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Electron Transfer and Spin Chemistry in Iridium-Dipyrrin Dyads and Triads / Elektronentransfer und Spinchemie in Iridium-Dipyrrin-Dyaden und -TriadenKlein, Johannes Hubert January 2015 (has links) (PDF)
The successful synthesis of a family of donor-iridium complex-acceptor triads (T1–T6, pMV1 and mMV1) and their electrochemical and photophysical properties were presented in this work. Triarylamines (TAA) were used as donors and naphthalene diimide (NDI) as acceptor. A bis-cyclometalated phenylpyrazole iridium dipyrrin complex acts as a photosensitiser. In addition, a molecular structure of T1 was obtained by single crystal X-ray diffraction.
Transient absorption spectroscopy experiments of these triads resembled that upon excitation a photoinduced electron transfer efficiently generates long-lived, charge-separated (CS) states. Thereby, the electron-transfer mechanism depends on the excitation energy.
The presence of singlet and triplet CS states was clarified by magnetic-field dependent transient-absorption spectroscopy in the nanosecond time regime. It was demonstrated that the magnetic field effect of charge-recombination kinetics showed for the first time a transition from the coherent to the incoherent spin-flip regime.
The lifetime of the CS states could be drastically prolonged by varying the spacer between the iridium complex and the NDI unit by using a biphenyl instead of a phenylene unit in T4.
A mixed-valence (MV) state of two TAA donors linked to an iridium metal centre were generated upon photoexcitation of triad pMV1 and mMV1. The mixed-valence character in these triads was proven by the analysis of an intervalence charge-transfer (IV-CT) band in the (near-infrared) NIR spectral region by femtosecond pump-probe experiments. These findings were supported by TD-DFT calculations.
The synthesis of dyads (D1–D4) was performed. Thereby the dipyrrin ligand was substituted with electron withdrawing groups. The electrochemical and photophysical characterisation revealed that in one case (D4) it was possible to generate a CS state upon photoexcitation. / In dieser Arbeit wurden die erfolgreiche Synthese einer Donor-Iridiumkomplex-Akzeptor-Familie (Triaden T1–T6, pMV1 und mMV1) und deren elektrochemischen und photophyiskalischen Eigenschaften vorgestellt. Als Donor wurden Triarylamine (TAA) verwendet, als Akzeptoreinheit diente ein Naphthalin-Diimid (NDI). Ein bis-cyclometallierter Phenylpyrazol-Iridium-Dipyrrin-Komplex übernahm die Aufgabe des Photosensibilisators. Die synthetischen Arbeiten konnten mit einer molekularen Struktur von T1 mittels Röntgenbeugung eines Einkristalls ergänzt werden.
Bei Photoanregung der Triaden mit transienter Absorptions-Spektroskopie wurde die sehr effiziente Bildung von langlebigen, ladungsgetrennten (CS) Zuständen beobachtet. Es wurde zudem herausgefunden, dass der Elektronentransfer (ET)-Mechanismus von der verwendeten Anregungswellenlänge abhängt.
Der Nachweis von Singulett und Triplett CS-Zuständen wurde mittels magnetfeldabhängiger, transienter Absorptions-Spektroskopie erbracht. Eine Analyse des Magnetfeldeffekts der Ladungsrekombinations-Kinetik zeigte zum ersten Mal einen Übergang von einem kohärenten zu einem inkohärenten Spinumkehrprozess.
Die Lebenszeit des CS-Zustandes ließ sich dramatisch verlängern indem die Phenylen- durch eine Biphenyl-Brückeneinheit zwischen dem Iridiumkomplex und dem NDI ersetzt wurde.
Gemischvalente Zustände konnten mittels photinduziertem Elektronentransfer in den Triaden pMV1 und mMV1 erzeugt werden. Im Fall von pMV1 wurde eine intensive Intervalenz-Ladungstransfer (IV-CT) Bande im nahinfraroten Spektralbereich mittels Femtosekunden transienter Anregungs-Abfrage-Spektroskopie beobachtet werden. Die Analyse dieser IV-CT Bande wurde mit TD-DFT Rechnungen vervollständigt.
Die Synthese von Dyaden (D1–D4) wurde erfolgreich durchgeführt, dabei wurde der Dipyrrin-Ligand mit elektronenziehenden Substituenten versehen. Die spektroskopische und elektrochemische Analyse erbrachte nach erfolgter Lichtanregung in einem Fall (D4) ebenfalls einen CS-Zustand.
