Jerry F. Moore

Laser desorption postionization for imaging MS of biological material.

Vacuum ultraviolet single photon ionization (VUV SPI) is a soft ionization technique that has the potential to address many of the limitations of matrix-assisted laser desorption/ionization (MALDI) for imaging MS. Laser desorption postionization (LDPI) uses VUV SPI for postionization and is experimentally analogous to a MALDI instrument with the addition of a pulsed VUV light source. This review discusses progress in LDPI-MS over the last decade, with an emphasis on imaging MS of bacterial biofilms, analytes whose high salt environment make them particularly resistant to imaging by MALDI-MS. This review first considers fundamental aspects of VUV SPI including ionization mechanisms, cross sections, quantum yields of ionization, dissociation and potential mass limits. The most common sources of pulsed VUV radiation are then described along with a newly constructed LDPI-MS instrument with imaging capabilities. Next, the detection and imaging of small molecules within intact biofilms is demonstrated by LDPI-MS using 7.87 eV (157.6 nm) VUV photons from a molecular fluorine excimer laser, followed by the use of aromatic tags for detection of selected species within the biofilm. The final section considers the future prospects for imaging intact biological samples by LDPI-MS.

Laser Desorption Postionization Mass Spectrometry of Antibiotic-Treated Bacterial Biofilms using Tunable Vacuum Ultraviolet Radiation

Laser desorption postionization mass spectrometry (LDPI-MS) with 8.0-12.5 eV vacuum ultraviolet synchrotron radiation is used to single photon ionize antibiotics and extracellular neutrals that are laser desorbed both from neat and intact bacterial biofilms. Neat antibiotics are optimally detected using 10.5 eV LDPI-MS but can be ionized using 8.0 eV radiation, in agreement with prior work using 7.87 eV LDPI-MS. Tunable vacuum ultraviolet radiation also postionizes laser desorbed neutrals of antibiotics and extracellular material from within intact bacterial biofilms. Different extracellular material is observed by LDPI-MS in response to rifampicin or trimethoprim antibiotic treatment. Once again, 10.5 eV LDPI-MS displays the optimum trade-off between improved sensitivity and minimum fragmentation. Higher energy photons at 12.5 eV produce significant parent ion signal, but fragment intensity and other low mass ions are also enhanced. No matrix is added to enhance desorption, which is performed at peak power densities insufficient to directly produce ions, thus allowing observation of true VUV postionization mass spectra of antibiotic treated biofilms.

Depth profiling and imaging capabilities of an ultrashort pulse laser ablation time of flight mass spectrometer

An ultrafast laser ablation time-of-flight mass spectrometer (AToF-MS) and associated data acquisition software that permits imaging at micron-scale resolution and sub-micron-scale depth profiling are described. The ion funnel-based source of this instrument can be operated at pressures ranging from 10(-8) to ~0.3 mbar. Mass spectra may be collected and stored at a rate of 1 kHz by the data acquisition system, allowing the instrument to be coupled with standard commercial Ti:sapphire lasers. The capabilities of the AToF-MS instrument are demonstrated on metal foils and semiconductor wafers using a Ti:sapphire laser emitting 800 nm, ~75 fs pulses at 1 kHz. Results show that elemental quantification and depth profiling are feasible with this instrument.

Laser Desorption 7.87 eV Postionization Mass Spectrometry of Antibiotics in Staphylococcus epidermidis Bacterial Biofilms

This paper describes the development of laser desorption 7.87 eV vacuum UV (VUV) postionization MS to detect antibiotics within intact bacterial colony biofilms. As >99% of the molecules ejected by laser desorption are neutrals, VUV photoionization of these neutrals can provide significantly increased signal as compared to the detection of directly emitted ions. Postionization with VUV radiation from the molecular fluorine laser single photon ionizes laser desorbed neutrals with ionization potentials below the 7.87 eV photon energy. Antibiotics with structures indicative of sub‐7.87 eV ionization potentials were examined for their ability to be detected by 7.87 eV laser desorption postionization MS. Tetracycline, sulfadiazine, and novobiocin were successfully detected neat as dried films physisorbed on porous silicon oxide substrates. Tetracycline and sulfadiazine were then detected within intact Staphylococcus epidermidis colony biofilms, the former with LOD in the micromolar concentration range.

Estimation of useful yield in surface analysis using single photon ionisation

Abstract Secondary ion mass spectrometry (SIMS), laser sputter neutral mass spectrometry (SNMS) and laser desorption photoionisation (LDPI) have been used to investigate the desorption of molecules from self-assembled monolayers of phenylsulphides. LDPI, using an F2 excimer laser to single photon ionise gave the lowest fragmentation. A useful yield greater than 0.5% was found for analysis of diphenyldisulphide self-assembled monolayers. It is shown that using a free electron laser to postionise will lead, in the future, to analysis of many atoms and molecules with useful yields approaching 30%.

