The Phenolic Compounds Profile and Cosmeceutical Significance of Two Kazakh Species of Onions: Alliumgalanthum and A. turkestanicum.

Numerous species of Allium genus have been used in the traditional medicine based on their vast biological effects, e.g., antimicrobial, digestion stimulant, anti-sclerotic, soothing, antiradical or wound healing properties. In this work, unpolar and polar extracts from two lesser-investigated species of Allium growing in Kazakhstan, Alliumgalanthum Kar. & Kir. (AG) and A. turkestanicum Regel. (AT), were studied for their composition and biological effects. In the HPLC-ESI-QTOF-MS/MS analyses of water and alcoholic extracts simple organic acids, flavonoids and their glycosides were found to be the best represented group of secondary metabolites. On the other hand, in the GC-MS analysis diethyl ether, extracts were found to be rich sources of straight-chain hydrocarbons and their alcohols, fatty acids and sterols. The antimicrobial activity assessment showed a lower activity of polar extracts, however, the diethyl ether extract from AT bulbs and AG chives showed the strongest activity against Bacillus subtilis ATCC 6633, B. cereus ATCC 10876, some species of Staphylococcus (S. aureus ATCC 25923 and S. epidermidis ATCC 12228) and all tested Candida species (Candida albicans ATCC 2091, Candida albicans ATCC 10231, Candida glabrata ATCC 90030, Candida krusei ATCC 14243 and Candida parapsilosis ATCC 22019) with a minimum inhibitory concentration of 0.125-0.5 mg/mL. The highest antiradical capacity exhibited diethyl ether extracts from AG bulbs (IC50 = 19274.78 ± 92.11 mg Trolox eq/g of dried extract) in DPPH assay. In ABTS scavenging assay, the highest value of mg Trolox equivalents, 50.85 ± 2.90 was calculated for diethyl ether extract from AT bulbs. The same extract showed the highest inhibition of mushroom tyrosinase (82.65 ± 1.28% of enzyme activity), whereas AG bulb ether extract was the most efficient murine tyrosinase inhibitor (54% of the enzyme activity). The performed tests confirm possible cosmeceutical applications of these plants.

Orthogonality in the selection of biphasic solvent systems for off-line two-dimensional countercurrent chromatography from Polygonum cuspidatum Sieb. et Zucc.

Off-line two-dimensional countercurrent chromatography has been widely applied to the isolation of complex samples, but little research on the investigation of orthogonality in the selection of biphasic solvent systems is available. In the present work, the orthogonality in the selection of a biphasic solvent system for liquid-liquid chromatographic separation of aqueous extract and ether extract from the traditional Chinese medicinal plant Polygonum cuspidatum Sieb. et Zucc was evaluated by the correlation coefficient and space occupancy rate. In total, 25 different biphasic solvent systems were tested, and 313 system combinations were analysed. A convex hull methodology was used to determine the separation space and to optimize separation conditions. The correlation coefficient matrix was transformed into dendrograms and a colour map to visualize the dissimilarity between, and orthogonality for, all solvent systems. The aqueous extracts from Polygonum cuspidatum were separated using selected biphasic solvent systems with high orthogonality: ethyl acetate-ethanol-water (70:1:70, v/v) and petroleum ether-ethyl acetate-water (1:5:5, v/v). The ether extracts from Polygonum cuspidatum were also separated using selected biphasic solvent systems with high orthogonality: petroleum-ethyl acetate-methanol-aqueous 0.25 M NH3•H2O (5:5:5:5, v/v) and petroleum-ethyl acetate-methanol-water (5:5:5:5, v/v). Thirteen compounds were successfully obtained. The experimental results demonstrated that the evaluation of orthogonality provided an alternative strategy to select an applicable solvent system for the separation of complex samples using off-line two-dimensional countercurrent chromatography.

Homolytic and Heterolytic Cleavage of ß-Ether Linkages in Hardwood Lignin by Steam Explosion.

