Prospective study of signalling pathways in myeloma bone disease with regard to activity of the disease, extent of skeletal involvement and correlation to bone turnover markers.

AIMS: The aim of our study was to address the utility of serum levels of selected parameters of myeloma bone disease (MBD) signalling with regard to the pathogenesis of multiple myeloma (MM), activity, markers of bone turnover and extent of skeletal changes. PATIENTS AND METHODS: We assessed prospectively 77 individuals with monoclonal gammopathies - 46 patients with active MM (AMM), 12 patients with smouldering MM (SMM) and 19 individuals with monoclonal gammopathy of undetermined significance (MGUS) to determine the role of HGF, MIP-1α, Syndecan-1, osteoprotegerin, Activin A, DKK1, Annexin A2 and NF-κB. RESULTS: We found significant differences of most of the parameters between MGUS and AMM, and with respect to the activity of MM assessed by International Staging System. Most of the parameters of MBD signalling correlated with traditional markers of bone turnover. CONCLUSIONS: All the signalling pathways were activated in MM with more pronounced osteoclastogenesis in comparison with bone formation but not in MGUS regardless of its risk category, suggesting that MBD is not activated in MGUS until the process of transformation into MM. The parameters of MBD signalling might precede the increase of conventional parameters of bone turnover suggesting their possible role in early indication of anti-resorption therapy.

The activation of gold and the water-gas shift reaction: insights from studies with model catalysts.

The activation of gold in catalytic reactions has been the subject of intensive research that has led to the transformation of one of the least chemically reactive elements to a catalyst with excellent activity and selectivity. Scientists have performed numerous systematic experimental and theoretical studies using model systems, which have explained the role of Au in chemical reactions with progressively increasing degrees of structural and chemical complexity. We present an overview of recent studies of model Au(111), CeOx/Au(111), and Au/CeOx/TiO2(110) surfaces that use Au in different structural configurations specifically for the water-gas shift reaction (WGS, CO + H2O → CO2 + H2), an important industrial process for the purification of CO. We demonstrate the significance of key structural components of the Au-based supported catalysts such as the metal-oxide interface (Au-Ox) toward the WGS catalytic activity, a "structure-activity" relationship. In the WGS reaction, Au(111) or Au nanoparticles have poor catalytic performance due to their inability to activate one of the most important steps of the reaction, the breaking of O-H bonds in the dissociation of water (H2O → OH + H). The relatively large energetic barrier can be overcome by using O on Au(111) to facilitate the formation of OH at low temperatures, with eventual CO2 and H2 production upon reaction between CO and the adsorbed OH. However, the inability to replace the reacted O prevents a sustainable catalytic process from occurring on Au(111). The addition of a small concentration of CeOx nanoparticles on top of the Au(111) surface facilitates this rate-determining step and easily continues the catalytic cycle in the production of H2. We have discovered that CeOx nanoparticles in contact with Au(111) are rich in Ce(3+). They also have a distinct metal-oxide interface, which sustains excellent activity for the WGS reaction via the formation of a unique carboxylate intermediate, making CeOx/Au(111) more active than Cu/ZnO(0001̅), Cu(100), and Cu(111) which are the typical catalysts for this reaction. Taking this knowledge one step further, bringing these components (oxide and metal nanoparticles) together over a second oxide in Au/CeOx/TiO2 produces a system with unique morphological and electronic properties. The result is a superior catalyst for the WGS reaction, both as a model system (Au/CeOx/TiO2(110)) and as powder material (Au/CeOx/TiO2(anatase)) optimized directly in a series of systematic investigations.

Adsorption of hydrogen on the surface and sub-surface of Cu(111).

