Quantitative Insights on Environmental Implications of Functionalizing Fullerenes

摘要#1235916Kim，JaehongC60是一种独特的全碳球体家族中最常见和最稳定的形式，被称为巴克明斯特富勒烯，或简称富勒烯。虽然过去的环境研究大多集中在原始的C60上，但对富勒烯进行化学修饰变得越来越常见，这使得评估它们作为富勒烯衍生物的潜在环境影响变得困难。经过化学修饰或功能化的C60为包括水和表面消毒的生物杀菌材料在内的不同领域提供了巨大的应用机会，这是因为C60的S具有调节光能转移到环境氧的独特性质，产生活性单线态氧(1O2)。然而，1O2的产生也会在无意中释放到环境中时对生物系统产生负面影响。由于C60非常不溶于水，它会形成稳定的纳米级聚集体，从而失去产生1O2的能力。然而，人们已经发现，功能化的C60可以使C60在水中实现更多的分散，并产生1O2。这些性质受到附着在富勒烯笼子上的化学官能团的类型和数量的强烈影响，但到目前为止还没有对富勒烯聚集体的光化学活性和官能化之间的关系进行系统的研究。智力优势：本项目将研究一系列富勒烯衍生物，以更好地了解C60的官能化与其对环境和应用感兴趣的关键性质之间的关系。这些特性包括在可见光和UVA范围内对光的吸收，将能量转移到氧气并产生1O2的能力，水溶性或作为聚集体分散的能力，以及与微生物的表面相互作用。利用一套分析技术和微生物学工具，制定了实验计划，以检查(1)物理和化学性质；(2)光化学性质；(3)抗菌和抗病毒性质的动力学和机理。这项拟议的研究是为根据富勒烯衍生物的官能化程度预测其在水中的性质奠定基础的首批研究之一，并将大大有助于在环境影响的背景下推进富勒烯功能化的知识。本研究还将为功能化富勒烯在环境修复中的利用提供必要的信息。朝着这些目标迈出的现实的第一步将是检查选定的富勒烯衍生物的关键关系，这些关系在可用性和商业化潜力方面具有极其重要的意义。更广泛的影响：教育研究生是拟议项目的一个组成部分，国际学生联合会打算在代表性不足的群体中招收学生。该项目将在合格专业人员短缺的新兴领域培训学生。这些学生将获得纳米化学、光化学和环境工程应用的跨学科经验。该项目还将利用现有的高中生暑期实习计划。

Abstract#1235916Kim, JaehongC60 is the most common and stable form of a unique family of all-carbon spheroids known as Buckminsterfullerenes, or fullerenes for short. While past environmental studies mostly focused only on pristine C60, it is becoming more common to chemically modify fullerenes, which makes it difficult to assess their potential environmental impacts as fullerene derivatives. Chemically modified, or functionalized, C60 provides tremendous opportunities for applications in diverse fields including biocidal materials for water and surface disinfection, due to C60's unique property of mediating the transfer of light energy to ambient oxygen, producing reactive singlet oxygen (1O2). The production of 1O2, however, can also have negative consequences to biological systems upon unintended release into the environment. Since C60 is very insoluble in water, it forms stable, nano-sized aggregates that lose the ability to produce 1O2. Functionalizing C60, however, has been found to allow C60 to achieve more dispersion in water and generate 1O2. These properties are strongly affected by the type and the number of chemical functional groups attached to the fullerene cage, yet no systematic studies have been conducted on the relationship between photochemical activity and functionalization of fullerene aggregates to date.Intellectual Merit: This project will examine a series of fullerene derivatives to better understand the relationship between functionalization of C60 and its key properties of interest for environmental implications and applications. Such properties include absorption of light in visible and UVA range, capability to transfer energy to oxygen and produce 1O2, water solubility or ability to disperse as aggregates, and surface interactions with microorganisms. Experimental plans were developed to examine (1) physical and chemical properties; (2) photochemical properties; and (3) kinetics and mechanisms of antibacterial and antiviral properties, using a suite of analytical techniques and microbiological tools. The proposed study is one of the first studies to establish a foundation for predicting the properties of fullerene derivatives in water based on their functionalities and will significantly contribute to advancing knowledge on functionalizing fullerene in the context of environmental implications. This study will also provide the necessary information for the utilization of functionalized fullerenes in environmental remediation. The first, realistic step toward these goals would be examining the key relationships on a selected range of fullerene derivatives that are of utmost significance in terms of availability and commercialization potential. Broader impacts: Educating graduate students is an integral part of the proposed project and the PI intends to recruit students in underrepresented groups. This project will train students in an emerging area where qualified professionals are in short supply. These students will gain interdisciplinary experience with applications of nanochemistry, photochemistry and environmental engineering. The project will also leverage an existing high school student summer internship program.