Sulfoxides as an intramolecular sulfenylating agent for indoles and diverse applications of the sulfide-sulfoxide redox cycle in organic chemistry

This dissertation involves study of various aspects of sulfoxide chemistry. Specifically designed t-butyl and propanenitrile sulfoxides tethered to indole-2-carboxamide were used as a source of intramolecular sulfenylating agents to synthesize novel indolo[3,2-b]-1-5-benzothiazepinones which are structurally analogous to the other biologically active benzothiazepinones. This study reveals that the intramolecular cyclization of sulfoxide follows an electrophilic sulfenylation (Sulfoxide Electrophilic Sulfenylation, SES) reaction pathway. Evidence of the absence of sulfenic acid as a transient reactive intermediate in such intramolecular cyclization is also provided. In another study, sulfoxide was used as a “protecting group” of thioether to synthesize 8-membered, indole substituted, thiazocine-2-acetic acid derivative via Ring Closing Metathesis (RCM). Protection (oxidation) of inert (to RCM) sulfide to sulfoxide followed by RCM produced cyclized product in good yields. Deprotection (reduction) of sulfoxide was achieved using Lawessons Reagent (L.R.). Application of the sulfide-sulfoxide redox cycle to solve the existing difficulties in using RCM methodology to thioethers is illustrated. A new design of a “molecular brake”, based on the sulfide-sulfoxide redox cycle is described. N-Ar rotation in simple isoindolines is controlled by the oxidation state of the proximate sulfur atom. Sulfide [S(II)] shows “free” [brake OFF] N-Ar rotation whereas sulfoxide displayed hindered [brake ON] N-Ar rotation. The semi-empirical molecular orbital (PM3) calculations revealed concerted pyramidalization of amidic nitrogen with N-Ar rotation.

