Intramolecular hydroamination represents a potentially general, simple strategy to access various nitrogen heterocycles. While important progress has been accomplished in recent years, six-membered ring formation via alkene hydroamination is typically difficult and limited to terminal alkenes, suggesting that only 2-methylpiperidines can be accessed reliably with current methods. As part of the Beauchemin group efforts on metal-free concerted hydroamination methods, the first part of this thesis describes the development of a Cope-type hydroamination-Meisenheimer rearrangement (CHMR) sequence that is applicable in inter- and intramolecular reactions. Data acquired from optimization on a difficult substrate (coniine) and the successful application of the CHMR sequence to the syntheses of N-norreticuline and 10-desbromoarborescidine are reported. The amination of alkenes is surprisingly scarcely used in the synthesis of complex alkaloids despite its potential for the construction of structurally challenging molecules while avoiding functional group interconversions. Hence, the second part of this thesis describes the studies on a novel amination sequence, consisting of an intermolecular Diels-Alder followed by an intramolecular hydroamination reaction, in the efforts towards the synthesis of biologically active and structurally complex Manzamine A. As such, the synthesis of the model substrates, including the development of a novel family of aminodienes, as well as the assessment of their reactivity towards [4+2] cycloadditions is reported.

A number of theories have attempted to explicate mechanisms underpinning the transition from recreational drug use to substance dependence. A highly reliable correlate of dependence is the value ascribed to the drug. However, supernormal drug valuation may be insufficient to fully account for a subgroup of dependent individuals for whom the course of dependence is chronic and relapsing and who persist in drug use in the face of devastating costs. Three candidate secondary mechanisms for dependence are considered in this thesis: cue reactivity, cost discounting, and sensitivity to negative affect. Neither cue reactivity nor cost discounting were found to be significantly associated with severity of alcohol dependence in samples of young adult drinkers. By contrast, induced negative affect was found to be reliably associated with augmented alcohol motivation, and sensitivity to this effect was related to symptoms of depression and self-reported drinking to cope with negative affect: both risk factors for the development of dependence. These findings delineate a particular subset of dependent individuals for whom negative affect may represent a substantial trigger to continued drug use. There are a lack of brief interventions to abolish or limit negative affect driven drug motivation. This thesis trialled three potential interventions. A natural walk intervention in hazardous drinkers showed no evidence of limiting this effect in two experiments. Brief instruction in acceptance-based coping showed no evidence of limiting annoyance in response to an aversive noise induction procedure in an alcohol dependent population, and was therefore also eliminated as a potential intervention. However, engagement with pleasant environmental images, as a proxy for environmental enrichment, significantly reduced negative affect driven alcohol choice in student drinkers who reported a desire to visit the locations shown (high liking), compared to low-liking individuals and controls. This provides preliminary evidence for the efficacy of environmental enrichment type interventions, justifying further trials. In treatment of dependence more generally, interventions to increase access to healthy, non-drug sources of positive reinforcement may prove effective.

