Environmental Assessment of Osage orange extraction and its Dyeing Properties on Protein Fabrics Part I: Standardization of Extraction
Heba F. Mansour
Ultrasonic and conventional heating methods were performed to select the best solvent for Osage orange extraction. Distilled water and other co-solvents, such as water-acetone and water- ethanol mixtures were tested at concentrations of 10% v/v. Two grams of Osage orange powder was suspended in 20 cm3 of solvent in a thermostatic and ultrasonic bath. Extraction process was followed by the dyeing of woolen fabric to evaluate data. Ultrasonic assisted extraction at 60°C for 30 min possessed much higher dye absorbance and color strength at lower temperature and time rather than using the conventional heating method. 15% v/v water-acetone co-solvent released 32% of the total dye absorbency and 21% of color strength on the dyed woolen samples, this was followed by water-ethanol co-solvent then water which released 27 and 21% of dye absorbency and 19 and 16% of color strength, respectively. These data are relative to 10, 6 and 4% of dye absorbency and 18, 15 and 11% of color strength with the same co-ordinate solvents in case of using the conventional heating method. Absorption of dye is dependent on solvent polarity. In non-hydrogen-bond donating solvents, solvation of dye molecules probably occurs via dipole-dipole interactions, whereas in hydrogen-bond donating solvents the phenomenon is more hydrogen bonding in nature. Given that both ultrasonic and water acetone co-solvent in extracting Osage orange natural dye, are environmentally and new ecological acceptable for dyeing protein fabrics.
Received: August 03, 2010;
Accepted: November 25, 2010;
Published: February 01, 2011
In the mid 1960s an international awareness of environment, ecology and pollution
control has created an upsurge in the interest in natural dyes. Recently, the
dye industry is more and more forced to reduce toxic effluents and to stop the
production of potentially dangerous dyes or pigments (Glover,
Osage orange (Maclura pomifera) is a tree in the Moraceae family (Cox
and Leslie, 1999). The common name is derived from its fruit, which resembles
the shape of an orange and from the fact that its hardwood was used by the Osage
Indian tribe to make bows. Osage orange is native to Southern Oklahoma and Northern
Texas and is planted throughout the United States. Although the fruit is not
edible for humans, its extract exhibits antimicrobial and anti-insect activities
and the Native Americans have used osage orange for cancer treatment (Mahmoud,
1981). Several phenolic compounds have been isolated and identified from
various parts of this plant, namely, isoflavonoids from the fruit (Wolfrom
et al., 1946; Delle Monache et al., 1994),
flavonols and xanthones from the heartwood and stem bark (Wolfrom
et al., 1964a; Wolfrom and Bhat, 1965a) and
flavanones and xanthones from the root bark (Wolfrom et
al., 1964b; Wolfrom and Bhat, 1965b; Delle
Monache et al., 1984).
For technical application of natural dyes, a number of requirements have to be fulfilled. Most problems are derived from technical demands, for example:
Solvents play a significant role in textile conservation, including cleaning
and dissolving conservation materials (Timar-Balazsy and Eastop,
From an industrial point of view it would be easier to resort to extracts despite
there is at present no definite answer to this prospective solution. The simplest
extract would be a watery one although not all the dye pigments are water-soluble.
Use of organic solvents might give rise to extracts incompletely water-soluble
(De Santis and Moresi, 2007). In principle, it would
be much easier for the industrial dyers willing to revive the natural dyeing
techniques to replace Osage orange particles with concentrated extracts of its
pigments, provided that the solvent chosen guarantees a series of properties
||Its extraction capacity is extremely high for practically
all the natural pigments present in the raw materials of interest
||Its boiling temperature and latent heat of vaporization is
quite low to allow its separation at low temperatures with minimum energy
The present investigation, therefore, was aimed at identifying the most appropriate leaching solvent for Osage orange pigments to produce an optimum concentrated extract used for dyeing woolen fabric. This has been carried out ultrasonically in comparison with the conventional heating method, using water, in addition to the co-solvents of water-acetone and water-ethanol mixtures at different concentrations, temperature and time intervals.
MATERIALS AND METHODS
This study was taken place via a scientific mission at the School of Chemical and Physical Science, Faculty of Science at Victoria University of Wellington, New Zealand in 2007-2008.
Fabric: One hundred percent mill scoured wool fabric purchased from
the New Zealand market, was further scoured with a solution containing 2 g L-1
of each of sodium carbonate and Nonidet 7 P 40 Substitute (Sigma- Aldrich NZ
Ltd) at 60°C for 30 min. using a liquor ratio of 50:1. The fabric was thoroughly
rinsed in worm and cold water, then left to dry at ambient temperature.
