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

这项拟议的研究将利用多肽材料作为一种新型的绿色基质来存储有机分子并在固态中进行合成反应。所获得的数据将为未来固体多肽材料的研究和应用提供基础知识。包合物和共晶的形成将使用筛选技术来确定。新材料的晶体结构和稳定性将被阐明。最后，将详细研究分子在固体中的反应性。*将利用多肽的层状超分子结构和客体分子在层间空间的结合。提出该体系结构可用于多种有机物种的选择性包合、稳定和储存，也可用作固相反应的反应容器。通过氢键和范德华力等弱的非共价相互作用的适当控制，可以获得所需的包合性质和反应活性。*反应将以热或光化学反应方式进行。将详细研究两个模型反应：二肽的热诱导环化反应和驻留在多肽基质中的不饱和分子的[2+2]光二聚反应。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、晶体的固态结构和所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的其他类型的固相反应。此外，将研究较长的寡肽的反应性作为它们形成的分子大小和晶体结构的函数。*将研究短肽分子在固态中的化学转化以及与其他分子结合在多肽固体中的化学反应，作为目前使用的溶剂型合成方法的潜在替代品。所获得的知识将为未来的经济发展做出贡献，用符合绿色化学原则的新程序取代目前的工业过程。这项拟议的研究还将通过引入含有生物活性分子的新型多肽固体，并通过确定这些生物兼容的、环境友好的材料的稳定性极限，来确定多肽在制药、食品和化妆品行业中的新用途。*拟议的计划意味着研究生和本科生层面的年轻研究人员将参与进来，有很好的机会学习有机合成、固态化学、物理化学分析(包括结晶学、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.