Ett vanligt förfarande i parapsykologiska s.k. ganzfeldexperiment är att med hjälp av vitt brus, som spelas upp i hörlurar, försöka omsluta försökspersoner i ett slags totalt och oföränderligt perceptuellt tillstånd. I föreliggande studie undersöks konsekvenserna av att använda vitt brus som bakgrundsljud. 30 försökspersoner har lyssnat till åtta ljudslingor innehållandes fyra typer av brus vid två olika ljudnivåer, för att sedan i ett enkätformulär uppskatta hur dessa ljud påverkat dem. Resultatet visar på signifikanta effekter av så väl brustyp som amplitud, och dessutom en signifikant interaktionseffekt dem emellan. Utifrån resultatet verkar valet av vitt brus brus som akustisk komponent i ganzfeldstudier vara teoretiskt ogrundat och direkt ofördelaktigt. Vidare diskuteras bakgrundsbrusets tänkbara inverkan på försöksdeltagarnas förmåga att genomföra de uppgifter som ingår i ett typiskt ganzfeldexperiment, och slutligen konstateras att medan brunt brus förvisso verkar vara det mest omtyckta av försöksdeltagarna, är det också det mest suggestiva. Därför synes skärt brus vara ett lämpligare val av bakgrundsljud än något annat brus som användes i undersökningen.

This research project is a part of our endeavor to developing a new hydrogen sulfide (H2S) splitting cycle for hydrogen production. In view of that the Bunsen reaction is the key step for the overall efficiency, the objective of this research is to develop an effective and efficient process to carry out the Bunsen reaction in the presence of organic solvents. Organic solvents can help dissolve iodine crystal, lower the reaction temperature and reduce the corrosiveness accompanying the reaction. Through screening of the ordinary organic solvents, aromatic hydrocarbons stood out and toluene was used in this project.<p> In order to study the Bunsen reaction rate in the presence of toluene, the iodine solubility in HI solution was extensively explored at room temperature. Although the iodine solubility in water is small (0.3404g/L at 25â), it was found that the iodine solubility in HI solution increases greatly as the [HI] increases. At lower [HI] (0~0.238 M), the iodine solubility is linear to [HI] with a relationship of [iodine solubility] = 0.57[HI] + 0.0030; at higher [HI] (0.238 ~7.6 M), the relationship of the iodine solubility and [HI] conforms to [iodine solubility]/[HI] = 0.190[HI] + 0.58.<p> In the second part, the iodine distribution behavior between HI solution and toluene phase was studied at room temperature. It was determined that the iodine distribution coefficient (D = [I2]HI solution/[I2]toluene) increases as the increase of [HI]. At lower [HI] (0~1.89 M), the distribution coefficient has a quadratic relationship with [HI] as D = 1.4027[HI]2 + 0.8638[HI] + 0.0088; at higher [HI] (1.89~7.54 M) the distribution coefficient is linear to [HI] with a relationship of D=5.5937[HI]-3.5632.<p> On the basis of the above work, in a semi-batch reactor, the Bunsen reaction rate in the presence of toluene was measured. In a mixture of toluene and water, iodine prefers to stay in toluene phase. The Bunsen reaction was readily initiated by feeding SO2 into water phase. Experimental results indicated that the rate of the Bunsen reaction in the presence of toluene is equal to the molar flow rate of feeding SO2 when the iodine concentration is higher than a certain value. This specific value depends on the reaction conditions, such as the interface area between water and toluene phase, the dispersion efficiency and the flow rate of SO2.

