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<p> Affinity capillary electrophoresis (ACE) is a versatile technique for assessing non-covalent molecular interactions in free solution provided that there are significant changes in apparent analyte mobility as a result of specific complexation. The thermodynamics of receptor binding are vital for controlling the selectivity in molecular recognition, which are dependent on the electrolyte composition of solution. In addition, the conformational properties of the complex (e.g., size, shape) can also contribute a secondary influence on receptor selectivity that has been relatively unexplored in ACE to date. In this study, dynamic 1:1 host-guest inclusion complexation involving a anionic resorcin[4]arene with a group of neutral corticosteroids was examined by ACE, where the macrocycle serves as both an intrinsic buffer and electrokinetic host. The tetraethylsulphonate derivative of 2-methylresorcin[4]arene (TESMR) was first synthesized via an acid-catalyzed condensation reaction, which was then fully characterized in terms of its weak acidity (pKa), mobility, UV spectral and buffer capacity properties. TESMR solutions were demonstrated to have stable intrinsic buffer and ion transport properties at pH 7.5 even at low ionic strength. It was determined that over a 200 % enhancement in the apparent binding constant (KB) was realized by ACE when using TESMR as an intrinsic buffer at pH 7.5 relative to an extrinsic sodium phosphate buffer system, which was also confirmed by 1H-NMR. The coupling of thermodynamic (KB) and electrokinetic (μep, AC) factors associated with complex formation in buffered aqueous solutions that minimize the effects of extrinsic electrolytes serves to enhance enthalpy-driven molecular recognition processes by ACE.</p> / Thesis / Master of Science (MSc)

Perceptual learning occurs because observers become more sensitive to informative aspects of the stimuli. Learning the informative aspects of one stimulus set does not transfer to another stimulus set of the same class. In this dissertation, the argument will be made that if observers learn how to discover informative aspects, learning will be more generalizable. However, discovery requires that the informative aspects are not easily apparent. To this end, stimulus orientation structure can be manipulated to contain informative structure in one orientation band, and non-informative structure in the other orientation band. Such a manipulation was inspired by research on face perception: Faces are best identified when decisions are based more on the horizontal relative to the vertical facial structure. Hence, the first three chapters focus on understanding the horizontal bias during face identification, and the final two chapters introduce a novel stimulus set for which horizontal bias may be learned. Chapter 2 identifies a neural marker of horizontal bias that is correlated with face identification accuracy, suggesting that we can predict how well observers identify faces based on their neural sensitivity to horizontal relative to vertical structure. Chapter 3 shows that when face identification accuracy declines due to healthy ageing, so too do behavioural and neural horizontal bias, but Chapter 4 shows that perceptual learning can increase horizontal bias in healthy older adults. Chapter 5 uses texture stimuli and shows that observers can learn to discover informative horizontal structure embedded in uninformative vertical structure. Chapter 6 extends these findings to show that adequate practice results in learning that generalizes to novel textures for which the orientation-selective processing is relevant. The results presented inform our understanding of the neural representations associated with orientation-selective processing, and suggest that observers can learn to discover informative structure conveyed by a particular orientation band. / Thesis / Doctor of Philosophy (PhD)

This research conducted equilibrium experiments to determine ion exchange equilibria data for the inorganic cations Ca2+, Na+, and NH4+ for binary cation exchange involving sulfonic acid, polystyrene gel resins saturated with Na+ or NH4+. A linear least-square fitting was developed to find representative ion exchange capacity (IEC) and selectivity coefficient (K) values. Equilibrium experiments were utilized to test the developed new linearization method for binary systems: Ca-NH4; Ca-Na; and Na-NH4 using three commercial strong acid cation (SAC) exchange resins. It was determined that SAC exchange resins saturated with NH4+ were more selective towards Ca2+ than resins saturated with Na+. The valency and the size of the hydrated radius of the counterion influenced the selectivity of binary systems. A higher valence