Reactive & Functional Polymers 73 (2013) 1559–1566

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Reactive & Functional Polymers

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Adsorption and functional properties of natural lac dye on chitosan fiber

Li Liu a, Jun Zhang 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
Suzhou Institute of Trade and Commerce, 287 Xuefu Road, Suzhou 215009, China

a r t i c l e i n f o a b s t r a c t

Article history: Natural lac dye was applied to the dyeing of chitosan fiber in order to prepare healthy and hygienic textile
Received 6 February 2013 materials, and the adsorption and functional properties of lac dye on chitosan fiber were studied. The
Received in revised form 29 July 2013 functional properties of the dyed chitosan fiber depended greatly on the adsorption quantity of lac
Accepted 20 August 2013
dye, which was related to dyeing temperature, neutral electrolyte dosage, and initial dye concentration.
Available online 3 September 2013
Lac dye displayed a very high adsorption capability on chitosan fiber, and a high utilization rate. The
research on equilibrium adsorption showed that the Langmuir–Nernst isotherm was the most appropri-
Keywords:
ate model to describe the behavior of lac dye, and the electrostatic interactions between lac dye and
Chitosan fiber
Lac dye
chitosan fiber contributed to Langmuir adsorption whereas the non-electrostatic interactions contributed
Adsorption to partition adsorption. The functionality analyses showed that the dyed chitosan fiber exhibited the
Dyeing good antioxidant activities determined by the DPPH radical scavenging assay and the ABTS radical decol-
Functionality orization assay, and the good deodorizing performance towards ammonia. This study points out that the
lac dyed chitosan fiber can be utilized as functional textile materials with the requirements of antioxidant
activity and deodorizing performance.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction relatively poor antioxidant activity [9,10], which has great signifi-
cance for developing medical and healthy clothing, and bioactive
In recent years, much attention has been paid to chitin and dressings. Thus, it is essential to upgrade its antioxidant activity
chitosan as biological macromolecule polymers because they have and other functionalities. A new approach to enhancing the func-
several distinctive biomedical properties such as nontoxicity, bio- tionalities of chitosan polymer is to incorporate the active ingredi-
compatibility, biodegradability, and antibacterial activity [1,2]. In ents (e.g. polyphenolic compounds) of natural plant extracts onto
fiber and textile fields, considerable research efforts have been fo- its polysaccharide backbone [11–14]. Recently, polyphenol oxi-
cused on the application of chitin and chitosan in the development dases have been utilized to graft natural flavonoids with powerful
of functional textiles and wound dressings [1,2]. The related tech- antioxidant activity onto chitosan/viscose blend fiber [9]. In com-
nology approaches can be mainly divided into two meaningful cat- parison with other chemical modification approaches of chitosan
egories: one is the use of chitosan as a functional finishing agent to fiber, the enzymatically functionalization has the environmental
treat textiles [3–6], and the other is the application of chitin, chito- benefits of nontoxicity, health and safety [9,10], and may exert a
san and their blends with other polymers to the manufacturing of minimal impact on the mechanical properties of chitosan fiber.
functional fibers by wet spinning [1,7,8]. Nowadays, chitosan and On the other hand, fiber and textile processing are moving to-
viscose-chitin blend fibers have been commercially produced. Chi- wards the directions of the eco-friendly technologies, and the func-
tin and chitosan fibers as textiles materials have various merits tionalization of products. Many creative technologies have been
including no allergenic reaction, low antigenicity, high safety, tried to introduce eco-friendly and health-care functions to textile
organism compatibility, gentleness to the body, antibacterial and products. Among those technologies, the applications of the ex-
deodorizing effects, wound-healing, moisture-retaining, and they tracts from natural materials to the dyeing and finishing of textiles
can be applied in the development of the products such as under- have received much attention as natural extracts including dyes
wear, sleepwear, sportswear, socks, towel, tablecloth, upholstery, generally exhibit good biodegradability and compatibility with
medical clothing, wound-dressings, and cosmetic films [7]. the environment [15], and most of them possess a wide range of
Although chitosan fiber possesses good antimicrobial activity functional and medicinal properties such as UV protection
and allows manufacturers to produce functional textiles, it shows [16,17], antimicrobial activity [18–20], antioxidant activity
[9,19,21], and deodorizing ability [22]. Furthermore, natural dyes
with functionalities can be introduced to textiles to achieve the ef-
⇑ Corresponding author. Tel.: +86 512 6716 4993; fax: +86 512 6724 6786. fects of the simultaneous coloration and functional finishing. At
E-mail address: [email protected] (R.-C. Tang). present, the textile products dyed and finished with natural

