J.

of Supercritical Fluids 62 (2012) 8895

Contents lists available at SciVerse ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Pressurized liquid extraction of Orthosiphon stamineus oil: Experimental and modeling studies
Farzad Pouralinazar a , Mohd Aziz Che Yunus a , Gholamreza Zahedi b,
a b

Centre of Lipids Engineering Applied Research, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, UTM Skudai, 81310 Johor Bahru, Johor, Malaysia Process Systems Engineering Centre (PROSPECT), Faculty of Chemical Engineering, Universiti Teknologi Malaysia, UTM Skudai, 81310 Johor Bahru, Johor, Malaysia

a r t i c l e

i n f o

a b s t r a c t
Extraction of Orthosiphon stamineus oil has been the subject of current study. In this case rst based on BoxBehnken experimental design method, experimental work was carried out to nd the effect of temperature, extraction time and the number of extraction cycles on extraction yield. Seventeen different experimental data were obtained and response surface modeling (RSM) was employed to nd relation between extraction yield and process variables. A second order polynomial based on statistical analysis with 95% condence limits was found as the best estimator of extraction yields. In the next step of the study, articial neural network (ANN) as a soft computing method was applied to predict the oil yield. A multilayer perceptron (MLP) was used in this study. In order to implement an ANN, temperature, extraction time and the number of extraction cycles were selected as input variables and oil yield was considered as target variable. 70% of data were utilized for training and 30% of the remaining data were used for testing the best obtained network. The results illustrated that ANN method is more reliable than RSM method for extraction prediction and optimization. The optimum operating conditions were found at 100 C, 10 min and 2 cycles. 2011 Elsevier B.V. All rights reserved.

Article history: Received 12 April 2011 Received in revised form 13 December 2011 Accepted 13 December 2011 Keywords: Orthosiphon stamineus Response surface modeling Accelerated solvent extraction Articial neural networks

1. Introduction Orthosiphon stamineus (OS), Benth (Lamiaceae) or Cats Whisker is known as Misai kucing by the locals in Malaysia. This multipurpose herb can be found in South East Asia such as Malaysia, Indonesia, Thailand and Philippines. Traditionally this plant is used by the medicine practitioners for the treatment of joint inammation. Apart from that, OS is also used for the treatment of gout, arthritis, rheumatism and remedy for kidney stones. Commercially, OS is famous because of its slimming property. OS is known as Java Tea in the market for its safe and effective mild herbal diuretic that throws out excess uids, nitrogen substances and sodium chloride. Moreover, OS contains huge amount of potassium that replaces what may be lost from the body in the normal diuretic process [1]. A medicinal benet of OS has made it one of the well-known plants in the region; for instance, it has been used for the treatment of eruptive fever, epilepsy, gallstone, hepatitis, rheumatism, hypertension, syphilis and renal calculus [2]. OS contains several chemically active components such as terpenoids (diterpenes and triterpenes), polyphenols (lipophilic avonoids and phenolic acids), and sterols [3]. The therapeutic effect of OS is attributed to its polyphenols which lead to decrease of oxidative

Corresponding author. Fax: +60 7 5581463. E-mail addresses: grzahedi@cheme.utm.my, grzahedi@yahoo.com (G. Zahedi). 0896-8446/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.supu.2011.12.009

stress by avoiding the formation of lipid peroxidation products in biological systems [4]. Sinensetin, eupatorin, 30-hydroxy-5,6,7,40tetramethoxyavone, lipophilic avonoids, the phenolic acid and rosmarinic acid are dominant in OS leaves [2]. In the present study, isolation of OS oil is one of the objectives. There have been conventional methods for concentrating and isolating of constituents, but they have some drawbacks such as time consuming, laborious and low selectivity and extraction yields. Furthermore, they utilize the large amount of organic solvents. Therefore scientists tried to develop better techniques for lowering the demerits of conventional extraction methods; hence, systems such as solid phase microextraction (SPME), solvent free solid injection, supercritical uid extraction (SFE) and pressurized liquid extraction or accelerated solvent extraction (ASE) were introduced. At the present study SPME method is easy to implement but the purity of extraction is not high. SFE provides almost 100% pure samples but it is energy consuming because of high pressure and temperatures which are involved. ASE technique is an intermediate solution which was selected with ethanol as an environmental friendly solvent in this study [5]. Several studies have been conducted on extraction and isolation of bioactive compounds and antioxidants. The extraction of the carotenoid from micro algae Haematococcus pluvialis and Dunaliella salina using ethanol as a solvent was studied by Denery et al. [6] and Herrero et al. [5] demonstrated optimization of antioxidant from Spirulina platensis micro alga. In addition, their

