Adenine as an organocatalyst for the ring-opening polymerization of lactide: scope, mechanism and access to adenine-functionalized polylactide

Nucleobase-functionalized polymers are widely used in the fields of supramolecular chemistry and self-assembly, and their development for biomedical applications is also an area of interest. They are usually synthesized by tedious multistep procedures. In this study, we assess adenine as an organoinitiator/ organocatalyst for the ring-opening polymerization of lactide. L-Lactide can be quantitatively polymerized in the presence of adenine. Reaction conditions involving short reaction times and relatively low temperatures enable the access to adenine end-capped polylactide in a simple one-step procedure, in bulk, without additional catalyst. DFT calculations show that the polymerization occurs via hydrogen bond catalysis. The mechanism involves (i) a hydrogen bond between the NH9 of adenine and the carbonyl moiety of lactide, leading to an electron deficient carbon atom, and (ii) a second hydrogen bond between the N3 of adenine and the NH2 of a second adenine molecule, followed by a nucleophilic attack of the latter activated amine on the former electron deficient carbon on the monomer. For longer reaction times and higher temperatures, macrocyclic species are formed, and a mechanism involving the imidazole ring of adenine is proposed based on literature studies. Depending on the reaction conditions, adenine can thus be considered as an organoinitiator or an organocatalyst for the ring-opening polymerization of lactide.

Adenine as an organocatalyst for the ring-opening polymerization of lactide: scope, mechanism and access to adenine-functionalized polylactide

Nucleobase-functionalized polymers are widely used in the fields of supramolecular chemistry and self-assembly, and their development for biomedical applications is also an area of interest. They are usually synthesized by tedious multistep procedures. In this study, we assess adenine as an organoinitiator/organocatalyst for the ring-opening polymerization of lactide. L-Lactide can be quantitatively polymerized in the presence of adenine. Reaction conditions involving short reaction times and relatively low temperatures enable the access to adenine end-capped polylactide in a simple one-step procedure, in bulk, without additional catalyst. DFT calculations show that the polymerization occurs via hydrogen bond catalysis. The mechanism involves (i) a hydrogen bond between the NH9 of adenine and the carbonyl moiety of lactide, leading to an electron deficient carbon atom, and (ii) a second hydrogen bond between the N3 of adenine and the NH2 of a second adenine molecule, followed by a nucleophilic attack of the latter activated amine on the former electron deficient carbon on the monomer. For longer reaction times and higher temperatures, macrocyclic species are formed, and a mechanism involving the imidazole ring of adenine is proposed based on literature studies. Depending on the reaction conditions, adenine can thus be considered as an organoinitiator or an organocatalyst for the ring-opening polymerization of lactide.

A sustainable model for supporting entrepreneurship in developing countries

Principal Topic Small and micro-enterprises are believed to play a significant part in economic growth and poverty allevition in developing countries. However, there are a range of issues that arise when looking at the support required for local enterprise development, the role of micro finance and sustainability. This paper explores the issues associated with the establishment and resourcing of micro-enterprise develoment and proposes a model of sustainable support of enterprise development in very poor developing economies, particularly in Africa. The purpose of this paper is to identify and address the range of issues raised by the literature and empirical research in Africa, regarding micro-finance and small business support, and to develop a model for sustainable support for enterprise development within a particular cultural and economic context. Micro-finance has become big business with a range of models - from those that operate on a strictly business basis to those that come from a philanthropic base. The models used grow from a range of philosophical and cultural perspectives. Entrepreneurship training is provided around the world. Success is often measured by the number involved and the repayment rates - which are very high, largely because of the lending models used. This paper will explore the range of options available and propose a model that can be implemented and evaluated in rapidly changing developing economies. Methodology/Key Propositions The research draws on entrepreneurial and micro-finance literature and empirical research undertaken in Mozambique, which lies along the Indian ocean sea border of Southern Africa. As a result of war and natural disasters over a prolonged period, there is little industry, primary industries are primitive and there is virtually no infrastructure. Mozambique is ranked as one of the poorest countries in the world. The conditions in Mozambique, though not identical, reflect conditions in many other parts of Africa. A numebr of key elements in the development of enterprises in poor countries are explored including: Impact of micro-finance Sustainable models of micro-finance Education and training Capacity building Support mechanisms Impact on poverty, families and the local economy Survival entrepreneurship versus growth entrepreneurship Transitions to the formal sector. Results and Implications The result of this study is the development of a model for providing intellectual and financial resources to micro-entrepreneurs in poor developing countries in a sustainable way. The model provides a base for ongoing research into the process of entrepreneurial growth in African developing economies. The research raises a numeber of issues regarding sustainability including the nature of the donor/recipient relationship, access to affordable resources, the impact of individual entrepreneurial activity on the local economny and the need for ongoing research to understand the whole process and its impact, intended and unintended.

