REG: Surface Analytical Instrumentation for Research on Guest-Host Association Between Self-Assembled Monolayers andOrganic Adsorbates

摘要CTS-9732691 Vinay Gupta/U。的病。 寻求资金购买表面分析仪器，用于研究自组装表面和有机吸附物之间的宾主关系。 该研究提出的目的是解决有关固定在固体表面的受体分子的功能的基本问题，并了解如何支持在固体基质上的受体层的分子组织可以被操纵，以增强与有机吸附物的主客体相互作用？ 为了实现这一目标，含有受体空腔的大环有机硫化物分子将被合成用于固定在自组装单分子膜（SAMs）内。 宾主协会将在解决方案中进行调查，两种类型的选择性相互作用将是拟议的研究的重点：一个，其中包括非极性吸附物是由空间互补性与受体腔驱动;和另一个，其中极性相互作用，如氢键辅助空间匹配。 使用由大环受体分子和正烷硫醇的共吸附形成的混合自组装膜，将操纵固定化受体层的微观结构。 受体分子的表面密度和进入受体腔的空间位阻的作用将被探讨。 为了研究分子柔性的影响，将受体分子拴系到固体表面的烷基链的长度和刚性将是不同的。 为了表征与溶液接触时SAM内的结构变化，将修改商业傅里叶变换红外（FTIR）分光光度计，以进行偏振调制反射-吸附光谱（PM-FTIRRAS）。 为了监测客体-主体复合物形成的速率和幅度，将设计和设置执行表面等离子体共振（SPR）光谱的装置。 这些研究成果为具有化学和生物传感功能的超分子组装体的设计提供了理论依据。 ***

ABSTRACT CTS-9732691 Vinay Gupta/U. of Ill. Funds are sought for the purchase of surface analytical instrumentation for research on guest-host association between self-assembled surfaces and organic adsorbates. The research proposed aims to address fundamental questions regarding the function of receptor molecules immobilized at solid surfaces, and to understand how the molecular organization of receptor layers supported on solid substrates can be manipulated to enhance guest-host interaction with organic adsorbates? Towards this goal, macrocyclic organosulfide molecules containing a receptor cavity will be synthesized for immobilization within self-assembled monolayers (SAMs). Guest-host association will be investigated in solution, and two types of selective interactions will be the focus of the proposed research: one wherein the inclusion of apolar adsorbates is driven by steric complementarity with the receptor cavity; and another wherein polar interactions such as hydrogen bonding aide steric matching. Using mixed SAMs formed by coadsorption of the macrocyclic receptor molecules and n-alkanethiols, the microscopic structure of the immobilized receptor layers will be manipulated. Role of surface density of receptor molecules and steric barriers in accessing the receptor cavity will be explored. To investigate the influence of molecular flexibility, the length and rigidity of alkyl chains that tether receptor molecules to solid surfaces will be varied. For characterization of the structural changes within the SAMs when in contact with solutions, a commercial Fourier transform infrared (FTIR) spectrophotometer will be modified to perform polarization-modulation reflection-adsorption spectroscopy (PM-FTIRRAS). To monitor the rate and the magnitude of guest-host complex formation, an apparatus to perform surface plasmon resonance (SPR) spectroscopy will be designed and set-up. Tangible outcomes of the research proposed are design principles for supramolecular assemblies with ef fective chemical and biosensing functions. ***