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Development of site investigation and remediation strategies at petroleum- hydrocarbon contaminated siteYang, Jui-Hsin 13 February 2012 (has links)
Soil and groundwater is the final receptor environment of contamination on land, especially easy to contaminate groundwater aquifers, because of the underground environment often obscure, it is difficult to clarify the scope of pollution, in addition, the transport and chemical transformation process are also difficult to evaluate. Resulting that although consumes on huge cost and materials, and times on oil contaminated site investigation and remediation, obtaining the solution of the problem is still hard. In this study, it combines with the environmental site assessment and the triad rapid investigation, the establishment of site contamination conceptual model, the key designated contaminated area, collect samples of the implementation for laboratory analysis, Moreover, use cyclic evaluation process, continuously updated site conceptual model, to clarify the distribution of contaminated sites, impact of pollution, hydro-geological characteristics and pollution sources. It also discussed the effective reduction of pollution critical area, to obtain high-density results, in order to improve sampling and analysis to make the efficiency of the case of site investigation, and using environmental forensic techniques to determine and provide the evidence of pollution sources.
ESA phase I implements the key results of the preliminary delineation of contaminated areas, soil and groundwater pollution concerns and possible sources of material. ESA phase II evaluates preliminary assessment of sites contaminated soil contamination is a high carbon number of oil and contaminants move to the surface to deeper soil 9 m at the lower, deeper pollution range is unknown. Groundwater test results garnered less than control standards, but the detection of trace gas station in MTBE, it is included in the possible sources of pollution. Taking ESA phase II assessment in a further analysis, the soil contaminants are TPHC10-C40 based, contamination depth of 8m, gas station area within the tank and pipeline testing values are low, there is no sign of oil leakage. Pollution more than 5m in depth the most serious, TPH concentrations in general are 10,000 mg/kg or more, the depth of 5m and the following have been significantly reduced, TPH concentrations than in the 5,000 mg/kg or less. Interviews showed that the specific relationship between the people, suspected underground oil refining line set 40 years ago, suspected of shipping oil from the waste obtained after the hull, after the system by then resold for profit.
Identification of pollution sources than the results, TPHC10-C40 carbon number distribution or pattern of the peak are more similar to diesel. TIC illustration showed that the distillate oil mixture for two, than the peak apex, suggesting that the low-carbon should be diesel fuel, and the high-carbon would be fuel. Pr/Ph ratio than, presumably with the CPC diesel from different sources. Alkyl bicyclic sesquiterpene class fingerprint comparison results, the shape of the fingerprint sample slightly different, but the main features of the same types of compounds. Analysis of aromatic compounds, indicators showed that the samples compound ratio of methyl phenanthrene and methyl dibenzothiophene isomers, dibenzothiophene, and phenanthrene isomers are closer. Integrated fingerprint analysis (fingerprinting) results, similar to the site characteristics of pollutants, for the same pollution source. The site is semi-volatile pollutants, substances insoluble in water, more stored in the main pollution silt/clay layer, subject to geological conditions, ground remediation techniques are more difficult to grasp in the transmission path, remediation systems that require high density, break through the bottleneck transmission path, but a majority of sites on private land, during the remediation process it is difficult to obtain the burgage, therefore, it would be fit the inappropriate comprehensive ground handling. Subsequent remediation plan can be removed towards the high pollution of soil pollution, and long-term monitoring of permeable reactive barrier type with natural degradation. Recommendations for the future studies can be dust inhalation and skin contact with soil, groundwater ingestion, inhalation and skin contact exposure pathways for risk assessment, site management provided a basis for administrative control.
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Kan omsorgspersonernas mentaliseringsförmåga avläsas i barns reaktioner vid 3 respektive 9 månaders ålder?Nyman, Mona January 2012 (has links)
Syftet med denna uppsats har varit att belysa hur barn i tre respektive nio månaders ålder responderar på omsorgspersoners mentaliseringsförmåga. Uppsatsen är genomförd som en pilotstudie med ett begränsat urval för att pröva mentaliseringsförmågan som utgångspunkt för metod och tillämpning i samspelsstudier. Fyra familjer har ingått i undersökningen och filmer av deras samspel har kodats och analyserats. Uppsatsen ger intressanta hypoteser för fortsatta studier i ämnet om hur omsorgspersoners mentaliseringsförmåga kan avläsas i barns responser. En slutsats som dras är att omsorgspersonernas samspel och följsamhet i vad barnet eventuellt tänker avspeglas i barnens responser, något som kan generera vidare forskning om vad som är av vikt för att barn skall fortsätta att utvecklas.
