Comparative Studies of Selected Criteria Enabling Optimization of the Extraction of Polar Biologically Active Compounds from Alfalfa with Supercritical Carbon Dioxide

The aim of this research was to provide crucial and useful data about the selection of the optimization criteria of supercritical carbon dioxide extraction of alfalfa at a quarter-technical plant. The correlation between more general output, including total phenolics and flavonoids content, and a more specified composition of polar constituents was extensively studied. In all alfalfa extracts, polar bioactive constituents were analyzed by both spectrometric (general output) and chromatographic (detailed output) analyses. Eight specific phenolic acids and nine flavonoids were determined. The most dominant were salicylic acid (221.41 µg g⁻¹), ferulic acid (119.73 µg g⁻¹), quercetin (2.23 µg g⁻¹), and apigenin (2.60 µg g⁻¹). For all seventeen analyzed compounds, response surface methodology and analysis of variance were used to provide the optimal conditions of supercritical fluid extraction for each individual constituent. The obtained data have shown that eight of those compounds have a similar range of optimal process parameters, being significantly analogous for optimization based on total flavonoid content.     

Can 2‐acylpyrroles form an intramolecular hydrogen bond?

The formation of intramolecular hydrogen bonding by certain N‐substituted 2‐acylpyrroles has been demonstrated by B3LYP/aug‐cc‐pVDZ calculations, the quantum theory of atoms in molecules, and the natural bond orbital method. Total electron energy densities H_BCP at the bond critical point of the H?O bond were applied to analyze the strength of these interactions. The relations between quantum theory of atoms in molecules, carbonyl stretching vibrational modes ν_{C = O}, and natural bond orbital parameters associated with the formation of the C–H?O interaction have been established. The short contacts were found experimentally in the crystal structure of a new 2‐acylpyrrole derivative 5‐chloro‐2‐oxopentyl‐1‐(5‐chloro‐2‐oxopentyl)pyrrolo‐2‐carboxylate. The influence of 2‐ and N‐substitution of 2‐acylpyrroles on C‐H?O interaction energy is discussed. It was found that the methylene group may act as a proton donor leading to a red‐shift or blue‐shift phenomenon of the ν_C–H stretching mode. Copyright © 2015 John Wiley & Sons, Ltd.     

SO 2 sorption properties of fly ash zeolites

In the presented study, the sulfur dioxide sorption properties of fly ash zeolite X were investigated. Sorption tests were performed on fly ash zeolite samples that were not prepared specially for sorption, in addition to dried samples and samples in the presence of water vapor. The samples saturated with water vapor showed the highest sorption capacity. The sorption capacity of the samples additionally dried prior to the sorption experiment was higher than that of the samples that were not specially prepared for the sorption test. Regeneration tests indicated relatively good regeneration properties. The obtained results were described with the use of Langmuir, Sips, and Dubinin–Astakhov models, with the Dubinin–Astakhov model providing the best fit.     

ToF‐SIMS spectrometry to observe fatty acid profiles of breast tissues in broiler chicken subjected to varied vegetable oil diet

This study is aimed to observe changes in fatty acid profiles by time of flight secondary ion mass spectrometry (ToF‐SIMS) in breast muscle tissues of broilers. Four different groups were identified. The source of fat in group I was soy oil (rich in linoleic acid, ω‐6), group II received linseed oil (ω‐3), and the third group was fed a mixture of the two mentioned oils. Broilers in the control group were fed with beef tallow, used in mass commercial production. The results reveal that the use of vegetable oils in animal nutrition determines the lipid profile of fatty acids. ToF‐SIMS measurements showed that the lipid profile of muscle fibers and intramuscular fat reflect the composition of fats used as feed additives. In both structures, the ratio of ω‐6/ω‐3 fatty acids, which is most favorable for human health, was found in the groups in which a mixture of vegetable oils and a supplement of linseed oil were used.     

