Fluorescent imino and secondary amino chitosans as potential sensing biomaterials

Abstract

A variety of fluorescent imino and secondary amino chitosans were synthesized under very mild conditions by reaction of the biopolymer amino functions with aromatic aldehydes in an acidified methanolic suspension. Simultaneous reactions of several aldehydes with chitosan were successfully carried out, and kinetic studies showed that 1-pyrenecarboxaldehyde reacts the fastest among them. An unprecedented study on the evaluation of the degree of N-substitution (DS, ranging from 31.7% to 12.0%) for the chitosan Schiff bases by using solid state CPMAS (13)C NMR is performed. A linear correlation between the DS obtained for the secondary amino chitosans by (1)H NMR (55.3-10.2%) and those obtained by CPMAS (13)C NMR (34.4-13.8%) has allowed us to calculate an empirical correlation factor that could be applied on chitosan-based aromatic systems. The new chiral-labelled chitosan derivatives exhibit a stable fluorescent behaviour, which was used to explore solvent sensoring applications.

Keywords: 1-Pyrenecarboxaldehyde (PubChem CID: 232848); 4-Hydroxybenzaldehyde (PubChem CID: 126); 4-N,N-Dimethylamino-1-naphthaldehyde (PubChem CID: 608052); 4-N,N-Diphenylaminobenzaldehyde (PubChem CID: 77846); 4-Nitrobenzaldehyde (PubChem CID: 541); Biphenyl-4-carboxaldehyde (PubChem CID: 76689); Chitosan; Chitosan Schiff Bases; Fluorescence; Secondary Amino Chitosans; Sensing biomaterials; Solid state NMR.