In-source decay of hyperbranched polyesteramides in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Muscat, Dirk; Henderickx, Huub; Kwakkenbos, Gerard; Benthem, Rolf van; Koster, Chris G. de; Fokkens, Roel H.; Nibbering, Nico M. M.

doi:10.1016/s1044-0305(99)00141-5

Cited by 34 publications

(43 citation statements)

References 25 publications

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“…Other minor peak series in Figure 6 can be ascribed to the byproduct arising from the side reactions during RAFT polymerization, 44,45 fragmentation of polymer chain and dithioester moiety by MALDI-generated ions. [46][47][48][49] These results clearly showed that the CPDN moieties were attached at polymer chain ends. The molecular weight of PMMA by MALDI-TOF mass spectra, was 4.77 Â 10 3 g/mol (M w /M n = 1.16), which was much smaller than the GPC value (M n,GPC = 9.81 Â 10 3 g/mol, PDI = 1.20).…”

Section: Resultsmentioning

confidence: 99%

Single-Electron Transfer Living Radical Polymerization (SET−LRP) of Methyl Methacrylate (MMA) with a Typical RAFT Agent as an Initiator

et al. 2009

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A typical reversible addition-fragmentation chain transfer (RAFT) agent, 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN), was used as a single electron transfer-living radical polymerization (SET-LRP) initiator for methyl methacrylate (MMA) polymerization at 25°C. At 1:1 molar ratio of [CPDN] 0 /[Cu(0)] 0 , the apparent rate constants of propagation (k p app ) were 0.037, 0.049, and 0.072 h -1 for [MMA] 0 /[CPDN] 0 of 225/0.2, 225/0.5, and 225/1, respectively. The number-average molecular weight of poly(methyl methacrylate) (PMMA) increased linearly with monomer conversion, and narrow molecular weight distributions (M w /M n <1.50) were found at most cases. At high molar ratio of [CPDN] 0 to [Cu(0)] 0 , such as 1:0.1 in this work, the polymerization was also controllable, whereas it a presented markedly depressed polymerization rate and an obvious induction period. 1 H NMR spectroscope and matrix assisted laser desorption/ionization time-of-flight mass spectrometry confirmed that PMMA chain was end-capped by CPDN species with high fidelity. The tacticity of PMMA from 1 H NMR calculation was about 3.15% isotactic (mm), 29.65% atactic (mr) and 67.20% syndiotactic (rr) triads, consistent with the tacticity distribution for traditional radical polymerizations. Chain extension reactions substantiated further that the obtained PMMA from CPDN mediated SET-LRP was living, and can be reactivated for chain extension reaction. This work demonstrates that a typical RAFT agent can act as a SET-LRP initiator as well as an atom transfer radical polymerization initiator. Furthermore, these results also suggested that the single electron transfer initiation-reversible addition-fragmentation chain transfer control (SET-RAFT) invented by Dhamodharan may not be RAFT at all, but rather SET-LRP initiated by a RAFT reagent, or a combination of SET-LRP and RAFT. Analogously, the exact polymerization process in this work may also proceed in two manners, a fully SET-LRP process and a combination of SET-LRP/RAFT process, which is needed to clarify in the future.

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Section: Resultsmentioning

confidence: 99%

Single-Electron Transfer Living Radical Polymerization (SET−LRP) of Methyl Methacrylate (MMA) with a Typical RAFT Agent as an Initiator

et al. 2009

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“…It is proposed that the fragment ions seen in the TOF measurements could well be short-lived ions that do not survive for the requisite length of time to be observed by FTMS. Observation of low mass fragment ions is not uncommon in TOF-MS [26,27], as "prompt fragmentation" can occur in the ion-source region. Furthermore, in delayed extraction ion sources (employing time-lag energy focusing), fast metastable fragmentation might occur during the delay time before extraction (on the 100 to 1200 ns time scale).…”

Section: Resultsmentioning

confidence: 99%

Hydrocarbon polymer analysis by external MALDI fourier transform and reflectron time of flight mass spectrometry

Jaber

Wilkins

2005

J. Am. Soc. Mass Spectrom.

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The traditional solvent-based matrix-assisted laser desorption ionization (MALDI) preparation method has been used to analyze nonpolar polymers of various molecular weights. High resolution silver cationized oligomers with masses of up to 12 KDa were measured using 9.4 tesla Fourier transform mass spectrometry (FTMS) with an external ionization source. It was observed that when time-of-flight mass spectrometry was used, the spectra of polyethylene polymers showed abundant low mass fragment ions. However, these fragments were absent from the FTMS spectra. (J Am Soc Mass

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“…PSD‐MALDI has been used successfully in biopolymer characterization,19–29 but has been used less extensively for synthetic polymers, reasonably on account of the enhanced complexity of the samples involved. PSD‐MALDI‐TOF analysis has been performed to study polymers such as polycarbonate,30 polyurethanes,31 polyamides,32 polyesters,33 and polyesteramides 34, 35…”

mentioning

confidence: 99%

Sequence determination in aliphatic poly(ester amide)s by matrix‐assisted laser desorption/ionization time‐of‐flight and time‐of‐flight/time‐of‐flight tandem mass spectrometry

Rizzarelli

Puglisi²,

Montaudo

2005

Rapid Comm Mass Spectrometry

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Poly(ester amide)s from dimethyl sebacate or sebacic acid and 2-aminoethanol or 4-amino-1-butanol were characterized by post-source decay matrix-assisted laser desorption/ionization time-of-flight (PSD-MALDI-TOF) and time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS). Sodiated oligomers were selected as precursor ions for dissociation studies. PSD analysis was performed on dimethyl sebacate, dicarboxylic, carboxylic and amino alcohol, and diamino alcohol terminated oligomers. PSD-MALDI-TOF mass spectra yielded information on the fragmentation mechanisms of the poly(ester amide) chains, showing that the main cleavages proceed through a beta-hydrogen transfer rearrangement. MALDI-TOF/TOF-MS/MS provided structural information concerning ester/amide sequences in the polymer chains. As expected, together with the ions appearing in the PSD-MALDI mass spectrum, several new abundant fragment ions in the low-mass range are present in MALDI-TOF/TOF-MS/MS spectra. These new product ions proved to be diagnostic and made it possible to establish the presence of random sequences of ester and amide bonds in the poly(ester amide)s samples.

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In-source decay of hyperbranched polyesteramides in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Cited by 34 publications

References 25 publications

Single-Electron Transfer Living Radical Polymerization (SET−LRP) of Methyl Methacrylate (MMA) with a Typical RAFT Agent as an Initiator

Single-Electron Transfer Living Radical Polymerization (SET−LRP) of Methyl Methacrylate (MMA) with a Typical RAFT Agent as an Initiator

Hydrocarbon polymer analysis by external MALDI fourier transform and reflectron time of flight mass spectrometry

Sequence determination in aliphatic poly(ester amide)s by matrix‐assisted laser desorption/ionization time‐of‐flight and time‐of‐flight/time‐of‐flight tandem mass spectrometry

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