The possible existence of extraterrestrial life forms has been of interest to humans for many millennia. In the past few decades space travel has provided an opportunity to search life outside of Earth. Chiral molecules are critical molecules in Earth-based life and are among the first chemical molecules sought after as proof of potential extraterrestrial life; however, identification of these chiral molecules is difficult due the lack of sensitive instruments. The objective of this work is to develop a benchmark reaction to be used as a guide in the development of instrumentation, such as a polarimeter, to be used in the search for extraterrestrial life. To achieve this objective, to investigate the enzyme mandelate racemase (MR), which catalyzes the racemization between the enantiomers of mandelate. MR is a member of the enolase superfamily, which contains a (alpha/beta)7-b barrel domain, the fold most frequently found among all known protein structures. Activity of the enzyme was measured at low temperatures and in non-aqueous media, as these are the conditions that represent extraterrestrial terrain. We find that mandelate racemase (MR) is active in concentrated ammonium salt solutions and water-in-oil microemulsions in a temperature range between 30C to 70C; however, the enzyme is not active in several organic cryosolvents. The stability of the structure of MR was also explored. Using differential scanning calorimetry (DSC) we observe the unfolding of the enzyme was irreversible and therefore kinetically controlled. We also found proof for divergent evolution of the enolase superfamily, providing evidence for divergent evolution across the MR and muconate lactonizing enzyme (MLE) subfamilies has been demonstrated. However, we also conclude that reactions yielding a polarimetric signal, such as racemizations employed in this work, are suitable as a tool to find signs of life.

This study measured Ambient concentrations of air pollutants and Volatile Organic Compounds (VOCs) in industrial park in Kaohsiung City. The spatial distribution was investigated during different time periods and seasons. The ozone formation potential (OFP) of VOCs species were evaluated based on the maximum incremental reactivity (MIR). Also, this study using factor analysis to estimate the polluted source. The season distribution of air pollutants showed concentration in spring higher than summer, owing to air activities of summer are acute include wet precipitation, photochemical reaction, and convection. The time period distribution showed the results which NOx and O3 concentration occurred peaks at 7:00 − 8:00, 18:00 − 19:00 and 13:00 − 16:00, respectively. The reason is photochemical reaction, lead to concentration trend with time of NOx inversely to O3. The concentration trend with time of CO and PM10 similar to NOx. The polluted sources were estimated mobile. By the way, O3 is proportional to temperature, but it is Inversely proportional to humility. The seasons distribution of VOCs showed most abundant species included 2-butanone, toluene, and n-pentane in spring, while included toluene, acetone, m,p-xylene, and methyl methacrylate in summer. According to percent composition, most abundant categories in spring and summer were both aromatics, ketones, and alkanes. The TVOC concentration was spring (164.6 £gg/m3) higher than summer (116.4 £gg/m3). The time periods distribution of VOCs showed most abundant categories included aromatics and ketones in morning and evening, while included aromatics and alkanes in night. The TVOC concentration of evening (163.2 ¡Ó 62.7 £gg/m3) was highest, followed by night (159.9 ¡Ó 87.4 £gg/m3), Lowest was morning (98.4 ¡Ó 32.3 £gg/m3). Results showed alkanes and alkenes own higher concentration in night, ketones and esters in evening, and aromatics in evening and night. The reason is related with sunshine, inversion layer, and lower wind speed. By the way, TVOC is proportional to temperature. In spring, the OFP was 566.0 £gg-O3/m3, OFP/TVOC was 3.44. In summer the OFP was 629.3 £gg-O3/m3, OFP/TVOC was 5.41. It was worth mentioning highest OFP categories in spring and summer was both aromatics (332.2 £gg-O3/m3, 380.3 £gg-O3/m3), and highest OFP species was toluene (138.8 £gg-O3/m3) and methyl methacrylate (171.7 £gg-O3/m3) , respectively. The results from factor analyses showed the predominant source included mobile polluted source, petrol evaporation, related electronic industry, metallurgy industry, refinery, and architectural coatings escape in spring. The predominant source included mobile polluted source, petrol evaporation, plastic industry, steel industry, and related electronic industry in summer.

