Stable Organic Interfaces Having Unnatural Compositions: Nanoscale Control of Heterogeneity

休斯顿大学的T. Randall Lee教授得到了化学系大分子、超分子和纳米化学项目的支持，设计和合成新的有机化学试剂。提出的研究的一个主要目标是调整薄有机涂层的化学成分，以提供自然界中没有的成分的表面。考虑到所针对的独特组合物，涂层很可能是非粘性的，因此不仅可用于涂层电子设备（例如，超薄手机，笔记本电脑和平板电视），还可用于人造植入物（例如，心脏支架）和用于医疗应用的纳米颗粒（例如，癌症治疗）。在资助期间，PI寻求通过一些教育/外展活动来扩大妇女和少数民族的参与，包括韦尔奇暑期学者项目、休斯敦大学STEM中心、美国国家科学基金会支持的休斯顿路易斯斯托克斯少数民族参与联盟（H-LSAMP）项目，以及对当地高中生的校园访问和研究指导。提出的研究旨在设计、合成和利用多齿吸附剂在金上生成非自然的“冲突”自组装单层（sam）。强调了当前技术感兴趣的三个系统：(1)设计和合成多齿吸附剂，用于制造高度稳定的薄膜涂层，具有相不相容或结构不同的化学实体的独特控制表面组成，以产生均匀混合的异质“冲突”界面；(2)使用特定的氟化吸附质分子生成具有明确定义的组成和结构的纳米级薄膜，其最终目标是确定构建具有可控疏水性、抗粘附性和润滑性的有机界面所需的关键元素（例如，最小氟化程度）；(3)薄膜结构的生成和研究，包括表面接枝的低聚薄膜，其中末端官能团模拟工业相关聚合物的骨架，目的是评估定义良好的聚合物表面的界面性质和反应性。目标多齿状吸附剂提供的优势包括，其薄膜的稳定性明显高于正烷硫醇，这在一定程度上导致了纳米级润滑、耐腐蚀性、纳米颗粒稳定性和抗粘合剂涂层的进步。此外，由于多齿状吸附剂的表面迁移率有限，这些具有不同化学尾基的吸附剂的混合单层提供了“冲突”的有机纳米级涂层，具有定制的化学非均质性和可控的纳米级粗糙度。

Professor T. Randall Lee of the University of Houston is supported by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry to design and synthesize new organic chemical agents. A major goal of the proposed research is to tune the chemical composition of thin organic coatings to afford surfaces with compositions that are not found in nature. Given the unique compositions targeted, the coatings are likely to be extraordinarily non-adhesive and therefore useful for coating not only electronic devices (e.g., ultrathin cell phones, laptops, and flat-screen televisions), but also artificial implants (e.g., heart stents) and nanoparticles for medical applications (e.g., cancer therapy). During the grant period, the PI seeks to broaden the participation of women and minorities through several educational/outreach activities, including the Welch Summer Scholars program, the UH STEM Center, the NSF-supported Houston Louis Stokes Alliance for Minority Participation (H-LSAMP) program, and visits to campus and research mentoring for local high school students. The proposed research seeks to design, synthesize, and utilize multidentate adsorbates for the generation of unnatural "conflicted" self-assembled monolayers (SAMs) on gold. Three systems of current technological interest are emphasized: (1) the design and synthesis of multidentate adsorbates for fabricating highly stable thin-film coatings with uniquely controlled surface composition of chemical entities that are either phase incompatible or structurally dissimilar, for the purpose of generating homogeneously mixed heterogeneous "conflicted" interfaces; (2) the use of specifically fluorinated adsorbate molecules to generate nanoscale films having well-defined composition and structure, with an ultimate goal of defining the critical elements (e.g., minimum degree of fluorination) needed to construct organic interfaces with controlled hydrophobicity, anti-adhesiveness, and lubricity; and (3) the generation and study of thin-film architectures, including surface-grafted oligomeric films, in which the terminal functional groups mimic the backbones of industrially relevant polymers, with the goal of evaluating the interfacial properties and reactivity of well-defined polymer surfaces. Advantages offered by the targeted multidentate adsorbates include films with markedly greater stability than those derived from n-alkanethiols, leading in part to advances in nanoscale lubrication, corrosion resistance, nanoparticle stabilization, and anti-adhesive coatings. Furthermore, due to the restricted surface mobility of the multidentate adsorbates, mixed monolayers of these adsorbates functionalized with disparate chemical tailgroups offer "conflicted" organic nanoscale coatings with tailored chemical heterogeneity and controlled nanoscale roughness.