Ultrasonic assisted eco-friendly textile wet technology using arta plant . Part 1: Optimum condition of extraction HEBA MANSOUR* & KHADIJAH QASHKARY Fashion Design Department, Faculty of Arts & Design, King Abdul-Aziz University, KSA. E.mail*: hfmansour@kau.edu.sa, heba1fm@yahoo.co.uk Abstract: Through the recent scientific awareness to reach an eco-friendly and saving energy of textile dyeing and antimicrobial finishing, this part of a series studies deals with the optimum extraction condition of arta as a new natural dye using ultrasonic energy (US) compared with conventional heating (CH). Spectroscopic analysis showed the presence of flavonoid compounds in arta extract. It was desirable from the economical point of view that (US) method possessed higher dye absorption, at lower temperature and time with lesser amount of arta and solvent compared with (CH) method. Solvation of dye depends on the dipole dipole interactions in non-hydrogen bond donating solvents. pH 9 and the optimized extract temperature and time increased the solubility and diffusion coefficients. Efficiency of (US) energy was attributed to the cavitation phenomenon in a liquid medium that accelerated the rate of diffusion of arta molecules in the extract bath and intense the liquid agitation. Key words: Arta, extraction, ultrasonic energy, solvents, , natural dyes, eco-friendly. 1 1- Introduction Stringent environmental standards imposed by many countries in response to the toxic and allergic reactions associated with synthetic dyes (Bechtold et al., 2003; Gulrajani and Gupta, 1999), which damage the ecological system of the receiving surface water, creating a lot of disturbance to the ground water resources (Georgiou et al., 2002; Tsui et al., 2003; Araceli et al., 2009; Uddin et al., 2009). A widespread interest has emerged applying natural colorants (Shaukat et al., 2009; Bechtold et al., 2007; Feng et al., 2007; Siva, 2007). Arta plant belongs to the Polygonaceae family. Its scientific name is Calligonum comosum L’Herit, its local Name is Arta`, A`bal, waragat Alshams and its Arabic Name is known as Arti, Arta`,waragat alshams , Ramo, Tape. Since the nineteenth century A.D, it is used for treating various ailments, and for tanning and dyeing clothes with red or russet brown color. (plantdiversityofsaudiarabia.info/biodiversity-saudi/ethenobotany.htm; Heather, 1981) Many problems are derived from the technical application of natural dyes. So, a number of requirements have to be fulfilled such as: i) the adaptation of conventional dyeing processes on modern techniques, ii) determination of the standard extraction and dyeing condition of the plant material and iii) expectation and selection of plant materials that yield products with acceptable fastness properties (Uddin et al., 2009; Borland, 2000). At present trends, standardization of extraction parameters are studied carefully to evaluate and identify the color components and dyeing characteristics on textile fabrics, which possess technical and commercial importance on the extraction and dyeing processes cost (Shaukat et al., 2009). Commonly, conventional aqueous extraction gives less amount of coloring component for coloring textiles. Thus, these methods are, in general, time- and 2 solvent-consuming and may promote the degradation of these compounds. To overcome the drawbacks conditions popular common solvents such as acetone, ethanol, and methanol have been successfully used to obtain natural dyes and pigment-rich extracts (Shaukat et al., 2009; Heba and Gamal, 2011; Cristea and Vilarem, 2006). It was reported that the solvent gave high extraction capacity, had quite low boiling temperature and latent heat of vapor vaporization. As a result, lead to extract the dye at low temperatures with minimum energy consumption and insignificant reactivity with pigments to avoid any loss in the color quality (Peta et al., 2003; Grigonisa et al., 2005; Spigno et al., 2007; Durling et al., 2007; Michiels et al., 2012). The present investigation identified the most appropriate leaching extraction parameters of arta pigment to produce an optimum concentrated extract that will be used for textile dyeing and antimicrobial finishing. This has been carried out using power ultrasonic (US) in comparison with conventional heating (CH) where the color components and chemical constituents were isolated and established based on spectroscopic investigations. 2- Materials and methods 2-1-Materials Arta; purchased from Saudi market was washed to remove dust particles and left to dry at room temperature, then was grinded to powder form in an electrically grinder. Distilled water, acetone, ethanol, sodium hydroxide and acetic acid were all of analytical grade. 