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Title: Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis

The use of atomic force microscopy controlled nano-thermal analysis probes for reproducible spatially resolved thermally-assisted sampling of micrometer-sized areas (ca. 11 m 17 m wide 2.4 m deep) from relatively low number average molecular weight (M n < 3000) polydisperse thin films of poly(2-vinylpyridine) (P2VP) is presented. Following sampling, the nano-thermal analysis probes were moved up from the surface and the probe temperature ramped to liberate the sampled materials into the gas phase for atmospheric pressure chemical ionization and mass spectrometric analysis. Furthermore, the procedure and mechanism for material pickup, the sampling reproducibility and sampling size are discussed and the oligomer distribution information available from slow temperature ramps versus ballistic temperature jumps is presented. For the M n = 970 P2VP, the Mn and polydispersity index determined from the mass spectrometric data were in line with both the label values from the sample supplier and the value calculated from the simple infusion of a solution of polymer into the commercial atmospheric pressure chemical ionization source on this mass spectrometer. With a P2VP sample of higher Mn (M n = 2070 and 2970), intact oligomers were still observed (as high as m/z 2793 corresponding to the 26-mer), but a significant abundancemore » of thermolysis products were also observed. In addition, the capability for confident identification of the individual oligomers by slowly ramping the probe temperature and collecting data dependent tandem mass spectra was also demonstrated. We also discuss the material type limits to the current sampling and analysis approach as well as possible improvements in nano-thermal analysis probe design to enable smaller area sampling and to enable controlled temperature ramps beyond the present upper limit of about 415°C.« less
Authors:
 [1] ;  [1] ;  [2] ;  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Mass Spectrometry and Laser Spectroscopy Group
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Analytical Chemistry
Additional Journal Information:
Journal Volume: 89; Journal Issue: 5; Journal ID: ISSN 0003-2700
Publisher:
American Chemical Society (ACS)
Research Org:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; atomic force microscopy; mass spectrometry; thermally-assisted sampling; thermal desorption; temperature ramps; polymers; atmospheric pressure chemical ionization
OSTI Identifier:
1347323

Hoffmann, William D., Kertesz, Vilmos, Srijanto, Bernadeta R., and Van Berkel, Gary J.. Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis. United States: N. p., Web. doi:10.1021/acs.analchem.6b04733.
Hoffmann, William D., Kertesz, Vilmos, Srijanto, Bernadeta R., & Van Berkel, Gary J.. Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis. United States. doi:10.1021/acs.analchem.6b04733.
Hoffmann, William D., Kertesz, Vilmos, Srijanto, Bernadeta R., and Van Berkel, Gary J.. 2017. "Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis". United States. doi:10.1021/acs.analchem.6b04733. https://www.osti.gov/servlets/purl/1347323.
@article{osti_1347323,
title = {Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis},
author = {Hoffmann, William D. and Kertesz, Vilmos and Srijanto, Bernadeta R. and Van Berkel, Gary J.},
abstractNote = {The use of atomic force microscopy controlled nano-thermal analysis probes for reproducible spatially resolved thermally-assisted sampling of micrometer-sized areas (ca. 11 m 17 m wide 2.4 m deep) from relatively low number average molecular weight (Mn < 3000) polydisperse thin films of poly(2-vinylpyridine) (P2VP) is presented. Following sampling, the nano-thermal analysis probes were moved up from the surface and the probe temperature ramped to liberate the sampled materials into the gas phase for atmospheric pressure chemical ionization and mass spectrometric analysis. Furthermore, the procedure and mechanism for material pickup, the sampling reproducibility and sampling size are discussed and the oligomer distribution information available from slow temperature ramps versus ballistic temperature jumps is presented. For the Mn = 970 P2VP, the Mn and polydispersity index determined from the mass spectrometric data were in line with both the label values from the sample supplier and the value calculated from the simple infusion of a solution of polymer into the commercial atmospheric pressure chemical ionization source on this mass spectrometer. With a P2VP sample of higher Mn (Mn = 2070 and 2970), intact oligomers were still observed (as high as m/z 2793 corresponding to the 26-mer), but a significant abundance of thermolysis products were also observed. In addition, the capability for confident identification of the individual oligomers by slowly ramping the probe temperature and collecting data dependent tandem mass spectra was also demonstrated. We also discuss the material type limits to the current sampling and analysis approach as well as possible improvements in nano-thermal analysis probe design to enable smaller area sampling and to enable controlled temperature ramps beyond the present upper limit of about 415°C.},
doi = {10.1021/acs.analchem.6b04733},
journal = {Analytical Chemistry},
number = 5,
volume = 89,
place = {United States},
year = {2017},
month = {2}
}