and a smaller hydrated radius resulted in an increased affinity of the resin for ions. Results can be used to estimate the technical and economic feasibility of a design process along with the estimation of the effect of a change in operating conditions. In addition, the removal of toxic heavy metals was also investigated with an initial metal concentration of 0.1 mg/L. Results showed that the maximum percent removal of toxic heavy metal ions, Cr3+, Pb2+, Ba2+, and Cd2+ ranged from ~ 95-99% when present in a solution containing a high molar concentration of Ca2+, Na+, and NH4+. It was observed that SAC exchange resins can effectively remove toxic heavy metals at very low concentrations. The high selectivity that SAC exchange resins possess towards heavy metals proves that they can be used as a pretreatment method for the removal of toxic heavy metals from municipal and industrial wastewaters. Moreover, the performance of SAC exchange resins for the removal of Ca2+ from waste solutions was investigated through computer modelling. Results showed that ion exchange is an efficient method for the removal of Ca2+. A sensitivity analysis showed that the variation in K and IEC greatly influenced the breakthrough time as an increase in both parameters resulted in greater Ca2+ uptake. Modelling results can be used to optimize the design of ion exchange systems for the pretreatment of inorganic cations which can reduce membrane scaling. / Thesis / Master of Applied Science (MASc)

The overall objective of the project, on which this thesis is based, is to develop a novel hydrocarbon-based proton exchange membrane (PEM) material that can produce a proton conductivity of 0.1 S/cm at the operating conditions of 50 % relative humidity and 120 oC, which is the performance target set by the U.S. DOE for automotive application. As a part of this project, our efforts have been focused on the investigation of the effects of solution-casting conditions on the final morphology and properties of disulfonated poly(arylene ether sulfone) multiblock copolymer films from the viewpoint of phase separation of block copolymers. Of equal importance to this work, is a possibility of utilizing a rheological technique for monitoring the transformation and kinetics of block copolymers during solvent removal process, which was initially examined in order to provide fundamental quantitative understanding and practical information on the solvent removal process. Our results demonstrated that solvent selectivity and drying temperature as well as the block length had considerable effects on the final morphology and properties. The proton conductivity could be significantly increased by simply utilizing a selective solvent, dimethylacetamide (DMAC), which is good and marginal for the sulfonated and unsulfonated blocks, respectively, rather than N-methyl-2-pyrrolidone (NMP), a neutral solvent for both blocks. The drying temperature was also observed to have considerable effects on the final properties, being coupled with the effects of solvent selectivity. Also, it was shown that the multiblock copolymer consisting of longer blocks was more sensitive to the processing conditions. From the morphological study using transmission electron microscopy and small-angle X-ray scattering, evidences for the above observations were obtained. In the second part of this dissertation, the evolution of GÎ and GË of the solutions of a styrene-butadiene-styrene (SBS) triblock copolymer in toluene was obtained as a function of concentration using a modified parallel-plate device and a rheology test scheme developed in this study in an effort to quantify the phase separation kinetics. Then, the information on the phase transformation and kinetics of the SBS block copolymer in the solution was obtained by analyzing the GÎ and GË data with the Avrami equation. The Avrami exponent was found to be approximately 1, which indicates that the phase transformation occurred by a one-dimensional growth mechanism. The rate constant showed a strong concentration-dependence. After the initial increase up to 45 vol %, the rate constant drastically decreased and, finally, converged to 0 at 70 vol %. It is believed that, at the concentration range below 45 vol %, the phase separation became more intense as the polymer molecules had more chances to interact owing to the concentration increase. However, above 45 vol %, the phase transformation became weaker due to the limited mobility of the polymer molecules, which finally led to a “kinetically frozen-in” structure, in which the polymer molecules could not move any longer. Thus, it can be concluded that the solvent removal rate is one of the dominant factors that decide the final microstructures of solution-cast block copolymer films. / Ph. D.

