Fast and accurate determination of absolute individual molecular weight distributions from mixtures of polymers via size exclusion chromatography- electrospray ionization mass spectrometry

Gruendling, T., Guilhaus, M., & Barner-Kowollik, C. (2009) Fast and accurate determination of absolute individual molecular weight distributions from mixtures of polymers via size exclusion chromatography- electrospray ionization mass spectrometry. Macromolecules, 42(17).

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We present a method to determine accurate and absolute molecular weight distributions (MWDs) as well as absolute concentrations of the individual macromolecular components in mixtures of polymers of the same monomer class yet differing in their end groups. Data gained from size exclusion chromatography coupled online to refractive index (RI) detection and electrospray ionization mass spectrometry (ESI-MS) are processed by a sophisticated computer algorithm based on the maximum entropy principle. The procedure yields, for the first time, absolute molecular weight distributions of each component corrected for chromatographic band broadening. Molecular weights of up to 10 kDa are accessible with a conventional quadrupole ion-trap mass analyzer. The method is applicable to variable polymer systems regardless of the monomer class and without the need for an external calibration or additional model assumptions. It was validated using binary and ternary mixtures of poly(methyl methacrylate) carrying labile functional groups. For the ternary mixture, maximum deviations of the reconstructed molecular weight averages and mass concentrations from the original values were 8% and 5%, respectively. © 2009 American Chemical Society.

