Marked influence of the bridging carbonyl ligands on the photo- and electrochemistry of the clusters [Ru-3(CO)(8)(mu-CO)(2)-(alpha-diimine)] (alpha-diimine = 2,2 '-bipyridine, 4,4 '-dimethyl-2,2 '-bipyridine and 2,2 '-bipyrimidine)

Bonding, photochemical and electrochemical properties of the clusters [Ru-3(CO)(8)(mu-CO)(2)(alpha-diimine)] (alpha-diimine=2,2'-bipyridine (1), 4,4'-dimethyl-2,2'-bipyridine (2) and 2,2'-bipyrimidine (3)) are strongly influenced by the presence of bridging carbonyl ligands. Irradiation at 471 nm initially results in the population of a sigma(Ru-3)pi*(alpha-diimine) excited state. From this state, fast decay takes place to the optically hardly directly accessible pi(Ru/mu-CO) pi*(alpha-diimine) lowest excited state. These assignments agree with theoretical (TD-DFT) results, resonance Raman and picosecond time-resolved infrared spectra. The involvement of the bridging carbonyl ligands in the electron transfer increases the energetic barrier for the formation of open-structure photoproducts such as biradicals and zwitterions. Zwitterions were therefore only obtained in strongly coordinating media such as pyridine at 250 K. The bridging carbonyl ligands also stabilize the radical anions produced upon one-electron reduction of the clusters [Ru-3(CO)(8)(mu-CO)(2)(alpha-diimine)] and observed with cyclic voltammetry, EPR and IR spectroelectrochemistry (for alpha-diimine=2,2'-bipyrimidine). In contrast, open-triangle intermediates formed along the reduction path to [Ru(CO)(2)(alpha-diimine)](n) and [Ru-2(CO)(8)](2-) are more reactive than their triosmium analogues.

Molecular dynamics simulation of interactions between a sodium dodecyl sulfate micelle and a poly(ethylene oxide) polymer

We have performed atomistic molecular dynamics simulations of an anionic sodium dodecyl sulfate (SDS) micelle and a nonionic poly(ethylene oxide) (PEO) polymer in aqueous solution. The micelle consisted of 60 surfactant molecules, and the polymer chain lengths varied from 20 to 40 monomers. The force field parameters for PEO were adjusted by using 1,2-dimethoxymethane (DME) as a model compound and matching its hydration enthalpy and conformational behavior to experiment. Excellent agreement with previous experimental and simulation work was obtained through these modifications. The simulated scaling behavior of the PEO radius of gyration was also in close agreement with experimental results. The SDS-PEO simulations show that the polymer resides on the micelle surface and at the hydrocarbon-water interface, leading to a selective reduction in the hydrophobic contribution to the solvent-accessible surface area of the micelle. The association is mainly driven by hydrophobic interactions between the polymer and surfactant tails, while the interaction between the polymer and sulfate headgroups on the micelle surface is weak. The 40-monomer chain is mostly wrapped around the micelle, and nearly 90% of the monomers are adsorbed at low PEO concentration. Simulations were also performed with multiple 20-monomer chains, and gradual addition of polymer indicates that about 120 monomers are required to saturate the micelle surface. The stoichiometry of the resulting complex is in close agreement with experimental results, and the commonly accepted "beaded necklace" structure of the SDS-PEO complex is recovered by our simulations.

Untitled (Abstraction of labour time eternal recurrence monad)

