Effective recovery of limonene-rich concentrate from lemon residues using terpene-based deep eutectic solvents based on statistical experimental design.

INTRODUCTION: Waste by-products of the juice industry appear valuable for the circular economy concept, considering that the peel accounts for almost half of the total fruit weight. Therefore, the recovery of these highly valuable components from relevant biowaste has become a very interesting research topic. OBJECTIVE: The current study aims to develop an extraction process integrated with hydrophobic deep eutectic solvent (DES) based on statistical experimental design approach. MATERIAL AND METHODS: Homogenizer-assissted extraction (HAE) was used to recover the citrus extract rich in limonene (the main component of the volatile mixture) from lemon peels. Menthol-based deep eutectic mixtures were accompanied by carboxylic acids (formic, acetic, and propionic acids). Optimization continued on the combination that gave the highest efficiency (in terms of limonene content) among the solvents prepared at different molar ratios (1/1, 1/2, and 2/1). Process parameters were analyzed to optimize the process through central composite design with response surface method (RSM). D-Limonene yield was quantified with gas chromatography-mass spectrometry (GC-MS) with solid-phase microextraction (SPME) technique. The quality of the lemon peel extracts was also evaluated with respect to in vitro bioactivity assays (phenolic content and 2,2-diphenyl-1-picrylhydrazyl [DPPH] free radical scavenging activity). RESULTS: The maximum yield (3.80 mg-limonene per g fresh sample) was achieved by 2 mg solid/30 mL DES, ~53 sec, and ~8500 rpm. Statistically most effective variable was identified as solid mass, followed by second powers of mixing speed and extraction time at p < 0.0001.

Developing a recovery process for bioactives from discarded by-products of winemaking industry based on multivariate optimization method: Deep eutectic solvents as eco-friendly extraction media.

INTRODUCTION: The recovery process for bioactives from discarded by-products of the winemaking industry is of great value considering both environmental and economic aspects. OBJECTIVE: The goal of this study is to investigate the extraction of phenolic antioxidants from grape (Vitis vinifera) seeds by means of carboxylic acid-based deep eutectic solvents (DESs) in order to propose an environmentally friendly method based on a multivariate optimization approach. MATERIAL AND METHODS: Carboxylic acid-based DESs were designed with several molar ratios (1/1, 1/2, and 2/1). Two polyols (glycerol and ethylene glycol) were used as hydrogen bond donors, while formic acid, acetic acid, and propionic acid were selected as hydrogen bond acceptors. The process parameters (water content, extraction time, and solid mass) were analyzed to optimize the process through Box-Behnken design with response surface method, after determination of the best combination for the highest total phenolic content (TPC) and the antioxidant activity yields. RESULTS: The maximum TPC yield (153.17 ± 0.003 mg-GAE/g-GS) and antioxidant activity yield (82.26 ± 0.004 mg-GAE/g-GS) were achieved by 50% water addition into the DES (ethylene glycol/acetic acid, 1/1), 85 sec extraction time, and 0.1 g grape seed.

Development of an Optimized Method to Obtain a Limonene-Rich Concentrate from the Discarded Lemon Peels.

In this study, lemon peels were used as volatile component source. Automatic solvent extraction has been used for the recovery of limonene rich citrus volatile extract for the first time. The process parameters (amount of raw material, immersion time and washing time) were analyzed to optimize the process by means of Box-Behnken design via response surface methodology. The optimum conditions were achieved by ~10 g fresh lemon peel, and ~15 min immersion time and ~13 min washing time. The difference between the actual (89.37 mg/g limonene) and predicted (90.85 mg/g limonene) results was satisfactory (<2 %). α-Terpinene, ß-pinene, citral, É£-terpinene and linalool were determined as other major volatiles in the peel extract. FT-IR and 1 H- and 13 C-NMR spectroscopies were applied to verify the identified volatile compounds.

Design of encapsulation method for chlorogenic acid and caffeine in coffee waste by-product.