Phenylindane monomers 5(6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindane (DAPI), 5,6-diamino-1-(4-aminophenyl)-1,3,3-trimethylindane (TAPI) and 6-hydroxy-1-(4-hydroxyphenyl)-1,3,3-trimethylindane (DHPI) were synthesized and characterized. DAPI, as well as other diamines, were then utilized in solution step polycondensation with a number of commercially available dianhydrides using either the two-step ester-acid solution imidization or the high temperature solution imidization routes. High molecular weight soluble fully cyclized polyimides were successfully synthesized using a 1:1 molar ratio of dianhydride to diamine. The polyimides were film forming and were characterized by size exclusion chromatography (SEC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and selective gas permeation methods, as well as other techniques. The O2 permeation and O2/N2 selectivity values obtained for materials prepared in this thesis are discussed in relation to the concept of an "upper bound", as defined in the literature concerning gas separation membranes. The series of polyimides based on DAPI and several dianhydrides were found to have high glass transition temperatures (247°C-368°C) and very good short-term thermal stability as shown by TGA, despite the partially aliphatic character of DAPI. The 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis-1,3-isobenzenefurandione (6FDA)/DAPI system also exhibited low weight loss under nitrogen at 400°C, which was comparable to that of a wholly aromatic polyimide based on 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA)/4,4'-oxydianiline (ODA) which is known to have high thermal stability. In addition, the 6FDA/DAPI polyimides had a refractive index value of 1.571 from which the dielectric constant was calculated, giving an attractively low estimated value of 2.47. The rigid, bulky and isomeric structure of DAPI in the repeat unit imparted film forming characteristics that allowed production of solvent cast membranes which displayed a range of O2 permeability and O2/N2 selectivity characteristics. High O2 permeabilities were observed for polyimides in which the DAPI structure predominated in relation to the overall polymer repeat unit, i.e. in combination with low molar mass dianhydrides. The more flexible dianhydrides afforded a greater degree of molecular freedom and were thought to result in a more tightly packed polymer conformation which decreased the rate of gas penetration through thin films. The DAPI/3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) system showed the best combination of O2 permeability and O2/N2 selectivity values (2.8Ba and 7.3, respectively). Modest variations in the DAPI isomeric ratio did not significantly effect the gas permselectivity properties. High molecular weight polyimides based on DAPI and BTDA were synthesized by three different routes. The ester-acid and thermal imidization methods produced polyimides with the highest Tgs and best thermal stability in air, as compared to the chemical imidization procedure. For example, a Tg increase of 22°C and a 68°C increase in the 5% weight loss were found for the ester-acid imidized DAPI/BTDA polyimide over those found for the chemically imidized version. The higher Tg and 5% weight loss values were attributed to the elimination of residual uncyclized amide acid moieties. Polyimides derived from 6FDA were synthesized by the high temperature solution imidization method. Thin films, cast from NMP, were tough and creasable and afforded high Tg (>295°C) systems with good thermal stability. When combined with rigid diamines, 6FDA contributed to high O2 permeation and moderate O2/N2 selectivity. The high O2 permeability was ascribed to hindered interchain packing attributed to the bulky CF3 groups. The exceptionally high oxygen permeability and O2/N2 selectivity values of the 9,9-bis(4-aminophenyl) fluorene (FDA)/6FDA system, were near the desirable "upper bound" for gas separation membrane materials, while those of 3,7-diamino-2,8-dimethyl-dibenzothiophene-5,5-dioxide (DDBT)/6FDA were actually above the upper bound. High performance polymers based on 4,4'-bis [4-(3,4-dicarboxyphenoxy)]biphenyl dianhydride (BPEDA), 2,2'-bis [4-(3,4-dicarboxyphenoxy)phenyl] propane dianhydride (BPADA), 2,2-bis(3-amino-4-methylphenyl)hexafluoroisopropylidene dianhydride (Bis-AT-AF) and 3,7-diamino-2,8-dimethyl-dibenxothiophene-5,5-dioxide (DDBT) were also synthesized in this work. Additionally, they were characterized with regard to molecular weight, glass transition temperature, and thermal stability. Polyimide systems containing hydroxyl moieties in the repeat unit were also investigated. Incorporation of hydroxyl moieties in the repeat unit enhanced chain stiffness via intermolecular hydrogen bonding and showed Tg increases of ~30°C Hydroxyl moieties also decreased the thermal stability values typically observed for polyimides. High O2/N2 selectivity was achieved with all of the 4,4'-diaminobiphenyl-3,3'-diol (HAB) containing polymers. However, these materials also had low O2 permeabilities, which suggested a tightly packed structure, possibly facilitated by hydrogen bonding. In contrast to suggestions in the literature, the comparison between a polyimide having pendant hydroxyl groups and another having the same repeat unit without them did not reveal a significant change in permselectivity behavior. The synthesis, characterization and crosslinking behavior of functional polyimides containing phenol, amine and acetylene moieties are also described. A crosslinking reaction of oligomers containing phenol moieties with a tetrafunctional epoxy resin was achieved 100°C below the "dry" glass transition temperature and was attributed to residual solvent. Utilization of this crosslinking mechanism could allow membrane optimization by investigating the influence of a number of variables, such as the concentration of the phenolic moiety, epoxy weight percent, catalyst concentration and residual solvent content. / Ph. D.

