Sandoval Catalina, Ortega Anakenna, Sanchez Susana A, Morales Javier, Gunther German
Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Santiago, Chile.
Departamento de Polímeros, Facultad de Química, Universidad de Concepción, Concepción, Chile.
PLoS One. 2015 Apr 23;10(4):e0123669. doi: 10.1371/journal.pone.0123669. eCollection 2015.
Reactors found in nature can be described as micro-heterogeneous systems, where media involved in each micro-environment can behave in a markedly different way compared with the properties of the bulk solution. The presence of water molecules in micro-organized assemblies is of paramount importance for many chemical processes, ranging from biology to environmental science. Self-organized molecular assembled systems are frequently used to study dynamics of water molecules because are the simplest models mimicking biological membranes. The hydrogen bonds between sucrose and water molecules are described to be stronger (or more extensive) than the ones between water molecules themselves. In this work, we studied the capability of sucrose moiety, attached to alkyl chains of different length, as a surface blocking agent at the water-interface and we compared its properties with those of polyethylenglycol, a well-known agent used for this purposes. Published studies in this topic mainly refer to the micellization process and the stability of mixed surfactant systems using glycosides. We are interested in the effect induced by the presence of sucrose monoesters at the interface (direct and reverse micelles) and at the palisade (mixtures with Triton X-100). We believe that the different functional group (ester), the position of alkyl chain (6-O) and the huge capability of sucrose to interact with water will dramatically change the water structuration at the interface and at the palisade, generating new possibilities for technological applications of these systems.
Our time resolved and steady state fluorescence experiments in pure SEs micelles show that sucrose moieties are able to interact with a high number of water molecules promoting water structuration and increased viscosity. These results also indicate that the barrier formed by sucrose moieties on the surface of pure micelles is more effective than the polyoxyethylene palisade of Triton X-100. The fluorescence quenching experiments of SEs at the palisade of Triton X-100 micelles indicate a blocking effect dependent on the number of methylene units present in the hydrophobic tail of the surfactant. A remarkable blocking effect is observed when there is a match in size between the hydrophobic regions forming the apolar core (lauryl SE/ Triton X-100). This blocking effect disappears when a mismatch in size between hydrophobic tails, exists due to the disturbing effect on the micelle core.
自然界中发现的反应器可被描述为微非均相体系,其中每个微环境中涉及的介质与本体溶液的性质相比,其行为可能有显著差异。在从生物学到环境科学的许多化学过程中,微组织聚集体中水分子的存在至关重要。自组装分子体系常被用于研究水分子的动力学,因为它们是模拟生物膜的最简单模型。据描述,蔗糖与水分子之间的氢键比水分子自身之间的氢键更强(或更广泛)。在本工作中,我们研究了连接不同长度烷基链的蔗糖部分作为水界面处表面封闭剂的能力,并将其性质与用于此目的的知名试剂聚乙二醇的性质进行了比较。关于该主题的已发表研究主要涉及胶束化过程以及使用糖苷的混合表面活性剂体系稳定性。我们感兴趣的是蔗糖单酯在界面(正、反胶束)和栅栏层(与Triton X - 100的混合物)存在时所诱导的效应。我们认为,不同的官能团(酯基)、烷基链的位置(6 - O)以及蔗糖与水相互作用的巨大能力将显著改变界面和栅栏层处的水结构,为这些体系的技术应用创造新的可能性。
我们在纯蔗糖酯胶束中进行的时间分辨和稳态荧光实验表明,蔗糖部分能够与大量水分子相互作用,促进水结构形成并增加粘度。这些结果还表明,纯胶束表面由蔗糖部分形成的屏障比Triton X - 100的聚氧乙烯栅栏层更有效。在Triton X - 100胶束栅栏层处进行的蔗糖酯荧光猝灭实验表明,封闭效应取决于表面活性剂疏水尾部中存在的亚甲基单元数量。当形成非极性核的疏水区域尺寸匹配时(月桂基蔗糖酯/Triton X - 100),观察到显著的封闭效应。当疏水尾部尺寸不匹配时,由于对胶束核心的干扰作用,这种封闭效应消失。