Becoming most fully ourselves : gender, voice, and ritual in dissertations

The writing and defense of the dissertation serve both as demonstration one is able to do the work of a scholar and as a rite of initiation. In contrast to much academic writing, dissertations generally adhere to narrowly conceived notions of academic discourse. I explore this within the context of an academic community in which under-representation remains a serious issue. This dissertation is about women writing dissertations. I draw from conversations with fifteen women, in or beyond, the process; friends’ anecdotes; published accounts; and, autobiographically, my experience. I suggest the dissertation’s initiatory role is at least as important as its scholarly role; during the process one establishes a sense of self as scholar, writer, and researcher. Students come to the dissertation with some notion of self as writer and scholar – a culturally negotiated sense that is more, or less, congruent with the culturally established self required for successful completion of the dissertation. The degree of congruence (or alternatively, harmony and dissonance) shapes the process of doing a dissertation. I argue that both the community and the language in which dissertations must generally be written are gendered masculine. Negotiating a voice that is acceptable in a dissertation while maintain fidelity to a sense of who one is seems more problematic as one’s distance from the center of dominant culture increases. Believing that agency lies in altering the reiteration of such processes, I worked with my committee to find ways to alter the process yet still do a dissertation I write in a variety of voices – essay and poetry as well as analytical – play with visual qualities of text, and experiment with non-verbal interpretations. These don’t exhaust possibilities, but do give a sense of how the rich variety of expression found in academe cam be brought into the dissertation. I thus demonstrate that one need not reconstitute herself through characteristic academic discourse in order to be initiated into the community of scholars. I suggest both the desirability of encouraging flexibility in the language, form, and process, of dissertations, and the theoretical necessity for such flexibility if the academic community is to become diverse. The writing and defense of the dissertation serve both as demonstration one is able to do the work of a scholar and as a rite of initiation. In contrast to much academic writing, dissertations generally adhere to narrowly conceived notions of academic discourse. I explore this within the context of an academic community in which under-representation remains a serious issue. This dissertation is about women writing dissertations. I draw from conversations with fifteen women, in or beyond, the process; friends’ anecdotes; published accounts; and, autobiographically, my experience. I suggest the dissertation’s initiatory role is at least as important as its scholarly role; during the process one establishes a sense of self as scholar, writer, and researcher Students come to the dissertation with some notion of self as writer and scholar – a culturally negotiated sense that is more, or less, congruent with the culturally established self required for successful completion of the dissertation. The degree of congruence (or alternatively, harmony and dissonance) shapes the process of doing a dissertation. I argue that both the community and the language in which dissertations must generally be written are gendered masculine. Negotiating a voice that is acceptable in a dissertation while maintain fidelity to a sense of who one is seems more problematic as one’s distance from the center of dominant culture increases. Believing that agency lies in altering the reiteration of such processes, I worked with my committee to find ways to alter the process yet still do a dissertation I write in a variety of voices – essay and poetry as well as analytical – play with visual qualities of text, and experiment with non-verbal interpretations. These don’t exhaust possibilities, but do give a sense of how the rich variety of expression found in academe cam be brought into the dissertation. I thus demonstrate that one need not reconstitute herself through characteristic academic discourse in order to be initiated into the community of scholars. I suggest both the desirability of encouraging flexibility in the language, form, and process, of dissertations, and the theoretical necessity for such flexibility if the academic community is to become diverse. The writing and defense of the dissertation serve both as demonstration one is able to do the work of a scholar and as a rite of initiation. In contrast to much academic writing, dissertations generally adhere to narrowly conceived notions of academic discourse. I explore this within the context of an academic community in which under-representation remains a serious issue. This dissertation is about women writing dissertations. I draw from conversations with fifteen women, in or beyond, the process; friends’ anecdotes; published accounts; and, autobiographically, my experience. I suggest the dissertation’s initiatory role is at least as important as its scholarly role; during the process one establishes a sense of self as scholar, writer, and researcher Students come to the dissertation with some notion of self as writer and scholar – a culturally negotiated sense that is more, or less, congruent with the culturally established self required for successful completion of the dissertation. The degree of congruence (or alternatively, harmony and dissonance) shapes the process of doing a dissertation. I argue that both the community and the language in which dissertations must generally be written are gendered masculine. Negotiating a voice that is acceptable in a dissertation while maintain fidelity to a sense of who one is seems more problematic as one’s distance from the center of dominant culture increases. Believing that agency lies in altering the reiteration of such processes, I worked with my committee to find ways to alter the process yet still do a dissertation I write in a variety of voices – essay and poetry as well as analytical – play with visual qualities of text, and experiment with non-verbal interpretations. These don’t exhaust possibilities, but do give a sense of how the rich variety of expression found in academe cam be brought into the dissertation. I thus demonstrate that one need not reconstitute herself through characteristic academic discourse in order to be initiated into the community of scholars. I suggest both the desirability of encouraging flexibility in the language, form, and process, of dissertations, and the theoretical necessity for such flexibility if the academic community is to become diverse. The writing and defense of the dissertation serve both as demonstration one is able to do the work of a scholar and as a rite of initiation. In contrast to much academic writing, dissertations generally adhere to narrowly conceived notions of academic discourse. I explore this within the context of an academic community in which under-representation remains a serious issue. This dissertation is about women writing dissertations. I draw from conversations with fifteen women, in or beyond, the process; friends’ anecdotes; published accounts; and, autobiographically, my experience. I suggest the dissertation’s initiatory role is at least as important as its scholarly role; during the process one establishes a sense of self as scholar, writer, and researcher Students come to the dissertation with some notion of self as writer and scholar – a culturally negotiated sense that is more, or less, congruent with the culturally established self required for successful completion of the dissertation. The degree of congruence (or alternatively, harmony and dissonance) shapes the process of doing a dissertation. I argue that both the community and the language in which dissertations must generally be written are gendered masculine. Negotiating a voice that is acceptable in a dissertation while maintain fidelity to a sense of who one is seems more problematic as one’s distance from the center of dominant culture increases. Believing that agency lies in altering the reiteration of such processes, I worked with my committee to find ways to alter the process yet still do a dissertation I write in a variety of voices – essay and poetry as well as analytical – play with visual qualities of text, and experiment with non-verbal interpretations. These don’t exhaust possibilities, but do give a sense of how the rich variety of expression found in academe cam be brought into the dissertation. I thus demonstrate that one need not reconstitute herself through characteristic academic discourse in order to be initiated into the community of scholars. I suggest both the desirability of encouraging flexibility in the language, form, and process, of dissertations, and the theoretical necessity for such flexibility if the academic community is to become diverse.

The Diverse Impacts of the Neo-liberal Social Policies on Children’s Welfare and Social Work with Young People: The Finnish Perspective

This article discusses the impacts of globalization, neo-liberal social policies and the Finnish economic recession of the 1990s on children's and young people's welfare. It summarises some of the impacts of Finnish social policies on the everyday lives of families with children and highlights some of the features of the recent and current debates surrounding youth delinquency and the societal reactions to young generations. All this contributes to a contradictory and conflicting societal context which challenges experts in the field of child welfare social work experts to operate - as expected - at the right moment, legally and effectively. Instead of being overly-defensive for the ‘good old’ ways of practicing social work with children, the authors invite social work scholars and practitioners to reconceptualise both the concept of children's citizenship and its position both in child welfare theory and practice in the context of children's global rights.

