The reactive chemisorption of alkyl iodides at Cu(110) and Ag(111) surfaces: a combined STM and XPS study

The chemisorption of methyl and phenyl iodide has been studied at Cu(110) and Ag(111) surfaces at 290 K with STM and XPS. At both surfaces dissociative adsorption of both molecules leads to chemisorbed iodine, with the STM showing c(2 x 2) and (square root 3 x square root 3)R30 structures at the Cu(110) and Ag(111) surfaces, respectively. At the Cu(110) surface a comparison of coexisting c(2 x 2) I(a) and p(2 x 1) O(a) domains shows the iodine adatoms to be chemisorbed in hollow sites with evidence at low coverage for diffusion in the (110) direction. In the case of methyl iodide no carbon adsorption is observed at either the silver or the copper surfaces, but chemisorbed phenyl groups are imaged at the Cu(110) surface after exposure to phenyl iodide. The STM images show the phenyl groups as bright features approximately 0.7 nm in diameter and 0.11 nm above the iodine adlayer, reaching a maximum surface concentration after approximately 6 Langmuir exposure. However, the phenyl coverage decreases with subsequent exposures to PhI and is negligible by approximately 1000 L exposure, consistent with the formation and desorption of biphenyl. The adsorbed phenyls are located above hollow sites in the substrate, they are stabilized at the top and bottom of step edges and in paired chains (1.1 nm apart) on the terraces with a regular interphenyl spacing within the chains of 1.0 nm in the (110) direction. The interphenyl ring spacing and diffusion of individual phenyls from within the chains shows that the chains do not consist of biphenyl species but may be a precursor to their formation. Although the XPS data shows carbon present at the Ag(111) surface after exposure to PhI, no features attributable to phenyl groups were observed by STM.     

Sum frequency generation from Langmuir-Blodgett multilayer films on metal and dielectric substrates

Sum frequency generation (SFG) vibrational spectra of cadmium arachidate multilayer films adsorbed on a substrate with high nonresonant susceptibility, i.e., gold, and on a low nonresonant susceptibility substrate, i.e., fused quartz, have been investigated in the C-H stretching region in air. The films were formed by Langmuir-Blodgett (LB) deposition and their spectra recorded using SFG spectrometers employing both 532-nm nanosecond and 800-nm femtosecond lasers, with counter-propagating and co-propagating beam geometries, respectively. Both kinds of substrate were rendered hydrophobic by coating them with per-deuterated octadecanethiol (gold) or per-deuterated cadmium arachidate (fused quartz) monolayers. Single per-protonated arachidate layers in otherwise per-deuterated 10-layer films were used to show that the SFG resonances arise only from the topmost and lowermost layers in a LB film comprised of an even number of per-protonated layers, although the SFG spectra from the two hydrophobic substrates are different from each other. The differences in the spectra from the same ten-layer per-protonated films deposited on the two types of hydrophobic substrate have been explained in terms of a simple model that accounts for resonant and nonresonant contributions.     

A Simulation Model for Planning Services for Renal Patients in Europe

A discrete-event simulation model is being developed to provide information for national and regional health planners about the effect of different treatment policies and practices on the increasing numbers of patients with irreversible kidney failure. The simulation program, written in Pascal using Pascal-SIM, describes the activities of individual patients whose progress through treatment depends on their characteristics and treatment history, as well as on treatments availability. Programming techniques have been developed to cope with the multiple scheduling of patient entities and the resultant queue-management problems. In order to provide simulation runs on request, for any population group, appropriate data is selected from the European Dialysis and Transplant Association Registry data base for use in the simulation program. Results are shown on a computer screen while the simulation is running, and are saved for further analysis to provide feedback to the requesting organization.     

Photo-oxidation of proteins and its role in cataractogenesis.

Proteins comprise approximately 68% of the dry weight of cells and tissues and are therefore potentially major targets for photo-oxidation. Two major types of processes can occur with proteins. The first of these involves direct photo-oxidation arising from the absorption of UV radiation by the protein, or bound chromophore groups, thereby generating excited states (singlet or triplets) or radicals via photo-ionisation. The second major process involves indirect oxidation of the protein via the formation and subsequent reactions of singlet oxygen generated by the transfer of energy to ground state (triplet) molecular oxygen by either protein-bound, or other, chromophores. The basic principles behind these mechanisms of photo-oxidation of amino acids, peptides and proteins and the potential selectivity of damage are discussed. Emphasis is placed primarily on the intermediates that are generated on amino acids and proteins, and the subsequent reactions of these species, and not the identity or chemistry of the sensitizer itself, unless the sensitizing group is itself intrinsic to the protein. A particular system is then discussed--the cataractous lens--where UV photo-oxidation may play a role in the aetiology of the disease, and tryptophan-derived metabolites act as UV filters.     

Spectral properties of Neumann Laplacian of horns

We study the Neumann Laplacian of unbounded regions in ⁿ with cusps at infinity so that the corresponding Dirichlet Laplacian has compact resolvent. Typical of our results is that of the region {(x, y)²x, y|<1} the Neumann Laplacian has absolutely continuous spectrum [0, ) of uniform multiplicity four and an infinity of eigenvaluesE _o<E ₁... and that for the region {(x, y)²y|1}, it has absolutely continuous spectrum [1/4, ) of uniform multiplicity 2 and an infinity of eigenvaluesE ₀=0<E ₁.... We use the Enss theory with a suitable asymptotic dynamics.The second author's research is partially funded under NSF grand number DMS-8801918     

Development of a 3-D, multi-nuclear continuous wave NMR imaging system

The development of a 3-D, multi-nuclear continuous wave NMR imaging (CW-NMRI) system is described and its imaging capability is demonstrated on a range of materials exhibiting extremely short T(2) relaxation values. A variety of radiofrequency resonators were constructed and incorporated into a new gradient and field offset coil assembly, while the overall system design was modified to minimise microphonic noise which was present in an earlier prototype system. The chemically combined (27)Al in a high temperature refractory cement was imaged, and the CW-NMRI system was found to be sensitive to small differences in (27)Al content in these samples. The penetration of (23)Na in salt water into samples of ordinary Portland cement (OPC) was investigated, with enhanced uptake observed for samples with larger pore size distributions. The solid (13)C component in a carbonated cement sample was also imaged, as were the (7)Li nuclei in a sample of powdered Li(2)CO(3). A spatial resolution of 1mm was measured in an image of a rigid polymeric material exhibiting a principal T( *)(2) value of 16.3 micros. Finally, a high-resolution 3-D image of this rigid polymer is presented.     

The LEBIT facility at MSU

The low-energy beam and ion trap facility LEBIT at the NSCL at MSU has demonstrated that rare isotopes produced by fast-beam fragmentation can be slowed down and prepared such that precision experiments with low-energy beams are possible. For this purpose high-pressure gas-stopping is employed combined with advanced ion manipulation techniques. Penning trap mass measurements on short-lived rare isotopes have been performed with a 9.4 T Penning trap mass spectrometer. Examples include ⁶⁶As, which has a half-live of only 96 ms, and the super-allowed Fermi-emitter ³⁸Ca, for which a mass accuracy of 8 ppb (280 eV) has been achieved. The high accuracy of this new mass value makes ³⁸Ca a new candidate for the test of the conserved vector current hypothesis.      

Experiments with thermalized rare isotope beams from projectile fragmentation: a precision mass measurement of the superallowed beta emitter 38Ca

The mass of the short-lived radio nuclide 38Ca (T(1/2) = 440 ms) has been measured with the 9.4-T Penning trap mass spectrometer of the Low-Energy Beam and Ion Trap Facility. A mass uncertainty of deltam = 280 eV has been achieved, corresponding to deltam/m = 8 x 10(-9). The result makes 38Ca, a superallowed beta emitter, a new candidate to test the conserved-vector-current hypothesis. The experiment is also the first demonstration that short-lived radioactive isotopes produced by projectile fragmentation of relativistic heavy-ion beams can be slowed down and prepared such that precision experiments of this kind are possible.     

Time-dependent strength of colloidal gels

Colloidal silica gels are shown to stiffen with time, as demonstrated by both dynamic light scattering and bulk rheological measurements. Their elastic moduli increase as a power law with time, independent of particle volume fraction; however, static light scattering indicates that there are no large-scale structural changes. We propose that increases in local elasticity arising from bonding between neighboring colloidal particles can account for the strengthening of the network, while preserving network structure.