Interlaboratory studies on in vitro test methods for estimating in vivo resorption of calcium phosphate ceramics

A potential standard method for measuring the relative dissolution rate to estimate the resorbability of calcium-phosphate-based ceramics is proposed. Tricalcium phosphate (TCP), magnesium-substituted TCP (MgTCP) and zinc-substituted TCP (ZnTCP) were dissolved in a buffer solution free of calcium and phosphate ions at pH 4.0, 5.5 or 7.3 at nine research centers. Relative values of the initial dissolution rate (relative dissolution rates) were in good agreement among the centers. The relative dissolution rate coincided with the relative volume of resorption pits of ZnTCP in vitro. The relative dissolution rate coincided with the relative resorbed volume in vivo in the case of comparison between microporous MgTCPs with different Mg contents and similar porosity. However, the relative dissolution rate was in poor agreement with the relative resorbed volume in vivo in the case of comparison between microporous TCP and MgTCP due to the superimposition of the Mg-mediated decrease in TCP solubility on the Mg-mediated increase in the amount of resorption. An unambiguous conclusion could not be made as to whether the relative dissolution rate is predictive of the relative resorbed volume in vivo in the case of comparison between TCPs with different porosity. The relative dissolution rate may be useful for predicting the relative amount of resorption for calcium-phosphate-based ceramics having different solubility under the condition that the differences in the materials compared have little impact on the resorption process such as the number and activity of resorbing cells.

Influence of phosphate addition on the arsenic uptake by wheat (Triticum Durum) grown in arsenic polluted soils

Arsenic (As) uptake and distribution in the roots, shoots, and grain of wheat (Triticum durum) grown in 2 As polluted soils (192 and 304 mg kg ^-1 respectively), and an uncontaminated soil (14 mg kg^-1 ), collected from Scarlino plain (Tuscany, Italy), was investigated with respect with phosphorus fertilization. Three different level of phosphorus (P) fertilization: PO [0 kg ha^-1], Pl [75 kg ha^-1], and P2 [150 kg ha^-1], as KH₂PO₄ of P, were applied. The presence of high concentrations of As in soils reduced plants growth, decreased grain yield and increased root, shoot and grain As concentrations, especially in the absence of P fertilization. The P fertilization decreased the As concentration in all the tissues as well as the translocation of As to the shoot and grain. This observation may be useful in certain areas of the world with high levels of As in soils, to reduce the potential risk posed to human health by As entering the food-chain. © by PSP.

Influence of phosphate on the arsenic uptake by wheat (Triticum durum L.) irrigated with arsenic solutions at three different concentrations

In this study we have investigated the uptake and distribution of arsenic (As) and phosphate (P_i) in roots, shoots, and grain of wheat grown in an uncontaminated soil irrigated with solutions containing As at three different concentrations (0.5, 1 and 2 mg l^-1) and in the presence or in the absence of P fertilization. Arsenic in irrigation water reduced plants growth and decreased grain yield. When P_i was not added (P-), plants were more greatly impacted compared to the plus P_i (P+) treatments. The differences in mean biomass between P- and P+ treatments at the higher As concentrations demonstrated the role of P_i in preventing As toxicity and growth inhibition. Arsenic concentrations in root, shoot and grain increased with increasing As concentration in irrigation water. It appears that P fertilization minimizes the translocation of As to the shoots and grain whilst enhancing P status of plant. The observation that P fertilization minimises the translocation of arsenic to the shoots and grain is interesting and may be useful for certain regions of the world that has high levels of As in groundwater or soils. © 2008 Springer Science+Business Media B.V.

High-affinity phosphate/arsenate transport in white lupin (Lupinus albus) is relatively insensitive to phosphate status

The development of proteoid roots under phosphorus deficiency by white lupin (Lupinus albus) may result in increased arsenate uptake, as arsenate is a phosphate analogue. This, together with its high biomass production, rapid growth and ability to survive in soils with low phosphate and nitrogen contents, low pH and high metal contents make them an interesting species to investigate with respect to revegetation, and possibly also for long-term phytoremediation, of arsenic contaminated soils. Kinetic parameters for arsenate uptake for P-deficient and P-sufficient plants, as well as for proteoid and nonproteoid roots were obtained. Down-regulation of arsenate uptake by phosphate, as well as phosphate/arsenate competition for P-deficient and P-sufficient plants was studied. Arsenate uptake was reduced by phosphate, but small differences were found between P-deficient and P-sufficient plants. Arsenate uptake by proteoid roots was higher than for nonproteoid roots of P-deficient plants, with higher V_max and similar K_m values. Down-regulation of the high affinity phosphate/arsenate uptake system by phosphate does take place but seems to be slower than in other plants. This study suggests that the low sensitivity of the phosphate/arsenate uptake system to regulation by phosphate may be related to the adaptations of white lupin to low P available environments. Such adaptation are absent in plants unable to develop proteoid roots.

