DEVELOPMENT OF PHOTOREDOX CATALYSIS-MEDIATED FUNCTIONALIZATION METHODS FOR ARENES AND OLEFINS

ABSTRACT Megan Elizabeth Schutzbach-Horton: DEVELOPMENT OF PHOTOREDOX CATALYSIS-MEDIATED FUNCTIONALIZATION METHODS FOR ARENES AND OLEFINS (Under the direction of David A. Nicewicz) I. Introduction to Organic Photoredox Catalysis This chapter provides a brief discussion of relevant photophysical properties and the thermodynamics of photoinduced electron transfer. The development of acridinium ion catalysts and their use by our lab is also included. II. Development of Photoredox Catalysis-Mediated Methods for the Hydrofunctionalization of Glycals Efforts to-date on the development of glycal hydrofunctionalization methods using acridinium-mediated photoredox catalysis are summarized. This work includes data obtained by Heqing Sun on the use of exo-glycals as substrates in a hydroalkoxylation reaction. The latter portion of the chapter summarizes efforts towards the use of endo-glycals as substrates in a variety of hydrofunctionalization methods, including hydroamination and hydroalkoxylation reactions. III. Development of a Photoredox-Mediated Method for the Anti-Markovnikov Hydroazidation of Activated Olefins This chapter discusses the use of acridinium-mediated photoredox catalysis in the development of an anti-Markovnikov hydroazidation method that is complementary to existing work. Using mild conditions that feature the use of TMSN3 and TFE, we report the synthesis of 31 organic azides in yields ranging from 22 – 98%. IV. Development of a Method for the Nucleophilic Defluorination of Electron-Neutral and Electron-Rich Fluoroarenes In this chapter, the development of a general method for the use of electron-neutral and electron-rich fluoro(hetero)arenes as substrates in a CRA-SNAr reaction is discussed. Using both an acridinium catalyst, as well as a novel xanthylium catalyst, conditions were developed for 78 examples of nucleophilic defluorination in a manner that is complementary to existing SNAr chemistry.Doctor of Philosoph

Updated guidelines, updated curriculum: The GAISE College Report and introductory statistics for the modern student

Since the 2005 American Statistical Association's (ASA) endorsement of the Guidelines for Assessment and Instruction in Statistics Education (GAISE) College Report, changes in the statistics field and statistics education have had a major impact on the teaching and learning of statistics. We now live in a world where "Statistics - the science of learning from data - is the fastest-growing science, technology, engineering, and math (STEM) undergraduate degree in the United States," according to the ASA, and where many jobs demand an understanding of how to explore and make sense of data. In light of these new reports and other changes and demands on the discipline, a group of volunteers revised the 2005 GAISE College Report. The updated report was endorsed by the Board of Directors of the American Statistical Association in July 2016. To help shed additional light on the revision process and subsequent changes in the report, we review the report and share insights into the committee's thoughts and assumptions.Comment: in press, CHANC

Effects of Body Shape on Literal Objectification: When Ideal May Be Less Than Ideal

Objectification, or the tendency to adopt an externalized view of self/other, is a ubiquitous process disproportionately affecting women (Fredrickson & Roberts, 1997). Recent work has examined literal objectification, defined as “any outcome in which a person is perceived as, or behaves, objectlike, relative to humanlike” (Heflick & Goldenberg, 2014, p. 225). Focusing on women’s physical appearance heightens literal objectification, including reduced perceptions of warmth, competence, and morality (Heflick et al., 2011). We investigated whether participants’ ratings of literal objectification vary as a function of body type. Seventy-one college women (Mage = 19.23) viewed three photos of women, manipulated to depict low, average, and high ideal body shapes. Participants rated the degree to which each woman possessed competence, warmth and morality, and their desire to collaborate on a group project with them. Average images were rated as significantly higher on warmth, morality, and collaboration desirability than high ideal and low ideal images, and marginally more competent than high ideal images. High ideal images were rated as significantly lower on warmth and marginally lower on collaboration desirability than low ideal images. Future research should extend this work to evaluate behavioral manifestations of literal objectification and explore what other factors might moderate these effects

Endocrine-Disrupting Effects of Cattle Feedlot Effluent on an Aquatic Sentinel Species, the Fathead Minnow

Over the last decade, research has examined the endocrine-disrupting action of various environmental pollutants, including hormones, pharmaceuticals, and surfactants, in sewage treatment plant effluent. Responding to the growth of concentrated animal feeding operations (CAFOs) and the pollutants present in their wastewater (e.g., nutrients, pharmaceuticals, and hormones), the U.S. Environmental Protection Agency developed a new rule that tightens the regulation of CAFOs. In this study, we collected wild fathead minnows (Pimephales promelas) exposed to feedlot effluent (FLE) and observed significant alterations in their reproductive biology. Male fish were demasculinized (having lower testicular testosterone synthesis, altered head morphometrics, and smaller testis size). Defeminization of females, as evidenced by a decreased estrogen:androgen ratio of in vitro steroid hormone synthesis, was also documented. We did not observe characteristics in either male or female fish indicative of exposure to environmental estrogens. Using cells transfected with the human androgen receptor, we detected potent androgenic responses from the FLE. Taken together, our morphologic, endocrinologic, and in vitro gene activation assay data suggest two hypotheses: a) there are potent androgenic substance(s) in the FLE, and/or b) there is a complex mixture of androgenic and estrogenic substances that alter the hypothalamic–pituitary–gonadal axis, inhibiting the release of gonadotropin-releasing hormone or gonadotropins. This is the first study demonstrating that the endocrine and reproductive systems of wild fish can be adversely affected by FLE. Future studies are needed to further investigate the effects of agricultural runoff and to identify the biologically active agents, whether natural or pharmaceutical in origin

