin-lattice relaxation time measurements.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 156-159 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The second example of F/H reduction of a fluorine aromatic derivative in a fast-atom bombardment mass spectrometric experiment is described. It concerns a tetrafluorophenyl derivative bearing two 3,5-dimethylpyrazol-1-yl substituents.
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  • 176
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    Notes: Fast atom/ion bombardment mass spectrometry was used to investigate the structures of protonated molecules of macrocyclic nitrogen-containing crown ethers with two polyoxyethylene chains linked by two thiourea groups. The collision-induced dissociation (CID) of their MH+ ions, using the mass analysed ion kinetic energy (MIKE) spectrometry method reveals four clearly defined competitive fragmentations. The product-ion intensities clearly show that, in the MH+ ions of asymmetric crown ethers, the proton is preferentially located in the region of the longer polyoxyethylene chain. The characteristics of CID MIKE spectra of isomeric crown ethers are discussed.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 177-179 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: Deprotonated o, m-, and p-methoxyacetanilide show pronounced peaks in their collision-induced tandem mass spectra (MS/MS) produced by losses of the elements of C2H6. It is proposed that this reaction is a ‘cross-ring’ internal SN2 reaction involving an incipient methyl anion. For example, p-CH3O—C6H4—-—CO—CH3→ [(p-CH3O—C6H4—N=C=O)CH3-]→-O—C6H4—N=C=O+C2H6.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 188-190 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Physics
    Notes: Automated ‘open access’ mass spectrometry with liquid interfaces is now considered routine in our laboratories at Sandwich, UK. Synthetic chemists log samples into a queue on the mass spectrometer and return a short time later to take the mass spectrum and the sample away. The whole process occurs without any intervention by a mass spectroscopist (D. V. Bowen, M. Dalton, G. Perkins, F. Pullen and D. Richards, Rapid Commun. Mass Spectrom. Vol. 8, p. 632 (1994)). Fast response liquid chromatography/mass spectrometry is a further development in ‘open access’ mass spectrometry driven by the needs of chromatographers, for whom it is important that the identity of each component present in a high-performance liquid chromatographic separation is known. This Communication describes the development of such a system for our laboratories.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 413-426 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Several studies concerning the analysis and quantification of biological and pharmaceutical compounds have been effected during the past 20-30 years using different techniques of desorption-ionization. In most cases, however, the authors have not been interested in the mass spectrometric fragmentation mechanisms of these products. Plasma desorption mass spectrometry (PDMS) is a powerful technique for analysing, without matrix interferences, solid biological and pharmaceutical compounds. In this work, we use PDMS in order to study the influence of the amine (amide) function on the fragmentation processes of nitrogen-containing compounds. For this work, quaternary ammonium salts, trisubstituted amines, disubstituted amines and a compound with an amide function were chosen. Classical PD mass spectra, accurate mass measurements, transitions in the field free region (FFR), labelled compound spectra and thermodynamical data are reported for the structural study of these compounds. Our results allow us to propose fragmentation rules for positively charged nonfunctional biological nitrogen compounds. These rules relate to a class of structurally informative decomposition reactions that can be applied to the determination and of identification of structural unknowns.
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    Notes: Two different approaches, i.e. fast-atom bombardment tandem mass spectrometry and gas chromatography combined with mass spectrometry (GC/MS) have been employed for the characterization of a mixture of biologically relevant polyphenols (kaempferide, kaempferol, luteolin and oleouropein). The best results have been achieved by the first approach which allows an easy structural identification of the different compounds, also in the presence of isomers. GC/MS of the trimethylsilyl derivatives leads to a complex chromatogram due to the presence of derivatives exhibiting a different level of silylation; the only species related to oleouropein are due to pyrolysis products (silylated fragments of sugars) and there is no evidence for the related silylated aglycone.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 461-487 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An annual directory of companies that supply mass spectrometers and mass spectrometry components and services.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 488-490 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Micellar electrokinetic chromatography/mass spectrometry (MEKC/MS) using an electrospray-chemical ionization (ES-CI) source is described. The interface between micellar electrokinetic chromatography and mass spectrometry consists of an electrospray-type nebulizer and an atmospheric pressure chemical ionization source that uses a needle electrode. Aromatic amines (aniline, p-nitroaniline, and 1-naphthylamine) are analysed by MEKC/MS, using a phosphate buffer that includes 20 mM sodium dodecyl sulfate (SDS), and protonated molecular ions of the samples are clearly recorded on the ion electropherograms. The results show that the ES-CI technique is very promising as an MEKC/MS interface since MEKC/MS uses a high concentration of nonvolatile salts and surfactants.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 491-494 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Negative electrospray ionization mass spectrometry (NESI-MS) of a series of native gangliosides containing one, two or three sialic acid groups, sulphatide-I and cholesterol 3-sulphate was undertaken, using a magnetic sector instrument. The results show that NESI-MS of gangliosides leads to the formation of multiple-charged molecular ions of the type [M — H]-, [M — 2H]2- and [M — 3H]3-. The number of charges appears to be correlated to the number of sialic acid groups present. NESI-MS of sulphatide-I predominantly gave ions of type [M — H]- whilst cholesterol 3-sulphate gave a more complex ionization pattern. The sensitivity of the NESI-MS system was enhanced by using water+methanol, 9:1 (v/v) as solvent, containing 300 pmol/μL of NH4HCO3. The application of NESI-MS to these compounds is discussed.
