AVS 63rd International Symposium & Exhibition
    Applied Surface Science Wednesday Sessions
       Session AS-WeA

Paper AS-WeA2
Extended Molecular Identification with TOF-SIMS Imaging MS/MS

Wednesday, November 9, 2016, 2:40 pm, Room 101B

Session: Multiple Technique Approaches for Real-World Industrial Problem Solving
Presenter: John Hammond, Physical Electronics
Authors: J.S. Hammond, Physical Electronics
G.L. Fisher, Physical Electronics
S.R. Bryan, Physical Electronics
S. Iida, ULVAC-PHI, Japan
T. Miyayama, ULVAC-PHI, Japan
Correspondent: Click to Email

TOF-SIMS has become widely accepted as the most powerful spectroscopy and imaging surface analysis tool for organic and polymer samples based on the capabilities of 2 nm surface sensitivity and 100 nm spatial resolution. For most polymer additives as well as lipids, disease markers and fatty acids on biological tissue samples, the molecular ions have masses up to m/z 1000. At this higher mass range, traditional TOF-SIMS lacks the mass resolution and mass accuracy to uniquely identify the detected ions. A new TOF-SIMS instrument combining, in parallel, imaging MS and imaging MS/MS provides the capability to provide a multi-technique approach to real world problem solving with extended molecular identification of higher mass ions [1].

A series of saturated and unsaturated fatty acid standards as well anti-oxidant polymer additives were analyzed with a PHI nanoTOF II TOF-SIMS Parallel Imaging MS/MS. The MS/MS spectra were generated with a 1 daulton precursor selection window followed by 1.5 keV collision-induced dissociation (CID). The MS1 and MS2 parallel imaging of polymer surfaces with a mixture of polymer additives were obtained with a raster scanned Bi3+ ion source with a sub-micron spatial resolution

The structural elucidation of the fatty acid CID MS/MS spectra can be interpreted by charge-remote fragmentation [2]. The location of unsaturated bonds in the fatty acids can be defined from these spectra. The complex structures of the anti-oxidants can be easily identified with the high energy CID MS/MS. Using the high signal/background of the MS2 images, bunched or unbunched imaging with the Bi3+ ion source can produce sub-micron spatial resolution with unique molecular identification of additives on the polymer films. These results also point to a broader utility of this technique for biological tissue imaging.

4. References

[1] P.E. Larson, J.S. Hammond, R.M.A. Heeren, G.L. Fisher, Method and Apparatus to Provide Parallel Acquisition of MS/MS Data, U.S. Patent 20150090874, 2015.

[2] M. L. Gross,, Int. J. Mass Spectrom., 200 (2000) 611