Synthesis and Characterization of Chitosan Linked by Methylene Bridge and Schiff Base of 4,4-Diaminodiphenyl Ether-Vanillin

Ahmad Fatoni(1*), Poedji Loekitowati Hariani(2), Hermansyah Hermansyah(3), Aldes Lesbani(4)

(1) Bhakti Pertiwi School of Pharmacy Science Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sriwijaya University
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sriwijaya University
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sriwijaya University
(4) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sriwijaya University
(*) Corresponding Author


The synthesis chitosan-methylene bridge-Schiff base of 4,4-diaminodiphenyl ether-vanillin using casting method has been done. The aims of this research were modification chitosan with Schiff base of 4,4-diaminodiphenyl ether-vanillin, formaldehyde and its characterization using FTIR spectroscopy, SEM analysis, 1H-NMR and X-Ray Diffraction analysis. The first step was a synthesis of modified chitosan between chitosan and Schiff base of 4,4-diaminodiphenyl ether-vanillin. The second step was chitosan modified Schiff base of 4,4-diaminodiphenyl ether-vanillin then reacted with formaldehyde through casting method. The result showed that chitosan can be modified with Schiff base of 4,4-diaminodiphenyl ether-vanillin and formaldehyde and this modified chitosan can be linked by methylene bridge (-NH-CH2-NH-) and had azomethine group (-C=N-). The functional group of –C=N in modified chitosan before and after adding formaldehyde appeared at a constant wavenumber of 1597 cm-1. The functional group C-N in methylene bridge detected at 1388 and 1496 cm-1. The chitosan-Schiff base of 4,4-diaminodiphenyl ether-vanillin and Chitosan-methylene bridge-Schiff base of 4,4-diaminodiphenyl ether-vanillin had index crystalline (%)16.04 and 25.76, respectively. The chemical sift of signal proton azomethine group (-C=N-) in modified chitosan detected at 8.44–8.48 and 9.77 ppm. Proton from methylene bridge in modified chitosan appeared at 4.97–4.99 and 3.75 ppm. Surface morphology chitosan-methylene bridge-Schiff base of 4,4-diaminodiphenylether-vanillin had dense surfaces, mostly uniform and regular in shape.


chitosan; methylene bridge; Schiff base

Full Text:

Full Text PDF


[1] Wu, F.C., Tseng, R.L., and Juang, R.S., 2010, A review and experimental verification of using chitosan and its derivatives as adsorbents for selected heavy metals, J. Environ. Manage., 91 (4): 798–806.

[2] Kandile, N.G., and Nasr, A.S., 2011, Hydrogels based on a three component system with potential for leaching metals, Carbohydr. Polym., 85 (1), 120–128.

[3] Dai, B., Cao, M., Fang, G., Liu, B., Dong, X., Pan, M., and Wang, S., 2012, Schiff base-chitosan grafted multiwalled carbon nanotubes as a novel solid-phase extraction adsorbent for determination of heavy metal by ICP-MS, J. Hazard. Mater., 219-220, 103–110.

[4] Zhang, L., Zeng, Y., and Cheng, Z., 2016, Removal of heavy metal ions using chitosan and modified chitosan: A review, J. Mol. Liq., 214, 175–191.

[5] Gangolli, S.D., 1999, The Dictionary of Substances and their Effects (DOSE): O-S, Vol. 6, 2nd ed., The Royal Society of Chemistry, Cambridge.

[6] Liu, Y., Zhang, J., Li, Z., Luo, X., Jing, S., and Run, M., 2014, A pair of benzoxazine isomers from o-allylphenol and 4,4′-diaminodiphenyl ether: Synthesis, polymerization behavior, and thermal properties, Polymer, 55 (7), 1688–1697.

[7] Singh, V.K., Kadu, R., and Roy, H., 2014, 4,4′-Diaminodiphenyl ether derivatives: Synthesis, spectral, optical, thermal characterization and in-vitro cytotoxicity against Hep 3B and IMR 32 human cell lines, Eur. J. Med. Chem., 74, 552–561.

