Hooking Together Sigmoidal Monomers into Supramolecular Polymers

Supramolecular polymers show great potential in the development of new materials because of their inherent recyclability and their self‐healing and stimuli‐responsive properties. Supramolecular conductive polymers are generally obtained by the assembly of individual aromatic molecules into columnar arrays that provide an optimal channel for electronic transport. A new approach is reported to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π‐stacked anthracene and acridine units, which gives rise to micrometer‐sized fibrils that show pseudoconductivities in line with other conducting materials. This approach paves the way for the design of new supramolecular polymers constituted by acene derivatives with enhanced excitonic and electronic transporting properties.     

An [FeIII34] Molecular Metal Oxide

The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe₃₄] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral Fe^III ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.4 K and fields up to 35 T, reveal competing antiferromagnetic exchange interactions; DFT calculations showing that the magnitudes of the coupling constants are highly dependent on both the Fe‐O‐Fe angles and Fe?O distances. The simplicity of the synthetic methodology, and the structural similarity between [Fe₃₄], bulk iron oxides, previous Fe^III–oxo cages, and polyoxometalates (POMs), hints that much larger molecular Fe^III oxides can be made.     

Efficient BiVO4 Photoanodes by Postsynthetic Treatment: Remarkable Improvements in Photoelectrochemical Performance from Facile Borate Modification

Water‐splitting photoanodes based on semiconductor materials typically require a dopant in the structure and co‐catalysts on the surface to overcome the problems of charge recombination and high catalytic barrier. Unlike these conventional strategies, a simple treatment is reported that involves soaking a sample of pristine BiVO₄ in a borate buffer solution. This modifies the catalytic local environment of BiVO₄ by the introduction of a borate moiety at the molecular level. The self‐anchored borate plays the role of a passivator in reducing the surface charge recombination as well as that of a ligand in modifying the catalytic site to facilitate faster water oxidation. The modified BiVO₄ photoanode, without typical doping or catalyst modification, achieved a photocurrent density of 3.5 mA cm^?2 at 1.23 V and a cathodically shifted onset potential of 250 mV. This work provides an extremely simple method to improve the intrinsic photoelectrochemical performance of BiVO₄ photoanodes.     

Desorption of carboxylates and phosphonates from galvanized steel: Towards greener lubricants

This paper studies the removal of chemisorbed carboxylates and phosphonates from TiO₂-coated galvanized steel using NaOH_(aq). XPS and FTIR data show that NaOH_(aq) is effective at desorbing these species and so is an alternative to gas phase processes (eg, plasma cleaning). Tribological investigations show that NaOH_(aq)-treated surfaces show reduced friction and wear, relative to the “as-received” galvanized steel. This is ascribed to carbonate (present as an impurity in NaOH) that adsorbs to the surface of the substrate during NaOH_(aq) immersion. Carbonate removal through sonication in water generates surfaces that show friction similar to “as-received” galvanized steel. This work is useful in areas (eg, automotive manufacturing), where the effective removal of lubricants following tribological contact is key to subsequent paint adhesion.     

Influence of weak groups on polyelectrolyte mobilities

The ionization of dissociable groups in weak polyelectrolytes does not occur in a homogenous fashion. Monomer connectivity imposes constraints on the localization of the dissociated (charged) monomers that affect the local electric potential. As a result, the mean bare charge along a weak polyelectrolyte can vary depending on the proximity to topological features (e.g. presence of crosslinks or dangling ends). Using reaction‐ensemble Monte‐Carlo simulations we calculate the dissociation inhomogeneities for a few selected PE configurations, linear, rod‐like, flexible four‐arm star, and a star with stiff arms. An ensemble preaverage is used to obtain the annealed bare charge profile for these different polymer configurations. Using molecular dynamics simulations within a Lattice‐Boltzman fluid, we investigate how the electrophoretic mobility is affected by the bare charge inhomogeneities arising from the annealed weak polyelectrolytes. Surprisingly, the mobility obtained for the situations corresponding to the predicted charge profile for annealed weak polyelectrolytes are not significantly different than the mobility obtained when all the monomers have an identical charge (under the constraint that the total polyelectrolyte bare charge is the same). This is also true for the stiff rod‐like variants where conformational changes induced from the localization of the monomer charges are negligible. In salty solutions, we find that counterions are affected by the electric potential modulations induced by the topological features. Since the counterions crowd in regions where the electric potential caused by the dissociated monomers is highest, they wash‐out the bare charge inhomogeneities and contribute to a more uniform effective backbone charge.     

Excited state tracking during the relaxation of coordination compounds

The ability to locate minima on electronic excited states (ESs) potential energy surfaces both in the case of bright and dark states is crucial for a full understanding of photochemical reactions. This task has become a standard practice for small- to medium-sized organic chromophores thanks to the constant developments in the field of computational photochemistry. However, this remains a very challenging effort when it comes to the optimization of ESs of transition metal complexes (TMCs), not only due to the presence of several electronic ESs close in energy, but also due to the complex nature of the ESs involved. In this article, we present a simple yet powerful method to follow an ES of interest during a structural optimization in the case of TMCs, based on the use of a compact hole-particle representation of the electronic transition, namely the natural transition orbitals (NTOs). State tracking using NTOs is unambiguously accomplished by computing the mono-electronic wave function overlap between consecutive steps of the optimization. Here, we demonstrate that this simple but robust procedure works not only in the case of the cytosine but also in the case of the ES optimization of a ruthenium nitrosyl complex which is very problematic with standard approaches. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.     

Basal Histamine H4 Receptor Activation: Agonist Mimicry by the Diphenylalanine Motif

Histamine H₄ receptor (H₄R) orthologues are G-protein-coupled receptors (GPCRs) that exhibit species-dependent basal activity. In contrast to the basally inactive mouse H₄R (mH₄R), human H₄R (hH₄R) shows a high degree of basal activity. We have performed long-timescale molecular dynamics simulations and rigidity analyses on wild-type hH₄R, the experimentally characterized hH₄R variants S179M, F169V, F169V+S179M, F168A, and on mH₄R to investigate the molecular nature of the differential basal activity. H₄R variant-dependent differences between essential motifs of GPCR activation and structural stabilities correlate with experimentally determined basal activities and provide a molecular explanation for the differences in basal activation. Strikingly, during the MD simulations, F169^45.55 dips into the orthosteric binding pocket only in the case of hH₄R, thus adopting the role of an agonist and contributing to the stabilization of the active state. The results shed new light on the molecular mechanism of basal H₄R activation that are of importance for other GPCRs.     

Skin‐worn Soft Microfluidic Potentiometric Detection System

A flexible skin‐mounted microfluidic potentiometric device for simultaneous electrochemical monitoring of sodium and potassium in sweat is presented. The wearable device allows efficient natural sweat pumping to the potentiometric detection chamber, containing solid‐contact ion‐selective Na⁺ and K⁺ electrodes, during exercise activity. The fabricated microchip electrolyte‐sensing device displays good analytical performance and addresses sweat mixing and carry‐over issues of early epidermal potentiometric sensors. Such soft skin‐worn microchip platform integrates potentiometric measurement, microfluidic technologies with flexible electronics for real‐time wireless data transmission to mobile devices. The new fully integrated microfluidic electrolyte‐detection device paves the way for practical fitness and health monitoring applications.