Synthetic Methods for Improved Scope and Efficiency of Copper-Catalyzed Regioselective Alkene Boracarboxylation

The synthesis of carboxylic acids is important to the chemistry community, owing to the broad applicability of these compounds as fine chemicals and pharmaceuticals. Method development over the last decade has focused on the preparation of carboxylic acids through transition metal catalysis utilizing CO2 as a C1 synthon. Copper-catalyzed heteroelement(bora and sila)-carboxylation protocols provide functional group rich carboxylic acid products, yet remain underdeveloped and thus underutilized. Consequently, catalytic reductive difunctionalization methodologies in which CO2 and B(pin) (pin = pinacolate: 2,3-dimethyl-2,3-butanediolate) are installed across the double bond of a vinyl arene were recently developed. These boracarboxylation protocols provided novel, pharmaceutically relevant, α-aryl propionic acids bearing a β-boryl functionality in good to excellent yields; however, the alkene scope was limited. Here, solutions to substrate scope limitations and methods to improve reaction efficiency will be presented. Reactivity studies of sterically challenging α-substituted vinyl arene substrates revealed a complex kinetic interplay between catalytic reduction of CO2 and alkene migratory insertion reaction pathways. These results have impacted the ways in which the catalytic boracarboxylation system is altered to allow for transformation of challenging alkene substrates. The method in which the α-substituted vinyl arenes were boracarboxylated led to a glovebox-free benchtop synthesis of borylated Ibuprofen. Moreover, the benchtop method circumvents the need to use a prefunctionalized copper(I)-precatalyst through in-situ generation of the active catalytic species from readily available and easily synthesized starting materials. Guided by previous experimental studies, a catalytic phosphine additive, Xantphos, led to expansion of the boracarboxylation scope to unactivated alkenes. Insights from these studies are expected to contribute to increased use of Xantphos as a catalytic additive in copper(I)-boryl catalysis

Examining The Effectiveness Of Interventions Designed To Increase Mammography Adherence Among African American Women

The objective of this paper was to assess and synthesize the key findings, conclusions, and recommendations of mammography interventions targeting African American women conducted between 1999 and 2010. Collection of materials for this study included searches of academic databases using the following inclusion criteria: 1) publication in the English language, 2) between 1999 and 2010, 3) conducted in the United States, 4) targeting African American women. Titles and abstracts of identified studies were evaluated independently by two researchers. A total of 24 studies met the inclusion criteria. Interventions were categorized as either practice-based or community-based. Classifications were then sub-categorized based on the employment of targeted or tailored strategies. Culturally-appropriate tailored and targeted messages are an effective approach to increase screening mammography adherence. Community-wide interventions that employ lay health advisors were found to assist in offsetting issues related to trust and access. Interventions delivered in faith-based settings were effective mediums for increasing adherence to screening guidelines. Stepped-care interventions were an efficient, cost-effective method for increasing adherence among non-compliant populations. The majority of the identified studies relied upon theoretical frameworks to guide the intervention. Community-based interventions should progress from atheoretical to theory-based intervention frameworks

Social Cognitive Models of Fruit and Vegetable Consumption, Moderate Physical Activity, and Sleep Behavior in Overweight and Obese Men

Background. Approximately 35% of men in the United States are obese, though little theoretical work examining predictors correlates of obesity exists for this population. The purpose of this study was to test the capacity of Bandura’s social cognitive model of health behavior to account for variance in fruit and vegetable consumption, moderate physical activity, and sleep behavior in overweight and obese men. Methods. Data were collected from overweight and obese men using previously validated questionnaires. Structural equation models were built to examine the direct and indirect effects the social cognitive theory constructs of self-efficacy, outcome expectation, socio-structural factors, and goals on the behaviors under investigation. Results. A total of 305 men participated in this study (Mage=44.52; SD=6.95). Overall fit for the social cognitive models of health behavior were adequate, accounting for 35.0%, 31.2%, and 21.1% of the variance in the fruit and vegetable consumption, moderate physical activity, and sleep behavior correlates, respectively. Self-efficacy had the greatest total effect on fruit and vegetable consumption (βtotal=.500) and sleep behavior (βtotal=.406), while goals has the greatest total effect on moderate physical activity (βtotal=.495). The indirect effects of self-efficacy on the three behaviors demonstrates the relative importance of self-efficacy as a mediator for health behavior change. Discussion. Men are underrepresented in behavioral obesity prevention and treatment research. This study provides support for the social cognitive model of health behavior as a theoretical framework for predicting behaviors hypothesized to protect against and treat obesity in men. Additionally, this study represents the first attempt to model correlates social cognitive constructs on sleep behavior

COMPARING STUDENT BEHAVIORS AND SCHOOL SATISFACTION BETWEEN STUDENTS WITH AUTISM SPECTRUM DISORDER AND TYPICALLY DEVELOPING PEERS

