New chitosan-imine derivatives: from green chemistry to removal of heavy metals from water
Keywords:Biopolymers, Chitosan, Green chemistry, Deacetilation degree, Water treatment
Three novel imine-chitosan derivatives were synthesized by condensation of the amino terminals of chitosan and 4-bromomethyl-2-hydroxybenzaldehyde A1, 4-formyl-2-hydroxybenzoic acid A2, and (E)-6-((2-(pyridin-2-yl)hydrazono)methyl)picolinaldehyde A3. Noteworthy, is the aqueous synthesis of imine-chitosan compounds using relatively mild conditions (70 °C) in a green chemistry fashion. The new compounds were characterized by 1H-NMR, FT-IR, elemental analysis, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). A solubility study at different pH values was performed for the three compounds, obtaining very different behaviors when compared to that of the pristine chitosan. Finally, by means of atomic absorption the ability to remove heavy metal ions, such as Pb(II) and Hg(II), was investigated for the imine-chitosan derivatives, which showed a high removal percentage at basic pH (between 8-10) but low removal percentage at pH lower than 5. Additionally, the nature of the substituent determines the solubility of the resulting adducts thus widening the potential applications of chitosan derivatives.
T. R. A. Sobahi, M. Y. Abdelaal, and M. S. I. Makki, “Chemical modification of chitosan for metal ion removal,” Arabian Journal of Chemistry, vol. 7, no. 5, pp. 741–746, Nov. 2014.
Z. Karim, A. P. Mathew, M. Grahn, J. Mouzon, and K. Oksman, “Nanoporous membranes with cellulose nanocrystals as functional entity in chitosan: Removal of dyes from water,” Carbohydrate Polymers, vol. 112, pp. 668–676, Nov. 2014.
T. Uragami, T. Saito, and T. Miyata, “Pervaporative dehydration characteristics of an ethanol/water azeotrope through various chitosan membranes,” Carbohydrate Polymers, vol. 120, pp. 1–6, Apr. 2015.
W. Zhang, J. Zhang, Q. Jiang, and W. Xia, “The hypolipidemic activity of chitosan nanopowder prepared by ultrafine milling,” Carbohydrate Polymers, vol. 95, no. 1, pp. 487–491, Jun. 2013.
P. Chantarasataporn and et al., “Water-based oligochitosan and nanowhisker chitosan as potential food preservatives for shelf-life extension of minced pork,” Food Chemistry, vol. 159, pp. 463–470, Sep. 2014.
E. P. Minet and et al., “Slow delivery of a nitrification inhibitor (dicyandiamide) to soil using a biodegradable hydrogel of chitosan,” Chemosphere, vol. 93, no. 11, pp. 2854–2858, Nov. 2013.
J. Pérez and et al., “N,O6-partially acetylated chitosan nanoparticles hydrophobically-modified for controlled release of steroids and vitamin E,” Carbohydrate Polymers, vol. 91, no. 1, pp. 143–151, Jan. 2013.
N. Mati and et al., “Chitosan as an adhesive,” European Polymer Journal, vol. 60, pp. 198–212, Nov. 2014.
R. Jayakumar and et al., “Chitosan conjugated DNA nanoparticles in gene therapy,” Carbohydrate Polymers, vol. 79, no. 1, pp. 1–8, Jan. 2010.
R. Jayakumar, M. Prabaharan, R. L. Reis, and J. F. Mano, “Graft copolymerized chitosan—present status and applications,” Carbohydrate Polymers, vol. 62, no. 2, pp. 142–158, Nov. 2005.
R. Jayakumar, N. Nwe, S. Tokura, and H. Tamura, “Sulfated chitin and chitosan as novel biomaterials,” International Journal of Biological Macromolecules, vol. 40, no. 3, pp. 175–181, Feb. 2007.
Y. Wang, H. Chen, J. Wang, and L. Xing, “Preparation of active corn peptides from zein through double enzymes immobilized with calcium alginate–chitosan beads,” Process Biochemistry, vol. 49, no. 10, pp. 1682–1690, Oct. 2014.
A. Anitha and et al., “Synthesis, characterization, cytotoxicity and antibacterial studies of chitosan, O-carboxymethyl and N,Ocarboxymethyl chitosan nanoparticles,” Carbohydrate Polymers, vol. 78, no. 4, pp. 672–677, Nov. 2009.