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results showed the possibility of fast and easy isolation of natural antioxidants from natural sources such as micro algae [6]. Cho et al. optimized conditions for the extraction of secondary volatile metabolites in Angelicas roots by accelerated solvent extraction [7]. Akowuah et al. studied extraction of OS using soxhlet extraction. Since dynamic characteristics of extraction are quite complicated, experimental-based optimization is a methodology allowing better understanding of relationship between independent and dependant variables; in other words, the effect of independent variables on response or dependent variables can be understood easily. However, some investigators have mentioned that in case there are a large amount of experiments, it will become impractical to conduct all tests [8]. Therefore, response surface modeling (RSM) as an effective statistical tool can be used for investigating the inuences of various variables, affecting the responses [9]. The beauty of novel optimization techniques is that the interactions of variables affecting the dependent variables are considered accurately [10]. Similarly, Guo et al. stated that the methods of statistics are inuential and powerful [11]. Many parameters may affect the response; therefore, it is important to choose the best statistical model in order to minimize the number of experiments, as well as evaluating the effects of important variables and interactions among them in multivariable system, as stated by Bhunia and Ghangrekar [12]. Recently, modeling, optimization and process characterization have been conducted by statistical design of experiments in many processes [11,1318]. Another approach which will be employed for prediction of oil yield is articial neural networks (ANNs). In fact, ANN is able to make a non-linear mapping between input and output [19,20]. ANNs have been used for different kinds of processes such as fermentation [21], crossow microltration [22] drying trend of various food and agricultural vegetables such as carrot [23], tomato [24], ginseng [25], cassava and mango [26] and osmotic dehydration [27], but application of articial neural networks in simulation of accelerated solvent extraction process (in particular for OS) is a unique study that has not been investigated by other researchers. In spite of the fact that many studies have been conducted by experimental design technique and articial network (ANN) for various processes, but to the best of our knowledge there is no study on RSM of accelerated solvent extraction of OS and also on ANN modeling of accelerated solvent extraction of OS. 2. Materials and method 2.1. Sample preparation The leaves were collected in Bumbung Lima, Penang State, Malaysia from 30- to 45-day-old white-owered plants. Specimen was labeled, numbered and annotated with the date of collection and deposited at Chemical Engineering Pilot Plant, CEPP, Universiti Teknologi Malaysia. Figs. 1 and 2 depict OS in the form of white owers and pretreated form, respectively. Some samples must be mixed with drying or dispersing agent before being loaded into the cell. Pelletized diatomaceous earth (DE) is a drying agent and it is easier to work with than other drying agent like sodium sulfate (NA2 SO4 ). DE dries the sample quickly, provides a cleaner transfer of the mixture to the cell, and extracts well. There is a guideline that determines which drying agent is useful and based on the guideline 5 g sample to 1 g DE is introduced. Therefore, 5 g OS to 1 g DE was mixed and loaded into cell. 2.2. Accelerated solvent extraction To perform the extractions with an accelerated solvent extraction system, ASE 100, from Dionex Corporation (Sunnyvale, CA,

Fig. 1. Orthosiphon stamineus (Misai kucing).

USA) was used. Extractions were performed at three different extraction temperatures (80, 100 and 120 C), static times (5, 10 and 15 min) and number of extraction cycles (1, 2 and 3) according to the BoxBehnken design of experiment (which will be discussed in next section). In this study, ethanol was selected as a solvent based on its Generally Recognized as Safe (GRAS) statue [5] since ethanols boiling point is 78.4 C and analyte solubilities are increased by ASE at temperatures above the boiling point [34,35]. Temperature range was chosen between 80 and 120 C. Different static times between 5 and 15 min were chosen. In order to run the system and do our experiments, rst samples were prepared based on the ratio of 5 g OS and 1 g DE. At rst, 0.5 g DE was loaded at the bottom of the cell and then 5 g of OS and nally 0.5 g of DE was loaded at the top of the OS within the cell. Before placing the cell into the rig, all the operation conditions were arranged in accordance to BoxBehnken design of experiment (DOE); afterwards, 17 experiments were carried out so that the cell is loaded into system and nally the extract is poured in the collection cell. Next, the collection cell was removed and was placed in a rotary evaporator for a while in order to evaporate ethanol from the solution extract. Accordingly ethanol was separated and stored in a container and concentrated extract remains in it. Finally, extract was poured in a small container and it was placed in an oven with a xed temperature of 75 C to ensure that all ethanol is evaporated. Then the container was weighed and subtracted from the empty weight so that the real weight of extract was calculated. The obtained data are given in Table 1.