Pigment leaching and estimation of extraction yields: To select the best solvent for Osage orange, distilled water and other co-solvents, such as water-acetone and water- ethanol mixtures all of analytical grade, were tested at concentrations of 10% v/v. Two gram of Osage orange powder (Hands Ashford NZ, LTD, ChristChurch, NZ) was suspended in 20 cm3 of solvent and in a thermostatic bath as well ultrasonic bath at 60°C, for 120 min.
Once water-acetone co-solvent and ultrasonic assisted extraction were chosen as the preferable technique of extraction, 10% w/v Osage orange powder, dissolved in 2.5-25% v/v acetone, at 25- 60°C, for 30-120 min, were carried out to determine the standardization method of extraction.
Dyeing: Ultrasonic assisted dyeing was performed at a liquor ratio of 30:1 for 60 min at 60°C.
After dyeing, the woollen samples were rinsed in cold running water until no more colour was adsorbed and held for stripping with 25% aqueous DMF for 30 min. at 60°C, using a liquor ratio of 50:1, followed by washing-off at a liquor ratio of 50:1, with 2 g L-1 Nonidet ® P 40 Substitute at 60°C, for 30 min. Finally, the samples were rinsed twice in warm and cold water, then left to dry at ambient temperature.
Measurements: The absorbance of Osage orange extract and the reflectance measurements on the dry dyed wool were carried out using Cary 100 UV-Vis Spectrophotometer.
To select the leaching solvent capable of maximizing the extraction yield of
Osage orange, several trials were carried out by distilled water and the co-solvents
of water-acetone and water-ethanol mixtures at 25-60°C for 30-120 min. The
ultrasonic efficiency had been determined simultaneously with the recognized
standard procedure of extraction parameters and compared experimentally with
the conventional heating method. Practically coincident with that pertaining
to water, the yield coefficients for the co-solvents were definitively greater,
whether using ultrasonic or the conventional heating method with much higher
values in case of ultrasonic. Water-acetone mixture was found to be the most
selective co- solvent for extracting the Osage orange dye, followed by water-ethanol
and distilled water. As shown in Fig. 1 and 2
water-acetone mixture released over 32% of the total dye absorbency, exhibiting
21% of the total color strength when dyeing the woolen sample. Water-ethanol
extracted 27% dye and exhibited 19% color strength, while water extracted less
than 21% dye and exhibited 16% color strength. This was relative to 10, 6 and
4% of absorbance and 18, 15 and 11% color strength respectively with the co-ordinate
solvents when using the conventional heating method. Figure 3
and 4a, b showed the absorption and color
strength values of Osage orange powder extracted by acetone at different concentrations
of 2.5-25% v/v at temperatures from 25-60°C, for time intervals varied between
30-120 min. It can be noted that the maximum values were achieved when extracted
the Osage orange powder in 20% v/v acetone at 60°C, for 60 min.
||Effect of solvents on the absorbency of Osage orange powder
using the conventional [CH] and ultrasonic [US] assisted extraction
||Effect of solvents on the color strength of Osage orange dyed
wool using the conventional [CH] and ultrasonic [US] assisted extraction
||Effect of acetone concentration on the absorbency and color
strength of Osage orange dyed wool using ultrasonic assisted extraction
||(a) Effect of ultrasonic assisted extraction time on the absorbency
of Osage orange at different temperatures and (b) Effect of ultrasonic assisted
extraction time on the color strength of Osage orange dyed wool at different
It is very well known that the extraction parameters affected the color strength of the dyed wool and are influenced by the properties of solvents in which they are carried out.
These include the dipole moment, dielectric constant and refractive index values.
The most important property in this regard is the solvent polarity which can
change the position of the absorption or emission band of molecules by solvating
a solute molecule or any other molecular species introduced into the solvent
matrix (Muhammad Rau et al., 2008).
By the way, dye molecules or pigments are complex organic molecules which might
carry charge centers and are thus prone to absorption changes in various media
(Oliveira et al., 2002; Bevilaqua
et al., 2006). These changes are important to understand various
physical-organic reactions of these macromolecules which have become important
in dye extraction from solution (Hollen et al., 1979).
Acetone acts as the non hydrogen-bond donating solvents (also called as non-HBD
type of solvents), while water and ethanol are the hydrogen-bond donating solvents
(also called as HBD type solvents) (Muhammad Rau et al.,
2008). The absorbency values of Osage orange in these solvents are given
in Fig. 1. It can noted from this figure that the absorption
maximum of the extract is affected by the solvent type, thus the change in values
can be noted as a probe for various types of interactions between the solute
and the solvent.
Water and ethanol are considered as polar protic solvents, their polarity stems
from the bond dipole of the O-H bond, whereas the large difference in the electro-
negativities of the oxygen and hydrogen atom, combined with the small size of
the hydrogen atom, warrant separating the Osage orange molecules that contain
the OH groups from those polar compounds that do not. On the other hand acetone
considered as dipolar aprotic solvent, containing a large multiple bond between
carbon and either oxygen or nitrogen e.g. C-O double bond (Muhammad
Rau et al., 2008).
