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Procedia Food Science 1 (2011) 1672 – 1678
11th International Congress on Engineering and Food (ICEF11)
Supercritical fluid extraction with a modifier of antioxidant compounds from jabuticaba (Myrciaria cauliflora) byproducts: economic viability
Rodrigo N. Cavalcanti, Priscilla C. Veggi, Maria Angela A. Meireles*a
aLASEFI/DEA/FEA (School of Food Engineering)/UNICAMP (University of Campinas) – R. Monteiro Lobato, 80; 13083-862,
Campinas, SP, Brazil ([email protected])
Abstract
Jabuticaba (Myrciaria cauliflora) is a grape-like fruit that is found extensively throughout Brazil. In spite of the very few studies done on its chemical constituents, some authors have reported the potential use of jabuticaba as a source of antioxidant compounds, which are believed to play an important role in the prevention of many oxidative and inflammatory diseases. Local populations enjoy jabuticaba as a favorite fruit, but the majority of these crops are wasted during harvesting and processing. Thus, the application of innovative technologies such as supercritical fluid extraction (SFE) for processing by-products is important to obtain high quality yields, which increases the value of the product. In addition, processing by-products currently represents an increasing niche market, which is mainly due to their ecological, economic and social implications. In order to evaluate their industrial applicability, it is essential to perform a critical analysis of the chemical composition and economic viability of the extracts obtained. The objective of this study is to evaluate the feasibility of antioxidant recovery by SFE with a co-solvent using varying conditions of pressure and temperature. SFE was carried out under two temperatures (323 and 333 K) and three pressures (10, 20 and 30 MPa) using ethanol as a modifier at 20% v/v, for a total of six different extraction conditions. The assays were performed in triplicate. The extracts were evaluated for their global yield (X0) and antioxidant capacity by radical scavenging activity using the DPPH method.
© 2011 Published by Elsevier B.V. Open access under CC BY-NC-ND license. Selection and/or peer-review under responsibility of 11th International Congress on Engineering and Food (ICEF 11) Executive Committee.
Keywords: Myrciaria cauliflora; by-product; antioxidant compounds; jabuticaba; supercritical fluid extraction; manufacturing cost; economical evaluation.
ꢀD Corresponding author. Tel.: +55-19-3521-4033; fax: +55-19-3521-4027.
E-mail address: [email protected].ꢁ
2211–601X © 2011 Published by Elsevier B.V. Open access under CC BY-NC-ND license. Selection and/or peer-review under responsibility of 11th International Congress on Engineering and Food (ICEF 11) Executive Committee.
doi:10.1016/j.profoo.2011.09.247
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1.ꢀIntroduction
It has been suggested that diets high in fruits and vegetables are linked to a reduced incidence of heart disease, cancer and some neurodegenerative disorders [1-4]. Inflammation is a major factor in the promotion of chronic inflammatory diseases, as well as the etiology of cancers and heart disease [3,5]. Oxidative damage is balanced by endogenous antioxidants, but additional protection, provided by nutritive and non-nutritive elements from food, is critical for disease chemoprevention.
Though considered one of the countries with the richest biodiversity in the world, Brazil has been inefficiently using its natural resources [6]. Indeed, plants have been of crucial importance for human healthcare for centuries [7]. The extracts of some plants have antioxidant, antiulcer, antimalarial, anticancer and anti-inflammatory activities. In particular, the antioxidant activity of plant extracts is mainly attributed to the presence of phenolic compounds, volatile and non-volatile compounds, such as flavonoids, and phenolic acids and phenolic diterpenes. By making better use of Brazil’s natural vegetative products through the use of extraction research and technology, it may lead to better treatment or even cures for many common diseases and disorders.
Polyphenolic compounds inhibit several oxidative and inflammatory enzymes, and they have been shown to have antiallergenic, antiviral, antibacterial, antifungal, antitumor, and antihemorrhagic activities [5]. Colorful fruits are a potentially rich source of many dietary phenolic and flavonoid compounds and are believed to play an important role in the prevention of many oxidative and inflammatory diseases [1].
