Inelastic mean-free path and mean escape depth of 10-140 eV electrons in SiO2 nanoparticles determined by Si 2p photoelectron yields.

We report on photoelectron spectra of SiO2 nanoparticles (d = 157 ± 6 nm) above the Si 2p threshold in the photon energy range 118-248 eV with electron kinetic energy 10-140 eV and analyze the photoelectron yield as a function of photon energy. Comparison of the experimental results with Monte-Carlo simulations on electron transport allows us to quantify the inelastic mean-free path and mean escape depth of photoelectrons in the nanoparticle samples. The influence of the nanoparticle geometry and electron elastic scattering on photoelectron yields is highlighted. The results show that the previously proposed direct proportionality of the photoelectron signal to the inelastic mean-free path or the mean escape depth does not hold for photoelectron kinetic energies below 30 eV due to the strong influence of electron elastic scattering. The present results deviate for photoelectron kinetic energies below 30 eV from the previously proposed direct proportionality of the photoelectron signal to the inelastic mean-free path or the mean escape depth, which is the result of a strong influence of electron elastic scattering. The presented inelastic mean-free paths and mean escape depths appear to be useful for the quantitative interpretation of photoemission experiments on nanoparticles and for modeling of the experimental results.

Unfolding dynamics of a beta-sheet protein studied by mass spectrometry.

The unfolding dynamics of cellular retinoic acid-binding protein I (CRABP I), an 18 kDa predominantly beta-sheet protein, were studied by monitoring the hydrogen-deuterium (H-D) exchange reaction under various solution conditions. A bimodal charge state distribution was observed when a denaturing agent was added to the protein aqueous solution. These two populations exhibit different kinetics of H-D exchange, with the high charge state ions undergoing very rapid isotope exchange, while the low charge state protein ions exchange cooperatively but at much slower rates. Transiently populated intermediate states were detected indirectly using hydrogen exchange measurement in aqueous solution at various pHs. At pH 2.5 and room temperature, three distinct populations of CRABP I ions exist over an extended period of time, each corresponding to a specific degree of backbone amide hydrogen atom protection. Mass spectral data are complementary to hydrogen exchange measurements by NMR, since the former samples a much faster time-scale of dynamic events in solution.

Detection of fast capillary electrophoresis peptide and protein separations using electrospray ionization with a time-of-flight mass spectrometer.

Fast capillary electrophoresis (CE) separations on bare and coated fused silica have been detected on-line using a time-of-flight mass spectrometer which is capable of acquiring spectra at a rate suitable for the narrow peaks generated by CE. Protein and peptide separations producing peaks 1-2 s in width have been detected with an integration time of 0.125 s/spectrum, each spectrum being the sum of 1024 complete m/z range scans. The effects of the liquid sheath flow rate, electric field strength, and integration time on sensitivity and peak shape have been examined. A sensitivity limit of 8 fmol has been established for leucine enkephalin.