Analysis of cationic surfactants by mass spectrometry/mass spectrometry with fast atom bombardment

Lyon, P. A.; Crow, Frank W.; Tomer, Kenneth B.; Gross, Michael L.

doi:10.1021/ac00277a004

Cited by 53 publications

(26 citation statements)

References 17 publications

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“…Positive and negative ion fast atom bombardmentmass spectrometry (FAB-MS) and FAB-MS/MS data were used previously to successfully characterize aliphatic quaternary salts. 12 It was noted, however, that fragmentation was seen in the FAB mass spectrum whereas little or none was observed in the FD-MS data. 11 The spectra shown in Fig.…”

Section: Quaternary Saltmentioning

confidence: 99%

“…The main decomposition pathways of aliphatic dimethyl quaternary salts were described previously from FAB-MS/MS data. 12 These pathways indicated that the most intense ion peaks in the spectra were the imminium ion at m/z 58 and fragments arising from loss of an alkyl chain with concurrent hydrogen transfer. Intense ion peaks in the FD-MS/MS spectra (Fig.…”

Section: Quaternary Saltmentioning

confidence: 99%

“…Ion peaks at m/z 134 in both spectra are consistent with the loss of dodecane or tetradecane from the precursor ion. The ion peak at m/z 135 indicates that the alkyl chain may also be lost as a radical ([C 12 ).…”

Section: Quaternary Saltmentioning

confidence: 99%

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The characterization of complex mixtures by field desorption-tandem mass spectrometry

Jackson

Jennings

Scrivens

et al. 1998

Rapid Commun. Mass Spectrom.

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This paper shows the first application of field desorption-tandem mass spectrometry (FD-MS/MS) in a hybrid sector, orthogonal acceleration time-of-flight mass spectrometer. This instrumentation has significant advantages in detection limits for MS/MS experiments over four sector mass spectrometers. This is important when using FD ionization from which low ion currents are generated. Data are shown from a few classes of industrial compounds and the proposed fragmentation pathways are described. # 1998 John Wiley & Sons, Ltd. Received 2 September 1998; Revised 28 September 1998; Accepted 1 October 1998 Field desorption (FD) was one of the first forms of soft ionization used in mass spectrometry 1 but poor sensitivity and limited applicability have restricted the impact of the technique. The approach does, however, find a niche application in the area of non-polar chemical systems. These compound classes, which include hydrocarbons and industrial ester formulations, often occur as complex mixtures and are difficult to study by any other mass spectrometric ionization method. This makes the problem of the low ion currents generated by FD even more acute, however, since there are generally a large number of compounds in each sample to be studied. The technique also generates ion currents that can be transitory in nature. This makes significant demands on the instrumentation used for FD-MS experiments.One of the advantages of FD is that ions are generated with a low internal energy (less than 1 eV).2 This means that few or no fragment ion peaks are observed in FD spectra. The lack of fragmentation is an advantage when profiling complex mixtures but provides little, if any, structural information. Tandem mass spectrometry (MS/MS) approaches must therefore be used in order to aid the characterization of structure. FD-MS/MS is a challenging experiment as a consequence of the low signal-to-noise ratios and transitory nature of the ion currents which are generated.We have used a ZAB-T four sector mass spectrometer (Micromass, Manchester, UK) of BEBE geometry, fitted with an array detector, to perform these experiments with some success. 3 The applicability is, however, limited to simple mixtures with relatively strong FD signals. This paper shows the first application of FD-MS/MS in a tandem, hybrid, orthogonal acceleration time-of-flight (oa-TOF) tandem mass spectrometer. This type of instrument offers advantages for the FD-MS/MS experiment, over four sector mass spectrometers, as a consequence of the greater ability to detect the very low ion currents that are generated. It is shown, for a variety of systems including poly(styrene)s, complex ester formulations and quaternary salts, that structural information may be inferred from the FD-MS/ MS data. EXPERIMENTAL Mass spectrometryFD-MS/MS data were obtained in an AutoSpec 5000-oa-TOF tandem mass spectrometer fitted with the standard FD source (Micromass) and using commercially available 13 mm activated carbon emitters (Linden ChroMassSpec, Bremen, Germany). The hybrid se...

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Section: Quaternary Saltmentioning

confidence: 99%

Section: Quaternary Saltmentioning

confidence: 99%

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The characterization of complex mixtures by field desorption-tandem mass spectrometry

Jackson

Jennings

Scrivens

et al. 1998

Rapid Commun. Mass Spectrom.

