Mass analysis of water-soluble polymers by mobility measurement of charge-reduced ions generated by electrosprays

Aqueous solutions of poly(ethylene glycol) (PEG) in a 10 mM ammonium acetate buffer are electrosprayed, and the maximum charge state on the resulting gas-phase ions is reduced to unity using a radioactive source. The mobility distribution of these charged particles is then measured in air in a differential mobility analyzer of unusually high resolution. The relation Z(m) between the mobility Z of a polymer molecule and its mass m is determined by means of narrowly distributed PEG mass standards. The molecular weight range of available standards is extended by generating clusters containing from one up to six molecules of the primary PEG standard. The mass at the peak of the distribution of the lowest standard (PEG-4k) is determined by MALDI mass spectrometry and agrees with the manufacturer's value and previous MALDI literature data. The masses for the 50K and 120K standards are found to differ by 8.6 and 6.6%, respectively, from the manufacturer's value. Using known relationships, the particle diameter d of the ions is calculated from the measured mobility. Plots of d versus m(1/3) give straight lines over the full mass range studied (4000-700 000 Da, particle diameter from 3 to 12 nm), indicating that these PEG particles are indeed spherical and have a density rho independent of size. The slope of the d versus m(1/3) curve provides a density rho = 1.25 g/cm(3), close to the known bulk density, rho(PEG) = 1.21 g/cm(3).