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Extraction of natural dye from Gardenia and chromaticity analysis according to chi parameter
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JIEC-2245; No. of Pages 7 Journal of Industrial and Engineering Chemistry xxx (2014) xxx–xxx
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Extraction of natural dye from Gardenia and chromaticity analysis according to chi parameter In Kwon Hong, Hyeon Jeon, Seung Bum Lee * Department of Chemical Engineering, Dankook University, Yongin-si 448-701, Gyeonggi-do, Republic of Korea
A R T I C L E I N F O
Article history: Received 11 April 2014 Received in revised form 29 September 2014 Accepted 3 October 2014 Available online xxx Keywords: Chromaticity Crocin Solubility parameter Chi parameter UV absorbance
A B S T R A C T
Various methods of extracting natural dyes have been studied because of the increase of eco-friendly, non-toxic natural dyes. In this study, the natural dyes extraction process was optimized using Gardenia jasminoides Ellis containing crocin. Hansen solubility parameter values and chi parameter values ðx12 Þ of various organic solvents and crocin were calculated, and the extracted pigments were analyzed by experiments. Comparing to calculated values and analyzed values, the relevancy was found and the solvents yielding color close to the target color were selected. Four kinds of solvents (methanol, ethanol, 1-propanol, and 2-propanol) having color close to the target color were selected because their x12 values were small and their Hansen solubility parameter values were similar to the Hansen solubility parameter value of crocin. These selected solvents were each mixed with distilled water at various volume ratios, and the extraction process was conducted. The results showed that L; a; b values closest to the target color were obtained when using 40–60 vol% of the solvents. Also, trends of x12 values and the color difference ðDE Þ values were well matched up with UV absorbance. ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
Introduction For ages, natural dyes extracted from plants, animals, and minerals have been used to dye clothing, but their use gradually dwindled with the development of synthetic pigments [1– 3]. However, most synthetic pigments have the toxic substances and carcinogenic ingredients, that can lead to various illnesses, such as atopic dermatitis. Due to the hazards of these synthetic pigments, the use of natural dyes, which are eco-friendly, offering a variety of colors, is gradually increasing [4–6]. Many researches about natural dyes from a variety of plants are being conducted even lichen that people commonly think useless [7–9]. Natural dyes maintain an ecological balance and do not pollute the environment during their production and use. Moreover, it can be used for food, cosmetics, clothing etc., because of their high biodegradability, low toxicity, and low allergy compared to synthesis pigments [10,11]. Natural dyes are organic compounds with a hydroxyl group attached to their nucleus, and most are water-soluble. Gardenia jasminoides Ellis is an evergreen shrub that is grown in temperate regions, belonging to Rubiaceae, and has
* Corresponding author. Tel.: +82 31 8005 3559; fax: +82 31 8005 3536. E-mail address: [email protected] (S.B. Lee).
been used as traditional medicine because of its homeostatic, antiinflammatory, analgesic, and antipyretic properties [12–14]. Its oval fruit becomes well ripe red in late autumn. The extract from the fruit, which can show yellow, red, and blue colors, are widely used as natural pigment [15]. Crocin, which is the yellow pigment, is used in many fields as substitute for synthetic pigments, because it is non-toxic and chemically stable [16,17]. Especially, crocin’s pharmacological effects, such as the prevention of cardiovascular diseases [18,19], inhibition of tumor cells proliferation [20], and protection of neural stem cells [21,22], and protection of interstitial cells [23], have been reported [24]. The solubility parameter represents the quantitative degree of affinity between a solute and a solvent, so it is used as an indicator of solubility. It includes the dispersion solubility parameter, polar solubility parameters, and hydrogen bonding solubility parameter. Solvents having similar solubility parameter values can be well mixed. The Flory-Huggins chi parameter ðxÞ has been used for several years to characterize the behavior of a polymer solution. However, in the present study, the chi parameter ðx12 Þ derived from the New Flory theory is used instead of x. The widely-used Hansen solubility parameter and chi parameter ðx12 Þ are directly related to each other, so the chi parameter ðx12 Þ can be estimated if the Hansen solubility parameter value is known. In this study, the solubility parameter
http://dx.doi.org/10.1016/j.jiec.2014.10.004 1226-086X/ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
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of crocin, which is the extracted yellow dye from the gardenia fruit, was calculated, and the chromaticity analysis of dyes extracted from solvents of various chi parameter values ðx12 Þ were conducted. In addition, the optimum solvent condition was determined to extract the target color dye.
Experimental Materials The organic solvents used in the experiments including distilled water are diethyl ether (99.0%), n-butyl acetate (99.5%), ethylbenzene (99.8%), m-xylene (99.0%), o-xylene (98.5%), toluene (99.5%), ethyl acetate (99.5%), methyl acetate (93.0%), acetone (99.7%), 1butanol (99.5%), 2-propanol (99.0%), 1-propanol (99.5%), ethanol (99.9%), and methanol (99.8%). The gardenia fruits needed for the experiments were obtained by filtering bark and dirt using a sieve.
Fig. 1. Structure of crocin.
Results and discussion Extraction of crocin from Gardenia Calculation of solubility parameter The molar volume and the Hansen solubility parameter value of each solvent are listed in Table 1, and then total Hansen solubility parameter value and chi parameter value ðx12 Þ were calculated [25]. After a solvent of 200 ml and gardenia fruits of 1 g ground were stirred to extract pigment at room temperature (25 8C) for 1 h, the amount of extract was evaluated by using UV-Spectrophotometer (OPTIZEN 2120 UV, MECASYS), and after that the CIEL a b chromaticity analysis of the pigment was conducted. Then, the four solvents that gave the lower chi parameter values ðx12 Þ were chosen, and each were mixed with distilled water by various volume ratios. Finally, after the Hansen solubility parameter values and molar volumes of these mixtures were calculated, then, extraction and chromaticity analysis were conducted. Chromaticity analysis using CIEL a b color space The CIEL a b color space defined by the International Commission on Illumination in 1976 was used to quantify the results of this study. L represents the brightness, ranging in value from 0(black) to 100(white). þa is the red direction, a is the green direction, þb is the yellow direction, and b is the blue direction. Therefore, the center represents the achromatic color, and chroma increases when the point moves away from the center with increases of the aandb values [26]. A color difference meter (CT310, Konica Minolta) was used to obtain the L; a; andb values, and the L; a; b coordinate was represented.