Fig. 2. Pretreated Orthosiphon stamineus (OS).

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Table 1 Experimental range and levels of independent variables. Variables Range and level Low level (1) Temperature ( C) Extraction time (min) Extraction cycle
a

Center level (0) 100 10 2

High level (+1) 120 15 3

Xi a 20 5 1

80 5 1

number of experiments is reduced. RSM constitutes an experimental methods category for the determination of a relationship between independent and dependant variables [30,31]. In RSM development, at the beginning, a rst order model was developed to nd a relationship between input and output variables. It was found that the model is not accurate and in this case a secondorder model was developed in the next attempt [30]. The second order model has the following form:
k k k 2 ii xi + i=1 i=1 j=1 k

Step change values.

Y =+ First, the cell was lled with sample; then, solvent was poured in it. The pressure of the system should reach 1500 psia (102.4 atm). Then temperature conditions were set according to the experimental design; thereafter, extraction was conducted when all system valves were closed. The cell was washed with extraction solvent and 60% of the cell volume was used to rinse it. N2 gas was used to discharge solvent from the cell and nally the system was depressurized. In order to avoid any extract carry-over between extractions, system was rinsed completely after each extraction. Rotavapor R-200 (Bchi Labortechnik AG, Flawil, Switzerland) was used for evaporation purpose. All the extracts one by one, were evaporated and were placed in an oven at a temperature of 75 C for 24 h. Dry extracts were weighed. Fig. 3 depicts schematic of Experimental rig (ASE100). 2.3. Experimental design In this study, for obtaining a relationship between the responses, i.e., oil recovery, and three process parameters (temperature, extraction time, and the number of extraction cycles), the BoxBehnken experimental design was employed [28]. Number of runs in BoxBehnken design is calculated in accordance with N = 2k*(k 1) + cp, where k is the number of independent variables and cp is the number of central point repeats [28,29]. BoxBehnken design based on RSM provides a design of experiments through which not only optimum conditions are achieved, but also the
i=1

i xi +

ij xi xj +

(1)

where Y is the process response or output (dependent variable), k is the representative of the number of independent variables; is called intercept term and j are indexes for independent variables; x1 , x2 , . . ., xk are the coded independent variables, i, ii, and ij are called linear, quadratic, and interaction effects, respectively, and is the random error, which shows discrepancies between observed and predicted values. The uncoded independent variables (X1 , X2 , . . ., Xk ) are coded in accordance with the transfer equation given below [9,3032]: xi = Xi X0 Xi (2)

where xi , Xi , X0 , and Xi are dimensionless coded value for the ith independent variable, uncoded value for the ith independent variable, uncoded value for the ith independent variable at the center point, and Xi is value of the step change, respectively. In order to nd the tted function, as well as contour and surface plots a Statistica 6 software was employed. 2.4. Statistical analysis In this study, each experiment repeated three times to observe the reproducibility. STATISTICA software package version 6.0 was used for regression and graphical analysis of obtained data [33]. Analysis of variance known as ANOVA was used in order to nd

Fig. 3. Schematic accelerated solvent extraction.

