Light-assisted functionalization and assembly of zeolite L based hybrid materials

以L沸石为代表的纳米多孔性微粒子由于具有层次化的超分子结构，可以将纳米和微系统组装成更大的功能实体，因此对各种客体的组装具有重要意义。高效设计大型功能系统的先决条件是对组装过程的完全控制。它是通过选择性地对L沸石表面进行化学修饰和随后将单个单晶连接成更大实体的光学机械辅助的多种组合来实现的。作为一个有远见的目标，我们的目标是将这些构建块集成到一个更大的全功能光子学工具箱中，从而为软物质和生物实体的通用光辅助组装策略铺平道路。遵循前TRR61项目期间的成功道路，我们将化学表面修饰和后修饰聚合物刷结构与L沸石全息光钳组装相结合，在这个项目中将实现组装范式的转变：光将作为一个完整的组装工具。它不仅将是光机械结构的一种手段，还将用于光化学键合。在即将到来的项目中，我们将能够获得新型聚合物杂化(有机、无机、金属)组装。光将是目标功能，导致在传感、信息处理和生物医学光子学方面的应用。一方面，我们将利用已建立的诺里什-I类化学，通过定点产生还原相应金属盐的自由基物种，用金属纳米颗粒对L沸石晶体进行功能化处理。此外，同样的光化学也可以应用于光诱导释放表面结合的货物。我们将通过可见光诱导的动态二硒化物交换反应来研究表面修饰和晶体组装的新方法。我们将把我们的绑定策略扩展到DNA链的固定。如果互补链连接到不同的沸石上，DNA杂交将允许一种新的生物杂化组装技术。另一方面，我们将利用负载本身或结构化表面附着的特点，使用新颖的光学操纵和捕获技术来设计复杂的功能化(负载)沸石L纳米容器组装。光学操作将从空间分辨的三维全息光钳，包括完全控制幅度和相位，扩展到由复杂的偏振光场补充的非各向同性陷阱。最终将实现功能光学系统，包括负载L分子筛作为光学传感器，L分子筛链形成灵活可重构的波导，以及偏振敏感的金属有机络合物阵列，以诱导高效的多维等离子体波场。

Nanostructured porous microparticles such as zeolite L crystals are particularly interesting for assembly of nano- and microsystems to larger functional entities due to their hierarchical supramolecular organization of various guest molecules. A prerequisite for an efficient design of larger functional systems is the complete control over the assembly process. It is achieved by a versatile combination of selective chemical modification of the zeolite L surface and subsequent optomechanically-assisted linkage of individual single crystals into larger entities. As a visionary goal, we aim to integrate these building blocks into a larger fully functional photonics toolbox, thereby paving the way to a general light-assisted assembly strategy for soft and bio matter entities.Following the successful path of the previous project periods of former TRR 61, in which we combined chemical surface modification and postmodifiable polymer brush structures with zeolite L assembly by holographic optical tweezers, we will implement a paradigm shift in assembly in this project: Light will act as an integral assembly tool. It will not only be a means for optomechanical structuring, it will also be employed for photochemical bonding. In the upcoming project, we will be able to derive novel polymer hybrid (organic, inorganic, metal) assemblies. Light will be the target functionality, leading to applications in sensing, information processing and biomedical photonics. On the one hand, we will use the established Norrish-Type-I chemistry to functionalize zeolite L crystals with metal nanoparticles by site-selective generation of radical species that will reduce respective metal salts. Additionally, the same photochemistry can be applied for photo-induced release of surface-bound cargos. We will study novel approaches for surface modification and crystal assembly by a visible light induced dynamic diselenide exchange reaction. We will extend our binding strategies to the immobilization of DNA strands. If complementary strands are attached to different zeolites, DNA hybridization allows for a new biohybrid technique of assembling.On the other hand, we will use novel optical manipulation and trapping techniques to design sophisticated assemblies of functionalized (loaded) zeolite L nanocontainers exploiting the features of the load itself or structured surface attachments. Optical manipulation will be extended from spatially resolved three-dimensional holographic optical tweezers including full control of amplitude and phase to non-isotropic traps supplemented by complex polarization light fields. Finally, functional optical systems will be realized including loaded zeolite L as optical sensors, chains of zeolite L to create flexible and reconfigurable wave guides, and polarization-sensitive arrays of metallo-organic complexes to induce efficient multidimensional plasmonic wave fields.