1381-5148/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.reactfunctpolym.2013.08.007
1560 L. Liu et al. / Reactive & Functional Polymers 73 (2013) 1559–1566

extracts have won the favor of the consumers who are quite aware Youngchito Bio. Co. Ltd., China. To remove the finish oils added
of environmental problems, and their market is increasing. to the fiber in post-spinning treatments, the sample was treated
In the light of recent developments, this study aims to use nat- in a scouring bath containing 0.5 g L1 nonionic surfactant (poly-
ural dyeing to enhance the functionalities of chitosan fiber. The oxyethylene alkyl ether) at 60 °C for 30 min using a 50:1 liquor ra-
selection of lac dye was based on the fact that most of the phenolic tio. The scoured fiber was then rinsed thoroughly in distilled water,
hydroxyl group-containing anthraquinone compounds from plants and allowed to dry in the open air.
have good antioxidant activity [23–26]. Lac dye is also composed of Lac dye was purchased from Yunnan Tonghai Young’s Natural
polyphenolic anthraquinone compounds. It is a natural reddish col- Products Co. Ltd., China. 2,20 -Azino-bis (3-ethylbenzothiazoline-
orant produced by the insect Coccus lacca or Laccifer lacca [27], and 6-sulphonic acid) diammonium salt (ABTS) and 2,2-diphenyl-1-
can be obtained in large amounts as a by-product of shellac indus- picrylhydrazyl (DPPH) were obtained from Sigma–Aldrich (Shang-
try. The two major anthraquinone-based ingredients in lac dye are hai) Trading Co. Ltd.. Sodium sulfate, ethanol absolute, potassium
laccaic acids A and B, and the minor components are laccaic acids dihydrogen phosphate, sodium hydroxide, potassium persulphate
C, D and E (Fig. 1) [27]. and ammonia aqueous solution were of analytical reagent grade,
Lac dye has been considered for general use as a colorant of and purchased from Sinopharm Chemical Reagent Shanghai Co.
foods and cosmetics, and also applied to dye silk, wool and cotton Ltd., China. The nonionic surfactant was provided by Jiangsu Hai’an
fibers [27–30]. It has been reported that the modifications of fibers Petrochemical Plant, China and used as received.
with plasma etching [31], and synthetic and natural polymer pre-
treatment (e.g., poly (ethyleneimine) and chitosan) [32–34] as well 2.2. Adsorption and dyeing experiments
as ultrasonic assisted dyeing [29,35] were capable of increasing the
uptake of lac dye. In addition, the kinetic studies of the adsorption All adsorption and dyeing experiments were carried out in the
of lac dye on silk and cotton fibers showed that the lac dyeing pro- sealed and conical flasks immersed in a XW–ZDR low-noise oscil-
cess followed the pseudo second-order model [27,30,33], and the lated dyeing machine (Jiangsu Jingjiang Xingwang Dyeing and Fin-
isotherms of the adsorption of lac dye on silk fiber and chitosan- ishing Machinery Factory, China). The liquor ratio was 100:1. At
treated cotton fiber were found to be a Langmuir type [27,28,34]. the end of adsorption and dyeing, the chitosan fiber was washed
In spite of the above investigations, little attention has been paid in distilled water and then dried in the open air.
to the functionalities of the fibers dyed with lac dye. In this study,
chitosan fiber was dyed with lac dye, and the antioxidant activity 2.2.1. Effect of electrolyte on the uptake of lac dye
and deodorizing properties of the dyed fiber were investigated. Tak- To assess the effect of electrolyte on the adsorption properties,
ing the fact into consideration that the research about the adsorp- chitosan fibers were dyed with the solutions of 2% owf (on the
tion isotherms of lac dye on chitosan fiber helps to understand weight of fiber) lac dye and Na2SO4 over a range of concentrations
the adsorption mechanism and to control the dyeing process, this between 0 and 20 g L1. After immersing chitosan fibers in the
study was also concerned with the thermodynamics and mecha- solutions at 30 °C, the temperature was raised to 50 °C at a rate
nism of the adsorption of lac dye on chitosan fiber. Also, the build- of 1 °C min1 with a holding time of 60 min. The percentage of
ing-up property of lac dye on chitosan fiber was discussed. exhaustion was a major parameter to be investigated.

