Carbon-13 labeling for quantitative analysis of molecular movement in heterogeneous organic materials using secondary ion mass spectrometry.

Secondary ion mass spectrometry (SIMS) is used to probe the movement of macromolecules in heterogeneous organic systems. Using 13C tracer labeling and two model systems, polystyrene/poly(2-vinylpyridine) (PS/P2VP) and polystyrene/poly(4-bromostyrene) (PS/P4BrS), the diffusion of 13C-labeled PS has been investigated near the respective heterogeneous interfaces using a CAMECA-IMS-6F magnetic sector mass spectrometer. 13C labeling has been shown to greatly minimize matrix effects (i.e., changes in secondary ion yields due to changing chemical environment) in heterogeneous systems. P2VP is a nitrogen-rich polymer (C7H7N monomer composition), making it an excellent model polymer for exploration of this technique for potential future use in biological applications, and probing the PS/P4BrS interface demonstrates the versatility of this technique for analysis of various heteroatom-containing materials. Results confirm that the 13C-labeling method does indeed allow for quantitative analysis of molecular movement in heterogeneous organic systems containing matrix-enhancing heteroatoms such as nitrogen. Therefore, extension of this method to more complicated biological systems involving multiple heteroatoms (oxygen, nitrogen, etc.), layers, and heterogeneous interfaces, as well as two- and three-dimensional profiling and imaging using SIMS, can be envisaged.

Changes in thermodynamic interactions at highly immiscible polymer/polymer interfaces due to deuterium labeling.

Deuterium labeling has been shown previously to affect thermodynamic interactions at polymer surfaces, polymer/polymer heterogeneous interfaces, and in bulk (away from a surface or interface). However, the changes in polymer-polymer interactions due to deuterium labeling have not been thoroughly investigated for highly immiscible systems. It is shown here that deuterium labeling can influence polymer-polymer interactions at heterogeneous interfaces with highly immiscible systems, namely, polystyrene/poly(2-vinylpyridine) (PS/P2VP), polystyrene/poly(4-vinylpyridine) (PS/P4VP), and polystyrene/poly(methyl methacrylate) (PS/PMMA). Using secondary ion mass spectrometry, segregation of deuterium labeled polystyrene (dPS) in a dPS + unlabeled PS (dPS:hPS) blend layer was observed at the dPS:hPS/hP2VP, dPS:hPS/hP4VP, and dPS:hPS/hPMMA heterogeneous interfaces. However, a reference system involving PS on a PS brush shows no segregation of dPS to the interface.