Molecular surface analysis by TOF-SIMS

Author(s):  
Robert W. Odom

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) performs surface sensitive analysis of the elemental and molecular composition of solids. TOFSIMS is a relatively new embodiment of static secondary ion mass spectrometry (SSIMS) in which the dose of primary ions incident on the surface is typically less than 1012 ions/cm2. Since typical solid surfaces have an atomic density of 1015 atoms/cm2, this primary ion dose nominally removes less than 0.1% of a monolayer. Hence, SIMS analyses performed under these static conditions represent near surface analysis in which secondary ions are produced from the top few monolayers of the surface. The actual sampling depth is determined by the primary ion momentum, angle of incidence and chemistry of the surface. Since low dose primary ions cause minimal perturbation of the chemistry of the solid surface, SSIMS analyses often produce molecular or pseudo-molecular ions characteristic of the chemical composition of the surface. Thus, molecular ions or structurally significant fragment ions are often observed in SSIMS analyses of surfaces containing inorganic and organic residues, polymers surfaces, coatings, and biological materials such as tissues and membranes.

Author(s):  
R.W. Linton ◽  
T.F. Fister ◽  
S.S. Summers ◽  
G.S. Strossman ◽  
M.J. Holland ◽  
...  

The objective of this research is to develop imaging time-of-flight secondary ion mass spectrometry (TOF-SIMS) to characterize ultra-thin organic films on microscopic particles. An initial application is to evaluate the surface chemistry of polycyclic organic matter (POM) on combustion-generated particles as an area of fundamental interest in the assessment of the environmental fate and impact of carcinogenic pollutants.Controlled deposition of POM monolayers was achieved using either gas or solution phase coating on model particles such as silica, as well as on authentic environmental particles such as coal flyash or soot. Another aspect of the work was to monitor surface transformations of adsorbed POM involving photochemical degradation or reactions with gaseous pollutants such as nitrogen oxides. For the first time, variations in POM adsorption and reactivity have been probed as a function of particle type by the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) to perform surface analysis on single particles. Results using a pulsed gallium microbeam source on a TOF-SIMS indicated that 0.1 monolayer coverages of individual POM species can be detected as quasimolecular ions from single particles with diameters typically in the 5 μm range. Primary ion doses were <1013 ions/cm2 to minimize surface damage during a typical 10 min spectrum acquisition from an 40x40 ftm image field. Correlation of in situ measurements using TOF-SIMS with traditional solvent extraction and chromatographic results, including LC or GC-MS, allowed for more detailed assessments of the sensitivity and quantitative capabilities of TOF-SIMS. The combination of monolayer analysis with microanalysis creates severe challenges to sensitivity since the total number of molecules within the analytical volume is so small (< 107 POM molecules on a lμm2 particle area)


Author(s):  
Bruno Schueler ◽  
Robert W. Odom

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) provides unique capabilities for elemental and molecular compositional analysis of a wide variety of surfaces. This relatively new technique is finding increasing applications in analyses concerned with determining the chemical composition of various polymer surfaces, identifying the composition of organic and inorganic residues on surfaces and the localization of molecular or structurally significant secondary ions signals from biological tissues. TOF-SIMS analyses are typically performed under low primary ion dose (static SIMS) conditions and hence the secondary ions formed often contain significant structural information.This paper will present an overview of current TOF-SIMS instrumentation with particular emphasis on the stigmatic imaging ion microscope developed in the authors’ laboratory. This discussion will be followed by a presentation of several useful applications of the technique for the characterization of polymer surfaces and biological tissues specimens. Particular attention in these applications will focus on how the analytical problem impacts the performance requirements of the mass spectrometer and vice-versa.


2020 ◽  
Author(s):  
Feifei Jia ◽  
Jie Wang ◽  
Yanyan Zhang ◽  
Qun Luo ◽  
Luyu Qi ◽  
...  

<p></p><p><i>In situ</i> visualization of proteins of interest at single cell level is attractive in cell biology, molecular biology and biomedicine, which usually involves photon, electron or X-ray based imaging methods. Herein, we report an optics-free strategy that images a specific protein in single cells by time of flight-secondary ion mass spectrometry (ToF-SIMS) following genetic incorporation of fluorine-containing unnatural amino acids as a chemical tag into the protein via genetic code expansion technique. The method was developed and validated by imaging GFP in E. coli and human HeLa cancer cells, and then utilized to visualize the distribution of chemotaxis protein CheA in E. coli cells and the interaction between high mobility group box 1 protein and cisplatin damaged DNA in HeLa cells. The present work highlights the power of ToF-SIMS imaging combined with genetically encoded chemical tags for <i>in situ </i>visualization of proteins of interest as well as the interactions between proteins and drugs or drug damaged DNA in single cells.</p><p></p>


1996 ◽  
Vol 122 (1-2) ◽  
pp. 1-15 ◽  
Author(s):  
Keyang Xu ◽  
Andrew Proctor ◽  
David M. Hercules

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