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

Vinay Gupta/U。的病了。正在寻求资金购买表面分析仪器，用于研究自组装表面与有机吸附剂之间的主客关系。该研究旨在解决关于固定在固体表面的受体分子功能的基本问题，并了解如何操纵支撑在固体底物上的受体层的分子组织以增强与有机吸附剂的客-主相互作用。为了实现这一目标，将合成含有受体腔的大环有机硫化物分子，并将其固定在自组装单层（SAMs）中。将在溶液中研究客-主关联，两种类型的选择性相互作用将是拟议研究的重点：其中极性吸附物的包含是由与受体腔的空间互补驱动的；另一种是氢键等极性相互作用辅助空间匹配。利用大环受体分子与正烷硫醇共吸附形成的混合SAMs，可以对固定化受体层的微观结构进行调控。受体分子的表面密度和位阻在进入受体腔中的作用将被探讨。为了研究分子柔韧性的影响，将受体分子连接到固体表面的烷基链的长度和刚性将会改变。为了表征SAMs与溶液接触时的结构变化，将对商用傅里叶变换红外（FTIR）分光光度计进行改进，以执行偏振调制反射-吸附光谱（PM-FTIRRAS）。为了监测主客复合物形成的速率和大小，将设计和建立一个表面等离子体共振（SPR）光谱装置。提出的具体研究成果是具有有效化学和生物传感功能的超分子组件的设计原则。＊＊＊

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. ***