Accepted Manuscript

Title: Fabrication of a new polysaccharide-based adsorbent for

water purification

Authors: Xiaoliang Qi, Wei Wei, Ting Su, Jianfa Zhang, Wei
Dong

PII: S0144-8617(18)30506-X
DOI: https://doi.org/10.1016/j.carbpol.2018.04.112
Reference: CARP 13566

To appear in:

Received date: 17-3-2018

Revised date: 19-4-2018
Accepted date: 27-4-2018

Please cite this article as: Qi, Xiaoliang., Wei, Wei., Su, Ting., Zhang, Jianfa.,
& Dong, Wei., Fabrication of a new polysaccharide-based adsorbent for water
purification.Carbohydrate Polymers https://doi.org/10.1016/j.carbpol.2018.04.112

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Fabrication of a new polysaccharide-based adsorbent for

water purification

Xiaoliang Qi, Wei Wei, Ting Su, Jianfa Zhang, Wei Dong*

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Center for Molecular Metabolism, Nanjing University of Science & Technology,

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Nanjing 210094, China.

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*Corresponding author: email: [email protected] (W. Dong).

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Highlights:
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1. New salecan-based anionic hydrogels were designed for adsorption of dye;

2. Salecan hydrogels were synthesized via free radical polymerization grafting
technique;
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3. Effect of salecan content on the physical and adsorption properties of the

hydrogels were investigated;
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4. Adsorption process could be well described by the pseudo-second-order

kinetic and Freundlich isotherm models.
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Abstract

Expanding the application of polysaccharide material has attracted tremendous

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attention in the fields of wastewater treatment, agriculture and biomedical engineering,

on account of its tunable and unique properties. Herein, we employ a water-soluble,

sustainable and low cost bacterial polysaccharide, salecan as a matrix,

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poly(acrylamide-co-itaconic acid) (PAI) as a synthetic component to synthesize

salecan-g-PAI hydrogels through a simple chemical crosslinking method. Their

physicochemical properties were fully characterized by various methods including

Fourier transformed infrared spectroscopy, X-ray diffraction, thermogravimetry,

scanning electron microscope and rheometry. We found that salecan not only acted as

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the interaction sites to regulate the water content of the developing hydrogels, but also

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endowed them with tailorable morphology. The designed salecan-g-PAI hydrogels

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exhibited excellent adsorption properties toward methylene blue (MB) dye, and the

adsorption process could be well described by the pseudo-second-order kinetic and

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Freundlich isotherm models. Altogether, this study broadens the application of
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salecan polysaccharides and provides a new device for dye decontamination.
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Keywords: salecan, hydrogels, poly(acrylamide-co-itaconic acid), methylene blue,

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dye decontamination
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1. Introduction
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The pollution of dyes from many chemical industries, such as printing, paper,

textile and plastics, is becoming a global problem that disturbs the ecological
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equilibrium of biosphere and endangers the health of human beings (Abou Taleb, Abd

El-Mohdy & Abd El-Rehim, 2009; Dragan & Apopei, 2011). Consequently, various

treatment processes including adsorption, flocculation, coagulation, oxidation,

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membrane separation, ion exchange and catalytic degradation, are employed for

removal of dyes from contaminated water (Peng, Hu, Zeng, Li, Liang & Chang, 2016).

Of these treatment processes, adsorption is regarded superior to other methods in

terms of ease of operation and simplicity of design (Wang & Wang, 2016).

Natural polymeric materials, especially polysaccharides, have aroused particular

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attention for application as adsorbents in wastewater decontamination owing to their

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biodegradability, renewability and biocompatibility (Dai & Huang, 2017; Dai et al.,

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2017; Liu, Wisniewski, Kennedy, Jiang, Tang & Liu, 2016; Singh, Kaur, Rana &

Kennedy, 2016; Singh, Kaur, Rana & Kennedy, 2017). Salecan is a linear

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water-soluble polysaccharide, composed of different monosaccharide units, obtained
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by bacterial fermentation (Figure 1) (Qi et al., 2017c). As a newly developing
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polysaccharides, salecan displays favorable biological characteristics such as

biocompatibility and anti-oxidative properties (Sun, Xu, Yang, Weng, Wang & Zhang,
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2017; Xiu et al., 2011). Moreover, salecan possesses abundant functional hydroxyl
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groups, which can act as reactive sites to adsorb dyes (Tu et al., 2017). These
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characteristics remind us that salecan polysaccharides may be a favorable candidate

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for dye adsorption.

Generally speaking, polysaccharide-derived adsorbents cannot bring desirable

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adsorption performance in practical applications because the removal of dyes based

on the adsorption technology occurred in aqueous environment, where the water

molecules could damage the polar affinity between dyes and adsorbents (Dragan &

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Apopei, 2011; Tu et al., 2017; Yao, Zhang, Wang & Wang, 2015). Therefore, a rigid

hydrophobic structure is indispensable for polysaccharide-based sorbent synthesis. In

this consideration, the incorporation of a synthetic polymer into a polysaccharides

network through graft copolymerization technology is a feasible and convenient

method to modify the properties of polysaccharides (Dragan & Apopei, 2011; Singha,

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Mahapatra, Karmakar, Dutta, Mondal & Chattopadhyay, 2017). By selecting

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appropriate rigid synthetic polymer, the resulting hydrogel sorbents would possess a

