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Dragonfruit Dye Procedure Article

Preparation of dyes from dragonfruit peel.

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0% found this document useful (0 votes)
88 views15 pages

Dragonfruit Dye Procedure Article

Preparation of dyes from dragonfruit peel.

Uploaded by

etr420
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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sustainability

Article
Natural Dyeing and Antimicrobial Functionalization of Wool
Fabrics Dyed with Chinese Dragon Fruit Extract to Enhance
Sustainable Textiles
Mohmadarslan Kutubuddin Sadannavar 1,2 , Aravin Periyasamy 3 , Syed Rashedul Islam 4 , Faizan Shafiq 1,2 ,
Xue Dong 1,2 and Tao Zhao 1,2, *

1 College of Chemistry & Chemical Engineering, Donghua University, Shanghai 201620, China;
sunnysadannavar@gmail.com (M.K.S.); faizan@mail.dhu.edu.cn (F.S.); xuedong125521@163.com (X.D.)
2 Key Laboratory of Science & Technology of Eco-Textile, Ministry of Education, Donghua University,
Shanghai 201620, China
3 Department of Bio Products and Bio System, School of Chemical Engineering, Aalto University,
02150 Espoo, Finland; aravinprince.periyasamy@aalto.fi
4 Department of Textile Engineering, Uttara University, Dhaka 1230, Bangladesh; sri060791@gmail.com
* Correspondence: tzhao@dhu.edu.cn

Abstract: Recently, the natural dyeing process has achieved great importance in the textile wet
processing industry due to its clean dyeing, eco-friendliness, and nontoxicity in nature. In the
above research project, a unique natural dye extracted from dragon fruit was applied to wool fabric
using various mordanting agents to encourage the use of natural dyes and lessen the negative
environmental effects caused by synthetic dyeing. The color characteristics (K/S), fastness properties,
Fourier transform infrared spectroscopy (FTIR), absorption spectra, and thermal and ultraviolet (UV)
resistance of the extracted dye and dyed wool samples were tested and characterized. The K/S values
of the dyed wool fabrics were between 5.75 and 13.29. The color fastness ratings obtained from the
dyed wool fabric were found to be between good and excellent. Hence, the overall results proved
that the novel natural dye obtained from dragon fruit can be utilized for dyeing wool material for the
Citation: Sadannavar, M.K.;
production of eco-friendly and sustainable antimicrobial textiles.
Periyasamy, A.; Islam, S.R.; Shafiq, F.;
Dong, X.; Zhao, T. Natural Dyeing
and Antimicrobial Functionalization
Keywords: dragon fruit; natural dyeing; wool; mordanting; antibacterial; textiles
of Wool Fabrics Dyed with Chinese
Dragon Fruit Extract to Enhance
Sustainable Textiles. Sustainability
2024, 16, 6832. https://doi.org/ 1. Introduction
10.3390/su16166832 Natural products in the textile processing industry are gaining significant importance
Academic Editors: Slavenka Petrak due to their eco-friendliness, low toxicity, non-carcinogenic nature, and natural biodegrad-
and Martinia Ira Glogar ability. The dyeing process in textile manufacturing plays a vital role in the acceptability of
textiles. Natural dyes are coloring compounds that are derived from several sources (such
Received: 14 July 2024 as animals, fungi, insects, minerals) and various plant parts (such as fruits, roots, flowers,
Revised: 1 August 2024
leaves, woods, and seeds), and they have the ability to impart color to substances that have
Accepted: 5 August 2024
a wide range of shades [1]. Researchers are turning towards natural dyes as a potential
Published: 9 August 2024
alternative to synthetic dyes because bulk production and the extensive use of synthetic
dyes may result in environmental damage and may be hazardous to human health due to
the toxicity of synthetic dyes [2]. Several natural dyes not only diffuse color to the textile
Copyright: © 2024 by the authors.
material but also possess several functional characteristics, such as antimicrobial activity,
Licensee MDPI, Basel, Switzerland. fragrance, insect repellence, and UV protection. Numerous studies on the effects of natural
This article is an open access article dyes on textiles have produced useful findings for researchers. Several other advanced
distributed under the terms and and modified methods for improving the natural dyeing of wool have also been studied.
conditions of the Creative Commons Shabbir et al. investigated and contrasted the antibacterial capabilities and color features of
Attribution (CC BY) license (https:// several naturally occurring dyes obtained from plants such as T. erecta, T. chebula, and A.
creativecommons.org/licenses/by/ tinctoria on wool yarn. The findings demonstrated that woolen yarns dyed with carefully
4.0/). chosen natural dyes produced vibrant hues with acceptable color and fastness attributes.

Sustainability 2024, 16, 6832. https://doi.org/10.3390/su16166832 https://www.mdpi.com/journal/sustainability


