Development of Photolabile Protecting Groups and Photochromic Systems Based on Intramolecular Excited State Proton Transfer

美国国家科学基金会化学部的有机和大分子化学项目支持格鲁吉亚大学的弗拉基米尔V. Popik教授，他提出开发一种新的光不稳定保护基团（PPG）家族，该家族基于邻羟基苯甲醇衍生物中底物的光化学消除。初步结果表明，PPG基于该反应，而一般适用，是特别适合于直接笼醇。这个新的PPG平台也将被研究用于二醇、碳水化合物和羰基化合物的光不稳定保护。本项目开发的PPG预期具有较长的保质期和良好的黑暗水解稳定性，以及较高的光脱保护量子产率和化学产率。预计新开发的PPG的底物释放速度足够快，可以进行空间和时间分辨的生化研究。裂解反应的机制和动力学将被详细研究，以帮助我们在设计新的PPGs.Brother的影响，拟议的研究将有助于新的笼工具，有机合成，生物化学和医疗技术。在这项工作中开发的PPG和光致变色系统可以作为设计可以被光活化的新药物和药物递送系统的基础，以及打开光刻和信息记录的新方法。本计画将提供本科生与研究生在合成、物理有机化学与光化学之介面上跨学科的训练。来自代表性不足群体的学生将被招募参加这个项目。将建立一个光化学实验室，为格鲁吉亚大学和当地科学家提供进行光化学实验的仪器和专门知识。研究的跨学科性质，预计将产生广泛的合作与其他研究小组，在本地和国际。

The Organic and Macromolecular Chemistry Program in the Chemistry Division at the National Science Foundation supports Professor Vladimir V. Popik of the University of Georgia who proposes to develop a new family of photolabile protecting groups (PPGs) based on photochemical elimination of substrates from o-hydroxybenzyl alcohol derivatives. Preliminary results suggest that PPGs based on this reaction, while generally applicable, are especially suitable for the direct caging of alcohols. This new PPG platform will also be investigated for the photolabile protection of glycols, carbohydrates, and carbonyl compounds. PPGs developed in this project are expected to have long shelf-life and good hydrolytic stability in the dark, as well as high quantum and chemical yield of photo-deprotection. Substrate release from the newly-developed PPGs is expected to be fast enough to allow for spatial- and time-resolved biochemical studies. The mechanism and dynamics of the cleavage reaction will be studied in detail to assist us in the design of novel PPGs.Broader impacts of the proposed research will contribute new caging tools to organic synthesis, biochemistry, and medical technology. PPGs and photochromic systems developed in this work might serve as a basis for the design of new drugs and drug delivery systems that can be photoactivated, as well as open new approaches to photolithography and information recording. This project will provide undergraduate and graduate students with interdisciplinary training on the interface of synthetic, physical organic chemistry, and photochemistry. Students from underrepresented groups will be recruited to work on this project. A photochemical laboratory will be established, which will provide the University of Georgia and local scientists with apparatus and expertise to conduct photochemical experiments. The interdisciplinary nature of the research is expected to produce extensive collaboration with other research groups, both locally and internationally.