Rhodium cationic complexes using dithioethers as chiral ligands. Application in styrene hydroformylation

Addition of the dithioethers (−)-DIOSR2 (R=Me, iPr) (2,3-O-isopropylidene-1,4-dimethyl (and diisopropyl) thioether-L-threitol) to a dichloromethane solution of [Rh(COD)2]ClO4 (COD=1,5-cyclooctadiene) yielded the mononuclear complexes [Rh(COD)(DIOSR2)]ClO4. X-ray diffraction methods showed that the [Rh(COD)(DIOSiPr2)]ClO4 complex had an square-planar coordination geometry at the rhodium atom with the iPr groups in anti position. Cyclooctadiene complexes react with carbon monoxide to form dinuclear tetracarbonylated complexes [(CO)2Rh(μ-DIOSR2)2(CO)2](ClO4)2. [Rh(COD)(DIOSR2)]ClO4 are active catalyst precursors in styrene hydroformylation at 30 atm and 65°C which give conversions of up to 99% with a regioselectivity in 2-phenylpropanal as high as 74%. In all cases enantioselectivities are low.

Development and application of a method for the purification of free shigatoxigenic bacteriophage from environmental samples

Shiga toxin producing Escherichia coli (STEC) strains are foodborne pathogens whose ability to produce Shiga toxin (Stx) is due to the integration of Stx-encoding lambdoid bacteriophage (Stx phage). Circulating, infective Stx phages are very difficult to isolate, purify and propagate such that there is no information on their genetic composition and properties. Here we describe a novel approach that exploits the phage's ability to infect their host and form a lysogen, thus enabling purification of Stx phages by a series of sequential lysogen isolation and induction steps. A total of 15 Stx phages were rigorously purified from water samples in this way, classified by TEM and genotyped using a PCR-based multi-loci characterisation system. Each phage possessed only one variant of each target gene type, thus confirming its purity, with 9 of the 15 phages possessing a short tail-spike gene and identified by TEM as Podoviridae. The remaining 6 phages possessed long tails, four of which appeared to be contractile in nature (Myoviridae) and two of which were morphologically very similar to bacteriophage lambda (Siphoviridae).

Models, moulds and mass production: the mechanics of stylistic influence form the Mediterranean to Bactria

Classical Greek and Roman influence on the material culture of Central Asia and northwestern India is often considered in the abstract. This article attempts to examine the mechanisms of craft production and movement of artisans and objects which made such influence possible, through four case studies: (1) Mould-made ceramics in Hellenistic eastern Bactria; (2) Plaster casts used in the production of metalware from Begram; (3) Terracotta figurines and the moulds used to produce them, from various archaeological sites; and (4) Mass production of identical gold adornments in the nomadic tombs from Tillya Tepe. The implications of such techniques for our understanding of the development of Gandhāran art are also discussed.

A fast two-grid and finite section method for a class of integral equations on the real line with application to an acoustic scattering problem in the half-plane

We consider the numerical treatment of second kind integral equations on the real line of the form ∅(s) = ∫_(-∞)^(+∞)▒〖κ(s-t)z(t)ϕ(t)dt,s=R〗 (abbreviated ϕ= ψ+K_z ϕ) in which K ϵ L_1 (R), z ϵ L_∞ (R) and ψ ϵ BC(R), the space of bounded continuous functions on R, are assumed known and ϕ ϵ BC(R) is to be determined. We first derive sharp error estimates for the finite section approximation (reducing the range of integration to [-A, A]) via bounds on (1-K_z )^(-1)as an operator on spaces of weighted continuous functions. Numerical solution by a simple discrete collocation method on a uniform grid on R is then analysed: in the case when z is compactly supported this leads to a coefficient matrix which allows a rapid matrix-vector multiply via the FFT. To utilise this possibility we propose a modified two-grid iteration, a feature of which is that the coarse grid matrix is approximated by a banded matrix, and analyse convergence and computational cost. In cases where z is not compactly supported a combined finite section and two-grid algorithm can be applied and we extend the analysis to this case. As an application we consider acoustic scattering in the half-plane with a Robin or impedance boundary condition which we formulate as a boundary integral equation of the class studied. Our final result is that if z (related to the boundary impedance in the application) takes values in an appropriate compact subset Q of the complex plane, then the difference between ϕ(s)and its finite section approximation computed numerically using the iterative scheme proposed is ≤C_1 [kh log⁡〖(1⁄kh)+(1-Θ)^((-1)⁄2) (kA)^((-1)⁄2) 〗 ] in the interval [-ΘA,ΘA](Θ<1) for kh sufficiently small, where k is the wavenumber and h the grid spacing. Moreover this numerical approximation can be computed in ≤C_2 N log⁡N operations, where N = 2A/h is the number of degrees of freedom. The values of the constants C1 and C2 depend only on the set Q and not on the wavenumber k or the support of z.