Plasmonic polymer nanocomposites contain plasmonic nanoparticles that are dispersed within a polymer. The polymer matrix strongly influences the optical properties of plasmonic nanoparticles. It is imperative to understand the interaction between plasmonic nanoparticles and polymers so that one can develop functional devices using nanocomposites. The utilization of plasmonic nanoparticles as fillers has great potential to transform critical nanotechnologies where light management is crucial, such as refractive index based nanosensors, optical coatings, and light actuated devices. Despite the great potential, effective integration of plasmonic nanoparticles with polymers remains challenging. This dissertation presents i) the effects of dielectric media on the optical properties of plasmonic nanoparticles, ii) the sensing of polymer brush formation on nanoparticles, iii) the fabrication of plasmonic nanocomposite thin-films with controlled optical properties, and iv) the development of electrically conductive membranes for electrostatic speakers. The optical response of plasmonic nanoparticles (referred to as wavelength of localized surface plasmon resonance, λLSPR) is sensitive to changes in refractive index of the medium. The sensitivity (S) plays a critical role in determining the performance of nanoparticles in sensing applications. In this dissertation, I have conducted a systematic study on the sensitivity of plasmonic nanoparticles as a function of various parameters: shape, size, composition, initial plasmonic resonance wavelength, cross-sectional area, and aspect ratio. Among the parameters investigated, aspect ratio (R) is determined to be the key parameter that controls S, following an empirical equation, S = 46.87 R + 109.37. This relationship provides a guideline for selecting fillers in plasmonic polymer nanocomposites, and it predicts the final effect of plasmonic nanoparticles on the optical properties of polymer nanocomposites. Plasmonic nanoparticles are employed to probe polymer grafting on the surfaces of metal nanoparticles. Using ultraviolet-visible (UV-vis) spectroscopy, I have demonstrated the quantification of polymer grafting density on the surface of plasmonic nanoparticles. The λLSPR of plasmonic nanoparticles red-shifts as the polymer concentration near the nanoparticle surface increases. I have investigated the formation of polymer brush by grafting the nanoparticles with thiolated polyethylene glycol (PEG-SH) and revealed the three–regime kinetics in situ. Importantly, this study suggests that a latent regime arises due to fast polymer adsorption and prolonged chain rearrangement on nanoparticle surfaces. When the polymer chains rearrange and chemically tether to the surface, they contract and allow more polymer chains to graft onto the particle surface until saturation. This analytical method provides a new surface probing technique for polymer brush analysis, complementary to conventional methods such as quartz crystal microbalance, atomic force microscope, and microcantilivers. Commercial tinted glass employs expensive metalized films to reduce light transmittance but has limited spectral selectivity. To reduce the cost of metalized films and to improve the spectral selectivity, I have employed plasmonic nanoparticles in polymers to fabricate spectral-selective tinted films. First, I have synthesized two-dimensional (2D) plasmonic silver nanoparticles (AgNPs) using multi-step growth. The nanoparticles have a tunable plasmon resonance and provide spectral selectivity. The multi-step growth forgoes polymeric ligands such as poly(vinylpyrrolidone) (PVP) and solely relies on a small molecule sodium citrate. Briefly, small citrate-capped Ag seeds are first grown into small 2D AgNPs. The small 2D AgNPs are then used to grow large 2D AgNPs via multiple growth steps. The PVP-free method allows for fast synthesis of 2D AgNPs with large sizes and tunable plasmon resonance across the visible and NIR region. The 2D AgNPs are integrated with polymers to produce thin-film plasmonic nanocomposites. By controlling the planar orientation of the 2D