Bordenave Nicolas, Grelier Stéphane, Coma Véronique
Université Bordeaux 1, INRA, CNRS, UMR 5103 US2B, 351 cours de la Libération, F-33405 Talence, France.
Biomacromolecules. 2008 Sep;9(9):2377-82. doi: 10.1021/bm800375v. Epub 2008 Aug 14.
The specific C-6 oxidation by TEMPO of chitosan and chitosan derivatives were studied to obtain tailored bioactive biopolymers. The modifications on chitosan presented many difficulties and showed the adverse effect of the amine moieties of chitosan on this reaction. Thus, protections of the amino groups by N-acetylation or N-phthaloylation were studied and followed by the C-6 specific oxidations of the resulting polymers. The desired 6-carboxychitosan could not be obtained after deprotection; the reactions with TEMPO led to degradation of the polymers. The specific oxidation of a potentially bioactive derivative of chitosan was then achieved by the oxidation of a quaternized chitosan: N, N, N-trimethylchitosan. N, N, N-Trimethyl-6-carboxychitosan was characterized by FTIR spectroscopy, 1H, and 13C NMR spectroscopy.
研究了壳聚糖及其衍生物通过TEMPO进行的特定C-6氧化反应，以获得定制的生物活性生物聚合物。壳聚糖的改性存在许多困难，并且显示出壳聚糖的胺基对该反应的不利影响。因此，研究了通过N-乙酰化或N-邻苯二甲酰化对氨基进行保护，然后对所得聚合物进行C-6特异性氧化。脱保护后无法获得所需的6-羧基壳聚糖；与TEMPO的反应导致聚合物降解。然后通过季铵化壳聚糖：N，N，N-三甲基壳聚糖的氧化实现了壳聚糖潜在生物活性衍生物的特异性氧化。通过FTIR光谱、1H和13C NMR光谱对N，N，N-三甲基-6-羧基壳聚糖进行了表征。