The heuristic application of explanatory theories in international relations

Explanatory theorists increasingly insist that their theories are useful even though they cannot be deductively applied. But if so, then how do such theories contribute to our understanding of international relations? I argue that explanatory theories are typically heuristically applied: theorists’ accounts of specific empirical episodes are shaped by their theories’ thematic content, but are not inferred from putative causal generalizations or covering laws. These accounts therefore gain no weight from their purely rhetorical association with theories’ quasi-deductive arguments: they must be judged on the plausibility of their empirical claims. Moreover, the quasi-deductive form in which explanatory theories are typically presented obscures their actual explanatory role, which is to indicate what sort of explanation may be required, to provide conceptual categories, and to suggest an empirical focus. This account of how theoretical explanations are constructed subverts the nomothetic–idiographic distinction that is often used to distinguish International Relations from History.

Using attribute importance rankings within discrete choice experiments: an application to valuing bread attributes

We present a new Bayesian econometric specification for a hypothetical Discrete Choice Experiment (DCE) incorporating respondent ranking information about attribute importance. Our results indicate that a DCE debriefing question that asks respondents to rank the importance of attributes helps to explain the resulting choices. We also examine how mode of survey delivery (online and mail) impacts model performance, finding that results are not substantively a§ected by the mode of survey delivery. We conclude that the ranking data is a complementary source of information about respondent utility functions within hypothetical DCEs

Informed, uninformed and participative consent in social media research

The use of online data is becoming increasingly essential for the generation of insight in today’s research environment. This reflects the much wider range of data available online and the key role that social media now plays in interpersonal communication. However, the process of gaining permission to use social media data for research purposes creates a number of significant issues when considering compatibility with professional ethics guidelines. This paper critically explores the application of existing informed consent policies to social media research and compares with the form of consent gained by the social networks themselves, which we label ‘uninformed consent’. We argue that, as currently constructed, informed consent carries assumptions about the nature of privacy that are not consistent with the way that consumers behave in an online environment. On the other hand, uninformed consent relies on asymmetric relationships that are unlikely to succeed in an environment based on co-creation of value. The paper highlights the ethical ambiguity created by current approaches for gaining customer consent, and proposes a new conceptual framework based on participative consent that allows for greater alignment between consumer privacy and ethical concerns.

Massive Open Online Courses and sustainability

Massive Open Online Courses (MOOCs) have become very popular among learners millions of users from around the world registered with leading platforms. There are hundreds of universities (and other organizations) offering MOOCs. However, sustainability of MOOCs is a pressing concern as MOOCs incur up front creation costs, maintenance costs to keep content relevant and on-going support costs to provide facilitation while a course is being run. At present, charging a fee for certification (for example Coursera Signature Track and FutureLearn Statement of Completion) seems a popular business model. In this paper, the authors discuss other possible business models and their pros and cons. Some business models discussed here are: Freemium model – providing content freely but charging for premium services such as course support, tutoring and proctored exams. Sponsorships – courses can be created in collaboration with industry where industry sponsorships are used to cover the costs of course production and offering. For example Teaching Computing course was offered by the University of East Anglia on the FutureLearn platform with the sponsorship from British Telecom while the UK Government sponsored the course Introduction to Cyber Security offered by the Open University on FutureLearn. Initiatives and Grants – The government, EU commission or corporations could commission the creation of courses through grants and initiatives according to the skills gap identified for the economy. For example, the UK Government’s National Cyber Security Programme has supported a course on Cyber Security. Similar initiatives could also provide funding to support relevant course development and offering. Donations – Free software, Wikipedia and early OER initiatives such as the MIT OpenCourseware accept donations from the public and this could well be used as a business model where learners could contribute (if they wish) to the maintenance and facilitation of a course. Merchandise – selling merchandise could also bring revenue to MOOCs. As many participants do not seek formal recognition (European Commission, 2014) for their completion of a MOOC, merchandise that presents their achievement in a playful way could well be attractive for them. Sale of supplementary material –supplementary course material in the form of an online or physical book or similar could be sold with the revenue being reinvested in the course delivery. Selective advertising – courses could have advertisements relevant to learners Data sharing – though a controversial topic, sharing learner data with relevant employers or similar could be another revenue model for MOOCs. Follow on events – the courses could lead to follow on summer schools, courses or other real-life or online events that are paid-for in which case a percentage of the revenue could be passed on to the MOOC for its upkeep. Though these models are all possible ways of generating revenue for MOOCs, some are more controversial and sensitive than others. Nevertheless unless appropriate business models are identified the sustainability of MOOCs would be problematic.

Is children's reading “good enough”? Links between online processing and comprehension as children read syntactically ambiguous sentences

We monitored 8- and 10-year-old children’s eye movements as they read sentences containing a temporary syntactic ambiguity to obtain a detailed record of their online processing. Children showed the classic garden-path effect in online processing. Their reading was disrupted following disambiguation, relative to control sentences containing a comma to block the ambiguity, although the disruption occurred somewhat later than would be expected for mature readers. We also asked children questions to probe their comprehension of the syntactic ambiguity offline. They made more errors following ambiguous sentences than following control sentences, demonstrating that the initial incorrect parse of the garden-path sentence influenced offline comprehension. These findings are consistent with “good enough” processing effects seen in adults. While faster reading times and more regressions were generally associated with better comprehension, spending longer reading the question predicted comprehension success specifically in the ambiguous condition. This suggests that reading the question prompted children to reconstruct the sentence and engage in some form of processing, which in turn increased the likelihood of comprehension success. Older children were more sensitive to the syntactic function of commas, and, overall, they were faster and more accurate than younger children.

