Hyphenation of aqueous liquid chromatography to pyrolysis-gas chromatography and mass spectrometry for the comprehensive characterization of water-soluble polymers

J Chromatogr A. 2008 Apr 4;1186(1-2):222-7. doi: 10.1016/j.chroma.2007.10.035. Epub 2007 Oct 18.


A recently developed hyphenated system for "organic" size-exclusion chromatography-pyrolysis-gas chromatography-mass spectrometry (SEC-Py-GC-MS) is adapted to allow the use of aqueous LC eluents as applied in the characterization of water-soluble polymers. The system uses syringe-based transfer of multiple LC-fractions to the GC instrument with solvent elimination and subsequent pyrolysis in a programmed temperature vaporization injector. The problems of the large-volume injections of aqueous, salt containing eluents into the Py-GC-MS are solved by using a 'sintered-bed liner' for elimination of the water at a high temperature, a volatile salt and the installation of a back-flush option. After optimization, the system was applied for the determination of the combined molecular weight-chemical composition of a polyethylene glycol-polypropylene glycol block copolymer. This analysis was done with the system in the aqueous SEC-Py-GC-MS mode. Also demonstrated is the automated at-line characterization of a random polystyrene-polymethylmethacrylate copolymer, now with the system in the gradient reversed-phase LC-Py-GC-MS mode. The methods proposed in the present work are very useful for the detailed characterization of water-soluble copolymers.

MeSH terms

  • Chromatography, Gel
  • Chromatography, Liquid
  • Gas Chromatography-Mass Spectrometry / methods*
  • Polyethylene Glycols / analysis
  • Polyethylene Glycols / chemistry
  • Polymers / chemistry*
  • Polymethyl Methacrylate / analysis
  • Polymethyl Methacrylate / chemistry
  • Solubility
  • Temperature*
  • Water / chemistry*


  • Polymers
  • Water
  • Polyethylene Glycols
  • Polymethyl Methacrylate