The controls of water and O2 availability, microbial activity and temperature on acid (H2SO4) production rates in commercial-scale sulphur (S0) blocks were quantified and recommendations were made for minimizing H2SO4 production in S0 blocks. Acidic drainage from the S0 blocks (pH 0.4-1.0) was attributed to mixing of fresh infiltrating water and low-pH resident water (mean pH=-2.1) with resident water comprising ~4-8% of the drainage. Although clean S0 is strongly hydrophobic, preferential water infiltration occurred rapidly through fractured S0 blocks in which the bulk hydraulic conductivity was estimated to be similar to gravel or clean sand (Ks=1x10-1 to 1x10-3 m/s). Microbial colonization of fracture faces generated localized hydrophilic conditions that helped create preferential pathways for water infiltration. Liquid water contact (compared to water vapour) was essential for S0 oxidation (i.e., H2SO4 production), therefore H2SO4 production in the S0 blocks was limited to fractures and friable S0 through which water flowed. H2SO4 production was greatest in the upper 1 m of the S0 block (70 to >97% of annual H2SO4 production) and the result of autotrophic microbial S0 oxidation.<p> S0 oxidation rates were very sensitive to temperature and increased by a factor of 4.3 for a temperature increase of 10°C (Q10). Therefore minimizing temperature (<5°C) in S0 blocks would be an effective strategy for controlling H2SO4 production. Heat released during S0 oxidation did have a measurable effect on in situ temperatures and should be considered in the design of insulated cover systems. Although autotrophic microbial activity was insensitive to O2 concentrations when they were >1 vol.%, the total mass production rate of H2SO4 is approximately proportional to the O2 concentration at the surface of the S0 block (assuming in situ O2 concentrations decrease to <1 vol. %). Therefore, cover systems that minimize the surficial O2 concentration are recommended.<p> Cover systems limiting H2O infiltration would be effective for minimizing the volume of acidic drainage, but may have no impact on H2SO4 production rates within the block. In this study, H2O infiltration through a typical soil cover (~95% efficiency) would easily satisfy the annual H2O demand for H2SO4 production (2.6 mm/m2 in the upper 1 m). Greater near-surface H2SO4 production rates may appear to make surficial biocide application an attractive option for minimizing S0-oxidizing microbial activity, however, this approach might simply drive the zone of H2SO4 production to greater depths and have no affect on the total mass production of H2SO4.

A variety of behavioural tests were used to examine both sensory and motor function of freely behaving unilaterally spinal cord-injured and uninjured rats. The first experiment was designed to determine whether sensory and motor differences existed between uninjured Fischer, Lewis, Long-Evans, Sprague-Dawley and Wistar rats using endpoint, quantitative kinematic, and kinetic measurements. The second experiment examined differences in sensorimotor responses to cervical spinal cord hemisection in Lewis, Long-Evans and Wistar rats. For the third experiment, reflex and locomotor abilities of unilateral cervical or thoracic spinal cord hemisected Long-Evans rats were determined using endpoint, semi-quantitative kinematic, and kinetic measurements. The fourth experiment was designed to investigate the importance of the rubrospinal tract and ascending dorsal column pathways to overground locomotion. This experiment was conducted to help explain the behavioural observations made following cervical spinal cord hemisection. Furthermore, this experiment examined the effects of combined unilateral rubrospinal and dorsal column injury on overground locomotion using endpoint and kinetic measurements. Finally, the fifth experiment set out to investigate the contribution of tracts running in the ventrolateral spinal cord on overground locomotion in freely behaving Long-Evans rats. These animals were assessed using endpoint and kinetic measurements. The results of these studies revealed that motor and sensory functions are not similar for all uninjured strains of rats. Specifically, Fischer rats tend to have considerable differences in their morphological features and sensorimotor abilities compared to the other strains examined. Results from the other experiments indicate that adult freely behaving female rats develop a characteristic gait when pathways important for locomotion are injured unilaterally, regardless of strain. The rubrospinal tract and ascending dorsal column pathways appear to be important for both skilled and flat-ground locomotion as well as forelimb use while rearing. Pathways traveling within the ventrolateral pathway, however, are not necessary or sufficient for locomotion or limb useage while rearing when injured by themselves. Animals with ventrolateral spinal funiculus injuries regain normal forelimb use and skilled locomotor abilities. Injury to the ventrolateral spinal funiculus, however, results in mild (compared to rubrospinal and dorsal column injured animals) yet long-lasting locomotor changes based on ground reaction force determination. These findings are in agreement with the current opinion that there is a substantial amount of functional redundancy of pathways traveling in the ventral and ventrolateral funiculi.

