Mass Spectrometry of Chemical Polymers

McEwen, Charles N.; Peacock, Patricia M.

doi:10.1021/ac020214u

Cited by 56 publications

(48 citation statements)

References 99 publications

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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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Section: Introductionmentioning

confidence: 99%

Fragmentation pathways of polymer ions

Wesdemiotis

Solak

Polce

et al. 2011

Mass Spectrometry Reviews

183

297

View full text Add to dashboard Cite

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“…The year 2006 was selected as starting point because in this year Montaudo et al 6 extensively reviewed the use of MALDI‐MS/MS analysis in the characterization of polymers. For more information about the literature before 2006 kindly refer to the following reviews on this topic 2, 6–12. The sections of this perspective are arranged according to the ionization technique employed and it is distinguished between the analysis of homopolymers and copolymers.…”

Section: Introductionmentioning

confidence: 99%

Tandem mass spectrometry of synthetic polymers

2009

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The detailed characterization of macromolecules plays an important role for synthetic chemists to define and specify the structure and properties of the successfully synthesized polymers. The search for new characterization techniques for polymers is essential for the continuation of the development of improved synthesis methods. The application of tandem mass spectrometry for the detailed characterization of synthetic polymers using the soft ionization techniques matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and electrospray ionization mass spectrometry (ESI-MS), which became the basic tools in proteomics, has greatly been increased in recent years and is summarized in this perspective. Examples of a variety of homopolymers, such as poly(methyl methacrylate), poly(ethylene glycol), as well as copolymers, e.g. copolyesters, are given. The advanced mass spectrometric techniques described in this review will presumably become one of the basic tools in polymer chemistry in the near future.

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“…The use of this technique allowed polymer molecules to be ionized and desorbed without fragmenting the molecules [14,15]. Its use for the analysis of synthetic polymers has been recently reviewed by McEwen and Peacock [16]. MALDI provides the weight average molecular weight (M w ), the number average molecular weight (M n ), and the polydispersity (PD).…”

Section: Introductionmentioning

confidence: 99%