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The Dark Triad and Faking Ability on Self-Report Personality Inventories and Autobiographical AccountsMacNeil, Bonnie 21 October 2008 (has links)
Three studies were undertaken to examine the relationship between the Dark Triad (i.e., psychopathy, Machiavellianism, and narcissism) and faking ability. Study 1 examined the relationship between psychopathy and the ability to fake good and fake bad on self-report personality inventories in a sample of 84 male federal offenders. Results showed that when faking good, successful fakers scored significantly higher than unsuccessful fakers on carefree nonplanfulness, and significantly lower on stress immunity. When faking bad, successful and unsuccessful fakers did not differ significantly on psychopathy total or subscale scores. Study 2 examined the effect of the Dark Triad on the ability to fake good and fake bad on self-report personality inventories in a sample of 166 undergraduates. Results indicated that when faking good, total psychopathy significantly predicted successful faking for 1 of 3 methods of evaluation, while Machiavellianism significantly predicted success at faking good for 2 of 3 methods of evaluation. Narcissism was unrelated to success at faking good. In addition, the Dark Triad constructs did not predict success at faking bad. Study 3 examined the relationship between the Dark Triad constructs and the ability to fake good interpersonally. In this study, 32 undergraduates comprising four groups (i.e., controls, and individuals high in psychopathy, Machiavellianism, and narcissism) provided videotaped self-presentations. A separate group of 134 university students subsequently rated the veracity of these presentations. Results indicated that when faking good, psychopathy and narcissism groups were rated as more believable than the control group. Conversely, the Machiavellianism group was less successful at faking good than the control group. Contributions of this research to the fields of personality assessment and self-presentation are discussed. / Thesis (Ph.D, Psychology) -- Queen's University, 2008-10-14 11:24:45.946
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Affective Dynamics of Rejected Children in Triadic Peer Interactions in Early ChildhoodLAVICTOIRE, LINDSAY 22 September 2010 (has links)
Entry into elementary school marks the beginning of a crucial shift in the amount and quality of time that children spend with their peers (Coie & Dodge, 1988). For many 5-year olds, kindergarten provides the opportunity to encounter their first stable peer group. It is in the context of these interactions that children practice essential social skills, as well as develop a capacity to interact with others. For various reasons, however, many children have difficulty gaining acceptance into fundamental peer groups. For these children, the opportunities for peer interactions present in the early school years are limited and often characterized by a high degree of aggressive affect (Coie & Dodge, 1988). Although previous research has reliably identified the individual affective states characteristic of rejected children during a typical peer interaction (Newcomb, Bukowski, & Pattee, 1993), it should be kept in mind that these expressions are embedded within a larger peer context, which plays an important role in how these dynamic processes unfold in real time (O’Connell, Pepler, & Craig, 1999). The purpose of the present study was to explore the application of a dynamic systems (DS) technique, state space grids (SSG), to the study of kindergarten peer processes and their impact on long-term psychopathology. Participants were 267 kindergarten children from a single school serving a predominantly low socioeconomic neighbourhood. In order to examine the social dynamics of interacting triads, moment-to-moment changes in affect were documented. Parent and teacher ratings of child conduct problems were also obtained at four measurement points. Consistent with previous research, both controversial and rejected children were more likely to express aggressive affect. Differential effects across sociometric groups were also replicated for both externalizing and internalizing ratings, where rejected children were found to have significantly higher scores. Extending upon past research, the expression of particular triadic affective states were found to differ significantly across sociometric groups. Furthermore, specific triadic affective states were found to be related to the developmental trajectories of clinical outcomes. Overall, results of the present study extend previous findings on the expression of individual affective states through the application of DS principles and methodology. / Thesis (Master, Psychology) -- Queen's University, 2010-09-20 22:48:51.92
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Riskbedömning av trikloretylenförekomster : MIFO-inventering fas 1 och en jämförelse mellan traditionella och alternativa karakteriseringsmetoderSkröder, Theres January 2014 (has links)
Västerås is a city with an industrial heritage. One of the larger companies in Västerås is ABB AB, which has multiply businesses located at the area Finnslätten. High concentrations of trichloroethene (TCE) were found in the soil and groundwater at Finnslätten 1 during a phase II environmental site assessment. Due to the result of the assessment a supplementary investigation and a site specific risk assessment were made of building 358. The source zone and plume of trichloroethene have not been characterized even after several investigations at the site. The aim of this study was to make a risk assessment of three other buildings inside the area were degreasing with TCE have historical taken place. The collected information resulted in a risk class 2 of the three objects and shows that the buildings might be potential pre-emission sources of trichloroethene. The second aim contains a comparison between traditional and alternative approaches to enlighten the importance of effective characterization methods. Two potential characterization strategies were chosen; TRIAD approach and CMF approach. The result showed the importance of systematic project planning, dynamic work planning strategy and the use of multiple techniques to form the best “hybrid” during characterization of DNAPL. In order to bring the investigation to a successful conclusion it is of great importance to consider the uncertainties or diminish the uncertainties by collecting essential information.
