Crystal Structure and Thermodynamic Stability of Ba/Ti‐Substituted Pollucites for Radioactive Cs/Ba Immobilization

As an analogue of the mineral pollucite (CsAlSi₂O₆), CsTiSi₂O_6.5 is a potential host phase for radioactive Cs. However, as ¹³⁷Cs and ¹³⁵Cs transmute to ¹³⁷Ba and ¹³⁵Ba, respectively, through the beta decay, it is essential to study the structure and stability of this phase upon Cs → Ba substitution. In this work, two series of Ba/Ti‐substituted samples, Cs_xBa_(1?x)/2TiSi₂O_6.5 and Cs_xBa_1?xTiSi₂O_7?0.5x, (x = 0.9 and 0.7), were synthesized by high‐temperature crystallization from their respective precursors. Synchrotron X‐ray diffraction and Rietveld analysis reveal that while Cs_xBa_(1?x)/2TiSi₂O_6.5 samples are phase‐pure, Cs_xBa_1?xTiSi₂O_7?0.5x samples contain Cs_3x/(2+x)Ba_(1?x)/(2+x)TiSi₂O_6.5 pollucites (i.e., also two‐Cs‐to‐one‐Ba substitution) and a secondary phase, fresnoite (Ba₂TiSi₂O₈). Thus, the Cs_xBa_1?xTiSi₂O_7?0.5x series is energetically less favorable than Cs_xBa_(1?x)/2TiSi₂O_6.5. To study the stability systematics of Cs_xBa_(1?x)/2TiSi₂O_6.5 pollucites, high‐temperature calorimetric experiments were performed at 973 K with or without the lead borate solvent. Enthalpies of formation from the constituent oxides (and elements) have thus been derived. The results show that with increasing Ba/(Cs + Ba) ratio, the thermodynamic stability of these phases decreases with respect to their component oxides. Hence, from the energetic viewpoint, continued Cs → Ba transmutation tends to destabilize the parent silicotitanate pollucite structure. However, the Ba‐substituted pollucite co‐forms with fresnoite (which incorporates the excess Ba), thereby providing viable ceramic waste forms for all the Ba decay products.     

Nanofibrillated cellulose in wood coatings: mechanical properties of free composite films

Composite films of nanofibrillated cellulose (NFC), derived from beech wood pulp, and 8 commercial acrylic and alkyd polymeric binders were prepared. Structural and mechanical properties of the composites were assessed by microscopy and tensile tests before and after aging. While the NFC was compatible with acrylate polymers, it formed undesired aggregates during processing with the alkyd polymers. Modulus of elasticity, tensile strength, and elongation at break of prepared films depended on the initial properties of the neat polymers. All composite films were stiffer, stronger, and less extensible than the corresponding neat polymer films. The reinforcing effect increased with increasing NFC content. Aging by artificial weathering strongly affected the mechanical properties of neat polymer and composite films. Alkyd films became, compared to the acrylate films, much stiffer and more brittle after artificial weathering. The results of the mechanical tests are regarded as promising step to use NFC as novel component in wood coatings.     

Layer‐by‐Layer Nanoparticles as an Efficient siRNA Delivery Vehicle for SPARC Silencing

Efficient and safe delivery systems for siRNA therapeutics remain a challenge. Elevated secreted protein, acidic, and rich in cysteine (SPARC) protein expression is associated with tissue scarring and fibrosis. Here we investigate the feasibility of encapsulating SPARC‐siRNA in the bilayers of layer‐by‐layer (LbL) nanoparticles (NPs) with poly(L‐arginine) (ARG) and dextran (DXS) as polyelectrolytes. Cellular binding and uptake of LbL NPs as well as siRNA delivery were studied in FibroGRO cells. siGLO‐siRNA and SPARC‐siRNA were efficiently coated onto hydroxyapatite nanoparticles. The multilayered NPs were characterized with regard to particle size, zeta potential and surface morphology using dynamic light scattering and transmission electron microscopy. The SPARC‐gene silencing and mRNA levels were analyzed using ChemiDOC western blot technique and RT‐PCR. The multilayer SPARC‐siRNA incorporated nanoparticles are about 200 nm in diameter and are efficiently internalized into FibroGRO cells. Their intracellular fate was also followed by tagging with suitable reporter siRNA as well as with lysotracker dye; confocal microscopy clearly indicates endosomal escape of the particles. Significant (60%) SPARC‐gene knock down was achieved by using 0.4 pmole siRNA/μg of LbL NPs in FibroGRO cells and the relative expression of SPARC mRNA reduced significantly (60%) against untreated cells. The cytotoxicity as evaluated by xCelligence real‐time cell proliferation and MTT cell assay, indicated that the SPARC‐siRNA‐loaded LbL NPs are non‐toxic. In conclusion, the LbL NP system described provides a promising, safe and efficient delivery platform as a non‐viral vector for siRNA delivery that uses biopolymers to enhance the gene knock down efficiency for the development of siRNA therapeutics.     

