Steam reforming of methanol over oxide decorated nanoporous gold catalysts: a combined in situ FTIR and flow reactor study.

Methanol as a green and renewable resource can be used to generate hydrogen by reforming, i.e., its catalytic oxidation with water. In combination with a fuel cell this hydrogen can be converted into electrical energy, a favorable concept, in particular for mobile applications. Its realization requires the development of novel types of structured catalysts, applicable in small scale reactor designs. Here, three different types of such catalysts were investigated for the steam reforming of methanol (SRM). Oxides such as TiO2 and CeO2 and mixtures thereof (Ce1Ti2Ox) were deposited inside a bulk nanoporous gold (npAu) material using wet chemical impregnation procedures. Transmission electron and scanning electron microscopy reveal oxide nanoparticles (1-2 nm in size) abundantly covering the strongly curved surface of the nanoporous gold host (ligaments and pores on the order of 40 nm in size). These catalysts were investigated in a laboratory scaled flow reactor. First conversion of methanol was detected at 200 °C. The measured turn over frequency at 300 °C of the CeOx/npAu catalyst was 0.06 s-1. Parallel investigation by in situ infrared spectroscopy (DRIFTS) reveals that the activation of water and the formation of OHads are the key to the activity/selectivity of the catalysts. While all catalysts generate sufficient OHads to prevent complete dehydrogenation of methanol to CO, only the most active catalysts (e.g., CeOx/npAu) show direct reaction with formic acid and its decomposition to CO2 and H2. The combination of flow reactor studies and in operando DRIFTS, thus, opens the door to further development of this type of catalyst.

The origin of a large apparent tortuosity factor for the Knudsen diffusion inside monoliths of a samaria-alumina aerogel catalyst: a diffusion NMR study.

Pulsed field gradient (PFG) NMR was applied to measure tortuosity factors for carbon dioxide diffusion in the Knudsen and gas regimes inside monoliths of a samaria-alumina aerogel catalyst, a high porosity material containing micropores in addition to meso- and macropores. The apparent tortuosity factor obtained from PFG NMR measurements for the Knudsen diffusion in the meso- and macropores of the catalyst has an unexpectedly large value of approximately 6 if carbon dioxide adsorption in the micropores and other types of surface adsorption sites of the catalyst is ignored. At the same time, the corresponding apparent tortuosity factor in the gas regime was found to be around 2. Application of a proposed model which describes fast molecular exchange between the surface adsorption sites and the main pore volume of the catalyst yields corrected tortuosity factors which depend only on the pore system geometry. Using this model, the corrected tortuosity factors were found to be around 2 for both diffusion regimes, in agreement with the expectations based on a high porosity of the studied catalyst.

Maggot excretion products from the blowfly Lucilia sericata contain contact phase/intrinsic pathway-like proteases with procoagulant functions.

For centuries, maggots have been used for the treatment of wounds by a variety of ancient cultures, as part of their traditional medicine. With increasing appearance of antimicrobial resistance and in association with diabetic ulcers, maggot therapy was revisited in the 1980s. Three mechanisms by which sterile maggots of the green bottle fly Lucilia sericata may improve healing of chronic wounds have been proposed: Biosurgical debridement, disinfecting properties, and stimulation of the wound healing process. However, the influence of maggot excretion products (MEP) on blood coagulation as part of the wound healing process has not been studied in detail. Here, we demonstrate that specific MEP-derived serine proteases from Lucilia sericata induce clotting of human plasma and whole blood, particularly by activating contact phase proteins factor XII and kininogen as well as factor IX, thereby providing kallikrein-bypassing and factor XIa-like activities, both in plasma and in isolated systems. In plasma samples deficient in contact phase proteins, MEP restored full clotting activity, whereas in plasma deficient in either factor VII, IX, X or II no effect was seen. The observed procoagulant/intrinsic pathway-like activity was mediated by (chymo-) trypsin-like proteases in total MEP, which were significantly blocked by C1-esterase inhibitor or other contact phase-specific protease inhibitors. No significant influence of MEP on platelet activation or fibrinolysis was noted. Together, MEP provides contact phase bypassing procoagulant activity and thereby induces blood clotting in the context of wound healing. Further characterisation of the active serine protease(s) may offer new perspectives for biosurgical treatment of chronic wounds.