2.2. Pigment leaching and estimation of extraction yields To determine the standardization method of extraction, the extract parameters were carried out using power ultrasonic (US) in comparison with conventional heating (CH), using 3 (1-15) % w/v arta powder, dissolved in pure distilled water and (5- 75 % v/v) aqueous solutions of acetone and ethanol at pH (3-9), for (15- 90 min) at (25- 90)°C for conventional heating and 60oC in case of (US) method. 3.3. Spectral analysis The absorption spectra were recorded for the determination of absorbance on Pharmacia Biotech Ultrospec 3000 UV/Vis spectrophotometer in the wavelength range 300-800 nm. Infrared spectra of the compounds were recorded on a PerkinElmer FTIR spectrum (version 10, 03.08) in the frequency range 4000-450 cm_1. 3- Results and discussion As shown in Figures 1 and 3, the yield coefficients of co-solvents with both conventional (CH) and ultrasonic (US) methods were more efficient than mono-solvent and water-acetone was found to be the most selective co- solvent. As shown in Figure 2, in case of (CH); 25% (v/v) acetone released over 51% of the total arta extract absorbance in comparison with 30% and 19% water-ethanol and pure distilled water respectively. This was relevant to (39, 30 and 22) % of the total arta extract absorbance from 20% (v/v) water-acetone, 25% (v/v) water-ethanol and pure distilled water in case of (US) as shown in Figure 4. The maximum arta extract absorption occurred with much less solvent concentration (20% acetone, 25% ethanol) in case of (US) in comparison with (25% acetone, 40% ethanol) in case of (CH) as shown in Figure 5, where their comparative absorbance percentages were evaluated in Figure 6. The dye molecules are complex organic molecules which might carry charge centers and are thus prone to absorption changes in various solvents media (Muhammad et al., 2008; Oliveira et al., 2002). 4 Acetone acts as the non-hydrogen-bond donating (non-HBD) solvents, in case water-acetone, the salvation of extract is non-HBD type of solvent mainly occurs through ion -dipole interaction and hydrogen bonding. In this situation, the methyl groups of acetone are responsible for the solvation of the arta extract, thus, decreasing the amount of non-HBD acetone solvent concentration increasing the amount of HBD solvent. (Bevilaqua et al., 2006; Muhammad et al., 2008). Water and ethanol are considered as polar protic solvents, they are the hydrogen-bond donating (HBD) 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 arta molecules that contain the OH groups from those polar compounds that do not (Oliveira et al., 2002; Muhammad 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 water itself rather than with the dye extract molecules (Wang et al., 2007; 23 Zhang et al., 2007; Oliveira et al., 2002; Bevilaqua et al., 2006) Less concentrations of solvents than the optimum condition might bring an increased concomitant extraction of other compounds lower the pigment concentrations and decrease the absorbance value (Grigonisa et al., 2005). As shown in Figure 7, the maximum arta extract absorbance was achieved at pH 9 due to the increased solubility and diffusion coefficients. While the decrease of absorbance extraction at pH values 3, 5 and 7 was due to the possible degradation of pigment compounds caused by hydrolysis and polymerizations (Alonso et al., 2001). 5 Expectedly as shown in Figure 8, when the amount of arta increased, the extract absorption also increased whether using (CH) or (US) methods with much higher values with (US). A decline was achieved with the increase up to 12% in case of (US) while the other case showed continuously proportional absorbency increase with the amount increase. As shown in Figure 9; the maximum dye absorption attained with 15% w/v arta in case of (CH) compared with 12% w/v in the (US) was evaluating difference in absorbance percentage of a ratio (46: 54) % respectively. In Figures 10 and 12 a; it is clear that the standard parameter of extraction time was achieved after (105 and 120) min. with difference in absorbance percentage of (47 to 53) in case (CH) and (US) respectively. By the way; as shown in Figures 11and 12b, the standard parameter of extraction temperature was achieved at (60 and 70) o C with difference in absorbance percentage of ratio (35: 65) in case (CH) and (US) respectively. A decline was achieved with the increase in time in case of (US) while the other case showed continuously proportional absorbency increase with the increase of temperature and time. Generally, the increase in extract absorbency may be explained by the de-aggregation of arta molecules