Restructuring and redispersion of silver on SiO2 under oxidizing/reducing atmospheres and its activity toward CO oxidation

The effects of oxygen-hydrogen pretreatments of nanosilver catalysts in cycle mode on the structure and particle size of silver particles, and subsequently the activity of the catalyst toward CO oxidation (or CO selective oxidation in the presence of H-2) are reported in this paper. Ag/SiO2 catalyst with silver particle sizes of ca. 6 similar to 8 nm shows relatively high activity in the present reaction system. The adopting of a cycle of oxidation/reduction pretreatment has a marked influence on the activity of the catalyst. Oxygen pretreatment at 500 degrees C results in the formation of subsurface oxygen and activates the catalyst. As evidenced by in-situ XRD and TEM, the following H-2 treatment at low temperatures (100 similar to 300 degrees C) causes surface faceting and redispersing of the silver particles without destroying the subsurface oxygen species. The subsequent in-situ FTIR and catalytic reaction results show that CO oxidation occurs at -75 degrees C and complete CO conversion can be obtained at 40 degrees C over such a nanosilver catalyst pretreated with oxygen at 500 degrees C followed by H-2 at 100 degrees C. However, prolonged hydrogen treatment at high temperatures (> 300 degrees C) after oxygen pretreatment at 500 degrees C induces the aggregation of silver particles and also depletes so much subsurface oxygen species that the pathway of CO oxidation by the subsurface oxygen species is inhibited. Meanwhile, the ability of the catalyst to adsorb reactants is greatly depressed, resulting in a 20 similar to 30% decrease in the activity toward CO oxidation. However, the activity of the catalyst pretreated with oxygen at 500 degrees C followed by hydrogen treatment at high temperatures (> 300 degrees C) is still higher than that directly pretreated with H,. This kind of catalytic behavior of silver catalyst is associated with physical changes in the silver crystallites because of surface restructuring and crystallite redispersion during the course of oxygen-hydrogen pretreatment steps.

Dynamic effects of cofactors and DNA on the oligomeric state of human mitochondrial DNA helicase

We examined the effects of cofactors and DNA on the stability, oligomeric state and conformation of the human mitochondrial DNA helicase. We demonstrate that low salt conditions result in protein aggregation that may cause dissociation of oligomeric structure. The low salt sensitivity of the mitochondrial DNA helicase is mitigated by the presence of magnesium, nucleotide, and increased temperature. Electron microscopic and glutaraldehyde cross-linking analyses provide the first evidence of a heptameric oligomer and its interconversion from a hexameric form. Limited proteolysis by trypsin shows that binding of nucleoside triphosphate produces a conformational change that is distinct from the conformation observed in the presence of nucleoside diphosphate. We find that single-stranded DNA binding occurs in the absence of cofactors and renders the mitochondrial DNA helicase more susceptible to proteolytic digestion. Our studies indicate that the human mitochondrial DNA helicase shares basic properties with the SF4 replicative helicases, but also identify common features with helicases outside the superfamily, including dynamic conformations similar to other AAA⁺ ATPases.

Non-anonymous ballot aggregation: an axiomatic generalization of Approval Voting

We study axiomatically situations in which the society agrees to treat voters with different characteristics distinctly. In this setting, we propose a set of intuitive axioms and show that they jointly characterize a new class of voting procedures, called Type-weighted Approval Voting. According to this family, each voter has a strictly positive and finite weight (the weight is necessarily the same for all voters with the same characteristics) and the alternative with the highest number of weighted votes is elected. The implemented voting procedure reduces to Approval Voting in case all voters are identical or the procedure assigns the same weight to all types. Using this idea, we also obtain a new characterization of Approval Voting.

