Arabian Journal of Chemistry (2018) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Facile and green preparation of bioactive and UV

protective silk materials using the extract from red
radish (Raphanus sativus L.) through adsorption
technique
Yuyang Zhou a,*, Zhi-Yi Yang b, Ren-Cheng Tang a

a
National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, 199 Renai
Road, Suzhou 215123, China
b
Lushan College of Guangxi University of Science and Technology, Liuzhou 545000, China

Received 18 June 2018; accepted 1 November 2018

KEYWORDS Abstract Recently, there is a growing trend towards the fabrication of bioactive materials by using
Green chemistry; natural extracts, which can achieve diverse functionalities and environmental benefits simultane-
Natural extract; ously. This study presents a facile approach towards the preparation of bioactive and UV protective
Silk; silk materials using the extract from red radish (an edible root vegetable). The adsorption mecha-
Adsorption; nism of red radish extract on silk was studied. The results showed that red radish extract displayed
Antioxidant activity; higher exhaustion rate at lower pH. The equilibrium adsorption study indicated that the Langmuir
Antibacterial activity; and Freundlich isotherms were suitable to describe the adsorption behavior of red radish extract on
Ultraviolet protection silk, revealing that the ion–ion interactions, hydrogen bonding, and van der Waals forces play
major roles in the adsorption process. The silk treated with red radish extract over 5% owf, exhib-
ited excellent antioxidant activity, high antibacterial activities against Escherichia coli and Staphy-
lococcus aureus, and very good UV protective property. The functionalities of the treated silk
showed a gradual decline in the continuous washing process due to the release of red radish extract
during washing. In general, the results demonstrate that the red radish treated silk materials have a
promising future for the preparation of healthy and hygiene-related textiles.
Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
E-mail address: zhouyuyang_suda@hotmail.com (Y. Zhou).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
1. Introduction
With the growing awareness of environmental protection,
increasing attention has been drawn to the substitution for
non-regenerated resources with regenerated resources in order
to get the resources and environments onto the right track of
circulation. In the field of textile industry, bio-based colorants

https://doi.org/10.1016/j.arabjc.2018.11.003
1878-5352 Ó 2018 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Zhou, Y. et al., Facile and green preparation of bioactive and UV protective silk materials using the extract from red radish (Rapha-
nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
2 Y. Zhou et al.

principally derived from natural plants, are gaining popularity

owing to their non-toxic, degradable, and eco-friendly perfor-
mances (Shahid et al., 2013; Shahid-ul-Islam and Mohammad,
2015). Besides the benefits to the environment, considerable
studies have also confirmed the multiple functionalities of nat-
ural bioactive extracts such as antibacterial activity, antioxi-
dant activity, anti-inflammatory activity, etc., (Li et al., 2018;
Majouli et al., 2017; Msaada et al., 2017; Rahman et al.,
2017; Elbadrawy and Sello, 2016) with promising application
prospects in the manufacture of hygiene-related and medical
textiles (Mahmood et al., 2015; Shahid-ul-Islam et al., 2013;
Shahid-ul-Islam et al., 2018; Tawiah et al., 2016; Wang
et al., 2013).
Silk, a significant natural macromolecular protein pro-
duced by Bombyx mori silkworms, has long been regarded
as one of the most popular textile materials for manufacturing
high-end textile products due to its luxury appearance and
excellent wearing comfort. In recent years, the inherent per-
formances of silk including good biocompatibility, non-
toxicity, favorable mechanical performances, etc., make it
one of the most appropriate materials for the fabrication of
medical and biological textiles (Koh et al., 2015;
Maghdouri-White et al., 2016). As we all know, fabrics are
constantly in contact with our skin which provides nutrient
rich substrate and suitable temperature, facilitating the
growth of pathogen. On the other hand, the bacterial growth
Fig. 1 Schemes of the red radish root (a) and red radish extract
on the textiles can also impact the fabric appearance as a
powder (b) as well as chemical structures of the red radish extract
result of the microbial deterioration and pigmentation
(c).