The solubility parameter is important in the selection of a solvent. If a solvent which has a solubility parameter value similar to that of the solute is selected, the solvent would have the thermodynamic property to better dissolve the solute. According to the Hansen Solubility Parameter model suggested by van Krevelen, total solubility parameter (d), which accounts for the dispersion effect, polar effect, and hydrogen bonding effect is represented as follows [27].
d2t ¼ d2d þ d2p þ d2h
(1) 2
2
2
In this equation, dd , d p , and dh are the solubility parameters representing the dispersion effect, polar effect, and hydrogen 2 2 2 bonding effect, respectively. dd , d p , and dh can be calculated quantitatively considering group contribution. The method of group contribution is a way to calculate the degrees of contribution of the various atomic groups in a molecular structure to the entire molecule. Dyes are basically classified by their structures. The structure of crocin is a kind of carotenoid [28]. Fig. 1 and Table 2 show the molecular structure of crocin and the solubility parameter value of its functional group, respectively [29]. The 1=2 solubility parameter value of crocin is 29:96 ðJ=cm3 Þ , as calculated by equation (1) and Table 2. Comparing this value and the solubility parameters values of the solvents calculated on Table 1, it is expected that the solubility of crocin was large for methanol, ethanol, 1-propanol, and 2-propanol.
Table 1 Hansen Solubility Parameters of Various Solvents. Solvent
V [cm3/mol]
dd [MPa1/2]
d p [MPa1/2]
dh [MPa1/2]
dt [MPa1/2]
Diethyl ether n-Butyl acetate Ethylbenzene m-Xylene o-Xylene Toluene Ethyl acetate Methyl acetate Acetone 1-Butanol 2-Propanol 1-Propanol Ethanol Methanol Water
104.8 132.5 123.1 123.5 121.2 106.8 98.5 79.7 74.0 91.5 76.8 75.2 58.5 40.7 18.0
14.5 15.8 17.8 16.5 17.8 18.0 15.8 15.5 15.5 16.0 15.8 16.0 15.8 15.1 15.6
2.9 3.7 0.6 7.2 1.0 1.4 5.3 7.2 10.4 5.7 6.1 6.8 8.8 12.3 16.0
5.1 6.3 1.4 2.4 3.1 2.0 7.2 7.6 7.0 15.8 16.4 17.4 19.4 22.3 42.3
15.8 17.4 17.8 18.2 18.0 18.2 18.1 18.7 20.0 23.1 23.5 24.5 26.5 29.6 47.8
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Table 2 Hansen Solubility Parameters of Crocin’s Group Contributions and Molar Volumes at 25.
Structural group
DV [cm3/mol]
DV d2d [cal/mol]
DV d2p [cal/mol]
DV d2h [cal/mol]
DV d2d þ d2p þ d2h [cal/mol]
CH3 –OH– –O– –COO– –CH< >C5 5 –CH5 5 CH2<
33.5 10 3.8 18 1 5.5 13.5 16.1
1125 1770 0 – 820 800 875 1180 62,350
0 700 500 3111.11 0 60 18 0 19,442.22
0 4650 450 1250 0 180 180 0 72,820
1125 7120 950 4361.11 820 1040 1073 1180 17,669.11
Chromaticity analysis of pure solvents Since the Hansen solubility parameter theory constitutes a more comprehensive measure of the interaction than the Hildebrand method, a more precise prediction of solubility can be given by using Hansen solubility parameter instead of the Hildebrand method. Therefore, x12 is calculated by a corresponding Hansen solubility parameter term, A12 . 2
A12 ¼ ðdd2 dd1 Þ þ 0:25 d p2 d p1
2
2
þ 0:25ðdh2 dh2 Þ
(2)
The factor of 0.25 was mainly determined from empirical data, because its theoretical foundation was not well established. The chi parameter ðx12 Þ is estimated from the following equation [30]
x12 ¼
VA12 RT
(3)
d ¼ 33:06 and d2 are the solubility parameters of the solvent and solute, respectively. Fig. 2 shows the UV absorbance of respective solvents using UVspectrophotometer. Since the UV absorbance is proportional to the concentration of extracted crocin, so the amount of the extract of crocin could be evaluated according to the respective solvent. The gardenia has two wavelength sites, the maximum absorbance peak of genipin is at the wavelength of 238 nm, and that of crocin is at the wavelength of 410 nm. In Fig. 2, the peak of genipin appeared at 4
230–250 nm, and the peak of crocin appeared at 400–420 nm. Since the peaks of absorbance appeared between 400 and 420 nm, so the extracted solvents have same molecular structure of crocin. Therefore, the amount of extract was evaluated by calculating the average of absorbance. According to decreasing chi parameter ðx12 Þ of crocin and solvents, the absorbance increases as follows: diethylether (0.0550), ethylacetate (0.2694), 2-propnaol (0.4654), 1-propanol (0.7848), ethanol (1.7836), and methanol (2.5430). It suggests that the extracted amount of crocin increases with UV absorbance [31,32]. The chi parameter ðx12 Þ represents the interaction between the solvent and the solute. After calculating value of the chi parameter ðx12 Þ of each solvent, the values were sorted in descending order. The L; a; b values obtained by chromaticity analysis are shown on Table 3. The trend of chi parameters ðDE Þ in Table 3 match up with the UV absorbance in Fig. 2. The target color of crocin was set to L; a; b (97,17,93), and then the L; a; b values of the target color and the L; a; b values of dyes extracted from the mixtures of the top four pure solvents and distilled water so that in which the ratio the color difference ðDE Þ is the lowest. Through the L; a; b values analyzed and the L; a; b values of target color, DL ; Da ; Db were calculated, and the color difference ðDE Þ was obtained by using these values [33]. Red Green : Da ¼ a2 a1
(4)
Yellow Blue : Db ¼ b2 b1
(5)
Brightness : DL ¼ L2 L1
(6)
1 /2 Color difference : DE ¼ DL2 þ Da2 þ Db
(7)
Diethylether (χ12=5.62) Ethyl acetate (χ12=3.75) 2-Propanol (χ12=2.40) 1-Propanol (χ12=2.26)
3
Absorbance
Ethanol (χ12=1.91) Methanol (χ12=1.74)
2
1
0 200
300
400
500
600
Wavelength [nm] Fig. 2. UV-spectrum of extracted crocin using pure solvents.
