Neste trabalho é apresentado a síntese, caracterização e estudo fotofísico de novos derivados triazinil-benzazólicos fluorescentes por transferência protônica intramolecular no estado excitado (ESIPT). Trata-se da síntese do cloreto cianúrico com diferentes 2-(2'-hidroxifenil)benzazóis, dois grupos bastante atrativos do ponto de vista sintético e tecnológico. O cloreto cianúrico devido a sua versatilidade sintética e os 2-(2'- hidroxifenil)benzazóis por apresentarem propriedades fotofísicas muito interessantes, como uma intensa emissão de fluorescência com um grande deslocamento de Stokes. Estes novos derivados foram caracterizados por RMN-¹H, IV, TGA, ponto de fusão, análise elementar e HR-MS. / The synthesis, characterization and photophysic analysis of new fluorescent triazinbenzazolic derivatives by excited state of intramolecular protonic transference (ESIPT) is presented in this study. It deals with the synthesis of the cyanuric chloride with different 2-(2'-hidroxyfenyl)benzazoles. Two very attractive groups from the synthetic and technological point of view. The cyanuric chloride due to its synthetic versatility and the 2-(2'-hydroxyphenyl)benzazoles because they present very interesting photophysical properties, such as an intense fluorescence emission with a great Stoke shift. These new derivatives were characterized by RMN-¹H, IV, TGA, fusion point, elementary analysis and HR-MS.

Neste trabalho é apresentado a síntese, caracterização e estudo fotofísico de novos derivados triazinil-benzazólicos fluorescentes por transferência protônica intramolecular no estado excitado (ESIPT). Trata-se da síntese do cloreto cianúrico com diferentes 2-(2'-hidroxifenil)benzazóis, dois grupos bastante atrativos do ponto de vista sintético e tecnológico. O cloreto cianúrico devido a sua versatilidade sintética e os 2-(2'- hidroxifenil)benzazóis por apresentarem propriedades fotofísicas muito interessantes, como uma intensa emissão de fluorescência com um grande deslocamento de Stokes. Estes novos derivados foram caracterizados por RMN-¹H, IV, TGA, ponto de fusão, análise elementar e HR-MS. / The synthesis, characterization and photophysic analysis of new fluorescent triazinbenzazolic derivatives by excited state of intramolecular protonic transference (ESIPT) is presented in this study. It deals with the synthesis of the cyanuric chloride with different 2-(2'-hidroxyfenyl)benzazoles. Two very attractive groups from the synthetic and technological point of view. The cyanuric chloride due to its synthetic versatility and the 2-(2'-hydroxyphenyl)benzazoles because they present very interesting photophysical properties, such as an intense fluorescence emission with a great Stoke shift. These new derivatives were characterized by RMN-¹H, IV, TGA, fusion point, elementary analysis and HR-MS.

No description available.

This research work has investigated the electrochemistry of glutathione (GSH)and homocysteine (HCSH) in order to develop sensors for these biological thiols.Ru(bpy)33+ and IrCl62− have been used as mediators for the electrooxidation of GSH andHCSH because direct oxidation of these thiols is slow at most conventional electrodes.The electrochemical detection of GSH and HCSH has been pursued because of their biological roles. Concerted proton electron transfer (CPET) and stepwise proton electron transfer(PT/ET) pathways have been observed in the electrooxidation of GSH and HCSH.Oxidation of GSH by Ru(bpy)33+ carried out in deuterated and undeuterated buffered (pH= pD = 5.0) and unbuffered solutions (pH = pD 5.0−9.0) indicates a CPET pathway. AtpH 7.0 buffered solution, the involvement of the buffer was obvious, with rate increasing as the buffer concentration increases − an indication of a general base catalysis. The oxidation of GSH by IrCl62− follows through CPET at pH 7.0 when the optimum concentration of the buffer is established. The plot of the rate vs. buffer concentration gave a curvature at lower buffer concentration and then a plateau at higher concentration,which implies a change in the rate determining step as the buffer concentration increases.At lower buffer concentration, proton transfer was seen to be the rate determining step asthe reduction current increases upon scan rate increase. In the oxidation of HCSH by IrCl62−, CPET was observed at pH = pD values of7.0 and 8.0, whereas PT/ET was seen at pH = pD values of 9.0 and 10. Increase in the buffer concentration at pH 7.0 revealed the contribution of the buffer, in that, the oxidation proceeds more efficiently, seeing that the catalytic peak current shifts more negatively and the peak broadness diminishes. Increase in the temperature for the electrooxidation of HCSH resulted in increase in the rate.

