MALINTO: A New MALDI Interpretation Tool for Enhanced Peak Assignment and Semiquantitative Studies of Complex Synthetic Polymers.

The newly developed MALDI interpretation tool ("MALINTO") allows for the accelerated characterization of complex synthetic polymers via MALDI mass spectrometry. While existing software provides solutions for simple polymers like poly(ethylene glycol), polystyrene, etc., they are limited in their application on polycondensates synthesized from two different kinds of monomers (e.g., diacid and diol in polyesters). In addition to such A2 + B2 polycondensates, MALINTO covers branched and even multicyclic polymer systems. Since the MALINTO software works based on input data of monomers/repeating units, end groups, and adducts, it can be applied on polymers whose components are previously known or elucidated. Using these input data, a list with theoretically possible polymer compositions and resulting m/z values is calculated, which is further compared to experimental mass spectrometry data. For optional semiquantitative studies, peak areas are allocated according to their assigned polymer composition to evaluate both comonomer and terminating group ratios. Several tools are implemented to avoid mistakes, for example, during peak assignment. In the present publication, the functions of MALINTO are described in detail and its broad applicability on different linear polymers as well as branched and multicyclic polycondensates is demonstrated. Fellow researchers will benefit from the accelerated peak assignment using the freely available MALINTO software and might be encouraged to explore the potential of MALDI mass spectrometry for (semi)quantitative applications.

Semiquantitative Approach for Polyester Characterization Using Matrix-Assisted Laser Desorption Ionization/Time-of-Flight Mass Spectrometry Approved by 1H NMR.

Matrix-assisted laser desorption ionization/time-of-flight (MALDI/ToF) mass spectrometry and 1H NMR were used for the structural investigation of isophthalic and maleic acid copolyesters with neopentyl glycol. Since both methods provided information on the ratio of incorporated acid components and terminating groups, results were compared and linear correlations (R2 = 0.96-0.98) could be found. This suggests that MALDI/ToF MS is a suitable tool for the semiquantitative characterization of polyester systems. For the isophthalic/maleic acid ratio, MALDI results yielded constantly lower values than 1H NMR, which was attributed to varying ionization efficiencies of homo- and copolyesters. Ratios of carboxylic and hydroxylic terminating groups, which are conventionally still measured by time consuming complex titrations, were measured with MALDI and 1H NMR and were in good agreement. Both methods either excluded or distinguished unreacted monomers in the polyester bulk in contrast to acid-base titrations where those monomers severely distort the results. Additional structural information could be gained including the observation of cyclic structures (MALDI), E/Z isomerism from maleic to fumaric acid, and the statistical distribution of the acid components within the polyester chain (1H NMR). While 1H NMR peak assignments have to be verified by 13C NMR and multidimensional techniques, MALDI/ToF MS provides a straightforward technique that can be applied to other polyester systems without major alterations.