Submitted by RENATO CARVALHO RESENDE (htc.renato@gmail.com) on 2017-03-30T23:23:31Z No. of bitstreams: 1 Dissertação Mestrado Renato Carvalho Resende.pdf: 9175175 bytes, checksum: 3d504c6ae855f8c5ee734700afd5a7cc (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2017-04-06T14:17:14Z (GMT) No. of bitstreams: 1 resende_rc_me_bauru.pdf: 9175175 bytes, checksum: 3d504c6ae855f8c5ee734700afd5a7cc (MD5) / Made available in DSpace on 2017-04-06T14:17:14Z (GMT). No. of bitstreams: 1 resende_rc_me_bauru.pdf: 9175175 bytes, checksum: 3d504c6ae855f8c5ee734700afd5a7cc (MD5) Previous issue date: 2017-03-06 / Os elastômeros termoplásticos (TPE) têm sido bastante empregados em substituição às borrachas tradicionais, por terem custo reduzido de matéria prima, facilidade no processamento e serem recicláveis. Apresentam propriedades mecânicas semelhantes, porém quando utilizados em componentes de vedação apresentam limitada resistência à corrosão em água clorada. Assim, o desenvolvimento de tratamento superficial que não modifique as características originais, mas tornem o material mais resistente são desejáveis. Para tanto, este trabalho pretende desenvolver uma metodologia a plasma para melhorar esse quesito. O elastômero termoplástico de copoliéster (COPE) foi escolhido por ser o mais empregado em componentes de vedação. O tratamento a plasma de baixa pressão com hexafluoreto de enxofre (SF6) foi empregado visando tornar a superfície do COPE hidrofóbica através da incorporação de grupos fluorados. A implantação iônica por imersão em plasmas (IIIP) de argônio foi utilizada para criar uma camada superficial mais coesa e entrelaçada, além da possibilidade de torná-la hidrofóbica após envelhecimento. Para o tratamento com SF6, os parâmetros de excitação do plasma (12 Pa e 80 W) foram mantidos, variando-se o tempo do tratamento entre 2 e 180 minutos de modo a encontrar uma condição ótima para esse processo. Para a IIIP de Ar os parâmetros de excitação do plasma (5 Pa e 60 min) foram mantidos e a potência da radiofrequência foi variada entre 10 e 150 W. A energia de superfície e ângulo de contato foram obtidos pelo método da gota séssil em um goniômetro automatizado. A morfologia da superfície foi avaliada por microscopia eletrônica de varredura (MEV) e microscopia de força atômica (AFM). Espectroscopia de energia dispersiva (EDS) e espectroscopia de fotoelétrons de raios X (XPS) foram utilizadas para análises da composição química e estrutura molecular. Corrosão por plasma de O2 e imersão em água clorada foram utilizados para avaliar a resistência antes e após os tratamentos a plasma. Os resultados mostram que as amostras tratadas por 90, 120 e 180 minutos em plasmas de SF6 tornam-se hidrofóbica, mesmo após o envelhecimento, apresentando incorporação de flúor, alterando assim a composição química e morfológica da superfície do COPE. Melhorias substanciais foram observadas nessas amostras após os ensaios de corrosão, indicando que um aumento na vida útil do material em situações reais de uso possam ter sido alcançadas. A IIIP de Ar tornou as amostras inicialmente mais hidrofílicas do que a amostra como-recebida, porém após a ação do tempo, algumas amostras permaneceram hidrofóbicas enquanto outras amostras retornaram à condição inicial. Apesar da hidrofobicidade não ter sido alcançada em todas as amostras, alterações na rugosidade e na morfologia foram verificadas, principalmente nas amostras tratada com 100 W de potência do plasma, ocasionando em melhora na resistência do COPE à água clorada. Essa melhora na resistência é atribuída ao aumento da conectividade da estrutura pelo estabelecimento de reticulações geradas pelo processo de IIIP, densificando o material tornando a permeação de íons da solução mais difícil. / Thermoplastic elastomers have been widely used in substitution for conventional rubber, given that the feedstock is cheaper, easier to process and recyclable. Its mechanical properties are similar, but when applied to sealing components its resistance is limited due to the chlorine present in water, therefore, it is interesting to develop a surface treatment that do not alter the original characteristics, but make the material more robust. To achieve such result, we chose to submit the copolyester thermoplastic elastomer (COPE) to plasma. This material was naturally chosen, once it is widely used for sealing purposes in this specific industry. By using low pressure plasma with sulfur hexafluoride, we expect to alter COPEs surface by incorporating fluorine groups, thus making it hydrophobic. We also submitted the sample to a second treatment, by submersion to argon plasma, making the outer layer less defective and more entangled with aging, as observed in previous experiments. For SF6 treatment, the exiting plasma parameters (12Pa and 80W) were kept and the treatment time was varied between 2 to 180 minutes in order to find the optimal treatment time. For Argon IIIP, the plasma exciting parameters (5Pa and 60 min) were maintained, while the radio frequency variation was between 10 to 150W. Surface energy and contact angle were obtained by and automatic goniometer, through the sessile drop method. The surface's morphology was analyzed by electronic scanning microscope and atomic force microscopy. Dispersive energy spectroscopy and X-ray photoelectric spectroscopy were responsible for the chemical composition and molecular structure analyses the new surface's resistance was tested by O2 plasma corrosion and immersed in chlorinated water. Results show the samples treated for 90,120 and 180 minutes in SF6 plasma became hydrophobic, even after aging. The samples were substantially improved and its resistance prolonged its lifespan in conventional usage. Argon IIIP made the surface more hydrophilic. However, after time part of the material restored its original characteristics. Although hydrophobic it was not achieved, the roughness and morphology alteration (especially when treated with 100W of plasma) improved COPE'S resistance. The results are explained by the increase in the structure's ability to connect by the establishment of reticulate one generated by the IIP process, making the component denser and the ionic solution less permeable.

In 1982, routine screening of the Pseudopterogorgia elizabethae stirred the scientific community by showing the presence of cytotoxic metabolites with antimicrobial activity. Since this discovery a vast amount of research has been conducted in synthesising metabolites of the soft coral. Herein we report the developments towards the synthesis of two metabolites (+)-Erogorgiaene and (+)-Elisabethadione utilising three key reactions in setting up the molecules three chiral centres. The use of asymmetric allylation, oxy-Cope rearrangement and cationic cyclisation was utilised to set up the desired stereocentres from a starting cinnamyl aldehyde. Natural elisabethadione was synthesised in a racemic form as a 2:1 mixture of diastereoisomers at the C-13 stereocentre.

