Industrial Crops & Products 120 (2018) 203–213

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Industrial Crops & Products

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Ultrasound-microwave assisted extraction of natural colorants from T

sorghum husk with different solvents
⁎ ⁎⁎
Jakpa Wizia, Lu Wanga, Xiuliang Houa, , Yongying Taob, Bomou Maa, Yiqi Yangc,d,
a
Key Laboratory of Science & Technology of Eco-Textiles, Ministry of Education, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu, 214122, China
b
Luolai Lifestyle Technology Co. Ltd., 1699 Xinghu road, Nantong, Jiangsu, 226009, China
c
Department of Textiles, Merchandising & Fashion Design, 234, HECO Building, University of Nebraska–Lincoln, Lincoln, NE, 68583-0802, United States
d
Department of Biological Systems Engineering, 234, HECO Building, University of Nebraska–Lincoln, Lincoln, NE, 68583-0802, United States

A R T I C LE I N FO A B S T R A C T

Keywords: Ultrasound-microwave-assisted (UMA) extraction method with blended solvent 70% ethanol/30% water with
Sorghum husk HCl significantly improved extraction of biocolorants from sorghum husk. Sorghum is a staple food in many
Ultrasound-microwave assisted extraction parts of the world. As the demand for the grain soars, there is an equivalent increase in quantity of sorghum husk
Solvent generated. Sorghum husk is a promising source for natural functional dye. However, the phenolic colorants in
Dyeing
sorghum husk are bound to the cell wall and are difficult to extract. This paper is focused on improving the
Color
extraction of natural dye from sorghum husk and investigating the effect of the extraction methods and solvents
on the dyeing properties of sorghum husk extracts (SHE). UMA extraction method with blended solvent 70%
ethanol/30% water with HCl (1 ml HCl per 100 ml) had a SHE yield of 16.7%, which was 3.6 times the yield of
4.6% by conventional shaking (CS) method with water as solvent. SHE extracted by the UMA method had high
contents of apigeninidin as well as luteolinidin and higher thermal stabilities than SHE extracted with water.
SHE with different solvents produced different shades when dyeing wool and cotton fabrics. SHE by 70%
ethanol/30% water with or without HCI had similar dye strength and significantly higher dye strength compared
to SHE extracted by water. The dyed wool and cotton fabrics had good colorfastness to laundry, crocking and
light. UMA extraction with blended solvent 70% ethanol/30% water with HCI was an efficient method to extract
dye from sorghum husk and provided the potential for industrial application. The use of sorghum husk as a
source of industrial dye will significantly add value to the sorghum plant and reduce the disposal of sorghum
husk.

1. Introduction techniques which are more effective and efficient. A solvent-extraction

There has been an increasing tendency towards the use of sustain-
able and environmentally friendly natural dyes (Shahid-Ul-Islam and
Sun, 2017). The pursuit of dyes and coloring matter from nature for
textiles is on the rise due to the awareness of the adverse effect of some
synthetic dyes on the environment and human health. It was reported
that an estimated 10–15% dye was lost in the effluent during the dyeing
processes (Iqbal and Ashiq, 2007). The use of environmentally benign
dyes and chemicals is a way to control the effect of harmful effluents
(Sivakumar et al., 2009). In addition, dyes from nature are of interest
for their functional properties like deodorizing effect, antimicrobial,
antioxidant and UV protection on textiles products. (Shahid-Ul-Islam
and Sun, 2017).
The growing demand for natural dyes necessitates extraction
procedure is commonly used in industry. An efficient solid-liquid ex-
traction method for natural colorants will enhance its usage in the
textiles and food industries. Some studies have provided extraction
methods that are compatible with the environment and safety concerns.
Among the new dye extraction techniques, the use of pressurized fluids,
ultrasound and microwave techniques seem to be the most favorable
(Duval et al., 2016).
Sorghum is a cereal crop grown in the tropical, subtropical and arid
regions and happens to be the fifth leading crop in terms of production
after wheat, maize, rice, and barley with an annual production of about
57 million tons globally (Awika et al., 2004). Sorghum is a staple food,
livestock feed and has been used to produced bioethanol in many parts
of the world (Kim and Dale, 2004). Sorghum is a rich source of various
phytochemicals such as tannins, phenolic acids, 3-deoxyanthocyanidins

⁎
Corresponding author at: Jiangnan University, Key Laboratory of Science & Technology of Eco-Textiles, Ministry of Education, 214122, Wuxi, China.
⁎⁎
Corresponding author at: 234, HECO Building, University of Nebraska Lincoln, Lincoln, NE 68583 0802, United States.
E-mail addresses: houxl@jiangnan.edu.cn (X. Hou), yyang2@unl.edu (Y. Yang).

