Final Report

J. K. Blasie ; W.F. DeGrado ; J.G. Saven ; M.J. Therien

关键词: COLD NEUTRONS;    COMMUNICATIONS;    DESIGN;    ELECTRON TRANSFER;    FUNCTIONALS;    HARMONIC GENERATION;    OPTIMIZATION;    ORGANIC POLYMERS;    PROTEINS;    SCATTERING;    SIMULATION;    SYMMETRY;    SYNCHROTRONS;    SYNTHESIS;    THERMODYNAMICS;    TRANSIENTS;    X-RAY SPECTROSCOPY Photonic Biomolecular Materials;    Electronic Biomolecular Materials;   

DOI  :  10.2172/1040884
RP-ID  :  DOE-ER46156-Final
PID  :  OSTI ID: 1040884
Others  :  TRN: US201211%%561

学科分类：材料科学（综合）

美国|英语

来源: SciTech Connect

【 摘 要 】

The overall objective is to create robust artificial protein modules as scaffolds to control both (a) the conformation of novel cofactors incorporated into the modules thereby making the modules possess a desired functionality and (b) the organization of these functional modules into ordered macroscopic ensembles, whose macroscopic materials properties derive from the designed microscopic function of the modules. We focus on two specific types of cofactors for imparting functionality in this project; primarily nonlinear optical (NLO) chromophores designed to exhibit extraordinary molecular hyperpolarizabilities, as well as donor-bridge-acceptor cofactors designed to exhibit highly efficient, 'through-bonds' light-induced electron transfer (LIET) over nano-scale distances. The ensembles range from 2-D to 3-D, designed to possess the degree of orientational and positional order necessary to optimize their macroscopic response, the latter ranging from liquid-crystalline or glass-like to long-range periodic. Computational techniques, firmly based in statistical thermodynamics, are utilized for the design the artificial protein modules, based on robust {alpha}-helical bundle motifs, necessarily incorporating the desired conformation, location, and environment of the cofactor. Importantly, this design approach also includes optimization of the interactions between the modules to promote their organization into ordered macroscopic ensembles in 2-D and 3-D via either directed-assembly or self-assembly. When long-range periodic order is required, the design can be optimized to result a specified lattice symmetry. The structure and functionality of the individual modules are fully characterized at the microscopic level, as well as that of the ensembles at the macroscopic level, employing modern experimental physical-chemical and computational techniques. These include, for example, multi-dimensional NMR, various pump-probe transient spectroscopies to ultrafast time-scales, and hyper-Rayleigh scattering at the microscopic level, and synchrotron radiation-based x-ray scattering and x-ray spectroscopy, cold neutron scattering, molecular dynamics simulation, and optical harmonic generation at the macroscopic level. This overall approach has some distinct advantages, compared to more traditional approaches, for example, those based on organic polymers, biopolymers or undressed cofactors. The resulting functional ensembles thereby have potential for important device applications in the areas of optical communications and photovoltaics. The approach also has an absolute requirement for a tightly coupled collaborative effort necessary to span the rigorous demands for the design, synthesis and characterization of such novel photonic and electronic biomolecular materials.