700
Entering these values in photoshop color picker, we found that a lower value of the chi parameter ðx12 Þ for the solvents yielded color closer to the target color excluding the distilled water. Therefore, the color differences ðDE Þ of methanol ðx12 ¼ 1:74Þ, ethanol ðx12 ¼ 1:91Þ, 1-propanol ðx12 ¼ 2:26Þ, and 2-propanol ðx12 ¼ 2:40Þ were calculated in order of methanol (20.25), ethanol (660.52), 1-propanol (1793.28), and 2-propanol (2887.38), so these solvents would be appropriate for the extraction of the crocin dye. This is because the polar molecule crocin dissolves well in the solvents because alcohol is a polar solvent. In addition, although the value of the Hansen solubility parameter of distilled water is larger than that of the Hansen solubility parameter of crocin, and the chi parameter ðx12 Þ of distilled water is also larger than that of crocin, the color of distilled water is closer to the target color. This is because the crocin dissolved well in water molecule of large polarity.
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Table 3 CIE chromaticity analysis according to chi parameter and L, a, b values.
χ12
L
a
Diethyl ether
5.62
96.13
-1.01
3.38
n-Butyl acetate
5.40
96.41
-1.87
5.58
Ethylbenzene
5.31
96.61
-0.59
2.59
m -Xylene
5.29
96.62
-0.28
1.68
o-Xylene
4.62
96.52
-0.36
1.94
Toluene
4.20
97.24
0.00
1.31
Ethyl acetate
3.75
96.20
-6.73
16.67
Methyl acetate
3.11
96.04
-5.76
14.40
Acetone
3.00
96.12
-6.92
17.52
1-Butanol
2.74
97.95
-12.38
33.97
2-Propanol
2.40
98.21
-6.99
17.68
1-Propanol
2.26
97.97
-12.36
33.30
Ethanol
1.91
97.27
-18.35
56.68
Methanol
1.74
95.77
-21.46
88.63
Water
2.02
95.63
-16.33
63.10
Solvent
b
color
Table 4 Hansen solubility parameters of aqueous solution according to volume percent. Solvent
vol%
dd [MPa1/2]
d p [MPa1/2]
dh [MPa1/2]
V [cm3/mol]
Methanol
100 80 60 40 20 0
15.1 15.2 15.3 15.4 15.5 15.6
12.3 13.04 13.78 14.52 15.26 16
22.3 26.3 30.3 34.3 38.3 42.3
40.7 36.16 31.62 27.08 22.54 18
Ethanol
100 80 60 40 20 0
15.8 15.76 15.72 15.68 15.64 15.6
8.8 10.24 11.68 13.12 14.56 16
19.4 23.98 28.56 33.14 37.72 42.3
58.5 50.4 42.3 34.2 26.1 18
1-Propanol
100 80 60 40 20 0
16 15.92 15.84 15.76 15.68 15.6
6.8 8.64 10.48 12.32 14.16 16
17.4 22.38 27.36 32.34 37.32 42.3
75.2 63.76 52.32 40.88 29.44 18
2-Propanol
100 80 60 40 20 0
15.8 15.76 15.72 15.68 15.64 15.6
6.1 8.08 10.06 12.04 14.02 16
16.4 21.58 26.76 31.94 37.12 42.3
76.8 65.04 53.28 41.52 29.76 18
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Chromaticity analysis of mixed solvents The composition value used in calculating the values of the solubility parameter of the solvent mixtures is the volume fraction ð’Þ of each component. For a binary mixture, the equation using all four solubility parameters is given by Eq. (8). This equation is correct for more than two components, whose the Hansen solubility parameter values are known. Additionally, it is useful for both solvents and solids, and for azeotropes, near azeotropes, or nonazeotropic blends.
dblend ¼ ’comp1 dcomp1 þ ’comp2 dcomp2
(8)
volumes, as given in Table 4.Fig. 3 shows the absorbance of the dyes extracted by using the mixture of water and 4 pure solvents having the highest absorbance at respective volume ratios. As a result, the highest absorbance is showed at 40 vol% 2-propanol (2.5428), 40 vol% 1-propanol (2.5476), 40 vol% ethanol (2.9770), and 60 vol% methanol (2.8900).Chromaticity analysis value of each mixed solvent and the L; a; b values using CIEL a b color space are provided in on Table 5. More distilled water ðx12 ¼ 2:02Þ was mixed with methanol ðx12 ¼ 1:74Þ; color difference ðDE Þ was closer to the target color in order of 80 vol% methanol (19.22), and 60 vol% methanol (15.34); and color difference ðDE Þ increased in the order of 40 vol% methanol (165.94), and 20 vol% methanol (534.60). Compared to pure methanol ðDE ¼ 20:25Þ, the color differences ðDE Þ of 60–80 vol% methanol were low, so crocin was extracted well. At this time, the total solubility parameters of the mixed solvents, which were 80 vol% methanol ðd ¼ 33:06Þ and 60 vol% methanol ðd ¼ 36:63Þ, increased with additions of distilled water. In the case of ethanol ðx12 ¼ 1:91Þ, color differences ðDE Þ
3.0
3.0
2.5
2.5
2.0
2.0
Absorbance
Absorbance
Traditionally, without specific data, it is normally assumed that there is no volume change upon mixing of solvents [30]. After mixing the distilled water with each of the four solvents having a low value of chi parameter ðx12 Þ in various volume ratios, we calculated the Hansen solubility parameter values and the molar
80 vol% 60 vol% 40 vol% 20 vol%
1.5
1.0
1.5
80 vol% 60 vol% 40 vol% 20 vol%
1.0
0.5
0.0 350
0.5
375
400
425
450
0.0 350
475
375
3.0
3.0
2.5
2.5
2.0
2.0
1.5
80 vol% 60 vol% 40 vol% 20 vol%
1.0
400
425
450
475
Wavelength [nm]
Absorbance
Absorbance
Wavelength [nm]
1.5
80 vol% 60 vol% 40 vol% 20 vol%
1.0
0.5
0.0 350
5
0.5
375
400
425
Wavelength [nm]
450
475
0.0 350
375
400
425
450
475
Wavelength [nm]
Fig. 3. UV-spectrums of extracted crocin with mixing ratio in aqueous solution.