[8] Wang, G., Li, P., Peng, Z., Huang, M., and Kong, L., 2011, Formulation of vanillin cross-linked chitosan nanoparticles and its characterization, Adv. Mater. Res., 335-336, 474–477.

[9] Shakeel, F., Haq, N., And Siddiqui, N.A., 2015, Solubility and thermodynamic function of vanillin in ten different environmentally benign solvents, Food Chem., 180, 244–248.

[10] Balachandran, V., and Parimala, K., 2012, Vanillin and isovanillin: Comparative vibrational spectroscopic studies, conformational stability and NLO properties by density functional theory calculations, Spectrochim. Acta, Part A, 95, 354–368.

[11] Cucos, P., Tuna, F., Sorace, L., Matei, I., Maxim, C., Shova, S., Gheorghe, R., Caneschi, A., Hillebrand, M., and Andruh, M., 2014, Magnetic and luminescent binuclear double-stranded helicates, Inor. Chem., 53 (14), 7738–7747.

[12] Fajardo, A.R., Lopes, L.C., Rubira, A.F., and Muniz, E.C., 2012, Development and application of chitosan/poly(vinyl alcohol) films for removal and recovery of Pb(II), Chem. Eng. J., 183, 253–260.

[13] Li, M., Xu, J., Li, R., Wang, D., Li, T., Yuan, M., and Wang, J., 2014, Simple preparation of aminothiourea-modified chitosan as corrosion inhibitor and heavy metal ion adsorbent, J. Colloid Interface Sci., 417, 131–136.

[14] Monier, M., 2012, Adsorption of Hg2+, Cu2+ and Zn2+ ions from aqueous solution using formaldehyde cross-linked modified chitosan–thioglyceraldehyde Schiff's base, Int. J. Biol. Macromol., 50, 773–781.

[15] Dey, R.K., Jha, U., Singh, A.C., Samal, S., and Ray, A.R., 2006, Extraction of metal ions using chemically modified silica gel covalently bonded with 4,4'-diaminodiphenylether and 4,4'-diaminodiphenylsulfone-salicylaldehyde Schiff bases, Anal. Sci., 22 (8), 1105–1110.

[16] Wang, X., Deng, W., Xie, Y., and Wang, C., 2013, Selective removal of mercury ions using a chitosan–poly(vinyl alcohol) hydrogel adsorbent with three-dimensional network structure, Chem. Eng. J., 228, 232–242.

[17] Kandile, N.G., Razek, T.M.A., Al-Sabagh, A.M., and Khattab, M.M.T., 2014, Synthesis and evaluation of some amine compounds having surface active properties as H2S scavenger, Egypt. J. Pet., 23 (3), 323–329.

[18] Chi, N.T.Q., Luu, D.X. and Kim, D., 2011, Sulfonated poly(ether ether ketone) electrolyte membranes cross-linked with 4,4′-diaminodiphenyl ether, Solid State Ionics, 187 (1), 78–84.

[19] Uysal, Ş., and Uçan, H.I., 2010, The synthesis and characterization of single substitute melamine cored Schiff bases and their [Fe(III) and Cr(III)] complexes, J. Inclusion Phenom. Macrocyclic Chem., 68 (1-2), 165–173.

[20] Coates, J., 2006, “Interpretation of Infrared Spectra, A Practical Approach” in The Encyclopedia of Analytical Chemistry, John Wiley and Sons, New York, 1–23.

[21] Liu, Y., Li, Z., Zhang, J., Zhang, H., Fan, H., and Run, M., 2013, Polymerization behavior and thermal properties of benzoxazine based on 4,4′-diaminodiphenyl ether, J. Therm. Anal. Calorim., 111 (2), 1523–1530.

[22] Peng, H., Xiong, H., Li, J., Xie, M., Liu, Y., Bai, C., and Chen, L., 2010, Vanillin cross-linked chitosan microspheres for controlled release of resveratrol, Food Chem., 121 (1), 23–28.