An AHRC funded project titled: Picturing ideas? Visualising and Synthesising Ideas as art (2009-10). Outputs including: 4 exhibitions; 4 publications; 3 papers; 2 largescale backlit digital prints; 1 commissioned print. (See Additional Information) ----ABSTRACT: Utilising the virtuality of digital imagery this practice-led project explored the possibility of the cross-articulation between text and image and the bridging or synthesising potential of the visual affect of ideas. A series of digital images were produced 'picturing' or 'visualising' philosophical ideas derived from the writings of the philosopher Giles Deleuze, as remodellings of pre-existing philosophical ideas; developed through dialogues and consultation with specialists in the fields from which the ideas were drawn (philosophy, psychology, film) as well as artists and theorists concerned with ideas of 'mental imagery' and visualisation. Final images were produced as a synthesis (or combination) of these visualisations and presented in the format of large scale, backlit digital prints at a series of prestigious international exhibitions (see details above). Evaluation took the form of a four page illustrated text in Frieze magazine (August 2009) and three papers delivered at University of Ulster, Goldsmiths College of Art and Loughborough University. The project also included the publication of a catalogue essay (EAST 09) and an illustrated poem (in the Dark Monarch publication). A print version of the image was commissioned by Invisible Exports Gallery, New York and subsequently exhibited in The Devos Art Museum, School of Art & Design at Northern Michigan University and in a publication edited by Cedar Lewisohn for Tate Publishing. The project was funded by an AHRC practice-led grant (17K) and Arts Council of England award (1.5K). The outputs, including high profile, publicly accessible exhibitions, prestigious publications and conference papers ensured the dissemination of the research to a wide range of audiences, including scholars/researchers across the arts and humanities engaged in practice-based and interdisciplinary theoretical work (in particular in the fields of contemporary art and art theory and those working on the integration of art and theory/philosophy/psychology) but also the wider audience for contemporary art.

Generation, description and storage of dendritic morphology data

It is generally assumed that the variability of neuronal morphology has an important effect on both the connectivity and the activity of the nervous system, but this effect has not been thoroughly investigated. Neuroanatomical archives represent a crucial tool to explore structure–function relationships in the brain. We are developing computational tools to describe, generate, store and render large sets of three–dimensional neuronal structures in a format that is compact, quantitative, accurate and readily accessible to the neuroscientist. Single–cell neuroanatomy can be characterized quantitatively at several levels. In computer–aided neuronal tracing files, a dendritic tree is described as a series of cylinders, each represented by diameter, spatial coordinates and the connectivity to other cylinders in the tree. This ‘Cartesian’ description constitutes a completely accurate mapping of dendritic morphology but it bears little intuitive information for the neuroscientist. In contrast, a classical neuroanatomical analysis characterizes neuronal dendrites on the basis of the statistical distributions of morphological parameters, e.g. maximum branching order or bifurcation asymmetry. This description is intuitively more accessible, but it only yields information on the collective anatomy of a group of dendrites, i.e. it is not complete enough to provide a precise ‘blueprint’ of the original data. We are adopting a third, intermediate level of description, which consists of the algorithmic generation of neuronal structures within a certain morphological class based on a set of ‘fundamental’, measured parameters. This description is as intuitive as a classical neuroanatomical analysis (parameters have an intuitive interpretation), and as complete as a Cartesian file (the algorithms generate and display complete neurons). The advantages of the algorithmic description of neuronal structure are immense. If an algorithm can measure the values of a handful of parameters from an experimental database and generate virtual neurons whose anatomy is statistically indistinguishable from that of their real counterparts, a great deal of data compression and amplification can be achieved. Data compression results from the quantitative and complete description of thousands of neurons with a handful of statistical distributions of parameters. Data amplification is possible because, from a set of experimental neurons, many more virtual analogues can be generated. This approach could allow one, in principle, to create and store a neuroanatomical database containing data for an entire human brain in a personal computer. We are using two programs, L–NEURON and ARBORVITAE, to investigate systematically the potential of several different algorithms for the generation of virtual neurons. Using these programs, we have generated anatomically plausible virtual neurons for several morphological classes, including guinea pig cerebellar Purkinje cells and cat spinal cord motor neurons. These virtual neurons are stored in an online electronic archive of dendritic morphology. This process highlights the potential and the limitations of the ‘computational neuroanatomy’ strategy for neuroscience databases.

