Textile & Leather Review ISSN 2623-6281 | www.tlr-journal.com | 10.31881/TLR Green Application of Ultrasonic Waves for Extraction of Yellow Colorant from Haar Singhar and its Colouring Behaviour in Cotton Dyeing Hunaira Nasreen, Shahid Adeel, Muhammad Yameen, Nimra Amin, Meral Ozomay, Muhammad Abdul Qayyum How to cite: Nasreen H, Adeel S, Yameen M, Amin N, Ozomay M, Qayyum MA. Green Application of Ultrasonic Waves for Extraction of Yellow Colorant from Haar Singhar and its Colouring Behaviour in Cotton Dyeing. Textile & Leather Review. 2023; 6:18-36. https://doi.org/10.31881/TLR.2022.67 How to link: https://doi.org/10.31881/TLR.2022.67 Published: 16 January 2023 This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License https://doi.org/10.31881/TLR.2022.67 https://doi.org/10.31881/TLR.2022.67 https://creativecommons.org/licenses/by-sa/4.0/ https://creativecommons.org/licenses/by-sa/4.0/ NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 18 https://doi.org/10.31881/TLR.2022.67 Green Application of Ultrasonic Waves for Extraction of Yellow Colorant from Haar Singhar and its Colouring Behaviour in Cotton Dyeing Hunaira NASREEN1, Shahid ADEEL2*, Muhammad YAMEEN1, Nimra AMIN2, Meral OZOMAY3, Muhammad Abdul QAYYUM4 1Department of Biochemistry, Government College University Faisalabad, Faisalabad, Pakistan 2Department of Applied Chemistry, Government College University Faisalabad, Faisalabad, Pakistan 3Department of Textile Engineering, Faculty of Technology, Marmara University, Istanbul, Turkey 4Department of Chemistry, Division of Science and Technology, University of Education, Lahore, Pakistan *shahidadeelappliedchemist@outlook.com Article https://doi.org/10.31881/TLR.2022.67 Received 30 August 2022; Accepted 4 January 2023; Published 16 January 2023 ABSTRACT Natural dyes have grown in popularity due to their eco-friendliness. They can be used as a substitute for synthetic dyes to minimize environmental pollution. This research investigates the natural colouring behaviour of haar singhar flower (HSF) extract in cotton dyeing. Colorant was extracted under various conditions utilizing various extraction mediums such as aqueous, basic, and acidic. On cotton, it was discovered that applying 55 mL of aqueous extract containing 1.5 g/100 mL sodium chloride for 40 minutes at 70 °C yielded the best colour output. A new hue with good colour fastness was developed utilizing chemical and bio-mordants. The existence of nyctanthin as a colouring agent in haar singhar flowers was discovered through FTIR analysis of the extract. The CIE Lab system revealed that using 2 g/100 mL of pistachio shell as a bio-mordant resulted in good quality reddish yellow hues. It was discovered that ultrasonic radiations have a high potential for isolating colourants and dyeing cotton fabric under decreased conditions of temperature, time and volume. The application of biomordants has made the procedure greener, more efficient, and safer. KEYWORDS bio mordants, chemical mordants, cotton, haar singhar, nyctanthin, ultrasound INTRODUCTION Synthetic dyes are widely utilized in textile, food, cosmetic, and pharmaceutical industries because of their high colouring power, reproducibility and low price [1,2,3]. These dyes offer a wide spectrum of colours as well as excellent fastness [4]. The widespread use of synthetic dyes is one of the major components of environmental pollution [5]. Around 8500 mt of dyestuff is discharged each year worldwide, with 55% of their effluent being spilt into water bodies without being purified. This high concentration of dyes stuff obstructs light from entering deep into water bodies, disrupting the aquatic environment. They affect the aquatic photosynthetic activity and degrade water quality, posing a threat to agricultural land and marine life [6]. These pollutants contain non-biodegradable https://doi.org/10.31881/TLR.2022.67 mailto:shahidadeelappliedchemist@outlook.com NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 19 https://doi.org/10.31881/TLR.2022.67 carcinogenic elements and need a significant amount of time, money, and work to treat [7,8]. In all sectors, including textiles, food, pharmaceuticals, and cosmetics the manufacturers are compelling to switch such products with green, and sustainable products [9]. Antioxidant, anti-allergic, and antibacterial characteristics are found in most natural dyes [10,11]. Because of their significant advantages, these dyes can be labelled green, eco-friendly with high UV protection, and therapeutic qualities [12,13]. Some natural dyes yield brighter, better, faster, luminous, attractive, softer, and calmer colour shades in the textile industry, as well as insect-repellent, and sanitizing qualities [14]. These dyes have some disadvantages, such as a low exhaustion rate, slowness and unsatisfactory light and washing fastness. In natural dyeing, mordants are used to increase colouration qualities and fastness [15]. Mordants are significant in