Uranium removal from contaminated groundwater by synthetic resins

Synthetic resins are shown to be effective in removing uranium from contaminated groundwater. Batch and field column tests showed that strong-base anion-exchange resins were more effective in removing uranium from both near-neutral-pH (6.5)- and high-pH (8)-low-nitrate-containing groundwaters, than metal-chelating resins, which removed more uranium from acidic-pH (5)-high-nitrate-containing groundwater from the Oak Ridge Reservation (ORR) Y-12 S-3 Ponds area in Tennessee, USA. Dowex 1-X8 and Purolite A-520E anion-exchange resins removed more uranium from high-pH (8)-low-nitrate-containing synthetic groundwater in batch tests than metal-chelating resins. The Dowex™ 21K anion-exchange resin achieved a cumulative loading capacity of 49.8 mg g^-1 before breakthrough in a field column test using near-neutral-pH (6.5)-low-nitrate-containing groundwater. However, in an acidic-pH (5)-high-nitrate-containing groundwater, metal-chelating resins Diphonix and Chelex-100 removed more uranium than anion-exchange resins. In 15 mL of acidic-pH (5)-high-nitrate-containing groundwater spiked with 20 mg L^-1 uranium, the uranium concentrations ranged from 0.95 mg L^-1 at 1-h equilibrium to 0.08 mg L^-1 at 24-h equilibrium for Diphonix and 0.17 mg L^-1 at 1-h equilibrium to 0.03 mg L^-1 at 24-h equilibrium for Chelex-100. Chelex-100 removed more uranium in the first 10 min in the 100 mL of acidic-(pH 5)-high-nitrate-containing groundwater (~5 mg L^-1 uranium); however, after 10 min, Diphonix equaled or out-performed Chelex-100. This study presents an improved understanding of the selectivity and sorption kenetics of a range of ion-exchange resins that remove uranium from both low- and high-nitrate-containing groundwaters with varying pHs..

Facile Syntheses of Three Major Metabolites of Thioridazine

NMR studies were conducted with the aim of determining the diastereoisomeric ratio of a commercially supplied sample of mesoridazine (MES) and to compare the results with a freshly synthesised sample of MES. The results indicated that the commercially supplied MES consisted almost entirely of one diastereoisomeric pair, which was in agreement with previous findings reported by Eap et al. (J Chromatogr 669:271-279, 1995). The synthesised sample of MES was analysed by NMR in two stages: 1) as the initial product isolated as the free base from the direct synthesis, and 2) as the free base isolated from the crystallised besylate salt of the synthetic product. The NMR results show that the initial synthetic product consisted of two equal pairs of diastereoisomers. The diastereoisomeric pairs were further separated by the addition of the chiral shift reagent (R)-(-)-N-(3,5 dinitrobenzoyl)-alpha-benzylamine to reveal equal quantities of all four enantiomers, clearly observed at the methyl sulfoxide proton peak of the NMR scan. The sample obtained from the crystallisation of MES besylate, however, indicated a significant difference, with a diastereoisomeric ratio of 75:25. The results suggest that MES besylate undergoes preferential crystallisation of one pair of diastereoisomers, with the other pair remaining in solution. (C) 2004 Wiley-Liss, Inc.

Survival of Swiss-Webster mouse cerebellar granule neurons is promoted by a combination of potassium channel blockers