Simultaneous determination of terpenes and cannabidiol in hemp (Cannabis sativa L.) by fast gas chromatography with flame ionization detection

Hemp (Cannabis sativa L.) has become widely used in several sectors due to the presence of various bioactive compounds such as terpenes and cannabidiol. In general, terpenes and cannabidiol content is determined separately, which is time consuming. Thus, a fast gas chromatography with flame ionization detection method was validated for simultaneous determination of both terpenes and cannabidiol in hemp. The method enabled a rapid detection of 29 different terpenes and cannabidiol within a total analysis time of 16 min, with satisfactory sensitivity (limit of detection = 0.03–0.27 µg/mL, limit of quantitation = 0.10–0.89 µg/mL). The inter‐ and intraday precision (RSD) was <7.82 and <3.59%, respectively. Recoveries at two spiked concentration levels (low, 3.15 µg/mL; high, 20.0 µg/mL) were determined on both apical leaves (78.55–101.52%) and inflorescences (77.52–107.10%). The reproducibility (RSD) was <5.94 and <5.51% in apical leaves and inflorescences, respectively. The proposed and validated method is highly sensitive, robust, fast, and accurate for determination of the main terpenes and cannabidiol in hemp and could be routinely used for quality control.     

An Update on Synthesis of Coumarin Sulfonamides as Enzyme Inhibitors and Anticancer Agents

Coumarin is an important six-membered aromatic heterocyclic pharmacophore, widely distributed in natural products and synthetic molecules. The versatile and unique features of coumarin nucleus, in combination with privileged sulfonamide moiety, have enhanced the broad spectrum of biological activities. The research and development of coumarin, sulfonamide-based pharmacology, and medicinal chemistry have become active topics, and attracted the attention of medicinal chemists, pharmacists, and synthetic chemists. Coumarin sulfonamide compounds and analogs as clinical drugs have been used to cure various diseases with high therapeutic potency, which have shown their enormous development value. The diversified and wide array of biological activities such as anticancer, antibacterial, anti-fungal, antioxidant and anti-viral, etc. were displayed by diversified coumarin sulfonamides. The present systematic and comprehensive review in the current developments of synthesis and the medicinal chemistry of coumarin sulfonamide-based scaffolds give a whole range of therapeutics, especially in the field of oncology and carbonic anhydrase inhibitors. In the present review, various synthetic approaches, strategies, and methodologies involving effect of catalysts, the change of substrates, and the employment of various synthetic reaction conditions to obtain high yields is cited.     

The Current Directions of Searching for Antiparasitic Drugs

Parasitic diseases are still a huge problem for mankind. They are becoming the main cause of chronic diseases in the world. Migration of the population, pollution of the natural environment, and climate changes cause the rapid spread of diseases. Additionally, a growing resistance of parasites to drugs is observed. Many research groups are looking for effective antiparasitic drugs with low side effects. In this work, we present the current trends in the search for antiparasitic drugs. We report known drugs used in other disease entities with proven antiparasitic activity and research on new chemical structures that may be potential drugs in parasitic diseases. The described investigations of antiparasitic compounds can be helpful for further drug development.     

Silver Nanowires and Silanes in Hybrid Functionalization of Aramid Fabrics

New functionalization methods of meta- and para-aramid fabrics with silver nanowires (AgNWs) and two silanes (3-aminopropyltriethoxysilane (APTES)) and diethoxydimethylsilane (DEDMS) were developed: a one-step method (mixture) with AgNWs dispersed in the silane mixture and a two-step method (layer-by-layer) in which the silanes mixture was applied to the previously deposited AgNWs layer. The fabrics were pre-treated in a low-pressure air radio frequency (RF) plasma and subsequently coated with polydopamine. The modified fabrics acquired hydrophobic properties (contact angle Θ_W of 112–125°). The surface free energy for both modified fabrics was approximately 29 mJ/m², while for reference, meta- and para-aramid fabrics have a free energy of 53 mJ/m² and 40 mJ/m², respectively. The electrical surface resistance (R_s) was on the order of 10² Ω and 10⁴ Ω for the two-step and one-step method, respectively. The electrical volume resistance (R_v) for both modified fabrics was on the order of 10² Ω. After UV irradiation, the Rs did not change for the two-step method, and for the one-step method, it increased to the order of 10¹⁰ Ω. The specific strength values were higher by 71% and 63% for the meta-aramid fabric and by 102% and 110% for the para-aramid fabric for the two-step and one-step method, respectively, compared to the unmodified fabrics after UV radiation.     