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statistical signicance in all analyses. Pareto chart was used in order to determine the inuence of independent variables on extraction yield. On the whole, results were assessed with various descriptive statistics such as, F value, degrees of freedom (df), determination 2 ), sum of coefcient (R2 ), adjusted determination coefcient (Ra squares (SS), mean sum of squares (MSS). F value is an important parameter to ensure that the function or model is selected appropriately. The F tabulated was obtained by nN (numerator = df) and nD (denominator = n df + 1) at the desired probability level (i.e., = 0.05 or 95% condence). 3. Articial neural network modeling 3.1. Overview of neural networks Neural network is a deductive model, including complex units, which are similar to the neurons of the body. The units are in the shape of linked loop structure, operating like axon and dendrites [36]. In other words ANN attempts to understand and model brain behavior. The back propagation in ANN is commonly used network especially in chemical engineering because of simplicity, compact design and exibility [37]. Multilayer perceptron (MLP) is famous neural network structure which is employed to categorize and estimate neural problems. A neural network consists of an input layer for receiving data from an external source, one or more hidden layers for processing and an output layer for displaying the output values (Fig. 4). In each layer there are neurons, which are connected to previous and next layers. A neuron has input, output, weight and bias and transfer function. In back propagation, rst feed forward is made and net parameters known as weight and bias are adjusted so that a particular input leads to a specic target value. The network is adjusted based on a comparison of the output and the target. This trend continues until the network output matches target [38]. In fact, input neurons receive the data values and pass them on rst hidden layer neurons; then the data are multiplied to weight factor and bias is added to the value; afterwards, result passes through a non-linear transformation function. A result from transformation part forms input for either next hidden layer or output layer. Finally, output values are checked with target and back propagation continues until the global error approaches a small, determined error. Component of output error from the nth neuron on the output layer nally is dened as the following function: em = dm cm (3)

Table 2 BoxBehnken design with coded/actual values and results. Run Coded level of variables x1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 1 1 0 0 1 1 0 1 0 0 1 0 1 1 0 0 0 x2 1 0 0 1 1 2 0 0 1 1 1 1 1 0 0 0 0 x3 0 1 0 1 0 1 0 1 1 1 1 1 0 1 0 0 0 Actual level of variables x1 80 120 100 100 80 80 100 120 100 100 120 100 120 80 100 100 100 x2 5 10 10 5 15 10 10 10 15 15 5 5 15 10 10 10 10 x3 2 1 2 1 2 3 2 3 3 1 2 3 2 1 2 2 2 Observed result Recovery (%) 7.129 10.800 22.800 11.000 10.601 12.600 22.040 13.060 17.604 11.550 13.010 14.690 10.324 9.0401 22.203 22.430 21.800

where i is an index representing the hidden layer, j is an index for input layer, vij are weights and aj is output from rst layer. Summation in this formula is started from 1 to L in which L represents L input layers m hidden layers. 3.2. Development of a neural network model In this study, a feed-forward neural network was used to represent non-linear relationships among variables [39]. In order to train ANN, the data were categorized into two parts: training data and test data. Training is a process in which ANN modies weights based on input data [4042]. Test is a procedure through which accuracy of the network is checked. 70% of data were utilized for training of the network and 30% were dedicated to test procedure [43]. Oil yield data resulted from ASE were used for ANN model development. The network was trained with well-known algorithms such as Conjugate gradient, Quasi-Newton and LevenbergMarquardt in MATLAB environment. tansig as a non-linear transfer function and purline as a linear transfer function were utilized in this study. Temperature, extraction time and the number of extraction cycles were employed as input variables where oil yield was considered as an output variable. 4. Results and discussion 4.1. Statistical model Results of BoxBehnken design with coded, uncoded variables and oil recovery is shown in Table 2. In this study, temperature in the quadratic form had the most dominant effect on the oil yield. The model equation representing the response (z) was expressed as function of temperature (x1 ), extraction time (x2 ), the number of extraction cycles the number of the number of extraction cycles (x3 ) for coded unit as the following: Z = 217.085 + 3.816x1 + 5.2703x2 + 17.26x3
2 2 2 0.0179x1 0.193x2 3.717x3 0.01625x1 x3

where dm is the desired output value and cm is the calculated value; moreover, the total squared error function E is dened by the following equation:
2 em

(dm cm ) .

(4)

Weights are adjusted to minimize the total error function [37]. As error reaches specied minimum limit the teaching process terminates. In this study, error function is Mean Square Error (MSE) instead of total error function, which can be shown by the following formula: Ej = 1 n
n

(Ci Cir )2 .
i=1

(5)

In this formula Cir is real output and Ci is an estimated output for j in the input [36]. In Fig. 4 input layer, hidden layer and output layer have been shown nicely. In order to nd output neuron j, the following formula is introduced for f:
l

0.01539x1 x2 + 0.118x2 x3

(7)

bj = f
i=1

vij aj

(6)

The obtained polynomial equation needs to be analyzed by analysis of variance (ANOVA). In other words, signicance of the model should be tested; therefore, ANOVA was carried out and the results are given in Table 3 [32].