Developing strong social enterprises : a documentary approach

Social enterprises are diverse in their mission, business structures and industry orientations. Like all businesses, social enterprises face a range of strategic and operational challenges and utilize a range of strategies to access resources in support of their venture. This exploratory study examined the strategic management issues faced by Australian social enterprises and the ways in which they respond to these. The research was based on a comprehensive literature review and semi-structured interviews with 11 representatives of eight social enterprises based in Victoria and Queensland. The sample included mature social enterprises and those within two years of start-up. In addition to the research report, the outputs of the project include a series of six short documentaries, which are available on YouTube at http://www.youtube.com/user/SocialEnterpriseQUT#p/u. The research reported on here suggests that social enterprises are sophisticated in utilizing processes of network bricolage (Baker et al. 2003) to mobilize resources in support of their goals. Access to network resources can be both enabling and constraining as social enterprises mature. In terms of the use of formal business planning strategies, all participating social enterprises had utilized these either at the outset or the point of maturation of their business operations. These planning activities were used to support internal operations, to provide a mechanism for managing collective entrepreneurship, and to communicate to external stakeholders about the legitimacy and performance of the social enterprises. Further research is required to assess the impacts of such planning activities, and the ways in which they are used over time. Business structures and governance arrangements varied amongst participating enterprises according to: mission and values; capital needs; and the experiences and culture of founding organizations and individuals. In different ways, participants indicated that business structures and governance arrangements are important ways of conferring legitimacy on social enterprise, by signifying responsible business practice and strong social purpose to both external and internal stakeholders. Almost all participants in the study described ongoing tensions in balancing social purpose and business objectives. It is not clear, however, whether these tensions were problematic (in the sense of eroding mission or business opportunities) or productive (in the sense of strengthening mission and business practices through iterative processes of reflection and action). Longitudinal research on the ways in which social enterprises negotiate mission fulfillment and business sustainability would enhance our knowledge in this area. Finally, despite growing emphasis on measuring social impact amongst institutions, including governments and philanthropy, that influence the operating environment of social enterprise, relatively little priority was placed on this activity. The participants in our study noted the complexities of effectively measuring social impact, as well as the operational difficulties of undertaking such measurement within the day to day realities of running small to medium businesses. It is clear that impact measurement remains a vexed issue for a number of our respondents. This study suggests that both the value and practicality of social impact measurement require further debate and critically informed evidence, if impact measurement is to benefit social enterprises and the communities they serve.

The role of digressive learning and uniqueness on performance : longitudinal evidence from young firms

The ability to differentiate from competitors through the selection of unique offerings is an important cornerstone of competitive performance. Developing unique products and services to offer in the marketplace is not only important for established firms, but also an important strategic choice for young firms (Baum and Haveman, 1997). Unlike large and established firms, young firms tend to have less access to adequate resources, well-developed sources of information, contact networks, and considerable experience and management know-how. That is, these firms differ significantly in their attributes and performance from larger and well-established firms (c.f. Miller and Chen, 1994). Although young firms are disadvantaged by the paucity of resources in putting together its unique product offering(s), they develop different pathways in advancing their assortment of capabilities that enables them to stay ahead of competitors.

Equitable remedies for elder financial abuse in inter vivos transactions

Elder law is a growing area of legal practice due to the increasing numbers and proportions of older people in Australian society. The older generation has greater access to financial resources by way of retirement capital than ever before. Coupled with the current generation’s high level of debt and an increasing dependence on inheritances to meet these debts, this has created an environment in which the potential for elder financial abuse is increasing. This article examines how equitable remedies can be used as an avenue of redress for elder financial abuse. The effectiveness of these remedies, and in particular the prospect of a costs order being awarded against the perpetrator of the abuse in successful claims, may act as a deterrent and assist in preventing elder financial abuse from occurring.

