Institute of Chemistry, Karl-Franzens-University Graz, Graz, Austria.
Langmuir. 2012 Aug 7;28(31):11440-7. doi: 10.1021/la302110a. Epub 2012 Jul 23.
The adsorption of carboxymethyl cellulose (CMC), one of the most important cellulose derivatives, is crucial for many scientific investigations and industrial applications. Especially for surface modifications and functionalization of materials, the polymer is of interest. The adsorption properties of CMC are dependent not only on the solutions state, which can be influenced by the pH, temperature, and electrolyte concentration, but also on the chemical composition of the adsorbents. We therefore performed basic investigation studies on the interaction of CMC with a variety of polymer films. Thin films of cellulose, cellulose acetate, deacetylated cellulose acetate, polyethylene terephthalate, and cyclo olefin polymer were therefore prepared on sensors of a QCM-D (quartz crystal microbalance) and on silicon substrates. The films were characterized with respect to the thickness, wettability, and chemical composition. Subsequently, the interaction and deposition of CMC in a range of pH values without additional electrolyte were measured with the QCM-D method. A comparison of the QCM-D results showed that CMC is favorably deposited on pure cellulose films and deacetylated cellulose acetate at low pH values. Other hydrophilic surfaces such as silicon dioxide or polyvinyl alcohol coated surfaces did not adsorb CMC to a significant extent. Atomic force microcopy confirmed that the morphology of the adsorbed CMC layers differed depending on the substrate. On hydrophobic polymer films, CMC was deposited in the form of larger particles in lower amounts whereas hydrophilic cellulose substrates were to a high extent uniformly covered by adsorbed CMC. The chemical similarity of the CMC backbone seems to favor the irreversible adsorption of CMC when the molecule is almost uncharged at low pH values. A selectivity of the cellulose CMC interaction can therefore be assumed. All CMC treated polymer films exhibited an increased hydrophilicity, which confirmed their modification with the functional molecule.
羧甲基纤维素(CMC)是最重要的纤维素衍生物之一,其吸附作用对于许多科学研究和工业应用至关重要。特别是对于材料的表面改性和功能化,该聚合物具有重要意义。CMC 的吸附性能不仅取决于溶液状态,溶液状态可以受到 pH 值、温度和电解质浓度的影响,还取决于吸附剂的化学组成。因此,我们对 CMC 与各种聚合物薄膜的相互作用进行了基础研究。为此,我们在石英晶体微天平(QCM-D)传感器和硅衬底上制备了纤维素、醋酸纤维素、脱乙酰化醋酸纤维素、聚对苯二甲酸乙二醇酯和环烯烃聚合物的薄膜。这些薄膜的厚度、润湿性和化学组成都进行了表征。随后,我们使用 QCM-D 方法测量了在没有额外电解质的情况下,CMC 在一系列 pH 值下的相互作用和沉积情况。对 QCM-D 结果的比较表明,在低 pH 值下,CMC 有利于沉积在纯纤维素薄膜和脱乙酰化醋酸纤维素上。其他亲水表面,如二氧化硅或聚乙烯醇涂层表面,并没有显著吸附 CMC。原子力显微镜证实,吸附 CMC 层的形态取决于基底。在疏水性聚合物薄膜上,CMC 以较少的量以较大颗粒的形式沉积,而亲水纤维素基底则以较大程度被吸附的 CMC 均匀覆盖。CMC 主链的化学相似性似乎有利于在低 pH 值下,当分子几乎不带电时,CMC 的不可逆吸附。因此,可以假设纤维素与 CMC 之间存在选择性相互作用。所有经 CMC 处理的聚合物薄膜都表现出更高的亲水性,这证实了它们被功能性分子修饰。