[23] Khoee, S., and Zamani, S., 2007, Synthesis, characterization and fluorimetric studies of novel photoactive poly(amide-imide) from anthracene 9-carboxaldehyde and 4,4′-diaminodiphenyl ether by microwave irradiation, Eur. Polym. J., 43 (5), 2096–2110.

[24] Zhou, G., Ruhan, A., Ge, H., Wang, L., Liu, M., Wang, B., Su, H., Yan, M., Xi, Y., and Fan, Y., 2014, Research on a novel poly (vinyl alcohol)/lysine/vanillin wound dressing: Biocompatibility, bioactivity and antimicrobial activity, Burns, 40 (8), 1668–1678.

[25] Li, N., and Bai, R., 2005, A novel amine-shielded surface cross-linking of chitosan hydrogel beads for enhanced metal adsorption performance, Ind. Eng. Chem. Res., 44 (17), 6692–6700.

[26] Jiangtao, W., and Hedong, W., 2011, Preparation of soluble p-aminobenzoyl chitosan ester by Schiff's base and antibacterial activity of the derivatives, Int. J. Biol. Macromol., 48 (3), 523–529.

[27] Kumari, S., Rath, P., Kumar, A.S.H., and Tiwari, T.N., 2015, Extraction and characterization of chitin and chitosan from fishery waste by chemical method, Environ. Technol. Innovation, 3, 77–85.

[28] Mohammed, M.H., Williams, P.A., and Tverezovskaya, O., 2013, Extraction of chitin from prawn shells and conversion to low molecular mass chitosan, Food Hydrocolloids, 31 (2), 166–171.

[29] Huang, R., Yang, B., and Liu, Q., 2013, Removal of chromium(VI) Ions from aqueous solutions with protonated crosslinked chitosan, J. Appl. Polym. Sci., 129 (2), 1–8.

[30] Du, W.L., Niu, S.S., Xu, Z.R., and Xu, Y.L., 2009, Preparation, characterization, and adsorption properties of chitosan microspheres crosslinked by formaldehyde for copper(II) from aqueous solution, J. Appl. Polym. Sci., 111 (6), 2881–2885.

[31] Karunakaran, M., Vijayakumar, C.T., Selvan, D.M., and Magesh, C., 2013, o-Cresol, thiourea and formaldehyde terpolymer – A cation exchange resin, J. Saudi Chem. Soc., 17 (1), 1–8.

[32] Can, M., Bulut, E., and Özacar, M., 2012, Synthesis and characterization of pyrogallol-formaldehyde nano resin and its usage as an adsorbent, J. Chem. Eng. Data, 57 (10), 2710–2717.

[33] Poljanšek, I., and Krajnc, M., 2005, Characterization of phenol-formaldehyde prepolymer resins by in line FT-IR spectroscopy, Acta Chim. Slov., 52, 238−244.

[34] Machado, M.O., Lopes, E.C.N., Sousa, K.S., and Airoldi, C., 2009, The effectiveness of the protected amino group on crosslinked chitosans for copper removal and the thermodynamics of interaction at the solid/liquid interface, Carbohydr. Polym., 77 (4), 760–766.

[35] Ding, P., Huang, K.L., Li, G.Y., and Zeng, W.W., 2007, Mechanisms and kinetics of chelating reaction between novel chitosan derivatives and Zn(II), J. Hazard. Mater., 146 (1-2), 58–64.

[36] Pereira, F.S., de Souza, G.G., Moraes, P.G.P., Barroso, R.P., Lanfredi, S., Gomes, H.M., Filho, A.J. C., and Gonzales, R.P., 2015, Study of chitosans interaction with Cu(II) from the corresponding sulfate and chloride salts, Cellulose, 22 (4), 2391–2407.

[37] Wang, Q., Zhang, J., Shi, D., and Du, Min., 2015, Synthesis, characterization and inhibition performance of vanillin-modified chitosan quaternary ammonium salts for Q235 steel corrosion in HCl solution, J. Surfactants Deterg., 18 (5), 825–835.

