Synthesis and Catalytic Oxidation of Organic Substrates by Light-Harvesting Metalloporphyrins

note: Some notation in this abstract may not appear exactly as formatted in the thesis. In this work, ruthenium, iron, and manganese light-harvesting metalloporphyrins have been successfully synthesized to serve as biomimetic models of the active site of Cytochrome P450 for the development of a green and efficient oxidation catalyst. The covalent introduction of light-harvesting boron-dipyrrin (BODIPY) fluorophores on the porphyrin macrocycle allows for the absorption of a broader range of visible light in addition to that captured by the porphyrin aromatic system alone. It is expected that this core-antenna system will increase the absorbed light energy and transfer it to the reaction center, and thereby increase the efficiency of the catalyst. Fluorescence spectrometry was used to identify the presence of energy transfer from the BODIPY units to the porphyrin core, in which the fluorescence spectrum of the BODIPY overlaps with the absorbance spectra of the porphyrin chromophore at the Q band region. The manganese(IV)-oxo light-harvesting porphyrin was also formed by both photochemical and chemical oxidation of the manganese(III) precursors. A kinetic plot of the observed rate constants for the reaction of manganese(IV)-oxo light-harvesting porphyrin with varying concentrations of thioanisole shows a linear relationship where the slope gives the second-order rate constant kox (M-1 s -1) = 0.4158, which was contrary to what was expected given the greater range of light energy able to be utilized. Ruthenium, iron, and manganese light-harvesting porphyrins served as oxidation catalysts that underwent preliminary oxidation trials with both sulfide and alkene substrates. In the presence of visible light, the ruthenium BODIPY porphyrin displayed an enhanced catalytic activity for both the sulfoxidation and epoxidation with PhI(OAc)2 and 2,6-dichloropyridine Noxide as oxygen sources, respectively. The epoxidation and sulfoxidation reactions catalyzed by both iron and manganese, however, fell below expectations. Possible explanations for the lack of reactivity include stable μ-oxo dimer formation or photodegradation of the catalysts

Intercultural encounter with nō master Udaka Michishige

In this paper, I aim to explore the process and results of my personal experience at the Summer Intensive Program of the International Noh Institute (INI) led by Kongō school master Udaka Michishige in Kyoto, 2016. During that period of time I had the opportunity to appreciate the various intricacies of nō practice, focusing mostly on shite’s training, practicing utai, basic kata, and learning a couple of shimai or short choreographic sequences. Through this opportunity, I was able to interact directly with the creative process that characterizes the nō theatre device in its traditional setting. Under a unique approach that Udaka-sensei had developed for more than thirty years to facilitate international students a meaningful interaction with nō theatre tradition.In questa sede, intendo esplorare il processo ed i risultati relativi all’esperienza di training tramite il Programma Estivo Intensivo dall'International Noh Institute (INI) condotto dal maestro Udaka Michishige della scuola Kongō nell’agosto del 2016. Durante quel periodo ho potuto apprezzare da un punto di vista pragmatico i molteplici aspetti relativi alla prassi e all’allenamento dell’attore shite. Grazie a questa opportunità ho potuto interagire direttamente con il processo creativo che caratterizza il dispositivo teatrale nō, nonché esperire il metodo specifico che Udaka-sensei aveva sviluppato durante più di trent’anni concedendo in questo modo a studenti internazionali un’esperienza significativa e rara nell’ambito tradizionale nō. Questo contributo vuole essere in memoriam ad Udaka-sensei, figura rilevante in ambito nō ed al contempo mostrare la mia più profonda gratitudine per quella preziosa opportunità

