Visible-Light Augmented Lithium Storage Capacity in a Ruthenium(II) Photosensitizer Conjugated with a Dione-Catechol Redox Couple

Controlling redox activity of judiciously appended redox units on a photo-sensitive molecular core is an effective strategy for visible light energy harvesting and storage. The first example of a photosensitizer - electron donor coordination compound in which the photoinduced electron transfer step is used for light to electrical energy conversion and storage is reported. A photo-responsive Ru-diimine module conjugated with redox-active catechol groups in [Ru(II)(phenanthroline-5,6-diolate)₃]⁴⁻ photosensitizer can mediate photoinduced catechol to dione oxidation in the presence of a sacrificial electron acceptor or at the surface of an electrode. Under potentiostatic condition, visible light triggered current density enhancement confirmed the light harvesting ability of this photosensitizer. Upon implementation in galvanostatic charge-discharge of a Li battery configuration, the storage capacity was found to be increased by 100 %, under 470 nm illumination with output power of 4.0 mW/cm⁻². This proof-of-concept molecular system marks an important milestone towards a new generation of molecular photo-rechargeable materials.     

Nanomaterials for electrochemical detection of pollutants in water: A review

The survival of living beings, including humanity, depends on a continuous supply of clean water. However, due to the development of industry, agriculture, and population growth, an increasing number of wastewaters is discarded, and the negative effects of such actions are clear. The first step in solving this situation is the collection and monitoring of pollutants in water bodies to subsequently facilitate their treatment. Nonetheless, traditional sensing techniques are typically laboratory-based, leading to potential diminishment in analysis quality. In this paper, the most recent developments in micro- and nano-electrochemical devices for pollutant detection in wastewater are reviewed. The devices reviewed are based on a variety of electrodes and the sensing of three different categories of pollutants: nutrients and phenolic compounds, heavy metals, and organic matter. From these electrodes, Cu, Co, and Bi showed promise as versatile materials to detect a grand variety of contaminants. Also, the most commonly used material is glassy carbon, present in the detection of all reviewed analytes.     

Recent advances and challenges in the recovery and purification of cellular exosomes

Exosomes are nanovesicles secreted by most cellular types that carry important biochemical compounds throughout the body with different purposes, playing a preponderant role in cellular communication. Because of their structure, physicochemical properties and stability, recent studies are focusing in their use as nanocarriers for different therapeutic compounds for the treatment of different diseases ranging from cancer to Parkinson's disease. However, current bioseparation protocols and methodologies are selected based on the final exosome application or intended use and present both advantages and disadvantages when compared among them. In this context, this review aims to present the most important technologies available for exosome isolation while discussing their advantages and disadvantages and the possibilities of being combined with other strategies. This is critical since the development of novel exosome‐based therapeutic strategies will be constrained to the effectiveness and yield of the selected downstream purification methodologies for which a thorough understanding of the available technological resources is needed.     

Exsolution of Nickel Nanoparticles from Mixed-Valence Metal Oxides: A Quantitative Evaluation by Magnetic Measurements

A fast and accurate experimental method is demonstrated to assess the fraction of exsolved metallic nanoparticles using magnetic measurements. As a benchmark, nanometric metallic nickel exsolved from (La_1−xSr_x)(Cr_1−yNi_y)O_3−δ is used for its high relevance as a solid oxide fuel cell component. The method is based on the difference in the magnetic response of the exsolved metallic nickel (ferromagnetic) and Sr-doped lanthanum chromite ceramic matrix (paramagnetic). The exsolved nickel results in coherent nanoparticles pinned on the surface of the Sr-doped lanthanum chromite ceramic matrix, as evidenced by electron microscopy analyses. The results obtained indicate the procedure as a fast and sensitive method to study the exsolution of ferromagnetic nanoparticles.     

Sterically Facilitated Intramolecular Nucleophilic NMe2 Group Substitution in the Synthesis of Fused Isoxazoles: Theoretical Study

The influence of steric repulsion between the NMe₂ group and a second ortho-(peri-)substituent in the series of 1-dimethylaminonaphthalene and N,N-dimethylanilene ortho-oximes on the ease of the NMe₂ group’s intramolecular nucleophilic substitution is studied. Possible reaction intermediates for three mechanisms are calculated (ωB97xd/def-2-TZVP), and their free Gibbs energies are compared to model reaction profiles. Supporting experiments have proved the absence of studied reactivity in the case of simple 2-dimethylaminobenzaldoxime, which allowed us to establish reactivity limits. The significant facilitation of NMe₂ group displacement in the presence of bulky substituents is demonstrated. The possibility of fused isoxazoles synthesis via the intramolecular nucleophilic substitution of a protonated NMe₂ group in the aniline and naphthalene series is predicted.     

Solidifying framework nucleic acids

正Living organisms have developed their unique strategies during the natural evolution for building hard tissues with minerals, including silica, calcium carbonate, calcium phosphate, and ferric oxide [1]. Such biomineralized materials generally have complex hierarchical structures with excellent mechanical properties. Although bioinspired approaches have led to the creation of well-defined synthetic structural materials ranging from micro to macro scales, the rational design of discrete biomimetic structures at the nanoscale remains a grand challenge.     

Effects of multiple delays on dynamics of a five-neuron network model

A five-neuron network model with multiple delays is proposed. This paper presents the combined effect of different delays on the dynamics of the proposed network. Pitchfork bifurcation is discussed in detail with the variation of the value of coupled weight or attenuation rate of internal neurons. By analyzing the corresponding characteristic equation, some stable criteria on delay-dependence and delay-independence are derived including multiple delays and coupled weights and the periodic oscillation arises bifurcated from the trivial equilibrium after the network loses its stability. Stable regions on delay-dependence are displayed in the two delayed parameter plane. It is shown that multiple delays can produce stability switching between resting state and periodic activity. Finally, theoretical results are justified by providing two illustrative examples.     

Infinitely many reducts of homogeneous structures

It is shown that the countably infinite dimensional pointed vector space (the vector space equipped with a constant) over a finite field has infinitely many first order definable reducts. This implies that the countable homogeneous Boolean-algebra has infinitely many reducts.     

Spatially restricted Double Z-Simplified Box Orbital basis sets: Optimization and comparison with some standard basis sets

As part of previous studies, we introduced a new type of basis function named Simplified Box Orbitals (SBOs) that belong to a class of spatially restricted functions which allow the zero differential overlap (ZDO) approximation to be applied with complete accuracy. The original SBOs and their Gaussian expansions SBO-3G form a minimal basis set, which was compared to the standard Slater-type orbital basis set (STO-3G). In the present paper, we have developed the SBO basis functions at double-zeta (DZ) level, and we have assessed the option of expanding the SBO-DZ as a combination of Gaussian functions. Finally, we have determined the quality of the new basis set by comparing the molecular properties calculated with SBO-nG with those achieved with some standard basis sets.