https://doi.org/10.1016/j.indcrop.2018.04.068
Received 3 December 2017; Received in revised form 18 March 2018; Accepted 21 April 2018
Available online 07 May 2018
0926-6690/ © 2018 Elsevier B.V. All rights reserved.
J. Wizi et al. Industrial Crops & Products 120 (2018) 203–213

and anthocyanins (Dykes et al., 2009). These phytochemicals have Table 1

health benefits such being anti-carcinogenic, anti-inflammatory, anti- SHE yield for different extraction methods and solvents.
oxidant, fighting cardiovascular disease and obesity (Awika and Extraction yield of SHE % improvement due to
Rooney, 2004; Barros et al., 2012; Dykes et al., 2013; Wu et al., 2013). solvents ultrasound-microwave
Hence, there is an increased interest in growing sorghum (Dykes et al., CS method (A) UMA method (B) assistance (B-A)/A × 100
2013). Sorghum husk is a byproduct which is easy to obtain, in-
Water 4.6 ± 0.15 5.6 ± 0.55 21.7
expensive and readily available biomass. 70% ethanol/ 5.6 ± 0.60 10.6 ± 0.50 89.3
The abundant sorghum husk could be a promising source for natural 30% Water
functional dye (Hou et al., 2017). However, the cell wall bound phe- 70% ethanol/ 10.4 ± 0.30 16.7 ± 0.60 60.6
nolic compounds are not easily extracted from the hull of cereals using 30% Water
with HCl
conventional shaking (CS) extraction method with 70% (v/v) ethanol/
30% water as solvent, sorghum husk extracts (SHE) had a yield of Note: Extraction condition for CS method was 80 °C for 60 min and UMA
6.15% based on weight of powdered sorghum husk (Hou et al., 2017) method was 55 °C for 20 min.
and hence an effective alternative is needed for maximum polyphenol
extraction. In industry, phenolic compounds extraction involves sol-
vent-extraction procedures of which water and ethanol are more en-
vironment-friendly solvents (Kayodé et al., 2012). Barros et al. (2013)
significantly improved phenolic compounds extraction at temperatures
above 100 °C with water and ethanol/water from sorghum bran. There
was a significant improvement in extraction of biocolorant from sor-
ghum leaf sheaths with the addition of HCl to ethanol/water solvent.
The crude extract from the leaf sheaths had high antioxidant capacity
(Barros et al., 2013; Kayodé et al., 2012). The ultrasound-assisted ex-
traction technology with ethanol/water solvent was employed to obtain
high extraction yields of phenolic compounds from sorghum husk (Hou
et al., 2016). Microwave-assisted procedure was applied to extract
phenolic acids from sorghum bran (Chiremba et al., 2012). Akogou
et al. (2018) suggested that future research should focus on the im-
provement of the extraction methods for sorghum biocolorants.
Ultrasound-assisted extraction is an emerging potential technology
that can accelerate heat and mass transfer and has been successively
used in the extraction field (Chemat et al., 2017a; Sivakumar et al., Fig. 1. The absorbance curves of SHE liquid and SHE powder extracted by UMA
2011). Sivakumar et al. (2009) undertook a comparative colorant ex- method with different solvents (a) water; (b) 70% ethanol/30% water; (c) 70%
traction from beetroot using ultrasound and static/magnetic stirring. ethanol/30% water with HCl.
Colorant extraction from beetroot was significantly improved using
ultrasound. An earlier research had indicated that ultrasound-assisted
Table 2
extraction was effective in extracting oil from pomegranate seed and The UV–vis absorbance of the solution extracted from sorghum husk by UMA
this resulted in few changes in fatty acid composition (Barizão et al., method and 70% ethanol/30% water with HCl as blended solvent under dif-
2015). ferent extraction conditions.
The application of microwave irradiation proves to be a rapid and
Extraction Extraction Absorbance at Absorbance at Integration of
an improved method of extracting dye from pomegranate peels and also time (min) temperature λ = 281 nm λ = 400 nm absorbance in
significantly reduces extraction time (Sinha et al., 2012). Microwave (°C) visible region
presents the disadvantage of inhomogeneous heating (Bonrath, 2004). (from λ = 400
Therefore, ultrasound-assisted extraction in combination with micro- to 800 nm)
wave-assisted extraction, i.e, ultrasound-microwave-assisted (UMA)
10 65 1.00 0.32 260.49
extraction will be one of the most promising hybrid techniques for fast 20 65 1.05 0.36 259.20
and efficient extraction (Chemat et al., 2017b). The simultaneous use of 20 55 1.25 0.47 327.75
microwave and ultrasound in a single reactor has been implemented in 20 45 1.23 0.45 273.33
30 65 0.81 0.19 179.02
order to combine the effects of enhanced energy with improved matter
transportation (Barrera Vázquez et al., 2014; Leonelli and Mason,
2010). The earlier studies reported that UMA extraction had better
2. Experimental
yield for the total anthraquinones from the stems and leaves of Het-
erophyllaea pustulata Hook.f. (Rubiáceae) (Barrera Vázquez et al.,
2.1. Materials and chemicals
2014), juglone from walnut green husk (Xu et al., 2016; Yin et al.,
2016), polysaccharides from Cornus officinalis (Yin et al., 2016).
The dried sorghum husks were purchased from Changling, China.
However, the great potential of this hybrid technique has not yet been
Worsted wool fabric was purchased from Wuxi Xiexin Textile Company,
adequately exploited (Chemat et al., 2017b).
China. The wool fabric had the following characteristics: Gabardine,
This paper is focused on improving the extraction of natural dye
warp and weft 17 × 2 tex, warp density 402 threads per 10 cm, weft
from sorghum husk and also investigates the effect of extraction
density 225 threads per 10 cm, weight 237 g/m2. Bleached cotton fabric
methods and solvents on the dyeing properties of SHE. The results could
was purchased from Luolai Lifestyle Technology Co. Ltd. and had the
promote the industrial application of the biocolorants from sorghum
following characteristics: satin weave, warp and weft 14 tex, warp
husk in the textile industry.
density 570 threads per 10 cm, weft density 335 threads per 10 cm and
weight 115 g/m2.
Acetic acid, hydrochloric acid (HCl), sodium carbonate, sodium
hydroxide, ethanol, aluminum potassium sulfate (KAl(SO4)2·12H2O)