<p>Pyrolysis of biomass consists of heating solid biomass inthe absence of air to produce solid, liquid and gaseous fuels.In the first part of this thesis rapid pyrolysis of wood(birch) and some agricultural residues (olive waste, sugarcanebagasse and wheat straw in untreated and in pelletized form) athigh temperature (800ºC–1000ºC) is studied ina free fall reactor at pilot scale. These conditions are ofinterest for gasification in fluidized beds. Of main interestare the gas and char yields and compositions as well as thereactivity of the produced char in gasification.</p><p>A higher temperature and smaller particles increase theheating rate resulting in a decreased char yield. The crackingof the hydrocarbons with an increase of the hydrogen content inthe gaseous product is favoured by a higher temperature and byusing smaller particles. Wood gives more volatiles and lesschar than straw and olive waste. The higher ash content inagricultural residues favours the charring reactions. Charsfrom olive waste and straw are more reactive in gasificationthan chars from birch because of the higher ash content. Thecomposition of the biomass influences the product distribution.Birch and bagasse give more volatiles and less char thanquebracho, straw and olive waste. Longer residence time inrapid pyrolysis increase the time for contact between tar andchar which makes the char less reactive. The secondary charproduced from tar not only covers the primary char but alsoprobably encapsulates the ash and hinders the catalytic effectof the ash. High char reactivity is favoured by conditionswherethe volatiles are rapidly removed from the particle, i.e.high heating rate, high temperature and small particles.</p><p>The second part of this thesis deals with slow pyrolysis inpresence of steam for preparation of active carbon. Theinfluence of the type of biomass, the type of reactor and thetreatment conditions, mainly temperature and activation time,on the properties and the yield of active carbons are studied.The precursors used in the experiments are birch (wood) anddifferent types of agricultural residues such as sugarcanebagasse, olive waste, miscanthus pellets and straw in untreatedand pelletized form.</p><p>The results from the pyrolysis of biomass in presence ofsteam are compared with those obtained in inert atmosphere ofnitrogen. The steam contributes to the formation of solidresidues with high surface area and good adsorption capacity.The yield of liquid products increases significantly at theexpense of the gaseous and solid products. Large amount ofsteam result in liquid products consisting predominantly ofwater-soluble polar compounds.</p><p>In comparison to the stationary fixed bed reactor, therotary reactor increases the production of energy-rich gases atthe expense of liquid products.</p><p>The raw materials have strong effect on the yields and theproperties of the pyrolysis products. At equal time oftreatment an increase of the temperature results in a decreaseof the yield of solid residue and improvement of the adsorptioncapacity until the highest surface area is reached. Furtherincrease of the temperature decreases the yield of solidproduct without any improvement in the adsorption capacity. Therate of steam flow influences the product distribution. Theyield of liquid products increases while the gas yielddecreases when the steam flow is increased.</p><p><b>Keywords</b>: rapid pyrolysis, pyrolysis, wood, agriculturalresidues,biomass, char, tar, gas, char reactivity,gasification, steam, active carbon</p>

Perseverative cognition is the repetitive cognitive representation of a stressor, which includes the concepts of worry and rumination. These thoughts delay post-stress cardiovascular recovery, which may lead to an increased risk for cardiovascular disease. This may be due to the negative emotional content of perseverative cognition or because it involves cognitive effort. The aim of this study was to identify the unique influences of negative emotional content and cognitive effort during recovery. Participants (N = 120) were given a demanding task purportedly as a measure of intelligence and then given false negative feedback. Immediately following, participants engaged in one of four recovery instruction conditions: think about task performance, perform a cognitive load task, watch a distracting video, or remain quietly seated. EKG, impedance cardiography, and blood pressure were recorded throughout. Perseverative cognition and cognitive load both resulted in significantly less heart rate recovery compared to the distracting video. Higher test motivation and anxiety were related to more blunted reactivity and delayed recovery of respiratory sinus arrhythmia. Reduced recovery during perseverative cognition and cognitive effort indicate that the cognitive load produced by perseveration is the pernicious component that explains its link to increased risk for cardiovascular disease. Further, the relationship between motivation/anxiety and blunted reactivity and recovery suggest effort may be important in the link between perseverative cognition and cardiovascular disease.

Expectancy theory provides a useful framework within which to examine the link between cognitive representations of anticipated alcohol related outcomes and affective processes that ought to shape behavior at the level of implicit, or automatic, processing. The role of affect in alcohol expectancies is an important one as it reflects the approach-avoid contingency associated with reward learning presumed to underlie addictive processes. This study examined the relationship between affect and expectancy operation by using suboptimally presented alcohol related cues to prime affectively congruent evaluations of otherwise unrelated targets. Hypotheses predicted that drinkers who reported higher positive and arousing expectancies for alcohol outcomes would make affective evaluations (but not semantic categorizations) more accurately when target stimuli were preceded with an alcohol picture or word prime. Analysis of drinking and expectancy variables revealed positive relationships between drinking frequency and social/physical pleasure expectancies, as well as tension reduction expectancies. No relationships were found between drinking quantity and expectancies. Evaluation response accuracy was not related to alcohol expectancies. Discussion centers on potential reasons for lack of findings, including experimenter error and design limitations.

