Volume 93, Issue 11

Contact electrification (CE) has been utilized in various energy conversion systems in recent years. This work presents a constant electric energy output that was generated based on the CE at the water–metal interface. When a grounded Pt mesh is placed in water that is heated to boil, a continuous flow of electrons between the Pt mesh and the ground is generated. A possible mechanism for the generation of such electric current is based on the CE between the surface of the Pt mesh and water molecules. The local high-pressure thin liquid film regions between vapor bubbles and surface of Pt mesh promote this CE process. The constant water evaporation and bubble detachment enable the continuous electric current output. In this work, the impact of the heating temperature and the bias voltages on the generation of the current was also studied. This work provides an alternative approach to generate unidirectional current on the basis of CE at the water–metal interface, and it also offers new insights in the design of CE-based systems for the generation of electricity.

Ascorbic acid, i.e., vitamin C, is a well-known essential nutrient, and has attracted considerable attention as a new candidate for cancer therapy. Previously, R2c consisting of silicon tetra- tert -butylphthalocyanine (SiPc) and two 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radicals has been encapsulated into the hydrophobic cavity of dimeric bovine serum albumin (BSA), i.e., R2c@(BSA) 2 , and the system was found to behave as a highly sensitive and selective fluorescent probe for detecting ascorbic acid not only in aqueous solutions but also in vivo . In this study, kinetics of the reaction of R2c@(BSA) 2 with ascorbic acid have been studied based on the temporal evolution of fluorescence. Global fitting of the concentration dependence using the Runge-Kutta method revealed the existence of stepwise two proton-coupled electron transfer processes. The rate constants for the reactions with ascorbic acid ( k AA ) and ascorbate radical ( k AR ) were 3 × 10 and 1 × 10 5  min −1  M −1 , respectively, suggesting that the reaction with ascorbate radical was much faster than that with ascorbic acid. These results were further corroborated by theoretical calculations of the Gibbs free energy differences and by spin statistical factors. The analysis presented herein will aid in understanding the two proton-coupled electron transfer processes in the reaction with ascorbic acid.

Superparamagnetic Iron Oxide Nanoparticles (SPIONs) are widely used in various areas of the biomedical field: for diagnosis (Magnetic Resonance Imaging), for therapeutic applications (hyperthermia, nanovectorization). These applications require a good stability in water and no aggregation of SPIONs, with well-controlled physicochemical and magnetic properties. In this work, SPIONs functionalized by citrate ligands are synthesized in a one-step process with the aim of producing stable water-dispersible nanoparticles with a well-crystallized spinel structure. Microwave technology is implemented to achieve this objective given the ease, speed and reproducibility of the method. For their future use in biomedical applications, the sterilization of these SPIONs are essential by an autoclave treatment. The influence of this treatment on the physicochemical and magnetic properties of the SPIONs is determined by a systematic characterization before and after sterilization by Transmission Electronic Microscopy, Dynamic Light Scattering, X-ray Diffraction, Fourier Transformed Infra-Red, ThermoGravimetric Analysis and magnetic measurements.

Biomimicry, biomimesis and bioinspiration define distinctly different approaches for deepening the understanding of how living systems work and employing this knowledge to meet pressing demands in engineering. Biomimicry involves shear imitation of biological structures that most often do not reproduce the functionality that they have while in the living organisms. Biomimesis aims at reproduction of biological structure-function relationships and advances our knowledge of how different components of complex living systems work. Bioinspiration employs this knowledge in abiotic manners that are optimal for targeted applications. This article introduces and reviews these concepts in a global historic perspective. Representative examples from charge-transfer science and solar-energy engineering illustrate the evolution from biomimetic to bioinspired approaches and show their importance. Bioinspired molecular electrets, aiming at exploration of dipole effects on charge transfer, demonstrate the pintail impacts of biological inspiration that reach beyond its high utilitarian values. The abiotic character of bioinspiration opens doors for the emergence of unprecedented properties and phenomena, beyond what nature can offer.

Inorganic systems containing two or more kinds of anions, such as rare-earth metal oxyhydrides, have a number of interesting properties that can be used in the design and development of new functional materials with desired characteristics. Chemical synthesis of these materials can be accomplished by oxidation of metal hydrides. However, the oxidation process of a metal hydride is directly accompanied by the release of hydrogen; both processes are a combination of two sequential reactions. This is usually not favorable for the formation and crystallization of the ternary oxyhydride composition. One possible way to overcome this problem is to introduce an appropriate amount of oxygen atoms into certain interstitial positions adjacent to the metal sites of the hydride lattice. Guided by the ideas of orthogonality, we have proposed a theoretical model capable of providing a thorough understanding of the chemical processes occurring in a multicomponent system at the molecular level. This model opens the way for predicting a wide range of new, stable multi-anion compounds of different compositions. It can also control functionality by adding noncovalent interactions between different kinds of anions, which can lead to the formation of chiral structures or a significant increase in ferro- and piezoelectric properties.