A variety of behavioural tests were used to examine both sensory and motor function of freely behaving unilaterally spinal cord-injured and uninjured rats. The first experiment was designed to determine whether sensory and motor differences existed between uninjured Fischer, Lewis, Long-Evans, Sprague-Dawley and Wistar rats using endpoint, quantitative kinematic, and kinetic measurements. The second experiment examined differences in sensorimotor responses to cervical spinal cord hemisection in Lewis, Long-Evans and Wistar rats. For the third experiment, reflex and locomotor abilities of unilateral cervical or thoracic spinal cord hemisected Long-Evans rats were determined using endpoint, semi-quantitative kinematic, and kinetic measurements. The fourth experiment was designed to investigate the importance of the rubrospinal tract and ascending dorsal column pathways to overground locomotion. This experiment was conducted to help explain the behavioural observations made following cervical spinal cord hemisection. Furthermore, this experiment examined the effects of combined unilateral rubrospinal and dorsal column injury on overground locomotion using endpoint and kinetic measurements. Finally, the fifth experiment set out to investigate the contribution of tracts running in the ventrolateral spinal cord on overground locomotion in freely behaving Long-Evans rats. These animals were assessed using endpoint and kinetic measurements. The results of these studies revealed that motor and sensory functions are not similar for all uninjured strains of rats. Specifically, Fischer rats tend to have considerable differences in their morphological features and sensorimotor abilities compared to the other strains examined. Results from the other experiments indicate that adult freely behaving female rats develop a characteristic gait when pathways important for locomotion are injured unilaterally, regardless of strain. The rubrospinal tract and ascending dorsal column pathways appear to be important for both skilled and flat-ground locomotion as well as forelimb use while rearing. Pathways traveling within the ventrolateral pathway, however, are not necessary or sufficient for locomotion or limb useage while rearing when injured by themselves. Animals with ventrolateral spinal funiculus injuries regain normal forelimb use and skilled locomotor abilities. Injury to the ventrolateral spinal funiculus, however, results in mild (compared to rubrospinal and dorsal column injured animals) yet long-lasting locomotor changes based on ground reaction force determination. These findings are in agreement with the current opinion that there is a substantial amount of functional redundancy of pathways traveling in the ventral and ventrolateral funiculi.

This research project is a part of our endeavor to developing a new hydrogen sulfide (H2S) splitting cycle for hydrogen production. In view of that the Bunsen reaction is the key step for the overall efficiency, the objective of this research is to develop an effective and efficient process to carry out the Bunsen reaction in the presence of organic solvents. Organic solvents can help dissolve iodine crystal, lower the reaction temperature and reduce the corrosiveness accompanying the reaction. Through screening of the ordinary organic solvents, aromatic hydrocarbons stood out and toluene was used in this project.<p> In order to study the Bunsen reaction rate in the presence of toluene, the iodine solubility in HI solution was extensively explored at room temperature. Although the iodine solubility in water is small (0.3404g/L at 25â), it was found that the iodine solubility in HI solution increases greatly as the [HI] increases. At lower [HI] (0~0.238 M), the iodine solubility is linear to [HI] with a relationship of [iodine solubility] = 0.57[HI] + 0.0030; at higher [HI] (0.238 ~7.6 M), the relationship of the iodine solubility and [HI] conforms to [iodine solubility]/[HI] = 0.190[HI] + 0.58.<p> In the second part, the iodine distribution behavior between HI solution and toluene phase was studied at room temperature. It was determined that the iodine distribution coefficient (D = [I2]HI solution/[I2]toluene) increases as the increase of [HI]. At lower [HI] (0~1.89 M), the distribution coefficient has a quadratic relationship with [HI] as D = 1.4027[HI]2 + 0.8638[HI] + 0.0088; at higher [HI] (1.89~7.54 M) the distribution coefficient is linear to [HI] with a relationship of D=5.5937[HI]-3.5632.<p> On the basis of the above work, in a semi-batch reactor, the Bunsen reaction rate in the presence of toluene was measured. In a mixture of toluene and water, iodine prefers to stay in toluene phase. The Bunsen reaction was readily initiated by feeding SO2 into water phase. Experimental results indicated that the rate of the Bunsen reaction in the presence of toluene is equal to the molar flow rate of feeding SO2 when the iodine concentration is higher than a certain value. This specific value depends on the reaction conditions, such as the interface area between water and toluene phase, the dispersion efficiency and the flow rate of SO2.

