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1.
Phys Rev Lett ; 107(11): 116805, 2011 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-22026694

RESUMEN

Using resonant x-ray spectroscopies combined with density functional calculations, we find an asymmetric biaxial strain-induced d-orbital response in ultrathin films of the correlated metal LaNiO3 which are not accessible in the bulk. The sign of the misfit strain governs the stability of an octahedral "breathing" distortion, which, in turn, produces an emergent charge-ordered ground state with an altered ligand-hole density and bond covalency. Control of this new mechanism opens a pathway to rational orbital engineering, providing a platform for artificially designed Mott materials.

2.
Science ; 258(5083): 775-8, 1992 Oct 30.
Artículo en Inglés | MEDLINE | ID: mdl-1439784

RESUMEN

An x-ray resonance effect in an organic thin film on an x-ray reflecting mirror is reported. The resonance effect is the result of interference between reflected and refracted x-rays at the air-organic thin film interface and occurs at incident angles slightly above the critical angle of the film. In excellent agreement with theory, the primary resonant x-ray electric field that is confined in the organic thin film is approximately 20 times as intense as the electric field of the incident beam when measured at a position close to the center of the film. Resonance-enhanced x-rays can be used to characterize the internal structure of Langmuir-Blodgett thin film membranes. This effect may also find use in x-ray-based thin film devices and in the structural analysis of adlayers and surfaces that have thus far proved difficult, if not impossible, to study because of sensitivity limitations.


Asunto(s)
Microanálisis por Sonda Electrónica , Membranas Artificiales , Fluorescencia , Propiedades de Superficie , Rayos X , Zinc
3.
Science ; 248(4951): 52-6, 1990 Apr 06.
Artículo en Inglés | MEDLINE | ID: mdl-2321026

RESUMEN

The ion distribution in an electrolyte solution in contact with a charged polymerized phospholipid membrane was directly measured with long-period x-ray standing waves. The 27-angstrom-thick lipid monolayer was supported on a tungsten/silicon mirror. X-ray standing waves were generated above the mirror surface by total external reflection of a 9.8-kiloelectron volt x-ray beam from a synchrotron undulator. The membrane surface, which contained negatively charged phosphate headgroups, was bathed in a dilute ZnCl2 solution. The concentration of Zn2+ in the condensed layer at the membrane surface and the Zn2+ distribution in the diffuse layer were measured as a function of headgroup charge. The Debye length of the diffuse layer varied between 3 and 58 angstroms. The results qualitatively agree with the Gouy-Chapman-Stern model.


Asunto(s)
Electroquímica , Membranas Artificiales , Fenómenos Químicos , Química Física , Electrólitos , Concentración de Iones de Hidrógeno , Aceleradores de Partículas , Fosfolípidos , Polímeros , Soluciones , Agua , Rayos X , Zinc/análisis
4.
Science ; 241(4874): 1788-91, 1988 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-3175619

RESUMEN

Structural information on an atomic scale has been obtained for a Langmuir-Blodgett (LB) trilayer system by means of long-period x-ray standing waves. The LB trilayer of zinc and cadmium arachidate was deposited on a layered synthetic microstructure (LSM) consisting of 200 tungsten/silicon layer pairs with a 25 A period. A 30 A thermally induced inward collapse of the zinc atom layer that was initially located in the LB trilayer at 53 A above the LSM surface has been observed. The mean position and width of the zinc atom layer was determined with a precision of +/- 0.3 A.


Asunto(s)
Membranas/ultraestructura , Difracción de Rayos X , Aceleradores de Partículas
5.
Science ; 265(5178): 1555-7, 1994 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-8079168

RESUMEN

The x-ray standing waves generated by dynamical Bragg diffraction were used to directly measure lattice locations of trace elements within and at the surface of a mineral single crystal. These high-precision measurements were made on natural Iceland spar calcite cleaved along the (1014) plane and reacted with a dilute aqueous lead solution. Within the bulk crystal, naturally occurring trace manganese was found within (1014) planes, consistent with its substitution for calcium. At the crystal surface, sorbed lead was found to be highly ordered and mostly within (1014) planes. This demonstrates a powerful application of synchrotron radiation in the earth and environmental sciences.