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perfect balance between mechanical strength and biodegradability, making them more

suitable for dye removal (Qi et al., 2017d; Singha, Mahapatra, Karmakar, Dutta,

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Mondal & Chattopadhyay, 2017).
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Based on above-stated background, here we present a novel salecan-based
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hydrogel achieved by grafting acrylamide (AM) and itaconic acid (IA) onto salecan

for the adsorption of dye. In this novel hydrogel material, salecan was selected as the
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host polymer network for its outstanding biocompatibility and biodegradability, while
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AM and IA were chosen as the functional monomers for their rapid co-polymerization
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velocity and versatile operation. We expected that the fusion of excellent properties of
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each components will confer designed hydrogels with high dye adsorption

performance. The structure and morphology of the resulting absorbents were

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systematically characterized by Fourier transformed infrared spectroscopy (FTIR),

X-ray diffraction (XRD), thermogravimetry (TG), rheometry and scanning electron

microscope (SEM). Moreover, the swelling behaviors of these hydrogels in various

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media were also investigated. Finally, their adsorption kinetic and isotherm were

evaluated.

2 Experimental section

2.1 Reagents and materials

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Salecan was prepared by the Nanjing University of Science & Technology

Center for Molecular Metabolism. N,N’-methylenebisacrylamide

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(BisAA, 98.0%),

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itaconic acid (IA, 99.0%), acrylamide (AM, 99.0%) and ammonium persulfate (APS,

99.0%) were procured from TCI (Shanghai, China). Methylene blue trihydrate

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(C16H18ClN3S·3H2O) was supplied by Aladdin (Shanghai, China). All materials were
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used without further purification. Deionized water (18.2 MΩ/cm) was used in all
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solutions.
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2.2 Preparation of the salecan-g-PAI hydrogel

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Calculated amount of salecan solution (2.0%, w/v) was first added into a 50 mL
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three-neck flask and degassed with argon for 30 min to eliminate the dissolved
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oxygen at 37 °C. After heating the salecan solution to 65 °C, 1 mL of initiator APS

(3.2%, w/v) was introduced and vigorously stirred for 15 min to generate radicals.
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Later, other reagents such as BisAA (2.0%, w/v), IA (0.1 g), AM (0.9 g) were

sequentially incorporated into the above-mentioned solution. Next, the volume of

pre-gel solution was fixed to 10 mL by adding deionized water. Subsequently, the

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resultant mixture was heated to 75 °C and maintained for 150 min to complete

polymerization reaction. The obtained hydrogel was carefully gotten out from the

glass mold and swollen via being immersed in the deionized water for 48 h to wash

out any soluble polymers, unreacted initiator and monomer. During this time, the

deionized water was refreshed two times daily. Eventually, the hydrolyzed hydrogel

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samples were cut into the small blocks and dried for further use. The feed

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compositions of salecan-g-PAI are displayed in Table 1.

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Table 1: Composition ratios used for fabrication of salecan-g-PAI hydrogel.

Designation
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Composition
PAI (SAI1) SAI2 SAI3 SAI4
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Salecan (2.0%, w/v) (mL) 0 2.5 5 7.5

IA (96.0%, w/w) (g) 0.1 0.1 0.1 0.1
AM (96.0%, w/w) (g) 0.9 0.9 0.9 0.9
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BisAA (2.0%, w/v) (mL) 2 2 2 2

APS (3.2%, w/v) (mL) 1 1 1 1
Deionized water (mL) 11 8.5 6 3.5
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2.3 Characterization
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2.3.1 Fourier transform infrared spectroscopy (FTIR)

The chemical composition of salecan, PAI and salecan-g-PAI hydrogels was

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examined by the attenuated reflection Fourier transform infrared spectroscopy

(ATR-FTIR) using a FTIR spectrometer (Nicolet IS-10, Thermo Fisher Scientific,

USA). The experiments were carried out in the ATR mode in the wavelength range

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of 550−4000 cm−1 with 32 scans and a resolution of 4 cm−1.

2.3.2 X-ray diffraction analysis (XRD)

XRD patterns of the salecan and hydrogels were collected using a Bruker D8

diffractometer with Cu Kα radiation (λ = 0.154 nm) at a voltage of 20 kV and a

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current of 20 mA. The samples were scanned from 10 to 40°.

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2.3.3 Thermogravimetric analysis (TGA)

TGA were obtained from a TGA Q600 instrument (Tokyo, Japan), in the

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temperature range of 25–600 °C at a heating rate of 15 °C/min under the nitrogen
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atmosphere.
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2.3.4 Scanning electron microscopy (SEM)

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SEM micrographs of the samples were obtained on a JSM-6380LV instrument

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(JEOL, Tokyo, Japan) at an accelerating voltage of 5 kV. The hydrogels in

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equilibrium swelling state were frozen in liquid nitrogen and lyophilized. Prior to
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analysis, hydrogels were coated with gold using a sputter coater to increase

conductivity.
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2.3.5 Rheological tests of hydrogels

The storage and loss moduli of designed hydrogels were measured using an

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Anton Paar model MCR 101 rheometer (Anton Paar, Graz, Austria) operating at 25 °C.