AgNPs through layer-by-layer assembly, the polymer nancomposites have achieved reduced light transmittance and enhanced reflectance across the visible and NIR range. In contrast to conventional polymer nanocomposites where the AgNPs are randomly oriented, the thin-film polymer nanocomposites exhibit excellent control over nanoparticle density and hence the optical properties, that is, tunable light transmittance and reflectance across the visible and NIR. Lastly, graphene is used to prepare conductive free-standing polymer thin-films. Graphene, an ultralight weight 2D material with excellent electrical and mechanical properties, has potential for use in thin-film composites essential for photovoltaics, electrostatic speakers, sensors, and touch displays. Current graphene-based composite films contain graphene flakes randomly mixed in a polymer matrix and usually possess poor mechanical and electrical properties. In this dissertation, I have developed thin-film nanocomposites comprised of chemical vapor deposited (CVD) graphene and high-performance polyetherimide (PI). The CVD-grown graphene is polycrystalline, and it cannot be used as a free-standing film. By enforcing the polycrystalline graphene with a thin layer of PI, I have prepared free-standing thin-film composites with a high aspect ratio of 105. Mechanical and electrical property characterization reveals a Young's modulus of 3.33 GPa and a resistance of 200 - 500 Ω across the membrane. A typical spring constant of the membrane is ~387 N/m. Dynamic electromechanical actuation shows that the membrane vibrates at various input frequencies. The polymer/graphene film has excellent acoustic properties, and when used as a speaker membrane, it reduces the electrical power consumption by a factor of 10-100 over the frequency range of 600–10,000 Hz. / Doctor of Philosophy / Nanomaterials such as plasmonic nanoparticles and graphene have optical, electrical, and mechanical properties that are important for light filters, sensors, printing, photovoltaics, touch screens, speakers, and biomedical devices. To fully employ the nanomaterials, a support such as polymer is often required. However, when the nanomaterials and polymers are combined, their optical, electrical, and mechanical properties drastically change. Therefore, it is imperative to understand the interactions between nanomaterials and polymers, as well as the resulting properties. Towards this goal, I have studied the sensitivity of plasmonic nanoparticles in a dielectric media and then utilized the sensitivity to investigate polymer brush formation on nanoparticle surfaces. In addition, I have investigated the integration of plasmonic nanoparticles and graphene with polymers to develop thin-film nanocomposites for window coatings and audio speakers, respectively. Plasmonic nanoparticles can detect trace amounts of chemicals, biomolecules, toxics, warfare agents, and environmental pollutants. Sensitivity is the key criterion that determines the performance of nanoparticles for such applications. Firstly, I have conducted a detailed and comprehensive study of the plasmonic sensitivity as a function of various nanoparticle parameters including shape, size, composition, cross-sectional area, initial plasmonic resonance wavelength, and aspect ratio. I have found that the sensitivity scaled linearly with aspect ratio. The strong dependence of sensitivity on aspect ratio provides insight into designing effective plasmonic sensors. Based on the sensitivity study, I have used plasmonic nanoparticles as sensors to probe and understand the mechanism of polymer brush formation in situ. When the concentration of polymer increases on the nanoparticle surfaces, the optical response of the nanoparticle changes. Through functionalizing the plasmonic nanoparticles with polymers, I have confirmed the three different regimes of polymer brush formation. Plasmonic nanoparticles resonating in the visible and near infrared have a great potential in designing polymer nanocomposites for window coatings. Among different exotic shapes, two-dimensional nanoplates are the most important