204
J. Wizi et al.
Fig. 2. SEM of sorghum husk before and after extraction and SHE by CS and UMA extraction method.
Fig. 3. FTIR spectra of SHE powder extracted by UMA method with different
solvents (a) Water; (b) 70% ethanol/30% water; (c) 70% ethanol/30% water
with HCl.
Fig. 4. The main chemical composition for SHE (a) apigeninidin (b) luteoli-
nidin.
and ferrous sulphate (FeSO4·7H2O) were all AR grades from Sinopharm
Chemical Reagent Co., Ltd, China. Standard apigeninidin chloride with
a HPLC purity of 97% was supplied by Zzbio Company in Shanghai-
China.
2.2. CS method and UMA method for extraction of sorghum husk
In this paper, two extraction methods and three solvents were used
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Industrial Crops & Products 120 (2018) 203–213
to extract dye from sorghum husk. For CS method, sorghum husk was
extracted using thermostatted water bath shaker (Rapid Precision
Machinery Co., Ltd, Xiamen, China). For UMA method, sorghum husk
was extracted with an ultrasound-microwave response instrument (XO-
SM200 type, Nanjing Xianou instrument manufacturing Ltd., China)
with ultrasound at 25 KHz frequency and microwave at 2450 MHz
frequency. The property of the extraction solvent plays a critical role in
the extraction process. In a large number of ultrasound-assisted ex-
traction studies, water and ethanol/water were selected as extraction
solvents because they are the least toxic and could provide good re-
covery (Duval et al., 2016). For the two extraction methods, sorghum
husk was extracted with three solvents namely, water, 70% ethanol//
30% water (v/v) and 70% ethanol//30% water with 1 ml HCl per
100 ml respectively.
Sorghum husk was powdered with a universal disintegrator (Taisite
company, China) and sieved with 0.8 mm mesh. The sorghum husk
powder was added to different solvents at a material-to-liquor ratio of
1:30. For CS method, the sorghum husk powder was extracted at 80 °C
for 60 min at a shaking rate of 80 times/min. For UMA method, the
sorghum husk powder was extracted at different temperatures (45 °C,
55 °C and 65 °C) at different time (10, 20 and 30 min) using ultrasound
power of 360W and varied microwave power from 14 to 33 W.
Ultrasound probe had a diameter of 15 mm and its emitting surface area
was 1.766 cm2. Ultrasonication was performed in pulsed modes with
pulse duration of 2 s and a resting interval of 2 s. An ultrasound in-
tensity of 7.45 W/cm2 was calculated according to the method (Chemat
et al., 2017b). It was considered that the actual input power was con-
verted to heat which was dissipated in the medium. During the UMA
extraction, the temperature of mixture was measured with a digital
thermometer located in the center of the reactor and was held con-
stantly at a desired value by a thermostatic bath driving cooling water
through jacket.
The extracted dye liquor was filtered with stainless steel sieve (200
meshes per square inch). The filtrate was centrifuged at 8000 rpm for
20 min with a high-speed refrigerated centrifuge Avanti J-E (Beckman
Coulter, USA). The supernatant was concentrated under reduced pres-
sure using a rotary evaporator at 50 °C in order to remove ethanol from
the supernatant and some water. The concentrated extracts were dried
using freeze dryer (FD-1C-50, Beijing Boyikang experimental instru-
ment co., Ltd, China). SHE was used as dye without further purification.
SHE yield for each method and solvent was determined according to
the following equation (Kazemi et al., 2016).
J. Wizi et al.
Fig. 5. Total ion chromatograms (TIC) of SHE solution extracted by UMA with different solvents (a) water; (b) 70% ethanol/30% water; (c) 70% ethanol/30% water
with HCl.
Mass of SHE
Yield (%) = × 100
Mass of sorg hum husk powder used
2.3. Morphology of sorghum husk and SHE
A HITACHI SU1510 scanning electron microscope (SEM, Japan) was
used to observe the morphologies of sorghum husk and SHE. The
samples were mounted with conductive adhesive tape, sputter coated
with gold palladium, and observed under an accelerating voltage of
5 kV. The magnification was 3000 times the original size.
2.4. Chemical composition of SHE
FTIR spectrum of SHE was measured with a Fourier-transform in-
frared spectrophotometer (Nicolet iS10, USA). SHE powder was re-
corded from 4000 to 500 cm−1 at a resolution of 4 cm−1 using
Attenuated Total Reflection (ATR) method.
Mass spectra (MS) were obtained by MALDI SYNAPT Q-TOF MS,
Waters Corporation, USA. The main testing conditions were the same
