Concerted HO2 elimination from alpha-Aminoalkylperoxyl free radicals : Experimental and theoretical evidence from the gas phase NH2 center dot CHCO2- + O-2 reaction

We have investigated the gas-phase reaction of the alpha-aminoacetate (glycyl) radical anion (NH2(sic)CHCO2-) with O-2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O-2 to form the hydroperoxyl radical (HO2(sic)) and an even-electron imine (NHCHCO2-), with experiments and master equation simulations revealing that reaction proceeds at the ion molecule collision rate. This reaction is facilitated by a low-energy concerted HO2(sic) elimination mechanism in the NH2CH(OO(sic))CO2- peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus alpha-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of (sic)NO to (sic)NO2 commonly encountered in peroxyl radical chemistry.

Direct observation of the gas phase reaction of the cyclohexyl radical with dioxygen using a distonic radical ion approach

Alkylperoxyl radicals are intermediates in the oxidation Of hydrocarbons. The reactive nature of these intermediates, however, has made therin elusive to direct observation and isolation. We have employed ion trap mass spectrometry to synthesize and characterize 4-carboxylatocyclohexyl radical anions ((center dot)C(6)H(10)-CO(2)(-)) and observe their reactivity in the presence of dioxygen. The resulting reaction is facile (k = 1.8 x 10(-10) cm(3) molecule(-1) s(-1) or 30% of calculated collision rate) and results in (i) the addition Of O(2) to form stabilized 4-carboxylatocyclohexylperoxyl radical anions ((center dot)OO-C(6)H(10)-CO(2)(-)), providing the first direct observation of a cyclohexylperoxyl radical, and (ii) elimination of HO(2)(center dot) and HO(center dot) radicals consistent with recent laser-induced fluorescence studies of the reaction of neutral cyclohexyl radicals with O(2). Electronic structure calculations at the B3LYP/6-31+G(d) level of theory reveal viable pathways for the observed reactions showing that formation of the peroxyl radical is exothermic by 37 kcal mol(-1) with subsequent transition states its low as -6.6 kcal mol(-1) (formation of HO(2)(center dot)) and -9.1 kcal mol(-1) (formation of HO(center dot)) with respect to the entrance channel. The combined computational and experimental data Suggest that the structures of the reaction products correspond to cyclohexenes and epoxides from HO(2)(center dot) and HO(center dot) loss, respectively, while alternative pathways leading to cyclohexanone or ring-opened isomers ate not observed, Activation of the charged peroxyl radical (center dot)OO-C(6)H(10)-CO(2)(-) by collision induced disassociation also results in the loss Of HO(2)(center dot) and HO(center dot) radicals confirming that these products are directly connected to the peroxyl radical intermediate.

Children's perspectives on values and rules in Australian early education

In recent years, issues relating to moral and conventional values have been emphasized in educational policies. This study examines young children’s (100 children aged 4–8 years) own understandings of values and rules for how to treat others and participate in school. Eleven classrooms, within seven different elementary schools in Queensland, were visited. Children were interviewed regarding their views about moral and conventional issues, rules and participation in everyday school life. According to the children, ‘doing the right thing’ in school involved both a concern for others’ wellbeing and for the social order in school, including conventions, rules and behaviour connected with discipline. The children’s responsibility seemed, however, to be to adapt to the (school) system, rather than being an active participant in constructing the system.

Issues in Learning and Education for the Ageing

The population is ageing worldwide. This chapter is a discussion of issues in ageing, the importance of learning and education for the elderly, and then the more specific issues of why, how and what elders want to learn.

Teaching for quality learning at university

by J. Biggs and C. Tang, Maidenhead, England, Open University Press, 2007, 360 pp., £29.99, ISBN-13: 978-0-335-22126-4

Ageing in Fiji : how older teachers perceive ageing and their lives

Worldwide the population is ageing and data concerning how people want to age actively is limited. The paper is a description of an inductive interpretive-descriptive study of how a sample of older retired teachers in Fiji viewed ageing and their lives as older people. The objectives were to determine and describe perceptions of ageing held by a sample of retired teachers. The methodology consisted of responses to an open ended questionnaire similar to a phenomenographic approach and the analysis was interpretive – descriptive. A purposive sample of 30 retired teachers between the ages of 55 and 60 responded to the questionnaire. The results indicate that most of the respondents were positive about lifelong learning and in particular learning new things; that they were involved in a range of post retirement activities for personal and financial reasons; that there were some barriers and facilitators to their activities; that they generally accepted ageing and being older; and that more should be done by Government and other agencies to provide for a better life for older people in Fiji. These results should be considered in future planning for ageing populations in Fiji, the Pacific region and in other developing countries.

