Malaysian Journal of Analytical Sciences Vol 25 No 3 (2021): 376 - 387

 

 

 

 

 

SITE-SELECTIVE CARBOXYMETHYLATION OF CHITOSAN UNDER HETEROGENEOUS CONDITIONS

 

(Penentuan Tapak bagi Proses Pengkarboksimetil pada Kitosan dalam Keadaan Heterogen)

 

Nur Ellina Annisa Salehuddin1, Nurul Adilah Rodzali1, Ku Halim Ku Bulat2, Nadhratun Naiim Mobarak1*

 

1 Department of Chemical Sciences, Faculty of Science and Technology

Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia

2School of Fundamental Science

Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu, Malaysia

 

*Corresponding author:  nadhratunnaiim@ukm.edu.my

 

 

Received: 11 March 2021; Accepted: 22 May 2021; Published:  27 June 2021

 

 

Abstract

The substitution sites on chitosan are affected by the presence of a base. Herein, the effects of pH on the site-selective carboxymethylation of chitosan were investigated. Carboxymethyl chitosan was synthesized by reacting chitosan with monochloroacetic acid at different pH under heterogeneous conditions. Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy confirmed that carboxymethylation was successful, with the appearance of peaks around 1326-1320 cm−1 (C–N groups) and 1257-1253 cm−1 (C–O–C groups) and allowed differentiation between the carboxymethyl substitution sites on chitosan. Additionally, the peaks at approximately 3.28 and 4.12 ppm in the 1H nuclear magnetic resonance (NMR) spectra confirmed that substitution occurred at amine and hydroxyl groups, respectively. Overall, the carboxymethylation of chitosan under heterogeneous conditions at pH 8.5-11 gave O-substitution, at pH 12-13 gave N,O-substitution, and at pH 14 gave N-substitution. This pH dependence of the site-selective substitution of chitosan is important for polymer electrolyte application.

 

Keywords:  carboxymethyl chitosan, pH effect, substitution site, heterogeneous conditions

 

Abstrak

Tapak penggantian kitosan dipengaruhi oleh kehadiran bes. Dalam kajian ini, kesan pH terhadap tapak penggantian pengkarboksimetil kitosan telah dikaji. Karboksimetil kitosan disintesis melalui tindak balas kitosan dengan asid monokloroasetik pada pH berbeza dalam keadaan heterogen. Spektroskopi inframerah transformasi Fourier (ATR-FTIR) mengesahkan bahawa karboksimetilasi telah berjaya dilakukan dengan kemunculan puncak sekitar 1326–1320 cm−1 (kumpulan C–N) dan 1257–1253 cm−1 (kumpulan C–O–C), yang menunjukkan perbezaan tapak penggantian karboksimetil pada kitosan. Selain itu, puncak sekitar 3.28 dan 4.12 ppm dalam spektrum resonans magnetik nukleus (1H NMR) mengesahkan bahawa penggantian berlaku pada kumpulan amina dan hidroksil. Secara keseluruhan, karboksimetilasi kitosan dalam keadaan heterogen pada pH 8.5-11 memberikan penggantian pada tapak O, pH 12-13 memberikan penggantian pada tapak N dan O, dan pH 14 memberikan penggantian pada tapak N. Kebergantungan tapak pemilihan untuk penggantian kitosan dengan pH ini adalah penting untuk aplikasi elektrolit polimer.

 

Kata kunci:  karboksimetil kitosan, kesan pH, tapak penggantian, keadaan heterogen

 

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