Four-Step Spin Crossover in a New Cyano-Bridged Iron-Silver Coordination Polymer

Spin-crossover complexes with multistep transitions attract much attention due to their potential applications as multi-switches and for data storage. A four-step spin crossover is observed in the new iron(II)-based cyanometallic guest-free framework compound Fe(2-ethoxypyrazine)₂{Ag(CN)₂}₂ during the transition from the low-spin to the high-spin state. A reverse process occurs in three steps. Crystallographic studies reveal an associated stepwise evolution of the crystal structures. Multiple transitions in the reported complex originate from distinct Fe^II sites which exist due to the packing of the ligand with a bulky substituent.     

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.     

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.     

q-Analogues of two “divergent” Ramanujan-type supercongruences

The Ramanujan Journal - Guillera and Zudilin proved three “divergent” Ramanujan-type supercongruences by means of the Wilf–Zeilberger algorithmic technique. In this paper we prove...     

13C chemical shift tensors in MOF α-Mg3(HCOO)6: Which component is more sensitive to host-guest interaction?

Metal–organic frameworks (MOFs) are a class of important porous materials with many current and potential applications. Their applications almost always involve the interaction between host framework and guest species. Therefore, understanding of host–guest interaction in MOF systems is fundamentally important. Solid-state NMR spectroscopy is an excellent technique for investigating host–guest interaction as it provides information complementary to that obtained from X-ray diffraction. In this work, using MOF α-Mg₃(HCOO)₆ as an example, we demonstrated that ¹³C chemical shift tensor of organic linker can be utilized to probe the host–guest interaction in MOFs. Obtaining ¹³C chemical shift tensor components (δ₁₁, δ₂₂, and δ₃₃, where δ₁₁ ≥ δ₂₂ ≥ δ₃₃) in this MOF is particularly challenging as there are six coordinatively equivalent but crystallographically non-equivalent carbons in the unit cell with very similar local coordination environment. Two-dimensional magic-angle-turning experiments were employed to measure the ¹³C chemical shift tensors of each individual crystallographically non-equivalent carbon in three microporous α-Mg₃(HCOO)₆ samples with different guest species. The results indicate that the δ₂₂ component (with its direction approximately being co-planar with the formate anion and perpendicular to the C−H bond) is more sensitive to the adsorbate molecules inside the MOF channel due to the weak C−H···O hydrogen bonding or the ring current effect of benzene. The ¹³C isotropic chemical shift, on the other hand, seems much less sensitive to the subtle changes in the local environment around formate linker induced by adsorption. The approach described in this study may be used in future studies on host–guest interaction within MOFs.