In this work, a bioinspired approach is used to prepare nanotubular structures with tunable hydrophobicity and water adhesion by a soft template surfactant-free electropolymerization in organic solvent. Various highly conjugated carbazole-based molecules are used as monomer. The presence of water in the organic solvent enables the formation of porous and rough nanostructures. Their shapes depend essentially on the nature of the monomer and the way it polymerizes. Various morphologies were obtained from nanoparticles network to horizontally or vertically aligned nanotubes. The nanostructured surfaces reach superhydrophobic properties and their dynamical behavior varies with the monomer from sticky to slippery. For example, using 9,3′:6′,9″-tercarbazole (TC) very long nanotubes are observed but their number is higher at constant potential. At high deposition charge, it is observed that most of the tubes are even collapsed leading to a strong increase of surface hydrophobicity with apparent contact angle up to 143° with strong water adhesion comparable to rose petals or gecko foot.

Flavylium-based molecular switches are attractive molecular components to devise stimuli-responsive host-guest systems such as rotaxanes and pseudorotaxanes. These compounds display a pH-dependent reaction network of several species that reversibly interconvert within different time scales. Therefore, to explore and take profit of exceptional stimuli-responsive properties of these systems, detailed kinetic and thermodynamic characterizations are often required. In this work, we present the results of such characterization for a new flavylium compound decorated with a trimethylalkylammonium substituent designed to form a pseudorotaxane with cucurbit[7]uril (CB7). The formation of the pseudorotaxane was characterized in detail, and the thermodynamic and kinetic aspects of the flavylium interconversion reactions in the assembly were investigated and compared with the free molecular switch.

Substituted β 3 oligoamides form a unique self-assembling system where each monomer folds into a helix containing approximately three β 3 amino acids per turn, yielding a geometrically well-defined cylindrical building block that, when N-acylated, is able to self-assemble head-to-tail into nanorods that can reach several 100 μm length. It was shown in previous works that self-assembly can be achieved with a three residue long oligoamide as well that lacks any intramolecular H-bonds, yet it crystallizes in a helix-like conformation. The self-assembly properties of these small oligoamides are however elusive, suggesting a more complex system than the self-assembly of the H-bond stabilized helical monomers. Here we focus on the self-assembly behaviour of a three residue oligoamide, Ac-β 3 [LIA] where the letters denote the side chain of the analogous α amino acid. Ac-β 3 [LIA] can yield highly inhomogeneous suspensions in water with a broad range of large fibrous structures that seem to be very stable, yet occasionally fibre growth is only observed upon heating. The small size of the monomer suggests a highly dynamic equilibrium yet all previous attempts failed to clearly identify low molecular weight species. Therefore a special methodology was employed in this study to characterize the suspensions at different size ranges: SANS that is optimal to measure the small oligomers and cross sectional diameter of the assemblies, DLS that is sensitive to the large populations and therefore the length of the superstructures, and NMR that is sensitive to monomeric and small oligomeric form, in conjunction with IR spectroscopy to probe the folding and AFM to image the morphology of the assemblies. Temperature ramping was used to perturb the system to probe the dynamicity of the self-assembly. It was found that the anomalous self-assembly behaviour of Ac-β 3 [LIA] is caused by its two stable conformations, a helix-building “horseshoe” fold and a linear conformer. The latter is exclusively found in monomeric form in solution whereas the horseshoe fold is stable in solid phase and in fibrous assemblies. Small oligomers were absent. Thus the self-assembly of Ac-β 3 [LIA] is arrested by the activation energy need of the conformation change; fibre growth might be triggered by conditions that allow increased conformational freedom of the monomers. This observation may be used to develop strategies for controlled switchable self-assembly.

This paper deals with gender gap in Mathematics across Africa. Reducing the gender gap in Mathematics in Africa, is the major aim of African Women in Mathematics Association (AWMA) through various activities. Using macrodata from two international surveys and microdata from two African universities (Joseph Ki-Zerbo of Burkina Faso and Monastir in Tunisia), differences in favor to men in the participation of female teachers and teacher-researchers in Mathematics, Physics, Chemistry and Computer Sciences are highlighted. Some practices, considered by AWMA, aiming to reduce the Gender Gap are also evoked.