Structural transitions of epitaxial ceria films on Si(111).

The structural changes of a (111) oriented CeO2 film grown on a Si(111) substrate covered with a hex-Pr2O3(0001) interface layer due to post deposition annealing are investigated. X-ray photoelectron spectroscopy measurements revealing the near surface stoichiometry show that the film reduces continuously upon extended heat treatment. The film is not homogeneously reduced since several coexisting crystalline ceria phases are stabilized due to subsequent annealing at different temperatures as revealed by high resolution low energy electron diffraction and X-ray diffraction. The electron diffraction measurements show that after annealing at 660 °C the ι-phase (Ce7O12) is formed at the surface which exhibits a (√7 × âˆš7)R19.1° structure. Furthermore, a (√27 × âˆš27)R30° surface structure with a stoichiometry close to Ce2O3 is stabilized after annealing at 860 °C which cannot be attributed to any bulk phase of ceria stable at room temperature. In addition, it is shown that the fully reduced ceria (Ce2O3) film exhibits a bixbyite structure. Polycrystalline silicate (CeSi(x)O(y)) and crystalline silicide (CeSi1.67) are formed at 850 °C and detected at the surface after annealing above 900 °C.

Synthesis of stable AuAg bimetallic nanoparticles encapsulated by diblock copolymer micelles.

We present a facile method for the preparation of bimetallic AuAg nanoparticles (NPs) with controlled size and composition rendering them ideally suitable for optical and catalytic applications. In analogy to methods for the generation of monometallic Au and Ag NPs, AuAg NPs were prepared inside polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block-copolymer micelles formed in toluene, by loading the P4VP cores of the micelles first with AgNO(3) and then with HAuCl(4). In contrast to the reverse sequence of loading, homogenously bimetallic AuAg particle arrays were achieved after reduction carried out in solution with hydrazine monohydrate as the reducing agent. TEM reveals that stable and spherical NPs can be prepared well separated from one another and with a narrow size distribution with diameters of ∼3 nm. The bimetallic NP composition was confirmed by energy-dispersive X-ray spectroscopy (EDX) of single NPs. The atomic ratio of Ag and Au contained in single particles is in good agreement with the relative concentrations of both metals used in the synthesis which was confirmed by atomic absorption spectroscopy. The atomic ratio Au : Ag was systematically varied between 3 : 1 and 1 : 3. For all ratios UV-vis spectra showed a single plasmon band. Its wavelength varied from 430 for Au : Ag = 1 : 3 to 515 nm for Au : Ag = 3 : 1, showing a linear dependence on the relative amount of gold within the range of plasmon wavelengths from monometallic gold (538 nm) to silver (415 nm).

Supported colloidal nanoparticles in heterogeneous gas phase catalysis: on the way to tailored catalysts.

Using colloidally synthesized nanoparticles for the preparation of supported catalysts offers several advantages (e.g. precise control of particle size and morphology) when compared to traditional preparation techniques. Although such nanoparticles have already been very successfully used for catalytic applications in the liquid phase, applications in heterogeneous gas phase catalysis are still scarce. One aspect, usually considered as a problem, is organic stabilizers typically employed during the nanoparticle synthesis since they or their decomposition products are supposed to block catalytically active sites on the nanoparticle surface. Thus, in many studies so far, the removal of the organic ligands prior to use in gas phase catalysis has been proposed. In this perspective article, however, we will discuss a number of benefits such ligand shells may have for heterogeneous gas phase catalysis, including the protection against chemical modification, prevention of sintering and tuning of SMSI effects.

Photoemission study of praseodymia in its highest oxidation state: the necessity of in situ plasma treatment.

