XPS characterization of Bi and Mn collected on atom-trapping silica for AAS

The chemical state of analyte species collected on a water-cooled silica tube during atom-trapping atomic absorption spectrometric determination is investigated with the use of X-ray photoelectron spectroscopy (XPS) for Bi and Mn. Analysis of the Bi 4f(7/2) peak reveals that the chemical state of Bi is +3 during initial trapping (before the atomization stage), but an additional 0-valence state of Bi is also observed after the atomization stage. With the use of the measured Mn 2p(3/2) binding energy together with the observed 3s multiplet splitting, the chemical state of Mn is determined as +2 in all stages. Together with our previous determination of 0 valence for Au, it is now postulated that the stability of certain valence states of the three elements (Au, Bi, and Mn) on the silica matrix can be correlated to their electrochemical reduction potentials

Modification of the Size of Supported Clusters by Coadsorption of an Organic Compound: Gold and l-Cysteine on Rutile TiO(2)(110).

Using X-ray photoelectron spectroscopy we studied the coadsorption of the amino acid l-cysteine and gold on a rutile TiO(2)(110) surface under ultrahigh vacuum conditions. Irrespective of the deposition order, i.e., irrespective of whether l-cysteine or gold is deposited first, the primary interaction between l-cysteine and the gold clusters formed at the surface takes place through the deprotonated thiol group of the molecule. The deposition order, however, has a profound influence on the size of the gold clusters as well as their location on the surface. If l-cysteine is deposited first the clusters are smaller by a factor two to three compared to gold deposited onto the pristine TiO(2)(110) surface and then covered by l-cysteine. Further, in the former case the clusters cover the molecules and thus form the outermost layer of the sample. We also find that above a minimum gold cluster size the gold cluster/l-cysteine bond is stronger than the l-cysteine/surface bridging oxygen vacancy bond, which, in turn, is stronger than the gold cluster/vacancy bond

XPS characterization of Bi and Mn collected on atom-trapping silica for AAS

The chemical state of analyte species collected on a water-cooled silica tube during atom-trapping atomic absorption spectrometric determination is investigated with the use of X-ray photoelectron spectroscopy (XPS) for Bi and Mn. Analysis of the Bi 4f7/2 peak reveals that the chemical state of Bi is +3 during initial trapping (before the atomization stage), but an additional 0-valence state of Bi is also observed after the atomization stage. With the use of the measured Mn 2p3/2 binding energy together with the observed 3s multiplet splitting, the chemical state of Mn is determined as +2 in all stages. Together with our previous determination of 0 valence for Au, it is now postulated that the stability of certain valence states of the three elements (Au, Bi, and Mn) on the silica matrix can be correlated to their electrochemical reduction potentials

X-ray photoelectron spectroscopic characterization of Au collected with atom trapping on silica for atomic absorption spectrometry

The nature of analyte species collected on a cooled silica tube for atom-trapping atomic absorption spectrometric determination was investigated with the use of X-ray photoelctron spectroscopy (XPS). An XPS spectrum of gold deposited on atom-trapping silica tubes reveals a Au 4f7/2 peak with a binding energy of 84.8 (±0.2) eV, which falls in the middle of the binding energies corresponding to zerovalent Au(0) at 84.0 eV and that of monovalent Au(I) at 85.2 eV. The corresponding energy for Au vapor deposited on silica is also 84.8 eV. Deposition of AuCl4- solution on silica results in two different Au 4f7/2 peaks with binding energies of 84.8 and 87.3 eV corresponding, respectively, to Au(0) and Au(III). Deposition of the same AuCl4- solution on platinum metal again gives two peaks, this time at 84.4 and 87.0 eV energies corresponding again to Au(0) and Au(III). Combining all these data, we conclude that gold is trapped on atom-trapping silica surface as zerovalent Au(0) with a 0.8-eV matrix shift with respect to the metal surface. A similar 0.6-eV shift is also observed between the binding energy of 4f7/2 Hg22+ measured in Hg2(NO3)2·2H2O powder and that deposited on silica

A chemical genetic approach reveals distinct EphB signaling mechanisms during brain development.

