Lipophilic Extracts Research Articles

The Combination Effects of Immersion and Moderate Electric Field (MEF) Treatments on Enhancement of Deliverable Iron From Kale Leaves (Brassica oleracea L. Var. Sabellica)

Abstract Objectives Due to anti-nutrients found in leafy greens and the physical-chemical properties of inorganic iron found in plant sources, iron bioavailability is lower relative to heme iron rich in red meat. We tested a series of novel food processing techniques (i.e., vacuum treatment, bath-immersion, and moderate electric field (MEF) to improve iron content and potential delivery, using kale (Brassica oleracea L. var. sabellica) as our model green leafy vegetable. Methods A ferrous sulfate (FeSO4) solution was prepared and fresh kale samples (n = 3 per treatment) were immersed in the solution alone (control), treated with vacuum alone, vacuum + water bath (30–50°C), or vacuum + water bath + MEF (15 V/cm at frequency of 60 Hz at 40–60°C) for up to 15 min. Effects of immersion (24 h at 4°C) after each treatment step were also tested. Treated samples were rinsed in deionized water before freezing and lyophilization prior to analysis. Concentrations of chlorophyll and iron chlorophyll derivatives were measured in both lipophilic and polar leaf extracts using ultra high liquid chromatography-diode array detection (UHPLC-DAD). Atomic absorption spectrometry was used to measure iron concentrations. Differences between treatment groups were analyzed with one-way ANOVA, followed by Tukey's posthoc testing for pairwise comparisons (P < 0.05 considered statistically significant). Results Vacuum followed by immersion produced kale with ∼1500x more iron than the kale control, while MEF-treated kale had the greatest increase in iron concentration without immersion (∼4000x than control). Two novel metabolites, tentatively iron chlorophyllin derivatives, were observed in the lipophilic extracts of the MEF and immersed kale samples, and identifies are being pursued via UHPLC-high resolution mass spectrometry metabolomics. Conclusions The novel food processing techniques employed here produced kale with iron concentrations significantly higher than the kale control, as well as other iron-rich plant foods (e.g., ∼40x times higher than black beans). Future testing will determine if this” iron-enhanced” kale has the potential to better deliver iron as compared to untreated kale, an FeSO4 supplement, or a heme-rich source. Funding Sources This research was supported by OARDC via a SEEDS grant and also via Hatch #W4122.

The Effects of Chemotherapy on Circulating Plasma Carotenoids and Fat-Soluble Vitamins in Breast Cancer Patients

Abstract Objectives Chemotherapy upregulates inflammatory processes as measured by circulating concentrations of pro-inflammatory cytokines and their signaling lipids. Our objective was to observe if breast cancer chemotherapy influenced the circulating concentrations of provitamin A and non-provitamin A carotenoids and fat-soluble vitamins (FSVs) in free-living patients. Methods Serum samples were collected from patients (n = 34) immediately prior to standard adjuvant and neo-adjuvant chemotherapy for breast cancer, and 4 months following chemotherapy commencement. Patient multivitamin and non-steroidal anti-inflammatory (NSAID) drug use was noted at both visits. Lipophilic extracts of serum were analyzed using ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) to quantify α- and β-carotene, lycopene, lutein, zeaxanthin, β-cryptoxanthin, retinol, α-tocopherol and phylloquinone. Linear mixed models were developed to assess the relationship between the main factors (i.e., chemotherapy, multivitamin, and NSAID use), and their interaction effects, on serum carotenoid and fat-soluble vitamin concentrations. Random effects included a fixed intercept for each subject. Results Chemotherapy was significantly associated with reduced serum concentrations of α-carotene (P = 0.053) and retinol (P = 0.042), with a trend observed for reduced β-carotene (P = 0.076) and phylloquinone (P = 0.082). There was no main effect of multivitamin or NSAID use on any analytes investigated. An interaction effect was observed for chemotherapy * multivitamin use, with increased concentrations of serum retinol (P = 0.004) and lycopene (P = 0.004), and a trend observed for zeaxanthin (P = 0.087) for those who took multivitamins. Chemotherapy * NSAID use was also significantly associated with a trend in increased serum lutein (P = 0.061) for those who consumed NSAIDS. Conclusions Our results suggest randomized, controlled trials of multivitamin use and/or provitamin A carotenoid-rich food consumption merit further investigation in patients undergoing chemotherapy treatment. Funding Sources This research was supported by The Ohio State University Stefanie Spielman Breast Cancer Center Kroger Fund, Pelotonia, NIH R01CA189947, NIH Award Number Grant P30 CA016058, OSU, and OSUCCC.

W/O/W double emulsion-loaded alginate capsules containing Lactobacillus plantarum and lipophilic sea buckthorn (Hippophae rhamnoides L.) pomace extract in different phases.

In this study, double emulsion containing L. plantarum F1 cells and prebiotic mannitol in the inner water phase, lipophilic sea buckthorn pomace extract as an antioxidant in the oil phase, and alginate in the outer water phase showed high encapsulation yield (82.19%), good cell survival rate (76.99%) and low chemical degradation of the oil (peroxide value - 3.8 meq O2/kg fat) after 42 days of storage. Gelation of the outer water phase enhanced the viability of L. plantarum F1 cells both during storage and under gastrointestinal conditions due to strong physical barrier formation. Encapsulated L. plantarum F1 viability throughout the 30-day storage period decreased to the value meeting the minimum required dose for probiotics. In vitro digestion of the loaded alginate capsules showed high survival rate of encapsulated cells under gastric conditions and significant reduction at the end of the duodenal phase of digestion.

Bioactive Sugarcane Lipids in a Circular Economy Context.

Most of the global sugar and ethanol supply trade comes from the harvesting of Saccharum officinarum (i.e., sugarcane). Its industrial processing results in numerous by-products and waste streams, such as tops, straw, filter cake, molasses and bagasse. The recovery of lipids (i.e., octacosanol, phytosterols, long-chain aldehydes and triterpenoids) from these residues is an excellent starting point for the development of new products for various application fields, such as health and well-being, representing an important feature of the circular economy. By selecting green scalable extraction procedures, industry can reduce its environmental impact. Refluxed ethanol extraction methods have been demonstrated to meet these characteristics. On the other hand, effective non-solvent methodologies such as molecular distillation and supercritical CO2 extraction can fractionate lipids based on high temperature and pressure application with similar yields. Sugarcane lipophilic extracts are usually analyzed through gas chromatography (GC) and liquid chromatography (LC) techniques. In many cases, the identification of such compounds involves the development of high-temperature GC–MS/FID techniques. On the other hand, for the identification and quantification of thermolabile lipids, LC–MS techniques are suitable for the separation and identification of major lipid classes. Generically, its composition includes terpenes, phytosterols, tocopherol, free fatty acids, fatty alcohols, wax esters, triglycerides, diglycerides and monoglycerides. These compounds are already known for their interesting application in various fields such as pharma and cosmetics due to their anti-hypercholesterolemic, anti-hyperglycemic, antioxidant and anti-inflammatory properties.

On the Issue of Creating a Cream of Reparative Action for the Treatment and Prevention of Cheilitis