2.2.2. Adsorption rates of lac dye

2. Experimental The rates of the adsorption of lac dye on chitosan fiber at three
temperatures (40, 50 and 60 °C) were measured. The adsorption
2.1. Materials was performed with 2% owf lac dye in the absence and presence
of 5 g L1 Na2SO4 for 5 to 120 min.
The pure chitosan fiber (2.5 dtex; 38 mm) not subjected to
chemical cross-linking was purchased from Shandong Weifang 2.2.3. Equilibrium adsorption isotherms of lac dye
The adsorption isotherms for lac dye on chitosan fiber were
measured in a series of lac dye solutions of various concentrations
(1–40% owf) at 40, 50 and 60 °C in the presence of 5 g L1 Na2SO4.
The isotherms were determined on the basis of the adsorption for
120 min as the previous tests showed that the equilibrium adsorp-
tion was reached in 60 min.

2.2.4. Build-up property of lac dye

The building-up property of lac dye on chitosan fiber was mea-
sured in the dye solutions of the concentration of 1–50% owf. The
fibers were immersed into the solutions at 30 °C, and subsequently
the dye solutions were heated to 50 °C at a rate of 1 °C min1 and
the treatment continued for 60 min.

2.3. Measurements of adsorptions

The absorption spectra as well as the absorbance (kmax = 494

nm) of lac dye were measured using a Shimadzu UV-1800
UV–vis spectrophotometer (Shimadzu Co., Japan). Using a previ-
ously established absorbance/concentration relationship at the
kmax of the lac dye solution, the quantity of lac dye in solution
was able to be calculated, and the percentage of exhaustion (%E)
was determined using Eq. (1), where m0 and m1 are the quantities
Fig. 1. Chemical structures of the laccaic acids. of lac dye before and after adsorption (mg). The quantity of lac dye
 L. Liu et al. / Reactive & Functional Polymers 73 (2013) 1559–1566 1561

on chitosan fiber was calculated by the difference in the initial and and allowing the mixture to stand in the dark at room temperature
final concentrations of lac dye in solution as well as the weight of for 12–16 h before use. The radical was stable in this form for more
the dried fiber. than 2 days when stored in the dark at room temperature. Before
m0  m1 usage, the ABTS+ solution was diluted with a phosphate buffer
%E ¼ 100  ð1Þ (0.1 M, pH 7.4) to reach an absorbance of 0.700 ± 0.025 at
m0
734 nm. Then, 10 mg of chitosan fiber was added to 10 ml of ABTS+
solution. After 30 min, the scavenging capability of ABTS+ at
2.4. Test of the desorption of lac dye from the dyed chitosan fiber 734 nm was calculated using Eq. (2), where Acontrol is the initial
concentration of the ABTS+ and Asample is the absorbance of the
The desorption of lac dye from the dyed chitosan fiber in water remaining ABTS+ in the presence of fiber sample.
was tested at 50 °C using a liquor ratio of 100:1. The original chito-
san fiber was dyed with 4% owf lac dye according the method de-
2.6.3. Deodorizing performance
scribed in Section 2.2.4; after dyeing, the fiber was completely
The gas detecting tube method was used to measure ammonia
rinsed in distilled water, washed at 40 °C for 5 min, and finally
gas concentration and assess the deodorizing ability of chitosan fi-
dried in the open air. The desorption rate at different times was
ber [22,37,38]. Ammonia aqueous solution was diluted 5 times be-
calculated by the difference in the concentrations of lac dye on
fore use. The deodorizing ability was tested as follows: a proper
chitosan fiber before and after desorption.
amount of ammonia was injected into a 4 L airtight polyethylene