Many of the chemicals that comprise the characteristics of functional foods are bioactive substances that belong to a group of compounds from the secondary metabolism of plants. These are also called phytochemical compounds, and they can be defined as highly active in terms of nutritional, physiological and/or medicinal factors [8]. Thus, many functional activities are attributed to the extracts and their active ingredients, which are derived from plants and native trees. These activities, among others, include antioxidant, anticancer, anti-HIV, antimicrobial, antimalarial, and hypoglycemic properties [9].
Jabuticaba (Myrciaria cauliflora Berg.) belongs to the Myrtaceae family and is a fruit that is native to
Brazil. It exhibits spontaneous and extensive occurrence in the country from Para to the Rio Grande do Sul states [10]. The fruit is a smooth, sub-globular berry that is black-purple when ripe, has a 1.6 to 2.2 cm diameter, and contains 1 to 4 seeds. The peel is thin and very fragile, and the pulp has a white to translucent color and is sweet and slightly acidic [11].
Because of jabuticaba’s grape-like character, many products can be made from it, such as wine, juice, jelly, liqueur and vinegar [12]. Furthermore, Myrciaria cauliflora has been used in the treatment of various diseases, as its peel is featured in popular treatments of hemoptysis, asthma, diarrhea and chronic inflammation of the tonsils [13]. The few studies that have been done on the chemical constituents, especially in relation to fractions of the fruit, are presented primarily in local publications [14,15]. However, it has been reported that the fruit of the jabuticaba tree has high tannin [16], vitamin C [17] and flavonoid contents, especially in its peel [17-20], which indicates a great potential antioxidant capacity and thus a possible role in the prevention of many diseases related to oxidative stress.
In Brazil, part of the production of these fruits consumed by local populations, but the majority is wasted during harvest because of high production per tree, the short shelf life of fresh fruit, and especially the lack of use of these fruits as processed products [21,22]. Thus, the need to use the waste produced during the manufacture of jabuticaba juices, jams, liqueurs and other products has prompted the application of Generally Recognized as Safe (GRAS) technology, such as supercritical fluid extraction (SFE). This procedure can be used to obtain bioactive compounds, and it is an important tool used in industry as it has broad environmental and safety appeal.
Conventional extraction processes are based on the use of large amounts of organic solvents and the application of heat and/or agitation [23]. The main disadvantages are the large amounts of solvent required, thermal degradation, and the presence of residue of organic solvents, which is often
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unacceptable in the food industry [24]; In contrast, the use of GRAS technology provides a safer method for the extraction process.
SFE has considerable advantages compared to conventional techniques. The solvent can easily be removed from the mixture by pressure reduction and/or temperature adjustment. Also, there is a lower energy requirement compared to other methods, and the extraction is relatively fast due to the low viscosity, high diffusivity, and appropriate solvent power of the supercritical fluid. In addition, because SFE requires the use of little or no organic solvent and carbon dioxide is recirculated into the system, it is a safe and environmentally friendly technology.
There are few industrial applications of SFE technology in Latin America. The main reasons for this are high investment and manufacturing costs due to the high pressures required for the extraction process [25]. Thus, with regard to industrial applications of supercritical technology, an analysis of economic factors should be performed. The development of SFE units on an industrial scale promotes the reduction of costs for equipment utilized in the process. Thus, SFE processes have become increasingly economically attractive, which has promoted the emergence of industrial extraction units [26]. However, data regarding scale-up and the estimated costs of manufacturing to obtain supercritical extracts are still scarce in the literature. Such information is of great importance to stimulate the shift from the laboratory scale to an industrial scale [27].
The aim of this study is to evaluate the performance of antioxidant compound recovery through the manufacturing process of the residue of jabuticaba jelly. The product was obtained through varying conditions of pressure and temperature using SFE with a co-solvent.