INTRODUCTION: Coffee silver skin (CSS) is a thin covering over green coffee seeds inside coffee cherry. It is a good source of bioactive compounds like chlorogenic acid and caffeine. It is produced as a by-product of the roasting process. OBJECTIVE: The goal of this study is to apply spray drying method to encapsulate 5-O-caffeoylquinic acid (chlorogenic acid) and caffeine extracted from CSS. METHODS: The main-plots for optimisation were feed solid concentration (2.5, 5, 10°Bx), and the sub-plots of the whole-plot were carrier material type (maltodextrin, modified starch, arabic gum) and inlet air temperature (130, 160, 190°C). Responses included were drying yield, chlorogenic acid concentration, caffeine content, Carr index, and solubility values. RESULTS: Suitable conditions were spray drying inlet temperature of 190°C, extract concentration of 10°Bx, and wall material composition [modified starch/arabic gum (MS:AG)] 10.5:9.5. As the feeding CSS extract concentration increased, the amount of chlorogenic acid and caffeine in the final powder increased, while the powder's flow characteristics improved. CONCLUSIONS: The concentration stage might be used to produce free-flowing powdered particles with good bioactive retention for use in the food processing industry.

Preservation of active components in olive leaf extract by spray drying method in biodegradable polymers: Optimization, in vitro gastrointestinal digestion and application.

INTRODUCTION: Encapsulation of the bioactive ingredients in biodegradable and edible polymers is an alternative novel application method to keep these kind of natural products stable. OBJECTIVE: The purpose is to optimize the encapsulation system of olive leaf extract by spray drying method, and to apply the products into a model food. METHODS: Olive leaf extract was encapsulated in arabic gum/maltodextrin blend by spray drying method. Combined design approach under I-optimal design type was used to optimize the system. Characterisation studies under moisture content, water activity, solubility, bulk density, tapped density, Carr index, particle size distribution, powder morphology and glass transition temperature were applied to the microparticles obtained under optimum conditions. The bioavailability of the encapsulated active material was tested by in vitro gastrointestinal digestion. Furthermore, microparticles produced under optimum conditions were also evaluated for a potential functional food application. RESULTS: The optimum conditions were achieved by arabic gum/maltodextrin (3.7:6.3) with 10% (w/v) in the mixture of wall material and active material under 165.5°C to achieve maximum encapsulation efficiency (86.92%), encapsulation yield (71.32%) and antioxidant activity (5.74 mg Trolox equivalent antioxidant capacity/g dry microparticle). CONCLUSIONS: Olive leaf extract encapsulated in arabic gum/maltodextrin may be a good alternative additive to prevent the lipid oxidation in fat-containing food products as well as improvement of the product quality by functional properties.

Adsorption of rutin from olive mill wastewater using copolymeric hydrogels based on N-vinylimidazole: Kinetic, equilibrium, and thermodynamics assessments.

Olive mill wastewater, also known as olive wastewater, contains biologically active components with various beneficial effects on health. The development of novel adsorbent materials for the recovery of these biologically active substances is important area of research. In this study, copolymeric hydrogels based on N-vinylimidazole (VIm), a new material that has never been used as an adsorbent in the separation of phenolic components, were synthesized. The hydrogels synthesized in this study is copolymer structures based on N-vinylimidazole (VIm) containing [2- (methacryloxy) ethyl] dimethylpentylammonium bromide (QDMAC5) in different moles. QDMAC5 was obtained by quaternization of 2- (dimethylamino) ethyl methacrylate (DMA) with 1-bromopentane (C5). The production of copolymer hydrogels was carried out by free radical solution polymerization. The syntheses were carried out only by changing the monomer composition so that the crosslinker ratio remained constant (1.2 mol%). The QDMAC5 content in the copolymers was 5, 10, 20, 30, and 50 mol%. So, the resulting structures were named PVQ-5%, PVQ-10%, PVQ-20%, PVQ-30%, and PVQ-50%, respectively. Functional group characterizations of hydrogels were made by Fourier Transform Infrared Spectrometry (FTIR). The surface of the hydrogels was analyzed by Scanning Electron Microscopy (SEM). Finally, thermogravimetric analyzes (TGA) were performed to investigate the thermal degradation behavior. The recovery of the rutin present in olive mill wastewater has been investigated as a model study. Kinetic data has been represented by the selected models (pseudo-first order, pseudo-second order, and intraparticle diffusion) convincingly (R2 > 0.76), while the equilibrium findings have fitted well to Langmuir, Freundlich, and Temkin equations (R2 > 0.77). Rutin adsorption process on N-vinylimidazole (VIm) based copolymeric hydrogels has been found as exothermic and spontaneous chemisorption process depending on the thermodynamic analysis.