vessel. The loose fiber was suspended in the vessel at 25 °C and
2.5. Determination of the pH value of dyebath 60% relative humidity for 60 min. The change of the concentration
of ammonia gas in the vessel was measured by a corresponding gas
In order to discuss the mechanism of the adsorption of lac dye detector tube with GASTEC GV-100S gas sampling pump (GASTEC
on chitosan fiber, the change in the pH value of dyebath during the Co., Japan). The deodorizing performance was calculated using Eq.
process of lac dye adsorption was studied. The chitosan fiber was (3):
dyed with 4% owf lac dye according to the method described in
Section 2.2.4; the pH value of dyebath at different time intervals Cb  Cs
Deodorization performanceð%Þ ¼  100 ð3Þ
was measured using a PHS-3C pH meter (Shanghai INESA Scientific Cb
Instrument Co., Ltd., China).
where Cb is the concentration (mg m3) of ammonia in the vessel
2.6. Evaluations of functionalities without chitosan fiber (blank state), and Cs is the concentration
(mg m3) of ammonia in the vessel in the presence of sample.
The measures of antioxidant activity and deodorizing perfor-
mance were employed for the chitosan fibers dyed with lac dye 3. Results and discussion
as mentioned in the experiment of building-up property. The se-
lected concentrations of lac dye were 0, 4%, 12%, 20%, 30%, and 3.1. Effect of electrolyte on the uptake of lac dye
40% owf. All determinations were performed in triplicate, and the
average of the data was used. The effect of electrolyte amount on the uptake of lac dye by
chitosan fiber is shown in Fig. 2. In this case, Na2SO4, a widely used
2.6.1. Antioxidant activity determined by the DPPH radical scavenging neutral electrolyte in dyeing process, was chosen. It was found that
assay the adsorption of lac dye on chitosan fiber was obviously influ-
The DPPH radical scavenging activity was measured using a enced in the presence of Na2SO4. With increasing concentration
previously reported method [9]. The bleaching rate of a stable free of Na2SO4, the percentage of exhaustion of lac dye decreased
radical, DPPH_, is monitored at a characteristic wavelength in the clearly. This might be attributed to the competitive effect between
presence of the sample. In its radical form, DPPH_ absorbs at lac dye ions and sulfate ions from the salt for the sites of chitosan
517 nm, but upon reduction by an antioxidant or radical species fiber available for the adsorption. Due to the presence of amino
its absorption decreases. Briefly, 0.1 mM solution of DPPH_ in etha- groups, the chitosan fiber carries a positive charge, whereas lac
nol was prepared and 3 ml of this solution was mixed with 300 mg dye has phenolic and carboxylic acid groups in its molecule provid-
of chitosan fiber and 7 ml ethanol. The reaction mixture was sha- ing a negative charge. Because of the opposite charges of the sur-
ken vigorously and stored in the dark at room temperature. After face active sites of chitosan fiber and lac dye molecules, there is
30 min, the absorbance was measured at 517 nm. Lower absor- a strong electrostatic interaction between lac dye and chitosan
bance of the reaction mixture indicates higher DPPH_ scavenging
activity. The DPPH_scavenging activity was calculated using the fol-
lowing Eq. (2):
Acontrol  Asample
Antioxidant activ ityð%Þ ¼  100 ð2Þ
Acontrol
where Acontrol is the initial concentration of the DPPH_ and Asample is
the absorbance of the remaining DPPH_ in the presence of fiber
sample.