2.ꢀMaterials & Methods
The residue from jabuticaba jelly production was provided by Santa Maria farm (Campinas, São Paulo,
Brazil). The selection of raw materials was based on their social importance, availability, current demand, economic viability, ecological impact and potential yield of the target compounds. The aim was to produce a matrix rich in bioactive compounds, which would yield high value from the obtained product. The size reduction (grinding) was performed with a knife mill (Tecnal TE-631 model series 01071, Piracicaba, São Paulo, Brazil), and the sample was packed in a plastic bag and stored in a domestic freezer (Metalfrio, HC-4, Sao Paulo, Brazil) at -18°C.
SFEs were carried out using a system equipped with a 415 cm3 extraction vessel (3.4×10-2 m diameter and 37.5×10-2 m height; internal dimensions). The column was partially filled with raw material. The assays were performed at two temperatures (323 and 333 K) and three pressures (10, 20, and 30 MPa) using ethanol as a modifier at 20% v/v, for a total of six different extraction conditions. Carbon dioxide (99.5% purity, Gama Gases Especiais, São Paulo, Brazil) was admitted into the system at a fixed flow rate fixed of 9.1×10í5 kg/s, keeping the S/F (the ratio between the mass of solvent (S) and mass of solid (F)) constant at 40. The global yield (X0) was calculated as the percentage (%) of mass extract (mextract) out of the total initial mass of raw material (mRM) loaded in the extraction cell, as shown in Equation 1:
mextract
%X 0
u100
(1)
mRM
The radical scavenging activity of DPPH (2,2-diphenyl-1-picrylhydrazyl) was used to determine the antioxidant activity, according to the method of Kordali et al. [28]. The DPPH solution was prepared by dissolving DPPH radical in ethanol at a concentration of 60 μM. The standard calibration curve was prepared at different concentrations of DPPH: 0, 10, 20, 30, 40, 50 and 60 μM. It was then prepared in tubes with different dilutions of the supercritical extracts in ethanol (0.05, 0.1 and 0.2 mg/cm3). Subsequently, an aliquot of 0.1 cm3 of each dilution of the extract was transferred to tubes with 3.9 cm3 of DPPH solution and mixed in a shaker tube in the dark. The control was 0.1 cm3 of ethanol. Pure ethanol was used as a blank to calibrate the spectrophotometer. The readings were taken immediately at 0 and 30
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minutes of reaction time and at a wavelength of 517 nm in a UV-vis spectrophotometer (Hitachi, model U-3010, Tokyo, Japan). The antioxidant activity of the extracts was calculated by scavenging ability (%SA) at 0.2 mg/cm3 extract concentration according to Equation 2:
ꢀAbs Control ꢂ Abs Sample ꢁu100
%SA
(2)
Abs Control
SuperPro Designer 6.0® was used for process simulation and economical evaluation. The main expenditures that compose the cost of manufacturing (COM) are similar to the ones described by Turton et al. [29], which are given by fixed cost of investment (FCI) and operating cost: raw materials (CRM), utilities (CUT), and operating labor (COL) costs. The process was designed to run 7,920 h per year, which corresponds to 330 days per year of continuous operation 24 h per day. For the scale-up, the procedure assumed that the industrial-scale unit has the same performance as the laboratory-scale unit; this study considered setups with extractors of 0.05 and 0.3 m3.
3.ꢀResults & Discussion
Figure 1 shows the global yield and antioxidant compound recovery obtained using varying operational conditions (temperature and pressure) by SFE of jabuticaba jelly residue. The extraction yield varied little with pressure. On the other hand, increasing the temperature significantly increased the global yields. However, both pressure and temperature conditions had great influence on the recovery of antioxidant compounds. Unlike for the global yield, an increase in temperature resulted in a decrease in antioxidant compound recovery. This is likely due to the fact that most of these antioxidant compounds, such as vitamin C, polyphenols and anthocyanins, are unstable and highly susceptible to thermal degradation.