BACKGROUND: Cheilitis is an inflammatory disease of the lips, its red border, mucous membranes, and skin. There are meteorological, actinic, hypo-, and avitaminosis cheilitis, according to medical indications. Classification of cheilitis includes many types of diseases and is somewhat conditional. For these types of cheilitis treatment are most appropriate to use biologically active substances, in particular lipophilic extract of bee pollen. Lipophilic extract of bee pollen is a complex, concentrated plant-bee product with unique consumer and medicinal qualities. It should be noted that experiments have shown that the bee pollen lipophilic extract has a reparative effect higher than the widespread sea buckthorn oil. AIM: The aim of the work is to create therapeutic and prophylactic cream with lipophilic extract of bee pollen for the cheilitis treatment and prevention. MATERIALS AND METHODS: Cream preparation was conducted by phase inversion. Thermal and colloidal stability, pH values, the quantitative content of carotenoids, viscosity, osmotic activity, and microbiological purity were determined by generally accepted methods. RESULTS: Samples of the cream containing lipophilic extract of bee pollen are a homogeneous mass of soft consistency with light yellow color and pleasant specific odor. In estimating, the thermal stability cream samples cheilitis curing were successfully tested and proved to be stable. When centrifuging, the absence of stratification of the cream into fatty and aqueous phases after the test has showed the stability of the cream. The pH of the cream samples corresponds to the pH of the skin. During a qualitative test green color indicates the presence of carotenoids. Quantitative determination of the carotenoids amount in the cream for treatment and prevention cheilitis (in recalculation to β-carotene) corresponds to the set content of carotenoids in the cream of 5.4 mg. The viscosity of the developed cream at 16.2 s−1 is 68.38 ± 0.21 Pa x s, that fully corresponds to the viscosity of creams. In the study of osmotic activity, it was found that the cream with a glycerol content of 7% provides moderate osmotic activity of the drug for 8 h, which may indicate the absence of overdrying and irritating effect. In terms of microbiological purity, the investigated cream with lipophilic extract of bee pollen meets the requirements of the State Pharmacopoeia for finished medicines for topical use (category 2). CONCLUSION: For the cheilitis treatment and prevention has suggested the composition of the cream which contains biologically active substance – lipophilic extract of bee pollen. The technology of the cream with lipophilic extract of bee pollen was developed. Thermal and colloidal stability, pH values were studied; the quantitative content of carotenoids, viscosity, osmotic activity, and microbiological purity was determined. The research carried out made it possible to make sure of the correctness and rationality of the developed technology of the cream for the treatment and prevention of cheilitis.

Cannabinoids from inflorescences fractions of Trema orientalis (L.) Blume (Cannabaceae) against human pathogenic bacteria.

BackgroundCannabinoids; tetrahydrocannabinol (THC), cannabidiol (CBD) and cannabinol (CBN), might show antibacterial activity. Trema orientalis is a species in the Cannabaceae that is closely related to Cannabis through plastome phylogenetic evidence. This species is widely distributed throughout tropical Asia and is used as traditional medicine, particularly for the treatment of infectious diseases. However, no studies on the antibacterial activity of cannabinoid-containing inflorescences extracts are available. Thus, the aim of this study was to determine cannabinoid content and antibacterial activity of inflorescences fractions from T. orientalis native to Thailand.MethodsWe hypothesized that inflorescences from T. orientalis might display cannabinoids similar to Cannabis because of their close taxonomic relationship. We extracted the mature inflorescences and infructescence of T. orientalis in three disparate populations from different Thailand floristic regions. Extractions were subsequently partitioned into hydrophilic and lipophilic fractions using distilled water and chloroform. The lipophilic extracts were further fractionated by the column chromatography with gradient elution and analyzed by gas chromatography-mass spectrometry (GC-MS). Characterized cannabinoids were used in bioassays with multidrug-resistance bacteria.ResultsLipophilic extracts and fractions of inflorescences from all Thailand floristic regions consistently displayed cannabinoids (THC, CBD and CBN) in various quantities. These extracts exhibited inhibitory activity for Staphylococcus aureus, Pseudomonas aeruginosa, and Acinetobacter baumannii strains with minimum inhibitory concentration values varying from 31.25 to 125 µg/mL.ConclusionOur study is the first to report cannabinoid detection in extracts from inflorescences of T. orientalis, a species in the Cannabaceae. These extracts and their fractions containing cannabinoids showed pronounced antibacterial activity. The use of analytic methods also demonstrated reproducible cannabinoid extraction.

