Quantitative LC-MS of polymers: Determining accurate molecular weight distributions by combined size exclusion chromatography and electrospray mass spectrometry with maximum entropy data processing

Gruendling, T., Guilhaus, M., & Barner-Kowollik, C. (2008) Quantitative LC-MS of polymers: Determining accurate molecular weight distributions by combined size exclusion chromatography and electrospray mass spectrometry with maximum entropy data processing. Analytical Chemistry, 80(18).

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We report on the successful application of size exclusion chromatography (SEC) combined with electrospray ionization mass spectrometry (ESI-MS) and refractive index (RI) detection for the determination of accurate molecular weight distributions of synthetic polymers, corrected for chromatographic band broadening. The presented method makes use of the ability of ESI-MS to accurately depict the peak profiles and retention volumes of individual oligomers eluting from the SEC column, whereas quantitative information on the absolute concentration of oligomers is obtained from the RI-detector only. A sophisticated computational algorithm based on the maximum entropy principle is used to process the data gained by both detectors, yielding an accurate molecular weight distribution, corrected for chromatographic band broadening. Poly(methyl methacrylate) standards with molecular weights up to 10 kDa serve as model compounds. Molecular weight distributions (MWDs) obtained by the maximum entropy procedure are compared to MWDs, which were calculated by a conventional calibration of the SEC-retention time axis with peak retention data obtained from the mass spectrometer. Comparison showed that for the employed chromatographic system, distributions below 7 kDa were only weakly influenced by chromatographic band broadening. However, the maximum entropy algorithm could successfully correct the MWD of a 10 kDa standard for band broadening effects. Molecular weight averages were between 5 and 14% lower than the manufacturer stated data obtained by classical means of calibration. The presented method demonstrates a consistent approach for analyzing data obtained by coupling mass spectrometric detectors and concentration sensitive detectors to polymer liquid chromatography. © 2008 American Chemical Society.

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64 citations in Web of Science®
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ID Code: 99175
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :72
Export Date: 5 September 2016
Correspondence Address: Guilhaus, M.; Bioanalytical Mass Spectrometry Facility, UNSW Analytical Centre, University of New South Wales, Sydney, NSW 2052, Australia; email: m.guilhaus@unsw.edu.au
Chemicals/CAS: poly(methyl methacrylate), 39320-98-4, 9008-29-1; Polymers
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Keywords: Arsenic compounds, Calibration, Chlorine compounds, Chromatographic analysis, Chromatography, Concentration (process), Data processing, Detectors, Electron beam lithography, Electrospray ionization, Entropy, Esters, Gel permeation chromatography, High performance liquid chromatography, Image segmentation, Ionization of liquids, Liquid chromatography, Mass spectrometers, Mass spectrometry, Molecular weight distribution, Oligomers, Optical properties, Organic polymers, Polymers, Refractive index, Size exclusion chromatography, Spectrometers, Spectrometry, Spectrum analysis, Standards, Band broadening, Chromatographic systems, Computational algorithms, Coupling mass, Electrospray mass spectrometry, Electrospray-ionization mass spectrometry, Maximum entropy, Maximum entropy algorithm, Maximum entropy principle, Mo lecular weight distributions, Model compounds, Molecular weight averages, Peak profiles, Poly-methyl methacrylate, Quantitative information, Retention data, Retention time, Sensitive detectors, Synthetic polymers, Weight distributions, Molecular weight, oligomer, poly(methyl methacrylate), polymer, accuracy, algorithm, analytic method, article, elution, mass spectrometer, quantitative analysis, refraction index, sensitivity and specificity, Chromatography, Gel, Chromatography, Liquid, Reference Standards, Spectrometry, Mass, Electrospray Ionization
DOI: 10.1021/ac800591j
ISSN: 00032700
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 02:54

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