Highly clean recovery of natural antioxidants from lemon peels: Lactic acid-based automatic solvent extraction.

INTRODUCTION: Food industry generates large amounts of waste by-products rich in natural antioxidants. On the other hand, application of advanced processes for the recovery of these fine chemicals is another popular topic of recent years. OBJECTIVE: The purpose of this study is to propose a green extraction method by application of deep eutectic solvent-based automated solvent extraction (AMSE) from lemon peels. METHODS: The primary polyphenols (hesperidin, naringin, and p-coumaric acid) and the total polyphenols of the lemon peel extract were quantified and used as response for the optimisation of the AMSE conditions. The Box-Behnken design type of the response surface method (RSM) was chosen for optimisation study. Scavenging activity of the lemon peel extract against 2,2-diphenyl-1-picrylhydrazil (DPPH) free radical was also measured in vitro. RESULTS: The optimum conditions for the highest total phenolic (7.47 mg-gallic acid equivalent [GAE]/g-lemon peel [LP]), naringin (5.05 mg/g-LP), p-coumaric acid (3.27 mg/g-LP), and hesperidin (0.07 mg/g-LP) yields were obtained by 1.5 h of extraction time, 46% water (v/v), and 5 g of peel. The antioxidant activity changed between 37.31% and 94.10% in the peels. CONCLUSIONS: Extraction time was the most effective process factor for the total phenolic and p-coumaric acid yields, while water addition was statistically very important (p < 0.0001) for the naringin and hesperidin yields in the current AMSE system. The second-order models generated for the selected systems represent the data satisfyingly based on the high coefficients of determination (> 0.99), statistically significant p-values (<0.0001), coefficient of variation values (< 10%), and non-significant lack-of-fit values (p > 0.05).

Special designed deep eutectic solvents for the recovery of high added-value products from olive leaf: a sustainable environment for bioactive materials.

Deep Eutectic Solvents have been specially designed, and used for the extraction of phenolics from olive tree (Olea europea) leaves. 11 deep eutectic solvents containing a hydrogen bond donor (glycerol, ethylene glycol, lactic acid, urea, dimethyl urea and D-sorbitol) and a hydrogen bond acceptor (L-proline, citric acid, glycerol, ethylimidazole and methylimidazole) with several molar ratios have been designed. Addition of water into the solvent system increased the extraction efficiency by a remarkable difference (45%). After the best combination has been decided to extract the primary phenolic (oleuropein), operation conditions (water content in the deep eutectic solvent, speed of the homogenizer and time for the extraction) of the homogenizer-aided extraction (HAEX) for olive leaf extract has been optimized through Box-Behnken design of Response Surface Approach. The experimental yields of oleuropein, verbascoside and rutin were 15.50, 5.51 and 0.98 mg per gram dried leaf under the optimal conditions (48.9% of water in DES for 60 sec at 13310 rpm). Our best DES (citric acid/lactic acid) has yielded the most efficient extract rich in oleuropein, even with an ≈8% higher performance than that of a most commonly used solvent (75% ethanol).

Recovery of anthocyanins from sour cherry (Prunus cerasus L.) peels via microwave assisted extraction: monitoring the storage stability.