Biomass allocation, phosphorus nutrition and vesicular-arbuscular mycorrhizal infection in clones of Yorkshire Fog, Holcus lanatus L. (Poaceae) that differ in their phosphate uptake kinetics and tolerance to arsenate

Biomass and phosphorus allocation were determined in arsenate tolerant and non-tolerant clones of the grass Holcus lanatus L. in both solution culture and in soil. Arsenate is a phosphate analogue and is taken up by the phosphate uptake system. Tolerance to arsenate in this grass is achieved by suppression of arsenate (and phosphate) influx. When clones differing in their arsenate tolerance were grown in solution culture with a range of phosphate levels, a tolerant clone did not fare as well as a non-tolerant at low levels of phosphate nutrition in that it had reduced shoot biomass production, increased biomass allocation to the roots and lower shoot phosphorus concentration. At a higher level of phosphate nutrition there was little or no difference in these parameters, suggesting that differences at lower levels of phosphate nutrition were due solely to differences in the rates of phosphate accumulation. In experiments in sterile soil (potting compost) the situation was more complicated with tolerant plants having lower growth rates but higher phosphorus concentrations. The gene for arsenate tolerance is polymorphic in arsenate uncontaminated populations. When phosphorus concentration of tolerant phenotypes was determined in one such population, again tolerants had a higher phosphorus status than non-tolerants. Tolerants also had higher rates of vesicular-arbuscular mycorrhizal (VAM) infection. The ecological implications of these results are that it appears that suppression of the high affinity uptake system, is at least in part, compensated by increased mycorrhizal infection. © 1994 Kluwer Academic Publishers.

Suppression of the high affinity phosphate uptake system:A mechanism of arsenate tolerance in Holcus lanatus L.

In Holcus lanatus L. phosphate and arsenate are taken up by the same transport system. Short-term uptake kinetics of the high affinity arsenate transport system were determined in excised roots of arsenate-tolerant and non-tolerant genotypes. In tolerant plants the V_max of ion uptake in plants grown in phosphate-free media was decreased compared to non-tolerant plants, and the affinity of the uptake system was lower than in the non-tolerant plants. Both the reduction in V_max and the increase in K_m led to reduced arsenate influx into tolerant roots. When the two genotypes were grown in nutrient solution containing high levels of phosphate, there was little change in the uptake kinetics in tolerant plants. In non-tolerant plants, however, there was a marked decrease in the V_max to the level of the tolerant plants but with little change in the K_m. This suggests that the low rate of arsenate uptake over a wide range of differing root phosphate status is due to loss of induction of the synthesis of the arsenate (phosphate) carrier. © 1992 Oxford University Press.

Marine Collagen Reinforcement of Calcium Phosphate Bone Cements: A Biological Assessment

Induction of in vivo responses by implanted biomaterials is of great interest in the medical device field. Calcium phosphate bone cements (CPCs) can potentially promote natural bone remodelling and ingrowth in vivo and, as such are becoming more common place in a range of orthopaedic procedures. However, concerns remain regarding their mechanical and handling properties. Compressive modulus and fracture toughness of CPCs can be improved, without compromising injectability and setting time, through the incorporation of bovine collagen fibres1. Incorporation of marine derived collagen fibres has also yielded similar improvements2. It is hypothesised that, due to its role in bone formation and function, that incorporation of collagen in CPCs will also result in biological benefits.
The biological properties of α-TCP-CPC were largely unchanged by the incorporation of marine derived collagen. However, as a result of significant improvements to the mechanical properties, its incorporation may still result in a suitable alternative to some commercially available bone cements.

Extent and mechanism of phase separation during the extrusion of calcium phosphate pastes

