Mahaninia Mohammad H, Wilson Lee D
Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, SK S7N 5C9, Canada.
Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, SK S7N 5C9, Canada.
J Colloid Interface Sci. 2017 Jan 1;485:201-212. doi: 10.1016/j.jcis.2016.09.031. Epub 2016 Sep 17.
A systematic experimental study is reported that provides a molecular based understanding of cross-linked chitosan beads and their adsorption properties in aqueous solution containing phosphate dianion (HPO) species. Synthetically modified chitosan using epichlorohydrin and glutaraldehyde cross-linkers result in surface modified beads with variable hydrophile-lipophile character and tunable HPO uptake properties. The kinetic and thermodynamic adsorption properties of cross-linked chitosan beads with HPO species were studied in aqueous solution. Complementary structure and physicochemical characterization of chitosan beads via potentiometry, Raman spectroscopy, DSC, and dye adsorption measurements was carried out to establish structure-property relationships. The maximum uptake (Q) of bead systems with HPO at equilibrium was 52.1mgg; whereas, kinetic uptake results for chitosan bead/phosphate systems are relatively rapid (0.111-0.113min) with an intraparticle diffusion rate-limiting step. The adsorption process follows a multi-step pathway involving inner- and outer-sphere complexes with significant changes in hydration. Phosphate uptake strongly depends on the composition and type of cross-linker used for preparation of chitosan beads. The adsorption isotherms and structural characterization of bead systems illustrate the role of surface charge, hydrophile-lipophile balance, adsorption site accessibility, and hydration properties of the chitosan bead surface.
本文报道了一项系统的实验研究,该研究基于分子层面,对交联壳聚糖珠及其在含有磷酸二阴离子(HPO)物种的水溶液中的吸附特性进行了研究。使用环氧氯丙烷和戊二醛交联剂对壳聚糖进行合成改性,得到了具有可变亲水亲油特性和可调HPO吸附性能的表面改性珠。在水溶液中研究了交联壳聚糖珠与HPO物种的动力学和热力学吸附特性。通过电位滴定法、拉曼光谱、差示扫描量热法和染料吸附测量对壳聚糖珠进行了互补的结构和物理化学表征,以建立结构-性能关系。平衡时,珠体系对HPO的最大吸附量(Q)为52.1mg/g;而壳聚糖珠/磷酸盐体系的动力学吸附结果相对较快(0.111-0.113min),存在颗粒内扩散速率限制步骤。吸附过程遵循多步途径,涉及内球和外球配合物,水合作用有显著变化。磷酸盐的吸附强烈依赖于用于制备壳聚糖珠的交联剂的组成和类型。珠体系的吸附等温线和结构表征说明了壳聚糖珠表面的表面电荷、亲水亲油平衡、吸附位点可及性和水合性能的作用。