Neptunium(IV)-Hydroxamate Complexes:Their Speciation, and Kinetics and Mechanism of Hydrolysis

Simple hydroxamic acids such as acteohydroxamic acid (AHA) have been identified as suitable reagents for the control of Pu and Np in advanced separation processes for nuclear fuel reprocessing such as the Advanced PUREX or UREX based recycle processes, due to their ability to strip the tetravalent form of Pu and Np from tri-butyl phosphate into nitric acid. However, both free and metal bound hydroxamates are known to undergo acid catalysed hydrolysis at low pH, the kinetics of which must be characterised before implementation of PUREX/UREX based reprocessing flowsheets. In support of this implementation, a comprehensive thermodynamic and kinetic model that describes both the complex speciation and hydrolysis of AHA in the presence of Np(IV) has been developed. The model has two unique features: (i) in the case of the hydrolysis reaction kinetics, the model includes the hydrolysis of not only free AHA but also both the mono- and bishydroxamato-Np(IV) complexes; (ii) for the associated speciation calculations, the model explicitly includes the ionic strength dependence of not only the mono- and bishydroxamato-Np(IV) complexes but also the mono- and bisnitrato neptunium(IV) and monohydroxoneptunium(IV) complexes. For the latter three species, respective SIT coefficients of Δε1,NO3 = −0.13 ± 0.03 kg mol−1, Image ID:c8dt02194e-t1.gif, Δε2,NO3 = −0.37 ± 0.13 kg mol−1, Image ID:c8dt02194e-t2.gif Δε1,OH = −0.36 kg mol−1 and log10 K01,OH = −1.23 were also determined. Using experimental data from a series of kinetic studies on the Np(IV)–AHA system, this model has been used to determine the rate constants for hydrolysis of mono– and bis–acetohydroxamatoneptunium(IV) at 25 °C for the first time. These were found to be 3.5 × 10−5 ± 2.5 × 10−5 dm3 mol−1 s−1 and 1.9 × 10−3 ± 1.3 × 10−3 dm3 mol−1 s−1, respectively. Comparison of these values with the rate constants for hydrolysis of free AHA indicates that complexation of AHA with Np(IV) increases the rate of hydroxamate hydrolysis – an observation that we attribute to the electron withdrawing effect of the metal centre within the Np(IV)–AHA complex increasing the susceptibility of the AHA carbonyl carbon to nucleophilic attack, the accepted first step in its mechanism of hydrolysis

An Association of Multiple Well Differentiated Liposarcomas, Lipomatous Tissue and Hereditary Retinoblastoma

Well differentiated liposarcoma (atypical lipomatous tumour) is a low grade tumour, with no metastatic potential unless dedifferentiation supervenes. When superficial, it recurs locally only occasionally after marginal excision. We present a patient in whom bilateral childhood retinoblastoma was followed by later development of massive confluent areas of low grade liposarcoma and lipomatous tissue affecting the upper extremities and trunk. We discuss the role of mutations in the retinoblastoma gene (RB1) in linking these conditions and demonstrate the surgical management of an extremely unusual and challenging case

Criteria for effective zero-deforestation commitments

Zero-deforestation commitments are a type of voluntary sustainability initiative that companies adopt to signal their intention to reduce or eliminate deforestation associated with commodities that they produce, trade, and/or sell. Because each company defines its own zero-deforestation commitment goals and implementation mechanisms, commitment content varies widely. This creates challenges for the assessment of commitment implementation or effectiveness. Here, we develop criteria to assess the potential effectiveness of zero-deforestation commitments at reducing deforestation within a company supply chain, regionally, and globally. We apply these criteria to evaluate 52 zero-deforestation commitments made by companies identified by Forest 500 as having high deforestation risk. While our assessment indicates that existing commitments converge with several criteria for effectiveness, they fall short in a few key ways. First, they cover just a small share of the global market for deforestation-risk commodities, which means that their global impact is likely to be small. Second, biome-wide implementation is only achieved in the Brazilian Amazon. Outside this region, implementation occurs mainly through certification programs, which are not adopted by all producers and lack third-party near-real time deforestation monitoring. Additionally, around half of all commitments include zero-net deforestation targets and future implementation deadlines, both of which are design elements that may reduce effectiveness. Zero-net targets allow promises of future reforestation to compensate for current forest loss, while future implementation deadlines allow for preemptive clearing. To increase the likelihood that commitments will lead to reduced deforestation across all scales, more companies should adopt zero-gross deforestation targets with immediate implementation deadlines and clear sanction-based implementation mechanisms in biomes with high risk of forest to commodity conversion.ISSN:0959-3780ISSN:1872-949

Physicochemical behaviour of a dinuclear uranyl complex formed with an octaphosphinoylated para-tert-butylcalix[8]arene. Spectroscopic studies in solution and in the solid state

