High capacity multicomponent hydrogen storage materials: Investigation of the effect of stoichiometry and decomposition conditions on the cycling behaviour of LiBH4–MgH2

LiBH₄–MgH₂ is an attractive reversible hydrogen storage system, it combines two high capacity hydrides (18.3 and 7.6 wt.%, respectively) and the concerted dehydrogenation reaction has a smaller enthalpy change than either species on its own. The latter effect leads to a destabilisation of the hydrided products and results in a lowering of the dehydrogenation temperature. In situ neutron diffraction experiments have been undertaken to characterise the mechanism of decomposition of the LiBD₄–MgD₂ system, with an emphasis on investigating the synergistic effects of the components during cycling under various conditions. This study compares the effect of stoichiometry of the multicomponent system on the cycling mechanism. Results show that LiBD₄–MgD₂ in a 2:1 molar ratio can be reversibly dehydrogenated under low pressures of hydrogen or under vacuum, contrary to earlier reports in the literature, although the reaction was only partially reversed for the 2:1 mixture decomposed under vacuum. This work shows that the reaction pathway was affected by dehydrogenation conditions, but the stoichiometry of the multicomponent system played a minor role.     

Shaft Capacity of Continuous Flight Auger Piles in Sand

This paper presents the results of a series of field experiments performed to study the development of shaft resistance on continuous flight auger piles installed in sand. The test piles were instrumented in order to separate the shaft and base resistance, and to allow the determination of the distribution of shaft resistance along the pile shaft. The tests highlighted the importance of accurate calculation of the shaft resistance for nondisplacement piles. At a typical maximum allowable pile head settlement of 25?mm, more than 71% of the pile resistance was provided by shaft friction. Conventional methods of estimating shaft resistance were assessed. It was found that methods which incorporated parameters directly interpreted from in situ test results provided the most consistent estimates. In the final section, differences between the shaft resistances mobilized on displacement and nondisplacement piles are considered.     

SULFUR RECOVERY WITH REDUCED EMISSIONS, LOW CAPITAL INVESTMENT AND HYDROGEN CO-PRODUCTION

The main disadvantage of the Claus process is that by introducing air as oxidant a large volume of tail gas is produced. This must be treated to reduce atmospheric emissions of sulfur-containing gases. The costs of the tail-gas unit are a significant fraction of the total capital and operating costs for sulfur recovery. A new process uses thermal decomposition of hydrogen sulfide in the presence of carbon dioxide instead of air oxidation. The products of this reaction are hydrogen, carbon monoxide, elemental sulfur, water vapor and carbonyl sulfide. Carbonyl sulfide is easily converted to H₂S and C0₂ by liquid- or vapor-phase hydrolysis. Unreacted H₂S and C0₂ are recovered by absorption and recycled to the reactor. Since no air is introduced, there is no tail gas and the tail-gas unit is eliminated, giving a substantial reduction in capital investment. The concentrations of sulfur-containing gases in the product streams depend only on the operation of the absorber and stripper units and can be controlled to very low levels by increasing stripper boil-up. Process operating costs depend on the level of sulfur recovery required and can also be much lower than those of the modified Claus Process.

The process chemistry depends on a shift in the equilibrium of H₂S decomposition caused by reaction of hydrogen with C0₂ by the reverse of the water-gas-shift reaction. Catalysts for this chemistry have been identified. Reactor conversion is further improved by rapid cooling of the reactor effluent gas. Other aspects of process design and operation confer further advantages with respect to the Claus process; however, the process equipment used is similar to that used in a Claus plant. Retrofit of existing plant to the new technology can therefore be considered.     

Probing the Substrate Promiscuity of Isopentenyl Phosphate Kinase as a Platform for Hemiterpene Analogue Production

Isoprenoids are a large class of natural products with wide-ranging applications. Synthetic biology approaches to the manufacture of isoprenoids and their new-to-nature derivatives are limited due to the provision in nature of just two hemiterpene building blocks for isoprenoid biosynthesis. To address this limitation, artificial chemo-enzymatic pathways such as the alcohol-dependent hemiterpene (ADH) pathway serve to leverage consecutive kinases to convert exogenous alcohols into pyrophosphates that could be coupled to downstream isoprenoid biosynthesis. To be successful, each kinase in this pathway should be permissive of a broad range of substrates. For the first time, we have probed the promiscuity of the second enzyme in the ADH pathway—isopentenyl phosphate kinase from Thermoplasma acidophilum—towards a broad range of acceptor monophosphates. Subsequently, we evaluate the suitability of this enzyme to provide unnatural pyrophosphates and provide a critical first step in characterizing the rate-limiting steps in the artificial ADH pathway.     

Spot-scan imaging of microcrystals of an influenza neuraminidase-antibody fragment complex

Electron micrographs of two-dimensional microcrystals of a complex of an avian influenza virus neuraminidase and an antibody Fab fragment, termed 32/3, have been recorded using the spot-scan method of imaging. The crystals have a large unit cell (159.5 A x 159.5 A x 130.5 A) and a high solvent content (approximately 71% by volume) and are a challenging specimen for testing the spot-scan methodology. Crystalline order was preserved to beyond 4 A resolution as demonstrated by electron diffraction, using an embedding medium of a mixture of glucose and neutral potassium phosphotungstate. Using a Philips C400 computer control system interfaced to an EM420 electron microscope, and with the inclusion of additional software in the system, we have been able to record micrographs at low temperature with a relatively narrow (1500 A diameter) moving beam. There is evidence that the use of such a spot-scan beam reduces the effects of beam-induced specimen motion on the quality of micrographs. Conventional low-dose "flood-beam" images showed good isotropic optical diffraction in only 15% of cases whereas 30% of spot-scan images showed good diffraction. The best flood-beam images gave phases to only 15 A resolution after computer processing, whereas the best spot-scan images gave phases to 7 A resolution. Electron diffraction patterns were also recorded at low temperature, and the resulting diffraction amplitudes combined with phases from spot-scan images to yield a projection map of the structure. A 7 A resolution projection map of the complex is presented, and is compared with the projection map of the same avian influenza neuraminidase complexed with a different monoclonal Fab fragment, NC41, which has been solved to high resolution by X-ray diffraction.     