A cold radio frequency oxygen plasma treatment is demonstrated as a successful route to prepare clean, well-ordered, and stoichiometric PrO(2) layers on silicon. High structural quality of these layers is shown by x-ray diffraction. So far unobserved spectral characteristics in Pr 3d x-ray photoelectron (XP) spectra of PrO(2) are presented as a fingerprint for praseodymia in its highest oxidized state. They provide insight in the electronic ground state and the special role of praseodymia among the rare earth oxides. They also reveal that former XP studies suffered from a significant reduction at the surface.

Nanoporous gold catalysts for selective gas-phase oxidative coupling of methanol at low temperature.

Gold (Au) is an interesting catalytic material because of its ability to catalyze reactions, such as partial oxidations, with high selectivities at low temperatures; but limitations arise from the low O2 dissociation probability on Au. This problem can be overcome by using Au nanoparticles supported on suitable oxides which, however, are prone to sintering. Nanoporous Au, prepared by the dealloying of AuAg alloys, is a new catalyst with a stable structure that is active without any support. It catalyzes the selective oxidative coupling of methanol to methyl formate with selectivities above 97% and high turnover frequencies at temperatures below 80 degrees C. Because the overall catalytic characteristics of nanoporous Au are in agreement with studies on Au single crystals, we deduced that the selective surface chemistry of Au is unaltered but that O2 can be readily activated with this material. Residual silver is shown to regulate the availability of reactive oxygen.

Surface-chemistry-driven actuation in nanoporous gold.

Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry-driven actuation can be realized in high-surface-area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes of the order of a few tenths of a per cent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into a mechanical response, thus opening the door to surface-chemistry-driven actuator and sensor technologies.

The effect of sildenafil on gastric emptying in patients with end-stage renal failure and symptoms of gastroparesis.

BACKGROUND: Delayed gastric emptying is a common disorder among patients with end-stage renal failure (ESRF). Pyloric relaxation, a major determinant of gastric emptying, is a nitric oxide (NO)-mediated process. NO-induced smooth muscle relaxation is mediated through its second messenger cyclic guanosine monophosphate, which is broken by tissue phosphodiesterases (PDEs). Thus the inhibition of cyclic guanosine monophosphate breakdown by PDE inhibitors can potentiate NO-mediated responses and facilitate pyloric relaxation. In an animal model of diabetes mellitus, treatment with sildenafil (a PDE-5 inhibitor) restored NO-mediated pyloric relaxation and improved gastric emptying. The aim of our study was to examine the hypothesis that sildenafil may improve gastric emptying in patients with ESRF and symptoms of gastric paresis. METHODS: We studied 12 patients with ESRF (6 men; age range, 54-80 years; 5 with diabetic nephropathy; 4 +/- 1 years receiving long-term renal replacement therapy) after either placebo or a 25-mg tablet of sildenafil (Viagra; Pfizer Inc). Gastric emptying of a solid meal (one medium-sized fried egg mixed with 37 MBq [1 mCi] technetium Tc 99m phytate plus 1 slice of bread and 150 mL of water at the end of the meal) was assessed 1 hour after dosing by use of a single-headed camera. Images were acquired every 30 seconds for 90 minutes immediately after patients ate. RESULTS: The gastric emptying rate was decreased at baseline (after placebo), to 33% +/- 6% (normal, > or =50%). Treatment with sildenafil had no effect on gastric emptying rates after 90 minutes (from 33% +/- 6% after placebo to 30% +/- 6% after sildenafil, P =.9). CONCLUSIONS: Sildenafil did not improve gastric emptying in patients with ESRF and gastric paresis. Sildenafil may have opposing effects on gastric peristalsis (causing gastric relaxation) compared with its effects on pyloric relaxation. Studies combining sildenafil with prokinetic drugs are of interest.

QTL mapping for resistance against non-parasitic leaf spots in a spring barley doubled haploid population.