Research has investigated staff management procedures that produce treatment adherence and maintenance over time. Treatment integrity is one of the most important aspects of staff management; without adequate treatment adherence, behavior analysts are unable to determine whether treatment is effective, function has been identified, or intervention revisions are needed. The literature on staff management procedures has demonstrated that performance feedback and self-monitoring are effective procedures for increasing treatment integrity of behavior plans in the presence of the observer, however, few studies have evaluated the effectiveness of these procedures when the observer is absent. This study evaluated the effectiveness of performance feedback and self-monitoring procedures and the level of reactivity to the presence of an observer exhibited by staff trained to implement individualized behavior plans. The results showed that staff performance increased with the intervention almost exclusively in the conspicuous observation condition.

Tobacco smoking has been associated with the development, protraction, and exacerbation of chronically painful conditions. Conversely, there is reason to believe that smokers may be motivated to use tobacco as a means of coping with their pain. To date, no controlled, experimental studies have tested for a causal relationship between pain and smoking motivation. The primary aim of the current study was to test the hypothesis that laboratory-induced cold-pressor pain would enhance smoking motivation, as measured by self-reported urge to smoke and observation of immediate smoking behavior. The effect of a smoking cue was also tested. Smokers (n = 132) were randomly assigned to one of four conditions in this 2 (Pain Manipulation) X 2 (Smoking Cue Manipulation) crossed factorial between-subjects design. Results indicated that both pain induction and the presence of smoking cues increased urge ratings, and pain induction also produced a shorter latency to smoke. The relationship between pain and increased urge to smoke was partially mediated by pain-induced negative affect. This study provides the first experimental evidence that situational pain can be a potent motivator of smoking.

Changes in cerebrovascular reactivity (CVR) to carbon dioxide (CO2) are reported in many neurological conditions. My aim was to validate a method for computerized prospective targeting of CO2 levels (RespiractTM) as a bedside tool for impaired CVR. I hypothesized that 1) The RespiractTM and TCD method can be used to detect impairment of CVR after SAH and that 2) CVR is impaired in SAH patients. In 18 SAH patients and 26 controls CVR index was calculated dividing the percentage change in middle cerebral artery blood flow velocity (MCAv) by the change in PETCO2. The absolute MCAv values were similar in both groups, but CVR was significantly different (hypercapnia: 0.044 ± 0.076 - controls; 0.014 ± 0.037 - SAH; p=0.0007). I showed that impaired CVR can be detected at the bedside using TCD and CO2 challenge with the RespiractTM, control of CO2 is precise and minimal changes are required.

Changes in cerebrovascular reactivity (CVR) to carbon dioxide (CO2) are reported in many neurological conditions. My aim was to validate a method for computerized prospective targeting of CO2 levels (RespiractTM) as a bedside tool for impaired CVR. I hypothesized that 1) The RespiractTM and TCD method can be used to detect impairment of CVR after SAH and that 2) CVR is impaired in SAH patients. In 18 SAH patients and 26 controls CVR index was calculated dividing the percentage change in middle cerebral artery blood flow velocity (MCAv) by the change in PETCO2. The absolute MCAv values were similar in both groups, but CVR was significantly different (hypercapnia: 0.044 ± 0.076 - controls; 0.014 ± 0.037 - SAH; p=0.0007). I showed that impaired CVR can be detected at the bedside using TCD and CO2 challenge with the RespiractTM, control of CO2 is precise and minimal changes are required.

Non-suicidal self-injury (NSSI) is a complex and dangerous set of behaviours that has been gaining increased research attention in recent years. Although existing research indicates that NSSI is prevalent among both adolescent and young adult clinical and community samples, few studies have empirically examined models of factors involved in the etiology and maintenance of these behaviours, particularly the role of social factors. Further, although existing research supports the use of NSSI for emotion regulation purposes, less research attention has focused on the impact of emotion reactivity. The focus of the current project was to examine the role of emotional, interpersonal, and subcultural factors in NSSI. Utilizing a sample of 397 university students, Study 1 presents a psychometric re-evaluation of the Emotion Reactivity Scale (ERS; Nock et al., 2008), used to inform the most appropriate use of the measure in the subsequent studies. Results supported the reliability and validity of the ERS and suggested that the ERS is best utilized as a unidimensional measure of emotion reactivity. Study 2 examined an intra- and inter-personal model of NSSI among the same sample of 397 university students. Support was obtained for the Experiential Avoidance Model of NSSI (Chapman et al., 2006) as well as for the mediational influence of interpersonal relationships on NSSI via emotion regulation. Preliminary support was also provided for the influence of identification with more deviant subcultures, including Goth and Emo groups. Finally, Study 3 aimed to replicate support for the model among a sample of 178 members of self-injury internet forums. Contrary to hypotheses, little support was demonstrated for the model, and fewer significant associations were demonstrated for the influence of subcultural identification. Examination of the characteristics of the sample suggested that the online forum members represent a unique group in regard to the severity of their NSSI experiences that has been understudied in the existing literature. Alternative hypotheses to account for the observed findings are presented. Limitations and directions for future research are discussed.