Syntheses, optical and intramolecular magnetic properties of mono- and di-radicals based on nitronyl-nitroxide and oxoverdazyl groups appended to 2,6-bispyrazolylpyridine cores

This paper presents the synthesis of a series of nitronyl-nitroxide (NN), oxoverdazyl (OVZ) based mono-, and bi-radicals attached to 4-phenyl-2,6-bispyrazolylpyridine coupling unit, their optical, electron spin resonance (ESR) spectroscopic studies and computational analysis. The ESR studies revealed that the axial zero-field splitting (zfs) parameter of the NN biradical (|D/hc| = 0.00719 cm(-1)) is larger than the OVZ biradical (|D/hc| = 0.00601 cm(-1)). Additionally both biradicals displayed forbidden half-field transitions (ΔM(s) = ±2; g(av) ~ 4.01) at 170 K demonstrating their triplet nature. The cryogenic ESR measurements of the two biradicals showed a Curie magnetic behaviour of the ΔM(s) = ±2 signal intensities (χ(EPR)) down to 4.2 K. A detailed comparative analysis of the strength of hyperfine coupling, spin density distribution, zfs and the spin-spin exchange coupling (J) of both NN and OVZ based biradicals showed that the ground state spin multiplicity of both biradicals is probably triplet (S = 1) or it is nearly degenerate singlet-triplet states with J(NN)?J(OVZ).     

Thermoelastic Determination of Individual Stresses in Vicinity of a Near-Edge Hole Beneath a Concentrated Load

Thermoelastic data are combined with an Airy stress function to determine the individual stresses on and near the boundary of a circular hole which is located below a concentrated edge-load in a plate. Coefficients of the stress function are evaluated from the measured temperatures and the local traction-free conditions are satisfied by imposing s_rr = t_rq = 0 {sigma_{r{rm{r}}}} = {tau_{rtheta }} = 0 analytically on the edge of the hole. The latter has the advantage of reducing the number of coefficients in the stress function series. The method simultaneously smoothes the measured input data, satisfies the local boundary conditions and evaluates individual stresses on, and in the neighbourhood of, the edge of the hole. Attention is paid to how many coefficients to retain in the stress function series. Although the presence of high stress concentration factors, together with a hole-diameter-to-plate-thickness ratio of only two, result in some three-dimensional effects, these are relatively small and the agreement between the thermoelastic values, those from recorded strains and FEM-predicted surface stresses is good.     

Benzotrithiophene‐Based Hole‐Transporting Materials for 18.2 % Perovskite Solar Cells

New star‐shaped benzotrithiophene (BTT)‐based hole‐transporting materials (HTM) BTT‐1, BTT‐2 and BTT‐3 have been obtained through a facile synthetic route by crosslinking triarylamine‐based donor groups with a benzotrithiophene (BTT) core. The BTT HTMs were tested on solution‐processed lead trihalide perovskite‐based solar cells. Power conversion efficiencies in the range of 16 % to 18.2 % were achieved under AM 1.5 sun with the three derivatives. These values are comparable to those obtained with today's most commonly used HTM spiro‐OMeTAD, which point them out as promising candidates to be used as readily available and cost‐effective alternatives in perovskite solar cells (PSCs).     

Determining all Displacements,Strains and Stresses Full-Field from Measured Values of a Single Displacement Component

The ability to determine the individual components of displacement, strain and stress from measured values of a single component of displacement is demonstrated. Advantages of the method include its ability to significantly simplify the experimental technique by measuring only a single displacement component, to provide reliable results both full-field and at the edge of geometric discontinuities, and the lack of need to differentiate the recorded data physically. Results agree with those from thermoelastic stress analysis, strain gages and finite element analysis.     

Novel galactosyl donor with 2-naphthylmethyl (NAP) as the non-participating group at C-2 position: efficient synthesis of α-galactosyl ceramide

Predominant α-linked products can be generated in glycosylation involving galactosyl trichloroacetimidate donors with 2-naphthylmethyl (NAP) as the non-participating group at C-2 position. The above-mentioned donor was successfully utilized for the synthesis of α-galactosyl ceramide.     

Preparation and Characterization of Controlled-Release Floating Bilayer Tablets of Esomeprazole and Clarithromycin

Controlled-release effervescent floating bilayer tablets reduce dosage frequency and improve patient compliance with enhanced therapeutic outcomes. Generally, two different tablets of clarithromycin and esomeprazole, respectively, are given for the treatment of Helicobacter pylori infection and it might be worth incorporating both in a single tablet. In the current study, controlled-release floating bilayer tablets of clarithromycin and esomeprazole (F1–F4) were developed with different rates of polymeric materials by a direct compression method. During the formulation, Fourier-transform infrared spectroscopy (FTIR) analysis was performed for possible interactions between drugs and excipients. No interactions between drugs and excipients were noted. Moreover, the bilayer tablets’ thickness, diameter, friability, hardness, weight variation, dissolution, and percent purity were found within the acceptable limits. The floating lag time and total floating time of all formulations were found to be < 25 s and 24 h, respectively. The release of both the clarithromycin and esomeprazole started at the same time from the controlled-release floating bilayer tablets by anomalous non-Fickian diffusion, and the polymeric materials extended the drug release rate up to 24 h. In the case of F1, the results approached ideal zero-order kinetics. The dissolution profiles of the tested and reference tablet formulations were compared, but no significant differences were observed. It can be concluded that such controlled-release effervescent floating bilayer tablets can be efficiently used in clinical practice to reduce dosage frequency and increase patient compliance with continuous drug release for 24 h, which ultimately might enhance therapeutic efficacy.     

Lead and HTM Free Stable Two‐Dimensional Tin Perovskites with Suitable Band Gap for Solar Cell Applications

Organic‐inorganic hybrid perovskites have attracted great attention over the last few years as potential light‐harvesting materials for efficient and cost‐effective solar cells. However, the use of lead iodide in state‐of‐the‐art perovskite devices may demonstrate an obstacle for future commercialization due to toxicity of lead. Herein we report on the synthesis and characterization of low dimensional tin‐based perovskites. We found that the use of symmetrical imidazolium‐based cations such as benzimidazolium (Bn) and benzodiimidazolium (Bdi) allow the formation of 2D perovskites with relatively narrow band gaps compared to traditional ‐NH₃⁺ amino groups, with optical band gap values of 1.81 eV and 1.79 eV for Bn₂SnI₄ and BdiSnI₄ respectively. Furthermore, we demonstrate that the optical properties in this class of perovskites can be tuned by formation of a quasi 2D perovskite with the formula Bn₂FASn₂I₇. Additionally, we investigate the change in band gap in the mixed Sn/Pb solid solution Bn₂Sn_xPb_x?1I₄. Devices fabricated with Bn₂SnI₄ show promising efficiencies of around 2.3 %.     

Design, synthesis and X-ray structure of protein-ligand complexes: important insight into selectivity of memapsin 2 (beta-secretase) inhibitors

Structure-based design, synthesis, and X-ray structure of protein-ligand complexes of memapsin 2 are described. The inhibitors are designed specifically to interact with S2- and S3-active site residues to provide selectivity over memapsin 1 and cathepsin D. Inhibitor 6 has exhibited exceedingly potent inhibitory activity against memapsin 2 and selectivity over memapsin 1 (>3800-fold) and cathepsin D (>2500-fold). A protein-ligand crystal structure revealed cooperative interactions in the S2- and S3-active sites of memapsin 2. These interactions may serve as an important guide to design selectivity over memapsin 1 and cathepsin D.