Relationship between phonons and thermal expansion in Zn(CN)2 and Ni(CN)2 from inelastic neutron scattering and ab initio calculations

Zn(CN)2 and Ni(CN)2 are known for exhibiting anomalous thermal expansion over a wide temperature range. The volume thermal expansion coefficient for the cubic, three dimensionally connected material, Zn(CN)2, is negative (alpha(V) = −51  10(-6) K-1) while for Ni(CN)2, a tetragonal material, the thermal expansion coefficient is negative in the two dimensionally connected sheets (alpha(a) = −7  10(-6) K-1), but the overall thermal expansion coefficient is positive (alpha(V) = 48  10(-6) K-1). We have measured the temperature dependence of phonon spectra in these compounds and analyzed them using ab initio calculations. The spectra of the two compounds show large differences that cannot be explained by simple mass renormalization of the modes involving Zn (65.38 amu) and Ni (58.69 amu) atoms. This reflects the fact that the structure and bonding are quite different in the two compounds. The calculated pressure dependence of the phonon modes and of the thermal expansion coefficient, alpha(V), are used to understand the anomalous behavior in these compounds. Our ab initio calculations indicate that phonon modes of energy approx. 2 meV are major contributors to negative thermal expansion (NTE) in both the compounds. The low-energy modes of approx.8 and 13 meV in Zn(CN)2 also contribute significantly to the NTE in Zn(CN)2 and Ni(CN)2, respectively. The measured temperature dependence of the phonon spectra has been used to estimate the total anharmonicity of both compounds. For Zn(CN)2, the temperature-dependent measurements (total anharmonicity), along with our previously reported pressure dependence of the phonon spectra (quasiharmonic), is used to separate the explicit temperature effect at constant volume (intrinsic anharmonicity).

A policy critique of Stansted Airport's expansion to 25 million passengers per annum (MPPA)

In this paper we undertake a preliminary assessment of the regional planning and development implications of BAA Stansted Airport’s planning permission to grow to 25 million passengers per annum (mppa) by 2010. Our concern is not simply to consider the overall growth of the airport on the airport site itself but the nature and type of growth both on- and off-site. In this document we focus on the submitted planning permission documents and test them. The methodology we employed was to draw on published and unpublished numerical estimates of the airport’s growth – particularly including estimates produced by the airport owner, BAA, and their economic and planning consultants DTZ Pieda - and critically, and systematically analyse their figures. We adopted this approach because unless the figures which were employed in the initial calculations were correct then all of the subsequent projections which flow from them - and the polices which could then be based on them – could be flawed. The analysis is divided into two parts – firstly, are the growth forecasts correct?; and secondly, what do these forecasts actually mean in developmental terms? In effect, what we have done is to produce a critique of the existing body of evidence by questioning underpinning assumptions and then draw some preliminary conclusions for the region based on this analysis. A major focus of this report has been analyse the figures involved in the planning application to expand Stansted to 25mppa. Ironically, one of our key findings, that the local impact of Stansted’s proposed expansion in employment terms might well be less than was originally thought, might make it easier to gain the acceptance of the relevant local authorities involved to allow the development to take place. Our main overall findings are that the BAA projections over-estimate the local employment impact of the airport’s proposed growth and under-estimate its potential regional ‘transportation’ employment effect. These two findings are, of course, related to each other in important ways, and we also feel that they have potentially significant medium and long-term economic, competitiveness and planning policy implications for the East of England region

Belowground biomass functions and expansion factors in high elevation Norway spruce

Biomass allocation to above- and belowground compartments in trees is thought to be affected by growth conditions. To assess the strength of such influences, we sampled six Norway spruce forest stands growing at higher altitudes. Within these stands, we randomly selected a total of 77 Norway spruce trees and measured volume and biomass of stem, above- and belowground stump and all roots over 0.5 cm diameter. A comparison of our observations with models parameterised for lower altitudes shows that models developed for specific conditions may be applicable to other locations. Using our observations, we developed biomass functions (BF) and biomass conversion and expansion factors (BCEF) linking belowground biomass to stem parameters. While both BF and BCEF are accurate in belowground biomass predictions, using BCEF appears more promising as such factors can be readily used with existing forest inventory data to obtain estimates of belowground biomass stock. As an example, we show how BF and BCEF developed for individual trees can be used to estimate belowground biomass at the stand level. In combination with existing aboveground models, our observations can be used to quantify total standing biomass of high altitude Norway spruce stands.