as their optical properties can be easily tuned across a wide range of wavelengths. However, most of the current methods require polymers, long hours of reaction time, and multiple purification steps. I have developed a new multi-step strategy to synthesize Ag nanoplates which absorb in the range of 500–1660 nm. Utilizing the plasmonic nanoparticles, the spectral-selective plasmonic nanocomposites comprised of polymers and planarly oriented Ag nanoparticles of judiciously selected sizes and compositions were prepared. The plasmonic polymer nanocomposites spectral-selectively reflect, scatter, and filter light of any desired wavelength. The nanocomposites will impact on the tinted glass in modern energy-efficient buildings. The outstanding electrical and mechanical properties of graphene have stirred a large volume of research in the last 15 years. Most graphene-based technologies focus on graphene at the nano or micro scale. To further the practicality of graphene in large devices like audio speakers, large areas and thin films are needed to reduce energy consumption. Graphene on its own cannot be used over large areas due to the inherent defects arising during the growth. Here I present results on combining suspended sheets of single layer graphene with a mechanically strong polymer thin film. The acoustic properties of speakers made of polymer/graphene thin films are similar to those of conventional electrodynamic speakers in modern cellphones. The energy consumption, however, reduces sharply by a factor of 10-100 for the polymer/graphene based speakers. This sharp decrease in energy is attributed to the lightweight, flexibility, and excellent electrical conductivity. Apart from speakers, the membrane designed here also has huge potential in other devices like touch panels, capacitive sensors, and photovoltaics.

One potential alternative to chemical weed control is the use of microwave radiation, a particular form of indirect thermal weeding. Absorption of microwave radiation causes water molecules within the tissue to oscillate, thereby converting electromagnetic energy into heat. This technique is rapid, versatile and effective, as the electromagnetic waves heat the plant tissue and destroy cellular integrity. The objective of this research was to evaluate the potential use of dielectric heating for weed management. Ten weed species representing monocots and dicots were selected for this study: southern crabgrass, dallisgrass, yellow nutsedge, fragrant flatsedge, false green kyllinga, common ragweed, field bindweed, henbit, white clover, and pitted morningglory. There was a lag or warm up period between energizing the magnetron and actual microwave radiation production. To eliminate the gap between electric power supplied to magnetron and actual microwave radiation produced, a conveyer was used. Overall injury to grasses, sedges and broadleaf weeds was higher at each dose when weeds were treated by microwave radiation while moving on a conveyer in comparison to being stationary. Grasses showed slightly more tolerance to microwave treatments in comparison to broadleaf weeds. Older weeds (8 to 10 weeks old) showed more tolerance to microwave treatments in comparison to younger weed plants (4 to 6 weeks old). Microwave radiation was able to control a range of weed species, although larger weeds were more likely to regrow after treatment. Ambient temperature had a significant effect on injuries caused by microwave radiation to target weeds, with control increasing as the air temperature increased. Weed control using microwave radiation required more energy when weeds were treated at 13 C compared to 35 C. More energy was needed at lower air temperatures to raise the plant canopy temperature from ambient levels to beyond the biological limit. Microwave radiation at lower doses caused greater injury to common chickweed and yellow woodsorrel than bermudagrass, suggesting the potential for selective weed control in certain situations. A custom built microwave applicator provided similar control of emerged weeds as the contact herbicides diquat and acetic acid. / Ph. D.

