Coal firing power stations represent the second largest source of global NOx emissions. The current practice of predicting likely exit NOx levels from multi-burner furnaces on the basis of single burner test rig data has been proven inadequate. Therefore, to further improve current NOx reduction technologies and assist in the assessment of NOx levels in new and retrofit plant cases, an improved understanding of the impact of burner interactions is required. The aim of this research is two-fold: firstly, to experimentally investigate isothermal flow interactions in multi-burner arrays for different swirl directions and burner pitches in order to gain a better understanding of burner interaction effects within multi-burner furnaces. Secondly, to carry out numerical modelling in order to determine turbulence models which give the best agreement to experimental data. Experimental investigations were carried out using flow visualisation for qualitative and 3D laser Doppler anemometry for quantitative measurements. Numerical modelling was performed using the computational fluid dynamics software, Fluent, to compare performance between k-ε, k- ω and RSM turbulence models. Experimental investigation showed that the recirculation zone of the chequerboard configuration is more sensitive to the change in pitch than that of the columnar configuration. Further, it was found that the smaller pitch is more sensitive to change in configuration than the wider pitch. The analysis of fluctuating components, u’, v’ and w’ showed that the burner flow is highly anisotropic at burner exit. Numerical investigation showed that the k-ω turbulence model consistently performed below the other two models. The statistical comparison between k-ε and RSM turbulence models revealed that, for prediction of the swirl velocity profiles, the RSM model overall performed better than the k-ε turbulence model. The visual and statistical analyses of turbulent kinetic energy profiles also showed that the RSM turbulence model provides a closer match to the experimental data than the k-ε turbulence model.

"A series of one dimensional horizontal infiltration experiments were performed to investigate the predictive capabilities of the Kao and Hunt model. By modifying pristine laboratory apparatus, a reasonable range of soil temperatures was achieved. Experiments were run at approximately 5°C, 20°C, and 35°C. Distilled water was used as an infiltrating liquid and silica powder was used as soil. The infiltrating liquid was dispensed into the column at zero pressure head. The results of the experiments show that the model is adaptable to a range of temperature conditions by modifying terms for the liquid effects of the model, viscosity and surface tension. Experimental data and model predictions differed by 30 percent at most. Although the change in the rate of infiltration across the range of temperatures is perceivable, it is small in comparison to the effects caused by heterogeneity encountered in nature. "

Grb2, a modular protein comprised of a central SH2 domain flanked between a N-terminal SH3 (nSH3) domain and a C-terminal SH3 (cSH3) domain, is a component of cell signaling networks involved in the transmission of extracellular information in the form of growth factors and cytokines to downstream targets such as transcription factors within the nucleus. The Grb2-Sos1 interaction is mediated through the combinatorial binding of nSH3 and cSH3 domains of Grb2 to various sites - designated S1, S2, S3, and S4 - containing PXpsiPXR motifs within Sos1. Here, using a diverse array of biophysical techniques, including in particular isothermal titration calorimetry coupled with molecular modeling and semi-empirical analysis, I provide new insights into the Grb2-Sos1 interaction in thermodynamic and structural terms. My data show that Grb2 exists in monomer-dimer equilibrium in solution and that the dissociation of dimer into monomers is entropically-driven. The heat capacity change observed was much smaller than that expected from the rather large molecular surfaces becoming solvent-occluded upon dimerization, implying that monomers undergo conformational rearrangement upon dimerization. 3D structural models suggest strongly that such conformational rearrangement may arise from domain swapping. I further show that the nSH3 domain of Grb2 binds to the S1 site containing the proline-rich consensus motif PXpsiPXR with an affinity that is nearly three-fold greater than that observed for the binding of the cSH3 domain. It is also demonstrated that such differential binding of the nSH3 domain relative to the cSH3 domain is largely due to the requirement of a specific acidic residue, in the RT loop, to engage in the formation of a salt bridge with the arginine residue in the consensus motif PXpsiPXR. The data further reveal that, while binding of both SH3 domains to Sos1 is under enthalpic control, the nSH3 binding suffers from entropic penalty in contrast to entropic gain accompanying the binding of cSH3, implying that the two domains employ differential thermodynamic mechanisms for Sos1 recognition. Additionally, my data reveal that while the nSH3 domain of Grb2 binds with affinities in the physiological range to all four sites S1-S4, the cSH3 domain can only do so at the S1 site. Further scrutiny of these sites yields rationale for the recognition of various PXpsiPXR motifs by the SH3 domains in a discriminate manner. Unlike the PXpsiPXR motifs at S2, S3 and S4 sites, the PXpsiPXR motif at S1 site is flanked at its C-terminus with two additional arginine residues that are absolutely required for high-affinity binding of the cSH3 domain. In contrast, these two additional arginine residues augment the binding of the nSH3 domain to the S1 site but their role is not critical for the recognition of S2, S3 and S4 sites. Molecular modeling is employed to rationalize my new findings in structural terms. Taken together, this thesis provides novel insights into the physicochemical basis of a key protein-protein interaction pertinent to cellular signaling and cancer. My studies bear the potential for the development of novel therapies with less toxicity but more effectiveness for the treatment of disease.

