Porous peptide frameworks to host organic molecules and solid-state reactions

该研究将利用肽材料作为一种新型绿色基质，用于存储有机分子并在固态下进行合成反应。所得数据将为今后固体肽基材料的研究和应用提供基础知识。包合物和共晶的形成将通过筛选技术来确定。将阐明新材料的晶体结构和稳定性。最后，将详细研究固体中分子的反应性。******多肽的层状超分子结构和客体分子在层间空间的结合将被利用。该结构可用于多种有机物质的选择性包合、稳定和储存，也可作为固体反应的反应容器。通过氢键和范德华力等弱非共价相互作用的适当控制，可以获得理想的包合性和反应性。******反应可以通过热反应或光化学反应来诱导。将详细研究两种模式反应：热诱导的二肽环化和驻留在肽基质中的不饱和分子的[2+2]光二聚化。反应的发生率、转化率、产率和立体专一性将作为试剂的分子结构、晶体的固态结构和使用的外部条件的函数来研究。更好地理解这两种类型将有助于将合成策略扩展到这些材料中其他类型的固态反应。此外，较长的寡肽的反应性将被研究为它们形成的分子大小和晶体结构的函数。******短肽分子在固体状态下的化学转化以及涉及肽固体中结合的其他分子的化学反应将作为目前使用的基于溶剂的合成方法的潜在替代方法进行研究。所获得的知识将有助于未来的经济发展，用满足绿色化学原则的新程序取代当前的工业过程。拟议的研究还将通过引入新的肽类固体，其中生物活性分子被纳入，并通过确定这些生物相容性，环保材料的稳定性限制，确定肽类在制药，食品和化妆品行业的新用途。******提议的计划意味着年轻的研究人员在研究生和本科生水平的参与，有一个很好的机会学习有机合成，固态化学，物理化学分析，包括晶体学，热分析和光谱技术的新方法。

The proposed research will utilize peptide materials as a novel green matrix for storing organic molecules and conducting synthetic reactions in the solid state. The obtained data will form basic knowledge for future studies and applications of solid peptide-based materials. The formation of inclusion compounds and co-crystals will be determined using screening techniques. The crystal structure and stability of the new materials will be elucidated. Finally, the reactivity of molecules in the solids will be investigated in detail.******The layered supramolecular architecture of peptides and incorporation of guest molecules in the interlayer space will be exploited. It is proposed that the architecture can be used for selective inclusion, stabilization and storage of various organic species, as well as a reaction vessel for solid state reactions. The desired inclusion properties and reactivity could be achieved through a proper control by weak non-covalent interactions such as hydrogen bonds and van der Waals forces. ******The reactions will be induced either thermally or photochemically. Two model reactions will be investigated in detail: thermally induced cyclization of dipeptides and [2+2] photodimerization of unsaturated molecules residing in the peptide matrix. The incidence of the reactions, the conversion rate, yield and stereospecificity will be studied as a function of the molecular structure of the reagent, solid state structure of the crystal, and external conditions used. Better understanding of these two types will help to extend the synthetic strategies to other types of solid state reactions in these materials. Further, the reactivity of longer oligopeptides will be studied as a function of the molecular size and crystal structure they form. ******The chemical transformations of short peptide molecules in the solid state and chemical reactions that involve other molecules incorporated in the peptide solids will be studied as a potential alternative to currently used solvent-based synthetic methods. The obtained knowledge will contribute to future economic development by replacing current industrial processes with new procedures that satisfy the principles of Green Chemistry. The proposed research will also identify new uses of peptides in pharmaceutical, food and cosmetic industries through the introduction of novel peptide-based solids where the bioactive molecules are incorporated and through identification of the stability limits of these biocompatible, environmentally friendly materials.******The proposed plan implies involvement of young researchers both on graduate and undergraduate levels with a great opportunity to learn novel approaches to organic synthesis, solid state chemistry, physicochemical analysis including crystallography, thermal analysis and spectroscopic techniques.