Sustainability 2024, 16, 6832 2 of 15

The effects of the natural dyes T. chebula and A. tinctoria, of which T. chebula demonstrated
great results in terms of both antibacterial capabilities and color features, were particularly
effective in resisting S. aureus and B. subtilis bacteria [3].
Using distilled water and a Soxhlet device, Eser and Onal extracted natural dyes from
nettle leaves. The dyeing of the nettle leaves produced a rich color owing to the absorption
of light beams of various wavelengths. Thus, they concluded that nettle leaves are likely
a crucial raw material, particularly for dyeing wool fibers [4]. Motaghi, in his research,
dyed wool fabric with an aqueous extract of natural dyes from the skin of red onion and
barberry roots. The results demonstrated that wool material dyed with barberry roots
and red onion skin obtained significant ultraviolet protection factor (UPF) ratings and
antibacterial activity. Wool fabric can be effectively protected against ultraviolet radiation
by dyeing it with an aqueous extract of barberry roots and red onion skin, both of which
have strong UV-blocking properties. Both the red onion peel and the barberry roots used to
dye wool fabric had significant antibacterial effects on S. aureus [5].
Overall, the ultrasonic dyeing of wool with coconut coir extract as a natural dye
was carried out by using natural bio-mordants such as acacia, henna, pomegranate, and
turmeric extracts to increase the sustainability of the process. It was discovered that bio-
mordanting produced good color features, significantly increased the value of coloring,
and improved the fastness ratings of wool materials that had been dyed [6].
The natural dyes obtained from fruits include several different classes of compounds
that are responsible for dye ability and biological and other functional properties. Dragon
fruit is a vine cactus species belonging to the cactus family that has wide adaptability and
is grown in slightly heavy-textured soil. The fruit is highly attractive, with dark red skin
that is covered with green scales and red or white flesh that contains numerous small
black seeds, much like kiwi fruit. The red or dark pink color of the inner flesh and peel of
the dragon fruit is due to the presence of betacyanins, which become pigmented during
ripening. Dragon fruit has strong potential for use as a natural dye because it consists of
betacyanin, which is a violet–red substance that can be obtained from pigments known as
betalains; moreover, betacyanin includes nitrogen molecules and is soluble in water [7,8].
Keeping the above information in mind, in the above research experiment, natural
dye was extracted from dragon fruit by an ultrasonic method, and it was applied to wool
fibers. The development of different shades and the interactions between natural dyes
produced from dragon fruit and wool fibers were also investigated using a variety of
metallic mordants. Several functional properties, such as UV protection, antibacterial
activity, UPF, and thermal and fastness qualities, of dye wool fabric were tested and
characterized. A novel natural dye extracted from Chinese dragon fruit was reported for
the dyeing of wool fabric.

2. Materials and Methods


2.1. Materials
Pure 100% woolen fabric at 120 g/m2 (warp-27, weft-13) was obtained from Xiang
Shan Henda Co., Ltd., Shenzhen, China. Dragon fruits were obtained from a local fruit
supermarket in China. Absolute ethanol, potassium dichromate (K2 Cr2 O7 ), stannous chlo-
ride (SnCl2 ·2H2 O), and copper sulfate (CuSO4 ·5H2 O), which were supplied by Sinopharm
Chemical Reagent Co., Ltd., Shanghai, China, were used as mordanting agents. A non-ionic
detergent obtained from Hangzhou Xinsheng Dyeing & Printing Pvt. Ltd., Hangzhou,
China was applied in the fastness to washing procedure.

2.2. Methods
2.2.1. Extraction of Dye
An ultrasound-assisted extraction technique was used to extract natural dye from
dragon fruit. Initially, 60 g of fresh dragon fruit flesh was mixed with 400 mL of solvent
(240 mL of ethanol and 160 mL of distilled water) by maintaining a material to liquor ratio
(MLR) of 1:20. The mixture was blended for 10 min until the mixture was homogeneous
Sustainability 2024, 16, 6832 3 of 15

in color, after which the mixture was transferred to a conical flask. After that, the conical
flask was placed in an ultrasonic bath and sonicated for an hour at 60 ◦ C at a frequency
of 28–30 MHz and 160 volts of provided power [9]. Following sonication, the solutions
were filtered to remove any remaining dye particles using Grade 1 Whatman filter paper,
pore size—11 µm, diameter—90 mm, and parameter—0.25 psi wet burst. The unwanted
ethanol was evaporated by a rotary evaporator (RE52CS-1, Shanghai Yarong Biochemical
Instrument Factory, Shanghai, China) for reuse.

2.2.2. Pre-Mordanting
The wool fabrics were pre-mordanted in a shaker dyeing machine using 5% of the
weight of fabric (OWF) of potassium dichromate, stannous chloride, and copper sulfate as
mordanting chemicals for 60 min at 80 ◦ C with a material-to-liquor ratio of 1:20. After the
pre-mordanting procedure, the samples were dried for 30 min at room temperature. After
drying, the wool samples were further used for dyeing.

2.2.3. Dyeing
Wool samples were dyed in a shaker dyeing machine using a 1:40 material to liquor
ratio. Dyeing was performed for both the mordanted and un-mordanted samples to
examine the dye ability of the wool fabrics. Initially, dyeing was initiated at 40 ◦ C for
15 min before heating to 90 ◦ C for 50 min at a temperature increase rate of 1.5 ◦ C/min. To
remove the unfixed dye on the fiber surface, the dyed wool fabrics were passed through a
soaping process. Each soaping procedure lasted for 10 min. Following a first cold wash
at room temperature, a second hot wash at 70 ◦ C, a third hot wash at 70 ◦ C using 3 g/L
of a soaping detergent, and a fourth hot wash at 70 ◦ C were used to remove the soaping
detergent from the fabric. All of the previously washed samples were dried for 24 h at
room temperature.

2.2.4. Color Measurement and Analysis


The colorimetric characteristics of the dyed wool fabrics were measured using a Spectra
Flash-Data Color (SF-600) device. The Kubelka–Munk equation was used to compute the
spectrophotometer’s color yields (K/S) and CIE Lab values (L*, a*, b*, c*, and h◦ ). Each
sample was measured 3 times, and the average value was recorded.

K/S = ( I − R)2 /2R (1)

where K is the absorbance factor, S is the scattering factor, and R is the reflectance of the
dyed wool at the wavelength of greatest absorption (McDonald 1997).

