Chain End Contribution in Static Secondary Ion Mass Spectrometry of Oligomeric Poly(ethylene glycols)

Shard, Ag; Davies, Martyn C.; Schacht, Etienne

doi:10.1002/(sici)1096-9918(199611)24:12<787::aid-sia181>3.0.co;2-e

Cited by 24 publications

(13 citation statements)

References 25 publications

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“…This demonstrates the occurrence of H/D exchange reactions between the amino acid and the water adsorbed at the surface. This is in accordance with previous work on hydroxyl deuterium‐labelled group of oligomeric poly(ethylene glycols) . In the case of isoleucine and valine, a series of ions ranging from [M + 3] + up to [M + 5] + are detected at high pressure.…”

Section: Resultssupporting

confidence: 92%

Organic ion yield enhancement in secondary ion mass spectrometry using water vapour injection

Mouhib

Delcorte

Poleunis

et al. 2012

Surface & Interface Analysis

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The effects of water (H 2 O) and deuterated water (D 2 O) vapour, injected closely to the analyzed surface at relatively high pressure, on the enhancement of the ion yield in secondary ion mass spectrometry (SIMS) was investigated for a set of organic samples. The results show that the same signal enhancements occurred either upon Ga + or C 60 + bombardment. In addition, the increase of H 2 O vapour pressure during the bombardment causes a specific enhancement of the protonated ion intensity. For instance, the presence of H 2 O vapour induces an enhancement by one order of magnitude of the [M + H] + static SIMS intensity for the antioxidant Irgafos 168 and by more than two times for the amino acids.

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Section: Resultssupporting

confidence: 92%

Organic ion yield enhancement in secondary ion mass spectrometry using water vapour injection

Mouhib

Delcorte

Poleunis

et al. 2012

Surface & Interface Analysis

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show abstract

“…However, the relative peak intensities in the clusters of the high m/z fragments from various polypropylene glycols (PPGs) with different end groups were inconsistent with the simple statistical cleavage of the main chain, i.e., without preferential scission of the C±O or the C±C bond (Hittle et al, 1994b). Also for PEGs, it was shown that the (nMH) (M repeat unit, n 1 or 2) ions were primarily associated with a fragmentation starting at the polymer terminal chain (Shard et al, 1996b). Signi®cant end group effects were observed also for the negative ions.…”

Section: Interpretation Of Mass Spectra and Ion Formationmentioning

confidence: 99%

Static secondary ion mass spectrometry (S-SIMS) Part 1: methodology and structural interpretation

Vaeck

Adriaens

Gijbels

1999

Mass Spectrom. Rev.

184

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“…The fragmentation of low molecular weight polymers has been chosen for this purpose. Several polymers have already been investigated such as polystyrene (PS), ,,− poly(ethylene glycol) (PEG), and poly(methyl methacrylate) (PMMA) . In summary, it has been shown that SSIMS is sensitive to the nature of the end groups and to their isomers.…”

Section: Introductionmentioning

confidence: 99%

Molecular Weight Dependent Fragmentation of Selectively Deuterated Polystyrenes in ToF−SIMS

1999

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Two series of monodisperse polystyrenes were synthesized by an anionic polymerization initiated with sec-butyllithium. The number average molecular weights of the macrochains range from 1700 to 93300. The first series consist of deuterated repeat units and hydrogenated end groups (sec-PD8S−H). The other one was fully hydrogenated except for one end group, which was selectively deuterated (sec-PS−D). The sample molecular structures are C4H9(C8D8) n H and C4H9(C8H8) n D, respectively. These polymers were then analyzed by time-of-flight secondary ion mass spectrometry (ToF−SIMS). All secondary ion intensities are corrected for the carbon and deuterium isotopic distributions. Static SIMS spectra of sec-PD8S−H show characteristic peaks with even masses (fully deuterated, i.e., C7D7 +, C6D5 + at m/z = 98, 82) and odd peaks (containing at least one hydrogen atom, i.e., C7HD6 +, C6HD4 + at m/z = 97, 81). Typically, these odd peaks show decreasing intensities as the molecular weight increases. In the sec-PS−D SIMS spectra, the characteristic peaks are similar to those observed for the usual polystyrene with a more specific peak at m/z = 92 which is related to the deuterium end group. From the molecular weight dependent intensities, it can be deduced that a hydrogen transfer occurs from the sec-butyl end group to the first repeat unit and promotes the formation of the tropylium fragment. A rearrangement ion formation mechanism is proposed. For both polymers, characteristic peaks of the end group are detected. With the intensity ratios of a main chain fragment and these end groups characteristic peaks, we are able to calibrate the number average molecular weight at the polymer surface. Moreover, it is shown that the main chain deuteration influences the end group segregation toward the surface.

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Chain End Contribution in Static Secondary Ion Mass Spectrometry of Oligomeric Poly(ethylene glycols)

Cited by 24 publications

References 25 publications

Organic ion yield enhancement in secondary ion mass spectrometry using water vapour injection

Organic ion yield enhancement in secondary ion mass spectrometry using water vapour injection

Static secondary ion mass spectrometry (S-SIMS) Part 1: methodology and structural interpretation

Molecular Weight Dependent Fragmentation of Selectively Deuterated Polystyrenes in ToF−SIMS

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