(Gutarowska et al., 2017). In addition, non-allergy, non-
toxicity, antibacterial activity and anti-inflammatory activity
of textiles are the essential qualifications for medical applica-
cyanins are widely regarded as one of the most significant cat-
tion, however, silk is greatly hindered by its vulnerability in
egories among the water-soluble natural pigments (Horbowicz
the prevention of the bacterial adherence and growth (Li
et al., 2008), the adsorption mechanisms of anthocyanin to silk
et al., 2012). Therefore, the functionalization of silk for
are in need of study which can greatly benefit both the research
antibacterial purpose becomes increasing important for both
and practical applications. Moreover, the functionalities of red
clothing and medical materials, which is able to be achieved
radish treated silk towards repeated washing is also worthy of
by a green and sustainable functionalization process through
a study. Thus, the aim of this work lies in the fabrication of
the application of natural bioactive extracts.
multifunctional silk materials through the application of red
Red radish (Raphanus sativus L.) is an edible root vegetable
radish extract. The properties of red radish extract solution
(Fig. 1a and b) of the Brassicaceae family grown and con-
as a function of pH values were studied. The color character-
sumed throughout the world, and its extract has been widely
istics and fastness of treated silk were investigated. The
used as a natural food colorant (Giusti and Wrolstad, 2003).
adsorption mechanism of red radish extract on silk was also
Anthocyanins such as pelargonidin, cyanidin and delphinidin
explored. Finally, the functionalities including antioxidant
derivatives have been confirmed to be the major composition
and antimicrobial activities as well as UV protective property
of red radish extract (Fig. 1c), which can efficiently deactivate
of the treated silk as well as their washing durabilities were
the free radicals and defense against the microorganisms
examined and analyzed.
(Kong et al., 2003; Marı́n et al., 2015). Nevertheless, the stud-
ies regarding the application of red radish extract mainly
2. Materials and methods
focused on the food and medical sciences. In the textile
domain, very few reports as yet are available for the applica-
tion of red radish extract in textile functionalization. Although 2.1. Materials
the anthocyanins derived from other natural plants were used
for silk coloration (Huang et al., 2017; Jia et al., 2017; Vankar The crepe de chine silk fabrics (Specification code: 12103) were
and Shukla, 2011; Wang et al., 2014), the adsorption mecha- obtained from Wujiang Zhiyuan Textile Co. Ltd, China. Red
nism of anthocyanins to silk is still somewhat obscure which radish extract was acquired from Yunnan Tonghai Yang Nat-
is fundamental in determining the interactions between antho- ural Products Co. Ltd., China. The main coloring ingredient is
cyanins and silk. Additionally, more attention should also be anthocyanins which contain pelargonidin according to the pro-
paid to the exploration of the antioxidant and antibacterial duct description. ABTS agent was purchased from Shanghai D
activities as well as UV protective property of the antho- & B Chemicals Technology Co. Ltd., China. All the chemicals
cyanins treated silk, which contributes to the development of used were analytic reagents. A detergent designed for silk was
medical and protective textile materials. In general, antho- applied to the repeated washing cycles.

Please cite this article in press as: Zhou, Y. et al., Facile and green preparation of bioactive and UV protective silk materials using the extract from red radish (Rapha-
nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
Facile and green preparation of bioactive and UV protective silk materials
2.2. Treatment process
The treatment processes were implemented by immersing the
conical flasks containing fabric and treatment solution into
an XW–ZDR low-noise oscillated dyeing machine (Jingjiang
Xinwang Dyeing and Finishing Machinery Factory, China)
with a liquor ratio of 50:1. A citric acid-sodium phosphate buf-
fer solution was adopted for the pH adjustment.
2.2.1. pH effect on the uptake of red radish extract
5% owf (on the weight of fabric) red radish extract was applied
for silk treatment. The pH value was changed from 3.4 to 5.2.
The temperature was initially set at 30 °C, raised to 90 °C with
a speed of 2 °C/min, and then kept constant for 60 min.
2.2.2. Adsorption kinetics
The adsorption rate of the red radish extract on silk at three
temperatures (40, 60 and 80 °C) was measured. The adsorption
was performed with 10% owf red radish extract for 5 to
90 min.