This work covers recent advances in the Stetter reaction, including two novel domino Stetter reactions and preliminary studies on quaternary center formation via the intermolecular Stetter reaction. The N-heterocyclic carbene (NHC) catalyzed domino Stetter-aldol-Michael dimerization of o-formyl chalcone derivatives 36 affords spiro bis-indane homo-dimers 38 in good yields and moderate to high diastereomeric ratios. Three carbon-carbon bonds, including the hindered quaternary center at the spiro ring junction, form at a remarkable rate under mild reaction conditions. Spiro bis-indanes 39 are also produced in moderate to good yields through the Stetter-aldol-aldol reactions of o-formyl chalcones 36 with phthalaldehyde derivatives 27. The scope, limitations, and potential applications of these remarkable complexity-generating domino reactions are discussed. Preliminary results in the formation of quaternary centers via the intermolecular Stetter reaction are also disclosed. The viability of β,β-disubstitued Meldrum’s acid, diethyl malonate, and malononitrile alkylidenes as well as diphenylcyclopropenone and 3-phenylcyclobutenone as acceptors in the Stetter reaction are discussed.

Polymer electrolyte membrane fuel cells (PEFCs) have long been thought of as a promising clean alternative energy electrochemical device. They are lightweight, highly efficient, modular and scalable devices. A fuel such as H2 or methanol that can be readily produced from a variety of sources can be utilized in PEFCs to generate electricity with low or no emissions. Despite these advantages, fuel cell technologies have failed to reach mass commercialization mainly due to short operational lifetimes and the high cost of materials. In particular, the polymer membrane and the catalyst layer have been problematic in reducing the material cost. Currently, platinum is the dominant material used to catalyze fuel cell reactions. However platinum is very expensive and scarce. In order to pursue the mass commercialization of fuel cells, two methods have been proposed: 1) increasing the utilization of platinum to lower the loading required, and 2) replacing platinum completely with a non-precious material. The latter has been suggested to be the long term solution due to the increasing cost of platinum. This thesis explores the elimination of platinum through the use of nanostructured non-precious metal catalysts for polymer electrolyte fuel cells. Several catalysts have been synthesized without the use of platinum that are active for the oxygen reduction reaction (ORR) which occurs at the cathode. Three different synthetic techniques were utilized using different nitrogen precursors. Aside from the different nitrogen precursors, each set of experiments utilize a different approach to optimize the oxygen reduction performance. Different characterization techniques are used to learn more about the ORR on non-precious metal fuel cells. The first experiment utilizes ethylenediamine, a well-known nitrogen precursor for non-precious metal fuel cell catalysts. Ethylenediamine is deposited onto two different porous carbon black substrates to determine the effectiveness of different porosities in creating active sites for the ORR. Of the two carbon black species, Ketjenblack EC-600JD and Ketjenblack ED-300J, the former was found to be more porous and effective. This result was mainly attributed to the increased surface area of the carbon black which allowed for better dispersion and a greater active site density. In this experiment, the coating of ethylenediamine on carbon black was also refluxed for 3 hours prior to the pyrolysis. It was found that refluxed catalyst samples showed much improved performance than catalyst samples without this procedural modification. The next experiment utilized cyanamide as a nitrogen precursor. Cyanamide was chosen due to its ability to form larger amounts of pyridinic nitrogen on the surface of the catalyst after a high temperature pyrolysis stage. The catalysts were heat-treated at 1000oC and the performance was measured. NH3 was introduced during the pyrolysis, which could remove the excess coating from the carbon surface, and increase the surface area of the catalyst by unblocking the carbon pores. A third modification to the procedure was carried out, where the heat-treated sample was ball-milled, re-coated, and heat-treated again in ammonia conditions to increase the nitrogen functionalities and increase the active site density. The performance was slightly increased from the original heat-treated sample. However due to the decreased surface area, the limiting current density also decreased. It was believed that ball-milling the sample crushed the pores within the catalyst sample, thereby lowering the active surface area and thus the current density. Therefore, the last sample was prepared similarly to the procedure for the third sample, but without ball-milling. This sample had restored surface area and improved ORR performance over all the synthesized catalyst samples – these experiments allowed for important realizations regarding the nature of the Fe-cyanamide-KJ600 catalysts and allowed for a drastic improvement in onset and half-wave potentials from the first catalyst. The final experiment discussed in this thesis describes the work done with 1,2,4,5-tetracyanobenzene and tetracyanoethylene as phthalcyanine precursors for non-precious metal catalysts (NPMCs). Iron(II) acetate was mixed with these phthalocyanine precursors to form polymer sheets of iron phthalocyanine or its monomeric units. By the creation of these polymer sheets of iron phthalocyanine, it allowed for a uniform distribution of iron centres on the surface of the carbon after a heat-treatment step. This allowed for high active site density through the design of these sheet polymers and prevented agglomeration or blockage of active sites which is thought to be a common problem in the synthesis of many NPMCs. Both tetracyanobenzene and tetracyanoethylene as precursors were tested. The tetracyanobenzene catalyst was heat-treated at different temperature ranging from 700-1100oC and characterized through electrochemical tests for the ORR. As an overall conclusion to this work, several catalyst samples were made and different approaches were successfully employed to improve the ORR performance. Of the synthesis treatments utilized to improve performance, each specific catalyst had different parameters to tweak in order to improve ORR performance. With X-ray photoelectron spectroscopy (XPS) analysis, conclusions were also specific to the catalysts structure and synthesis procedure, however quaternary and pyrrolic nitrogen groups seemed to play an influential role to the ORR final performance. Although relative amount of pyridinic nitrogen was not seen to increase with increasing catalyst performance during the studies; it may still play an essential role in the reduction of oxygen on the catalyst surface. The author of this work has not ruled out that possibility. Several recommendations for future work were suggested to broaden the knowledge and understanding of nanostructure non-precious metal catalysts to design a high performing, durable, and low-cost alternative to platinum based catalysts.