Steam-explosion lignin (SEL) was extracted with ethanol from steam-exploded hardwood (okoumé, Aucoumea klaineana Pierre) pretreated at various severities after neutral or acidic impregnation. The SELs were subjected to structural characterization by 2D HSQC NMR, 31P NMR, and SEC and compared with milled-wood lignin (MWL). A strong decrease in the ß- O-4 content is observed with increasing steam-explosion severity accompanied by a gradual increase in molecular mass. Cα-oxidized S units (S', Hibbert's ketones) were quantified by NMR and used as a marker of the hydrolytic mechanism; naphthol was used as a carbonium-ion scavenger. It has been observed that mixed reactions of hydrolysis and homolysis are involved, but the SEL is mainly cleaved homolytically, favoring recondensation through radical coupling even at low reaction severity. However, acidic preimpregnation of wood prior to steam explosion enhanced the carbonium-ion pathway.

Taraxastane-type triterpenoids from the medicinal and edible plant Cirsium setosum.

Guided by TNF-α secretion inhibitory activity assay, four taraxastane-type triterpenoids, including two new ones, 22-oxo-20-taraxasten-3ß, 30-diol (1) and 22α-hydroxy-20-taraxasten-30ß, 30-triol (2), have been obtained from an active fraction of the petroleum ether-soluble extract of the the medicinal and edible plant Cirsium setosum. Their structures were elucidated by spectroscopic data and CD data analysis. In the TNF-α secretion inhibitory activity assay, compounds 1 and 2 were active with the IC50 of 2.6 and 3.8 µmol·L-1, respectively. In addition, compounds 1 and 2 showed moderately selective cytotoxicity against the human ovarian cancer (A2780) and colon cancer (HCT-8) cell lines.

Effect of rice variety and modification on antioxidant and anti-inflammatory activities.

The effects of variety and modification of rice on its antioxidant and anti-inflammatory activities were investigated. White rice varieties; Jasmine (JM) and Saohai (SH), and pigmented rice varieties; Doisket (DS) and Homnil (HN) were used. The modified rice samples were obtained from chemical modification using etherification reaction. The activities of the modified rice samples were compared with the ethanol extracts of the raw rice at the same rice concentration. Antioxidant activity was measured by the free radical scavenging activity tests and ferric reducing power assay. Results indicated that the ethanol extracts of raw rice had higher antioxidant activity than the modified rice. Among the raw rice tested, the pigmented rice showed higher antioxidant activity than white rice. Trolox equivalent antioxidant capacity values from free radical scavenging activity test were revealed that 50% ethanol extracts of HN and DS possessed the highest antioxidant activity. Ferric reducing power assay showed that 50% ethanol extracts of DS had the highest antioxidant activity. The anti-inflammatory activity was evaluated in vitro using a lipopolysaccharide-stimulated RAW264.7 macrophage cell model with enzyme-linked immunosorbent assay. Absolute ethanol extracts of HN reduced interleukin-6 secretion whereas that of DS suppressed interleukin-6 and tumor necrosis factor -α secretion. These results indicate that variety of rice, chemical modification, and extracting solvent were the factors that play an important role on antioxidant and anti-inflammatory activity. This study supports the potential use of the pigmented rice, especially DS, as a promising choice of a natural source because of its antioxidant and anti-inflammatory activities.

Characterization of complex polyether polyols using comprehensive two-dimensional liquid chromatography hyphenated to high-resolution mass spectrometry.

Polyether polyols are often used in formulated systems, but their complete characterization is challenging, because of simultaneous heterogeneities in chemical composition, molecular weight and functionality. One-dimensional liquid chromatography-mass spectrometry is commonly used to characterize polyether polyols. However, the separation power of this technique is not sufficient to resolve the complexity of such samples entirely. In this study, comprehensive two-dimensional liquid chromatography hyphenated with high-resolution mass spectrometry (LC × LC-HRMS) was used for the characterization of (i) castor oil ethoxylates (COEs) reacted with different mole equivalents of ethylene oxide and (ii) a blended formulation consisting of glycerol ethoxylate, glycerol propoxylate and glycerol ethoxylate-random-propoxylate copolymers. Retention in the first (hydrophilic-interaction-chromatography) dimension was mainly governed by degree of ethoxylation, while the second reversed-phase dimension resolved the samples based on degree of propoxylation (blended formulation) or alkyl chain length (COEs). For different COE samples, we observed the separation of isomer distributions of various di-, tri- and tetra-esters, and such positional isomers were studied by tandem mass spectrometry (LC-MS/MS). This revealed characteristic fragmentation patterns, which allowed discrimination of the isomers based on terminal or internal positioning of the fatty-acid moieties and provided insight in the LC × LC retention behavior of such species.