with the reference (Hou et al., 2017).
2.5. UV–vis absorbance spectra of SHE
The UV–vis absorbance spectra were measured with UV–vis spec-
trophotometer (TU-1901, Purkinje General Instrument Co. Ltd., Beijing,
China). Integration of absorbance in visible region (from λ = 400 to
800 nm) was used to characterize the color depth of the solution
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Industrial Crops & Products 120 (2018) 203–213
extracted from sorghum husk (Fitch et al., 2002).
2.6. Thermogravimetric analysis (TGA) of SHE
TGA of SHE was performed on thermogravimetric analyzer TGA/
SDTA 851e (Mettler Toledo, Switzerland) in nitrogen atmosphere with
a flow rate of 60 ml/min. The samples were heated from 30 °C to 600 °C
at a heating rate of 20 °C/min. Mass of the samples ranged from 4 to
5 mg.
2.7. Dyeing methods and conditions
SHE was used to dye wool and cotton fabrics in a thermostatic water
bath shaker. Due to SHE good affinity to wool and weak affinity to
cotton, direct dyeing (without mordant), post-mordant dyeing method
were used to dye wool fabrics and direct dyeing, pre-mordant dyeing
methods were used to dye cotton fabrics. According to the previous
research by our group (Fang et al., 2015), when the amount of SHE was
3 g/L, the adsorption of SHE onto wool reached equilibrium. In all
dyeing processes, the bath ratio of 30:1 was used. Therefore, the SHE
amount 9% (o.w.f) was used for wool and cotton fabrics in order to
compare the dyeing properties of SHE extracted by different solvents.
The wool fabrics were dyed at 90 °C, pH 5 for 60 min. The cotton
fabrics were dyed at 80 °C, pH 7 or 9 for 60 min. In pre-mordant or post-
mordant process, the initial dosage of mordant KAl(SO4)2·12H2O and
FeSO4·7H2O was 6% (o.w.f.) and 3% (o.w.f.) respectively and the fab-
rics were mordanted at 60 °C for 30 min. In all dyeing and mordant
processes, the temperature was increased from ambient temperature at
J. Wizi et al.
Fig. 6. The mass (m/z = 255) chromatograms of apigeninidin standard and SHE solution extracted by UMA with different solvents (a) water; (b) 70% ethanol/30%
water; (c) 70% ethanol/30% water with HCl.
a heating rate of 1 °C/min. The dyed fabrics were rinsed in water with
laundry detergent and then dried in an ambient temperature.
2.8. Evaluation of color and colorfastness of the dyed fabrics
Evaluation method and characteristic values (L*, a*, b*, c*, ho and
K/S) of color were the same with the reference (Hou et al., 2013). The
colorfastness to laundry was assessed according to AATCC Test Method
61-2009. The dyed fabrics were stitched unto a multi-fiber fabric (in-
cluding acetate, cotton, nylon, polyester, acrylic and wool) and washed.
The extent of dye stains on the multi-fiber fabric and color change of the
dyed fabrics were determined. Colorfastness to crocking was measured
following AATCC Test Method 8-2007. Colorfastness to light was
evaluated following AATCC Test Method 16-2004. The dyed fabrics and
AATCC blue wool lightfastness standards were exposed in an Atlas 150S
light fastness device (ATLAS Ltd., German) equipped with a xenon arc
lamp. Light-fastness rating was determined according to the color
change of the tested fabrics and blue wool lightfastness standards.
3. Results and discussion
3.1. Effects of extraction method and solvent on SHE
3.1.1. Yield
SHE yield for different extraction methods and solvents are shown
in Table 1. UMA method significantly improved SHE yield for all three
solvents in comparison with CS method. UMA method with blended
solvent 70% ethanol/30% water with HCl had the highest SHE yield of
16.7%, which was 3.6 times the lowest yield of 4.6% by CS method with
water as solvent. The absorbance curves for SHE liquid and powder
extracted by UMA method with different solvents are shown in Fig. 1. It
indicated SHE extracted by blended solvents of 70% ethanol/30% water
with HCl had the highest absorbance within the visible wavelengths
from 400 to 800 nm. The higher absorbance means the liquid had
higher content of colorants. Therefore, the blended solvents 70%
207
Industrial Crops & Products 120 (2018) 203–213
ethanol/30% water with HCl extracted maximum amounts of colorants
from sorghum husk. The significant increase in SHE yield resulted from
a combination of three effects, including the effect of simultaneous
ultrasound-microwave assistance, the effects of ethanol and HCl.
For UMA method, acoustic cavitation was generated by the ultra-