The interaction of atomic hydrogen with the Cu(111) surface was studied by a combined experimental-theoretical approach, using infrared reflection absorption spectroscopy, temperature programmed desorption, and density functional theory (DFT). Adsorption of atomic hydrogen at 160 K is characterized by an anti-absorption mode at 754 cm(-1) and a broadband absorption in the IRRA spectra, related to adsorption of hydrogen on three-fold hollow surface sites and sub-surface sites, and the appearance of a sharp vibrational band at 1151 cm(-1) at high coverage, which is also associated with hydrogen adsorption on the surface. Annealing the hydrogen covered surface up to 200 K results in the disappearance of this vibrational band. Thermal desorption is characterized by a single feature at ∼295 K, with the leading edge at ∼250 K. The disappearance of the sharp Cu-H vibrational band suggests that with increasing temperature the surface hydrogen migrates to sub-surface sites prior to desorption from the surface. The presence of sub-surface hydrogen after annealing to 200 K is further demonstrated by using CO as a surface probe. Changes in the Cu-H vibration intensity are observed when cooling the adsorbed hydrogen at 180 K to 110 K, implying the migration of hydrogen. DFT calculations show that the most stable position for hydrogen adsorption on Cu(111) is on hollow surface sites, but that hydrogen can be trapped in the second sub-surface layer.

A new type of strong metal-support interaction and the production of H2 through the transformation of water on Pt/CeO2(111) and Pt/CeO(x)/TiO2(110) catalysts.

The electronic properties of Pt nanoparticles deposited on CeO(2)(111) and CeO(x)/TiO(2)(110) model catalysts have been examined using valence photoemission experiments and density functional theory (DFT) calculations. The valence photoemission and DFT results point to a new type of "strong metal-support interaction" that produces large electronic perturbations for small Pt particles in contact with ceria and significantly enhances the ability of the admetal to dissociate the O-H bonds in water. When going from Pt(111) to Pt(8)/CeO(2)(111), the dissociation of water becomes a very exothermic process. The ceria-supported Pt(8) appears as a fluxional system that can change geometry and charge distribution to accommodate adsorbates better. In comparison with other water-gas shift (WGS) catalysts [Cu(111), Pt(111), Cu/CeO(2)(111), and Au/CeO(2)(111)], the Pt/CeO(2)(111) surface has the unique property that the admetal is able to dissociate water in an efficient way. Furthermore, for the codeposition of Pt and CeO(x) nanoparticles on TiO(2)(110), we have found a transfer of O from the ceria to Pt that opens new paths for the WGS process and makes the mixed-metal oxide an extremely active catalyst for the production of hydrogen.

High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level.

Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO(2)(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeO(x)/TiO(2)(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce(3+) oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO(2)(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water-gas shift reaction (H(2)O + CO --> H(2) + CO(2)) or for the oxidation of carbon monoxide (2CO + O(2) --> 2CO(2)). The enhanced stability of the Ce(3+) state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity.

Identification of 5-7 defects in a copper oxide surface.

A topological defect in a Cu(2)O surface oxide grown on Cu(111) has been identified. Using scanning tunneling microscopy, we observed the formation of pentagonal and heptagonal rings within the Cu(2)O surface oxide. These structures break the symmetry of the hexagonal oxide surface and are a consequence of the presence of oxygen vacancies in the Cu(2)O surface. We propose that the pentagonal and heptagonal rings are formed through the rotation of a -O-Cu-O- chain in a manner similar to the Stone-Wales transformation. The proposed transformation is supported by the results of density functional theory calculations.

CO oxidation on inverse CeO(x)/Cu(111) catalysts: high catalytic activity and ceria-promoted dissociation of O2.

A Cu(111) surface displays a low activity for the oxidation of carbon monoxide (2CO + O(2) → 2CO(2)). Depending on the temperature, background pressure of O(2), and the exposure time, one can get chemisorbed O on Cu(111) or a layer of Cu(2)O that may be deficient in oxygen. The addition of ceria nanoparticles (NPs) to Cu(111) substantially enhances interactions with the O(2) molecule and facilitates the oxidation of the copper substrate. In images of scanning tunneling microscopy, ceria NPs exhibit two overlapping honeycomb-type moiré structures, with the larger ones (H(1)) having a periodicity of 4.2 nm and the smaller ones (H(2)) having a periodicity of 1.20 nm. After annealing CeO(2)/Cu(111) in O(2) at elevated temperatures (600-700 K), a new phase of a Cu(2)O(1+x) surface oxide appears and propagates from the ceria NPs. The ceria is not only active for O(2) dissociation, but provides a much faster channel for oxidation than the step edges of Cu(111). Exposure to CO at 550-750 K led to a partial reduction of the ceria NPs and the removal of the copper oxide layer. The CeO(x)/Cu(111) systems have activities for the 2CO + O(2) → 2CO(2) reaction that are comparable or larger than those reported for surfaces of expensive noble metals such as Rh(111), Pd(110), and Pt(100). Density-functional calculations show that the supported ceria NPs are able to catalyze the oxidation of CO due to their special electronic and chemical properties. The configuration of the inverse oxide/metal catalyst opens new interesting routes for applications in catalysis.