The aim of this study was to increase understanding of the mechanism and dominant drivers influencing phase separation during ram extrusion of calcium phosphate (CaP) paste for orthopaedic applications. The liquid content of extrudate was determined, and the flow of liquid and powder phases within the syringe barrel during extrusion were observed, subject to various extrusion parameters. Increasing the initial liquid-to-powder mass ratio, LPR, (0.4-0.45), plunger rate (5-20 mm/min), and tapering the barrel exit (45°-90°) significantly reduced the extent of phase separation. Phase separation values ranged from (6.22 ± 0.69 to 18.94 ± 0.69 %). However altering needle geometry had no significant effect on phase separation. From powder tracing and liquid content determination, static zones of powder and a non-uniform liquid distribution was observed within the barrel. Measurements of extrudate and paste LPR within the barrel indicated that extrudate LPR remained constant during extrusion, while LPR of paste within the barrel decreased steadily. These observations indicate the mechanism of phase separation was located within the syringe barrel. Therefore phase separation can be attributed to either; (1) the liquid being forced downstream by an increase in pore pressure as a result of powder consolidation due to the pressure exerted by the plunger or (2) the liquid being drawn from paste within the barrel, due to suction, driven by dilation of the solids matrix at the barrel exit. Differentiating between these two mechanisms is difficult; however results obtained suggest that suction is the dominant phase separation mechanism occurring during extrusion of CaP paste.

The effect of niobium and tantalum on physicochemical and catalytic properties of silver and platinum catalysts based on MCF mesoporous cellular foams

MCF, NbMCF and TaMCF Mesostructured Cellular Foams were used as supports for platinum and silver (1 wt%). Metallic and bimetallic catalysts were prepared by grafting of metal species on APTMS (3-aminopropyltrimethoxysilane) and MPTMS (2-mercaptopropyltrimethoxysilane) functionalized supports. Characterizations by X-ray diffraction (XRD), ultraviolet–visible (UV–Vis) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray fluorescence (XRF) spectroscopy, and in situ Fourier Transform Infrared (FTIR) spectroscopy allowed to monitor the oxidation state of metals and surface properties of the catalysts, in particular the formation of bimetallic phases and the strong metal–support interactions. It was evidenced that the functionalization agent (APTMS or MPTMS) influenced the metals dispersion, the type of bimetallic species and Nb/Ta interaction with Pt/Ag. Strong Nb–Ag interaction led to the reduction of niobium in the support and oxidation of silver. MPTMS interacted at first with Pt to form Pt–Ag ensembles highly active in CH3OH oxidation. The effect of Pt particle size and platinum–silver interaction on methanol oxidation was also considered. The nature of the functionalization agent strongly influenced the species formed on the surface during reaction with methanol and determined the catalytic activity and selectivity.

Lanthanide oxide and phosphate nanoparticles for thermometry and bimodal imaging

Nesta tese relatam-se estudos de fotoluminescência de nanopartículas de óxidos e fosfatos dopados com iões trivalentes de lantanídeos, respectivamente, nanobastonetes de (Gd,Eu)2O3 e (Gd,Yb,Er)2O3 e nanocristais de (Gd,Yb,Tb)PO4, demonstrando-se também aplicações destes materiais em revestimentos inteligentes, sensores de temperatura e bioimagem. Estuda-se a transferência de energia entre os sítios de Eu3+ C2 e S6 dos nanobastonetes Gd2O3. A contribuição dos mecanismos de transferência de energia entre sítios para o tempo de subida 5D0(C2) é descartada a favor da relaxação directa 5D1(C2) 5D0(C2) (i.e., transferência de energia entre níveis). O maior tempo de decaimento do nível 5D0(C2) nos nanobastonetes, relativamente ao valor medido para o mesmo material na forma de microcristais, é atribuído, quer à existência de espaços livres entre nanobastonetes próximos (factor de enchimento ou fracção volúmica), quer à variação do índice de refracção efectivo do meio em torno dos iões Eu3+. A dispersão de nanobastonetes de (Gd,Eu)2O3 em três resinas epoxi comerciais através da cura por UV permite obter nanocompósitos epoxi- (Gd,Eu)2O3. Relatam-se estudos cinéticos e das propriedades térmicas e de fotoluminescência destes nanocompósitos. Estes, preservam as típicas propriedades de emissão do Eu3+, mostrando o potencial do método de cura por UV para obter revistimentos inteligentes e fotoactivos. Considera-se um avanço significativo a realização de uma nanoplataforma óptica, incorporando aquecedor e termómetro e capaz de medir uma ampla gama de temperaturas (300-2000 K) à escala nano, baseada em nanobastonetes de (Gd,Yb,Er)2O3 (termómetros) cuja superfície se encontra revestida com nanopartículas de ouro. A temperature local é calculada usando, quer a distribuição de Boltzmann (300-1050 K) do rácio de intensidades da conversão ascendente 2H11=2!4I15=2/4S3=2!4I15=2, quer a lei de Planck (1200-2000 K) para uma emissão de luz branca atribuída à radiação do corpo negro. Finalmente, estudam-se as propriedades de fotoluminescência correspondentes às conversões ascendente e descendente de energia em nanocristais de (Gd,Yb,Tb)PO4 sintetizados por via hidrotérmica. A relaxividade (ressonância magnética) do 1H destes materiais são investigadas, tendo em vista possíveis aplicações em imagem bimodal (luminescência e ressonância magnética nuclear).