sound through liquid and enhanced the disruption of plant cell wall
when the bubbles violently collapse at the surface of the solid matrix
(Holkar et al., 2016). This disruption increases movement of colorants
and contact between solvent and material (Dranca and Oroian, 2016;
Khadhraoui et al., 2018). Acoustic cavitation also generates violent
pressure (about 103 bar) (Holkar et al., 2016) on cell containing col-
orants and the subsequent penetration of the solvent into the cells in-
creases the solubility of the dye compound (Leonelli and Mason, 2010).
Compared with CS method, UMA method improved SHE yield and the
percentage improvement were 21.7%, 89.3% and 60.6% for three dif-
ferent solvents, namely water, 70% ethanol/30% water, and 70%
ethanol/30% water with HCl (Table 1).
The solvent has a significant effect on extraction of sorghum husk.
The difference in yield among the solvents resulted from the dissolving
power of each solvent on the dye compounds. The surface tension for
water at 25 °C is 71.97*10−3 N/m. However, the surface tension for
ethanol at 25 °C is 21.8*10−3 N/m. A higher surface tension of liquid
results in less cavitation. Meanwhile, acidity is important for extraction
of colorants in sorghum husk because it facilitates the release from the
cell wall. Kayodé et al. (2012) also indicated that the addition of HCl to
the ethanol/water solvent significantly improved the extractability of
the colorants from sorghum leaf sheaths. A recent study reported that
citric acid in water (pH 2.5) improved 3-deoxyanthocyanins extraction
from sorghum brans than only water due to lower pH (Barros et al.,
2013). Vatai et al. (2009) also reported that anthocyanins and phenols
were better extracted from grape marc with acidified solvent. Sorghum
husk is rich in cellulose and lignin. Thus, the incorporation of acid in
the extraction solvent might have improved disruption of the plant
tissue and thus allowed a better release of colorants. On the other hand,
SHE powder by different solvents showed different color (Fig. 1). SHE
J. Wizi et al.
Fig. 7. (1) The mass (m/z = 271) chromatograms and (2) Mass spectra (MS) at about t = 5.1 min of SHE solution extracted by UMA with different solvents (a) water;
(b) 70% ethanol/30% water; (c) 70% ethanol/30% water with HCl.
powder by blended solvents of 70% ethanol/30% water with HCl had a
reddish-brown color. Compared with SHE powder by water, SHE
powder by 70% ethanol/30% water as solvents had a deeper brown
color. The different colors presented the differences in composition for
SHE powders.
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Industrial Crops & Products 120 (2018) 203–213
3.1.2. Optimization of extraction conditions for UMA method
The UV–vis absorbance of the dye solution extracted from sorghum
husk by UMA method under different temperatures and times are
shown in Table 2. For UMA method, the optimized extraction tem-
perature and time were 55 °C and 20 min respectively. High tempera-
ture decreases liquid solvent viscosity, enabling penetration into the
matrix and enhancing colorant extraction. However, when the
J. Wizi et al.
Fig. 8. (1) Thermogravimetric analysis (TGA) and (2) Differential thermo-
gravimetric (DTG) curves of SHE extracted by UMA method with different
solvents (a) water; (b) 70% ethanol/30% water; (c) 70% ethanol/30% water
with HCl.
temperature is too high, the vapor pressure in the bubbles increases.
Therefore, when the bubble closes, it enhances the buffer action and
weakens the cavitation. On the other hand, the higher the liquid tem-
perature, the more likely ethanol volatilizes. The decline in absorbance
when extraction time was longer than 20 min at temperature of 65 °C
might be due to the degradation of colorants (Jacotet-Navarro et al.,
2016; Wang et al., 2015). The optimization of extraction conditions was
helpful to obtain the highest yield of the target compounds without
degradation.
3.1.3. Morphology
Fig. 2 shows the differences in morphology of sorghum husk and
SHE by CS and UMA extraction method. Sorghum husk after UMA ex-
traction showed serious disruptions on its surface in comparison to the
husk after CS extraction. According to the research (Khadhraoui et al.,
2018), ultrasound seemed to act through chain detexturation me-
chanism respecting the order of sequential steps: local erosion, shear
forces, sonoporation, fragmentation, capillary effect and detexturation.
SHE by UMA extraction showed obvious difference with SHE by CS