M. Peter and et al., “Novel biodegradable chitosan–gelatin/nanobioactive glass ceramic composite scaffolds for alveolar bone tissue engineering,” Chemical Engineering Journal, vol. 158, no. 2, pp. 353– 361, Apr. 2010.
T. Jiang, R. James, S. G. Kumbar, and C. T. Laurencin, “Chitosan as a biomaterial: Structure, properties, and applications in tissue engineering and drug delivery,” in Natural and Synthetic Biomedical Polymers, S. G. Kumbar, C. T. Laurencin, and M. Deng, Eds. Oxford, England: Elsevier, 2014, pp. 91–113.
M. Vakili and et al., “Application of chitosan and its derivatives as adsorbents for dye removal from water and wastewater: A review,” Carbohydrate Polymers, vol. 113, pp. 115–130, Nov. 2014.
H. Sashiwa and S. I. Aiba, “Chemically modified chitin and chitosan as biomaterials,” Progress in Polymer Science, vol. 29, no. 9, pp. 887– 908, Sep. 2004.
Y. Xie, X. Liu, and Q. Chen, “Synthesis and characterization of watersoluble chitosan derivate and its antibacterial activity,” Carbohydrate Polymers, vol. 69, no. 1, pp. 142–147, May 2007.
G. Q. Ying, W. Y. Xiong, H. Wang, Y. Sun, and H. Z. Liu, “Preparation, water solubility and antioxidant activity of branched-chain chitosan derivatives,” Carbohydrate Polymers, vol. 83, no. 4, pp. 1787–1796, Feb. 2011.
S. Nishimura, O. Kohgo, K. Kurita, and H. Kuzuhara, “Chemospecific manipulations of a rigid polysaccharide: syntheses of novel chitosan derivatives with excellent solubility in common organic solvents by regioselective chemical modifications,” Macromolecules, vol. 24, no. 17, pp. 4745–4748, Aug. 1991.
B. Shi, Z. Shen, H. Zhang, J. Bi, and S. Dai, “Exploring N-Imidazolyl- O-Carboxymethyl chitosan for high performance gene delivery,” Macromolecules, vol. 13, no. 1, pp. 146–153, Nov. 2011.
V. Saggiomo and U. Lüning, “On the formation of imines in water— a comparison,” Tetrahedron Letters, vol. 50, no. 32, pp. 4663–4665, Aug. 2009.
C. Godoy, A. K. Yatsimirsky, and J. M. Lehn, “Structure-stability correlations for imine formation in aqueous solution,” Journal of Physical Organic Chemistry, vol. 18, no. 10, pp. 979–985, Oct. 2005.
V. K. Rao and et al., “Synthesis of schiff’s bases in aqueous medium: a green alternative approach with effective mass yield and high reaction rates,” Green Chemistry Letters and Reviews, vol. 3, no. 3, pp. 217–223, Oct. 2010.
V. Nair, A. Panigrahy, and R. Vinu, “Development of novel chitosan– lignin composites for adsorption of dyes and metal ions from wastewater,” Chemical Engineering Journal, vol. 255, pp. 491–502, Oct. 2014.
T. Anitha, P. S. Kumar, K. S. Kumar, B. Ramkumar, and S. Ramalingam, “Adsorptive removal of Pb(II) ions from polluted water by newly synthesized chitosan–polyacrylonitrile blend: Equilibrium, kinetic, mechanism and thermodynamic approach,” Process Safety and Environmental Protection, vol. 98, pp. 187–197, Nov. 2015.
V. Mohanasrinivasan and et al., “Studies on heavy metal removal efficiency and antibacterial activity of chitosan prepared from shrimp shell waste,” 3 Biotech, vol. 4, no. 2, pp. 167–175, Apr. 2014.
A. Maleki, E. Pajootan, and B. Hayati, “Ethyl acrylate grafted chitosan for heavy metal removal from wastewater: Equilibrium, kinetic and thermodynamic studies,” Journal of the Taiwan Institute of Chemical Engineers, vol. 51, pp. 127–134, Jun. 2015.
Y. Xu and et al., “Preparation and characterization of carboxylfunctionalized chitosan magnetic microspheres and submicrospheres for Pb 2+ removal,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, vol. 482, pp. 353–364, Oct. 2015.