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Triadens roll i rättssalen : En analys av hur rätten värderar medicinskt underlag i mål rörande barnmisshandel i form av skakvåldNouri, Divina January 2018 (has links)
The purpose of this essay is to establish applicable law regarding the questions outlined in the paper about medical evidence in cases of child abuse in the form of shaken baby syndrome. In order to answer the essay's research questions about this, the essay has applied a legal-judicial method based on a hierarchical order of legislation, legislative history, case law, and doctrine. In the analysis, the conclusions are that medical expertise is generally valued highly by the courts while at the same it is being considered with caution in the individual case. Mostly, by the diagnosis of shaken baby syndrome, is considered resting on an uncertain scientific basis, the legal assessment of the question of liability has been affected so that the evidentiary requirement "beyond reasonable doubt" is not to be considered met in recent case law. The essay also addresses the discussion on an international scientific level regarding the diagnosis of shaken baby syndrome.
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Examining Ethical Leadership as a Moderator of the Relationship Between the Dark Triad and Counterproductive Work Behavior.Palmer, Joshua Clinton 01 May 2016 (has links)
In this study perceived ethical leadership was examined as a moderator of the relationship between the dark triad personality traits of narcissism, Machiavellianism, psychopathy and counterproductive work behavior (CWB) using a sample of 208 employees recruited through Amazon Mechanical Turk. These participants completed measures of personality (Short Dark Triad; Jones & Paulhus, 2014), counterproductive workplace behavior (Counterproductive Work Behavior Checklist; Spector et al., 2006), and employee perception of their direct supervisor’s ethical leadership (Brown, Treviño, & Harrison, 2005). Participants were compensated $0.65 for completing the survey. Correlation and moderation analyses (Hayes, 2012) were used to analyze data. Significant correlations suggest that individuals scoring high on Machiavellianism and psychopathy also reported engaging in more CWB. The relationship between Narcissism and counterproductive workplace behavior approached significance in the predicted direction. Machiavellianism and psychopathy were not negatively related to the employee’s perception of their supervisor’s ethical leadership. Narcissism was significantly positively related to an employee’s perception of their supervisor’s ethical leadership. Finally, ethical leadership did not moderate the relationship between Machiavellianism or psychopathy and CWB. Ethical leadership did not moderate the relationship between Narcissism and CWB, but results were approaching significance in the predicted direction. These results suggest that employees who are manipulative and lack empathy were more likely to engage in harmful behaviors in the workplace such as abuse, production deviance, sabotage, theft, and withdrawal. Further, employees who were more narcissistic and have a grandiose view of themselves were more likely to view their leaders as ethical. Overall, the results of this study indicate that perceived ethical leadership does not affect the frequency in which employees high in narcissism, Machiavellianism, and psychopathy reported engaging in counterproductive work behaviors.
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ANTECEDENTS OF ENTREPRENEURIAL INTENTION: EXAMINING THE IMPACT OF GENDER IDENTITY, GRIT, THE DARK TRIAD, AND BARRIERS TO ENTREPRENEURSHIPVoegel, Luke 01 December 2017 (has links)
Entrepreneurs play a vital role in the modern day economy. Knowing what causes an individual to become an entrepreneur has fostered much attention in academic literature, but not enough of the research has looked into individual level variables that could cause an individual to have an entrepreneurial intention. This study addresses this need in research by utilizing the Theory of Planned Behavior to investigate entrepreneurial intention. Not all entrepreneurs are alike. Some entrepreneurs are motivated by financial gains while others are motivated by social concerns. The individual characteristics of entrepreneurs may not be identical, but it is believed that there are similarities. This current study uses a self-report survey approach to examine the potential impact that barriers to entry into entrepreneurship will have upon an individual’s commercial and social entrepreneurial intention. This study will also examine the moderating effect of gender identity, grit, and the Dark Triad of personality upon the previously established relationship of the three TPB antecedents to intention and commercial and social entrepreneurial intention.
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Personality Neuroscience and Dark ValuesPersson, Björn January 2014 (has links)
Personality neuroscience offers a new theory of the biological basis of personality traits. It involves the use of neuroscientific methodologies to study individual differences in behavior, motivation, emotion, and cognition. Personality psychology has contributed much in identifying the important dimensions of personality, but relatively little to understanding the biological sources of those dimensions. In recent years, personality psychology has become the foundation for the study of personality disorders, and by extension, neuroscience. First, I provide a theoretical foundation for the neuroscience of normal and abnormal personality traits. Second, I conduct two empirical studies on deviant personality traits captured by the Dark Triad (i.e., Machiavellianism, narcissism, and psychopathy) and relate them to universal human values. Study I shows that darker personalities endorse values that are self-enhancing, and that justify self-serving behavior. Study II investigates the relationship between the aforementioned constructs and empathy based on the idea that empathy is an important moderating factor of dark traits. In the discussion, suggestions for future studies in neuroscience are presented, as well as some limitations relating to the constructs.
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