Organometallic pincer-type complexes: recent applications in synthesis and catalysis

YCY pincer palladacycles, where YCY is typically an SCS, NCN, PCP, SeCSe anionic six-electron donor ligand (e.g. see 1-6, Scheme 1.1), are a well-established family of organometallic complexes with manifold applications in catalysis, synthesis and materials science [1-24]. Their synthesis can be achieved by many routes including C-H activation, oxidative addition, transmetalation and trans-cyclopalladation [25].

RAGE Architecture for Reusable Serious Gaming Technology Components

For seizing the potential of serious games, the RAGE project - funded by the Horizon-2020 Programme of the European Commission - will make available an interoperable set of advanced technology components (software assets) that support game studios at serious game development. This paper describes the overall software architecture and design conditions that are needed for the easy integration and reuse of such software assets in existing game platforms. Based on the component-based software engineering paradigm the RAGE architecture takes into account the portability of assets to different operating systems, different programming languages and different game engines. It avoids dependencies on external software frameworks and minimizes code that may hinder integration with game engine code. Furthermore it relies on a limited set of standard software patterns and well-established coding practices. The RAGE architecture has been successfully validated by implementing and testing basic software assets in four major programming languages (C#, C++, Java and Typescript/JavaScript, respectively). A demonstrator implementation of asset integration with an existing game engine was created and validated. The presented RAGE architecture paves the way for large scale development and application of cross-engine reusable software assets for enhancing the quality and diversity of serious gaming.

Remote sensing of assimilation number for marine phytoplankton

Estimating primary production at large spatial scales is key to our understanding of the global carbon cycle. Algorithms to estimate primary production are well established and have been used in many studies with success. One of the key parameters in these algorithms is the chlorophyll-normalised production rate under light saturation (referred to as the light saturation parameter or the assimilation number). It is known to depend on temperature, light history and nutrient conditions, but assigning a magnitude to it at particular space-time points is difficult. In this paper, we explore two models to estimate the assimilation number at the global scale from remotely-sensed data that combine methods to estimate the carbon-to-chlorophyll ratio and the maximum growth rate of phytoplankton. The inputs to the algorithms are the surface concentration of chlorophyll, seasurface temperature, photosynthetically-active radiation af the surface of the sea, sea surface nutrient concentration and mixed-layer depth. A large database of in situ estimates of the assimilation number is used to develop the models and provide elements of validation. The comparisons with in situ observations are promising and global maps of assimilation number are produced.

Characterisation of Silicone Elastomer Vaginal Rings Containing HIV Microbicide TMC120 by Raman Spectroscopy

Silicone elastomer vaginal rings are currently being pursued as a controlled-release strategy for delivering microbicidal substances for the prevention of heterosexual transmission of HIV. Although it is well established that the distribution of drugs in delivery systems influences the release characteristics, in practice the distribution is often difficult to quantify in-situ. Therefore, the aim of this work was to determine whether Raman spectroscopy might provide a rapid, non-contact means of measuring the concentrations of the lead candidate HIV microbicide TMC120 in a silicone elastomer reservoir-type vaginal ring. Vaginal rings loaded with TMC120 were manufactured and sectioned before either Raman mapping an entire ring cross-section (100 µm resolution) or running line scans at appropriate time intervals up to 30 h after manufacture. The results demonstrated that detectable amounts of TMC120, above the silicone elastomer saturation concentration, could be detected up to 1 mm into the sheath, presumably as a consequence of permeation and subsequent reprecipitation. The extent of permeation was found to be similar in rings manufactured at 25 and 80°C.

The Industrial Context of Occupational Mobility: Change in Structure

The neglect of a consideration of history has been a feature of mobility research. ‘History’ affects the results of analyses of social mobility by altering the occupational/industrial structure and by encouraging exchange mobility. Changes in industrial structure are rooted more directly in historical causes and can be seen as more fundamental than changes in occupational structure. Following a substantial review of the secondary literature on changes in industrial and occupational structure in Northern Ireland, loglinear analyses of intra- and intergenerational mobility tables for sociologically-derived cohort generations that incorporate occupational and industrial categories are presented. Structural and inheritance effects for industry are as significant as those for occupation. Given the well-established finding of ‘constant social fludity’ in mobility tables once structural effects are controlled, the inclusion of categorization by industry is necessary in order to reach an accurate understanding of occupational mobility and the role of historical change in mobility.

A possible model of benzimidazole binding to beta-tubulin disclosed by invoking an inter-domain movement.