In the experiment, 50 mm diameter parallel rough plate was used and plate-to-plate

distance was set at 1.0 mm. Usually, 12 h after the formation of hydrogel (50 mm in

diameter and 2 mm in thickness), a dynamic strain sweep measurement was first

conducted to determine the linear viscoelastic regime of the hydrogel networks. Then,

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frequency sweeps (0.1–10 Hz) were performed at a fixed strain of 0.1% at 25 °C.

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2.4 Measurement of swelling characteristics

2.4.1 Swelling kinetics

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In this study, swelling properties of the hydrogel samples were investigated
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employing the conventional gravimetric procedure as described previously (Qi et al.,
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2017d). In brief, lyophilized hydrogels of the given amount (0.1g) were put into

excess deionized water. Subsequently, the hydrated hydrogels were taken out from
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buffers at certain time points and weighed by an electronic balance after removing
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excess liquid on the gel surface with blotting paper. The swelling ratio (SR) was
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defined by following formula:

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SR= (Wt –W0)/W0 (1)

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Where, Wt (g) and W0 (g) are the mass of the swollen and dried material, respectively.

Furthermore, equilibrium swelling ratio (ESR) was also acquired by replacing Wt

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with We (the mass of saturated swollen hydrogels) in formula (1).

2.4.2 pH and salt sensitivity

To verify the effect of pH on swelling, weighed dried hydrogels (0.1g) were

immersed in excess solutions with different pH values for 4 days to ensure

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equilibrium water uptake (The pH value of each solution was adjusted by 1 mol/L

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NaOH and 1 mol/L HCl. The ionic strength of each solution was tuned to 0.1 M by

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introducing an appropriate amount of NaCl.). The equilibrium swelling ratio at

different pH was determined using formula (1). The equilibrium swelling ratios of

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gels in different types of salt (KCl, CaCl2 and FeCl3) were explored in the same
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manner.
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2.4.3 Water retention capacity

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The freeze-dried products were first kept in excess distilled water for 3 days to
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ensure equilibrium water uptake. Subsequently, the swollen products were centrifuged
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at 4200 rpm and weighed at pre-determined time intervals. The water-retention (WR)
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ratio was calculated based on the expression:

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WR (%) = (Wt –W0)/(We –W0) × 100 (3)

where Wd represents the initial dried specimens, Wt represents the swollen mass of the

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specimens after a certain time, and We represents the equilibrium swollen mass of the

specimens.

2.5 Dye adsorption and its mechanism

2.5.1 Dye Adsorption experiment

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Adsorption assay was conducted to assess dye adsorption behavior of designed

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salecan-g-PAI hydrogels. In this research, hydrophilic dye, MB, was chosen for

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experiment. Typically, 0.05 g of dried hydrogel samples were introduced into a series

of MB solutions (30 mL) with different concentrations at 25 °C. After reaching the

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adsorption equilibrium, the initial and final dye concentrations were analyzed using a
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V-630 UV/vis spectrophotometer (JASCO, Tokyo, Japan) at the maximum absorption
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wavelength of MB. The equilibrium adsorption capacity (qe, mg/g) of dye onto

salecan-g-PAI gel was defined as follows:

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qe = (C0 - Ce) × V/m (4)

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where C0 and Ce represent the initial and final concentrations of MB solution, V

represents the volume of the MB solution, and m represent the dry mass of adsorbent.
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2.5.2 Adsorption isotherms

The adsorption isotherms were analyzed by Langmuir and Freundlich isotherm

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models. The Langmuir isotherm adsorption equation was defined as follows:

qe = qmKLCe/(KLCe + 1) (5)

where qm (g/kg−1) represents the maximum adsorption under ideal conditions, KL

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represents the Langmuir constant (m3/g−1), and Ce represents the concentration of dye

adsorbed at equilibrium (mg/L−1).

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The Freundlich isotherm adsorption formulae is expressed as:

qe = KFCe1/n U
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(6)
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where KF indicates the Freundlich isotherm constant, Ce indicates the amount of

adsorption at equilibrium, and the exponent 1/n means adsorption capacity.

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2.5.3 Adsorption kinetics

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The adsorption kinetics of dye onto salecan-g-PAI hydrogels were investigated

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by the pseudo-first order and pseudo-second order kinetic models, as expressed in eq

7 and eq 8:
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qt = qe (1-e-k1t) (7)

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 qt = tqe2K2/(tK2qe +1) (8)

where qe and qt (mg/g) are the amounts of dyes adsorbed at equilibrium and at time t,

respectively; k1 and k2 (min−1) are the rate constant of the pseudo-first order and

pseudo-second order kinetics, respectively.

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3. Results and discussion

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3.1 Hydrogel formation mechanism

The salecan-g-PAI hydrogels are simply prepared by free-radical cross-linking

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polymerization of AM and IA in the presence of salecan using BisAA as a cross-linker
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under a nitrogen atmosphere. The proposed reaction mechanism is shown in Figure 1.
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Initially, the initiator (APS) was decomposed under heat at 65 °C to produce sulfate

anion-radicals. These anion-radicals abstracted hydrogen from hydroxyl groups of

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salecan chains to generate alkoxy radicals. After introduction of the IA and AM

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monomer molecules, the active radical centers on the salecan skeleton could initiate
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vinyl groups of the monomers, causing the growth of graft chain. During the chains
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propagation process, the end vinyl groups of the cross-linker (BisAA) reacted with the

various polymer chains to construct a cross-linked network (Dai & Huang, 2017; Qi et
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al., 2017d).