Book Review of “Indigenous Social Work around the World. Towards Culturally Relevant Education and Practice”, 2008, edited by Mel Gray, John Coates and Michael Yellow Bird

One could be seduced into a critique of this volume that focuses on its potential to overstate the momentum for a shift in Western social work ideology when faced with the conundrum of cultural difference. One could posit that the discussion is too broad, the topics covered too numerous, the opportunity for detail missed, the urgency of the messages unnecessarily exaggerated, the “proof” not beyond anecdote and so forth. I reject this temptation to conform to the dominant professional dynamic most emphatically and offer that what Gray, Coates and Yellow Bird have presented to the social work field in this volume is the first tangible step towards an alternative paradigm for an occupation afflicted with unsustainable hypocrisy and thus at the brink of irrelevancy.

Alarm systems and catastrophes from a diverse point of view

Using a chain of urns, we build a Bayesian nonparametric alarm system to predict catastrophic events, such as epidemics, black outs, etc. Differently from other alarm systems in the literature, our model is constantly updated on the basis of the available information, according to the Bayesian paradigm. The papers contains both theoretical and empirical results. In particular, we test our alarm system on a well-known time series of sunspots.

Tailored instructional methods for students with diverse levels of computer knowledge and skills

The purpose of this online course is to ensure new nursing graduate students know how to use computer technologies required to complete academic and research activities. Powerful computers, high speed internet, digitalized resources and databases are widely available in educational institutes. New renovation and updates are being released at faster pace than ever. All these developments are necessary for a student to utilize computer programs and synthesize large amount of data in a limited time for any given academic research project. [See PDF for complete abstract]

Communication Across Cultures - Use of Video to Promote Culturally Competent Patient Management

Diverse belief systems exist among dental and medical patients related to health, healing and wellness. Culturally competent health care may be defined as the ability to provide care to patients with diverse values, beliefs and behaviors, including modifying delivery of care to meet patients’ social and cultural needs. [See PDF for complete abstract]

Smooth Muscle Hyperplasia due to ACTA2/MYH11 Mutations: Identification of Novel Pathology and Pathways Leading to Aneurysms and Diverse Vascular Occlusive Diseases

Missense mutations in smooth muscle cell (SMC) specific ACTA2 (á-actin) and MYH11 (â-myosin heavy chain) cause diffuse and diverse vascular diseases, including thoracic aortic aneurysms and dissections (TAAD) and early onset coronary artery disease and stroke. The mechanism by which these mutations lead to dilatation of some arteries but occlusion of others is unknown. We hypothesized that the mutations act through two distinct mechanisms to cause varied vascular diseases: a loss of function, leading to decreased SMC contraction and aneurysms, and a gain of function, leading to increased SMC proliferation and occlusive disease. To test this hypothesis, ACTA2 mutant SMCs and myofibroblasts were assessed and found to not form á-actin filaments whereas control cells did, suggesting a dominant negative effect of ACTA2 mutations on filament formation. A loss of á-actin filaments would be predicted to cause decreased SMC contractility. Histological examination of vascular tissues from patients revealed SMC hyperplasia leading to arterial stenosis and occlusion, supporting a gain of function associated with the mutant gene. Furthermore, ACTA2 mutant SMCs and myofibroblasts proliferated more rapidly in static culture than control cells (p<0.05). We also determined that Acta2-/- mice have ascending aortic aneurysms. Histological examination revealed aortic medial SMC hyperplasia, but minimal features of medial degeneration. Acta2-/- SMCs proliferated more rapidly in culture than wildtype (p<0.05), and microarray analysis of Acta2-/- SMCs revealed increased expression of Actg2, 15 collagen genes, and multiple focal adhesion genes. Acta2-/- SMCs showed altered localization of vinculin and zyxin and increased phosphorylated focal adhesion kinase (FAK) in focal adhesions. A specific FAK inhibitor decreased Acta2-/- SMC proliferation to levels equal to wildtype SMCs (p<0.05), suggesting that FAK activation leads to the increased proliferation. We have described a unique pathology associated with ACTA2 and MYH11 mutations, as well as an aneurysm phenotype in Acta2-/- mice. Additionally, we identified a novel pathogenic pathway for vascular occlusive disease due to loss of SMC contractile filaments, alterations in focal adhesions, and activation of FAK signaling in SMCs with ACTA2 mutations.

Adherence to host extracellular matrix and serum components by Enterococcus faecium isolates of diverse origin.

