Direct detection of additives and degradation products from polymers by liquid extraction surface analysis employing chip‐based nanospray mass spectrometry

Paine, Martin R. L.; Barker, Philip; Maclauglin, S. A.; Mitchell, Todd W.; Blanksby, Stephen J.

doi:10.1002/rcm.6116

Cited by 32 publications

(27 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Alkoxyamines are readily detected as protonated or alkali metal adduct ions by electrospray ionisation (ESI), [48] matrix assisted laser desorption ionisation (MALDI), [70,71] liquid extraction surface analysis (LESA), [72] or desorption electrospray ionisation (DESI). [73] However, in the absence of another basic moiety, protonation of an alkoxyamine nitrogen raises the O-C BDE by over 100 kJ mol -1 .…”

Section: Resultsmentioning

confidence: 99%

“…The former dissociation is consistent with previous reports on the charge-directed dissociation of substituted piperidines. [72] In the absence of the desired charge-remote dissociation of the alkoxyamine moiety, an alternative strategy was sought. Only limited examples in the literature describe the tandem mass spectrometric analysis of alkoxyamines upon negative ion electrospray ionisation.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Experimental evidence for competitive N O and O C bond homolysis in gas-phase alkoxyamines

Marshall

Gryn’ova

Coote

et al. 2015

International Journal of Mass Spectrometry

Self Cite

View full text Add to dashboard Cite

The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO-R3) and a stable nitroxyl radical (R1R2NO•) via homolysis of the labile O-C bond. Competing homolysis of the alkoxyamine N-O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O-C and N-O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N-O and O-C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC-R1R2NO-R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M − H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O-C and/or N-O bonds. The relative efficacy of N-O and O-C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O-C bond are observed and product ions resulting from cleavage of the N-O bond are minor or absent. A limited number of examples were encountered however, where N-O homolysis is a competitive dissociation pathway because the O-C bond is stabilised by adjacent heteroatom(s) (e.g. R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O-C homolysis pathway. homolysis is a competitive dissociation pathway because the O-C bond is stabilised by adjacent heteroatom(s) (e.g., R 3 = CH 2 F). The dissociation threshold energies were compared for different alkoxyamine substituents (R 3 ) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods.Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O-C homolysis pathway.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Experimental evidence for competitive N O and O C bond homolysis in gas-phase alkoxyamines

Marshall

Gryn’ova

Coote

et al. 2015

International Journal of Mass Spectrometry

Self Cite

View full text Add to dashboard Cite

show abstract

“…Several authors have reported good results after using this high-sensitive instrument, allowing the simultaneous identification and quantification of the proteins of interest (Grobosch et al, 2012;Janeckova et al, 2012;Lazartigues et al, 2011;Li et al, 2011;Paine et al, 2012;Rust et al, 2012;Wu et al, 2011).…”

Section: Ab Sciex Qtrap R 5500 Lc/ms/ms Systemmentioning

confidence: 99%

Next Generation Instruments and Methods for Proteomics

Mena

Albar

2013

Foodomics

View full text Add to dashboard Cite

“…Nowadays there are various analytical tools for analyzing polymer additives. A direct analytical method for the detection of several HALS in solid polymer samples using liquid extraction surface analysis mass spectrometry (LESA-MS) was reported by Paine et al [16,17]. Although this method provides a simple and fast analysis, it does not readily allow absolute quantitation.…”

Section: Introductionmentioning

confidence: 99%

Analytical evaluation of the performance of stabilization systems for polyolefinic materials. Part I: Interactions between hindered amine light stabilizers and phenolic antioxidants

Beißmann

Grabmayer

Wallner

et al. 2014

Polymer Degradation and Stability

View full text Add to dashboard Cite

Direct detection of additives and degradation products from polymers by liquid extraction surface analysis employing chip‐based nanospray mass spectrometry

Cited by 32 publications

References 26 publications

Experimental evidence for competitive N O and O C bond homolysis in gas-phase alkoxyamines

Experimental evidence for competitive N O and O C bond homolysis in gas-phase alkoxyamines

Next Generation Instruments and Methods for Proteomics

Analytical evaluation of the performance of stabilization systems for polyolefinic materials. Part I: Interactions between hindered amine light stabilizers and phenolic antioxidants

Contact Info

Product

Resources

About