Application of response surface methodology and central composite design for the optimisation of supercritical fluid extraction of essential oils from Myrtus communis L. leaves

Essential oils of Myrtus communis L. leaves were obtained using supercritical fluid extraction (SFE) and hydrodistillation methods. The experimental parameters of SFE such as pressure, temperature, modifier volume, static and dynamic extraction time were optimised using a central composite design after a 2ⁿ⁻¹ fractional factorial design. The chemical compositions of the SFE extract were identified by GC–MS and determined by GC–FID. The major components of essential oils obtained by hydrodistillation were α-pinene (31.8%), 1,8-cineole (24.6%), limonene (14.8%), linalool (8.3%) and α-terpinolene (4.8%). However, by using the supercritical carbon dioxide in optimum conditions, only three components represented more than 85% of the extract. Therefore, by using the proper SFE conditions, the supercritical extraction is more selective than the conventional hydrodistillation methods. The oil yields based on the hydrodistillation was 0.47% (v/w). Extraction yields based on the SFE varied in the range of 0.5–6.3% (w/w) under different conditions.     

Effect of illumination and chlorophylls on stability of tomato carotenoids

Lipidic extract from tomato peels, or tomato peels plus stalks, dissolved in ethanol were submitted to illumination. Lycopene, β-carotene, phytoene and phytofluene isomerisation and degradation, during storage at room temperature for 28 days, were studied. Degradation of chlorophylls a and b were analysed in lipidic extracts from stalks. Total lycopene and all-E-lycopene degradation was found to fit to a first-order model. The degradation rate constant was lower in extracts from peels −0.0137 (all-E-lycopene) and −0.0737 (total lycopene), than in those from peel plus stalk −0.0415 (all-E-lycopene) and −0.0854 (total lycopene). Z-lycopene isomers showed an inconsistence change during storage, in all analysed samples. Concentration of β-carotene from extracts of tomato peels plus stalks decreased slightly during storage. Phytoene and phytofluene degradation were not significantly affected by both storage conditions and chlorophylls. The obtained results showed that some compounds from stalks, such as chlorophylls, could favour lycopene and β-carotene degradation during storage under illumination.     

Tomato pulp as source for the production of lycopene powder containing high proportion of cis-isomers

Cis-isomers of lycopene has been demonstrated to possess higher biological activity than its all-trans form. The objectives of this study were to compare the extraction efficiency and degree of isomerization of lycopene by employing supercritical carbon dioxide (SCD) and solvents, as well as process the lycopene extract into powder containing high proportion of cis-isomers from tomato pulp as source. Results showed that a high yield of lycopene was achieved by SCD at 350 bar and 70 °C, with cis-isomers making up 41.4% of total lycopene. However, with temperature at 80 and 90 °C, the maximum isomerization was accomplished, and cis-lycopene constituted 51.0 and 53.8% of total lycopene, respectively. For solvent extraction, the highest yield of all-trans-lycopene was attained by ethanol–hexane (4/3 v/v) at 25 and 50 °C, whereas the maximum isomerization (47.0% cis-lycopene) occurred at 75 °C. A powder product containing 34.5% cis-isomers of lycopene was obtained by spray-drying, and the total amount of lycopene in spray-dried powder was much greater than that in freeze-dried powder. The maximum yield of lycopene in the powder product could be obtained through processing by adding sodium alginate to the eluate directly after SCD extraction and open-column chromatography with formation of 41.4% cis-lycopene. The method developed in this study may be used for possible commercial production of highly active lycopene powder.     

Improving the stability of lycopene Z-isomers in isomerised tomato extracts

Tomato-based foods rich in Z-lycopene are potentially more bioavailable and have greater bioefficacy compared to natural tomato products which mainly contain all-E-lycopene. To prepare a stable tomato extract with a high level of Z-lycopene, geometrical isomerisation of lycopene was studied in organic solvents either alone or in the presence of a tomato extract. Interconversion between the isomers was observed in all systems with 13Z-lycopene being the least stable. Heating a tomato extract containing mainly the all-E-isomer in ethyl acetate produced successively 13Z-, 9Z- and 5Z-lycopene. An isomerised tomato oleoresin with a minimal content of the most unstable 13Z-lycopene could be obtained by refluxing tomato oleoresin in ethyl acetate for 1 week. In this isomerised tomato oleoresin, total lycopene and lycopene isomer profiles were shown to remain constant for 1 year at room temperature. Accordingly, this product is a valid source of stable and potentially highly bioavailable lycopene.     

