Preparation and Characterization of Iridium Hydride and Dihydrogen Complexes Relevant to Biomass Deoxygenation

Goldberg, Jonathan M University of Washington ProQuest Dissertations & 2017 해외박사(DDOD)

This thesis describes the fundamental organometallic reactivity of iridium pincer complexes and their applications to glycerol deoxygenation catalysis. These investigations provide support for each step of a previously proposed glycerol deoxygenation mechanism. Chapter 1 outlines the motivations for this work, specifically the goal of using biomass as a chemical feedstock over more common petroleum-based sources. A discussion of the importance of transforming glycerol to higher value products, such as 1,3-propanediol, is discussed. Chapter 2 describes investigations into the importance of pincer ligand steric factors on the coordination chemistry of the iridium metal center. Full characterization of a five-coordinate iridium-hydride complex is presented; this species was previously proposed to be a catalyst resting state for glycerol deoxygenation. Chapter 3 investigates hydrogen addition to R4(POCOP)Ir(CO) [R4POCOP = kappa3-C6H3-2,6-(OPR2)2 for R = tBu, iPr] and R4(PCP)Ir(CO) [R4(PCP) = kappa3-C6H3-2,6-(CH 2PR2)2 for R = tBu, iPr] to give cis- and/or trans-dihydride complexes. Two mechanisms of hydrogen addition are presented (concerted oxidative addition and proton-catalyzed addition); the mechanism of hydrogen addition is dependent on the steric environment at the metal center. Chapter 4 presents spectroscopic evidence for two new iridium-dihydrogen complexes only stable under high pressures of hydrogen (40--80 atm) and low temperatures. Furthermore, iridium-catalyzed isotope exchange between H2 and CD3OD is presented and its potential implications in supporting the glycerol deoxygenation mechanism. Chapter 5 outlines a fundamental reaction of oxidative addition of iodine to (tBu)4(POCOP)Ir(CO) complexes. Characterization of a cationic monoiodo iridium carbonyl complex as a potential oxidative addition intermediate is presented.

Beyond ledgers and bar lines: Relational visions of music and education through the voices of seven teachers

Goldberg, Jeffrey L Harvard University 2002 해외박사(DDOD)

This study presents seven teachers, chosen for their interdisciplinary and integrated approaches to music and education, as they express their pedagogy while facing various challenges. At a time when public education in the U.S. reflects growing economic inequalities of the larger society, when music programs have been marginalized, reduced or eliminated as schools increasingly respond to corporate and commercial needs, and when an increased influence of standardized testing (itself incompatible with pedagogies for musical creativity) is a powerful force driving music out of public school systems (Fowler, 1996; Goldberg, 2001; Orfield, 1999), I identified seven public school teachers (grades 7–12) whose approach to music offers an alternative to the pedagogy of standardization. Through individual and group interviews with these teachers and supplementary data (lesson plans, class observations), I addressed the following questions: (1) How do these teachers think about music and education? (2) How have their classroom experiences informed their vision (and vice versa)? (3) How do (or did) these particular teachers deal with challenges (institutional, political, etc.) that limit the degree to which they can carry out their educational vision?. The selected teachers share an approach to music and education I describe as relational (Goldberg, 2001), which is interdisciplinary, integrative, generalist, collaborative, contextual, and embraces different ways of knowing. The teachers range from “music” teachers who include “other” subjects in their classrooms to vice versa, and from teachers with plentiful resources and curricular freedom to those with few resources and curricular constraints. My work as a musician and teacher informs my choosing relational characteristics to select these teachers, as does relevant literature on music and teaching (Berry, 1972; Blacking, 1973; Page, 1995a; Stewart, 1994; Small, 1977). Rather than assess classrooms or programs, I aspired to gain greater understanding of what these teachers are saying, offering other educators pedagogical models through their stories, struggles, and visions. As the teachers reflect on the discipline of music and their own political contexts, their roles as “visionaries,” “oppressed,” “survivors,” “magicians,” and “pragmatists” may inspire others interested in music and education.

GIUSEPPE DE NITTIS : AN ITALIAN PERSPECTIVE ON THE PARISIAN CITYSCAPE, 1867-1884 (FRANCE)

GOLDBERG, CAROLINE VIRGINIA WALTER New York University 1995 국내박사

Court calligraphy in the early Tang Dynast

Goldberg, Steve Jay Yale University 1981 해외박사

AN ANALYSIS OF HARMONIC LANGUAGE IN THE SONGS OF ARTHUR HONEGGER (1892-1955) (HONEGGER ARTHUR, FRANCE, ART-SONGS)

GOLDBERG, LESLIE ANN Boston University 1991 국내박사

The implementation of an elementary mathematics curriculum: A series of case studies

Goldberg, Adam Howard Columbia University Teachers College 2005 해외박사(DDOD)