natural dyeing processes because they interact and make fabric-mordant complexes. Biomordants substitute chemical mordants in fabric dyeing for environmentally friendly textile dyeing [16,17,18]. Traditional extraction processes are eco-friendly and greener for isolating colourants, but they are laborious time-consuming, and inefficient [19,20]. Modern methods of extraction and dyeing such as ultrasonic radiations, ultraviolet radiations, microwave radiations, and gamma rays have aided the green dyeing process by increasing colour strength and colourfastness [21,22]. Ultrasonic radiation is the most effective and energy-efficient advanced technique of radiation. The cavitation mechanism in the ultrasound extraction method results in two strategies of cavitation and heating, as cavitation molecules knock at the surface of a solid substrate and create strong vibrations that quickly mix the altered layer by fully dispersing the molecules at the surface, cavitation removes air. It improves the fabric's surface physically, which boosts dye adsorption [23,24,25]. The ultrasonic approach is more effective, saving money, energy, and labour since it bursts the cell wall without physically harming the physiologic property [26,27]. This research focuses on the use of a natural colourant (nyctanthin) extracted from the haar singhar flower for the dyeing of cotton fabric. Flavanols, glycosides, D-mannitol, and nicotiflorin are among the phytochemicals found in this plant [28]. The haar singhar flowers have antibacterial, anti- inflammatory, and antimicrobial activities, and the whole plant has medicinal activities. Haar singhar treats rheumatoid arthritis, pyrexia, malaria, cancer, parasitic infections, skin ailments, sciatica etc. [29]. Cotton is an excellent natural fabric having a hydroxyl bond allowing it to interact with colourant molecules and mordant through terminal hydroxyl groups [30]. https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 20 https://doi.org/10.31881/TLR.2022.67 a) b) c) Figure 1. a) Chemical structure of (cellulose) cotton b) Haar singhar flower extract c) Colorant (Nyctanthin) To the best knowledge of the researchers, no such detailed investigation on the dyeing of haar singhar plant for textiles has been conducted. Colouring has been examined in Nyctanthes arbortritis as a natural yellow colourant to dye cotton fabric under the effect of US radiations for the first time, with the addition of a long-lasting and pleasing colour with excellent fastness attributes. The goals of this research are: a) Isolation of colourant in a selective medium using the US radiations. b) Evaluation of the physical and chemical makeup of materials before and after US irradiation via FTIR. c) Production of the best shade with the least amount of mordants, optimizing the mordanting temperature. d) Assessment of the colourfastness of coloured cotton fabric by pre and post-mordanting under optimal conditions. METHODOLOGY Sample collection Haar singhar (Nyctanthes arbortritis) flowers were bought from the herbal market in Faisalabad. Flowers were washed with water, dried in the air, and then ground into a fine powder. Cotton fabric was obtained from a fabric store in Faisalabad, Punjab, Pakistan for dyeing. All the chemicals used were commercial-grade, including sodium hydroxide, hydrochloric acid, and iron sulphate. Pine nutshell (Pinus gerardiana), walnut shell (Juglans regia), and Pistachio shell (Pistacia vera) were among the natural bio-mordants procured from the herbal market Faisalabad. https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 21 https://doi.org/10.31881/TLR.2022.67 Extraction of colorant Aqueous, alkaline (NaOH), and acidic media (Conc. HCl) was used to extract colourants from the powder. Extraction of colourant was carried out by boiling 4.0 g of haar singhar flower powder (HSFP) in the selected media (HCl 1 mL/100 mL, Na2CO3 2 g/10 mL) for 45 minutes at 60 °C, with the material to liquid ratio of 1:25 and then filtered. Optimization of dyeing parameters Using an optimum extract of haar singhar flowers, different dyeing parameters were examined to achieve higher colour strength, along with the following: - Dye powder (g/100 mL) 4 - Time (min) 20, 30, 40, 50, and 60 - Salt concentration (%) 0.5, 1, 1.5, 2, and 2.5 - Temperature (°C) 50, 60, 70, 80, and 90 - pH 6, 7, 8, 9, and 10 - Volume (mL) 25,35,45,55, and 65 Mordanting Before and after the dyeing of cotton fabric bio and chemical mordants were utilized at defined conditions to produce a range of colours as well as increase the fastness characteristics of dyed fabrics. Bio-mordants included 0.5, 1, 1.5, 2, and 2.5% extracts of Pine nutshell (Pinus gerardiana), walnut shell (Juglans regia), and Pistachio shell (Pistacia vera), as well as chemical mordants such as salts of iron and aluminium along with sodium potassium tartrate (0.5, 1, 1.5, 2, and 2.5%) were employed at selected conditions. Analysis of the properties of