I. M. N. Vold, K. M. Vårum, E. Guibal, and O. Smidsrød, “Binding of ions to chitosan—selectivity studies,” Carbohydrate Polymers, vol. 54, no. 4, pp. 471–477, Dec. 2003.
E. Guibal, “Interactions of metal ions with chitosan-based sorbents: a review,” Separation and Purification Technology, vol. 38, no. 1, pp. 43–74, Jul. 2004.
W. S. Wan, L. C. Teong, and M. A. K. M. Hanafiah, “Adsorption of dyes and heavy metal ions by chitosan composites: A review,” Carbohydrate Polymers, vol. 83, no. 4, pp. 1446–1456, Feb. 2011.
M. Ruiz, A. M. Sastre, and E. Guibal, “Palladium sorption on glutaraldehyde-crosslinked chitosan,” Reactive and Functional Polymers, vol. 45, no. 3, pp. 155–173, Oct. 2000.
W. S. Wan, C. S. Endud, and R. Mayanar, “Removal of copper(II) ions from aqueous solution onto chitosan and cross-linked chitosan beads,” Reactive and Functional Polymers, vol. 50, no. 2, pp. 181–190, Jan. 2002.
A. Ramesh, H. Hasegawa, W. Sugimoto, T. Maki, and K. Ueda, “Adsorption of gold(III), platinum(IV) and palladium(II) onto glycine modified crosslinked chitosan resin,” Bioresource Technology, vol. 99, no. 9, pp. 3801–3809, Jun. 2008.
L. Zhou, Y. Wang, Z. Liu, and Q. Huang, “Characteristics of equilibrium, kinetics studies for adsorption of Hg(II), Cu(II), and Ni(II) ions by thiourea-modified magnetic chitosan microspheres,” Journal of Hazardous Materials, vol. 161, no. 2-3, pp. 995–1002, Jan. 2009.
L. Martinez and et al., “Cross-linking of chitosan and chitosan/ poly(ethylene oxide) beads: A theoretical treatment,” European Journal of Pharmaceutics and Biopharmaceutics, vol. 67, no. 2, pp. 339–348, Sep. 2007.
N. Li and R. Bai, “Development of chitosan-based granular adsorbents for enhanced and selective adsorption performance in heavy metal removal,” Water Science and Technology, vol. 54, no. 10, pp. 103–105, 2006.
X. Su and I. Aprahamian, “Hydrazone-based switches, metalloassemblies and sensors,” Chemical Society Reviews, vol. 43, no. 6, pp. 1963–1981, Jan. 2014.
L. A. Tatum, X. Su, and I. Aprahamian, “Simple hydrazone building blocks for complicated functional materials,” Accounts of Chemical Research, vol. 47, no. 7, pp. 2141–2149, Apr. 2014.
J. M. Lehn, “Conjecture: imines as unidirectional photodriven molecular motors-motional and constitutional dynamic devices,” Chemistry: A European Journal, vol. 12, no. 23, pp. 5910–5915, Aug. 2006.
M. N. Chaur, D. Collado, and J. M. Lehn, “Configurational and constitutional information storage: Multiple dynamics in systems based on pyridyl and acyl hydrazones,” Chemistry: A European Journal, vol. 17, no. 1, pp. 248–258, Jan. 2011.
E. L. Romero, R. F. D. Vries, F. Zuluaga, and M. N. Chaur, “Multiple dynamics of hydrazone based compounds,” Journal of the Brazilian Chemical Society, vol. 26, no. 6, pp. 1265–1273, 2015.
X. Su, T. F. Robbins, and I. Aprahamian, “Switching through coordination-coupled proton transfer,” Angewandte Chemie International Edition, vol. 50, no. 8, pp. 1841–1844, Feb. 2011.
S. M. Landge and et al., “Isomerization mechanism in hydrazonebased rotary switches: Lateral shift, rotation, or tautomerization?” Journal of the American Chemical Society, vol. 133, no. 25, pp. 9812– 9823, May 2011.
M. L. Croteau, X. Su, D. E. Wilcox, and I. Aprahamian, “Metal coordination and isomerization of a hydrazone switch,” ChemPlusChem, vol. 79, no. 8, pp. 1214–1224, Aug. 2014.
C. C. Carmona, I. Y. Váquiro, L. M. Jaramillo, J. M. Lehn, and M. N. Chaur, “Grid-type complexes of m2+ (M = Co, Ni, and Zn) with highly soluble bis(hydrazone)thiopyrimidine-based ligands: Spectroscopy and electrochemical properties,” Inorganica Chimica Acta, vol. 468, pp. 131–139, Nov. 2017.