Bricks vs clicks: entrepreneurial online banking behaviour and relationship banking

Purpose – Little research has been conducted on the effects of information technology on financing entrepreneurial businesses or small and medium sized enterprises (SMEs). The purpose of this paper is to examine the impacts of entrepreneurial online banking and relationship banking on the severity of financial problems perceived by entrepreneurs and their interactive effect. It also investigates how characteristics of individual businesses and entrepreneurial demographics influence SMEs’ financial situation. Design/methodology/approach – An ordered logistic model is used on a UK dataset to empirically test the hypotheses derived in this paper. The empirical evidence is drawn from the 2004 UK survey of SME finances, which contains a sample of 2,500 firms. Findings – This paper finds that both entrepreneurial online banking behaviour and relationship banking alleviates the severity of financial problems perceived by entrepreneurs. The relationship affect is less evident for entrepreneurs who most frequently use an online approach to communicate with their banks than for those using traditional methods. Business and entrepreneur characteristics also have a strong impact on the severity of the financial problems suffered by SMEs. Originality/value – This paper provides evidence supporting the favourable impacts of the application of information technology on entrepreneurial finance from the perspective of entrepreneur/business. It also identifies a substitute relationship between entrepreneurial online banking behaviour and relationship banking, a relationship which contradicts existing evidence.

The determinants of online loan applications from small businesses

Purpose – The purpose of this paper is to examine both the characteristics of the business customers and the types of venture which make use of online loan applications. Despite the growth in the use of technology in banking and the advent of online banking, little research has been conducted on the factors underlying online loan application behaviour amongst business banking customers. Design/methodology/approach – A multivariate analysis is conducted on a USA dataset to empirically test the hypotheses derived in this paper. The empirical evidence is drawn from the US Survey of Small Business Finances, which contains 3,561 sample ventures, representing 5.3 million small businesses in the USA. Findings – The paper finds that online loan behaviour is largely determined by the characteristics of the entrepreneur, rather than that of the venture. It is also found that factors that trust, evident in the length of the relationship between the applicants and their primary lender, is important. Moderating these effects is further evidence that suggests the number of lenders and distance between lenders and applicants has a marked effect on online loan behaviour. Originality/value – This paper identifies the factors determining small business online loan application behaviour. This is important because the nature of online loan behaviour is changing the existing relationships between banks and customers. Whilst online loan applications afford banks the opportunity to substantially reduce costs, the danger is that long term relationships with customers are harder to cement.

Written Cypriot Greek in online chat: Usage and attitudes

This paper investigates the attitudes of Greek-Cypriot internet users towards written Cypriot Greek (CG) in online chat. CG does not have a standard official orthography and it is only used in informal oral communication. With the emergence of computer-mediated communication (CMC), a novel Romanized form of CG is used instead of Standard Greek (SG) in online environments (Themistocleous 2005). To investigate language attitudes, an online questionnaire was distributed electronically to Greek-Cypriot internet users. The results show that the majority of the informants have positive attitudes towards written CG, a practice that goes against the results of previous attitudinal surveys. In this paper, I demonstrate how the internet can influence and change the attitudes of Greek-Cypriots towards their regional variety. It is argued that the unconventional and norm-free character of CMC allows internet users to use their non-standard variety in a domain where the standard would be expected to be used.

A novel approach for distributed application scheduling based on prediction of communication events

The evolution of commodity computing lead to the possibility of efficient usage of interconnected machines to solve computationally-intensive tasks, which were previously solvable only by using expensive supercomputers. This, however, required new methods for process scheduling and distribution, considering the network latency, communication cost, heterogeneous environments and distributed computing constraints. An efficient distribution of processes over such environments requires an adequate scheduling strategy, as the cost of inefficient process allocation is unacceptably high. Therefore, a knowledge and prediction of application behavior is essential to perform effective scheduling. In this paper, we overview the evolution of scheduling approaches, focusing on distributed environments. We also evaluate the current approaches for process behavior extraction and prediction, aiming at selecting an adequate technique for online prediction of application execution. Based on this evaluation, we propose a novel model for application behavior prediction, considering chaotic properties of such behavior and the automatic detection of critical execution points. The proposed model is applied and evaluated for process scheduling in cluster and grid computing environments. The obtained results demonstrate that prediction of the process behavior is essential for efficient scheduling in large-scale and heterogeneous distributed environments, outperforming conventional scheduling policies by a factor of 10, and even more in some cases. Furthermore, the proposed approach proves to be efficient for online predictions due to its low computational cost and good precision. (C) 2009 Elsevier B.V. All rights reserved.