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Fig. 4. Structure of a neural network.

Table 3 Analysis of variance (ANOVA) of the response surface model to predict the response. Factors (coded) Model X1 2 X1 X2 2 X2 X3 2 X3 X1 X2 X1 X3 X2 X3 Ea Total SS
a b c d e

SSb 423.7579 7.6245 216.0512 2.2578 98.1558 30.2642 58.1339 9.4556 0.4225 1.3924 4.8154 468.0075

dfc 9 1 1 1 1 1 1 1 1 1 7 16

MSSd 47.0842 7.6245 216.0512 2.2578 98.1558 30.2642 58.1339 9.4556 0.4225 1.3924 0.6879

F value, Fcal 68.4462 11.0834 314.0640 3.2821 142.6847 43.9937 84.5067 13.7452 0.6142 2.0241

Probability (p) > F 0.000000e 0.012605 0.000000e 0.112941 0.000007e 0.000295e 0.000037e 0.007580e 0.458913 0.197822

E is indicating the error. Sum of squares. Degrees of freedom. Mean sum of squares. p values <0.05 were considered to be signicant.

were formed based on the obtained statistical quadratic model. In this case one variable kept in constant state (center level) and then the surface and contour plots were generated. Figs. 7 and 6 represent the response surface and contour plots, respectively. They show the effect of temperature and the number of extraction cycles on the oil yield at the static time of 10 min. Pressure was equal to 1500 psia in all experiments. At low temperatures the oil yield increases with temperature; however, at higher temperatures the oil yield decreased with increment of temperature. The reason might be due to reduced selectivity of constituents at high temperature [7]. The number of extraction cycles has a dominant effect on the oil yield so that response increased with the rise of the number of extraction cycles. Figs. 8 and 9 illustrate the effect of temperature and static time on the oil yield at the xed effect of two the number of extraction cycles. Static time has a positive linear effect on the oil yield,

It is obvious from Table 3 that the obtained equation is quite tted. Higher Fishers F-test, which is a criteria for proving how tted the function is, shows better t of the model. Since Fcal > Ftab (68.4462 > 3.685), it can be concluded that with 95% condence level Eq. (7) is reliable. In this study R2 was found as 0.9897, indicating that only 1.03% difference was observed. In addition, the value of adjusted determi2 ) was found as 0.9764, meaning high reliability nation coefcient (Ra of statistical model [8,9,31]. Pareto chart is introduced (Fig. 5). The length of bars shows the standardized effects of independent factors and their interactions on the oil yield recovery [44]. The main reason that the factors such as X2 , X2 X3 , and X1 X3 remained inside the reference line in Fig. 5 is that they have least contribution in prediction of the oil yield. In order to understand the effect of variables on the response better, three-dimensional (3D) plots for the measured response

Fig. 5. Pareto chart showing the standardized effect of independent variables and their interaction on the oil yield extraction.

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Fig. 6. Effect of temperature and the number of extraction cycles on the oil yield (contour plot).

Fig. 9. Effect of temperature and the number of extraction cycles on the oil yield (response surface plot).

Fig. 7. Effect of the number of extraction cycles and temperature on the oil yield (response surface plot).

In Figs. 10 and 11, response surface and contour plots depict the effect of the number of extraction cycles and static time on the oil yield at the xed temperature of 100 C. There was not a signicant interaction between static time and the number of extraction cycles on the basis of Pareto charts. Increasing the temperature from 80 to 100 C at constant pressure of 1500 psi and constant static time of 10 min increased the amount of oil yield; however, increasing the temperature from 100 to 120 C reduced the amount of oil yield. In case of two constants, the number of extraction cycles and 1500 psia pressure, by increasing the temperature at low levels of static time, better oil yield was obtained; in contrast, low oil yield was obtained at high levels of static time. There is a signicant interaction between static time and temperature based on the Pareto chart. Temperature as a single and independent variable increases the ability of the solvent to solubilize the compounds and, reduce the viscosity of the liquid solvent which is allowing better penetration of the solvent into the solid matrix. High temperature (above 100 C) rst increases solubility and mass transfer, but may reduce selectivity. 100 C was found as the optimum temperature in this study. The use of the number of extraction cycles is to enter fresh solvent during the extraction process, helping to maintain good extraction equilibrium. Different cycles sometimes are applied in a method, so that ush volume is divided by the number of the cycles .The trend is in a way that when the rst step is complete, extract