The polymer industry is an ever growing industry, and, as it grows, companies are continuously looking for ways to study and understand the behaviors of polymers in relation to the processing and production. This is to ensure the production of high quality products and to improve existing products.An important parameter during polymer processing is temperature. Temperature control affects several rheological parameters such as viscosity, and in turn the quality of the final products. Frictional or viscous heating is a very important part of polymer processing and occurs in almost every polymer processing operation.The objective of this research is to design the apparatus and setup the equipment to examine the validity of the Theory of Purely Entropic Elasticity (PPE) on non-isothermal flow of concentrated polymeric solutions under a wide range of shear rates. A basic rheological study of the polymer in use is performed. PEE once played an important role in polymer processing. PEE is the assumption that the internal energy of a polymeric material is solely dependent on temperature, and specifically is not dependent on the polymer deformation, as developed by Astarita and co-workers [1-3, 16].The design and results are presented. Potential improvements and future considerations are also presented.

Calcium aluminate cement (CAC) is a rapid hardening cementitious material often used in niche concrete repairs where high early-age strength and robust durability are required. This research project characterized the implications of the additions of various mineral and chemical admixtures to plain CAC to mitigate strength reductions associated with conversion, an inevitable strength reduction associated with the densification of metastable hydrates (CAH10 and C2AH8) to stable hydrates (C3AH6 and AH3). The effect of these admixtures on early-age strength development, volume change, and the correlation to macro-scale performance were reported in this dissertation. Various mixtures of CAC were investigated including: pure CAC, binary blends of CAC with fly ash (Class C) or CaCO3, and ternary blends of CAC with slag and silica fume. Characterization of the influence of these admixtures on hydration was completed using x-ray diffraction, isothermal calorimetry, and chemical shrinkage. Investigations on the implications of early-age volume change were conducted for autogenous deformation. In addition to laboratory testing, the final phase of the project was to correlate and elucidate the data generated in the laboratory to real-world field performance. Field trials were conducted to evaluate and monitor the behavior of CAC systems and investigate the link between laboratory generated research and actual large scale behavior. / text

This thesis reports theoretical and experimental investigations carried out to better understand the effect of process parameters on the microstructure of transient liquid phase (TLP) joint. The theoretical investigations were carried out using analytical and numerical models to simulate base metal dissolution and isothermal solidification stages of the TLP bonding process. The experimental investigation was carried out by using standard metallographic technique to study the microstructure of bonded materials using optical and Scanning Electron Microscopes. Deviation from parabolic relationship between solid/liquid interface migration and holding time during TLP bonding is suggested as a new alternate phenomenon responsible for the anomalous increase in processing time required to produce eutectic microconstituent free joint with increase in bonding temperature. The results of TLP joining of commercial pure nickel using a Ni-P filler alloy showed that an increase in bonding temperature would be beneficial provided that sufficient holding time is allowed for complete isothermal solidification of liquated insert. Otherwise, an increase in bonding temperature may result in formation of thicker deleterious eutectic along the TLP joint. Furthermore, it was observed that the joint centerline eutectic product and interface second phase particles that form during TLP bonding of Inconel 738 using Ni-P filler can be significantly reduced by post bond heat treatment. The effectiveness of this approach, however, requires proper selection of heat treatment temperature above Ni-P binary eutectic temperature.

