Green Extraction Techniques for Obtaining Bioactive Compounds from Mandarin Peel (Citrus unshiu var. Kuno): Phytochemical Analysis and Process Optimization.

In this study, an efficient utilization and valorization of mandarin peel (Citrus unshiu Marc. var. Kuno) was investigated using innovative and green extraction techniques. The first step of this study included the extraction and analysis of the volatile compounds by performing a supercritical CO2 (SC-CO2) extraction under different operating pressure conditions (100 and 300 bar). The analysis of volatile compounds of the obtained extracts was conducted by gas chromatography-mass spectrometry (GC-MS), and limonene was found to be the dominant volatile component (13.16% at 100 bar; 30.65% at 300 bar). After SC-CO2 treatment, the exhausted citrus peel waste enriched with bioactive compounds was subjected to subcritical water extraction (SWE) in a wide temperature range (130-220 °C) using different solvent-solid ratio (10-30 mL/g) in time periods from 5 to 15 min, in order to obtain bioflavonoids. Identification and quantification of present bioflavonoids was conducted by high-performance liquid chromatography with a with a diode array detector (HPLC), and hesperidin (0.16-15.07 mg/g) was determined as the most abundant flavanon in mandarin peel with other polyphenolic compounds that were possible by-products of thermal degradation. At higher temperatures, the presence of 5-hydroxymethylfurfural (5-HMF) and chlorogenic acid were detected. Antiradical activity and total phenolic content in the extracts were determined using spectrophotometric methods, while the process optimization was performed by response surface methodology (RSM).

Application of Deep Eutectic Solvents for the Extraction of Carnosic Acid and Carnosol from Sage (Salvia officinalis L.) with Response Surface Methodology Optimization.

Salvia officinalis L. is a good source of antioxidant compounds such as phenolic diterpenes carnosic acid and carnosol. From 17 deep eutectic solvents (DESs) used, choline chloride: lactic acid (1:2 molar ratio) was found to be the most suitable for the extraction of targeted compounds. The influence of H2O content, extraction time, and temperature (for stirring and heating and for ultrasound-assisted extraction (UAE)), H2O content, extraction time, and vibration speed for mechanochemical extraction on the content of targeted compounds were investigated. Carnosic acid content obtained by the extraction assisted by stirring and heating was from 2.55 ± 0.04 to 14.43 ± 0.28 µg mg-1, for UAE it was from 1.62 ± 0.29 to 14.00 ± 0.02 µg mg-1, and for mechanochemical extraction the yield was from 1.80 ± 0.02 to 8.26 ± 0.45 µg mg-1. Determined carnosol content was in the range 0.81 ± 0.01 to 4.83 ± 0.09 µg mg-1 for the extraction with stirring and for UAE it was from 0.56 ± 0.02 to 4.18 ± 0.05 µg mg-1, and for mechanochemical extraction the yield was from 0.57 ± 0.11 to 2.01 ± 0.16 µg mg-1. Optimal extraction conditions determined by response surface methodology (RSM) were in accordance with experimentally demonstrated values. In comparison with previously published or own results using conventional solvents or supercritical CO2, used DES provided more efficient extraction of both targeted compounds.

Coumarins in Food and Methods of Their Determination.

Coumarin is a natural product with aromatic and fragrant characteristics, widespread in the entire plant kingdom. It is found in different plant sources such as vegetables, spices, fruits, and medicinal plants including all parts of the plants-fruits, roots, stems and leaves. Coumarin is found in high concentrations in certain types of cinnamon, which is one of the most frequent sources for human exposure to this substance. However, human exposure to coumarin has not been strictly determined, since there are no systematic measurements of consumption of cinnamon-containing foods. The addition of pure coumarin to foods is not allowed, since large amounts of coumarin can be hepatotoxic. However, according to the new European aroma law, coumarin may be present in foods only naturally or as a flavoring obtained from natural raw materials (as is the case with cinnamon). In this paper, the overview of the current European regulations on coumarin levels in food is presented, along with the most common coumarin food sources, with a special emphasis on cinnamon-containing food. Human exposure to coumarins in food is also reviewed, as well as the methods for determination and separation of coumarin and its derivatives in food.

Valorization of Yarrow (Achillea millefolium L.) By-Product through Application of Subcritical Water Extraction.

In the present study, valorization of yarrow (Achillea millefolium) by-product from the filter tea industry was investigated through the application of subcritical water for the extraction of bioactive compounds. The influence of different process parameters (temperature 120-200 °C, extraction time 10-30 min, and HCl concentration in extraction solvent 0-1.5%) on extract quality in terms of content of bioactive compounds and antioxidant activity was investigated. Optimal conditions of the extraction process (temperature 198 °C, extraction time 16.5 min, and without acidifer) were determined and, when applied, the most efficient exploitation of by-products is achieved, that is, attainment of extracts rich in total phenols and flavonoids and high antioxidant activity. In addition, by applying the high performance liquid chromatographic analysis, the content of chlorogenic acid was determined as well as the hydroxymethylfurfural content in obtained extracts. The results demonstrated that subcritical water can be successfully used for utilization of yarrow by-products for obtaining extracts rich in antioxidants.