Textbooks and other curricular materials play a fundamental role in the education process. Considering their importance, the question of how, and to what degree, teachers are using these resources becomes a vital one. This study examined the implementation process of teachers using the Houghton Mifflin Mathematics elementary mathematics program. An instrument consisting of background questions and four separate surveys were administered anonymously to teachers in three school districts in the Northeastern United States during the 2004--2005 school year. One urban, one suburban, and one ex-urban district were chosen to determine if implementation varied across district types. The four surveys used in this study were: the Esposito Survey of Program Adoption which measured teacher perception of the curriculum adoption process; the Feeney Survey of Implementation Fidelity which measured the fidelity with which the new program was implemented; The Goldberg Survey of Program Appraisal which measured teacher satisfaction with the adopted program; and the Ross et al. Survey of Commitment to Reform which measured teacher commitment to reform teaching in mathematics. Additionally, the author describes in detail the development of the Program Appraisal survey. The results of this study indicated that overall, teachers had a positive perception of the implementation of the Houghton Mifflin Mathematics program. When the survey results were analyzed, several interesting district-type differences emerged. For example, the data suggested that teachers in the urban district were using the program with the highest degree of fidelity. Correlations were also calculated to examine relationships between components of the implementation process. One such result showed a positive correlation between teachers' perceptions of the adoption process and their fidelity to, and satisfaction with, the curriculum. The methodology and results of this study can be helpful to school administrators seeking to implement a new curricular program.

Price control during the Korean emergency : the petroleum industry in the U.S.A.

Goldberg, Benjamin UMI 2014 국내박사

Parental Reflective Functioning, Emotion Regulation, and Stress Tolerance: A Preliminary Investigation

Goldberg, Ben Yale University 2011 해외박사(DDOD)

While strong and interdependent associations between reflective functioning, emotion regulation, and stress tolerance have been theorized in the attachment security and psychoanalytic literature, this is one of the initial reports of the investigation of such associations. Twenty-six mothers of young children were administered a novel self-report measure of parental reflective functioning, two distinct stress induction tasks, and three self-report measures of emotion regulation. It was predicted that greater maternal reflective functioning, as measured by the PRFQ-1 self-report measure, would predict greater stress tolerance, as measured by persistence times in the Simulated Baby Paradigm and PASAT-C, as well as greater ability for emotion regulation, as measured by the DERS, ERQ, and BRIEF-A self-report measures. It was also hypothesized that greater emotion regulation would predict greater stress tolerance. Initial correlations generally did not support these hypotheses. However, further analysis of the data suggested that maternal reflective functioning may mediate the relationship between the self-appraisal of one's capacity for emotion regulation and behavior in a stressful, parenting-specific task. These findings suggest a complex and interdependent relationship between parental reflective, emotion regulation, and stress tolerance.

Part I. Solvolysis regioselectivity and x-ray structure of the duocarmycin SA alkylation subunit. Part II. Solution phase synthesis of compound libraries targeting the erythropoietin receptor. Part III. Identification of a new class of angiogenesis inhibitors which function by blocking the inter

Goldberg, Joel Adam The Scripps Research Institute 2000 해외박사(DDOD)

The solvolysis regioselectivity and stereochemistry of the alkylation subunit of duocarmycin SA, a member of a potent class of antitumor antibiotics which derive their biological properties through the sequence-selective alkylation of adenine in the minor groove of DNA, proceeds with a 4–6.5:1 ratio of normal addition and ring expansion products, and is consistent with a S_N2 process. Comparison of the solvolysis regioselectivity of related alkylation subunits reveals a correlation to the alignment of the reactive cyclopropane bonds observed in their X-ray structures. Solution phase combinatorial synthesis exploiting iminodiacetic acid anhydride was utilized to prepare symmetrical compound libraries targeting the erythropoietin receptor, and this methodology was extended to an alternative, isoindoline-based cyclic anhydride template. The solution phase synthesis of symmetrical biaryl libraries is also detailed in which heterogeneous conditions were developed for catalysis, isolation and purification. The process of new blood vessel growth from existing vasculature, known as angiogenesis, is critical to several pathological conditions, most notably cancer. Recent findings have shown that proteinase MMP2 can only be effectively activated and utilized for angiogenesis after binding to integrin α_vβ₃ in an RGD independent manner. The screening of small-molecule compound libraries led to the identification of compounds which disrupt the MMP2-α_vβ₃ interaction in an in vitro binding assay. The most potent agent was further found to prevent the degradation of the protein matrix without directly inhibiting MMP2 activity or disrupting the binding of α_vβ₃ to its classical (RGD) ligand, vitronectin. Synthesis and screening of analogs and substructures of this compound allowed for the identification of requisite functional groups and led to the synthesis of a more water-soluble derivative which has potent anti-angiogenic and antitumor activity in vivo.

Electric Field Measurements in Non-Equilibrium Electric Discharge Plasmas Using Picosecond Four-Wave Mixing

Goldberg, Benjamin M The Ohio State University 2015 해외박사(DDOD)

This dissertation presents the results of development of a picosecond four wave mixing technique and its use for electric field measurements in nanosecond pulse discharges. This technique is similar to coherent anti-Stokes Raman spectroscopy and is well suited for electric field measurements in high pressure plasmas with high spatial and temporal resolution. The results show that the signal intensity scales proportionally to the square of the electric field, the signal is emitted as a coherent beam, and is polarized parallel to the electric field vector, making possible electric field vector component measurements. The signal is generated when a collinear pair of pump and Stokes beams, which are generated in a stimulated Raman shifting cell (SRS), generate coherent excitation of molecules into a higher energy level, hydrogen for the present work. The coherent excitation mixes with a dipole moment induced by an external electric field. The mixing of these three "waves'" allows the molecules to radiate at their Raman frequency, producing a fourth, signal, wave which is proportional to the square of the electric field. The time resolution of this technique is limited by the coherence decay time of the molecules, which is a few hundred picoseconds.