coloured cotton fabric Spectra Flash SF 600 was used to investigate the colour strength of all mordanted and dyed fabrics. Mordanted dyed fabrics were examined for colourfastness using ISO standard rubbing, washing, and light fastness methods. FTIR was used to determine the colourant molecule isolated from haar singhar flowers. To evaluate the research findings, ANOVA was utilized as a statistical analysis. https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 22 https://doi.org/10.31881/TLR.2022.67 RESULTS AND DISCUSSION Ultrasonic radiation has been proven to have potential applications in every sector of life. This is because these waves cause acoustic cavitation, which transfers energy into the matrix by scratching the outer layer of the matrix. The plant cell walls rupture when these rays collide with the matrix, allowing more mass to be transferred into the solvent by permeating deeper, and this kinetics results in a beneficial powder-solvent interaction for isolating functional biomolecules [31]. Plant-based dyes, particularly from the haar singhar flower, have produced a variety of hues when separated in various mediums. Table 1. Shade strength and tonal impact of cotton fabric dyed with floral extracts under ultrasonic radiation Extracts used Time (min) Sample code K/S L* a* b* c* h Aqueous 0 NRF/NRE 2.4235 73.08 6.24 40.35 22.52 30.34 20 RF/RE 7.2657 73.12 8.09 46.66 53.78 31.53 Basic 0 NRF/NRE 1.1311 79.50 5.63 55.97 18.62 25.81 40 RF/RE 6.8059 77.51 7.36 61.29 35.64 34.92 Acidic 0 NRF/NRE 1.5926 65.74 5.02 28.58 26.91 27.68 30 RF/RE 4.9999 76.37 7.41 30.35 47.41 27.64 Ultrasonic irradiated cotton fabric in a wet state increases its dye ability toward natural dyes. In the aqueous medium, both the extract and the cotton were irradiated for 20 minutes, providing excellent results, as shown in Figure 2a. In Figure 2b, it was revealed that when the medium was switched to acidic conditions, both the extract and the cotton fabric irradiated for 30 minutes generated excellent results. While a short irradiation duration did not encourage cell wall breaking, a prolonged irradiation time may have helped in the separation of other components that influenced shade firmness during dyeing. It was reported that irradiating cotton fabric for 30 minutes gave excellent results when using irradiated alkaline extract (Figure 2c). https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 23 https://doi.org/10.31881/TLR.2022.67 0 1 2 3 4 5 6 7 8 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD 0 1 2 3 4 5 6 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD 0 1 2 3 4 5 6 7 8 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD a) 0 1 2 3 4 5 6 7 8 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD 0 1 2 3 4 5 6 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD 0 1 2 3 4 5 6 7 8 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD b) 0 1 2 3 4 5 6 7 8 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD 0 1 2 3 4 5 6 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD 0 1 2 3 4 5 6 7 8 10 20 30 40 50 K /S Ultrasonic Radiation Time (min) NRE.NRCF NRE.RCF RE.NRCF RE.RCF UAD c) Figure 2. Extraction of colourant from haar singhar flower (HSF) in media such as a) aqueous, b) acidic, and c) basic for colouration of cotton fabric before and after ultrasonic irradiation https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 24 https://doi.org/10.31881/TLR.2022.67 The results reveal that employment of ultrasonic irradiations for up to 20 minutes, there is no alteration in the functional peak of H-bonding in the cellulosic fabric (Figure 3a) and 3b)). According to FTIR analysis taken from untreated and ultrasonic-treated cotton fabric, the -OH stretching peak (3276 cm-1) and CH and C=O stretching peaks 1250 cm-1 1010 cm-1 did not alter following ultrasonic irradiations for up to 20 minutes. Hydroxyl linkage characteristics peak as functional units of cellulosic fabric, such as cotton, demonstrates that the chemical nature of cotton fabric was not altered by these radiations, which is very beneficial to the textile sector. The FTIR spectra dyed cotton fabric with haar singhar flower extract revealed strong IR bands indicating hydroxyl (3300–3450 cm-1), amino stretching peaks at 2890 cm-1, C=C of benzene (1200 cm-1), and 1015 cm-1 (C=o of benzene). FTIR spectrum shows the existence of nyctanthin, representing that it is used as a dye in cotton. a) b) Figure 3. a) FTIR spectral analysis of un-radiated and b) irradiated cotton fabric https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 25 https://doi.org/10.31881/TLR.2022.67 Figure 4. FTIR analysis of dyed cotton fabric with haar singhar flower extract Only the optimal amount of powder for extracting colourant from haar singhar flower extract in an aqueous media can produce significant colour on fabric. Other functional components are isolated above the optimal concentrations, affecting the adsorption of the active colourant (nyctanthin) and reducing the colour strength after 40 minutes of ultrasonic treatment. It was observed that 4 g of the crude powder, followed by 40 minutes of irradiation, yielded excellent shades in an aqueous media, with satisfactory results on irradiated cotton fabric. Application of salt in textile dyeing aids to obtain optimum colourant depletion because it transfers the colourant molecules from extract to cotton fabric within a short range of attractive forces. Results show that 1.5 g/100 mL of sodium chloride gave maximum exhaustion, and increase the colourant output. The pH of the dye bath is critical for cotton fabric colouring, for the reason that the active sites of cotton fabric (OH) are susceptible to binding in an aqueous extract with active sites of nyctanthin. Table 2 show that following US treatment, an aqueous extract with a pH of 7 gave excellent results on irradiated cotton fabric. As a result, an aqueous extract of 55 mL at 7 pH produced from 4 g of dye powder gave good results on cotton fabric after being exposed to US radiation for 40 minutes. Table 2. Selection of dyeing conditions using central composite design for cotton dyeing using flower extract Experiment no. pH Volume (ml) Time (min) Temperature (0C) Salt concentration (g/100ml) Colour strength (K/s) 1 7 55 30 80 1 2.3318 2 9 55 30 60 1 1.8689 3 7 35 30 60 1 2.1736 https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 26 https://doi.org/10.31881/TLR.2022.67 Experiment no. pH Volume (ml) Time (min) Temperature (0C) Salt concentration (g/100ml) Colour strength (K/s) 4 9 35 30 80 1 2.6943 5 7 55 30 60 2 2.5707 6 9 55 30 80 2 2.4320 7 7 35 30 80 2 1.7221 8 9 35 30 60 2 2.3320 9 7 55 50 60 1 2.4575 10 9 55 50 80 1 1.8923 11 7 35 50 80 1 1.7692 12 9 35 50 60 1 2.0571 13 7 55 50 80 2 2.7580 14 9 55 50 60 2 1.7467 15 7 35 50 80 2 1.996 16 9 35 50 70 2 2.0326 17 7 55 40 70 1.5 3.5438 18 9 55 40 70 1.5 1.8084 19 6 45 40 70 1.5 2.8694 20 10 45 40 70 1.5 1.8408 21 8 25 40 70 0.5 1.9100 22 8 65 20 70 2.5 1.9498 23 8 45 60 70 1.5 1.7868 24 8 45 40 70 1.5 1.7674 25 8 45 40 50 1.5 3.1204 26 8 45 40 90 1.5 1.8548 27 8 45 40 70 1.5 1.9344 28 8 45 40 70 1.5 1.7123 29 8 45 40 70 1.5 2.0634 30 8 45 40 70 1.5 1.5984 31 8 45 40 70 1.5 1.5593 32 8 45 40 70 1.5 1.6640 Because the equilibrium of the dye bath can only be obtained at low heating, and too much heating promotes dissociation rather than adsorption, lowering the colour, the level of dyeing of cotton fabric with plant-based colourant is constantly reliant on the time and temperature. Dyeing ultrasonic- treated cotton fabric at 70 °C for 40 minutes using an aqueous extract with 7 pH made from 4 g powder including 1.5% sodium chloride yielded the highest colour strength as compared with other samples (Table 2) ANOVA statistics for a 2nd order model with 5 key variables, 5 quadratic impacts, and 2 way interactions have been seen in Table 4. We progressively changed the model by removing non-significant https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 27 https://doi.org/10.31881/TLR.2022.67 components, excluding the key variables, which were included intact. Table 4 shows the p-value is supported by a variance inflation factor (VIF) greater than 1. By experimenting with several permutations of extraction and irradiation conditions, the colouring parameters were statistically optimized. Most of these variables have positive effects on colour strength versus extract amount, time, temperature, pH of the dye bath, and concentration of salt for attaining high exhaustion, but the effects of salt, pH of dye bath and time are extremely significant (p=0.000). Table 3. Statistical evaluation of results obtained after dyeing of cotton with flower extracts using various trials Term Effect Coef SE Coef T-Value P-Value VIF Constant 5.6008 0.0957 65.48 0.000 pH -1.544 -0.622 0.120 -7.32 0.000 2.00 Volume -0.129 -0.125 0.135 -1.00 0.044 1.30 Time -0.614 -0.367 0.126 -3.25 0.009 1.12 Temperature -3.927 1.978 0.132 -16.16 0.000 1.52 Salt -0.450 0.365 0.135 -2.33 0.045 1.30 pH* pH 4.561 2.431 0.199 11.49 0.000 1.06 Volume* volume 3.251 1.631 0.300 5.45 0.000 1.90 Temperature* temperature -2.999 -1.484 0.250 -6.12 0.000 1.35 pH* volume 6.690 3.360 0.255 14.17 0.000 1.29 pH* time -4.544 -2.297 0.255 -9.96 0.000 1.29 pH* temperature 6.5.01 3.200 0.279 12.61 0.000 1.34 Volume* time -4.140 -2.070 0.240 -9.79 0.000 1.010 Volume* temperature 2.295 1.150 0.270 5.27 0.003 1.34 Volume* salt -2.810 -1.405 0.215 -8.55 0.000 1.79 Time* salt 5.860 2.930 0.239 13.44 0.000 1.10 Temperature* salt -5.200 -2.605 0.269 -8.69 0.000 1.30 Table 4. ANOVA: Colour strength versus dyeing parameters (temperature, volume, pH, time, and salt concentration) Source DF ADJ SS ADJ MS F-Value P-Value Model 164 41.1195 2.5574 50.19 0.000 pH 1 15.4198 2.9038 59.57 0.000 Volume 1 3.6450 2.6950 55.08 0.034 Time 1 0.0507 0.0494 0.100 0.000 Temperature 1 0.5835 0.6036 12.35 0.008 Salt 1 0.2675 0.3005 5.31 0.045 Square 3 12.7145 