Iron oxide catalyst have been used to perform high temperature water-gas shift reactions (HTWGSR). They have shown to be affective for application in a pyrolysis gas pre-conditioning step to create a hydrogen enriched gas and possibly removing the need for bio-crude condensation before further treatment or use. A small-scale experimental study of an iron oxide catalyst with additives provided by Topsoe, exposed to different H2O:CO ratios temperatures was conducted. The catalyst was first activated following steps given by the supplier. The different H2O:CO ratios tested on the catalyst were 2:1, 4:1 and 6:1 at 350 °C and 2:1, 4:1 and 6:1 at 450 °C. The space velocity was kept constant at 52500 L/(kgcat·h) for all the experiments. No significant deactivation was observed through the 18-hour experiment, based on Brunauer-Emmett-Teller (BET) results. The results show that the highest conversion of CO was achieved at 4:1 H2O:CO ratio at 450 °C, the best H2 selectivity was at 2:1 H2O:CO ratio at 350 °C, and the highest yield was obtained at 6:1 ratio at 450 °C. The initial condition (4:1 H2O:CO ratio at 350 °C) showed anomalous activity as it had a surprisingly low H2 selectivity (25%) and a comparatively high conversion of CO (20.8%). This could have been due to systematic error or possibly due to other side reactions (production of methane) happening. Literature on similar behaviour was not found. A two-way Analysis of Variance (ANOVA) test was conducted and concluded that all 3 noll hypotheses could be rejected, furthermore, have 3 separate 2x2 factorial design tests been done using MATLAB where the results show that all effects including interaction effects were active with the most significant effect being the change in temperature and the least significant being the change in H2O:CO ratio above 4:1. The results show that this particular iron oxide catalyst with additives provided by Topsoe operates best at temperatures around 450 °C at a H2O:CO ratio of 4:1 or above. It shows no signs of deactivation and may be able to perform WGSR for extended periods of time. / Järnoxidkatalysatorer har använts för att utföra reaktioner för vatten-gasskift vid höga temperaturer (HTWGSR). De har visat sig vara effektiva för tillämpning i ett pyrolysgasförberedningssteg för att skapa en väteberikad gas och eventuellt eliminera behovet av kondensering av biologisk råolja innan ytterligare behandling eller användning. En småskalig experimentell studie av en järnoxidkatalysator med tillsatser från leverantören Topsoe, utsatt för olika H2O:CO-förhållanden vid olika temperaturer, genomfördes. Katalysatorn aktiverades först enligt de anvisningar som lämnats av leverantören. De olika förhållandena som testades på katalysatorn var 2:1, 4:1 och 6:1 vid 350 °C samt 2:1, 4:1 och 6:1 vid 450 °C. Utrymmeshastigheten (space velocity) hölls konstant på 52500 L/(kgcat·h) för alla experiment. Ingen signifikant inaktivering observerades under det 18 timmar långa experimentet, baserat på Brunauer-Emmett-Teller (BET) resultat. Resultaten visar att den högsta konverteringen av CO uppnåddes vid 4:1 H2O:CO-förhållande vid 450 °C. Bästa H2-selektiviteten observerades vid 2:1 H2O:CO-förhållande vid 350 °C, medan högsta utbytet erhölls vid 6:1-förhållande vid 450 °C. Det initiala förhållandet (4:1 H2O:CO vid 350 °C) visade anomalt beteende med en låg H2-selektivitet (25%) och en jämförelsevis hög konvertering av CO (20,8%). Detta kan ha berott på systematiskt fel eller möjligen på andra sidoreaktioner (produktion av metan). Litteratur om liknande beteende hittades inte. En tvåvägs Analysis of Variance (ANOVA) test genomfördes och slutsatsen var att alla tre nollhypoteser kunde förkastas. Dessutom har tre separata 2x2-faktoriella designtester utförts med hjälp av MATLAB, där resultaten visar att alla effekter, inklusive interaktionseffekter, var aktiva. Den mest signifikanta effekten var förändringen i temperatur, medan den minst signifikanta var förändringen i H2O:CO-förhållandet över 4:1. Resultaten visar att den specifika järnoxidkatalysatorn med tillsatser från Topsoe fungerar bäst vid temperaturer runt 450 °C och vid ett H2O:CO-förhållande på 4:1 eller högre. Den visar inga tecken på inaktivering och kan möjligen utföra WGSR under förlängda tidsperioder.

Yes / A deactivated alkene precursor (IC50=81 mu M) to the azinomycin epoxide natural product can be bioactivated by several cytochromes P450 (CYP) to generate antiproliferative metabolites with increased potency (IC50=1-30 mu M) in CHOwt cells. CYP1A1 and 3A4 were shown to generate exclusively the unnatural and the natural-configured azinomycin epoxide diastereoisomer respectively, while CYP1B1 produced both epoxides in a 3:1 mixture. The antiproliferative activity is linked to DNA damage as demonstrated using the comet assay.