Pharmacognostic analysis of Salvia hispanica L. seeds

The aim. The aim of this work was to conduct a microscopic and phytochemical study of the seeds of chia (Salvia hispanica L.).
 Materials and methods. Chia seeds were examined macroscopically and microscopically. To study the qualitative composition of the main groups of biologically active substances, histochemical, microchemical and chemical reactions were used. Hydroxycinnamic acids were identified by paper chromatography. To obtain a lipophilic extract, a Soxhlet apparatus and an exhaustive chloroform extraction method were used. The study of the quantitative content of fatty acids was carried out by gas chromatography. The content of polysaccharides in the raw material was determined by the gravimetric method. According to the SPhU method, the raw material swelling index was determined.
 Results. The main macro- and microscopic features of chia seeds have been established. Histochemical reactions, microchemical reactions made it possible to establish the presence of mucus and fatty oils in chia seeds. With the help of chemical reactions, the presence of flavonoids in the raw material was established. The quantitative content of fatty oils is 24.0±1.2 %. The content of water-soluble polysaccharides in the whole raw material was 4.01±0.07 %, in the crushed raw material - 5.04 ± 0.05 %. As a result of determining the swelling index, it was found that this indicator for the whole chia seeds was 20, and for the crushed ones – 17. The content of hydroxycinnamic acids in the chia seeds was 1.07±0.03 %. 9 fatty acids have been identified, among which linoleic acid predominates in terms of content.
 Conclusions. The presence and quantitative content of mucus, fatty oils, water-soluble polysaccharides, flavonoids, hydroxycinnamic acids, fatty acids was confirmed in the seeds of chia (Salvia hispanica L.). The obtained data can be used to develop regulatory documentation for chia seeds in order to use this raw material in pharmacy and medicine

Tree bark characterization envisioning an integrated use in a biorefinery

Tree barks are considerable waste streams in forest industries, and a potentially interesting resource for biorefineries. Barks of six relevant tree species, namely poplar (Populus × canadensis), black locust (Robinia pseudoacacia), red oak (Quercus rubra), willow (Salix sp.), Corsican pine (Pinus nigra subsp. laricio), and larch (Larix decidua), were anatomically and chemically characterized. Anatomical analysis illustrated the structural heterogeneity of the different barks with occurrence of various cell types and their arrangement in phloem, periderm, and rhytidome. Summative chemical analysis showed a high extractive content (14–30 wt%) for all barks. Black locust bark presented a substantial suberin content (10 wt%). The lignin content was similar for most barks (22–29 wt%), except for Corsican pine bark (45 wt%). Analytical pyrolysis demonstrated that softwood bark lignin was mostly G type with a small amount of H units, whereas for hardwood species S, G, and H units were present, with low S/G ratios (0.3–0.7). The cell wall structural polysaccharides were rather low. Total monosaccharides ranged from 35 to 44 wt%, with glucose being predominant for almost all barks, followed by xylose in hardwood and mannose in softwood barks. Identification of the lipophilic extractives highlighted the predominance of resin acids for softwood barks, and fatty acids and triterpenoids for all barks. Analysis of the polar bark extracts revealed large variations in the content of phenolics (265–579 mg gallic acid equivalent/g extract), flavonoids (177–391 mg catechin equivalent/g extract), and condensed tannins (88–670 mg catechin equivalent/g extract). Furthermore, the polar extracts presented a high antioxidant potential (500–1209 mg trolox equivalent/g extract), as determined by the FRAP assay. Additionally, a very strong antioxidant activity (AAI > 2), as evaluated by the DPPH assay, was observed for all barks. In summary, the results highlight the marked anatomical and chemical interspecies variability in barks, thus suggesting the need for tailored biorefining approaches.Graphical abstract

Antimicrobial activity of the volatile substances from essential oils

BackgroundEssential oils are volatile and lipophilic liquid extracts made from plants as secondary metabolites that can be obtained by distillation. To date, several studies have investigated the direct antimicrobial activity of liquid essential oils. However, this study investigated the antimicrobial properties of the volatile substances present in various essential oils.MethodsA modified zone of inhibition protocol was developed using agar petri dishes with a center glass vial to allow evaporation and aerosolization of the potential active constituents from essential oils. In total, nineteen essential oils were tested against five Gram positive bacterial species, five Gram negative bacterial species and one fungi.ResultsThis study found potent antimicrobial activity from the volatile constituents of several essential oils. Rosemary, tea tree, and cassia volatiles were found to be the best broad-spectrum antibacterial agents, whereas clove volatiles had almost no antimicrobial activity.ConclusionsThese results support the anecdotal historical evidence of the antimicrobial activity of the volatile constituents essential oils. Modern medical implications for this work may be related to the use of aromatic essential oils for respiratory or dermatological infections.

