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Structural Characterization of Polymers by MALDI Spiral- TOF Mass Spectrometry Combined with Kendrick Mass Defect Analysis

High-resolution mass spectrometry (HRMS) continues to play an important role in the compositional characterization of larger organic molecules. In the field of polymer characterization, however, the application of HRMS has made only slow progress because of lower compatibility between matrix-assisted laser desorption/ionization (MALDI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS). In this study, a newly developed type of MALDI high-resolution time-of-flight mass spectrometry (TOFMS) with a spiral ion trajectory (MALDI spiral-TOFMS) was applied to the structural and compositional characterization of polymers. To create a graphical distribution of polymer components on a two-dimensional plot converted from complex mass spectra, we adopted a slightly modified Kendrick mass defect (KMD) analysis based on accurate masses determined using spiral-TOFMS. By setting the Kendrick mass scale based on the mass of the repeating units of a given polymer, components with common repeat units lined up in the horizontal direction on the KMD plot, whereas those components with different structures were shifted vertically. This combination of MALDI spiral-TOFMS measurement and KMD analysis enabled the successful discrimination of the polymer components in a blend of poly(alkylene oxide)s, the compositional analysis of poly(ethylene oxide)/poly(propylene oxide) block copolymers, and profiling of the end-group distribution of poly(ε- caprolactone)s synthesized under different conditions.


Polymer characterization has the potential to be particularly useful in assisting the design of sophisticated polymeric materials with dedicated functions. Matrixassisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is an important tool in this technique [1, 2]. Currently, conventional TOFMS instruments used for polymer characterization apply a single reflector with a flight path of approximately 17 m (2.1 m×8 turns) along the spiral ion trajectory, which yields a high mass-resolving power of 80,000 at full width at half maximum (FWHM) for m/z ca. 2500 of a peptide sample. In a previous study, we applied MALDI spiral- TOFMS to the detailed structural characterization of polyphenols [5, 6] and radical-polymerized copolymers [7]. In these former studies [5, 6], we were able to identify the structures of repeating units of polyphenols. In the latter study [7], copolymer compositions and several types of end-group combinations could be identified, allowing the compositional distribution to be evaluated. In both cases, MALDI spiral-TOFMS could be used to provide an accurate judgment of the mass differences at ca. 16 Da to discriminate O and CH4, between which the mass difference is only 0.036 Da. We therefore anticipate  MALDI spiral-TOFMS to make a significant contribution to the development of the structural characterization of polymers. 

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