Influence of supporting ligand microenvironment on the aqueous stability and visible light-induced CO-release reactivity of zinc flavonolato species

The visible light-induced CO-release reactivity of the zinc flavonolato complex [(6-Ph₂TPA)Zn(3-Hfl)]ClO₄ (1) has been investigated in 1?:?1 H₂O?:?DMSO. Additionally, the effect of ligand secondary microenvironment on the aqueous stability and visible light-induced CO-release reactivity of zinc flavonolato species has been evaluated through the preparation, characterization, and examination of the photochemistry of compounds supported by chelate ligands with differing secondary appendages, [(TPA)Zn(3-Hfl)]ClO₄ (3; TPA = tris-2-(pyridylmethyl)amine) and [(bnpapa)Zn(3-Hfl)]ClO₄ (4; bnpapa = N,N-bis((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine)). Compound 3 undergoes reaction in 1?:?1 H₂O?:?DMSO resulting in the release of the free neutral flavonol. Irradiation of acetonitrile solutions of 3 and 4 at 419 nm under aerobic conditions results in quantitative, photoinduced CO-release. However, the reaction quantum yields under these conditions are lower than that exhibited by 1, with 4 exhibiting an especially low quantum yield. Overall, the results of this study indicate that positioning a zinc flavonolato moiety within a hydrophobic microenvironment is an important design strategy toward further developing such compounds as CO-release agents for use in biological systems.     

An approach for disaccharide chiron synthesis using a Ferrier-type rearrangement

We report a new approach for the synthesis of new chiral synthons in which two unsaturated sugars are linked via a glycosidic bond. The di-unsaturated disaccharide can be further functionalized using effective, highly selective methods and used in convergent syntheses of relatively complex glycoconjugates. Our approach utilizes in situ generation of active glycosyl donors via Ferrier-type rearrangement under phase-transfer conditions and subsequent reaction with a nucleophile.     

Substituent effects in trans‐p,p′‐disubstituted azobenzenes: X‐ray structures at 100 K and DFT‐calculated structures

The crystal and molecular structures of two para‐substituted azobenzenes with π‐electron‐donating –NEt₂ and π‐electron‐withdrawing –COOEt groups are reported, along with the effects of the substituents on the aromaticity of the benzene ring. The deformation of the aromatic ring around the –NEt₂ group in N,N,N′,N′‐tetraethyl‐4,4′‐(diazenediyl)dianiline, C₂₀H₂₈N₄, (I), may be caused by steric hindrance and the π‐electron‐donating effects of the amine group. In this structure, one of the amine N atoms demonstrates clear sp²‐hybridization and the other is slightly shifted from the plane of the surrounding atoms. The molecule of the second azobenzene, diethyl 4,4′‐(diazenediyl)dibenzoate, C₁₈H₁₈N₂O₄, (II), lies on a crystallographic inversion centre. Its geometry is normal and comparable with homologous compounds. Density functional theory (DFT) calculations were performed to analyse the changes in the geometry of the studied compounds in the crystalline state and for the isolated molecules. The most significant changes are observed in the values of the N=N—C—C torsion angles, which for the isolated molecules are close to 0.0°. The HOMA (harmonic oscillator model of aromaticity) index, calculated for the benzene ring, demonstrates a slight decrease of the aromaticity in (I) and no substantial changes in (II).     

New Insight on Carbon Dioxide-Mediated Hydrogen Production**

A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7–8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO₂ under UV-C, the hydrogen production amounted to 0.6 μmol h⁻¹ during 24 h of radiation.     

The Influence of Different Pretreatment Methods on Color and Pigment Change in Beetroot Products

Vegetable processing pomace contains valuable substances such as natural colors that can be reused as functional ingredients. Due to a large amount of water, they are an unstable material. The aim of our research was to assess how the pretreatment method (thermal or nonthermal) affects the properties of powders obtained from beet juice and pomace after the freeze-drying process. The raw material was steamed or sonicated for 10 or 15 min, and then squeezed into juice and pomace. Both squeezed products were freeze-dried. The content of dry substance; L*, a*, and b* color parameters; and the content of betalain pigments were analyzed. Pretreatments increased the proportion of red and yellow in the juices. Steam and ultrasound caused a significant reduction in parameter b* in the dried pomace. A significant increase in betanin in lyophilizates was observed after pretreatment with ultrasound and steam for 15 min. As a result of all experiments, dried juices and pomaces can also be used as a colorant source. However, there is higher potential with pomaces due to their additional internal substances as well as better storage properties. After a few hours, juice was sticky and not ready to use.     

Effect of Botanical Extracts on the Growth and Nutritional Quality of Field-Grown White Head Cabbage (Brassica oleracea var. capitata)

Nutraceuticals and functional foods are gaining more attention amongst consumers interested in nutritious food. The consumption of foodstuffs with a high content of phytochemicals has been proven to provide various health benefits. The application of biostimulants is a potential strategy to fortify cultivated plants with beneficial bioactive compounds. Nevertheless, it has not yet been established whether the proposed higher plants (St. John’s wort, giant goldenrod, common dandelion, red clover, nettle, and valerian) are appropriate for the production of potential bio-products enhancing the nutritional value of white cabbage. Therefore, this research examines the impact of botanical extracts on the growth and nutritional quality of cabbage grown under field conditions. Two extraction methods were used for the production of water-based bio-products, namely: ultrasound-assisted extraction and mechanical homogenisation. Bio-products were applied as foliar sprays to evaluate their impact on total yield, dry weight, photosynthetic pigments, polyphenols, antioxidant activity, vitamin C, nitrates, micro- and macroelements, volatile compounds, fatty acids, sterols, and sugars. Botanical extracts showed different effects on the examined parameters. The best results in terms of physiological and biochemical properties of cabbage were obtained for extracts from common dandelion, valerian, nettle, and giant goldenrod. When enriched with nutrients, vegetables can constitute a valuable component of functional food.     