Single photon ionisation of self assembled monolayers

Self assembled monolayers formed from benzenethiol, diphenylsulphide and diphenyldisulphide have been analysed using secondary ion mass spectrometry (SIMS), sputter neutral mass spectrometry (SNMS) and laser desorption photoionisation mass spectrometry (LDPI). The peak corresponding to the parent ion was much stronger in LDPI than with SIMS or SNMS analysis and fragmentation was lower. A useful yield of order 0.5% was obtained for LDPI from diphenyldisulphide.

Characterization of surface modifications by white light interferometry: applications in ion sputtering, laser ablation, and tribology experiments.

In materials science and engineering it is often necessary to obtain quantitative measurements of surface topography with micrometer lateral resolution. From the measured surface, 3D topographic maps can be subsequently analyzed using a variety of software packages to extract the information that is needed. In this article we describe how white light interferometry, and optical profilometry (OP) in general, combined with generic surface analysis software, can be used for materials science and engineering tasks. In this article, a number of applications of white light interferometry for investigation of surface modifications in mass spectrometry, and wear phenomena in tribology and lubrication are demonstrated. We characterize the products of the interaction of semiconductors and metals with energetic ions (sputtering), and laser irradiation (ablation), as well as ex situ measurements of wear of tribological test specimens. Specifically, we will discuss: i. Aspects of traditional ion sputtering-based mass spectrometry such as sputtering rates/yields measurements on Si and Cu and subsequent time-to-depth conversion. ii. Results of quantitative characterization of the interaction of femtosecond laser irradiation with a semiconductor surface. These results are important for applications such as ablation mass spectrometry, where the quantities of evaporated material can be studied and controlled via pulse duration and energy per pulse. Thus, by determining the crater geometry one can define depth and lateral resolution versus experimental setup conditions. iii. Measurements of surface roughness parameters in two dimensions, and quantitative measurements of the surface wear that occur as a result of friction and wear tests. Some inherent drawbacks, possible artifacts, and uncertainty assessments of the white light interferometry approach will be discussed and explained.

Ultraviolet and infrared spectroscopy for effluent analysis in a molten salt electrochemical cell

An apparatus that combines gas phase spectroscopy over two wavelength ranges for analysis of effluent from a molten salt electrochemical cell is described. The cell is placed in a quartz tube that is sealed at the top with a cap containing feedthrus for power, thermometry, and gas flow. A resistance furnace brings the cell assembly to the desired temperature while the cap remains cooled by water. Inert gas continually purges the cell headspace carrying effluent from the electrolysis sequentially through two gas cells, one in a Fourier transform infrared (FTIR) spectrometer and one in a fiber-optic coupled ultraviolet visible spectrometer. Strong vibrational absorptions in the IR can easily identify common effluent components such as HCl, CO, CO2, and H2O. Electronic bands can identify IR-inactive molecules of importance including Cl2 and O2. Since the absorptivity of all of these species is known, determinations of the gas concentration can be made without using standards. Spectra from the electrolysis of...

The Application of laser-driven acoustic waves in modern mass spectrometry

The generation of the acoustic vibration of laser back-irradiated thin metal foils and their influence on desorption of organic molecules from the foils front surface were studied. The possible mechanisms of this phenomenon are discussed.

Laser-driven acoustic waves in back-irradiated thin solid foils

Acoustic waves, generated in solids by irradiation of a surface with powerful laser pulses, are widely used to study mechanical, thermal and elastic properties of materials. Application of this technique to MEMS technology will open new insights into fabrication and characterization but will require understanding of acoustic wave generation in small-sized objects. To that end, acoustic wave generation was studied in thin (10-50 μm) metal and semiconductor foils (including Mo, Si, W, Ni, Ta, Au) back-side irradiated by nanosecond IR and UV laser pulses over a range of peak intensities. Both interferometric techniques and capacitance transducers were employed for detection of surface displacements in the foils. By varying the peak laser power over a wide range of intensities (1-500 MW/cm2) detection of the transition from a thermoelastic to a laser-plasma driven shock-wave mechanism for acoustic wave generation was possible. Measurements show that this transition is accompanied by a dramatic change in the waveform of the generated shock-wave and that this waveform differs for various materials and foil thicknesses. Since thin foils were studied, the longitudinal and shear waves were experimentally indistinguishable, making the observed waveform very complex. Moreover, at higher peak laser powers, mechanical vibrations at resonance frequencies of the thin foils can occur and further complicate the analysis. Nevertheless, the observed phenomena can be described in the framework of a simplified theoretical model and can be used for materials testing in different applications.