A rare case of bifocal, extramedullary and hyposecretory relapse of multiple myeloma.

We present a rare extramedullary, bifocal, and hyposecretory manifestation of relapsed MM that could be mistaken for an infection. We stress the importance of complex evaluation including serum, urine, and bone marrow assessment and whole-body imaging.

Gold, copper, and platinum nanoparticles dispersed on CeO(x)/TiO(2)(110) surfaces: high water-gas shift activity and the nature of the mixed-metal oxide at the nanometer level.

At small coverages of ceria on TiO(2)(110), the CeO(x) nanoparticles have an unusual coordination mode. Scanning tunneling microscopy and density-functional calculations point to the presence of Ce(2)O(3) dimers, which form diagonal arrays that have specific orientations of 0, 24, and 42 degrees with respect to the [1 -1 0] direction of the titania substrate. At high coverages of ceria on TiO(2)(110), the surface exhibits two types of terraces. In one type, the morphology is not very different from that observed at low ceria coverage. However, in the second type of terrace, there is a compact array of ceria particles with structures that do not match the structures of CeO(2)(111) or CeO(2)(110). The titania substrate imposes on the ceria nanoparticles nontypical coordination modes, enhancing their chemical reactivity. This phenomenon leads to a larger dispersion of supported metal nanoparticles (M = Au, Cu, Pt) and makes possible the direct participation of the oxide in catalytic reactions. The M/CeO(x)/TiO(2)(110) surfaces display an extremely high catalytic activity for the water-gas shift reaction that follows the sequence Au/CeO(x)/TiO(2)(110) < Cu/CeO(x)/TiO(2)(110) < Pt/CeO(x)/TiO(2)(110). For low coverages of Cu and CeO(x), Cu/CeO(x)/TiO(2)(110) is 8-12 times more active than Cu(111) or Cu/ZnO industrial catalysts. In the M/CeO(x)/TiO(2)(110) systems, there is a strong coupling of the chemical properties of the admetal and the mixed-metal oxide: The adsorption and dissociation of water probably take place on the oxide, CO adsorbs on the admetal nanoparticles, and all subsequent reaction steps occur at the oxide-admetal interface. The high catalytic activity of the M/CeO(x)/TiO(2)(110) surfaces reflects the unique properties of the mixed-metal oxide at the nanometer level.

Destruction of SO2 on Au and Cu nanoparticles dispersed on MgO(100) and CeO2(111).

When going from periodic surfaces to isolated clusters or nanoparticles, there is a big increase in the reactivity of Au and Cu toward SO(2). Density functional calculations indicate that the enhancement in the SO(2) adsorption energy is due to the presence of corner sites (i.e., metal atoms with a low coordination number) and the fluxionality of the nanoparticles. Therefore, small Au particles bind SO(2) stronger than a periodic Au(100) surface. However, the S <--> Au and O <--> Au interactions are not strong enough to induce the rupture of the S-O bonds. In contrast, the dissociation of SO(2) on Cu particles is a very exothermic process, even more exothermic than on a periodic Cu(100) surface. Experiments of synchrotron-based high-resolution photoemission and X-ray absorption spectroscopy show big differences in the DeSOx activity of Au and Cu nanoparticles dispersed on MgO(100) and CeO(2)(111). The heat of adsorption of the SO(2) on Au nanoparticles supported on MgO(100) or CeO(2)(111) was 0.2 to 0.4 eV larger than on Au(100) with negligible dissociation of the molecule. The full decomposition of SO(2) was observed only after O vacancies were introduced in the ceria support. The O vacancies in ceria either played a direct role in the dissociation of SO(2) (cracking of the molecule at the oxide-metal interface) or enhanced the chemical activity of the supported Au nanoparticles. The addition of Cu particles to MgO(100) or CeO(2)(111) generates systems that are extremely active for the destruction of SO(2). At 100-150 K, the SO(2) adsorbs molecularly on the supported Cu particles. Heating to temperatures above 200 K leads to massive dissociation of the SO(2). A comparison of the behavior of SO(2) on Cu/MgO(100) and Cu/CeO(2-x)(111) shows how important the reducibility of the oxide support in DeSOx operations can be.