Aligning sustainability and the Torrens register : challenges and recommendations for reform

‘Sustainability’ is a policy mantra of modern governments particularly in relation to natural resources. The traditional connection between land ownership and access to natural resources, such as forestry, flora, fauna, minerals, water and energy, has given rise to an unprecedented number of restrictions and obligations on land owners in their use of the land and resources. The growing numbers of statutory exceptions and restrictions on rights of ownership and use of a fee simple holder presents serious challenges for the utility of the Torrens register, which was originally designed to record private interests in land or affecting title to land. Advocates proposing uniform Torrens legislation should give consideration to an alignment of government policies emphasising sustainability as a core requirement of effective land use and management, and the core Torrens concepts of indefeasibility and security of title. This article examines the challenges for a uniform Torrens system created by increases statutory regulation of land ownership and makes recommendations about how an effective alignment of sustainability objectives and Torrens principles may be achieved.

A qualitative investigation into the different health experiences of people living with type II diabetes, in the rural environments

Study Rationale The objective of the study was to explore if and how rural culture influences type II diabetes management and to better understand the social processes that rural people construct in coping with diabetes and its complications. In particular, the study aimed to analyse the interface and interactions between rural people with type II diabetes and the Australian health care system. Theoretical framework and methods The research applied constructivist grounded theory methods within an interpretive interactionist framework. Data from 39 semi-structured interviews with rural and urban people with type II diabetes plus a mix of rural health care providers were analysed to develop a theoretical understanding of the social processes that define diabetes management in that context. Results The analysis suggests that although type II diabetes imposes limitations that require adjustment and adaptation these processes are actively negotiated by rural people within the environmental context to fit the salient social understandings of autonomy and self-reliance. Thus people normalised self-reliant diabetes management behaviours because this was congruent with the rural culture. Factors that informed the actions of normalisation were the relationships between participants and health care professions, support and access to individual resources. Conclusions The findings point to ways in which rural self-reliance is conceived as the primary strategy of diabetic management. People face the paradox of engaging with a health care system that at the same time maximises individual responsibility for health and minimises the social support by which individuals manage the condition. The emphasis on self-reliance gives some legitimacy to a lack of prevention and chronic care services. Success of diabetic management behaviours is contingent on relative resources. Where there is good primary care there develop a number of downstream effects including a sense of empowerment to manage difficult rural environmental circumstances. This has particular bearing on health outcomes for people with fewer resources.

Integrating Poverty and Gender into Health Programmes : a Source Book for Health Professionals : Module on Curricular Integration

Over the past two to three decades, our understanding of poverty has broadened from a narrow focus on income and consumption to a multidimensional notion of education, health, social and political 1 participation, personal security and freedom and environmental quality. Thus, it encompasses not just low income, but lack of access to services, resources and skills; vulnerability; insecurity; and voicelessness and powerlessness. Multidimensional poverty is a determinant of health risks, health seeking behaviour, health care access and health outcomes. As analysis of health outcomes becomes more refined, it is increasingly apparent that the impressive gains in health experienced over recent decades are unevenly distributed. Aggregate indicators, whether at the global, regional or national level, often tend to mask striking variations in health outcomes between men and women, rich and poor, both across and within countries...

Measurement as legitimacy versus legitimacy of measures : Performance evaluation of social enterprise

Purpose The purpose of this paper is to review the growing emphasis on quantifiable performance measures such as social return on investment (SROI) in third sector organisations – specifically, social enterprise – through a legitimacy theory lens. It then examines what social enterprises value (i.e. consider important) in terms of performance evaluation, using a case study approach. Design/methodology/approach Case studies involving interviews, documentary analysis, and observation, of three social enterprises at different life-cycle stages with different funding structures, were constructed to consider “what measures matter” from a practitioner's perspective. Findings Findings highlight a priority on quality outcomes and impacts in primarily qualitative terms to evaluate performance. Further, there is a noticeable lack of emphasis on financial measures other than basic access to financial resources to continue pursuing social goals. Social implications The practical challenges faced by social enterprises – many of which are small to medium sized – in evaluating performance and by implication organisational legitimacy are contrasted with measures such as SROI which are resource intensive and have inherent methodological limitations. Hence, findings suggest the limited and valuable resources of social enterprises would be better allocated towards documenting the actual outcomes and impacts as a first step, in order to evaluate social and financial performance in terms appropriate to each objective, in order to demonstrate organisational legitimacy. Originality/value Findings distinguish between processes which may hold symbolic legitimacy for select stakeholder groups, and processes which hold substantive, cognitive legitimacy for stakeholders more broadly, in the under-researched context of social enterprise.