Cultured cerebellar granule neurons (CGN) are commonly used to assess neurotoxicity, but are routinely maintained in supraphysiological (25 mM) extracellular K⁺ concentrations [K⁺]_o. We investigated the effect of potassium channel blockade on survival of CGN derived from Swiss-Webster mice in supraphysiological (25 mM) and physiological (5.6 mM) [K⁺]_o. CGN were cultured for 5 days in 25 mM K⁺, then in 5.6 mM K⁺ or 25 mM K⁺ (control). Viability, assayed 24 h later by 3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide (MTT) reduction and by lactate dehydrogenase (LDH) release, was ∼50% in 5.6 mM K⁺ versus 25 mM K⁺ (p < .001). Potassium channel blockers, 2 mM 4-aminopyridine (4-AP), 2 mM tetraethylammonium (TEA) or 1 mM Ba²⁺, individually afforded limited protection in 5.6 mM K⁺. However, survival in 5.6 mM K⁺ with a combination of 4-AP, TEA and Ba²⁺ was similar to survival in 25 mM K⁺ without blockers (p < .001 versus 5.6 mM K⁺ alone). CGN survival in 25 mM K⁺ was attenuated 25% by 2 μM nifedipine (p > .001), but nifedipine did not attenuate neuroprotection by K⁺ channel blockers. Together, these results suggest that the survival of CGN depends on the K⁺ permeability of the membrane rather than the activity of a particular type of K⁺ channel, and that the mechanism of neuroprotection by K⁺ channel blockers is different from that of elevated [K⁺]_o.

Isotope Shift in the Dielectronic Recombination of Three-Electron ANd57+

Isotope shifts in dielectronic recombination spectra were studied for Li-like ^ANd⁵⁷⁺ ions with A=142 and A=150. From the displacement of resonance positions energy shifts dE^142?150(2s-2p_1/2)=40.2(3)(6)??meV [(stat)(sys)] and dE^142?150(2s-2p_3/2)=42.3(12)(20)??meV of 2s-2p_jtransitions were deduced. An evaluation of these values within a full QED treatment yields a change in the mean-square charge radius of ^142?150d?r²?=-1.36(1)(3)??fm². The approach is conceptually new and combines the advantage of a simple atomic structure with high sensitivity to nuclear size.

Adsorption characteristics of Cu and Ni on Irish peat moss

Peat has been widely used as a low cost adsorbent to remove a variety of materials including organic compounds and heavy metals from water. Various functional groups in lignin allow such compounds to bind on active sites of peat. The adsorption of Cu²⁺ and Ni²⁺ from aqueous solutions on Irish peat moss was studied both as a pure ion and from their binary mixtures under both equilibrium and dynamic conditions in the concentration range of 5–100 mg/L. The pH of the solutions containing either Cu²⁺ or Ni²⁺ was varied over a range of 2–8. The adsorption of Cu²⁺ and Ni⁺² on peat was found to be pH dependent. The adsorption data could be fitted to a two-site Langmuir adsorption isotherm and the maximum adsorption capacity of peat was determined to be 17.6 mg/g for Cu²⁺ and 14.5 mg/g for Ni²⁺ at 298 K when the initial concentration for both Cu²⁺ and Ni²⁺ was 100 mg/L, and the pH of the solution was 4.0 and 4.5, respectively. Column studies were conducted to generate breakthrough data for both pure component and binary mixtures of copper and nickel. Desorption experiments showed that 2 mM EDTA solution could be used to remove all of the adsorbed copper and nickel from the bed.

Formation of Novel Di-Nuclear Lanthanide Luminescent Sm(III), Eu(III) and Tb(III) Triple Stranded Helicates from a C2 Symmetrically 2,6-Dicarboxylic Amide based 1,3-Xylene Ligand in CH3CN

The synthesis of the C2-symmetrical ligand 1 consisting of two naphthalene units connected to two pyridine-2,6-dicarboxamide moieties linked by a xylene spacer and the formation of LnIII-based (Ln1/4 Sm, Eu, Tb, and Lu) dimetallic helicates [Ln2 · 13] in MeCN by means of a metal-directed synthesis is described. By analyzing the metal-induced changes in the absorption and the fluorescence of 1, the formation of the helicates, and the presence of a second species [Ln2 · 12] was confirmed by nonlinear- regression analysis. While significant changes were observed in the photophysical properties of 1, the most dramatic changes were observed in the metal-centred lanthanide emissions, upon excitation of the naphthalene antennae. From the changes in the lanthanide emission, we were able to demonstrate that these helicates were formed in high yields (ca. 90% after the addition of 0.6 equiv. of LnIII), with high binding constants, which matched well with that determined from the changes in the absorption spectra. The formation of the LuIII helicate, [ Lu2 · 13 ] , was also investigated for comparison purposes, as we were unable to obtain accurate binding constants from the changes in the fluorescence emission upon formation of [Sm2 · 13], [Eu2 · 13], and [Tb2 · 13].