Design and Implementation of Statistical Rate Monotonic Scheduling in KURT Linux

Statistical Rate Monotonic Scheduling (SRMS) is a generalization of the classical RMS results of Liu and Layland [LL73] for periodic tasks with highly variable execution times and statistical QoS requirements. The main tenet of SRMS is that the variability in task resource requirements could be smoothed through aggregation to yield guaranteed QoS. This aggregation is done over time for a given task and across multiple tasks for a given period of time. Similar to RMS, SRMS has two components: a feasibility test and a scheduling algorithm. SRMS feasibility test ensures that it is possible for a given periodic task set to share a given resource without violating any of the statistical QoS constraints imposed on each task in the set. The SRMS scheduling algorithm consists of two parts: a job admission controller and a scheduler. The SRMS scheduler is a simple, preemptive, fixed-priority scheduler. The SRMS job admission controller manages the QoS delivered to the various tasks through admit/reject and priority assignment decisions. In particular, it ensures the important property of task isolation, whereby tasks do not infringe on each other. In this paper we present the design and implementation of SRMS within the KURT Linux Operating System [HSPN98, SPH 98, Sri98]. KURT Linux supports conventional tasks as well as real-time tasks. It provides a mechanism for transitioning from normal Linux scheduling to a mixed scheduling of conventional and real-time tasks, and to a focused mode where only real-time tasks are scheduled. We overview the technical issues that we had to overcome in order to integrate SRMS into KURT Linux and present the API we have developed for scheduling periodic real-time tasks using SRMS.

Optimal Scheduling of Secondary Content for Aggregation in Video-on-Demand Systems

Dynamic service aggregation techniques can exploit skewed access popularity patterns to reduce the costs of building interactive VoD systems. These schemes seek to cluster and merge users into single streams by bridging the temporal skew between them, thus improving server and network utilization. Rate adaptation and secondary content insertion are two such schemes. In this paper, we present and evaluate an optimal scheduling algorithm for inserting secondary content in this scenario. The algorithm runs in polynomial time, and is optimal with respect to the total bandwidth usage over the merging interval. We present constraints on content insertion which make the overall QoS of the delivered stream acceptable, and show how our algorithm can satisfy these constraints. We report simulation results which quantify the excellent gains due to content insertion. We discuss dynamic scenarios with user arrivals and interactions, and show that content insertion reduces the channel bandwidth requirement to almost half. We also discuss differentiated service techniques, such as N-VoD and premium no-advertisement service, and show how our algorithm can support these as well.

Authenticated Index Structures for Aggregation Queries in Outsourced Databases

In an outsourced database system the data owner publishes information through a number of remote, untrusted servers with the goal of enabling clients to access and query the data more efficiently. As clients cannot trust servers, query authentication is an essential component in any outsourced database system. Clients should be given the capability to verify that the answers provided by the servers are correct with respect to the actual data published by the owner. While existing work provides authentication techniques for selection and projection queries, there is a lack of techniques for authenticating aggregation queries. This article introduces the first known authenticated index structures for aggregation queries. First, we design an index that features good performance characteristics for static environments, where few or no updates occur to the data. Then, we extend these ideas and propose more involved structures for the dynamic case, where the database owner is allowed to update the data arbitrarily. Our structures feature excellent average case performance for authenticating queries with multiple aggregate attributes and multiple selection predicates. We also implement working prototypes of the proposed techniques and experimentally validate the correctness of our ideas.

Mathematical modelling and optimisation of the formulation and manufacture of aggregate food products

In this PhD study, mathematical modelling and optimisation of granola production has been carried out. Granola is an aggregated food product used in breakfast cereals and cereal bars. It is a baked crispy food product typically incorporating oats, other cereals and nuts bound together with a binder, such as honey, water and oil, to form a structured unit aggregate. In this work, the design and operation of two parallel processes to produce aggregate granola products were incorporated: i) a high shear mixing granulation stage (in a designated granulator) followed by drying/toasting in an oven. ii) a continuous fluidised bed followed by drying/toasting in an oven. In addition, the particle breakage of granola during pneumatic conveying produced by both a high shear granulator (HSG) and fluidised bed granulator (FBG) process were examined. Products were pneumatically conveyed in a purpose built conveying rig designed to mimic product conveying and packaging. Three different conveying rig configurations were employed; a straight pipe, a rig consisting two 45° bends and one with 90° bend. It was observed that the least amount of breakage occurred in the straight pipe while the most breakage occurred at 90° bend pipe. Moreover, lower levels of breakage were observed in two 45° bend pipe than the 90° bend vi pipe configuration. In general, increasing the impact angle increases the degree of breakage. Additionally for the granules produced in the HSG, those produced at 300 rpm have the lowest breakage rates while the granules produced at 150 rpm have the highest breakage rates. This effect clearly the importance of shear history (during granule production) on breakage rates during subsequent processing. In terms of the FBG there was no single operating parameter that was deemed to have a significant effect on breakage during subsequent conveying. A population balance model was developed to analyse the particle breakage occurring during pneumatic conveying. The population balance equations that govern this breakage process are solved using discretization. The Markov chain method was used for the solution of PBEs for this process. This study found that increasing the air velocity (by increasing the air pressure to the rig), results in increased breakage among granola aggregates. Furthermore, the analysis carried out in this work provides that a greater degree of breakage of granola aggregates occur in line with an increase in bend angle.