Asunto(s)
Carbonato de Calcio/química , Cristalografía por Rayos X , Oligoelementos/análisis , Calcio/análisis , Cristalización , Plomo/análisis , Manganeso/análisis
6.
J Colloid Interface Sci ; 295(1): 50-64, 2006 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-16150454

RESUMEN

The X-ray standing wave technique was used to probe the sensitivity of Zn2+ and Sr2+ ion adsorption to changes in both the adsorbed ion coverage and the background electrolyte species and concentrations at the rutile (alpha-TiO2) (110)-aqueous interface. Measurements were made with various background electrolytes (NaCl, NaTr, RbCl, NaBr) at concentrations as high as 1 m. The results demonstrate that Zn2+ and Sr2+ reside primarily in the condensed layer and that the ion heights above the Ti-O surface plane are insensitive to ionic strength and the choice of background electrolyte (with <0.1 A changes over the full compositional range). The lack of any specific anion coadsorption upon probing with Br-, coupled with the insensitivity of Zn2+ and Sr2+ cation heights to changes in the background electrolyte, implies that anions do not play a significant role in the adsorption of these divalent metal ions to the rutile (110) surface. Absolute ion coverage measurements for Zn2+ and Sr2+ show a maximum Stern-layer coverage of approximately 0.5 monolayer, with no significant variation in height as a function of Stern-layer coverage. These observations are discussed in the context of Gouy-Chapman-Stern models of the electrical double layer developed from macroscopic sorption and pH-titration studies of rutile powder suspensions. Direct comparison between these experimental observations and the MUltiSIte Complexation (MUSIC) model predictions of cation surface coverage as a function of ionic strength revealed good agreement between measured and predicted surface coverages with no adjustable parameters.

7.
Phys Chem Chem Phys ; 8(8): 967-76, 2006 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-16482339

RESUMEN

Characterization of lead substitution for calcium in hydroxyapatite (CaHA) is carried out, using experimental techniques and Density Functional theoretical (DFT) analyses. Theoretical modeling is used to obtain information of the Pb chemical environment for occupancy at either Ca(I) or Ca(II) sites of CaHA. Effects of the larger ionic radius of Pb(+2) compared to Ca(+2) are apparent in embedded cluster calculations of local chemical bonding properties. DFT periodic planewave pseudopotential studies are used to provide first-principles predictions of local structural relaxation and site preference for Pb(x)Ca(10-x)HA over the composition range x< or = 6. General characteristics of the polycrystalline material are verified by X-ray diffraction and FTIR analysis, showing the presence of a single phase of CaHA structure. A short range structure around lead is proposed in order to interpret the Pb L-edge EXAFS spectrum of the solid solution Ca(6.6)Pb(3.4)HA. In this concentration we observe that lead mainly occupies Ca(II) sites; the EXAFS fit slightly favors Pb clustering, while theory indicates the importance of Pb-Pb avoidance on site (II).


Asunto(s)
Materiales Biocompatibles/química , Durapatita/química , Plomo/química , Ensayo de Materiales , Modelos Moleculares , Espectroscopía Infrarroja por Transformada de Fourier , Difracción de Rayos X
8.
Nature ; 354(6352): 377-80, 1991 Dec 05.
Artículo en Inglés | MEDLINE | ID: mdl-1956399

RESUMEN

The X-ray standing wave (XSW) method, developed in the 1960s, was used originally to determine heavy atom positions in and on silicon and germanium single crystals. An X-ray standing wave generated by the interference of coherent incident and reflected beams excites X-ray fluorescence from the heavy atom, the intensity of which as a function of incident angle provides an indication of the atom's distance from the X-ray reflecting surface. The availability of X-ray mirrors and the ability to prepare layered synthetic microstructures has made possible the study of biologically relevant structures using the XSW technique on length scales of typically tens to hundreds of ångströms, allowing heavy atoms in such structures to be located with ångström or subångström resolution. Many model biological systems (such as Langmuir-Blodgett films, which mimic membranes) require access to still larger scales, but it is not obvious that an XSW will remain coherent over such length scales. Here we report studies of a lipid multilayer system using the XSW method, in which we have been able to locate the metal atoms in a zinc arachidate bilayer with ångström resolution at a distance of almost 1,000 A above the surface of a gold mirror. Our results indicate that the XSW technique should be useful for structural studies of supramolecular aggregates, receptor-ligand interactions and multi-membrane stacks, in which length scales of this order are encountered.


Asunto(s)
Lípidos de la Membrana/química , Ácidos Araquidónicos/química , Oro , Rayos X , Zinc
9.
Phys Rev Lett ; 90(25 Pt 1): 255503, 2003 Jun 27.
Artículo en Inglés | MEDLINE | ID: mdl-12857143

RESUMEN

Term-by-term Fourier-expansion series, each made up of components having element-specific phases and amplitudes acquired with x-ray standing wave measurements on successive orders of Bragg reflections, are used to reconstruct impurity atom distributions in muscovite mica with respect to the (001) lattice without a priori assumptions on their structures.

10.
Langmuir ; 20(12): 4954-69, 2004 Jun 08.
Artículo en Inglés | MEDLINE | ID: mdl-15984256

RESUMEN

A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength.

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