Green Extraction Methods for Active Compounds from Food Waste-Cocoa Bean Shell.

This is the first report on the extraction of cocoa bean shell (CBS) using deep eutectic solvents (DESs). Screening results with 16 different choline chloride-based DESs showed how choline chloride:oxalic acid DES was the most suitable solvent for the extraction of the bioactive compounds from CBS and that concentrations varied greatly depending on the used solvent. The DES extraction was compared to the DESs coupled with microwave extraction (MAE), and the yields of the extracted compounds were higher for DES/MAE. For theobromine, the obtained yields for DES extraction were 2.145-4.682 mg/g, and for caffeine, were 0.681-1.524 mg/g, whereas for DES/MAE, the same compounds were obtained in 2.502-5.004 mg/g and 0.778-1.599 mg/g. Antioxidant activity was also determined, using DPPH method, obtaining 24.027-74.805% activity for DES extraction and 11.751-55.444% for DES/MAE. Water content significantly influenced the extraction of targeted active compounds from CBS, whereas extraction time and temperature did not show statistically significant influence. The extraction temperature only influenced antioxidant activity. The study demonstrated how extraction using DES and microwaves could be of a great importance in the future trends of green chemistry for the production of CBS extracts rich in bioactive compounds.

Application of Deep Eutectic Solvents for the Extraction of Rutin and Rosmarinic Acid from Satureja montana L. and Evaluation of the Extracts Antiradical Activity.

Satureja montana L. was used in the current research as the plant exhibits numerous health-promoting benefits due to its specific chemical composition. The extraction method based on deep eutectic solvents (DESs) was used for the extraction of rutin and rosmarinic acid from this plant. Five different choline chloride-based DESs with different volumes of water (10%, 30%, and 50% (v/v)) were used for the extraction at different temperatures (30, 50, and 70 °C) to investigate the influence on rosmarinic acid and rutin content obtained by high-performance liquid chromatography with diode-array detector (HPLC-DAD) in the obtained extracts. A principal component analysis was employed to explore and visualize the influence of applied parameters on the efficiency of the extraction procedure of rutin and rosmarinic acid. Among the tested DESs, choline chloride:lactic acid (mole ratio 1:2) and choline chloride:levulinic acid (mole ratio 1:2) were the most suitable for the extraction of rutin, while for rosmarinic acid choline chloride:urea (mole ratio 1:2) was the most effective solvent. The extract showing the best antiradical activity was obtained with choline chloride:urea (mole ratio 1:1) at 30 °C and 50% H2O (v/v).

Optimization of Ultrasound-Assisted Extraction of Some Bioactive Compounds from Tobacco Waste.

This is the first study on ultrasound-assisted extraction (UAE) of bioactive compounds from different types of tobacco industry wastes (scrap, dust, and midrib). The obtained results were compared with starting raw material (tobacco leaves) to see the changes in bioactive compounds during tobacco processing. Results suggested that tobacco waste extracts possess antioxidant activity and considerable amounts of targeted bioactive compounds (phenolics and solanesol). The content of chlorogenic acid varied between 3.64 and 804.2 µg/mL, caffeic acid between 2.34 and 10.8 µg/mL, rutin between 11.56 and 93.7 µg/mL, and solanesol between 294.9 and 598.9 µg/mL for waste and leaf extracts, respectively. There were noticeable differences between bioactive compounds content and antioxidant activity in extracts related to applied UAE conditions and the used type of tobacco waste. Results show that optimal UAE parameters obtained by response surface methodology (RSM) were different for each type of material, so process optimization proved to be necessary. Considering that tobacco waste is mostly discarded or not effectively utilized, the results clearly show that tobacco waste could be used as a potential source of some bioactive compounds.

Bioactive Profile of Various Salvia officinalis L. Preparations.

Salvia officinalis L., also known as the "Salvation Plant", has been long used and well-documented in traditional medicine around the globe. Its bioactive compounds, and especially its polyphenol profile, have been extensively researched and reviewed. However, sage's beneficial effects reach much further, and nowadays, with a range of new extraction techniques, we are discovering new components with new therapeutic effects, especially in the context of neurodegenerative diseases and various carcinomas. This review describes the bioactive profile of various sage preparations depending on the extraction techniques and extraction parameters, and this review lists the newest research findings on its health effects.

Assessment of Total Phenolic Content, In Vitro Antioxidant and Antibacterial Activity of Ruta graveolens L. Extracts Obtained by Choline Chloride Based Natural Deep Eutectic Solvents.

