Structure determination in a new type of amorphous molecular solids with different nonlinear optical properties: a comparative structural analysis.

The microscopic structures of two amorphous molecular solids with extremely nonlinear optical properties have been studied. They consist of organotetrel chalcogenide clusters with the chemical formula [(RSn)4S6]. The basic molecular building blocks are adamantane-like {Sn4S6} cores with organic ligands R attached to the Sn atoms. While the material equipped with R=naphthyl generates frequency doubling upon irradiation with a simple infrared laser diode, the material decorated with R=phenyl responds by emitting brilliant white light. The structural differences were investigated using x-ray scattering and extended x-ray absorption fine structure combined with molecular Reverse Monte Carlo. Transmission electron microscopy and scanning precession electron diffraction were used to examine structural differences from mesoscopic down to microscopic scales. Characteristic differences were found on all scales. While close core-to-core distances between {Sn4S6} cluster cores and molecular distortions are found in the white light emitting material, undistorted molecules and significantly larger core distances characterize the material showing frequency doubling. Here however, results of scanning precession electron diffraction reveal the formation of nanocrystalline structures in the amorphous matrix, which we identify as cause for the suppression of white light emission.

Structural origins of the unusual thermal stability of amorphous CuxGe50-xTe50(0⩽x⩽33.3).

We have investigated the local atomic structures of several compositions of the amorphous phase of the system CuxGe50-xTe50(0⩽x⩽33.3), based on extended x-ray absorption fine-structure as well as anomalous x-ray scattering experiments, and discuss the unusual trend regarding their thermal stability as a function of the Cu content. At low concentrations (x⩽15), Cu atoms tend to agglomerate in flat nanoclusters reminiscent of the crystalline phase of metallic Cu, leading to a more and more Ge-deficient Ge-Te host network structure with growing Cu content and an increasing thermal stability. At higher Cu concentrations (x⩾25), Cu is incorporated into the network, leading to an overall weaker bonding situation which is associated with a decreasing thermal stability.

Collective particle dynamics of molten NaCl by inelastic x-ray scattering.

An inelastic x-ray scattering experiment has been performed on molten NaCl over wide wave vector and energy transfer ranges. Data of high statistical quality are analyzed using a memory function approach within a generalized Langevin equation. The approach with two relaxation times for the memory function provides a very good data description over the whole wave vector range beyond the hydrodynamic regime. A slow thermal and a fast structural relaxation process in the memory function completely define the density fluctuations in molten NaCl and evidences the thermal-viscoelastic model as the minimal description for collective particle dynamics in molten alkali halides. The obtained excitation frequencies demonstrate a large positive dispersion effect, which can be related to the viscoelastic reaction of the molten salt. A transition from the viscoelastic to a hydrodynamic response of the molten salt at small wave vectors is observed. In the hydrodynamic regime the resulting thermal diffusivity agrees well with values obtained through light scattering. The modeling indicates some deficiencies at small wave vectors and large energy transfers and the spectra of the current correlation function evidences additional intensity at high frequency. The frequency of these additional modes approach a non-zero value at zero wave vector and indicates a non-acoustic character of these excitations. The frequency center of this additional inelastic intensity coincides with optic-type modes in molten NaCl predicted by simulations.

An equation of state for expanded metals.

We present a model equation of states for expanded metals, which contains a pressure term due to a screened-Coulomb potential with a screening parameter reflecting the Mott-Anderson metal-to-nonmetal transition. As anticipated almost 80 years ago by Zel'dovich and Landau, this term gives rise to a second coexistence line in the phase diagram, indicating a phase separation between a metallic and a nonmetallic liquid.

A high-flux upgrade for the BRISP spectrometer at ILL.

To date, the BRISP spectrometer represents the state-of-the-art for every instrument aiming to perform Brillouin neutron scattering. Exploiting accurate ray-tracing McStas simulations, we investigate an improved configuration of the BRISP primary spectrometer to provide a higher flux at the sample position, while preserving all the present capabilities of the instrument. This configuration is based on a neutron guide system and is designed to fit the instrument platform with no modifications of the secondary spectrometer. These evaluations show that this setup can achieve a flux gain factor ranging from 3 to 6, depending on the wavelength. This can expand the experimental possibilities of BRISP towards smaller samples, possibly using also complex sample environments.

Experimental evidence for a dynamical crossover in liquid aluminium.