An allosteric potentiator of M4 mAChR modulates hippocampal synaptic transmission.

Muscarinic acetylcholine receptors (mAChRs) provide viable targets for the treatment of multiple central nervous system disorders. We have used cheminformatics and medicinal chemistry to develop new, highly selective M₄ allosteric potentiators. VU10010, the lead compound, potentiates the M₄ response to acetylcholine 47-fold while having no activity at other mAChR subtypes. This compound binds to an allosteric site on the receptor and increases affinity for acetylcholine and coupling to G proteins. Whole-cell patch clamp recordings revealed that selective potentiation of M₄ with VU10010 increases carbachol-induced depression of transmission at excitatory but not inhibitory synapses in the hippocampus. The effect was not mimicked by an inactive analog of VU10010 and was absent in M₄ knockout mice. Selective regulation of excitatory transmission by M₄ suggests that targeting of individual mAChR subtypes could be used to differentially regulate specific aspects of mAChR modulation of function in this important forebrain structure.

Genetic programming based formulation for fresh and hardened properties of self-compacting concrete containing pulverised fuel ash

Self-compacting concrete (SCC) flows into place and around obstructions under its own weight to fill the formwork completely and self-compact without any segregation and blocking. Elimination of the need for compaction leads to better quality concrete and substantial improvement of working conditions. This investigation aimed to show possible applicability of genetic programming (GP) to model and formulate the fresh and hardened properties of self-compacting concrete (SCC) containing pulverised fuel ash (PFA) based on experimental data. Twenty-six mixes were made with 0.38 to 0.72 water-to-binder ratio (W/B), 183–317 kg/m³ of cement content, 29–261 kg/m³ of PFA, and 0 to 1% of superplasticizer, by mass of powder. Parameters of SCC mixes modelled by genetic programming were the slump flow, JRing combined to the Orimet, JRing combined to cone, and the compressive strength at 7, 28 and 90 days. GP is constructed of training and testing data using the experimental results obtained in this study. The results of genetic programming models are compared with experimental results and are found to be quite accurate. GP has showed a strong potential as a feasible tool for modelling the fresh properties and the compressive strength of SCC containing PFA and produced analytical prediction of these properties as a function as the mix ingredients. Results showed that the GP model thus developed is not only capable of accurately predicting the slump flow, JRing combined to the Orimet, JRing combined to cone, and the compressive strength used in the training process, but it can also effectively predict the above properties for new mixes designed within the practical range with the variation of mix ingredients.

Experimental observations of the stress regime in unsaturated compacted clay when laterally confined

Construction processes often involve reformation of the landscape, which will inevitably encompass compaction of artificially placed soils. A common application of fill materials is their use as backfill in many engineering applications, for example behind a retaining wall. The post-construction behaviour of clay fills is complex with respect to stresses and deformation when the fills become saturated over time. Heavily compacted fills swells significantly more than the lightly compacted fills. This will produce enhanced lateral stresses if the fill is laterally restrained. The work presented in this paper examines how the stress regime in unsaturated clay fills changes with wetting under laterally restrained conditions. Specimens of compacted kaolin, with different initial conditions, were wetted to various values of suction under zero lateral strain at constant net overburden pressure which allowed the concept of K _{0 (the ratio between the net horizontal stress and the net vertical stress) to be examined. Tests were also carried out to examine the traditional concept of the earth pressure coefficient ‘at rest' under loading and unloading and its likely effects on the stress–strain properties. The results have shown that the stress regime (i.e. the lateral stress) changes significantly during wetting under laterally restrained conditions. The magnitude of the change is affected by the initial condition of the soil. The results have also indicated that the earth pressure coefficient ‘at rest' during loading (under the normally consolidated condition) is unaffected by suction and such loading conditions inevitably lead to the development of anisotropic stress–strain properties}