EphB receptor tyrosine kinases control multiple steps in nervous system development. However, it remains unclear whether EphBs regulate these different developmental processes directly or indirectly. In addition, given that EphBs signal through multiple mechanisms, it has been challenging to define which signaling functions of EphBs regulate particular developmental events. To address these issues, we engineered triple knock-in mice in which the kinase activity of three neuronally expressed EphBs can be rapidly, reversibly and specifically blocked. We found that the tyrosine kinase activity of EphBs was required for axon guidance in vivo. In contrast, EphB-mediated synaptogenesis occurred normally when the kinase activity of EphBs was inhibited, suggesting that EphBs mediate synapse development by an EphB tyrosine kinase-independent mechanism. Taken together, our data indicate that EphBs control axon guidance and synaptogenesis by distinct mechanisms and provide a new mouse model for dissecting EphB function in development and disease

Ammonia adsorption on iron phthalocyanine on Au(111): Influence on adsorbate-substrate coupling and molecular spin.

The adsorption of ammonia on Au(111)-supported monolayers of iron phthalocyanine has been investigated by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and density functional theory calculations. The ammonia-induced changes of the x-ray photoemission lines show that a dative bond is formed between ammonia and the iron center of the phthalocyanine molecules, and that the local spin on the iron atom is quenched. This is confirmed by density functional theory, which also shows that the bond between the iron center of the metalorganic complex and the Au(111) substrate is weakened upon adsorption of ammonia. The experimental results further show that additional adsorption sites exist for ammonia on the iron phthalocyanine monolayer

Pyridine Adsorption on Single-Layer Iron Phthalocyanine on Au(111)

The adsorption of pyridine on monolayers of well-ordered, flat-lying iron phthalocyanine molecules on Au(111) is investigated by X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and density functional theory. It is found that pyridine both coordinates to the iron site of iron phthalocyanine and binds weakly to other sites. The iron coordination causes significant changes in the electronic structure of the iron phthalocyanine compound, with the implication of a change of the spin properties of the iron atoms due to the strong ligand field created by the pyridine axial ligand. Both low coverages and multilayer coverages of pyridine are considered. At low doses, the pyridine molecules are ordered, whereas in multilayers, no preferred orientation is observed. The orientation of the FePc molecules with respect to the Au(111) surface is not affected by the adsorption of pyridine

Mitochondria as a Target of Environmental Toxicants

Enormous strides have recently been made in our understanding of the biology and pathobiology of mitochondria. Many diseases have been identified as caused by mitochondrial dysfunction, and many pharmaceuticals have been identified as previously unrecognized mitochondrial toxicants. A much smaller but growing literature indicates that mitochondria are also targeted by environmental pollutants. We briefly review the importance of mitochondrial function and maintenance for health based on the genetics of mitochondrial diseases and the toxicities resulting from pharmaceutical exposure. We then discuss how the principles of mitochondrial vulnerability illustrated by those fields might apply to environmental contaminants, with particular attention to factors that may modulate vulnerability including genetic differences, epigenetic interactions, tissue characteristics, and developmental stage. Finally, we review the literature related to environmental mitochondrial toxicants, with a particular focus on those toxicants that target mitochondrial DNA. We conclude that the fields of environmental toxicology and environmental health should focus more strongly on mitochondri

Thermal Characterization of Polycrystalline CVD Diamond Thin Films

An experimental thermal characterization method is developed for high thermal conductivity thin films. The method utilizes Ta/Pt resistors on microfabricated free-standing thin film structures both for heating and temperature monitoring at different positions on the structures. The steady-state temperature at the heater and the sensor positions are monitored as a function of the power dissipated by the heater under vacuum environment, and the thermal conductivity is estimated by comparing these results to FEA and/or analytical models. The developed method is used to characterize the thermal conductivity of various different CVD diamond films of different grain sizes and films thicknesses. The measured thermal conductivity values range from 15 W/m·K to 300 W/m·K, which are at least one order of magnitude lower than that of natural diamond. It is also shown that the thermal conductivity of such films in the in-plane direction increases with increasing grain size and film