Variability in north temperate dung beetle assemblages at different spatial and temporal scales

This study examined the spatial and temporal variability of dung beetle assemblages across a variety of scales e.g. from the between-pad scale (examining the effects of dung size and type) to larger spatial scales encompassing southern Ireland. Dung beetle assemblage structure as sampled by dung pad cohort samples and dung baited pitfall trapping were compared. Generally, the rank order of abundance of dung beetle species was significantly correlated between pitfall catches and cohort pad samples. Across different dung sizes, in both pitfall catches and cohort pad samples, the relative abundance of species was frequently significantly different, but the rank order of abundance of dung beetle was usually significantly correlated. Considerable variations in pitfall catches at temporal scales of a few days appeared to be closely related to weather conditions and rotational grazing. However, despite considerable variation in absolute abundances between consecutive days of sampling, assemblage structure typically remained very similar. The relationship between dung pad size and dung beetle colonisation was investigated. In field experiments in which pads of different sizes (0.25 L, 0.5 L, 1.0 L and 1.5 L) were artificially deposited, there was a positive relationship between pad size and both biomass and number of beetles colonising dung pads and pitfall traps. In addition, with one exception, the field experiments indicated a general positive relationship between dung pad size and biomass density (dung beetle biomass per unit dung volume). A laboratory experiment indicated that pat residence times of A. rufipes were significantly correlated with dung pad size. Investigation of naturally-deposited cow dung pads in the field also indicated that both larval numbers and densities were significantly correlated with dung pad size. These results were discussed in the context of theory related to aggregation and coexistence of species, and resource utilisation by organisms in ephemeral, patchy resources. The colonisation by dung beetles of dung types from native herbivores (sheep, horse and cow) was investigated in field experiments. There were significant differences between the dung types in the chemical parameters measured, and there were significant differences in abundances of dung beetles colonising the dung types. Sheep dung was typically the preferred dung type. Data from these field experiments, and from published literature, indicated that dung beetle species can display dung type preferences, in terms of comparisons of both absolute and relative abundances. In addition, data from laboratory experiments indicate that both Aphodius larval production and pat residence times tended to be higher in those dung types which were preferred by adult Aphodius in the colonisation experiments. Data from dung-baited pitfall trapping (from this and another study) at several sites (up to 180 km distant) and over a number of years (between 1991 and 1996) were used to investigate spatial and temporal variation in dung beetle assemblage structure and composition (Aphodius, Sphaeridium and Geotrupes) across a range of scales in southern Ireland. Species richness levels, species composition and rank order of abundances were very similar between the assemblages. The temporal variability between seasons within any year exceeded temporal variability between years. DCA ordinations indicated that there was a similar level of variability between assemblage structure from the between-field (~1km) to regional (~180 km) spatial scales, and between year (6 years) temporal scales. At the biogeographical spatial scale, analysis of data from the literature indicated that there was considerable variability at this scale, largely due to species turnover.

Infant milk formula manufacture: process and compositional interactions in high dry matter wet-mixes

