ELECTRONICALLY ACTIVE AIB HELICES

建议的研究计划是设计和合成特定的 含有β-（芳族）- 丙氨酸和测量光诱导的电子动力学从 这些多组分的单重态和三重激发态 使用纳秒和皮秒瞬态的共价组装 吸收法 天然芳香族氨基酸将是 沿着螺旋线沿着插入位置来测试理论 因为它们参与了长距离电子转移。 基于最近发展的量子力学的理论方法 电子隧穿的路径积分蒙特卡罗方法 还将追求复杂的结构化环境， 应用于这些分子系统。 不同的技术， 合成化学，寡肽合成，时间分辨激光 光谱学和理论量子模拟方法 将使人们能够深入研究多肽的作用， 在调制远程电子转移相互作用的结构。 目前的目标是设计和建立一个新的系统， 观察复杂的电子相互作用现象;这 该计划是为了促进两个长期的融合而制定的 范围目标：了解中介的参与 加速、控制或引导电子的残基 转移反应性，并设计合成电子转移 proteins. 具体来说，将包括供体和受体氧化还原中心 在一系列富含疏水寡肽的序列内， 在α-氨基异丁酸（Aib）中， 已知的方法。 富含Aib的寡肽形成310个螺旋， 天然存在于微生物肽抗生素中。 瞬态 基于Q开关YAG/染料的吸收光谱仪， 闪光泵浦锁模YAG激光器将提供这种能力 为了在很宽的范围内跟踪电子转移动力学， 时间尺度（距离）。 能够合成 相关的寡肽将被广泛开发， 这种聚合物方法的一个显著优点是 电子给体/微扰剂/受体复合物。

The proposed research program is to design and synthetic specific synthetic helical oligopeptides containing beta-(aromatic)- alanines and to measure light-induced electron dynamics from singlet and triplet excited states of these multicomponent covalent assemblies using nanosecond and picosecond transient absorption methods. Natural aromatic amino acids will be introduced in intervening positions along the helix to test theories for their participation in long range electron transfer. Theoretical approaches based on the recently developed quantum path integral Monte Carlo approach to electron tunneling in complex structured environments will also be pursued and will be applied to these molecular systems. The diverse techniques of synthetic chemistry, oligopeptide synthesis, time-resolved laser spectroscopy, and theoretical quantum simulation methods together will enable an intense study of the role of polypeptide structure in modulating long range electron transfer interactions. The immediate aim is to design and build a novel system in which to observe complex electronic interaction phenomena; this program was developed to advance the confluence of two long range goals: to understand the participation of intermediary residues in accelerating, controlling, or directing electron transfer reactivity, and to design synthetic electron transfer proteins. Specifically, donor and acceptor redox centers will be included within the sequence of a series of hydrophobic oligopeptides rich in alpha-aminoisobutyric acid (Aib) which will be synthesized by known methods. Aib-rich oligopeptides form 310 helices and occur naturally in microbial peptide antibiotics. Transient absorption spectrometers based on Q-switched YAG/dye and flash-pumped mode-locked YAG lasers will provide the capability to follow electron transfer kinetics over a very wide range of time scales (distances). The ability to synthesize families of related oligopeptides will be extensively exploited and represents a significant advantage of this polymeric approach to structured electron donor/perturbant/acceptor complexes.