Cu and Fe oxides dispersed on SBA-15:a Fenton type bimetallic catalyst for N,N-diethyl-p-phenyl diamine degradation

A bimetallic oxidation catalyst has been synthesized via wet impregnation of copper and iron over a mesoporous SBA-15 silica support. Physicochemical properties of the resulting material were characterized by XRD, N2 physisorption, DRUVS, FTIR, Raman, SEM and HRTEM, revealing the structural integrity of the parent SBA-15, and presence of highly dispersed Cu and Fe species present as CuO and Fe2O3. The CuFe/SBA-15 bimetallic catalyst was subsequently utilized for the oxidative degradation of N,N-diethyl-p-phenyl diamine (DPD) employing a H2O2 oxidant in aqueous solution.

A quantitative study of the pathological changes in the cerebellum in 15 cases of variant Creutzfeldt–Jakob disease (vCJD)

Aims: To determine in the cerebellum in variant Creutzfeldt–Jakob disease (vCJD): (i) whether the pathology affected all laminae; (ii) the spatial topography of the pathology along the folia; (iii) spatial correlations between the pathological changes; and (iv) whether the pathology was similar to that of the common methionine/methionine Type 1 subtype of sporadic CJD. Methods: Sequential cerebellar sections of 15 cases of vCJD were stained with haematoxylin and eosin, or immunolabelled with monoclonal antibody 12F10 against prion protein (PrP) and studied using spatial pattern analysis. Results: Loss of Purkinje cells was evident compared with control cases. Densities of the vacuolation and the protease-resistant form of prion protein (PrPSc) (diffuse and florid plaques) were greater in the granule cell layer (GL) than the molecular layer (ML). In the ML, vacuoles and PrPSc plaques occurred in clusters regularly distributed along the folia with larger clusters of vacuoles and diffuse plaques in the GL. There was a negative spatial correlation between the vacuoles and the surviving Purkinje cells in the ML. There was a positive spatial correlation between the vacuoles and diffuse PrPSc plaques in the ML and GL. Conclusions: (i) all laminae were affected by the pathology, the GL more severely than the ML; (ii) the pathology was topographically distributed along the folia especially in the Purkinje cell layer and ML; (iii) pathological spread may occur in relation to the loop of anatomical connections involving the cerebellum, thalamus, cerebral cortex and pons; and (iv) there were pathological differences compared with methionine/methionine Type 1 sporadic CJD.

The use of analysis of variance (ANOVA) in applied microbiology

Experiments combining different groups or factors and which use ANOVA are a powerful method of investigation in applied microbiology. ANOVA enables not only the effect of individual factors to be estimated but also their interactions; information which cannot be obtained readily when factors are investigated separately. In addition, combining different treatments or factors in a single experiment is more efficient and often reduces the number of replications required to estimate treatment effects adequately. Because of the treatment combinations used in a factorial experiment, the DF of the error term in the ANOVA is a more important indicator of the ‘power’ of the experiment than the number of replicates. A good method is to ensure, where possible, that sufficient replication is present to achieve 15 DF for each error term of the ANOVA. Finally, it is important to consider the design of the experiment because this determines the appropriate ANOVA to use. Some of the most common experimental designs used in the biosciences and their relevant ANOVAs are discussed by. If there is doubt about which ANOVA to use, the researcher should seek advice from a statistician with experience of research in applied microbiology.

Sol–gel derived coating applied to long-period gratings for enhanced refractive index sensing properties

Long-period fibre gratings (LPGs) have previously been used to detect quantities such as temperature, strain, and refractive index (RI). We report here, to the best of our knowledge, the first investigation on refractive index sensing properties of LPGs with sol–gel derived titanium and silicon oxide coatings. It is revealed that the RI sensitivity of an LPG is affected by both the thickness and the index value of the coating; a coating with higher index and thickness will enhance the LPG RI sensitivity significantly. The surrounding refractive index induced LPG resonance shift has been evaluated over the LPGs' most sensitive RI region from 1.42 to 1.44. We have identified that, in this region, the uncoated LPG has an RI sensitivity of (-673.0 ± 0.4) nm/uri (unit of refractive index) while the LPG coated with titanium oxide exhibits a sensitivity as high as (-1067.15 ± 0.04) nm/uri. The experimental results also reveal that, even in the RI insensitive region around 1.33, there still is a marked enhancement in RI sensitivity of the sol–gel coated LPG compared to the uncoated one. This is potentially significant as coated LPGs may be extended to low RI gas and semi-liquidized based sensing applications.

Performance modelling and analysis of multiple coexisting IEEE 802.15.4 wireless sensor networks

With the features of low-power and flexible networking capabilities IEEE 802.15.4 has been widely regarded as one strong candidate of communication technologies for wireless sensor networks (WSNs). It is expected that with an increasing number of deployments of 802.15.4 based WSNs, multiple WSNs could coexist with full or partial overlap in residential or enterprise areas. As WSNs are usually deployed without coordination, the communication could meet significant degradation with the 802.15.4 channel access scheme, which has a large impact on system performance. In this thesis we are motivated to investigate the effectiveness of 802.15.4 networks supporting WSN applications with various environments, especially when hidden terminals are presented due to the uncoordinated coexistence problem. Both analytical models and system level simulators are developed to analyse the performance of the random access scheme specified by IEEE 802.15.4 medium access control (MAC) standard for several network scenarios. The first part of the thesis investigates the effectiveness of single 802.15.4 network supporting WSN applications. A Markov chain based analytic model is applied to model the MAC behaviour of IEEE 802.15.4 standard and a discrete event simulator is also developed to analyse the performance and verify the proposed analytical model. It is observed that 802.15.4 networks could sufficiently support most WSN applications with its various functionalities. After the investigation of single network, the uncoordinated coexistence problem of multiple 802.15.4 networks deployed with communication range fully or partially overlapped are investigated in the next part of the thesis. Both nonsleep and sleep modes are investigated with different channel conditions by analytic and simulation methods to obtain the comprehensive performance evaluation. It is found that the uncoordinated coexistence problem can significantly degrade the performance of 802.15.4 networks, which is unlikely to satisfy the QoS requirements for many WSN applications. The proposed analytic model is validated by simulations which could be used to obtain the optimal parameter setting before WSNs deployments to eliminate the interference risks.

