Nafion/tetraruthenated porphyrin glassy carbon-modified electrode: characterization and voltammetric studies of sulfite oxidation in water–ethanol solutions

In this work, the modification of a glassy carbon electrode with tetraruthenated porphyrins electrostatically assembled onto a Nafion film, previously adsorbed on the electrode surface, is reported. This modified electrode was characterized by scanning electron microscopy–energy-dispersive X-ray, Raman spectroscopy, UV-Vis spectroelectrochemistry, and cyclic voltammetry. The Nafion film onto the glassy carbon electrode shows a smooth disposition; when the tetraruthenated porphyrin is incorporated on the Nafion film, the complex is adsorbed in a homogeneous way. The modified electrode catalyzes HSO₃⁻ oxidation in water–ethanol solutions and shows an enhanced stability compared with the electrode modified with the dip coating method. Rotating disk electrode experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film. I/E curves show a Tafel slope of 120 mV/decade corresponding to a first electron-transfer reaction, depending on the potential, as the determining step. Spectroelectrochemical experiments demonstrated that Ru(II) is the active site for the electrocatalysis.     

1H and 13C NMR analysis of 2‐acetamido‐3‐mercapto‐3‐methyl‐N‐aryl‐butanamides and 2‐acetamido‐3‐methyl‐3‐nitrososulfanyl‐N‐aryl‐butanamide derivatives

The complete assignment of the ¹H and ¹³C NMR spectra of various 2‐acetamido‐3‐mercapto‐3‐methyl‐N‐aryl‐butanamides and 2‐acetamide‐3‐methyl‐3‐nitrososulfanyl‐N‐aryl‐butanamides with p‐methoxy, o‐chloro and m‐chloro substituents is reported. Copyright © 2013 John Wiley & Sons, Ltd.     

Dietary Flavonoids: Cardioprotective Potential with Antioxidant Effects and Their Pharmacokinetic,Toxicological and Therapeutic Concerns

Flavonoids comprise a large group of structurally diverse polyphenolic compounds of plant origin and are abundantly found in human diet such as fruits, vegetables, grains, tea, dairy products, red wine, etc. Major classes of flavonoids include flavonols, flavones, flavanones, flavanols, anthocyanidins, isoflavones, and chalcones. Owing to their potential health benefits and medicinal significance, flavonoids are now considered as an indispensable component in a variety of medicinal, pharmaceutical, nutraceutical, and cosmetic preparations. Moreover, flavonoids play a significant role in preventing cardiovascular diseases (CVDs), which could be mainly due to their antioxidant, antiatherogenic, and antithrombotic effects. Epidemiological and in vitro/in vivo evidence of antioxidant effects supports the cardioprotective function of dietary flavonoids. Further, the inhibition of LDL oxidation and platelet aggregation following regular consumption of food containing flavonoids and moderate consumption of red wine might protect against atherosclerosis and thrombosis. One study suggests that daily intake of 100 mg of flavonoids through the diet may reduce the risk of developing morbidity and mortality due to coronary heart disease (CHD) by approximately 10%. This review summarizes dietary flavonoids with their sources and potential health implications in CVDs including various redox-active cardioprotective (molecular) mechanisms with antioxidant effects. Pharmacokinetic (oral bioavailability, drug metabolism), toxicological, and therapeutic aspects of dietary flavonoids are also addressed herein with future directions for the discovery and development of useful drug candidates/therapeutic molecules.     

Antimicrobial Properties of Plant Fibers

Healthcare-associated infections (HAI), or nosocomial infections, are a global health and economic problem in developed and developing countries, particularly for immunocompromised patients in their intensive care units (ICUs) and surgical site hospital areas. Recurrent pathogens in HAIs prevail over antibiotic-resistant bacteria, such as methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa. For this reason, natural antibacterial mechanisms are a viable alternative for HAI treatment. Natural fibers can inhibit bacterial growth, which can be considered a great advantage in these applications. Moreover, these fibers have been reported to be biocompatible and biodegradable, essential features for biomedical materials to avoid complications due to infections and significant immune responses. Consequently, tissue engineering, medical textiles, orthopedics, and dental implants, as well as cosmetics, are fields currently expanding the use of plant fibers. In this review, we will discuss the source of natural fibers with antimicrobial properties, antimicrobial mechanisms, and their biomedical applications.     

Synthesis and spectral characterization of mercury(II) complexes with the bidentate Schiff base ligand N,N′-bis(2,3-dimethoxybenzylidene)-1,2-diaminoethane: The crystal structures of [Hg((23-MeO-ba)2en)I2] and [Hg((23-MeO-ba)2en)Br2]

Three mercury(II) complexes, [Hg((23-MeO-ba)₂en)X₂] (X = I (1), Br (2) and Cl(3)), and the ligand (23-MeO-ba)₂en ((23-MeO-ba)₂en = N,N′-bis(2,3-dimethoxybenzylidene)-1,2-diaminoethane) have been synthesized and characterized by elemental analyses, FT-IR and ¹H NMR spectroscopy. The crystal and molecular structures of 1 and 2 were determined by X-ray crystallography from single-crystal data. The metal-to-ligand ratio was found to be 1:1. The mercury(II) center in 1 and 2 has a distorted tetrahedral geometry with HgN₂I₂ and HgN₂Br₂ chromophores, respectively. The Schiff base ligand (23-MeO-ba)₂en acts as a chelating ligand, coordinating via the two nitrogen atoms to the mercury(II) center, and it adopts an E,E conformation. The coordination sphere of the mercury(II) center in 1 and 2 is completed by the two I and Br atoms, respectively. In complex 1 an inter-molecular non-classical hydrogen bond of the type C-H?O was found, while in complex 2 inter- and intra-molecular non-classical hydrogen bonds of the type C-H?X (X = O and Br) were found. The ¹H NMR spectra of the complexes exhibit downfield as well as upfield shifts of the free ligand resonances, reflecting changes in the ligand’s geometry during its coordination.     

Oxygen Isotope Labeling Experiments Reveal Different Reaction Sites for the Oxygen Evolution Reaction on Nickel and Nickel Iron Oxides

Nickel iron oxide is considered a benchmark nonprecious catalyst for the oxygen evolution reaction (OER). However, the nature of the active site in nickel iron oxide is heavily debated. Here we report direct spectroscopic evidence for the different active sites in Fe‐free and Fe‐containing Ni oxides. Ultrathin layered double hydroxides (LDHs) were used as defined samples of metal oxide catalysts, and ¹⁸O‐labeling experiments in combination with in situ Raman spectroscopy were employed to probe the role of lattice oxygen as well as an active oxygen species, NiOO^?, in the catalysts. Our data show that lattice oxygen is involved in the OER for Ni and NiCo LDHs, but not for NiFe and NiCoFe LDHs. Moreover, NiOO^? is a precursor to oxygen for Ni and NiCo LDHs, but not for NiFe and NiCoFe LDHs. These data indicate that bulk Ni sites in Ni and NiCo oxides are active and evolve oxygen via a NiOO^? precursor. Fe incorporation not only dramatically increases the activity, but also changes the nature of the active sites.     

Allylic phosphinates via palladium-catalyzed allylation of H-phosphinic acids with allylic alcohols

A novel catalytic allylation of H-phosphinic acids is described. Using Pd/xantphos (2 mol %), H-phosphinic acids react directly with allylic alcohols to produce P-allylated disubstituted phosphinic acids.     

A dynamic micromixer for arbitrary control of disguised chemical selectivity

A new type of dynamic micromixer combining the concepts of parallel multi-lamination and hydrodynamic focusing was developed for arbitrary control of disguised chemical selectivity.