Notre thèse est divisée en 2 chapitres indépendants correspondant chacun à un article. Dans le premier chapitre, nous définissons une notion de surfaces isotropes dans les octonions, i.e. sur lesquelles certaines formes symplectiques canoniques s'annulent. En utilisant le produit vectoriel dans O, nous définissons une application rho de la grassmanienne des plans de O dans la sphère de dimension 6. Cela nous permet d'associer à chaque surface Sigma de O une fonction rho_Sigma de la surface sur la sphère. Alors, nous montrons que les surfaces isotropes de O telles que cette fonction est harmonique sont solutions d'un système complètement intégrable. En utilisant les groupes de lacets, nous construisons une représentation de type Weierstrass de ces surfaces. Par restriction au corps des quaternions, nous retrouvons comme cas particulier les surfaces lagrangiennes hamiltoniennes stationnaires de R^4. Par restriction à Im(H), nous retrouvons les surfaces CMC de R^3. Dans le second chapitre, nous étudions les applications supersymétriques harmoniques définies sur R^{2|2} et à valeurs dans un espace symétrique, du point de vue des systèmes intégrables. Il est bien connu que les applications harmoniques de R^2 à valeurs dans un espace symétrique sont solutions d'un système intégrable. Nous montrons que les applications superharmoniques de R^{2|2} dans un espace symétrique sont solutions d'un système intégrable, et que l'on a une représentation de type Weierstrass en termes de potentiels holomorphes (ainsi qu'en termes de potentiels méromorphes). Nous montrons également que les applications supersymétriques primitives de R^{2|2} dans un espace 4-symétrique donnent lieu, par restriction à R^2, à des solutions du système elliptique du second ordre associé à l'espace 4-symétrique considéré (au sens de C.L. Terng).Ceci nous permet d'obtenir, de manière conceptuelle, une sorte d'interprétation supersymétrique de tous les systèmes elliptiques du second ordre associés à un espace 4-symétrique, en particulier du système intégrable construit au chapitre 1 (et plus particulièrement des surfaces lagrangiennes hamiltoniennes stationnaires dans un espace symétrique).

本論文主要在探討拖延行為及其相關因素，共分成以下三個研究： 研究一的目的是編製一份拖延行為量表及拖延時感受量表。在拖延行為量表方面，區分為「學業拖延量表」及「一般拖延量表」兩種。 研究二的目的是探討時間觀、成就目標與拖延行為的關係。其中，在時間觀部分，包含有「未來」、「現在快樂主義」、「現在宿命論」、「過去－正向」、「過去－負向」五種時間觀取向；而「成就目標」則分成「趨向精熟」、「趨向表現」、「逃避精熟」、「逃避表現」四種目標導向。除此之外，本研究亦針對不同性質任務的拖延情形及性別、年級、是否有兼職或打工、創新行為與拖延行為、拖延時感受的關係，進行探討。 研究三的目的是探討拖延行為、情緒調節與拖延時感受的關係。其中，情緒調節部份分成「重新評估」及「壓抑」兩種調節方式。 經由統計分析的結果，各研究有以下的發現： 研究一以大學生為對象，有效樣本277人，扣除性別漏填3人，男有88人，女有186人。經由主成份分析結果，拖延行為量表中的「學業拖延量表」、「一般拖延量表」均為單一因素的量表，並且該兩種量表在內部一致性的信度分析方面，Cronbach α值分別為.70（學業拖延量表）、.90（一般拖延量表），在效標關聯效度方面，也均與「自我概念」、「學業成績表現」呈顯著負相關（r=-.21&#12316;-.33，p<.001）。而「拖延時感受量表」經因素分析結果共得「自圓其說」、「自責後悔」、「僥倖心理」、「自我調適」、「灰心逃避」五個因素，這五個因素在內部一致性的信度分析方面，除了「自我調適」分量表（3題）的Cronbach α值為.56外，其他四個因素的α值則介於.74&#12316;.82之間。 研究二也是以大學生為對象，有效樣本541人，扣除性別漏填1人，男有193人，女有347人。利用研究一所編製的量表進行施測，結果發現無論是在學業拖延或是一般拖延上，約有50﹪以上的人認為自己的拖延情形在中間程度（五點量表，中數為3）以上；而在拖延時感受部分，人在拖延時最常出現的感受是「自責後悔」（M=3.60，SD=.70）與「自我調適」（M=3.52，SD=.65）。在不同性質任務的拖延程度上，「自己不想做但又必須做的事情」最會拖延（M=2.99，SD=.84），「自己想做也喜歡做的事情」最不會拖延（M=1.95，SD=.70）。而「性別」、「是否有兼職或打工」在拖延程度上並無顯著的差異存在；但是，在拖延時的感受部分，男生在拖延時比女生較常感到「自圓其說」，女生則比男生在拖延時較常感到「自責後悔」；「沒有兼職或打工」的人比「有兼職或打工」者在拖延時較常感到「自圓其說」。至於，拖延行為與創新行為的關係，拖延程度越高的人創新行為的表現越低；而拖延時較少感到「自我調適」，或較常感到「灰心逃避」的人，其創新行為表現也較低。 在時間觀、成就目標與拖延行為關係方面，除了時間觀中的「未來」時間觀與拖延行為呈顯著負相關（r=-41、-.47，p<.001）之外、「現在快樂主義」與「過去－負向」兩種時間觀則均與拖延行為呈正相關（r=.08&#12316;.20，p<.05），亦即時間觀越是「現在快樂主義」、「過去－負向」，越不是「未來」取向者，其拖延的情形越高。至於，成就目標與拖延行為的關係，無論是「趨向精熟」、「趨向表現」、「逃避精熟」還是「逃避表現」的目標導向，則或多或少均與拖延行為呈負相關（r=-.13&#12316;.22，p<.01）；但是，成就目標對拖延行為的影響，則因為時間觀的作用達顯著時而式微。 研究三則以研究一所編製的量表對研究二的樣本進行分析，主要想要了解情緒調節是否能作為拖延行為與拖延時感受的調節變項。