2.2.5. Scanning Electron Microscopy


The surface morphology of the undyed and dyed samples was obtained via SEM (HI-
TACHI TM-1000, Chiyoda, Japan) at a magnification of 800× using an acceleration voltage
of 5 kV. All the samples were sputtered under vacuum with gold before the assessment.

2.2.6. FTIR
The FTIR spectra of dye extracted from dragon fruit and wool samples were mea-
sured using an AVATAR 380 instrument (Thermo Electron, Waltham, MA, USA) with a
wavenumber range of 400–4000 cm−1 and a resolution of 1 cm−1 .

2.2.7. Color Fastness Assessment


The International Organization for Standardization (ISO) standard test methods were
used to evaluate the color fastness of the dyed wool fabrics for their wash, rubbing, light,
and perspiration fastness properties. These methods included ISO 105-C10, ISO 105-X12,
ISO 105-B02, and ISO 105-E04 [10].
Sustainability 2024, 16, 6832 4 of 15

2.2.8. Evaluation of UV Protection Properties


The UPF is a measurement of a fabric’s ability to resist UV rays. According to the
EU standard 13758-2001, the UPF values of undyed and dyed samples were determined
using a YG912E textile anti-ultraviolet tester [11]. The transmittance of both UV-A and
UV-B radiation was measured across the wavelength range of 290 to 400 nm at 10 nm
intervals. Every sample was tested five times at different locations, and the average value
was reported.

2.2.9. Thermogravimetric Analysis


TGA was used to determine the degradation temperature of the samples because it
provides information on the decomposition of samples. TGA was performed on undyed
and dyed samples using a TQ 209 FI Libra® Netzhch, GMBH, SELB, Germany analyzer by
heating the dyed and undyed wool samples to 900 ◦ C at an increasing rate of 20 ◦ C/min
under continuous nitrogen gas flow.

2.2.10. UV-Visible Spectral Analysis


Spectroscopy is a versatile technique used to detect the presence of molecules in
a compound. A TU-1901 UV-Vis spectrophotometer (Taiyuan, China) was used in the
current study. The prepared solution of dye extracted from dragon fruit was analyzed at
wavelengths ranging from 200 to 800 nm.

2.2.11. Liquid Chromatography Mass Spectroscopy


To identify the degradation products from the dragon fruit extracted natural dye, the
sample was analyzed by triple quadruple mass spectrometry (Xevo TQ-S cronos, SCIEX
corporation, Milford, MA, USA). To separate the degraded products, a separate Terra C-18
capillary column was connected to the LC–MS instrument. The mixture of acetonitrile
and water (70/30, v/v) was filtered through a 0.22 m Millipore syringe filter to create a
mobile phase. The flow rate of the elute was maintained at 0.08 mL min−1 , and the injection
volume was 20 µL. The eluent from the chromatographic column was inserted into the
UV–Vis diode array detector, the ESI interface, and the quadruple ion trap mass analyzer. In
the mode of positive ions, MS analysis was carried out using a mass spectrometer attached
to an ESI ion source. The ESI probe tip and capillary potentials were set at 2.5 kV and 25 V,
respectively, by maintaining the mass range at 50–400 m/z. The temperature of the heated
capillary was adjusted to 200 ◦ C. The chemical structures of the obtained intermediate
products were determined according to fragment analysis from peak-by-peak software.

2.2.12. Antibacterial Test


The American Association of Textile Chemists and Colorists (AATCC) 100-1999 was
used to quantitatively assess the antibacterial activity of samples of both undyed and dyed
wool against both E. coli and S. aureus bacteria. By evaluating the difference in colony
counts between dyed and undyed samples during incubation, the antibacterial activity of
the wool samples was quantified. The results are reported as a percentage of the inhibition
ratio according to

Acontrol − Asample
 
Inhibition Ratio (%) = × 100 (2)
Acontrol

where Acontrol is the absorbance (or another relevant measure) of the control sample (with-
out the inhibitor). Asample is the absorbance (or another relevant measure) of the sample
containing the inhibitor.
where Acontrol is the absorbance (or another relevant measure) of the control sample
(without the inhibitor). Asample is the absorbance (or another relevant measure) of the
sample containing the inhibitor.