2.6.2. Antioxidant activity determined by the ABTS radical

decolorization assay
The spectrophotometric analysis of ABTS+ radical scavenging
activity was determined according to a previously reported meth-
od [36]. ABTS was dissolved in water to a 7 mM concentration. The
ABTS radical cation (ABTS+) was produced by reacting ABTS stock
solution with 2.45 mM potassium persulfate (final concentration), Fig. 2. Effect of Na2SO4 amount on the uptake of lac dye by chitosan fiber.
1562 L. Liu et al. / Reactive & Functional Polymers 73 (2013) 1559–1566

fiber. With addition of electrolyte, Na2SO4 in the solution can re-

lease SO2
4 , which might compete with lac dye molecules for the
surface active sites of chitosan fiber, and thus decrease the adsorp-
tion quantity of lac dye. As shown in Fig. 2, the concentration of
Na2SO4 in the solution increased from 0 to 20 g L1, the percentage
of exhaustion of lac dye decreased from 95.2% to 75.9%.

3.2. Adsorption rates of lac dye

The rate curves of the adsorption of lac dye on chitosan fiber at

different temperatures are shown in Fig. 3. It was found that in the
absence of neutral electrolyte, the initial rates of adsorption were
all very fast, and the adsorption quantity reached to a high value
in short times. In addition, the adsorption amount of lac dye at
Fig. 4. Adsorption isotherms of lac dye on chitosan fiber at three temperatures in
equilibrium decreased with increasing application temperature,
the presence of Na2SO4.
indicating that the adsorption process is exothermic. The phenom-
enon is the result of a reduction in the affinity of lac dye to chitosan
fiber, which is accompanied by an elevated temperature. The rapid The Nernst model includes only one parameter and is presented
adsorption of lac dye on chitosan fiber would lead to the serious as follows:
problem of uneven dyeing when the fiber is processed in textile
factories. Therefore, some effective measures should be taken to Cf ¼ K p Cs ð5Þ
reduce the adsorption rate of lac dye. It is well known that neutral where Kp is the partition coefficient.
electrolyte is usually used as a retarding agent in the process of The empirical Freundlich isotherm is expressed as:
wool dyeing. So it was tested for the dyeing of chitosan fiber.
Fig. 3 shows that the addition of Na2SO4 was capable of lowering C f ¼ K F C ns ð6Þ
the dyeing rate of chitosan fiber, but caused a decrease in the quan- where KF is the Freundlich affinity constant, and n is an indicator of
tity of dye adsorption. This finding indicates that neutral electro- adsorption intensity or surface heterogeneity.
lyte can be utilized to control the rate and quantity of the The Langmuir–Nernst dual model containing electrostatic
adsorption of lac dye on chitosan fiber. (Langmuir) and non-electrostatic (partition) modes can be de-
scribed by the expression:
3.3. Equilibrium adsorption isotherms of lac dye SK L C s
Cf ¼ CP þ CL ¼ K P CS þ ð7Þ
1 þ K LCs
The isotherms of the adsorption of lac dye on chitosan fiber in
the presence of Na2SO4 are depicted in Fig. 4. In order to analyze where CP and CL are the concentrations of lac dye on chitosan fiber
these isotherms well, four isothermal models, namely Langmuir, by Nernst type partitioning and Langmuir adsorption, respectively;
Nernst, Freundlich, and Langmuir–Nernst (the dual adsorption S is the saturation concentration of lac dye on chitosan fiber by
equation consisting of the partition and Langmuir models), were Langmuir adsorption; KP and KL are the partition coefficient and
selected to compare the adsorption equilibrium of lac dye on chito- the Langmuir affinity constant, respectively.
san fiber. All the experimental adsorption isotherms in Fig. 4 were fitted
The expression for the widely used Langmuir isotherm is: to the four isotherm models using the nonlinear least-squares fit-
ting procedure, and thus the parameters in Eqs. (4)–(7) were ob-
SK L C s tained. The adsorption parameters for the Langmuir–Nernst
Cf ¼ ð4Þ
1 þ K LCs model were summarized in Table 1 (the data for other models
not shown). Fig. 5 shows the plots of the fitting of Langmuir,
where Cf (mg g1) and Cs (mg L1) are the concentrations of lac dye Nernst, Freundlich, and Langmuir–Nernst models to the experi-
on chitosan fiber and in the solution at equilibrium, respectively; S mental data at 50 °C. The Langmuir–Nernst curve almost went
is the saturation concentration of lac dye on chitosan fiber; KL is the through all the experimental data exactly, showing a precise fit-
Langmuir affinity constant. ting to the experimental data. However, the fitting to Langmuir,
Nernst and Freundlich models was not good enough. Similar re-
sults were also obtained for the adsorption isotherms at other
temperatures.
For the purpose of assessing the fitting results, the normalized
deviations (ND) of the experimental values used to estimate the ex-
tent of fitting were calculated according to Eq. (8), and listed in
Table 2.

Table 1
Parameters in the Langmuir–Nernst equation for the adsorption of lac dye on chitosan
fiber.

Temperature (°C) KL (103 L mg1) S (mg g1) KP (103 L g1)

40 12.91 33.53 88.30
50 40.52 18.78 90.65
Fig. 3. Adsorption rates of lac dye on chitosan fiber at three temperatures in the 60 52.74 13.84 85.90
absence and presence of Na2SO4.
 L. Liu et al. / Reactive & Functional Polymers 73 (2013) 1559–1566 1563

Fig. 5. Different isotherm equation plots for the adsorption of lac dye on chitosan Fig. 6. Variation of in the pH value of dyebath during the adsorption process of lac
fiber at 50 °C. dye.