Rural self-reliance: the impact on health experiences of people living with type II diabetes in rural Queensland, Australia

Objective: The objective of the study was to explore whether and how rural culture influences type II diabetes management and to better understand the social processes that rural people construct in coping with diabetes and its complications. In particular, the study aimed to analyse the interface and interactions between rural people with type II diabetes and the Australian health care system, and to develop a theoretical understanding that reflects constructs that may be more broadly applicable. Methods: The study applied constructivist grounded theory methods within an interpretive interactionist framework. Data from 39 semi-structured interviews with rural and urban type II diabetes patients and a mix of rural health care providers were analysed to develop a theoretical understanding of the social processes that define diabetes management in that context. Results: The analysis suggests that although type II diabetes imposes limitations that require adjustment and adaptation, these processes are actively negotiated by rural people within the environmental context to fit the salient social understandings of autonomy and self-reliance. Thus, people normalized self-reliant diabetes management behaviours because this was congruent with the rural culture. Factors that informed the actions of normalization were relationships between participants and health care professionals, support, and access to individual resources. Conclusions: The findings point to ways in which rural self-reliance is conceived as the primary strategy of diabetes management. People face the paradox of engaging with a health care system that at the same time maximizes individual responsibility for health and minimizes the social support by which individuals manage the condition. The emphasis on self-reliance gives some legitimacy to a lack of prevention and chronic care services. Success of diabetes management behaviours is, however, contingent on relative resources. Where there is good primary care, there develops a number of downstream effects including a sense of empowerment to manage difficult rural environmental circumstances. This has particular bearing on health outcomes for people with fewer resources.

Realigning capital portfolios : international students' educational experiences in higher education

This paper reports on first year experiences of international students who use English as an additional language (EAL) in higher education in Australia. It examines how valued resources can foster a positive educational experience of these students from sociological perspectives. It draws data from an interview study, exploring narrative accounts of 17 EAL international students from nine countries about their educational relations and strategies across their first year of study. Their narratives were analysed through Bourdieu's concepts of field, habitus, capital and legitimation, as well as tools of narrative inquiry. The paper finds that the students took up strategies to realign their capital portfolios with new rules of the game. Their decisions were dependent on their personal trajectories and conditions on offer. This paper suggests that more effort needs to be made to understand international students' differentiated access to valued resources in higher education.

A Floor Control Server in a Distributed Conference Service

The conferencing systems in IP Multimedia (IM) networks are going through restructuring, accomplished in the near future. One of the changes introduced is the concept of floors and floor control in its current form with matching entity roles. The Binary Floor Control Protocol (BFCP) is a novelty to be exploited in distributed tightly coupled conferencing services. The protocol defines the floor control server (FCS), which implements floor control giving access to shared resources. As the newest tendency is to distribute the conferencing services, the locations of different functionality units play an important role in developing the standards. The floor control server location is not yet single-mindedly fixed in different standardization bodies, and the debate goes on where to place it within the media server, providing the conferencing service. The thesis main objective is to evaluate two distinctive alternatives in respect the Mp interface protocol between the respective nodes, as the interface in relation to floor control is under standardization work at the moment. The thesis gives a straightforward preamble in IMS network, nodes of interest including floor control server and conferencing. Knowledge on several protocols – BFCP, SDP, SIP and H.248 provides an important background for understanding the functionality changes introduced in the Mp interface and therefore introductions on those protocols and how they are connected to the full picture is given. The actual analysis on the impact of the floor control server into the Mp reference point is concluded in relation to the locations, giving basic flows, requirements analysis including a limited implementation proposal on supporting protocol parameters. The overall conclusion of the thesis is that even if both choices are seemingly useful, not one of the locations is clearly the most suitable in the light of this work. The thesis suggests a solution having both possibilities available to be chosen from in separate circumstances, realized with consistent standardization. It is evident, that if the preliminary assumption for the analysis is kept regarding to only one right place for the floor control server, more work is to be done in connected areas to discover the one most appropriate location.