extraction and had a lot of ball-like formation with diameter of 1–2 μm.
How these ball-like formations emerged will be studied in the future.
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Industrial Crops & Products 120 (2018) 203–213
3.2. Effect of extraction solvents on chemical composition of SHE
Fourier Transform Infrared (FTIR) spectra of SHE is shown in Fig. 3.
SHE powders by three solvents all presented absorption peaks at
3400 cm−1, 2920 cm−1, 1600 cm−1, 1050 cm−1. The peak at
3400 cm−1 is the stretching vibration of OeH, whereas the peak at
2920 cm−1 is the stretching vibration of CeH. The peak at 1600 cm−1
corresponded to the stretching vibration of C]C, which is a char-
acteristic absorption peak of phenyl. The peak at 1050 cm−1 corre-
sponded to the stretching vibration of CeO. The presence of flavonoid
and phenolic components in SHE were proved by the above-mentioned
intense peaks. However, SHE powder extracted by 70% ethanol/30%
water with or without HCl both showed an intense peak at 833 cm−1.
Apigeninidin (molecular weight of 255) and luteolinidin (molecular
weight of 271) are the predominant 3-deoxyanthocyanidins in SHE
extracted by CS with water (Hou et al., 2017), the leaf sheaths of sor-
ghum (Geera et al., 2012; Kayodé et al., 2012) and sorghum grains
(Dykes et al., 2014). Fig. 4 shows the structures for apigeninidin and
luteolinidin. The greater stability of 3-deoxyanthocyanins compared to
anthocyanins is a major reason for the interest in their use as natural
colorants (Geera et al., 2012).
Figs. 5–7 respectively show the total ion chromatograms (TIC), the
mass (m/z = 255 and 271) chromatograms, and mass spectra (MS) at
about t = 5.1 min of SHE solution extracted by UMA with different
solvents. From TIC (Fig. 5), SHE solutions extracted by UMA with 70%
ethanol/30% water and 70% ethanol/30% water with HCl showed a
new peak at t = 7.4 min and didn’t present the peak at t = 11.62 min
compared with SHE solution extracted by water. It indicated that SHE
extracted with different solvents have minor differences in chemical
constituents. The mass (m/z = 255) chromatograms shows that api-
geninidin standard and SHE all had the peak at t = 3.7 min which
corresponded to apigeninidin for different solvents. SHE extracted by
blended solvent 70% ethanol/30% water with HCl had the highest area
of 1422 at peak t = 3.7 min and SHE extracted by water had the lowest
peak area of 33 at t = 3.7 min (Fig. 6). It indicated that the content of
apigeninidin for SHE increased with the addition of ethanol and HCl in
the solvent. The mass (m/z = 271) chromatograms and MS at about
t = 5.1 min of SHE shows that the chromatogram peak from
5.17–5.20 min was luteolinidin. SHE extracted by solvent 70% ethanol/
30% water had highest area of 433 at peak t = 5.18 min, i.e, highest
content of luteolinidin and SHE extracted by water had lowest peak
area of 95 at t = 5.20 min, i.e, lowest content of luteolinidin (Fig. 7).
The 3-deoxyanthocyanidins offers many applications in dye, food,
beverages and pharmaceutical industries (Awika and Rooney, 2004).
They are recognized as health-promoting phytochemicals. The ex-
tracted natural dye which contains 3-deoxyanthocyanidin are known to
have better fading resistance in chromatic properties (Geera et al.,
2012; Awika et al., 2004). Therefore, the optimum solvent for the ex-
traction of dye from sorghum husk for dyeing industry is blended sol-
vent of 70% ethanol/30% water with HCl.
3.3. Effect of extraction solvents on dyeing properties of SHE
3.3.1. Effect of extraction solvents on thermal stabilities of SHE
Fig. 8 shows the TGA and DTG curves of SHE extracted by UMA
method with different solvents. The weight residue percentage at 600 °C
was highest for SHE extracted with 70% ethanol/30% water and was
lowest for SHE extracted with water as solvent. The weight loss below
100 °C resulted from the evaporation of water in SHE powder. With
increasing temperature from 100 to 180 °C, the weight of SHE slightly
decreased and the highest weight loss was 5.1%. The fast weight loss
from 180 °C to higher temperature was associated primarily with the
thermal decomposition of SHE powder. The first and second decom-
position peaks occurred around 200 °C and 293 °C respectively for SHE
extracted with different solvents. However, the weight loss rate was
faster for SHE extracted with water. It might result from the
J. Wizi et al. Industrial Crops & Products 120 (2018) 203–213

