Synthesis and Characterization of Supported Mixed MoW Carbide Catalysts.

For mixed MoW carbide catalysts, the relationship between synthesis conditions, evolution of (mixed) phases, extent of mixing, and catalytic performance of supported Mo/W carbides remains unclear. In this study, we prepared a series of carbon nanofiber-supported mixed Mo/W-carbide catalysts with varying Mo and W compositions using either temperature-programmed reduction (TPR) or carbothermal reduction (CR). Regardless of the synthesis method, all bimetallic catalysts (Mo:W bulk ratios of 1:3, 1:1, and 3:1) were mixed at the nanoscale, although the Mo/W ratio in individual nanoparticles varied from the expected bulk values. Moreover, the crystal structures of the produced phases and nanoparticle sizes differed depending on the synthesis method. When using the TPR method, a cubic carbide (MeC1-x ) phase with 3-4 nm nanoparticles was obtained, while a hexagonal phase (Me2C) with 4-5 nm nanoparticles was found when using the CR method. The TPR-synthesized carbides exhibited higher activity for the hydrodeoxygenation of fatty acids, tentatively attributed to a combination of crystal structure and particle size.

Clinical characteristics of functional dyspepsia depending on chemosensitivity to capsaicin.

BACKGROUND: Augmented chemosensitivity to capsaicin has been demonstrated in approximately half of functional dyspepsia (FD) patients. AIM: We determined clinical characteristics of FD patients with and without chemical hypersensitivity at baseline and after capsaicin ingestion for 4 weeks. METHODS: N=49 outpatients with confirmed FD received an oral sensitivity test with 0.75 mg capsaicin at three occasions, before and after ingesting 0.25 mg capsaicin tid for 4 weeks. Symptomatic response to capsaicin allowed stratification to a capsaicin positive (chemosensitive) and a capsaicin negative (not chemosensitive) patient group. Symptom diaries were completed in the week before and during capsaicin ingestion. RESULTS: A total of 53% FD had a positive capsaicin test, Crohnbach alpha was 0.85. Basic clinical characteristics were comparable in capsaicin positive and negative FD, but median daily aggregate upper gastrointestinal symptoms scores were significantly higher in capsaicin positive (median: 9.4; 5.4/11.7) than in capsaicin negative patients (6.6; 4.1/8.1) (P<.05). After capsaicin ingestion, upper gastrointestinal symptoms scores were reduced by -3.3 (-4.9/-1.9; P<.001) in capsaicin positive and -2.6 (-3.8/-0.3; P<.05) in capsaicin negative patients. Lower abdominal symptoms were comparable in capsaicin positive and negative patients at baseline (NS). After capsaicin ingestion lower gastrointestinal symptoms scores were reduced by -1.0 (-1.8/-0.1; P<.05) in capsaicin positive but not significantly altered (-0.6; -1.7/+0.9; NS) in capsaicin negative patients. After long-term capsaicin ingestion, the capsaicin test turned negative in 53% of chemosensitive patients (P<.01). CONCLUSIONS: Differences in upper GI symptoms distinguished capsaicin positive and negative patients. Symptom improvement after long-term capsaicin ingestion was indirect proportional to the capsaicin test result.

Practical aspects of diffractive imaging using an atomic-scale coherent electron probe.

Four-dimensional scanning transmission electron microscopy (4D-STEM) is a technique where a full two-dimensional convergent beam electron diffraction (CBED) pattern is acquired at every STEM pixel scanned. Capturing the full diffraction pattern provides a rich dataset that potentially contains more information about the specimen than is contained in conventional imaging modes using conventional integrating detectors. Using 4D datasets in STEM from two specimens, monolayer MoS2 and bulk SrTiO3, we demonstrate multiple STEM imaging modes on a quantitative absolute intensity scale, including phase reconstruction of the transmission function via differential phase contrast imaging. Practical issues about sampling (i.e. number of detector pixels), signal-to-noise enhancement and data reduction of large 4D-STEM datasets are emphasized.

Creating a Stable Oxide at the Surface of Black Phosphorus.