Rue (R. graveolens) has been an extensively studied medicinal plant due to its rich phytochemicals content, such as furanocoumarins and flavonoids. The aim of this study was to determine the effects of varying extraction conditions on the total phenolic content, the antioxidant and antibacterial property of rue leaves crude extracts using deep eutectic solvents with different water content. These extraction conditions include the temperature and the extraction time. The extract obtained at 30 °C, with 20% water and at 90 min, with 13.3 µg mL-1 concentration, was found to possess the highest total phenolic content (38.24 ± 0.11 mg of GAE g-1 of DM) and the highest antioxidant activity (72.53 ± 0.31%). In this study, the same extract showed the best antibacterial efficiency against all the tested strains, especially gram-negative P. aeruginosa.

Extraction of Carnosic Acid and Carnosol from Sage (Salvia officinalis L.) Leaves by Supercritical Fluid Extraction and Their Antioxidant and Antibacterial Activity.

Sage (Salvia officinalis L.) is a good source of antioxidant compounds, carnosic acid and carnosol being the prominent ones. Both are soluble in CO2, and our goal was to investigate the application of supercritical CO2 extraction to obtain sage extracts rich in these compounds. The effect of pressure, temperature, and CO2 flow rate on the carnosic acid and carnosol yield was studied. These variables were optimized by response surface methodology (RSM). The pressure significantly affected carnosol extraction, while the extraction of carnosic acid was affected by the pressure, temperature, and CO2 flow rate. Carnosic acid content varied from 0.29⁻120.0 µg mg-1, and carnosol content from 0.46⁻65.5 µg mg-1. The optimal conditions according to RSM were a pressure of 29.5 MPa, a temperature of 49.1°C, and a CO2 flow rate of 3 kg h-1, and the sage extract yield was calculated to be 6.54%, carnosic acid content 105 µg mg-1, and carnosol content 56.3 µg mg-1. The antioxidant activities of the sage extracts were evaluated by the scavenging activities of 2,2-diphenyl-1-picrylhydrazyl (DPPH). Sage extract obtained at 30 MPa and 40°C with 2 kg h-1 CO2 flow rate with a carnosic acid content of 72 µg mg-1 and carnosol content of 55 µg mg-1 exhibited the highest antioxidant activity (80.0 ± 0.68%) amongst the investigated supercritical fluid extracts at 25 µg mL-1 concentration. The antimicrobial properties of extracts were tested on four bacterial strains: Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, and Staphylococcus aureus. The extract with a carnosic acid content of 116 µg mg-1 and a carnosol content of 60.6 µg mg-1 was found to be the most potent agent against B. subtilis.

Development of supercritical CO2 extraction of bioactive phytochemicals from black poplar (Populus nigra L.) buds followed by GC-MS and UHPLC-DAD-QqTOF-MS.

The supercritical CO2 (SC-CO2) extraction process of black poplar (Populus nigra L.) buds was optimized (pressure, temperature) based on the yields of major phytochemicals (volatiles and non-volatiles). The optimal settings were 30 MPa/60 °C. Major volatiles determined by GC-MS in the optimized SC-CO2 extract (mg of benzyl salicylate equivalent (BSE) per 100 g of buds) were: pinostrobin chalcone (1574.2), ß-eudesmol (640.8), α-eudesmol (581.9), 2-methyl-2-butenyl-p-coumarate (289.9), pentyl-p-coumarate (457.0), γ-eudesmol (294.4), and benzyl salicylate (289.2). Partial qualitative similarity was observed between SC-CO2 extracts and corresponding hydrodistilled essential oil dominated by sesquiterpenes, but with lower yields. Major compounds (mg per 100 g of buds) identified by UHPLC-DAD-QqTOF-MS in the optimized SC-CO2 extract were: pinostrobin (751.7), pinocembrin (485.6), 3-O-pinobanksin acetate and methyl-butenyl-p-coumarate (290.2; 144.9 of pinobanksin and p-coumaric acid equivalents, respectively). SC-CO2 extraction was found useful for green, efficient and simultaneous extraction of both volatile/non-volatile, bioactive phytochemicals of poplar buds - precursors of poplar-type propolis.

Extraction of bioactive phenolics from black poplar (Populus nigra L.) buds by supercritical CO2 and its optimization by response surface methodology.

The scope of current study was to apply supercritical CO2 for extraction of black poplar buds (Populus nigra L.) and to optimize the extraction parameters (pressure and temperature) using response surface methodology aimed at maximum extraction yield, total phenolic content (TP), ferric reducing antioxidant power (FRAP) and individual amount of selected bioactive phenolics. The pressure and temperature influenced significantly the extract yield (0.38-10.28 g/100 g), TP content (21.62-31.09 µg GAE/mg), FRAP capacity (0.30-0.48 µmol Fe2+/mg), and the amounts of p-coumaric acid (0.33-1.52 µg/mg), pinocembrin (20.99-47.24 µg/mg) and galangin (4.04-10.25 µg/mg). The extraction of pinostrobin (51.73-79.56 µg/mg), pinobanksin (0.41-1.55 µg/mg), and chrysin (0.97-2.03 µg/mg) was significantly affected only by the operating pressure. Optimized extraction parameters (30 MPa and 60 °C) allow to obtain higher yield and extracts enriched with bioactive phenolics.