2.2.3. Equilibrium adsorption isotherms
Silk fabrics were treated with the red radish extract in a con-
centration range of 0.5–10% owf at constant temperatures of
60 and 80 °C at pH 3.5. The isotherms were determined
according to the adsorption quantity of red radish extract on
silk after 90 min treatment owing to the fact that the equilib-
rium adsorption could be reached within 60 min which was
proved in the previous tests.
2.2.4. Building-up properties
A series of concentrations (1–10% owf) of red radish extract
were used for silk treatment at pH 4. The temperature was ini-
tially set at 30 °C, raised to 80 °C with a speed of 1.5 °C/min
and kept constant for 60 min.
2.3. Measurements
2.3.1. Uptake of red radish extract by silk
The absorption spectrum and absorbance of red radish extract
solution were examined by Shimadzu UV-1800 UV/Vis spec-
trophotometer (Shimadzu Co. Ltd., Japan). The exhaustion
rate of red radish extract was calculated according to the rela-
tionship between the concentration and absorbance at the kmax
(520 nm) of the solutions based on Eq. (1), in which m0 and m1
respectively represent red radish extract quantity in the treat-
ment solution before and after treatment. The red radish
extract quantities on silk were determined by the differences
of the red radish extract concentrations in the solution before
and after treatment together with the weight of dried fabric.
m0  m1
Exhaustion ð%Þ ¼  100 ð1Þ
m0
2.3.2. Color characteristics
The L*, a* and b* values respectively representing the lightness,
redness-greenness, and yellowness-blueness of the fabric, were
examined by HunterLab UltraScan PRO reflectance spec-
trophotometer using illuminant D65 with a 10° standard
Please cite this article in press as: Zhou, Y. et al., Facile and green preparation of bioactive and UV protective silk materials using the extract from red radish (Rapha-
nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
3
observer. Four layers of the samples were tested by folding
them twice.
2.3.3. Color uniformity
The color uniformity of treated silk fabric was determined
according to the standard deviation d(kmax) of the K/S values
at the maximum adsorption wavelength (kmax = 530 nm). 10
different positions from the center to edge of the fabric sample
were selected for measurement. The d(kmax) was calculated
using Eq. (2), where kmax is the maximum adsorption wave-
length of red radish extract treated silk, n is the number of
measurement positions, (K/S)i,kmax is the K/S value of each
measurement at 530 nm and ððK=SÞkmax Þ is the average value
of 10 measurements. Thus, the smaller value of d(kmax) indi-
cates the better color uniformity.
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uP
u n h i2
u ðK=SÞi;kmax  ðK=SÞkmax
ti¼1
dðkmax Þ ¼ ð2Þ
n1
2.3.4. Color fastness
The 5% owf red radish extract treated silk fabrics were used in
all the color fastness assessments. All the methods regarding
the wash, rubbing and light fastness tests were documented
in our previous reports (Zhou et al., 2015; Zhou and Tang,
2016).
2.3.5. Functionalities
The functionality assessments were carried out using the sam-
ples collected from the Section 2.2.4.
The antioxidant activities of the samples were measured
through the ABTS_+ decolorization assessment by spectropho-
tometric analysis (Re et al., 1999). More descriptions were pre-
sent in our previous work (Zhou et al., 2015; Zhou et al.,
2016).
The antibacterial activities of the samples were determined
based on the GB/T 20944.3-2008. More descriptions were pre-
sent in our previous work (Zhou et al., 2015; Zhou et al.,
2016).
The UV transmittance and UPF value of the treated silk
fabrics were evaluated using Labsphere UV-1000F UV trans-
mittance analyzer (Labsphere Inc., USA). Four different posi-
tions of each sample were tested and the average data were
shown in the text.
2.3.6. Durability of functionalities
The functionalities of the samples after 1, 5, and 10 washing
cycles were evaluated. The washing process was implemented
at 40 °C according to our previously reported method (Zhou
and Tang, 2016).