應用階層迴歸分析的結果發現，基本上情緒調節與拖延行為對拖延時感受的影響並無顯著的交互作用存在。但是，若從情緒調節、拖延行為對拖延時感受的主要效果來看，兩者則分別對拖延時感受具有不同顯著的影響。以拖延行為對拖延時感受的影響來看，拖延程度越高的人在拖延時越常感到「僥倖心理」、「灰心逃避」、「自圓其說」。而以情緒調節對拖延時感受的影響來看，情緒調節越是以「重新評估」方式來調節的人，在拖延時則越常感到「自責後悔」、「自我調適」，越不會感到「自圓其說」、「灰心逃避」；情緒調節若越是以「壓抑」方式來調節的人，在拖延時則越常感到「自圓其說」。除此之外，本研究也發現，「重新評估」的情緒調節方式與學業拖延呈正相關（r=.09，p<.05），但是相關不大；而且若從時間觀與情緒調節的關係來看，「重新評估」情緒調節方式與「未來」、「現在快樂主義」時間觀呈正相關（r=.21&#12316;.27，p<.001），與「過去－負向」時間觀呈負相關（-.15，p<.001）。可見，這樣的結果與研究二中時間觀與拖延行為的關係加以對照來看，「重新評估」可能不是影響一個人是否經常學業拖延的直接原因，真正影響的是他站在怎樣的時間觀取向下來進行「重新評估」的情緒調節。 綜合三個研究結果，我們獲得以下幾個主要結論：（一）本論文所編製的學業拖延量表、一般拖延量表及拖延時感受量表，無論是在信、效度上均是可以接受的，可作為測量個體拖延程度與輔導其拖延問題的參考工具。（二）拖延已是大學校園內普遍的一種行為，而這種行為的程度並不因「性別」或「是否有兼職或打工」而有所不同；真正影響一個人是否經常拖延的原因主要與個體的時間觀取向有關，當一個人的時間觀越是傾向於「未來」時間觀，越不傾向於「現在快樂主義」、「過去－負向」的人，則越少拖延。（三）當任務是自己想做也喜歡做時，大學生比較不會拖延；相反地，當任務是自己不想做但又必須做時，大學生則比較會拖延。（四）雖然性別、是否兼職或打工在拖延行為程度上並無顯著的差異；但是，在拖延時感受的比較上，男生在拖延時比女生較常感到「自圓其說」，女生則比男生較常感到「自責後悔」，而沒有兼職或打工的學生則比有兼職或打工的學生在拖延時較常感到「自圓其說」。（五）拖延程度越高的人，在拖延時越常感到「僥倖心理」、「灰心逃避」、「自圓其說」。（六）情緒調節越是傾向以「重新評估」方式來調節的人，在拖延時越常感到「自責後悔」、「自我調適」，越少感到「自圓其說」、「灰心逃避」；而情緒調節越是以「壓抑」方式來調節的人，在拖延時則越常感到「自圓其說」。（七）拖延行為程度越高的人，其創新行為的表現也越低。 最後，本論文根據以上的研究發現，進行綜合討論與結論，並據以對學校、輔導及未來研究提出相關的綜合建議。 關鍵字：拖延、學業拖延、一般拖延、拖延時感受、創新行為、時間觀、成就目標、情緒調節。 / This dissertation mainly explores procrastination through three studies. Study 1’s objectives are to develop inventories about procrastination. The measurement instruments include academic procrastination, general procrastination , feelings when procrastinating. Study 2’s objectives are to explore relationships among time perspective（TP）, achievement goals and procrastination. The five factors of TP include future, present-hedonistic, present-fatalistic, past-positive and past-negative orientations（Zimbardo ＆ Boyd, 1999）. The achievement goal variable includes a 4-dimensional goal orientation: approach-mastery, approach-performance, avoidance-mastery and avoidance-performance（Elliot ＆ McGregor, 2001）. Furthermore, this study also investigates: a）procrastination of different tasks, b）the difference of procrastination behaviors and feelings when procrastinating based on different variables such as sex, grades, whether or not the students have part-time work, and c）relationship between procrastination and innovative behaviors（Scott ＆ Bruce, 1994）. Study 3’s objectives are to determine the relationships among procrastination, emotion regulation and feelings when procrastinating. The two forms of emotion regulation include reappraisal and suppression（Gross ＆ John, 2003）. The following are some findings based on the three studies: In study 1, the participants were 277 college students（88 males, and 186 females）.The data was analyzed using Principle Component Analysis. Results yielded the following: 1）Both academic procrastination and general procrastination were unidimensional scales. The former’s reliability was Cronbach’s alpha coefficient of .70 and the latter’s was .90. Two scales were related negatively to academic performance and self-concept（r=-.21&#12316;-.33, p<.001）. 2）Items of feelings when procrastinating were divided into five factors. These five factors were labeled as excuse-making（4 items, α=.82）, self-blame and regret（4 items, α=.74）, wishful thinking（3 items, α=.78）, self-adaptation（3 items, α=.56）, and dejection and avoidance（2 items, α=.78）. In study 2, the subjects were 541 college students（193 males, and 347 females）.All participants were measured by inventories developed in study 1. Results yielded the following: 1）More than 50﹪of students reported that their procrastination was higher than middle level. 