S. Ulrich, E. Buhler, and J. M. Lehn, “Reversible constitutional switching between macrocycles and polymers induced by shape change in a dynamic covalent system,” New Journal of Chemistry, vol. 33, no. 2, pp. 271–292, Jan. 2009.
E. L. Romero and et al., “New pyrazolino and pyrrolidino[ 60]fullerenes: the introduction of the hydrazone moiety for the formation of metal complexes,” Journal of Physical Organic Chemistry, vol. 30, no. 2, p. e3601, Feb. 2017.
M. A. Gordillo, M. Soto, G. Gutiérrez, R. F. D’Vries, and M. N. Chaur, “Theoretical and experimental comparative study of a derivative from 2-pyridinecarboxaldehyde which exhibits configurational dynamics,” Journal of Molecular Structure, vol. 1119, pp. 286–295, Sep. 2016.
M. A. Fernandez, J. C. Barona, D. Polo, and M. N. Chaur, “Photochemical and electrochemical studies on lanthanide complexes of 6-(hydroxymethyl) pyridine-2-carboxaldehyde[2-methylpyrimidine- 4,6-diyl]bis-hydrazone,” Revista Colombiana de Química, vol. 43, no. 1, pp. 5–11, Jan. 2014.
G. Muñoz, C. Valencia, N. Valderruten, E. Ruiz, and F. Zuluaga, “Extraction of chitosan from Aspergillus niger mycelium and synthesis of hydrogels for controlled release of betahistine,” Reactive and Functional Polymers, vol. 91-92, pp. 1–10, Jun. 2015.
L. G. Parada, G. D. Crespín, R. Miranda, and I. Katime, “Caracterización de quitosano por viscosimetría capilar y valoración potenciométrica,” Revista Iberoamericana de Polímeros, vol. 5, no. 1, pp. 1–6, Mar. 2004.
N. Balázs and P. Sipos, “Limitations of pH-potentiometric titration for the determination of the degree of deacetylation of chitosan,” Carbohydrate Research, vol. 342, no. 1, pp. 124–130, Jan. 2007.
Z. M. dos Santos, A. L. P. F. Caroni, M. R. Pereira, D. R. da Silva, and J. L. C. Fonseca, “Determination of deacetylation degree of chitosan: a comparison between conductometric titration and CHN elemental analysis,” Carbohydrate Research, vol. 344, no. 18, pp. 2591–2595, Dec. 2009.
A. Tolaimate and et al., “On the influence of deacetylation process on the physicochemical characteristics of chitosan from squid chitin,” Polymer, vol. 41, no. 7, pp. 2463–2469, Mar. 2000.
N. Kubota, N. Tatsumoto, T. Sano, and K. Toya, “A simple preparation of half n-acetylated chitosan highly soluble in water and aqueous organic solvents,” Carbohydrate Research, vol. 324, no. 4, pp. 268– 274, Mar. 2000.
A. Hirai, H. Odani, and A. Nakajima, “Determination of degree of deacetylation of chitosan by 1H NMR spectroscopy,” Polymer Bulletin, vol. 26, no. 1, pp. 87–94, Jul. 1991.
S. S. Razi, R. Ali, P. Srivastava, and A. Misra, “A selective quinolinederived fluorescent chemodosimeter to detect cyanide in aqueous medium,” Tetrahedron Letters, vol. 55, no. 5, pp. 1052–1056, Jan. 2014.
Z. Zhang and et al., “A novel dinuclear schiff-base copper(II) complex modified electrode for ascorbic acid catalytic oxidation and determination,” Dalton Transactions, vol. 41, no. 4, pp. 1252–1258, 2012.
L. Marin and et al., “Imino-chitosan biopolymeric films. obtaining, self-assembling, surface and antimicrobial properties,” Carbohydrate Polymers, vol. 117, pp. 762–770, Mar. 2015.
L. Marin and et al., “Antifungal vanillin–imino-chitosan biodynameric films,” Journal of Materials Chemistry B, vol. 1, no. 27, pp. 3353–3358, May 2013.
L. Marin, B. Simionescu, and M. Barboiu, “Imino-chitosan biodynamers,” Chemical Communications, vol. 48, no. 70, pp. 8778–8780, Jul. 2012.
