Termini and main-chain composition of monomethoxy-terminated poly(ethylene glycol) studied by two-dimensional column chromatography

Samples of poly(ethylene glycol) especially those with functionalized ends have dimeric, trimeric, and tetrameric components at twice, three times, and four times as high a molecular weight (MW) as that of the main component. We used two-dimensional column chromatography to evaluate the MW and identify the terminal groups in each component. The first step is high osmotic pressure chromatography to prepare a sufficient amount of fractions that contain different percentages of the multimeric components. In the second step, each of the fractions was characterized by using regular size exclusion chromatography and high-resolution NMR. Decomposition of the chromatogram combined with isolation of the terminal methoxy peak in the NMR spectrum led to unique identification of the terminal groups. We thus found that the monomeric component is monomethoxy-terminated whereas the dimeric and other multimeric components are mostly dihydroxy-terminated.