Diazocarbonyl and Related Compounds in the Synthesis of Azoles

Diazocarbonyl compounds have found numerous applications in many areas of chemistry. Among the most developed fields of diazo chemistry is the preparation of azoles from diazo compounds. This approach represents a useful alternative to more conventional methods of the synthesis of azoles. A comprehensive review on the preparation of various azoles (oxazoles, thiazoles, imidazoles, pyrazoles, triazoles, and tetrazoles) from diazocarbonyl and related compounds is presented for the first time along with discussion of advantages and disadvantages of «diazo» approaches to azoles.     

Heteroleptic LaIII Anilate/Dicarboxylate Based Neutral 3D-Coordination Polymers

Three new 3D metal–organic frameworks of lanthanum based on mixed anionic ligands, [(La₂(pQ)₂(BDC)₄)·4DMF]_n, [(La₂(pQ)₂(DHBDC)₄)·4DMF]_n, [(La₂(CA)₂(BDC)₄)·4DMF]_n (pQ—dianion of 2,5-dihydroxy-3,6-di-tert-butyl-para-quinone, CA—dianion of chloranilic acid, BDC-1,4-benzenedicarboxylate, DHBDC-2,5-dihydroxy-1,4-benzenedicarboxylate and DMF-N,N′-dimethylformamide), were synthesized using solvothermal methodology. Coordination polymers demonstrate the rare xah or 4,6T187 topology of a 3D framework. The homoleptic 2D-coordination polymer [(La₂(pQ)₃)·4DMF]_n was obtained as a by-product in the course of synthetic procedure optimization. The thermal stability, spectral characteristics and porosity of coordination polymers were investigated.     

Transformation of 3-(Furan-2-yl)-1,3-di(het)arylpropan-1-ones to Prop-2-en-1-ones via Oxidative Furan Dearomatization/2-Ene-1,4,7-triones Cyclization

The approach to 3-(furan-2-yl)-1,3-di(het)arylprop-2-en-1-ones based on the oxidative dearomatization of 3-(furan-2-yl)-1,3-di(het)arylpropan-1-ones followed by an unusual cyclization of the formed di(het)aryl-substituted 2-ene-1,4,7-triones has been developed. The cyclization step is related to the Paal–Knorr synthesis, but the furan ring formation is accompanied in this case by a formal shift of the double bond through the formation of a fully conjugated 4,7-hydroxy-2,4,6-trien-1-one system or its surrogate.     

Propolis-Based Nanofiber Patches to Repair Corneal Microbial Keratitis

In this research, polyvinyl-alcohol (PVA)/gelatin (GEL)/propolis (Ps) biocompatible nanofiber patches were fabricated via electrospinning technique. The controlled release of Propolis, surface wettability behaviors, antimicrobial activities against the S. aureus and P. aeruginosa, and biocompatibility properties with the mesenchymal stem cells (MSCs) were investigated in detail. By adding 0.5, 1, and 3 wt.% GEL into the 13 wt.% PVA, the morphological and mechanical results suggested that 13 wt.% PVA/0.5 wt.% GEL patch can be an ideal matrix for 3 and 5 wt.% propolis addition. Morphological results revealed that the diameters of the electrospun nanofiber patches were increased with GEL (from 290 nm to 400 nm) and Ps addition and crosslinking process cause the formation of thicker nanofibers. The tensile strength and elongation at break enhancement were also determined for 13 wt.% PVA/0.5 wt.% GEL/3 wt.% Ps patch. Propolis was released quickly in the first hour and arrived at a plateau. Cell culture and contact angle results confirmed that the 3 wt.% addition of propolis reinforced mesenchymal stem cell proliferation and wettability properties of the patches. The antimicrobial activity demonstrated that propolis loaded patches had antibacterial activity against the S. aureus, but for P. aeruginosa, more studies should be performed.     