Impact of the Type of Crosslinking Agents on the Properties of Modified Sodium Alginate/Poly(vinyl Alcohol) Hydrogels

Here, we report on studies on the influence of different crosslinking methods (ionic and chemical) on the physicochemical (swelling ability and degradation in simulated body fluids), structural (FT-IR spectra analysis) and morphological (SEM analysis) properties of SA/PVA hydrogels containing active substances of natural origin. First, an aqueous extract of Echinacea purpurea was prepared using a Soxhlet apparatus. Next, a series of modified SA/PVA-based hydrogels were obtained through the chemical crosslinking method using poly(ethylene glycol) diacrylate (PEGDA, M_n = 700 g/mol) as a crosslinking agent and, additionally, the ionic reaction in the presence of a 5% w/v calcium chloride solution. The compositions of SA/PVA/E. purpurea-based hydrogels contained a polymer of natural origin—sodium alginate (SA, 1.5% solution)—and a synthetic polymer—poly(vinyl alcohol) (PVA, M_n = 72,000 g/mol, 10% solution)—in the ratio 2:1, and different amounts of the aqueous extract of E. purpurea—5, 10, 15 or 20% (v/v). Additionally, the release behavior of echinacoside from the polymeric matrix was evaluated in phosphate-buffered saline (PBS) at 37 °C. The results indicate that the type of the crosslinking method has a direct impact on the release profile. Consequently, it is possible to design a system that delivers an active substance in a way that depends on the application.     

Effect of Polythiophene Content on Thermomechanical Properties of Electroconductive Composites

The thermal, mechanical and electrical properties of polymeric composites combined using polythiophene (PT) dopped by FeCl₃ and polyamide 6 (PA), in the aspect of conductive constructive elements for organic solar cells, depend on the molecular structure and morphology of materials as well as the method of preparing the species. This study was focused on disclosing the impact of the polythiophene content on properties of electrospun fibers. The elements for investigation were prepared using electrospinning applying two substrates. The study revealed the impact of the substrate on the conductive properties of composites. In this study composites exhibited good thermal stability, with T₅ values in the range of 230–268 °C that increased with increasing PT content. The prepared composites exhibited comparable PA T_g values, which indicates their suitability for processing. Instrumental analysis of polymers and composites was carried out using Fourier Transform Infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM).     

Investigation of Parameters Influencing Tubular-Shaped Chitosan-Hydroxyapatite Layer Electrodeposition

Tubular-shaped layer electrodeposition from chitosan-hydroxyapatite colloidal solutions has found application in the field of regeneration or replacement of cylindrical tissues and organs, especially peripheral nerve tissue regeneration. Nevertheless, the quantitative and qualitative characterisation of this phenomenon has not been described. In this work, the colloidal systems are subjected to the action of an electric current initiated at different voltages. Parameters of the electrodeposition process (i.e., total charge exchanged, gas volume, and deposit thickness) are monitored over time. Deposit structures are investigated by scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR). The value of voltage influences structural characteristics but not thickness of deposit for the process lasting at least 20 min. The calculated number of exchanged electrons for studied conditions suggests that the mechanism of deposit formation is governed not only by water electrolysis but also interactions between formed hydroxide ions and calcium ions coordinated by chitosan chains.     

Bee Venom in Wound Healing

Bee venom (BV), also known as api-toxin, is widely used in the treatment of different inflammatory diseases such as rheumatoid arthritis or multiple sclerosis. It is also known that BV can improve the wound healing process. BV plays a crucial role in the modulation of the different phases of wound repair. It possesses anti-inflammatory, antioxidant, antifungal, antiviral, antimicrobial and analgesic properties, all of which have a positive impact on the wound healing process. The mentioned process consists of four phases, i.e., hemostasis, inflammation, proliferation and remodeling. The impaired wound healing process constitutes a significant problem especially in diabetic patients, due to hypoxia state. It had been found that BV accelerated the wound healing in diabetic patients as well as in laboratory animals by impairing the caspase-3, caspase-8 and caspase-9 activity. Moreover, the activity of BV in wound healing is associated with regulating the expression of transforming growth factor (TGF-β1), vascular endothelial growth factor and increased collagen type I. BV stimulates the proliferation and migration of human epidermal keratinocytes and fibroblasts. In combination with polyvinyl alcohol and chitosan, BV significantly accelerates the wound healing process, increasing the hydroxyproline and glutathione and lowering the IL-6 level in wound tissues. The effect of BV on the wounds has been proved by numerous studies, which revealed that BV in the wound healing process brings about a curative effect and could be applied as a new potential treatment for wound repair. However, therapy with bee venom may induce allergic reactions, so it is necessary to assess the existence of the patient’s hypersensitivity to apitoxin before treatment.