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Chinese Journal of Materials Research  2016, Vol. 30 Issue (11): 825-833    DOI: 10.11901/1005.3093.2015.769
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Preparation and Properties of Amino Acid-modified Chitosan-based Material for Metal Ion Adsorption
Yi ZHANG,Zhuanlin ZHANG,Hao ZHANG(),Shuting LI
School of Textiles, Tianjin Polytechnic University, Tianjin 300387, China
Cite this article: 

Yi ZHANG, Zhuanlin ZHANG, Hao ZHANG, Shuting LI. Preparation and Properties of Amino Acid-modified Chitosan-based Material for Metal Ion Adsorption. Chinese Journal of Materials Research, 2016, 30(11): 825-833.

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Abstract  

For improving the heavy metal ion chelating ability of chelatingheavy metal ions and the microbiological stability of chitosan (CS), L-arginine (L-Arg) was immobilized on CS molecules, in presence of condensing agent 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC.HCl) and coupling reagent N-Hydroxysuccinimide (NHS), using chitosan as a matrix, a new kind of natural-macromolecular-based heavy metal ion chelating material, L-arginine GRafted Chitosan (CA)of chelating heavy metal ions, was prepared by grafting L-arginine (L-Arg) onto CS molecules, with chitosan as raw mate-rial, 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC.HCl) ascondensing agent and N-Hydroxysuccinimide (NHS) coupling reagent. The GRafting mechanism was deeply discussed and the GRafted conditions were optimized by signal factor experiments. The structure and composition of the product were characterized by elemental analysis, infrared spectrum (FT-IR), Raman spectra (RAM) and x-ray diffraction (XRD). Then, the processing parameters were optimized via experiments with single factor. The results show that a grafting ratio (GR) of 16.85% may be acquired when the for the following parameters: molar ratios of reagents CS:Arg:EDC =1:1:1 and EDC:NHS =3:1, reaction time 12 h and pH=5, the GRating ratio (GR) was up to 16.85%. By adjusting the ratio of reactants, products with different GR levels could be obtained. The results of adsorption experiments showed CA (GR=16.85%) had higher removalefficiency of high-concentrated Cu2+ and Ni2+ ions than CS.CA also possessedhigher antibacterial property compared with CS, whilst the CA with 16.85% GRof was up to 16.85%, it can almost completely inhibited the growth of colibacillus and staphylococcus aureus.

Key words:  organic polymer materials      amino acid-modified Chitosan      GRaft      metal ion absorption      antibacterial property     
Received:  30 December 2015     
Fund: *Supported by National Natural Science Foundation of China No.5150030497 and the Special Project of National Modern Agricultural Technology System of China No. CARS-44-D.

URL: 

https://www.cjmr.org/EN/10.11901/1005.3093.2015.769     OR     https://www.cjmr.org/EN/Y2016/V30/I11/825

Fig.1  Graft mechanism of CS and L-Arg in present of EDC/NHS
Fig.2  Effect of pH on GRaft ratio of CA other reaction conditions: nCS:nArg:nEDC=1:1:1, nEDC:nNHS=3:1, reaction time 12 h
Fig.3  Effect of molar ratio of NHS and EDC on GRaft ratio of CA, other reaction conditions: nCS:nArg:nEDC=1:1:1, pH=5, reaction time 12 h
Products CAⅠ CAⅡ CAⅢ CAⅣ CAⅤ
nCS:nArg:nEDC: 3:1:1 2:1:1 1:1:1 1:2:2 1:3:3
GR% 5.04 9.66 16.85 19.66 21.13
Var [X] 0.52 0.49 0.75 0.68 0.55
Table 1  Effect of different reactant input ratio on GRaft ratio of CA. Other reaction conditions: nEDC:nNHS=3:1, pH=5, reaction time 12 h
L-Arg CS CAⅠ CAⅡ CAⅢ
N%(Elemental Analysis) 31.95 7.36 8.93 10.24 12.48
Var [X] 0.61 0.34 0.46 0.49 0.45
N%(kjeldahl) 31.82 7.29 8.81 10.07 12.16
Var [X] 0.99 0.74 0.69 0.67 0.77
GR% - - 5.04 9.66 16.85
Table 2  Nitrogen content and GRaft ratio of L-Arg, CS and CA
Fig.4  Infrared (a) and Raman spectrum (b) of CS and CA
Fig.5  X-ray diffraction of CS and CA
Absorption materials Diatomite Zeolite Activated carbon CS CA
Cu2+ % 4.03 9.85 16.56 54.96 68.29
Var [X] 1.32 1.01 0.89 0.82 1.57
Ni2+ % 8.43 15.70 24.99 62.86 75.03
Var [X] 0.85 0.96 1.08 0.85 1.13
Table 3  Adsorptive properties for Cu+2 and Ni+2 ions of different absorption materials
Seed CS CAⅠ CAⅡ CAⅢ
Antibacterial rate%
(colibacillus)
60.94 73.25 80.25 88.54
Var [X] 0.37 0.20 0.42 0.38
Antibacterial rate%
(staphylococcus aureus)
74.14 77.59 82.76 91.38
Var [X] 0.25 0.41 0.32 0.52
Table 4  Antibacterial rate against two kinds of GRam bacteria of CS and CA
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