Fig. 8. Effect of temperature and extraction time cycles on the oil yield (contour plot).

for most of the times; however, for long static times, the negative quadratic effect also becomes signicant. Eleven-minute static time was found as the optimum time needed for a maximum response. In this case, there was a signicant interaction between temperature and static time.

Fig. 10. Effect of the number of extraction cycles and static time on the oil yield (contour plot).

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Fig. 13. Comparison of different training algorithms.

Fig. 11. Effect of the number of extraction cycles and static time on the oil yield (response surface plot).

Quasi-Newton and LevenbergMarquardt were employed. Fig. 13 depicts the comparison between training algorithms. Using Matlab 2010 programming software, LevenbergMarquardt was found as the best training algorithms in this study. The optimum amount of oil yield, 22.29%, was found at 100 C, 10 min, and 2 cycles on the basis of second-order polynomial model, whereas this amount was found 22.80% by ANN. The results show that ANN model is more reliable than RSM. 5. Conclusion In this study obtained results form second-order polynomial model, BoxBehnken design, predicted the response variable of the oil yield to change in the process parameters for accelerated solvent extraction of O. stamineus within the experimental ranges. Quadratic temperature, static time and the number of extraction cycles affected the oil yield, respectively on the basis of Pareto chart. In addition, interactions between temperature and static time and the number of extraction cycles and static time had a signicant effect on the oil yield. The results of statistical model were compared with an ANN model. R2 of RSM was found as 0.9897; meanwhile, for this value for ANN, it was 0.9999 which shows that ANN is more reliable than RSM model for subcritical extraction modeling. The result, which indicates that ANN is more accurate than RSM is in agreement with our previous study [45]. Acknowledgments The authors thank the Department of Chemical Engineering of the Universiti Teknologi Malaysia, as well as Chemical Engineering Pilot Plant, CEPP, for the special support that made this research possible the nancial support of Universiti Teknologi Malaysia under grant no. 4D042 is gratefully acknowledged. References
[1] W. Sumaryono, P. Proksch, V. Wray, L. Witte, T. Hartmann, Qualitative and quantitative analysis of the phenolic constituents from Orthosiphon aristatus, Planta Medica 57 (1991) 176180. [2] G.A. Akowuah, Z. Ismail, I. Norhayati, A. Sadikun, The effects of different extraction solvents of varying polarities on polyphenols of Orthosiphon stamineus and evaluation of the free radical-scavenging activity, Food Chemistry 93 (2005) 311317. [3] Y. Tezuka, P. Stampoulis, A.H. Banskota, S. Awale, K.Q. Tran, I. Saiki, et al., Constituents of the Vietnamese medicinal plant-Orthosiphon stamineus, Chemical & Pharmaceutical Bulletin 48 (2000) 17111719. [4] P.C. Hollman, M.B. Katan, Dietary avonoids; intake health effects and bioavailability, Food Chemistry and Toxicology 37 (1999) 937942.

Fig. 12. MSE versus number of epochs for MLP.

is directed to the collection vial along with used solvent. After that, the second cycle starts and the procedure continues until all cycles are complete. More than one cycle is used for samples with a very high concentration of analyte, as well as samples with difcult to penetrate matrices. Static time plays an important role in complete extraction. The effect of static time should always be explored in conjunction with static cycles, in order to produce a complete extraction in the most efcient way possible. 4.2. ANN modeling Table 4 shows comparison of different network generalization capabilities. In order to estimate oil yield data, one network, namely MLP, was utilized. Fig. 12 depicts the error percentage for tested data. Different training algorithms such as Conjugate gradient and
Table 4 Comparison of different networks. Observed data LevenbergMarquardt Quasi-Newton Conjugate gradient 7.1290 7.1286 11.3778 8.2974 10.3240 10.3250 14.1032 20.2625 14.6900 14.6857 16.2320 11.1037 13.0100 13.0104 12.8394 13.5550