Aboriginal and Torres Strait Islander university students conceptions of formal learning and experiences of informal learning

This paper describes an investigation of conceptions of learning held by 22 Aboriginal and Torres Strait Islander students from three universities in Queensland, Australia. Other areas investigated were students' experiences of informal learning, their reasons for studying and the strategies they used to learn. Research into conceptions of learning is gaining impetus and current beliefs include the premise that approaches to learning adopted by university students, and hence learning outcomes, are closely related to their conceptions of learning. There is substantial research focused on Aboriginal learning styles in early childhood and primary school which indicates that Aboriginal children prefer to learn in a practical way as well as through observation and imitation and trial and error. Very little research has focused specifically on Aboriginal university students' conceptions of learning. Results of this study found that these students view and approach formal university learning in much the same way as other university students and most hold quantitative conceptions of learning. The most interesting result was the difference between students' conceptions of formal learning and their experiences of informal learning. Many students' experiences of informal learning were grounded in practical activities or exhibited a cultural focus, however, most formal learning is not dependent upon practical or cultural knowledge. It is proposed that formal learning for Indigenous students recognise and include an Indigenous perspective such as integrating, where appropriate, practical strategies for learning. We also suggest that Indigenous students be helped to develop conceptions that will enable them to learn formal, theoretical material successfully.

Conceptions of learning held by Aboriginal students in a tertiary program in Indigenous primary health care

This paper is a description of a pilot investigation into conceptions of learning held by a sample of 10 Aboriginal students in a Bachelors degree courses. Results from this study suggest that this group of students view and approach learning in much the same way as other university students. They mostly hold quantitative conceptions of learning and use repetitive strategies which are potentially at odds with the objectives and procedures of the problems based program in which they are studying.

Learning in and out of university : Aboriginal and Torres Strait Islander students’ conceptions and strategies used to learn

Research suggests that students’ approaches to learning and learning outcomes are closely related to their conceptions of learning. This paper describes a phenomenographically inspired investigation into conceptions of formal learning held by 22 Aboriginal and Torres Strait Islander students from three Australian universities in Queensland; experiences of informal learning, reasons for studying and strategies used to learn were also investigated. The attrition rate for these students in tertiary education is higher than that of any other group of students. It was hoped that information gained may delineate factors that contribute to high attrition rates and therefore inform courses of action that may lead to improved teaching and learning practices for these students. Additionally, success in tertiary education for Aboriginal and Torres Strait Islander students may increase their involvement in mainstream society. Results showed that they view and approach university learning in much the same way as other university students. It was also apparent that, generally, the strategies these students used did not match the conceptions of learning they held. An interesting result was the difference between the conceptions of formal learning and explanations of informal learning

Learning in formal and informal contexts : conceptions and strategies of Aboriginal and Torres Strait Islander university students

Research suggests that students' approaches to learning and hence learning outcomes are closely related to their conceptions of learning. This paper describes an investigation into conceptions of formal learning held by 22 Aboriginal and Torres Strait Islander students from three Australian universities in Queensland; categories of informal learning, reasons for studying and strategies used to learn were also investigated. The attrition rate for these students in tertiary education is higher than that of any other group of students. The main aim of this study was to determine their conceptions of learning in order to provide information that might facilitate instruction more suited to their needs in order to address the high attrition rate. Results showed that these students view and approach university learning in much the same way as other university students. It was also apparent that, for the most part, the strategies these students used did not match the conceptions of learning they held. An interesting result was the difference between the conceptions of formal learning and perceptions of informal learning.

On the operationalisation of conceptions of learning in higher education and their association with students’ knowledge and experiences of their learning

Conceptions of learning, as well as other associated aspects of prior knowledge, are theoretically important factors in influencing the manner in which the content and context of learning are engaged. The present study reports on: (a) the operationalisation of some of these factors aimed at isolating sources of explanatory variation that can be used for modelling purposes; and (b) a conservative exploration of the discriminatory power of, and exhibited patterns of association between, such sources of variation as have been isolated. Based on a conservative analytical approach, the results of the present study do not support a single clearly defined empirical model of conceptions of learning and associated constructs. Instead, there is consistent evidence that underlying empirical structures appear to be sensitive to the response context and other factors.

The SOLO Taxonomy as a means of shaping and assessing learning in higher education

This paper is a discussion of the use of the SOLO (Structure of Observed Learning Outcomes) Taxonomy (Biggs & Collis, 1982, 1989; Biggs, 1991, 1992a, 1992b; Boulton‐Lewis, 1992, 1994) as a means of developing and assessing higher order thinking in Higher Education. It includes a summary of the research into its use to date as an instrument to find out what students know and believe about their own learning, to assess entering knowledge in a discipline, to present examples of structural organization of knowledge in a discipline, to provide models of levels of desired learning outcomes, and in particular to assess learning outcomes. A proposal is made for further research.