Circular dichroism of 9,10-dihydrophenanthrene derivatives reveals both the absolute configuration and conformation: a novel approach to Mislow's helicity rule

The absolute configuration and the conformation of 9,10-trans-disubstituted 9,10-dihydrophenanthrenes, known chiral metabolites of phenanthrene-9,10-oxide, have been determined by circular dichroism. The absolute configuration assignment is based on the sign of the long-wavelength Cotton effect (A-band), which is conformation invariant and originates from benzylic chirality. This provides a new interpretation of the Mislow biphenyl-helicity rule for the case of the 9,10-dihydrophenanthrene chromophore. The sign of the B-band Cotton effect reflects the conformation of the biphenyl chromophore in 9,10-dihydrophenanthrenes. It is shown that the origin of chiroptical properties of 9,10-dihydrophenanthrenes is closely related to those of 5,6-trans-disubstituted 1,3-cyclohexadienes.     

Modulatory Effect of Diosmin and Diosmetin on Metalloproteinase Activity and Inflammatory Mediators in Human Skin Fibroblasts Treated with Lipopolysaccharide

Diosmin is widely used as a venoactive drug in the pharmacological treatment of chronic venous disorders. It exerts a strong protective effect on blood vessels via an increase in the elasticity of vessel walls and reduces the permeability of capillary walls, thereby producing an anti-edematous effect. In this paper, we investigated the effectiveness of diosmin and diosmetin in modulating the level of proinflammatory factors in human skin fibroblasts treated with lipopolysaccharide (LPS). Two variants of the experiments were performed: the flavonoid was added 2 h prior to or 24 h after LPS stimulation. Our study revealed that both flavonoids reduced the levels of IL-6 and Il-1β as well as COX-2 and PGE2 but had no impact on IL-10. However, the addition of the compounds prior to the LPS addition was more effective. Moreover, diosmetin modulated the proinflammatory factors more strongly than diosmin. Our investigations also showed that both flavonoids were potent inhibitors of elastase and collagenase activity, and no differences between the glycoside and aglycone forms were observed.     

The DI-SPME Method for Determination of Selected Narcotics and Their Metabolites,and Application to Bone Marrow and Whole Blood Analysis

The present investigation utilised the quick and easy SPME/LC-MS method to determine selected narcotic substances and their metabolites in whole blood. The study included qualitative analysis and validation of the method. Analytes were determined in the linearity range of 25–300 ng/mL. The precision during and between days (in general CV < 13.41%), and the LOD which results in between 0.36 and 11.08 ng/mL, and the LOQ between 1.20 and 36.90 ng/mL were investigated. The validation results obtained, as well as the results of subsequent in-laboratory tests, confirmed the applicability of the method in the analysis of blood samples. An attempt to apply the method to the analysis of bone marrow samples has yielded promising results; however, more detailed studies are needed in this area.     

Synthesis and Luminescent Properties of s-Tetrazine Derivatives Conjugated with the 4H-1,2,4-Triazole Ring

New derivatives obtained by the combination of unique 1,2,4,5-tetrazine and 4H-1,2,4-triazole rings have great application potential in many fields. Therefore, two synthetic few-step methodologies, which make use of commercially available 4-cyanobenzoic acid (method A) and ethyl diazoacetate (method B), were applied to produce two groups of the aforementioned heterocyclic conjugates. In both cases, the target compounds were obtained in various combinations, by introducing electron-donating or electron-withdrawing substituents into the terminal rings, together with aromatic or aliphatic substituents on the triazole nitrogen atom. Synthesis of such designed systems made it possible to analyze the influence of individual elements of the structure on the reaction course, as well as the absorption and emission properties. The structure of all products was confirmed by conventional spectroscopic methods, and their luminescent properties were also determined.     

