Redox and Excited State Properties of Oligothiophene-Bearing Ru(II) Photodrugs

含低聚噻吩 Ru(II) 光药物的氧化还原和激发态性质

• 批准号: 2400127
• 负责人: Sherri McFarland
• 金额: $ 55万
• 依托单位: University of Texas at Arlington
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-06-01 至 2027-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2400127&HistoricalAwards=false
• 关键词: Redox; Excited; State; Properties; Oligothiophene

WIth support from the Chemical Structure, Dynamics, and Mechanism-B (CSDM-B) program, Professor Sherri McFarland at the University of Texas, Arlington will interrogate how molecular conformation, ionizability, and intermolecular interactions influence the behavior of photosensitizers, particularly oligothiophene-containing ruthenium compounds. Photosensitizers are compounds that harness the light energy to facilitate a desirable physical process or chemical transformation. Such molecules have utility in fields spanning solar energy conversion to chemical catalysis, and also photomedicine. This project focuses on a photosensitizer class that shows promise for cancer therapy and may follow a unique type of multimodal action that combines photocatalysis and intermolecular photochemical reactions with singlet oxygen sensitization. The project will use the tools of coordination chemistry plus photophysical and electrochemical techniques to explore the roles of isomerism, agglomeration and confinement, and environment on these pathways. The proposed work will train graduate students and undergraduates in highly multidisciplinary research at the nexus of chemistry, biology, physics, and engineering. This multifaceted training in synthesis, inorganic photophysics and spectroscopy, and electrochemistry will help to prepare the future workforce in science and technology. The broader impact objectives are aimed at improving scientific literacy and addressing educational equity in research. The McFarland team is particularly focused on addressing educational equity issues in undergraduate research and improving scientific literacy using bench-to-bedside projects with societal impact through curriculum-based research experiences (CUREs) for undergraduate STEM students. The project aims to equip tomorrow’s leaders with skills in science communication and expose them to entrepreneurship as it relates to bringing scientific discoveries from the laboratory to society.Under this award, Professor Sherri McFarland and her team will examine the redox and excited state properties of oligothiophene-containing Ru(II) complexes, compounds that have important applications as photosensitizers in fields ranging from solar energy conversion to photomedicine. Imidazo[4,5-f][1,10]phenanthroline (IP) ligands appended to oligothiophenes (nT) of sufficient chain length n adopt planarized lowest-energy triplet states that are of significant intraligand charge transfer (ILCT) character. Oligothiophenes are redox active, and the neighboring IP group may enable proton coupled electron transfer (PCET) to facilitate catalytic photoredox reactions from the 3ILCT states. These charge-separated excited states may also undergo chemical dimerization and generate singlet oxygen. The project aims to develop a photophysical model for these systems in simple solvents and in complex biological environments. Each system will be studied from the point of view of molecular structure, redox chemistry and photophysics, with longer term implications for phototherapy mechanisms. The UTA team will synthesize and characterize oligothiophene-appended Ru(II) complexes, [Ru(LL)2(IP-nT)]2+, to probe the effects of various factors on the proposed PCET-facilitated pathways: ionization state, excited state conformation, triplet energy and character, and bimolecular processes. Synthetic, spectroscopic, and electrochemical techniques will be used to test the importance of nT-based triplets with CT character and ionizable groups for multimodal action and probe how the excited state dynamics are influenced at biological interfaces based on factors such as ionization, conformation, and isomerism. This project aims to advance the fields of coordination chemistry, photochemistry and photophysics, and ultimately photomedicine, in the longer term.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学结构，动力学和机制-B（CSDM-B）计划的支持下，德克萨斯大学的Sherri McFarland教授将质疑分子构象，电离性和分子间相互作用如何影响照片感应者的行为，尤其是寡硫酸盐含有寡素的Ruthenium Amplecounts。光敏剂是利用轻能的化合物，以促进理想的物理过程或化学转化。这种分子在跨越太阳能转化为化学催化的田间和光学医学上具有效用。该项目的重点是光敏剂类别，该类别显示出对癌症治疗的希望，并可能遵循一种独特的多模式作用，该动作将光催化和分子间光化学反应与单线氧敏感性结合在一起。该项目将使用协调化学的工具以及光物理和电化学技术来探索异构主义，聚集和限制以及环境在这些途径中的作用。拟议的工作将在化学，生物学，物理学和工程学联系的高度多学科研究中培训研究生和本科生。这种在合成，无机摄影和光谱和电化学方面的多方面培训将有助于准备科学技术领域的未来劳动力。更广泛的影响目标旨在提高科学素养并解决研究中的教育公平。 McFarland团队尤其专注于解决本科研究中的教育公平问题，并使用基于课程的研究经验（Cures）为本科STEM学生提供具有社会影响的基准对床头项目提高科学素养。该项目旨在为明天的领导者提供科学沟通技巧，并将其暴露于企业家精神，因为它与将科学发现从实验室带到社会上。光学医学。 Imidazo [4,5-f] [1,10]均具有足够的链长n采用计划的最低能量的三胞胎状态，这些均具有重要的内部感应电荷传递（ILCT）特征。寡头碘是氧化还原活性的，相邻的IP组可以启用质子耦合的电子转移（PCET），以促进来自3ILCT状态的催化光电氧反应。这些电荷分离的激发态也可能经历化学二聚化并产生单线氧。该项目旨在在简单的解决方案和复杂的生物学环境中为这些系统开发一个光物理模型。将从分子结构，氧化还原化学和摄影的角度研究每个系统，对光疗机制具有长期影响。 UTA团队将合成并表征寡硫氰酸偶然的RU（II）配合物，[RU（LL）2（IP-NT）] 2+，以探测各种因素对拟议的PCET启用途径的影响：电离状态，激发状态，激发态状态会议，三重能量，三重能量，三重能量和特征以及生物生物生物的过程。合成，光谱和电化学技术将用于测试具有CT特征的基于NT的三胞胎和可电离组对多模式作用的重要性，并探测如何基于诸如电离，会议和异构症等因素的因素在生物学接口上影响激动人心的状态动力学。该项目旨在从长远来看，旨在推进协调化学，光化学和光体物理学以及最终摄影医学领域的领域。该奖项反映了NSF的法定任务，并被认为是通过基金会的智力优点和更广泛影响的评估标准通过评估而被视为珍贵的支持。