Posttraumatic stress disorder (PTSD) and alcohol use problems (AUP) commonly co-occur, have shared latent genetic risk, and are associated with many negative public health outcomes. Via a self-medication framework, trauma-related drinking to cope (TRD), an unexplored construct to date, may help explain why these two disorders co-occur, thus serving as an essential target for treatment and prevention efforts. The present study aimed to create a novel measure of TRD and examine its psychometric properties, investigate its indirect influences on the association between PTSD and AUP, as well as explore its potential shared molecular genetic risk with PTSD in a genetically-informative study of college students. A sample of 1,896 students with a history of trauma and alcohol use provided genotypic data and completed an online assessment battery. First, the psychometric properties of TRD and how it relates to relevant constructs were examined using descriptive statistics and structural equation modeling. Findings demonstrated support for the external validation of TRD, both with regard to PTSD and alcohol consumption and related problems, and suggested that TRD is a more specific measure of drinking to cope motives compared to the commonly used Drinking Motives Questionnaire coping subscale. Second, results from a correlated multiple mediator model indicated that, while accounting for the effects of generalized drinking motives, TRD partially mediated the relation between PTSD and AUP and that this relationship was stronger for males than for females. Results were substantiated using longitudinal data. Third, univariate and bivariate genotypic analyses were conducted for TRD and PTSD, most of which resulted in null findings likely due to insufficient sample sizes. However, genome wide association analysis identified several significant genetic variants associated with TRD in participants of European Ancestry. Genes associated with TRD included PRAME, a protein coding gene with antithetical effects to genes commonly implicated in alcohol metabolism, as well as several genes implicated in immune system functioning (e.g., IGH, IGHE, ELK2AP). Polygenic risk for PTSD was associated with PTSD in the present sample and nominally associated with TRD. Findings are discussed in the context of limitations, clinical implications, and future directions.

Difficulties experienced at work can cause feelings of burnout that become prolonged and intensified without acts of self-care. The intense nature of mental health workers' jobs may make them, more vulnerable to burnout than other professionals. Because mental health professionals' mental and emotional wellness can significantly affect their work, adequate self-care is critical to both their well-being and that of their clients. Previous researchers have investigated the self-care behaviors of mental health professionals, but little was known about how gender affected the use of these behaviors in burnout prevention among mental health professionals. The purpose of this quantitative study was to examine the relationship between self-care behaviors and burnout among a sample of 325 mental health professionals working in New York. Differences in the ways male and female mental health professionals practiced self-care behaviors were also investigated. Burnout and gender role theories were used as the theoretical framework. Study instruments included the MBI-HSS and the Brief COPE. Multiple regression analysis and independent sample t tests were employed to analyze survey data. Analysis revealed levels of self-care behaviors were significantly predictive of depersonalization, emotional exhaustion, and reduced personal accomplishment. Gender differences in self-care behaviors were indicated for substance use, self-blame, depersonalization, emotional exhaustion, and reduced personal accomplishment. Since burnout is a significant problem for many mental health professionals, understanding how self-care affects burnout is critical to promoting behavioral changes among these professionals. Self-care among mental health professionals may improve their professional and personal lives.

本研究主要的目的是在探討不為社會一般人所知道與關心的HIV感染者，在感染之後適應疾病的過程，面臨的困難，需要的服務，以及生活適應的問題。進而提出社會工作專業幫助感染者度過生命黑暗期的可能策略。只有當感染者不再因為感染而感受到生死的糾葛，不再因為感染，而被社會道德的節勒得喘不過氣來，防制愛滋的蔓延，才有可能。 本研究總結對HIV感染者的觀察與深入訪談後發現，感染者在知道自己感染之後，最能夠在它們身上感受到的是對曝光的擔心；孤獨的感受；死亡的陰影；以及階段任務受阻等心理層面上的壓力與現實上生活適應的困難交織而成的生死結。 感染者普遍說來，都十分擔心曝光。而孤獨的感受對感染者來說，一是因為擔心曝光、自殘形穢的自我封閉而造成；一是因為感到社會的遺棄，缺乏規屬感所產生。而由於感染的必死性，讓感染者不論目前的身體狀況如何，都生活在死亡的陰影之下，而這樣的死亡陰影，亦會影響到感染者求生與求死的意念。階段性任務受阻的感受，人生的任務無法達成，則是感染者普遍的遺憾。 而在心理層面的擔憂之外，感染者難以避免的會遭遇到實際生活適應上的困難。一般說來感染者會產生生活水準降低的問題；醫療相關的問題；擔心發病；空間剝奪的問題；因擔心曝光或告知所產生的心理壓力問題。 但是生死結並非在所有感染者身上都能起相同的作用，換句話說，不同的感染者對生死結的感受，會隨著他們的感染途徑；自覺社會烙印；原本的社會地位；感染事實被知悉的範圍以及得知感染的時間等前置因素而有所不同。這些前置因素，因為影響到感染者對生死結的感受，進而也會影響到感染者所採取的因應策略。感染者所採取的因應策略大致可以區分為幾種：改變生活方式與態度；告知；死亡的準備；特殊化以及利他。 針對以上感染者的生活適應困境本研究提出以下幾點建議，提供相關單位與實務工作者參考。給相關單位建議的部分有：1、基本生活水準的維持；2、健全醫療服務網；3、專業藥師提供用藥諮詢；4、在相關醫療院所聘用專任涉工員；5、義工的訓練與督導；6、設立協談專線；7、跨部會的定期會議。而對提供社會工作直接服務者的建議是：1、非批判式的接納；2、避免特殊化；3、多傾聽。

