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Peter J Eng

Publications and source records attributed to Peter J Eng.

6 recordsLinked to original sources

X-ray-induced dissociation of H2O and formation of an O2-H2 alloy at high pressure.

When subjected to high pressure and extensive x-radiation, water (H2O) molecules cleaved, forming O-O and H-H bonds. The oxygen (O) and hydrogen (H) framework in ice VII was converted into a molecular alloy of O2 and H2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrated that this crystalline solid differs from previously known phases. It remained stable with respect to variations in pressure, temperature, and further x-ray and laser exposure, thus opening new possibilities for studying molecular interactions in the hydrogen-oxygen binary system.

Journal Article↗

Determining the conformation of an adsorbed Br-PEG-peptide by long period X-ray standing wave fluorescence.

Long-period X-ray standing wave fluorescence (XSW) and X-ray reflectivity techniques are employed to probe the conformation of a Br-poly(ethylene glycol) (PEG)-peptide adsorbate at the hydrated interface of a polystyrene substrate. The Br atom on this Br-PEG-peptide construct serves as a marker atom allowing determination by XSW of its position and distribution with respect to the adsorption surface with angstrom resolution. Adsorption occurs on native or ion-beam-modified polystyrene films that are spin-coated onto a Si substrate and display either nonpolar or polar surfaces, respectively. A compact, oriented monolayer of Br-PEG-peptide can be formed with the peptide end adsorbed onto the polar surface and the PEG end terminating with the Br tag extending into the aqueous phase. The 108-141 A distance of the Br atom from the polystyrene surface in this oriented monolayer is similar to the estimated approximately 150 A length of the extended Br-PEG-peptide. This Br-polystyrene distance depends on adsorption time and surface properties prior to adsorption. Incomplete multilayers form on the polar surface after sufficient adsorption time elapses. By contrast, adsorption onto the nonpolar surface is submonolayer, patchy, and highly disordered with an isotropic Br distribution. Overall, this combination of X-ray surface scattering techniques with a novel sample preparation strategy has several advantages as a real space probe of adsorbed or covalently bound biomolecules at the liquid-solid interface.

Adsorption↗

Facilities for high-pressure research with the diamond anvil cell at GSECARS.

An overview of facilities for high-pressure research with the diamond anvil cell (DAC) at the GeoSoilEnviroCARS (GSECARS) sector at the Advanced Photon Source (Argonne, Illinois) is presented. There are three operational experimental stations (13-ID-C, 13-ID-D and 13-BM-D) where DAC instrumentation is installed for various types of experiments at high pressure and extreme temperature conditions. A fourth station (13-BM-C) is under construction and will be operational in 2006. While most X-ray diffraction experiments have been undertaken with powder samples so far, there is a growing demand for single-crystal diffraction (SCD) at high pressure. As one of the principal components at GSECARS, SCD is currently under rapid development. Other relevant techniques have also been developed for obtaining complementary information from powder or single-crystal samples at high pressure. For example, an on-line Brillouin system is installed and operational at 13-BM-D for acoustic velocity and single-crystal elasticity determinations. In addition, various X-ray spectroscopy techniques (e.g. X-ray emission and X-ray Raman) are employed for measuring electronic and magnetic properties. Future developments are discussed with the DAC program at GSECARS.

Journal Article↗

Trace metal ion partitioning at polymer film-metal oxide interfaces: long-period X-ray standing wave study.

The distributions of Pb(II) and As(V)O4(3-) ions in the interfacial region between thin poly(acrylic acid) (PAA) coatings and aalpha-A12O3(0001), alpha-Al2O3(1-102), and alpha-Fe2O3(0001) single-crystal substrates were studied using long-period X-ray standing wave fluorescent yield (XSW-FY) and X-ray reflectivity techniques. The PAA film serves as a simplified analogue of natural organic matter (NOM) coatings on mineral surfaces. Such coatings are often assumed to play an important role in the partitioning and speciation of trace heavy metals in soils and aquatic systems. On the alpha-Al2O3(1-102) surface, Pb(II) ions were found to preferentially bind to the PAA coating, even at sub-micromolar Pb(II) concentrations, and to partition increasingly onto the metal oxide surface as the Pb(II) concentration was increased ([Pb(II)] = 5 x 10(-8) to 2 x 10(-5) M, pH = 4.5; 0.01 M NaCl background electrolyte). This observation suggests that the binding sites in the PAA coating outcompete those on the alpha-Al2O3(1-102) surface for Pb(II) under these conditions. The As(V)O4(3-) oxoanion partitions preferentially to the L-Al2O3(1-102) surface for the As(V)O4(3-) concentrations examined (1 x 10(-7) to 5 x 10(-7) M, pH = 4.5; 0.01 M NaCl background electrolyte). Partitioning of Pb(II) (at 1 x 10(-7) M and pH 4.5) was also examined at PAA/alpha-Al2O3(0001), and PAA/alpha-Fe2O3(0001) interfaces using XSW-FY measurements. Our results show that the PAA coating was the dominant sink for Pb(II) in all three samples; however, the relative order of reactivity of these metal oxide surfaces with respect to Pb(II) sorption is alpha-Fe2O3(0001) > alpha-Al2O3(1-102) > alpha-Al2O3(0001). This order is consistent with that found in previous studies of the PAA-free surfaces. These XSW results strongly suggest that the characteristics of the organic film (i.e., binding affinity, type, and density of binding sites) as well as metal oxide substrate reactivity are key factors determining the distribution and speciation of Pb(II) and As(V)O4(3-) at organic film/metal oxide interfaces.

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The formation of sp3 bonding in compressed BN.

Attributed to their specific atomic bonding, the soft, graphite-like, hexagonal boron nitride (h-BN) and its superhard, diamond-like, cubic polymorph (c-BN) are important technological materials with a wide range of applications. At high pressure and temperature, h-BN can directly transform to a hexagonal close-packed polymorph (w-BN) that can be partially quenched after releasing pressure. Previous theoretical calculations and experimental measurements (primarily on quenched samples) provided substantial information on the transition, but left unsettled questions due to the lack of in situ characterization at high pressures. Using inelastic X-ray scattering to probe the boron and nitrogen near K-edge spectroscopy, here we report the first observation of the conversion process of boron and nitrogen sp(2)- and p-bonding to sp(3) and the directional nature of the sp(3) bonding. In combination with in situ X-ray diffraction probe, we have further clarified the structure transformation mechanism. The present archetypal example opens two enormous, element-specific, research areas on high-pressure bonding evolutions of boron and nitrogen; each of the two elements and their respective compounds have displayed a wealth of intriguing pressure-induced phenomena that result from bonding changes, including metallization, superconductivity, semiconductivity, polymerization and superhardness.

Boron Compounds↗

Bonding changes in compressed superhard graphite.

Compressed under ambient temperature, graphite undergoes a transition at approximately 17 gigapascals. The near K-edge spectroscopy of carbon using synchrotron x-ray inelastic scattering reveals that half of the pi-bonds between graphite layers convert to sigma-bonds, whereas the other half remain as pi-bonds in the high-pressure form. The x-ray diffraction pattern of the high-pressure form is consistent with a distorted graphite structure in which bridging carbon atoms between graphite layers pair and form sigma-bonds, whereas the nonbridging carbon atoms remain unpaired with pi-bonds. The high-pressure form is superhard, capable of indenting cubic-diamond single crystals.

Journal Article↗