Patterns of Hierarchical Molecular Self-Assemblies 2

分层分子自组装模式 2

• 批准号: 258513149
• 负责人: Professor Dr. Motomu Tanaka
• 金额: --
• 依托单位: Institut Charles Sadron
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2014
• 资助国家: 德国
• 起止时间: 2013-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/258513149?language=en
• 关键词: Patterns; Hierarchical; Molecular; Self; Assemblies

The primary aim of the proposed project is to design novel patterns of molecular self-assembled systems in two-dimensional planar films, as well as in three-dimensional microbubbles, by the mechanistic understanding of their hierarchical structure formation. This is a collaborative effort of a Fluorocarbon Chemistry group synthesizing highly fluorinated amphiphiles and self-assembled colloidal systems (leader, Marie Pierre Krafft) and a Soft Matter Physics group (leader, Motomu Tanaka) focusing on the characterization of nanopatterned films at the interface. Highly fluorinated amphiphiles are self-assembled into monodisperse, disk-like domains with a diameter of several tens of nanometers, forming highly organized hexagonal arrays in both 2D and 3D systems. The ultimate goal of the project is to control and optimize these unique surface patterns in terms of size and organization in order to exploit them in 3D systems, such as microbubbles with a shell comprising such self-assembled nanodomains. To achieve this goal, we propose two specific aims. First, planar thin films, such as Langmuir monolayers, Langmuir-Blodgett and spin-coated multilayers, nanostructured by surface domains of fluorinated compounds mixed with hydrocarbon amphiphiles (e.g. phospholipids and polymers) will be investigated. Special emphasis will be to determine the impact of molecular structures on the hierarchical ordering of 1) molecules within surface domains and 2) correlation between domains within the films, and 3) impact of the surface domains on the film mechanics. The obtained results will be utilized to tune the size and ordering of domains at different length scales (from a few Å up to sub-microns), and thus to control the mechanical properties. Second, we will prepare stable, narrowly dispersed microbubbles bestowed with a shell containing the nanodomains studied and optimized in 2D films. As perfluoroalkylated phosphates form microbubbles that can last for weeks in aqueous dispersions, it is possible to investigate the impact of the molecular structure of the amphiphiles and their hierarchical self-assembly on the stability, echogeneicity, aptitude at generating harmonics and mechanics of the microbubbles. The extension of the strategy from 2D systems to 3D systems (emulsions and bubbles) with soft and flexible shells possessing dynamic, pressure-responding properties is an important scientific challenge that has never been taken up. It should be emphasized that the mechanistic understanding of the hierarchical structure formation in 2D films with aid of surface-sensitive techniques provides with the most effective way to optimize the systems. From a practical standpoint, this concept will offer major advances in the development of microbubbles for diagnosis and therapy.

该项目的主要目的是通过对其分层结构形成的机械理解，在二维平面膜以及三维微泡中设计分子自组装系统的新模式。这是一个氟碳化合物化学组合成高度氟化的两亲物和自组装胶体系统（领导者，玛丽皮埃尔Krafft）和软物质物理组（领导者，田中元）的合作努力，专注于在界面纳米图案薄膜的表征。高度氟化的两亲物自组装成直径为几十纳米的单分散的盘状结构域，在2D和3D系统中形成高度有序的六边形阵列。该项目的最终目标是在尺寸和组织方面控制和优化这些独特的表面图案，以便在3D系统中利用它们，例如具有包含这种自组装纳米结构域的外壳的微泡。为了实现这一目标，我们提出了两个具体目标。首先，平面薄膜，如朗缪尔单层，朗缪尔-布洛杰特和旋涂多层膜，纳米结构的氟化化合物与烃两亲物（如磷脂和聚合物）混合的表面域将进行研究。特别强调的是确定分子结构对1）表面域内分子的层次排序的影响，2）膜内域之间的相关性，以及3）表面域对膜力学的影响。所获得的结果将被用来调整在不同的长度尺度（从几微米到亚微米）的域的大小和顺序，从而控制机械性能。第二，我们将制备稳定的，分散性很好的微泡，微泡的外壳含有在2D电影中研究和优化的纳米结构域。由于全氟烷基化磷酸盐形成的微泡可以在水性分散体中持续数周，因此可以研究两亲物的分子结构及其分级自组装对微泡的稳定性、回声性、产生谐波的能力和力学的影响。将该策略从2D系统扩展到3D系统（乳液和气泡），具有柔软和灵活的外壳，具有动态的压力响应特性，这是一项重要的科学挑战。应该强调的是，借助表面敏感技术对2D膜中的分级结构形成的机械理解提供了优化系统的最有效方法。从实用的角度来看，这一概念将为诊断和治疗微泡的发展提供重大进展。

项目成果

Size, Shape, and Lateral Correlation of Highly Uniform, Mesoscopic, Self-Assembled Domains of Fluorocarbon-Hydrocarbon Diblocks at the Air/Water Interface: A GISAXS Study.

空气/水界面处氟碳-烃二嵌段的高度均匀、介观、自组装域的尺寸、形状和横向相关性：GISAXS 研究

• DOI: 10.1002/cphc.201700325
• 发表时间: 2017
• 期刊: Chemphyschem : a European journal of chemical physics and physical chemistry
• 作者: M. Veschgini;W. Abuillan;S. Inoue;A. Yamamoto;S. Mielke;X. Liu;O. Konovalov;M.P. Krafft;M. Tanaka
• 通讯作者: M. Tanaka

Nonlinear Viscoelasticity of Highly Ordered, Two-Dimensional Assemblies of Metal Nanoparticles Confined at the Air/Water Interface.

限制在空气/水界面的高度有序、二维金属纳米颗粒组件的非线性粘弹性

• DOI: 10.1021/acs.langmuir.8b02713
• 发表时间: 2018
• 期刊: Langmuir : the ACS journal of surfaces and colloids
• 作者: S. Masuda;S. Mielke;F. Amadei;A. Yamamoto;P. Wdaang;T. Taniguchi;K. Yoshikawa; K. Tama;M. Tanaka
• 通讯作者: M. Tanaka

Influence of Perfluorohexane-Enriched Atmosphere on Viscoelasticity and Structural Order of Self-Assembled Semifluorinated Alkanes at the Air-Water Interface.

富全氟己烷气氛对空气-水界面自组装半氟化烷烃粘弹性和结构有序的影响

• DOI: 10.1002/cphc.201900316
• 发表时间: 2019
• 期刊: Chemphyschem : a European journal of chemical physics and physical chemistry
• 作者: S. Mielke;W. Abuillan;M. Veschgini;X. Liu;O. Konovalov;M.P. Krafft;M. Tanaka
• 通讯作者: M. Tanaka

Influence of Semifluorinated Alkane Surface Domains on Phase Behavior and Linear and Nonlinear Viscoelasticity of Phospholipid Monolayers.

半氟化烷烃表面域对磷脂单层相行为及线性和非线性粘弹性的影响

• DOI: 10.1021/acs.langmuir.9b03521
• 期刊: Langmuir : the ACS journal of surfaces and colloids
• 作者: S. Mielke;X. Liu;M.P. Krafft;M. Tanaka
• 通讯作者: M. Tanaka

2D Spherulites of a Semi-Fluorinated Alkane: Controlled Access to Either Radial Or Ring-Banded Morphologies.

• DOI: 10.1002/cphc.201701064
• 发表时间: 2018-01
• 期刊: Chemphyschem : a European journal of chemical physics and physical chemistry
• 作者: Xianhe Liu;S. Mielke;Christophe Contal;D. Favier;Akihisa Yamamoto;Motomu Tanaka;M. Krafft