kinetic control of the self-assembly of (poly)peptides into 2- and 3-dimensional assemblies for hierarchical ordering of inorganic nanoparticles

嵌段共聚物的合成及其在溶液中的自组装行为在过去的几十年里得到了广泛的研究。体内药物输送或表面图案化等应用只是这些系统提供的各种有趣机会中的两个。虽然衍生结构的复杂性不断增加，但天然或从头（多）肽组装体（例如蛋白质）仍然远远超过它们的合成类似物。因此，所提出的对（多）肽自组装成二维和三维组装体进行动力学控制以实现无机纳米粒子的分级有序的项目，其目标是生成从头（多）肽的二维和三维组装体在不同的初始溶液条件（例如pH、温度、离子强度）下，在不同溶液条件下获得的组装体的结构变化将提供关于某些肽基序的相互作用的信息，并且可以用于修饰（多）肽序列或自组装途径。当2D和3D组装被证明是稳健的时，进一步的实验将包括逐步的方法，其中（多）肽和/或无机纳米颗粒的几种不同的螺旋束将被并入到预组装的（多）肽中以产生混合结构。此外，还将测试（多）肽与纳米颗粒的直接共组装，并与之前提到的方法进行比较。第三种方法将用于产生混合纳米结构的功能化的（多）肽与氨基酸单元，显示金属特异性interactions.We将监测自组装过程中原位使用光谱和散射方法，而中间和最终组装的结构将集中研究小角散射和显微镜技术。在这里，低温透射电子显微镜（cryoTEM）将常规用于成像的天然，溶解状态的组件。此外，cryoTEM层析成像将被应用于获得（多）肽（杂合）组装体的完整三维真实空间信息。虽然该项目是基础性的，但该项目中开发的例程和技术将有助于创建基于从头（多）肽杂合组装体的二维分级有序结构，预计将改善等离子体太阳能电池的光吸收制造。

The synthesis of block copolymers and their self-assembly behavior in solution have extensively been investigated in the last decades. Applications like in-vivo drug delivery or the patterning of surfaces are only two of the various interesting opportunities that these systems offer. Though the complexity of the derived structures is constantly increasing, natural or de-novo (poly)peptide assemblies (e.g. proteins) still exceed their synthetic analogs by far.Therefore, the proposed project kinetic control of the self-assembly of (poly)peptides into 2- and 3-dimensional assemblies for hierarchical ordering of inorganic nanoparticles will aim for the generation of 2D and 3D assemblies of de-novo (poly)peptides under different initial solution conditions (e.g. pH, temperature, ionic strength). Structural changes of the assemblies obtained at different solution conditions will provide information on the interactions of certain peptide motifs and can be used to either modify the (poly)peptide sequence or the self-assembly pathway. When 2D and 3D assemblies prove to be robust, further experiments will include a step-wise approach where several different helical bundles of (poly)peptides and/or inorganic nanoparticles will be incorporated into pre-assembled (poly)peptides to create hybrid structures. In addition direct co-assembly of (poly)peptides with nanoparticles will be tested as well and compared to the approach mentioned before. A third method for the generation of hybrid nanostructures that will be applied is the functionalization of the (poly)peptides with amino acid units that show metal-specific interactions.We will monitor the self-assembly process in-situ using spectroscopic and scattering methods, whereas intermediate and final assembled structures will be investigated intensively by small angle scattering and by microscopy techniques. Here cryogenic transmission electron microscopy (cryoTEM) will be utilized routinely for imaging the native, solubilized state of the assemblies. Furthermore, cryoTEM tomography will be applied to obtain full 3-dimensional real-space information of the (poly)peptide (hybrid)assemblies.Though the project is fundamental, the developed routines and techniques within this project will help to create 2D hierarchically ordered structures based on de-novo (poly)peptide hybrid assemblies that are expected to improve the light absorption fabrication of plasmonic solar cells.