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Figure 1: Proposed mechanisms for the formation of salecan-g-PAI network.

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3.2 Characterization of prepared hydrogels
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3.2.1 FTIR
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Figure 2A displays the FT-IR spectra of salecan, salecan-g-PAI and PAI.

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Considering the spectrum of salecan, a broad absorption peak located at about 3289
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cm−1 was associated with O–H stretching vibration (Wei et al., 2016). The peak at

around 1039 cm−1 likely corresponded to the C−OH stretching in the glucopyranose
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ring (Qi et al., 2017a). It is noteworthy that the characteristic peaks of salecan
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appeared between 899 and 814 cm−1 (Qi et al., 2017b). More specifically, the small
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peak at 899 cm−1 suggested that D-glucopyranose was connected by a β-configuration,

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and the weak band at 814 cm−1 can be referred to the existence of a few

α-glucopyranose molecules (Hu, Wang, Zhang, Xu, Dong & Zhang, 2017b).

As for spectrum of pure PAI hydrogel, the presence of acrylamide segment in the

PAI hydrogel was manifested by a sharp peak at 1635 cm−1 in terms of the stretching
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vibrations of the carbonyl group of the amide I band (Dragan, Lazar, Dinu & Doroftei,

2012; Singha, Mahapatra, Karmakar, Dutta, Mondal & Chattopadhyay, 2017); the

itaconic acid component in the PAI hydrogel was evidenced by an intense absorption

peak at approximately 1252 cm−1, assigning to the stretching vibration of –COOH

groups (Zhang, Wang, Shi, Huang, Zhao & Zhao, 2017; Zhu, Ma, Wang & Zhang,

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2015); whereas the introduction of the cross-linker (BisAA) unit could be verified by

the appearance of a strong band at 1158 cm−1 due to the C−N stretching vibrations of

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BisAA (secondary amine) (Qi et al., 2017d).

The FT-IR spectrum of the salecan-g-PAI hydrogel contained the characteristic

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peaks of both PAI and salecan, as follows: the appearance of acrylamide unit was
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supported by the peak at 1635 cm−1 corresponding to the N−H stretching, the band
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situated at 1252 cm−1 as a result of C=O stretching of itaconic acid, the peak at 1158

cm−1 were assigned to the stretching vibration of C−N in BisAA and the typical peak
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of salecan can be seen at 895 cm−1 attributed to stretching of C−OH from the
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glucopyranose ring (Qi et al., 2017d). In addition, the characteristic peak of salecan at

895 cm−1 was obviously weakened after forming salecan-based grafted hydrogel,
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implying the participation of salecan polysaccharide in the ring-opening graft

copolymerization reaction. Similar conclusions could be drawn from other

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polysaccharide-grafted hydrogels (Dai & Huang, 2017; Sun, Wang, Jing &

Mohanathas, 2013; Wang & Wang, 2010).

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Figure 2. Structural analyses of salecan, salecan-g-PAI, PAI: (A) FT-IR, (B) XRD and (C)TGA.
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3.2.2 XRD analysis

XRD is intensively used as an efficient technique to evaluate the crystallinity of

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various hydrogels. Wide-angle XRD patterns of salecan, PAI, and salecan-g-PAI are

shown in Figure 2B. As observed in Figure 2B, salecan presented a strong peak

centred at around 2θ of 21°, which was typical fingerprint of semicrystalline

polysaccharide structure of salecan, corresponding to the hydrogen-bonding

interactions among functional moieties of salecan chains, liking –OH (Hu, Wang,

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Zhang, Xu, Dong & Zhang, 2017a). Similar phenomenon has been observed in other

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polysaccharides (Dai & Huang, 2017; Kyzas, Siafaka, Lambropoulou, Lazaridis &

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Bikiaris, 2014). However, in comparison with salecan, only a broad hole at 2θ = 21°

was found for salecan-g-PAI hydrogel, implying that the original crystallinity of

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salecan was destroyed after the hydrogel formation. The absence of characteristic
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diffraction peaks of salecan for the salecan-g-PAI hydrogel was because the grafting
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of AM and IA onto salecan backbone arose in an amorphous manner along the chains

of salecan, bringing about the devastation of established intermolecular hydrogen

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bonds between hydroxyl groups and finally, the disappearance of the original salecan
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crystalline structure (Dai & Huang, 2017).

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3.2.3 Thermostability testing

The thermal behaviors of salecan, PAI and salecan-g-PAI was evaluated using
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thermogravimetric analysis. Their TGA curves are displayed in Figure 2C. Clearly,

the pyrolysis process of salecan exhibited three steps: 25–225, 226–367, and 368–

600 °C with mass losses of 11.84%, 44.42%, and 22.66%, respectively. The first step

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of mass loss was associated with the volatilization of water adsorbed by the salecan.

The latter two stages were primarily caused by the degradation of salecan backbone,

which is consistent with our previous results (Hu, Wang, Zhang, Xu, Dong & Zhang,

2017a; Qi et al., 2017b). To be more exact, breakage of branched groups, scission of

the glucosidic units and cleavage of the C−O bonds were occurred in this two stages.

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The TGA curve of PAI hydrogel displayed two-stage destruction pattern, in

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addition to the usual expulsion of water step below 225 °C (11.03% mass loss).

