Capillary electrophoretic separation of uncharged polymers using polyelectrolyte engines. Theoretical model

Fixed-size moving window evolving factor analysis and base peak chromatograms have been used for peak purity detection in data generated with LC-MS. The two methods were evaluated with both real and simulated data and were found to be fast and complementary to each other. When a possibly impure peak is detected, it is suggested that further information can be obtained from local principal component analysis modelling and comparative mass chromatogram plots.     

Experimental Confirmation of a Predicted Porous Hydrogen-Bonded Organic Framework

Hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure-property predictions to generate energy-structure-function (ESF) maps for a series of triptycene-based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low-energy HOF (TH5-A) with a remarkably low density of 0.374 g cm⁻³ and three-dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5-A polymorph experimentally. This material has a high accessible surface area of 3,284 m² g⁻¹, as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date.     

Metal-metal interactions in dinuclear ruthenium complexes containing bridging 4,5-di(2-pyridyl)imidazolates and related ligands

The dinuclear bis(2,2'-bipyridine)ruthenium complex of 4,5-di(2-pyridyl)imidazolate has been prepared and separated into its (meso and rac) diastereoisomers. The 2-phenyl substituted analogue forms the meso isomer selectively. All three complexes have been characterised by 1H NMR and X-ray crystallography. Electrochemical measurements and spectroelectrochemistry of the mixed-valence states reveal strong metal-metal interactions and IVCT bands that are highly dependent on the electrolyte.     

The influence of a transverse magnetic field on a subnormal glow discharge in air

In subnormal glow discharge under d.c. excitation at different pressure in a varying transverse magnetic field (0 to 30 G) some measurements have been carried out for various initial average tube currents. The voltage across the discharge increases and average tube current and residual current decreases in the magnetic field. With the help of Beckman’s expression [4] for the axial field and the electron density distribution in a transverse magnetic field the observed variation of current and voltage can be satisfactorily explained. The variation of axial electric field with transverse magnetic field can be represented to a fair degree of accuracy by the derived equation. The behaviour of residual current with magnetic field has been observed in these oscillations.     

Electronic structure of lanthanum transition-metal oxyarsenides LaMAsO (M = Fe,Co, Ni) and LaFe1−xM′xAsO (M′ = Co,Ni) by X-ray photoelectron and absorption spectroscopy

The electronic structures of the quaternary oxyarsenides LaMAsO (M = Fe, Co, Ni) were examined with X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES). Interpretation of the metal 2p_3/2 and arsenic 3d_5/2 binding energies, as well as a satellite feature in the Co 2p XPS spectrum, suggests charges that are much less extreme than expected (i.e., not M²⁺ and As^3?) because of the strong covalent character within the M–As bonds. As M is varied, the differing degrees of charge transfer from M to As atoms within these bonds are manifested by shifts in the As 3d_5/2 binding energies and changes in the As K-edge intensities. This charge transfer is isolated within the [MAs] layer and does not influence the O 1s and La 3d XPS spectra. Fitting the experimental valence band spectra of these oxyarsenides LaMAsO yielded electron populations of states that support the formal charge assignment [La³⁺O^2?][M²⁺As^3?]. The mixed-metal series LaFe_1?xM′_xAsO (M′ = Co, Ni) was examined by XANES; analysis of the metal K- and L-edges, as well as of the Co 2p XPS satellite feature, revealed that no metal–metal charge transfer takes place.     

An Introduction to Closed/Open Neighborhood Sums: Minimax, Maximin, and Spread

For a graph G of order |V(G)| = n and a real-valued mapping f:V(G)?\mathbbR{f:V(G)\rightarrow\mathbb{R}}, if S ì V(G){S\subset V(G)} then f(S)=?_{w ? S} f(w){f(S)=\sum_{w\in S} f(w)} is called the weight of S under f. The closed (respectively, open) neighborhood sum of f is the maximum weight of a closed (respectively, open) neighborhood under f, that is, NS[f]=max{f(N[v])|v ? V(G)}{NS[f]={\rm max}\{f(N[v])|v \in V(G)\}} and NS(f)=max{f(N(v))|v ? V(G)}{NS(f)={\rm max}\{f(N(v))|v \in V(G)\}}. The closed (respectively, open) lower neighborhood sum of f is the minimum weight of a closed (respectively, open) neighborhood under f, that is, NS^-[f]=min{f(N[v])|v ? V(G)}{NS^{-}[f]={\rm min}\{f(N[v])|v\in V(G)\}} and NS^-(f)=min{f(N(v))|v ? V(G)}{NS^{-}(f)={\rm min}\{f(N(v))|v\in V(G)\}}. For W ì \mathbbR{W\subset \mathbb{R}}, the closed and open neighborhood sum parameters are NS_W[G]=min{NS[f]|f:V(G)? W{NS_W[G]={\rm min}\{NS[f]|f:V(G)\rightarrow W} is a bijection} and NS_W(G)=min{NS(f)|f:V(G)? W{NS_W(G)={\rm min}\{NS(f)|f:V(G)\rightarrow W} is a bijection}. The lower neighbor sum parameters are NS^-_W[G]=maxNS^-[f]|f:V(G)? W{NS^{-}_W[G]={\rm max}NS^{-}[f]|f:V(G)\rightarrow W} is a bijection} and NS^-_W(G)=maxNS^-(f)|f:V(G)? W{NS^{-}_W(G)={\rm max}NS^{-}(f)|f:V(G)\rightarrow W} is a bijection}. For bijections f:V(G)? {1,2,?,n}{f:V(G)\rightarrow \{1,2,\ldots,n\}} we consider the parameters NS[G], NS(G), NS ⁻[G] and NS ⁻(G), as well as two parameters minimizing the maximum difference in neighborhood sums.     

Assessing the Importance of Cation Size in the Tetragonal-Cubic Phase Transition in Lithium-Garnet Electrolytes**

Lithium garnets are promising solid-state electrolytes for next-generation lithium-ion batteries. These materials have high ionic conductivity, a wide electrochemical window and stability with Li metal. However, lithium garnets have a maximum limit of seven lithium atoms per formula unit (e.g., La₃Zr₂Li₇O₁₂), before the system transitions from a cubic to a tetragonal phase with poor ionic mobility. This arises from full occupation of the Li sites. Hence, the most conductive lithium garnets have Li between 6–6.55 Li per formula unit, which maintains the cubic symmetry and the disordered Li sub-lattice. The tetragonal phase, however, forms the highly conducting cubic phase at higher temperatures, thought to arise from increased cell volume and entropic stabilisation permitting Li disorder. However, little work has been undertaken in understanding the controlling factors of this phase transition, which could enable enhanced dopant strategies to maintain room temperature cubic garnet at higher Li contents. Here, a series of nine tetragonal garnets were synthesised and analysed by variable temperature XRD to understand the dependence of site substitution on the phase transition temperature. Interestingly the octahedral site cation radius was identified as the key parameter for the transition temperature with larger or smaller dopants altering the transition temperature noticeably. A site substitution was, however, found to make little difference irrespective of significant changes to cell volume.