Adsorption of Azobenzene on Hexagonal Boron Nitride Nanomesh Supported by Rh(111).

Adsorption properties of azobenzene, the prototypical molecular switch, were investigated on a hexagonal boron nitride (h-BN) monolayer ("nanomesh") prepared on Rh(111). The h-BN layer was produced by decomposing borazine (B3N3H6) at 1000-1050 K. Temperature-programmed desorption (TPD) studies revealed that azobenzene molecules adsorbed on the "wire" and "pore" regions desorb at slightly different temperatures. Angle-resolved high-resolution electron energy loss spectroscopy (HREELS) measurements demonstrated that the first molecular layer is characterized predominantly by an adsorption geometry with the molecular plane parallel to the surface. Scanning tunneling microscopy (STM) indicated a clear preference for adsorption in the pores, manifesting a templating effect, but in some cases one-dimensional molecular stripes also form, implying attractive molecule-molecule interaction. Density functional theory (DFT) calculations provided further details regarding the adsorption energetics and bonding and confirmed the experimental findings that the molecules adsorb with the phenyl rings parallel to the surface, preferentially in the pores, and indicated also the presence of an attractive molecule-molecule interaction.

Tailoring the hexagonal boron nitride nanomesh on Rh(111) with gold.

It is known that the hexagonal boron nitride (h-BN) monolayer has a periodically corrugated structure on Rh(111), termed "nanomesh", while the h-BN layer is planar on the close packed surfaces of coinage metals (Cu, Ag, Au) due the weak interactions. Our studies are aimed at understanding the metal-h-BN interaction, when both Rh and Au are present. On the one hand, the growth and thermal properties of gold deposited on h-BN nanomesh prepared on Rh(111) were studied. On the other hand, the formation of h-BN was examined on Au/Rh surface alloys prepared by the deposition of Au on Rh(111) and subsequent annealing at 1000 K. In each case, the h-BN was prepared by the decomposition of borazine at about 1000 K. Low energy ion scattering (LEIS), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) measurements revealed that the growth of Au on h-BN/Rh(111) at room temperature leads to the formation of mainly three dimensional (3D) gold nanoparticles, although at low coverages (<0.2 ML) 2D particles formed as well. Stepwise annealing to higher temperatures induces the intercalation of Au below the nanomesh, which was complete at around 1050 K. Some agglomeration and desorption of Au also took place. Interestingly, the nanomesh structure was observable after intercalation up to relatively large Au coverages. Measurements performed in the reverse order, namely exposing a Au/Rh(111) surface alloy to borazine, revealed that Rh atoms get covered by h-BN (or by its precursors) at significantly smaller borazine exposures than Au atoms. The nanomesh structure was essentially present up to a gold coverage of 0.9 ML, but with a smaller pore diameter, while it gradually disappeared at higher gold amounts. In this way the application of surface alloy supports provides a key for gradual tuning of the mesh morphology. Density functional theory calculations confirmed the decreased pore diameter of the BN layer upon the formation of a surface Rh-Au alloy layer.

CO oxidation on Pt(111) at near ambient pressures.

The oxidation of CO on Pt(111) was investigated simultaneously by near ambient pressure X-ray photoelectron spectroscopy and online gas analysis. Different CO:O2 reaction mixtures at total pressures of up to 1 mbar were used in continuous flow mode to obtain an understanding of the surface chemistry. By temperature-programmed and by isothermal measurements, the onset temperature of the reaction was determined for the different reactant mixtures. Highest turnover frequencies were found for the stoichiometric mixture. At elevated temperatures, the reaction becomes diffusion-limited in both temperature-programmed and isothermal measurements. In the highly active regime, no adsorbates were detected on the surface; it is therefore concluded that the catalyst surface is in a metallic state, within the detection limits of the experiment, under the applied conditions. Minor bulk impurities such as silicon were observed to influence the reaction up to total inhibition by formation of non-platinum oxides.

Probing the interaction of Rh, Co and bimetallic Rh-Co nanoparticles with the CeO2 support: catalytic materials for alternative energy generation.