in the extract bath. In case of (US) method, the decline in the absorbance value may be not only attributed to the hydrolytic decomposition of the extract molecules under the influence of sonic energy during prolonged extraction than 105 min. (Kongkachuichaya et al., 2002), but also prolong extraction time might potentially increases the loss of solvent by evaporation (Durling et al., 2007). The efficiency of ultrasonic-assisted extraction due to ultrasonic energy reflecting the additional enhancing effect in saving energy is generally attributed to the cavitation 6 phenomenon in a liquid medium. As a result, it produces some mechanical effects which lead to break up of aggregates with higher relative molecular mass and accelerate the rate of diffusion of the arta molecules in the extract bath and intense agitation of the liquid (Vajnhandl and Le Marechal 2005; Shanker and Padma 2005; Padma et al., 2006; Kamel et al. 2005, 2007; Mansour, 2009; Mansour and Heffernan, 2010). The flavonoid pigment extracted from the arta leaves using acetone was confirmed by FTIR spectroscopy as shown in Figs 13. It was recorded the number of peaks lying between 3428.94 cm-1, 2924.2 cm-1, 2335.72 cm-1, 1615.33 cm-1, 1384.35 cm-1 and 1019.57 cm-1. The broad band (3600-3000) corresponds to hydroxyl group (bonded). Band around 2900 cm-1 could be attributed to aliphatic CH3 and CH2. The bands from 2800 to 2000 cm-1 are normally void of other absorptions, so the presence of alkyne or nitrile groups can be easily seen. The bands from (1638-1484) cm-1 may be attributed to C=C group of an aromatic ring. Bands at (1433-1368) cm-1 due to the CH3 and CH2, bending, and the present bands at (1300-1000) cm-1 indicated C-O group, while the bands below 900 cm-1 indicated the existence of C-H deformation of an aromatic proton. This confirmed the presence of flavonoid compounds in the arta extract so that the bands in the 1650-1050 cm1 range are characteristic flavone skeleton. Conclusions The effect of arta extraction parameters using ultrasonic (US) compared to conventional heating (CH) to probe their effects on the absorption spectra have been studied. Results indicated the presence of flavonoid and ultrasonic is rather effective than conventional heating at lower temperature and shorter time with lesser arta and solvent amounts. 7 Fig. 1. Effect of solvent type and concentrations on the absorbance arta using (CH). Fig. 2. Optimum solvents concentrations on the absorbance percentage of) arta using (CH) Fig. 3. Effect of solvent type and concentrations on the absorbance of arta using (US) Fig. 4. Optimum solvents concentrations on the absorbance percentage of arta using (US). 8 Fig. 5. Comparison between (US) and (CH) of the optimum solvents on the arta absorbance Fig.6. Comparison between (US) and (CH) of the optimum solvents on the total absorbance Fig. 7. Effect of pH values on the absorbance of arta Fig. 8. Effect of arta amount (w/v) on the absorbance using (US) and (CH 9 Fig.9. Comparison between (US) and (CH) of the arta amount on the total absorbance Fig. 10. Effect of extraction time on the absorbance using (US) and (CH) Fig. 11. Effect of extraction temperature on the absorbance using (US) and (CH) B A Fig.12 (a,b). Comparison between (US) and (CH) of extraction time and temperature on the total absorbance 10 Fig. 13. FTIR spectra of arta extract 11 References Alonso, R.M., Korta, E., Barranco, A., Berrueta, L.A., Gallo, B., Vicente, F. 2001. Pressurized liquid extraction for the determination of polyphenols in apple. Journal of Chromatography A, 933: 37-43. Araceli, R., Juan, G., Gabriel, O., Maria, M. 2009. Adsorption of anionic and cationic dyes on activated carbon from aqueous solutions: equilibrium and kinetics. Journal of Hazardous Material, 172(2-3): 1311-1320. Bechtold, T., Turcanu, A., Ganglberger, E., Geissler, S. 2003. Natural dyes in modern textile dye houses, how to combine experiences of two centuries to meet the demands of the future?. Journal of Cleaner Production, 11(5): 499-509. Bechtold, T., Amalid, M.A., Rita, A.M. 2007. Reuse of ash-tree (Fraxinus excelsior L.) bark as natural dyes for textile dyeing: process conditions and process stability. Coloration Technology, 123 (4): 271–279. Bevilaqua, T., Goncalves, T.F., Venturini, C.G., Machado, V.G. 2006. Solute-solvent and solvent- solvent interactions in the preferential solvation of 4-[4 (dimethylamino)styr‐yl]-1-methylpyridinium iodide in 24 binary solvent mixtures. Spectrochim Acta A Mol Biomol Spectrosc., 65(3): 535-542 Borland, V.S. 2000. Natural resources: animal and vegetable fibers for the 21st century. American Textile Industry, 29: 66–70 Cristea, D., Vilarem, G. 