Although water has the highest dielectric constant among ethanol and acetone
solvents, its extraction demonstrated the lowest value of absorbency. This might
due to the formation of strong hydrogen bond between the dye extract and water
molecules (Bruce et al., 2000). The dye absorbance
is also influenced by the presence of co-solvents. Water-acetone mixture exhibited
the highest value of absorbance, followed by the second water-ethanol mixture.
In case water-acetone, the salvation of extract is non-HBD type of solvent mainly
occurs through charge-dipole type of interaction, whereas in HBD type of solvent,
the interaction also occurs by hydrogen bonding besides the usual ion-dipole
interaction. In this situation, the methyl groups of acetone are responsible
for the solvation of the dye extract. Thus, decreasing the amount of non-HBD
acetone solvent concentration increasing the amount of HBD solvent (water) shall
break these interactions with the dye molecule, thereby decreasing the value
Water-ethanol mixtures belong to HBD type of solvents, whereas the dye cation
is preferentially solvated by the alcoholic component in all mole fractions
in aqueous mixtures with ethanol. It is well known that water makes strong hydrogen-bonded
nets in the water-rich region, which are not easily disrupted by the co-solvent
(Gomez et al., 2004). This can explain the strong
preferential salvation by the alcoholic component in this region since water
preferentially interacts with itself rather than with the dye. In the alcohol-rich
region, the alcohol molecules are freer to interact with the water and with
the dye, since their nets formed by hydrogen bonds are weaker than in water.
In this situation, the alcohol molecules can, to a greater or lesser extent,
interact with water through hydrogen bonding (Bevilaqua
et al., 2006).
Wool fiber is considered as relatively easy fiber to dye, the ease with which
the polymer system of wool will take in dye molecules is due to polarity of
its polymer and its amorphous nature. The polarity will readily attract any
polar Osage orange molecules and draw them into the polymer system. The studies
of wool dyeing process have been in two distinct theories (The Gilbert- Rideal's
and Donnan theories). The Gilbert and Rideal theory based on Langmuir's theories
of surface adsorption, in which the activity coefficient of Osage orange extract
ions adsorbed into the wool phase are reduced due to specific binding with sites
on wool, which is the formation of ion pairs. This theory proposed that dyeing
process is an anion exchange process, in which the Osage orange extract molecules
displace smaller anions, depending on four steps: a) diffusion to fiber surface,
b) transfer across that surface, c) diffusion within to appropriate sites and
d) binding at those sites. On the other hand, according to the Donnan equilibrium
theory, the Osage orange extract was considered to partition between the external
solution and internal solution phase in the wool. The later phase is believed
to contain a high concentration of fixed ionic groups and hence solute molecules
have reduced activity co-efficient in that phase due to coulombic interaction,
whereas Osage orange is a water soluble dye containing hydroxyl groups that
would interact ionically with the protonated terminal amino groups of wool fibres
at acidic pH via ion exchange reaction. Reichardt (1994),
Kawski (2002) and Gomez et al.
(2004) as shown in the following scheme.
With the demand for more environmentally friendly methods and increasing productivity, the newer ultrasonic energy in assisting the extraction of Osage orange natural dye have been developed, over the conventional heating extraction methods, involving come shorter extraction times and much higher dye absorbance and color strength at lower temperature. Water-acetone co-solvent and ultrasonic have been found to be the suitable alternatives to the conventional water heating method.
The maximum color yield of dye is dependent on solvent polarity. Solvation of dye molecules probably occurs via dipole-dipole interactions in non-hydrogen- bond donating solvents, whereas in hydrogen-bond donating solvents the phenomenon is more hydrogen bonding in nature. The dye uptake depends on (The Gilbert- Rideal's and Donnan theories) depending on the coulombic interaction between the anionic groups (OH) in fact: O- of Osage orange extract and the protonated amino groups of wool fibers.
Greet appreciation to Professor Gerald Smith and the department of Chemical and physical science at Victoria University of Wellington, NZ. for their kindly support during the scientific mission.
1: Aydin, A.H. and T. Zeki, 2003. The sorption behaviors between natural dyes and wool fibre. Int. J. Chem., 13: 85-91.
2: Bevilaqua, T., T.F. Goncalves, C.G. Venturini and V.G. Machado, 2006. Solute-solvent and solvent-solvent interactions in the preferential solvation of 4-[4 (dimethylamino)styryl]-1-methylpyridinium iodide in 24 binary solvent mixtures. Spectochim Acta Part A Mol. Biomol. Spectroscopy, 65: 535-542.