Effects of a hydrodynamic process on extraction of carotenoids from tomato

We evaluated the results of using a proprietary hydrodynamic method, which was introduced with the hope of increasing accessibility of beneficial nutrition-enhancing fruit and vegetable products. Tomato, a major dietary source of carotenoids, notably lycopene, was tested because of its many health benefits to consumers. Samples before and after treatment were compared for lycopene, phytoene, and phytofluene contents. Extractable lycopene and other carotenoids increased significantly. In nature, lycopene exists almost exclusively as the all-trans stereoisomer. Cis-lycopene isomers form during cooking and digestion, resulting in higher percentages in plasma and tissues than ingested. Cis-lycopene isomers are more bioavailable than all-trans lycopene. Extraction using this proprietary method increased extracted cis-lycopene to as high as 43% of the total lycopene, indicating increased isomerisation. This method could therefore contribute significantly to the delivery of health benefits of biologically available lycopene from tomato products for metabolic functions.     

Effects of supercritical fluid extraction parameters on lycopene yield and antioxidant activity

The effects of various parameters of supercritical carbon dioxide (SC-CO₂) fluid extractions of tomato skins on the extraction yields and antioxidant activities of lycopene-rich extracts were investigated. A Box–Behnken design was applied to study the effects of three independent variables (temperature ranging from 40 to 100 °C, pressure ranging from 20 to 40 MPa, and flow rate ranging from 1.0 to 2.0 mL/min) on lycopene yield. The model showed good agreement with the experimental results, by the coefficient of determination (r² = 0.9834). Temperature, pressure, and the quadratic term for the temperature of SC-CO₂ extraction were large significantly positive factors affecting lycopene yield (P < 0.05). The maximum total lycopene content of 31.25 μg/g of raw tomato was extracted at the highest temperature of 100 °C, 40 MPa and 1.5 mL/min. TEAC assay was applied to assess the antioxidant activity of lycopene-rich extracts from SC-CO₂ fluid extraction. The effects of SC-CO₂ fluid extraction parameters on the antioxidant activities of the extracts differed with the yield. For each unit of lycopene extract, the antioxidant activity level was constant below 70 °C, but then gradually decreased above 70 °C due to isomerization occurring as a result of the higher temperature. The ratio of all-trans-lycopene to the cis-isomers changed from 1.70 to 1.32 when the operating temperature was adjusted from 40 to 100 °C, indicating an increased bioavailability due to the generation of the cis-isomers. No significant effects of pressure or flow rate of SC-CO₂ fluid extraction on the antioxidant activity were observed.     

丁香精油的超临界CO_2和溶剂回流萃取及其GC-MS分析

研究了超临界CO2流体萃取技术(SFE)和溶剂回流法萃取丁香精油,所得精油经气相色谱(GC)-质谱(MS)分析。结果显示:溶剂回流法宜采用正己烷为溶剂,最佳工艺条件为:料液比(g∶mL)1∶15、回流温度80℃、回流时间30min;SFE最佳工艺条件为:萃取温度45℃、萃取压力12MPa、解析温度50℃、萃取时间90min。验证试验显示:SFE法收油率达到21.04%,高于溶剂回流法(17.401%),所得精油色泽和流动性较优。经GC-MS分析显示:所得精油的组成相似,但含量不同,溶剂回流法除β-石竹烯的含量略高外,3种主要活性物质丁香酚、乙酰基丁香酚、β-石竹烯的的含量和提取率均低于SFE法提取的精油。SFE法是提取丁香精油值得推广和有前景的一种方法。     