2006. Improving light fastness of natural dyes on cotton yarn. Dyes and Pigments, 70(3): 238–245. Durling, N.E., Catchpole, O.J., Grey, J.B., Webby, R.F., Mitchell, K.A., Foo, L,Y., Perrym, 12 N.B. 2007. Extraction of phenolics and essential oil from dried sage (Salvia officinalis) using ethanol-water mixtures. Food Chemistry, 10:1417-1424. Feng, X.X., Zhang, L.L., Chen, J., Zhang, J.C. 2007. New insights into solar UV protective properties of natural dyes. Journal of Cleaner Production, 15 (4): 366–372. Georgiou, D., Melidis, P.A., Gimouho-poulos, K. 2002. Degradation of azo-reactive dyes by ultraviolet radiation in the presence of hydrogen peroxide. Dyes and pigments, 52 (2): 69-78. Grigonisa, D., Grigonisa, P.R., Venskutonisa, B., Sivikb, M., Sandahlb, C.S., Eskilsson, C. 2005. Comparison of different extraction techniques for isolation of antioxidants from sweet grass (Hierochloë odorata). The Journal of Supercritical Fluids, 33(3): 223-233 Gulrajani, M.L. 1999. Natural Dyes- Part 1, Present status of Natural Dyes. Colourage, 46 (7): 25-27. Heba, M., Gamal, AM. 2011. Environmental Assessment of of Osage Orange extraction and its dyeing properties on protein fabrics, Part 1. Standardization of extraction”. Journal of environmental science and technology, 4: 395-402 Heather, C.R. 1981. The art of Arabian Costume, A Saudi Arabian Profile. Fribourg, Switzerland. Kamel, M., El shishtawy, R., Yousef, B.M., Mashaly, H.M. 2005. Ultrasonic assisted dyeing III. ‘‘Dyeing of wool with lac as a natural dye”. Dyes Pigments, 63:103–110. Kamel, M., Mansour, H.F., Mashaly, H., Haroun, A.A. 2007. Clean dyeing technology on cotton fabrics with natural basic dyes using ultrasonic technique. Man-Made Textiles in India, L: 8-12 13 Kongkachuichaya, P., Shitangkoonb, A., Chinwongamorna, N. 2002. Studies on Dyeing of Silk Yarn with Lac Dye:Effects of Mordants and Dyeing Conditions. Science Asia, 28: 161-166 Mansour, H. 2009. Environment and energy efficient dyeing of woollen fabric with sticta coronata. Clean Technologies and Environmental Policy, 12 (5): 571 Mansour, H., Heffernan, S. 2010. Environmental aspects on dyeing silk fabric with sticta coronata lichen using ultrasonic energy and mild mordants. Clean Technologies and Environmental Policy, 13(1):207-213. Michiels, J.A., Kevers, C., Pincemail, J., Defraigne, J.O., Dommes, J. 2012. Extraction conditions can greatly influence antioxidant capacity assays in plant food matrices. Food Chemistry, 130 (4): 986-993. Muhammad, R.A., Ahmed, S.A., Muhammad, K. 2008. Solvent effect on the spectral properties of Neutral Red. Chemistry Central Journal, 2: 2-19 Oliveira, C.S., Bronco, K.P., Baptista, M.S., Indig, G.L. 2002. Solvent and concentration effects on the visible spectra of tri-para-dialkylamino-substituted triarylmethane dyes in liquid solutions. Spectrochim Acta A Mol Biomol Spectrosc, 58 (13): 2971-2982. Padma, V.S., Shanker, R., Mahanta, D., Tiwari, S.C. 2006. Ecofriendly sonicator dyeing of cotton with Rubia cordifolia Linn. Using biomordant. Dyes and Pigments, 76(1): 207-212. Patel, B.H., Agarwal, B.J., Patel, H.M. 2003. Novel padding technique for dyeing Babool dye on cotton. Colourage, 50: 21–26. plantdiversityofsaudiarabia.info/biodiversity-saudi.../ethenobotany.htm. 14 Shanker, R., Padma, V.S. 2005. Ultrasonic energized dyeing of wool with Mirabilis jalpa flowers. Colourage, 52(2): 57–61 Shaukat, A., Tanveer, H., Rakhshanda, N. 2009. Optimization of alkaline extraction of natural dye from Henna leaves and its dyeing on cotton by exhaust method. Journal of Cleaner Production, 17: 61–66 Spigno, G., Tramelli, L., Faveri, D.M. 2007. Effects of extraction time, temperature and solvent on concentration and antioxidant activity of grape marc phenolic. Journal of Food Engineering, 81(1): 200-208. Siva, R. 2007. Status of natural dyes and dye-yielding plants in India. Current Science, 92 (7): 1-9 Tsui, L.S., Roy, W.R., Gole, M.A. 2003. Removal of dissolved textile dyes from waste water by a compost sorbent. Colouration Technology, 119 (1): 14-8. Uddin, M.T., Akhtarul, I.S., Mahmoud, R.D. 2009. Adsorptive removal of methylene blue by tea waste. Journal of Hazardous Material, 164 (1): 53-60. Vajnhandl, S., Le Marechal, A.M. 2005. Ultrasound in textile dyeing and the decolouration and mineralisation of textile dyes. Dyes Pigments, 65:89–101 Wang, J., Sun, B., Cao, Y., Tian, Y., Li, X. 2007. Optimisation of ultrasound-assisted extraction of phenolic compounds from wheat bran. Food Chemistry,106 (2): 804–810. Zhang, Z.S., Li, D., Wang, L.J., Ozkan, N., Chen, X.D., Mao, Z.H. 2007. Optimization of ethanol–water extraction of lignans from flaxseed. Separation and Purification, 57(1): 17–2 15 16