[38] Kaya, I., Bilici, A., and Gül, M., 2008, Schiff base substitute polyphenol and its metal complexes derived from o-vanillin with 2,3-diaminopyridine: Synthesis, characterization, thermal, and conductivity properties, Polym. Adv. Technol., 19 (9), 1154–1163.

[39] Chauhan, N.P.S., 2014, Preparation and characterization of bio-based terpolymer derived from vanillin oxime, formaldehyde, and p-hydroxyacetophenone, Des. Monomers Polym., 17 (2), 176–185.

[40] García, J.M., Jones, G.O., Virwani, K., McCloskey, B.D., Boday, D.J., ter Huurne, G.M., Hom, H.W., Coady, D.J., Bintaleb, A.M., Alabdulrahman, A.M.S., Alsewailem, F., Almegren, H.A.A.and Hedrick, J.L., 2014, Recyclable, strong thermosets and organogels via paraformaldehyde condensation with diamines, Science, 344 (6185), 732–735.

[41] Yi, L., Li, C., Huang, W., and Yan, D., 2015, Soluble polyimides from 4,4′-diaminodiphenyl ether with one or two tert-butyl pedant groups, Polymer, 80, 67–75.

[42] Shoji, E., and Nasuno, N., 2014, Synthetic route to soluble sulfonated poly(arylene sulfone imide), Polym. J., 46 (10), 694–698.

[43] Chen, B.K., Wong, J.M., Wu, T.Y., Chen, L.C., and Shih, C., 2014, Improving the conductivity of sulfonated polyimides as proton exchange membranes by doping of a protic ionic liquid, Polymers, 6 (11), 2720–2736.

[44] Samal, S., Das, R.R., Dey, R.K., and Acharya, S., 2000, Chelating resins VI: Chelating resins of formaldehyde condensed phenolic Schiff bases derived from 4,4′-diaminodiphenyl ether with hydroxybenzaldehydes–synthesis, characterization, and metal ion adsorption studies, J. Appl. Polym. Sci., 77 (5), 967–981.

[45] Lal, S., Arora, S., and Sharma, C., 2016, Synthesis, thermal and antimicrobial studies of some Schiff bases of chitosan, J. Therm. Anal. Calorim., 124 (2), 909–916.

[46] Kasaai, M.R., 2010, Determination of the degree of N-acetylation for chitin and chitosan by various NMR spectroscopy techniques: A review, Carbohydr. Polym., 79 (4), 801–810.

[47] Fang, J., Guo, X., Harada, S., Watari, T., Tanaka, K., Kita, H., and Okamoto, K., 2002, Novel sulfonated polyimides as polyelectrolytes for fuel cell application. 1. Synthesis, proton conductivity, and water stability of polyimides from 4,4‘-diaminodiphenyl ether-2,2‘-disulfonic acid, Macromolecules, 35 (24), 9022–9028.

[48] Samal, S., Das, R.R., Mohapatra, N.K., Acharya, S., and Dey, R.K., 2000, Synthesis, characterization, and metal-ion uptake studies of chelating resins derived from formaldehyde-condensed azodyes of aniline and 4,4′-diaminodiphenylmethane coupled with phenol/resorcinol, J. Appl. Polym. Sci., 77 (14), 3128–3141.

[49] He, L.H., Xue, R., Yang, D.B., Liu, Y., and Song, R., 2009, Effects of blending chitosan with PEG on surface morphology, crystallization and thermal properties, Chin. J. Polym. Sci., 27 (4), 501−510.

[50] Mujeeb, V.M.A., Alikutty, P., and Muraleedharan, K., 2014, Synthesis, characterization and vanadium (V) sorption studies on some chitosan derivatives, J. Water Process Eng., 4, 143–148.


Article Metrics

Abstract views : 7272 | views : 9714

Copyright (c) 2017 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.