Learning Journey as an Educator Ethnography

What makes an effective teacher? This is the question I have tried to answer as I developed this ethnographic narrative. What is written here for you to read is an outline of what my experiences have been for the past two years, although it could have been my first year of teaching, but because I set back in the program, I will talk about both my first and second year of teaching. It traces back to the early expectations and hopes to more complex understandings of my students and myself. It has been 19 months since I started writing my ethnography, therefore you will notice my verb tense throughout the whole writing process. There are also new perspectives for each section. The project begins with a reflective piece about my personal educational experiences and my journey to become a teacher. I do wish to warn you that I have included specifically, details about my personal upbringing that may make a few people uncomfortable, but all in all this is who I am and what has helped shaped me through out the years. The work of this ethnography centers on my experience in my current position as an Intern teacher at a high school in Pomona, California. This opens with a study of three focus students who I had the privilege of visiting in their homes. This allowed me to discover who my students truly are and lay a foundation for my teaching goals. It is then followed by a section on the school, classroom, and community environment because this is what helps further analyze what shapes my students and it opens up opportunities to understanding where, how and why my students perform at the level they do. Finally, this project although the majority analytical, it is also very personal. In the last section presented, I reflect on the journey as an educator and what changes can be made to better suit my students. This section allows me to analyze how effective I have been and continue to be as an educator

Manipulating the Optical Properties of Hollow Pd/Ag and Pt/Ag Nanoparticles Synthesized by Galvanic Replacement Reaction

Considerable efforts have recently been devoted to the fabrication of metallic nanostructures on account of their tunable morphologies which can lead to new and fascinating optical properties. These properties of a metallic nanostructure are most determined by their size, shape, composition and structure. Hollow metallic nanostructures have attracted much interest as their surface plasmonic properties and catalytic activities are completely different from those of solid nanoparticles. Galvanic replacement reaction (GRR) was known to be a powerful synthetic technique for converting solid metal nanostructures into hallow ones. These hollow nanostructures have high specific surface area, low density, use less material and are cost effective. On the other hand, bimetallic-nanoparticles, in which two kinds of metals are contained in one particle, exhibit fascinating properties compared to those of the corresponding single-component particles. These particles are appeared to result from both the electronic and structural effects of the bimetallic structures. Nanoparticles fabricated from Ag-based alloys find extensive applications in catalysis, electro catalysis, and optics because their surface plasmon resonance (SPR) bands appear in the visible region. It has been reported that the surface plasmon resonance peaks of hollow bimetallic Au/Ag nanostructures could be readily tuned by controlling the Ag-Au ratio of the replacement reaction. However, fewer attempts have been made to study the optical properties of Pt/Ag and Pd/Ag based bimetallic nanoparticles compared to those of the Ag-Au system, probably because Pt and Pd nanoparticles do not usually exhibit surface plasmon resonance peaks in the visible spectrum. However, it has been demonstrated recently that the surface plasmon resonance peak of Pd nanoparticles could be tuned to 520 nm by the formation of large hollow nanocages. Hence, in this project, we have shown the efforts to come up with a new synthetic route for the controllable synthesis of Pt/Ag and Pd/Ag based bimetallic nanoparticles which exhibit tunable SPR extinction peaks in the visible region by applying galvanic replacement reaction on Ag templates in the presence of K2PtCl4 and K2PdCl4 salts. This report also focuses on the investigation of the characteristic optical properties of these composite hollow nanostructure

Shakespeare on the Edge of Intercultural Theatre: Lear Dreaming by Ong Keng Sen, a New Nō Performance

This article provides a general framework to the interview with Singaporean theatre creator and foremost advocate of Asian interculturalism, Ong Keng Sen, conducted on 30th of April, 2021. Aiming to focus on one of his latest works: Lear Dreaming, which premiered in Singapore, 2011 and was presented during the Singapore Theatre Festival in Paris, 2015, the interview covers a wide range of perspectives regarding Ong’s collaborative practice and the different strategies his work engages with, not only from a production point of view but also as part of a constant exploration regarding the continuities of contemporary practice of Asian theatre traditions. Harnessing the results from the unavoidable disruptions within the different traditions, his work enables an artistic practice that is acutely mindful of cultural mobility by exploring every possibility of innovation without losing sight of its relevant traditional background.Questo articolo mira a fornire un quadro generale ed introduttivo dell’intervista condotta il 30 aprile 2021 con l’autore teatrale singaporiano, nonché uno dei principali sostenitori dell’interculturalità teatrale, Ong Keng Sen. L’intervista vuole portare alla luce uno degli ultimi lavori del maestro, Lear Dreaming, in anteprima a Singapore nel 2011 e presentato a Parigi nel 2015. Coprendo un’ampia gamma di prospettive riguardanti le collaborazioni professionali di Ong con attori ed addetti ai lavori, si delineano le diverse strategie con cui il suo lavoro si esplicita, non solo da un punto di vista produttivo ma anche come innovatore delle tradizioni teatrali asiatiche