The interaction of CeO2-supported Rh, Co and bimetallic Rh-Co nanoparticles, which are active catalysts in hydrogen production via steam reforming of ethanol, a process related to renewable energy generation, was studied by X-ray diffraction (XRD), high resolution electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). Furthermore, diffuse reflectance infrared spectroscopy (DRIFTS) of adsorbed CO as a probe molecule was used to characterize the morphology of metal particles. At small loadings (0.1%), Rh is in a much dispersed state on ceria, while at higher contents (1-5%), Rh forms 2-8 nm particles. Between 473-673 K pronounced oxygen transfer from ceria to Rh is observed and at 773 K significant agglomeration of Rh occurs. On reduced ceria, XPS indicates a possible electron transfer from Rh to ceria. The formation of smaller ceria crystallites upon loading with Co was concluded from XRD and HRTEM; for 10% Co, the CeO2 particle size decreased from 27.6 to 10.7 nm. A strong dissolution of Co into ceria and a certain extent of encapsulation by ceria were deduced by XRD, XPS and LEIS. In the bimetallic system, the presence of Rh enhances the reduction of cobalt and ceria. During thermal treatments, reoxidation of Co occurs, and Rh agglomeration as well as oxygen migration from ceria to Rh are hindered in the presence of cobalt.

LEIS and XPS investigation into the growth of cerium and cerium dioxide on Cu(111).

The controlled growth of Ce and CeO2 on Cu(111) was investigated applying low energy ion scattering spectroscopy (LEIS) and X-ray photoelectron spectroscopy (XPS). Previous LEIS studies on metallic and oxidised cerium deposits using other metallic substrates reported serious difficulties related to the neutralization of noble gas ions. For this reason, special attention was paid here to reveal possible matrix effects for the neutralization ("neutralization effects"), which would severely hinder quantitative evaluation of the LEIS data. The adsorption of O2 on Cu(111) induced no neutralization effects either with He(+) or Ne(+). Similarly, no neutralization effects were identified using He(+) upon the deposition of metallic Ce on Cu(111), but it arises for the Ce peak monitored with Ne(+). The initial growth of Ce is two dimensional up to ΘCe ∼ 0.5 ML, while almost complete coverage of Cu(111) is achieved at ΘCe = 2 ML. CeO2(111) was deposited evaporating Ce in a background of O2 at a sample temperature of 523 K. No neutralization effects were observed either with He(+) or Ne(+). In harmony with literature data, the growth mode is three dimensional. Here it was demonstrated that the continuity of the film, which could be efficiently checked by LEIS, is influenced by the applied oxygen pressure in the range of 5 × 10(-7)-3 × 10(-6) mbar. At pO2 = 3 × 10(-6) mbar the film was not completely closed even at relatively large coverages (16 ML), and a significant part of copper atoms were oxidized to Cu(1+). Deposition of CeO2 at pO2 = 5 × 10(-7) mbar was characterized by a nearly perfect wetting, with metallic copper atoms at the interface, and with a slightly more reduced ceria layer.

Growth of gold on a pinwheel TiO(∼1.2) encapsulation film prepared on rhodium nanocrystallites.

Rh nanoparticles of 50-100 nm diameter and 20-40 atomic layer thickness with a (111) flat top facet parallel to the support surface were grown on a TiO2(110) surface via physical vapor deposition (PVD) at room temperature (RT) followed by annealing at 1050 K. These nanoparticles were completely encapsulated by an ordered hexagonal pinwheel TiO∼1.2 ultrathin oxide (w-TiO-UTO) film. STM, XPS, and low energy ion scattering (LEIS) methods were used to characterize the postdeposition of gold and the effects of annealing on the Au/w-TiO-UTO/Rh-particle system. The adlayer exhibits 3D growth and Rh-Au bond formation at 500 K. The 3D Au nanoparticles of 2-3 nm diameter and ∼1 nm height are partially covered by TiOx species at RT and sinter via an Ostwald-ripening in the range of 500-800 K. The adparticles are gradually getting free of TiOx decoration, and at around 900 K they exhibit a double layer height with 2D character. Two different arrangements were found for these Au particles: (i) a compressed Au(111)-(1 × 1) and (ii) a reconstructed Au(111)-(2 × 1), both of them pseudomorphic with the Rh lattice underneath. Above 900 K, the thickness of these 2D particles tends to become a single layer, while they spread out and form a continuous gold layer on the Rh nanoparticles. This behavior indicates a thermally activated replacement of the w-TiO-UTO film by an Au ultrathin layer. The gold layer is stable up to 1000 K, where extended 1D interfaces are formed between gold and w-TiO-UTO layers.

Interaction of Rh with Rh nanoparticles encapsulated by ordered ultrathin TiO(1+x) film on TiO2(110) surface.

