From Molecular Simplicity to Supramolecular Complexity: Low Symmetry Packings of Ionic Spherical Micelles

从分子简单性到超分子复杂性：离子球形胶束的低对称性堆积

基本信息

批准号：
1807330
负责人：
Mahesh Mahanthappa
金额：
$ 49.13万
依托单位：
University of Minnesota-Twin Cities
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-08-15 至 2022-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1807330&HistoricalAwards=false
关键词：
Molecular Simplicity Supramolecular Complexity Low

项目摘要

Surfactants are small molecules in which a water-soluble headgroup is attached to an insoluble tail. Common examples of useful surfactants are soaps and detergents. As a result of the different solubilities of the headgroup and the tail, surfactants spontaneously form ordered assemblies in water. The assemblies can range from very simple spheres dispersed in water to much more sophisticated geometries. However, predicting the geometry of a complex assembly from the chemical structure of the surfactant remains a significant challenge. Motivated by the desire to control surfactant assembly and access complex structures with unusual and useful properties, Prof. Mahesh Mahanthappa and his research team at the University of Minnesota-Twin Cities seek to understand how surfactant structure dictates the packing geometry and the stability of an assembly. Their discoveries could have broad implications for the future design and development of surfactants for applications such as enhanced oil recovery, personal care product formulation, drug encapsulation, and therapeutic delivery. The project also contributes to the interdisciplinary research training of undergraduate and graduate students, including members of underrepresented groups. Public outreach demonstrations using visually appealing soap bubble froths showcase the properties of surfactants and help to arouse the interest of students in science.A delicate balance of non-covalent interactions drives the supramolecular assembly of minimally hydrated amphiphiles into different lyotrophic liquid-crystalline phases. Of particular interest is the complex Frank-Kasper (FK) phases, which apparently arise from a frustrated non-covalent force balance that minimizes local variations in amphiphile solvation, while maximizing global micelle cohesion across the supramolecular assembly. Specific experiments of this project aim to 1) understand how the ionic amphiphile tail structure, counterion symmetry, and chirality impact micellar aggregation and consequent packing of the micelles into high coordination number, low symmetry lattices; 2) evaluate whether these complex packings are long-lived metastable states or thermodynamic equilibrium phases; and 3) assess whether non-ionic amphiphiles might form these complex phases. An important goal is to uncover new molecular design criteria that drive the formation of lyotropic liquid crystals with exceptional translational order, at length scales far exceeding those of their constituent molecular and supramolecular micelle building blocks.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

表面活性剂是小分子，其中水溶性头基连接到不溶性尾部。有用的表面活性剂的常见例子是肥皂和洗涤剂。由于头基和尾部的溶解度不同，表面活性剂在水中自发形成有序组装体。这些组件的范围可以从非常简单的分散在水中的球体到更复杂的几何形状。然而，从表面活性剂的化学结构预测复杂组件的几何形状仍然是一个重大挑战。出于控制表面活性剂组装和获得具有不寻常且有用特性的复杂结构的愿望，明尼苏达大学双城分校的 Mahesh Mahanthappa 教授和他的研究团队试图了解表面活性剂结构如何决定堆积几何形状和组装的稳定性。他们的发现可能对未来表面活性剂的设计和开发产生广泛的影响，这些表面活性剂的应用包括提高石油采收率、个人护理产品配方、药物封装和治疗递送。该项目还有助于本科生和研究生（包括代表性不足群体的成员）的跨学科研究培训。使用视觉上吸引人的肥皂泡泡沫进行的公共宣传演示展示了表面活性剂的特性，并有助于激发学生对科学的兴趣。非共价相互作用的微妙平衡驱动最小水合两亲物的超分子组装成不同的溶营养液晶相。特别令人感兴趣的是复杂的 Frank-Kasper (FK) 相，它显然是由于非共价力平衡受阻而产生的，该平衡最大限度地减少了两亲溶剂化的局部变化，同时最大限度地提高了超分子组装体中的整体胶束内聚力。该项目的具体实验旨在1）了解离子两亲物尾部结构、反离子对称性和手性如何影响胶束聚集以及随后将胶束堆积成高配位数、低对称性晶格； 2）评估这些复杂填料是否是长寿命亚稳态或热力学平衡相； 3) 评估非离子两亲物是否可能形成这些复杂相。一个重要的目标是发现新的分子设计标准，驱动具有特殊平移顺序的溶致液晶的形成，其长度尺度远远超过其组成分子和超分子胶束构建块的长度尺度。该奖项反映了 NSF 的法定使命，并被认为是值得的通过使用基金会的智力优势和更广泛的影响审查标准进行评估来获得支持。

项目成果

期刊论文数量（10）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Tuning Diblock Copolymer Particle Packing Symmetry with Variable Molecular Weight Core-Homopolymers

DOI：
10.1021/acs.macromol.2c01267
发表时间：
2022-09
期刊：
Macromolecules
影响因子：
5.5
作者：
A. J. Mueller;A. Lindsay;Ashish Jayaraman;S. Weigand;T. Lodge;M. Mahanthappa;F. Bates
通讯作者：
A. J. Mueller;A. Lindsay;Ashish Jayaraman;S. Weigand;T. Lodge;M. Mahanthappa;F. Bates

Dodecagonal quasicrystals of oil-swollen ionic surfactant micelles

DOI：
10.1073/pnas.2101598118
发表时间：
2021-08-03
期刊：
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
影响因子：
11.1
作者：
Jayaraman, Ashish;Baez-Cotto, Carlos M.;Mahanthappa, Mahesh K.
通讯作者：
Mahanthappa, Mahesh K.

Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids