Diels-Alder Approaches Towards T-2 Toxin and Related Trichothecenes

The trichothecenes are a group of some 80 structurally complex sesquiterpenoids of considerable environmental importance. It is difficult to obtain many of these compounds in significant amounts from natural sources, and much effort has been directed towards devising efficient, practicable syntheses of these molecules and their analogues. In the course of this research, a study of intermolecular Diels-Alder routes towards potential trichothecene precursors was carried out. Particular attention was paid to devising a general route towards T2 toxin (185), a highly oxygenated trichothecene which has yet to yield to total synthesis. To this end the cycloaddition reaction between a suitably functionalised 1,3-butadiene and an alkyl coumalate was investigated. Two major areas of study were undertaken: the Diels-Alder reaction between isoprene and a coumalic acid derivative and the cycloaddition reaction between a 2-silyloxy-substituted buta-1,3-diene and methyl coumalate. The Diels-Alder reaction between isoprene and methyl coumalate suffered from poor regioselectivity and afforded low yields of the desired adduct (157a). Significant improvements in both the regioselectivity and yield of desired adduct were obtained when coumalyl chloride (191) was employed as dienophile. Seleno- and iodolactonisation of carboxylic acid (186a) derived from adduct (157a) afforded the unexpected bicyclo [2.2.2] octane systems (192) and (195) respectively, neither of which could be converted into useful trichothecene precursors. Alternatively, bromination of the conjugate addition product (158), followed by a sequence of acetolysis and hydrolysis, furnished a 1:1 mixture of alpha-allylic alcohol (200a) and beta-allylic alcohol (200b). alpha-Allylic alcohol (200a) possesses ideal functionality for further elaboration to T2 toxin, and was accordingly converted into the corresponding gamma-lactone (203), thereby establishing the desired a-configuration of the 8-hydroxyl group. Catalytic osmylation of the conjugate addition product (158) afforded cis diol (205a) as the major product, which after a sequence of silylation, dehydration and finally fluoride-induced desilylation was transformed into the same alpha-allylic alcohol (200a)'. Cycloaddition between 2-silyloxy-substituted buta-1,3-dienes and methyl coumalate was observed to be a highly regiospecific process, affording the expected silyl enol ethers in respectable yields. In an attempt to prepare alpha-bromoketone (228) it was observed that the product obtained from bromination of the t-butyldimethylsilyl enol ether (218a) depended upon the reaction conditions employed. In the absence of pyridine the expected alpha-bromoketone was obtained. Interestingly, however, in the presence of pyridine the alpha-bromo silyl enol ether (231) was formed regioselectively

The Synergistic Leadership Theory: Contextualizing Multiple Realities of Female Leaders

The authors describe the Synergistic Leadership Theory (SLT), which includes four factors: Leadership Behavior, Organizational Structure, External Factors, and Beliefs, Attitudes, and Values. The factors are described and contributions to existing leadership theory are explained. They further apply the factors to four cases in order to illustrate the application of the theory to leadership practice. The authors conclude that SLT, in including the female perspective, provides an expanded framework for taking a macro-perspective of the interactions among beliefs, external forces, people, and organizations

The Synergistic Leadership Theory: Contextualizing Multiple Realities of Female Leaders

The authors describe the Synergistic Leadership Theory (SLT), which includes four factors: Leadership Behavior, Organizational Structure, External Factors, and Beliefs, Attitudes, and Values. The factors are described and contributions to existing leadership theory are explained. They further apply the factors to four cases in order to illustrate the application of the theory to leadership practice. The authors conclude that SLT, in including the female perspective, provides an expanded framework for taking a macro-perspective of the interactions among beliefs, external forces, people, and organizations

A survey of attitudes of agricultural society leaders toward leadership development education