Phenotypic variability for resistance against non-parasitic leaf spots (NPLS) has been observed between varieties. For the genetic characterization of NPLS resistance, a population with 430 doubled haploid (DH) lines was developed from the cross between the NPLS-resistant Hordeum vulgare breeding line IPZ24727 and the NPLS-sensitive barley cultivar Barke. A molecular map was constructed based on 164 AFLPs, 30 SSRs and one STS marker derived from the mlo gene. Field trials were performed over four environments in which NPLS and other agronomic traits were assessed. Estimates of genotypic variance were highly significant for NPLS. Moreover, no transgression was found for the trait. Quantitative trait loci (QTLs) for NPLS resistance were mapped in the DH population on chromosomes 1H, 4H, and 7H, with the most important effect on chromosome 4H. The QTLs for NPLS explained together 39% of the phenotypic and 49% of the genotypic variance, thereby showing additive gene action. Consequently, marker-assisted selection for improving NPLS resistance is possible.

Determination of atomic structure of the metal-oxide interface: Pd nanodeposits on an FeO(111) film.

Palladium was vapor deposited on a thin FeO(111) film grown on a Pt(111) substrate. Scanning tunneling microscopy study has revealed that Pd wets the FeO substrate and at elevated temperatures forms extended Pd(111) monolayer islands in contrast to other oxide supports previously studied. For the first time, we have imaged the metal-oxide interface structure with atomic resolution and explained the results on the basis of ab initio calculations.

Cluster, facets, and edges: site-dependent selective chemistry on model catalysts.

More than activity, selectivity of catalytic reactions is the focus of research in the 21(st) century. We review studies on model systems that address the issue of directing a catalytic reaction on disperse metal catalysts by controlling the specific surface site. Three examples are explored: methanol dehydrogenation over Pd/alumina, NO dissociation on Pd/alumina, and reaction studies for molecules relevant in a Fischer-Tropsch scenario on a bimetallic Pd/Co/alumina model catalyst. We show how surface science can be used by combining a variety of experimental techniques to study the chemistry of model catalysts at the atomic level.

Physicians' preferences and expectations in traumatic brain injury rehabilitation--results of a case-based questionnaire survey.

PURPOSE: Analysis of medical decisions in the differential allocation of traumatic brain injury (TBI) rehabilitation programmes. METHOD: Medical specialists routinely involved in the treatment and rehabilitation of TBI patients from acute hospitals, rehabilitation centres, and the Medical Services of the Workers' Pension Insurance of Sachsen-Anhalt and Mecklenburg-Vorpommern were included in a systematic survey, in which they had to give their opinions on the individually optimal rehabilitation setting and therapies and probable outcome on the basis of case vignettes. These specialists are crucial for decision-making in rehabilitation resource allocation. RESULTS: Both allocation and prognosis depended mainly on patient characteristics. In a mixed logistic regression model, which takes into account that: (a) patient and physician characteristics may influence each other; and (b) that expert assessments might be correlated, setting preferences were related to chronicity and degree of motor and cognitive impairment, but also to the institutional background of the reviewer. Neuropsychological therapy dominated intervention recommendations, followed by physio- and occupational therapy. A comparatively great demand of psychotherapy and medicosocial assessment was recognized. Preferred rehabilitation setting did not influence the physicians' subjective prognosis. Older, chronic and motorically impaired patients were considered to profit less from rehabilitation. Physician characteristics and recommendations of either rehabilitation setting or therapies did not influence prognostic expectations. CONCLUSIONS: Physician characteristics influenced setting preferences. Preferences for type of treatment and ADL-prognosis depended on patients' variables only. Expected effects of rehabilitation were independent on rehabilitation setting and kinds of treatment.

Physicians' preferences and expectations in stroke rehabilitation--results of a case-based questionnaire survey.