Infant milk formula (IMF) is fortified milk with composition based on the nutrient content in human mother's milk, 0 to 6 months postpartum. Extensive medical and clinical research has led to advances in the nutritional quality of infant formula; however, relatively few studies have focused on interactions between nutrients and the manufacturing process. The objective of this research was to investigate the impact of composition and processing parameters on physical behaviour of high dry matter (DM) IMF systems with a view to designing more sustainable manufacturing processes. The study showed that commercial IMF, with similar compositions, manufactured by different processes, had markedly different physical properties in dehydrated or reconstituted state. Commercial products made with hydrolysed protein were more heat stable compared to products made with intact protein, however, emulsion quality was compromised. Heat-induced denaturation of whey proteins resulted in increased viscosity of wet-mixes, an effect that was dependant on both whey concentration and interactions with lactose and caseins. Expanding on fundamental laboratory studies, a novel high velocity steam injection process was developed whereby high DM (60%) wet-mixes with lower denaturation/viscosity compared to conventional processes could be achieved; powders produced using this process were of similar quality to those manufactured conventionally. Hydrolysed proteins were also shown to be an effective way of reducing viscosity in heat-treated high DM wet-mixes. In particular, using a whey protein concentrate whereby β-Lactoglobulin was selectively hydrolysed, i.e., α-Lactalbumin remained intact, reduced viscosity of wet-mixes during processing while still providing good emulsification. The thesis provides new insights into interactions between nutrients and/or processing which influence physical stability of IMF both in concentrated liquid and powdered form. The outcomes of the work have applications in such areas as; increasing the DM content of spray drier feeds in order to save energy, and, controlling final powder quality.

Magnetic resonance water proton relaxation in protein solutions and tissue: T(1rho) dispersion characterization.

BACKGROUND: Image contrast in clinical MRI is often determined by differences in tissue water proton relaxation behavior. However, many aspects of water proton relaxation in complex biological media, such as protein solutions and tissue are not well understood, perhaps due to the limited empirical data. PRINCIPAL FINDINGS: Water proton T(1), T(2), and T(1rho) of protein solutions and tissue were measured systematically under multiple conditions. Crosslinking or aggregation of protein decreased T(2) and T(1rho), but did not change high-field T(1). T(1rho) dispersion profiles were similar for crosslinked protein solutions, myocardial tissue, and cartilage, and exhibited power law behavior with T(1rho)(0) values that closely approximated T(2). The T(1rho) dispersion of mobile protein solutions was flat above 5 kHz, but showed a steep curve below 5 kHz that was sensitive to changes in pH. The T(1rho) dispersion of crosslinked BSA and cartilage in DMSO solvent closely resembled that of water solvent above 5 kHz but showed decreased dispersion below 5 kHz. CONCLUSIONS: Proton exchange is a minor pathway for tissue T(1) and T(1rho) relaxation above 5 kHz. Potential models for relaxation are discussed, however the same molecular mechanism appears to be responsible across 5 decades of frequencies from T(1rho) to T(1).

Antisense Gene Silencing and Bacteriophages as Novel Disinfection Processes for Engineered Systems

The growth and proliferation of invasive bacteria in engineered systems is an ongoing problem. While there are a variety of physical and chemical processes to remove and inactivate bacterial pathogens, there are many situations in which these tools are no longer effective or appropriate for the treatment of a microbial target. For example, certain strains of bacteria are becoming resistant to commonly used disinfectants, such as chlorine and UV. Additionally, the overuse of antibiotics has contributed to the spread of antibiotic resistance, and there is concern that wastewater treatment processes are contributing to the spread of antibiotic resistant bacteria.

Due to the continually evolving nature of bacteria, it is difficult to develop methods for universal bacterial control in a wide range of engineered systems, as many of our treatment processes are static in nature. Still, invasive bacteria are present in many natural and engineered systems, where the application of broad acting disinfectants is impractical, because their use may inhibit the original desired bioprocesses. Therefore, to better control the growth of treatment resistant bacteria and to address limitations with the current disinfection processes, novel tools that are both specific and adaptable need to be developed and characterized.

In this dissertation, two possible biological disinfection processes were investigated for use in controlling invasive bacteria in engineered systems. First, antisense gene silencing, which is the specific use of oligonucleotides to silence gene expression, was investigated. This work was followed by the investigation of bacteriophages (phages), which are viruses that are specific to bacteria, in engineered systems.


For the antisense gene silencing work, a computational approach was used to quantify the number of off-targets and to determine the effects of off-targets in prokaryotic organisms. For the organisms of Escherichia coli K-12 MG1655 and Mycobacterium tuberculosis H37Rv the mean number of off-targets was found to be 15.0 + 13.2 and 38.2 + 61.4, respectively, which results in a reduction of greater than 90% of the effective oligonucleotide concentration. It was also demonstrated that there was a high variability in the number of off-targets over the length of a gene, but that on average, there was no general gene location that could be targeted to reduce off-targets. Therefore, this analysis needs to be performed for each gene in question. It was also demonstrated that the thermodynamic binding energy between the oligonucleotide and the mRNA accounted for 83% of the variation in the silencing efficiency, compared to the number of off-targets, which explained 43% of the variance of the silencing efficiency. This suggests that optimizing thermodynamic parameters must be prioritized over minimizing the number of off-targets. In conclusion for the antisense work, these results suggest that off-target hybrids can account for a greater than 90% reduction in the concentration of the silencing oligonucleotides, and that the effective concentration can be increased through the rational design of silencing targets by minimizing off-target hybrids.

