Derivatization aids in the determination of end groups in poly(alkylene glycol)s by matrix‐assisted laser desorption/ionization mass spectrometry

Abstract

A method for end-group characterization by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry following preliminary derivatization with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and capryloyl chloride is described and applied to poly(alkylene glycol)s. The MALDI mass spectra of the products revealed peaks of sodiated derivative cations, whose shift by the respective increments allowed the determination of the number of end functional groups with active hydrogens. This approach is particularly efficient for the distinction of cyclic and linear dehydration products among minor components.

Matrix effect in matrix‐assisted laser desorption/ionization mass spectra of derivatized oligomeric polyols

“…Little attention has, however, been paid to the application of simple derivatization reactions such as silylation, acylation, and alkylation, which are widely used in GC/MS . In recent works we have demonstrated the considerable potential of such derivatization reactions in the elucidation of the structures of polymers and oligomers and, in particular, in qualitative and quantitative end‐group (OH, COOH, NH 2 ) analysis. In addition, such derivatives can provide higher ionization efficiency and resolution of cationized oligomeric molecules under MALDI conditions.…”

Characterization of Low-Molecular Weight Iodine-Terminated Polyethylenes by Gas Chromatography/Mass Spectrometry and Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry with the Use of Derivatization

“…Silylation, which is very popular in gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS), 43,44 appeared to be useful in structure elucidation, differentiation of linear, cyclic or three-dimensional oligomers. 45,46 It should be noted that, in some cases, the matrix can interact with derivatized analytes. Such a situation has been observed in the analysis of silylated polyols when carboxyl-containing matrices (DHB, HABA) could subtract silyl groups from derivatized analytes during co-crystallization.…”

A Novel Derivatization Reagent in the Determination of the Number of OH End Groups in Poly(ethylene glycol) by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

“…9) Borisov and co-workers reported the potential of trimethylsilylation and acylation methods in determining the number of OH groups (or other groups with active hydrogens) and for the structural elucidation of poly(ethylene glycol) (PEG) and poly(1,2-propylene glycol) by MALDI-MS. 10) However, complete trimethylsilylation or acylation required ten hours incubation in an ultrasonic bath, and tetrahydrofuran solvent was needed for the dehydration process. In the present study, we investigated the potential of a novel derivatization reagent, trifluoroacetic anhydride (TFAA), for the determination of the number of OH end groups in PEG by MALDI-MS.…”