Crown ethers based photo take-apartable molecular hosts

描述：（申请人的描述）基础和应用研究目标 大分子物体和超分子自组装一般已经 在过去的十年里稳步上升。分子工程已经发展到了 在那里几乎可以制造任何复杂形状的分子物体 并获得某些所需的性能。一个系统的方法来构建 这些目的包括识别设计成保持 结构块在一起而不妨碍组装步骤。 现在，随着化学家能够组装越来越复杂的系统， 对我们来说，很明显，下一个合乎逻辑的步骤的时候到了。 分子操纵，也就是说，开发智能的方式和规则， 分子分解这就需要寻找和发展 可以根据需要选择性地松开的分子锁和闩锁。一 这些紧固件的可预见的应用，这是特别相关的， 光生物学领域，是它们在合理设计中的利用， 能够光可逆地容纳有机客体的分子主体。 在我们的初步研究中，我们已经确定了一个强大的系统， 满足分子组装所有标准的二噻烷-羰基加合物 并且当在存在放射性物质的情况下照射时， 电子转移敏化剂。 在拟议的研究过程中，理性设计将适用于 开发一系列由冠醚和/或 通过我们的耐光系绳连接的穴标单元。络合选择性 和新的分子系统的光化学/光物理学将被检查 评估其在光生物学中的应用前景，例如， 光动力疗法的潜在载体等。

DESCRIPTION: (Applicant's Description) Basic and applied research targeting large molecular objects and supramolecular self-assembly in general has been on a steady rise over the past decade. Molecular engineering has reached a point where virtually any complicated shape of a molecular object can be manufactured and certain desired properties achieved. A systematic approach to constructing such objects includes identifying efficient bonding mechanisms designed to hold the construction blocks together and yet not frustrating the assembly step. Now as chemists are capable of assembling more and more complicated systems, it became evident to us that the time has come for the next logical step in molecular manipulations, that is, to develop intelligent ways and rules of molecular disassembly. This requires the search for and development of molecular buckles and latches that can be selectively unfastened on demand. One foreseeable application of these fasteners, which is particularly relevant to the field of photobiology, is their utilization in the rational design of molecular hosts capable of photoreversible accommodation of organic guests. In our preliminary studies we have identified a robust system based on dithiane-carbonyl adducts that satisfies all the criteria of molecular assembly and yet is capable of site-specific disassembly when irradiated in the presence of electron-transfer sensitizers. During the course of the proposed research rational design will be applied to develop a series of novel molecular hosts comprised of crown ethers and/or cryptand units linked via our photolabile tethers. The complexation selectivity and photochemistry/photophysics of the novel molecular systems will be examined to evaluate the prospects of their application in photobiology, e.g. as potential carriers for photodynamic therapies etc.