The incorporation of metal cations into polymer backbones: An important consideration in the interpretation of ESI-MS spectra

Hart-Smith, G. & Barner-Kowollik, C. (2009) The incorporation of metal cations into polymer backbones: An important consideration in the interpretation of ESI-MS spectra. Polymer, 50(22).

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Poly(acrylic acid) (polyAA), poly(N-isopropylacrylamide) (polyNIPAAm) and poly(diisopropyl vinyl phosphonate) (polyDISP) samples were subjected to electrospray ionisation-mass spectrometry (ESI-MS) analysis employing quadrupole-ion trap as well as high resolution quadrupole time-of-flight (Q-TOF) detectors, and the resulting spectra screened for the detection of polymers in which metal cations have become incorporated into the chain backbone following deprotonation reactions during the ESI process. Adducts formed from such polymer-metal salts were detected in spectra produced from each of the samples under investigation, indicating that the formation, ionisation and detection of polymer-metal salts can be readily achieved under typical ESI-MS experimental conditions. Specifically (under conditions of MeOH containing 0.1 mM sodium acetate) polyAA is most susceptible to the incorporation of metal ions (up to 3 replacements), followed by polyNIPAAm with two replacements and polyDISP with one replacement. The results obtained from the present investigation clearly demonstrate that for synthetic polymers capable of undergoing deprotonation under ESI conditions, the potential detection of polymer-metal salt adducts must be considered during spectral data interpretation to avoid erroneous species assignments. © 2009 Elsevier Ltd. All rights reserved.

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ID Code: 99214
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :6 Export Date: 5 September 2016 CODEN: POLMA Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstraße 18, 76128 Karlsruhe, Germany; email: References: Fenn, J.B., Mann, M., Meng, C.K., Wong, S.F., (1990) Mass Spectrometry Reviews, 9, pp. 37-70; Hillenkamp, F., Karas, M., Beavis, R.C., Chait, B.T., (1991) Analytical Chemistry, 63, pp. 1193A-1203A; Vestal, M.L., (2001) Chemical Reviews, 101, pp. 361-375; McLuckey, S.A., Wells, J.M., (2001) Chemical Reviews, 101, pp. 571-606; Makarov, A., (2000) Analytical Chemistry, 72, pp. 1156-1162; Hanton, S.D., (2001) Chemical Reviews, 101, pp. 527-569; Barner-Kowollik, C., Davis, T.P., Stenzel, M.H., (2004) Polymer, 45, pp. 7791-7805; Weidner, S.M., Trimpin, S., (2008) Analytical Chemistry, 80, pp. 4349-4361; Within the present article, the term analyte specifically refers to products present within the polymer samples of interest prior to ESI-MS sample preparation, as opposed to compounds formed during sample preparationArakawa, R., Egami, S., Okuno, S., (2006) Journal of Mass Spectrometry, 41, pp. 549-550; Wyatt, M.F., Schaeffer, N., Tan, B., Cooper, A.I., (2007) Journal of the American Society for Mass Spectrometry, 18, pp. 1507-1510; Danis, P.O., Karr, D.E., Mayer, F., Holle, A., Watson, C.H., (1992) Organic Mass Spectrometry, 27, pp. 843-846; Llauro, M.-F., Loiseau, J., Boisson, F., Delolme, F., Ladavière, C., Claverie, J., (2004) Journal of Polymer Science Part A: Polymer Chemistry, 42, pp. 5439-5462; Arnould, M.A., Vargas, R., Buehner, R.W., Wesdemiotis, C., (2005) European Journal of Mass Spectrometry, 11 (2), pp. 243-256; Giordanego, R., Viel, S., Allard-Breton, B., Thevand, A., Charles, L., (2009) Rapid Communications in Mass Spectrometry, 23, pp. 1557-1562; Giordanego, R., Viel, S., Allard-Breton, B., Thevand, A., Charles, L., (2009) Journal of the American Society for Mass Spectrometry, 20, pp. 25-33; Pike, R.M., Cohen, R.A., (1960) Journal of Polymer Science, 44, pp. 531-538; Lai, J.T., Filla, D., Shea, R., (2002) Macromolecules, 35, pp. 6754-6756; Gil, E.S., Hudson, S.M., (2004) Progress in Polymer Science, 29, pp. 1173-1222; Bingöl, B., Hart-Smith, G., Barner-Kowollik, C., Wegner, G., (2008) Macromolecules, 41, pp. 1634-1639; Hart-Smith, G., Lovestead, T.M., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Biomacromolecules, 8, pp. 2404-2415; The compounds represented as PHTZ and PHTH describe analyte molecules potentially formed during the AA and NIPAAm polymerisations, in which proton (H) and/or dormant RAFT (Z) end-groups are generated, and trithioester moieties (T) are present within the chain backbone. The potential generation of trithioester moieties within chain backbones stems from the symmetrical nature of the employed RAFT agent, in which two identical R-group functionalities are capable of fragmenting off the CTA during the RAFT processMaximum allowable mass accuracy values were estimated from the m/z's observed for dormant R-group radical initiated chains over different mass spectra produced from RAFT mediated polymer samples; these chains are established as the dominant products produced in the majority of RAFT mediated polymerisations, hence can be assigned to the generated mass spectra with a significant degree of confidenceUR -
Keywords: Electrospray Ionisation (ESI), Mass spectrometry, Polyacids, Deprotonation reaction, Electrosprays, Experimental conditions, High resolution, Ion traps, Ionisation, Metal cation, Metal salt, N-isopropylacrylamides, Phosphonates, Poly(acrylic acid) (polyAA), Polymer backbones, Quadrupoles, Sodium acetate, Spectral data, Synthetic polymers, Time of flight, Acrylic monomers, Amides, Carboxylic acids, Detectors, Electrospray ionization, Ionization, Mass spectrometers, Metal ions, Metals, Organic acids, Positive ions, Salts, Polymers, polyacrylic acid, polymer blend, spectroscopy
DOI: 10.1016/j.polymer.2009.09.022
ISSN: 00323861
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 10 Oct 2016 00:00

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