The effect of aging and natural organic matter on the Th(OH)4 solubility

The solution chemistry of actinides, particularly hydrolysis, is of major importance in the design of nuclear waste repositories and in relation to nuclear fuel reprocessing cycles. In this study the formation and solubility of the Th(OH)₄ solid phase has been investigated as a function of the aging time and the presence of natural organic matter (e.g. humic acid) in 0.1 M NaClO₄, at weak acid pH and under normal atmospheric conditions. Th(OH)₄ has been prepared by alkaline precipitation and characterized by TGA, ATR–FTIR, XRD, and solubility measurements. According to the experimental data Th(OH)₄ is stable and remains the solubility limiting solid phase even in the presence of increased humic acid concentration in solution. Increasing humic acid concentration doesn’t affect the crystallite size and the solubility product of Th(OH)₄. Th(OH)₄ solubility is basically pH depended and governed by the presence of colloidal species. However, solid phase aging, which in absence of humic acid favors crystallinity, affects significantly the Th(OH)₄ solubility.     

A Combinatorial Property of Points and Balls,a Colored Version

Any finite set X⊂ℝ ^d colored with colors, contains a rainbow subset Y⊂X, such that any ball that contains Y contains a positive fraction of the points of X. The bound on the number of colors is tight. This work was done while the author was visiting the Mathematical Sciences Research Institute, Berkeley. The author was supported by the UCL Graduate School Research Grant, #1.03/04.RP.EMB.     

A validated HPLC determination of the flavone aglycone diosmetin in human plasma

Diosmetin, 3',5,7-trihydroxy-4'-methoxy flavone, is the aglycone of the flavonoid glycoside diosmin that occurs naturally in foods of plant origin. Diosmin exhibits antioxidant and anti-inflammatory activities, improves venous tone and it is used for the treatment of chronic venous insufficiency. Diosmin is hydrolyzed by enzymes of intestinal micro flora before absorption of its aglycone diosmetin. A specific, sensitive, precise, accurate and robust HPLC assay for the determination of diosmetin in human plasma was developed and validated. Diosmetin and the internal standard 7-ethoxycoumarin were isolated from plasma by liquid-liquid extraction and separated on a C8 reversed-phase column with methanol-water-acetic acid (55:43:2, v/v/v) as the mobile phase at 43 degrees C. Peaks were monitored at 344 nm. The method was linear in the 10-300 ng/mL concentration range (r > 0.999). Recovery for diosmetin and internal standard was greater than 89.7 and 86.8%, respectively. Intra-day and inter-day precision for diosmetin ranged from 1.6 to 4.6 and from 2.2 to 5.3%, respectively, and accuracy was better than 97.9%.     

Radium removal from aqueous solutions by adsorption on non-treated and chemically modified biomass by-product

The adsorption efficiency of a biomass by-product (olive cake) regarding the removal of radium (²²⁶Ra) from aqueous solutions has been investigated prior and after its chemical treatment. The chemical treatment of the biomass by-product included phosphorylation and MnO₂-coating. The separation/removal efficiency has been studied as a function of pH, salinity (NaCl) and calcium ion concentration (Ca²⁺) in solution. Evaluation of the experimental data shows clearly that the phosphorylated biomass by-product presents the highest adsorption capacity and efficiency followed by the MnO₂-coated material and the non-treated biomass by-product. However, regarding the effect of salinity and the presence of competitive cations (e.g. Ca²⁺) on the adsorption/removal efficiency, the MnO₂-coated material shows the lowest decline in efficiency (only 2 % of the relative adsorption efficiency) followed by the non-treated and the phosphorylated biomass by-product. The results of the present study indicate that depending on the physicochemical characteristics of the radium-contaminated water, all three types of the biomass by-product could be effectively used for the treatment of radium-contaminated waters. Nevertheless, the MnO₂-coated material is expected to be the most effective adsorbent and an alternative to MnO₂ resins for the treatment of environmentally relevant waters.     