Commuting, CO2 and the location of offices

This paper investigates the extent to which office activity contributes to travel-related CO2 emission. Using ‘end-user’ figures[1], travel accounts for 32% of UK CO2 emission (Commission for Integrated Transport, 2007) and commuting and business travel accounts for a fifth of transport-related CO2 emissions, equating to 6.4% of total UK emissions (Building Research Establishment, 2000). Figures from the Department for Transport (2006) report that 70% of commuting trips were made by car, accounting for 73% of all commuting miles travelled. In assessing the environmental performance of an office building, the paper questions whether commuting and business travel-related CO2 emission is being properly assessed. For example, are office buildings in locations that are easily accessible by public transport being sufficiently rewarded? The de facto method for assessing the environmental performance of office buildings in the UK is the Building Research Establishment’s Environmental Assessment Method (BREEAM). Using data for Bristol, this paper examines firstly whether BREEAM places sufficient weight on travel-related CO2 emission in comparison with building operation-related CO2 emission, and secondly whether the methodology for assigning credits for travel-related CO2 emission efficiency is capable of discerning intra-urban differences in location such as city centre and out-of-town. The results show that, despite CO2 emission per worker from building operation and travel being comparable, there is a substantial difference in the credit-weighting allocated to each. Under the current version of BREEAM for offices, only a maximum of 4% of the available credits can be awarded for ensuring the office location is environmentally sustainable. The results also show that all locations within the established city centre of Bristol will receive maximum BREEAM credits. Given the parameters of the test there is little to distinguish one city centre location from another and out of town only one office location receives any credits. It would appear from these results that the assessment method is not able to discern subtle differences in the sustainability of office locations

A step toward the wet surface chemistry of glycine and alanine on Cu{110}: destabilization and decomposition in the presence of near-ambient water vapor

The coadsorption of water with organic molecules under near-ambient pressure and temperature conditions opens up new reaction pathways on model catalyst surfaces that are not accessible in conventional ultrahigh-vacuum surfacescience experiments. The surface chemistry of glycine and alanine at the water-exposed Cu{110} interface was studied in situ using ambient-pressure photoemission and X-ray absorption spectroscopy techniques. At water pressures above 10-5 Torr a significant pressure-dependent decrease in the temperature for dissociative desorption was observed for both amino acids, accompanied by the appearance of a newCN intermediate, which is not observed for lower pressures. The most likely reaction mechanisms involve dehydrogenation induced by O and/or OH surface species resulting from the dissociative adsorption of water. The linear relationship between the inverse decomposition temperature and the logarithm of water pressure enables determination of the activation energy for the surface reaction, between 213 and 232 kJ/mol, and a prediction of the decomposition temperature at the solidliquid interface by extrapolating toward the equilibrium vapor pressure. Such experiments near the equilibrium vapor pressure provide important information about elementary surface processes at the solidliquid interface, which can be retrieved neither under ultrahigh vacuum conditions nor from interfaces immersed in a solution.

Self-centred memories: the reminiscence bump and the self

The self-memory relationship is thought to be bidirectional, in such a way that memories provide context for the self, and equally, the self exercises control over retrieval (Conway, 2005). Autobiographical memories are not distributed equally across the life span; instead, memories peak between ages 10 and 30. This reminiscence bump has been suggested to support the emergence of a stable and enduring self. In the present study, the relationship between memory accessibility and self was explored with a novel methodology that used generation of self images in the form of I am statements. Memories generated from I am cues clustered around the time of emergence for that particular self image. We argue that, when a new self-image is formed, it is associated with the encoding of memories that are relevant to that self and that remain highly accessible to the rememberer later in life. This study offers a new methodology for academics and clinicians interested in the relationship between memory and identity.

Suitability of pesticide risk indicators for less developed countries: a comparison