3. Results and discussion
3.1. UV–vis absorption spectroscopy of the red radish extract
Substantial information including the solubility, stability, UV–
Vis absorption characteristic, etc. can be obtained from the
UV–Vis absorption spectra of red radish extract solution,
which is closely related to the application properties. As seen
4 Y. Zhou et al.
Fig. 2 UV–Vis absorption spectra of the red radish extract
solution at pH 4.
in Fig. 2, the red radish extract solution showed two strong
characteristic peaks located at 220 and 295 nm in the UV
absorption region, indicating its inherent UV absorption capa-
bility. This result implies that the red radish extract is able to
be served as a potential UV protective agent to enhance the
UV protective property of silk textiles. The red radish extract
showed a peak at 520 nm in the visible light region, indicating
the presence of pelargonidin in the composition of red radish
extract (Noda et al., 2002). Thus, the concentration of red rad-
ish extract in the solution was able to be estimated by measur-
ing the absorbance at 520 nm. The red radish extract exhibited
a good linear relation between its absorbance and concentra-
tion with a high R2 up to 0.9994 (Fig. 3a), indicating that it
has no agglomeration in the solution within such concentra-
tion range. In order to obtain accurate results, the red radish
extract solutions were diluted to this concentration range
before the UV–Vis absorption spectroscopy study in the fol-
lowing experiment.
Fig. 3b showed the spectra of the red radish extract at dif-
ferent pH values. Obviously, the kmax of the spectra gradually
shifted to longer wavelength as the pH values increased, and
correspondingly the visual color of the solutions changed. This
phenomenon is due to the higher degree of hydroxyl group
ionization on the B-ring of pelargonidin at higher pH values
(Giusti and Wrolstad, 2003). Moreover, the drastic increase
Fig. 3 UV–Vis absorption spectra of the red radish extract as a function of concentration (a) and pH (b).
Please cite this article in press as: Zhou, Y. et al., Facile and green preparation of bioactive and UV protective silk materials using the extract from red radish (Rapha-
nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
of the kmax occurred between pH 5 and 6, which is attributed
to the structural transformation of pelargonidin from quino-
noidal base to quinonoidal mono-anion (Asenstorfer et al.,
2003; Heredia et al., 1998). In addition, the absorbance of
the spectra decreased as the pH values changed from 2 to 5
and then again started increasing at higher pH values. Previous
reports also showed that the anthocyanins are inclined to
degrade at high pH and at high temperature (Ekici et al.,
2014; Fracassetti et al., 2013). Therefore, the following treat-
ment processes were implemented below pH 5.
3.2. Adsorption properties of the red radish extract
3.2.1. Effect of pH
The pH value of the treatment solution is a significant param-
eter, which greatly influences the uptake of the red radish
extract by silk owing to the fact that pH value has effects on
the surface charge of silk and the ionization degree of the con-
stituents of red radish extract.
In this section, the pH effect on the uptake of the red radish
extract by silk and the color characteristics of the treated silk
were investigated. As shown in Fig. 4a, the exhaustion of the
red radish extract increased with decreased pH. This result
manifests that the adsorption of the red radish extract on silk
is mainly achieved through the electrostatic interactions
between the negatively charged pelargonidin and positively
charged silk. Additionally, silk displays a higher degree of
swelling in a more acidic condition, facilitating a higher
adsorption quantity of pelargonidin on silk because of the
easier diffusion of pelargonidin from the surface to inner side
of silk fiber.
Fig. 4b shows that pH exerted an impact on the color char-
acteristics of the treated silk. The original silk displayed a
white and lustrous appearance. After treated with the red rad-
ish extract, the silk fabric presented a mild magenta color.
With an increase in pH, the treated silk fabric showed
decreases in both a* and b* values, indicating that the treated
fabrics changed from high saturated red to bluish-red color.
In addition, the lightness of treated silk increased with increas-
ing pH, revealing the decrease of color depth. It can also be
concluded that the color differences of the treated silk at var-
ious pH values is the combined effects of the different adsorp-
tion quantities of pelargonidin on silk and the color variations
of pelargonidin at different pH values.
Facile and green preparation of bioactive and UV protective silk materials 5

Fig. 4 pH dependence of the uptake of the red radish extract by silk (a), and color characteristics of the treated silk (b).

Ct and Ce are the adsorption quantities of red radish extract

at time t and at equilibrium, respectively.
t 1 1
¼ þ t ð3Þ
Ct kC2e Ce
If the adsorption complies with the pseudo second-order
kinetic equation, t/Ct would have a linear relation with t.