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30 citations in Web of Science®
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ID Code: 99211
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :31
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Universität Karlsruhe (TH), Engesserstr. 18, 76128 Karlsruhe, Germany; email:
References: Fenn, J.B., (2003) Angew. Chem., Int. Ed., 42 (33), pp. 3871-3894; Karas, M., Hillenkamp, F., (1988) Anal. Chem., 60, pp. 2299-2301; Barner-Kowollik, C., Davis, T.P., Stenzel, M.H., (2004) Polymer, 45, pp. 7791-7805; Buback, M., Frauendorf, H., Günzler, F., Vana, P.J., (2007) Polym. Sci., Polym. Chem., 45 (12), pp. 2453-2467; Lovestead, T.M., Hart-Smith, G., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Macromolecules, 40 (12), pp. 4142-4153; Szablan, Z., Huaming, M., Adler, M., Stenzel, M.H., Davis, T.P., Barner-Kowollik, C., (2007) J. Polym. Sci., Part A: Polym. Chem., 45 (10), pp. 1931-1943; Szablan, Z., Junkers, T., Koo, S.P.S., Lovestead, T.M., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Macromolecules, 40 (19), pp. 6820-6833; Hart-Smith, G., Chaffey-Millar, H., Barner-Kowollik, C., (2008) Macromolecules, 47 (9), pp. 3023-3041; Xu, J., He, J., Fan, D., Wang, X., Yang, Y., (2006) Macromolecules, 39 (25), pp. 8616-8624; Olaj, O.F., Bitai, I., Hinkelmann, F., (1987) Macromol. Chem. Phys., 755 (7), pp. 1689-1702; Barner-Kowollik, C., Buback, M., Egorov, M., Fukuda, T., Goto, A., Olaj, O.F., Russell, G.T., Zetterlund, P.B., (2005) Prog. Polym. Sci., 30 (6), pp. 605-643; Olaj, O.F., Vana, P., Kornherr, A., Zifferer, G., (1999) Macromol. Chem. Phys., 200 (9), pp. 2031-2039; Kostanski, L.K., Keller, D.M., Hamielec, A.E., (2004) J. Biochem. Biophys. Methods, 55 (2), pp. 159-186; Grubisic, Z., Rempp, P., Benoit, H., (1967) J. Polym. Sci., Part B: Polym. Lett., 5, pp. 753-759; Zammit, M.D., Davis, T.P., (1997) Polymer, 55, pp. 4455-4468; Zammit, M.D., Coote, M.L., Davis, T.P., Willett, G.D., (1998) Macromolecules, 31, pp. 955-963; Tamai, Y., Konishi, T., Einaga, Y., Fujii, M., Yamakawa, H., (1990) Macromolecules, 23 (18), pp. 4067-4075; Flory, P.J., Fox Jr., T.G., (1951) J. Am. Chem. Soc., 73, pp. 1904-1908; Schnöll-Bitai, I., Mader, C., (2006) J. Chromatogr. A, 1137 (2), pp. 198-206; Buback, M., Busch, M., Lämmel, R.A., (1996) Macromol. Theory Simul., 5 (5), pp. 845-861; Montaudo, G., Carroccio, S., Montaudo, A.S., Puglisi, C., Samperi, F., (2004) Macromol. Symp., 218, pp. 101-112; Montaudo, G., Samperi, F., Montaudo, M.S., (2006) Prog. Polym. Sci., 31 (3), pp. 277-357; Peacock, P.M., McEwen, C.N., (2004) Anal. Chem., 76 (12), pp. 3417-3427; Peacock, P.M., McEwen, C.N., (2006) Anal. Chem., 78 (12), pp. 3957-3964; Barner-Kowollik, C., Vana, P., Davis, T.P., (2002) J. Polym. Sci., Part A: Polym. Chem., 40 (5), pp. 675-681; Zammit, M.D., Davis, T.P., Haddleton, D.M., (1996) Macromolecules, 29, pp. 492-494; Byrd, H.C.M., McEwen, C.N., (2000) Anal. Chem., 72 (19), pp. 4568-4576; Schriemer, D.C., Li, L., (1997) Anal. Chem., 69 (20), pp. 4176-4183; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2008) Anal. Chem., 80, pp. 6915-6927; Aaserud, D.J., Prokai, L., Simonsick, W., (1999) J. Anal. Chem., 71 (21), pp. 4793-4799; Prokai, L., Simonsick, W., (1993) J. Commun. Mass Spectrom., 7, pp. 853-856; Baumgarten, J.L., Busnel, J.P., Meira, G.R., (2002) J. Liq. Chromatogr. Relat. Technol., 25 (13-15), pp. 1967-2001; Reiter, J., (1992) J. Comput. Phys., 103 (1), pp. 169-183; Skilling, J., Bryan, R.K., (1984) Mon. Not. R. Astron. Soc., 211 (1), pp. 111-124; Splinter, S.J., McIntyre, N.S., (1998) Surf. Interface Anal., 26 (3), pp. 195-203; Striegel, A.M., (2005) Anal. Chem., 77 (5), pp. 104a-113a; Montaudo, M.S., Montaudo, G., (1999) Macromolecules, 32 (21), pp. 7015-7022; Kok, S.J., Wold, C.A., Hankemeier, T., Schoenmakers, P.J., (2003) J. Chromatogr. A, 1017 (1-2), pp. 83-96; Nielen, M.W.F., Buijtenhuijs, F.A., (1999) Anal. Chem., 71 (9), pp. 1809-1814; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2009) Macromol. Rapid Commun., 30, pp. 589-597; Itakura, M., Sato, K., Lusenkova, M.A., Matsuyama, S., Shimada, K., Saito, T., Kinugasa, S., (2004) J. Appl. Polym. Sci., 94, pp. 1101-1106; Gridnev, A.A., Ittel, S.D., Fryd, M., (1995) J. Polym. Sci., Part A: Polym. Chem., 33, pp. 1185-1188; Wagner, H.L., Hoeve, C.A.J., (1971) J. Polym. Sci., Part A-2, 9, pp. 1763-1776; Tung, L.H., Runyon, J.R., (1969) J. Appl. Polym. Sci., 13 (11), pp. 2397-2409; Meira, G.R., Vega, J.R., (2001) Dekker Encyclopedia of Chromatography, p. 71. , Cazes, J., Ed.; Marcel-Dekker: New York; (1988) Maximum Entropy and Bayesian Methods, , Kluwer Academic Publishers: Cambridge; Shannon, C.E., (1948) Bell Syst. Tech. J., 27, pp. 379-623; Shore, J.E., Johnson, R.W., (1980) IEEE Trans., 26 IT-26; Shore, J.E., Johnson, R.W., (1983) IEEE Trans., 942 IT-29; Sivia, D.S., (1996) Data Analysis: A Bayesian Tutorial, , Oxford University Press: New York; Perrier, S., Barner-Kowollik, C., Quinn, J.F., Vana, P., Davis, T.P., (2002) Macromolecules, 35, pp. 8300-8306; Barner-Kowollik, C., Quinn, J.F., Morsley, D.R., Davis, T.P., (2001) J. Polym. Sci., Part A: Polym. Chem., 39, pp. 1353-1365; Johnston-Hall, G., Theis, A., Monteiro, M.J., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2005) Macromol. Chem. Phys., 206, pp. 2047-2053; Bednarek, M., Biedron, T., Kubisa, P., (2000) Macromol. Chem. Phys., 201, pp. 58-66; Gidden, J., Jackson, A.T., Scrivens, J.H., Bowers, M.T., (1999) Int. J. Mass Spectrom., 188, pp. 121-130; Trimpin, S., Plasencia, M., Isailovic, D., Clemmer, D.E., (2007) Anal. Chem., 79, pp. 7965-7974; Ude, S., De La Mora, J.F., Thomson, B.A., (2004) J. Am. Chem. Soc., 126, pp. 12184-12190; Cappadona, S., Levander, F., Jansson, M., James, P., Cerutti, S., Pattini, L., (2008) Anal. Chem., 80 (13), pp. 4960-4968; Felinger, A., Káré, M., (2004) Chem. Intell. Lab. Syst., 72, pp. 225-232; Shao, X., Cai, W., Pan, Z., (1999) Chemom. Intell. Lab. Syst., 45, pp. 249-256
Keywords: Absolute molecular weight distribution, Band-broadening, Computer algorithm, Electrospray ionization mass spectrometry, End groups, External calibration, Ion traps, Mass analyzers, Mass concentration, Maximum entropy principle, Model assumptions, Poly(methyl methacrylate), Polymer systems, Quadrupoles, Ternary mixtures, Algorithms, Binary mixtures, Chromatographic analysis, Electrospray ionization, Esters, Functional groups, Ionization, Mass spectrometers, Mass spectrometry, Molecular weight distribution, Monomers, Organic polymers, Polymers, Refractive index, Size exclusion chromatography
DOI: 10.1021/ma900755z
ISSN: 00249297
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: 09 Oct 2016 23:42

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