School of Fundamental Science, Massey University, Palmerston North, 4442, New Zealand.
The Macdiarmid Institute for Advanced Materials and Nanotechnology, Wellington, 6140, New Zealand.
Soft Matter. 2021 Sep 29;17(37):8517-8522. doi: 10.1039/d1sm00989c.
Electrostatic complexation of negatively charged polysaccharides with β-lactoglobulin (β-lg) has been shown to bolster the protein films at oil/water interfaces thereby improving emulsion stability. However, recent sub-phase exchange experiments demonstrated that highly charged polysaccharides such as low methyl-esterified pectin are complementary only if sequentially introduced to a pre-formed interfacial β-lg film. In this study, results of transient interfacial shear rheology show that, by using high-methylesterified pectins instead, complexes can be formed in pre-mixed solutions with β-lg at pH 4 that can lead to reinforced protein films at dodecane/water interfaces. Using this one-shot adsorption of such complexes, pectins as well as short chain polysaccharides like homogalacturonan nearly doubled the steady state shear elastic moduli as compared to that of a pure β-lg film. The lag times of film formation were established to be primarily decided by the charge density and pattern on the polysaccharide. Based on the results from mixed solutions of β-lg monomers, it is proposed that the polysaccharide at pH 4 strengthens the resulting interfacial layer by concatenating adsorbed β-lg molecules thereby establishing cross-links in the aqueous phase.
带负电荷的多糖与β-乳球蛋白(β-lg)的静电络合已被证明可以增强油/水界面处的蛋白质膜,从而提高乳液稳定性。然而,最近的亚相交换实验表明,只有在预先形成的界面β-lg 膜上依次引入带高电荷的多糖(如低甲酯化果胶),才会具有互补性。在这项研究中,瞬态界面剪切流变学的结果表明,使用高甲酯化果胶代替低甲酯化果胶,在 pH 值为 4 的条件下,可以在预混合的β-lg 溶液中形成复合物,从而导致十二烷/水界面处的蛋白质膜得到增强。通过这种一次性吸附复合物,可以使果胶以及短链多糖(如半乳糖醛酸聚糖)的稳态剪切弹性模量几乎增加一倍,与纯β-lg 膜相比。形成膜的滞后时间主要取决于多糖上的电荷密度和模式。基于β-lg 单体混合溶液的结果,提出在 pH 值为 4 时,多糖通过连接吸附的β-lg 分子来增强所得的界面层,从而在水相中建立交联。