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    Notes: High-performance liquid chromatography in combination with mass spectrometric detection (atmospheric-pressure chemical ionization, APCI) was used to determine various isoflavones. Negative-ion APCI ionization has proved to be a suitable technique for determining this class of natural compound, as it provides quality mass spectra which give not only the molecular weight of the isoflavones, but also their molecular structures; consistent collision-induced dissociation pathways were elucidated and fragments are reported. Deuterium oxide was used to induce peak shifts in the mass spectra in order to determine the number of exchangeable hydrogen atoms in each molecule.
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    Notes: Reversed-phase high-performance liquid chromatography/mass spectrometry (LC/MS), with an atmospheric-pressure chemical ionization (APCI) interface, has been applied to the identification of metabolites and derivatives of paclitaxel (taxol) in plasma and urine of patients treated with this new anticancer drug. Protonated molecules with substantial fragmentation were obtained using this ionization technique. The three ion series observed are characteristic of the intact molecule, the taxane ring, and the side chain at C13. Their analysis gives information about chemical modifications of the taxane structure at different positions of the molecule. Urine and plasma extracts were evaluated using the capacity to perform MS analysis directly on the entire effluent from conventional LC columns. Excellent spectra were obtained with 50 pmol of separated compounds in full scan mode. This technique allowed highly sensitive identification of 6α-hydroxytaxol, the major human biliary metabolite, and of 7-epitaxol in extracts of plasma and urine from patients. Taxol hydrolysis derivatives were observed for the first time in urine 24 hours after the end of the infusion period. Sensitivity could be increased further using single ion monitoring (SIM) mode, once a target derivative was identified. These results demonstrate that LC/MS with an APCI interface is useful for the characterization and pharmacokinetic analysis of taxoids in biological matrices.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 509-511 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The reduction phenomenon of polar compounds that has already been described in fast-atom bombardment (FAB) mass spectrometry also occurs in frit-FAB mass spectrometry.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 512-514 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A compact Wien filter/magnetic deflector, double-focusing mass spectrometer was constructed and tested. The Wien filter is sited inside the gap common with the magnetic deflector. The instrument first-order ion-optical parameters and the second-order aberration coefficients are given. A brief description of the instrument is followed by the experimental results obtained on a methane sample. Jon currents of 1.6 × 10-8 A were collected at a resolution of 170 for a main path radius of 56 mm.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 300-304 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Biphenyl derivatives undergo extensive intraannular substituent migrations and subsequent intramolecular ipso substitutions giving rise to a fluorenyi cation and a biphenylene radical cation as common products in mass spectrometry. For biphenyls bearing an alkyl group, interannular substituent migration resulting in a substituted tropylium ion is also observed. Electron-withdrawing groups are found to be much more favourable to these reactions than the electron-donating ones.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 519-524 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Fumonisin B1, a mycotoxin produced by a common fungal contaminant of corn, Fusarium moniliforme, was analyzed by capillary electrophoresis-electrospray ionization mass spectrometry. System performance was maximal with uncoated columns. System efficiencies of approximately 44 000 plates/m and reproducible analysis times of about 13 min were obtained. System efficiency with methyl-coated columns was approximately 24 000 plates/m. Reproducible analysis times of about 3.5 min were obtained with these columns. With uncoated columns, the concentration limit of detection was 156 ppb with a s/n ratio of approximately 10. The estimated injected mass at 156 ppb was 1.1 pg. Repeated injections of extracts containing constant fumonisin B1 concentrations showed that peak areas were slightly inconsistent, although generally similar to variations encountered with liquid chromatography-electrospray ionization mass spectrometry. The source of this inconsistency was traced to sample solubility, errors inherent in electrophoresis injections, and electrospray instability. Minimizing these problem areas will produce a technique with peak area reproducibilities comparable to liquid chromatography-electrospray ionization mass spectrometry, but with potentially greater resolving power.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 312-316 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The stoichiometry of a noncovalent, hydrogen-bonded supramolecular complex, hub(M)3·RCA3, was characterized using electrospray ionization from chloroform. The intact (1:3) complex was observed in the negative-ion mode as a Cl--bound species using Ph4PCl as the source of the charge donor. Collisionally and thermally induced dissociation of the (1:3) complex resulted in the simultaneous loss of all the three RCA units, indicating a cooperative binding of RCA units in the (1:3) complex. These results suggest that the attachment of small, organic-soluble ions may be a useful technique for mass spectrometric characterization of neutral supramolecular complexes that are stable or soluble only in non-polar organic solvents.