Spatial and temporal effects of free-air CO2 enrichment (POPFACE) on leaf growth, cell expansion and cell production in a closed canopy of poplar

Leaf expansion in the fast-growing tree,Populus × euramericana was stimulated by elevated [CO2] in a closed-canopy forest plantation, exposed using a free air CO2 enrichment technique enabling long-term experimentation in field conditions. The effects of elevated [CO2] over time were characterized and related to the leaf plastochron index (LPI), and showed that leaf expansion was stimulated at very early (LPI, 0–3) and late (LPI, 6–8) stages in development. Early and late effects of elevated [CO2] were largely the result of increased cell expansion and increased cell production, respectively. Spatial effects of elevated [CO2] were also marked and increased final leaf size resulted from an effect on leaf area, but not leaf length, demonstrating changed leaf shape in response to [CO2]. Leaves exhibited a basipetal gradient of leaf development, investigated by defining seven interveinal areas, with growth ceasing first at the leaf tip. Interestingly, and in contrast to other reports, no spatial differences in epidermal cell size were apparent across the lamina, whereas a clear basipetal gradient in cell production rate was found. These data suggest that the rate and timing of cell production was more important in determining leaf shape, given the constant cell size across the leaf lamina. The effect of elevated [CO2] imposed on this developmental gradient suggested that leaf cell production continued longer in elevated [CO2] and that basal increases in cell production rate were also more important than altered cell expansion for increased final leaf size and altered leaf shape in elevated [CO2].

Metal cluster expansion by addition of low valent group 14 reagents: III. Reaction of bis[bis(trimethylsilyl)methyl]tin with M3(CO)12 or its derivatives (M = Fe, Ru, or Os): the crystal and molecular structures of M3(μ-SnR2)2(CO)10(R = CH(SiMe3)2; M = Ru or Os)

The stannylene [SnR2] (R = CH(SiMe3)2) reacts in different ways with the three dodecacarbonyls of the iron triad: [Fe3(CO)12] gives [Fe2(CO)8(μ-SnR2)], [Ru3(CO)12] gives the planar pentametallic cluster [Ru3(CO)10(μ-SnR2)2], for which a full structural analysis is reported, while [Os3(CO)12] fails to react. Different products are also obtained from three nitrile derivatives: [Fe3-(CO)11(MeCN)] gives [Fe2(CO)6(μ-SnR2)2], which has a structure significantly different from that of known Fe2Sn2 clusters, [Ru3(CO)10(MeCN)2] gives the pentametallic cluster described above, while [Os3(CO)10(MeCN)2] gives the isostructural osmium analogue, which shows the unusual feature of a CO group bridging two osmium atoms.

Metal cluster expansion by addition of low-valent group 4B reagents: crystal and molecular structure of [Os3SnH2(CO)10{CH(SiMe3)2}2]; a compound with hydrogen bridging osmium and tin

Cluster expansion of [Os3H2(CO)10] with [SnR2][R = CH(SiMe3)2] take place in high yield to give [Os3SnH2(CO)10R2], the first closed triosmium–main-group metal cluster to be structurally characterized; a novel feature is the presence of a hydrogen atom bridging the tin atom and one of the osmium atoms.

Biomass functions and expansion factors in young Norway spruce (Picea abies [L.] Karst) trees

Roots, stems, branches and needles of 160 Norway spruce trees younger than 10 years were sampled in seven forest stands in central Slovakia in order to establish their biomassfunctions (BFs) and biomassexpansionfactors (BEFs). We tested three models for each biomass pool based on the stem base diameter, tree height and the two parameters combined. BEF values decreased for all spruce components with increasing height and diameter, which was most evident in very young trees under 1 m in height. In older trees, the values of BEFs did tend to stabilise at the height of 3–4 m. We subsequently used the BEFs to calculate dry biomass of the stands based on average stem base diameter and tree height. Total stand biomass grew with increasing age of the stands from about 1.0 Mg ha−1 at 1.5 years to 44.3 Mg ha−1 at 9.5 years. The proportion of stem and branch biomass was found to increase with age, while that of needles was fairly constant and the proportion of root biomass did decrease as the stands grew older.

'Agricultural poverty' and the expansion of artisanal mining in sub-Saharan Africa: Experiences from southwest Mali and southeast Ghana

Why do people engage in artisanal and small-scale mining (ASM) – labour-intensive mineral extraction and processing activity – across sub-Saharan Africa? This paper argues that ‘agricultural poverty’, or hardship induced by an over-dependency on farming for survival, has fuelled the recent rapid expansion of ASM operations throughout the region. The diminished viability of smallholder farming in an era of globalization and overreliance on rain-fed crop production restricted by seasonality has led hundreds of thousands of rural African families to ‘branch out’ into ASM, a move made to secure supplementary incomes. Experiences from Komana West in Southwest Mali and East Akim District in Southeast Ghana are drawn upon to illustrate how a movement into the ASM economy has impacted farm families, economically, in many rural stretches of sub-Saharan Africa.