Utilization of economical and environmental methods as an alternative process to recover the industrial crops and food products into high-added value compounds is of great significant. In the current study, microwave assisted extraction (MAE) was optimized by response surface methodology (RSM) in order to evaluate the waste of sour cherry as a source of phenolic compounds rich in anthocyanins. The process parameters (microwave power, irradiation time and ethanol solvent concentration) of MAE method were optimized by face centered composite design of RSM. Responses such as total phenolic componds (TPC), total anthocyanin (TA) contents and antioxidant capacity (DPPH) of extracts were measured spectrophotometrically after extractions of samples. The optimized result of MAE was 500 W of microwave power, 90 s of irradation time and 80% ethanol solvent concentration. Antioxidant capacity was tested using by 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical. Chromatographic analysis (HPLC) was also used to measure the concentration of major anthocyanin (cyanidin-3-glucoside) of the samples. Maximum predicted TPC, TA and DPPH yields on optimized conditions were 44.15 mg-GAE/g-FM (mg- gallic acid equivalent per g- fresh matter), 12.47 mg-cyanidin-3-glucoside/g-FM and 69.90 (%, inhibition), respectively. A stability assay under different conditions (light, dark, ambient condition, refrigerator and deep freezer) has been also performed in order to display the stability of bioactivity profile. All of the process parameters were significant at the level of p < 0.0001.

Comparison of microwave-assisted techniques for the extraction of antioxidants from Citrus paradisi Macf. biowastes.

Microwave-assisted extraction (MAE) and solvent-free microwave extraction and Soxhlet extraction were applied to Ray Ruby grapefruit leaves (Citrus paradisi Macf.) to compare extract efficiency. Face centered composite designs were constructed via response surface methodology. Effects of factors of MAE were investigated on total phenolic content (TPC) and naringin content (NC). The optimized conditions were established as 1.4 kWL-1 for microwave power density, 20.00 gL-1 for solid/solvent ratio, 218.180 s for extraction time, while responses were calculated as 14.210 mg of gallic acid equivalent per g of the dried leaf (mg GAE g-1DL) and 13.198 mg of naringin per g of dried leaf (mg Ng-1DL) for TPC and NC, respectively. SFME and classical Soxhlet methods were also conducted for comparison reasons.

Improving the quality of vegetable oils treated with phytochemicals: a comparative study.

In this study, sunflower, corn, peanut and hazelnut oils were investigated according to their oxidative stability and antioxidant activity parameters. The related vegetable oils were treated with gallic acid, rutin and carotenoid. Olive leaf extract having a large variety of phytochemical was also valorized. After the leaf samples were extracted through a homogenizer, they were added into the vegetable oils, respectively. Moreover, synthetic antioxidants were also dissolved into the oils for control reasons. Stability of the vegetable oils against the oxidation was evaluated via Rancimat by measuring induction time. The quality parameters of treated and untreated oil samples were compared depending on phenolic and carotenoid contents, antioxidant activity and induction time.

Olive tree (Olea europaea L.) leaf as a waste by-product of table olive and olive oil industry: a review.

Research into finding new uses for by-products of table olive and olive oil industry are of great value not only to the economy but also to the environment where olives are grown and to the human health. Since leaves represent around 10% of the total weight of olives arriving at the mill, it is worth obtaining high added-value compounds from those materials for the preparation of dietary supplements, nutraceuticals, functional food ingredients or cosmeceuticals. In this review article, olive tree (Olea europaea L.) leaf is reviewed as being a potential inexpensive, renewable and abundant source of biophenols. The importance of this agricultural and industrial waste is emphasised by means of describing its availability, nutritional and therapeutic effects and studies conducted on this field. © 2017 Society of Chemical Industry.

Optimization of ultrasound-assisted extraction of phenolic compounds from grapefruit (Citrus paradisi Macf.) leaves via D-optimal design and artificial neural network design with categorical and quantitative variables.

BACKGROUND: The extraction of phenolic compounds from grapefruit leaves assisted by ultrasound-assisted extraction (UAE) was optimized using response surface methodology (RSM) by means of D-optimal experimental design and artificial neural network (ANN). For this purpose, five numerical factors were selected: ethanol concentration (0-50%), extraction time (15-60 min), extraction temperature (25-50 °C), solid:liquid ratio (50-100 g L-1 ) and calorimetric energy density of ultrasound (0.25-0.50 kW L-1 ), whereas ultrasound probe horn diameter (13 or 19 mm) was chosen as categorical factor. RESULTS: The optimized experimental conditions yielded by RSM were: 10.80% for ethanol concentration; 58.52 min for extraction time; 30.37 °C for extraction temperature; 52.33 g L-1 for solid:liquid ratio; 0.457 kW L-1 for ultrasonic power density, with thick probe type. Under these conditions total phenolics content was found to be 19.04 mg gallic acid equivalents g-1 dried leaf. CONCLUSION: The same dataset was used to train multilayer feed-forward networks using different approaches via MATLAB, with ANN exhibiting superior performance to RSM (differences included categorical factor in one model and higher regression coefficients), while close values were obtained for the extraction variables under study, except for ethanol concentration and extraction time. © 2018 Society of Chemical Industry.