13.7355 230.81 0.000 pH* pH 1 8.9383 8.8483 159.92 0.000 Volume* volume 1 1.5059 1.5059 30.34 0.000 https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 28 https://doi.org/10.31881/TLR.2022.67 Source DF ADJ SS ADJ MS F-Value P-Value Temperature* temperature 1 1.9080 1.9380 40.06 0.000 2-Way Interaction 9 21.2860 2.9845 55.61 0.000 pH* volume 1 8.7877 8.8777 169.56 0.000 pH* time 1 4.1086 4.0986 79.20 0.000 pH* temperature 1 5.7703 6.8903 140.77 0.000 Volume* time 1 3.9481 4.9281 80.25 0.000 Volume* temperature 1 0.8906 0.8006 18.25 0.001 Volume* salt 1 3.1859 3.1867 45.90 0.000 Time* salt 1 6.9031 8.8831 144.83 0.000 Temperature* salt 1 5.9015 4.8055 92.87 0.000 Error 11 0.4998 0.0600 0.000 Lack-of-fit 6 0.2031 0.0406 0.60 0.000 Pure error 6 0.4167 0.0553 0.000 Total 25 43.6383 0.000 Mordanting is regarded as essential in natural colouring since it is the only approach to address the problem of low fastness [32,33]. In comparison to chemical salts of Al3+, Fe2+, and sodium potassium tartrate, green plant anchors i.e. extracts of pistachio, walnut, and pine nut shell were used at 20–90 °C. At 60 °C, pre-chemical mordanting with 2.5% Al3+, 1.5 g/100 ml Fe2+, and sodium potassium tartrate, as well as pre-bio-mordanting with 0.5 g/100 ml walnut and pine nut shells and 2.5% pistachio shell gave good shade strength and fastness features. Chemical mordants have given vibrant colours as well as superior colour strength when compared to bio-mordants [34-36]. As a result, plant-based anchors can be used to substitute metal salt in the process, making it more sustainable. Table 5. Shade variables of optimum dyed and mordanted cotton fabrics using haar singhar flower extract Mordanted samples conc.(g/100ml) K/S L* a* b* c* h* Fe (1.5g/100mL) ( Chemical pre) 3.5775 72.64 7.73 34.74 40.52 39.44 Fe(1g/100mL) (Chemical post) 1.6239 70.36 4.22 59.27 44.86 41.76 Al (2.5g/100mL) (Chemical pre) 4.4485 72.86 4.17 44.74 34.46 33.70 Al (2g/100mL) (Chemical post) 2.8908 61.89 8.16 43.61 48.22 48.12 SPT(1g/100mL) (Chemical pre) 5.1453 76.60 1.22 48.18 47.63 46.82 SPT (2g/100mL) (Chemical post) 1.6671 87.79 0.95 12.99 35.92 34.89 Walnut (0.5g/100mL) (Bio pre) 3.1399 69.92 0.99 40.78 30.53 29.35 Walnut (1g/100mL) (Bio post) 1.3091 82.71 3.33 31.73 19.19 16.66 Pistachio (2.5g/100mL) (Bio pre ) 0.8632 75.65 3.88 59.78 36.62 36.12 Pistachio (2g/100mL) (Bio post) 7.9806 82.59 3.66 23.59 35.64 32.92 Pine nut (0.5g/100mL) (Bio pre ) 1.5584 73.21 4.55 39.24 24.61 24.84 Pine nut (2.5g/100mL) (Bio post) 1.6967 71.27 4.09 45.41 27.64 26.91 https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 29 https://doi.org/10.31881/TLR.2022.67 0 1 2 3 4 5 6 0.5 1 1.5 2 2.5 K /S Pre chemical mordant conc.(g/100ml) Fe Al SPT 0 0.5 1 1.5 2 2.5 3 3.5 0.5 1 1.5 2 2.5 K /S Post chemical mordant conc.(g/100ml) Fe Al SPT a) 0 1 2 3 4 5 6 0.5 1 1.5 2 2.5 K /S Pre chemical mordant conc.(g/100ml) Fe Al SPT 0 0.5 1 1.5 2 2.5 3 3.5 0.5 1 1.5 2 2.5 K /S Post chemical mordant conc.(g/100ml) Fe Al SPT b) Figure 5. Effect of pre a), and post chemical mordants b) on haar singhar dyed on cotton fabric colour strength 0 0.5 1 1.5 2 2.5 3 3.5 0.5 1 1.5 2 2.5 K /S Pre biomordant conc.(g/100ml) Walnut Pistachio Pine nut 0 1 2 3 4 5 6 7 8 9 0.5 1 1.5 2 2.5 K /S Post biomordant conc.(g/100ml) Walnut Pistachio Pine nut a) https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 30 https://doi.org/10.31881/TLR.2022.67 0 0.5 1 1.5 2 2.5 3 3.5 0.5 1 1.5 2 2.5 K /S Pre biomordant conc.(g/100ml) Walnut Pistachio Pine nut 0 1 2 3 4 5 6 7 8 9 0.5 1 1.5 2 2.5 K /S Post biomordant conc.(g/100ml) Walnut Pistachio Pine nut b) Figure 6. Effect of pre-bio-mordants a), and post-bio-mordants b) on haar singhar dyed on cotton fabric colour strength. Fastness characteristics following the application of chemical and bio mordants, it was discovered that functional molecules formed such a strong bond with the functional component of the colourant and the cotton fabric (–OH) that the shade formed hindered receding when exposed to light, washing, and dry and wet rubbing to a significant extent [37, 38]. The colourant molecule obtained from the haar singhar flower extract is light, rubbing, and washing resistant. This is because biomordants employ their –OH groups and ligation system to create new colours that resist separation from fabric. In chemical mordanting, the salts of Al, SPT, and Fe contribute to the establishment of a stable metal and dye complex on cotton fabric resulting in less colour separation and a good fastness rating. Thus, utilizing environmentally friendly mordants before and after dyeing has improved not only the natural dyeing of cotton using irradiated haar singhar flower extract but has also made the process more sustainable by introducing soothing hues, wash fastness, light fastness, dry and wet rubbing fastness are all processes to enhance colourfastness. Table 6. Fastness ratings of pre and post mordanted dyed fabric Mordanted samples concentration (g/100 ml) LF WF DRF WRF Dyed mordanted fabrics Fe (1.5 g/100 mL) ( Chemical pre mordanted) 4 ¾ 4 3/4 Fe(1 g/100 mL) (Chemical post mordanted) 5 4 5 4/5 https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 31 https://doi.org/10.31881/TLR.2022.67 Mordanted samples concentration (g/100 ml) LF WF DRF WRF Dyed mordanted fabrics Al (2.5 g/100 mL) (Chemical pre mordanted) 5 4/5 5 4/5 Al (2 g/100 mL) (Chemical post) 5 4/5 5 4/5 SPT(1 g/100 mL) (Chemical pre mordanted) 5 4/5 5 4/5 SPT (2 g/100 mL) (Chemical post mordanted) 5 4/5 5 4/5 Walnut (0.5 g/100 mL) (Pre biomordanted) 5 4/5 5 4/5 Walnut (1 g/100 mL) (Post bio mordanted) 5 4/5 5 4/5 Pistachio (2.5 g/100 mL) (Pre bio mordanted ) 5 4/5 5 4/5 Pistachio (2 g/100 mL) (Post bio mordanted) 5 4/5 5 4/5 Pine nut (0.5 g/100 mL) (Pre bio mordanted) 5 4/5 5 4/5 Pine nut (2.5 g/100 mL) (Post bio mordanted) 5 4/5 5 4/5 LF (light fastness), WF (wash fastness), DRF (dry rubbing fastness), and WRF (wet rubbing fastness). CONCLUSION Natural dyes are less toxic, and non-allergic, which is why they are becoming more popular in the textile industry. It has been discovered that a novel technique of extraction, namely ultrasonic extraction, has the potential for yielding the natural colourant while using less time, energy, and solvent. Mordanting is utilized to improve the colour strength of the dyed fabric. Under ultrasonic irradiation, the haar singhar flower extract was investigated as a new dye-producing plant. The https://doi.org/10.31881/TLR.2022.67 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 32 https://doi.org/10.31881/TLR.2022.67 introduction of bio-based mordants and ecologically friendly chemical mordants have been found to enhance the colour strength of cotton fabrics by making an additional binding with the dye and fabric, resulting in a new shade with outstanding colour fastness. Author Contributions Conceptualization: Adeel S; Methodology: Nasreen H and Amin N; Supervision: Yameen M; Investigation: Ozomay M; Writing draft: Nasreen H; Writing-Review and editing: Qayyum MA; Formal Anlaysis: Ozomay M. Conflicts of Interest The authors declare no conflict of interest. Funding This research received no external funding Acknowledgements We are highly thankful to Department of Biochemistry for providing necessary chemicals and assorted glassware and to Department of Applied Chemistry for providing facilities to conduct experiments. This article was published under the competence of Guest Editor Shahid Adeel. REFERENCES [1] Adeel S, Azeem M, Habib N, Hussaan N, Kiran A, Haji A, Haddar W. Sustainable application of microwave assisted extracted tea based tannin natural dye for chemical and bio-mordanted wool fabric. Journal of Natural Fibers. 2023; 20(1): 2136322. [2] Svetozarević M, Šekuljica N, Onjia A, Barać N, Mihajlović M, Knežević-Jugović Z, Mijin D. Biodegradation of synthetic dyes by free and cross-linked peroxidase in microfluidic reactor. Environmental Technology and Innovation. 2022; 26:102373. https://doi.org/10.1016/j.eti.2022.102373 [3] Ozdemir MB, Karadag R. Madder (Rubia tinctorum L.) as an Economic Factor Under Sustainability Goals in the Textile Dyeing. Journal of Natural Fibers. 2023; 20(1):2128968. https://doi.org/10.1080/15440478.2022.2128968 [4] Singh A, Sheikh J. Cleaner functional dyeing of wool using kigelia africana natural dye and Terminalia chebula bio-mordant. Sustainable Chemistry and Pharmacy. 2020; 17:100286. https://doi.org/10.1016/j.scp.2020.100286 https://doi.org/10.31881/TLR.2022.67 https://doi.org/10.1016/j.eti.2022.102373 https://doi.org/10.1080/15440478.2022.2128968 https://doi.org/10.1016/j.scp.2020.100286 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 33 https://doi.org/10.31881/TLR.2022.67 [5] Ardila-Leal LD, Poutou-Piñales RA, Pedroza-Rodríguez AM, Quevedo-Hidalgo BE. A Brief History of Colour, the Environmental Impact of Synthetic Dyes and Removal by Using Laccases. Molecules. 2021; 26(13):3813. https://doi.org/10.3390/molecules26133813 [6] Hynes NRJ, Kumar JS, Kamyab H, Sujana JAJ, Al-Khashman OA, Kuslu Y, Ene A, Kumar BS. Modern enabling techniques and adsorbents based dye removal with sustainability concerns in textile industrial sector-A comprehensive review. Journal of cleaner production. 2020; 272(1):122636. https://doi.org/10.1016/j.jclepro.2020.122636 [7] Mansour R, Ben Ali H. Investigating the use of chitosan: toward improving the dyeability of cotton fabrics dyed with Roselle (Hibiscus sabdariffa L.). Journal of Natural Fibers. 2021; 18(7):1007-1016. https://doi.org/10.1080/15440478.2019.1675217 [8] Elgarahy AM, Elwakeel KZ, Mohammad SH, Elshoubaky GA. A critical review of biosorption of dyes, heavy metals and metalloids from wastewater as an efficient and green process. Cleaner Engineering and Technology. 2021; 4:100209. https://doi.org/10.1016/j.clet.2021.100209 [9] Madhukar Thakker A. Sustainable processing of cotton fabrics with plant-based biomaterials Sapindus mukorossi and Acacia concinna for health-care applications. The Journal of The Textile Institute. 