Mass Spectrometry of Synthetic Polymers

Peacock, Patricia M.; McEwen, Charles N.

doi:10.1021/ac040064i

Cited by 69 publications

(58 citation statements)

References 127 publications

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“…Matrix-assisted laser desorption/ionization (MALDI) and ESI are now the most commonly employed ionization sources for the MS analysis of synthetic polymers, as attested to the literature published during the few last years (Peacock & McEwen, 2006;Weidner & Trimpin, 2008). Both techniques are well-known to produce quasi-molecular ions for masses up to 100,000 Da, with no or just a few fragmentations depending on the fragility of the polymer and of the harshness of the instrumental parameters.…”

Section: A Maldi-ms Versus Esi-msmentioning

confidence: 99%

APCI/APPI for synthetic polymer analysis

Terrier

Desmazières

Tortajada

et al. 2011

Mass Spectrometry Reviews

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Modern mass spectrometry of synthetic polymers involves soft ionization techniques. Whereas matrix-assisted laser desorption/ionization (MALDI) and electrospray (ESI) are employed routinely, atmospheric pressure chemical ionization (APCI) and more recently atmospheric pressure photoionization (APPI) are used to a lesser extent. However, these latter ionization methods coupled to liquid-phase separation techniques create new opportunities for the characterization of polymers, especially for low molecular weight compounds or for the polymers that are poorly ionizable by the usual methods. After a part devoted to the description of classical MS methods employed for polymer analysis (MALDI, ESI, and their use with chromatography), APCI and APPI techniques will be described, discussed, and selected examples will present the interest of these ionization sources (or interfaces for LC/MS) in the field of polymer analysis.

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Section: A Maldi-ms Versus Esi-msmentioning

confidence: 99%

APCI/APPI for synthetic polymer analysis

Terrier

Desmazières

Tortajada

et al. 2011

Mass Spectrometry Reviews

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“…A single-stage mass spectrometry (MS) experiment provides the masses of the components of a polymeric analyte, from which the molecular weight distribution may be derived. Depending on the molecular weight of the sample and mass measurement accuracy, the acquired masses can be converted to elemental compositions (Nielen, 1999;Hanton, 2001;McEwen & Peacock, 2002;Montaudo & Lattimer, 2002;Murgasova & Hercules, 2002Pasch & Schrepp, 2003;Peacock & McEwen, 2004, 2006. This compositional information is readily translated into structural insight about the monomer units and chain end substituents of the polymer, provided the synthetic route involves well-defined initiation, propagation, and termination steps or the polymerization mechanism has been elucidated and is clearly understood (Jackson & Simonsick, 1997;Scrivens & Jackson, 2000;Wesdemiotis et al, 2000;Polce et al, 2001;Arnould et al, 2004).…”

Section: Introductionmentioning

confidence: 99%

Fragmentation pathways of polymer ions

Wesdemiotis

Solak

Polce

et al. 2011

Mass Spectrometry Reviews

183

297

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Tandem mass spectrometry (MS/MS) is increasingly applied to synthetic polymers to characterize chain-end or in-chain substituents, distinguish isobaric and isomeric species, and determine macromolecular connectivities and architectures. For confident structural assignments, the fragmentation mechanisms of polymer ions must be understood, as they provide guidelines on how to deduce the desired information from the fragments observed in MS/MS spectra. This article reviews the fragmentation pathways of synthetic polymer ions that have been energized to decompose via collisionally activated dissociation (CAD), the most widely used activation method in polymer analysis. The compounds discussed encompass polystyrenes, poly(2-vinyl pyridine), polyacrylates, poly(vinyl acetate), aliphatic polyester copolymers, polyethers, and poly(dimethylsiloxane). For a number of these polymers, several substitution patterns and architectures are considered, and questions regarding the ionization agent and internal energy of the dissociating precursor ions are also addressed. Competing and consecutive dissociations are evaluated in terms of the structural insight they provide about the macromolecular structure. The fragmentation pathways of the diverse array of polymer ions examined fall into three categories, viz. (1) charge-directed fragmentations, (2) charge-remote rearrangements, and (3) charge-remote fragmentations via radical intermediates. Charge-remote processes predominate. Depending on the ionizing agent and the functional groups in the polymer, the incipient fragments arising by pathways (1)-(3) may form ion-molecule complexes that survive long enough to permit inter-fragment hydrogen atom, proton, or hydride transfers.

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“…M ass spectrometry (MS) is one of the most used analytical techniques for characterization of synthetic polymers [1][2][3]. Time-of-flight (TOF) mass analyzers are preferred for their analysis because of TOF's high sensitivity and the wide mass range of the resulting spectra [4].…”

mentioning

confidence: 99%

Laser desorption/ionization fourier transform mass spectrometry of thin films deposited on silicon by plasma polymerization of acetylene

Miladinović

Vriendt

Robotham

et al. 2010

J. Am. Soc. Mass Spectrom.

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Thin films deposited on silicon substrate by three different methods of plasma polymerization of acetylene were analyzed by direct laser desorption/ionization Fourier transform mass spectrometry. High-resolution mass spectra showed the presence of carbon clusters and hydrocarbon oligomers in different relative abundances. During unipolar and continuous discharge polymerization of acetylene-hydrogen gas mixtures, quadrupole mass spectra of the plasma constituents showed the presence of molecular species with m/z lower than 100 -mainly peaks of C 4 H 2 and C 6 H 2 . Films produced had smooth surfaces and the corresponding LDI-FTMS spectra displayed only carbon cluster signals in the positive ion mode and both hydrocarbon and carbon cluster signals (with much higher relative abundance of carbon cluster signals) in the negative ion mode. Alternatively, during bipolar discharge with either higher acetylene gas flux (Ͼ40 cm 3 /min) or longer deposition times (Ͼ10 min), quadrupole mass spectra of the plasma constituents showed signals corresponding to polycyclic aromatic hydrocarbons (PAH) with m/z higher than 100. SEM pictures of the bipolar thin films demonstrated the presence of "flower" structures and nanoparticles developed on the surface. LDI-FTMS spectra of such thin films showed either total absence or lower relative abundance of carbon cluster signals, compared with hydrocarbon signals. (J Am Soc Mass Spectrom 2010, 21, 411-420)

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Mass Spectrometry of Synthetic Polymers

Cited by 69 publications

References 127 publications

APCI/APPI for synthetic polymer analysis

APCI/APPI for synthetic polymer analysis

Fragmentation pathways of polymer ions

Laser desorption/ionization fourier transform mass spectrometry of thin films deposited on silicon by plasma polymerization of acetylene

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