Exploration of Active Roles of Water in Aqueous Supramolecular Chemistry

疏水效应引起的自组装（HE-SA）通常被默认为非极性基团的疏水相互作用（HI）过程。这种默认是HE-SA行为在许多情况下（包括生物系统）令人困惑的原因之一，因为水的作用被忽视了。计算机模拟表明，氦离子来源于水结构（动态氢键网络）的自由能。水的结构在散装水和水水合的疏水分子之间是不同的，被称为疏水水合作用（HH），这导致了驱动HE-SA的能量差。因此，HH水要么被排斥以获得熵（传统的HE-SA），要么通过焓/熵补偿被保留作为组件内的组装组件。后一种情况在生物系统中普遍存在，水组分负责这些功能，这是传统HE-SA的灵感和动力。我的研究目标是通过实验了解水在自组装胶体的构建和功能中的作用，这将促进水介导功能的超分子合成和水材料和技术的产业创新。我和我的团队已经(1)探索了具有各种结构的水不溶性金属羰基化合物的合成和水自组装；(2)发现了第一个不含HI的水组装，其中包括水作为主要组装成分；(3)开发了许多用于水表征的实用技术。在这一进展的基础上，拟议的研究计划将针对三个目标来全面了解HE-SA:(1)研究将已经从金属羰基有机金属学到的知识转移到有机系统的可能性，这对于促进HE-SA的广泛研究至关重要；(2)探索发现的有机金属组件中的水组分，了解其在功能胶体构建中的作用；(3)阐明HE-SA中水的行为与有机金属构件的化学结构的关系，包括小分子、线性和环状大分子。该研究将进一步深化对HE-SA的传统认识，并为探索自组装胶体的水介导功能开辟新的领域，从而提升加拿大在国际上的研究地位，加强加拿大在水生物医学、农业和家用产品等领域的创新研发能力，从而为加拿大的支柱产业做出贡献。学生将接受相关技术技能、研究兴趣，特别是科学视野方面的培训，因此他们将在培训后担任领导角色，进一步推动该领域的发展，创造高科技工作岗位，并将加拿大建立为创新中心。

Hydrophobic effect-caused self-assembly (HE-SA) is conventionally defaulted as a process of hydrophobic interaction (HI) of non-polar groups. This default is one reason for the perplexity of HE-SA behavior in many cases, including biological systems, because the roles of water are neglected. Computer simulations have proposed that HEs stem from the free energy of water structure (dynamic hydrogen bonding network). The water structures are different between bulk water and the water hydrating hydrophobic molecules, known as hydrophobic hydration (HH), which cause an energy difference driving HE-SA. Consequently, the HH water is either repelled to gain entropy (conventional HE-SA) or reserved to act as an assembling component involved within the assemblies via an enthalpy/entropy compensation. The latter scenario is commonly observed in biological systems and the water component is responsible for the functions, which is the inspiration and motivation to advance the conventional HE-SA. The goal of my research is to experimentally understand the role of water in the construction and function of self-assembled colloids, which will promote supramolecular synthesis for water-mediated functions and industrial innovation of aqueous materials and technologies. My team and I have (1) explored the synthesis and aqueous self-assembly of water-insoluble metal carbonyl compounds with various structures, (2) discovered the first aqueous assembly without HI, which involves water as a major assembling component and (3) developed a number of practical techniques for water characterizations. Building on this progress, the proposed research program will target three objectives towards the comprehensive knowledge of HE-SA: (O1) Examine the possibility to transfer the knowledge already learned from the metal carbonyl organometallic to organic systems, which is essential to promote extensive studies to advance HE-SA; (O2) Explore the water component within the discovered organometallic assembly to learn its role in the construction of functional colloids; (O3) Elucidate water behavior in the HE-SA in relation to the chemical structure of the organometallic building blocks, including small molecules, linear and cyclic macromolecules. The research will advance the conventional knowledge of HE-SA and create a new niche to explore water-mediated functions for self-assembled colloids, which will promote Canada's position in research internationally, strengthen the R & D capacity for the innovation of aqueous biomedical, agricultural and household products, etc. and thus contribute to Canada's pillar industries. The students will be trained in relevant technical skills, research interests and, particularly, scientific vision, so they will be expected to take a leadership role after the training to further advance the field, create high tech jobs and establish Canada as an innovation hub.