Sustainability 2024, 16, 6832 3. Results 5 of 15


3.1. Color Efficiency and Color Values of the Dyed Samples
Wool samples were pre-mordanted using copper sulfate, potassium dichromate,
3. Results
and stannous chloride. Table 1 shows the impact of the dyed wool samples with and
3.1. Color Efficiency and Color Values of the Dyed Samples
without a mordant on the color coordinates L*, a*, b*, c, and h and color strength. In
termsWool samples were
of mordanting, pre-mordanted
stannous chlorideusing (SnClcopper
2·2H2O)sulfate, potassium
outperformed all dichromate, and
other dyed sam-
stannous chloride. Table 1 shows the impact of the dyed wool samples
ples, with a K/S value of 13.29. The lowest color efficiency (5.75) of all the mordants waswith and without
adisplayed
mordant on by the
the color coordinates
potassium L*, a*, (K
dichromate b*,2Cr
c, 2O
and h and color
7) mordant. strength.
Both In terms
the samples of
dyed
mordanting, stannous chloride
without a mordant and copper sulfate(SnCl · 2H
2 (CuSO 2 O) outperformed all other dyed samples,
4·5H2O) showed almost identical K/S values
with
aofK/S value
(9.93) andof(8.17),
13.29.respectively.
The lowest color efficiency (5.75) of all the mordants was displayed
by the potassium
The dichromate of
color characteristics (Kdyed
2 Cr2 Owool7 ) mordant.
materialBoth the on
depend samples dyed without
the affinity of the dye a
mordant and copper sulfate (CuSO 4 · 5H 2 O) showed almost identical
particles for the wool and the dyeing mechanism. As a result, wool materials dyed withK/S values of (9.93)
and (8.17),
dragon respectively.
fruit extract showed great color efficiency when mordanting chemicals were
used, particularly when stannous chloride was used as a mordant [12]. The color char-
Table 1. Color characteristics of dyed wool fabrics with and without mordants.
acteristics of the wool samples dyed with dragon fruit extract demonstrated that various
color shades were produced
Mordant K/S using several
L* different
a* mordantingb* chemicals,C* as shown h in
Figure 1.
Without mordant
According to the L*,8.17 43.66
a*, b*, C and h° values, 45.62 5.26
when individually 45.93
assessed, there6.57
was
K2 Cr2 O7 5.75 46.88 27.68 6.24 28.38 12.71
a slight increase in lightness when potassium dichromate was used as a mordant,
CuSO4 ·5H2 O 9.93 38.12 28.98 17.30 33.75 30.84
whereas there was a decrease in lightness for the other mordant. Stannous chloride and
SnCl2 ·2H2 O 13.29 39.11 31.36 5.12 31.77 9.27
the sample dyed without a mordant were slightly more red, showing 31.36 and 45.62 red
(a*) values, whereas potassium dichromate and copper sulfate showed similar red (a*)
Theofcolor
values 27.68characteristics of dyed wool
and 28.98, respectively. On thematerial depend
other hand, on the
copper affinity
sulfate of the dye
displayed the
particles for the (b*)
highest yellow wool and of
value the17.30.
dyeingThemechanism. As a result,
color saturation valueswool materials
(C*) were founddyed
to bewith
the
dragon
highestfruit extract showed
in samples great color
dyed without efficiency
a mordant when while
(45.93), mordanting chemicals
they were foundwere
to be used,
the
particularly when stannous chloride was used as a mordant [12]. The
lowest in samples dyed with potassium dichromate (28.38). The samples dyed with color characteristics
of the wool
copper samples
sulfate dyed
had the with dragon
highest fruitofextract
hue angle 30.84,demonstrated that various
whereas the lowest colorwas
hue value shadesob-
were produced using several different mordanting
tained for the samples dyed without a mordant [13]. chemicals, as shown in Figure 1.

Figure1.1.Color
Figure Colorshades
shadesobtained
obtainedby
bywool
woolsamples
samplesafter
aftermordanting,
mordanting,dyeing,
dyeing,and
andcontrol
controlsample.
sample.

According to the L*, a*, b*, C and h◦ values, when individually assessed, there was a
slight increase in lightness when potassium dichromate was used as a mordant, whereas
there was a decrease in lightness for the other mordant. Stannous chloride and the sample
dyed without a mordant were slightly more red, showing 31.36 and 45.62 red (a*) values,
whereas potassium dichromate and copper sulfate showed similar red (a*) values of 27.68
and 28.98, respectively. On the other hand, copper sulfate displayed the highest yellow (b*)
value of 17.30. The color saturation values (C*) were found to be the highest in samples
dyed without a mordant (45.93), while they were found to be the lowest in samples dyed
with potassium dichromate (28.38). The samples dyed with copper sulfate had the highest
hue angle of 30.84, whereas the lowest hue value was obtained for the samples dyed
without a mordant [13].
Mordant K/S L* a* b* C* h
Without mordant 8.17 43.66 45.62 5.26 45.93 6.57
K2Cr2O7 5.75 46.88 27.68 6.24 28.38 12.71
Sustainability 2024, 16, 6832 CuSO4·5H2O 9.93 38.12 28.98 17.30 33.75 30.84
6 of 15
SnCl2·2H2O 13.29 39.11 31.36 5.12 31.77 9.27

3.2.Surface
3.2. SurfaceMorphology
MorphologyofofWoolWoolFabric
Fabric
SEM was
SEM was used
used to
to examine
examine thethesurface
surfacemorphology
morphologyofofboth bothdyed
dyedand
andundyed
undyed samples.
sam-
WoolWool
ples. fibers fibers
are clearly composed
are clearly of scaled
composed ofand fibrillar
scaled and components. Figure 2a Figure
fibrillar components. shows the2a
SEM image of undyed fabric, where the surface was found to be smooth
shows the SEM image of undyed fabric, where the surface was found to be smooth and and clean with
normal
clean fibrils,
with whichfibrils,
normal are usually
whichfound on the fabric
are usually foundsurface.
on theFigure
fabric2b–e shows
surface. the surface
Figure 2b–e
morphology of the dyed wool fabric with and without mordants.
shows the surface morphology of the dyed wool fabric with and without mordants.The dyed fabrics showed
The
undamaged
dyed wool and
fabrics showed the deposition
undamaged woolofand
somethedye particlesofonsome
deposition the wool surface. on
dye particles Hence,
the
compared
wool withHence,
surface. undyed fabrics, natural
compared dyes have
with undyed morenatural
fabrics, desirable interactions
dyes have more with the hair
desirable
cuticle surfaces
interactions withofthe
wool.
hair The energy-dispersive
cuticle surfaces of wool.X-ray
The analysis (EDX) graph
energy-dispersive proved
X-ray the
analysis
presence of elements like carbon, nitrogen, and oxygen.
(EDX) graph proved the presence of elements like carbon, nitrogen, and oxygen.

