The identification of synthetic homopolymer end groups and verification of their transformations using MALDI-TOF mass spectrometry

J Mass Spectrom. 2010 Jun;45(6):587-611. doi: 10.1002/jms.1743.


Recent advances in the resolving power of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) enable the detailed characterization of linear homopolymers, and in particular provide invaluable data for the determination of their end-group functionalities. With the growing importance of macromolecular coupling reactions in building complex polymer architectures, the ability to accurately monitor end-group transformations is becoming increasingly important for synthetic polymer chemists. This tutorial demonstrates the application of MALDI-TOF MS in determining both end-group functionalities and their transformations for linear homopolymers. Examples of both polycaprolactone and polystyrene are examined, and the strengths and weaknesses of various approaches to data analysis are given.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Calibration
  • Linear Models
  • Polyesters / chemistry
  • Polymers / chemistry*
  • Polystyrenes / chemistry
  • Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / methods*


  • Polyesters
  • Polymers
  • Polystyrenes
  • polycaprolactone