Advances in the Direct Study of Carbon Burning in Massive Stars.

The ^{12}C+^{12}C fusion reaction plays a critical role in the evolution of massive stars and also strongly impacts various explosive astrophysical scenarios. The presence of resonances in this reaction at energies around and below the Coulomb barrier makes it impossible to carry out a simple extrapolation down to the Gamow window-the energy regime relevant to carbon burning in massive stars. The ^{12}C+^{12}C system forms a unique laboratory for challenging the contemporary picture of deep sub-barrier fusion (possible sub-barrier hindrance) and its interplay with nuclear structure (sub-barrier resonances). Here, we show that direct measurements of the ^{12}C+^{12}C fusion cross section may be made into the Gamow window using an advanced particle-gamma coincidence technique. The sensitivity of this technique effectively removes ambiguities in existing measurements made with gamma ray or charged-particle detection alone. The present cross-section data span over 8 orders of magnitude and support the fusion-hindrance model at deep sub-barrier energies.

SIMS instrumentation and methodology for mapping of co-localized molecules.

We describe an innovative mode for localizing surface molecules. In this methodology, individual C60 impacts at 50 keV are localized using an electron emission microscope, EEM, synchronized with a time-of-flight mass spectrometer for the detection of the concurrently emitted secondary ions. The instrumentation and methodologies for generating ion maps are presented. The performance of the localization scheme depends on the characteristics of the electron emission, those of the EEM and of the software solutions for image analysis. Using 50 keV C60 projectiles, analyte specific maps and maps of co-emitted species have been obtained. The individual impact sites were localized within 1-2 µm. A distinctive feature of recording individual impacts is the ability to identify co-emitted ions which originate from molecules co-located within ~10 nm.

Characteristics of positive and negative secondary ions emitted from [Formula: see text] and [Formula: see text] impacts.

The current limitation for SIMS analyses is insufficient secondary ion yields, due in part to the inefficiency of traditional primary ions. Massive gold clusters are shown to be a route to significant gains in secondary ion yields relative to other commonly used projectiles. At an impact energy of 520 keV, [Formula: see text] is capable of generating an average of greater than ten secondary ions per projectile, with some impact events generating >100 secondary ions. The capability of this projectile for signal enhancement is further displayed through the observation of up to seven deprotonated molecular ions from a single impact on a neat target of the model pentapeptide leu-enkephalin. Positive and negative spectra of leu-enkephalin reveal two distinct emission regimes responsible for the emission of either intact molecular ions with low internal energies or small fragment species. The internal energy distribution for this projectile is measured using a series of benzylpyridinium salts and compared with the small polyatomic projectile [Formula: see text] at 110 keV as well as distributions previously reported for electrospray ionization and fast atom bombardment. These results show that [Formula: see text] offers high secondary ion yields not only for small fragment ions, e.g. CN-, typically observed in SIMS analyses, but also for characteristic molecular ions. For the leu-enkephalin example, the yields for each of these species are greater than unity.

Characterization of individual nano-objects with nanoprojectile-SIMS.

Secondary ion mass spectrometry (SIMS) applied in the event-by-event bombardment/detection mode is uniquely suited for the characterization of individual nano-objects. In this approach, nano-objects are examined one-by-one, allowing for the detection of variations in composition. The validity of the analysis depends upon the ability to physically isolate the nano-objects on a chemically inert support. This requirement can be realized by deposition of the nano-objects on a Nano-Assisted Laser Desorption/Ionization (NALDI™) plate. The featured nanostructured surface provides a support where nano-objects can be isolated if the deposition is performed at a proper concentration. We demonstrate the characterization of individual nano-objects on a NALDI™ plate for two different types of nanometric bacteriophages: Qß and M13. Scanning electron microscope (SEM) images verified that the integrity of the phages is preserved on the NALDI™ substrate. Mass spectrometric data show secondary ions from the phages are identified and resolved from those from the underlying substrate.

Simultaneous detection and localization of secondary ions and electrons from single large cluster impacts.

The use of large cluster primary ions (e.g. C60, Au400) in secondary ion mass spectrometry has become prevalent in recent years due to their enhanced emission of secondary ions, in particular, molecular ions (MW ≤ 1500 Da). The co-emission of electrons with SIs was investigated per projectile impact. It has been found that SI and electrons yields increased with increasing projectile energy and size. The use of the emitted electrons from impacts of C60 for localization has been demonstrated for cholesterol deposited on a copper grid. The instrumentation, methodologies, and results from these experiments are presented.

Surface characterization of biological nanodomains using NP-ToF-SIMS.

This paper describes the application of nanoparticle bombardment with time-of-flight secondary ion mass spectrometry (NP-ToF-SIMS) for the analysis of native biological surfaces for the case of sagittal sections of mammalian brain tissue. The use of high energy, single nanoparticle impacts (e.g. 520 keV Au400) permits desorption of intact lipid molecular ions, with enhanced molecular ion yield and reduced fragmentation. When coupled with complementary molecular ion fragmentation and exact mass measurement analysis, high energy nanoparticle probes (e.g. 520 keV Au400 NP) provide a powerful tool for the analysis of the lipid components from native brain sections without the need for surface preparation and with ultimate spatial resolution limited to the desorption volume per impact (~103 nm3).

On the Surface Mapping using Individual Cluster Impacts.