PREDICTING INFLUENZA WAVES WITH HEALTH INSURANCE DATA

In recent years, many of the most developed countries have started to create influenza surveillance systems, because influenza still is very costly, not just concerning the health systems, but also economically. In most of these systems statistical methods are applied, unfortunately with rather moderate results. In contrast to statistical methods case-based reasoning explicitly uses former episodes. Because we already successfully applied our prognostic method, which combines case-based reasoning (CBR) with temporal abstraction, to kidney functions, we use it again to forecast influenza. Because health centers collect extensive laboratory data but their availability is usually delayed for at least two weeks, we use quickly available data from the main German health insurance scheme. In this article, we propose the use of CBR for influenza forecast and we show promising results.     

Human obesity is associated with a chronic elevation in brain 5-hydroxytryptamine turnover

The afferent signals that evoke changes in energy intake with regard to body weight regulation are presumed to arise partly from body stores, with the most likely candidate being adipose tissue depots. However, clinical investigation of the neuronal circuitry involved in the central nervous system's processing of such satiety signals remains largely unexplored. Using percutaneously placed catheters in either the right or left internal jugular veins, we were able to quantify the release of central nervous system monoamine and indoleamine neurotransmitters in 64 weight-stable male subjects with varying degrees of adiposity. Veno-arterial plasma concentration differences and internal jugular blood or plasma flow were used, according to the Fick Principle, to quantify the amount of neurotransmitter stemming from the brain. By combining this technique with a noradrenaline and adrenaline isotope dilution method for examining neuronal transmitter release, we were able to examine the association between central nervous system neurotransmitters and efferent sympathetic nervous outflow and adrenomedullary function in human obesity. We found that brain 5-hydroxytryptamine (serotonin) turnover is chronically elevated in proportion to adiposity and is increased postprandially to a similar degree in lean and obese individuals. There was no difference in the degree of sympathetic nervous activity or rate of adrenaline secretion in the subjects examined. It therefore seems that in human obesity, in the face of a chronic elevation in peripheral satiety signals, brain serotonergic processes are switched on accordingly, but the subsequent physiological response involving a reduction in food intake, increased thermogenesis and sympathetic activity is in some way impeded.     

Two-equivalent electrochemical reduction of a cyano-complex [Tl(CN)2] and the novel di-nuclear compound [(CN)5Pt−Tl]

Extending our recent insights in two-electron transfer microscopic mechanisms for a Tl^III/Tl^I redox system [D.E. Khoshtariya, et al., Inorg. Chem. 41 (2002) 1728], the electrochemical response of glassy carbon electrode in acidified solutions of Tl^III (ClO₄)₃ containing different concentrations of sodium cyanide has been extensively studied for the first time by use of cyclic voltammetry and the CVSIM curve simulation PC program. The complex [Tl^III(CN)₂]⁺ has been thoroughly identified electrochemically and shown to display a single well-defined reduction wave (which has no anodic counterpart), ascribed to the two-equivalent process yielding [Tl^I(aq)]⁺. This behavior is similar to that of [Tl^III(aq)]³⁺ ion in the absence of sodium cyanide, disclosed in the previous work, and is compatible with the quasi-simultaneous yet sequential two-electron transfer pattern (with two reduction waves merged in one), implying the rate-determining first electron transfer step (resulting in the formation of a covalently interacting di-thallium complex as a metastable intermediate), and the fast second electron transfer step. Some preliminary studies of the two-equivalent reduction of directly metal-metal bonded stable compound [(CN)₅Pt^II-Tl^III]⁰ has been also performed displaying two reduction waves compatible with a true sequential pattern.     

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