CrossRef | Direct Link |
3: Bruckner, U., S. Struckmeier, J.H. Dittrich and R.D. Reumann, 1997. Natural dyes selected for color fastness on synthetic fiber fabrics. Textilvered-lung, 32: 112-115.
4: Bruce, R.L., N.V. Broadwood and D.G. King, 2000. Kinetics of wool dyeing with acid dyes. Textile Res. J., 70: 525-531.
5: Cox, P. and P. Leslie, 1999. Osage Orange. In: Texas Trees a Friendly Guide, Cox, P. and P. Leslie (Eds.). Corona Publishing Co., Corona Publishing Co., San Antonio, TX., pp: 147-149
6: De Santis, D. and M. Moresi, 2007. Production of alizarin extracts from Rubia tinctorum and assessment of their dyeing properties. Ind. Crops Prod., 26: 151-162.
7: Delle Monache, F., F. Ferrari and M. Pomponi, 1984. Flavanones and xanthones from Maclura pomifera. Phytochemistry, 23: 1489-1492.
8: Delle Monache, G., R. Scurria, A. Vitali, B. Botta and B. Monacelli et al., 1994. Comparison of methods for extraction of flavones and xanthones Phytochemistry, 37: 839-839.
9: Deo, H.T. and B.K. Desai, 1999. Dyeing of cotton and jute with tea as a natural dye. Coloration Technol., 115: 224-227.
10: Glover, B., 1995. Are natural colorants good for your health: Are synthetic ones better. Textile Chem. Colorist, 27: 17-20.
11: Gomez, M.L., C.M. Previtali and H.A. Montejano, 2004. Photophysical properties of safranine O in protic solvents. Spectrochim Acta Part A Mol. Biomol. Spectroscopy, 60: 2433-2439.
12: Hollen, N., J. Saddler and A.L. Langford, 1979. Textiles. 5th Edn., Macmillan Publishing Co., UK
13: Kawski, A., 2002. On the estimation of excited-state dipole moments from solvatochromic shifts of absorption and fluorescence spectra. Z. Naturforsch, 57A: 255-262.
Direct Link |
14: Mahmoud, Z.F., 1981. Antimicrobial component from Maclura pomifera fruit. Planta Med., 42: 299-301.
15: Muhammad Rau, A., A. Ahmed Soliman and M. Khattab, 2008. Solvent effect on the spectral properties of neutral red. Chem. Central J., 2: 2-19.
16: Oliveira, C.S., K.P. Bronco, M.S. Baptista and G.L. Indig, 2002. Solvent and concentration effects on the visible spectra of tri-para-dialkylamino-substituted triarylmethane dyes in liquid solutions. Spectochim Acta Part A Mol. Biomol. Spectroscopy, 58: 2971-2982.
17: Reichardt, C., 1994. Solvatochromic dyes as solvent polarity indicators. Chem. Rev., 94: 2319-2358.
18: Wolfrom, M.L., W.D. Harris, G.F. Johnson, J.E. Mahan, S.M. Moffet and B. Wildi, 1946. Osage orange pigments. XI. complete structures of osajin and pomiferin. J. Am. Chem. Soc., 68: 406-418.
19: Wolfrom, M.L., E.E. Dickey, P. McWain, J.H. Looker, O.M. Windrath and F.Jr. Komitsky, 1964. Osage orange pigments. XIII. isolation of three new pigments from the root bark. J. Org. Chem., 29: 689-691.
20: Wolfrom, M.L, F.Jr. Komitsky, J.H. Looker, E.E. Dickey and P. McWain et al., 1964. Osage orange pigments. XIV. the structure of macluraxanthone1a-c. J. Org. Chem., 29: 692-697.
21: Wolfrom, M.L. and H.B. Bhat, 1965. Osage orange pigments-XVII: 1,3,6,7-tetrahydroxyxanthone from the heartwood. Phytochemistry, 4: 765-768.
22: Wolfrom, M.L, F.Jr. Komitsky and J.H. Looker, 1965. Osage orange pigments. XV. structure of osajaxanthone synthesis of dihydroosajaxanthone monomethyl ether1a. J. Org. Chem., 30: 144-149.
23: Wolfrom, M.L., F.Jr. Komitsky and P.M. Mundell, 1965. Osage orange pigments. XVI. the structure of alvaxanthone. J. Org. Chem., 30: 1088-1091.
24: Timar-Balazsy, A. and D. Eastop, 1998. Chemical Principles of Textile Conservation. 1st Edn., Elsevier Science Ltd., UK., ISBN-13: 978-0-7506-2620-0
25: Bechtold, T., A. Mahmud-Ali and R. Mussak, 2007. Natural dyes for textile dyeing: A comparison of methods to assess the quality of Canadian golden rod plant material. Dyes Pigments, 75: 287-293.