Highly Reactive Nonheme Iron(III) Iodosylarene Complexes in Alkane Hydroxylation and Sulfoxidation Reactions

High‐spin iron(III) iodosylarene complexes bearing an N‐methylated cyclam ligand are synthesized and characterized using various spectroscopic methods. The nonheme high‐spin iron(III) iodosylarene intermediates are highly reactive oxidants capable of activating strong C? H bonds of alkanes; the reactivity of the iron(III) iodosylarene intermediates is much greater than that of the corresponding iron(IV) oxo complex. The electrophilic character of the iron(III) iodosylarene complexes is demonstrated in sulfoxidation reactions.     

Influence of Hydrogen Peroxide on Disinfection and Soil Removal during Low-Temperature Household Laundry

In the Water, Energy and Waste Directive, the European Commission provides for the use of household washing programmes with lower temperatures (30–40 °C) and lower water consumption. However, low washing temperatures and the absence of oxidising agents in the liquid detergents, and their reduced content in powder detergents, allow biofilm formation in washing machines and the development of an unpleasant odour, while the washed laundry can become a carrier of pathogenic bacteria, posing a risk to human health. The aim of the study was to determine whether the addition of hydrogen peroxide (HP) to liquid detergents in low-temperature household washing allows disinfection of the laundry without affecting the properties of the washed textiles even after several consecutive washes. Fabrics of different colours and of different raw material compositions were repeatedly washed in a household washing machine using a liquid detergent with the addition of 3% stabilised HP solution in the main wash, prewash or rinse. The results of the antimicrobial activity, soil removal activity, colour change and tensile strength confirmed the excellent disinfection activity of the 3% HP, but only if added in the main wash. Its presence did not discolour nor affect the tensile strength of the laundry, thus maintaining its overall appearance.     

Modulation of Melanogenesis and Antioxidant Status of Melanocytes in Response to Phototoxic Action of Doxycycline

Doxycycline is a commonly used tetracycline antibiotic showing the broad spectrum of antibacterial action. However, the use of this antibiotic is often connected with the risk of phototoxic reactions that lead to various skin disorders. One of the factors influencing the photosensitivity reactions is the melanin content in melanocytes. In this study, the impact of doxycycline and UVA irradiation on cell viability, melanogenesis and antioxidant defense system in cultured normal human epidermal melanocytes (HEMn‐DP) was examined. The exposure of cells to doxycycline and UVA radiation resulted in concentration‐dependent loss in melanocytes viability and induced melanin biosynthesis. Significant changes were stated in cellular antioxidant enzymes activity: SOD, CAT and GPx, which indicates alterations of antioxidant defense system. The results obtained in vitro may explain the mechanisms of phototoxic reactions that occur in normal human epidermal melanocytes in vivo after exposure of skin to doxycycline and UVA radiation.     

Palladium-catalyzed synthesis of β-hydroxy compounds via a strained 6,4-palladacycle from directed C–H activation of anilines and C–O insertion of epoxides

A palladium-catalyzed C–H activation of acetylated anilines (acetanilides, 1,1-dimethyl-3-phenylurea, 1-phenylpyrrolidin-2-one, and 1-(indolin-1-yl)ethan-1-one) with epoxides using O-coordinating directing groups was accomplished. This C–H alkylation reaction proceeds via formation of a previously unknown 6,4-palladacycle intermediate and provides rapid access to regioselectively functionalized β-hydroxy products. Notably, this catalytic system is applicable for the gram scale mono-functionalization of acetanilide in good yields. The palladium-catalyzed coupling reaction of the ortho-C(sp²) atom of O-coordinating directing groups with a C(sp³) carbon of chiral epoxides offers diverse substrate scope in good to excellent yields. In addition, further transformations of the synthesized compound led to biologically important heterocycles. Density functional theory reveals that the 6,4-palladacycle leveraged in this work is significantly more strained (>10 kcal mol⁻¹) than the literature known 5,4 palladacycles.

The combined experimental and computational study on palladium-catalyzed regioselective C–H functionalization of O-coordinating directing groups with epoxides is described.     

Charge-density waves in pure and intercalated Nb3Te4

High-resolution transmission electron microscopy (HRTEM), resistivity measurements and electronic band structure calculations performed by means of the extended Hückel tight-binding method are presented for the quasi one-dimensional compounds A_xNb₃Te₄ (A = In, Tl, Zn, Ag, Hg). HRTEM and electron diffraction performed on pure Nb₃Te₄ at room- and liquid nitrogen temperatures, reveal both the basic structure and the low-temperature charge-density waves (CDWs) modulation. Resistivity vs. temperature plots show characteristic CDW anomalies, dependent on the type and concentration of the atoms, intercalated into the large hexagonal tunnels of the host structure. It is shown that intercalation of Tl and In results in a flattening of the corresponding Fermi surfaces and that CDW formation is largely dependent on the coincidence between the Fermi level E_F and a small peak in the density of states spectrum, mainly developed from the Nb dz² orbitals. This peak is positioned in a minimum between the filled and empty states of the spectrum and tends to split into a doublet as a consequence of intercalation.     

Long cycles in fullerene graphs

It is conjectured that every fullerene graph is hamiltonian. Jendrol’ and Owens proved [J. Math. Chem. 18 (1995), pp. 83–90] that every fullerene graph on n vertices has a cycle of length at least 4n/5. In this paper we, improve this bound to 5n/6 − 2/3.     

An open-source surface barrier discharge plasma pretreatment for reduced cracking of outdoor wood coatings

The development of a simple surface barrier discharge plasma device is presented to enable more widespread access to and utilization of plasma technology. The application of the plasma device was demonstrated for pretreatment of wood prior to application of protective coatings for outdoor usage. The coatings' overall performance was increased, showing a reduction or absence of cracking due to weathering on plasma-pretreated specimens. Moreover, after ten months of outdoor weathering, the plasma-pretreated specimens showed fewer infections with biotic factors and improved adhesion performance in cross-cut tests, while the surface gloss performed independently from plasma pretreatment. In contrast to that, plasma-pretreated specimens were slightly more prone to discoloration due to outdoor weathering, whereas the plasma pretreatment did not impact the initial color after coating application.

Graphic abstract

     

Three-component one-pot synthetic route to 2-amino-5-alkylidene-thiazol-4-ones

A fast and straightforward three-component reaction to 2-amino-5-alkylidene-thiazol-4-ones is described. The one-pot methodology, reported for the first time, involves Knoevenagel condensation of aromatic aldehydes and rhodanine followed by displacement of the thiocarbonyl sulfur with primary or secondary amines in the same reaction mixture. The reactions were performed using a dedicated microwave reactor, which enabled short reaction times and easy work-up.     

Synthesis and PPAR-gamma ligand-binding activity of the new series of 2'-hydroxychalcone and thiazolidinedione derivatives

Fifteen chalcones and three thiazolidinedione (TZD) chalcones were prepared to evaluate their peroxisome proliferator-activated receptor-gamma (PPAR-gamma) ligand-binding activities. Among the three TZDs, one compound possessed PPAR-gamma transactivation potential, while the others showed antagonistic activity against PPAR-gamma transactivation. Among the chalcones, compound 5 was the most potent, and structure-activity relationship studies indicated that a methoxyl group in position C-4 and hydroxyl group in position C-4' or 5' in chalcone plays a key role in determining the potency of PPAR-gamma activation.