Synthesis and evaluation of lipophilic BTBP ligands for An/Ln separation in nuclear waste treatment: the effect of alkyl substitution on extraction properties and implications for ligand design

Four new 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) ligands, which contain either additional alkyl groups on the pyridine rings or seven-membered aliphatic rings attached to the triazine rings, have been synthesized, and the effects of the additional alkyl substitution in the 4- and 4′-positions of the pyridine rings on their extraction properties with LnIII and AnIII cations in simulated nuclear waste solutions have been studied. The speciation of ligand 13 with some trivalent lanthanide nitrates was elucidated by 1H NMR spectroscopic titrations and ESI-MS. Although 13 formed both 1:1 and 1:2 complexes with LaIII and YIII, only 1:2 complexes were observed with EuIII and CeIII. Quite unexpectedly, both alkyl-substituted ligands 12 and 13 showed lower solubilities in certain diluents than the unsubstituted ligand CyMe4-BTBP. Compared to CyMe4-BTBP, alkyl-substitution was found to decrease the rates of metal-ion extraction of the ligands in both 1-octanol and cyclohexanone. A highly efficient (DAm > 10) and selective (SFAm/Eu > 90) extraction was observed for 12 and 13 in cyclohexanone and for 13 in 1-octanol in the presence of a phase-transfer agent. The implications of these results for the design of improved extractants for radioactive waste treatment are discussed.

A review of the spatial economics of non-timber forest product extraction: implications for policy

Patterns of forest cover and forest degradation determine the size and types of ecosystem services forests provide. Particularly in low-income countries, nontimber forest product (NTFP) extraction by rural people, which provides important resources and income to the rural poor, contributes to the level and pattern of forest degradation. Although recent policy, particularly in Africa, emphasizes forest degradation, relatively little research describes the spatial aspects of NTFP collection that lead to spatial degradation patterns. This paper reviews both the spatial empirical work on NTFP extraction and related forest degradation patterns, and spatial models of behavior of rural people who extract NTFPs from forest. Despite the impact of rural people's behavior on resulting quantities and patterns of forest resources, spatial–temporal models/patterns rarely inform park siting and sizing decisions, econometric assessments of park effectiveness, development projects to support conservation, or REDD protocols. Using the literature review as a lens, we discuss the models' implications for these policies with particular emphasis on effective conservation spending and leakage.

Automatic keyphrase extraction: a comparison of methods

There are many published methods available for creating keyphrases for documents. Previous work in the field has shown that in a significant proportion of cases author selected keyphrases are not appropriate for the document they accompany. This requires the use of such automated methods to improve the use of keyphrases. Often the keyphrases are not updated when the focus of a paper changes or include keyphrases that are more classificatory than explanatory. The published methods are all evaluated using different corpora, typically one relevant to their field of study. This not only makes it difficult to incorporate the useful elements of algorithms in future work but also makes comparing the results of each method inefficient and ineffective. This paper describes the work undertaken to compare five methods across a common baseline of six corpora. The methods chosen were term frequency, inverse document frequency, the C-Value, the NC-Value, and a synonym based approach. These methods were compared to evaluate performance and quality of results, and to provide a future benchmark. It is shown that, with the comparison metric used for this study Term Frequency and Inverse Document Frequency were the best algorithms, with the synonym based approach following them. Further work in the area is required to determine an appropriate (or more appropriate) comparison metric.

The impact of buffer zone size and management on illegal extraction, park protection and enforcement

Many protected areas or parks in developing countries have buffer zones at their boundaries to achieve the dual goals of protecting park resources and providing resource benefits to neighbouring people. Despite the prevalence of these zoning policies, few behavioural models of people’s buffer zone use inform the sizing and management of those zones. This paper uses a spatially explicit resource extraction model to examine the impact of buffer zone size and management on extraction by local people, both legal and illegal, and the impact of that extraction on forest quality in the park’s core and buffer zone. The results demonstrate trade-offs between the level of enforcement, the size of a buffer zone, and the amount of illegal extraction in the park; and describe implications for “enrichment” of buffer zones and evaluating patterns of forest degradation.

Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6'-bis(1,2,4-triazinyl)-2,2'-bipyridine ligand dissolved in alkylated cyclohexanone diluents

Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) and Eu(III) from nitric acid solutions by the CyMe4-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO3, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO3, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, DAm and SFAm/Eu decreased in the order of alkyl substitution 2 > 4 ~ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluents.

