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Andreas Wucher

Publications and source records attributed to Andreas Wucher.

6 recordsLinked to original sources

Molecular depth profiling with cluster ion beams.

Peptide-doped trehalose thin films have been characterized by bombardment with energetic cluster ion beams of C60+ and Aux+ (x = 1, 2, 3). The aim of these studies is to acquire information about the molecular sputtering process of the peptide and trehalose by measurement of secondary ion mass spectra during erosion. This system is important since uniform thin films of approximately 300 nm thickness can be reproducibly prepared on a Si substrate, allowing detailed characterization of the resulting depth profile with different projectiles. The basic form of the molecular ion intensity as a function of ion dose is described by a simple analytical model. The model includes parameters such as the molecular sputtering yield, the damage cross section of the trehalose or the peptide, and the thickness of a surface layer altered by the projectile. The results show that favorable conditions for successful molecular depth profiling are achieved when the total sputtering yield is high and the altered layer thickness is low. Successful molecular depth profiles are achieved with all of the cluster projectiles, although the degree of chemical damage accumulation was slightly lower with C60. With C60 bombardment, the altered layer thickness of about 20 nm and the damage cross section of about 5 nm2 are physically consistent with predictions of molecular dynamics calculations available for similar chemical systems. In general, the model presented should provide guidance in optimizing experimental parameters for maximizing the information content of molecular depth profiling experiments with complex molecular thin film substrates.

Algorithms↗

Energetic ion bombardment of Ag surfaces by C60+ and Ga+ projectiles.

The ion bombardment-induced release of particles from a metal surface is investigated using energetic fullerene cluster ions as projectiles. The total sputter yield as well as partial yields of neutral and charged monomers and clusters leaving the surface are measured and compared with corresponding data obtained with atomic projectile ions of similar impact kinetic energy. It is found that all yields are enhanced by about one order of magnitude under bombardment with the C60+ cluster projectiles compared with Ga+ ions. In contrast, the electronic excitation processes determining the secondary ion formation probability are unaffected. The kinetic energy spectra of sputtered particles exhibit characteristic differences which reflect the largely different nature of the sputtering process for both types of projectiles. In particular, it is found that under C60+ impact (1) the energy spectrum of sputtered atoms peaks at significantly lower kinetic energies than for Ga+ bombardment and (2) the velocity spectra of monomers and dimers are virtually identical, a finding which is in pronounced contrast to all published data obtained for atomic projectiles. The experimental findings are in reasonable agreement with recent molecular dynamics simulations.

Carbon↗

Molecular depth profiling of histamine in ice using a buckminsterfullerene probe.

We employ a buckminsterfullerene ion source to probe the distribution of histamine molecules at the water-ice/vacuum interface. The experiments utilize secondary ion mass spectrometry to detect molecular ions that are desorbed from a frozen aqueous histamine solution. The results show that this cluster ion probe induces an extraordinarily high sputter yield of 2400 ice molecules per impact event as determined by a quartz crystal microbalance. As a consequence of this high yield, we show that it is possible to produce molecular depth profiles of the top several hundred nanometers below the ice surface without destruction of the molecular ion signal by accumulation of beam-induced chemical damage. Similar profiles are reported for desorbed neutral molecular fragments by utilizing a high-power femtosecond-pulsed laser for photoionization. While this type of information could not be achieved using atomic projectiles, it is possible to remove the damage induced by such projectiles by subsequent cluster bombardment. These experiments are particularly important for organic surface analysis since they suggest that cluster ion probes may successfully be employed to remove overlayers that may mask the desired molecular information in static secondary ion mass spectral analysis.

Combinatorial Chemistry Techniques↗

Depth profiling of Langmuir-Blodgett films with a buckminsterfullerene probe.

Bombardment with C60+ primary ions of monolayer and multilayer barium arachidate Langmuir-Blodgett (LB) films is investigated. The behavior of cluster versus atomic (Ga+) bombardment is monitored by the barium-cationized arachidate ion (mass-to-charge ratio (m/z) 449) and a characteristic fragment ion (m/z 209) using 1-, 7-, and 15-layer model systems. The removal rate of material from the films is shown to be on the order of several hundred molecules per C60 impact, a value 100-fold larger than Ga+ impact. The enhancement in secondary ion yield is also shown to be larger for the 15-layer film (400x) than for the monolayer film (100x). Moreover, most of the increase in yield is shown to be associated with ejection of sputtered species rather than an increase in ionization probability. High yields associated with cluster bombardment are also shown to be amenable to depth profiling experiments in which the two ions can be monitored as the film is being removed. In this modality, chemical damage associated with bombardment is removed before it can accumulate on the surface. Due to the similarity of fatty acid LB films to cellular membranes, these results suggest that C60+ primary ion beams may improve the prospects for TOF-SIMS studies of biological systems.

Fullerenes↗

Molecule-specific imaging with mass spectrometry and a buckminsterfullerene probe: application to characterizing solid-phase synthesized combinatorial libraries.

We employ a newly developed buckminsterfullerene (C(60)) primary ion beam with time-of-flight secondary ion mass spectrometry to create molecule-specific images of resin particles employed in the solid-phase synthesis of peptide combinatorial libraries. This new cluster ion source, when operated at an incident energy of 20 keV, is remarkably effective at desorbing small peptides directly from a polymer surface and opens new possibilities for characterizing large arrays of diverse sets of molecules. In addition, the C(60) ion beam may be focused to a spot of 1.5 microm in diameter, enabling molecule-specific images of single 100 microm resin particles to be acquired. We report three significant aspects associated with utilizing the C(60) projectile that show how this technology can be taken to a more advanced level, especially when compared to results obtained with more conventional atomic primary ions. First, the useful yield of molecular ions is generally observed to be enhanced by at least 3 orders of magnitude over those previously possible. Second, the energy dissipation process associated with the C(60) impact is most efficient at desorbing molecules on soft substrates such as polymer surfaces rather than harder substrates such as metals or semiconductors. Third, there is a greatly reduced tendency for insulating surfaces to build up excess charge, obviating the need for charge compensation. Using a small five-member peptide library as a model, we show that by utilizing the focusing properties of the C(60) beam, it is possible to assay the surface composition of 100-microm polymer beads at a rate of up to 10 particles/s. Moreover, even at the picomole level, there are enough sequence ions in the mass spectrum to determine a unique composition. The results illustrate the ability to quickly assay large libraries without the use of tags and suggest the strategy may be applicable to a range of high-throughput experiments.

Combinatorial Chemistry Techniques↗

Laser desorption and imaging of proteins from ice via UV femtosecond laser pulses.

We have employed 200-fs, 400-nm laser pulses to desorb intact protein molecular ions directly from a frozen aqueous matrix. The resulting spectra obtained using a variety of proteins varying in molecular weight from 1060 (bradykinin) to 5778 Da (insulin) are compatible with those obtained with traditional matrix-assisted laser desorption/ionization experiments. High-quality spectra could be generated using a fluence of 4.0-9.0 J/cm2 to desorb proteins from an aqueous solution frozen onto metal substrates with a sensitivity in the femtomole range. Although the mechanism behind this effect is still not clear, we speculate that it involves explosive boiling of the ice layer due to rapid heating of the substrate. Imaging experiments conducted on the ice layer suggest that the yield of protein is approximately independent of the film thickness and is very reproducible from shot to shot. The results are particularly significant since they open the possibility of examining a range of biomaterials directly from the in vivo aqueous environment.

Ice↗