Products of Photo- and Thermochemical Rearrangement of 19-Membered di-tert-Butyl-Azoxybenzocrown

The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, tert-butyl substituents in benzene rings in the para positions to oligooxyethylene fragments (meta positions to azoxy group, i.e., t-Bu-19-Azo-O have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered o-hydroxy-m,m′-di-tert-butyl-azobenzocrown (t-Bu-19-o-OH) and 19-membered p-hydroxy-m,m′-di-tert-butyl-azobenzocrown (t-Bu-19-p-OH). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group (t-Bu-19-al) or intramolecular ester group (t-Bu-20-ester), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, t-Bu-17-p-OH. The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to t-Bu-20-ester as the main product. The structures of the four crystalline products of the rearrangement—t-Bu-19-o-OH, t-Bu-19-p-OH, t-Bu-20-ester and t-Bu-17-p-OH—were determined by the X-ray method. Structures in solution of atypical derivatives (t-Bu-19-al and t-Bu-20-ester) and t-Bu-19-p-OH were defined using NMR spectroscopy. For the newly obtained hydroxyazobenzocrowns, the azo–phenol⇄quinone–hydrazone tautomeric equilibrium was investigated using spectroscopic methods. Complexation studies of alkali and alkaline earth metal cations were studied using UV-Vis absorption spectroscopy. ¹H NMR spectroscopy was additionally used to study the cation recognition of metal cations. Cation binding studies in acetonitrile have shown high selectivity towards calcium over magnesium for t-Bu-19-o-OH.     

An In Vitro Anticancer,Antioxidant, and Phytochemical Study on Water Extract of Kalanchoe daigremontiana Raym.-Hamet and H. Perrier

Kalanchoe species are succulents with anti-inflammatory, antioxidant, and analgesic properties, as well as cytotoxic activity. One of the most popular species cultivated in Europe is Kalanchoe daigremontiana Raym.-Hamet and H. Perrier. In our study, we analyzed the phytochemical composition of K. daigremontiana water extract using UHPLC-QTOF-MS and estimated the cytotoxic activity of the extract on human ovarian cancer SKOV-3 cells by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay, flow cytometry, luminometric, and fluorescent microscopy techniques. The expression levels of 92 genes associated with cell death were estimated via real-time PCR. The antioxidant activity was assessed via flow cytometry on human keratinocyte HaCaT cell line. The DPPH (2,2-diphenyl-1-picrylhydrazyl) radical and FRAP (ferric-reducing antioxidant power) assays were also applied. We identified twenty bufadienolide compounds in the water extract and quantified eleven. Bersaldegenin-1,3,5-orthoacetate and bryophyllin A were present in the highest amounts (757.4 ± 18.7 and 573.5 ± 27.2 ng/mg dry weight, respectively). The extract showed significant antiproliferative and cytotoxic activity, induced depolarization of the mitochondrial membrane, and significantly arrested cell cycle in the S and G2/M phases of SKOV-3 cells. Caspases-3, 7, 8, and 9 were not activated during the treatment, which indicated non-apoptotic cell death triggered by the extract. Additionally, the extract increased the level of oxidative stress in the cancer cell line. In keratinocytes treated with menadione, the extract moderately reduced the level of oxidative stress. This antioxidant activity was confirmed by the DPPH and FRAP assays, where the obtained IC₅₀ values were 1750 ± 140 and 1271.82 ± 53.25 μg/mL, respectively. The real-time PCR analysis revealed that the extract may induce cell death via TNF receptor (tumor necrosis factor receptor) superfamily members 6 and 10.