Proteomics study on the effect of combined treatment of electrical pulses and tomato lipophilic extract in the downregulation of proliferating cell nuclear antigen in triple-negative breast cancer cell

Objective: To analyze the effect of electrical pulses (EP) with tomato lipophilic extract (TLE) on human, triple negative breast cancer (TNBC) cell (MDA-MB-231) and human epithelial, non-cancerous breast cell (MCF-10A) and to gain insights into the mechanisms of action. Methods: We prepared TLE using the solvent extraction method. We identified the constituents of TLE using LC-MS analysis. TLE with the dose of 250 μg/ml was combined with 800 V/cm, 100 μs, eight electrical pulses to treat cancerous MDA-MB-231 and non-cancerous MCF-10A breast cells, and their survivability was studied. We studied the proteins responsible for TLE's anticancer activity in TNBC cells using label-free, quantitative proteomics study. To understand the relationship between changes protein and transcription level, we did a real-time quantitative PCR (RT-qPCR) study. We detected Hydrogen Peroxide (H2O2) levels of both untreated and TLE/EP treated cells to determine how oxidative stress regulates various intracellular pathways. Results: TLE comprises fatty acids that heighten MDA-MB-231 cell proliferation. However, electrical pulses application nullifies these cell proliferative effects of fatty acids, as evident by the significant MDA-MB-231 cell viability reduction for TLE+EP treatment. Tomato extract, electrical pulses, and combinational treatment did not affect normal breast MCF-10A cells. A total of 1877 proteins were identified from the proteomics study. Conclusion: Applying EP in combination with TLE suppresses and reverses back the proliferative effects caused by TLE. EP and TLE+EP treatments increase hydrogen peroxide reactive oxygen species production in TNBC to inflict cell death due to excessive oxidative stress. Proteins, such as PCNA, LDHB, and ENO1, were downregulated in EP treatment, and it was confirmed with the mRNA levels by qPCR results. Our findings render innovative perceptions into the mechanisms of electrical pulses with TLE. Significance: Our research serves as a technological platform capable of identifying the set of proteins responsible for minimizing TNBC cell proliferation when treated with TLE+EP.

How acidity rules synergism and antagonism in liquid–liquid extraction by lipophilic extractants—Part II: application of the ienaic modelling

ABSTRACT In this article Part II, we consider the application of ienaic modeling for solvent extraction of rare earths in the case of the mixed DMDOHEMA/HDEHP extractant system. The system exhibits a synergistic extraction effect depending on the acid concentration and the extractant mole fraction, as demonstrated in the experimental article Part I. In this work, we directly compare experimental findings with theoretical predictions of the droplet model. The model considers the effective free energy of transfer as a combination of competing molecular forces, but contrary to previous micelle models that focus only on the dominant stoichiometry, it allows calculations of free energies of every possible spherical aggregate. The resulting image of the extraction process is that different behaviors can be obtained depending on the acidity and mole fraction of extractants, which are associated with different aggregation regimes in a complex free energy landscape of the system. Nevertheless, self-assembly is tuned by the extraction of all solutes, and not only the target metal cations.

Green Extraction by Ultrasound, Microencapsulation by Spray Drying and Antioxidant Activity of the Tucuma Coproduct (Astrocaryum vulgare Mart.) Almonds.