This thesis reports theoretical and experimental investigations carried out to better understand the effect of process parameters on the microstructure of transient liquid phase (TLP) joint. The theoretical investigations were carried out using analytical and numerical models to simulate base metal dissolution and isothermal solidification stages of the TLP bonding process. The experimental investigation was carried out by using standard metallographic technique to study the microstructure of bonded materials using optical and Scanning Electron Microscopes. Deviation from parabolic relationship between solid/liquid interface migration and holding time during TLP bonding is suggested as a new alternate phenomenon responsible for the anomalous increase in processing time required to produce eutectic microconstituent free joint with increase in bonding temperature. The results of TLP joining of commercial pure nickel using a Ni-P filler alloy showed that an increase in bonding temperature would be beneficial provided that sufficient holding time is allowed for complete isothermal solidification of liquated insert. Otherwise, an increase in bonding temperature may result in formation of thicker deleterious eutectic along the TLP joint. Furthermore, it was observed that the joint centerline eutectic product and interface second phase particles that form during TLP bonding of Inconel 738 using Ni-P filler can be significantly reduced by post bond heat treatment. The effectiveness of this approach, however, requires proper selection of heat treatment temperature above Ni-P binary eutectic temperature.

Pterin-4a-carbinolamine dehydratase (PCD) is an essential component of the phenylalanine hydroxylase (PAH) system, catalyzing the regeneration of the essential cofactor 6(R)-L-erythro-5,6,7,8-tetrahydrobiopterin [6(R)BH4]. Mutations in PCD or its deactivation by hydrogen peroxide result in the generation of 7(R,S)BH4, which is a potent inhibitor of PAH that has been implicated in primapterinuria, a variant form of phenylketonuria, and in the skin depigmentation disorder vitiligo. We have synthesized and separated the 7(R) and 7(S) diastereomers confirming their structure by NMR. Both 7(R)- and 7(S)BH4 function as poor cofactors for PAH, whereas only 7(S)BH4 acts as a potent competitive inhibitor vs. 6(R)BH4 (Ki=2.3-4.9 µM). Kinetic and binding studies, as well as characterization of the pterin-enzyme complexes by fluorescence spectroscopy, revealed that the inhibitory effects of 7(R,S)BH4 on PAH are in fact specifically based on 7(S)BH4 binding. The molecular dynamics simulated structures of the pterin-PAH complexes indicate that 7(S)BH4 inhibition is due to its interaction with the polar region at the pterin binding site close to Ser-251, whereas its low efficiency as cofactor is related to a suboptimal positioning toward the catalytic iron. 7(S)BH4 is not an inhibitor for tyrosine hydroxylase (TH) in the physiological range, presumably due to the replacement of Ser-251 by the corresponding Ala297. Taken together, our results identified structural determinants for the specific regulation of PAH and TH by 7(S)BH4, which in turn aid in the understanding of primapterinuria and acute vitiligo.