The slope and intercept of the linear regression line were
employed to calculate the k and Ce values. In addition, the half
adsorption time (t1/2) as well as the initial adsorption rate (ri)
was calculated according to Eqs. (4) and (5), respectively.
1
t1=2 ¼ ð4Þ
kCe

Fig. 5 Adsorption rates of the red radish extract for silk at
various temperatures.
3.2.2. Adsorption kinetics
The adsorption kinetics plays a significant part in the treat-
ment process which can provide important references to design
the adsorption system. In this section, the adsorption rates of
red radish extract were investigated according to its adsorption
amount (Ct) as a function of time (t). As depicted in Fig. 5, the
adsorption quantity of red radish extract at 80 °C displayed an
abrupt increase in the first 20 min and then increased gradually
over time. Moreover, the adsorption rates of red radish extract
for silk at 40 and 60 °C were lower than that at 80 °C.
In order to obtain the parameters of adsorption kinetics at
various temperatures, the pseudo second-order kinetic equa-
tion (Eq. (3)) was used to fit the experiment data (Ho and
McKay, 1999), where k is the adsorption rate constant, and
ri ¼ kC2e ð5Þ
2
The correlation coefficients (R ) of the kinetic model are
listed in Table 1. Clearly, the R2 values for the linear plots
of red radish extract were very high, proving the validity of
the pseudo-second-order kinetic equation in describing the
adsorption process of red radish extract. The ri and k of the
treatment process at 80 °C were much higher than those at
40 and 60 °C, leading to the lower t1/2. This result indicates
that raising the temperature of treatment process is very effec-
tive in reducing the equilibrium adsorption time. Moreover, it
can be seen that the C1 of the treatment process at 60 and
80 °C was higher than that at 40 °C, which is caused by the fact
that silk fiber displays higher swelling extent at high tempera-
ture, contributing to an easier penetration of red radish extract
into silk inferior.
3.2.3. Adsorption isotherms
The equilibrium adsorption isotherms are essential in the
exploration of the interactions between the red radish extract

Table 1 Adsorption kinetic parameters of the red radish extract for silk at various temperatures.
Temp. (°C) ri (mgg1∙min1) k (g∙mg1∙min1) t1/2 (min) C1 (mg∙g1) R2
40 15.04 0.0035 4.35 65.36 0.9983
60 20.45 0.0044 3.35 68.49 0.9989
80 131.58 0.0273 0.53 69.44 0.9999

Please cite this article in press as: Zhou, Y. et al., Facile and green preparation of bioactive and UV protective silk materials using the extract from red radish (Rapha-
nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
6 Y. Zhou et al.
Fig. 6 Equilibrium adsorption isotherms of the red radish
extract for silk (Langmuir, solid line; Freundlich, dash line).
and silk fiber. The adsorption isotherms of the red radish
extract on silk at pH 3.5 at 60 and 80 °C are shown in
Fig. 6. The experimental isotherm points were described by
Langmuir and Freundlich adsorption models.
The Langmuir adsorption model is based on the assump-
tion that when one reactive site of adsorbent is occupied by
one solute molecule, no further adsorption at this site can
occur (Zhou and Tang, 2017). Langmuir isotherm is very com-
monly used for the characterization of chemisorption process.
The expression of Langmuir adsorption is shown in Eq. (6),
where Cf (mgg1) and Cs (mgL1) respectively represent the
concentration of the red radish extract on the silk fiber and
in the solution when the treatment process reaches equilib-
rium; S stands for the saturated concentration of the red radish
extract on silk; KL is the Langmuir affinity constant.
SKL Cs
Cf ¼
1 þ KL Cs
The Freundlich isotherm is another significant adsorption
model to describe the equilibrium adsorption process of the
solute on a heterogeneous surface, and thus it is not assumed
to be a monolayer capacity (Chairat et al., 2005). The Fre-
undlich equation is expressed as Eq. (7), in which KF repre-
sents the Freundlich affinity constant, and n acts as an
indicator of surface heterogeneity or the intensity of
adsorption.
