Microstructural and conformational studies of polyether copolymers

Jackson, Anthony T.; Scrivens, James H.; Williams, Jonathan P.; Baker, Erin; Gidden, Jennifer; Bowers, Michael T.

doi:10.1016/j.ijms.2004.09.025

Cited by 75 publications

(82 citation statements)

References 34 publications

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“…Although many articles describing cation affinity of PEGs have been published for the last few decades [13][14][15][16][17][18][19][20][21][22], we have first presented the differences in cation selectivity between cyclic and helical POEs, by using …”

Section: Discussionmentioning

confidence: 99%

Alkali-cation affinities of polyoxyethylene dodecylethers and helical conformations of their cationized molecules studied by electrospray mass spectrometry

Yokoyama

Hirajima

Morigaki

et al. 2007

J. Am. Soc. Mass Spectrom.

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Relative alkali-cation affinity of polyoxyethylene (POE) dodecylethers in gas phase was studied by electrospray ionization (ESI) mass spectrometry using dodecylether-poly-ethoxylate (C 12 EO:n, "n" denotes ethyleneoxide unit number) nonionic surfactants, and possible helical conformations of the cationized molecules were demonstrated. The alkali-cation affinity highly depended on the cation diameters. The mass spectra of C 12 EO:8 cationized by alkali-metal ions were dominated by potassiated molecules. The results indicated that the POE moiety could have specific affinity to K ϩ ions based on a host-guest interaction between POE helix and potassium ions. This is very similar to the relationships between 18-crown-6 and K ϩ . The ESI mass spectra exhibited the multiply cationized C 12 EO:n in addition to the singly cationized molecules. The critical EO unit numbers necessary for producing the multiply-charged cationized molecules also depended on the cation diameters. In addition, the POE surfactants highly preferred alkali cations to proton. The results were strongly supported by molecular mechanics/dynamics calculations. A helical conformation of the POE moiety of C 12 EO:15 including two K ϩ ions gave a potential minimum, while a lowest energy structure of the protonated molecule took irregular conformations due to the formation of local hydrogen bonds. (J Am Soc Mass

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Section: Discussionmentioning

confidence: 99%

Alkali-cation affinities of polyoxyethylene dodecylethers and helical conformations of their cationized molecules studied by electrospray mass spectrometry

Yokoyama

Hirajima

Morigaki

et al. 2007

J. Am. Soc. Mass Spectrom.

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“…As MS allows individual co-oligomer ions to be measured, the overall composition can be determined as long as any peak overlap can efficiently be resolved [8]. MS data could thus indicate the number of each co-monomers but not the position of the repeat units throughout the molecule and distinction of block copolymers from random copolymers requires MS/MS experiments to be performed [9]. Fragmentation pathways along the chain allow the copolymer to be sequenced since each co-monomer shows distinct dissociation behavior.…”

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confidence: 99%

Tandem mass spectrometry of poly(methacrylic acid) oligomers produced by negative mode electrospray ionization

Giordanengo

Viel

Allard-Breton

et al. 2009

J. Am. Soc. Mass Spectrom.

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Dissociation of small poly(methyl acrylic acid) (PMAA) anions produced by electrospray was characterized by tandem mass spectrometry. Upon collisional activation, singly, and doubly deprotonated PMAA oligomers were shown to fragment via two major reactions, dehydration and decarboxylation. The elimination of a water molecule would occur between two consecutive acid groups in a charged-remote mechanism, giving rise to cyclic anhydrides, and was shown to proceed as many times as pairs of neutral pendant groups were available. As a result, the number of dehydration steps, together with the abundance of the fragment ions produced after the release of all water molecules, revealed the polymerization degree of the molecule in the particular case of doubly charged oligomers. For singly deprotonated molecules, the exact number of MAA units could be reached from the number of carbon dioxide molecules successively eliminated from the fully dehydrated precursor ions. In contrast to dehydration, decarboxylation reactions would proceed via a charge-induced mechanism. The proposed dissociation mechanisms are consistent with results commonly reported in thermal degradation studies of poly(acrylic acid) resins and were supported by accurate mass measurements. These fragmentation rules were successfully applied to characterize a polymeric impurity detected in the tested PMAA sample. (J Am Soc Mass

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“…So, in order to clearly identify the PHMG polymers, it is necessary to understand the fragmentation pattern of the PHMG polymers since in some cases the measured m/z values of polymeric species themselves are not sufficient to confirm the identity of the observed polymers. 43,44 Post-source decay (PSD) was therefore carried out using the LIFT technique for some polymeric species shown in Figure 1(a). 40 Figure 3 shows the resulting PSD spectra obtained for the type A polymer species of (M n +H) + , n = 5 (a), 7 (b), and 8 (c).…”

Section: Resultsmentioning

confidence: 99%

MALDI-TOF Analysis of Polyhexamethylene Guanidine (PHMG) Oligomers Used as a Commercial Antibacterial Humidifier Disinfectant

Hwang

Nam

Yang

et al. 2013

Bulletin of the Korean Chemical Society

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Polyhexamethylene guanidine (PHMG) polymers used as an active ingredient in an antibacterial humidifier disinfectant were reported to cause harm to the human health when inhaled, although physical contact with this material was known to present low toxicity to humans. It is therefore necessary to develop an optimal analysis method which enables detection and analysis of PHMG polymers. MALDI-TOF investigations of PHMG are performed with a variety of matrices, and it is found that CHCA and 2,5-DHB are excellent matrices which well reflects the polymer population even at high mass. For the provided PHMG sample, the number-average (M n ) and weight-average (M w ) molecular masses were determined to be 744.8 and 810.7, respectively, when the CHCA was used as a matrix. The rank of the matrices in terms of averaged molecular weight was CHCÃ 2,5-DHB > 5-NSA > DHAP, THAP > ATT > IAA ~ super-DHB ~ HABA. In addition, PSD of the PHMG oligomer ions exhibited a few unique fragmenation characteristics. The formation of a-and c-type fragments was the major fragmentation pathway, and the 25-Da loss peaks generally accompanied a-and c-type fragments.

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Microstructural and conformational studies of polyether copolymers

Cited by 75 publications

References 34 publications

Alkali-cation affinities of polyoxyethylene dodecylethers and helical conformations of their cationized molecules studied by electrospray mass spectrometry

Alkali-cation affinities of polyoxyethylene dodecylethers and helical conformations of their cationized molecules studied by electrospray mass spectrometry

Tandem mass spectrometry of poly(methacrylic acid) oligomers produced by negative mode electrospray ionization

MALDI-TOF Analysis of Polyhexamethylene Guanidine (PHMG) Oligomers Used as a Commercial Antibacterial Humidifier Disinfectant

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