The industrial processing amazon fruits, like tucuma, generates a large amount of coproducts with large nutritional potential. Thus, this work obtained the oily extract of the tucuma almonds coproducts by green extraction using palm oil by the ultrasound method and then microencapsulated by atomization and verification of its antioxidant activity. Thermogravimetric techniques, infrared spectroscopy, scanning electron microscopy, moisture content, water activity were applied to characterize the microparticles. Total carotenoids were determined by UV spectroscopy and antioxidant activity was measured by 2,2′-azino-di-(3-ethylbenzthiazoline sulfonic acid and co-oxidation in the system β-carotene/linoleic acid. The oily extract and microparticle had total carotenoid contents of 3.305 mg/100 g ± 0.01 and 2.559 mg/100 g ± 0.01, respectively. The antioxidant activity assessed through the 2,2′-azino-di-(3-ethylbenzthiazoline sulfonic acid value was 584.75 μM/trolox ± 0.01 (oily extract) and 537.12 μM/trolox ± 0.01 (microparticle) were determined. In the system β-carotene/linoleic acid showed oxidation of 49.9% ± 1.8 lipophilic extract and 43.3% ± 2.3 microparticle. The results showed that the oily extract of the tucuma almond coproduct can be used as a carotenoid-rich source and microencapsuled with possible application for functional foods production.

Phytochemical characterization of phloem in maritime pine and stone pine in three sites in Portugal

This study analyzes the content and chemical profile of extractives present in the young phloem of mature trees of maritime pine (Pinus pinaster) and stone pine (P. pinea) in three sites in Portugal located in different climatic environments.The cross-sites average of extractives was similar in both pines with 38.5% in P. pinea and 37.7% in P. pinaster phloem. The hydrophilic fraction represented 82% and 70% of P. pinea and P. pinaster total extractives respectively, with large contents of phenolic compounds, flavonoids and tannins, and showed very high oxygen scavenging and reducing ability. Lipophilic extractives were present in higher proportion in P. pinaster phloem than in P. pinea phloem, and showed a large content of resin acids, with the predominance of abietic acid in P. pinaster, and dehydroabietic acid in P. pinea phloems, and of alkanoic acids.P. pinaster and P. pinea have specific defences related to phloem production of resin and phenolic compounds with the ratio phenolic-to-oleoresin compounds higher for P. pinea (4.7 vs 2.3 for P. pinaster) and constant in the three sites. The phytochemical content and composition of the young phloem of P. pinaster and P. pinea showed site differences highlighting the relationship between environment and metabolic production.

Characteristics of Pleurotus sp. TD36 and its ability to reduce wood extractives in pretreatment for pulping

Lipophilic extractives of wood cause pitch deposition during pulp and paper production, leading to serious economic losses and environmental pollution. Natural seasoning of wood material before pulping can reduce wood extractives, but there is no control of the pulp yield and quality. Pretreatment of the wood chips with selected fungi is regarded as better controlled seasoning with effective removal of problematic extractives. Commercially available fungal preparations are effective mostly for softwood, but not quite suitable for Acacia mangium and hybrid hardwood—the main pulpwood of Vietnam. In this paper, a fungal isolate TD36 was identified as white-rot basidiomycete Pleurotus sp. TD36 based on the biological characteristics and phylogenetic analysis. Having high activity of ligninolytic enzymes, amylase and protease, Pleurotus sp. TD36 was able to degrade lignin-like compounds (guaiacol, Remazol Brilliant Blue), starch and casein. Degradation of wood extractives was evaluated by laccase and sterol esterase assays of the fungus in shake flask cultures and in pretreatment of Acacia wood chips. Favorable conditions for wood pretreatment were selected, including: inoculum size, 1% v/w; wood moisture, 60% v/w; temperature, 28–30 °C and 30 days. Under such conditions, Pleurotus sp. TD36 removed about 68 ± 2.75% of wood acetone extractives soluble in chloroform. Of that, about 73–89% of fatty acids and fatty alcohols, 76% of free sterols and 63% of sterol ester, were removed. Fungal pretreatment did not significantly affect the cellulose content of wood and Kraft pulp yield.