Proximate Composition and Nutritional Value of Three Macroalgae: Ascophyllum nodosum, Fucus vesiculosus and Bifurcaria bifurcata.

Proximate composition (moisture, protein, lipid and ash content) and nutritional value (fatty acid, amino acid and mineral profile) of three macroalgae (Ascophyllum nodosum, Fucus vesiculosus and Bifurcaria bifurcate) were studied. Chemical composition was significantly (p < 0.001) different among the three seaweeds. In this regard, the B. bifurcata presented the highest fat content (6.54% of dry matter); whereas, F. vesiculosus showed the highest protein level (12.99% dry matter). Regarding fatty acid content, the polyunsaturated fatty acids (PUFAs) were the most abundant followed by saturated fatty acids (SFAs) and monounsaturated fatty acids (MUFAs). On the other hand, the three seaweeds are a rich source of K (from 3781.35 to 9316.28 mg/100 g), Mn (from 8.28 to 1.96 mg/100 g), Na (from 1836.82 to 4575.71 mg/100 g) and Ca (from 984.73 to 1160.27 mg/100 g). Finally, the most abundant amino acid was glutamic acid (1874.47-1504.53 mg/100 dry matter), followed by aspartic acid (1677.01-800.84 mg/100 g dry matter) and alanine (985.40-655.73 mg/100 g dry matter).

Solvent-Free Microwave-Assisted Extraction of Polyphenols from Olive Tree Leaves: Antioxidant and Antimicrobial Properties.

Response surface methodology (RSM) and artificial neural networks (ANN) were evaluated and compared in order to decide which method was the most appropriate to predict and optimize total phenolic content (TPC) and oleuropein yields in olive tree leaf (Oleaeuropaea) extracts, obtained after solvent-free microwave-assisted extraction (SFMAE). The SFMAE processing conditions were: microwave irradiation power 250-350 W, extraction time 2-3 min, and the amount of sample 5-10 g. Furthermore, the antioxidant and antimicrobial activities of the olive leaf extracts, obtained under optimal extraction conditions, were assessed by several in vitro assays. ANN had better prediction performance for TPC and oleuropein yields compared to RSM. The optimum extraction conditions to recover both TPC and oleuropein were: irradiation power 250 W, extraction time 2 min, and amount of sample 5 g, independent of the method used for prediction. Under these conditions, the maximal yield of oleuropein (0.060 ± 0.012 ppm) was obtained and the amount of TPC was 2.480 ± 0.060 ppm. Moreover, olive leaf extracts obtained under optimum SFMAE conditions showed antibacterial activity against S.aureus and S.epidermidis, with a minimum inhibitory concentration (MIC) value of 1.25 mg/mL.

Effect of olive leaf extract rich in oleuropein on the quality of virgin olive oil.

Effect of olive leaf extract rich in oleuropein on the quality of virgin olive oil was investigated. After extracting the dried and ground olive leaves with the assistance of homogenizer, the dried extract was partially dissolved into the oil to increase the oxidative stability of the oil. A face central composite design through response surface methodology was used to investigate the effects of enrichment conditions (extract content, time and mixing speed) on the responses, total phenolic content and oleuropein concentration of the enriched olive oil. Furthermore, antioxidant activity of the oil was determined by 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt method. Additionally, oxidative stability of the enriched oil was assessed by the Rancimat method. Total carotenoid content, peroxide value, α-tocopherol and chlorophyll were also measured, respectively. Addition of 0.15% natural antioxidant increased the stability of the oil (≈46%). The antioxidant capacity of the enriched oil was almost 2.5 times higher than that of the untreated oil. Furthermore, olive leaf extract improved the quality of the virgin olive oil with respect to tocopherol, carotenoid and chlorophyll contents and peroxide value, respectively. The leaf sampling was also performed both in the autumn and summer to evaluate the possible seasonal effects on phenolic profile in order to be careful for selecting the proper harvesting time to apply the extract into the oil.

