Harnessing Interfacial Phenomena at Self-Assembled Organic Ultrathin Films

这项提议的研究旨在利用有组织的、有机的、分子膜组件来开启、驱动和控制固体/液体界面的物理化学过程，从而促进纳米技术的发展。更具体地说，表面限制的电荷转移相互作用和酶反应将被用于（宏观）分子和纳米颗粒的二维组装，其次，我们将研究纳米颗粒表面曲率对不混溶有机吸附剂的自发组织和混合行为的影响。虽然酶催化反应和有机电子供体-受体化合物是公认的概念，但它们在表面化学、分子组装或纳米光刻和纳米制造方面的应用是相对较新的和未开发的。酶反应和电荷转移相互作用是潜在的有用工具。这些提供了对分子界面组装和材料加工的化学特异性控制，可以在与软有机质相容的温和条件下进行。提出的研究还解决了围绕纳米结构对自组装单层膜中化学基团的组织和混溶性所起作用的知识缺陷。该研究的预期结果是通过电刺激在固/液界面可逆操纵分子和纳米颗粒的氧化还原响应相互作用，支持纳米制造的有机表面的酶定向光刻，以及对分子相分离和限制几何中的混相的物理化学理解。

The proposed research is aimed at harnessing organized, organic, molecular film assemblies to switch on, drive, and control physicochemical processes at solid/liquid interfaces in ways that will facilitate the development of nanotechnologies. More specifically, surface-confined charge-transfer interactions and enzyme reactions will be exploited for the two-dimensional assembly of (macro-)molecules and nanoparticles, and secondly, we will examine the effect of nanoparticle surface curvature on the spontaneous organization and mixing behavior of immiscible organic adsorbates. While enzyme-catalyzed reactions and organic electron-donor-acceptor compounds are well-established concepts, their application in surface chemistry, molecular assembly or nanolithography and nanofabrication is relatively new and undeveloped. Enzyme reactions and charge-transfer interactions are potentially useful tools. These offer chemically specific control over the interfacial assembly of molecules and processing of materials and can be carried out under mild conditions that are compatible with soft organic matter. The proposed research also addresses the knowledge deficit surrounding the role that nanostructure plays on the organization and miscibility of chemical groups in self-assembled monolayer films. The expected outcomes of the proposed research are redox-responsive interactions for reversibly manipulating molecules and nanoparticles at solid/liquid interfaces via electrical stimuli, enzyme-directed lithography of organic surfaces in support of nanofabrication, as well as a physicochemical understanding of molecular phase separation and miscibility in confined geometries.