The increase in the pressure (10-30 MPa) of the system provided an increase and, subsequently, a decrease in the concentration of antioxidant compounds present in the supercritical extracts at both temperatures. This phenomenon indicates the high susceptibility of the solubility of antioxidant compounds to the density, moisture and vapor pressure of the system.
Figure 2 shows the results of the manufacturing costs of global yield and antioxidant compound recovery using extraction cells at 0.05 and 0.3 m3 (in dollars per kilograms of product, US$/kg). The cost of manufacturing is much higher for the process of obtaining the antioxidant compounds than for the global yield of the extract. This is closely related to the percentage of antioxidant compounds in the extract; i.e., the higher the percentage of antioxidant compounds in the extract, the lower the manufacturing cost is.
It is possible to evaluate the variation in the costs of manufacturing with the operational conditions such as temperature, pressure and size of the extraction cell. The manufacturing cost of the global yield did not vary significantly with temperature and pressure, showing only a small decrease in costs when the size of the extraction cell was increased from 0.05 to 0.3 m3, which is expected, as the scale-up represents a higher viability of the industrial process.
The manufacturing costs of the antioxidant compounds (COM-CA) showed high variability with the variation in temperature, pressure and size of the extraction cell. Like COM-X0, COM-CA decreased with scale-up, though the decrease in this case was more pronounced. The increase in COM-CA with temperature was likely due to energy costs. The increase in pressure (10 to 20 MPa) corresponded with a decrease followed by a pronounced increase in manufacturing costs. This phenomenon is closely related to antioxidant compound recovery and energy costs.
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Fig. 1. Antioxidant activity and global yield (X0) of supercritical extracts of jabuticaba jelly residue expressed as the percentage of antioxidant compounds in dry extract (%) and the percentage of mass extract in raw material mass (%)
Fig. 2. Cost of manufacturing of global yield (COM-X0) and antioxidant compounds (COM-CA) obtained by SFE using CO2 with ethanol
4.ꢀConclusion
Evaluating the extraction and yield of antioxidant compounds, as well as the manufacturing costs for each condition of temperature and pressure, it was possible to form a conclusion regarding the economic viability of SFE technology relative to jabuticaba fruit. The extraction condition at 323 K and 20 MPa had
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the highest yield of antioxidant compounds and the lowest cost of manufacturing (COM-CA). Thus, these conditions were selected as the best choices for SFE with ethanol to obtain antioxidants from jabuticaba jelly residue. Further studies should be performed to evaluate other variables such as co-solvent type, extraction time, solvent flow, and the solute/solvent ratio in order to optimize supercritical extraction to obtain higher yields at a lower cost.
Acknowledgements
The authors are grateful to CNPq and FAPESP for doctoral fellowships and financial support.
References
[1] Arts I.C.W., Hollman P.C.H. Polyphenols and disease risk in epidemiologic studies. American Journal of Clinical Nutrition
2005; 81(1): 317–325.
[2] Collins A. R. Antioxidant intervention as a route to cancer prevention. European Journal of Cancer 2005; 41(13): 1923–
1930.
[3] Hu F.B., Willett W.C. Optimal diets for prevention of coronary heart disease. Journal of the American Medical Association
2002; 288(20): 2569–2578.
[4] Youdim K. A., Joseph J. A. A possible emerging role of phytochemicals in improving age-related neurological dysfunctions: a multiplicity of effects. Free Radical Biology and Medicine 2001; 30(6): 583–594.
[5] Middleton E, Jr.-Kandaswami C., Theoharides T. C. The effects of plant flavonoids on mammalian cells: implications for inflammation heart disease and cancer. Pharmacology Reviews 2000; 52(4): 673–751.
[6] Calixto J.B. Twenty-five years of research on medicinal plants in Latin América: a personal view. Journal of
Ethnopharmacology 2005; 100: 131-143.
[7] Balbani A. P. S., SILVA D. H. S., Montovani J. C. Patents of drugs extracted from Brazilian medicinal plants. Expert
opinion on therapeutic patents 2009; 19(4): 461-473.
