A new method for the synthesis of mixed orthoesters from O-allyl acetals

Two new methods for the synthesis of orthoesters and compounds containing an orthoester moiety (dihydroisoxazoles) are presented. Mixed orthoesters of general formulas RC(OR¹)(OR²)₂ and RC(OR¹)(OR²)(OR³) were prepared via addition of ROH (R = Bu or m-methylphenyl) to O-allyl acetals (acrolein acetals: diethyl or cyclic, i.e., 2-vinyl-1,3-dioxanes or dioxolanes). The catalytic systems for these reactions were generated from [RuCl₂(PPh₃)₃] and Na₂CO₃; {[RuCl₂(COD)]_x} or {[OsCl₂(1,5-COD)]_x}, PPh₃, and Na₂CO₃. Compounds containing an orthoester moiety (dihydroisoxazoles) were prepared via tandem isomerization of O-allyl acetals (to O-vinyl acetals) catalyzed by ruthenium complexes followed by cycloaddition to in situ-generated 2,6-dichlorophenylnitrile oxide.     

Difluoromethylation of some C-H acids with chlorodifluoromethane under conditions of phase transfer catalysis (PTC)

Selected C-H acids react with difluorocarbene generated from chlorodifluoromethane with concentrated aqueous solution of sodium hydroxide, and a catalyst, benzyltriethylammonium chloride (TEBAC) in benzene or THF affording C-difluoromethyl substituted derivatives. This process is restricted to C-H acids of pK_a ≅ 16.3-19.1. The observed facts are rationalized.     

Study of effect of phosphate and uranium ions on the thermal properties of surfactant-modified natural red clay using TG–FTIR–MS techniques

Products of sorption of uranyl ions on HDTMA-red clay in the presence of phosphates were characterized by thermal analysis. It was established on the basis of DTG curves of the sorption products and FTIR spectra of the gaseous phase of sorption products decomposition that the thermal stability of the mineral increased when P(V) ions were sorbed along with U(VI) ions, i.e., the temperature of defragmentation/oxidation of surfactant increased when going from U(VI)–HDTMA-clay to U(VI)–P(V)–HDTMA-clay to P(V)–HDTMA-clay. The DSC curves of the sorption products showed that defragmentation/oxidation was an exothermic process and dehydration and dehydroxylation had an endothermic character. The investigated sorption system has practical importance, since an evident increase in U(VI) sorption over the entire pH range is observed when going from U(VI)–HDTMA-clay to U(VI)–P(V)–HDTMA-clay.

     

The heat risk during hardening of dental glass-ionomer cements using a light-curing

Journal of Thermal Analysis and Calorimetry - An use of a polymerization lamp to irradiate chemically hardened glass-ionomer materials may improve their properties and accelerate the setting time....     

A new mesogenic fluorene derivative: 2,7-bis(4-pentylphenyl)-9,9-diethyl-9H-fluorene

The title compound, 2,7-bis(4-pentylphenyl)-9,9-diethyl-9H-fluorene, is a new mesogenic compound containing the fluorene moiety. It exhibits a monotropic nematic liquid crystalline behaviour, with isotropisation temperature of 53°C. The compound is also polymorphic in the solid state, with one crystal phase melting at 103°C and another one melting at 71°C. The crystal and molecular structure of the high melting solid phase have been determined from single crystal X-ray diffraction analysis. Crystals are monoclinic, with cell dimensions a = 16.649(6) Å, b = 8.305(3) Å, c = 24.598(7) Å, β = 111.60(2)?, space group P2₁/c and four molecules in the unit cell. Refinement leads to R = 0.0558. The two terminal alkyl chains and one phenyl ring are disordered over two split positions. The imbricated molecular packing observed in the solid state seems to resemble that of the nematic phase that is formed upon cooling the melt.     

Crystal structure and mesogenic behaviour of a new fluorene derivative: 9,9‐dimethyl‐2,7‐bis(4‐pentylphenyl)‐9H‐fluorene

The title compound, C₃₇H₄₂, is a new mesogenic compound containing the fluorene moiety. It exhibits enantiotropic nematic liquid crystalline behaviour with melting at 125 °C and isotropization at 175 °C. The crystallographically independent unit contains two molecules oriented face‐to‐edge with respect to each other. The two molecules have nearly the same conformation of the bis‐phenyl fluorene moiety. The molecular packing in the crystal phase is nematic‐like.     

Green Extraction of Carotenoids from Fruit and Vegetable Byproducts: A Review

Carotenoids are characterized by a wide range of health-promoting properties. For example, they support the immune system and wound healing process and protect against UV radiation’s harmful effects. Therefore, they are used in the food industry and cosmetics, animal feed, and pharmaceuticals. The main sources of carotenoids are the edible and non-edible parts of fruit and vegetables. Therefore, the extraction of bioactive substances from the by-products of vegetable and fruit processing can greatly reduce food waste. This article describes the latest methods for the extraction of carotenoids from fruit and vegetable byproducts, such as solvent-free extraction—which avoids the costs and risks associated with the use of petrochemical solvents, reduces the impact on the external environment, and additionally increases the purity of the extract—or green extraction using ultrasound and microwaves, which enables a significant improvement in process efficiency and reduction in extraction time. Another method is supercritical extraction with CO₂, an ideal supercritical fluid that is non-toxic, inexpensive, readily available, and easily removable from the product, with a high penetration capacity.     