It was the purpose of this study to investigate attitudes toward leadership development education of one client group served by the ontario Ministry of Agriculture and Food. The survey, answered by 175 participants, attempted to answer the following questions: (a) What is a common definition of leadership?, (b) What leadership concepts are important to leadership development education? and, (c) What are client attitudes toward leadership development education? A descriptive research approach was used and the data were analyzed according to a model developed by Colaizzi. Concept maps were developed under the broad areas of: (a) Developing leader qualities; (b) Past experiences that developed leadership skills that worked on the jOb; (c) Leadership skills developed from present day positions; and (d) How leadership skills may be developed in future situations. A description of the dynamics of leadership development was written and the essential dynamics of leadership skill development in one volunteer organization was described. This study supports the linkages perspective of leadership within voluntary organizations developed by Vandenberg, Thullen and Fear (1987). The linkages perspective consists of three major components: perception, property and process. As a perception, leadership is the set of beliefs each group member holds regarding the behaviours and qualities characteristic of effective leaders. As a property, leadership represents the qualities attributed by group members to persons perceived as effectively (or potentially) influencing the goal achievement process. As a process, leadership involves the use of non-coercive influence to facilitate group accomplishment of valued goals. Leadership concepts important for development in a leadership development education program related to personal, organizational and societal development. The top five concepts in terms of rank order are communicating effectively, forming and working with groups, working creatively (tie), developing followers, managing meetings, directing projects or activities, understanding financial matters, managing negotiations (tie), developing resources and understanding and developing oneself (tie). Several recommendations are relevant for extension personnel as educators. Theoretical concepts on leadership need to be shared to extension practitioners involved in leadership development. currently used teaching materials for leadership development should be evaluated to see if they include concepts from preferrred theoretical leadership perceptions

The neural and social correlates of automatic behaviours

The research in this thesis will focus primarily on the role motor cortex excitability has on social and non-social action behaviours, and in particular behaviours relating to; echophenomena, motor action, contagious behaviours, impulsivity, and action imitation. Inhibition and facilitation, specifically in relation to contagious behaviours, imitation, and impulsivity, will be explored to a greater extent in order to further understanding on how these might be altered in neurodevelopmental conditions. Initial studies chapter 3 to 5 investigated contagious yawning, a form of imitative behaviour related to echophenomena, in typically developed controls (TDC). Echophenomena is related to early social cognition and is altered in some neurodevelopmental conditions such as Autism spectrum disorders and Gilles de la Tourette’s syndrome. The first study was a within subjects’ design that utilised both physiological (TMS) measures of cortical activity alongside behavioural measures of contagious yawning. Subsequent studies were both within and between subjects’ designs and sought to modulate motor cortex excitability during both automatic social and non-social behaviours. These same neurophysiological techniques were then used to explore the relationship between corticospinal excitability and impulsive behaviours. Measures of impulsivity were assessed using modified ‘traffic light’ behavioural paradigms

A spectral study of a radio-frequency plasma-generated flux of atomic oxygen

The active environment of a radio-frequency (RF) plasma generator, with and without low-pressure oxygen, has been characterized through the identification of emission lines in the spectral region from 250 to 900 nm. The environment is shown to be dependent on the partial pressure of oxygen and the power applied to the RF generator. Atomic oxygen has been found in significant amounts as well as atomic hydrogen and the molecular oxygen species O2((sup 1)Sigma). The only charged species observed was the singly charged molecular ion O2(+). With a polymer specimen in the plasma chamber, carbon monoxide was also observed. The significance of these observations with respect to previous studies using this type of generator to stimulate material degradation in space is discussed. The possibility of using these generators as atomic oxygen sources in the development of oxygen atom fluorescence sensors is explored

Confidentiality as a group norm and its concomitant effect on self-disclosures by participants in personal growth groups