Regarding the work with phages, the disinfection rates of bacteria in the presence of phages was determined. The disinfection rates of E. coli K12 MG1655 in the presence of coliphage Ec2 ranged up to 2 h-1, and were dependent on both the initial phage and bacterial concentrations. Increasing initial phage concentrations resulted in increasing disinfection rates, and generally, increasing initial bacterial concentrations resulted in increasing disinfection rates. However, disinfection rates were found to plateau at higher bacterial and phage concentrations. A multiple linear regression model was used to predict the disinfection rates as a function of the initial phage and bacterial concentrations, and this model was able to explain 93% of the variance in the disinfection rates. The disinfection rates were also modeled with a particle aggregation model. The results from these model simulations suggested that at lower phage and bacterial concentrations there are not enough collisions to support active disinfection rates, which therefore, limits the conditions and systems where phage based bacterial disinfection is possible. Additionally, the particle aggregation model over predicted the disinfection rates at higher phage and bacterial concentrations of 108 PFU/mL and 108 CFU/mL, suggesting other interactions were occurring at these higher concentrations. Overall, this work highlights the need for the development of alternative models to more accurately describe the dynamics of this system at a variety of phage and bacterial concentrations. Finally, the minimum required hydraulic residence time was calculated for a continuous stirred-tank reactor and a plug flow reactor (PFR) as a function of both the initial phage and bacterial concentrations, which suggested that phage treatment in a PFR is theoretically possible.

In addition to determining disinfection rates, the long-term bacterial growth inhibition potential was determined for a variety of phages with both Gram-negative and Gram-positive bacteria. It was determined, that on average, phages can be used to inhibit bacterial growth for up to 24 h, and that this effect was concentration dependent for various phages at specific time points. Additionally, it was found that a phage cocktail was no more effective at inhibiting bacterial growth over the long-term than the best performing phage in isolation.

Finally, for an industrial application, the use of phages to inhibit invasive Lactobacilli in ethanol fermentations was investigated. It was demonstrated that phage 8014-B2 can achieve a greater than 3-log inactivation of Lactobacillus plantarum during a 48 h fermentation. Additionally, it was shown that phages can be used to protect final product yields and maintain yeast viability. Through modeling the fermentation system with differential equations it was determined that there was a 10 h window in the beginning of the fermentation run, where the addition of phages can be used to protect final product yields, and after 20 h no additional benefit of the phage addition was observed.

In conclusion, this dissertation improved the current methods for designing antisense gene silencing targets for prokaryotic organisms, and characterized phages from an engineering perspective. First, the current design strategy for antisense targets in prokaryotic organisms was improved through the development of an algorithm that minimized the number of off-targets. For the phage work, a framework was developed to predict the disinfection rates in terms of the initial phage and bacterial concentrations. In addition, the long-term bacterial growth inhibition potential of multiple phages was determined for several bacteria. In regard to the phage application, phages were shown to protect both final product yields and yeast concentrations during fermentation. Taken together, this work suggests that the rational design of phage treatment is possible and further work is needed to expand on this foundation.

Early clopidogrel versus prasugrel use among contemporary STEMI and NSTEMI patients in the US: insights from the National Cardiovascular Data Registry.