Psychrophilic and mesophilic anaerobic digestion of brewery effluent: a comparative study

Two expanded granular sludge bed-anaerobic filter (EGSB-AF) bioreactors (3.38 l active volume) were used to directly compare psychrophilic (15 degrees C), anaerobic digestion (PAD) to mesophilic (37 degrees C) anaerobic digestion (MAD) for the treatment of a brewery wastewater (chemical oxygen demand (COD) concentration of 3,136+/-891 mg l(-1)). Bioreactor performance was evaluated by COD removal efficiency and biogas yields at a range of hydraulic and organic loading rates. Specific methanogenic activity (SMA) assays were also employed to investigate the activity of the biomass in the bioreactors. No significant difference in the COD removal efficiencies (which ranged from 85-93%) were recorded between PAD and MAD during the 194-d trial at maximum organic and hydraulic loading rates of 4.47 kg m(-3) day(-1) and 1.33 m(3) m(-3) day(-1), respectively. In addition, the methane content (%) of the biogas was very similar. The volumetric biogas yield from the PAD bioreactor was approximately 50% of that from the MAD bioreactor at an organic loading rate of 4.47 kg COD m(-3) day(-3) and an applied liquid up-flow velocity (V(up)) of 2.5 m h(-1). Increasing the V(up) in the PAD bioreactor to 5 m h(-1) resulted in a volumetric biogas production rate of approximately 4.1 l d(-1) and a methane yield of 0.28 l CH(4) g(-1) COD d(-1), which were very similar to the MAD bioreactor. Significant and negligible biomass washout was observed in the mesophilic and psychrophilic systems, respectively, thus increasing the sludge loading rate applied to the former and underlining the robustness of the latter, which appeared underloaded. A psychrotolerant mesophilic, but not truly psychrophilic, biomass developed in the PAD bioreactor biomass, with comparable maximum SMA values to the MAD bioreactor biomass. PAD, therefore, was shown to be favourably comparable to MAD for brewery wastewater treatment and biogas generation.     

Application of artificial neural network for prediction of particle size in pharmaceutical cocrystallization using mechanochemical synthesis

Neural Computing and Applications - Milling by mechanical means is vital unit operation in pharmaceutical processing which can be used for controlling particle size reduction. This approach can be...     

A Flexi-PEGDA Upconversion Implant for Wireless Brain Photodynamic Therapy

Near-infrared (NIR) activatable upconversion nanoparticles (UCNPs) enable wireless-based phototherapies by converting deep-tissue-penetrating NIR to visible light. UCNPs are therefore ideal as wireless transducers for photodynamic therapy (PDT) of deep-sited tumors. However, the retention of unsequestered UCNPs in tissue with minimal options for removal limits their clinical translation. To address this shortcoming, biocompatible UCNPs implants are developed to deliver upconversion photonic properties in a flexible, optical guide design. To enhance its translatability, the UCNPs implant is constructed with an FDA-approved poly(ethylene glycol) diacrylate (PEGDA) core clad with fluorinated ethylene propylene (FEP). The emission spectrum of the UCNPs implant can be tuned to overlap with the absorption spectra of the clinically relevant photosensitizer, 5-aminolevulinic acid (5-ALA). The UCNPs implant can wirelessly transmit upconverted visible light till 8 cm in length and in a bendable manner even when implanted underneath the skin or scalp. With this system, it is demonstrated that NIR-based chronic PDT is achievable in an untethered and noninvasive manner in a mouse xenograft glioblastoma multiforme (GBM) model. It is postulated that such encapsulated UCNPs implants represent a translational shift for wireless deep-tissue phototherapy by enabling sequestration of UCNPs without compromising wireless deep-tissue light delivery.     

Environmental Geochemistry of Leachate From Leached Brown Coal Ash

The long-term disposal of ash from brown coal combustion requires a thorough understanding of the geochemical controls on leachate quality. The geochemistry of leachate in ash generated from the combustion of coal in the Latrobe Valley region of Victoria, Australia, has been studied in the field and laboratory. The field studies, conducted over 14 months, showed active leaching and changes in leachate chemistry in the ash with mobilization of some trace elements. A further series of laboratory columns demonstrated similar leaching dynamics. Geochemical modeling indicated that both sulfate and carbonate minerals are the most likely solubility-controlling mineral phases in the ash. For regularly detected trace elements, such as As, Ba, and B but particularly Mo, Se, and Sr, the trends suggest that adsorption and coprecipitation controls are also important. The overall approach adopted in this paper has enabled a more realistic assessment of the controlling processes for solute transport during the active leaching phase of ash disposal, thereby improving long-term environmental management.     

Patient collaboration as a criterion for the therapeutic alliance.

In this article we show that a focus on patient collaboration, as a marker for the therapeutic alliance, is advantageous not only for theory and research but also for clinical practice. This point of view in no way minimizes the importance of the therapist's activity or the clinical significance of the interaction between patient and therapist. Rather, it focuses attention on how the therapist's personality, skill, and technique interact with the problems the patient brings to psychotherapy. (PsycINFO Database Record (c) 2011 APA, all rights reserved)