Laser desorption-Fourier transform mass spectrometry for the characterization of polymers

Brown, Robert S.; Weil, David A.; Wilkins, Charles L.

doi:10.1021/ma00158a053

Cited by 77 publications

(40 citation statements)

References 10 publications

(11 reference statements)

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“…It is interesting to note that even before the application of MALDI-MS to synthetic polymers there have been experimental efforts to apply laser desorption FT-MS without using a matrix. Brown et al [93] achieved well-resolved spectra for PS, PEI, poly(ethylene glycol methyl ether) (PEG-ME) and PEG up to M p values of about 6000 Da by using a CO 2 laser for ionization and the addition of alkali chlorides (Na; K) to the samples.…”

Section: Recent Developmentsmentioning

confidence: 99%

MALDI-TOF mass spectrometry in the analysis of synthetic polymers

1998

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Section: Recent Developmentsmentioning

confidence: 99%

MALDI-TOF mass spectrometry in the analysis of synthetic polymers

1998

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“…Spectra obtained for two polystyrene molecular weight standards obtained under silver nitrate laser desorption/chemical ionization (LDjCI) conditions are shown in Figure 1. Although polystyrene can undergo alkali metal attachment under conventional LDIFTMS conditions, it is less efficient compared with the corresponding reactions of heteroatom-containing polymers [1]. As a consequence, lower abundances of molecular ions are produced, spectral quality is inferior, and the upper mass limit is much lower than that seen in spectra of poly(ethylene glycol), for example.…”

Section: Polymer Spectramentioning

confidence: 99%

“…Possibly because of the presence of multiple aromatic rings, polystyrene is one of the more tractable hydrocarbon polymers when analyzed using standard volatilization/ionization methods. For example, polystyrenes have been studied by laser desorption/ ionization [1,2], secondary ion mass spectrometry [3][4][5][6][7], field desorption-ionization/mass spectrometry (FO/MS) [8][9][10], plasma desorption ionization [11], laser desorption/resonance-enhanced multiphoton ionization [12], liquid chromatography/mass spectrometry [13], and thermal desorption electron ioniza-tion and chemical ionization mass spectrometry [14,15]. Most recently, polystyrenes have also been characterized by matrix-assisted laser desorption/ionization [16,17].…”

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confidence: 99%

“…Previously, it has been shown that direct carbon dioxide laser desorption/Fourier transform mass spectrometry (LD/FTMS) is an excellent tool for characterization of heteroatom-containing polymers, providing both accurate molecular weight distribution information as well as high-resolution spectra useful for structural characterization [1,20,21]. Ionization is facilitated by alkali metal attachment to oxygen or nitrogen in the analyte.…”

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confidence: 99%

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Silver nitrate chemical ionization for analysis of hydrocarbon polymers by laser desorption fourier transform mass spectrometry

Kahr

Wilkins

1993

J. Am. Soc. Mass Spectrom.

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Addition of silver nitrate to nonpolar hydrocarbon polymer solutions prior to their analysis by laser desorption Fourier transform mass spectrometry is shown to allow efficient silver ion chemical ionization. High-quality mass spectra are thus obtained for polymers, such as polystyrene, polyisoprene, polybutadiene, and polyethylene, that previously failed to yield useful mass spectra using conventional laser desorption. Accurate mass measurement experiments and isotopic ratios verify that the spectra are those of silver-attached oligomer ion distributions. Mass measurement errors for complete oligomer distributions average between 3 and 12 ppm for oligomers with masses between 400 and 6000 D whereas unit mass resolution is maintained throughout the entire spectral range.

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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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Laser desorption-Fourier transform mass spectrometry for the characterization of polymers

Cited by 77 publications

References 10 publications

MALDI-TOF mass spectrometry in the analysis of synthetic polymers

MALDI-TOF mass spectrometry in the analysis of synthetic polymers

Silver nitrate chemical ionization for analysis of hydrocarbon polymers by laser desorption fourier transform mass spectrometry

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

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