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Table 5 Chi parameter and CIE chromaticity analysis of aqueous solution.
Solvent
Methanol
Ethanol
1-Propanol
2-Propanol
vol %
L
a
b
∆ E+
10 0
95.77
-21.46
88.63
20.25
80
95.58
-20.86
88.36
19.22
60
94.30
-19.58
97.09
15.34
40
95.52
-19.06
74.96
165.94
20
95.59
-16.27
60.34
534.60
0
95.63
-16.33
63.10
448.17
100
97.27
-18.35
56.68
660.52
80
95.71
-20.60
80.38
86.94
60
94.45
-20.25
94.70
9.98
40
94.97
-19.98
91.05
8.40
20
94.13
-18.01
80.14
87.32
0
95.63
-16.33
63.10
448.17
100
97.97
-12.36
33.30
1793.28
80
95.01
-20.95
86.94
28.14
60
95.38
-20.50
80.65
83.70
40
93.37
-20.36
88.82
20.97
20
96.79
-18.36
64.03
420.58
0
95.63
-16.33
63.10
448.17
100
98.21
-6.99
17.68
2887.38
80
95.98
-20 .61
78.13
117.59
60
95.61
-20.92
94.84
10.34
40
95.36
-20.58
95.17
10.11
20
93.02
-17.08
89.57
13.81
0
95.63
-16.33
63.10
448.17
decreased and then increased according to the addition of distilled water as follows: 80 vol% ethanol (86.94), 60 vol% ethanol (9.98), 40 vol% ethanol (8.40), and 20 vol% ethanol (87.32). However, these values were lower than those of pure ethanol ðDE ¼ 66GG0:52Þ and distilled water ðDE ¼ 448:17Þ, indicating the good extraction of crocin. The total solubility parameters of the mixed solvents were represented 80 vol% ethanol ðd ¼ 30:47Þ, 60 vol% ethanol ðd ¼ 34:63Þ, and 40 vol% ethanol ðd ¼ 38:94Þ. In the case of 1-propanol ðx12 ¼ 2:26Þ, color differences ðDE Þ were 80 vol% 1propanol (28.14), 60 vol% 1-propanol (83.70), 40 vol% 1-propanol (20.97), and 20 vol% 1-propanol (420.58) according to the addition
Color
of distilled water, and in the case of 2-propanol ðx12 ¼ 2:40Þ, color differences ðDE Þ were 80 vol% 2-propanol (117.59), 60 vol% 2propanol (10.34), 40 vol% 2-propanol (10.11), and 20 vol% 2propanol (13.81). These values were very low compared to those of pure 1-propanol ðDE ¼ 1793:28Þ and pure 2-propanol (ðDE ¼ 2887:38Þ). Overall, colors of the mixed solvents were the closest to the target color at 60 vol% methanol, 40–60 vol% ethanol, 40 vol% 1-propanol, and 40–60 vol% 2-propanol, and the color differences ðDE Þ were low at these points. It suggests that the trends of the color differences ðDE Þ in Table 5 match up with the results in Fig. 3. The UV absorbance was increased as the color
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difference ðDE Þ was decreased in all solvents. Moreover, L, which represents the brightness, and a, which represents red-green color, were similar according to the mixing ratio of distilled water, but b, which represents yellow-blue color, changed significantly. Therefore, the color difference ðDE Þ was most affected by b. Conclusion In this study, the target color (L ¼ 97, a ¼ 17, b ¼ 93) was set using the yellow dyes of G. jasminoides Ellis, and dye extraction process, UV-spectrum and chromaticity analysis were conducted according to the chi parameter ðx12 Þ by using 15 kinds of solvents. The selected solvents, which showed colors close to the target color, were each mixed with distilled water at various volume ratios to investigate the condition that would yield color closest to the target color. As a result of the first investigation, four kinds of solvents (methanol, ethanol, 1-propanol, 2-propanol), whose Hansen solubility parameters were similar to crocin’s and whose chi parameter ðx12 Þ values were low, were selected to obtain dyes whose color had high absorbance and were as close to the target color as possible. Then, the selected four kinds of solvents were mixed with distilled water at various volume ratios. L; a; andb values close to those of the target color were obtained when the pure solvent ratio was 40–60 vol%. Based on the result of the chromaticity analysis, L, which represents the brightness and a, which represents red-green, were similar, but b, which represents yellow-blue, changed significantly. Therefore, it was concluded that the color difference ðDE Þ was most affected by b. When using pure solvents, DE of methanol was the least closest to the target color, but 60 vol% methanol, 40–60 vol% ethanol, 40 vol% 1propanol, and 40–60 vol% 2-propanol were close to the target color in a binary system. In conclusion, natural yellow dyes can be extracted by using a mixture of alcohol and distilled water. The UV absorbance was increased with decreasing chi parameter ðx12 Þ in pure solvents and the color differences ðDE Þ in mixed solvents. Acknowledgement The present research was conducted by the research fund of Dankook University in 2014.