The controls of water and O2 availability, microbial activity and temperature on acid (H2SO4) production rates in commercial-scale sulphur (S0) blocks were quantified and recommendations were made for minimizing H2SO4 production in S0 blocks. Acidic drainage from the S0 blocks (pH 0.4-1.0) was attributed to mixing of fresh infiltrating water and low-pH resident water (mean pH=-2.1) with resident water comprising ~4-8% of the drainage. Although clean S0 is strongly hydrophobic, preferential water infiltration occurred rapidly through fractured S0 blocks in which the bulk hydraulic conductivity was estimated to be similar to gravel or clean sand (Ks=1x10-1 to 1x10-3 m/s). Microbial colonization of fracture faces generated localized hydrophilic conditions that helped create preferential pathways for water infiltration. Liquid water contact (compared to water vapour) was essential for S0 oxidation (i.e., H2SO4 production), therefore H2SO4 production in the S0 blocks was limited to fractures and friable S0 through which water flowed. H2SO4 production was greatest in the upper 1 m of the S0 block (70 to >97% of annual H2SO4 production) and the result of autotrophic microbial S0 oxidation.<p> S0 oxidation rates were very sensitive to temperature and increased by a factor of 4.3 for a temperature increase of 10°C (Q10). Therefore minimizing temperature (<5°C) in S0 blocks would be an effective strategy for controlling H2SO4 production. Heat released during S0 oxidation did have a measurable effect on in situ temperatures and should be considered in the design of insulated cover systems. Although autotrophic microbial activity was insensitive to O2 concentrations when they were >1 vol.%, the total mass production rate of H2SO4 is approximately proportional to the O2 concentration at the surface of the S0 block (assuming in situ O2 concentrations decrease to <1 vol. %). Therefore, cover systems that minimize the surficial O2 concentration are recommended.<p> Cover systems limiting H2O infiltration would be effective for minimizing the volume of acidic drainage, but may have no impact on H2SO4 production rates within the block. In this study, H2O infiltration through a typical soil cover (~95% efficiency) would easily satisfy the annual H2O demand for H2SO4 production (2.6 mm/m2 in the upper 1 m). Greater near-surface H2SO4 production rates may appear to make surficial biocide application an attractive option for minimizing S0-oxidizing microbial activity, however, this approach might simply drive the zone of H2SO4 production to greater depths and have no affect on the total mass production of H2SO4.

No description available.