New O-Aryl-Carbamoyl-Oxymino-Fluorene Derivatives with MI-Crobicidal and Antibiofilm Activity Enhanced by Combination with Iron Oxide Nanoparticles

Antimicrobial resistance is one of the major public health threats at the global level, urging the search for new antimicrobial molecules. The fluorene nucleus is a component of different bioactive compounds, exhibiting diverse pharmacological actions. The present work describes the synthesis, chemical structure elucidation, and bioactivity of new O-aryl-carbamoyl-oxymino-fluorene derivatives and the contribution of iron oxide nanoparticles to enhance the desired biological activity. The antimicrobial activity assessed against three bacterial and fungal strains, in suspension and biofilm growth state, using a quantitative assay, revealed that the nature of substituents on the aryl moiety are determinant for both the spectrum and intensity of the inhibitory effect. The electron-withdrawing inductive effect of chlorine atoms enhanced the activity against planktonic and adhered Staphylococcus aureus, while the +I effect of the methyl group enhanced the anti-fungal activity against Candida albicans strain. The magnetite nanoparticles have substantially improved the antimicrobial activity of the new compounds against planktonic microorganisms. The obtained compounds, as well as the magnetic core@shell nanostructures loaded with these compounds have a promising potential for the development of novel antimicrobial strategies.     

Comprehensive Evaluation of Late Season Peach Varieties (Prunus persica L.): Fruit Nutritional Quality and Phytochemicals

Peaches are one of the most preferred seasonal fruits, and a reliable source of nutrients. They possess biologically active substances that largely differ among varieties. Hence, revealing the potential of several late season peaches is of present interest. Three commonly consumed varieties (“Flat Queen”; “Evmolpiya”; “Morsiani 90”) were studied in terms of nutritive and phytochemical content, as well as antioxidant activity with the use of reliable spectrophotometric and High Performance Liquid Chromatographic (HPLC) methods. An analysis of the soil was also made. The phytochemical data were subjected to principal component analysis in order to evaluate their relationship. The “Morsiani 90” variety had the highest minerals concentration (2349.03 mg/kg fw), total carbohydrates (16.21 g/100 g fw), and α-tocopherol (395.75 µg/100 g fresh weight (fw)). Similar amounts of TDF (approx. 3 g/100 g fw) were reported for all three varieties. “Flat Queen’s” peel extract was the richest in monomeric anthocyanins (2279.33 µg cyanidin-3-glucoside (C3GE)/100 g fw). The “Morsiani 90” variety extracts had the highest antioxidant potential, defined by 2,2-diphenil-1-picrylhydrazyl (DPPH), ferric-reducing antioxidant power (FRAP) and cupric ion-reducing antioxidant capacity (CUPRAC) assays.     

Tuning the glass transition of siloxane-based poly(ionic liquid)s towards high ion conductivity

Herein, we report a simple and versatile synthetic approach towards siloxane-based poly(ionic liquid)s (PILs) with unusually low glass transition temperatures (T_g) down to −73°C, and thus “liquid-like” behavior at room temperature. We designed a polydimethylsiloxane-derived copolymer carrying dialkylimidazolium moieties, and by careful selection of the side-chain length and the type of anions we were able to manipulate its T_g over a wide range and reach high ionic conductivities (σ_DC) up to 4.8 × 10⁻⁵ S/cm at 300 K. The ionized species make up only a minor fraction (<25 mol%) of the overall repeating units and are supposedly randomly distributed: Yet our results indicate dramatic effects on the thermal properties due to repulsive interactions between ionic and non-ionic segments.     

Site-Selective Pd-Catalyzed C(sp3)−H Arylation of Heteroaromatic Ketones

A ligand-controlled site-selective C(sp³)−H arylation of heteroaromatic ketones has been developed using Pd catalysis. The reaction occurred selectively at the α- or β-position of the ketone side-chain. The switch from α- to β-arylation was realized by addition of a pyridone ligand. The α-arylation process showed broad scope and high site- and chemoselectivity, whereas the β-arylation was more limited. Mechanistic investigations suggested that α-arylation occurs through C−H activation/oxidative addition/reductive elimination whereas β-arylation involves desaturation and aryl insertion.     

Luminescent Analysis of Blood Serum for Diagnostics of Pathological and Pre-Pathological States of Cancer Patients

Journal of Fluorescence - This study is devoted to the development of a methodological approach to mathematical analysis and data interpretation of blood serum phosphorescence intensity in cancer...     

On the control of time discretized dynamic contact problems

We consider optimal control problems with distributed control that involve a time-stepping formulation of dynamic one body contact problems as constraints. We link the continuous and the time-stepping formulation by a nonconforming finite element discretization and derive existence of optimal solutions and strong stationarity conditions. We use this information for a steepest descent type optimization scheme based on the resulting adjoint scheme and implement its numerical application.