ELECTRONICALLY ACTIVE AIB HELICES

提出的研究方案是设计和合成具体的 合成的含有β-(芳香)-的螺旋寡肽- 丙氨酸，并测量光致电子动力学 这些多组分的单重态和三重态激发态 利用纳秒和皮秒瞬变进行共价组装 吸收法。天然芳香氨基酸将是 在螺旋线上的中间位置引入以检验理论 因为他们参与了远程电子转移。 基于最新发展的量子理论的方法 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，并将 应用于这些分子系统。各种不同的技术 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 这将使对多肽作用的深入研究成为可能 结构在调节长程电子转移相互作用中的作用。 目前的目标是设计和构建一种新的系统，其中 观察复杂的电子相互作用现象；这 开发了程序来促进两个Long的汇合 范围目标：了解中介的参与 电子加速、控制或引导电子的残留物 转移反应性，并设计合成电子转移 蛋白质。 具体地说，将包括供体和受体氧化还原中心。 在一系列富含疏水低聚肽的序列内 在α-氨基异丁酸(AIB)中，将由 已知的方法。富含AIB的寡肽形成310个螺旋和 天然存在于微生物多肽抗生素中。瞬变 基于调Q开关的YAG/染料吸收光谱仪 闪光灯泵浦锁模YAG激光器将提供这一能力 在非常宽的范围内跟踪电子转移动力学 时间刻度(距离)。合成家庭的能力 相关寡肽将被广泛开发并代表 这种聚合方法的一个显著优势是结构化 电子给体/微扰剂/受体络合物。

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.