Confidentiality as a group norm and how it affected self-disclosures in personal growth groups were compared between control and treated groups. The sample consisted of 53 students enrolled in a graduate level group counseling course. The students were randomly assigned to six groups: three control and three experimental groups. Each group had two facilitators. The groups all met in the same place, at the same time and observed the same protocols. The process group model was followed. This study had four hypotheses and three main objectives: first, to determine what effect establishing confidentiality as a norm had on a participant's self-disclosures, second, to determine if the group members believed that the norm of confidentiality would be breached by either the group facilitators or the group members; and, finally, to examine the attitudes and opinions of control and treated group members towards the belief that confidentiality as a group norm would promote more self-disclosures in personal growth groups. The qualitative and quantative data revealed that confidentiality as a norm did not produce significantly greater self-disclosures. Group members generally believed that confidentiality among members would be observed and members had a high belief that their group facilitators would not violate their stated ethical standards. There was no significant difference between control and treated groups in their belief that confidentiality as a norm was important for self-disclosures to occur

Developing and Assessing the Validity of a Scale to Assess Pet Dog Quality of Life: Lincoln P-QoL

There has been little investment in exploring the impact of the child-dog relationship on the dog. Since child-dog interactions can pose potentially serious threats to a dog’s physical and psychological health, as well as the wider satisfaction of the owner with their dog, we describe the development and validation of an owner-completed pet dog quality of life scale (Lincoln P-QOL), to enable professionals and families to monitor dog wellbeing and employ suitable interventions as required. Four-hundred and two dog-owners (194 lived with a neuro-typically developing child; 208 lived with a child with a neuro-developmental disorder) responded to an online survey. Respondents recorded whether they had observed their dog displaying any of the 22 behavioural responses which have been identified as being common in 11 child-dog interactions. These behavioural responses appeared to group into three categories of behaviours (i.e. behavioural constructs), representing Excitability, Calmness and Fearfulness in the dog. To assess convergent validity of the quality of life scale respondents completed additional measures including, dog body condition score, health issues (incorporating psychological factors such as anxiety and physical proxies of wellbeing, such as skin irritations) and dog-owner relationship satisfaction. Excitability and Fearfulness constructs were associated with a negative impact on dog health and the owner-dog relationship. Calmness was associated with a positive impact on the dog-owner relationship. A range of interactions, including carefully expressed child-dog physical affection and spending quiet time together appear to had a beneficial impact on dog quality of life, whereas rough contact, child meltdowns and grooming/bathing had a negative effect. We found little evidence to support a difference in the overall quality of life of dogs living with neuro-typically developing children compared to those with a neuro-developmental disorder. However, parents and practitioners need to be aware of the potential increased risk to dog wellbeing when meltdowns, grooming/bathing and quiet time involve a child with a neuro-developmental disorder. This is the first validated scale for the assessment of dog wellbeing around children, additionally, the behavioural constructs identified may form the rational basis of a more general dog behaviour/stress assessment tool in social situations

A systematic review evaluating the implementation of technologies to assess, monitor and treat neurodevelopmental disorders: A map of the current evidence

Technology-based interventions provide an attractive option for improving service provision for neurodevelopmental disorders (NDD), for example, widening access to interventions, objective assessment, and monitoring; however, it is unclear whether there is sufficient evidence to support their use in clinical settings. This review provides an evidence map describing how technology is implemented in the assessment/diagnosis and monitoring/ treatment of NDD (Prospero CRD42018091156). Using predefined search terms in six databases, 7982 articles were identified, 808 full-texts were screened, resulting in 47 included papers. These studies were appraised and synthesised according to the following outcomes of interest: effectiveness (clinical effectiveness/ service delivery efficiencies), economic impact, and user impact (acceptability/ feasibility). The findings describe how technology is currently being utilised clinically, highlights gaps in knowledge, and discusses future research needs. Technology has been used to facilitate assessment and treatment across multiple NDD, especially Autism Spectrum (ASD) and attention-deficit/hyperactivity (ADHD) disorders. Technologies include mobile apps/tablets, robots, gaming, computerised tests, videos, and virtual reality. The outcomes presented largely focus on the clinical effectiveness of the technology, with approximately half the papers demonstrating some degree of effectiveness, however, the methodological quality of many studies is limited. Further research should focus on randomised controlled trial designs with longer follow-up periods, incorporating an economic evaluation, as well as qualitative studies including process evaluations and user impact