[8] Goldberg I. Functional Foods: designer foods, pharmafoods, and nutraceuticals. New York: Chapman & Hall; 1994.
[9] Leal P. F., Braga M. E. M., Sato D. N., Carvalho J. E., Marques M. O. M., Merieles, M. A. A. Functional properties of spice extracts obtained via supercritical fluid extraction. J. Agric. Food Chem. 2003; 51: 2520-2525.
[10] Pereira, M. 2003. Propagação via estacas apicais, caracterização morfológica e molecular de jabuticabeiras (Myrciaria spp).
PhD Thesis, University of Sao Paulo, Piracicaba, Brazil.
[11] Whalen P.J., Bason M.L., Booth R.I., Walker C.E., Williams P.J. Measurement of extrusion effects by viscosity profile using the rapid viscoanalyser. Cereal Foods World 1997; 42(6): 469-475.
[12] Andersen O., Andersen V. U. As Fruteiras Silvestres Brasileiras. Rio de Janeiro, Brazil: Globo; 1988. [13] Santos D.T., Meireles M.A.A. Jabuticaba as a source of functional pigments. Pharmacognosy Reviews 2009; 3(5): 127-132. [14] Pereira M.C.T., Salomão L.C.C., Mota W.F., Vieira G. Atributos físicos e químicos de frutos de oito clones de jabuticabeiras. Rev. Bras. de Frutic 2000; 22: 16-21.
[15] Oliveira A.L., Brunini M.A., Salandini C.A.R., Bazzo F.R. Caracterização tecnológica de jabuticabas Sabará provenientes de diferentes regiões de cultivo. Rev. Bras. Frutic 2003; 25: 397-400.
[16] Morton J. Fruits of Warm Climates. New York: Winterville; 1987. [17] Giacometti D., Lleras E. In: Bermejo, J. E. H., Leon, J., editors. Neglected Crops: 1492 from a different perspective, Rome:
FAO; 1994, p. 229-237.
[18] Einbond L.S., Reynertson K.A., Luo X.-D., Basile M.J., Kennelly E.J. Anthocyanin antioxidants from edible fruits. Food
Chemistry 2004; 84(1): 23-28.
[19] Trevisan L. V., Bobbio P. A., Bobbio F. O. Anthocyanins organic acids and carbohydrats of Mirciaria jabuticaba, Berg.
Journal of Food Science 1972; 37(6): 818–819.
1678
Rodrigo N. Cavalcanti et al. / Procedia F o od Science 1 (2011) 1672 – 1678
[20] Zanatta C. F., Cuevas E., Bobbio F. O., Winterhalter P., Mercadante A. Determination of anthocyanins from camu-camu
(Myrciaria dubia) by HPLC-PDA, HPLC-MS, and NMR. Journal of Agricutural and Food Chemistry 2005; 53(24): 9531-9535.
[21] Lago E.S., Gomes E. & Silva R. Produção de geléia de jambolão (Syzygium cumini lamarck): processamento, parâmetros físico – químicos e avaliação sensorial. Ciênc. Tecnol. Aliment. 2006; 26(4): 847-852.
[22] Asquieri, E. R., Candido, M. A., Damiani, C., Assis, E. M. Fabricación de vino blanco y tinto de jabuticaba (Myrciaria jabuticaba Berg) utilizando la pulpa y la cáscara respectivamente. Alimentaria 2004; 355: 97-109.
[23] Luque De Castro, M. D., García-Ayuso, L. E. Soxhlet extraction of solid materials: an outdated technique with a promising innovative future. Analytica Chimica Acta 1998; 369: 1-10.
[24] Lopez-Sebastian S., Ramoas E., Ibanez E., Bueno J.M., Ballester L., Tabera J. Reglero G. Dearomatization of Antioxidant
Rosemary Extracts by Treatment with Supercritical Carbon Dioxide. Journal of Agricutural and Food Chemistry 1998; 46(1): 13- 19.
[25] Perrut, M. Supercritical fluid applicantions: industrial developments and economic issues. Industrial and Engineering