N  
1X jC f ;exp;i  C f ;calc;i j it exhibits a completely negligible weight loss which has been con-
NDð%Þ ¼ 100  ð8Þ
N i¼1 C f ;exp;i firmed in our additional experiment. In this present study, the iso-
therm experiments were completed in the longer period of time
where Cf,exp,i and Cf,calc,i are the experimental and calculated values (120 min) at constant temperatures (40, 50 and 60 °C). It is be-
(the amount of adsorbed lac dye on chitosan fiber), respectively; lieved that the weakly acidic lac dye solution would become
the latter is a result of calculation using Eqs. (4)–(7) on the basis weakly alkaline in a short time. With an increase in the pH of dye-
of the parameters which were obtained by the fitting procedure; bath as well as the uptake of lac dye by chitosan fiber, the residual
the index ‘‘i’’ refers to the sequence number of adsorption data; N lac dye in solution would have the high extent of the dissociation
is the total number of data sets. of carboxyl groups, and become more negatively charged. Within
The results in Table 2 showed that the Langmuir–Nernst model the experimental range of pH, the ionized carboxyl groups make
gave the best fit to the adsorption isotherms due to the lowest nor- it possible that lac dye electrostatically interacts with chitosan
malized deviation. This suggests that the Langmuir–Nernst iso- fiber.
therm is the most appropriate model to describe the behavior of The presence of amine groups in chitosan fiber means that the
lac dye on chitosan fiber. From the above results, it may be con- pH of dyebath substantially alters the charged state of the fiber
cluded that the uptake of lac dye by chitosan fiber is a consequence and the mechanism of lac dye adsorption. The pKa value of primary
of both Langmuir and Nernst adsorptions. The electrostatic interac- amine groups in chitosan is approximately 6.3 [40,41]. At this pH,
tions operating between the anionic lac dye molecules and the pro- the ionized fraction of amine groups corresponds to 50%. At pHs
tonated amino groups in chitosan fiber contribute to Langmuir below 6.3, chitosan fiber becomes more positively charged because
adsorption, whereas the non-electrostatic interactions between of the protonation of amine groups; the strong electrostatic inter-
lac dye and chitosan fiber contribute to partition adsorption. action between the protonated amine groups in chitosan and the
It is well known that the pH of solution can exert remarkable dissociated carboxyl groups in lac dye can take place. At pHs above
impact on the adsorption of an adsorbate on chitosan polymer. 6.3, chitosan fiber becomes less protonated and less positively
The pH of dyebath can affect the protonation of amine groups in charged, thus leading to the decreased extent of the electrostatic
chitosan fiber and the ionization of carboxyl groups in lac dye, interaction between chitosan fiber and lac dye.
and accordingly the pH dependent change in the mechanism of Considering the pH variation of dyebath during the adsorption
lac dye adsorption occurs. In order to discuss the mechanism of process, and the pKa values of amine groups in chitosan and car-
lac dye adsorption well, the change in the pH value of dye-bath boxyl groups in lac dye, it is regarded that the electrostatic interac-
during the adsorption process was determined. As shown in tion between lac dye and chitosan fiber can occur, and contribute
Fig. 6, the pH of lac dye solution changed with elevated tempera- to Langmuir adsorption. Meanwhile, there are the non-electro-
ture and prolonged time during the adsorption process. At the ini- static interactions (hydrogen bonding, van der Waals forces and
tial stage, the dyebath was weakly acidic (pH 5.50) on account of hydrophobic interaction) between lac dye and chitosan fiber,
the partial ionization of carboxyl groups in lac dye whose pKa which contribute to partition adsorption. But the extent of the con-
was 5.96 ± 0.15 [39]. However as the temperature went up from tribution of Langmuir adsorption to total adsorption would be af-
30 to 40 °C over 10 min, the pH increased quickly from 5.50 to fected by some factors, such as pH of dyebath, lac dye
7.45 because of the rapid adsorption of lac dye onto chitosan fiber, concentration, temperature, etc.
and further ranged from 7.84 to 8.19 at the stage of holding tem- To demonstrate the effect of initial lac dye concentrations and
perature. Here it has to be mentioned that because chitosan fiber temperature on adsorption clearly, the percent of the contribution
is immersed in a weakly acidic medium only for a very short time, of Langmuir or Nernst adsorption to total adsorption [42] was cal-
culated using the parameters in Table 1, and the known Cs accord-
Table 2
ing to Eq. (7) at each initial lac dye concentration, and depicted in
Normalized deviations (ND) of isotherm models. Fig. 7. As shown in Fig. 7, the contribution of Langmuir adsorption
to total adsorption decreased with increasing initial lac dye con-
Models ND (%)
centration, while the contribution of Nernst adsorption increased.
40 °C 50 °C 60 °C This observation may be explained by the fact that the adsorption
Langmuir 19.76 20.13 17.43 is mainly controlled by the specific adsorbing sites in chitosan fiber
Freundlich 8.56 12.70 11.78 at lower initial lac dye concentrations. In terms of the dependence
Nernst 31.51 27.75 24.25
of the adsorption of lac dye on temperature, the contribution of
Langmuir–Nernst 4.44 2.04 3.10
Langmuir adsorption to total adsorption decreased with increasing
1564 L. Liu et al. / Reactive & Functional Polymers 73 (2013) 1559–1566