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“…During the 1980s and early 1990s several reports on the use of FAB/MS for identifying surface-activeagents (surfactants) in commercial product [3][4][5][6] and environmental samples [7][8][9][10] appeared in the literature. The majority of reports describe the use of FAB/MS for the qualitative analysis of surfactants while only a limited number of reports describe the quantitative analysis of surfactants by FAB/MS [7][9] [11].…”

Section: Introductionmentioning

confidence: 99%

Identifying Hydrocarbon and Fluorocarbon Surfactants in Specialty Chemical Formulations of Environmental Interest by Fast Atom Bombardment/Mass Spectrometry

Field¹,

Schultz²,

Barofsky³

2003

Chimia

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Hydrocarbon-and fluorocarbon-based surfactants are used in specialty or 'niche' chemical formulations that are designed for applications such as aircraft deicing and anti-icing, 'spreaders' that increase the effectiveness of pesticide formulations, and for fighting hydrocarbon-fuel fires. The identity of the surfactants in specialty formulations is usually proprietary information. However, this information is needed to design studies that monitor the occurrence and fate of all the components of specialty chemical formulations that enter the environment and pose a risk toward aquatic organisms. Fast atom bombardment/mass spectrometry (FAB/MS), while not a new technique, remains the fastest technique for identifying surfactants in complex mixtures because no sample preparation is required. FAB/MS was applied to samples of an aircraft deicer and anti-icer and aqueous-film-forming-foams (AFFF) for the purpose of identifying the major classes of hydrocarbon and fluorocarbon surfactants. High mass accuracy FAB/MS measurements were made to identify an unknown fluorosurfactant in an AFFF formulation. Rapid identification of surfactants that are released into the environment facilitates the subsequent selection of quantitative analytical methods that can be used to monitor the occurrence and fate of surfactants in the environment.

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“…Their analysis by tandem mass spectrometry [1] has experienced a steady growth after desorption ionization methods [2] enabled the volatilization and ionization of these thermally labile materials. In the most common approach, the polyglycol sample (M) is converted to gaseous quasimolecular ions [M + X]+ by fast-atom bombardment (FAB) [3,4]. In the positive FAB mode, a proton or alkali metal cation (X+) is attached to M to form an [M + XJ+ adduct, which is later mass-selected and subjected to colllsionally activated dissociation (CAD), leading to structurally diagnostic fragments [1].…”

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confidence: 99%

Dissociation characteristics of [M + X]⁺ ions (X = H, Li, Na, K) from linear and cyclic polyglycols

Selby

Wesdemiotis

Lattimer³

1994

J. Am. Soc. Mass Spectrom.

122

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The unimolecular reactions of protonated and metalated polyglycols with kiloelectronvolt translational energies have been studied by collisionally activated dissociation and neutralization-reionization mass spectrometry. The former method provides information on the ionic dissociation products, whereas the latter allows for the identification of the complementary neutral losses. Protonated linear polyglycols mainly undergo charge-initiated decompositions that lead to eliminations of smaller oligomers, On the other hand, protonated crown ethers ("cyclic" polyglycols) favor charge-induced reactions that proceed by cleavages of two ethylene oxide units in the form of 1,4-dioxane. Replacement of one O by NH in the crown ether dramatically changes its unimolecular chemistry; now, charge-remote 1,4-eliminations from ring-opened isomers are preferred. Charge-remote reactions are also the major decomposition channels of all metalated precursors studied. The linear polyglycols decompose primarily by 1,4-H2 eliminations and to a lesser extent by homolytic cleavages near chain ends. The reverse is true for metalated crown ethers, which preferentially produce distonic radical cations by the loss of saturated radicals; these reactions are proposed to involve prior rearrangement to open-chain isomers. The nature of the metal ion (Li(+), Na(+), or K(+)) does not greatly affect the unimolecular chemistry of the cationized polyglycol. In general, metalated precursors form many abundant fragment ions over the entire mass range; hence, collisional activation of such ions at high kinetic energy should be particularly useful for structure elucidations.

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Analysis of cationic surfactants by mass spectrometry/mass spectrometry with fast atom bombardment

Cited by 53 publications

References 17 publications

The characterization of complex mixtures by field desorption-tandem mass spectrometry

The characterization of complex mixtures by field desorption-tandem mass spectrometry

Identifying Hydrocarbon and Fluorocarbon Surfactants in Specialty Chemical Formulations of Environmental Interest by Fast Atom Bombardment/Mass Spectrometry

Dissociation characteristics of [M + X]⁺ ions (X = H, Li, Na, K) from linear and cyclic polyglycols

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Analysis of cationic surfactants by mass spectrometry/mass spectrometry with fast atom bombardment

Cited by 53 publications

References 17 publications

The characterization of complex mixtures by field desorption-tandem mass spectrometry

The characterization of complex mixtures by field desorption-tandem mass spectrometry

Identifying Hydrocarbon and Fluorocarbon Surfactants in Specialty Chemical Formulations of Environmental Interest by Fast Atom Bombardment/Mass Spectrometry

Dissociation characteristics of [M + X]+ ions (X = H, Li, Na, K) from linear and cyclic polyglycols

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Dissociation characteristics of [M + X]⁺ ions (X = H, Li, Na, K) from linear and cyclic polyglycols