Laser desorption/ionization Fourier transform mass spectrometry and fast atom bombardment spectra of nonvolatile polymer additives

Johlman, Carolyn L.; Wilkins, Charles L.; Hogan, Jeremiah D.; Donovan, Tracy; Laude, David A.; Youssefi, M.

doi:10.1021/ac00210a014

Cited by 34 publications

(10 citation statements)

References 19 publications

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“…As the UV light interacts with the SP film, a second set of peaks appears (Figure 9, middle). These peaks, shifted down by 284 amu, are attributed to the formation of an acid fluoride end group, -CFO, at the first ether oxygen from the end according to the following overall reaction R,-(CF2CF2CF2-0)m-CF2CF2C00-CH2CH2-0-C6H5 -R,-(CF2CF2CF20)w_1-CF2CF2CF0 + CF3CF2C00-CH2CH2-0-C6H5 (7) The ion observed is the Cu+-cationized acid fluoride. As the film is exposed to even more UV radiation, only the acid fluoride end groups are left in the mass spectrum (Figure 9, bottom).…”

Section: Resultsmentioning

confidence: 99%

Transition-metal cationization of laser desorbed perfluorinated polyethers with FTICR mass spectrometry

Cromwell¹,

Reihs²,

Vries³

et al. 1993

J. Phys. Chem.

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Mass spectra of perfluorinated polyether (PFPE) films on metal substrates have been measured using a novel transition-metal cationization technique combined with FTMS. Full parent mass distributions were obtained with this technique. Two pulsed lasers were employed: a low fluence laser for PFPE desorption and a high fluence laser for metal ion formation. Cationization was observed to occur in the gas phase above the sample surface. The dynamics of the process are discussed. Applications to measure average molecular weights and study photochemistry of PFPE samples are presented. Electron attachment to PFPEs was also studied. Only negative ion fragments were observed from this process.

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Section: Resultsmentioning

confidence: 99%

Transition-metal cationization of laser desorbed perfluorinated polyethers with FTICR mass spectrometry

Cromwell¹,

Reihs²,

Vries³

et al. 1993

J. Phys. Chem.

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“…Of the ions produced in Figure 1, the process leading to formation of [TPP + K]+ at mjz 653 is most studied and best understood because it is also the vehicle by which most infrared LDIjtime-of-flight and LDIjFT-ICR mass spectra of organic molecules are produced [38][39][40][41][42][43][44]. Specifically, a weak ionic association results from the gas-phase ion-molecule reaction [20][21][22][23]35] between an intact neutral TPP and a precursor ion from the salt.…”

Section: General Features Of Tetraphenylporphyrin Spectramentioning

confidence: 99%

Competitive ionization of tetraphenylporphyrin in a laser-generated metal ion plasma

Hogan

Laude

1993

J. Am. Soc. Mass Spectrom.

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The ionization of tetraphenylporphyrin (TPP) in a laser-desorbed metal ion plasma is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Competitive reaction pathways observed to generate abundant molecular ion species include electron detachment, cation attachment, charge exchange, metallation, and transmetallation in the positive ion mode and electron capture, metallation, and transmetallation in the negative ion mode. In general, cation attachment reactions dominate positive ion spectra below the laser irradiance threshold for plasma ignition, although the metallation product from [TPP](+) reaction with the metal atom, M, is observed. Negative ion products are not observed in the FT-ICR spectrum when a plasma is not formed. Under plasma ignition conditions, positive ion spectra include [TPP](+) formed by charge exchange with M(+), which is also present in the spectrum. Negative ion spectra are dominated by [TPP](-); which is formed by attachment to thermal electrons generated in the plasma. Metallation reactions involving TPP and the metal substrate are examined. Positive ion metallation products are observed both in the absence of a plasma through reaction of [TPP](+) with M and by a second pathway under plasma ignition conditions through reaction of TPP with M(+). In negative ion mode, metallation is only observed under plasma ignition conditions through reaction of [TPP](-) with M. Observation of metallated products is found to be consistent with formation of stable metal oxidation states in the metallated porphyrin.

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“…Also, these techniques deposit large amounts of energy at the sample surface and typically generate predominantly fragment ions of the polymer itself. Laser desorption (LD) and laser desorption/Fourier-transform ion cyclotron resonance (LD-FTICR) mass spectrometry have also been applied with considerable success to the detection of many classes of nonvolatile compounds including organic polymers. − Johlman et al demonstrated that LD-FTICR could be used to identify polymer additives in polyethylene extracts. The spectra were found to contain intense quasimolecular ions (Na + and K + adducts) as well as fragments. − …”

Section: Introductionmentioning

confidence: 99%

Spatially Resolved in-Situ Analysis of Polymer Additives by Two-Step Laser Mass Spectrometry

et al. 1996

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Two-step laser mass spectrometry has been employed for the direct in-situ analysis of a variety of additives in different polymers. Because of the high sensitivity and optical selectivity of this approach, mass spectra can be obtained directly from the polymer material. The effects of CO2 laser irradiation (λ = 10.6 μm) on samples of poly(oxymethylene) (POM), poly(vinyl chloride) (PVC), polypropylene (PP), and poly(ethylene terephthalate) (PET) and the mechanism of additive desorption have been examined. Several hydroxyphenylbenzotriazole (Tinuvin) UV stabilizers as well as a phenolic antioxidant (Santo White) were successfully detected in typical industrial polymers. The detection limit for Santo White antioxidant in POM was found to be as low as 28 ppm. Finally, depth profiling by stepwise CO2 laser ablation was carried out for a POM injection bar containing 0.1 wt % antioxidant. These spatially resolved measurements established that the near surface concentration of antioxidant was 40% lower than in the bulk.

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Laser desorption/ionization Fourier transform mass spectrometry and fast atom bombardment spectra of nonvolatile polymer additives

Cited by 34 publications

References 19 publications

Transition-metal cationization of laser desorbed perfluorinated polyethers with FTICR mass spectrometry

Transition-metal cationization of laser desorbed perfluorinated polyethers with FTICR mass spectrometry

Competitive ionization of tetraphenylporphyrin in a laser-generated metal ion plasma

Spatially Resolved in-Situ Analysis of Polymer Additives by Two-Step Laser Mass Spectrometry

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