Raman Spectroscopy of Fish Oil Capsules: Polyunsaturated Fatty Acid Quantitation Plus Detection of Ethyl Esters and Oxidation.

Fish oils are the primary dietary source of ω-3 polyunsaturated fatty acids (PUFA), but these compounds are prone to oxidation, and commercial fish oil supplements sometimes contain less PUFA than claimed. These supplements are predominantly sold in softgel capsules. In this work, we show that Fourier transform (FT)-Raman spectra of fish oils (n = 5) and ω-3 PUFA concentrates (n = 6) can be acquired directly through intact softgel (gelatin) capsules. These spectra could be used to rapidly distinguish supplements containing ethyl esters from those containing triacylglyceride oils. Raman spectroscopy calibrated with partial least-squares regression against traditional fatty acid methyl ester analyses by gas chromatography-mass spectrometry could be used to rapidly and nondestructively quantitate PUFA and other fatty acid classes directly though capsules. We also show that FT-Raman spectroscopy can noninvasively detect oxidation with high sensitivity. Oils with peroxide values of as low as 10 mequiv kg-1, which are on the cusp of falling outside of specification, could be readily distinguished from oils that were within specification (7 mequiv kg-1).

Targeted Metabolomic Analysis of Polyphenols with Antioxidant Activity in Sour Guava (Psidium friedrichsthalianum Nied.) Fruit.

Psidium is a genus of tropical bushes belonging to the Myrtaceae family distributed in Central and South America. The polar extract of Psidium friedrichsthalianum Nied. was partitioned with ethyl ether, ethyl acetate, and n-butanol, and the total phenolic content and antioxidant activity were measured by Folin-Ciocalteu and ABTS assays, respectively. The ethyl acetate fraction exhibited both the highest phenolic content and antioxidant activity. Due to the complexity of this fraction, an analytical method for the comprehensive profiling of phenolic compounds was done by UPLC-ESI/QqQ in MRM (multiple reaction monitoring) mode. In this targeted analysis, 22 phenolic compounds were identified, among which several hydroxybenzoic, phenylacetic, and hydroxycinnamic acid derivatives were found. This is the first time that (+)-catechin, procyanidin B1, procyanidin B2, and (-)-epicatechin have been reported as constituents of sour guava. A fractionation by exclusion size, C18-column chromatography, and preparative RRLC (rapid resolution liquid chromatography) allowed us to confirm the presence of ellagic acid and isomeric procyanidins B, well-known bioactive compounds. The content of phenolic compounds in this fruit shows its potential for the development of functional foods.

Selection of Lipases for the Synthesis of Biodiesel from Jatropha Oil and the Potential of Microwave Irradiation to Enhance the Reaction Rate.

The present study deals with the enzymatic synthesis of biodiesel by transesterification of Jatropha oil (Jatropha curcas L.) with ethanol in a solvent-free system. Seven commercial lipase preparations immobilized by covalent attachment on epoxy-polysiloxane-polyvinyl alcohol composite (epoxy-SiO2-PVA) were tested as biocatalysts. Among them, immobilized lipases from Pseudomonas fluorescens (lipase AK) and Burkholderia cepacia (lipase PS) were the most active biocatalysts in biodiesel synthesis, reaching ethyl ester yields (FAEE) of 91.1 and 98.3% at 72 h of reaction, respectively. The latter biocatalyst exhibited similar performance compared to Novozym® 435. Purified biodiesel was characterized by different techniques. Transesterification reaction carried out under microwave irradiation exhibited higher yield and productivity than conventional heating. The operational stability of immobilized lipase PS was determined in repeated batch runs under conventional and microwave heating systems, revealing half-life times of 430.4 h and 23.5 h, respectively.

Synthesis and Antiviral Bioassay of New Diphenyl Ether-based Compounds.

A set of diphenyl ether derivatives bearing different heterocycles were synthesized from 4-phenoxybenzohydrazide 1 in good yield. Synthesized compounds were screened against a broad panel of viruses in different cell cultures and some of the synthesized compounds showed promising antiviral properties.