Enterococcus faecium has emerged as an important cause of nosocomial infections over the last two decades. We recently demonstrated collagen type I (CI) as a common adherence target for some E. faecium isolates and a significant correlation was found to exist between acm-mediated CI adherence and clinical origin. Here, we evaluated 60 diverse E. faecium isolates for their adherence to up to 15 immobilized host extracellular matrix and serum components. Adherence phenotypes were most commonly observed to fibronectin (Fn) (20% of the 60 isolates), fibrinogen (17%) and laminin (Ln) (13%), while only one or two of the isolates adhered to collagen type V (CV), transferrin or lactoferrin and none to the other host components tested. Adherence to Fn and Ln was almost exclusively restricted to clinical isolates, especially the endocarditis-enriched nosocomial genogroup clonal complex 17 (CC17). Thus, the ability to adhere to Fn and Ln, in addition to CI, may have contributed to the emergence and adaptation of E. faecium, in particular CC17, as a nosocomial pathogen.

Evaluating the relative status of health and safety programs for minority academic and research institutions

A variety of occupational hazards are indigenous to academic and research institutions, ranging from traditional life safety concerns, such as fire safety and fall protection, to specialized occupational hygiene issues such as exposure to carcinogenic chemicals, radiation sources, and infectious microorganisms. Institutional health and safety programs are constantly challenged to establish and maintain adequate protective measures for this wide array of hazards. A unique subset of academic and research institutions are classified as historically Black universities which provide educational opportunities primarily to minority populations. State funded minority schools receive less resources than their non-minority counterparts, resulting in a reduced ability to provide certain programs and services. Comprehensive health and safety services for these institutions may be one of the services compromised, resulting in uncontrolled exposures to various workplace hazards. Such a result would also be contrary to the national health status objectives to improve preventive health care measures for minority populations.^ To determine if differences exist, a cross-sectional survey was performed to evaluate the relative status of health and safety programs present within minority and non-minority state-funded academic and research institutions. Data were obtained from direct mail questionnaires, supplemented by data from publicly available sources. Parameters for comparison included reported numbers of full and part-time health and safety staff, reported OSHA 200 log (or equivalent) values, and reported workers compensation experience modifiers. The relative impact of institutional minority status, institution size, and OSHA regulatory environment, was also assessed. Additional health and safety program descriptors were solicited in an attempt to develop a preliminary profile of the hazards present in this unique work setting.^ Survey forms were distributed to 24 minority and 51 non-minority institutions. A total of 72% of the questionnaires were returned, with 58% of the minority and 78% of the non-minority institutions participating. The mean number of reported full-time health and safety staff for the responding minority institutions was determined to be 1.14, compared to 3.12 for the responding non-minority institutions. Data distribution variances were stabilized using log-normal transformations, and although subsequent analysis indicated statistically significant differences, the differences were found to be predicted by institution size only, and not by minority status or OSHA regulatory environment. Similar results were noted for estimated full-time equivalent health and safety staffing levels. Significant differences were not noted between reported OSHA 200 log (or equivalent) data, and a lack of information provided on workers compensation experience modifiers prevented comparisons on insurance premium expenditures. Other health and safety program descriptive information obtained served to validate the study's presupposition that the inclusion criteria would encompass those organizations with occupational risks from all four major hazard categories. Worker medical surveillance programs appeared to exist at most institutions, but the specific tests completed were not readily identifiable.^ The results of this study serve as a preliminary description of the health and safety programs for a unique set of workplaces have not been previously investigated. Numerous opportunities for further research are noted, including efforts to quantify the relative amount of each hazard present, the further definition of the programs reported to be in place, determination of other means to measure health outcomes on campuses, and comparisons among other culturally diverse workplaces. ^

Culturally sensitive cancer education: Effect on knowledge, cancer fatalism, and participation in mobile mammography screening among African-American women