Case management services in the community: Benefits and outcomes

The purpose of this study is to advance knowledge in the area of case management services by investigating what characteristics are most frequent in clients who complete the case management program and in clients who did not complete the case management provided through the Montclair Community Collaborative (MCC). This research addresses case management services and centers on obtaining client data pertaining to case management services, focusing on the family\u27s outcome. The general research methodology consisted of a qualitative review (content analysis) of an existing data set (case records). This study examined a random sample of 130 MCC case management studies

Factors that influence the behavior of a person against the risk of starting a business in Latin America

El desempleo y la baja calidad de los empleos existentes, han creado la necesidad de emprender y pasar de ser empleado a emprendedor. Sin embargo, existen algunos factores que caracterizan a este comportamiento. La presente investigación identifica algunos de los factores que incrementan en una persona el riesgo de emprender un negocio en América Latina. Los principales factores que influyen en este comportamiento son: la experiencia, el conocimiento, la habilidad y la edad entre las once variables utilizadas en el periodo 2009-2011. Los modelos de redes neuronales utilizados clasifican a la variable dependiente (miedo al fracaso) con un porcentaje de acierto del 68% en el periodo de estudi

MIGRACIÓN DE RETORNO Y EL EMPLEO EN MÉXICO

La migración de retorno no es un fenómeno nuevo, sin embargo; manifiesta ciertas características que la hacen ser diferente de épocas pasadas. La crisis económica que apaciguó la economía norteamericana en el año 2008 y las políticas antimigrantes de Estados Unidos han venido endureciéndose, incentivado los flujos de retorno. Aunado a ello la poca colaboración entre estos dos países ha hecho que los migrantes queden desprotegidos en el extranjero y por tanto en la actualidad exista una mayor afluencia de migrantes de retorno a nuestro país, los cuales se tienen que reincorporar a la sociedad y al entorno laboral. La hipótesis del trabajo es la siguiente: los migrantes retornados se concentran en actividades precarias y en empleos de mala calidad. Tomando en cuenta, que la situación económica de México no es muy diferente a la que enfrentaron en Estados Unidos, ya que en el 2009 el Instituto Nacional de Estadística y Geografía (INEGI) estimó que la economía mexicana decreció 6.5 por ciento, México fue el país de Latinoamérica que experimentó un mayor impacto de la crisis. El motivo es su mayor interrelación con la economía estadounidense. En el 2010, se observó en el país una recuperación, el crecimiento económico fue de 5.5 por ciento, como una respuesta a la mejoría de la economía estadounidense, sin embargo la estructura laboral mexicana en estos años se ha caracterizado por altas tasas de desempleo y mayor precarización del mercado laboral (Samaniego, 2010). Por tanto, se pretende realizar un análisis de la migración de retorno y empleo en México. Lo anterior a partir de una muestra proporcionada por el Censo de Población y Vivienda 2010, de manera que los datos permitan perfilar características demográficas del retorno de migrantes y sus tendencias de empleo e ingresos

The Mirror

Art is a transformative experience that is rarely attained because of a refusal to acknowledge what is true or honest, because of the certain vulnerability and aspect of danger that is inseparable with honesty. It is a rare occurrence, not because it is elitist or undemocratic, and not because it is not sincerely sought after, but because it exposes the artist's vulnerabilities to the world and in doing so creates a conflict of interest, whereby, the artist must choose to either preserve himself and his ego or acknowledge that to truly be an artist and to truly make art is to make honest statements or reflections and stand with them. Honesty, and, therefore, Art, is not easy, which is what makes it such a rare and special occurrence.</p