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Actually, the initial stage (226–468 °C, 69.91% mass loss) corresponded to the loss of

–COOH and –NH2 groups, whereas the decomposition of hydrogel network was

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initiated mostly in the second stage (469–600 °C, 3.66% mass loss) (Liu, Jiang, Zhu
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& Wang, 2014). Thermal degradation of salecan-g-PAI owned similar thermal profile
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to that of PAI. In addition, it was found that Tm (maximum mass loss rate) of the

salecan-g-PAI hydrogel increased (366 °C) and was much bigger than that of pure
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salecan (281 °C), implying that the thermal stability of the salecan enhanced after the
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introduction of AM and IA component.

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3.2.4 Scanning electron microscopy (SEM)

To better understand the network architecture of the designed hydrogels, the

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dehydrated materials were imaged by SEM. It was obvious from Figure 3 that all

hydrogels had an organized interconnected porous structure. Meanwhile, gels that

contained higher amounts of salecan appeared to possess larger apertures. The pore

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size distribution obtained by the image analyzing program Nano Measurer 1.2.5

(Fudan University, China) displayed that pore sizes of the hydrogels lay in the 29.2–

136.5 μm range. More specifically, before the addition of salecan, the pure PAI

hydrogel possess the smallest pore of nearly 29.2±3.7 μm. By elevating the salecan

dose in the pregel solution to 2.5, 5.0, and 7.5 mL, the pore size gradually enhanced to

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about 57.4±11.5, 96.2±17.1, and 136.5±22.3 μm, which is consistent with the findings

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of other polysaccharide-incorporated hydrogels (Lu et al., 2015; Tu et al., 2017).

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Typically, the pore diameter of hydrogel is dependent on its water uptake capability

(Wei et al., 2017). Hydrogel with a higher salecan contained more water

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(as will be described subsequently), led to the formation of a bigger ice crystal
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aggregates during the sublimation process and eventually, bigger pores (Qi et al.,
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2017a; Wei et al., 2017).

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Figure 3. SEM pictures of the salecan-g-PAI hydrogels: (A) SAI1, (B) SAI2, (C) SAI3 and (D)

SAI4.

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3.2.5 Mechanical properties of the hydrogels

Rheological investigations provide information about the mechanical properties

of the fabricated salecan-g-PAI hydrogel. For each gel sample, a dynamic strain

sweep measurement was first conducted to determine the linear viscoelastic regime of

the hydrogel networks. Next, the storage modulus (G′, describing the quantity of

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deformational energy stored in hydrogel materials) and loss modulus (G″, disclosing

the hydrogel’s capability to dissipate energy) were measured as a function of

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oscillation frequency (Qi et al., 2017d; Ramin et al., 2017). As shown in Figure 4, the

G′ value was bigger than G″ throughout the tested frequency range (0.1–10 Hz) for

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salecan-g-PAI, and their lines did not across each other, displaying the solid-like
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behaviors (Clarke, Pashuck, Bertazzo, Weaver & Stevens, 2017; Qi et al., 2017b).
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Similar characters are observed for other samples (Clarke, Pashuck, Bertazzo, Weaver

& Stevens, 2017; Ramin et al., 2017). Meanwhile, we found that the mechanical
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strength of the salecan-g-PAI hydrogels were affected by the salecan dose as seen in
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Figure 4A. More specifically, the storage modulus decreased continuously with the
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increase of salecan content, from 963 Pa (SAI1) to 198 Pa (SAI4). These data were
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likely that, addition of hydrophilic salecan raised the hydrogel affinity for water,

which was prone to the formation of gel containing high water content, leading to a
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more loose network and eventually, a decrease in gel stiffness.

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Figure 4: Storage modulus (A) and loss modulus (B) of prepared hydrogels with different salecan

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content (SAI1, SAI2, SAI3, SAI4)

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3.3 Swelling and deswelling characteristics of salecan-g-PAI hydrogels

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The ability of the fabricated hydrogel to uptake and retain water is vital features
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to take into consideration when developing hydrogel adsorbents. For that purpose,
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swelling and deswelling properties of the salecan-g-PAI hydrogel was

comprehensively assessed. We first explored the water uptake performance of these

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hydrogels in deionized water. After that, the influence of pH and salt on gel swelling
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was investigated. Ultimately, their deswelling profile was assessed.

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3.3.1 Swelling in deionized water

The swelling kinetics for the salecan-g-PAI hydrogels in deionized water are
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depicted in Figure 5A. Clearly, all hydrogel samples showed a similar tendency with

different degrees of swelling. As can be seen from Figure 5A, the water absorbency

increased sharply during the initial state of hydration (0–200 min), and then turn into

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slower until achieving a plateau. Meanwhile, the equilibrium swelling ratio (ESR)

increased when the content of salecan enhanced. Hydrogels without salecan had the

smallest ESR (19.6), whereas hydrogels with 7.5 mL of salecan had the biggest

swelling ratio (62.5). The improved swelling capacity could be belonged to the

following reason: the −OH groups on the salecan backbone enhanced the affinity of

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hydrogel network for water molecules, resulting in easier diffusion of water molecules

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into the polymeric network. Similar results have been reported by Dai et al. (Dai &

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Huang, 2017) in the water absorbency study of cellulose-g-poly(acrylic

acid-co-acrylamide) hydrogel and Singha et al. (Singha, Mahapatra, Karmakar, Dutta,