Spectrophotometric titrations of an octaphosphinoylated para-tert-butylcalix[8]arene (B8bL8) by uranyl nitrate and vice versa in anhydrous ethanol indicate that the species with 2:1 (uranyl:calixarene) stoichiometry is the major complex in solution. Based on these results, a synthesis route was designed to isolate this complex. The latter is an orange, non-hygroscopic polycrystalline powder, with chemical formula [(UO2)2(NO3)4(B8bL8) 2H2O]2(H2O). (Compd. 1), as ascertained by elemental analysis. Spectroscopic characterization of Compd. 1 in the solid and liquid states suggests that a neutral dinuclear uranyl calixarene complex was formed. MIR and FIR spectra indicate that, four phosphinoyl arms of the calixarene and two monodentate nitrates are bound to each 6-coordinate uranyl ion in the complex because no vibrational frequencies from un-coordinated O@P groups or from ionic nitrates are present; in addition the spectra reveal that water molecules form intramolecular hydrogen bonding with monodentate nitrates. The de-convoluted luminescence and XPS spectra obtained in the solid state point to a similar chemical environment around each uranyl ion, as confirmed by the mono-exponential decay of the luminescence. The more rigid conformation acquired by the calixarene in the complex and the non-symmetrical arrangement of the coordinated nitrates result in a particular feature of the emission spectra at 77 K. No evidence of cation-cation interaction was found. A rough approach to the molecular structure of the complex by molecular modelling based on the experimental findings yielded a molecule that was useful for understanding the physicochemical behaviour of Compd. 1.This work was supported by CONACYT [grant Nr. 36689-E], Mexico; and the Swiss National Science Foundation [grant SCOPES 2000–2002: No. 7BUPJ062293.00/1], Switzerland

Enhanced M1 Macrophage Polarization in Human Helicobacter pylori-Associated Atrophic Gastritis and in Vaccinated Mice

Background: Infection with Helicobacter pylori triggers a chronic gastric inflammation that can progress to atrophy and gastric adenocarcinoma. Polarization of macrophages is a characteristic of both cancer and infection, and may promote progression or resolution of disease. However, the role of macrophages and their polarization during H. pylori infection has not been well defined. Methodology/Principal Findings: By using a mouse model of infection and gastric biopsies from 29 individuals, we have analyzed macrophage recruitment and polarization during H. pylori infection by flow cytometry and real-time PCR. We found a sequential recruitment of neutrophils, eosinophils and macrophages to the gastric mucosa of infected mice. Gene expression analysis of stomach tissue and sorted macrophages revealed that gastric macrophages were polarized to M1 after H. pylori infection, and this process was substantially accelerated by prior vaccination. Human H. pylori infection was characterized by a mixed M1/M2 polarization of macrophages. However, in H. pylori-associated atrophic gastritis, the expression of inducible nitric oxide synthase was markedly increased compared to uncomplicated gastritis, indicative of an enhanced M1 macrophage polarization in this pre-malignant lesion. Conclusions/Significance: These results show that vaccination of mice against H. pylori amplifies M1 polarization of gastric macrophages, and that a similar enhanced M1 polarization is present in human H. pylori-induced atrophic gastritis

The Separation of 241

Electrical power sources used in outer planet missions are a key enabling technology for data acquisition and communications. State–of-the-art power sources generate electricity from alpha decay of 238Pu via thermoelectric conversion. However, production of 238Pu requires specialist facilities including a nuclear reactor, a source of 237Np for target irradiation and hotcells to chemically separate neptunium and plutonium within the irradiated targets. These specialist facilities are expensive to build and operate, so naturally, a more economical alternative is attractive to the industry. Within Europe 241Am is considered a promising alternative heat source for radioisotope thermoelectric generators (RTGs) and radioisotope heating units (RHUs). As a daughter product of 241Pu decay, 241Am exists in 1000 kgs quantities within the UK civil plutonium stockpile. A chemical separation process is required to extract the 241Am in a pure form and this paper describes the AMPPEX process (Americium and Plutonium Purification by Extraction), successfully developed over the past five years to isolate 241Am in high yield (> 99%) and to a high purity (> 99%). The process starts by dissolving plutonium dioxide in nitric acid with the aid of a silver(II) catalyst, which is generated electrochemically. The solution is then conditioned and fed to a PUREX type solvent extraction process, where the plutonium is separated from the americium and silver. The plutonium is converted back to plutonium dioxide and the americium is fed forward to a second solvent extraction step. Here the americium is selectively extracted leaving the silver in the aqueous phase. The americium is stripped from the solvent and recovered from solution as americium oxalate, which is calcined to give americium dioxide as the final product. This paper will describe the development of the separation process over a series of six solvent extraction separation trials using centrifugal contactors. The material produced (~ 4g 241Am) was used to make ceramic pellets to establish the behaviour of americium oxide material under high temperature (1450°C) sintering conditions. The chemical separation process is now demonstrated at concentrations expected on the full scale facility taking this process to TRL 4-5