Detailed MALDI comparison of NiPAm glycopolymers

•Screening with different matrices of PNiPAm glycopolymers with MALDI MS was shown.•Comparison between mannose and glucose PNiPAm glycopolymers.•MALDI MS experiments were performed to gain additional structural information.•The automatic interpretation of MS data via a special software was presented.

A series of poly(N-isopropylacrylamide) (PNiPAm) statistical glycopolymers with either glucose or mannose based comonomers were analyzed in detail by matrix-assisted laser/desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). A systematic differentiation between first the protected copolymers and secondly the deprotected ones were performed. Furthermore, MALDI-TOF MS was exploited to investigate which matrix and cationization agent combination was best suited with respect to end group preservation, suppression of certain polymeric species as well as the signal to noise (S/N) ratio. The combination of the matrix DCTB and NaCl as cationization agent proved superior for all polymers, regardless whether in protected or deprotected form. Software analysis of the mass spectra using the computational tool COCONUT is shown to provide accurate information on the overall composition of the copolymers.

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