Central composite design for the optimization of supercritical carbon dioxide fluid extraction of fatty acids from Borago officinalis L. flower

Abstract: In the present study, fatty acids and essential oils of the flower of borage (Borago officinalis L.) were obtained by supercritical carbon dioxide fluid extraction under different conditions. The extracts obtained were compared to oils of borage flower oil isolated by hydrodistillation. The obtained oils were analyzed by gas chromatography mass spectrometry. The compounds were identified according to their retention indices and mass spectra. The experimental parameters of supercritical fluid extraction (SFE) were optimized using a central composite design after a full factorial experimental design. Extraction yields based on SFE varied in the range of 0.02% to 1.96% (w/w), and the oil yield based on the hydrodistillation was 0.05% (v/w). The optimum conditions of SFE were obtained at a pressure of 350 atm, a temperature of 65 °C, a methanol modifier volume of 100 μL, and static and dynamic extraction time of 10 min. Main components of the extracts under optimum SFE conditions were palmitic acid, linoleic acid, γ‐linolenic acid, and oleic acid. The results indicated that by using the suitable extraction conditions, SFE is more effective than the conventional hydrodistillation method in the extraction of fatty acids and the preservation of its quality. Practical Application: SFE is a good technique for the extraction of oils from plants. The extraction yields by SFE are more than the conventional method. SFE is used on a large scale for production of essential oils and pharmaceutical products from plants.     

天然色素超临界CO2萃取技术研究进展

本文介绍了超临界萃取技术在食用天然色素研发中的应用现状,对近十年来超临界CO2萃取天然色素的研究报告作了统计,重点介绍了的辣椒红素、胡萝卜素、蕃茄红素、玉米黄色素等超临界CO2萃取技术的研究进展。     

An Improved Ultrasonic-Assisted Extraction Method by Optimizing the Ultrasonic Frequency for Enhancing the Extraction Efficiency of Lycopene from Tomatoes

In order to assess the optimization of the ultrasonic frequency in a range of 18–146 kHz for extracting lycopene from tomatoes and evaluate its influence on the extraction efficiency, an improved ultrasonic-assisted extraction (IUAE) method was proposed by using a novel ultrasonic extraction and detection system, in which the ultrasonic frequency information could be converted to intuitive waveforms that are easily identified by eyes. Additionally, to improve the extraction yield of lycopene, in this work, the optimization of various process parameters by ultrasonic treatment, including extraction time, solvent/material ratio, extraction temperature, and ultrasonic power for improving the yield of lycopene were investigated. These results indicated that all of the considered parameters had effected on the yield of lycopene significantly, and the optimum extraction conditions were as follows: extraction time duration 20 min; ratio of solvent to material 2:1; extraction temperature 25 °C; ultrasonic power 200 W; ultrasonic frequency 46–48 kHz. In comparison with other extraction methods, such as conventional solvent extraction (CSE), supercritical fluid extraction (SFE), supercritical carbon dioxide co-extraction (SC-CO₂), and existing UAE, the IUAE method achieved a far more extraction yield, a reduction of extraction time, and a smaller amount of solvent at lower temperature, which showed a great promising prospect in the extraction and separation of natural products.     

番茄果皮中番茄红素的超临界二氧化碳流体萃取

本项研究表明：超临界二氧化碳流体萃取能够作为传统的有机试剂萃取的替代方法有效地从番茄果皮组织中萃取番茄红素等类胡萝卜素。在本项研究中，多种有机试剂被用来对样品组织进行预处理。这种预处理可明显地提高超临界流体萃取的效率。用四氢呋喃对组织进行预处理后，超临界流体萃取物中总类胡萝卜素的含量比丙酮-乙醚萃取物的高31％，其中番茄红素占90％。这一流程可以考虑被应用到工业生产中去。     

Supercritical carbon dioxide fluid extraction of Hibiscus cannabinus L. seed oil: A potential solvent-free and high antioxidative edible oil