F. Pouralinazar et al. / J. of Supercritical Fluids 62 (2012) 8895 [5] M. Herrero, P.J. Martn-lvarez, F.J. Senorns, A. Cifuentes, E. Ibnez, Optimization of accelerated solvent extraction of antioxidants from Spirulina platensis microalga, Food Chemistry 93 (2005) 417423. [6] J.D. Denery, K. Dragull, C.S. Tang, Q.X. Li, Pressurized uid extraction of carotenoids from Haematococcus pluvialis and Dunaliella salina and kavalactones from Piper methysticum, Analytica Chimica Acta 501 (2004) 175181. [7] S.K. Cho, A.M. Abd ElAty, J.H. Choi, M.R. Kima, J.H. Shim, Optimized conditions for the extraction of secondary volatile metabolites in Angelica roots by accelerated solvent extraction, Journal of Pharmaceutical and Biomedical Analysis 44 (2007) 11541158. [8] H.L. Liu, Y.W. Lan, Y.C. Cheng, Optimal production of sulphuric acid by Thiobacillus thiooxidans using response surface methodology, Process Biochemistry 39 (2004) 19531961. [9] K. Adinarayana, P. Ellaiah, Response surface optimization of the critical medium components for the production of alkaline protease by a newly isolated Bacillus sp., Journal of Pharmacy and Pharmaceutical Sciences 5 (2002) 272278. [10] P.D. Haaland, Experimental Design in Biotechnology, Marcel Dekker, NY, 1989. [11] W.Q. Guo, N.Q. Ren, X.J. Wang, W.S. Xiang, J. Ding, Y. You, B.F. Liu, Optimization of culture conditions for hydrogen production by Ethanoligenens harbinense B49 using response surface methodology, Bioresource Technology 100 (2009) 11921196. [12] P. Bhunia, M.M. Ghangrekar, Statistical modeling and optimization of biomassgranulation and COD removal in UASB reactors treating low strength wastewaters, Bioresource Technology 99 (2008) 42294238. [13] J.T. Batalon, P.S. Madamba, Optimization of coir dust compaction using the response surface methodology approach, Journal of Agricultural Engineering Research 78 (2001) 167175. [14] M.Y. Can, E. Yildiz, Phosphate removal from water by y ash: factorial experimental design, Journal of Hazardous Materials B135 (2006) 165170. [15] N. Mallick, S. Gupta, B. Panda, R. Sen, Process optimization for poly(3hydroxybutyrate-co-3-hydroxyvalerate) co-polymer production by Nostoc muscorum, Biochemical Engineering Journal 37 (2007) 125130. [16] J. Ren, W.T. Lin, Y.J. Shen, J.F. Wang, X.C. Luo, M.Q. Xie, Optimization of fermentation media for nitrite oxidizing bacteria using sequential statistical design, Bioresource Technology 99 (2008) 79237927. [17] N. Aslan, I. Unal, Optimization of some parameters on agglomeration performance of Zonguldak bituminous coal by oil agglomeration, Fuel 88 (2009) 490496. [18] C. Yi, J. Shi, S.J. Xue, Y. Jiang, D. Li, Effects of supercritical uid extraction parameters on lycopene yield and antioxidant activity, Food Chemistry 113 (2009) 10881094. [19] D.E. Rumelhart, J.L. McClelland, R.J. Williams, Parallel Recognition in Modern Computers Processing: Explorations in the Microstructure of Cognition, vol. 1, MIT Press, Cambridge, MA, 1986 (Foundations). [20] F. Despagne, D.L. Massart, Neural networks in multivariate calibration, Analyst 123 (1998) 157R178R. [21] E. Latrille, G. Corrieu, J. Thibault, pH prediction and nal fermentation time determination in lactic acid batch fermentations, Computers & Chemical Engineering 17 (1993) 423428. [22] M. Dornier, M. Decloux, G. Trystram, A. Lebert, Dynamic modeling of crossow microltration using neural networks, Journal of Membrane Science 98 (1995) 263273. [23] S. Erenturk, K. Erenturk, Comparison of genetic algorithm and neural network approaches for the drying process of carrot, Journal of Food Engineering 78 (2007) 905912. [24] K. Movagharnejad, M. Nikzad, Modeling of tomato drying using articial neural network, Computers and Electronics in Agriculture 59 (2007) 7885.