7
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Extraction of natural dye from Gardenia and chromaticity analysis according to chi parameter In Kwon Hong, Hyeon Jeon, Seung Bum Lee * Department of Chemical Engineering, Dankook University, Yongin-si 448-701, Gyeonggi-do, Republic of Korea
A R T I C L E I N F O
Article history: Received 11 April 2014 Received in revised form 29 September 2014 Accepted 3 October 2014 Available online xxx Keywords: Chromaticity Crocin Solubility parameter Chi parameter UV absorbance
A B S T R A C T
Various methods of extracting natural dyes have been studied because of the increase of eco-friendly, non-toxic natural dyes. In this study, the natural dyes extraction process was optimized using Gardenia jasminoides Ellis containing crocin. Hansen solubility parameter values and chi parameter values ðx12 Þ of various organic solvents and crocin were calculated, and the extracted pigments were analyzed by experiments. Comparing to calculated values and analyzed values, the relevancy was found and the solvents yielding color close to the target color were selected. Four kinds of solvents (methanol, ethanol, 1-propanol, and 2-propanol) having color close to the target color were selected because their x12 values were small and their Hansen solubility parameter values were similar to the Hansen solubility parameter value of crocin. These selected solvents were each mixed with distilled water at various volume ratios, and the extraction process was conducted. The results showed that L; a; b values closest to the target color were obtained when using 40–60 vol% of the solvents. Also, trends of x12 values and the color difference ðDE Þ values were well matched up with UV absorbance. ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
Introduction For ages, natural dyes extracted from plants, animals, and minerals have been used to dye clothing, but their use gradually dwindled with the development of synthetic pigments [1– 3]. However, most synthetic pigments have the toxic substances and carcinogenic ingredients, that can lead to various illnesses, such as atopic dermatitis. Due to the hazards of these synthetic pigments, the use of natural dyes, which are eco-friendly, offering a variety of colors, is gradually increasing [4–6]. Many researches about natural dyes from a variety of plants are being conducted even lichen that people commonly think useless [7–9]. Natural dyes maintain an ecological balance and do not pollute the environment during their production and use. Moreover, it can be used for food, cosmetics, clothing etc., because of their high biodegradability, low toxicity, and low allergy compared to synthesis pigments [10,11]. Natural dyes are organic compounds with a hydroxyl group attached to their nucleus, and most are water-soluble. Gardenia jasminoides Ellis is an evergreen shrub that is grown in temperate regions, belonging to Rubiaceae, and has
* Corresponding author. Tel.: +82 31 8005 3559; fax: +82 31 8005 3536. E-mail address: [email protected] (S.B. Lee).
been used as traditional medicine because of its homeostatic, antiinflammatory, analgesic, and antipyretic properties [12–14]. Its oval fruit becomes well ripe red in late autumn. The extract from the fruit, which can show yellow, red, and blue colors, are widely used as natural pigment [15]. Crocin, which is the yellow pigment, is used in many fields as substitute for synthetic pigments, because it is non-toxic and chemically stable [16,17]. Especially, crocin’s pharmacological effects, such as the prevention of cardiovascular diseases [18,19], inhibition of tumor cells proliferation [20], and protection of neural stem cells [21,22], and protection of interstitial cells [23], have been reported [24]. The solubility parameter represents the quantitative degree of affinity between a solute and a solvent, so it is used as an indicator of solubility. It includes the dispersion solubility parameter, polar solubility parameters, and hydrogen bonding solubility parameter. Solvents having similar solubility parameter values can be well mixed. The Flory-Huggins chi parameter ðxÞ has been used for several years to characterize the behavior of a polymer solution. However, in the present study, the chi parameter ðx12 Þ derived from the New Flory theory is used instead of x. The widely-used Hansen solubility parameter and chi parameter ðx12 Þ are directly related to each other, so the chi parameter ðx12 Þ can be estimated if the Hansen solubility parameter value is known. In this study, the solubility parameter
http://dx.doi.org/10.1016/j.jiec.2014.10.004 1226-086X/ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
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of crocin, which is the extracted yellow dye from the gardenia fruit, was calculated, and the chromaticity analysis of dyes extracted from solvents of various chi parameter values ðx12 Þ were conducted. In addition, the optimum solvent condition was determined to extract the target color dye.
Experimental Materials The organic solvents used in the experiments including distilled water are diethyl ether (99.0%), n-butyl acetate (99.5%), ethylbenzene (99.8%), m-xylene (99.0%), o-xylene (98.5%), toluene (99.5%), ethyl acetate (99.5%), methyl acetate (93.0%), acetone (99.7%), 1butanol (99.5%), 2-propanol (99.0%), 1-propanol (99.5%), ethanol (99.9%), and methanol (99.8%). The gardenia fruits needed for the experiments were obtained by filtering bark and dirt using a sieve.
Fig. 1. Structure of crocin.
Results and discussion Extraction of crocin from Gardenia Calculation of solubility parameter The molar volume and the Hansen solubility parameter value of each solvent are listed in Table 1, and then total Hansen solubility parameter value and chi parameter value ðx12 Þ were calculated [25]. After a solvent of 200 ml and gardenia fruits of 1 g ground were stirred to extract pigment at room temperature (25 8C) for 1 h, the amount of extract was evaluated by using UV-Spectrophotometer (OPTIZEN 2120 UV, MECASYS), and after that the CIEL a b chromaticity analysis of the pigment was conducted. Then, the four solvents that gave the lower chi parameter values ðx12 Þ were chosen, and each were mixed with distilled water by various volume ratios. Finally, after the Hansen solubility parameter values and molar volumes of these mixtures were calculated, then, extraction and chromaticity analysis were conducted. Chromaticity analysis using CIEL a b color space The CIEL a b color space defined by the International Commission on Illumination in 1976 was used to quantify the results of this study. L represents the brightness, ranging in value from 0(black) to 100(white). þa is the red direction, a is the green direction, þb is the yellow direction, and b is the blue direction. Therefore, the center represents the achromatic color, and chroma increases when the point moves away from the center with increases of the aandb values [26]. A color difference meter (CT310, Konica Minolta) was used to obtain the L; a; andb values, and the L; a; b coordinate was represented.
