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高分子化学计划支持佐治亚大学的弗拉基米尔·V·波皮克教授，他建议开发一种新的耐光性保护基团(PPG)家族，其基础是光化学消除邻羟基苯甲醇衍生物的底物。初步结果表明，基于该反应的PPG虽然普遍适用，但特别适合于醇类的直接笼化。这一新的PPG平台还将被用于乙二醇类、碳水化合物和羰基化合物的耐光性保护。在本项目中开发的PPG有望具有较长的货架期和在黑暗中良好的水解稳定性，以及高的光去保护量子和化学产率。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。我们将对裂解反应的机理和动力学进行详细的研究，以帮助我们设计新型的PPG。这项研究的广泛影响将为有机合成、生物化学和医学技术提供新的笼子工具。在这项工作中开发的PPG和光致变色系统可以作为设计可被光激活的新药物和药物输送系统的基础，以及打开光刻和信息记录的新方法。该项目将为本科生和研究生提供关于合成、物理有机化学和光化学界面的跨学科培训。来自代表性不足群体的学生将被招募到这个项目中工作。将建立一个光化学实验室，为佐治亚大学和当地科学家提供进行光化学实验的仪器和专业知识。这项研究的跨学科性质预计将产生与当地和国际上的其他研究小组的广泛合作。

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.