Guidelines for Assessment and Instruction in Statistics Education (GAISE) College Report 2016

In 2005 the American Statistical Association (ASA) endorsed the Guidelines for Assessment and Instruction in Statistics Education (GAISE) College Report. This report has had a profound impact on the teaching of introductory statistics in two- and four-year institutions, and the six recommendations put forward in the report have stood the test of time. Much has happened within the statistics education community and beyond in the intervening 10 years, making it critical to re-evaluate and update this important report. For readers who are unfamiliar with the original GAISE College Report or who are new to the statistics education community, the full version of the 2005 report can be found at http://www.amstat.org/education/gaise/GaiseCollege_full.pdf and a brief history of statistics education can be found in Appendix A of this new report. The revised GAISE College Report takes into account the many changes in the world of statistics education and statistical practice since 2005 and suggests a direction for the future of introductory statistics courses. Our work has been informed by outreach to the statistics education community and by reference to the statistics education literature

Sex-specific associations of a ferroalloy metal mixture with motor function in Italian adolescents.

BACKGROUND: Motor function is critical for childrens health, yet remains an understudied neurodevelopmental domain. Exposure to metals has been linked with motor function, but no study has examined the joint effects of metal mixtures. METHODS: We evaluated cross-sectional associations between a metal mixture and motor function among 569 adolescents (10-14 years old) living near the ferroalloy industry. Concentrations of blood lead, hair manganese, hair copper, and hair chromium were quantified using inductively coupled plasma mass spectrometry. Neuropsychologists administered multiple fine motor function assessments: pursuit aiming, finger tapping, visual reaction time (VRT), and subtests from the Luria Nebraska battery. We estimated associations between motor function and the metal mixture using quantile-based g-computation and multivariable linear regression, adjusting for child age, sex, and socioeconomic status. We explored sex-specific associations in stratified models. RESULTS: Associations between the metal mixture and motor function were mostly null but were modified by sex. We observed a beneficial association among females: a quartile increase in all metals in the mixture was associated with a 2.6% faster average response time on the VRT (95% confidence interval [CI] = -4.7%, -0.5%), driven by Cu and Cr. In contrast, this association was adverse among males (ß = 1.5% slower response time [95% CI = -0.7%, 3.9%]), driven by Cu and Mn. CONCLUSIONS: Results suggest that males may be more susceptible to the adverse effects of metal exposure on motor function during adolescence than females. Future studies, particularly prospective study designs, are warranted to further understand the associations of metal mixtures with motor function

Bringing Upstairs Care Downstairs; Integration of Rehabilitation Medicine, Care Management, and the Hospital Elder Life Program (HELP) into an Emergency Department.

Introduction: Services such as physical therapy (PT), occupational therapy (OT), speech-language pathology (SLP), social work (SW), care management, and elder life specialists have long been an established part of care for patients admitted to Maine Medical Center (MMC) but not for patients in the Emergency Department (ED). Methods and Results: Driven in part by changes in Medicare reimbursement models, care management established a presence in the Emergency Department (ED) in 2003 with a focus on care planning and cost avoidance. In recent years PT, OT, SLP, SW, and the Hospital Elder Life Program (HELP) have increased their ED involvement substantially. These services not only support care management decisions but have become an invaluable part of the ED team. The timing, staffing models, and roles of these services in our emergency department are described. Discussion: There was strong leadership support to create these positions in the ED. Increased patient volume hospital wide has required staffing flexibility. Initial concerns for slowing the ED where anecdotally resolved. Other hospitals in our system are interested in this approach. Conclusions: While the value of this work feels self-evident and is already established for admitted patients, descriptive and outcome-oriented studies for ED patients would be enlightening

Seven-Year Neurodevelopmental Scores and Prenatal Exposure to Chlorpyrifos, a Common Agricultural Pesticide

Background: In a longitudinal birth cohort study of inner-city mothers and children (Columbia Center for Children’s Environmental Health), we have previously reported that prenatal exposure to chlorpyrifos (CPF) was associated with neurodevelopmental problems at 3 years of age

Endocrine-disrupting effects of cattle feedlot effluent on an aquatic sentinel species, the fathead minnow.

Over the last decade, research has examined the endocrine-disrupting action of various environmental pollutants, including hormones, pharmaceuticals, and surfactants, in sewage treatment plant effluent. Responding to the growth of concentrated animal feeding operations (CAFOs) and the pollutants present in their wastewater (e.g., nutrients, pharmaceuticals, and hormones), the U.S. Environmental Protection Agency developed a new rule that tightens the regulation of CAFOs. In this study, we collected wild fathead minnows (Pimephales promelas) exposed to feedlot effluent (FLE) and observed significant alterations in their reproductive biology. Male fish were demasculinized (having lower testicular testosterone synthesis, altered head morphometrics, and smaller testis size). Defeminization of females, as evidenced by a decreased estrogen:androgen ratio of in vitro steroid hormone synthesis, was also documented. We did not observe characteristics in either male or female fish indicative of exposure to environmental estrogens. Using cells transfected with the human androgen receptor, we detected potent androgenic responses from the FLE. Taken together, our morphologic, endocrinologic, and in vitro gene activation assay data suggest two hypotheses: a) there are potent androgenic substance(s) in the FLE, and/or b) there is a complex mixture of androgenic and estrogenic substances that alter the hypothalamic-pituitary-gonadal axis, inhibiting the release of gonadotropin-releasing hormone or gonadotropins. This is the first study demonstrating that the endocrine and reproductive systems of wild fish can be adversely affected by FLE. Future studies are needed to further investigate the effects of agricultural runoff and to identify the biologically active agents, whether natural or pharmaceutical in origin