A low temperature X-ray single-crystal diffraction and polarised infra-red study of epidote

The effects of low-temperature on the crystal structure of a natural epidote [Ca1.925Fe0.745Al2.265Ti0.004 Si3.037O12(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6) angstrom and beta = 115.396(8)degrees at room conditions, Sp. Gr. P2(1)/m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe3+ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000-2,500 cm(-1) are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)-O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe3+ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)-O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for "rigid body motions". A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for "non-correlated motion". The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U-eq (defined as one-third of the trace of the orthogonalised U-ij tensor) by similar to 40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U-eq of the octahedral and oxygen sites decrease similarly by similar to 35%, whereas those of the tetrahedral cations by similar to 22%

A comparison between elite swimmers and kayakers on upper body push and pull strength and power performance

The aim of the present study was to compare the load-power curve expressed at bench press (PR) and prone bench pull (PU) between elite swimmers and kayakers. Another aim was to calculate the strength and power PR/PU ratio in the same populations. Fifteen elite swimmers (SW: age = 23.8 ± 2.9 y; body mass = 82.8 ± 5.6 kg; body height = 184.1 ± 4.6 cm) and 13 elite kayakers (KA: age = 23.8 ± 2.9 y; body mass = 91.0 ± 3.5 kg; body height = 180.1 ± 5.4 cm) were assessed for PR 1RM and PU 1RM. They were then assessed for power produced at 40, 60 and 80% of 1RM in both PR and PU. The area under the load-power curve (AUC) and PR/PU ratios were calculated for both the SW and KA groups. The KA group showed significantly higher PR1RM (+18.2%; p = 0.002) and PU1RM (+25.7%; p < 0.001) compared to the SW group. Significant group differences were also detected for PUAUC (p < 0.001) and for the PR/PU power ratio (p < 0.001). No significant group differences were detected for PRAUC (p = 0.605) and for the PR/PU strength ratio (p = 0.065; 0.87 and 0.82 in SW and KA, respectively). The present findings indicate that elite KA were stronger and more powerful than elite SW in the upper body. Not consistently with other athletic populations, both KA and SW athletes were stronger and more powerful in upper body pull compared to push moves

Are differences in stage at presentation a credible explanation for reported differences in the survival of patients with colorectal cancer in Europe?

Popular reporting of a comparison of cancer survival rates across 17 European countries, based on data collected by national and regional cancer registries, has left an impression of inadequate treatment of patients in the UK. A subsequent study has suggested that the poor survival rates reported for the UK can, in large part, be explained by more advanced stage at presentation. We believe this conclusion to be unsound and use this study as an example to illustrate the methodological difficulties which may arise during such international comparisons. As the NHS cancer plan aspires to achieve for the UK parity with the best cancer care in Europe, careful thought needs to be given to identifying countries with which the UK can usefully compare itself and the most appropriate indicators for this comparison. http://www.bjcancer.com © 2001 Cancer Research Campaignhttp://www.bjcancer.co

The effect of pressure on open-framework silicates: elastic behaviour and crystal-fluid interaction

The elastic behaviour and the structural evolution of microporous materials compressed hydrostatically in a pressure-transmitting fluid are drastically affected by the potential crystal-fluid interaction, with a penetration of new molecules through the zeolitic cavities in response to applied pressure. In this manuscript, the principal mechanisms that govern the P-behaviour of zeolites with and without crystal-fluid interaction are described, on the basis of previous experimental findings and computational modelling studies. When no crystal-fluid interaction occurs, the effects of pressure are mainly accommodated by tilting of (quasi-rigid) tetrahedra around O atoms that behave as hinges. Tilting of tetrahedra is the dominant mechanism at low-mid P-regime, whereas distortion and compression of tetrahedra represent the mechanisms which usually dominate the mid-high P regime. One of the most common deformation mechanisms in zeolitic framework is the increase of channels ellipticity. The deformation mechanisms are dictated by the topological configuration of the tetrahedral framework; however, the compressibility of the cavities is controlled by the nature and bonding configuration of the ionic and molecular content, resulting in different unit-cell volume compressibility in isotypic structures. The experimental results pertaining to compression in "penetrating" fluids, and thus with crystal-fluid interaction, showed that not all the zeolites experience a P-induced intrusion of new monoatomic species or molecules from the P-transmitting fluids. For example, zeolites with well-stuffed channels at room conditions (e.g. natural zeolites) tend to hinder the penetration of new species through the zeolitic cavities. Several variables govern the sorption phenomena at high pressure, among those: the "free diameters" of the framework cavities, the chemical nature and the configuration of the extra-framework population, the partial pressure of the penetrating molecule in the fluid (if mixed with other non-penetrating molecules), the rate of P-increase, the surface/volume ratio of the crystallites under investigations and the temperature at which the experiment is conducted. An overview of the intrusion phenomena of monoatomic species (e.g. He, Ar, Kr), small (e.g. H2O, CO2) and complex molecules, along with the P-induced polymerization phenomena (e.g. C2H2, C2H4, C2H6O, C2H6O2, BNH6, electrolytic MgCl2*21H2O solution) is provided, with a discussion of potential technological and geological implications of these experimental findings