Purpose. To evaluate the effectiveness of a culturally sensitive educational intervention that used an African American lay survivor of breast cancer to increase knowledge of breast cancer, decrease cancer fatalism, and increase participation in mobile mammography screening among African American women. ^ Design. Experimental pretest/posttest design. ^ Setting. Two predominantly African American churches in a large southwestern metropolitan city. ^ Sample. Participants included 93 African American women, 40 years of age and older. Participants were randomly assigned to an intervention group (n = 48) or a control group (n = 45). ^ Methods. Pretest and post-test measures included the Breast Cancer Knowledge Test and the Powe Fatalism Inventory. In addition, demographic and breast screening practices were collected by questionnaire. The intervention group received a breast cancer educational testimonial from an African American lay survivor of breast cancer, who answered questions and addressed concerns, while stressing the importance of taking responsibility for one's own health and spreading disease prevention messages throughout the African American community. The control group viewed the American Cancer Society “Keep In Touch” video prepared specifically for African American women. Participants in both groups were given culturally sensitive educational materials designed to increase knowledge about breast cancer, and were instructed on breast self-examination by an African American registered nurse, using ethnically appropriate breast models. In addition, after the post-test, all eligible participants were given an opportunity to have a free mammogram via a mobile mammography unit parked at the church. ^ Findings. Participants in the intervention group had a significant increase (p = .03) in knowledge of breast cancer and a significant decrease (p = .000) in fatalism scores compared to those individuals in the control group. The intervention group had a 61% participation rate in screening, while the control group had a 39% participation rate in screening. However, the difference was not statistically significant at the .05 level (p = .07). ^ Conclusions. Results demonstrate that culturally sensitive breast cancer education is successful in increasing knowledge and decreasing cancer fatalism. While there was a trend toward behavior change in the intervention group, more research needs to be done in this area. ^

User Created Content in Virtual Worlds and Cultural Diversity

User created content (UCC) has often been celebrated as a grassroots cultural revolution that as a genuine expression of creativity, localism and non-commercialism can arguably also cater for a sustainable culturally diverse environment. The present article puts these claims under scrutiny and in a more differentiated manner seeks to identify the value of UCC within digital game environments considering the constraints upon players and upon creative play that these impose. The article subsequently tests whether UCC in its dynamic sense of a creative and communicative process can be seen as a channel for the promotion of cultural diversity and if so, what the State should (and could) do about this.

Growth and Persistence of Diverse Intertidal Crusts: Survival of the Slow in a Fast-Paced World

Encrusting algae are conspicuous components of hard-substratum benthic communities in the photic zone despite being poor competitors and slow growers. Little is known about their growth rates or about mechanisms controlling key processes such as wound healing and surviving overgrowth. We manipulated 12 crustose species (including red and brown algae and a lichen) from the intertidal zone of Washington, USA, studying their varying responses to identical experimental conditions. Three of 8 crust species tested showed increased growth rates with size. Species healed from standardized wounds at different rates and using different mechanisms (e.g. lateral vs vertical regeneration) as seen in cross-sections. Three species showed altered growth rates at unwounded margins of wounded crusts, suggesting intrathallus communication. Year-long experiments involving simulated overgrowth showed that some species can maintain healthy tissue in a covered area, and one (the coralline Lithothamnion phymatodeum) even grew new tissue there. Other species gradually lost color, thickness, and area in covered areas. Hildenbrandia occidentalis survived remarkably well when covered, possibly due to its very slow growth and low metabolic demand. One suggested mechanism underlying the high variation in responses among crusts is the degree to which their thalli may be anatomically integrated by features such as cell fusions; physiological work testing translocation via these features is needed. Other mechanisms allowing persistence include rapid wound healing and frequent recruitment.

SNPs for parentage testing and traceability in globally diverse breeds of sheep

DNA-based parentage determination accelerates genetic improvement in sheep by increasing pedigree accuracy. Single nucleotide polymorphism (SNP) markers can be used for determining parentage and to provide unique molecular identifiers for tracing sheep products to their source. However, the utility of a particular "parentage SNP" varies by breed depending on its minor allele frequency (MAF) and its sequence context. Our aims were to identify parentage SNPs with exceptional qualities for use in globally diverse breeds and to develop a subset for use in North American sheep. Starting with genotypes from 2,915 sheep and 74 breed groups provided by the International Sheep Genomics Consortium (ISGC), we analyzed 47,693 autosomal SNPs by multiple criteria and selected 163 with desirable properties for parentage testing. On average, each of the 163 SNPs was highly informative (MAF≥0.3) in 48±5 breed groups. Nearby polymorphisms that could otherwise confound genetic testing were identified by whole genome and Sanger sequencing of 166 sheep from 54 breed groups. A genetic test with 109 of the 163 parentage SNPs was developed for matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry. The scoring rates and accuracies for these 109 SNPs were greater than 99% in a panel of North American sheep. In a blinded set of 96 families (sire, dam, and non-identical twin lambs), each parent of every lamb was identified without using the other parent's genotype. In 74 ISGC breed groups, the median estimates for probability of a coincidental match between two animals (PI), and the fraction of potential adults excluded from parentage (PE) were 1.1×10(-39) and 0.999987, respectively, for the 109 SNPs combined. The availability of a well-characterized set of 163 parentage SNPs facilitates the development of high-throughput genetic technologies for implementing accurate and economical parentage testing and traceability in many of the world's sheep breeds.