Pesticide risk indicators provide simple support in the assessment of environmental and health risks from pesticide use, and can therefore inform policies to foster a sustainable interaction of agriculture with the environment. For their relative simplicity, indicators may be particularly useful under conditions of limited data availability and resources, such as in Less Developed Countries (LDCs). However, indicator complexity can vary significantly, in particular between those that rely on an exposure–toxicity ratio (ETR) and those that do not. In addition, pesticide risk indicators are usually developed for Western contexts, which might cause incorrect estimation in LDCs. This study investigated the appropriateness of seven pesticide risk indicators for use in LDCs, with reference to smallholding agriculture in Colombia. Seven farm-level indicators, among which 3 relied on an ETR (POCER, EPRIP, PIRI) and 4 on a non-ETR approach (EIQ, PestScreen, OHRI, Dosemeci et al., 2002), were calculated and then compared by means of the Spearman rank correlation test. Indicators were also compared with respect to key indicator characteristics, i.e. user friendliness and ability to represent the system under study. The comparison of the indicators in terms of the total environmental risk suggests that the indicators not relying on an ETR approach cannot be used as a reliable proxy for more complex, i.e. ETR, indicators. ETR indicators, when user-friendly, show a comparative advantage over non-ETR in best combining the need for a relatively simple tool to be used in contexts of limited data availability and resources, and for a reliable estimation of environmental risk. Non-ETR indicators remain useful and accessible tools to discriminate between different pesticides prior to application. Concerning the human health risk, simple algorithms seem more appropriate for assessing human health risk in LDCs. However, further research on health risk indicators and their validation under LDC conditions is needed.

Historicizing counterurbanization: in-migration and the reconstruction of rural space in Berkshire (UK), 1901-51

This article uses census data for Berkshire to argue that large-scale counterurbanization began much earlier than is generally recognized in some parts of southern England. This was not just movement down the urban hierarchy, which as Pooley and Turnbull have demonstrated was a long-term feature of England’s settlement system, but in some cases at least amenity-driven migration to rural areas of the kind increasingly recognized as a core component of recent counterurbanization. Despite a reduction of acreage Berkshire’s rural districts saw a 54% rise in population between 1901 and 1951. The sub-regional pattern of growth is assessed to gauge whether ‘clean break’ migration to the remote west of the county (which remained effectively out of commuting range from London throughout the period) was taking place, or whether counterurbanization was confined to the more accessible eastern districts. However, whilst population did increase in both west and east, it was in fact the central districts that grew most impressively. Three case study parishes are investigated in order to gauge the nature and consequences of counterurbanization at a local level. Professional and business migrants figure prominently, seeking to preserve and promote the rural attributes of their new communities, without however cutting their ties to urban centres. It is argued that migration to rural Berkshire in the first half of the twentieth century cannot adequately be described either as a form of extended suburbanization or an anti-metropolitan ‘clean break’. Rather, early counterurbanization marks the first stage on the long road to a post-productivist countryside, in which countryside becomes detached from agriculture, there is socio-economic convergence between town and country, and the ‘rural’ increasingly becomes defined by landscape and identity rather than economic function.

BET surface area of carbonaceous adsorbents: verification using geometric considerations and GCMC simulations on virtual porous carbon models

The applicability of BET model for calculation of surface area of activated carbons is checked by using molecular simulations. By calculation of geometric surface areas for the simple model carbon slit-like pore with the increasing width, and by comparison of the obtained values with those for the same systems from the VEGA ZZ package (adsorbate-accessible molecular surface), it is shown that the latter methods provide correct values. For the system where a monolayer inside a pore is created the ASA approach (GCMC, Ar, T = 87 K) underestimates the value of surface area for micropores (especially, where only one layer is observed and/or two layers of adsorbed Ar are formed). Therefore, we propose the modification of this method based on searching the relationship between the pore diameter and the number of layers in a pore. Finally BET; original andmodified ASA; and A, B and C-point surface areas are calculated for a series of virtual porous carbons using simulated Ar adsorption isotherms (GCMC and T = 87 K). The comparison of results shows that the BET method underestimates and not, as it was usually postulated, overestimates the surface areas of microporous carbons.