Adsorbate-driven morphological changes of a gold surface at low temperatures.

Using STM, infrared absorption reflection spectroscopy experiments and density functional calculations we show that low temperature adsorption of CO on gold surfaces modified by vacancy islands leads to morphological changes and the formation of nanosized Au particles. These results demonstrate a dynamic response of a surface during adsorption with consequences for the surface reactivity.

Prospective comparison of conventional radiography, low-dose computed tomography and magnetic resonance imaging in monoclonal gammopathies.

AIMS: We carried out a prospective study in order to identify the best imaging approach for patients with newly diagnosed multiple myeloma (MM) and monoclonal gammopathy of undetermined significance (MGUS). METHODS: We assessed the extent of myeloma bone disease (MBD) in 112 individuals - 84 patients with MM and 28 individuals with MGUS. For the detection of osteolytic involvement we used whole-body magnetic resonance imaging (WB-MRI), low-dose computed tomography (LD-CT) and conventional radiography (CR). Each method assessed the presence of osteolytic involvement, compressive fractures and extramedullary involvement in the following regions: skull, spine and chest, pelvis and humerus and femur. We compared the difference in the number and extent of osteolytic involvement, especially the findings in CR negative patients. RESULTS: Conventional radiography showed no superiority in any of the evaluated regions, and failed in the detection of extramedullary massess and spine involvement. WB-MRI was best at imaging the spine including extramedullary involvement, however, detection of osteolytic lesions of the skull was limited in comparison with both CR and LD-CT. Both WB-MRI and LD-CT were comparable in imaging of lesions of pelvis, humerus, femur and the presence of extramedullary masses. LD-CT showed superiority in detection of skull lesions but lower sensitivity in spine compared to WB-MRI. CONCLUSIONS: Our results confirm that relying solely on CR in the diagnostics of MM is insufficient. We suggest that the most suitable method for primary assessment of osteolytic involvement in monoclonal gammopathies should include either whole-body MRI together with CR of the skull or, with an equivalent sensitivity, whole body LD-CT.

Inverse Oxide/Metal Catalysts in Fundamental Studies and Practical Applications: A Perspective of Recent Developments.

Inverse oxide/metal catalysts have shown to be excellent systems for studying the role of the oxide and oxide-metal interface in catalytic reactions. These systems can have special structural and catalytic properties due to strong oxide-metal interactions difficult to attain when depositing a metal on a regular oxide support. Oxide phases that are not seen or are metastable in a bulk oxide can become stable in an oxide/metal system opening the possibility for new chemical properties. Using these systems, it has been possible to explore fundamental properties of the metal-oxide interface (composition, structure, electronic state), which determine catalytic performance in the oxidation of CO, the water-gas shift and the hydrogenation of CO2 to methanol. Recently, there has been a significant advance in the preparation of oxide/metal catalysts for technical or industrial applications. One goal is to identify methods able to control in a precise way the size of the deposited oxide particles and their structure on the metal substrate.

Characterization of molybdenum carbide nanoparticles formed on Au(111) using reactive-layer assisted deposition.