The solubility parameter is important in the selection of a solvent. If a solvent which has a solubility parameter value similar to that of the solute is selected, the solvent would have the thermodynamic property to better dissolve the solute. According to the Hansen Solubility Parameter model suggested by van Krevelen, total solubility parameter (d), which accounts for the dispersion effect, polar effect, and hydrogen bonding effect is represented as follows [27].
d2t ¼ d2d þ d2p þ d2h
(1) 2
2
2
In this equation, dd , d p , and dh are the solubility parameters representing the dispersion effect, polar effect, and hydrogen 2 2 2 bonding effect, respectively. dd , d p , and dh can be calculated quantitatively considering group contribution. The method of group contribution is a way to calculate the degrees of contribution of the various atomic groups in a molecular structure to the entire molecule. Dyes are basically classified by their structures. The structure of crocin is a kind of carotenoid [28]. Fig. 1 and Table 2 show the molecular structure of crocin and the solubility parameter value of its functional group, respectively [29]. The 1=2 solubility parameter value of crocin is 29:96 ðJ=cm3 Þ , as calculated by equation (1) and Table 2. Comparing this value and the solubility parameters values of the solvents calculated on Table 1, it is expected that the solubility of crocin was large for methanol, ethanol, 1-propanol, and 2-propanol.
Table 1 Hansen Solubility Parameters of Various Solvents. Solvent
V [cm3/mol]
dd [MPa1/2]
d p [MPa1/2]
dh [MPa1/2]
dt [MPa1/2]
Diethyl ether n-Butyl acetate Ethylbenzene m-Xylene o-Xylene Toluene Ethyl acetate Methyl acetate Acetone 1-Butanol 2-Propanol 1-Propanol Ethanol Methanol Water
104.8 132.5 123.1 123.5 121.2 106.8 98.5 79.7 74.0 91.5 76.8 75.2 58.5 40.7 18.0
14.5 15.8 17.8 16.5 17.8 18.0 15.8 15.5 15.5 16.0 15.8 16.0 15.8 15.1 15.6
2.9 3.7 0.6 7.2 1.0 1.4 5.3 7.2 10.4 5.7 6.1 6.8 8.8 12.3 16.0
5.1 6.3 1.4 2.4 3.1 2.0 7.2 7.6 7.0 15.8 16.4 17.4 19.4 22.3 42.3
15.8 17.4 17.8 18.2 18.0 18.2 18.1 18.7 20.0 23.1 23.5 24.5 26.5 29.6 47.8
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Table 2 Hansen Solubility Parameters of Crocin’s Group Contributions and Molar Volumes at 25.
Structural group
DV [cm3/mol]
DV d2d [cal/mol]
DV d2p [cal/mol]
DV d2h [cal/mol]
DV d2d þ d2p þ d2h [cal/mol]
CH3 –OH– –O– –COO– –CH< >C5 5 –CH5 5 CH2<
33.5 10 3.8 18 1 5.5 13.5 16.1
1125 1770 0 – 820 800 875 1180 62,350
0 700 500 3111.11 0 60 18 0 19,442.22
0 4650 450 1250 0 180 180 0 72,820
1125 7120 950 4361.11 820 1040 1073 1180 17,669.11
Chromaticity analysis of pure solvents Since the Hansen solubility parameter theory constitutes a more comprehensive measure of the interaction than the Hildebrand method, a more precise prediction of solubility can be given by using Hansen solubility parameter instead of the Hildebrand method. Therefore, x12 is calculated by a corresponding Hansen solubility parameter term, A12 . 2
A12 ¼ ðdd2 dd1 Þ þ 0:25 d p2 d p1
2
2
þ 0:25ðdh2 dh2 Þ
(2)
The factor of 0.25 was mainly determined from empirical data, because its theoretical foundation was not well established. The chi parameter ðx12 Þ is estimated from the following equation [30]
x12 ¼
VA12 RT
(3)
d ¼ 33:06 and d2 are the solubility parameters of the solvent and solute, respectively. Fig. 2 shows the UV absorbance of respective solvents using UVspectrophotometer. Since the UV absorbance is proportional to the concentration of extracted crocin, so the amount of the extract of crocin could be evaluated according to the respective solvent. The gardenia has two wavelength sites, the maximum absorbance peak of genipin is at the wavelength of 238 nm, and that of crocin is at the wavelength of 410 nm. In Fig. 2, the peak of genipin appeared at 4
230–250 nm, and the peak of crocin appeared at 400–420 nm. Since the peaks of absorbance appeared between 400 and 420 nm, so the extracted solvents have same molecular structure of crocin. Therefore, the amount of extract was evaluated by calculating the average of absorbance. According to decreasing chi parameter ðx12 Þ of crocin and solvents, the absorbance increases as follows: diethylether (0.0550), ethylacetate (0.2694), 2-propnaol (0.4654), 1-propanol (0.7848), ethanol (1.7836), and methanol (2.5430). It suggests that the extracted amount of crocin increases with UV absorbance [31,32]. The chi parameter ðx12 Þ represents the interaction between the solvent and the solute. After calculating value of the chi parameter ðx12 Þ of each solvent, the values were sorted in descending order. The L; a; b values obtained by chromaticity analysis are shown on Table 3. The trend of chi parameters ðDE Þ in Table 3 match up with the UV absorbance in Fig. 2. The target color of crocin was set to L; a; b (97,17,93), and then the L; a; b values of the target color and the L; a; b values of dyes extracted from the mixtures of the top four pure solvents and distilled water so that in which the ratio the color difference ðDE Þ is the lowest. Through the L; a; b values analyzed and the L; a; b values of target color, DL ; Da ; Db were calculated, and the color difference ðDE Þ was obtained by using these values [33]. Red Green : Da ¼ a2 a1
(4)
Yellow Blue : Db ¼ b2 b1
(5)
Brightness : DL ¼ L2 L1
(6)
1 /2 Color difference : DE ¼ DL2 þ Da2 þ Db
(7)
Diethylether (χ12=5.62) Ethyl acetate (χ12=3.75) 2-Propanol (χ12=2.40) 1-Propanol (χ12=2.26)
3
Absorbance
Ethanol (χ12=1.91) Methanol (χ12=1.74)
2
1
0 200
300
400
500
600
Wavelength [nm] Fig. 2. UV-spectrum of extracted crocin using pure solvents.