Fate of Lipophilic Wood Extractives in Oxygen-Based Cellulose Bleaching

The impact of totally chlorine-free (TCF) bleaching chemicals on the composition and behavior of detrimental lipophilic wood extractives in a mixed hardwood sulfite pulp was studied to determine their potential for pitch control without the need for additional reagents. Toward this end, the acetone extracts of pulp were analyzed with commonly used gas chromatography (GC) and more sophisticated ultraperformance convergence chromatography (UPC2). During EO(P)–Z–P bleaching, the highest decrease in the lipophilic extractive content was achieved after ozone bleaching (Z), with a 38% reduction of GC-FID/MS-detectable resins. Oxygen-reinforced alkaline extraction EO(P) and peroxide bleaching (P) were less effective in terms of resin quality and quantity (−30 and −27%, respectively). Analyzing the acetone extracts after alkaline hydrolysis revealed a different pattern: EO(P) with −44%, P with −20%, and Z with only −8% less lipophilic extractives. A series of oxidized compounds, such as acyl chain-oxidized sterol esters and acylglycerols, and acidic secosterol analogues, were detected for the first time with UPC2-ESI-QToF-MS after ozone bleaching. These compounds lead to an underestimation of the GC-detectable resin content and may be involved in the formation of deposits during lignocellulosic processing. Reaction pathways for lipophilic extractives during ozone bleaching were established.

How Acidity Rules Synergism and Antagonism in Liquid–Liquid Extraction by Lipophilic Extractants—Part I: Determination of Nanostructures and Free Energies of Transfer

ABSTRACT Efficient formulations used in hydrometallurgy are often based on synergistic action of two oil-soluble extractants at an optimized mole fraction. In this series of two papers, we describe the N,N’-dimethyl-N,N’-dioctylhexylethoxymalonamide (DMDOHEMA)/di(2-ethylexyl) phosphoric acid (HDEHP) system, and how expression of the synergistic effect varies with acidity, using the three common representations: distribution ratios, yields, and free energies of transfer. The experimental results are detailed in this first part (Part I) with the so-called supramolecular approach, which considers the reverse micelle-like aggregates formed by the lipophilic extractant molecules. It shows that no specific aggregation state is observed at the maximum of synergism and antagonism. Besides, the critical aggregation concentration that characterizes the micellization free energy appears to follow some synergistic trends but cannot explain how acid tunes synergism to antagonism of this mixed system. Based on these results, Part II proposes a theoretical model based on the ienaic approach to interpret acid effect on synergism and antagonism.

Increases of Lipophilic Antioxidants and Anticancer Activity of Coix Seed Fermented by Monascus purpureus.

Lipophilic tocols, γ-oryzanol, and coixenolide in coix seed before and after fermentation by Monascus purpureus were determined. Antioxidant and anticancer activities of raw and fermented coix seed were evaluated using free-radical-scavenging assays and polyunsaturated fatty acid oxidation model, and human laryngeal carcinoma cell HEp2, respectively. Compared to the raw seed, the tocols, γ-oryzanol, and coixenolide contents increased approximately 4, 25, and 2 times, respectively, in the fermented coix seed. Especially, γ-tocotrienol and γ-oryzanol reached 72.5 and 655.0 μg/g in the fermented coix seed. The lipophilic extract from fermented coix seed exhibited higher antioxidant activity in scavenging free radicals and inhibiting lipid oxidation. The inhibitory concentrations for 50% cell survival (IC50) of lipophilic extract from fermented coix seed in inhibiting HEp2 cells decreased by 42%. This study showed that coix seed fermented by M. purpureus increased free and readily bioavailable lipophilic antioxidants and anticancer activity. Therefore, fermentation could enhance the efficacy of the health promoting function of coix seeds.

Chemical Composition, Antioxidant and Cytoprotective Potentials of Carica papaya Leaf Extracts: A Comparison of Supercritical Fluid and Conventional Extraction Methods.

