Synthesis and fluorescent property of carboxymethyl chitosan with different degrees of carboxymethylation and its application for fluorescence turn-on detection of Cd(II) ion.

Recently, carboxymethyl chitosan (CMCS) has proved to be an intrinsically fluorescent material with aggregation-induced emission characteristic. In order to elucidate the influence of CMCS's chemical structure and solution behavior on its fluorescent intensity, two series of CMCS with different degrees of carboxymethylation (DCM) are synthesized by adjusting the mass ratio of monochloroacetic acid and sodium hydroxide to chitosan at various reaction temperature and time, and then characterized using Fourier-transform infrared spectroscopy and nuclear magnetic resonance. Their solution behaviors at different pH values are studied via zeta potential and ultraviolet-visible measurements. The data reveal that the isoelectronic point (IEP) of a CMCS decreases with increasing DCM, and all the CMCSs have good water solubility at pH range below their IEPs. Fluorescence spectra indicate that a CMCS shows the highest fluorescent intensity in a slightly acidic environment next to its IEP, and the photoluminescence of a CMCS solution increases significantly after heat treatment above T = 70 °C. Furthermore, we compare for the first time the use of heated CMCS solutions for the fluorescence turn-on detection of cadmium ion in pure and tap water, respectively. The limit of detection is found to be ca. 1 μM for the Cd in pure water.