Figure
Figure2.2. SEM,
SEM,EDX,
EDX,and
andmapping
mappingimages
imagesofof(a)
(a)undyed
undyedwool,
wool,(b)
(b)wool
wooldyed
dyedwithout
withoutmordant,
mordant,
and
and (c–e) wool dyed with different mordant, (f) carbon mapping, (g) nitrogen mapping, (h)(h)
(c–e) wool dyed with different mordant, (f) carbon mapping, (g) nitrogen mapping, oxy-
oxygen
gen mapping, and (i) mixed mapping.
mapping, and (i) mixed mapping.

3.3. FTIR
The FTIR spectra of the raw wool fabric, dye extracted from dragon fruit, wool fabric
dyed without a mordant, and mordanted dyed wool fabric are shown in Figure 3, with
the complexation reaction mechanism shown in Figures 3–6. The O-H and N-H stretching
of the keratin extract’s ordered and folded structure was detected at 3100–3400 cm−1 .
The presence of a triple band in the wavenumber range between 2800 and 3000 cm−1 is
attributed to C-H vibrations. The absorption bands of the raw wool at wavenumber 1623
are attributed to amide I, N-H bending.
1631, which clearly indicated successful dyeing [15]. The peak shift is attributed to the
hydrogen bonding interaction between the amide I group and the carboxylic group of
the betalain pigment of wool. The intensity of the peaks was greater for all dyed samples
Sustainability 2024, 16, 6832 because of the presence of C=O groups and O-H groups in the betalains within 7 of 15
dragon
fruit.

Sustainability 2024, 16, x FOR PEER REVIEW


Figure 3. FTIR spectra of raw wool, natural dye extracted from dragon fruit, wool dyed without8 of 16
Figure 3. FTIR spectra of raw wool, natural dye extracted from dragon fruit, wool dyed without
mordant, wool dyed with copper sulfate mordant, wool dyed with potassium dichromate mordant,
mordant, wool dyed with copper sulfate mordant, wool dyed with potassium dichromate mor-
and wool dyed with tin chloride mordant.
dant, and wool dyed with tin chloride mordant.

Figure 4. Complex reaction mechanism of wool–potassium dichromate mordant for extracted natural
Figure 4. Complex reaction mechanism of wool–potassium dichromate mordant for extracted nat-
dye from dragon fruit.
ural dye from dragon fruit.
Sustainability 2024, 16, 6832 Figure 4. Complex reaction mechanism of wool–potassium dichromate mordant for extracted nat- 8 of 15
ural dye from dragon fruit.

Sustainability 2024, 16, x FOR PEER REVIEW 9 of 16


Figure 5. Complex reaction mechanism of wool–copper sulfate mordant for natural dye extracted
Figure 5. Complex reaction mechanism of wool–copper sulfate mordant for natural dye extracted
fromdragon
from dragonfruit.
fruit.

Complex reaction
Figure6.6. Complex
Figure reaction mechanism
mechanism of
of wool–stannous
wool–stannous chloride
chloride mordant
mordant for
for natural
natural dye
dye extracted
ex-
from dragon
tracted fruit. fruit.
from dragon

For Fastness
3.4. Color the FTIRProperties
spectra of
of dye
Woolextracted fromwith
Samples Dyed dragon fruit,
Dragon large peak at 3234 cm−1 is
theExtract
Fruit
alsoTable
attributed to the O-H stretch. −1
2 shows the light, wash,The peaks in theand
perspiration, wavenumber range between
rubbing properties of all 2800
woolcm
and 3000dyed − 1
cm withare and
attributed to aCH and CHCompared –1
samples without mordant. 2 vibrations.
to The
thosepeak at 1644
of the cm is sam-
un-mordant attributed
ples, the mordanting improved the overall fastness qualities of the mordanted samples In
to C=O stretching vibrations, which appear as carbonyl groups for ketone structures.
[18–20].

Table 2. Color fastness properties of dyed wool fabrics with and without mordants.

Perspiration Fastness Rubbing Fastness


Light Fastness Washing Fastness
Mordants ISO 105-E04 ISO 105-X12
Sustainability 2024, 16, 6832 9 of 15

dye extracted from dragon fruit, the active carbonyl and hydroxyl groups are normally
carboxylic acids [14–17].
In all dyed samples, the absorption band of wool at wavenumber 1623 shifted to 1631,
which clearly indicated successful dyeing [15]. The peak shift is attributed to the hydrogen
bonding interaction between the amide I group and the carboxylic group of the betalain
pigment of wool. The intensity of the peaks was greater for all dyed samples because of the
presence of C=O groups and O-H groups in the betalains within dragon fruit.

3.4. Color Fastness Properties of Wool Samples Dyed with Dragon Fruit Extract
Table 2 shows the light, wash, perspiration, and rubbing properties of all wool samples
dyed with and without a mordant. Compared to those of the un-mordant samples, the
mordanting improved the overall fastness qualities of the mordanted samples [18–20].

Table 2. Color fastness properties of dyed wool fabrics with and without mordants.

