Concentration Dependence of Anti- and Pro-Oxidant Activity of Polyphenols as Evaluated with a Light-Emitting Fe2+-Egta-H2O2 System

Hydroxyl radical (^•OH) scavenging and the regeneration of Fe²⁺ may inhibit or enhance peroxidative damage induced by a Fenton system, respectively. Plant polyphenols reveal the afore-mentioned activities, and their cumulative net effect may determine anti- or pro-oxidant actions. We investigated the influence of 17 phenolics on ultra-weak photon emission (UPE) from a modified Fenton system (92.6 µmol/L Fe²⁺, 185.2 µmol/L EGTA (ethylene glycol-bis(β-aminoethyl-ether)-N,N,N′,N,-tetraacetic acid) and 2.6 mmol/L H₂O₂ pH = 7.4). A total of 8 compounds inhibited (antioxidant effect), and 5 enhanced (pro-oxidant effect) UPE at all studied concentrations (5 to 50 µmol/L). A total of 4 compounds altered their activity from pro- to antioxidant (or vice versa) along with increasing concentrations. A total of 3 the most active of those (ferulic acid, chlorogenic acid and cyanidin 3-O-glucoside; mean UPE enhancement by 63%, 5% and 445% at 5 µmol/L; mean UPE inhibition by 28%, 94% and 24% at 50 µmol/L, respectively) contained catechol or methoxyphenol structures that are associated with effective ^•OH scavenging and Fe²⁺ regeneration. Most likely, these structures can determine the bidirectional, concentration-dependent activity of some phenolics under stable in vitro conditions. This is because the concentrations of the studied compounds are close to those occurring in human fluids, and this phenomenon should be considered in the case of dietary supplementation with isolated phenolics.     

USAEME-GC/MS Method for Easy and Sensitive Determination of Nine Bisphenol Analogues in Water and Wastewater

A new, simple and sensitive method for isolating nine compounds from the bisphenol group (analogues: A, B, C, E, F, G, Cl₂, Z, AP) based on one-step liquid–liquid microextraction with in situ acylation followed by gas chromatography-mass spectrometry was developed and validated using influent and effluent wastewaters. The chemometric approach based on the Taguchi method was used to optimize the main conditions of simultaneous extraction and derivatization. The recoveries of the proposed procedure ranged from 85 to 122%, and the repeatability expressed by the coefficient of variation did not exceed 8%. The method’s limits of detection were in the range of 0.4–64 ng/L, and the method’s limits of quantification ranged from 1.3 to 194 ng/L. The developed method was used to determine the presence of the tested compounds in wastewater from a municipal wastewater treatment plant located in northeastern Poland. From this sample, eight analytes were detected. Concentrations of bisphenol A of 400 ng/L in influent and 100 ng/L in effluent were recorded, whereas other bisphenols reached 67 and 50 ng/L for influent and effluent, respectively. The removal efficiency of bisphenol analogues in the tested wastewater treatment plant ranged from 7 to approximately 88%.     

On stress analysis of load for microperiodic composite half-plane with slant lamination

Meccanica - The paper deals with the plane problem of normal and tangential load for microperiodic composite with slant lamination. The boundary condition was considered as a normal and tangential...     

Interpolating between Positive and Completely Positive Maps: A New Hierarchy of Entangled States

A new class of positive maps is introduced. It interpolates between positive and completely positive maps. It is shown that this class gives rise to a new characterization of entangled states. Additionally, it provides a refinement of the well-known classes of entangled states characterized in terms of the Schmidt number. The analysis is illustrated with examples of qubit maps.     

On the topological classification of pseudofree group actions on 4-manifolds: II

This paper is concerned with the algebraic aspects of the classification of pseudofree, locally linear group actions on a simply connected 4-manifold, particularly with the splitting and stability properties of the associated Hermitian intersection module and its isometry group. Our main result is the proof of stability of the equivariant intersection form for a large class of pseudofree actions. We also prove a topological rigidity theorem stating that two locally linear, pseudofree actions on a closed, oriented, simply connected 4-manifold, with the equivariant intersection forms indefinite and of rank at least 3 at each irreducible character, are topologically conjugate by an orientation preserving homeomorphism if and only if their oriented local representations at the corresponding fixed points are linearly equivalent.Partially supported by the N.S.F.     

Titanium(IV)-mediated synthesis of 2,3-diisothiocyanato-succinic acid diesters and 3,6-dithioxo-piperazine derivatives

Oxidative homocoupling of titanium(IV) enolates of 2-isothiocyanato-carboxylic esters resulted in the synthesis of 2,3-diisothiocyanato-succinic acid diesters. The reactions were carried out using DIPEA/TiCl₄ oxidizing system and led to chiral dimers (instead of meso) as main products. Titanium(IV) enolates derived from hindered 2-isothiocyanato-carboxylates did not undergo the oxidative homocoupling but gave 3,6-dithioxo-piperazines.     

Standardization protocols and optimized precursor sets for the efficient application of automated parallel synthesis to lead optimization: a Mitsunobu example

A strategy has been developed for the efficient application of automated parallel synthesis to specific aspects of the lead optimization processes employed in drug discovery. The method involves the synthesis of collections of compounds using sets of precursors designed to encompass established medicinal chemistry principles and that have been concurrently optimized with respect to a specific chemical transformation. The strategy is illustrated using an automated Mitsunobu protocol employing sets of aliphatic alcohols and phenols as precursors. The former has been formatted to perform simple alkyl homologation exercises, with the latter being designed for use in diversity-based studies.     

Synthesis of Chiral 2,4-Chiral 2,4-Dichloro-6-menthoxy-1,3,5-triazines and 2-Chloro-4, 6-Dimenthoxy-1,3,5-triazines as Enantiodifferentiating Coupling Reagents. An X-ray Study on 2,4,6-Trimenthoxy-1,3,5-triazine

Chiral mono-di-and trimenthoxy-1,3,5-triazines ware obtained from natural menthol and cyanuric chloride and applied as enantioselective coupling reagents in the synthesis of dipeptides.