2021; 112(5):718-726. https://doi.org/10.1080/00405000.2020.1776537 [10] Verma M, Gahlot N, Jeet Singh SS, Rose NM. UV protection and antibacterial treatment of cellulosic fibre (cotton) using chitosan and onion skin dye. Carbohydrate Polymers. 2021; 257:117612. https://doi.org/10.1016/j.carbpol.2020.117612 [11] Dulo B, Phan K, Githaiga J, Raes K, De Meester S. Natural quinone dyes: a review on structure, extraction techniques, analysis and application potential. Waste and Biomass Valorization. 2021; 12:6339-6374. https://doi.org/10.1007/s12649-021-01443-9 [12] Xiong Y, Zhang P, Warner RD, Hossain MN, Leonard W, Fang Z. Effect of sorghum bran incorporation on the physicochemical and microbial properties of beef sausage during cold storage. Food Control. 2022; 132:108544. https://doi.org/10.1016/j.foodcont.2021.108544 [13] Nathan VK, Rani ME. Natural dye from Caesalpinia sappan L. heartwood for eco-friendly coloring of recycled paper based packing material and its in silico toxicity analysis. Environmental Science and Pollution Research. 2021; 28(22):28713-28719. https://doi.org/10.1007/s11356-020-11827-4 [14] Ghanmi H, Sebeia N, Jabli M, Al-Ghamdi YO, Algohary AM. Insight into Fuzzy Logic and Response Surface methodologies for predicting wool and polyamide dyeing behaviors with a biological extract of Juglans Regia. Fibers and Polymers. 2022; 23(12):3473-3481. https://doi.org/10.1007/s12221-022-4552-y [15] Maulik SR, Debnath C, Pandit P. Sustainable dyeing and printing of knitted fabric with natural dyes. In: Maity S, Rana S, Pandit P, Singha K, editor. Advanced Knitting Technology. Woodhead Publishing; 2022. p. 537-565. https://doi.org/10.1016/B978-0-323-85534-1.00008-8 https://doi.org/10.31881/TLR.2022.67 https://doi.org/10.3390/molecules26133813 https://doi.org/10.1016/j.jclepro.2020.122636 https://doi.org/10.1080/15440478.2019.1675217 https://doi.org/10.1016/j.clet.2021.100209 https://doi.org/10.1080/00405000.2020.1776537 https://doi.org/10.1016/j.carbpol.2020.117612 https://doi.org/10.1007/s12649-021-01443-9 https://doi.org/10.1016/j.foodcont.2021.108544 https://doi.org/10.1007/s11356-020-11827-4 https://doi.org/10.1007/s12221-022-4552-y https://doi.org/10.1016/B978-0-323-85534-1.00008-8 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 34 https://doi.org/10.31881/TLR.2022.67 [16] Kadam S, Sharma A, ul-Islam S, Bramhecha I, Sheikh J. Utilization of rice straw as a source of biomolecules for sustainable multifunctional fnishing vis a vis dyeing of wool. Journal of Natural Fibers. 2020; 17(10):1508-1518. https://doi.org/10.1080/15440478.2019.1581120 [17] Eid BM, Ibrahim NA. Recent developments in sustainable fnishing of cellulosic textiles employing biotechnology. Journal of Cleaner Production. 2020; 284:124701. https://doi.org/10.1016/j.jclepro.2020.124701 [18] Boruah G, Phukan AR, Kalita BB, Pandit P, Jose S. Dyeing of mulberry silk using binary combination of henna leaves and monkey jack bark. Journal of Natural Fibers. 2021; 18(2):229-237. https://doi.org/10.1080/15440478.2019.1616649 [19] Fosu AY, Kanari N, Vaughan J, Chagnes A. Literature Review and Thermodynamic Modelling of Roasting Processes for Lithium Extraction from Spodumene. Metals. 2020; 10(10):1312. https://doi.org/10.3390/met10101312 [20] Jiang H, Guo R, Mia R, Zhang H, Lü S, Yang F, Mahmud S, Liu H. Eco-friendly dyeing and finishing of organic cotton fabric using natural dye (gardenia yellow) reduced-stabilized nanosilver: full factorial design. Cellulose. 2022; 29(4):2663-2679. https://doi.org/10.1007/s10570-021-04401-9 [21] Lachguer K, El Ouali M, Essaket I, El Merzougui S, Cherkaoui O, Serghini MA. Eco-Friendly dyeing of wool with natural dye extracted from moroccan Crocus sativus l. flower waste. Fibers and Polymers. 2021; 22(12):3368-3377. https://doi.org/10.1007/s12221-021-0256-y [22] Hosseinnezhad M, Gharanjig K, Adeel S, Rouhani S, Imani H, Razani N. The effect of ultrasound on environmentally extraction and dyeing of wool yarns. Journal of Engineered Fibers and Fabrics. 2022; 17:15589250221104471. https://doi.org/10.1177/15589250221104471 [23] Zulqarnain A, Durrani AI, Saleem H, Rubab S. Development of an Ultrasonic-Assisted Extraction Technique for the Extraction of Natural Coloring Substance Chlorophyll from Leaves of Carica papaya. Journal of Oleo Science. 2021; 70(10):1367-1372. [24] Ojha KS, Aznar R, O’Donnell C, Tiwari BK. Ultrasound technology for the extraction of biologically active molecules from plant animal and marine sources. TrAC Trends in Analytical Chemistry. 2020; 122:115663. https://doi.org/10.1016/j.trac.2019.115663 [25] Babar AA, Bughio NUA, Peerzada MH, Naveed T, Dayo AQ. Exhaust reactive dyeing of lyocell fabric with ultrasonic energy. Ultrasonics Sonochemistry. 