Can carbon surface oxidation shift the pore size distribution curve calculated from Ar, N(2) and CO(2) adsorption isotherms? Simulation results for a realistic carbon model

Using the virtual porous carbon model proposed by Harris et al, we study the effect of carbon surface oxidation on the pore size distribution (PSD) curve determined from simulated Ar, N(2) and CO(2) isotherms. It is assumed that surface oxidation is not destructive for the carbon skeleton, and that all pores are accessible for studied molecules (i.e., only the effect of the change of surface chemical composition is studied). The results obtained show two important things, i.e., oxidation of the carbon surface very slightly changes the absolute porosity (calculated from the geometric method of Bhattacharya and Gubbins (BG)); however, PSD curves calculated from simulated isotherms are to a greater or lesser extent affected by the presence of surface oxides. The most reliable results are obtained from Ar adsorption data. Not only is adsorption of this adsorbate practically independent from the presence of surface oxides, but, more importantly, for this molecule one can apply the slit-like model of pores as the first approach to recover the average pore diameter of a real carbon structure. For nitrogen, the effect of carbon surface chemical composition is observed due to the quadrupole moment of this molecule, and this effect shifts the PSD curves compared to Ar. The largest differences are seen for CO2, and it is clearly demonstrated that the PSD curves obtained from adsorption isotherms of this molecule contain artificial peaks and the average pore diameter is strongly influenced by the presence of electrostatic adsorbate-adsorbate as well as adsorbate-adsorbent interactions.

Explaining history to children: Otto and Marie Neurath’s work on the ‘Visual history of mankind’

This essay traces the development of Otto Neurath’s ideas that led to the publication of one of the first series of children’s books produced by the Isotype Institute in the late 1940s, the Visual History of Mankind. Described in its publicity material as ‘new in content’ and ‘new in method’, it embodied much of Otto Neurath’s thinking about visual education, and also coincided with other educational ideas in the UK in the 1930s and 1940s. It exemplified the Isotype Institute’s approach: teamwork, thinking about the needs of younger readers, clear explanation, and accessible content. Further, drawing on correspondence, notes and drawings from the Otto and Marie Neurath Isotype Collection at the University of Reading, the essay presents insights to the making of the books and the people involved, the costs of production and the influence of this on design decisions, and how the books were received by teachers and children.

Who owned Earls Colne in 1798....or how to squeeze more from the Land Tax

In this important article Richard Hoyle, one of the country’s leading historians of the early modern period, introduces new perspectives on the Land Tax and its use in the analysis of local communities in the late eighteenth and early nineteenth centuries. He uses as his case study the parish of Earls Colne in Essex, on which he has already written extensively with Professor Henry French. The article begins with an overview of the tax itself, explaining its history and the procedures for the collection of revenues – including the numerous changes which took place. The sizeable problems confronting any would-be analyst of the data are clearly identified, and Hoyle observes that because of these apparently insoluble difficulties the potential of the tax returns has never been fully realised. He then considers the surviving documentation in The National Archives, providing an accessible introduction to the sources and their arrangement, and describing the particularly important question o f the redemption of the tax by payment of a lump sum. The extent of redemption (in the years around 1800-1804) is discussed. Hoyle draws attention to the potential for linking the tax returns themselves with the redemption certificates (which have never been subjected to historical analysis and thereby proposes new ways of exploiting the evidence of the taxation as a whole. The article then discusses in detail the specific case of Earls Colne, with tabulated data showing the research potential. Topics analysed include the ownership of property ranked by size of payment, and calculations whereby the amount paid may be used to determine the worth of land and the structure of individual estates. The important question of absentee owners is investigated, and there is a very valuable consideration of the potential for looking at portfolio estate ownership, whereby owners held land in varying proportions in a number of parishes. It is suggested that such studies will allow us to be more aware of the entirety of property ownership, which a focus on a single community does not permit. In the concluding paragraph it is argued that using these sources we may see the rise and fall of estates, gain new information on landownership, landholding and farm size, and even approach the challenging topic of the distribution of wealth.

Razzisti a parole (per tacer dei fatti)

Based on a wide bibliographic apparatus, and on a discourse-analysis approach, but written in a very accessible way to reach also a non-specialist audience, the pamphlet focuses on misleading and biased representations – through every-day stereotypes, media clichés, political speeches – of migration and migrants in today’s Italy, and is exciting a national debate about the strong relationship between language abuses, political and social misrepresentation, lack of citizenship for migrants and asylum seekers in Italy.