•iNOS, CD163 and ARG-I were investigated in GBM tumors and in the surrounding parenchyma from the same patients.•CD163 expression was higher within GBM specimens than in surrounding periphery in both ...male and female patients, and was inversely correlated with mean survival times.•A prevailing iNOS-like profile was present within the tumor, at variance with the peripheral parenchyma surrounding the tumor.•No significant association was found between ARG-I or iNOS expression and survival time.
Microglia and macrophages appear to be the most common cells in the GBM microenvironment. In the present study we investigated the status of macrophages/microglia activation in surgical specimens from 41 patients diagnosed with grade IV GBM. For each patient we analyzed both the center of tumor and the parenchyma surrounding the tumor. The specimens were stained for: i) IBA1, a 17-kDa EF hand protein specifically expressed in microglia/macrophages ii) CD163, a cell surface antigen associated with M2 phenotype; iii) iNOS, taken as a functional marker of M1 phenotype, and iv) ARG-I, taken as a functional marker of M2 phenotype. Staining was scored in a double-blinded score on a scale from 0 to 5. Our results suggest that CD163 expression is higher within the tumor than in surrounding periphery in both male and female patients; while iNOS is higher within the tumor in males, no significant difference was found for ARG-1. In addition, analyzing the data in TGCA database, we found that CD163 expression was significantly and inversely correlated with mean survival times, with average survival times ranging from 448days in patients having low expression, to 319 in mid, and 353 in patients with high CD163 expressing tumors. In contrast, no significant association was found between survival time and ARG-1 or iNOS expression.
•Supported MnOx catalysts studied for tail-end NH3-SCR in marine exhaust cleaning.•Alkali poisoning represents a major concern for SCR catalyst durability.•Highly dispersed MnOx on TiO2 are very ...active but show little tolerance to KCl.•KCl poisoning impacts on surface acidity and MnOx lattice oxygen availability.•ZSM5 support enhances KCl-tolerance of MnOx active phase.
MnOx-based catalysts supported at different loadings on TiO2 (2–10wt%) and H-ZM5 (2–20wt%) were tested for the NH3-SCR of NO in the temperature range 50–250°C. All catalysts showed enhanced activity at low temperature compared to conventional SCR catalyst. A detailed characterization of catalysts (BET, H2-TPR, NH3- and O2-TPD) revealed the predominance of MnO2, with an enhanced dispersion when supported on TiO2. SCR activity at low temperature correlated with lattice oxygen availability, which in turn increased for highly dispersed MnOx. The poisoning effects deriving from a hypothetical Sea Water Scrubber Desulphurization unit placed upstream of the SCR unit were investigated by ex-situ addition of KCl to the catalysts. KCl affected the acidic properties, and particularly the oxygen mobility of the catalysts, lowering, as a consequence, their SCR activity. The strong acidic character of ZSM5 enhanced the tolerance to such poisoning effect.
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•ZnO-CuO dispersion on activated carbon enhances H2S adsorption capacity.•Effect of Cu:Zn ratio investigated at fixed total metal loading in the sorbent.•H2S dynamic adsorption tests ...run at 30°C in N2 followed by TPD of H2S and SO2.•Cu addition improves adsorption capacity and active phase utilization factor.•Reactive H2S adsorption forms both metal sulphates and sulphides.
Sorbents for low temperature reactive adsorption of H2S were prepared by dispersing mixed Zn and Cu oxides onto a commercial activated carbon at fixed total metal loading and Cu:Zn atomic ratios from 0:1 to 1:1. Fresh and spent sorbents were characterized by means of ICP-MS, SEM-EDX, XRD, BET and pore size distribution, DRIFT and sulphur elemental analysis. H2S (50–3000ppmv in N2) removal tests were run under dynamic conditions at 30°C. Due to the high dispersion of the metal oxide phase and its favorable interaction with the carbonaceous support, the functionalized sorbents showed a strongly enhanced adsorption capacity with respect to the raw activated carbon, under dry conditions. Furthermore, the utilization factor of the active phase (moles of S captured per mole of Cu+Zn) increased along with the Cu content up to 76%, thus demonstrating a clear promoting effect of Cu-insertion on the reactivity of ZnO, already at low Cu concentration. Temperature Programmed Desorption (TPD) of H2S and SO2 from saturated sorbents showed that H2S adsorption was coupled with oxidation phenomena leading to the formation of metal sulphates apart from metal sulphides and/or elemental sulphur, testifying the complexity of the surface reactions.
•Rh on La-γ-Al2O3 is highly stable and active catalyst for CH4 dry reforming.•Severe inhibition of dry reforming at 800°C upon sulphur addition already at 1ppmv.•Transient carbon formation on Rh ...induced by S addition.•Reversible S-poisoning effect.