The supercritical fluid extraction (SFE) trends and antioxidant activities of Hibiscus cannabinus seed oils were studied. SFE results indicate that extraction pressure is the major factor determining the oil yield. In comparison, classic Soxhlet extraction (SOX/L) yielded higher oil content than SFE (P < 0.05). However, no significant differences in oil content were observed in SFE at 600 bars/80 °C, rapid Soxhlet extraction (SOX/S) and conventional ultra-sonic assisted solvent extraction (SONIC) (P > 0.05). Antioxidant activities of H. cannabinus seed oils were compared with 7 types of commercial edible oils. DPPH scavenging activity test indicated that H. cannabinus seed oil extracted by SFE at 200 bars/80 °C possessed the highest antiradical activity whereas beta-carotene bleaching (BCB) assay revealed that all H. cannabinus seed oils (except for SFE at 400 bars/80 °C and 600 bars/80 °C) exhibited higher antioxidant activity than all commercial edible oils (P < 0.05). Thus, SFE – H. cannabinus seed oil may serve as an excellent source of solvent-free edible oil with high antioxidant properties.     

Flavour compounds of Lavandula angustifolia L. to use in food manufacturing: Comparison of three different extraction methods

Sixty compounds of Lavandula angustifolia L. cultivated in Friuli Venezia Giulia (North-East Italy) were identified and quantified by GC-MS and GC-FID from essential oils obtained by means of hydrodistillation, and from extracts obtained by supercritical CO₂ extraction (SFE) and ultrasound-assisted extraction (US). Using absolute calibration, a true quantification of 1-8 cineol, camphor, linalool, linalyl acetate and β-caryophyllene was carried out. The best extracts, in terms of amount of isolated compounds, flavour quality and stability were those obtained with SFE. Sonication performed at low amplitude for 5 min offered respect to high amplitude a promising alternative to hydrodistillation as a source of lavender flavouring ready to use for alcoholic beverages or/and confectionery products.     

Solubility of Carotenoids in Supercritical CO2

Carotenoids have been shown to provide a range of health benefits and to decrease the risk of disease. Although carotenoids are naturally present in plants advanced extraction technologies to remove carotenoids from plant materials are needed to prepare concentrated materials. Because carotenoids are sensitive to heat, oxygen, and light, large-scale supercritical fluid extraction (SFE) has drawn attention as a separation technology. SFE with solvents such as CO₂ offers an organic-chemical-free process that yields quality end food products, compared to traditional extraction methods that organic solvents. In the SFE process for plant materials, an important step is to measure and predict the solubility of target components in the supercritical fluid at various pressure and temperature conditions to optimize the extraction process. The solubility of targeted carotenoids in supercritical fluids is related to its physical and chemical properties such as polarity, molecular structure, and nature of the material particles, and it is also related to the operating conditions such as temperature, pressure, density of solvent and co-solvents, and solvent flow rate in the supercritical region. The solubility of β-carotene, α-carotene, and other carotenoids under different extraction conditions has been reviewed. It would be interesting and useful for researchers and food industries to compare the data of the solubility of carotenoids to develop optimum extraction process and to get maximum yields.     

The impact of industrial processing on health-beneficial tomato microconstituents

The effect of industrial processing was investigated on the stability of tomato carotenoids, phenolic compounds and ascorbic acid. A deep insight in the processed products allowed the quantification of caffeic acid hexosides, which are far more important contributors than the well-known chlorogenic acid, dicaffeoylquinic acids and quercetin oligosaccharides (new feruloyl, sinapoyl and syringoyl derivatives of quercetin apiosylrhamnosylglucoside). (E)-β-Carotene and (E)-lycopene were also quantified along with different mono- and di-(Z)-isomers of lycopene which were tentatively assigned. Processing of fresh tomato into paste had an overall positive effect on the contents in phenolic compounds, no effect on lycopene and a slight and high detrimental effect on β-carotene and ascorbic acid, respectively. The balance between the increase in tomato matrix extractability and microconstituent catabolism was further observed in two contrasted transformations of paste into sauce. Overall, the nutritional quality of tomato-processed products, except for ascorbic acid, is mainly preserved through manufacture.     