The temperature dependence of the dynamic structure factor at next-neighbour distances has been investigated for liquid aluminium. This correlation function is a sensitive parameter for changes in the local environment and its Fourier transform was measured in a coherent inelastic neutron scattering experiment. The zero frequency amplitude decreases in a nonlinear way and indicates a change in dynamics around 1.4 ∙ Tmelting. From that amplitude a generalized viscosity can be derived which is a measure of local stress correlations on next-neighbour distances. The derived generalized longitudinal viscosity shows a changing slope at the same temperature range. At this temperature the freezing out of degrees of freedom for structural relaxation upon cooling sets in which can be understood as a precursor towards the solid state. That crossover in dynamics of liquid aluminium shows the same signatures as previously observed in liquid rubidium and lead, indicating an universal character.

Transition from hydrodynamic to viscoelastic propagation of sound in molten RbBr.

Inelastic neutron scattering was applied to measure the acoustic-type excitations in the molten alkali halide rubidium bromide. For molten RbBr neutron scattering is mainly sensitive to the number density fluctuation spectrum and is not influenced by charge fluctuations. Utilizing a dedicated Brillouin scattering spectrometer, we focused on the small-wave-vector range. From inelastic excitations in the spectra a dispersion relation was obtained, which shows a large positive dispersion effect. This frequency enhancement is related to a viscoelastic response of the liquid at high frequencies. Towards small wave vectors we identify the transition to hydrodynamic behavior. This observation is supported by a transition of the sound velocity from a viscoelastic enhanced value to the adiabatic speed of sound for the acoustic-type excitations. Furthermore, the spectrum transforms into a line shape compatible with a prediction from hydrodynamics.

Transverse excitations in liquid Sn.

Transverse acoustic (TA) excitation modes were observed in inelastic x-ray scattering (IXS) spectra of liquid Sn. The excitation energies and widths of the TA modes are in good agreement with results of an ab initio molecular dynamics simulation. By comparing current correlation spectra between the experimental and theoretical results quantitatively, we have concluded that the TA modes can be detected experimentally through the quasi-TA branches in the longitudinal current correlation spectra. The lifetime and propagation length of the TA modes were determined to be ~0.7 ps and 0.8-1.0 nm, respectively, corresponding to the size of cages formed instantaneously in liquid Sn.

Transverse acoustic excitations in liquid Ga.

The transverse acoustic excitation modes were detected by inelastic x-ray scattering in liquid Ga in the Q range above 9 nm(-1) although liquid Ga is mostly described by a hard-sphere liquid. An ab initio molecular dynamics simulation clearly supports this finding. From the detailed analysis for the S(Q,omega) spectra with a good statistic quality, the lifetime of 0.5 ps and the propagating length of 0.4-0.5 nm can be estimated for the transverse acoustic phonon modes, which may correspond to the lifetime and size of cages formed instantaneously in liquid Ga.

High frequency dynamics in liquid nickel: An inelastic x-ray scattering study.

Owing to their large relatively thermal conductivity, peculiar, nonhydrodynamic features are expected to characterize the acousticlike excitations observed in liquid metals. We report here an experimental study of collective modes in molten nickel, a case of exceptional geophysical interest for its relevance in earth interior science. Our result shed light on previously reported contrasting evidences: In the explored energy-momentum region, no deviation from the generalized hydrodynamic picture describing nonconductive fluids is observed. Implications for high frequency transport properties in metallic fluids are discussed.

The possibility of transverse excitation modes in liquid Ga.

The dynamic structure factor S(Q,ω) of liquid Ga was measured at 100 °C using a high resolution inelastic x-ray scattering (IXS) spectrometer at 3-ID-C/APS. The spectra obtained clearly demonstrate the existence of longitudinal propagating modes at small Q values, like a previous IXS result at 42 °C obtained by Scopigno et al and an inelastic neutron scattering (INS) one at 47 °C obtained by Bove et al, but unlike an INS study at 57 °C by Bermejo et al. The dispersion relation of the excitations deviates positively from the hydrodynamic prediction by about 13%. There are two new findings from this experiment. Firstly, an additional lower energy excitation is necessary to reproduce S(Q,ω) spectra in the Q range beyond 10 nm(-1), in agreement with the result of a first-principles molecular dynamic simulation, which may indicate a transverse acoustic mode in this peculiar liquid metal. Secondly, the quasielastic line comprises a Gaussian contribution at Q values near the first maximum in S(Q), which may indicate the existence of short-lived covalent correlation in liquid Ga with a lifetime of 0.39 ps.

State dependent particle dynamics in liquid alkali metals.