Although it is well established that benzimidazole (BZMs) compounds exert their therapeutic effects through binding to helminth beta-tubulin and thus disrupting microtubule-based processes in the parasites, the precise location of the benzimidazole-binding site on the beta-tubulin molecule has yet to be determined. In the present study, we have used previous experimental data as cues to help identify this site. Firstly, benzimidazole resistance has been correlated with a phenylalanine-to-tyrosine substitution at position 200 of Haemonchus contortus beta-tubulin isotype-I. Secondly, site-directed mutagenesis studies, using fungi, have shown that other residues in this region of the protein can influence the interaction of benzimidazoles with beta-tubulin. However, the atomic structure of the alphabeta-tubulin dimer shows that residue 200 and the other implicated residues are buried within the protein. This poses the question: how might benzimidazoles interact with these apparently inaccessible residues? In the present study, we present a mechanism by which those residues generally believed to interact with benzimidazoles may become accessible to the drugs. Furthermore, by docking albendazole-sulphoxide into a modelled H. contortus beta-tubulin molecule we offer a structural explanation for how the mutation conferring benzimidazole resistance in nematodes may act, as well as a possible explanation for the species-specificity of benzimidazole anthelmintics.

Proof of polar ejection from the close-binary core of the planetary nebula Abell 63

We present the first detailed kinematical analysis of the planetary nebula Abell 63, which is known to contain the eclipsing close-binary nucleus UU Sge. Abell 63 provides an important test case in investigating the role of close-binary central stars on the evolution of planetary nebulae. Longslit observations were obtained using the Manchester echelle spectrometer combined with the 2.1-m San Pedro Martir Telescope. The spectra reveal that the central bright rim of Abell 63 has a tube-like structure. A deep image shows collimated lobes extending from the nebula, which are shown to be high-velocity outflows. The kinematic ages of the nebular rim and the extended lobes are calculated to be 8400 +/- 500 and 12900 +/- 2800 yr, respectively, which suggests that the lobes were formed at an earlier stage than the nebular rim. This is consistent with expectations that disc-generated jets form immediately after the common envelope phase. A morphological-kinematical model of the central nebula is presented and the best-fitting model is found to have the same inclination as the orbital plane of the central binary system; this is the first proof that a close-binary system directly affects the shaping of its nebula. A Hubble-type flow is well-established in the morphological-kinematical modelling of the observed line profiles and imagery. Two possible formation models for the elongated lobes of Abell 63 are considered, (i) a low-density, pressure-driven jet excavates a cavity in the remnant asymptotic giant branch (AGB) envelope; (ii) high-density bullets form the lobes in a single ballistic ejection event.

Evidence for rescattering in intense, femtosecond laser interactions with a negative ion

It is now well established that energetic electron emission, nonsequential ionization, and high harmonic generation, produced during the interaction of intense, femtosecond laser pulses with atoms (and atomic positive ions), can be explained by invoking rescattering of the active electron in the laser field, the so-called rescattering mechanism. In contrast for negative ions, the role of rescattering has not been established experimentally. By irradiating F- ions with ultrashort laser pulses, F+ ion yields as a function of intensity for both linearly and circularly polarized light have been measured. We find that, at intensities well below saturation for F+ production by sequential ionization, there is a small but significant enhancement in the yield for the case of linearly polarized light, providing the first clear experimental evidence for the existence of the rescattering mechanism in negative ions.

Tools for analysing configuration interaction wavefunctions

The configuration interaction (CI) approach to quantum chemical calculations is a well-established means of calculating accurately the solution to the Schrodinger equation for many-electron systems. It represents the many-body electron wavefunction as a sum of spin-projected Slater determinants of orthogonal one-body spin-orbitals. The CI wavefunction becomes the exact solution of the Schrodinger equation as the length of the expansion becomes infinite, however, it is a difficult quantity to visualise and analyse for many-electron problems. We describe a method for efficiently calculating the spin-averaged one- and two-body reduced density matrices rho(psi)((r) over bar; (r) over bar' ) and Gamma(psi)((r) over bar (1), (r) over bar (2); (r) over bar'(1), (r) over bar'(2)) of an arbitrary CI wavefunction Psi. These low-dimensional functions are helpful tools for analysing many-body wavefunctions; we illustrate this for the case of the electron-electron cusp. From rho and Gamma one can calculate the matrix elements of any one- or two-body spin-free operator (O) over cap. For example, if (O) over cap is an applied electric field, this field can be included into the CI Hamiltonian and polarisation or gating effects may be studied for finite electron systems. (C) 2003 Elsevier B.V. All rights reserved.

