Collaborative Research in Nanostructure Control via Surfactant Mixing and Polymerization

特拉华大学/加州大学圣巴巴拉分校摘要 - 0436195/0436124项目摘要大部分纳米技术致力于在表面上创建二维结构。然而，学习仿生自组装的组成-结构-功能关系将产生纳米级、三维囊泡结构，用于特定任务，包括药物输送、催化、特异性识别等。该提案基于我们小组的专业知识，将纳米结构的物理和化学与生物学的自组装和特定识别过程相结合，解决了推进聚合物和表面活性剂功能纳米容器自组装所需的科学和工程。基本主题集中在带相反电荷的表面活性剂和/或水溶助长剂自组装成单层囊泡，该单层囊泡可以通过聚合固定，产生可以进一步功能化的稳定的中空胶囊。具体目标是： 1．研究可聚合表面活性剂与有机和无机单体形成的囊泡的形成和聚合，以最好地保留模板囊泡的尺寸、形状和多分散性；2．添加嵌段共聚物来修改和控制囊泡特性，以调整自发曲率（大小）、弯曲弹性（多分散性）和囊泡之间的空间相互作用（稳定性）。特别是，将配制可聚合阴离子和阳离子表面活性剂与可能产生单分散囊泡系统的共聚物的接近等摩尔的混合物；3．检查表面活性剂和水溶助长剂（弱表面活性、两亲性和高水溶性有机盐）混合物中形成的囊泡的新特性，并探究 pH 或光照变化引起的微观结构变化。项目 1 将涉及由 Kaler 小组在美国特拉华州进行的合成和配制，以及由 Zasadzinski 小组在加州大学圣巴巴拉分校进行的显微镜表征。项目 2 所需的配方将在 UCSB 完成，Zasadzinski 小组将使用光散射和电子显微镜进行表征，Kaler 小组将使用中子自旋回波和中子散射进行表征。项目 3 将由 Kaler 小组在美国特拉华州启动，其特点是由 Zasadzinski 小组完成的显微镜检查。时间从3年减少到2年，会导致我们项目无法走得那么远；然而，所有的具体目标都将受到审查，并确定最有前途的路线。 智力优点：带相反电荷的表面活性剂和水溶助长剂的自组装开辟了仿生结构的探索新领域，并可能将囊泡形成过程置于热力学控制之下。利用热力学控制意味着能够通过简单、廉价的去污剂的简单操作来确定囊泡的尺寸、多分散性、稳定性等。 固定此类结构的化学反应（即聚合）开辟了形成保留模板纳米结构的纳米级材料的新方法。拟议的工作扩展并联系了这两个领域，并将提供新颖的实验观察和进一步的理论理解。技术影响：表面活性剂配方，特别是表面活性剂混合物，广泛用于许多工业过程中。通过混合表面活性剂或添加水溶助剂来控制表面活性剂微观结构的能力可以为新型有机和无机材料（例如聚合物乳胶和分子筛）提供新的有机模板。廉价地制造聚合囊泡可以为印刷或农业应用中的大量使用开辟道路。使用由生物表面活性剂制成的自发囊泡将带来有用的药物应用。控制囊泡的聚集和融合对于药物递送方案至关重要，最小化游离表面活性剂浓度也是如此。更广泛的影响：这项工作的科学方面将通过开发和理解其热力学和机械特性（包括其平衡状态的性质）来发现新​​的纳米级表面活性剂结构。对这些混合物的研究已经导致人们对自组装的许多基本原理进行了富有成效的重新审视。对有机和无机聚合的研究可以开辟制造新材料的方法，其应用范围可能超出上述范围。参与这项工作的本科生和研究生将接触到一系列表征工具和适当的分析方法，从而为该领域的学术或工业工作做好准备。 K-12 学生将接触到与这项工作相关的概念，包括表面活性剂和聚合物特性以及纳米技术元素。时间减少效果声明：我们提出了三个具体目标：1。研究由可聚合表面活性剂与有机和无机单体形成的囊泡的形成和聚合，以最好地保留模板囊泡的尺寸、形状和多分散性；2．添加嵌段共聚物来修改和控制囊泡特性，以调整自发曲率（尺寸）、弯曲弹性（多分散性）和囊泡之间的空间相互作用（稳定性）。特别是，将配制可聚合阴离子和阳离子表面活性剂与可能产生单分散囊泡系统的共聚物的接近等摩尔的混合物；3．检查表面活性剂和水溶助长剂（弱表面活性、两亲性和高水溶性有机盐）混合物中形成的囊泡的新特性，并探测由 pH 或光照变化引起的微观结构变化。项目 1 将涉及由 Kaler 小组在美国特拉华州进行的合成和配制，以及由 Zasadzinski 小组在加州大学圣巴巴拉分校进行的显微镜表征。项目 2 所需的配方将在 UCSB 完成，Zasadzinski 小组将使用光散射和电子显微镜进行表征，Kaler 小组将使用中子自旋回波和中子散射进行表征。项目 3 将由 Kaler 小组在美国特拉华州发起，其特点是由 Zasadzinski 小组完成的显微镜检查。时间从3年减少到2年，会导致我们项目无法进行得那么远；然而，所有具体目标都将在某种程度上得到审查，并为后续提案确定最有希望的路线。

University of Delaware/ University of California Santa BarbaraABSTRACT - 0436195/0436124Project SummaryMuch of nanotechnology is devoted to creating two-dimensional structures on surfaces. However,learning the composition-structure-function relationships for biomimetic self-assembly will lead to nanoscale, three-dimensional vesicle structures for specific tasks including drug delivery, catalysis, specific recognition, among others. This proposal addresses the science and engineering needed to advance the self-assembly of functional nano-containers of polymers and surfactants, based on our group's expertise with the combining the physics and chemistry of nanostructures with the self-assembly and specific recognition processes of biology. The basic theme is centered on the self-assembly of oppositely charged surfactants and/or hydrotropes into unilamellar vesicles that can be fixed by polymerization to yield stable, hollow capsules that can be further functionalized. Specific aims are:1. Study the formation and polymerization of vesicles formed from polymerizable surfactants andorganic and inorganic monomers to best retain the size, shape and polydispersity of templating vesicles;2. Modify and control vesicle properties adding block co-polymers to adjust the spontaneous curvature (size), bending elasticity (polydispersity) and the steric interactions between vesicles (stability). In particular, near equimolar mixtures of polymerizable anionic and cationic surfactants with copolymers that likely create monodisperse vesicle systems will be formulated;3. Examine the novel properties of vesicles formed in mixtures of surfactant and hydrotropes (which are weakly surface-active, amphiphilic, and highly water-soluble organic salts), and to probe microstructural changes therein caused by changes in pH or light exposure.Project 1 will involve synthesis and formulation carried out primarily at U. Delaware by Kaler'sgroup and microscopy characterization at UCSB by Zasadzinski's group. The formulations needed for project 2 will be done at UCSB and characterization will be carried out using light scattering and electron microscopy by Zasadzinski's group, and neutron spin-echo and neutron scattering by Kaler's group. Project 3 will be initiated