Green Extraction and Valorization of By-Products from Food Processing.

Agro-industrial valorization has been a hot topic recently since it leads to resource conservation and is economically and environmentally valuable [...].

Monte Carlo, molecular dynamic, and experimental studies of the removal of malachite green using g-C3N4/ZnO/Chitosan nanocomposite in the presence of a deep eutectic solvent.

Deep-eutectic solvents (DES) have emerged as promising candidates for preparing nanocomposites. In this study, a DES-based graphitic carbon nitride (g-C3N4)/ZnO/Chitosan (Ch) nanocomposite was synthesized to remove malachite green (MG) dye from water. The DES was prepared by mixing and heating citric acid as a hydrogen bond acceptor and lactic acid as a hydrogen bond donor. This is the first report of the removal of MG using DES-based nanocomposites. Experiments on kinetics and isothermal adsorption were conducted to systematically explore the adsorption performances of nanocomposite toward dye. At 25 °C, the highest adsorption performance was obtained with alkaline media (>90 % removal). The greatest adsorption capacity (qm) was 59.52 mg g-1 at conditions (30 mg L-1 MG solution, pH 9, 3 mg nanocomposite per 10 mL of MG solution, 25 °C, 150 rpm, and 150 min) based on the calculation from the best-fitting isotherm model (Langmuir). The adsorption process was most appropriately kinetically described by the PSO model. The Monte Carlo (MC) and molecular dynamic (MC) results are correlated with experimental findings to validate the theoretical predictions and enhance the overall understanding of the adsorption process. Electronic structure calculations reveal the nature of interactions, including hydrogen bonding and electrostatic forces, between the nanocomposite and MG molecules.

Improving physicochemical and nutritional attributes of rice starch through green modification techniques.

Rice, has long been an inseparable part of the human diet all over the world. As one of the most rapidly growing crops, rice has played a key role in securing the food chain of low-income food-deficit countries. Starch is the main component in rice granules which other than its nutritional essence, plays a key role in defining the physicochemical attributes of rice-based products. However, rice starch suffers from weak techno-functional characteristics (e.g., retrogradability of pastes, opacity of gels, and low shear/temperature resistibility. Green modification techniques (i.e. Non-thermal methods, Novel thermal (e.g., microwave, and ohmic heating) and enzymatic approaches) were shown to be potent tools in modifying rice starch characteristics without the exertion of unfavorable chemical reagents. This study corroborated the potential of green techniques for rice starch modification and provided deep insight for their further application instead of unsafe chemical methods.

Optimisation of ultrasound-assisted extraction of rosehip (Rosa canina L.) with response surface methodology.

BACKGROUND: Ultrasound-assisted extraction of polyphenols from rosehip (Rosa canina L.) was investigated. The aim of the study was to examine the extraction parameters such as extraction time (30-90 min), temperature (30-50 °C) and solvent concentration (40-100% ethanol, v/v), and to obtain the best possible combinations of these parameters by using response surface methodology. RESULTS: The experiments were performed according to the face-centred central design. Total phenolic content was expressed in gallic acid equivalent (GAE) per gram of dried matter (DM). The second-order polynomial model gave a satisfactory description of the experimental data. 47.23 mg GAE g(-1) DM was predicted at the optimum operating conditions (40% EtOH composition, 50 °C of temperature, and 81.23 min of extraction time). CONCLUSION: All of the parameters (ethanol concentration, extraction time and extraction temperature) used in this research have the significant effect on the extraction efficiency of total phenolic content in rosehip extracts (P < 0.05). The solvent concentration was proved to be the most significant effective on the yields obtained by ultrasound-assisted extraction.