2）People procrastinated more with tasks that they have to do but do not want to do; and less with tasks that they want to do and like to do. 3）No significant relationship was found between procrastination and sex, or whether or not the students have part-time work. However, males were more inclined to excuse themselves than females when they were procrastinating. In contrast, females were more inclined to blame themselves and feel regretful than males when they were procrastinating. Non-part-time workers were more inclined to excuse themselves than part-time workers when they were procrastinating. 4）People with higher procrastination levels tended to have lower scores of innovative behavior. 5）People with higher scores of future orientation, lower present-hedonistic TP and past-negative TP tended to have lower procrastination levels. In study 3, study 2’s participants were also part of study 3. The study primarily aimed to understand how “emotion regulation” functions as a moderator of the relation between procrastination level and feelings when procrastinating. Data was analyzed using Hierarchical Multiple Regression. Basically, we did not find the interaction between procrastination level and emotion regulation to explain variance of feelings when procrastinating. However, when examining the effects of procrastination level and emotion regulation individually, both variables significantly affected variance of feelings when procrastinating. When the analyzing between procrastination level and feelings when procrastinating, people with higher procrastination levels tended to have higher scores of wishful thinking, dejection and avoidance, and excuse-making when they were procrastinating. This indicated that the relationship between emotion regulation and feelings when procrastinating, people with higher reappraisal scores tended to have higher scores of self-blame and regret, higher scores of self-adaptation, lower scores of excuse-making, and lower scores of dejection and avoidance. Further, people with higher suppression scores tended to have higher scores of excuse-making. In addition, this study also found that emotion regulation by reappraisal was marginally related to academic procrastination（r=.09,p<.05）; but from the relationship between TP and emotion regulation, we found that reappraisal was related positively to future TP（r=.21, p<.001） and present-hedonistic TP（r=.27, p<.001）, and related negatively to past-negative TP（r=-.15, p<.001）.Therefore, in contrast with point 5 in the results of study 2 in this dissertation, academic procrastination may not be directly affected by reappraisal. In fact, the relation between reappraisal and academic procrastination was determined by one’s TP. Through the results of above three studies. From this dissertation 7 key points were concluded: 1） Reliability and validity of procrastination inventories which were developed in this dissertation were acceptable. Therefore, these inventories could be used when we want to measure one’s procrastination level and to resolve problems of procrastination. 2）Procrastination was a common behavior in campus. No significant relationship was found between procrastination level and sex, or whether or not the students have part-time work. Procrastination level was mainly affected by one’s TP. People with higher scores of future orientation, lower scores of present-hedonistic and past-negative TP tended to exhibit greater procrastination behavior. 3）People procrastinated more with tasks that they have to do but do not want to do; and less with tasks that they want to do and like to do. 4）There were differences when feelings when procrastinating were compared with different sex or whether or not the students have part-time work. Males were more inclined to excuse themselves than females when they were procrastinating. Females were more inclined to blame themselves and feel regretful than males when they were procrastinating. Non-part-time workers were more inclined to excuse themselves than part-time workers when they were procrastinating. 