School satisfaction for families of students with autism is a well-researched area. However, research comparing levels of school satisfaction and the number of behavioral incidences between students with autism and typically developing peers is imperative to ascertain the effectiveness of behavioral interventions and how they relate to school satisfaction. This study seeks to answer two questions: (1) Is there a difference in the number of behavior problems for students with autism compared to typically developing peers, and (2) Is there a difference in school satisfaction and satisfaction with discipline for students with autism compared to typically developing peers? Using data from the NCES National Household Education Surveys Program of 2016 Our Children’s Future: A Survey of Young Children’s Care and Education study, statistical analyses showed that there were significant differences between the number of times contacted about behavior problems for students with behavior problems and typically developing peers. However, there were no significant differences in levels of school satisfaction or satisfaction of discipline for students with autism compared to typically developing peers. Article visualizations

Color separation gratings

In this paper, we describe the theory, fabrication and test of a binary optics 'echelon'. The echelon is a grating structure which separates electromagnetic radiation of different wavelengths, but it does so according to diffraction order rather than by dispersion within one diffraction order, as is the case with conventional gratings. A prototype echelon, designed for the visible spectrum, is fabricated using the binary optics process. Tests of the prototype show good agreement with theoretical predictions

A recalibration of coastal mosaic flows for a resilient riviera romagnola

LAUREA MAGISTRALEAttraverso la lente dei mosaici di terra può iniziare una ricalibrazione dei flussi costieri dell'Emilia Romagna. Il termine mosaici di terra deriva dall'ecologia del paesaggio sviluppato da Forman (Forman,1995) ed è descritto come un insieme di macchie, corridoi e matrici energeticamente aperti (gli elementi spaziali di base) che formano un modello sul terreno a misura d'uomo. In altre parole, un insieme di elementi paesaggistici collegati da flussi di energia e materiali. Questi flussi possono avere origine sia antropica che naturale e includere qualsiasi cosa, dalle attività animali e umane all'acqua, ai sedimenti e agli inquinanti. Attraverso questa lente possiamo visualizzare questo paesaggio dinamico nel suo insieme modellato da varie reti di flussi e alleviare i flussi conflittuali e congestionati per migliorare i modelli spaziali. Tale quadro ha il potenziale per riconfigurare un paesaggio di rigido controllo in un paesaggio di resilienza che accoglie armoniosamente i flussi antropici e naturali. Come affermato da Forman, i mosaici di terra sono il risultato di due fattori, la geologia e la cultura. Man mano che l'uomo diventa un agente geologico sempre più potente, abbiamo assistito a una drastica trasformazione dei mosaici da quelli dettati dai fenomeni naturali a quelli modellati dalle azioni umane. Con problemi urgenti come il cambiamento climatico, stiamo iniziando a sentire lo squilibrio di queste trasformazioni spaziali nelle comunità di tutto il mondo che vivono sui mosaici e fanno affidamento su di essi per tutte le necessità della vita. Il Delta del Po, antico e attivo, è un ottimo esempio di mosaico territoriale formato dalle forze convergenti dell'uomo e della geologia. È un paesaggio acquatico eccezionalmente dinamico che è stato modellato molte volte dall'acqua e dall'uomo allo stesso modo. Un tempo un mosaico dominato principalmente da fiumi, zone umide, lagune, saline e dune, ciò che rimane oggi è un paesaggio prevalentemente agricolo con città turistiche sulla spiaggia che costeggiano la costa e macchie di resti scarsamente distribuite a testimoniare un paesaggio dimenticato. Queste macchie sono una roccaforte fondamentale per la flora e la fauna autoctone che stanno diventando sempre più rare. L'integrazione coesa di questi elementi e dei successivi flussi, sia antropici che naturali, è la chiave per un mosaico paesaggistico coeso, resiliente, funzionale ed equilibrato. Oggi, dopo secoli di bonifiche, deviazioni di canali, costruzione di dighe ed estrazione di sedimenti e gas, la costa dell'Emilia Romagna risente dei flussi spaziali in lotta attraverso il paesaggio. Inoltre, questo tratto di costa sta subendo un aumento della frequenza e dell'intensità delle mareggiate che ha il potenziale di paralizzare l'economia basata sul turismo costiero della regione. Lido Degli Estensi è una città costiera del turismo estivo che, secondo quanto riferito, è in calo di visitatori mentre ha dovuto affrontare più inondazioni costiere. La frammentazione delle lagune interne e delle spiagge costiere e la mancanza di coesione nelle qualità spaziali hanno probabilmente contribuito al declino del loro principale motore economico. Lo spostamento dei flussi attraverso il paesaggio fornisce importanti spunti su cosa si può fare per mitigare questi problemi su scala spaziale. Questa proposta esamina il flusso di acqua, sabbia, persone e fauna selvatica per migliorare un tassello di un mosaico più ampio, Lido Degli Estensi, non solo riconoscendo i cambiamenti nei flussi ma utilizzandoli come opportunità per migliorare la dinamica del mosaico. Dato lo spostamento dei flussi attraverso e attraverso il mosaico costiero, rivalutare il modo in cui i flussi vengono gestiti per ripristinare l'equilibrio e migliorare le economie, integrando al contempo preziosi habitat ed ecosistemi.A recalibration of Emilia Romagna coastal flows can begin through the lens of land mosaics. The term of land mosaics comes from landscape ecology developed by Forman (Forman,1995) in and is described as an assemblage of energetically open patches, corridors and matrices (the basic spatial elements) that form a pattern on the land at a human scale. In other words, a set of landscape elements that are connected by flows of energy and materials. These flows can have both anthropic and natural origins and include anything from animal and human activities to water, sediment and pollutants. Through this lens we can visualize this dynamic landscape as a whole shaped by various networks of flows and alleviate conflicting and congested flows to improve spatial patterns. Such a framework has the potential to reconfigure a landscape of rigid control into a landscape of resilience that harmoniously accommodates both anthropic and natural flows. As stated by Forman, land mosaics are a result of two drivers, geology and culture. As man becomes an evermore powerful geological agent, we have seen a drastic transformation of mosaics from those dictated by natural phenomenon to those shaped by human actions. With pressing issues such as climate change we are beginning to feel the imbalance of these spatial transformations on communities world wide that live upon the mosaics and rely on them for all of life’s necessities. The Po River Delta, ancient and active, is an excellent example of a land mosaic formed by the converging forces of man and geology. It is an exceptionally dynamic waterscape that has been molded a multitude of times by water and man alike. Once a mosaic dominated primarily by rivers, wetlands, lagoons, salt marshes, and dunes, what remains today is a predominantly agrarian landscape with beachside tourist towns lining the coast and sparsely distributed patches of remnants to testify of a forgotten landscape. These patches are a critical stronghold for the native flora and fauna that are becoming more and more rare. The cohesive integration of these elements and subsequent flows, both anthropic and natural, is the key to a cohesive landscape mosaic that is resilient, functional and balanced. Today after centuries of reclamation, channel diversion, dam building and sediment and gas extraction, the Emilia Romagna coast is suffering from battling spatial flows across the landscape. In addition, this stretch of coastline is experiencing an increase in frequency and intensity of storm surges that has the potential to cripple the region's coastal tourism based economy. Lido Degli Estensi is a coastal summer tourism town that has reportedly been dropping in visitorship while facing more coastal flooding. The fragmentation of the inland lagoons and coastal beaches and lack of cohesion in spatial qualities have likely contributed to the decline in their main economic driver. The shifting of flows through the landscape give important insights to what can be done to mitigate these problems on a spatial scale. This proposal looks at the flow of water, sand, people and wildlife to improve a piece of a greater mosaic, Lido Degli Estensi by not only acknowledging changes in flows but by using them as opportunities to improve mosaic dynamics. Given the shifting of flows across and throughout the coastal mosaic, reevaluating how flows are managed to restore balance and improve economies, while integrating valuable habitat and ecosystems