Chemical Composition of the Essential Oil and Diethyl Ether Extract of Trinia glauca (L.) Dumort. (Apiaceae) and the Chemotaxonomic Significance of 5-O-Methylvisamminol.

Analyses by GC, GC/MS, and NMR spectroscopy (1D- and 2D-experiments) of the essential oil and Et2O extract of Trinia glauca (L.) Dumort. (Apiaceae) aerial parts allowed a successful identification of 220 constituents, in total. The major identified compounds of the essential oil were (Z)-falcarinol (10.6%), bicyclogermacrene (8.0%), germacrene D (7.4%), δ-cadinene (4.3%), and ß-caryophyllene (3.2%), whereas (Z)-falcarinol (47.2%), nonacosane (7.4%), and 5-O-methylvisamminol (4.0%) were the dominant constituents of the extract of T. glauca. One significant difference between the compositions of the herein and the previously analyzed T. glauca essential oils (only two reports) was noted. (Z)-Falcarinol was the major constituent in our case, whereas germacrene D (14.4 and 19.6%) was the major component of the previously studied oils. Possible explanations for this discrepancy were discussed. 5-O-Methylvisamminol, a (furo)chromone identified in the extract of T. glauca, has a limited occurrence in the plant kingdom and is a possible excellent chemotaxonomic marker (family and/or subfamily level) for Apiaceae.

Effects of heat treatment on oil-binding ability of rice flour.

Heat-treated (120 °C for 120 min) rice flour showed high affinity to oil (oil-binding ability). This oil-binding ability could be observed by shaking the heat-treated rice flour (2.0 g), oil (4.0 mL), and water (20 mL) vigorously in a test tube, and the oil bound to the rice flour sank into the water. To examine the time-dependent levels of the oil-binding ability, rice flour was heat-treated at 120 °C for 10, 20, 40, 60, and 120 min, and the precipitated volume of oil/rice flour complex increased with an increase of the heating time. The oil-binding ability of the rice flour was not affected by the treatments with diethyl ether or boiled chloroform/methanol (2:1) solutions, which suggested no relationship to the oil in the rice flour, but was lost upon alkali (0.2% NaOH solution) or pepsin treatment, which suggested its relationship to the rice proteins.

Facile synthesis of pyrazole- and benzotriazole-containing selenoethers.

Azole-containing selenoethers, 1,5-bis(3,5-dimethylpyrazol-1-yl)-3-selena pentane and 1,3-bis(1,2,3-benzotriazol-1-yl)-2-selena propane were prepared by the reaction of corresponding tosylate or chloride with sodium selenide generated in situ from elemental selenium and sodium formaldehydesulfoxylate (rongalite).

Antinociceptive effect of some extracts from Ajuga chamaecistus Ging. ssp. tomentella (Boiss.) Rech. f. aerial parts.

BACKGROUND: The genus Ajuga is used for the treatment of joint pain, gout, and jaundice in traditional Iranian medicine (TIM). Ajuga chamaecistus ssp. tomentella is an exclusive subspecies of Ajuga chamaecistus in the flora of Iran. The aim of this study was to evaluate antinociceptive properties of some extracts from aerial parts of A. chamaecistus ssp. tomentella. METHODS: Antinociceptive activities of total water and 80% methanol extracts, hexane, diethyl ether and n-butanolic partition fractions of the methanolic extract were analyzed using the formalin test in mice. Indomethacin (10 mg/kg) and normal saline were employed as positive and negative controls, respectively. RESULTS: Oral administration of all extracts (200, 400 and 600 mg/kg) 30 min before formalin injection had no effect against the acute phase (0-5 min after formalin injection) of the formalin-induced licking time, but hexane fraction (200 mg/kg) caused a significant effect (p < 0.001) on the chronic phase (15-60 min after formalin injection). Total water and diethyl ether extracts at a dose of 400 mg/kg showed a very significant analgesic activity on the chronic phase (p < 0.001 and p < 0.01, respectively). CONCLUSIONS: The results of this study suggest that the extracts of A. chamaecistus ssp. tomentella have an analgesic property that supports traditional use of Ajuga genus for joint pain and other inflammatory diseases.