Widening our knowledge concerning young looked after children: the case for research using sociological models of childhood

The Assessment and Action framework for looked after children, designed to improve outcomes for all children in public care and those at home on care orders, is now well established in the UK. This paper offers a critical evaluation of the framework by examining the model of childhood upon which it is premised and by exploring its relationship to children's rights as conceptualized in the United Nations Convention on the Rights of the Child (1989). It will be argued that the particular child development model which underpins the framework addresses the rights of looked after children to protection and provision but does not allow for their participation rights to be sufficiently addressed. A critical review of the research concerning the education and health of looked after children is used to illustrate these points. It will be argued that what are missing are the detailed accounts of looked after children themselves. It is concluded that there is a need for the development of additional research approaches premised upon sociological models of childhood. These would allow for a greater engagement with the participation rights of this group of children and complement the pre-existing research agenda

A Study of the Development of the Ability of the Archives Department of the Hudson's Bay Company to Carry Out Document Repairs

The objective of this thesis was to determine whether the establishment and operation of an archives services by the Hudson's Bay Company had an effect on the company's ability to carry out document repairs. Data collection methods included reviews of published material, archival records of the Hudson's Bay Company, and semi-structured interviews. The study found that the Hudson's Bay Company's commitment to operating a modern archives service in accordance with accepted archive administration practices had a substantial effect on its ability to carry out document repairs. The principled approach to repair, as practiced by the Public Record Office, was a major influence. A review of secondary sources placed this development squarely within the context of archival developments in 20th century England. Overall, the thesis findings add to the growing conversation about conservation history in England, in particular, archive conservation history as it occurred outside of the Public Record Office in the 20th century, by discussing how some methods of repair that were devised, adopted and extended by the Public Record Office in the 19th and 20th centuries were adopted and applied in the 20th century by a well-established business corporation.

A Method from the 'Lifeworld': Some Possibilities for Person Centred Planning for Children in Care

This paper describes a method for working with chldren who are the subjects of care planning and review under the Children Act 1989. The person centred planning model, as it is termed, has been well established in working with adults with special needs but can be extrapolated to encounters with children. It focuses on three fundamental areas: relationship, meaning and narrative. In underscoring these areas, the method restrains the bureaucracy and experience of stigma that is often present for those residing in State care.

The Cost of Sustainability Capital and the Creation of Sustainable Value by Companies

We develop and apply a valuation methodology to calculate the cost of sustainability capital, and, eventually, sustainable value creation of companies. Sustainable development posits that decisions must take into account all forms of capital rather than just economic capital. We develop a methodology that allows calculation of the costs that are associated with the use of different forms of capital. Our methodology borrows the idea from financial economics that the return on capital has to cover the cost of capital. Capital costs are determined as opportunity costs, that is, the forgone returns that would have been created by alternative investments. We apply and extend the logic of opportunity costs to the valuation not only of economic capital but also of other forms of capital. This allows (a) integrated analysis of use of different forms of capital based on a value-based aggregation of different forms of capital, (b) determination of the opportunity cost of a bundle of different forms of capital used in a company, called cost of sustainability capital, (c) calculation of sustainability efficiency of companies, and (d) calculation of sustainable value creation, that is, the value above the cost of sustainability capital. By expanding the well-established logic of the valuation of economic capital in financial markets to cover other forms of capital, we provide a methodology that allows determination of the most efficient allocation of sustainability capital for sustainable value creation in companies. We demonstrate the practicability of the methodology by the valuation of the sustainability performance of British Petroleum (BP).

Low-pressure synthesis and characterisation of hydroxyapatite derived from mineralise red algae

There is a great need to design functional bioactive substitute materials capable of surviving harsh and diverse conditions within the human body. Calcium-phosphate ceramics, in particular hydroxyapatite are well established substitute materials for orthopaedic and dental applications. The aim of this study was to develop a bioceramic from alga origins suitable for bone tissue application. This was achieved by a novel synthesis technique using ambient pressure at a low temperature of 100 degrees C in a highly alkaline environment. The algae was characterised using SEM, BET, XRD and Raman Spectroscopy to determine its physiochemical properties at each stage. The results confirmed the successful conversion of mineralised red alga to hydroxyapatite, by way of this low-pressure hydrothermal process. Furthermore, the synthesised hydroxyapatite maintained the unique micro-porous structure of the original algae, which is considered beneficial in bone repair applications. (C) 2007 Elsevier B.V. All rights reserved.

A nonradioactive method for the assay of polyphosphate kinase activity and its application in the study of polyphosphate metabolism in Burkholderia cepacia

Studies of polyphosphate (polyP) metabolism in microorganisms have been hampered by the lack of a convenient method for the assay in cell extracts of the activity of polyphosphate kinase (PPK), the enzyme principally responsible for microbial polyP biosynthesis. We report the development of such an assay, based on the well-established metachromatic reaction, with toluidine blue, of the polyP formed during the PPK-catalyzed reaction. The method was successfully used in the characterization of PPK activity in crude extracts of an environmental Burkholderia cepacia isolate. The development of a protocol for the physical recovery of polyP from solution is also reported. (C) 2002 Elsevier Science (USA). All rights reserved.