Temperature programmed desorption (TPD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM) have been used to characterize molybdenum carbide nanoparticles prepared on a Au(111) substrate. The MoC(x) nanoparticles were formed by Mo metal deposition onto a reactive multilayer of ethylene, which was physisorbed on a Au(111) substrate at low temperatures (<100 K). The resulting clusters have an average diameter of approximately 1.5 nm and aggregate in the fcc troughs located on either side of the elbows of the reconstructed Au(111) surface. Core level XPS shows that the electronic environment of the Mo and C atoms in the nanoparticles is similar to that found in Mo(2)C(0001) single crystals and carburized Mo metal surfaces. Peak intensities in XPS and AES spectra were used to estimate an average Mo/C atomic ratio of 1.2 +/- 0.3 for nanoparticles annealed above 600 K.

Comparison of the results and complications of palmar and dorsal miniinvasive approaches in the surgery of scaphoid fractures. A prospective randomized study.

AIMS: To compare the functional results and complications associated with palmar percutaneous and dorsal limited approaches in the surgical treatment of nondisplaced or minimally displaced scaphoid fractures type B2. METHODS: A total of 76 patients with acute nondisplaced or minimally displaced type B2 scaphoid fractures were included in a prospective randomised study. The assignment patients to groups according to type of operative approach was based on systematic sampling. Clinical follow-up, X-ray or CT imaging were performed at four, eight and twelve weeks and one year after the surgery. Patient satisfaction and the results of DASH form were evaluated as well. The differences were statistically tested. RESULTS: We found significantly better flexion and grip strength in the group of palmar percutaneous aprroach during the follow-up examination at eight weeks after the surgery. Significantly better flexion of the same group persisted at twelve-week follow-up examination. No differences in results or complications were statistically significant up to one year follow up. CONCLUSIONS: We found no advantage to the palmar percutaneous approach in the treatment of nondisplaced and minimally displaced scaphoid fractures type B2 compared to dorsal limited approach.

Structure and special chemical reactivity of interface-stabilized cerium oxide nanolayers on TiO2(110).

Novel interface-stabilized ceria nanophases have been grown on TiO2(110) by physical vapor deposition. At low coverage, dumbbell nanostructures constituted by reconstructed titania and ceria clusters are formed, while long range ordered nanoxides can be obtained by increasing the ceria dose. Scanning tunneling microscopy and photoemission spectroscopy were used to characterize the electronic properties of the films, showing that the TiO2 substrate can effectively stabilize ceria in reduced form over a wide range of experimental conditions. Epitaxial coupling is a very useful tool for tuning the chemical properties of mixed oxide systems. The special electronic properties of the films have a direct counterpart in the chemical activity, which has been investigated by temperature programmed desorption using methanol as a probe molecule. The experimental results indicate an exceptional activity of the ceria-titania interface in the selective dehydration of methanol to formaldehyde at an unprecedented low temperature (330 K).

Catalysis. Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2.

The transformation of CO2 into alcohols or other hydrocarbon compounds is challenging because of the difficulties associated with the chemical activation of CO2 by heterogeneous catalysts. Pure metals and bimetallic systems used for this task usually have low catalytic activity. Here we present experimental and theoretical evidence for a completely different type of site for CO2 activation: a copper-ceria interface that is highly efficient for the synthesis of methanol. The combination of metal and oxide sites in the copper-ceria interface affords complementary chemical properties that lead to special reaction pathways for the CO2→CH3OH conversion.

Nanopattering in CeOx/Cu(111): A New Type of Surface Reconstruction and Enhancement of Catalytic Activity.

Our results indicate that small amounts of an oxide deposited on a stable metal surface can trigger a massive surface reconstruction under reaction conditions. In low-energy electron microscopy (LEEM) experiments, no reconstruction of Cu(111) is observed after chemisorbing oxygen or after reducing O/Cu(111) in a CO atmosphere. On the other hand, LEEM images taken in situ during the reduction of CeO2/CuO1-x/Cu(111) show a complex nonuniform transformation of the surface morphology. Ceria particles act as nucleation sites for the growth of copper microterraces once CuO1-x is reduced. Can this reconstructed surface be used to enhance the catalytic activity of inverse oxide/metal catalysts? Indeed, CeOx on reconstructed Cu(111) is an extremely active catalyst for the water-gas shift process (CO + H2O → H2 + CO2), with the Cu microterraces providing very efficient sites for the dissociation of water and subsequent reaction with CO.