The impact of sulphur poisoning during dry reforming (DR) of methane on a Rh/γ-Al2O3 catalyst was studied by adding up to 30ppmv of SO2 or H2S to the feed (CH4/CO2/N2=1/1/2) at reaction temperatures in the range 800–900°C. As low as 1ppmv of sulphur in the feed adversely affected the H2 and CO yield, and S-poisoning reached a saturation level for contents ≥10ppmv, independently from the type of S-bearing compound. The impact of S addition on the RWGS reaction, occurring simultaneously to DR, was also investigated under steady state operation. Transient poisoning experiments showed a rapid drop of syn-gas production and a corresponding increase in the temperature level, suggesting that sulphur directly bonded to Rh active sites. An increase of coke formation on the catalyst was detected with respect to S-free conditions, and this effect was studied by Raman spectroscopy and thermogravimetric analysis. Sulphur inhibition was reversible and the Rh-catalyst slowly recovered its initial activity after the removal of sulphur from the feed.
Ni- and Ru-based catalytic pellets supported on commercial γ-Al
2
O
3
pellets modified with magnesium oxide have been prepared for application in the catalytic conversion of ethanol into butanol. ...MgO/γ-Al
2
O
3
pellets with or without added metals have been characterized by XRD, SEM/EDX, TGA, N
2
physisorption, H
2
TPR, and CO
2
TPD in order to investigate the effect of MgO coverage and metal distribution on the surface and red-ox properties of the materials and, in turn, their effects on the catalytic performance. The conversion of ethanol into butanol has been investigated in a continuous flow reactor at 350-400 °C under diluted conditions (3% ethanol) in order to rank the different catalytic pellets and identify the best formulations and preparation procedures
via
a comparison with powder catalysts previously proposed in the literature with similar compositions. Results show enhanced catalytic performance for MgO-covered alumina pellets with respect to a pure MgO powder catalyst in spite of the lower MgO load. A significant further positive effect is found when Ni or Ru enters a solid solution with MgO.
Ni- and Ru-based catalytic pellets supported on commercial γ-Al
2
O
3
pellets modified with magnesium oxide have been prepared for application in the catalytic conversion of ethanol into butanol.
Reactive adsorption of hydrogen sulphide (H2S) from gaseous streams at room temperature with mixed Zn and Cu active phase supported onto γ-alumina is dealt in this manuscript. Sorbents with a fixed ...total metal content and variable Cu:Zn ratios were prepared by impregnation of commercial γ-alumina spheres in order to investigate the role of the support and the possible synergic effect between the two metals on the adsorption mechanism and performance. H2S (500–3000 ppmv in N2) removal tests were run under dynamic conditions at 30 °C. Experimental techniques such as BET and pore size distribution by N2-adsorption, SEM-EDX, XRD and DRIFT analysis were coupled for the characterization of fresh and spent sorbents. TPD/TPO experiments on saturated sorbents were performed to assess their regenerability and allowed the speciation of adsorbed sulphur species, testifying the complexity of the surface reactions and the effect of the support.
A CuO/CeO2 catalyst with 4 wt % CuO nominal content has been prepared by solution combustion synthesis (SCS) and characterized by ICP-MS, BET surface area analysis, XPS, HRTEM, and H2, and/or CO TPR. ...The catalyst, showing a rather homogeneous distribution of copper that strongly interacts with ceria, has been tested in CO-PROX reaction. The enhanced performance of the catalyst compared to that of an impregnated sample with the same copper loading has been explained by modeling the experimental CO2 temperature-programmed desorption (TPD) curve, which allowed the determination and quantification of different active sites. The temperature range of activity and the ratio of the amount of sites activating CO and H2 oxidation, respectively, estimated for the two catalysts through the model explain the superior performance of the sample prepared by SCS despite its lower surface area.
To investigate the specificity of the neck shaft angle (NSA) to predict hip fracture in males.
We consecutively studied 228 males without fracture and 38 with hip fracture. A further 49 males with ...spine fracture were studied to evaluate the specificity of NSA for hip-fracture prediction. Femoral neck (FN) bone mineral density (FN-BMD), NSA, hip axis length and FN diameter (FND) were measured in each subject by dual X-ray absorptiometry. Between-mean differences in the studied variables were tested by the unpaired t-test. The ability of NSA to predict hip fracture was tested by logistic regression.
Compared with controls, FN-BMD (p < 0.01) was significantly lower in both groups of males with fractures, whereas FND (p < 0.01) and NSA (p = 0.05) were higher only in the hip-fracture group. A significant inverse correlation (p < 0.01) was found between NSA and FN-BMD. By age-, height- and weight-corrected logistic regression, none of the tested geometric parameters, separately considered from FN-BMD, entered the best model to predict spine fracture, whereas NSA (p < 0.03) predicted hip fracture together with age (p < 0.001). When forced into the regression, FN-BMD (p < 0.001) became the only fracture predictor to enter the best model to predict both fracture types.
NSA is associated with hip-fracture risk in males but is not independent of FN-BMD.
The lack of ability of NSA to predict hip fracture in males independent of FN-BMD should depend on its inverse correlation with FN-BMD by capturing, as the strongest fracture predictor, some of the effects of NSA on the hip fracture. Conversely, NSA in females does not correlate with FN-BMD but independently predicts hip fractures.
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