Charge-Transfer Dynamics and Energy Transduction

描述（由申请人提供）：我们试图通过肽和小蛋白的设计和合成来理解蛋白质和辅因子构象和化学动力学在生物能量转导中的作用。为了实现这一目标，我们将详细说明从根本上不同于天然光合系统和电子转移蛋白质，这将最终使我们能够破译的基本工程标准，重要的是光子能转化为电化学势能的新类别的从头蛋白质。这些研究利用从头四-α-螺旋蛋白质工程结合供体-间隔区-受体超分子和共价连接的多辅因子组件。我们将努力关联这些系统的结构、功能和动力学，利用来自计算蛋白质设计、肽合成、超分子化学和超快动力学实验的信息，包括瞬态光泵/光探针和可见光泵/红外探针光谱;这项工作将提供一个更深入，更积极的理解（i）蛋白质折叠，（ii）如何局部静电力，围绕供体，受体，和生色团可以独立调节，（iii）蛋白质中电子和质子耦合的电子转移和自由基产生的功能方面，以及（iv）蛋白质介导的能量转导的基本动力学。

DESCRIPTION (provided by applicant): We seek to understand the roles that protein and cofactor conformational and chemical dynamics play in biological energy transduction through the design and synthesis of peptides and small proteins. Towards this goal, we will elaborate new classes of de novo proteins that differ radically from natural photosynthetic systems and electron transfer proteins that will ultimately enable us to decipher the essential engineering criteria important for the efficient conversion of photonic energy into electrochemical potential energy. These investigations exploit de novo tetra-a-helical proteins engineered to bind donor-spacer-acceptor supermolecules and covalently linked multicofactor assemblies. We will strive to correlate structure, function, and dynamics in these systems, utilizing information derived from computational protein design, peptide synthesis, supermolecular chemistry, and ultrafast dynamical experiments that include transient optical pump / optical probe and visible pump / IR probe spectroscopies; this work will provide a deeper, more active understanding of (i) protein folding, (ii) how local electrostatic forces that surround donor, acceptor, and chromophore can be independently modulated, (iii) functional aspects of electron and proton coupled electron transfer and radical generation in proteins, and (iv) the essential dynamics of protein mediated energy transduction.