BACKGROUND: P2Y12 antagonist therapy improves outcomes in acute myocardial infarction (MI) patients. Novel agents in this class are now available in the US. We studied the introduction of prasugrel into contemporary MI practice to understand the appropriateness of its use and assess for changes in antiplatelet management practices. METHODS AND RESULTS: Using ACTION Registry-GWTG (Get-with-the-Guidelines), we evaluated patterns of P2Y12 antagonist use within 24 hours of admission in 100 228 ST elevation myocardial infarction (STEMI) and 158 492 Non-ST elevation myocardial infarction (NSTEMI) patients at 548 hospitals between October 2009 and September 2012. Rates of early P2Y12 antagonist use were approximately 90% among STEMI and 57% among NSTEMI patients. From 2009 to 2012, prasugrel use increased significantly from 3% to 18% (5% to 30% in STEMI; 2% to 10% in NSTEMI; P for trend <0.001 for all). During the same period, we observed a decrease in use of early but not discharge P2Y12 antagonist among NSTEMI patients. Although contraindicated, 3.0% of patients with prior stroke received prasugrel. Prasugrel was used in 1.9% of patients ≥75 years and 4.5% of patients with weight <60 kg. In both STEMI and NSTEMI, prasugrel was most frequently used in patients at the lowest predicted risk for bleeding and mortality. Despite lack of supporting evidence, prasugrel was initiated before cardiac catheterization in 18% of NSTEMI patients. CONCLUSIONS: With prasugrel as an antiplatelet treatment option, contemporary practice shows low uptake of prasugrel and delays in P2Y12 antagonist initiation among NSTEMI patients. We also note concerning evidence of inappropriate use of prasugrel, and inadequate targeting of this more potent therapy to maximize the benefit/risk ratio.

The F4 fimbrial chaperone FaeE is stable as a monomer that does not require self-capping of its pilin-interactive surfaces.

Many Gram-negative bacteria use the chaperone-usher pathway to express adhesive surface structures, such as fimbriae, in order to mediate attachment to host cells. Periplasmic chaperones are required to shuttle fimbrial subunits or pilins through the periplasmic space in an assembly-competent form. The chaperones cap the hydrophobic surface of the pilins through a donor-strand complementation mechanism. FaeE is the periplasmic chaperone required for the assembly of the F4 fimbriae of enterotoxigenic Escherichia coli. The FaeE crystal structure shows a dimer formed by interaction between the pilin-binding interfaces of the two monomers. Dimerization and tetramerization have been observed previously in crystal structures of fimbrial chaperones and have been suggested to serve as a self-capping mechanism that protects the pilin-interactive surfaces in solution in the absence of the pilins. However, thermodynamic and biochemical data show that FaeE occurs as a stable monomer in solution. Other lines of evidence indicate that self-capping of the pilin-interactive interfaces is not a mechanism that is conservedly applied by all periplasmic chaperones, but is rather a case-specific solution to cap aggregation-prone surfaces.

Biological controls on resuspension and the relationship between particle size and the Kolmogorov length scale in a shallow coastal sea

Measurements of suspended particle matter (SPM) and turbulence have been obtained over five tidal surveys during spring and summer 2010 at station L4 (5025 degrees N 04.22 degrees W, depth 50 m), in the Western English Channel. The relationship between turbulence intensity and bed stress is explored, with an in-line holographic imaging system evaluating the extent to which material is resuspended. Image analysis allows for the identification of SPM above a size threshold of 200 pm, capturing particle variability across tidal cycles and the two seasons. Dissipation of turbulent kinetic energy, which exceeds 10(-5) W kg(-1), yields maximum values of bed stress of between 0.17 and 0.20 N m(-2), frequently resulting in the resuspension of material from the bed. Resuspension is shown to promote aggregation of SPM into flocs, where the size of such particles is theoretically determined by the Kolmogorov microscale, l(k). During the spring surveys, flocs of a size larger than lk were observed, though this was not repeated during summer. It is proposed that the presence of gelatinous, biological material in spring allows flocculated particles to exceed l(k). This suggests that under specific circumstances, the limiting factor on the growth of flocculated SPM is not only turbulence, as previously thought, but the presence or absence of certain types of biological particle.

Laboratory Simulation Of Chemical Processes Induced By Estuarine Mixing - The Behavior Of Iron And Phosphate In Estuaries

A series of well stirred tank reactors has been shown to provide an adaptable laboratory analogue of a one-dimensional estuarine mixing profile which can be applied dynamically to the study of the chemistry of estuarine mixing. Simulations of the behaviour of iron and phosphate in the low salinity region of an estuary have been achieved with this system. The well documented general features of iron removal, involving rapid aggregation of river-borne colloids, were reproduced. Phosphate removal is attributable in part to the coagulation process, although specific adsorption of phosphate by colloids also appears to be significant.