Role of insulin-like growth factor-type 1 receptor (IGF-IR) signalling in tamoxifen-resistant breast cancer

The aim of the first part of this thesis was to determine the role played by IGF-IR in mediating the growth of EGFR-positive tamoxifen-resistant variants of MCF-7 Tam-R and T47D T47D-R breast cancer cell lines. The results identify a general tamoxifen-resistant mechanism whereby the autocrine release and action of IGF-II, mediated through the IGF-IR, plays a significant and crucial supporting role in regulating basal EGFR/MAPK signalling and cell proliferation and this occurs via a c-SRC-dependent mechanism in both Tam-R and T47D-R cells. The latter aim of this thesis was to determine further mechanisms of cross-talk between EGFR and IGF-IR in a range of EGFR-positive cancer cell lines. These studies identified a novel physical interaction between the EGFR and IRS-1 in each of these cell lines. In Tam-R breast and LNCaP prostate cancer cells, recruitment of IRS-1 by EGFR limited the availability of IRS-1 to associate with IGF-IR, thus inhibiting IGF-IR signalling capacity. Blockade of EGFR activity with gefitinib allowed re-association of IRS-1 with IGF-IR and re-establishment of IGF-IR signalling, the dominant growth regulatory mechanism of gefitinib resistance in Tam-R cells. Thus, gefitinib played an active role in limiting its own efficacy in these cells by promoting activation of a resistance pathway. Importantly, induction of this pathway by gefitinib could be abrogated by co-treatment with an IGF-IR inhibitor. Such findings identify the IGF-IR as a potential therapeutic target for the treatment of both tamoxifen-resistant and gefitinib-resistant breast and prostate cancers