Quantification of energy of activation to supramolecular nanofibre formation reveals enthalpic and entropic effects and morphological consequence

We show a self-assembly process leading to fibres from a system that starts far from equilibrium because of fast solvent – anti-solvent mixing and analyse the activation energies associated with the aggregation. It is in some ways reminiscent of diverse natural fibrous materials that have kinetic behaviour dominated by a rate limiting induction period followed by rapid growth. A full thermodynamic rationale for these systems and related synthetic ones is required for a full understanding of the driving force of their non-equilibrium self-assembly. Here we determine quantitatively the enthalpy and entropy of activation for the processes leading to the growth of fibres of this type, that contrasts with analysis of other systems where final energetic states are analysed. A dramatic effect is revealed whereby comparatively small changes in temperature or solvent composition (the ratio of water to ethanol) lead to alterations in the relative importance of enthalpy and entropy of activation and massive changes in the speed of fibre formation. The characteristics of the kinetic model adopted show a correlation with the fibre morphology of the self-assembled materials, which are isostructural according to diffraction experiments: The control of growth can lead to fibres only two bilayers thick. The crossover in behaviour is characteristic of the solvent mixture and the thermodynamic analysis points to the origins of this effect where different assembly routes are viable under only marginally different conditions

Self‐Assembled Surfactant‐Polyoxovanadate Soft Materials as Tuneable Vanadium Oxide Cathode Precursors for Lithium‐Ion Batteries

The mixing of [V10O28]6− decavanadate anions with a dicationic gemini surfactant (gem) leads to the spontaneous self-assembly of surfactant-templated nanostructured arrays of decavanadate clusters. Calcination of the material under air yields highly crystalline, sponge-like V2O5 (gem-V2O5). In contrast, calcination of the amorphous tetrabutylammonium decavanadate allows isolation of a more agglomerated V2O5 consisting of very small crystallites (TBA-V2O5). Electrochemical analysis of the materials’ performance as lithium-ion intercalation electrodes highlights the role of morphology in cathode performance. The large crystallites and long-range microstructure of the gem-V2O5 cathode deliver higher initial capacity and superior capacity retention than TBA-V2O5. The smaller crystallite size and higher surface area of TBA-V2O5 allow faster lithium insertion and superior rate performance to gem-V2O5

Search for dark matter produced in association with bottom or top quarks in √s = 13 TeV pp collisions with the ATLAS detector

A search for weakly interacting massive particle dark matter produced in association with bottom or top quarks is presented. Final states containing third-generation quarks and miss- ing transverse momentum are considered. The analysis uses 36.1 fb−1 of proton–proton collision data recorded by the ATLAS experiment at √s = 13 TeV in 2015 and 2016. No significant excess of events above the estimated backgrounds is observed. The results are in- terpreted in the framework of simplified models of spin-0 dark-matter mediators. For colour- neutral spin-0 mediators produced in association with top quarks and decaying into a pair of dark-matter particles, mediator masses below 50 GeV are excluded assuming a dark-matter candidate mass of 1 GeV and unitary couplings. For scalar and pseudoscalar mediators produced in association with bottom quarks, the search sets limits on the production cross- section of 300 times the predicted rate for mediators with masses between 10 and 50 GeV and assuming a dark-matter mass of 1 GeV and unitary coupling. Constraints on colour- charged scalar simplified models are also presented. Assuming a dark-matter particle mass of 35 GeV, mediator particles with mass below 1.1 TeV are excluded for couplings yielding a dark-matter relic density consistent with measurements