Wydro Paweł, Krajewska Barbara, Hac-Wydro Katarzyna
Faculty of Chemistry, Jagiellonian University, 30-060 Kraków, Ingardena 3, Poland.
Biomacromolecules. 2007 Aug;8(8):2611-7. doi: 10.1021/bm700453x. Epub 2007 Jul 14.
Owing to its distinct chemico-biological properties, chitosan, a cationic biopolymer, offers a great potential in multifarious bioapplications. One such application is as a dietary antilipidemic supplement to be used to reduce obesity/overweight and to lower cholesterol. The lipid-binding efficiency of chitosan, however, remains debatable. Accordingly, in this study we investigated the interactions of chitosan with selected lipids, cholesterol and fatty acids, the latter including saturated (stearic acid) and unsaturated (oleic, linoleic, alpha-linolenic) acids. The experiments were performed with the Langmuir monolayer technique, in which surface pressure-area isotherms were recorded for the lipid monolayers spread on the acetate buffer pH 4.0 subphase in the absence and presence of chitosan. We found that the presence of chitosan in the subphase strongly influenced the shape and location of the isotherms, proving that there existed attractions between chitosan and lipid molecules. The attractions were revealed by changes of the molecular organization of the monolayers. The common feature of these changes was that all the monolayers studied underwent expansion, in each case reaching saturation with increasing chitosan concentration. In agreement with the lipid molecular structures, the highest expansions were observed for the most unsaturated fatty acids, linoleic and alpha-linolenic, the lowest for stearic acid, with oleic acid and cholesterol being the intermediate cases. By contrast, the main distinguishing feature of these changes was that, although none of the monolayers studied changed its state when completely saturated with chitosan, compared to the parent ones the compactness of the monolayers was modified. The solid monolayers of stearic acid and cholesterol were loosened, whereas those of all the unsaturated acids, liquid in nature, were tightened. On the basis of these results we tentatively propose a mechanism of the chitosan action that includes both electrostatic and hydrophobic lipid-chitosan interactions as well as hydrogen bonding between them.
壳聚糖作为一种阳离子生物聚合物,因其独特的化学和生物学性质,在多种生物应用中具有巨大潜力。其中一种应用是作为膳食抗血脂补充剂,用于减轻肥胖/超重并降低胆固醇。然而,壳聚糖的脂质结合效率仍存在争议。因此,在本研究中,我们研究了壳聚糖与选定脂质、胆固醇和脂肪酸(后者包括饱和脂肪酸(硬脂酸)和不饱和脂肪酸(油酸、亚油酸、α-亚麻酸))之间的相互作用。实验采用朗缪尔单分子层技术进行,记录了在不存在和存在壳聚糖的情况下,铺展在pH 4.0乙酸盐缓冲液亚相上的脂质单分子层的表面压力-面积等温线。我们发现亚相中壳聚糖的存在强烈影响等温线的形状和位置,证明壳聚糖与脂质分子之间存在吸引力。这些吸引力通过单分子层分子组织的变化得以揭示。这些变化的共同特征是,所有研究的单分子层都发生了膨胀,在每种情况下,随着壳聚糖浓度的增加达到饱和。与脂质分子结构一致,观察到最不饱和的脂肪酸亚油酸和α-亚麻酸膨胀最大,硬脂酸膨胀最小,油酸和胆固醇处于中间情况。相比之下,这些变化的主要区别特征是,尽管所有研究的单分子层在完全被壳聚糖饱和时都没有改变其状态,但与原始单分子层相比,单分子层的致密性发生了改变。硬脂酸和胆固醇的固体单分子层变得疏松,而所有本质上为液体的不饱和酸的单分子层则变得紧密。基于这些结果,我们初步提出了壳聚糖作用的机制,该机制包括静电和疏水的脂质-壳聚糖相互作用以及它们之间的氢键作用。