Atomic ordering in nano-layered FePt

Monte Carlo simulation of chemical ordering kinetics in nano-layered L1₀ AB binary intermetallics was performed. The study addressed FePt thin layers considered as a material for ultra-high-density magnetic storage media and revealed metastability of the L1₀ c-variant superstructure with monoatomic planes parallel to the surface and off-plane easy magnetization. The layers, originally perfectly ordered in a c-variant of the L1₀ superstructure, showed homogeneous disordering running in parallel with a spontaneous re-orientation of the monoatomic planes leading to a mosaic microstructure composed of a- and b-L1₀-variant domains. The domains nucleated heterogeneously on the surface of the layer and grew discontinuously inwards its volume. Finally, the domains relaxed towards an equilibrium microstructure of the system. Two “atomistic-scale” processes: (i) homogeneous disordering and (ii) nucleation of the a- and b-L1₀-variant domains showed characteristic time scales. The same was observed for the domain microstructure relaxation. The discontinuous domain growth showed no definite driving force and proceeded due to thermal fluctuations. The above complex structural evolution has recently been observed experimentally in epitaxially deposited thin films of FePt.

Modelling the effect of water immersion thermal processing on polyacetylene levels and instrumental colour of carrot disks

C₁₇ polyacetylenes are a group of bioactive compounds present in carrots which have recently gained scientific attention due to their cytotoxicity against cancer cells. In common with many bioactive compounds, their levels may be influenced by thermal processes, such as boiling or water immersion. This study investigated the effect of a number of water immersion time/temperature combinations on concentrations of these compounds and attempted to model the changes. Carrot samples were thermally treated by heating in water at temperatures from 50–100 °C and holding times of 2–60 min. Following heating, levels of falcarinol (FaOH), falcarindiol (FaDOH), falcarindiol-3-acetate (FaDOAc) and Hunter colour parameters (L^*, a^*, b^*) were determined. FaOH, FaDOH, FaDOAc levels were significantly reduced at lower temperatures (50–60 °C). In contrast, samples heated at temperatures from 70–100 °C exhibited higher levels of polyacetylenes (p < 0.05) than did raw unprocessed samples. Regression modelling was used to model the effects of temperature and holding time on the levels of the variables measured. Temperature treatment and holding time were found to significantly affect the polyacetylene content of carrot disks. Predicted models were found to be significant (p < 0.05) with high coefficients of determination (R²).

Theory of the Kinetics of Chemical Potentials in Heterogeneous Catalysis

Simple and powerful: The reaction kinetics at surfaces of heterogeneous catalysts is reformulated in terms of the involved chemical potentials. Based on this formulism, an approach of searching for good catalysts is proposed without recourse to extensive calculations of reaction barriers and detailed kinetic analyses. (see picture; R=reactant, I=surface intermediate, P=product, and =standard chemical potential).

Chemical and mechanical stability of sodium sulfate activated slag after exposure to elevated temperature

The chemical and mechanical stability of slag activated with two different concentrations of sodium sulfate (Na₂SO₄) after exposure to elevated temperatures ranging from 200 to 800 °C with an increment of 200 °C has been examined. Compressive strengths and pH of the hardened pastes before and after the exposure were determined. The various decomposition phases formed were identified using X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. The results indicated that Na₂SO₄ activated slag has a better resistance to the degradation caused by exposure to elevated temperature up to 600 °C than Portland cement system as its relative strengths are superior. The finer slag and higher Na₂SO₄ concentration gave better temperature resistance. Whilst the pH of the hardened pastes decreased with an increase in temperature, it still maintained a sufficiently high pH for the protection of reinforcing bar against corrosion.