95

[25] A.I. Martynenko, S.X. Yang, Biologically inspired neural computation for ginseng drying rate, Biosystem Engineering 95 (3) (2006) 385396. [26] J.A. Hernandez-Perez, M.A. Garcia-Alvarado, G. Trystram, B. Heyd, Neural networks for heat and mass transfer prediction during drying of cassava and mango, Innovative Food Science and Emerging Technologies 5 (2004) 5764. [27] I.C. Trelea, A.L. Raoult-Wack, G. Trystram, Application of neural network modelling for the control of dewatering and impregnation soaking process (osmotic dehydration), Food Science and Technology International 3 (1997) 459465. [28] G.E. Box, W.G. Hunter, J.S. Hunter, Statistics for Experimenters, Wiley, New York, 1978. [29] D.C. Montgomery, Design and Analysis of Experiments, John Wiley & Sons, New York, 2001. [30] E. Bayraktar, Response surface optimization of the separation of dl-tryptophan using an emulsion liquid membrane, Process Biochemistry 37 (2001) 169175. [31] M.Y. Can, Y. Kaya, O.F. Algur, Response surface optimization of the removal of nickel from aqueous solution by cone biomass of Pinus sylvestris, Bioresource Technology 97 (2006) 17611765. [32] R. Sen, T. Swaminathan, Response surface modeling and optimization to elucidate and analyze the effects of inoculum age and size on surfactin production, Biochemical Engineering Journal 21 (2004) 141148. [33] S.D. Kaan Yetilmezsoy, Response surface modeling of Pb(II) removal from aqueous solution by Pistacia vera L.: BoxBehnken experimental design, Journal of Hazardous Materials 171 (2009) 551562. [34] R. Draiscia, C. Marchiafava, L. Palleschi, P. Cammarata, S. Cavalli, Accelerated solvent extraction and liquid chromatographytandem mass spectrometry quantitation of corticosteroid residues in bovine liver, Journal of Chromatography B 7 (2001) 217223. [35] D. De Faveri, P. Torre, P. Perego, A. Converti, Statistical investigation on the effects of starting xylose concentration and oxygen mass owrate on xylitol production from rice straw hydrolyzate by response surface methodology, Journal of Food Engineering 65 (3) (2004) 383389. [36] G. Zahedi, Z. Karami, H. Yaghoobi, Prediction of hydrate formation temperature by both statistical models and articial neural network approaches, Energy Conversion and Management 50 (2009) 20522059. [37] M. Anitha, H. Singh, Articial neural network simulation of rare earths solvent extraction equilibrium data, Desalination 232 (2008) 5970. [38] H. Demuth, M. Beale, M. Hagan, Neural Network Toolbox Users Guide, The MathWorks Inc., 2010. [39] J.A. Lazzs, Estimation of solid vapor pressures of pure compounds at different temperatures using a multilayer network with particle swarm algorithm, Fluid Phase Equilibria 289 (2010) 176184. [40] J.A. Lazzs, Neural network based on quantum chemistry for predicting melting point of organic compounds, Chinese Journal of Chemical Physics 22 (2009) 1926. [41] J.A. Lazzs, rho-T-P prediction for ionic liquids using neural networks, Journal of the Taiwan Institute of Chemical Engineers 40 (2009) 213232. [42] J.A. Lazzs, Estimation of density as a function of temperature and pressure for imidazolium-based ionic liquids using a multilayer net with particle swarm optimization, International Journal of Thermophysics 30 (2009) 883910. [43] M. Kashaninejad, A.A. Dehghani, M. Kashiri, Modeling of wheat soaking using two articial neural networks (MLP and RBF), Journal of Food Engineering 91 (2009) 602607. [44] A.B. Solanki, J.R. Parikh, R.H. Parikh, Formulation and optimization of piroxicam proniosomes by 3-factor, 3-level BoxBehnken design, AAPS PharmSciTech 8 (2007) 4349. [45] G. Zahedi, A. Azarpour, Optimization of supercritical carbon dioxide extraction of Passiora seed oil, Journal of Supercritical Fluids 58 (1) (2011) 4048.