PURPOSE: Analysis of medical decisions in the differential allocation of stroke rehabilitation programmes. METHOD: Medical specialists routinely involved in the treatment and rehabilitation of stroke patients from acute hospitals, rehabilitation centres, and the Medical Services of the Workers' Pension Funds of Sachsen-Anhalt and Mecklenburg-Vorpommern were included in a systematic survey, in which they had to give their opinions on the individually optimal rehabilitation setting and therapies and probable outcome on the basis of case vignettes. These specialists are crucial for decision-making in rehabilitation resource allocation. RESULTS: Both allocation and prognosis did not depend only on patient but also on physician characteristics. Neurologists tended to prefer outpatient rehabilitation and expected a greater effect of rehabilitation upon ADL-function than specialists from other professions. Preferred rehabilitation setting did not influence the physicians' subjective prognosis. For patients who qualified both for in- and outpatient rehabilitation, the two settings, therapeutic potentials were considered to be equivalent. CONCLUSIONS: Differences in setting and treatment preferences between experts concerning optimal treatment cannot be resolved on the basis of available evidence. Further data are required that allow to decide which type of rehabilitation is best suited for a given patient.

99Tc(m)-tetrofosmin scintimammography for detecting breast cancer: a comparative study with 99Tc(m)-MIBI.

Scintimammography using 99Tc(m)-MIBI (99Tc(m)-sestamibi) has demonstrated promising results in the detection of breast cancer. Recently scintimammography using 99Tc(m)-tetrofosmin has been suggested as a better diagnostic tool and a more convenient agent to use in this condition. In this study we compared both agents in 35 consecutive women with abnormal mammographic or physical findings. Thirty-four of them underwent MIBI scan, followed by tetrofosmin scan 2 days later (performed on all 35 women). Within 2 weeks, a pathological diagnosis was obtained either by needle or open biopsy. In both scans the uptake ratio between the lesion and the background uptake was calculated. Twenty patients who underwent tetrofosmin scan and 19 patients with MIBI scan had malignant breast tumours, while 15 women had benign lesions. The sensitivity, specificity, positive and negative predictive values and total accuracy of the MIBI scan were 89.4%, 80%, 85%, 85.7% and 85.3%, respectively; almost identical values were obtained with tetrofosmin (90%, 80%, 85.6%, 85.7% and 85.7%, respectively). The uptake ratios in the MIBI and tetrofosmin scans were 1.68 +/- 0.52 and 1.7 +/- 0.47, respectively. No differences were found between the two scintimammographies in all the parameters examined. In conclusion, MIBI and tetrofosmin breast scans are accurate and equally efficient for the detection of breast malignancies.

Physicians' estimates of rehabilitation requirements after stroke and traumatic brain injury--a questionnaire survey in East Germany.

PURPOSE: The provision of rehabilitation services is organized differently in Germany than most other countries, with large indication-specific in-patient centres. This study is aimed at the rehabilitative knowledge of physicians who initiate and conduct rehabilitation in Germany. METHODS: Medical specialists routinely involved in the treatment and rehabilitation of patients with stroke and traumatic brain injury (TBI) from acute hospitals, rehabilitation centres, and the Medical Services of the Workers' Pension Funds of Sachsen-Anhalt and Mecklenburg-Vorpommern were included in a systematic questionnaire survey aiming at the rehabilitation requirements of patients under their care or evaluation. These specialists are crucial for decision-making in rehabilitation ressource allocation. RESULTS: According to these experts, rehabilitation requirements for stroke and TBI patients are dominated by deficits in motor functions and daily-living. They are aware that TBI rehabilitation includes a greater focus on memory functions, problem-solving and attention, and in stroke on language functions. According to the surveyed specialists, the present system of medical rehabilitation in Germany covers the requirements of stroke and TBI patients only partially. Deficits are identified in out-patient and day clinic rehabilitation. CONCLUSIONS: Although the knowledge of rehabilitation requirements is adequate in general, its large ranges reflect the necessity for further analysis. The opinions of the surveyed specialists reflect their respective professional setting. Advantages and disadvantages of the German system require further investigation.

99mTc-MIBI scintigraphy in musculoskeletal tumors.

