Abstract
In recent years, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) plays an essential role in the analysis of polymers. To acquire a more reliable strategy for polymer profiling, we characterized four representative polymers including polyethylene glycol 6000, polyvinylpyrrolidone K12, polymer polyol KPOP-5040, and polyether polyol DL-4000. The preparation methods of these four polymer samples have been optimized from six aspects, including matrix, cationization reagent, solvent, mixing ratio of cationization reagent to polymer, mixing ratio of matrix to polymer, and laser intensity. After investigating the effects of seven commonly used matrices on the ionization efficiency of four polymers, trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile (DCTB) was found to be the only matrix suitable for the analysis of all the four polymers. Our experimental results suggested that different polymers showed a certain preference for different cationization reagents. For example, the polymer polyol KPOP-5040 was suitable for sodium iodide as the cationization reagent, while polyvinylpyrrolidone K12 was more suitable for silver trifluoroacetate (AgTFA). For the choice of solvent, tetrahydrofuran is a reagent with rapid evaporation and a wide range of dissolution which can achieve the best results for the analysis of four polymers. The optimized method was successfully applied to the identification of DSPE-PEG-NH2 with different polymerized degrees. This MALDI-TOF strategy potentially provided the supplementary function through the polymer’s application in biomedical and visible probing.
Highlights
Compared with electrospray mass spectrometry (MS), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has the characteristics of high sensitivity, easy operation, and wide application (Danis et al, 1992; Roy et al, 1995; Nielen, 1999; Falkenhagen and Weidner, 2010; Peng and Kinsel, 2010)
Silver trifluoroacetate was used as a fixed cationization reagent for all polymers, in order to examine the effects of different matrices on the ionization efficiency of the four polymers separately
The KPOP-5040 was suitable for sodium iodide as the cationization reagent, while AgTFA was more suitable for polyvinylpyrrolidone K12 (PVPK12)
Summary
Compared with electrospray mass spectrometry (MS), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has the characteristics of high sensitivity, easy operation, and wide application (Danis et al, 1992; Roy et al, 1995; Nielen, 1999; Falkenhagen and Weidner, 2010; Peng and Kinsel, 2010). With the development of MALDI-TOF MS, it is increasingly used in the research of polymer structure analysis, including the number of repeating polymer units, molecular weight distribution, terminal structure, and other information, which could perfectly complement the other traditional techniques such as NMR and XRD. Since polymers have the characteristics of large molecular weight range and limited solubility, optimization for the polymer preparation method is significant (Hanton and Parees, 2005). MALDI-TOF MS was used to characterize four representative polymers including polyethylene glycol 6000(PEG-6000), polyvinylpyrrolidone K12 (PVPK12), polymer polyol KPOP-5040 (KPOP-5040), and polyether polyol DL-4000 (DL-4000). The preparation methods of these four polymer samples had been further optimized in this study
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