A. T. Paulino and et al., “Effect of magnetite on the adsorption behavior of Pb(II), Cd(II), and Cu(II) in chitosan-based hydrogels,” Desalination, vol. 275, no. 1-3, pp. 187–196, Jul. 2011.
M. X. Weinhold and et al., “Strategy to improve the characterization of chitosan for sustainable biomedical applications: SAR guided multidimensional analysis,” Green Chemistry, vol. 11, no. 4, pp. 498–509, Feb. 2009.
J. Brugnerotto and et al., “An infrared investigation in relation with chitin and chitosan characterization,” Polymer, vol. 421, no. 8, pp. 3569–3580, Apr. 2001.
M. Jiang and et al., “Preparation and characterization of watersoluble chitosan derivative by michael addition reaction,” International Journal of Biological Macromolecules, vol. 47, no. 5, pp. 696–699, Dec. 2010.
M. Bengisu and E. Yilmaz, “Oxidation and pyrolysis of chitosan as a route for carbon fiber derivation,” Carbohydrate Polymers, vol. 50, no. 2, pp. 165–175, Nov. 2002.
T. Wanjun, W. Cunxin, and C. Donghua, “Kinetic studies on the pyrolysis of chitin and chitosan,” Polymer Degradation and Stability, vol. 87, no. 3, pp. 389–394, Mar. 2005.
A. Pawlak and M. Mucha, “Thermogravimetric and FTIR studies of chitosan blends,” Thermochimica Acta, vol. 396, no. 1-2, pp. 153–166, Feb. 2003.
Z. H. Zhang, Z. Han, X. A. Zeng, X. Y. Xiong, and Y. J. Liu, “Enhancing mechanical properties of chitosan films via modification with vanillin,” International Journal of Biological Macromolecules, vol. 81, pp. 638–643, Nov. 2015.
L. E. Abugoch, C. Tapia, M. C. Villamán, M. Yazdani, and M. Díaz, “Characterization of quinoa protein–chitosan blend edible films,” Food Hydrocolloids, vol. 25, no. 5, pp. 879–886, Jul. 2011.
H. E. Salama, G. R. Saad, and M. W. Sabaa, “Synthesis, characterization and biological activity of schiff bases based on chitosan and arylpyrazole moiety,” International Journal of Biological Macromolecules, vol. 79, pp. 996–1003, Aug. 2015.
M. A. Diab, A. Z. El-Sonbati, and D. M. D. Bader, “Thermal stability and degradation of chitosan modified by benzophenone,” Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 79, no. 5, pp. 1057–1062, Sep. 2011.
D. R. Rueda, T. Secall, and R. K. Bayer, “Differences in the interaction of water with starch and chitosan films as revealed by infrared spectroscopy and differential scanning calorimetry,” Carbohydrate Polymers, vol. 40, no. 1, pp. 49–56, Sep. 1999.
C. G. T. Neto and et al., “Thermal analysis of chitosan based networks,” Carbohydrate Polymers, vol. 62, no. 2, pp. 97–103, Nov. 2005.
L. S. Guinesi and . T. Gomes, “The use of DSC curves to determine the acetylation degree of chitin/chitosan samples,” Thermochimica Acta, vol. 444, no. 2, pp. 128–133, May 2006.
G. Crini and P. M. Badot, “Application of chitosan, a natural aminopolysaccharide, for dye removal from aqueous solutions by adsorption processes using batch studies: A review of recent literature,” Progress in Polymer Science, vol. 33, no. 4, pp. 399–447, Apr. 2008.
M. S. Chiou, P. Y. Ho, and H. Y. Li, “Adsorption of anionic dyes in acid solutions using chemically cross-linked chitosan beads,” Dyes and Pigments, vol. 60, no. 1, pp. 69–84, Jan. 2004.
C. Tejada and Á. Villabona and L. Garcés, “Adsorption of heavy metals in waste water using biological materials,” Tecno Lógicas, vol. 18, no. 34, pp. 109–123, 2015.
How to Cite
Revista Facultad de Ingeniería, Universidad de Antioquia is licensed under the Creative Commons Attribution BY-NC-SA 4.0 license. The material published in the journal can be distributed, copied and exhibited by third parties if the respective credits are given to the journal. No commercial benefit can be obtained and derivative works must be under the same license terms as the original work.