UNLABELLED: The aim of this study was to assess the value of 99mTc-hexakis2-methoxyisobutylisonitrile (MIBI) scintigraphy in patients with clinical and radiologic features of primary or metastatic musculoskeletal tumors. METHODS: The scintigraphic findings for 84 patients were compared with the surgical and histologic findings. Each patient underwent three-phase bone scanning with 99mTc-methylene diphosphonate (MDP) and dynamic and static MIBI scintigraphy. The MIBI scans were evaluated by visual and quantitative analysis. The count ratio of the lesion to the adjacent or contralateral normal area (L/N) was calculated from the region of interest drawn on the MIBI scan. The Mann-Whitney test was used to determine the differences between the uptake ratios of malignant and benign lesions. RESULTS: Although increased MDP uptake was not specific for bone malignancy, a significant difference was found between benign tumors (L/N = 1.22 +/- 0.43) and malignant tumors (L/N = 2.25 +/- 1.03) on MIBI scans. Sensitivity and specificity were 81% and 87%, respectively. Forty-six of 53 proven benign lesions did not show significant MIBI uptake. The negative predictive value was 88%. In all seven sites of pathologic fracture, significant uptake was seen. However, three malignant lesions were not detected by MIBI scintigraphy, whereas seven benign lesions showed false-positive results. CONCLUSION: The major diagnostic worth of MIBI scintigraphy is its high negative predictive value. Although not capable of replacing tissue biopsy as a definitive diagnostic modality for musculoskeletal neoplasms, MIBI scintigraphy does appear to have a role in better preoperative assessment and in distinguishing between pathologic and simple fractures.

Yeast Ran-binding protein Yrb1p is required for efficient proteolysis of cell cycle regulatory proteins Pds1p and Sic1p.

Ubiquitin-dependent proteolysis of specific target proteins is required for several important steps during the cell cycle. Degradation of such proteins is strictly cell cycle-regulated and triggered by two large ubiquitin ligases, termed anaphase-promoting complex (APC) and Skp1/Cullin/F-box complex (SCF). Here we show that yeast Ran-binding protein 1 (Yrb1p), a predominantly cytoplasmic protein implicated in nucleocytoplasmic transport, is required for cell cycle regulated protein degradation. Depletion of Yrb1p results in the accumulation of unbudded G(1) cells and of cells arrested in mitosis implying a function of Yrb1p in the G(1)/S transition and in the progression through mitosis. Temperature-sensitive yrb1-51 mutants are defective in APC-mediated degradation of the anaphase inhibitor protein Pds1p and in degradation of the cyclin-dependent kinase inhibitor Sic1p, a target of SCF. Thus, Yrb1p is crucial for efficient APC- and SCF-mediated proteolysis of important cell cycle regulatory proteins. We have identified the UBS1 gene as a multicopy suppressor of yrb1-51 mutants. Ubs1p is a nuclear protein, and its deletion is synthetic lethal with a yrb1-51 mutation. Interestingly, UBS1 was previously identified as a multicopy suppressor of cdc34-2 mutants, which are defective in SCF activity. We suggest that Ubs1p may represent a link between nucleocytoplasmic transport and ubiquitin ligase activity.

Glucose and ras activity influence the ubiquitin ligases APC/C and SCF in Saccharomyces cerevisiae.

In budding yeast, the Ras/cAMP pathway is involved in the coordination of cell growth and cell division. Glucose-rich medium stimulates Ras/cAMP signaling, which causes an increase in the critical cell size for cell cycle entry. Here we show that glucose and activated Ras proteins also influence the function of the anaphase-promoting complex (APC/C), a ubiquitin-protein ligase required for sister chromatid separation and mitotic exit. We found that apc10-22 and other mutants defective in the APC/C are suppressed by reduced Ras signaling activity, by a deletion of the RAS2 gene, by a cdc25 mutation, by elevated levels of PDE2, or by growth without glucose. Viability of these mutants is also enhanced by decreased Cdk1 activity. In contrast, a constitutively activated RAS2(Val19) allele or shifts to glucose medium are deleterious to apc10-22 mutants. Remarkably, cdc34-2 mutants, which are impaired in SCF function, are differently affected with respect to Ras activity. Viability of cdc34-2 mutants at elevated temperatures is dependent on glucose and the RAS2 gene. We conclude that glucose and Ras proteins influence the APC/C and the SCF complex in an opposite manner. These ubiquitin ligases might represent novel targets for modulating cell division in response to growth conditions.