权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Manipulating Supramolecular Assembly in Water and Aqueous Mixtures

操纵水和水混合物中的超分子组装

基本信息

批准号：
1805167
负责人：
Henry Ashbaugh
金额：
$ 32万
依托单位：
Tulane University
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=1805167&HistoricalAwards=false
关键词：
Manipulating Supramolecular Assembly Water Aqueous

项目摘要

Deep cavity cavitands are container-shaped supramolecular complexes that contain a one-nanometer, rigid, non-polar binding pocket and a hydrophilic exterior coating that bestows good water solubility. Cavitands have proven useful "hosts" because of their ability to bind other molecules, or "guests", within their pockets and assemble in well-defined stoichiometries. They have applications in studies of protein solubility, in controlled release of pharmaceuticals, in separations, in the precise control of photochemical reactions, and as gelling agents. The fundamental understanding of these supramolecular complexes requires a molecular-level understanding of the interactions between hosts and guests in solution. A collaborative research project is proposed that combines molecular simulation and experimental studies aimed at investigating the impact of aqueous mixtures with co-solvent and polymeric additives on the forces driving cavitand assembly.The overarching goal of the proposed research is to develop molecular tools for controlling supramolecular cavitand assembly by manipulating the solvent properties that mediate host/guest interactions. The following topics will be studied: 1) How do alcoholic co-solvents moderate cavitand binding and assembly thermodynamics for a series of amphiphilic and non-polar guests? 2) How do changes in the hydrophobicity and hydrophilicity of the functional groups ringing the cavitand host pocket portals impact pocket hydration thermodynamics, drying/filling kinetics, and guest binding affinities? 3) What is the impact of water-soluble polymer crowding agents on the stability of moderately stable dimeric cavitand complexes? Molecular dynamics simulations of guest binding and cavitand complex formation will be performed over a range of solvent conditions and cavitand functions to examine water and alcohol structural correlations with host/guest complexes, complexation thermodynamics, wetting of host binding pockets, and osmotic stresses to gain molecular-scale insights into the forces stabilizing these assemblies. Complementary experiments will be performed to examine the effects of host functions and aqueous mixture compositions on the resulting cavitand complexes, using Nuclear Magnetic Resonance and light scattering, and the underlying assembly thermodynamics, using calorimetry. In addition to graduate and undergraduate student training, the proposed project will include an outreach program to the New Orleans Charter Science and Mathematics High School that serves a predominantly underrepresented minority student base.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.

深腔空化体是容器形的超分子复合物，它包含一个一纳米的、刚性的、非极性的结合袋和一个具有良好水溶性的亲水外涂层。空腔体已经被证明是有用的“寄主”，因为它们有能力将其他分子或“客人”结合在它们的口袋里，并在明确的化学计量中组装。它们在蛋白质溶解度的研究、药物的控释、分离、光化学反应的精确控制以及作为胶凝剂等方面都有应用。对这些超分子复合物的基本理解需要对溶液中宿主和客体之间的相互作用有分子水平的理解。提出了一项结合分子模拟和实验研究的合作研究项目，旨在研究含有共溶剂和聚合物添加剂的水混合物对驱动空腔和组装的力的影响。提出的研究的总体目标是通过操纵介导宿主/客体相互作用的溶剂性质来开发控制超分子空腔和组装的分子工具。以下主题将被研究：1)酒精共溶剂如何调节一系列两亲性和非极性客体的空腔和结合和组装热力学？2)围绕空腔和寄主口袋入口的官能团的疏水性和亲水性变化如何影响口袋水化热力学、干燥/填充动力学和客体结合亲和性？3)水溶性聚合物拥挤剂对中稳定型二聚体空腔配合物的稳定性有何影响？将在一系列溶剂条件和空腔功能下进行客体结合和空腔复合物形成的分子动力学模拟，以检查水和醇与宿主/客体复合物的结构相关性，络合热力学，宿主结合口袋的润湿性和渗透应力，以获得分子尺度上对稳定这些组装的力的见解。补充实验将使用核磁共振和光散射来检查宿主功能和水混合成分对产生的空腔和配合物的影响，并使用量热法来检查潜在的组装热力学。除了研究生和本科生的培训外，拟议的项目还将包括新奥尔良宪章科学和数学高中的外展计划，该高中主要服务于代表性不足的少数民族学生基地。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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）

Connecting Non-Gaussian Water Density Fluctuations to the Lengthscale Dependent Crossover in Hydrophobic Hydration

将非高斯水密度波动与疏水水合中的长度尺度相关交叉联系起来

DOI：
10.1021/acs.jpcb.2c04990
发表时间：
2022
期刊：
The Journal of Physical Chemistry B
影响因子：
0
作者：
Sinha, Imee;Cramer, Steven M.;Ashbaugh, Henry S.;Garde, Shekhar
通讯作者：
Garde, Shekhar

Pressure Induced Wetting and Dewetting of the Nonpolar Pocket of Deep-Cavity Cavitands in Water

水中深腔空穴非极性区的压力诱导润湿和反润湿

DOI：
10.1021/acs.jpcb.0c02568
发表时间：
2020
期刊：
The Journal of Physical Chemistry B
影响因子：
0
作者：
Tang, Du;Dwyer, Tobias;Bukannan, Hussain;Blackmon, Odella;Delpo, Courtney;Barnett, J. Wesley;Gibb, Bruce C.;Ashbaugh, Henry S.
通讯作者：
Ashbaugh, Henry S.

Proximal charge effects on guest binding to a non-polar pocket

近端电荷对客体与非极性口袋结合的影响

DOI：
10.1039/c9sc06268h
发表时间：
2020
期刊：
Chemical Science
影响因子：
8.4
作者：
Suating, Paolo;Nguyen, Thong T.;Ernst, Nicholas E.;Wang, Yang;Jordan, Jacobs H.;Gibb, Corinne L.;Ashbaugh, Henry S.;Gibb, Bruce C.
通讯作者：
Gibb, Bruce C.

Assessment of scaled particle theory predictions of the convergence of solvation entropies

溶剂化熵收敛的缩放粒子理论预测的评估