Fig. 9. Wool fabrics dyed by different dyeing methods with SHE extracted by UMA with different solvents.

Table 3 Table 4
The color characteristic values for wool fabrics dyed with SHE extracted by The color characteristic values for cotton fabrics dyed by different dyeing
UMA with different solvents. methods with SHE extracted by UMA with different solvents.
Dyed wool fabrics Color characteristic values Dyed cotton fabrics Color characteristic values

o
L* a* b* c* h K/S L* a* b* c* ho K/S

Fig. 9(A) 53.8 12.5 24.5 53.8 62.9 1.8 Fig. 10(a) 80.3 5.1 6.4 8.1 51.6 0.1
Fig. 9(B) 54.0 12.8 24.8 54.0 62.7 1.8 Fig. 10(b) 80.1 5.0 8.3 9.7 58.8 0.2
Fig. 9(C) 53.2 5.5 18.4 53.2 73.3 1.6 Fig. 10(c) 75.4 4.5 11.1 12.0 67.8 0.3
Fig. 9(D) 29.5 21.8 18.1 29.5 39.7 12.8 Fig. 10(d) 66.3 8.6 9.7 13.1 48.5 0.7
Fig. 9(E) 29.6 23.3 19.0 29.6 39.2 13.8 Fig. 10(e) 63.6 10.7 13.8 17.5 52.1 0.9
Fig. 9(F) 25.1 16.3 13.2 25.1 39.0 16.0 Fig. 10(f) 47.0 9.0 11.4 14.9 49.9 2.7
Fig. 9(G) 30.1 21.5 17.5 30.1 39.1 12.0 Fig. 10(g) 66.2 9.6 11.7 15.2 50.6 0.7
Fig. 9(H) 31.5 23.7 19.1 31.5 38.9 11.8 Fig. 10(h) 65.9 8.3 11.3 14.1 53.8 0.7
Fig. 9(I) 26.4 15.5 13.1 26.4 40.0 14.1 Fig. 10(i) 53.5 9.6 11.3 14.8 49.4 1.7

decomposition of more polysaccharide and protein in SHE. The dyeing all had good thermal stability suitable for dyeing and finishing pro-
and finishing of textile products are mostly below the temperature cesses of various fabrics. It was also indicated that SHE extracted with
180 °C (Hou et al., 2017). In general, SHE with three kinds of solvents blend solvent of ethanol and water had a higher purity.

Fig. 10. the cotton fabrics dyed by different dyeing methods with SHE extracted by UMA with different solvents.

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J. Wizi et al. Industrial Crops & Products 120 (2018) 203–213

Table 5
Colorfastness rating for dyed wool fabrics using Fe2+ post-mordant dyeing with SHE extracted by UMA with different solvents.
Dyed wool fabrics Colorfastness to laundry Colorfastness to crocking Colorfastness to light

Staining colorfastness Color change Dry Wet

Acetate Cotton Nylon Polyester Acrylic Wool

Fig. 9(C) 5 5 5 5 5 4–5 4–5 5 5 4

Fig. 9(F) 5 4–5 3–4 5 5 4–5 3 4–5 4 4
Fig. 9(I) 5 4–5 4 5 5 3–4 4–5 4–5 4 3–4

Table 6
Colorfastness rating for dyed cotton fabrics using Fe2+ pre-mordant dyeing with SHE extracted by UMA with different solvents.
Dyed cotton fabrics Colorfastness to laundry Colorfastness to crocking Colorfastness to light