Cf ¼ KF Cns
The parameters of Langmuir and Freundlich adsorption
were determined using the non-linear least squares procedure,
and listed in Table 2. From Table 2, it can be noted that the
experimental points at two temperatures fitted very well to
the Langmuir equation, whilst the Freundlich equation
Table 2 Langmuir and Freundlich adsorption parameters of the red radish extract for silk.
Temp. (°C) Langmuir
KL(Lg1) S (mgg1)
60 3.36 74.53
80 1.22 94.43
Please cite this article in press as: Zhou, Y. et al., Facile and green preparation of bioactive and UV protective silk materials using the extract from red radish (Rapha-
nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
showed a low correlation coefficient at 60 °C. In addition,
the fitted Langmuir lines went more exactly through all of
the experimental points than the fitted Freundlich lines
(Fig. 6). This demonstrates that the Langmuir adsorption
mechanism is somewhat more suitable for describing the
adsorption process than Freundlich adsorption mechanism.
As the temperature increased, the Langmuir and Freundlich
affinity constants (KL and KF) of the red radish extract
declined, revealing that the adsorption process is exothermic.
The Langmuir adsorption saturation at 80 °C was higher than
that at 60 °C, due to the great accessibility of silk fiber at a
high temperature. The Freundlich exponent n was higher at
80 °C, indicating that the reactive adsorption sites of silk fiber
have a higher degree of homogeneity at a high temperature.
According to the above results, the chemisorption process in
a monolayer plays the major role followed by a multilayer
physisorption.
The isoelectric point of silk fiber was confirmed to be 4.32
in our previous study (Zhou et al., 2016). Therefore, the silk
fiber is positively charged at pH 3.5 which was used in this
study, due to the protonation of amino groups in its structure.
Anthocyanins show four different forms including flavylium
cation, quinoidal bases, carbinol pseudobase, and chalcone
pseudobase forms based on the pH values (Asenstorfer et al.,
2003; Ekici et al., 2014; Jia et al., 2017). Thus, there exists a
dynamic equilibrium in the mixture of the four forms of antho-
cyanins at pH 3.5. During the adsorption process, as a small
quantity of negatively charged quinoidal bases is adsorbed
by the positively charged silk fiber, the dynamic ionization
equilibrium is broken which can promote the further disasso-
ciation and adsorption of anthocyanin. Additionally, the red
radish extract has multiple hydrogen groups in its anthocyanin
structure, and silk fiber bears a large amount of amide, amino,
and carboxyl groups. Thus, hydrogen bonding can occur
between silk fiber and the red radish extract. There also exist
ð6Þ
van der Waals forces between silk and the red radish extract,
which contribute to the Freundlich adsorption.
3.2.4. Building up property
The building-up performance of natural extracts is a signifi-
cant indicator, which is closely related to their utilization,
color yield and adsorption quantity on textiles in practical pro-
duction. In other words, a natural extract with better building-
up property is more suitable for achieving a final textile pro-
duct with large ranges of color depth and adsorption quantity
ð7Þ
which can cater to the different demands of consumers. The
building-up performance of natural extracts is closely related
to their chemical structures, affinities to fiber, adsorption
mechanisms, and adsorption capabilities. In this study, the
building-up property of the red radish extract on silk was
investigated using a temperature-rise approach rather than a
Freundlich
R2 KF (Lg1) n R2
0.9964 1.896 0.508 0.9826
0.9964 0.588 0.655 0.9982
Facile and green preparation of bioactive and UV protective silk materials
Fig. 7 Exhaustion and adsorption quantity of the red radish extract on silk (a) and L*a*b* values of the treated silk at various
concentrations (b).
constant temperature process in order to get closer to the prac-
tice manufacture process.
As shown in Fig. 7a, the adsorption quantity of the red rad-
ish extract increased continually along with its increasing con-
centration. The exhaustion of the red radish extract on silk still
maintained over 50% even at the concentration of 6% owf,
revealing its good building-up capability and high utilization,
which could further benefit both adsorption performance
and functionality of silk. It can be seen from Fig. 7b that the
silk fabrics displayed increasing a* values when treated with
increasing concentrations of the red radish extract, indicating
the enhancement of red color. However, the b* values and
color hue barely changed. The L* values showed a downtrend
as the concentration increased, indicating an increase in color
depth.