Uptake and efflux of rhenium in cells exposed to rhenium diseleno-ether and tissue distribution of rhenium and selenium after rhenium diseleno-ether treatment in mice.

UNLABELLED: We proposed a new water-soluble rhenium diseleno-ether compound (with one atom of Re and two atoms of Se) and investigated the uptake of Re into the nucleus of malignant cells in culture exposed to the compound for 48 h and its efflux from the nucleus after a post-exposure period of 48 h, as DNA is the main target of Re. We also studied the distribution of both Re and Se in the main organs after an oral administration of 10 or 40 mg/kg Re diseleno-ether to mice for four weeks, five days-a-week. MATERIALS AND METHODS: Re and Se concentrations were assayed by inductively coupled plasma mass spectrometry (ICP-MS). Statistical analysis was performed using the Wilcoxon signed-rank test, comparing two related groups. RESULTS: We observed that Re was well incorporated into the nucleus of malignant cells in the most sensitive cells MCF-7, derived from human breast cancer, and that there was no efflux of Re. In contrast, in MCF-7 resistant cells (MCF-7 Mdr and MCF-7 R), A549 and HeLa cells, there was significant efflux of Re from the nucleus after the wash-out period. In mice, an important and dose-dependent uptake of both Re and Se was observed in the liver, with lower concentrations in kidneys. The lowest concentrations were observed in blood, lung, spleen and bones. There was a significant increase of Re concentrations in the blood, liver and kidney in mice treated with Re diseleno-ether at the dose of 40 mg/kg/24 h versus those treated at the dose of 10 mg/kg/24 h. There was a significant increase of Se concentrations in all tissues with the dose of Re diseleno-ether of 10 mg/kg/24 h versus controls, and a significant increase in the liver in mice treated with dose of Re diseleno-ether of 40 mg/kg/24h versus those treated with 10 mg/kg/24 h. CONCLUSION: We are the first to demonstrate that a compound combining Re and Se in a single molecule, is able to deliver Re and Se to the organism via an oral route, for cancer treatment.

Isolation and identification of acaricidal compounds in Eupatorium adenophorum petroleum ether extract and determination of their acaricidal activity against Psoroptes cuniculi.

We used multiple silica gel column chromatography and thin-layer chromatography coupled with (1)H nuclear magnetic resonance (NMR) and (13)C NMR to separate and identify the active acaricidal ingredients in Eupatorium adenophorum petroleum ether extract. The acaricidal activity of each compound was tested against Psoroptes cuniculi in vitro. Three compounds had strong acaricidal activity against P. cuniculi in vitro. The insecticidal effect of 0.5% compound 9ß-hydroxy-ageraphorone was better than the insecticidal effect of fenvalerate, and compounds 9-oxo-ageraphorone and 9-oxo-10,11-dehydro-ageraphorone exhibited higher insecticidal effects than 9ß-hydroxy-ageraphorone. Thus, the E. adenophorum petroleum ether extract contains an effective composition of acaricides that could potentially be developed as a promising plant-origin acaricide.

Cytotoxic and potential anticancer constituents from the stems of Schisandra pubescens.

CONTEXT: The diethyl ether extract of the stems of Schisandra pubescens Hemsl. et Wils. (Schisandraceae) was found to exhibit cytotoxic activity in vitro. However, investigations of the bioactive constituents of this plant have been very limited. OBJECTIVE: Elucidation of the cytotoxic constituents of S. pubescens was performed. METHODS: Repeated silica gel column chromatography and preparative TLC were used for the chemical investigation of the diethyl ether extract of S. pubescens stems. All isolates were evaluated for their in vitro cytotoxicity against A549, PC-3, KB and KBvin human cancer cell lines. RESULTS: Nine known compounds were obtained, including four lignans, epischisandrone (1), tigloylgomisin P (2), cagayanone (3) and (-)-gomisin L2 (4), together with five triterpenoids, micranoic acid B (5), lancifodilactone H (6), coccinic acid (7), schisanlactone B (8) and anwuweizonic acid (9). Compounds 2-6 and 8 showed moderate to marginal cytotoxicity, with GI50 values of 11.83-35.65 µM. CONCLUSION: The isolation of 1-9 from S. pubescens and the cytotoxicities of 3-6 are first reported. Compounds 2-6 and 8 could be the active principles responsible for the anticancer effects of S. pubescens.