This paper gives a survey of the particle dynamics in the liquid alkali metals observed with inelastic x-ray and neutron scattering experiments. Liquid rubidium and sodium are chosen as model fluids to represent the behaviour of this group of fluids. In the dense metallic monatomic melt the microscopic dynamics is characterized by collective excitations similar to those in the corresponding solids. The collective particle behaviour is appropriately described using a memory function formalism with two relaxation channels for the density correlation. A similar behaviour is found for the single particle motion where again two relaxation mechanisms are needed to accurately reproduce the experimental findings. Special emphasis is given to the density dependence of the particle dynamics. An interesting issue in liquid metals is the metal to non-metal transition, which is observed if the fluid is sufficiently expanded with increasing temperature and pressure. This causes distinct variations in the interparticle interactions, which feed back onto the motional behaviour. The associated variations in structure and dynamics are reflected in the shape of the scattering laws. The experimentally observed features are discussed and compared with simple models and with the results from computer simulations.

Changes in acid precipitation-related water chemistry of lakes from southwestern New Brunswick, Canada, 1986-2001.

Between 1986 and 2001, thirty-nine lakes in southwestern New Brunswick in Atlantic Canada were surveyed for acid precipitation-related water quality changes. Most of the study lakes are located on granite bedrock and represent the most acid sensitive lakes in the province. Between 1987 and 1992, hydrogen ion deposition to the lake study area averaged 452 eq ha(-1) yr(-1), compared to 338 eq ha(-1) yr(-1) between 1993 and 2000, a 25% reduction. The lake chemistry data were evaluated by dividing the lakes into four clusters for each survey year based on their acid neutralizing capacity. Twenty percent of the lakes (cluster IV) had an average ANC of 40 microeq L(-1) or greater and maintained an average pH of greater than 6 over the duration of the study period. A pH of 6 or greater is considered a healthy benchmark for maintaining biodiversity. The remaining 31 lakes (clusters I to III) had an average ANC of less than 40 microeq L(-1) and maintained an average pH of less than 6. Other lake chemistry changes included a general decline in lake sulphate and colour over the duration of the survey period, followed by more recent improvements in calcium ion, pH and ANC, and notably higher but declining aluminum levels in lower ANC and pH lakes. Nitrate accounted for 37% of the acid deposition to the study area, however it was not detectable in the lakes. Although acid deposition has declined and these lakes are beginning to show signs of acid recovery, 80% of the study lakes remain acid sensitive having little buffering capacity with low calcium, pH and ANC.

The need for integrated linkages and long-term monitoring of mercury in Canada.

A nation-wide ecosystem science network for Canada was formed in 1994. At that time, mercury was a re-emerging issue in Canada and the Coordinating Office for the network sought collaboration to assess the issue. The key mechanisms by which the network has added value in addressing this issue are: 1) Information Dissemination, the network has organised, facilitated and co-hosted a number of regional. national and international mercury events (meetings, conferences and workshops) which have served to bring the expertise together, the network also disseminates information on it's web page. and the Coordinating Office hosts an annual National Science Conference: 2) Collaborative Mercury Monitoring, network partners advocated the need for a single hemispheric mercury network which resulted in the development of a compatible Canada-U.S. mercury deposition network, which may also be expanded into Mexico, and 3) Environmental Reporting, the network has collaborated with others to report on current mercury findings through initiatives such as the 1998 Northeast States and Eastern Canadian Mercury Study, a 1999 Mercury Case Study and is presently a partner in the University of Quebec's proposal to form a Collaborative Mercury Ecosystem Research Network in Canada.

The Northeast States and Eastern Canadian Provinces mercury study: a framework for action: summary of the Canadian chapter.

The objective of this paper is to give an overview of the findings of the Canadian chapter of the Northeast States and Eastern Canadian Provinces Mercury Study, which was conducted between 1995 and 1998. The Canadian chapter provided information on mercury emissions, sources and levels in air, water, biota and humans. Industry, governments and universities provided information for the Canadian chapter. The study showed that the Northeast States and Eastern Canadian Provinces (NES/ECP) is a region impacted by airborne mercury. Annual mercury emissions for the NES/ECP region are estimated to be approximately 19 t (12%) of the combined Canadian and US national anthropogenic mercury emissions of 155 t/year. 210Pb-dated lake sediment cores from Atlantic Canada showed a mercury enrichment factor of 2.5 for coastal sites with mercury increases starting in 1860. Regional mercury wet deposition for the NES/ECP region was 7-11 microg/m2/year. Provincial and federal fish health advisories have been updated in the ECP for children and women of child-bearing age limiting the consumption of freshwater fish, as well as fresh or frozen shark, tuna or swordfish.

Developing consensus: mercury science and policy in the NAFTA countries (Canada, the United States and Mexico).