The stability of the surface of in situ cleaved black phosphorus crystals upon exposure to atmosphere is investigated with synchrotron-based photoelectron spectroscopy. After 2 days atmosphere exposure a stable subnanometer layer of primarily P2O5 forms at the surface. The work function increases by 0.1 eV from 3.9 eV for as-cleaved black phosphorus to 4.0 eV after formation of the 0.4 nm thick oxide, with phosphorus core levels shifting by <0.1 eV. The results indicate minimal charge transfer, suggesting that the oxide layer is suitable for passivation or as an interface layer for further dielectric deposition.

Photothermal response in dual-gated bilayer graphene.

The photovoltaic and bolometric photoresponse in gapped bilayer graphene was investigated by optical and transport measurements. A pulse coincidence technique at 1.5 µm was used to measure the response times as a function of temperature. The bolometric and photovoltaic response times were found to be identical implying that the photovoltaic response is also governed by hot electron thermal relaxation. Response times of τ ∼ 100-20 ps were found for temperatures from 3-100 K. Above 10 K, the relaxation time was observed to be τ = 25 ± 5 ps, independent of temperature within noise.

Universal conductance fluctuations in Dirac materials in the presence of long-range disorder.

We study quantum transport in Dirac materials with a single fermionic Dirac cone (strong topological insulators and graphene in the absence of intervalley coupling) in the presence of non-Gaussian long-range disorder. We show, by directly calculating numerically the conductance fluctuations, that in the limit of very large system size and disorder strength, quantum transport becomes universal. However, a systematic deviation away from universality is obtained for realistic system parameters. By comparing our results to existing experimental data on 1/f noise, we suggest that many of the graphene samples studied to date are in a nonuniversal crossover regime of conductance fluctuations.

Dual-gated bilayer graphene hot-electron bolometer.

Graphene is an attractive material for use in optical detectors because it absorbs light from mid-infrared to ultraviolet wavelengths with nearly equal strength. Graphene is particularly well suited for bolometers-devices that detect temperature-induced changes in electrical conductivity caused by the absorption of light-because its small electron heat capacity and weak electron-phonon coupling lead to large light-induced changes in electron temperature. Here, we demonstrate a hot-electron bolometer made of bilayer graphene that is dual-gated to create a tunable bandgap and electron-temperature-dependent conductivity. The bolometer exhibits a noise-equivalent power (33 fW Hz(-1/2) at 5 K) that is several times lower, and intrinsic speed (>1 GHz at 10 K) three to five orders of magnitude higher than commercial silicon bolometers and superconducting transition-edge sensors at similar temperatures.

A placebo-controlled trial of an oral capsaicin load in patients with functional dyspepsia.

BACKGROUND: The pathophysiology of functional dyspepsia is poorly understood. Visceral hypersensitivity may play a key role. We studied a previously validated test to assess chemical hypersensitivity in functional dyspepsia by applying an oral capsaicin load. METHODS: A total of 116 outpatients with upper gastrointestinal (GI) symptoms participated in this double-blind, placebo-controlled trial of which 73 patients received a final diagnosis of functional dyspepsia. Patients swallowed a capsule containing 0.75 mg capsaicin or placebo. A graded questionnaire evaluated the severity of nine upper GI symptoms before and after capsule ingestion and an aggregate symptom score was calculated. A final score of >9 was considered as a positive test. KEY RESULTS: In functional dyspepsia, median perception scores were 10.8 (interquartile range: 4.5-18.8) after ingestion of capsaicin and 0.5 (0.0-2.5) after placebo (P < 0.001). Thirty-seven functional dyspepsia patients (54%) had a positive test after capsaicin ingestion, whereas only four (11%) patients with upper GI symptoms but without functional dyspepsia were capsaicin positive [median perception score: 1.5 (0.0-5.0)]. After placebo, symptom scores were low and not significantly different among patient groups (P > 0.05). Clinical characteristics, age, and gender distribution was similar in capsaicin positive and capsaicin negative functional dyspepsia patients (P > 0.05). The value of patient blinding was good. CONCLUSIONS & INFERENCES: Half of functional dyspepsia patients had chemical hypersensitivity, determined with an oral capsaicin load. Placebo response was negligible. The results of the capsaicin test were not associated with specific dyspepsia symptoms or Rome subgroups.

