Rapid Reactions of Ions and Radicals in Organized and Constrained Media: Polymer Films and Zeolites

有组织和约束介质中离子和自由基的快速反应：聚合物薄膜和沸石

• 批准号: 9610187
• 负责人: J. Kerry Thomas
• 金额: $ 49.75万
• 依托单位: University of Notre Dame
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-02-15 至 2001-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9610187&HistoricalAwards=false
• 关键词: Rapid; Reactions; Ions; Radicals; Organized

Supported by the Organic Dynamics Program, Professor Kerry Thomas of the University of Notre Dame studies rapid reactions of ions and radicals in organized and constrained media. Low-energy photochemical and high-energy radiolytic reactions of organic probe molecules held within zeolites and solid polymers permit assay of the rates of development of spectra of the resulting ions, allowing the exploration of the effects of host modification on the unique ion kinetics occurring in these systems. Small pools of organic solvents are created within the cavities of zeolites, constraining and stabilizing usually short-lived charge-separated ionic species which would otherwise be rapidly neutralized. Migration of energy and charge to probe molecules held within solid polymeric hosts is induced by excitation of the polymer. Both the zeolite and the polymer systems share a common feature, the rapid migration of energy deposited in one region to a selected region, creating chemistry at the targeted site. Fundamental questions of energy conversion, transport, and loss are at the heart of many important technological processes. Through an examination of the reactions with light and with high-energy electrons of organic molecules constrained to remain within a tightly-defined `cage` rather than freely moving in solution, Professor Thomas explores the mechanisms of formation and reaction of free electrons, organic radicals (compounds containing an odd number of electrons), and organic ions (compounds bearing either positive or negative charges). Ongoing studies target the role of the `host` both in the generation of these reactive species through the transfer of energy from the host to the organic molecules contained within it and in the moderation of the transport and reactivity of these reactive species. These studies shed light on energetic excitation processes such as those employed in x-ray photolithography, wherein high-resolution structures of use, for example, in microelectronic circuitry production, are produced through the radiation-induced formation or destruction of polymeric materials

在有机动力学计划的支持下，圣母大学的Kerry Thomas教授研究了有组织和约束培养基中离子和自由基的快速反应。 在沸石和固体聚合物中保持的有机探针分子的低能光化学和高能放射性反应允许测定所得离子的光谱的发育速率，从而探索了宿主修饰对这些系统中独特离子动力学的影响。 在沸石的空腔中产生了小的有机溶剂，这些溶剂通常会限制和稳定通常短暂的电荷分离离子物种，否则这些物种将迅速中和。 聚合物的激发诱导能量和电荷向持有固体聚合物宿主内的探针分子的迁移。 沸石和聚合物系统都具有共同的特征，即沉积在一个区域到选定区域的能量的快速迁移，在目标部位产生化学。 能源转化，运输和损失的基本问题是许多重要技术过程的核心。 通过检查光线和高能电子的有机分子的反应，被约束在紧密定义的“笼子”中，而不是在溶液中自由移动，托马斯教授探索了自由电子的形成和反应的机制，有机自由基，有机自由基（包含奇怪的电子）和有机离子的化合物（化合物）和有机离子或有机离子（构成型）。 正在进行的研究通过将能量从宿主转移到其中包含的有机分子以及这些反应性物种的传输和反应性的适度中，以“宿主”在这些反应性物种产生中的作用。 这些研究阐明了能量激发过程，例如X射线光刻术中使用的研究，其中高分辨率使用结构（例如，在微电动电路产生中）是通过辐射诱导的形成或聚合物材料的破坏而产生的。