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Mondal & Chattopadhyay, 2017) in guar gum-g-(acrylic
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acid-co-acrylamide-co-3-acrylamido propanoic acid) hydrogel.
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Figure 5: Swelling behavior of salecan-g-PAI hydrogels. Shown are swelling kinetics (A), ESR
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values for different pH values (B) and salt concentrations (C), and water retention kinetics (D).
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3.3.2 Swelling in various pH

Figure 5B shows the swelling behavior of salecan-g-PAI hydrogels under

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different pH conditions. According to Figure 5B, the equilibrium water absorbency of

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the designed salecan-g-PAI hydrogels clearly exhibited pH sensitivity. Taking SAI4

CC

as an example, the ESR evidently enhanced in the range of pH 2.0−6.0 (from 9.9 to
A

52.6), remained almost constant as the pH was increased from 7.0 to 9.0 (53.0) and

decreased slightly within pH 10.0−12.0 (from 45.0 to 30.5).

The intriguing pH-responsive swelling properties of the salecan-g-PAI hydrogels

can be attributed to the protonation and ionization balance of the –COOH groups
22 / 40
existing in the molecule chains of poly (itaconic acid), whose pKa1 value is around

3.85 and pKa2 value is around 5.44 (Zhang, Shen, Li, Cai & Liu, 2012). Under acidic

medium of pH 2.0 (below the pKa1 of PAI), the carboxyl groups in PAI chains existed

in the form of –COOH. Strong intramolecular and intermolecular hydrogen bonds

among –COOH groups could be established. Such hydrogen bonds constructed a

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steadier and ordered network structure that prevented traversing of water which,

R
finally, restricting swelling of hydrogel. As the pH of swelling medium reached to 6.0

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(above the pKa2 of PAI), the carboxyl groups became more deprotonated and changed

from −COOH to −COO− (Zhang, Wang, Shi, Huang, Zhao & Zhao, 2017). On the one

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hand, the aforementioned hydrogen bonds decreased and thus the diffusion of water
A
into hydrogel network was liberated, consequently benefiting the water absorption
M

(Xu, Bai, Ding, Wang & Suo, 2015). On the other hand, the reinforcement of the

electrostatic repulsion between carboxylate groups facilitated expansion of the

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polymeric network, allowing for more incorporation of water (Dai & Huang, 2017).
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When the pH value was higher than 6.0 (6.0<pH<10.0), no obvious conversion

occurred between −COOH and −COO− groups, leading to an almost constant swelling
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ratio (Dai & Huang, 2017). Further augmenting the pH of incubation media to 10.0,

the excess Na+ counterions in the swelling solutions could combine with −COO−
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groups, restraining anion−anion repulsions between carboxylate groups and resulting

in hydrogel shrinkage (Dai & Huang, 2017; Dragan, Lazar, Dinu & Doroftei, 2012).

Therefore, swelling was remarkably impaired in strongly alkaline solutions. Overall,

23 / 40
the swelling behavior of salecan-g-PAI hydrogels was sensitive to pH, which was

governed by the conformational changes of the poly (itaconic acid) chains (Zhang,

Wang, Shi, Huang, Zhao & Zhao, 2017).

3.3.3 Swelling in different saline solutions

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The swelling behavior of the salecan-g-PAI (SAI3) hydrogels in various salt

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solutions (KCl, CaCl2, and FeCl3) with different concentrations (0.1%-0.4%, w/w) is

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presented in Figure 5C. As the salt concentrations enhanced, the equilibrium swelling

ratio (ESR) of SAI3 obviously reduced. For example, the ESR values were 22.3, 18.0,

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13.6 and 11.3 for 0.1, 0.2, 0.3 and 0.4 wt% KCl, respectively. The mechanism of this
A
shrinking behavior can be understood as follows. When the concentration of saline
M

solution augmented, the osmotic pressure difference between the external solution and

the polymer network was strengthened due to the ionic interactions between mobile
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ions (such as K+) and the fixed charges (−COO−) that contributed to water release and,
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hence, the swelling capacity of the salecan-g-PAI hydrogel decreased (Chang, He,
E

Zhou & Zhang, 2011; Dai & Huang, 2017; Xu, Bai, Ding, Wang & Suo, 2015).
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Besides, the ionic species also exhibited very big influence on the swelling ability for

salecan-g-PAI hydrogels. For instance, at a given salt concentration (0.4 wt%), the
A

shrinking trend of SAI3 gel improved with the enhancing of ionic charge, indicating

minimum swelling ratio in FeCl3 solution (2.8) and maximum swelling value in KCl

solution (11.3). This phenomenon was caused by the fact that multivalent cations

24 / 40
(such as Fe3+) could be integrated with anionic groups of PAI to create a high dense

hydrogel structure, limiting water incorporation and thus, leading to small swelling

ratio (Qi et al., 2015; Wu, Zhang, Liu & Yao, 2012). In sum, the results from Figure

5C demonstrated that the water uptake of hydrogels depended on not only the

concentration of salt solutions but also the salt species.

