The coupling behavior of a microparticle embedded amino acid active-ester into a Poly( ethylene glycol)methacrylate-film, synthesized onto a silicon wafer by a grafting from approach, is characterized using dynamic time-of-flight secondary ion mass spectrometry (ToF-SIMS) to analyze the 3d distribution of the amino acids in the polymer film. Besides standard solid phase peptide synthesis, employing solubilized amino acids in a solvent, we used solid polymer microparticles, incorporating the amino acids. These microparticles were especially designed for a new technique to produce high-density combinatorial peptide microarrays: upon heating, the particles become viscous, which releases the embedded amino acids to diffuse and couple to the surface. In the scope of the development of this new particlebased application, ToF-SIMS is used to analyze a complex chemically modified polymer surface layer. Due to depth profile measurements, it is possible to investigate the particle-based coupling reaction not only on the surface, but also into the depth of the PEGMA film. (C) 2015 The Authors. Published by Elsevier B.V.