The international science community has recognized methylmercury in the aquatic food chain, as a potential environmental and human health risk. As a result, countries around the world have implemented a number of mercury management initiatives. The United States, Mexico and Canada in consultation with stakeholders are developing a trilateral North American Regional Action Plan (NARAP) on mercury. Through public involvement in the decision making process, the NARAP has offered opportunities for more transparency in transactions between governments, industry and stakeholders. In spite of the available scientific information, there are still important uncertainties associated with the mercury issue. These knowledge gaps include: the most appropriate methylmercury reference dose for sensitive groups; the percentage of the North American population that is at risk from methylmercury exposure; spatial and temporal mercury deposition patterns in each country; the link between mercury emissions, atmospheric deposition and methylmercury concentrations in fish; and the relative magnitude of contributions from natural and anthropogenic sources.

Lead, cadmium, arsenic and zinc in the ecosystem surrounding a lead smelter.

A lead smelter has been operating at Belledune in the province of New Brunswick, in eastern Canada, since 1966. This paper presents data on the concentrations of the four primary metals emitted from the smelter - lead, cadmium, arsenic and zinc - which were measured in the terrestrial environment near the smelter and the concentrate transport route. Deposition of these metals to the snowpack and the uptake by grass forage are discussed in relation to non-regulatory guidelines, toxicity and atmospheric emissions. A 1992 snowpack transect survey extending 0.5-40 km northwest, southeast and south of the smelter revealed lead concentrations of 2-3193 ppb, cadmium <0.10-49.7 ppb, arsenic <3.0-72.0 ppb, and zinc 3-401 ppb. Deposition estimates within this zone for lead were between 0.046 and 20.1 kg/ha/yr, cadmium <0.007 and 313 g/ha/yr, arsenic <0.016 and 453 g/ha/yr and zinc 0.020 and 2.52 kg/ha/yr. Concentrations of these metals in the snowpack were highest within 3 km of the smelter and were detectable at greater distances SE of the smelter. Lead was dispersed greater distances from the smelter than cadmium or arsenic. Snowpack samples collected within 5-20 m of the railway contained 140-7270 ppb of lead, 0.4-36.9 ppb of cadmium, <3.0-72.0 ppb of arsenic and 41-13100 ppb of zinc. Grass forage sampled within 0.6-16 km of the smelter contained lead 5-152 ppm, cadmium 0.10-4.1 ppm, and zinc 22-154 ppm. Highest concentrations of lead, cadmium and zinc in grass forage were found were found within 2.2 km of the smelter. Grass forage collected within 10-70 m of the railway contained lead 13-288 ppm, cadmium 0.4-1.3 ppm and zinc 98-831 ppm.

Identification of synthetic retinoids with selectivity for human nuclear retinoic acid receptor gamma.

The action of retinoids on gene regulation is mediated by three distinct nuclear retinoic acid receptor (RAR) subtypes called RAR alpha, beta and gamma. Since RAR gamma is predominantly expressed in adult skin, specific ligands for this subtype could (i) represent valuable tools to evaluate the biological role of RAR gamma in skin and (ii) provide therapeutic entities with a higher therapeutic index at lower teratogenic risk. Using in vitro binding studies and a functional transactivation assay, we have identified three compounds with high RAR gamma selectivity.

Selective synthetic ligands for human nuclear retinoic acid receptors.

From a series of naphthalene and benzoic acid derivatives we have identified synthetic retinoic acid analogues exhibiting high selectivity for the nuclear retinoic acid receptors RAR alpha (Am 580), RAR beta (CD 2019) and RAR gamma (CD 437) as well as ligands sharing high affinities for all RAR subtypes (CD 367). The compounds were evaluated in two complementary screening systems: (1) binding to nuclear proteins extracted from COS-7 cells after transfection with the appropriate expression vectors, and (2) induction of plasminogen activator in the embryonic mouse teratocarcinoma cell line F9. All compounds behaved as retinoic acid agonists in the F9 test.

Peritonitis and the patient with human immunodeficiency virus (HIV).

The prevalence of HIV positive patients (HIV pts) with ESRD is likely to increase and many will be going on CAPD. There are, however, factors which cause one to be concerned about a possible increased risk of peritonitis in these patients. These include not only their impaired immune and nutritional status, but often their mental status. We examined the incidence and type of peritonitis among the 184 patients who have been in our program since December 1983 for a total of 4,017 patient months (pt mo). During this time we treated 9 known HIV pts (4 drug users and 5 homosexuals) for a total of 114 pt mos. We also looked at albumin, cholesterol, and creatinine as possible risk markers. We found a greater than two fold incidence of peritonitis in the HIV positive patients and that low albumin was a significant risk factor in the HIV negative patients, but not in the HIV positive patients.