The Study of Chemical Profile and Antioxidant Properties of Poplar-Type Polish Propolis Considering Local Flora Diversity in Relation to Antibacterial and Anticancer Activities in Human Breast Cancer Cells

Nine samples of ethanolic extracts of poplar-type propolis (EEP) originated from South-Eastern Poland were analyzed in terms of the diversity of the flora around the apiary. The mineral composition, antioxidant properties, polyphenolic profile (HPTLC), and main polyphenolic constituents (HPLC-DAD) were determined. Only minor differences in chemical composition and antioxidant capacity between tested EEPs were found regardless of their botanical origin. However, the biological activity of the EEPs was more diversified. The tested EEPs showed stronger antibacterial activity against Gram-negative bacteria (Escherichia coli) compared to Gram-positive bacteria (Staphylococcus aureus and Staphylococcus epidermidis). Staphylococci biofilm inhibition occurred as a result of exposure to the action of four out of nine EEPs (P1–P4). Due to the various compositions of individual EEPs, a different MCF-7 cellular response was observed according to inhibition of cells migration and proliferation. Almost every sample inhibited the migration of breast cancer cells at a low concentration (0.04 µg/mL) of propolis. Even at the lowest concentration (0.02 µg/mL), each EEP inhibited the proliferation of MCF-7 cells, however, the level of inhibition varied between samples.     

Polyphenols Content,Antioxidant Properties and Allergenic Potency of Organic and Conventional Blue Honeysuckle Berries

Blue honeysuckle berries are a rich source of polyphenols with strong antioxidant properties. The purpose of this research was to determine the effect of organic and conventional cultivation on the polyphenols, antioxidant and allergenic potency of blue honeysuckle berry cultivars: ‘No 30’, ‘Jolanta’ and ‘Indygo’ in two growing seasons. Identification of individual polyphenols was performed using the HPLC method; the total polyphenols content and antioxidant activity were determined by spectrophotometric methods. The determination of allergic potency was tested by ELISA. In the second year of the study the total polyphenols were significantly higher in organic blue honeysuckle than in the conventional blue honeysuckle. In both growing seasons, the ‘Indygo’ cv. was characterized by the highest concentration of all bioactive compounds 3241.9 mg and 3787.2 mg per 100 g⁻¹ D.W. A strong correlation was found between the polyphenol content and the antioxidant activity for organic fruit in both years, as well as for allergenic potency. Contrary to the best bioactive properties was ‘Indigo’ cv., with the highest allergenic potency (108.9 and 139.2 ng g⁻¹ D.W.). The lowest content of specific allergens was found in the ‘No 30’ cv. Since honeysuckle is still a new cultivated plant, information about its allergenic potency is insufficient.     

Insight on the Interaction between the Camptothecin Derivative and DNA Oligomer Mimicking the Target of Topo I Inhibitors

The understanding of the mechanism of Topo I inhibition by organic ligands is a crucial source of information that has led to the design of more effective and safe pharmaceuticals in oncological chemotherapy. The vast number of inhibitors that have been studied in this respect over the last decades have enabled the creation of a concept of an ‘interfacial inhibitor’, thereby describing the machinery of Topo I inhibition. The central module of action of this machinery is the interface of a Topo I/DNA/inhibitor ternary complex. Most of the ‘interfacial inhibitors’ are primarily kinetic inhibitors that form molecular complexes with an “on–off” rate timing; therefore, all of the contacts between the inhibitor and both the enzyme and the DNA are essential to keep the complex stable and reduce the “off rate”. To test this hypothesis, we designed the compound using a C-9-(N-(2′-hydroxyethyl)amino)methyl substituent in an SN38 core, with a view that a flexible substituent may bind inside the nick of a model of the DNA and stabilize the complex, leading to a reduction in the “off rate” of a ligand in a potential ternary complex in vivo. Using docking analysis and molecular dynamics, free energy calculations on the level of the MM-PBSA and MM-GBSA model, here we presented the in silico-calculated structure of a ternary complex involving the studied compound 1. This confirmed our suggestion that compound 1 is situated in a groove of the nicked DNA model in a few conformations. The number of hydrogen bonds between the components of a ternary complex was established, which strengthens the complex and supports our view. The docking analysis and free energy calculations for the receptor structures which were obtained in the MD simulations of the ternary complex 1/DNA/Topo I show that the binding constant is stronger than it was for similar complexes with TPT, CPT, and SN38, which are commonly considered as strong Topo I inhibitors. The binary complex structure 1/DNA was calculated and compared with the experimental results of a complex that was in a solution. The analysis of the cross-peaks in NOESY spectra allowed us to assign the dipolar interactions between the given protons in the calculated structures. A DOSY experiment in the solution confirmed the strong binding of a ligand in a binary complex, having a K_a of 746 mM⁻¹, which was compared with a K_a of 3.78 mM⁻¹ for TPT. The MALDI-ToF MS showed the presence of the biohybrid, thus evidencing the occurrence of DNA alkylation by compound 1. Because of it having a strong molecular complex, alkylation is the most efficient way to reduce the “on–off” timing as it acts as a tool that causes the cog to brake in a working gear, and this is this activity we want to highlight in our contribution. Finally, the Topo I inhibition test showed a lower IC₅₀ of the studied compound than it did for CPT and SN38.