Detailed structural elucidation of polyesters and acrylates using Fourier transform mass spectrometry

• Published in: Analytical and bioanalytical chemistry Vol. 392; no. 4; pp. 575 - 583
• Main Authors: Simonsick, William J. Jr, Petkovska, Violeta I
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Berlin/Heidelberg : Springer-Verlag 01.10.2008; Springer-Verlag
• Subjects: Acrylates - analysis; Acrylates - chemistry; Analytical Chemistry; Biochemistry; Caproates - chemistry; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Collision-induced dissociation; composite polymers; Electrospray ionization; Food Science; Fourier Analysis; Fourier transform mass spectrometry; Laboratory Medicine; Lactones - chemistry; Laser desorption ionization; Mass Spectrometry - methods; Molecular Structure; Monitoring/Environmental Analysis; Paper in Forefront; Polyesters - analysis; Polyesters - chemistry; polymers; Stearic Acids - chemistry; Stearic Acids - isolation & purification; Tandem mass spectrometry; Triazines - chemistry; Laser desorption ionization; Fourier transform mass spectrometry; Tandem mass spectrometry; Copolymers; Collision-induced dissociation; Electrospray ionization; Polymers
• ISSN: 1618-2642; 1618-2650
• DOI: 10.1007/s00216-008-2322-3

The detailed structural characterization of complex polymer architectures, like copolymers and polymer mixtures, by mass spectrometry presents a challenge. Even though soft ionization analyses revolutionized the characterization of large molecules and provided a means for determining the polymer's molecular weight distribution, polydispersity, and end groups, full microstructure elucidation and monomer sequencing by soft ionization alone is not possible. The combination of high-resolution Fourier transform mass spectrometry (FTMS) and tandem mass spectrometry (MSn) provides a powerful analytical tool for addressing these challenges. This tool was used in our work to separate and identify the products of polymerization between 12-hydroxystearic acid (HSA) and stearic acid (SA), to provide precise information about the exact location of caprolactones on the Tris(2-hydroxyethyl)isocyanurate (THEIC) molecule, and to sequence a glycidyl methacrylate/methyl methacrylate (GMA/MMA) copolymer. The results highlight the value of ultrahigh resolution and tandem mass spectrometry for fine structural characterization and sequencing of polymers.