3.3. Color uniformity and fastness
The color uniformity is fundamental to the appearance quality
of the final products. For the practical application, in general,
natural extracts are inferior to synthetic colorants in color
evenness during treatment process, thus the color uniformity
of the red radish extract treated silk fabric is a significant per-
formance and worthy of study. The silk fabric treated with 5%
owf red radish extract was involved in the evaluation of color
uniformity. On the whole, the color of the treated silk fabric
was perceptually uniform. The further calculated standard
deviation d(kmax) of the K/S values at the maximum absorp-
tion wavelength of 530 nm was 0.0037. This result demon-
strates the excellent color uniformity of the red radish
treated silk.
The fastness of the red radish treated silk was also evalu-
ated and the results are shown in Table 3. It can be seen that
Table 3 Fastness of red radish dyed silk.
Sample Wash fastness
Color change Stain
Silk
Dyed silk 3 3
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nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
7
the color change and the color stain on silk and cotton were
moderate. Moreover, the treated silk showed a good level in
dry and wet rubbing fastness, while its light fastness was level
3.
3.4. Functionalities
3.4.1. Antioxidant activity
Recently, the antioxidant activity of textiles which are con-
stantly contacted with human skin, has attracted increasing
attention in the development of medical, healthy and hygienic
clothing. Anthocyanin has already been evidenced to be effec-
tive in radical scavenging (McGhie and Walton, 2007), making
it possible to serve as a natural antioxidant to impart silk with
antioxidant activity. Thus, the present work was to explore the
antioxidant activity of the silk treated with different concentra-
tions of red radish extract.
As depicted in Fig. 8, the original silk has poor antioxidant
activity with a free radical reduction rate of 34%. After treated
with the red radish extract, the silk fabrics showed a significant
improvement in antioxidant activity. The high radical-
scavenging activity of red radish extract treated silk was also
observed in the test, further, the color of ABTS_+ solution
faded within 10 min. The excellent antioxidant activity of red
radish extract is attributed to the function of anthocyanin
compound through several mechanisms including hydrogen
donation, metal chelation, and protein binding (Kong et al.,
2003). Moreover, the antioxidant activity of the samples con-
tinued to increase with increasing concentration of red radish
extract. 5% owf red radish extract can impart silk with an
antioxidant activity of 97%, indicating that medium dosage
of red radish extract is sufficient to prepare a silk fabric with
high antioxidant activity.
Rub fastness Light fastness
Dry Wet
Cotton
4 4 4 3
8 Y. Zhou et al.
Fig. 8 Antioxidant activity of the silk fabrics treated with the red
radish extract.
3.4.2. Antibacterial activities
Antibacterial treatment of textiles is aiming at preventing dis-
ease spread, avoiding the infections caused by injuries, inhibit-
ing the odor developed from perspiration and stains attached
Fig. 9 Antibacterial activity of the silk fabrics treated with the
red radish extract.
Fig. 10 UV transmittance curves (a) and T(UVA), T(UVB) and UPF (b) of the silk fabrics treated with the red radish extract.
Please cite this article in press as: Zhou, Y. et al., Facile and green preparation of bioactive and UV protective silk materials using the extract from red radish (Rapha-
nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
to the fibers, and restraining the textiles from mildew deterio-
ration (Mirjalili and Karimi, 2013). Anthocyanin has been
used as a natural antibacterial agent for many years (Marı́n
et al., 2015). Thus, the antibacterial activities of the silk treated
with 5 and 10% owf red radish extract were assessed.
As depicted in Fig. 9, the original silk fabric displayed very
poor antibacterial activities. The silk treated with 5% red rad-
ish extract showed antibacterial activities of 81 and 84%
against E. coli and S. aureus, respectively. Moreover, to
increase the concentration of red radish extract can efficiently
improve the antibacterial activity of the treated silk. This result
demonstrates that the radish extract treated silk can inhibit
both gram negative and gram positive strains. The antibacte-
rial mechanism of anthocyanins is that they can induce the
localized disintegration of bacterial outer membrane, leakage
of cytoplasm (with the presence of significant amounts of cyto-
plasmic material and membrane debris outside the cells), and
irregular shape of bacteria (Lacombe et al., 2010).