From BTBPs to BTPhens: the effect of ligand pre-organization on the extraction properties of quadridentate bis-triazine ligands

The synthesis, lanthanide complexation and solvent extraction of An(III) and Ln(III) radiotracers from nitric acid solutions by a pre-organized, phenanthroline-derived bis-triazine ligand CyMe4-BTPhen are described. It was found that the ligand separated Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and faster extraction kinetics compared to its 2,2’-bipyridine counterpart CyMe4-BTBP. The origins of the ligands extraction properties were established by a combination of solvent extraction experiments, X-ray crystallography, kinetics and surface tension measurements and lanthanide NMR spectroscopy.

Surface chemistry of glycine on Pt{111} in different aqueous environments

Adsorption of glycine on Ptf111g under UHV conditions and in different aqueous environments was studied by XPS (UHV and ambient pressure) and NEXAFS. Under UHV conditions, glycine adsorbs in its neutral molecular state up to about 0.15 ML. Further deposition leads to the formation of an additional zwitterionic species, which is in direct contact with the substrate surface, followed by the growth of multilayers, which also consist of zwitterions. The neutral surface species is most stable and decomposes at 360 K through a multi-step process which includes the formation of methylamine and carbon monoxide. When glycine and water are co-adsorbed in UHV at low temperatures (< 170 K) inter-layer diffusion is inhibited and the surface composition depends on the adsorption sequence. Water adsorbed on top of a glycine layer does not lead to significant changes in its chemical state. When glycine is adsorbed on top of a pre-adsorbed chemisorbed water layer or thick ice layer, however, it is found in its zwitterionic state, even at low coverage. No difference is seen in the chemical state of glycine when the layers are exposed to ambient water vapor pressure up to 0.2 Torr at temperatures above 300 K. Also the decomposition temperature stays the same, 360 K, irrespective of the water vapor pressure. Only the reaction path of the decomposition products is affected by ambient water vapor.

The long-term stability of a possible aqueous ammonium sulfate ocean inside Titan

We model the thermal evolution of a subsurface ocean of aqueous ammonium sulfate inside Titan using a parameterized convection scheme. The cooling and crystallization of such an ocean depends on its heat flux balance, and is governed by the pressure-dependent melting temperatures at the top and bottom of the ocean. Using recent observations and previous experimental data, we present a nominal model which predicts the thickness of the ocean throughout the evolution of Titan; after 4.5 Ga we expect an aqueous ammonium sulfate ocean 56 km thick, overlain by a thick (176 km) heterogeneous crust of methane clathrate, ice I and ammonium sulfate. Underplating of the crust by ice I will give rise to compositional diapirs that are capable of rising through the crust and providing a mechanism for cryovolcanism at the surface. We have conducted a parameter space survey to account for possible variations in the nominal model, and find that for a wide range of plausible conditions, an ocean of aqueous ammonium sulfate can survive to the present day, which is consistent with the recent observations of Titan's spin state from Cassini radar data [Lorenz, R.D., Stiles, B.W., Kirk, R.L., Allison, M.D., del Marmo, P.P., Iess, L., Lunine, J.I., Ostro, S.J., Hensley, S., 2008. Science 319, 1649–1651].

In vitro assessment of the bioaccessibility of brominated flame retardants in indoor dust using a colon extended model of the human gastrointestinal tract

An in vitro colon extended physiologically based extraction test (CEPBET) which incorporates human gastrointestinal tract (GIT) parameters (including pH and chemistry, solid-to-fluid ratio, mixing and emptying rates) was applied for the first time to study the bioaccessibility of brominated flame retardants (BFRs) from the 3 main GIT compartments (stomach, small intestine and colon) following ingestion of indoor dust. Results revealed the bioaccessibility of γ-HBCD (72%) was less than that for α- and β-isomers (92% and 80% respectively) which may be attributed to the lower aqueous solubility of the γ-isomer (2 μg L−1) compared to the α- and β-isomers (45 and 15 μg L−1 respectively). No significant change in the enantiomeric fractions of HBCDs was observed in any of the studied samples. However, this does not completely exclude the possibility of in vivo enantioselective absorption of HBCDs, as the GIT cell lining and bacterial flora – which may act enantioselectively – are not included in the current CE-PBET model. While TBBP-A was almost completely (94%) bioaccessible, BDE-209 was the least (14%) bioaccessible of the studied BFRs. Bioaccessibility of tri-hepta BDEs ranged from 32–58%. No decrease in the bioaccessibility with increasing level of bromination was observed in the studied PBDEs.