at U. Delaware by Kaler's group and characterized by microscopy done in Zasadzinski's group. The reduction in time from 3 to 2 years will cause us to not be able to get as far in the project; however, all of the specific aims will be examined and the most promising routes identified.Intellectual Merit: The self-assembly of oppositely charged surfactants and hydrotropes opens newareas of biomimetic structures for exploration, and will likely put the process of vesicle formation under thermodynamic control. Exploiting thermodynamic control means being able to determine the size, polydispersity, stability, etc. of vesicles by simple manipulation of simple, inexpensive detergents. Chemical reactions (i.e., polymerization) to fix such structures open new ways to form nanoscale materials that retain the nanostructure of the template. The proposed work expands and links these two areas, and will provide both novel experimental observations and further theoretical understanding.Technical Impact: Surfactant formulations, particularly surfactant mixtures, are widely used inmany industrial processes. The ability to control surfactant microstructure by mixing surfactants or adding hydrotropes could provide new organic templates for novel organic and inorganic materials such as polymer latices and molecular sieves. Manufacturing polymerized vesicles cheaply could open the way to high-volume usages in printing or agricultural applications. Work with spontaneous vesicles made of biological surfactants will lead to useful pharmaceutical applications. Controlling the aggregation and fusion of vesicles is of crucial importance to drug delivery schemes, as is minimization of the free surfactant concentration.Broader Impact: The scientific aspects of this proposed work will enable discovery of newnanoscale surfactant architectures through the development of and understanding of their thermodynamic and mechanical properties, including the nature of their equilibrium state. Study of these mixtures has already led to fruitful reexamination of many of the fundamental dogmas of self-assembly. Study of both organic and inorganic polymerizations can open ways to make new materials that could have application beyond those discussed above. Undergraduate and graduate students involved in this work will be exposed to a range of characterization tools and appropriate analytical methods, and thereby be prepared for either academic or industrial work in this area. K-12 students will be exposed to concepts relevant to this work, including surfactant and polymer properties and elements of nanotechnology.Statement of Effect of Time Reduction:We have proposed three specific aims:1. Study the formation and polymerization of vesicles formed from polymerizable surfactantsand organic and inorganic monomers to best retain the size, shape and polydispersity oftemplating vesicles;2. Modify and control vesicle properties adding block co-polymers to adjust the spontaneouscurvature (size), bending elasticity (polydispersity) and the steric interactions between vesicles(stability). In particular, near equimolar mixtures of polymerizable anionic and cationicsurfactants with copolymers that likely create monodisperse vesicle systems will be formulated;3. Examine the novel properties of vesicles formed in mixtures of surfactant and hydrotropes(which are weakly surface-active, amphiphilic, and highly water-soluble organic salts), and toprobe microstructural changes therein caused by changes in pH or light exposure.Project 1 will involve synthesis and formulation carried out primarily at U. Delaware by Kaler'sgroup and microscopy characterization at UCSB by Zasadzinski's group. The formulationsneeded for project 2 will be done at UCSB and characterization will be carried out using lightscattering and electron microscopy by Zasadzinski's group, and neutron spin-echo and neutronscattering by Kaler's group. Project 3 will be initiated at U. Delaware by Kaler's group andcharacterized by microscopy done in Zasadzinski's group. The reduction in time from 3 to 2years will cause us to not be able to get as far in the project; however, all of the specific aims willbe examined at some level and the most promising routes identified for subsequent proposals.