Control of the Supramolecular Assembly Behavior of Fullerene-Based Surfactants

这项建议旨在了解两亲富勒烯表面活性剂在不同环境中的超分子组装规律，以调节富勒烯聚集体的大小、形状和纳米结构，以期在先进技术和生物医学中得到应用。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(如甲苯)中的水诱导自组装；(3)富勒烯表面活性剂在相反电荷水凝胶网络链的约束下的诱导超分子组装。前两个系统的目标将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、非常疏水的富勒烯球上对亲水侧链进行分子剪裁)以及水/油比关联起来。从电荷位置、电荷数目、电荷表面积、亲水性聚乙二醇链间隔基团的长度和数目等方面，研究了6种对亲水侧链分子性质有系统变化的表面活性剂。第三个体系的目标是开发一种新的方法，通过反电荷型聚合物水凝胶网络链的约束来制备富勒烯表面活性剂的结晶状、长程、高度有序的超分子组装。研究了三种不同聚乙二醇链间距和聚乙二醇侧链数的富勒烯表面活性剂在不同凝胶网链性质(包括链柔性、电荷密度和交联度)约束下的超分子组装行为。C60富勒烯及其衍生物因其独特的光物理和电化学性质、HIV酶抑制能力和低毒性而被广泛开发为潜在的电子、光学和生物医学材料。然而，富勒烯在极性介质中的低溶解度和聚集态的难以控制一直是从富勒烯制备先进应用新材料的主要障碍。在有机化学和高分子化学项目的支持下，斯坦顿岛CUNY学院化学系的周水勤教授正在探索控制富勒烯聚集的因素。这项研究的成功完成将使材料科学家能够(1)通过定制亲水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出与材料功能有关的明确的纳米结构；(2)通过对具有不同分子构型的富勒烯表面活性剂(例如，刚性的、形状受限的疏水球)的超分子组装的基本了解，为一般胶体科学的范围增加新的基础知识；通过文献研究、实验设计、先进仪器操作和计算机数据处理等方面的培训，加强参与研究的研究生和本科生的研究活动和教学方法。

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.