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3.3.4 Deswelling behaviors

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Water retention ability is a key consideration for the use of hydrogel in dye

adsorption and wastewater treatment (Chang, He, Zhou & Zhang, 2011). Figure 5D

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shows the water retention ratio profile as a function of time at 37 °C oven. For all the
A
hydrogels, the water retention reduced rapidly in the initial stage of heating and then
M

dropped gradually, as the driving force for dehydration was slowly fell upon the

deswelling of the hydrogels (Xu, Bai, Ding, Wang & Suo, 2015). Moreover, it is
ED

worth noting that hydrogels containing higher salecan dehydrated at a faster rate and
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at the same time, expelled more water from the hydrogel network. For example, SAI1
E

excluded >90.5% of its absorbed water after 540 min of incubation, while SAI2, SAI3
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and SAI4 lost 92.7%, 94.9% and 96.4% of their absorbed water at this time point,

respectively. An explanation was that , hydrogel with a larger salecan content had a
A

stronger affinity for water molecules, which can act as water-releasing channels when

hydrogel shrinkage, thereby benefiting for dehydration (Xu, Bai, Ding, Wang & Suo,

2015).

25 / 40
3.4 The adsorption application of hydrogel

To evaluate the suitability of the as-prepared salecan-g-PAI hydrogels as

adsorbents for removal of dye from aqueous environment, preliminary adsorption

tests were performed using a batch experimental setup. The effects of various

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parameters on adsorption behaviors of salecan-g-PAI hydrogels, liking salecan dosage,

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solution pH, contact time and initial dye concentration, were investigated.

SC
3.4.1 Effect of salecan dosage

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Firstly, the influence of salecan dose on saturated adsorption capacity of the
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hydrogel was assessed under MB solution of pH 4.0 at 25 °C. Here, the initial volume
M

of MB was 30 mL and the initial concentration of MB was 300 mg/L. As illustrated in

Figure 6A, the adsorption ability of MB enhanced with an increasing amount of

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salecan. The equilibrium adsorption amounts of MB for the SAI4 hydrogels were the
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largest (107.1 mg/g). This finding was ascribed to the highest content of hydrophilic
E

salecan chains presented in SAI4 hydrogel, which could act as binding sites for dye
CC

(Wang & Wang, 2016). Moreover, SAI4 had largest pores among these prepared

hydrogels, also benefiting for the adsorption of MB (Zhang, Wang, Shi, Huang, Zhao
A

& Zhao, 2017). Table 2 lists the maximum adsorption capacities of salecan-g-PAI

hydrogels for MB compared with several polysaccharides-based hydrogels for the

adsorption of MB in the previously published works. We could conclude that

26 / 40
salecan-g-PAI hydrogels designed in this study possess a relatively suitable

adsorption, suggesting that salecan-based hydrogels were functional material for dye

adsorption.

Table 2: The maximum adsorption capacities of MB on different polysaccharide-based hydrogel

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adsorbent.

qm

R
Adsorbent (mg/g) Reference

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(Paulino, Guilherme, Reis, Campese,
gum Arabic/polyacrylamide/polyacrylate 48 Muniz & Nozaki, 2006)
guar gum-g-(acrylic acid-co-acrylamide- (Singha, Mahapatra, Karmakar,

co-3-acrylamido propanoic acid) 32.1 2017)U

Dutta, Mondal & Chattopadhyay,
N
starch/humic acid 110 (Chen et al., 2015)
A
(Mohammed, Grishkewich, Waeijen,
alginate/cellulose nanocrystal 255.5 Berry & Tam, 2016)
M

(Dragan, Lazar, Dinu & Doroftei,

chitosan/poly(acrylamide) 750 2012)
salecan-g-PAI 107.1 This work
ED
PT

Although the adsorption amounts of MB for the SAI4 hydrogels were the highest,

the resulting hydrogels were brittle. After taking the factors of gel stiffness and
E

adsorption ability into consideration, we chose SAI3 hydrogels with moderate

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mechanical strength and adsorption efficiency for subsequent experiments.

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27 / 40
 T
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A
Figure 6: Effect of salecan dose (A), solution pH (B), contact time (C) and initial dye
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concentration (D) on the adsorption capacity of salecan-g-PAI hydrogels.

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3.4.2 Effect of solution pH

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Solution pH is perhaps the most pivotal parameter determining the efficiency of

E

dye adsorption, since it not only influences the surface charge of the hydrogel but also
CC

the speciation of dye (Tu et al., 2017). The effect of solution pH on dye sorption onto

the SAI3 has been presented in Figure 6B. Here, the initial volume of MB was 30 mL
A

with a concentration of 300 mg/L and the adsorption assay was conducted at 25 °C.

The adsorption capacity of MB enhanced sharply with a pH increase from 2.0 to 6.0

but enhanced slowly with a further pH increase from 7.0 to 9.0. This phenomenon

28 / 40
could be attributable to a competitive adsorption between negative charges of the

hydrogel and the positive charges of dye (Peng, Hu, Zeng, Li, Liang & Chang, 2016).

At low pH value (<2.0), the sorption of dye was hindered because the effective

adsorption sites existing in hydrogel matrix were occupied by H+ ions. Conversely,

increment in pH facilitated ionization of the functional groups (liking carboxyl groups)

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IP
on the hydrogel network, which benefited the electrostatic attraction , thus promoting

R
dye adsorption and leading to higher qe values (Jiang, Chowdhury &

SC
Balasubramanian, 2017; Yang, Li, Wang, Zhang, Ma & Ye, 2010).

