Alkyl radical geometry controls geminate cage recombination in alkylcobalamins

Abstract: The radical pair that results from photolysis of adenosylcob(II1)alamin (AdoCbl"') undergoes primary geminate recombination with a first-order rate constant of 1 x lo9 s-l. In contrast, methylcob(II1)alamin (CH3Cbl"') and aristeromicylcob(II1)alamin (AriCblII', the carbocyclic analogue of AdoCbl"' in which the ribofuranose ring oxygen has been replaced with a methylene group) does not undergo primary geminate recombination. The ribofwanose group enables a high rate of geminate recombination in the [Ado' Cbl"'] radical pair. This may be due to a stereoelectronic (p-anomeric) effect that maintains a pyramidal geometry at the 5'-carbon of the 5'-deoxyadenosyl radical, or it may be due to hindered rotation about the C4t-C5, bond such that /?-elimination to the olefin is prevented. Recombination in the geminate singlet radical pair is in competition with diffusive escape to form a solvent-separated radical pair. Hyperfine coupling from Co" promotes intersystem crossing to the triplet radical pair (Chagovetz, A. M.; Grissom, C. B. J. Am. Chem. SOC. 1993, 115, 12152). Recombination of the [CH3' Cbl"] radical pair is not prevented by a lack of intersystem crossing, as neither unlabeled or I3C-labeled CH3Cbl"' undergoes geminate recombination. There is only a small difference in the rate of diffusive recombination in the solvent cage for AdoCbl"', AriCbl"', and CH3Cbl"' following photolysis: 2.01 x 10" s-l, 2.20 x lo4 s-l, and 1.16 x lo4 s-l. The rate of diffusive recombination is limited by productive collisions and not by radical geometry or intersystem crossing. The CF3' radical that results from photolysis of (trifluoromethyl)cob(III)alamin (CF3Cbl"') maintains its pyramidal geometry and undergoes faster diffusive recombination in the solvent cage at 51 x lo4 s-l. The C-Co bond dissociation enthalpy in AriCbl"' is 37 f 1.4 kcaymol. The profound difference in geminate recombination rates for AdoCbl"' and CH3Cbl"' is consistent with their different biological roles as enzymatic cofactors: AdoCbl"' is an initiator of radical chain chemistry in the active site, whereas CH3Cbl"' is a methyl group donor in an S~2-type process.

Can Beijing become a global media capital?

The commercialization of Chinese media has taken place over the past two decades; it has become a significant force since 2001 when China joined the World Trade Organisation. With demand for original content increasing and China contemplating a cultural trade deficit in media content, there is much discussion of agglomeration and clustering. Beijing, as the national media centre of China, witnesses a process of media agglomeration while bearing the problem of cultural export during the media commercialization. Michael Curtin‟s idea of media capital, which absorbs media resources and personnel and exports media products transnationally, provides a dynamic perspective of understanding media agglomeration and dispersion under different political social and cultural circumstances. Hence the question whether Beijing is going to transform into a transnational media capital is worth studying, in order to observe and comprehend China‟s media industry in transition. Drawing on Michael Curtin‟s three media capital trajectories, the paper interprets tensions and challenges generated in the process of media industry agglomeration and growth in Beijing. Emphasis is placed on the third trajectory, socio-cultural variation.

Measurements of particle emissions from nanotechnology processes, with assessment of measuring techniques and workplace controls

The overall aim of this project was to contribute to existing knowledge regarding methods for measuring characteristics of airborne nanoparticles and controlling occupational exposure to airborne nanoparticles, and to gather data on nanoparticle emission and transport in various workplaces. The scope of this study involved investigating the characteristics and behaviour of particles arising from the operation of six nanotechnology processes, subdivided into nine processes for measurement purposes. It did not include the toxicological evaluation of the aerosol and therefore, no direct conclusion was made regarding the health effects of exposure to these particles. Our research included real-time measurement of sub, and supermicrometre particle number and mass concentration, count median diameter, and alveolar deposited surface area using condensation particle counters, an optical particle counter, DustTrak photometer, scanning mobility particle sizer, and nanoparticle surface area monitor, respectively. Off-line particle analysis included scanning and transmission electron microscopy, energy-dispersive x-ray spectrometry, and thermal optical analysis of elemental carbon. Sources of fibrous and non-fibrous particles were included.

