Control of the Supramolecular Assembly Behavior of Fullerene-Based Surfactants

该提案旨在了解两亲性富勒烯表面活性剂在不同环境中的超分子组装规则，以调节富勒烯聚集体的大小，形状和纳米结构，以用于先进技术和生物医学中的预期应用。目标体系包括（1）富勒烯表面活性剂在水正相中的自组装;（2）富勒烯表面活性剂在油相中的水诱导自组装（例如，甲苯）;和（3）通过带相反电荷的水凝胶网络链的约束诱导富勒烯表面活性剂的超分子组装。前两个系统的目的是将自组装富勒烯胶体分散体的基本性质与富勒烯表面活性剂的独特分子构型（例如，在非常刚性、极疏水的富勒烯球上的亲水侧链的分子剪裁）以及水/油比相关联。六个表面活性剂的亲水性侧链的分子性质上的系统的品种将进行研究，在电荷的位置，电荷数，电荷表面积，亲水性聚乙二醇（PEG）链间隔的长度和数量。第三个系统的目标将是开发一种新的方法来制造晶体状的远程高度有序的超分子组装的富勒烯表面活性剂的相反电荷的聚合物水凝胶网络链的约束。本论文以三种不同PEG侧链长度和PEG侧链数目的富勒烯表面活性剂为研究对象，考察了它们在不同凝胶网络链性质（包括链柔性、电荷密度和交联密度）约束下的超分子组装行为。和生物医学材料，由于它们独特的物理和电化学性质、HIV酶抑制能力和低毒性。然而，富勒烯在极性介质中的低溶解度和难以控制其聚集态一直是由富勒烯制备用于高级应用的新材料的主要障碍。在有机及高分子化学计划的支持下，纽约市立大学史泰登岛学院化学系的周水琴教授正在探索控制富勒烯聚集的因素。本研究的成功完成将（1）允许材料科学家通过调整亲水性侧链附件的分子性质和调节水/油比以及特定的约束环境，从富勒烯表面活性剂的自组装中可预测地设计与材料功能相关的定义良好的纳米结构;（2）通过对具有不同分子构型的富勒烯表面活性剂的超分子组装的基本理解（例如，（3）透过有关文献研究、实验设计、先进仪器操作及电脑数据处理的训练，加强研究生及本科生的研究活动及教学方法。

This proposal aims to understand the rules of supramolecular assembly of amphiphilic fullerene surfactants in different environments to regulate the size, shape, and nanostructures of fullrene aggregates for envisioned applications in advanced technologies and biomedications. Target systems include (1) the self-assembly of fullerene surfactants in water normal phase; (2) the water-induced self-assembly of fullrene surfactants in oil phase (e.g., toluene); and (3) the induced supramolecular assembly of fullerene surfactants by a constraint of oppositely charged hydrogel network chains. The objective of the first two systems will be to correlate the fundamental properties of the self-assembled fullerene colloidal dispersions with the unique molecular configuration of fullerene surfactants (e.g, molecular tailoring of the hydrophilic side chains on a very rigid, extremely hydrophobic fullerene ball) as well as the water/oil ratios. Six surfactants with a systematic variety on the molecular properties of the hydrophilic side chains will be studied, in terms of charge location, charge number, charge surface area, hydrophilic polyethylene glycol (PEG) chain spacer length and number. The goal of the third system will be to develop a new method to fabricate crystal-like long-range highly ordered supramolecular assembly of fullerene surfactants by the constraints of oppositely charged polymer hydrogel network chains. Three fullerene surfactants with different PEG chain spacer length and PEG side chain number will be investigated to examine the supramolecular assembly behavior under the constraints of different gel network chain properties, including chain flexibility, charge density and cross-linking density.C60 fullerene and its derivatives have been intensively explored for potential electronic, optical, and biomedical materials due to their unique photophysical and electrochemical properties, HIV enzyme inhibition ability, and low toxicity. However, the low solubility of fullerenes in polar media and the difficult control of their aggregation states have been the major obstacles to fabricate new materials from fullerenes for advanced applications. With the support of the Organic and Macromolecular Chemistry Program, Professor Shuiqin Zhou, of the Department of Chemistry at CUNY College at Staten Island, is exploring the factors controlling the aggregation of fullerenes. The successful accomplishment of this study will (1) permit material scientists to predictably design well-defined nanostructures in relation to material functions from the self-assembly of fullerene surfactants by tailoring the molecular property of hydrophilic side chain appendages and tuning the water/oil ratios as well as the specific constraining environments; (2) add new basic knowledge to the scope of general colloidal science through a fundamental understanding of the supramolecular assembly of fullerene surfactants with a distinct molecular configuration (e.g., a rigid, shape-constrained, hydrophobic ball); and (3) enhance the research activities and pedagogy for participant graduate and undergraduate students through a training on literature study, experimental design, operation of advanced instruments and computer data processing.