Perspiration Fastness Rubbing Fastness


Light Fastness Washing Fastness ISO 105-E04 ISO 105-X12
Mordants
ISO 105-B02 ISO 105-C10
Acidic Alkali Dry Wet
Without mordant 4 5–6 4–5 4–5 4–5 4
K2 Cr2 O7 4–5 4–5 4–5 4–5 4 4
CuSO4 ·5H2 O 4 4–5 4–5 4–5 4–5 4
SnCl2 ·2H2 O 5–6 5–6 4–5 5 4–5 4

3.4.1. Light Fastness


All of the wool samples dyed with dragon fruit extract had excellent light fastness
characteristics. The copper-sulfate-mordanted wool samples were comparatively less light-
tolerant than the control, potassium dichromate, or stannous-chloride-mordanted dyed
wool samples. This is probably due to the photolytic degradation and weak coordination
bonding of copper sulfate with dye molecules. On the other hand, wool fabrics dyed with
dragon fruit extract and stannous chloride as the mordant displayed an exceptional rating
of light fastness. Overall, the findings show that the mordanting process increased the
light fastness of the dyed wool fabrics in comparison to that of the samples dyed without
a mordant.

3.4.2. Wash Fastness


From the wash fastness results in Table 2, all the dyed wool samples (un-mordanted
and mordanted) showed good to excellent wash fastness ratings ranging from 4 to 6. The
wool fabric dyed with stannous chloride as the mordanting agent showed the highest
wash fastness rating compared to that of another mordant of copper sulfate and potassium
dichromate. The wool sample dyed without a mordant showed an excellent wash fastness
rating due to the affinity of wool fibers for coloring compounds in the form of strong
hydrogen bonding and ionic bonding, respectively.

3.4.3. Perspiration Fastness


The results for the perspiration fastness of both the acidic and alkaline media of wool
fabric dyed with dragon fruit extract are displayed in Table 2. The samples treated with
and without a mordant displayed the same rating of 4–5 in an acidic medium. However,
stannous chloride had the greatest effect on alkaline perspiration, followed by copper
sulfate and potassium dichromate.

3.4.4. Rubbing Fastness


Rubbing fastness performance is based on the presence of unfixed dyes on the fiber
surface of dyed fabrics. The dry rubbing fastness of potassium-dichromate-mordanted sam-
ples was relatively lower than that of un-mordanted and mordanted samples with copper
Sustainability 2024, 16, 6832 10 of 15

sulfate and stannous chloride, which was due to the weak co-ordination complexation of
potassium ions. However, there was no difference between the results for the mordanted
and un-mordanted wool fabrics in the wet rubbing test.

3.5. UV Protection
Because of their natural light resistance, textile fabrics are often utilized for UV pro-
tection. The UV-A band encompasses wavelengths between 315 and 400 nm, the UV-B
band encompasses wavelengths between 280 and 315 nm, and the UV-C band encompasses
wavelengths below 280 nm [21,22].
Table 3 provides the UPF (mean) rating and percentage values of UV-A and UV-B
radiation transmission through wool fabric. All dyed samples with and without a mordant
showed greater UPF values than the undyed samples. The wool samples dyed with
stannous chloride mordant had the highest UPF values [16]. The enhanced UPF values
with various metallic mordants may be caused by the metallic salts bridging the dye
molecules and the variations in the phytochemical constituents of the mordanted samples.
Hence, from the above UPF values, it can be concluded that wool material dyed with
dragon fruit extract can block UV radiation [23,24].

Table 3. UV protection readings of undyed, dyed without mordant, and mordanted dyed wool fabrics.

Sample UPF (Mean) UV (A %) UV (B %)


Undyed wool 298 2.87 0.08
Sustainability 2024, 16, x FOR PEER REVIEW
Dyed without mordant 363 0.05 0.05 11 of 16
K2 Cr2 O7 517 0.10 0.05
CuSO4 ·5H2 O 680 0.05 0.08
SnCl2 ·2H2 O 1058 0.58 0.05
3.6. Thermal Properties
3.6. Thermal
The TGProperties
curves of dyed and undyed wool fabrics under a nitrogen atmosphere are
shown TheinTG
Figure
curves7 of
fordyed
three different
and undyed stages of theunder
wool fabrics weight loss pattern.
a nitrogen Due to
atmosphere arethe hy-
drophilicity of the wool fibers, the initial weight loss was attributed to the losshy-
shown in Figure 7 for three different stages of the weight loss pattern. Due to the of water
drophilicity
from the woolof the wool fibers,
between 50 °Ctheand initial weight
170 °C. Theloss was attributed
second to the loss of occurred
stage of degradation water be-
from the wool between 50 ◦ C and 170 ◦ C. The second stage of degradation occurred be-
tween 200 ◦°C and 400◦ °C. The breakdown of the helical structure of wool fibers and the
tween 200 C and 400 C. The breakdown of the helical structure of wool fibers and the
thermal degradation of keratin, which occurred at 230 °C and where the maximal de-
thermal degradation of keratin, which occurred at 230 ◦ C and where the maximal decom-
composition rate occurred,
position rate occurred, may bemay be to
referred referred to as the degradation
as the degradation process.
process. The third stageThe
of third
stage of degradation
degradation occurred occurred
above 800 above
◦ C and800was°C and wastoattributed
attributed the loss ofto the loss
several sideofchains
several side
chains
from thefrom the
wool wool peptides.
peptides.

Figure 7.
Figure TGA curves
7. TGA curvesofofundyed
undyedand dyed
and wool
dyed fabric
wool withwith
fabric dragon fruit extract.
dragon fruit extract.