Breadmaking performance of protein enriched, gluten-free breads

9 pages, 3 figures, 5 tables.-- Published online 19 February 2008.-- The original publication is available at www.springerlink.comSoybean enriched, rice-based gluten-free breads were designed incorporating a structuring agent (hydroxypropylmethylcellulose, HPMC) and a processing aid (transglutaminase, TG). At dough level the effect of increasing amounts of soybean protein isolate (SPI), HPMC and water was studied in the Mixolab. Mixing and thermal characteristics showed the significant effect induced by water, soybean protein isolate, HPMC and TG, allowing the selection of the appropriate amounts for the breadmaking performance of enriched gluten-free breads. The single addition or in combination of 4% HPMC, 13% soybean and 1% TG produced significant changes in the physical properties of the rice-based gluten-free breads. The presence of SPI blended with rice flour produced a significant decrease in the specific volume of the bread, although this detrimental effect was partially counteracted by its combination with HPMC, decreasing also the crumb hardness. The micrographs of the crumb showed the beneficial effect of the HPMC, obtaining a more open aerated structure. Protein enriched, gluten-free breads can be obtained with a combination of SPI, HPMC and TG.This work was financially supported by Comisión Interministerial de Ciencia y Tecnología Project (MCYT, AGL2005-05192-C04-01) and Consejo Superior de Investigaciones Científicas (CSIC). C. Marco gratefully acknowledges the Ministerio de Educación y Ciencia for her grant.Peer reviewe

Low-temperature behavior of natural kalsilite with P31c symmetry: An in situ single-crystal X-ray diffraction study

The low-temperature behavior of a natural kalsilite (ideal formula KAlSiO4) with P31c symmetry has been investigated by in situ single-crystal diffraction. A series of intensity data collections and structural refinements have been performed at 298, 250, 200, 150, and 100 K on decreasing temperature, and 175, 225, and 275 K on increasing T. The variations of the unit-cell parameters of kalsilite as a function of T are continuous, and show no evidence of any phase transitions or thermo-elastic anomalies in this temperature range. An expansion is observed along [0001] with decreasing temperature. The axial and volume thermal expansion coefficients ({alpha}j = lj-1{middle dot}{partial}lj/{partial}T, {alpha}V = V-1{middle dot}{partial}V/{partial}T) between 298 and 100 K, calculated by weighted linear regression through the data points, are {alpha}a = {alpha}b = 1.30(6){middle dot}10-5, {alpha}c = -1.5(1){middle dot}10-5, {alpha}V = 1.1(2){middle dot}10-5 K-1. The main structural change on decreasing temperature is a cooperative anti-rotation of tetrahedra forming the six-membered rings lying parallel to (0001). This tetrahedral rotation is coupled with a change in the distances between the extra-framework cations and the framework O atoms. A small decrease in the tetrahedral tilts perpendicular to [0001] is responsible for the negative thermal expansion along [0001]; the implications of these mechanisms for thermal expansion in nephelines and kalsilites are discussed

Neutron diffraction in gemology: Single-crystal diffraction study of brazilianite, NaAl3(PO4)(2)(OH)(4)