Spot the differences in traditional and social entrepreneurial intention : highlighting the role of human and social capital

There is general agreement in the scientific community that entrepreneurship plays a central role in the growth and development of an economy in rapidly changing environments (Acs & Virgill 2010). In particular, when business activities are regarded as a vehicle for sustainable growth at large, that goes beyond mere economic returns of singular entities, encompassing also social problems and heavily relying on collaborative actions, then we more precisely fall into the domain of ‘social entrepreneurship’(Robinson et al. 2009). In the entrepreneurship literature, prior studies demonstrated the role of intentionality as the best predictor of planned behavior (Ajzen 1991), and assumed that the intention to start a business derives from the perception of desirability and feasibility and from a propensity to act upon an opportunity (Fishbein & Ajzen 1975). Recognizing that starting a business is an intentional act (Krueger et al. 2000) and entrepreneurship is a planned behaviour (Katz & Gartner 1988), models of entrepreneurial intentions have substantial implications for intentionality research in entrepreneurship. The purpose of this paper is to explore the emerging practice of social entrepreneurship by comparing the determinants of entrepreneurial intention in general versus those leading to startups with a social mission. Social entrepreneurial intentions clearly merit to be investigated given that the opportunity identification process is an intentional process not only typical of for profit start-ups, and yet there is a lack of research examining opportunity recognition in social entrepreneurship (Haugh 2005). The key argument is that intentionality in both traditional and social entrepreneurs during the decision-making process of new venture creation is influenced by an individual's perceptions toward opportunities (Fishbein & Ajzen 1975). Besides opportunity recognition, at least two other aspects can substantially influence intentionality: human and social capital (Davidsson, 2003). This paper is set to establish if and to what extent the social intentions of potential entrepreneurs, at the cognitive level, are influenced by opportunities recognition, human capital, and social capital. By applying established theoretical constructs, the paper draws comparisons between ‘for-profit’ and ‘social’ intentionality using two samples of students enrolled in Economy and Business Administration at the University G. d’Annunzio in Pescara, Italy. A questionnaire was submitted to 310 potential entrepreneurs to test the robustness of the model. The collected data were used to measure the theoretical constructs of the paper. Reliability of the multi-item scale for each dimension was measured using Cronbach alpha, and for all the dimensions measures of reliability are above 0.70. We empirically tested the model using structural equation modeling with AMOS. The results allow us to empirically contribute to the argument regarding the influence of human and social cognitive capital on social and non-social entrepreneurial intentions. Moreover, we highlight the importance for further researchers to look deeper into the determinants of traditional and social entrepreneurial intention so that governments can one day define better polices and regulations that promote sustainable businesses with a social imprint, rather than inhibit their formation and growth.

Heritage language for young Chinese Australian adults in urban Australia : Capital and habitus in fields

Studies of Heritage Language learners‟ commitment and their ethnic identity are increasing, yet there is scant sociological research addressing topics relating to Chinese Heritage Language learners. Drawing on Bourdieu‟s signature notions of „habitus‟, „capital‟, and „field‟, this mixed methods study investigates two problems: (1) impacts of “Chineseness” and accessible resources on Chinese Heritage Language proficiency of young Chinese Australian adults in urban Australia; and (2) the meanings of Chinese Heritage Language to these young people.

Self-determination theory as applied to the design of a software learning system using whole-body controls

Whole-body computer control interfaces present new opportunities to engage children with games for learning. Stomp is a suite of educational games that use such a technology, allowing young children to use their whole body to interact with a digital environment projected on the floor. To maximise the effectiveness of this technology, tenets of self-determination theory (SDT) are applied to the design of Stomp experiences. By meeting user needs for competence, autonomy, and relatedness our aim is to increase children's engagement with the Stomp learning platform. Analysis of Stomp's design suggests that these tenets are met. Observations from a case study of Stomp being used by young children show that they were highly engaged and motivated by Stomp. This analysis demonstrates that continued application of SDT to Stomp will further enhance user engagement. It also is suggested that SDT, when applied more widely to other whole-body multi-user interfaces, could instil similar positive effects.

