Jayawardane Dharana, Pan Fang, Lu Jian R, Zhao Xiubo
Department of Chemical and Biological Engineering, University of Sheffield, Sheffield, S1 3JD, UK.
Soft Matter. 2015 Oct 28;11(40):7986-94. doi: 10.1039/c5sm01670c. Epub 2015 Sep 2.
Recent research has reported many attractive benefits from short peptide amphiphiles. A practical route for them to enter the real world of applications is through formulation with conventional surfactants. This study reports the co-adsorption of the surfactant-like peptide, V6K, with conventional anionic and cationic surfactants at the solid/water interface. The time-dependant adsorption behaviour was examined using spectroscopic ellipsometry whilst adsorbed layer composition and structural distribution of the components were investigated by neutron reflection with the use of hydrogen/deuterium labelling of the surfactant molecules. Both binary (surfactant/peptide mixtures) and sequential (peptide followed by surfactant) adsorption have been studied. It was found that at the hydrophilic SiO2/water interface, the peptide was able to form a stable, flat, defected bilayer structure however both the structure and adsorbed amount were highly dependent on the initial peptide concentration. This consequently affected surfactant adsorption. In the presence of a pre-adsorbed peptide layer anionic sodium dodecyl sulfate (SDS) could readily co-adsorb at the interface; however, cationic dodecyl trimethyl ammonium bromide (C12TAB) could not co-adsorb due to the same charge character. However on a trimethoxy octyl silane (C8) coated hydrophobic surface, V6K formed a monolayer, and subsequent exposure to cationic and anionic surfactants both led to some co-adsorption at the interface. In binary surfactant/peptide mixtures, it was found that adsorption was dependent on the molar ratio of the surfactant and peptide. For SDS mixtures below molar unity and concentrations below CMC for C12TAB, V6K was able to dominate adsorption at the interface. Above molar unity, no adsorption was detected for SDS/V6K mixtures. In contrast, C12TAB gradually replaced the peptide and became dominant at the interface. These results thus elucidate the adsorption behaviour of V6K, which was found to dominate interfacial adsorption but its exact adsorbed amount and distribution were affected by interfacial hydrophobicity and interactions with conventional surfactants.
近期研究报道了短肽两亲分子具有诸多诱人的益处。它们进入实际应用领域的一条切实可行的途径是与传统表面活性剂进行配方。本研究报道了类表面活性剂肽V6K与传统阴离子和阳离子表面活性剂在固/水界面的共吸附情况。使用椭圆偏振光谱法研究了随时间变化的吸附行为,同时通过对表面活性剂分子进行氢/氘标记,利用中子反射研究了吸附层的组成和各组分的结构分布。对二元(表面活性剂/肽混合物)和顺序(先肽后表面活性剂)吸附都进行了研究。结果发现,在亲水性SiO₂/水界面,该肽能够形成稳定、平坦、有缺陷的双层结构,然而结构和吸附量都高度依赖于初始肽浓度。这进而影响了表面活性剂的吸附。在预先吸附的肽层存在的情况下,阴离子十二烷基硫酸钠(SDS)能够很容易地在界面共吸附;然而,阳离子十二烷基三甲基溴化铵(C12TAB)由于电荷性质相同而无法共吸附。然而在三甲氧基辛基硅烷(C8)包覆的疏水表面上,V6K形成了单层,随后暴露于阳离子和阴离子表面活性剂都会导致在界面有一定程度的共吸附。在二元表面活性剂/肽混合物中,发现吸附取决于表面活性剂和肽的摩尔比。对于SDS混合物,摩尔比低于1且C12TAB浓度低于临界胶束浓度时,V6K能够在界面吸附中占主导。摩尔比高于1时,未检测到SDS/V6K混合物有吸附。相反,C12TAB逐渐取代肽并在界面占主导。因此,这些结果阐明了V6K的吸附行为,发现其在界面吸附中占主导,但其确切的吸附量和分布受到界面疏水性以及与传统表面活性剂相互作用的影响。