The chemical composition and the crystal structure of a gem-quality brazilianite from the Telírio pegmatite, near Linópolis, Minas Gerais, Brazil, [NaAl3(PO4)2(OH)4, a = 11.2448(5) Å, b = 10.1539(6) Å, c = 7.1031(3) Å, β = 97.351(4)°, V = 804.36(7) Å3, space group P21/n, Z = 4], have been reinvestigated by means of electron microprobe analysis in wavelength-dispersive mode, single-crystal X-ray and neutron diffraction. The chemical analysis shows that brazilianite from Telírio Claim approaches almost ideal composition. The neutron anisotropic structural refinement was performed with final agreement index R1 = 0.0290 for 211 refined parameters and 2844 unique reflections with Fo > 4σ(Fo), the X-ray refinement led to R1 = 0.0325 for 169 refined parameters and 2430 unique reflections with Fo > 4σ(Fo). The building-block units of the brazilianite structure consist of chains of edge-sharing AlO4(OH)2 and AlO3(OH)3 octahedra. Chains are connected, via corner-sharing, by P-tetrahedra to form a three-dimensional framework, with Na atoms located in distorted cavities running along [100]. Five independent H sites were located, here labeled as H(1), H(2a), H(2b), H(3), and H(4). The configuration of the OH groups, along with the complex hydrogen-bonding scheme, are now well defined. The O-H distances corrected for "riding motion" range between ~0.992 and ~1.010 Å, the O···O distances between ~2.67 and ~2.93 Å, and the O-H···O angles between ~151° and ~174°. The H(2a) and H(2b) are only ~1.37 Å apart and mutually exclusive (both with site occupancy factor of 50%). The differences between the crystal structure of brazilianite and wardite [ideally NaAl3(PO4)2(OH)4·2H2O] are discussed. This work fulfills the need for accurate crystal-chemical data for this gem mineral

Faba bean (Vicia faba minor) and pea seeds (Pisum sativum) as protein sources in lactating ewes' diets.

18 Massese lactating ewes, divided into 3 homogeneous groups for parity and milk yield, were used to evaluate the replacement effects of soybean meal by Faba bean (Vicia faba minor) and Pea (Pisum sativum) seeds. During a 70 days trial (beginning after weaning: 30±1.5 days after lambing) animals were fed three isonitrogenous and isocaloric diets. Each diet was characterised by the presence of only one protein feed. The diets consisted of alfalfa hay (1.1 kg/head/d) and a decreasing amount of mixed feed (from 1.1 to 0.7 kg/head/d) to fit animals' requirements. Milk yield, milk chemical composition, animals live weight and BCS, health state and hematochemical parameters were regularly monitored. No diets palatability problems were detected. No significant differences resulted for live weight, BCS, milk yield and milk chemical composition, except for milk protein: higher for faba bean (6.54%) and soybean (6.39%) respect pea (5.66%) diets, P<0.05. No differences resulted for blood parameters too and no clinical signs of illness were observed. Therefore faba bean and pea seeds seem to be able to replace the soybean well

Apparent digestibility of three diets in the Amiata breed donkey during lactation

The aim of the trial was to evaluate the apparent digestibility of three isonitrogenous and isocaloric diets for lactating donkeys: a diet with 8 kg of hay and 1.5 kg of commercial flaked mixed feed (CM) (Diet 1); a diet with 7 kg of hay and a 2.2 kg of CM (Diet 2) and a diet with 7 kg of hay, 1.5 kg of CM, 200 ml of corn oil and 0.2 kg of soybean meal (Diet 3). Four pluriparous donkeys (309±12 kg BW) at approximately 2-4 months of lactation were used. The trial was conducted according to a 3x3 Latin Square design with 1 or 2 subject per each cell. Feed and faeces samples were analysed for DM, OM, CP, EE, CF, NDF, ADF and gross energy. Acid insoluble ash was used as marker to calculate the apparent digestibility. The apparent digestibility of the main dietary components showed not significant differences among the three diets but generally they were lower in Diet 3. DM intakes of every diet exceeded the esti- mated energy requirement, whereas protein requirements were not significantly satisfied by Diet 1