Electronic states of a single layer of pentacene: standing-up and flat-lying configurations

The electronic properties of a single layer (SL) of pentacene molecules are investigated by high-resolution UV photoemission and near-edge X-ray absorption spectroscopy in different configurations of the SL, either standing up on an aromatic self-assembled monolayer or planar on a bare Cu(001) substrate. The weakly interacting pentacene molecules in the standing-up SL present a semiconducting character, and the empty states distribution reflects that of gas-phase pentacene, while the planar pentacene-Cu system shows a metallic interface with redistribution of the empty molecular states. The highest-occupied molecular orbital lineshape in the weakly interacting SL shows a double structure, attributed to two nonequivalent molecules in the ordered configuration.     

A supramolecular approach to sub-ppb aromatic VOC detection in air

Micromachining technology is coupled to a selective pre-concentration material for the development of a portable sub-ppb level monitoring system for aromatic volatile organic compounds (VOC); the high sensitivity of Metal Oxide (MOX) gas sensors is combined with a supramolecular concentration unit to increase selectivity and reduce the detection limits.     

Cavitand-functionalized porous silicon as an active surface for organophosphorus vapor detection

This paper reports on the preparation of a porous silicon-based material covalently functionalized with cavitand receptors suited for the detection of organophosphorus vapors. Two different isomeric cavitands, both containing one acid group at the upper rim, specifically designed for covalent anchoring on silicon, were grafted on H-terminated porous silicon (PSi) by thermal hydrosilylation. The covalently functionalized surfaces and their complexation properties were characterized by combining different analytical techniques, namely X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and mass spectroscopy analysis coupled with thermal desorption experiments. Complexation experiments were performed by exposing both active surfaces and a control surface consisting of PSi functionalized with a structurally similar but inactive methylene-bridged cavitand (MeCav) to dimethyl methylphosphonate (DMMP) vapors. Comparison between active and inactive surfaces demonstrated the recognition properties of the new surfaces. Finally, the nature of the involved interactions, the energetic differences between active and inactive surfaces toward DMMP complexation, and the comparison with a true nerve gas agent (sarin) were studied by DFT modeling. The results revealed the successful grafting reaction, the specific host-guest interactions of the PSi-bonded receptors, and the reversibility of the guest complexation.     

Weak Equivalence of Internal Categories

Weak equivalence is defined as equivalence in the bicategory of modules between internal categories. It is known that two categories are weakly equivalent if and only if their Cauchy completions are equivalent. We prove that this condition can be generalized to a suitable notion of intermediate category, stable under composition with weak equivalences. Applications to categorical Morita theory are given.     

Analysis of complex mixtures by capillary gas chromatography with statistical estimation of the number of components

Evaluation of the number of components by the Davis-Giddings single chromatogram method is applied to capillary gas chromatograms of a dichloromethane extract of camomile. Various runs with OV-1 or Carbowax 20M as the stationary phase were done under different experimental conditions (column temperature programming rate and column length). The results showed that the number of components obtained by this statistical procedure does not depend greatly on the nature of the stationary phase or on the experimental conditions. The component number of the camomile extract was about 200 and the stand-alone probability at unit resolution was 0.2–0.3.     

Effects of colloidal and dissolved silica on the dissolution of UO2 nuclear fuel in groundwater leaching tests

The influence of aqueous silica of two different physical forms (dissolved ions and SiO₂ colloid) on the dissolution of UO₂ nuclear fuel material was investigated at 95 °C temperature in autoclaves. It was tested that SiO₂ colloids can contribute to the surface degradation or act as carrier for uranium ions during a near field geochemical dissolution process. In the presence of colloids, well-crystallized secondary phases containing U and Si were formed on the surfaces, the latter attacked by the treatment. This was not the case when dissolved Si was used. SiO₂ colloids were partly found in their original form on the surfaces after 1000 hours at 95 °C. A surface charge model suggests that this different effects are due to the development of electrostatic interactions between the UO₂ and SiO₂ surfaces.This revised version was published online in November 2005 with corrections to the Cover Date.     

Frequency distribution, isotopic composition and physical characterization of plutonium-bearing particles from the Fig-Quince zone on Runit Island, Enewetak Atoll

Runit Island on Enewetak Atoll was very heavily impacted by the U.S. nuclear testing campaign in the northern Marshall Islands (1946–58). The primary source of contamination on Runit Island was the 1958 Quince safety test where a large quantity of device plutonium (Pu) was scattered over the area near the GZ. A second low-yield device was detonated on the same site 10 days later, further disturbing the soil and leaving behind a very heterogeneous pattern of contamination including milligram-size particles of plutonium. A limited cleanup of the Fig-Quince zone was carried out in 1979. During this period, the effectiveness of the cleanup operations was primarily evaluated on the basis of bulk soil concentration data with little consideration given to the heterogeneity and long-term material-, biological-, and environmental-specific impacts of residual high activity (hot) particle contamination. The aim of the present study was twofold; (i) to characterize the levels and distribution of residual contamination in the Fig-Quince zone, and (ii) to develop pertinent data on the frequency distribution, elemental and isotopic composition, and physico-chemical properties of hot particles isolated from surface soils from Fig-Quince with a view towards providing recommendations on the future management and possible cleanup of the site. Today, Runit Island remains under an administrative quarantine.