Tiera Marcio J, Qiu Xing-Ping, Bechaouch Sofiane, Shi Qin, Fernandes Júlio C, Winnik Françoise M
Departamento de Química e Ciências Ambientais, UNESP-Universidade Estadual Paulista, São José do Rio Preto, Brazil.
Biomacromolecules. 2006 Nov;7(11):3151-6. doi: 10.1021/bm060381u.
A polymer analogous synthesis involving the reductive amination of phosphorylcholine (PC)-glyceraldehyde with primary amines of deacetylated chitosan (M(w) approximately 57000 g mol(-1)) was used to prepare phosphorylcholine-substituted chitosans (PC-CH) with a degree of substitution (DS) ranging from approximately 11 to approximately 53 mol % PC-substituted glucosamine residues. The PC-CH derivatives were characterized by (1)H NMR spectroscopy, FTIR spectroscopy, and multiangle laser light scattering gel permeation chromatography (MALLS-GPC). The pK(a) of the PC-substituted amine groups (pK(a) approximately 7.20) was determined by (1)H NMR titration. The PC-CH samples (1.0 g L(-1)) were shown to be nontoxic using an MTT assay performed with human KB cells. Aqueous solutions of PC-CH samples (4.0 g L(-1)) of DS >or= 22 mol % PC-substituted glucosamine residues remained clear, independently of pH (4.0 < pH < 11.0). The remarkable water solubility and nontoxicity displayed by the new PC-CH samples open up new opportunities in the design of chitosan-based biomaterials and nanoparticles.
采用一种聚合物类似物合成方法，即通过磷酰胆碱（PC）-甘油醛与脱乙酰壳聚糖（分子量约为57000 g·mol⁻¹）的伯胺进行还原胺化反应，制备了取代度（DS）在约11至约53 mol%的磷酰胆碱取代壳聚糖（PC-CH），该取代度基于被PC取代的葡糖胺残基。通过¹H NMR光谱、FTIR光谱和多角度激光光散射凝胶渗透色谱（MALLS-GPC）对PC-CH衍生物进行了表征。通过¹H NMR滴定法测定了PC取代胺基的pKₐ（pKₐ约为7.20）。使用人KB细胞进行MTT试验表明，PC-CH样品（1.0 g·L⁻¹）无毒。取代度≥22 mol%（基于被PC取代的葡糖胺残基）的PC-CH样品（4.0 g·L⁻¹）的水溶液，无论pH值（4.0＜pH＜11.0）如何，均保持澄清。新型PC-CH样品所表现出的显著水溶性和无毒特性，为基于壳聚糖的生物材料和纳米颗粒的设计开辟了新的机遇。