3.7. Absorption Spectra


Figure 8 shows the absorption spectra of dye extracted from dragon fruit. The dye
extracted from dragon fruit using ethanol resulted in a deep-colored solution. Certain
plants (such as beets) and cacti (such as dragon fruit) have pigments called betalains,
which are soluble in water and contain nitrogen. Both the flesh and skin of dragon fruit
are red because of the presence of betalains. The use of dragon fruit extract as a natural
Sustainability 2024, 16, 6832 11 of 15

3.7. Absorption Spectra


Figure 8 shows the absorption spectra of dye extracted from dragon fruit. The dye
extracted from dragon fruit using ethanol resulted in a deep-colored solution. Certain
plants (such as beets) and cacti (such as dragon fruit) have pigments called betalains, which
are soluble in water and contain nitrogen. Both the flesh and skin of dragon fruit are red
because of the presence of betalains. The use of dragon fruit extract as a natural food
coloring agent may also be influenced by the amount of betalains in it. However, the
Sustainability 2024, 16, x FOR PEER REVIEW 12 ofkind
16
and level of maturity of the fruit may affect the amount of betalains in dragon fruit. In
general, betalains are found in larger amounts in redder breeds.

Dyeabsorption
Figure8.8.Dye
Figure absorptionspectrum
spectrumofofdragon
dragonfruit
fruitdye
dyeininthe
therange
rangeofof400
400nm
nmtoto700
700nm.
nm.

The UV-Vis spectrum showed that the dragon fruit extract had a limited band covering
3.8. Identification of Compounds
the 500–560 nm region, which is consistent with its dark pink color. This absorption range
The degraded
of 500–560 compounds
nm confirmed formed
the presence during pigments
of betalain the photo degradation
in the dragon fruit process
dye. A were
group
identified from the LC-MS test. LC-MS may act as a valuable tool
of red and yellow tyrosine-derived pigments called betalains are present in plants, for the analysis of
which
compounds
include reddish present in theviolet
to dark natural dyes. pigments
betalain Figures 9 with
and 10 describesproperties
antioxidant the chromatogram
that exert
and mass spectra obtained after the degradation of compounds.
various shades of violet color in wool fabric samples dyed with different mordantsThe presence of the be-
[25–28].
tacyanin compound was found at an m/z value of 360.0827, forming the biggest peak
among all the compounds.
3.8. Identification of Compounds The structure of betacyanin was identified by fragment anal-
ysis usingThe degraded compoundsAs
peak view software. the compounds
formed during theare highly
photo sensitive process
degradation to photoweredegrada-
identi-
tion,
fied itfrom
wastheobserved
LC-MSthat test.all the compounds
LC-MS may act asdisappeared after
a valuable tool for9the
h ofanalysis
photolytic treatment
of compounds
due to the
present inshift in the retention
the natural time 9ofand
dyes. Figures the10parent compound
describes owing to theand
the chromatogram changes in the
mass spectra
ionic strength of the sample solutions.
obtained after the degradation of compounds. The presence of the betacyanin compound
was found at an m/z value of 360.0827, forming the biggest peak among all the compounds.
3.9.
TheAntimicrobial
structure ofProperties
betacyanin was identified by fragment analysis using peak view soft-
ware. AsAs the compounds
shown in Figure 11, arethe
highly sensitivetest
antibacterial to photo degradation,
was carried it was observed
out according to AATCC that
all the compounds
100-1999 test standards.disappeared
The wool after 9 h were
samples of photolytic treatment
placed inside duedishes
the Petri to theduring
shift inthe
the
retention time of the parent compound owing to the changes in the
test. After completing the test, the wool samples were taken out to for colony counting ionic strength of the
sample
and solutions.
to ensure the visibility of the number of colony counts [29,30]. The antimicrobial ac-
tivities of undyed, dyed without a mordant, and mordanted dyed wool samples were
examined against both E. coli and S. aureus bacteria. The calculated results are shown in
Figure 11 and Table 4. The test results prove that approximately a 90–95% bacterial re-
duction was achieved after dyeing wool fabric with dragon fruit extract. The dyed wool
samples exhibited greater bactericidal effects against E. coli than against S. aureus due to
structural differences in the bacteria. There was no bacterial reduction in the undyed
samples, whereas the mordanted dyed wool samples showed the greatest bacterial re-
duction percentage among the samples dyed without a mordant. As mordanting im-
Sustainability 2024, 16, x FOR PEER REVIEW 13 of 16
Sustainability
Sustainability2024,
2024,16,
16,x6832
FOR PEER REVIEW 13 of 16
12 of 15

Figure 9.
Figure Chromatogram of
9. Chromatogram of dragon
dragon fruit
fruit dye.
dye.
Figure 9. Chromatogram of dragon fruit dye.

Figure 10.
Figure Mass spectra
10. Mass spectra of
of degraded
degraded compounds.
compounds.
Figure 10. Mass spectra of degraded compounds.
Sustainability 2024, 16, 6832 13 of 15

3.9. Antimicrobial Properties


As shown in Figure 11, the antibacterial test was carried out according to AATCC
100-1999 test standards. The wool samples were placed inside the Petri dishes during the
test. After completing the test, the wool samples were taken out to for colony counting and
to ensure the visibility of the number of colony counts [29,30]. The antimicrobial activities
of undyed, dyed without a mordant, and mordanted dyed wool samples were examined
Sustainability 2024, 16, x FOR PEER REVIEW 14 of
against both E. coli and S. aureus bacteria. The calculated results are shown in Figure 11
and Table 4. The test results prove that approximately a 90–95% bacterial reduction was
achieved after dyeing wool fabric with dragon fruit extract. The dyed wool samples
exhibited greaterThe
bactericidal effects
main reason foragainst E. coli than against
the antimicrobial activity S.
ofaureus
dragondue to structural
fruit was the presence
differences in the bacteria. groups,
antimicrobial There was no bacterial
such reduction
as phenolic in the undyed samples,
and non-phenolic compounds. whereas
Phenolic co
the mordanted dyed
pounds, wool
such as samples
quercetin,showed
affect S.the greatest
aureus bacterial
through reduction
protein percentage
denaturation, which leads
among the thesamples dyed without
inactivation a mordant.
of enzymes andAsthemordanting
inhibitionimproves the stability
of bacterial of the Howev
metabolism.
dye in fabric, many metallic mordants inhibit the growth of bacteria and kill
non-phenolic compounds such as saponins and steroids interact with the them at very
phospholip
low concentrations [31].
membrane of bacteria and reduce cell wall combinations, which causes cell death [32].