temperature, while the contribution of Nernst adsorption showed

the opposite regularity. This possibly results from the higher ex-
tent of fiber swelling and the higher kinetic energy of lac dye mol-
ecules at higher temperatures, which enable lac dye molecules to
be no longer localized at the specific adsorbing sites. The regulari-
ties discussed herein are in good accordance with those found in
our previous research on the adsorption of tea polyphenols on
wool, silk and nylon [42].
Table 1 shows that the Langmuir–Nernst adsorption parameters
exhibited much variation with temperature. The KL values in-
creased with increasing temperature whereas the KP values
showed a tendency toward a progressive fall. The increasing KL val-
ues could be a consequence of heat consumption for the disassoci-
ation of lac dye aggregates and the swelling of chitosan fiber that
accompanied an increase in temperature. The S values decreased Fig. 8. Influence of initial concentrations of lac dye on its uptake by chitosan fiber.
obviously with increasing temperature, this being attributed to a
decrease in the contribution of Langmuir adsorption to total
adsorption that accompanied an increase in temperature. molecular weight, high deacetylation degree, and high water-solu-
bility. As a raw material of textile fiber, chitosan polymer must
have high molecular weight in order to ensure the sufficient
3.4. Build-up property of lac dye
strength of a fiber. The antioxidant activity of pure chitosan fiber
with high molecular weight has not yet been reported. However,
The building-up property of lac dye depends on its affinity to
the antioxidant activity of chitosan–viscose bicomponent fiber
chitosan fiber, adsorption mechanism, and capability, which is of
has been determined, and this fiber showed very poor scavenging
great importance for practical application. In view of the practical
activity toward DPPH and superoxide anion radicals [10]. In Table 3,
application conditions, the build-up property of lac dye was deter-
the pure chitosan fiber showed very low inhibition activities to-
mined in a temperature-rise process in place of a constant temper-
wards DPPH and ABTS radicals, which were in accordance with
ature process.
the previously reported results of chitosan polymers, and chito-
The building-up property expressed by Cf as well as the exhaus-
san–viscose bicomponent fiber [10,43–45].
tion of lac dye is depicted in Fig. 8. The quantity of adsorption lin-
Lac dye consists of the anthraquinone compounds produced by
early increased with an increase in lac dye concentration, even in
the insect and containing phenolic hydroxyl and carboxy groups.
the case of a high concentration of dye. This observation implies
The hydroxyl-containing anthraquinone compounds from plant
that lac dye has good building-up property on chitosan fiber and
extracts usually exhibit certain antioxidant activities, depending
high affinity to chitosan fiber, which is consistent with the high
on their chemical structures [23–26], which were regarded to re-
KL and KP values for chitosan fiber as shown in Table 1. Fig. 8 also
sult from the presence of hydrogen-donating phenolic hydroxyl
reveals that the lower exhaustion was obtained as the application
groups in their parent structures. Lac dye solution had certain scav-
concentration of lac dye increased, but it still maintained a rela-
enging activity on free radicals, and its scavenging rate on
tively high value. This indicates that lac dye has a high utilization
DPPHand ABTS+ could be as high as 68% and 87%, respectively
rate when applied.
when lac dye reached a certain concentration [51]. Based on these
facts, it is presumed that lac dye should enhance the antioxidant
3.5. Antioxidant properties of the dyed chitosan fiber
activity of the dyed chitosan fiber due to the presence of hydro-
gen-donating phenolic hydroxyl groups in its parent structures. Ta-
The antioxidant activity of the chitosan fiber treated with lac
ble 3 represents the antioxidant activities of chitosan fiber samples
dye should depend on chitosan polymer and the quantity of lac
dyed at different lac dye concentrations. It is evident from Table 3
dye on the fiber. Some literature has reported the antioxidant
that the dyed chitosan fibers exhibited markedly enhanced antiox-
activities of chitosan and its derivatives, which were found to de-
idant performance measured by the DPPH free radical scavenging
pend on their molecular weight, deacetylation degree, substitu-
method and ABTS radical cation decolorization assay when com-
tional groups, concentration, and water-solubility [43–50]. The
pared to the untreated fiber. And also this enhancement was
high antioxidant activity was noted for the chitosan having low
dependent on the extent of the adsorption of lac dye on chitosan
fiber, and increased with a corresponding increase in lac dye con-
centration as shown in Fig. 8. This suggests that lac dye can provide
excellent antioxidant properties for chitosan fiber when applied
under an appropriate concentration, and may exhibit medical ac-
tions toward human body by contact with chitosan-based textiles.