Highly skewed T-cell receptor V-beta chain repertoire in the bone marrow is associated with response to immunosuppressive drug therapy in children with very severe aplastic anemia.

One of the major obstacles of immunosuppressive therapy (IST) in children with severe aplastic anemia (SAA) comes from the often months-long unpredictability of bone-marrow (BM) recovery. In this prospective study in children with newly diagnosed very severe AA (n=10), who were enrolled in the therapy study SAA-BFM 94, we found a dramatically reduced diversity of both CD4+ and CD8+ BM cells, as scored by comprehensive V-beta chain T-cell receptor (TCR) analysis. Strongly skewed TCR V-beta pattern was highly predictive for good or at least partial treatment response (n=6, CD8+ complexity scoring median 35.5, range 24-73). In contrast, IST in patients with rather moderate reduction of TCR V-beta diversity (n=4, CD8+ complexity scoring median 109.5, range 82-124) always failed (P=0.0095). If confirmed in a larger series of patients, TCR V-beta repertoire in BM may help to assign children with SAA up-front either to IST or to allogeneic stem-cell transplantation.

High-fidelity conformation of graphene to SiO2 topographic features.

High-resolution noncontact atomic force microscopy of SiO2 reveals previously unresolved roughness at the few-nm length scale, and scanning tunneling microscopy of graphene on SiO2 shows graphene to be slightly smoother than the supporting SiO2 substrate. A quantitative energetic analysis explains the observed roughness of graphene on SiO2 as extrinsic, and a natural result of highly conformal adhesion. Graphene conforms to the substrate down to the smallest features with nearly 99% fidelity, indicating conformal adhesion can be highly effective for strain engineering of graphene.

Successful SCT for Nijmegen breakage syndrome.

Nijmegen breakage syndrome (NBS) is characterized by chromosomal instability, radiation hypersensitivity, characteristic facial appearance, immunodeficiency and strong predisposition to lymphoid malignancy. Traditionally, NBS patients have not undergone hematopoietic SCT (HSCT) owing to concerns about increased toxicity. We therefore report on the HSCT experience in NBS patients in Europe. Six patients were transplanted either for resistant or secondary malignancy (four patients) or severe immunodeficiency (two patients). Five patients received reduced-intensity conditioning regimens. After a median follow-up of 2.2 years, five patients are alive and well. One patient who received myeloablative conditioning died from sepsis before engraftment. Acute GVHD grades I-II occurred in three of five patients, mild chronic GVHD in one. All five surviving patients exhibit restored T-cell immunity. The experience in these six patients suggests that HSCT in NBS is feasible, can correct the immunodeficiency and effectively treat malignancy. Acute toxicity seems to be reasonable with reduced-intensity conditioning regimens.

Allogeneic stem cell transplantation for pediatric and adolescent patients with CML: results from the prospective trial CML-paed I.

PURPOSE: Stem cell transplantation (SCT) can definitely cure chronic myeloid leukemia (CML), a rare disease in childhood. We prospectively evaluated the results of early SCT in pediatric CML after standardized pretreatment with hydroxyurea+/-interferon. PATIENTS AND METHODS: Between 1995 and 2004, 200 children (median age: 12.4 years) were enrolled and stratified: given the availability of an HLA-matched related donor (MRD), SCT was scheduled within 6 months and otherwise from an unrelated donor (UD) within 12 months following diagnosis. RESULTS: 176 patients underwent SCT; from MRD within median 4 months and from UD within median 11 months after diagnosis. At SCT, 158 patients were in chronic phase (CP1 or CP2), 9 patients were in accelerated phase and 9 patients were in blast crisis (BC). The conditioning regimen - total body irradiation or busulfan - exerted no different impact on overall survival (OS). Probability of OS at 5 years was 87+/-11% if grafted from a sibling (n=41), 52+/-9% from matched UD (MUD, n=71), and 45+/-16% from mismatched donors (MMD, n=55), respectively. A trend for better OS in CP1 was observed if SCT was performed within 6 months (n=49; 74+/-9%), compared to 7-12 months (n=52; 62+/-15%), and >12 months (n=43; 62+/-17%) after diagnosis, respectively (p=0.157). Probability of relapse at 5 years was 20+/-12%. Transplant-related mortality and graft-versus-host disease mainly contributed to the inferior outcome in UD and HLA-mismatched SCT. CONCLUSION: These data from the first prospective trial on CML restricted to children and adolescents might be considered for decision making when balancing the risks of SCT against the increasing use of imatinib as upfront treatment for CML.