2019; 58:1046. https://doi.org/10.1016/j.ultsonch.2019.05.028 [26] Sadeghi-Kiakhani M, Tehrani-Bagha AR, Safapour S, Eshaghloo-Galugahi S, Etezad SM. Ultrasound- assisted extraction of natural dyes from Hawthorn fruits for dyeing polyamide fabric and study its fastness, antimicrobial, and antioxidant properties. Environment, Development and Sustainability. 2021; 23(6):9163-9180. https://doi.org/10.1007/s10668-020-01017-0 https://doi.org/10.31881/TLR.2022.67 https://doi.org/10.1080/15440478.2019.1581120 https://doi.org/10.1016/j.jclepro.2020.124701 https://doi.org/10.1080/15440478.2019.1616649 https://doi.org/10.3390/met10101312 https://doi.org/10.1007/s10570-021-04401-9 https://doi.org/10.1007/s12221-021-0256-y https://doi.org/10.1177/15589250221104471 https://doi.org/10.1016/j.trac.2019.115663 https://doi.org/10.1016/j.ultsonch.2019.05.028 https://doi.org/10.1007/s10668-020-01017-0 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 35 https://doi.org/10.31881/TLR.2022.67 [27] Guo L, Kong D, Yao K, Li J, Li H, Lan N, Hua Y. Optimization and characterization of pigment production from Boletus edulis Bull.: Fr. by ultrasonic‐assisted extraction. Journal of Food Processing and Preservation. 2020; 44(7):e14534. https://doi.org/10.1111/jfpp.14534 [28] Talib A, Rehman FU, Adeel S, Ali A, Ahmad T, Hussaan, M Qayyum M.A. Sustainable isolation and application of plants extract-based natural dye for bio-dyeing of silk fabric. Coatings. 2023; 13(1): 112. https://doi.org/10.3390/coatings13010112 [29] Adeel S, Ahmad S, Habib N, ur-Rehman F, Mia R, Ahmed B. Coloring efficacy of Nyctanthes Arbortristis based yellow natural dye for surface-modified wool. Industrial Crops and Products. 2022; 188(Part A):115571. https://doi.org/10.1016/j.indcrop.2022.115571 [30] Atav R, Akkuş E, Ergünay U. Investigation of the dyeability of cotton fabrics with a halochromic dye according to exhaust and padding methods. Journal of Natural Fibers. 2021; 19(14):1-14. https://doi.org/10.1080/15440478.2021.1982442 [31] Sarfarazi M, Rajabzadeh Q, Tavakoli R, Ibrahim SA, Jafari SM. Ultrasound-assisted extraction of saffron bioactive compounds; separation of crocins, picrocrocin, and safranal optimized by artificial bee colony. Ultrasonics Sonochemistry. 2022; 86:105971. https://doi.org/10.1016/j.ultsonch.2022.105971 [32] Akram W, Adeel S, Amin N, Habib N, Inayat A, Mirnezhad S. Impact of MW rays on extraction and application of Ficus religiosa bark based natural colourant for cotton dyeing. Journal of Engineered Fibers and Fabrics. 2022; 17:15589250221078927. https://doi.org/10.1177/15589250221078927 [33] Habib N, Akram W, Adeel S, Amin N, Hosseinnezhad M, Ul Haq E. Environmental-friendly extraction of Peepal (Ficus Religiosa) bark-based reddish brown tannin natural dye for silk coloration. Environmental Science and Pollution Research. 2022; 29:35048-35060. https://doi.org/10.1007/s11356-022-18507-5 [34] Yameen M, Adeel S, Nasreen H, ur-Rehman F, Ghaffar A, Ahmad T, Inayat, A. Sustainable eco- friendly extraction of yellow natural dye from haar singhar (Nyctanthes arbor-tritis) for bio coloration of cotton fabric. Environmental Science and Pollution Research. 2022; 29:83810-83823. https://doi.org/10.1007/s11356-022-21450-0 [35] Kramar A, Kostic MM. Bacterial Secondary Metabolites as Biopigments for Textile Dyeing. Textiles. 2022; 2(2):252-264. https://doi.org/10.3390/textiles2020013 [36] Hosseinnezhad M, Gharanjig K, Jafari R, Imani H, Razani N. Cleaner colorant extraction and environmentally wool dyeing using oak as eco-friendly mordant. Environmental Science and Pollution Research. 2021; 28(6):7249-7260. https://doi.org/10.1007/s11356-020-11041-2 [37] Hayat T, Adeel S, ur-Rehman F, Batool F, Amin N, Ahmad T, Ozomay M. Waste black tea leaves (Camelia sinensis) as a sustainable source of tannin natural colorant for bio-treated silk dyeing. https://doi.org/10.31881/TLR.2022.67 https://doi.org/10.1111/jfpp.14534 https://doi.org/10.3390/coatings13010112 https://doi.org/10.1016/j.indcrop.2022.115571 https://doi.org/10.1080/15440478.2021.1982442 https://doi.org/10.1016/j.ultsonch.2022.105971 https://doi.org/10.1177/15589250221078927 https://doi.org/10.1007/s11356-022-18507-5 https://doi.org/10.1007/s11356-022-21450-0 https://doi.org/10.3390/textiles2020013 https://doi.org/10.1007/s11356-020-11041-2 NASREEN H et al. TEXTILE & LEATHER REVIEW | 2023 | 6 | 18-36 36 https://doi.org/10.31881/TLR.2022.67 Environmental Science and Pollution Research. 2022; 29(16):24035-24048. https://doi.org/10.1007/s11356-021-17341-5 [38] Eyupoglu C, Eyupoglu S, Merdan N. Investigation of Dyeing Properties of Mohair Fiber Dyed with Natural Dyes Obtained from Candelariella reflexa. Journal of Natural Fibers. 2022; 19(16):12829- 12848. https://doi.org/10.1080/15440478.2022.2076273 https://doi.org/10.31881/TLR.2022.67 https://doi.org/10.1007/s11356-021-17341-5 https://doi.org/10.1080/15440478.2022.2076273 INTRODUCTION METHODOLOGY Sample collection Extraction of colorant Optimization of dyeing parameters Mordanting Analysis of the properties of coloured cotton fabric RESULTS AND DISCUSSION CONCLUSION Acknowledgements