Rh films of 5-50 monolayers (ML) were grown on TiO2(110)-(1 × 1) surface by physical vapor deposition (PVD) at 300 K followed by annealing at max. 1050 K. In the coverage range of 5-15 ML, separated stripe-like Rh nanoparticles of approximately 30 × 150 nm lateral size and 10-20 layer thickness with a flat top (111) facet were formed. At higher coverages (15-50 ML), the Rh film sustained its continuity at least up to 950 K. For both cases, the Rh(111) top facets were completely covered by a long-range ordered hexagonal "wagon-wheel" TiO(1+x) ultrathin oxide (hw-TiO-UTO) film. STM-STS, XPS, LEIS, and TDS methods were used for morphologic and electronic characterization of surfaces prepared in this way. The main part of this study is devoted to the study of postdeposition of Rh on the hw-TiO-UTO layer at different temperatures (230 K, 310 K, 500 K) and to the effect of subsequent annealing. It was found that 2D nanoparticles of 0.2-0.3 nm height and 1-2 nm diameter are formed at RT and their average lateral size increases gradually in the range of 300-900 K. The LEIS intensity data and the CO TDS titration of the particles have shown that an exchange of the postdeposited Rh atoms with the hw-TiO-UTO layer proceeds to an extent of around 50% at 230 K and this value increases up to 80-90% in the range of 300-500 K. The total disappearance of the characteristic LEIS signal for Rh takes place at around 900 K where a complete hw-TiO-UTO adlayer forms on top of the postdeposited metal (100% exchange).

Formation of Rh-Au core-shell nanoparticles on TiO2(110) surface studied by STM and LEIS.

Rh-Au core-shell nanoparticles were fabricated on TiO(2)(110) surface by physical vapor deposition (PVD) of Rh followed by exposure of Au at elevated sample temperature (500 K). The morphology of the bimetallic particles was checked by scanning tunneling microscopy (STM). The chemical composition of the particles was characterized by low energy ion scattering (LEIS) method. It was shown that the "seeding + growing" method described previously for growth of monometallic particles in narrow size distribution (Berko, A. et al. J. Catal. 1999, 182, 511) can also be applied for fabrication of bimetallic nanoparticles. The large mean free path of surface diffusion of gold on the oxide support makes the accumulation of Au possible exclusively on the Rh seeds formed in the first step of the procedure. By performing careful STM and LEIS experiments, it was proven that, for appropriate Au and Rh coverages, the postdeposited Au completely and uniformly covers the Rh nanoparticles.

Biochemical markers of sperm function: male fertility and sperm selection for ICSI.

The expression of a 70 kDa chaperone protein, HspA2 (formerly called CK-M), has been identified in mature human spermatozoa. The central role of HspA2 has been established, as the expression level of this protein is related to sperm cellular maturity, DNA integrity, chromatin maturity, chromosomal aneuploidy frequency and sperm function, including fertilizing potential. The spermiogenetic events of cytoplasmic extrusion and remodelling of the plasma membrane, which facilitate the formation of zona pellucida binding site(s) in human spermatozoa, are related. Finally, the presence of the hyaluronic acid (HA) receptor on the plasma membrane of mature sperm coupled with the HA-coated slide sperm-binding assay, facilitates the testing of infertile men and the selection of single mature spermatozoa for ICSI. Because mature spermatozoa have no residual cytoplasm, the HA-bound sperm fraction is also enriched in spermatozoa that are normal by the Kruger strict morphology method.

[Doppler evaluation of the fetal arterial circulation: reference values of the Resistance Index and Pulsatility Index between the 28th and 41st weeks of gestation]. / A magzat artériás vérkeringésének ultrahangvizsgálata: a rezisztenciaindex és a pulzatilitási index referenciaértékei a terhesség 28. és 41. hete között.

The authors established reference ranges for the Resistance Index and the Pulsatility Index of the umbilical artery, the fetal descending aorta and the middle cerebral artery in order to facilitate the uniform evaluation of the Doppler ultrasound examination in obstetrics. 164 patients with uncomplicated pregnancies between the 28th and 41st weeks of gestation were recruited for the longitudinal assessment of Doppler Resistance Indices and Pulsatility Indices in the fetal and umbilical arteries. Data were retrospectively analysed in order to establish the weekly mean values and standard deviations. The mean values of the indices in three periods (I.: 28-31, II.: 32-36, III.: 37-41 weeks) were compared. The normal haemodynamic resistance is reflected by the Doppler indices within the weekly mean +/- 2SD range. The results designate decreasing haemodynamic impedance in the umbilical and in the middle cerebral arteries while the resistance to the blood flow in the abdominal aorta is constant throughout the third trimester of gestation. The introduction and the clinical application of the reference values provides appropriate interpretation of the physiologic fetal blood flow patterns which is the prerequisite of the diagnostic accuracy of the Doppler ultrasound in obstetrics.