Re-transplantation from the same unrelated donor in three adolescents with severe aplastic anemia after graft rejection.

Hematopoietic stem cell transplantation (HSCT) from a matched unrelated donor (MUD) has become the accepted salvage treatment for patients with severe aplastic anemia (SAA) lacking a matched sibling donor and failing immunosuppressive treatment. However, non-engraftment and early rejection remain main reasons for treatment related morbidity and mortality. We report on three adolescents who were grafted from MUD, rejected their graft and were re-grafted 47-51 days after first HSCT from the same donor. For conditioning, fludarabine, cyclophosphamide, ATG and/or OKT3 in combination with total lymphoid irradiation was used. Unmanipulated peripheral blood stem cells at a minimum dose of 8 x 10(6)/kg CD34+cells were infused. Acute toxicity was low. Two patients are alive and well for more than 3 years, one patient developed extended chronic graft-versus-host disease from which he died 34 months after second HSCT. Re-transplantation from MUD in the case of non-engraftment or rejection from the same donor is possible following immunoablation combined with intensive serotherapy in young patients with SAA.

Defect scattering in graphene.

Irradiation of graphene on SiO2 by 500 eV Ne and He ions creates defects that cause intervalley scattering as is evident from a significant Raman D band intensity. The defect scattering gives a conductivity proportional to charge carrier density, with mobility decreasing as the inverse of the ion dose. The mobility decrease is 4 times larger than for a similar concentration of singly charged impurities. The minimum conductivity decreases proportional to the mobility to values lower than 4e(2)/pih, the minimum theoretical value for graphene free of intervalley scattering. Defected graphene shows a diverging resistivity at low temperature, indicating insulating behavior. The results are best explained by ion-induced formation of lattice defects that result in midgap states.

Effect of repeated, long term capsaicin ingestion on intestinal chemo- and mechanosensation in healthy volunteers.

Repeated ingestion of capsaicin over a prolonged period reduces symptoms in functional dyspepsia, but initially induces upper abdominal symptoms. Sensitizing chemonociception might be the cause for this initial effect of capsaicin. The aim was to evaluate the effect of prolonged capsaicin ingestion on duodenal chemo- and mechanonociception. Healthy subjects ingested capsules containing either 0.25 mg capsaicin tid (n = 8) or placebo (n = 8) for 28 days. Before (day 0) and after (day 29) capsule ingestion the duodenum was distended with a balloon and perfused with a capsaicin solution. Mechanically and chemically induced sensation was evaluated by a graded questionnaire. Aggregate perception scores were calculated. Perception scores during balloon distensions with 12 and 18 mmHg were significantly lower after 4 weeks capsaicin when compared to baseline (P < 0.05). Balloon volumes to induce first sensation (63 +/- 14 mL (day 0) vs 92 +/- 22 mL (day 29); P < 0.05) and discomfort (101 +/- 12 mL vs 137 +/- 22 mL; P = 0.05) where significantly higher after 4 weeks capsaicin application; balloon pressures to induce sensations were not significantly different. Intraluminal capsaicin application induced first sensation after 3.4 +/- 1.5 min (day 0) and 7.5 +/- 4.6 min (day 29) (P < 0.05) and discomfort after 15.9 +/- 9.8 min and 22.4 +/- 7.3 min (P < 0.05). The quality of perception was not altered by repeated capsaicin ingestion. In the placebo group, mechano- and chemonociception remained unaltered at day 29. Four weeks ingestion of capsaicin desensitized both chemonociceptive and mechanonociceptive pathways in healthy volunteers. Symptom reduction after prolonged treatment with capsaicin in dyspeptic patients might be attributed to a dual desensitizing effect of capsaicin on chemonociceptors and mechanonociceptors.