Niobium oxides and niobates physical properties

Niobium oxides have been pointed as an alternative to tantalum in the production of solid electrolytic capacitors, with advantages regarding the dielectric constant, density and price. In this work, it is intended to create a new family of niobium oxides based capacitors, adapting the technology and production line currently used with tantalum. Despite the known potentialities of niobium oxides, and many types of niobates, in several technological applications, the understanding of these oxide systems is still noticeably insufficient. Hence, a careful bibliographic review is shown, which evidences the complexity of these materials, the difficulty in identifying of their different phases and polymorphs, as well as in the interpretation of their properties. In this context, several fundamental studies on niobium oxides are presented, namely structural, microstructural, optical and electrical characterizations, which allow not only to contribute in an important way for the general knowledge of the physical properties of these materials, but also to advance to a sustained development of the niobium oxides based solid electrolytic capacitors. Several processing parameters were studied, clearing the way towards the creation of a prototype. It was also decided to perform a preliminary study on the synthesis and characterization of other oxide systems based in niobium, namely rare-earth orthoniobates (RENbO4), which interest has been related to their optical properties and protonic conductivity. Hence, single and polycrystalline samples of RENbO4 were synthesized and characterized structural, optical and electrically, leaving open an interesting future work.

Stable isotope composition of smectite in suevites at the Ries crater, Germany: Implications for hydrous alteration of impactites

The 24-km diameter Ries crater, Germany, exhibits well-preserved crater filling and surficial melt-rich breccia deposits that are believed to have been altered by post-impact hydrothermal fluids. The alteration mineralogy of the crater filling breccias is characterized by clay (smectite, chlorite) and a zeolite assemblage, and secondary clay phases (smectite, minor halloysite) in surficial melt-bearing breccia deposits. Using stable isotope analysis of secondary smectitic clay fractions, evidence of significant hydrous alteration of impactites at large water/rock ratios was found. The estimated fluid temperatures, using data derived by delta(18)O and delta D fractionation, suggest smectite precipitation in surficial breccias in equilibrium with meteoric fluids at temperatures 16 +/- 5 degrees C in agreement with the long-term variation of modern precipitation in the area. The stable isotope composition of smectite in crater-fill breccia, however, suggests a trend of monotonously increasing temperatures from 43 to 112 degrees C. with increasing depth through the breccia sequence. This demonstrates a different origin of alteration and temperature distribution for the surficial and crater filling melt-bearing impact breccias in the Ries crater. Our results suggest that the inverted structure of hydrothermal systems observed in some terrestrial impact craters, including the Ries crater, could indicate the initial configuration of a thermal anomaly in the crater filling sequence, but which is replaced with a normal hydrothermal convection in crater proper, during the course of post-impact cooling. (C) 2010 Elsevier B.V. All rights reserved.

Uncoupling phosphate deficiency from its major effects on growth and transcriptome via PHO1 expression in Arabidopsis.

Inorganic phosphate (Pi) is one of the most limiting nutrients for plant growth in both natural and agricultural contexts. Pi-deficiency leads to a strong decrease in shoot growth, and triggers extensive changes at the developmental, biochemical and gene expression levels that are presumably aimed at improving the acquisition of this nutrient and sustaining growth. The Arabidopsis thaliana PHO1 gene has previously been shown to participate in the transport of Pi from roots to shoots, and the null pho1 mutant has all the hallmarks associated with shoot Pi deficiency. We show here that A. thaliana plants with a reduced expression of PHO1 in roots have shoot growth similar to Pi-sufficient plants, despite leaves being strongly Pi deficient. Furthermore, the gene expression profile normally triggered by Pi deficiency is suppressed in plants with low PHO1 expression. At comparable levels of shoot Pi supply, the wild type reduces shoot growth but maintains adequate shoot vacuolar Pi content, whereas the PHO1 underexpressor maintains maximal growth with strongly depleted Pi reserves. Expression of the Oryza sativa (rice) PHO1 ortholog in the pho1 null mutant also leads to plants that maintain normal growth and suppression of the Pi-deficiency response, despite the low shoot Pi. These data show that it is possible to unlink low shoot Pi content with the responses normally associated with Pi deficiency through the modulation of PHO1 expression or activity. These data also show that reduced shoot growth is not a direct consequence of Pi deficiency, but is more likely to be a result of extensive gene expression reprogramming triggered by Pi deficiency.