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 322-324 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 194
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 325-328 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A new application of mass spectrometry to experimental studies of molecular dynamics has been developed and implemented in which ion translational energy spectrometry at very high angular resolutions is utilized to study the unimolecular dissociation of metastable dications. A brief overview is presented of the experimental technique, which utilizes a ‘home-made’, three-sector (equivalent to BEE geometry) instrument. The fragmention kinetic energy spectrum obtained using such apparatus is capable of yielding information on the lifetimes of specific quantal states of dications of a wide variety of stable and radical species; two illustrative examples (CO2+ and SH2+) are presented.
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  • 195
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The GE2270 complex consists mainly of GE2270 A (MW 1289), a thiazolyl peptide antibiotic whose structure originates from the modification of a chain of 14 amino acids in a process which creates six thiazole rings and one pyridine. Together with the main component, a number of structurally related molecules are co-produced in small quantities by fermentation. A preparative high-performance liquid chromatrography method was developed to isolate GE2270 factors B1, B2, C1, Ca, C2a, C2b, D1, D2, E and T. Their structures, preliminarily determined by 1H-nuclear magnetic resonance spectroscopy in comparison with GE2270 A, were confirmed by low and high resolution fast-atom bombardment mass spectrometry and studies on the intact molecules and on their main hydrolysis products. Their molecular weights range from 1246 to 1306 Da. The structural differences between the factors lie in the extent of methylation and/or oxidation of thiazole rings (D and E) and asparagine, and in the aromatization of the oxazoline ring.
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  • 196
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 541-549 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The surface tension for three diacylphosphatidylcholines in glycerol was measured at different concentrations and, based on these data, the surface excess concentrations were calculated. These calculated values were then used to examine the correlation between surface excess concentration in glycerol and the observed secondary ion intensities produced during xenon bombardment of the same solutions. For the surface excess concentration of phospholipids in glycerol a behaviour, similar to that found for surfactants in water, could be established. The experimental results showed a straightforward correlation between the mass spectrometric response of the desorbed protonated molecular ions of diacylphosphatidylcholines and the calculated surface excess concentrations for the selected short time (∼1 min) of data acquisition. This finding supports a model which assumes desorption of precharged species in the first several monolayers of the liquid matrix. Furthermore, the surface excess concentration of each phospholipid in glycerol solutions of identical bulk concentration was found to be different, reflecting differences in surface activity, which explain observed suppression effects in phospholipid mixtures isolated from biological issues. Based on this observation and the existence of the same structural head group in phosphatidylcholines which are carrying the fixed positive charge, it can be assumed that differences in ionization efficiency are not responsible for the differences observed in the mass spectrometric response. An additional attempt was made to correlate surface tension, bulk concentration and secondary ion intensity of equimolar mixtures of dilauroyl- and distearoyl-phosphatidylcholine in glycerol. The results indicate a nonlinear desorption behaviour for phosphatidylcholine mixtures in the combined concentration range from 9.0 × 10-6 to 5.9 × 10-2 M.
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  • 197
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    Rapid Communications in Mass Spectrometry 9 (1995), S. iii 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 198
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    Rapid Communications in Mass Spectrometry 9 (1995) 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
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  • 199
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 555-558 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Fast-atom bombardment (FAB) mass spectra have been measured for resolved 132-hydroxychlorophyll a epimers. The fragmentation of each epimer was studied by tandem mass spectrometry using linked scans at constant B/E. The FAB spectra showed a very intense radical cation (M+·) and EI-type fragmentations. The most abundant fragment ions were formed by the losses of the phytyl, the 132-hydroxy, and the 132-methoxycarbonyl groups in various combinations. The fragment ions [M — OH]+, [M — phytadiene]+·, and [M — phytadiene — OH]+ were found to be characteristic of both 132-hydroxychlorophyll a epimers. Nevertheless, it was shown that the loss of the 132-hydroxy group occurs more easily from the 132(S)-epimer than from the 132(R)-epimer. This fragmentation difference offers a new possibility for the determination of the stereochemistry at the 132-chiral centre of purified 132-hydroxychlorophyll preparations.
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  • 200
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    Rapid Communications in Mass Spectrometry 9 (1995), S. 559-562 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Pyrolysis/gas chromatography/mass spectrometry (PY/GC/MS) of As4S6 (orpiment), As4S4 (realgar), As4O6 (arsenolite), NaH2AsO4 (sodium di-H-orthoarsenate) was performed using a platinum-filament pyrolyzer heated at 700°C for 10 s and coupled to a capillary gas chromatograph/ion trap mass spectrometer. As4 was observed as a pyrolysis fragment in the pyrograms of all compounds. Pyrolysis of NaH2AsO4 equivalent to 100 ng of As, produced a strong As4 chromatographic peak. As4S3 and As4S4 were detected as pyrolysis products of As4S6 (orpiment). As4S4 (realgar) and As4O6 (arsenolite) were detected as intact molecules after pyrolysis. By contrast, intact As4S6 was not detected after pyrolyses in the range 400-700°C. As4 was detected as an impurity in the painting layer of an Egyptian mummy. The mass spectra of such arsenic compounds, none of which is included in the NIST library of spectra, are reported. Advantages and limitations of PY/GC/MS as a technique for the qualitative detection of arsenic inorganic compounds are discussed.
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