Risk-adapted procedures for HSCT from alternative donor in children with severe aplastic anaemia.

The outcome of haematopoietic SCT (HSCT) from matched unrelated donors in children with severe aplastic anaemia (SAA) has improved significantly in the last decade and should be offered to all children who fail to respond to their first course of combined immunosuppressive therapy. High-resolution typing for HLA class I and II is mandatory for donor selection. In 10/10 or 9/10 alleles matched donors, a non-TBI conditioning based on fludarabine, CY and anti-thymocyte globulin is sufficient to allow for sustained engraftment when unmanipulated BM is used. Owing to increased rates of cGVHD after PBSC transplantation are reported in young patients, BM is the preferred stem cell source. HSCT from mismatched related and unrelated donors are still high-risk procedures. New techniques for graft manipulation such as CD3/CD19 depletion might improve engraftment and immune reconstitution. In T-cell depleted grafts, irradiation-based conditioning seems to be inevitable to reduce the high risk for rejection.

Polymerase chain reaction fingerprinting of Erwinia amylovora has a limited phylogenetic value but allows the design of highly specific molecular markers.

Erwinia amylovora, the causal agent of fire blight, is genetically very homogeneous, and current methodologies provide insufficient or contradictory information about the probable dispersal routes of the pathogen. With the final aim to obtain specific and reliable molecular markers for different lineages of the pathogen, we studied the molecular basis of rep-polymerase chain reaction (PCR) polymorphism using seven different arbitrary primers to fingerprint 93 E. amylovora strains from different countries, including Spain. Polymorphism was very low, and was displayed by only 11 E. amylovora strains, which produced 22 polymorphic bands. Five of 11 polymorphic bands cloned contained DNA that was present in more than 85% of the strains, whereas six bands were due to DNA present exclusively in the strains producing the rep-PCR polymorphism. Also, five of the polymorphic bands were due to the possession of either the ubiquitous plasmid pEA29, of plasmid pEU30, which was exclusively found in strains from North America, or of a 35-kb cryptic plasmid, present only in 28 strains from Northern Spain. We designed primer pairs from several cloned polymorphic bands that allowed the specific identification of the strains producing the polymorphism. Our results indicate that rep-PCR is not adequate for constructing genealogies of E. amylovora, although the strategy illustrated here, as well as the designed primers, can be used effectively in epidemiological studies with this pathogen.

Tuning the effective fine structure constant in graphene: opposing effects of dielectric screening on short- and long-range potential scattering.

We reduce the dimensionless interaction strength alpha in graphene by adding a water overlayer in ultrahigh vacuum, thereby increasing dielectric screening. The mobility limited by long-range impurity scattering is increased over 30%, due to the background dielectric constant enhancement leading to a reduced interaction of electrons with charged impurities. However, the carrier-density-independent conductivity due to short-range impurities is decreased by almost 40%, due to reduced screening of the impurity potential by conduction electrons. The minimum conductivity is nearly unchanged, due to canceling contributions from the electron-hole puddle density and long-range impurity mobility. Experimental data are compared with theoretical predictions with excellent agreement.

Density inhomogeneity driven percolation metal-insulator transition and dimensional crossover in graphene nanoribbons.

Transport in graphene nanoribbons with an energy gap in the spectrum is considered in the presence of random charged impurity centers. At low carrier density, we predict and establish that the system exhibits a density inhomogeneity driven two dimensional metal-insulator transition that is in the percolation universality class. For very narrow graphene nanoribbons (with widths smaller than the disorder induced length scale), we predict that there should be a dimensional crossover to the 1D percolation universality class with observable signatures in the transport gap. In addition, there should be a crossover to the Boltzmann transport regime at high carrier densities. The measured conductivity exponent and the critical density are consistent with this percolation transition scenario.