The leaves of Carica papaya (CP) are rich in natural antioxidants. Carica papaya has traditionally been used to treat various ailments, including skin diseases. This study aims to decipher the antioxidant effects and phytochemical content of different CP leaf extracts (CPEs) obtained using supercritical carbon dioxide (scCO2) and conventional extraction methods. The antioxidant activities of CPEs were evaluated by cell-free (1,1-diphenyl-2-picryl-hydrazyl (DPPH) and ferric-reduced antioxidative power (FRAP)) and cell-based (H2O2) assay. Both C. papaya leaf scCO2 extract with 5% ethanol (CPSCE) and C. papaya leaf scCO2 extract (CPSC) exhibited stronger DPPH radical scavenging activity than conventional extracts. In the FRAP assay, two hydrophilic extracts (C. papaya leaf ethanol extract (CPEE) and C. papaya freeze-dried leaf juice (CPFD)) showed relatively stronger reducing power compared to lipophilic extracts. Cell-based assays showed that CPFD significantly protected skin fibroblasts from H2O2-induced oxidative stress in both pre-and post-treatment. CPEE protected skin fibroblasts from oxidative stress in a dose-dependent manner while CPSCE significantly triggered the fibroblast recovery after treatment with H2O2. GC-MS analysis indicated that CPSCE had the highest α-tocopherol and squalene contents. By contrast, both CP hydrophilic extracts (CPEE and CPFD) had a higher total phenolic content (TPC) and rutin content than the lipophilic extracts. Overall, CPEs extracted using green and conventional extraction methods showed antioxidative potential in both cell-based and cell-free assays due to their lipophilic and hydrophilic antioxidants, respectively.

Theobromacacao Criollo var. Beans: Biological Properties and Chemical Profile.

Theobroma cacao provides precious products such as polyphenol-rich beans that are useful for nutraceutical purposes. The geographical area may influence the chemical composition of raw cocoa beans in terms of the polyphenols and biological qualities of the products. This work aimed to investigate the biological properties and the chemical composition of two different samples of Criollo var. cocoa raw beans coming from two areas (Indonesia; Peru). Beans underwent biphasic extraction obtaining lipophilic and hydroalcoholic extracts. The extracts were tested for antiradical, antimutagenic, and antigenotoxic effects. Cell viability inhibition toward breast, gastric/esophageal colorectal adenocarcinoma, and hepatoblastoma human cell lines was evaluated. Extracts were chemically investigated through UV-Vis spectroscopy and ultra-high-pressure liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry (UHPLC-ESI-QqTOF MS/MS). Results showed that the Indonesian bean hydroalcoholic extracts were able to scavenge 2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) cation radical better than the Peruvian hydroalcoholic extracts (ECs50: 72.63 vs. 322.20 μg/mL). Extracts showed antimutagenic and antigenotoxic activity. The viability inhibitory effect on breast and hepatic cancer cells was reached only for the Indonesian hydroalcoholic extracts at hundreds of μg/mL. Phenylpropenoyl-L-amino acids, hydroxycinnamoyl aminoacids conjugates, and procyanidin compounds were found mainly in the hydroalcoholic extracts, whereas fatty acids and lyso-phospholipids were found mainly in lipophilic fractions. Fatty acid and (epi)catechins appeared to be affected by different environmental conditions of the geographical areas.

Novel Insights into Mice Multi-Organ Metabolism upon Exposure to a Potential Anticancer Pd(II)-Agent

Pd(II)-compounds are presently regarded as promising anticancer drugs, as an alternative to Pt(II)-based drugs (e.g., cisplatin), which typically trigger severe side-effects and acquired resistance. Dinuclear Pd(II) complexes with biogenic polyamines such as spermine (Pd2Spm) have exhibited particularly beneficial cytotoxic properties, hence unveiling the importance of understanding their impact on organism metabolism. The present study reports the first nuclear magnetic resonance (NMR)-based metabolomics study to assess the in vivo impact of Pd2Spm on the metabolism of healthy mice, to identify metabolic markers with possible relation to biotoxicity/side-effects and their dynamics. The changes in the metabolic profiles of both aqueous and lipophilic extracts of mice kidney, liver, and breast tissues were evaluated, as a function of drug-exposure time, using cisplatin as a reference drug. A putative interpretation was advanced for the metabolic deviations specifically triggered by Pd2Spm, this compound generally inducing faster metabolic response and recovery to control levels for all organs tested, compared to cisplatin (except for kidney lipid metabolism). These results constitute encouraging preliminary metabolic data suggestive of potential lower negative effects of Pd2Spm administration.