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3.4.3 Effect of contact time
A
Time-dependent adsorption profile of the SAI3 hydrogel is plotted in Figure 6C.
M

Here, the initial concentration of MB was 300 mg/L with a pH of 7.0 and the

adsorption assay was measured at 25 °C. The initial appearance of MB solution was
ED

blue, and SAI3 hydrogel in the dye solution was invisible. The dye adsorption was
PT

rapid in the beginning and then reached saturation after 6 h. Finally, the blue color of
E

dye almost faded from the solution, whereas the transparent SAI3 hydrogel turned
CC

blue due to the dye adsorption. At the initial stage of adsorption reaction, the SAI3

hydrogels retained many free functional sites, and could combined with the molecules
A

of MB as soon as they were incorporated into dye solution (Yang, Li, Wang, Zhang,

Ma & Ye, 2010). However, the numbers of MB molecules on the gel surface

increased over contact time, which would hinder combination of free MB molecules,

29 / 40
leading to a smaller adsorption rate. When driving and repellant forces reached a

balance, the adsorption process would be arrive to equilibrium, and adsorption

process would not be affected by the contact time any more. Others have published

similar results (Peng, Hu, Zeng, Li, Liang & Chang, 2016; Tu et al., 2017).

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3.4.4 Effect of initial dye concentration

R
The influence of initial dye concentration on the adsorption capacity of MB by

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hydrogels was also studied. Figure 6D displays the qe of SAI3 in pH 7.0 MB

solutions with various concentrations at 25 °C. Dye adsorption capacities of hydrogels

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elevated with the enhancing initial concentration of MB dye. Specially, when the
A
initial concentration of MB was 10, 200 and 500 mg/ L, the qe of SAI3 hydrogels was
M

3.5, 66.8 and 110.5 mg/g, respectively. However, the removal rate of SAI3 was

declined with enhancing initial MB concentration. The removal rate of MB was

ED

reached to 34.9% when the initial MB concentration was 10 mg /L yet, if the initial
PT

MB concentration tuned to 500 mg/L, the dye removal rate decreased to 22.1%. A
E

reasonable explanation for this phenomenon was that: the surface of hydrogels
CC

possessed enough free functional sites for adsorption initially, and would react with

MB once they came into contact, resulting in a rapid adsorption rate. However,
A

adsorption was difficult since the enhancing numbers of MB combining on the surface

of hydrogels would repel free MB over time (Tu et al., 2017).

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3.4.5 The isotherms and kinetics of adsorption process

In this work, the adsorption isotherms and kinetics were utilized to understand

the dye adsorption process. We first adopted Freundlich and Langmuir isotherm

models to describe the adsorption isotherms of dye onto salecan-g-PAI (SAI3)

hydrogels. Data are shown in Figure 7A and 7B. Clearly, the sorption isotherm

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behavior of dye sorption onto the hydrogels was more appropriately described by the

R
Freundlich model because of a much higher correlation coefficient (0.9913). Similar

SC
results have been reported for sorption of MB on other polysaccharide hydrogels

(Dragan & Apopei, 2011; Peng, Hu, Zeng, Li, Liang & Chang, 2016; Singha,

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Mahapatra, Karmakar, Dutta, Mondal & Chattopadhyay, 2017).
A
Then, the kinetic behavior of dye sorption onto the hydrogels were investigated
M

using the pseudofirst-order and pseudosecond-order kinetic models. It can be obtained

from Figure 7C and 7D that the pseudo-second order model revealed better
ED

agreement of experimental data (0.9925) than the pseudo-first order kinetic model
PT

(0.8807), demonstrating that the main adsorption mechanism was chemical adsorption
E

(Tu et al., 2017; Zhang, Wang, Shi, Huang, Zhao & Zhao, 2017).
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A

31 / 40
 T
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A
Figure 7: (A) The Freundlich adsorption isotherm, (B) Langmuir adsorption isotherm, (C) PFO
M

kinetic model and (D) PSO kinetic model for the adsorption of the MB on the salecan-g-PAI

hydrogels.
ED
PT

4 Conclusions
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In conclusion, macroporous salecan-g-PAI hydrogels had been fabricated by

CC

grafting AM and IA onto salecan polysaccharide backbone and applied as novel

materials for dye adsorption. The successful formation of salecan-g-PAI hydrogels

A

were confirmed by a variety of spectroscopic techniques liking FTIR, XRD and TGA.

We found that the physicochemical properties of resulting hydrogels involving

mechanical performance, pore size and swelling, could be tuned by adjusting the

32 / 40
salecan concentration in the pre-gel solution. Considering these prominent

characteristics, the designed grafted hydrogels were employed as smart adsorbents for

dye adsorption. Satisfyingly, these salecan-g-PAI hydrogels were highly efficient

adsorbents for rapid removal of MB dyes from aqueous solutions. Maximum dye

adsorption occurred at SAI4 hydrogel was 107.1 mg/g. In addition, the adsorption

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process of the salecan-g-PAI hydrogel for MB was better explained by the PSO

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kinetic and Freundlich isotherm models. The approach presented in this work

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promoted the utilization of renewable salecan polysaccharides, which could construct

promising three-dimensional materials for adsorption applications.

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Acknowledgements
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This work was supported by the National Natural Science Foundation of China
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(51573078).
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