Synthesis, Properties and Dynamics of BODIPY-based Fluorophores

在这个由化学系化学结构、动态和机理B计划资助的项目中，路易斯安那州立大学化学系的Maria G Vicente教授与罗克赫斯特大学化学系的Petia N Bobadova-Parvanova教授合作，正在开发用于生物和材料应用的荧光染料，包括生物成像和化学传感。这项研究的目标是设计、合成并研究新型染料的光物理、电化学和细胞性质，以开发能够与蛋白质和其他生物分子结合的近红外吸收和发射荧光团。该项目涉及设计、合成和评估新的荧光染料及其偶联物的计算和实验方法，这些染料及其偶联物具有增强的稳定性、生物兼容性和实际应用性能。该项目涉及有机化学和无机化学、光谱学、化学动力学、计算建模、细胞和分子生物学、分子识别和生物医学成像，因此非常适合于各级科学家的教育。这一群体也处于有利地位，可以为科学方面代表性不足的学生提供最高水平的教育和培训。涉及K-12学生的外展活动也将是该资助项目的一部分。二吡咯亚硼(BODIPY)染料表现出丰富的光物理和光电性质，包括强烈的吸收和发射轮廓、高的摩尔消光系数、高的荧光量子产率和长的荧光寿命。以前的工作表明，碱性BODIPY核的反应可用于调节吸收和发射波长、斯托克斯位移、稳定性、量子产率、水溶性，以及引入共轭官能团。所提出的合成方法将使基于BODIPY的体系具有更高的稳定性、溶解性和光物理性质，在生物成像和生物传感方面具有实际应用。在这个项目中，主要的策略是：1)通过有效的分子内环化反应来合成具有更高刚性和近红外吸收/发射的融合BODIPY体系；2)区域选择性功能化，以创建摩尔消光系数、荧光发射、斯托克斯位移以及更高的氧化电位和溶解性的推拉式BODIPY体系和BODIPY二联体；以及3)使用多氟化来增强细胞的渗透性、稳定性和生物相容性。该项目利用计算方法来辅助目标设计并对BODIPY的机制和属性进行建模，并探索了BODIPY的合成和功能化的新方法。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Maria G Vicente of the Department of Chemistry at Louisiana State University, in collaboration with Professor Petia N Bobadova-Parvanova of the Department of Chemistry at Rockhurst University, are developing fluorescent dyes for use in biological and material applications, including in bioimaging, and chemosensing. The goal of this research is to design, synthesize and then investigate the photophysical, electrochemical, and cellular properties of the new dyes toward the development of near-infrared absorbing and emitting fluorophores that can be conjugated with proteins and other biomolecules. The project involves both computational and experimental methods to design, synthesize and evaluate new fluorescent dyes and their conjugates, of enhanced stability, biocompatibility and performance for practical applications. This project involves organic and inorganic chemistry, spectroscopy, chemical kinetics, computational modeling, cell and molecular biology, molecular recognition, and biomedical imaging, and is therefore well suited to the education of scientists at all levels. This group is also well-positioned to provide the highest level of education and training for students underrepresented in science. Outreach activities involving K-12 students will also be part of the funded project. Boron dipyrromethene (BODIPY) dyes display a rich array of photophysical and optoelectronic properties, including intense absorption and emission profiles, high molar extinction coefficients, high fluorescence quantum yields and long fluorescence lifetimes. Previous work demonstrated that reactions of the basic BODIPY core can be used for the tuning of the absorption and emission wavelengths, Stokes shifts, stability, quantum yields, water-solubility, and for introduction of functionality for conjugation. The proposed syntheses will afford BODIPY-based systems with enhanced stability, solubility, and photophysical properties for practical applications in bioimaging and biosensing. In this project, the main strategies are 1) use of benzo-annelation via efficient intramolecular cyclizations to produce fused BODIPY systems with enhanced rigidity, and near-IR absorptions/emissions, 2) regioselective functionalizations to create push-pull BODIPY systems and BODIPY dyads with enhanced molar extinction coefficients, fluorescence emissions, Stokes shifts, as well as with increased oxidation potentials and solubility, and 3) use of polyfluorination for enhancement of cellular permeability, stability, and biocompatibility. The project takes advantage of computational methods to assist the target design and to model BODIPY mechanisms and properties, and explores new methodologies for the synthesis and functionalization of BODIPYs.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.