5）People with higher procrastination levels were more inclined to have scores of wishful thinking, dejection and avoidance, and excuse-making when they were procrastinating. 6）People with higher reappraisal scores of emotion regulation tended to have higher scores of self-blame and regret, higher scores of self-adaptation, lower scores of excuse-making, and lower scores of dejection and avoidance. People with higher suppression scores of emotion regulation tended to have higher scores of excuse-making. 7）People with higher procrastination level tended to exhibit lower scores of innovative behavior. Key words: procrastination, academic procrastination, general procrastination, feelings when procrastinating, innovative behavior, time perspective（TP）, 2×2 achievement goal, emotion regulation

<p> Over the past decade, the development of surface-initiated living polymerization methods has brought a breakthrough to surface modification owing to their control ability. Surface-initiated atom transfer radical polymerization (si-ATRP), as the most popular one, has been widely employed to give novel polymer structures and functionalities to various surfaces for the purposes of tailoring surface properties, introducing new functions, or preparing so-called "smart surfaces", which can respond to external stimuli such as solvent type, pH, temperature, electric and magnetic fields etc. In this thesis, the mechanistic study of the si-ATRP was first carried out through modeling to gain good understanding of si-ATRP. Si-ATRP was then employed to prepare different types of polymer brushes to produce "smart surfaces". </p> <p> The kinetic model was developed using the method of moment. Combined with experimental data, a quantitative analysis was carried out for the si-ATRP mechanism. All information of grafted polymer chains, including active chain concentration, radical concentration, chain length, polydispersity, was illustrated. A new radical termination mechanism, termed as migration-termination, was proposed for si-ATRP. </p> <p> Si-ATRP was then employed to graft poly(oligo(ethylene glycol) methacrylate) (POEGMA) block poly(methyl methacrylate) (PMMA) brushes on silicon wafer surfaces. Simple solvent treatment gave nanoscale patterns via the phase segregation of POEGMA and PMMA segments. Various patterns including spherical aggregates, wormlike aggregates, stripe patterns, perforated layers and complete overlayers, were obtained by adjusting the upper block layer thickness. Furthermore, these nanopatterns had a unique stimuli-responsive property, i.e., switching between different morphologies reversibly after being treated with selective solvents. </p> <p> POEGMA-block-poly(2-(methacryloyloxy)ethyl trimethylammonium chloride) (PMETAC) brushes, having two hydrophilic segments, were synthesized by si-ATRP method. A variety of nanopatterns and their stimuli-responsive ability were observed. The adsorption behaviors of fibrinogen on these patterns were thoroughly studied by ellipsometry, water contact angel measurement, AFM and radio labelling method. </p> <p> A novel thermo-responsive copolymer, poly(2-(2-methoxyethoxy)ethyl methacrylate -co-oligo(ethylene glycol) methacrylate) (P(ME02MA-co-OEGMA)), was also grafted onto silicon wafers. Its thermo-responsive behavior and chain conformation in aqueous solution were studied by neutron reflectometry (NR). Both extended and collapsed brushes exhibited good protein adsorption resistance. </p> / Thesis / Doctor of Philosophy (PhD)