BTBPs versus BTPhens: some reasons for their differences in properties concerning the partitioning of minor actinides and the advantages of BTPhens

Two members of the tetradentate N-donor ligand families 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe4-BTPhen 2 has faster complexation kinetics than CyMe4-BTBP 1. The values for the HOMO−LUMO gap of 2 are comparable with those of CyMe4-BTBP 1 for which the HOMO−LUMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex ≥ heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped-flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol−1) energy barrier to rotation about the central biaryl C−C axis in order to achieve the cis−cis conformation that is required to form a complex, whereas the cis−cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe4-BTPhen 2 with Y(NO3)3 is also reported. The metal ion is 10- coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)°, 6.4(2)°, 9.7(2)°, respectively.

Liability of country foreignness and liability of regional foreignness: their effects on geographic diversification and firm performance

The costs of inter- and intra-regional diversification have been widely discussed in the existing international business literature, but the findings are mixed. Explanations for the mixed findings have important managerial implications, because business managers have to estimate accurately the costs of doing business within and across regions before they make their internationalization decisions. To explain the existing mixed findings, this study differentiates between liabilities of foreignness at the country and regional levels, and explores the joint effects of liability of country foreignness (LCF) and liability of regional foreignness (LRF) on the performance of internationalizing firms. Using data from 167 Canadian firms, we find that LCF may not necessarily be negatively correlated with intra-regional diversification, but LRF is positively correlated with inter-regional diversification. LCF moderates the relationship between LRF and inter-regional diversification, and also mediates the relationship between intra-regional diversification and firm performance. LRF mediates the relationship between inter-regional diversification and firm performance. Missing one or more of these variables may result in different cost estimates. Identification of the relationships between these variables helps to improve the accuracy of estimating the costs of doing business aboard.

Utilizing electronic effects in the modulation of BTPhen ligands with respect to the partitioning of minor actinides from lanthanides

Effects of bromine substitution at the 5 and 5,6-positions of the 1,10-phenanthroline nucleus of BTPhen ligand on their extraction properties for Ln(III) andAn(III) cations have been studied. Compared to C5-BTPhen, electronic modulation in BrC5-BTPhen and Br2C5-BTPhen enabled these ligands to be fine-tuned in order to enhance the separation selectivity of Am(III) from Eu(III)

Minor structural abnormalities in the infant face disrupt neural processing: a unique window into early caregiving responses

Infant faces elicit early, specific activity in the orbitofrontal cortex (OFC), a key cortical region for reward and affective processing. A test of the causal relationship between infant facial configuration and OFC activity is provided by naturally occurring disruptions to the face structure. One such disruption is cleft lip, a small change to one facial feature, shown to disrupt parenting. Using magnetoencephalography, we investigated neural responses to infant faces with cleft lip compared with typical infant and adult faces. We found activity in the right OFC at 140 ms in response to typical infant faces but diminished activity to infant faces with cleft lip or adult faces. Activity in the right fusiform face area was of similar magnitude for typical adult and infant faces but was significantly lower for infant faces with cleft lip. This is the first evidence that a minor change to the infant face can disrupt neural activity potentially implicated in caregiving.

The effect of alkyl substitution on the extraction properties of BTPhen ligands for the partitioning of trivalent minor actinides and lanthanides in spent nuclear fuels

Bis-triazinylphenanthroline ligands (BTPhens), which contain additional alkyl (n-butyl and sec-butyl) groups attached to the triazine rings, have been synthesized, and the effects of this alkyl substitution on their extraction properties with Ln(III) and An(III) cations in simulated nuclear waste solutions have been studied. The speciation of n-butyl-substituted ligand (C4- BTPhen) with some trivalent lanthanide nitrates was elucidated by 1 H-NMR spectroscopic titrations. These experiments have shown that the dominant species in solution were the 1:2 complexes [Ln(III)(BTPhen)2], even at higher Ln(III) concentrations, and the relative stability of 2:1 to 1:1 BTPhen-Ln(III) complexes varied with different lanthanides. As expected, sec-butylsubstituted ligand (sec-C4 BTPhen) showed higher solubility than C4-BTPhen in certain diluents. A greater separation factor (SFAm/Eu = ca. 210) was observed for sec-C4-BTPhen compared to C4-BTPhen (SFAm/Eu = ca. 125) in 1-octanol at 4 M HNO3 solutions. The greater separation factor may be due to the higher solubility of the 2:1 complex for sec-C4-BTPhen at the interface than the 1:1 complex of C4-BTPhen.

Efficient masking of corrosion and fission products such as Ni(II) and Pd(II) in the presence of the minor actinide Am(III) using hydrophilic anionic or cationic bis-triazines

Water soluble anionic and cationic bis-triazine ligands are able to suppress (mask) the extraction of corrosion and fission products such as Ni(II) and Pd(II) that are found in PUREX raffinates. Thus it is possible to separate these elements from the minor actinide Am(III). Although some masking agents have previously been developed that retard the extraction of Pd(II), this is the first time a masking agent has been developed for Ni(II).

Asset liability modelling and pension schemes: the application of robust optimization to USS

This paper uses a novel numerical optimization technique - robust optimization - that is well suited to solving the asset-liability management (ALM) problem for pension schemes. It requires the estimation of fewer stochastic parameters, reduces estimation risk and adopts a prudent approach to asset allocation. This study is the first to apply it to a real-world pension scheme, and the first ALM model of a pension scheme to maximise the Sharpe ratio. We disaggregate pension liabilities into three components - active members, deferred members and pensioners, and transform the optimal asset allocation into the scheme’s projected contribution rate. The robust optimization model is extended to include liabilities and used to derive optimal investment policies for the Universities Superannuation Scheme (USS), benchmarked against the Sharpe and Tint, Bayes-Stein, and Black-Litterman models as well as the actual USS investment decisions. Over a 144 month out-of-sample period robust optimization is superior to the four benchmarks across 20 performance criteria, and has a remarkably stable asset allocation – essentially fix-mix. These conclusions are supported by six robustness checks.

Circles of support and accountability: criminal justice volunteers as the 'Deliberative public'

This paper provides a review of the role played by volunteers within one particular offender management and reintegration scheme in the United Kingdom. Circles of Support and Accountability (COSA) draw on the expertise of volunteer members of the public to create supportive monitoring frameworks around sex offenders following their release from prison. The paper presents evidence as to the motivations of these volunteers, and argues that they play a crucial role in the success of the scheme, as they provide an instrumentally-useful form of reintegrative social contact to a socially-excluded offender population, and perform a symbolically important role as representatives of the wider community in taking ownership of offender management practices on behalf of the wider society. This is particularly significant in grounding those processes in the communicative practices of the social sphere, providing powerful reasons for intervention that reinforce the work that COSA do.

Search engine liability for autocomplete suggestions: personality, privacy and the power of the algorithm

This article is concerned with the liability of search engines for algorithmically produced search suggestions, such as through Google’s ‘autocomplete’ function. Liability in this context may arise when automatically generated associations have an offensive or defamatory meaning, or may even induce infringement of intellectual property rights. The increasing number of cases that have been brought before courts all over the world puts forward questions on the conflict of fundamental freedoms of speech and access to information on the one hand, and personality rights of individuals— under a broader right of informational self-determination—on the other. In the light of the recent judgment of the Court of Justice of the European Union (EU) in Google Spain v AEPD, this article concludes that many requests for removal of suggestions including private individuals’ information will be successful on the basis of EU data protection law, even absent prejudice to the person concerned.