Enhancing Metal Separations by Liquid–Liquid Extraction Using Polar Solvents

The less polar phase of liquid–liquid extraction systems has been studied extensively for improving metal separations; however, the role of the more polar phase has been overlooked for far too long. Herein, we investigate the extraction of metals from a variety of polar solvents and demonstrate that, the influence of polar solvents on metal extraction is so significant that extraction of many metals can be largely tuned, and the metal separations can be significantly enhanced by selecting suitable polar solvents. Furthermore, a mechanism on how the polar solvents affect metal extraction is proposed based on comprehensive characterizations. The method of using suitable polar solvents in liquid–liquid extraction paves a new and versatile way to enhance metal separations.     

Variational optimization of the 2DM: approaching three-index accuracy using extended cluster constraints

The reduced density matrix is variationally optimized for the two-dimensional Hubbard model. Exploiting all symmetries present in the system, we have been able to study 6 × 6 lattices at various fillings and different values for the on-site repulsion, using the highly accurate but computationally expensive three-index conditions. To reduce the computational cost we study the performance of imposing the three-index constraints on local clusters of 2 × 2 and 3 × 3 sites. We subsequently derive new constraints which extend these cluster constraints to incorporate the open-system nature of a cluster on a larger lattice. The feasibility of implementing these new constraints is demonstrated by performing a proof-of-principle calculation on the 6 × 6 lattice. It is shown that a large portion of the three-index result can be recovered using these extended cluster constraints, at a fraction of the computational cost.     

Silver halide colloid precursors for the synthesis of monolayer-protected clusters

A new method for the synthesis of monolayer-protected silver clusters (MPCs) based on the two-phase reduction of a stable negatively charged silver bromide sol is described. Phase transfer of the colloid to toluene is accomplished using tetra-n-octylammonium bromide as the phase transfer reagent. The advantage of this synthesis is to uncouple the formation of the silver halide colloid from its transfer and reduction in the organic phase, thus allowing control over each reaction step. The silver colloid in toluene was reduced with aqueous borohydride in the presence of 4-bromobenzenethiol as the passivating agent. The UV-visible absorption spectra indicate the intermediate formation of Ag(core)AgBr(shell) clusters during reduction. The resulting MPCs have been characterized by optical and transmission electron microscopy, energy-dispersive X-ray analysis, thermogravimetry, and UV-vis absorption spectroscopy. The formation of spiral cracks in the nanoparticulate agglomerates on solvent evaporation was observed. The spectra of thin films obtained by solvent evaporation have been analyzed using an effective medium theory.     

Controlling the gelation temperature of biomimetic polyisocyanides

The gelation temperature and mechanical properties of aqueous ethylene glycol-decorated polyisocyanide solutions strongly depends on the length of the glycol tail. Copolymerisation of monomers with different tail lengths allows for precise engineering of the gel properties.     

Evidence from current-density mapping for σ-delocalisation in the aromatic hexaiodobenzene cation

Calculation of high σ-delocalisation in the iodine periphery of the hexaiodobenzene cation, accompanied by a four-electron through-space σ ring current, provides direct computational evidence for the attribution to this ion of σ-aromaticity co-existing with the conventional π-aromaticity that it shares with its neutral parent.     

A facile strategy to prevent trifluoroacetylation of N-terminal proline peptides

Unwanted trifluoroacetylation occurred at the N-terminus of prolinyl peptides during detachment from the solid phase. This was observed when the N-α-Fmoc protecting group had been removed prior to the final TFA treatment. Subtly changing the SPPS protocol and incorporating Boc- in place of the Fmoc-protected proline as the N-terminal building block efficiently suppressed this side reaction.     

Computationally efficient evaluation of appointment schedules in health care

We consider the problem of evaluating and constructing appointment schedules for patients in a health care facility where a single physician treats patients in a consecutive manner, as is common for general practitioners, clinics and for outpatients in hospitals. Specifically, given a fixed-length session during which a physician sees K patients, each patient has to be given an appointment time during this session in advance. Optimising a schedule with respect to patient waiting times, physician idle times, session overtime, etc. usually requires a heuristic search method involving a huge number of repeated schedule evaluations. Hence, our aim is to obtain accurate predictions at very low computational cost. This is achieved by (1) using Lindley’s recursion to allow for explicit expressions and (2) choosing a discrete-time (slotted) setting to make those expressions easy to compute. We assume general, possibly distinct, distributions for the patients’ consultation times, which allows to account for multiple treatment types, emergencies and patient no-shows. The moments of waiting and idle times are obtained and the computational complexity of the algorithm is discussed. Additionally, we calculate the schedule’s performance in between appointments in order to assist a sequential scheduling strategy.     

Conservative independence-based causal structure learning in absence of adjacency faithfulness

This paper presents an extension to the Conservative PC algorithm which is able to detect violations of adjacency faithfulness under causal sufficiency and triangle faithfulness. Violations can be characterized by pseudo-independent relations and equivalent edges, both generating a pattern of conditional independencies that cannot be modeled faithfully. Both cases lead to uncertainty about specific parts of the skeleton of the causal graph. These ambiguities are modeled by an f-pattern. We prove that our Adjacency Conservative PC algorithm is able to correctly learn the f-pattern. We argue that the solution also applies for the finite sample case if we accept that only strong edges can be identified. Experiments based on simulations and the ALARM benchmark model show that the rate of false edge removals is significantly reduced, at the expense of uncertainty on the skeleton and a higher sensitivity for accidental correlations.     

Direct electroplating of copper on tantalum from ionic liquids in high vacuum: origin of the tantalum oxide layer

In this paper, it is shown that high vacuum conditions are not sufficient to completely remove water and oxygen from the ionic liquid 1-ethyl-3-methylimidazolium chloride. Complete removal of water demands heating above 150 °C under reduced pressure, as proven by Nuclear Reaction Analysis (NRA). Dissolved oxygen gas can only be removed by the use of an oxygen scavenger such as hydroquinone, despite the fact that calculations show that oxygen should be removed completely by the applied vacuum conditions. After applying a strict drying procedure and scavenging of molecular oxygen, it was possible to deposit copper directly on tantalum without the presence of an intervening oxide layer.     

Every Banach Space is Reflexive

The title above is wrong, because the strong dual of a Banach space is too strong to assert that the natural correspondence between a space and its bidual is an isomorphism. However, for many applications it suffices to replace the norm on the first dual by the weak*-structure in order to solve the non-reflexiveness problem [1]. But in this way, only the original vector space is recovered by taking the second dual. In this work we introduce a suitable numerical structure on vector spaces such that Banach balls, or more precisely totally convex modules, arise naturally in duality, namely as a category of Eilenberg–Moore algebras. This numerical structure naturally overlies the weak*-topology on the algebraic dual, so the entire Banach space can be reconstructed as a second dual. Moreover, the isomorphism between the original space and its bidual is the unit of an adjunction between the two-dualisation functors. Notice that the weak*-topology is normable only if it lives on a finite dimensional space; in that case the original space is trivial as well, hence reflexive. So the overlying numerical structure should be something more general than a norm or a seminorm and thus approach theory [2, 3] enters the picture.