ABSTRACT
In order to synthesize a promising material for developing a novel peptide/protein delivery system, guanidinylation of chitooligosaccharides with 1-amidinopyrazole hydrochloride was investigated herein. The production of guanidinylated chitooligosaccharides was demonstrated by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), and elemental analyses. Interestingly, we found that the reducing end in the guanidinylated chitooligosaccharides was converted to a cyclic guanidine structure (2-[(aminoiminomethyl)amino]-2-deoxy-d-glucose structure). This reaction was carefully proven by the guanidinylation of d-glucosamine. Although this is not the first report on the synthesis of the 2-[(aminoiminomethyl)amino]-2-deoxy-d-glucose, it has provided a rational synthetic route using the high reactivity of the reducing end. Furthermore, we found that the interaction between chitooligosaccharides and bovine serum albumin is weak when in a neutral pH environment; however, it is significantly improved by guanidinylation. The guanidinylated chitooligosaccharides are useful not only for the development of a novel drug delivery system but also as a chitinase/chitosanase inhibitor and an antibacterial agent.
Subject(s)
Chitin/analogs & derivatives , Guanidine/metabolism , Serum Albumin, Bovine/metabolism , Animals , Cattle , Chitin/chemistry , Chitin/metabolism , Chitosan , Cyclization , Guanidine/chemistry , Molecular Structure , Oligosaccharides , Oxidation-Reduction , Protein Binding , Serum Albumin, Bovine/chemistryABSTRACT
We introduce a simple method for producing guanidinylation of chitosan (CS) with 1amidinopyrazole hydrochloride (AP). Production of GCS is proved via NMR, IR, and elemental analyses. In a reaction using 4.5â¯eq of AP for 7â¯days at room temperature, we obtained GCS with 42.3% of degree of guanidinylation (DG). The DG value can be controlled by the reaction time and AP amount. Furthermore, remarkable enhancement of the interaction between GCS and bovine serum albumin by guanidinylation was observed. This simple guanidinylation method for CS could provide novel additives for protein/peptide delivery systems.