Calculating life : Nation, Nature, and the Nativisation of Nonhuman Genetics

In recent decades, nation-states have become major stakeholders in nonhuman genetic resource networks as a result of several international treaties. The most important of these is the juridically binding international Convention on Biological Diversity (CBD), signed at the Rio Earth Summit in 1992 by some 150 nations. This convention was a watershed for the identification of global rights related to genetic resources in recognising the sovereign power of signatory nations over their natural resources. The contracting parties are legally obliged to identify their native genetic material and to take legislative, administrative, and/or policy measures to foster research on genetic resources. In this process of global bioprospecting in the name of biodiversity conservation, the world's nonhuman genetic material is to be indexed according to nation and nationality. This globally legitimated process of native genetic identification inscribes national identity into nature and flesh. As a consequence, this new form of potential national biowealth forms also what could be called novel nonhuman genetic nationhoods. These national corporealities are produced in tactical and strategic encounters of the political and the scientific, in new spaces crafted through technical and institutional innovation, and between the national reconfiguration of the natural and cultural as framed by international political agreements. This work follows the creation of national genetic resources in one of the biodiversity-poor countries of the North, Finland. The thesis is an ethnographic work addressing the calculation of life: practices of identifying, evaluating, and collecting nonhuman life in national genetic programmes. The core of the thesis is about observations made within the Finnish Genetic Resources Programmes in 2004 2008, gathered via multi-sited ethnography and related methods derived from the anthropology of science. The thesis explores the problematic relations of the communal forms of human and nonhuman life in an increasingly technoscientific contemporaneity  the co-production and coexistence of human and nonhuman life in biopolitical formations called nations.

Social Networks and Everyday Practices in Russia

My doctoral dissertation in sociology and Russian studies, Social Networks and Everyday Practices in Russia, employs a "micro" or "grassroots" perspective on the transition. The study is a collection of articles detailing social networks in five different contexts. The first article examines Russian birthdays from a network perspective. The second takes a look at health care to see whether networks have become obsolete in a sector that is still overwhelmingly public, but increasingly being monetarised. The third article investigates neighbourhood relations. The fourth details relationships at work, particularly from the vantage point of internal migration. The fifth explores housing and the role of networks and money both in the Soviet and post-Soviet era. The study is based on qualitative social network and interview data gathered among three groups, teachers, doctors and factory workers, in St. Petersburg during 1993-2000. Methodologically it builds on a qualitative social network approach. The study adds a critical element to the discussion on networks in post-socialism. A considerable consensus exists that social networks were vital in state socialist societies and were used to bypass various difficulties caused by endemic shortages and bureaucratic rigidities, but a more debated issue has been their role in post-socialism. Some scholars have argued that the importance of networks has been dramatically reduced in the new market economy, whereas others have stressed their continuing importance. If a common denominator in both has been a focus on networks in relation to the past, a more overlooked aspect has been the question of inequality. To what extent is access to networks unequally distributed? What are the limits and consequences of networks, for those who have access, those outside networks or society at large? My study provides some evidence about inequalities. It shows that some groups are privileged over others, for instance, middle-class people in informal access to health care. Moreover, analysing the formation of networks sheds additional light on inequalities, as it highlights the importance of migration as a mechanism of inequality, for example. The five articles focus on how networks are actually used in everyday life. The article on health care, for instance, shows that personal connections are still important and popular in post-Soviet Russia, despite the growing importance of money and the emergence of "fee for service" medicine. Fifteen of twenty teachers were involved in informal medical exchange during a two-week study period, so that they used their networks to bypass the formal market mechanisms or official procedures. Medicines were obtained through personal connections because some were unavailable at local pharmacies or because these connections could provide medicines for a cheaper price or even for free. The article on neighbours shows that "mutual help" was the central feature of neighbouring, so that the exchange of goods, services and information covered almost half the contacts with neighbours reported. Neighbours did not provide merely small-scale help but were often exchange partners because they possessed important professional qualities, had access to workplace resources, or knew somebody useful. The article on the Russian work collective details workplace-related relationships in a tractor factory and shows that interaction with and assistance from one's co-workers remains important. The most interesting finding was that co-workers were even more important to those who had migrated to the city than to those who were born there, which is explained by the specifics of Soviet migration. As a result, the workplace heavily influenced or absorbed contexts for the worker migrants to establish relationships whereas many meeting-places commonly available in Western countries were largely absent or at least did not function as trusted public meeting places to initiate relationships. More results are to be found from my dissertation: Anna-Maria Salmi: Social Networks and Everyday Practices in Russia, Kikimora Publications, 2006, see www.kikimora-publications.com.