Applications of dihydroarenediols to chemoenzymatic synthesis : approaches to total synthesis of morphine alkaloids

The present studies describe, as a primary goal, our recent progess toward the synthesis of morphine alkaloids from aromatic precursors. Model substrates were synthesized which allowed investigation into Diels-Alder, radical cascade, and palladium-catalyzed bond-forming reactions as possible routes to the morphine alkaloid skeleton. As a secondary objective, three separate series of aromatic substrates were subjected to whole-cell oxidation with Escherichia coli JM 109 (pDTG601), a recombinant organism over-expressing the enzyme toluene dioxygenase. Included in this study were bromothioanisoles, dibromobenzenes, and cyclopropylbenzene derivatives. The products of oxidation were characterized by chemical conversion to known intermediates. The synthetic utility of one of these bacterial metabolites, derived from oxidation of o-dibromobenezene, was demonstrated by chemical conversion to (-)conduritol E.

An exploratory descriptive study of factors influencing students to seek or not to seek personal counselling on a college of applied arts and technology campus located in Southern Ontario /

This descriptive-exploratory study examined factors which were perceived by students at a College of Applied Arts and Technology (CAAT) campus as influencing them in choosing to come or not to come for personal counselling and why they would or would not retum. A total of 250 students selected through a sample of convenience were surveyed. A questionnaire survey was conducted with quantitative data collected using a 4-point, forced-choice Likert scale and yes/no questions and qualitative data collected using open-ended questions and invited comments. The responses were analyzed using means and modes for the Likert responses and percentages for the yes/no and check-off questions. The narrative responses were subjected to content analysis to identify themes. The mean score findings on factors influencing students to come for personal counselling were at or close to the mid- point of 2.5. Personal distress was the only variable found to have a negative response, meaning students would not come to counselling if they were in personal distress. On factors that would keep them from choosing to come to counselling, students seemed to trust counsellors and feel accepted by them and rejected the notion that peer pressure or the first session being unhelpful would keep them away from counselling. The counsellor's relationship with the student is the major determinant for repeat sessions. When asked what factors would influence students to not retum for personal counselling, students rejected the variables of peer pressure, the extra time needed for counselling, and not getting what they wanted in a session, but, in one instance, indicated that variables regarding the counselling relationship would keep them from returning.

NMR studies of strong hydrogen bond to fluoride ion

Systems such as MF/diol (M = alkali metal) and }1F/carboxylic acid were subjected to IH, I9F and 13C nmr study to investigate the nature of the very strong H-bonding of fluoride ions with these systems. Evidence indicates a strong H-bond in diol-fluoride systems (~H ~ -(56) kJ mol-I) which is stronger than most 'typical' H-bonds (~H = -(12-40) kJ mol-I), but weaker than that reported for carboxylic acid-fluoride systems (~H ~ -(120) kJ mol-I). Approximate fluoride H-bonded shifts (o(OH)OHF) were evaluated for MF/diol systems from IH chemical shift measurements. No direct correlation was observed between I9F chemical shift and H-bond strength. Thermodynamic parameters were calculated from temperature dependent IH and 19F shifts. Preliminary studies of BUn 4NF-acetylacetone by I9F nmr were conducted at low temperatures and a possible Jmax (ca. 400 Hz) is reported for the fluoride ion H-bonded to acetylacetone. Highfield shift for non-protonated carbons and downfield shift for protonated carbons were observed in carboxylic acid/KF systems. Significant decreas$in I3C TI due to strong H-bonding to fluoride ions were also detected in both diol and carboxylic acid systems. Anomalous results were obtained, such as increasing NOE with increasing temperature in neat 1,2-ethanediol (values above the theoretical maximum of 1.988) and in 1,2-ethanediol/KF. The large 13C NOE's for carboxy carbons in neat carboxylic acids which are. further enhanced by the addition of KF are also unusual.

Retrospective Exploration of the 3Rs Education Program: Systemic Facilitators and Barriers to Implementation

Individuals with intellectual disabilities (ID) have historically been denied basic rights and thus have been subjected to abuse. The 3Rs: Rights, Respect and Responsibility Human Rights Education Program was implemented and researched through a partnership with Community Living Welland Pelham and Brock University initially and then cascade training on the program was provided to five developmental service sector agencies from across the Niagara Region. This research evaluated the role of the 3Rs education program on the shift to a rights-based service agenda across those five agencies. Interviews were conducted with the Executive Director and Liaison staff from each of the agencies and a thematic analysis was used to describe factors that facilitated organizational changes and a cultural shift. Systemic barriers to the change were also explored. The results indicated that the 3Rs education program provides the catalyst necessary for the shift to a rights-based service agenda and that the resultant changes in practices now embedded in the organizations are reflective of a shift to a rights-based service agenda.