Inhibition of Hsp90 with Resorcylic Acid Macrolactones: Synthesis and Binding Studies

A series of resorcylic acid macrolactones, analogues of the natural product radicicol has been prepared by chemical synthesis, and evaluated as inhibitors of heat shock protein 90 (Hsp90), an emerging attractive target for novel cancer therapeutic agents. The synthesis involves acylation of an ortho‐toluic acid dianion, esterification, followed by a ring‐closing metathesis to form the macrocycle. Subsequent manipulation of the protected hydroxymethyl side chain allows access to a range of new analogues following deprotection of the two phenolic groups. Co‐crystallization of one of the new macrolactones with the N‐terminal domain of yeast Hsp90 confirms that it binds in a similar way to the natural product radicicol and to our previous synthetic analogues, but that the introduction of the additional hydroxymethyl substituent appears to result in an unexpected change in conformation of the macrocyclic ring. As a result of this conformational change, the compounds bound less favorably to Hsp90.     

Limit shape of convex lattice polygons with minimal perimeter

Let n be a positive integer and · any norm in . Denote by B the unit ball of · and the class of convex lattice polygons with n vertices and least ·-perimeter. We prove that after suitable normalization, all members of tend to a fixed convex body, as n→∞.     

Uranium adsorption by non-treated and chemically modified cactus fibres in aqueous solutions

The adsorption efficiency of Opuntia ficus indica fibres regarding the removal of hexavalent uranium [U(VI)] from aqueous solutions has been investigated prior and after the chemical treatment (e.g. phosphorylation and MnO₂-coating) of the biomass. The separation/removal efficiency has been studied as a function of pH, uranium concentration, adsorbent mass, ionic strength, temperature and contact time. Evaluation of the experimental data shows that biosorption is strongly pH-depended and that the MnO₂-coated product presents the highest adsorption capacity followed by the phosphorylated and non-treated material. Experiments with varying ionic strength/salinity don’t show any significant effect on the adsorption efficiency, indicating the formation of inner-sphere surface complexes. The adsorption reactions are in all cases exothermic and relatively fast, particularly regarding the adsorption on the MnO₂-coated product. The results of the present study indicate that adsorption of uranium from waters is very effective by cactus fibres and particularly the modified treated fibres. The increased adsorption efficiency of the cactus fibres is attributed to their primary and secondary fibrillar structure, which result in a relative relative high specific surface available for sorption.     

Connecting experimental probability and theoretical probability

In this reflective paper, I explore the thinking of a group of pre-service teachers as they reason about experimental probability and theoretical probability. I am particularly interested in investigating whether pre-service teachers could construct a bidirectional link between the experimental probability and theoretical probability, similar to the tentative model I introduce elsewhere (2008) for coordinating the two perspectives on distribution. Overall, this research study contributes to understanding how pre-service students can build connections to help teachers conceptualize and support students to embrace elements that act as connections between the two approaches to probability.     

ON THE BOX DIMENSION FOR A CLASS OF NONAFFINE FRACTAL INTERPOLATION FUNCTIONS

We present lower and upper bounds for the box dimension of the graphs of certain nonaffine fractal interpolation functions by generalizing the results that hold for the affine case.     

Chemical Perturbation of Oncogenic Protein Folding: from the Prediction of Locally Unstable Structures to the Design of Disruptors of Hsp90–Client Interactions

Protein folding quality control in cells requires the activity of a class of proteins known as molecular chaperones. Heat shock protein-90 (Hsp90), a multidomain ATP driven molecular machine, is a prime representative of this family of proteins. Interactions between Hsp90, its co-chaperones, and client proteins have been shown to be important in facilitating the correct folding and activation of clients. Hsp90 levels and functions are elevated in tumor cells. Here, we computationally predict the regions on the native structures of clients c-Abl, c-Src, Cdk4, B-Raf and Glucocorticoid Receptor, that have the highest probability of undergoing local unfolding, despite being ordered in their native structures. Such regions represent potential ideal interaction points with the Hsp90-system. We synthesize mimics spanning these regions and confirm their interaction with partners of the Hsp90 complex (Hsp90, Cdc37 and Aha1) by Nuclear Magnetic Resonance (NMR). Designed mimics selectively disrupt the association of their respective clients with the Hsp90 machinery, leaving unrelated clients unperturbed and causing apoptosis in cancer cells. Overall, selective targeting of Hsp90 protein–protein interactions is achieved without causing indiscriminate degradation of all clients, setting the stage for the development of therapeutics based on specific chaperone:client perturbation.