Supercritical carbon dioxide extraction of 2-acetyl-1-pyrroline from Pandanus amaryllifolius Roxb

A comparative evaluation of the extraction of 2-acetyl pyrroline (2-AP) from Pandanus amaryllifolius Roxb. using either solvent extraction (3:1 chloroform:methanol), Likens–Nickerson apparatus or supercritical fluid extraction (SFE) with carbon dioxide extraction was carried out. SFE at 450 bar pressure for 3 h at 60 °C, at a constant flow rate of 0.1 l min⁻¹ of CO₂, could extract 2-AP from P. amaryllifolius Roxb. in yields greater than those obtained by solvent extraction or Likens–Nickerson extraction. This extract could find novel applications in food flavouring.     

不同萃取方法对番茄籽油理化性质与脂肪酸含量的影响

分别采用超临界ＣＯ２萃取技术和传统溶剂法从番茄籽中萃取脂肪油，经过甲酯化处理后，用气相色谱法分析出亚油酸等５种脂肪酸占总脂肪酸的９８．５％．同时对油的其它理化指标进行了测定。对测定结果进行了比较分析，说明超临界ＣＯ２萃取所得番茄籽油品质更好。并对番茄籽油的营养学机理作了讨论。     

Optimization of subcritical fluid extraction of seed oil from Nitraria tangutorum using response surface methodology

Subcritical fluid extraction (SFE) technology was used to extract oil from Nitraria tangutorum seed. The best possible combination of extraction parameters was found using response surface methodology (RSM) in a three-variable, three-level Box-Behnken experimental design (BBD). The optimum extraction parameters were an extraction time of 40 min, an extraction pressure of 0.60 MPa, an extraction temperature of 44 °C and a raw material particle size of 0.45 mm. Conventional solvent extraction and supercritical CO₂ fluid extraction were comparatively used. The yield of seed oil obtained using SFE was 12.92%, which was similar to or higher than the other methods. The chemical compositions of the seed oil, determined by GC–MS, indicate that its unsaturated fatty acids content was 97%. SFE proved to be an effective technique for extracting oil from N. tangutorum.     

超临界CO_2萃取番茄红素的初步研究

近年的研究表明，番茄红素是一重要的类胡萝卜素。其功能在许多方面优于β－胡萝卜素。采用超临界ＣＯ２萃取技术从番茄加工副产品番茄皮中提取出番茄红素。研究了不同的压力、温度、流量和萃取时间对萃取率的影响。当萃取压力在１５～２５ＭＰａ，温度４０～５０℃，流量２０ｋｇ／ｈ，萃取１～２ｈ，既可将番茄皮中９０％以上的番茄红素萃取出来。     

Comparison of essential oil compositions of Salvia mirzayanii obtained by supercritical carbon dioxide extraction and hydrodistillation methods

Essential oil of Salvia mirzayanii cultivated in Iran was obtained by hydrodistillation and supercritical (carbon dioxide) extraction methods. The oil was analysed by capillary gas chromatography using flame ionization and mass spectrometric detections. The compounds were identified according to their retention indices and mass spectra (EI, 70 eV). The effects of different parameters such as pressure, temperature, modifier volume and extraction times (dynamic and static) on the supercritical fluid extraction (SFE) of S. mirzayanii oil were investigated. The results showed that, under a pressure of 35.5 MPa, temperature of 35 °C, 6% methanol, dynamic extraction time of 50 min and static extraction time of 30 min, extraction was more selective for the linalyl acetate. Thirty four compounds were identified in the hydrodistilled oil. The major components of S. mirzayanii were linalyl acetate (7.6%), 1,8-cineole (8.0%), linalool (9.0%) and 8-acetoxy linalool (11.0%). However, by using supercritical carbon dioxide in optimum conditions, only three components contain more than 63% of the oil. The yield of the obtained oil based on hydrodistillation was 2.20% (v/w). Extraction yield based on the SFE varied in the range of 1.50–9.67% (w/w) under different conditions. The results revealed that, in Iranian S. mirzayanii oil, linalyl acetate is a major component.