This paper describes the advantages of using single impacts of large cluster projectiles (e.g. C(60) and Au(400)) for surface mapping and characterization. The analysis of co-emitted time-resolved photon spectra, electron distributions and characteristic secondary ions shows that they can be used as surface fingerprints for target composition, morphology and structure. Photon, electron and secondary ion emission increases with the projectile cluster size and energy. The observed, high abundant secondary ion emission makes cluster projectiles good candidates for surface mapping of atomic and fragment ions (e.g., yield >1 per nominal mass) and molecular ions (e.g., few tens of percent in the 500 < m/z < 1500 range).

Photon emission from massive projectile impacts on solids.

First evidence of photon emission from individual impacts of massive gold projectiles on solids for a number of projectile-target combinations is reported. Photon emission from individual impacts of massive Au(n) (+q) (1 ≤ n ≤ 400; q = 1-4) projectiles with impact energies in the range of 28-136 keV occurs in less than 10 ns after the projectile impact. Experimental observations show an increase in the photon yield from individual impacts with the projectile size and velocity. Concurrently with the photon emission, electron emission from the impact area has been observed below the kinetic emission threshold and under unlikely conditions for potential electron emission. We interpret the puzzling electron emission and correlated luminescence observation as evidence of the electronic excitation resulting from the high-energy density deposited by massive cluster projectiles during the impact.

Photon, Electron and Secondary Ion Emission from Single C(60) keV Impacts.

This paper presents the first observation of coincidental emission of photons, electrons and secondary ions from individual C(60) keV impacts. An increase in photon, electron and secondary ion yields is observed as a function of C(60) projectile energy. The effect of target structure/composition on photon and electron emissions at the nanometer level is shown for a CsI target. The time-resolved photon emission may be characterized by a fast component emission in the UV-Vis range with a short decay time, while the electron and secondary ion emission follow a Poisson distribution.

Ejection of nanoclusters from gold nanoislet layers by 38 keV Au ions in the elastic stopping mode.

Total absolute yields of the ejected gold were obtained regardless of the type of the particles are--atoms, clusters, nanoclusters,--as well as absolute yields of gold nanoclusters, from nanoislet gold targets under bombardment by monoatomic gold ions at 45 degrees to the target surface with the energy 38 keV, i.e., in the "purely" elastic stopping mode -6 keV/nm up to the fluence of 4 x 10(12) cm2. Three targets had gold nanoislets on the substrate surface: 2-12 nm; -18 nm; -35 nm, the most probable sizes being 7.1; 9.4; 17.5 nm respectively. The part of the surface area covered with gold was known. Total transfer of gold was determined by means of the neutron-activation analysis and decreased from 450 to 20 at/ion. The number of the ejected gold nanoclusters was determined using TEM and decreased from approximately 0.06 to < 0.01 per one 38 keV Au ion with the increase of the most probable sizes of the nanoislets on the target from 7.1 to 17.5 nm. The yields appeared to be surprisingly high, which is of scientific and practical importance. Tentative estimations were made using molecular dynamics simulations.

Matrix implanted laser desorption ionization (MILDI) combined with ion mobility-mass spectrometry for bio-surface analysis.

The implantation of low velocity massive gold cluster ions allows homogeneous incorporation of a metallic matrix into the near-surface region of rat brain tissues. Subsequent analysis by laser desorption ionization mass spectrometry yields spectra exhibiting molecular ion peaks in the mass range up to 35 kDa similar to those observed by matrix-assisted LDI. Matrix-implanted LDI when combined with ion-mobility preseparation promises to be a useful technique for molecular imaging of biotissues with a laser microprobe.

Fragmentation of highly excited small neutral carbon clusters.

We present a combined experimental and theoretical study of fragmentation of small Cn clusters (n = 5,7,9) produced in charge transfer collisions of fast (nu = 2.6 a.u.) singly charged Cn+ clusters with He. Branching ratios for all possible fragmentation channels have been measured. Comparison with microcanonical Metropolis Monte Carlo simulations based on quantum chemistry calculations allows us to determine the energy distribution of the excited clusters just after the collision.

Orthogonal time-of-flight secondary ion mass spectrometric analysis of peptides using large gold clusters as primary ions.

Secondary ion mass spectrometry (SIMS) for biomolecular analysis is greatly enhanced by the instrumental combination of orthogonal extraction time-of-flight mass spectrometry with massive gold cluster primary ion bombardment. Precursor peptide molecular ion yield enhancements of 1000, and signal-to-noise improvements of up to 20, were measured by comparing SIMS spectra obtained using Au(+) and massive Au(400) (4+) cluster primary ion bombardment of neat films of the neuropeptide fragment dynorphin 1-7. Remarkably low damage cross-sections were also measured from dynorphin 1-7 and gramicidin S during prolonged bombardment with 40 keV Au(400) (4+). For gramicidin S, the molecular ion yield increases slightly as a function of Au(400) (4+) beam fluence up to at least 2 x 10(13) Au(400) (4+)/cm(2). This is in marked contrast to the rapid decrease observed when bombarding with ions such as Au(5) (+) and Au(9) (+). When gramicidin S is impinged with Au(5) (+), the molecular ion yield decreases by a factor of 10 after a fluence of only 8 x 10(12) ions/cm(2). Comparison of these damage cross-sections implies that minimal surface damage occurs during prolonged Au(400) (4+) bombardment. Several practical analytical implications are drawn from these observations.