Staining colorfastness Color change Dry wet

Acetate Cotton Nylon Polyester Acrylic Wool

Fig. 10(c) 5 4 4–5 5 5 5 3 5 5 3

Fig. 10(f) 5 4 4–5 5 5 4–5 3 5 4–5 3
Fig. 10(i) 5 5 4 5 5 4–5 3 5 4–5 3

3.3.2. Effects of extraction solvents and dyeing methods on the colors of the
dyed fabrics with SHE
Fig. 9 and Table 3, Fig. 10 and Table 4 respectively show wool and
cotton fabrics dyed with SHE extracted with different solvents using
different dyeing methods and their color characteristic values. For dyed
wool and cotton fabrics, SHE extracted by 70% ethanol/30% water and
70% ethanol/30% water with HCl yielded a significantly deeper color
on wool and cotton fabrics compared to SHE extracted by water. For all
three SHE powders, wool fabrics could be dyed with deeper colors than
cotton fabrics. Mordant dyeing with Al3+ or Fe2+ resulted in varying
shades of dyed wool and cotton fabrics, thereby enduing more color
options. On the contrary, increasing the dyeing pH from 7 to 9 de-
creased the color depths of dyed cotton fabrics with Al3+ and Fe2+ pre-
mordant dyeing (Fig. 10).
It is apparent from Figs. 9 and 10 and Tables 3 and 4 that the colors
of wool and cotton fabrics dyed with direct dyeing (without mordant)
are different from those dyed with either Al3+ or Fe2+ mordant dyeing.
Direct dyeing produced a lighter shade of brown especially on cotton
for its known lack of affinity for most natural dyes. However, in the case
of wool a comparatively brighter shade was evident because SHE had
good affinity for wool fabrics. Mordant dyeing was necessary for cotton
fabrics.
Take wool fabrics as an example. Mordant dyeing with Al3+ pro-
duced a reddish and brighter shade as indicated by higher a* and L*
(Table 3), whereas mordant dyeing with Fe2+ had a decrease in L*, a*,
b* and c* values for the dyed wool fabrics, indicating darker shades and
little shifts toward green co-ordinate in red yellow zone of CIE Lab color
space (Table 3). Wool fabric possesses amino and carboxyl groups
which provide attachment sites to dye molecules (Saxena and Raja,
2014). Mordanted wool fabric exhibited different shades resulting from
the chelation between SHE and the metal ions. Al3+ and Fe2+ form
complexes with the carboxyl and amino in wool fiber and with the two
adjacent phenolic hydroxyl groups in the phenolic colorants of SHE
(Hou et al., 2017).
In general, UMA method with blended solvent 70% ethanol/30%
water with HCl significantly improved the yield of SHE and SHE ex-
tracted by blend solvents had similar dye strength. The dyed wool
fabric showed bright and deep colors with and without mordants, but
cotton fabric needed mordants to improve brightness and depth of the
colors.
3.3.3. Colorfastness properties of dyed fabrics with SHE
Tables 5 and 6 respectively shows the colorfastness rating for dyed
wool and cotton fabrics using Fe2+ post-mordant or pre-mordant
dyeing with SHE extracted by UMA with different solvents. The dyed
wool and cotton fabrics all had good colorfastness to laundry, crocking,
and light.
Improving the color fastness to light is an important subject for
natural dye. SHE extracted by CS method with 70% ethanol/30% water
had better colorfastness to light in comparison with some natural
dyestuff which had a light fastness rating of 1–2 (Hou et al., 2017;
Shahid-Ul-Islam and Mohammad, 2013). Mordant and fiber substrate
are also important in determining the light fastness of colored fabrics.
Use of Fe2+ mordant resulted in significantly less fading than when
Al3+ was used, which might resulted from that Fe2+ had a negative
catalytic effect on the photochemical degradation of SHE (Cristea and
Vilarem, 2006). Wool fabrics exhibited better colorfastness to light than
cotton fabrics. Cotton fabrics demonstrated acceptable colorfastness
despite having a less bright color in comparison with wool fabrics.
In conclusion, the colorant extraction by UMA method with blend
solvent of 70% ethanol/30% water with HCI from sorghum husk pro-
vided the guarantee for industrial application.
3.4. Up-scaling of UMA extraction of sorghum husk
UMA extraction offers advantages in term of higher yield and good
dyeing properties with shorter extraction time and lower temperature
which are environmentally friendly compared with CS method. The
potential industrialization of UMA method can be implemented through
a transition from a lab reactor to a large scale one. Fig. 11 shows the up-
scaling of ultrasonic microwave reactor. The lab and up-scaling ultra-
sound microwave reaction system were both produced by Nanjing
Xianou instrument manufacturing Ltd., China. The up-scaling of UMA
extraction was carried out in the optimum conditions obtained from the
experiments at laboratory scale. The SHE yield obtained by UMA ex-
traction at a pilot scale was similar to that obtained at lab scale. This
result indicated that sorghum husk byproducts can be extracted by
green UMA method and used as a natural dye source from an en-
vironmental and industrial point of view.
4. Conclusions

UMA extraction method with blended solvent 70% ethanol/30%

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J. Wizi et al.
Fig. 11. (1) Lab ultrasound microwave reaction system (XO-SM200, ultrasound
and microwave power of 1.2 KW respectively, handling capacity of 0.1–1.5 l;)
(2) Up-scaling ultrasonic microwave reaction system (XO-SM-30KW, micro-
wave power of 20 KW, ultrasound power of 10 KW with two probes. Every
probe has a power of 5 KW and has a diameter of 50 mm. Handling capacity of
30–60 l.).
water with HCl (1 ml HCl per 100 ml) significantly improved extraction
of biocolorants from sorghum husk. It had a SHE yield of 16.7%, which
was 3.6 times the yield by CS method with water as solvent. For UMA
method, the optimized extraction temperature and time were 55 °C and
20 min respectively. SHE extracted by the above method had higher
contents of apigeninidin and luteolinidin, higher thermal stabilities
than SHE extracted by water. SHE extracted by UMA with different
solvents produced different shades when dyeing wool and cotton fab-
rics. SHE extracted with blended solvent of 70% ethanol/30% water
with or without HCI had similar dye strength and significantly higher
dye strength compared to SHE extracted by water. The dyed wool
fabrics showed bright and deep colors with or without mordants, but
cotton fabrics needed mordant to improve brightness and depth of the
colors. The dyed wool fabrics using Fe2+ post-mordant dyeing method
and the dyed cotton fabrics using Fe2+ pre-mordant dyeing method had
212
Industrial Crops & Products 120 (2018) 203–213
good colorfastness to laundry, crocking and light. UMA method with
blended solvent 70% ethanol/30% water with HCI was an efficient and
green method to extract dye from sorghum husk and provided the po-
tential for industrial application. The use of sorghum husk as a source of
industrial dye will significantly add value to the sorghum plant and
reduce the disposal of sorghum husk.
Acknowledgments
This research was financially supported by National Key R&D
Program of China (2017YFB0305700), Fundamental Research Funds
for the Central Universities (JUSRP51723B), Special Fund for the
Transformation of Scientific & Technological Achievements in Jiangsu
Province (BA2016117) and the 111 projects (B17021). It was also
supported by USDA-National Institute of Food and Agriculture (Hatch
Act, Multistate Research Project S-1054, NEB 37-037) and Agricultural
Research Division at the University of Nebraska-Lincoln, USA.
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