Ex vivo expansion of limbal stem cells is affected by substrate properties

Limbal epithelial stem cells play a key role in the maintenance and regulation of the corneal surface. Damage or destruction of these cells results in vascularisation and corneal opacity. Subsequent limbal stem cell transplantation requires an ex vivo expansion step and preserving cells in an undifferentiated state remains vital. In this report we seek to control the phenotype of limbal epithelial stem cells by the novel application of compressed collagen substrates. We have characterised the mechanical and surface properties of conventional collagen gels using shear rheology and scanning electron microscopy. In doing so, we provide evidence to show that compressive load can improve the stiffness of collagen substrates. In addition Western blotting and immunohistochemistry display increased cytokeratin 3 (CK3) protein expression relating to limbal epithelial cell differentiation on stiff collagen substrates. Such gels with an elastic modulus of 2900 Pa supported a significantly higher number of cells than less stiff collagen gels (3 Pa). These findings have substantial influence in the development of ocular surface constructs or experimental models particularly in the fields of stem cell research, tissue engineering and regenerative medicine.

An item response analysis of the motor and behavioral subscales of the unified Huntington's disease rating scale in huntington disease gene expansion carriers

Although the Unified Huntington's Disease Rating Scale (UHDRS) is widely used in the assessment of Huntington disease (HD), the ability of individual items to discriminate individual differences in motor or behavioral manifestations has not been extensively studied in HD gene expansion carriers without a motor-defined clinical diagnosis (ie, prodromal-HD or prHD). To elucidate the relationship between scores on individual motor and behavioral UHDRS items and total score for each subscale, a nonparametric item response analysis was performed on retrospective data from 2 multicenter longitudinal studies. Motor and behavioral assessments were supplied for 737 prHD individuals with data from 2114 visits (PREDICT-HD) and 686 HD individuals with data from 1482 visits (REGISTRY). Option characteristic curves were generated for UHDRS subscale items in relation to their subscale score. In prHD, overall severity of motor signs was low, and participants had scores of 2 or above on very few items. In HD, motor items that assessed ocular pursuit, saccade initiation, finger tapping, tandem walking, and to a lesser extent, saccade velocity, dysarthria, tongue protrusion, pronation/supination, Luria, bradykinesia, choreas, gait, and balance on the retropulsion test were found to discriminate individual differences across a broad range of motor severity. In prHD, depressed mood, anxiety, and irritable behavior demonstrated good discriminative properties. In HD, depressed mood demonstrated a good relationship with the overall behavioral score. These data suggest that at least some UHDRS items appear to have utility across a broad range of severity, although many items demonstrate problematic features.

Contact angle of a hemispherical bubble: an analytical approach

We have calculated the equilibrium shape of the axially symmetric Plateau border along which a spherical bubble contacts a flat wall, by analytically integrating Laplace’s equation in the presence of gravity, in the limit of small Plateau border sizes. This method has the advantage that it provides closed-form expressions for the positions and orientations of the Plateau border surfaces. Results are in very good overall agreement with those obtained from a numerical solution procedure, and are consistent with experimental data. In particular we find that the effect of gravity on Plateau border shape is relatively small for typical bubble sizes, leading to a widening of the Plateau border for sessile bubbles and to a narrowing for pendant bubbles. The contact angle of the bubble is found to depend even more weakly on gravity.

Indian summer monsoon variations could have affected the early Holocene woodland expansion in the Near East

Postglacial expansion of deciduous oak woodlands of the Zagros—Anti-Taurus Mountains, a major biome of the Near East, was delayed until the middle Holocene at ~6300 cal. yr BP. The current hypotheses explain this delay as a consequence of a regional aridity during the early Holocene, slow migration rates of forest trees, and/or a long history of land use and agro-pastoralism in this region. In the present paper, support is given to a hypothesis that suggests different precipitation seasonalities during the early Holocene compared with the late Holocene. The oak species of the Zagros—Anti-Taurus Mts, particularly Quercus brantii Lindl., are strongly dependent on spring precipitation for regeneration and are sensitive to a long dry season. Detailed analysis of modern atmospheric circulation patterns in SW Asia during the late spring suggests that the Indian Summer Monsoon (ISM) intensification can modify the amount of late spring and/or early summer rainfall in western/northwestern Iran and eastern Anatolia, which could in turn have controlled the development of the Zagros—Anti-Taurus deciduous oak woodlands. During the early Holocene, the northwestward shift of the Inter-Tropical Convergence Zone (ITCZ) could have displaced the subtropical anticyclonic belt or associated high pressure ridges to the northwest. The latter could, in turn, have prevented the southeastward penetration of low pressure systems originating from the North Atlantic and Black Sea regions. Such atmospheric configuration could have reduced or eliminated the spring precipitation creating a typical Mediterranean continental climate characterized by winter-dominated precipitation. This scenario highlights the complexity of biome response to climate system interactions in transitional climatic and biogeographical regions.