700
Entering these values in photoshop color picker, we found that a lower value of the chi parameter ðx12 Þ for the solvents yielded color closer to the target color excluding the distilled water. Therefore, the color differences ðDE Þ of methanol ðx12 ¼ 1:74Þ, ethanol ðx12 ¼ 1:91Þ, 1-propanol ðx12 ¼ 2:26Þ, and 2-propanol ðx12 ¼ 2:40Þ were calculated in order of methanol (20.25), ethanol (660.52), 1-propanol (1793.28), and 2-propanol (2887.38), so these solvents would be appropriate for the extraction of the crocin dye. This is because the polar molecule crocin dissolves well in the solvents because alcohol is a polar solvent. In addition, although the value of the Hansen solubility parameter of distilled water is larger than that of the Hansen solubility parameter of crocin, and the chi parameter ðx12 Þ of distilled water is also larger than that of crocin, the color of distilled water is closer to the target color. This is because the crocin dissolved well in water molecule of large polarity.
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Table 3 CIE chromaticity analysis according to chi parameter and L, a, b values.
χ12
L
a
Diethyl ether
5.62
96.13
-1.01
3.38
n-Butyl acetate
5.40
96.41
-1.87
5.58
Ethylbenzene
5.31
96.61
-0.59
2.59
m -Xylene
5.29
96.62
-0.28
1.68
o-Xylene
4.62
96.52
-0.36
1.94
Toluene
4.20
97.24
0.00
1.31
Ethyl acetate
3.75
96.20
-6.73
16.67
Methyl acetate
3.11
96.04
-5.76
14.40
Acetone
3.00
96.12
-6.92
17.52
1-Butanol
2.74
97.95
-12.38
33.97
2-Propanol
2.40
98.21
-6.99
17.68
1-Propanol
2.26
97.97
-12.36
33.30
Ethanol
1.91
97.27
-18.35
56.68
Methanol
1.74
95.77
-21.46
88.63
Water
2.02
95.63
-16.33
63.10
Solvent
b
color
Table 4 Hansen solubility parameters of aqueous solution according to volume percent. Solvent
vol%
dd [MPa1/2]
d p [MPa1/2]
dh [MPa1/2]
V [cm3/mol]
Methanol
100 80 60 40 20 0
15.1 15.2 15.3 15.4 15.5 15.6
12.3 13.04 13.78 14.52 15.26 16
22.3 26.3 30.3 34.3 38.3 42.3
40.7 36.16 31.62 27.08 22.54 18
Ethanol
100 80 60 40 20 0
15.8 15.76 15.72 15.68 15.64 15.6
8.8 10.24 11.68 13.12 14.56 16
19.4 23.98 28.56 33.14 37.72 42.3
58.5 50.4 42.3 34.2 26.1 18
1-Propanol
100 80 60 40 20 0
16 15.92 15.84 15.76 15.68 15.6
6.8 8.64 10.48 12.32 14.16 16
17.4 22.38 27.36 32.34 37.32 42.3
75.2 63.76 52.32 40.88 29.44 18
2-Propanol
100 80 60 40 20 0
15.8 15.76 15.72 15.68 15.64 15.6
6.1 8.08 10.06 12.04 14.02 16
16.4 21.58 26.76 31.94 37.12 42.3
76.8 65.04 53.28 41.52 29.76 18
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Chromaticity analysis of mixed solvents The composition value used in calculating the values of the solubility parameter of the solvent mixtures is the volume fraction ð’Þ of each component. For a binary mixture, the equation using all four solubility parameters is given by Eq. (8). This equation is correct for more than two components, whose the Hansen solubility parameter values are known. Additionally, it is useful for both solvents and solids, and for azeotropes, near azeotropes, or nonazeotropic blends.
dblend ¼ ’comp1 dcomp1 þ ’comp2 dcomp2
(8)
volumes, as given in Table 4.Fig. 3 shows the absorbance of the dyes extracted by using the mixture of water and 4 pure solvents having the highest absorbance at respective volume ratios. As a result, the highest absorbance is showed at 40 vol% 2-propanol (2.5428), 40 vol% 1-propanol (2.5476), 40 vol% ethanol (2.9770), and 60 vol% methanol (2.8900).Chromaticity analysis value of each mixed solvent and the L; a; b values using CIEL a b color space are provided in on Table 5. More distilled water ðx12 ¼ 2:02Þ was mixed with methanol ðx12 ¼ 1:74Þ; color difference ðDE Þ was closer to the target color in order of 80 vol% methanol (19.22), and 60 vol% methanol (15.34); and color difference ðDE Þ increased in the order of 40 vol% methanol (165.94), and 20 vol% methanol (534.60). Compared to pure methanol ðDE ¼ 20:25Þ, the color differences ðDE Þ of 60–80 vol% methanol were low, so crocin was extracted well. At this time, the total solubility parameters of the mixed solvents, which were 80 vol% methanol ðd ¼ 33:06Þ and 60 vol% methanol ðd ¼ 36:63Þ, increased with additions of distilled water. In the case of ethanol ðx12 ¼ 1:91Þ, color differences ðDE Þ
3.0
3.0
2.5
2.5
2.0
2.0
Absorbance
Absorbance
Traditionally, without specific data, it is normally assumed that there is no volume change upon mixing of solvents [30]. After mixing the distilled water with each of the four solvents having a low value of chi parameter ðx12 Þ in various volume ratios, we calculated the Hansen solubility parameter values and the molar
80 vol% 60 vol% 40 vol% 20 vol%
1.5
1.0
1.5
80 vol% 60 vol% 40 vol% 20 vol%
1.0
0.5
0.0 350
0.5
375
400
425
450
0.0 350
475
375
3.0
3.0
2.5
2.5
2.0
2.0
1.5
80 vol% 60 vol% 40 vol% 20 vol%
1.0
400
425
450
475
Wavelength [nm]
Absorbance
Absorbance
Wavelength [nm]
1.5
80 vol% 60 vol% 40 vol% 20 vol%
1.0
0.5
0.0 350
5
0.5
375
400
425
Wavelength [nm]
450
475
0.0 350
375
400
425
450
475
Wavelength [nm]
Fig. 3. UV-spectrums of extracted crocin with mixing ratio in aqueous solution.