3.4.3. UV protective property
Due to the acceleration of the ozone layer depletion, the sun-
light radiation is becoming stronger that seriously threatens
human beings (Hupel et al., 2011). Textiles, regarded as an
important layer between human skin and atmosphere, can pro-
vide UV blocking properties which are related to their fiber
type, fabric construction and nature of finishing chemicals
(Grifoni et al., 2014).
Fig. 10a showed the ultraviolet transmission spectra of the
original and treated silk fabrics. Original silk showed a high
ultraviolet transmittance, resulting in a low UPF (Fig. 10b).
The treated silk displayed a remarkable decrease in the ultravi-
olet transmittance over the UVA and UVB ranges, which is
consistent with the prediction made according to Fig. 2. The
UPF value of the silk treated with 6% owf red radish extract
was within the ‘very good’ scale based on the AS/NZS
4399:1996 (Sun and Tang, 2011). With the concentration of
red radish extract increasing, the treated silk fabric showed a
decline in ultraviolet transmittance, and an increase in UPF.
To compare the TUVA and TUVB values of silk fabrics before
and after treatment, it can be seen that the TUVA value dis-
played higher decline than TUVB value. This indicates that
the red radish extract on the silk fabric displays a higher effi-
ciency in absorbing UVA than UVA radiation.
Facile and green preparation of bioactive and UV protective silk materials
Fig. 11 Functionalities changes of the treated silk fabric after
repeated laundering cycles: antioxidant activity (a), antibacterial
activity (b), and UV protective performance (c).
3.5. Durability of functionalities
During usage, silk textile materials are inevitably subjected to
the repeated washing cycles. Thus, the aim of this study is to
clarify the durability of functionalities of the red radish extract
treated silk after repeated washing cycles. The fabric treated
with 5% owf red radish extract was involved in the measure-
ments of antioxidant and antibacterial activity. The 6% owf
red radish extract treated silk was applied to the assessment
of UV protective property. The results are shown in Fig. 11.
The antioxidant and antibacterial activities of the treated
silk gradually decreased after subjected to repeated washing
processes. After 10 washing cycles, the antioxidant activity of
the treated silk fabric declined to 51.5%, the bacterial reduc-
tion rate against E. coli and S. aureus of the treated silk
dropped 28% and 39%, respectively, and the UPF of the trea-
ted silk after 10 washing cycles decreased to 15. In conclusion,
the functionalities of the red radish treated silk showed a grad-
ual decrease after repeated washing cycles. Thus, efforts should
be made to enhance the functional durability of the red radish
treated silk in the future work, which will benefit the properties
and qualities of health and hygiene-related textiles. In addi-
tion, in order to prepare the medical materials for sustained
release purpose, red radish treated silk is also a good choice.
4. Conclusion
This study presents a facile and eco-friendly approach towards
the colored, bioactive and UV protective silk materials using
red radish extract. The adsorption quantity of red radish
extract on silk showed a high dependence with the pH value
of treatment solution. The study on equilibrium adsorption
demonstrated that the adsorption of red radish extract on silk
was achieved through the ion–ion interactions, hydrogen
bonding, and van der Waals forces between red radish extract
and silk fiber. The functionalities of the treated silk were
related to the quantity of red radish extract on silk. The 5%
owf red radish extract was sufficient to impart silk with very
good antioxidant and antibacterial activities. The functionali-
ties of the treated silk gradually decreased during repeated
Please cite this article in press as: Zhou, Y. et al., Facile and green preparation of bioactive and UV protective silk materials using the extract from red radish (Rapha-
nus sativus L.) through adsorption technique. Arabian Journal of Chemistry (2018), https://doi.org/10.1016/j.arabjc.2018.11.003
9
washing cycles. In conclusion, the red radish treated silk can
be applied to develop the healthy and hygiene materials.
Acknowledgements
This study was funded by Jiangsu Provincial Key Research
and Development Program of China (BE2015066), the Priority
Academic Program Development (PAPD) of Jiangsu Higher
Education Institutions (No. 2014-37) and the Research Inno-
vation Program for College Graduates of Jiangsu Province
(KYLX16_0137).
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