Lanthanide speciation in potential SANEX and GANEX actinide/ 2 lanthanide separations using Tetra-N-Donor extractants

Lanthanide(III) complexes with N-donor ex-tractants, which exhibit the potential for the separation of minor actinides from lanthanides in the management of spent nuclear fuel, have been directly synthesized and characterized in both solution and solid states. Crystal structures of the Pr3+, Eu3+, Tb3+, and Yb3+ complexes of 6,6′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin3-yl)-1,10-phenanthroline(CyMe4-BTPhen) and the Pr3+, Eu3+, and Tb3+ complexes of 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotria-zin-3-yl)-2,2′-bypyridine (CyMe4-BTBP) were obtained. The majority of these structures displayed coordination of two ofthe tetra-N-donor ligands to each Ln3+ ion, even when in some cases the complexations were performed with equimolar amounts of lanthanide and N-donor ligand. The structures showed that generally the lighter lanthanides had their coordination spheres completed by a bidentate nitrate ion, giving a 2+ charged complex cation, whereas the structures of the heavier lanthanides displayed tricationic complex species with a single water molecule completing their coordination environments. Electronic absorption spectroscopic titrations showed formation of the 1:2 Ln3+/LN4‑donor species (Ln = Pr3+, Eu3+, Tb3+) in methanol when the N-donor ligand was in excess. When the Ln3+ ion was in excess, evidence for formation of a 1:1 Ln3+/LN4‑donor complex species was observed. Luminescent lifetime studies of mixtures of Eu3+ with excess CyMe4-BTBP and CyMe4-BTPhen in methanol indicated that the nitrate-coordinated species is dominant in solution. X-ray absorption spectra of Eu3+ and Tb3+ species, formed by extraction from an acidic aqueous phase into an organic solution consisting of excess N-donor extractant in pure cyclohexanone or 30% tri-n-butyl phosphate (TBP) in cyclohexanone, were obtained. The presence of TBP in the organic phase did not alter lanthanide speciation. Extended X-ray absorption fine structure data from these spectra were fitted using chemical models established by crystallography and solution spectroscopy and showed the dominant lanthanide species in the bulk organic phase was a 1:2 Ln3+/LN‑donor species.

Synthesis of ligands for use in actinide extraction

The invention discloses an improved process for the preparation of 2,2,5,5-tetrasubstituted hexane-1,6-dicarbonyl compounds, and in particular diethyl 2,2,5,5-tetramethylhexanedioate and dimethyl 2,2,5,5-tetramethylhexanedioate, by the alkylation of 1,2-difunctional ethane compounds with enolates of carbonyl compounds. The process provides higher yields and greater synthetic brevity than existing processes.

The influence of markets and policy on spatial patterns of non-timber forest product extraction

When villagers extract resources, such as fuelwood, fodder, or medicinal plants from forests, their decisions over where and how much to extract are influenced by market conditions, their particular opportunity costs of time, minimum consumption needs, and access to markets. This paper develops an optimization model of villagers’ extraction behavior that clarifies how, and under what conditions, policies that create incentives such as improved returns to extraction in a buffer zone might be used instead of adversarial enforcement efforts to protect a forest’s pristine ‘‘inner core.’’

Contribution of non-volatile and volatile compounds to the umami taste and overall flavour of shiitake mushroom extracts and their application as flavour enhancers in cooked minced meat

Aqueous extracts of dried shiitake mushrooms (Lentinus edodes) were prepared as taste and flavour enhancers for meat formulations. Effects of time and temperature on the chemical and sensory properties of the extracts were examined. Extracts prepared at 70 °C had significantly higher concentrations (p<0.001) of the savoury tasting 5’-ribonucleotides than those prepared at 22 °C but increasing the extraction time from 30 to 360 mins only increased their recovery slightly (p=0.053). In contrast, higher temperature extracts had considerably smaller concentrations of the major volatile compounds, such as lenthionine, 1-octen-3-ol, 1,3-dithiethane and dimethyl disulfide, because of loss through volatilisation. A sensory discrimination test showed that the lower temperature extract was perceived to have less umami taste than the higher temperature extract (p=0.048). Incorporating the 70 °C shiitake extract into minced meat formulations led to significantly higher levels of savoury tasting 5’-ribonucleotides in the cooked meat but no significant difference in umami perception.