New insights in the deactivation of sulfonic modified SBA-15 catalysts for biodiesel production from low-grade oleaginous feedstock

Arenesulfonic-acid functionalized SBA-15 materials have been used in the production of biodiesel from low grade oleaginous feedstock. These materials display an outstanding catalytic activity, being able to promote the transformation of crude palm oil with methanol into fatty acid methyl esters with high yield (85%) under mild reaction conditions. However, high sensitivity of the catalyst against poisoning by different substances has also been detected. Thus, alkaline metal cations, such as sodium or potassium exert a negative influence on the catalytic activity of these materials, being necessary amounts around 500 ppm of sodium in the reaction media to decrease the catalytic activity of these materials to a half of its initial value in just two reaction runs. The deactivation of arenesulfonic acid functionalized SBA-15 materials seems to occur in this case by ion exchange of the acid protons at the sulfonic groups. Organic unsaponifiable compounds like lecithin or retinol also induce a negative influence in the catalytic activity of these sulfonic acid-based materials, though not so intense as in the case of alkaline metals. The deactivating mechanism associated to the influence of the organic compounds seems to be linked to the adsorption of such substances onto the catalytic acid sites as well as on the silica surface. The accumulation of lecithin in the surface of catalyst, observed by means of thermogravimetric analysis, suggest the creation of a strong interaction, probably by ion pair, between this compound and the sulfonic acid group.

Support enhanced α-pinene isomerization over HPW/SBA-15

A family of mesoporous SBA-15 supported H3PW12O40 (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N2 porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g−1) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15.

On the drug adsorption capacity of SBA-15 obtained from various detemplation protocols

The effect of the mild detemplation method, based on Fenton chemistry (with and without previous solvent extraction), and calcination was evaluated by the drug uptake capacity of SBA-15 materials. A number of characterization techniques were applied for evaluation and comparison of the materials properties such as TGA, CNH, N2 physisorption and 29Si NMR. The mild Fenton detemplation method rendered a nearly pristine SBA-15 without structural shrinkage, low residual template, improved surface area, pore volume and silanol concentration. The drug (ibuprofen) adsorption experiments were carried out by solution immersion in powdery form. The mild detemplated samples experienced an enhanced uptake that could be explained by the enhanced density of silanols (mmol/g), originated from the absence of calcination in the Fenton approaches. © 2014 Elsevier B.V.

Modifying the hierarchical porosity of SBA-15 via mild-detemplation followed by secondary treatments

Fenton-chemistry-based detemplation combined with secondary treatments offers options to tune the hierarchical porosity of SBA-15. This approach has been studied on a series of SBA-15 mesophases and has been compared to the conventional calcination. The as-synthesized and detemplated materials were studied with regard to their template content (TGA, CHN), structure (SAXS, TEM), surface hydroxylation (Blin-Carterets approach), and texture (high-resolution argon physisorption). Fenton detemplation achieves 99% of template removal, leading to highly hydroxylated materials. The structure is better preserved when a secondary treatment is applied after the Fenton oxidation, due to the intense capillary forces during drying in water. Two successful approaches are presented: drying in a low-surface-tension solvent (such as n-BuOH) and a hydrothermal stabilization to further condense the structure and make it structurally more robust. Both approaches give rise to remarkably low structural shrinkage, lower than calcination and the direct water-dried Fenton. Interestingly, the derived textural features are remarkably different. The n-BuOH exchange route gives rise to highly hierarchical structures with enhanced interconnecting pores and the highest surface areas. The hydrothermal stabilization produces large-pore SBA-15 structures with high pore volume, intermediate interconnectivity, and minimal micropores. Therefore, the hierarchical texture can be fine-tuned in these two fashions while the template is removed under mild conditions.

Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction

The potential use of the solvothermal extraction (SE) as a preliminary step to calcination for detemplating SBA-15 mesophases is investigated; aiming to reduce the amount of organics to be burnt and thereby the corresponding structural shrinkage. A systematic study was carried out by soxhlet extraction on mesophases hydrothermally aged between 90 and 130 C. The mesophases containing variable amounts of template were then treated by calcination or pyrolysis/calcination. TGA was applied to quantify the template amount after the various treatments. The as obtained materials were characterized by SAXS and Ar ad/desorption for structural and textural information while 1H NMR gave information about the integrity of the as-recycled template. The study shows that solvothermal conditions remove considerably the template, typically from 50 to 10-20 wt.%, mainly extracted from the primary mesopores. Possible reuse of the extracted template is questionable as it is poor in polyethyleneoxide compared to the synthesis block-copolymer, Pluronic P123. For all thermal protocols applied (direct calcination, calcination after solvent-extraction or pyrolysis/calcination after solvent extraction), the thermal shrinkage decreases with the aging temperature; that is consistent with the condensation degree of the silica. For each mesophase, it was found that the thermal shrinkage becomes less pronounced when the material is fully templated; thus the template can serve as structural support or can control the mass transfer of O2 and thereby the oxidation rate of the template burning. © 2013 Elsevier Inc. All rights reserved.