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

LPAR2 (lysophosphatidic acid receptor 2)

Review on LPAR2 (lysophosphatidic acid receptor 2), with data on DNA, on the protein encoded, and where the gene is implicated

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