<p>The purpose of this study is, on the basis of institutional theory, to contribute with more</p><p>understanding about resistance to management accounting change and also to survey reasons</p><p>for the resistance and how to cope with the resistance.</p><p>The study is a qualitative case study and semi-structured interviews have been used to</p><p>complement the study’s theoretical area, consisting of scientific articles.</p><p>The conclusion from the study is that resistance to management accounting change can be</p><p>understood and explained by the institutions of each organisation and its underlying structures. A</p><p>further conclusion is, with the structures in mind there are many reasons for resistance and also</p><p>many ways to cope with the resistance. A model has been produced in purpose to create</p><p>understanding and to survey the resistance to management accounting change.</p>

Intramolecular hydroamination represents a potentially general, simple strategy to access various nitrogen heterocycles. While important progress has been accomplished in recent years, six-membered ring formation via alkene hydroamination is typically difficult and limited to terminal alkenes, suggesting that only 2-methylpiperidines can be accessed reliably with current methods. As part of the Beauchemin group efforts on metal-free concerted hydroamination methods, the first part of this thesis describes the development of a Cope-type hydroamination-Meisenheimer rearrangement (CHMR) sequence that is applicable in inter- and intramolecular reactions. Data acquired from optimization on a difficult substrate (coniine) and the successful application of the CHMR sequence to the syntheses of N-norreticuline and 10-desbromoarborescidine are reported. The amination of alkenes is surprisingly scarcely used in the synthesis of complex alkaloids despite its potential for the construction of structurally challenging molecules while avoiding functional group interconversions. Hence, the second part of this thesis describes the studies on a novel amination sequence, consisting of an intermolecular Diels-Alder followed by an intramolecular hydroamination reaction, in the efforts towards the synthesis of biologically active and structurally complex Manzamine A. As such, the synthesis of the model substrates, including the development of a novel family of aminodienes, as well as the assessment of their reactivity towards [4+2] cycloadditions is reported.

A 12-month longitudinal study assessed the emotional reactions of an intercollegiate athletic team to a near fatal bus incident. PANAS-X and the Brief COPE, administered on five occasions, indicated NA declined over time. Most coping strategies showed significant changes in trajectory. Acceptance and Positive Reframing were high across waves. In October 2010, an intercollegiate athletic team and coaching staff were traveling by sleeper bus to an out-of-state match. The team members and coaches were in the back of the bus when they felt the bus swaying and heard the tires hit the rumble strips. The head coach went forward to find the bus driver unconscious and slumped over the steering wheel. Although the bus swerved into the oncoming lane of interstate traffic and back onto the other shoulder, the coach was able to steer the bus and stop it safely on the side of the road. The bus driver had suffered a fatal heart attack; fortunately, the coaches and players survived with only minor injuries. This study is a longitudinal follow up assessing the emotional reactions of the coaches and team to the bus incident across a twelve-month time frame. The Positive and Negative Affect Schedule - Expanded (PANAS-X; Watson & Clark, 1994) and the Brief COPE (Carver, 1997) were administered on five occasions. Negative affect declined over time, with a larger drop in waves more proximal to the incident. Positive affect demonstrated a curvilinear pattern showing increases on the second and third wave but dropped off at the end of the spring semester 2011 and the beginning of the fall semester 2011. There were significant changes in the coping trajectories for 10 of the 14 coping strategies from the Brief COPE. These data are of particular interest as we could locate no other studies in the published literature of individual athlete or team reactions to traumatic travel incidents, although ESPN (Lavigne, 2010) noted that bus safety should be a concern for team travel.