Pterin-4a-carbinolamine dehydratase (PCD) is an essential component of the phenylalanine hydroxylase (PAH) system, catalyzing the regeneration of the essential cofactor 6(R)-L-erythro-5,6,7,8-tetrahydrobiopterin [6(R)BH4]. Mutations in PCD or its deactivation by hydrogen peroxide result in the generation of 7(R,S)BH4, which is a potent inhibitor of PAH that has been implicated in primapterinuria, a variant form of phenylketonuria, and in the skin depigmentation disorder vitiligo. We have synthesized and separated the 7(R) and 7(S) diastereomers confirming their structure by NMR. Both 7(R)- and 7(S)BH4 function as poor cofactors for PAH, whereas only 7(S)BH4 acts as a potent competitive inhibitor vs. 6(R)BH4 (Ki=2.3-4.9 µM). Kinetic and binding studies, as well as characterization of the pterin-enzyme complexes by fluorescence spectroscopy, revealed that the inhibitory effects of 7(R,S)BH4 on PAH are in fact specifically based on 7(S)BH4 binding. The molecular dynamics simulated structures of the pterin-PAH complexes indicate that 7(S)BH4 inhibition is due to its interaction with the polar region at the pterin binding site close to Ser-251, whereas its low efficiency as cofactor is related to a suboptimal positioning toward the catalytic iron. 7(S)BH4 is not an inhibitor for tyrosine hydroxylase (TH) in the physiological range, presumably due to the replacement of Ser-251 by the corresponding Ala297. Taken together, our results identified structural determinants for the specific regulation of PAH and TH by 7(S)BH4, which in turn aid in the understanding of primapterinuria and acute vitiligo. Pey, A. L., Martinez, A., Charubala, R., Maitland, D. J., Teigen, K., Calvo, A., Pfleiderer, W., Wood, J. M., Schallreuter, K. U. Specific interaction of the diastereomers 7(R)- and 7(S)-tetrahydrobiopterin with phenylalanine hydroxylase: implications for understanding primapterinuria and vitiligo Pterin-4a-carbinolamine dehydratase (PCD) is an essential component of the phenylalanine hydroxylase (PAH) system, catalyzing the regeneration of the essential cofactor 6(R)-L-erythro-5,6,7,8-tetrahydrobiopterin [6(R)BH4]. Mutations in PCD or its deactivation by hydrogen peroxide result in the generation of 7(R,S)BH4, which is a potent inhibitor of PAH that has been implicated in primapterinuria, a variant form of phenylketonuria, and in the skin depigmentation disorder vitiligo. We have synthesized and separated the 7(R) and 7(S) diastereomers confirming their structure by NMR. Both 7(R)- and 7(S)BH4 function as poor cofactors for PAH, whereas only 7(S)BH4 acts as a potent competitive inhibitor vs. 6(R)BH4 (Ki=2.3-4.9 µM). Kinetic and binding studies, as well as characterization of the pterin-enzyme complexes by fluorescence spectroscopy, revealed that the inhibitory effects of 7(R,S)BH4 on PAH are in fact specifically based on 7(S)BH4 binding. The molecular dynamics simulated structures of the pterin-PAH complexes indicate that 7(S)BH4 inhibition is due to its interaction with the polar region at the pterin binding site close to Ser-251, whereas its low efficiency as cofactor is related to a suboptimal positioning toward the catalytic iron. 7(S)BH4 is not an inhibitor for tyrosine hydroxylase (TH) in the physiological range, presumably due to the replacement of Ser-251 by the corresponding Ala297. Taken together, our results identified structural determinants for the specific regulation of PAH and TH by 7(S)BH4, which in turn aid in the understanding of primapterinuria and acute vitiligo. / ¿ ¿

Numerous engineering applications have been proposed to exploit the load-carrying and non-contact nature of noncoalescing and nonwetting systems. One such application is a lab-on-a-chip , or LOC, in which liquid samples would be delivered from point-to-point by sliding over a film of air without requiring either the large driving forces required to pump liquid through a microchannel or liquid-solid contact that could lead to sample-to-sample contamination. Due to the axisymmetry of the flow fields in both the lubricating gas and droplet associated with a stationary nonwetting droplet, such a situation has a vanishing coefficient of static friction. However, once motion is imparted, droplet deformation requires that a force be applied to sustain such motion. The program of research in this dissertation focuses on investigating the lubrication force between a drop of silicone oil and a moving unwetted substrate due to the presence of a gas lubricating film driven by a rotating disk. The frictional (or lubrication) force was measured using an optical-lever technique as a function of: (1) linear velocity of the moving solid; (2) relative displacement of the drop toward the solid; (3) drop volume; and (4) viscosity. The data reveal an increase in magnitude of the measured force with either increasing relative squeezing of the drop against the glass or increasing speed of the rotating disk. Contrary to initial expectations, no pattern could be isolated regarding drop volume or viscosity of the oil. The experimental data collected will serve to validate numerical work as further models are developed.