Figure 11. Antibacterial activity of undyed


Figure 11. Antibacterial and of
activity dyed wool fabrics
undyed withwool
and dyed and without
fabrics mordant
with andagainst
without mord
E. coli and S.against
aureus. E. coli and S. aureus.

Table 4. Bacterial
Table reduction
4. Bacterialpercentage
reduction of undyed, dyed
percentage without
of undyed, mordant,
dyed and
without mordanted
mordant, and dyed
mordanted dy
wool fabrics.wool fabrics.

Sample Sample Microbial Growth


Microbial Growth Bacterial
Bacterial Reduction (%) Reduction (%)
E. coli E. coli S. aureus
S. aureus
Undyed wool Completely Present - -
Undyed wool Completely Present - -
Dyed
Dyed without without mordant
mordant Partially present91
Partially present 91 92 92
Potassium Potassium
Dichromate Dichromate Partially present94
Partially present 94 96 96
Copper Sulfate
Copper Sulfate Partially present
Partially present95 95 93 93
Stannous Chloride Partially present 94 95
Stannous Chloride Partially present 94 95

The main reason for the antimicrobial activity of dragon fruit was the presence of an-
4. Conclusions
timicrobial groups,
Thesuch as phenolic
natural dye was and non-phenolic
successfully compounds.
extracted Phenolic
from dragon fruitcompounds,
by ultrasonication a
such as quercetin, S. aureus
applied to wool fabrics. Using several mordanting chemicals, thetodyed
affect through protein denaturation, which leads the inac-
wool samp
tivation of enzymes and the inhibition of bacterial metabolism. However, non-phenolic
produced a variety of colors, ranging from light pink to dark pink and light brown w
compounds such as saponins and steroids interact with the phospholipid membrane of
great color strength. The morphology and chemical structure of the undyed and dy
bacteria and reduce cell wall combinations, which causes cell death [32].
wool samples were determined by SEM and FTIR, and the accuracy of the results
these processes was proven. The MS technique coupled with chromatographic sepa
4. Conclusions
tion was used for the identification and accurate determination of betacyanin co
The natural dye was successfully extracted from dragon fruit by ultrasonication and
pounds in complex matrices, eliminating the need for cleanup procedures. Using IS
applied to wool fabrics. Using several mordanting chemicals, the dyed wool samples
test methods, all the dyed samples demonstrated good to exceptional color fastne
properties in light, wash, perspiration, and rubbing fastness tests. However, the wo
fabric dyed with stannous chloride as the mordanting agent showed excellent fastne
properties. The antimicrobial properties of dragon-fruit-dyed wool samples were co
pared with those of undyed fabric samples against E. coli and S. aureus bacteria. The u
Sustainability 2024, 16, 6832 14 of 15

produced a variety of colors, ranging from light pink to dark pink and light brown with
great color strength. The morphology and chemical structure of the undyed and dyed
wool samples were determined by SEM and FTIR, and the accuracy of the results of these
processes was proven. The MS technique coupled with chromatographic separation was
used for the identification and accurate determination of betacyanin compounds in complex
matrices, eliminating the need for cleanup procedures. Using ISO test methods, all the
dyed samples demonstrated good to exceptional color fastness properties in light, wash,
perspiration, and rubbing fastness tests. However, the wool fabric dyed with stannous
chloride as the mordanting agent showed excellent fastness properties. The antimicrobial
properties of dragon-fruit-dyed wool samples were compared with those of undyed fabric
samples against E. coli and S. aureus bacteria. The undyed wool fabric showed no bacterial
reduction, while the fabrics dyed with or without a mordant exhibited the greatest bacterial
reduction against both E. coli and S. aureus. Despite this, the addition of mordants to the
wool samples resulted in a greater bacterial reduction than that in the non-mordanted wool
samples. The antimicrobial activity of these dyed wool fabrics will be a valuable addition
to products such as antimicrobial textiles for medical applications and other end uses.
As a result, this research developed a brand new source of dye extracted from dragon
fruit and demonstrated vibrant shades of color along with superior functional properties
when applied to wool fibers. This study paves the way for the use of natural dyes in the
textile dyeing industry for a cleaner production of sustainable textiles. In the future, several
other derivatives of plants can be utilized to extract natural dyes for the sustainable dyeing
of wool material to replace synthetic dyeing, resolving environmental issues in the textile
wet processing industry.

Author Contributions: T.Z. supervised the research; M.K.S. performed the experiments and wrote
this research paper; X.D. developed the FTIR and TGA graphs using the data; A.P. and F.S. reviewed
this research paper. S.R.I. helped to solve the comments in major revision. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data underlying this article will be shared upon reasonable request
to the corresponding author.
Acknowledgments: This research was carried out in the Key Laboratory of Science & Technology of
the Eco-Textile of Donghua University. This work is dedicated to Zhao Tao.
Conflicts of Interest: The authors declare no conflicts of interest.

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