3.6. Deodorizing properties of the dyed chitosan fiber

Concern for health and hygiene is constantly rising. Since peo-

ple are extremely sensitive to smells, deodorizing is becoming an
entrenched social need. The deodorizing performance of textiles
contributes to enhancing health and hygiene of mankind, and mak-
ing life more pleasant. In everyday life, the main odor substances
are ammonia, acetic acid, isovaleric acid, methyl mercaptan, tri-
methylamine, acetaldehyde, hydrogen sulfide, etc. Among these
Fig. 7. Contribution of Langmuir (solid points) and Nernst (blank points) adsorption odors, ammonia is one of the most common pernicious gases, espe-
to lac dye adsorption on chitosan fiber. cially in new buildings and newly renovated houses as well as in
 L. Liu et al. / Reactive & Functional Polymers 73 (2013) 1559–1566 1565

Table 3
Antioxidant activities and deodorizing ability of the dyed chitosan fibers.

Lac dye concentration Antioxidant activities (%) Deodorizing

(%owf) performance (%)
DPPH ABTS
method method
0 0.44 13.13 28.57
4 6.03 61.09 34.29
12 15.09 83.35 50.00
20 18.27 99.28 62.86
30 22.76 99.43 75.00
40 24.98 99.74 82.14

some livestock farms, lavatories, and special workshops [37]. Here,

Fig. 10. Desorption rate of lac dye from the dyed chitosan fiber in water.
the deodorizing performance of the dyed chitosan fiber towards
ammonia was evaluated.
It is clear from Table 3 that the deodorizing performance line- 4. Conclusions
arly increased when the initial lac dye concentration increased.
In particular, the deodorizing performance of the chitosan fiber The healthy and hygienic chitosan fiber was prepared using the
dyed with 40% owf lac dye was found to be highest at 82.14%, technology of dyeing with lac dye consisting of polyphenolic
showing excellent deodorization performance. The phenomenon anthraquinone compounds, and the adsorption properties of lac
might be due to the carboxy group-containing component of lac dye on chitosan fiber were studied. The equilibrium adsorption iso-
dye adsorbed by chitosan fiber which can react with ammonia by therm of lac dye could be described by the Langmuir–Nernst mod-
the neutralization reaction mechanism [38]. In addition, the el. The adsorption mechanism was shown to be the electrostatic
deodorizing performance displayed a good linear relationship with and non-electrostatic interactions between lac dye and chitosan fi-
the quantity of lac dye adsorbed by chitosan fiber as shown in ber, which contributed to Langmuir and Nernst adsorptions,
Fig. 9, which provided indirect evidence for the neutralization respectively. Reduced temperature and dosage of neutral electro-
deodorizing mechanism of ammonia. These results clearly demon- lyte as well as increased lac dye concentration were capable of
strate that the use of lac dye as a colorant significantly increases increasing the quantity of the adsorption of lac dye on chitosan fi-
the deodorizing ability of chitosan fiber. ber. The functional properties of the dyed chitosan fiber were
greatly related to the quantity of lac dye adsorption. The dyed
chitosan fiber exhibited markedly enhanced antioxidant activities
and deodorizing performance towards ammonia which increased
3.7. Desorption properties of lac dye from the dyed chitosan fiber in obviously with an increase in application concentration of lac
water dye. Chitosan fiber’s functionalities provided by lac dye had the
excellent washing resistance. Taking the functionalities and high
The healthy and hygienic textiles prepared by chitosan fiber are adsorption capability of lac dye on chitosan fiber into consider-
subjected to frequent washing during their usage. Hence the resis- ation, it is regarded that natural lac dye may be used as a functional
tance of functional lac dye on the textiles to washing is very impor- colorant for developing the functional chitosan fiber-based textiles.
tant. In the present study, the washing resistance was tested
through the desorption of lac dye from the dyed chitosan fiber in Acknowledgements
water at 50 °C. As seen in Fig. 10, the desorption rate of lac dye
was extremely low, and did not exceed 2%, although it increased This study was funded by Jiangsu Provincial Natural Science
as the time was prolonged. The simulated washing test suggests Foundation of China, Suzhou Research Program of Application
that the washing resistance of lac dye on chitosan fiber is very Foundation, and the Priority Academic Program Development
good, indicating the excellent durability of the functionalities of (PAPD) of Jiangsu Higher Education Institutions.
chitosan fiber provided by lac dye.

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