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Table 5 Chi parameter and CIE chromaticity analysis of aqueous solution.
Solvent
Methanol
Ethanol
1-Propanol
2-Propanol
vol %
L
a
b
∆ E+
10 0
95.77
-21.46
88.63
20.25
80
95.58
-20.86
88.36
19.22
60
94.30
-19.58
97.09
15.34
40
95.52
-19.06
74.96
165.94
20
95.59
-16.27
60.34
534.60
0
95.63
-16.33
63.10
448.17
100
97.27
-18.35
56.68
660.52
80
95.71
-20.60
80.38
86.94
60
94.45
-20.25
94.70
9.98
40
94.97
-19.98
91.05
8.40
20
94.13
-18.01
80.14
87.32
0
95.63
-16.33
63.10
448.17
100
97.97
-12.36
33.30
1793.28
80
95.01
-20.95
86.94
28.14
60
95.38
-20.50
80.65
83.70
40
93.37
-20.36
88.82
20.97
20
96.79
-18.36
64.03
420.58
0
95.63
-16.33
63.10
448.17
100
98.21
-6.99
17.68
2887.38
80
95.98
-20 .61
78.13
117.59
60
95.61
-20.92
94.84
10.34
40
95.36
-20.58
95.17
10.11
20
93.02
-17.08
89.57
13.81
0
95.63
-16.33
63.10
448.17
decreased and then increased according to the addition of distilled water as follows: 80 vol% ethanol (86.94), 60 vol% ethanol (9.98), 40 vol% ethanol (8.40), and 20 vol% ethanol (87.32). However, these values were lower than those of pure ethanol ðDE ¼ 66GG0:52Þ and distilled water ðDE ¼ 448:17Þ, indicating the good extraction of crocin. The total solubility parameters of the mixed solvents were represented 80 vol% ethanol ðd ¼ 30:47Þ, 60 vol% ethanol ðd ¼ 34:63Þ, and 40 vol% ethanol ðd ¼ 38:94Þ. In the case of 1-propanol ðx12 ¼ 2:26Þ, color differences ðDE Þ were 80 vol% 1propanol (28.14), 60 vol% 1-propanol (83.70), 40 vol% 1-propanol (20.97), and 20 vol% 1-propanol (420.58) according to the addition
Color
of distilled water, and in the case of 2-propanol ðx12 ¼ 2:40Þ, color differences ðDE Þ were 80 vol% 2-propanol (117.59), 60 vol% 2propanol (10.34), 40 vol% 2-propanol (10.11), and 20 vol% 2propanol (13.81). These values were very low compared to those of pure 1-propanol ðDE ¼ 1793:28Þ and pure 2-propanol (ðDE ¼ 2887:38Þ). Overall, colors of the mixed solvents were the closest to the target color at 60 vol% methanol, 40–60 vol% ethanol, 40 vol% 1-propanol, and 40–60 vol% 2-propanol, and the color differences ðDE Þ were low at these points. It suggests that the trends of the color differences ðDE Þ in Table 5 match up with the results in Fig. 3. The UV absorbance was increased as the color
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G Model
JIEC-2245; No. of Pages 7 I.K. Hong et al. / Journal of Industrial and Engineering Chemistry xxx (2014) xxx–xxx
difference ðDE Þ was decreased in all solvents. Moreover, L, which represents the brightness, and a, which represents red-green color, were similar according to the mixing ratio of distilled water, but b, which represents yellow-blue color, changed significantly. Therefore, the color difference ðDE Þ was most affected by b. Conclusion In this study, the target color (L ¼ 97, a ¼ 17, b ¼ 93) was set using the yellow dyes of G. jasminoides Ellis, and dye extraction process, UV-spectrum and chromaticity analysis were conducted according to the chi parameter ðx12 Þ by using 15 kinds of solvents. The selected solvents, which showed colors close to the target color, were each mixed with distilled water at various volume ratios to investigate the condition that would yield color closest to the target color. As a result of the first investigation, four kinds of solvents (methanol, ethanol, 1-propanol, 2-propanol), whose Hansen solubility parameters were similar to crocin’s and whose chi parameter ðx12 Þ values were low, were selected to obtain dyes whose color had high absorbance and were as close to the target color as possible. Then, the selected four kinds of solvents were mixed with distilled water at various volume ratios. L; a; andb values close to those of the target color were obtained when the pure solvent ratio was 40–60 vol%. Based on the result of the chromaticity analysis, L, which represents the brightness and a, which represents red-green, were similar, but b, which represents yellow-blue, changed significantly. Therefore, it was concluded that the color difference ðDE Þ was most affected by b. When using pure solvents, DE of methanol was the least closest to the target color, but 60 vol% methanol, 40–60 vol% ethanol, 40 vol% 1propanol, and 40–60 vol% 2-propanol were close to the target color in a binary system. In conclusion, natural yellow dyes can be extracted by using a mixture of alcohol and distilled water. The UV absorbance was increased with decreasing chi parameter ðx12 Þ in pure solvents and the color differences ðDE Þ in mixed solvents. Acknowledgement The present research was conducted by the research fund of Dankook University in 2014.
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