A study of Beijing‘s competitive advantage as an emergent media capital

The development of creative industries has been connected to urban development since the end of the 20th century. However, the causality of why creative industries always cluster and develop in certain cities hasn‘t been adequately demonstrated, especially as to how various resources grow, interact and nurture the creative capacity of the locality. Therefore it is vital to observe how the local institutional environment nurtures creative industries and how creative industries consequently change the environment in order to better address the connection between creative industries and localities. In Beijing, the relocation of CCTV, BTV and Phoenix to Chaoyang District raises the possibility of a new era for Chinese media, one in which the stodginess of propaganda content will give way to exciting new forms and genres. The mixing of media companies in an open commercial environment (away from the political power district of Xicheng) holds the promise of more freedom of expression and, ultimately, to a =media capital‘ (Curtin, 2003). These are the dreams of many media practitioners in Beijing. But just how realistic are their expectations? This study adopts the concept of =media capital‘ to demonstrate how participants, including state-media organisations, private media companies and international media conglomerates, are seeking out space and networks to survive in Beijing. Drawing on policy analysis, interviews and case studies, this study illustrates how different agents meet, confront and adapt in Beijing. This study identifies factors responsible for the media industries clustering in China, and argues that Beijing is very likely to be the next Chinese media capital, after enough accumulation and development, although as a lower tier version compared to other media capitals in the world. This study contributes to Curtin‘s =media capital‘ concept, develops his interpretation on the relationship of media industries and the government, and suggests that the influence over the government of media companies and professionals should be acknowledged. Therefore, empirically, this study assists media practitioners in understanding how the Chinese government perceives media industries and, consequently, how media industries are operated in China. The study also reveals that despite the government‘s aspirations, China‘s media industries are still greatly constrained by institutional obstacles. Hence Beijing really needs to speed up its pace on the path of media reform, abandon the old mindset and create more room for creativity. Policy-makers in China should keep in mind that the only choice left to them is to further the reform.

Research needed on cultural capital, STEM endeavours and instructional innovations : a call for "collaborations between nations"

New Australian curriculum documents and government initiatives advocate the inclusion of Asian perspectives, which is highly relevant to the STEM fields. For Australia and other countries, STEM education is an opportunity to develop competencies towards employment in high-demand areas, yet the world’s knowledge of STEM is changing rapidly, requiring continuous analysis to meet market demands. This paper presents the need for “collaborations between nations” through research to advance each country’s STEM agenda towards further globalisation of education with the sharing of knowledge. Research is needed on views of what constitutes cultural capital for STEM, which also involves understanding past and current STEM endeavours occurring within various countries. Most importantly for STEM education is uncovering instructional innovations aligned with countries’ cultures and STEM endeavours. Research questions are provided in this paper to stimulate ideas for investigating in these fields. Economically, and as demonstrated recently by Greece and Spain, countries throughout the world can no longer operate independently for advancing standards of living. The world needs to recognise interdependence not only in trade and resources but also through the knowledge base that exists within countries. Learning together globally means transitioning from independence to interdependence in STEM education that will help each country meet global demands.

Power of QTL detection using association tests with family controls

The power of testing for a population-wide association between a biallelic quantitative trait locus and a linked biallelic marker locus is predicted both empirically and deterministically for several tests. The tests were based on the analysis of variance (ANOVA) and on a number of transmission disequilibrium tests (TDT). Deterministic power predictions made use of family information, and were functions of population parameters including linkage disequilibrium, allele frequencies, and recombination rate. Deterministic power predictions were very close to the empirical power from simulations in all scenarios considered in this study. The different TDTs had very similar power, intermediate between one-way and nested ANOVAs. One-way ANOVA was the only test that was not robust against spurious disequilibrium. Our general framework for predicting power deterministically can be used to predict power in other association tests. Deterministic power calculations are a powerful tool for researchers to plan and evaluate experiments and obviate the need for elaborate simulation studies.

The cost of carbon : capital market effects of the proposed emission trading scheme (ETS)

In March 2008, the Australian Government announced its intention to introduce a national Emissions Trading Scheme (ETS), now expected to start in 2015. This impending development provides an ideal setting to investigate the impact an ETS in Australia will have on the market valuation of Australian Securities Exchange (ASX) firms. This is the first empirical study into the pricing effects of the ETS in Australia. Primarily, we hypothesize that firm value will be negatively related to a firm's carbon intensity profile. That is, there will be a greater impact on firm value for high carbon emitters in the period prior (2007) to the introduction of the ETS, whether for reasons relating to the existence of unbooked liabilities associated with future compliance and/or abatement costs, or for reasons relating to reduced future earnings. Using a sample of 58 Australian listed firms (constrained by the current availability of emissions data) which comprise larger, more profitable and less risky listed Australian firms, we first undertake an event study focusing on five distinct information events argued to impact the probability of the proposed ETS being enacted. Here, we find direct evidence that the capital market is indeed pricing the proposed ETS. Second, using a modified version of the Ohlson (1995) valuation model, we undertake a valuation analysis designed not only to complement the event study results, but more importantly to provide insights into the capital market's assessment of the magnitude of the economic impact of the proposed ETS as reflected in market capitalization. Here, our results show that the market assesses the most carbon intensive sample firms a market value decrement relative to other sample firms of between 7% and 10% of market capitalization. Further, based on the carbon emission profile of the sample firms we imply a ‘future carbon permit price’ of between AUD$17 per tonne and AUD$26 per tonne of carbon dioxide emitted. This study is more precise than industry reports, which set a carbon price of between AUD$15 to AUD$74 per tonne.