Aalto University School of Chemical Technology, Department of Forest Products Technology, P.O. Box 16300, 00076 Aalto, Finland.
Carbohydr Polym. 2014 Jan 16;100:107-15. doi: 10.1016/j.carbpol.2012.11.063. Epub 2012 Nov 29.
Cellulosic substrates were modified by using sequential adsorption of functionalized carboxymethyl cellulose (CMC) and "click" chemistry in aqueous media. First, the effect of degree of substitution (DS), and level of functionalization as well as ionic strength of the medium were systematically investigated in situ by using quartz crystal microbalance with dissipation (QCM-D) in terms of the extent of adsorption of propargyl and azido functionalized CMC. It was found that the functionalization of CMC did not prevent its adsorption on cellulose. However, it was only effective in the presence of electrolytes. Moreover, the adsorption was found to be more efficient for the functionalized CMCs with low initial DS. Next, "click" chemistry, copper (I)-catalyzed azide-alkyne cycloaddition reaction (CuAAC), was carried out for covalent attachment of different molecules on the pre-functionalized ultrathin cellulose films. The modified cellulosic surfaces were further characterized using AFM imaging and XPS. Finally, the method was successfully used in modification of nanofibrillar cellulose (NFC) in aqueous media.
纤维素底物通过在水介质中顺序吸附功能化羧甲基纤维素(CMC)和“点击”化学进行修饰。首先,通过使用石英晶体微天平(QCM-D)原位研究了取代度(DS)和功能化水平以及介质离子强度对炔丙基和叠氮功能化 CMC 吸附程度的影响。结果发现,CMC 的功能化并不妨碍其在纤维素上的吸附。然而,它只有在存在电解质的情况下才有效。此外,对于初始 DS 较低的功能化 CMC,吸附被发现更有效。接下来,进行铜(I)催化的叠氮-炔环加成反应(CuAAC)进行“点击”化学,以将不同的分子共价连接到预功能化的超薄纤维素膜上。使用 AFM 成像和 XPS 进一步对修饰的纤维素表面进行了表征。最后,该方法成功地用于水介质中纳米纤维纤维素(NFC)的修饰。