Formation of Carcinogens in Processed Meat and Its Measurement with the Usage of Artificial Digestion—A Review

Meat is a rich source of various nutrients. However, it needs processing before consumption, what in turn generates formation of carcinogenic compounds, i.a., polycyclic aromatic hydrocarbons (PAH), nitrosamines (NOCs), and the most mutagenic heterocyclic aromatic amines (HAAs). It was widely found that many factors affect the content of carcinogens in processed meat. However, it has recently been discovered that after digestion free HAAs are released, which are not detectable before enzymatic treatment. It was established that the highest percentage of carcinogens is released in the small intestine and that its amount can be increased up to 6.6-fold. The change in free HAAs content in analyzed samples was dependent on many factors such as meat type, doneness, particle size of meat, and the enzyme concentration used for digestion. In turn, introduction of bacteria naturally occurring in the human digestive tract into the model significantly decreases total amount of HAAs. Contrary, the addition of food ingredients rich in polyphenols, fiber, and water (pepper powder, onions, apples) increases free HAAs’ release up to 56.06%. Results suggests that in vitro digestion should be an integral step of sample preparation. Artificial digestion introduced before chromatographic analysis will allow to estimate accurately the content of carcinogens in processed meat.     

Manufacturing of Volumetric Glass–Based Composites with Single‐ and Double‐QD Doping

Quantum dot (QD)‐based light‐emitting materials are gaining increased attention because of their easily tunable optical properties desired for various applications in biology, optoelectronics, and photonics. However, few methods can be used to manufacture volumetric materials doped with more than one type of QD other than QD‐polymer hybrids, and they often require complicated preparation processes and are prone to luminescence quenching by QD aggregation and separation from the matrix. Here, simultaneous doping of a volumetric glass‐based nanocomposite with two types of QDs is demonstrated for the first time in a single‐step process using the nanoparticle direct doping method. Glass rods doped with CdTe, CdSe/ZnS, or co‐doped with both QDs, are obtained. Photoluminescence and lifetime experiments confirm temperature‐dependent double emission with maxima at 596 and 720 nm with mean lifetimes up to 16 ns, as well as radiative energy transfer from the short wavelength–emitting QDs to the long wavelength–emitting QDs. This approach may enable the simple and cost‐efficient manufacturing of bulk materials that produce multicolor luminescence with cascade excitation pumping. Applications that could benefit from this include broadband optical fiber amplifiers, backlight systems in LCD screens, high‐power LEDs, or down‐converting solar concentrators used to increase the efficiency of solar panels.     

Polypropylene/Poly (Trimethylene Terephthalate)–Blend Fibers

Polypropylene (PP)/polyester (PES)–blend fibers were prepared by extruder melt spinning. The polymer blend consisted of PP and a “master batch” (MB) based on polytrimethylene terephthalate (PTT) or polyethylene terephthalate (PET), binary PTT/PET or PP/PTT blends, and also on a ternary PP/(PTT/PET) blend. The phase structure of PP/PES–blend fibers was examined. PES microfibers showed separation from the PP matrix in blend fibers. The impact of MB composition and rheological characteristics on phase structure parameters indicate a significant contribution of the PTT in the binary MB on the length of dispersed PES microfibers in the PP matrix. However, the blends of PP and ternary MB (PP/PTT/PET) have a lower diameter and length of the PES microfibers. The presence of PTT/PET (PES) enhances the structural and mechanical properties of the blend PP/PES fibers. In addition, PTT increases the tensile strength of the PP/PES–blend fibers if a binary MB is used, while the fiber nonuniformity is reduced in the presence of a ternary MB.     

The Ising version of the t–J model

The t–J model is analysed in the limit of strong anisotropy, where the transverse components of electron spin are neglected. We propose a slave-particle-type approach that is valid, in contradiction to many of the standard approaches, in the low-doping regime and becomes exact for a half-filled system. We describe an effective method that allows to numerically study the system with the no-double-occupancy constraint rigorously taken into account at each lattice site. Then, we use this approach to demonstrate the destruction of the antiferromagnetic order by increasing the doping and formation of Nagaoka polarons in the strong interaction regime.