Synthesis of alkylated potato starch derivatives and their potential in the aqueous solubilization of benzo[a]pyrene.

For the development of renewable bioproducts able to solubilize organic persistent pollutant such as benzo[a]pyrene (BaP), modified potato starch was synthesized by alkylation. The addition of alkyl chains was performed with three different alkylation agents: epoxyalkane, alkenyl succinic anhydride and 1,4-butane sultone. Twelve alkylated starches were obtained with different molar substitutions (MS) and various alkyl chain lengths (to three carbons up to sixteen). The chemical structural characteristics were investigated by methods of (1)H NMR and FTIR. In comparison with the native starch, the ether modified starches showed in general an enhancement of their aqueous solubility whereas the ester modified starches stimulated the BaP aqueous solubilization. Indeed, the compounds P6 and P12, which increased 40-fold the BaP aqueous concentration, present high surfactant properties.

Profiling of phenolic compounds and antioxidant activity of dry extracts from the selected Sorbus species.

The antioxidant efficiency of dry extracts from inflorescences and/or leaves of seven Sorbus species was studied using four in vitro tests of SET (single electron transfer) and HAT-type (hydrogen atom transfer) mechanisms. The 70% methanol extracts and its diethyl ether, ethyl acetate, n-butanol and water fractions were tested in parallel with the phenolic standards, e.g., caffeic acid, quercetin, BHA, BHT, and Trolox. The SET-type activity of the extracts depended primarily on the extraction solvent. The most valuable extracts were n-butanol and ethyl acetate ones, which activity was high in the DPPH (EC(50) = 3.2-5.2 µg/mL), TEAC (2.8-4.0 mmol Trolox/g), and FRAP (9.8-13.7 mmol Fe2+/g) tests, and strongly correlated with the total phenolic levels (39.6-58.2% of gallic acid equivalents). The HPLC-PDA analysis of the extracts led to the identification of chlorogenic acid, isoquercitrin, hyperoside, rutin, quercetin 3-O-sophoroside, and sexangularetin 3-O-ß-D-glucopyranoside as the main components. Apart from flavonoids and hydroxycinnamic acids, proanthocyanidins have also a significant impact on the SET-type activity. The HAT-reactivity of the extracts in the linoleic acid peroxidation test (IC(50) = 36.9-228.3 µg/mL) depended more strongly on the plant tissue than on the extraction solvent, and its correlation with the phenolic content was weak. Both SET and HAT-type activity of the most potent Sorbus extracts was comparable with the activity of the standards, indicating their great potential as effective sources for health products.

The most frequently encountered volatile contaminants of essential oils and plant extracts introduced during the isolation procedure: fast and easy profiling.

INTRODUCTION: Unfortunately, contaminants of synthetic/artificial origin are sometimes identified as major constituents of essential oils or plant extracts and considered to be biologically active native plant metabolites. OBJECTIVE: To explore the possibility of early recognition and to create a list of some of the most common semi-volatile contaminants of essential oils and plant extracts. METHODOLOGY: Detailed GC and GC-MS analyses of the evaporation residues of six commercially available diethyl ethers and of a plastic bag hydrodistillate were performed. Average mass scans of the total ion chromatogram profiles of the analysed samples were performed. RESULTS: Almost 200 different compounds, subdivided into two groups, were identified in the analysed samples: (i) compounds that could be only of a synthetic/artificial origin, such as butylated hydroxytoluene and o-phthalic acid esters, i.e. requiring exclusion from the list of identified plant constituents; (ii) compounds possibly of synthetic and/or natural plant origin, i.e. compounds derived from the fatty acid metabolism or products of anaerobic intracellular/microbial fermentation. Average mass scans of the total ion chromatogram profiles provide meaningful and convenient information on uncovering important solvent-derived contamination. CONCLUSION: A database of the most common semi-volatile contaminants of essential oils and plant extracts has been generated that provides information on the likelihood of rejection or acceptance of contaminants as possible plant constituents. The suggested average mass scan approach enables fast and easy profiling of solvents, allowing even inexperienced researchers to pinpoint contaminants.