Chaotropic Polyoxometalates: From Fundamentals to Applications

该联盟独立发表的最新研究结果显示，聚氧乙烯酸盐（POM）广泛用于与重大社会挑战相关的各种应用，如能源转换或储存、环境科学和医学。这些报告中的一些表明，水合聚阴离子表现出超离液序列的行为，驱动显着的性能时，与有机物质的相互作用，并引起了新的观点，在他们的操纵在超分子水平。这个CHAOPOM项目的目标是评估基于POM的超分子相互作用，以便更好地理解和量化其离液特性，以及它们在生物应用新材料设计中的应用。虽然小的经典无机阴离子，如高氯酸盐或硫氰酸盐的离液性质已经知道了很长一段时间，这种现象只是最近才被发现的多金属氧酸盐。因此，令人兴奋的新的机会，可以预见，因为主要的驱动力源于水化性能的POM将最有可能被确定的财团。超越历史Hofmeister尺度的超离液效应的研究和后果将在拟议的研究项目中展开，该项目从基础方面到应用。我们的实验工作将得到理论计算的支持（分子动力学），以便更好地理解POM水合球在聚集过程中的作用。该项目的目标分为四个部分：（i）研究超分子主客体络合现象：解决了将POM与功能互补化合物组装的可能性，类似于硼簇与有机大环的相互作用。(ii)掌握从定向合成到分级超分子材料设计的离液效应：通过利用无机缩聚过程中的超离液效应，概念新颖的分子或扩展的POM基材料的合成变得可行。(iii)用于软物质工程和双层材料的基于POM的系统：超离液POM与非离子两亲分子强烈相互作用，从而有机会产生新型聚集体。(iv)生物活性评价：研究POM与潜在药物靶点的超离液特性的相互作用。

Recent results published independently by the consortium have revealed that polyoxometalates (POMs) are widely used for various applications related to big societal challenges, such as energy conversion or storage, environmental science, and medicine. Some of these reports demonstrate that hydrated polyanions exhibit super-chaotropic behavior that drives remarkable properties when interacting with organic substances and gives rise to new perspectives in their manipulation at the supramolecular level. The goal of this CHAOPOM project is the evaluation of POM-based supramolecular interactions for a better understanding and quantification of their chaotropic character, and their use in the design of new materials for biological applications. Although the chaotropic nature of small classical inorganic anions such as perchlorate or thiocyanate has been known for a long time, this phenomenon has only recently been discovered for POMs. As a result, exciting new opportunities can be envisioned since primary driving forces originating from hydration properties of POMs will most likely be identified by the consortium. The study and consequences of the super-chaotropic effect that go beyond the historical Hofmeister scale will be unfolded in the proposed research project, which spans from fundamental aspects to applications. Our experimental work will be supported by theoretical calculations (molecular dynamics) in order to better understand the role of the POM hydration sphere in the aggregation processes.The objectives of the project are subdivided into four parts: (i) Investigation of supramolecular host-guest complexation phenomena: address the possibility of assembling POMs with functionally complementary compounds, similar to the interaction of boron clusters with organic macrocycles. (ii) Mastering the chaotropic effect from directed synthesis to the design of hierarchical supramolecular materials: by exploiting the super-chaotropic effect in inorganic polycondensation processes, the synthesis of conceptually novel molecular or extended POM-based materials becomes viable.(iii) POM-based systems for soft-matter engineering and bilayer materials: super-chaotropic POMs interact strongly with nonionic amphiphilic molecules giving opportunities for generating novel types of aggregates. (iv) Evaluation of bioactivity: investigate the interactions of POMs with potential drug targets in terms of their super-chaotropic properties.