Synthesis, Properties and Dynamics of Near-IR BODIPY Fluorophores

在这个由化学部化学结构、动态和机制B项目资助的项目中，路易斯安那州立大学化学系的Maria da grapara H. Vicente教授将与罗克赫斯特大学化学系的副教授Petia Bobadova-Parvanova合作，开发一种新型荧光染料，用于生物成像、生物传感和生物分析等生物应用。本研究的目的是设计、合成并研究新型染料的光物理和细胞特性，以开发可与蛋白质和其他生物分子偶联的近红外吸收和发射荧光团。该项目采用计算和实验方法来设计、合成和评估新型荧光染料及其偶联物，涉及有机和无机化学、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，因此非常适合各级科学家的教育。这个群体也处于有利地位，可以为科学领域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资助项目的一部分。二吡咯甲烷硼（BODIPY）染料具有丰富的光物理和光电子特性，包括强吸收和发射谱、高摩尔消光系数、高荧光量子产率和长荧光寿命；基本BODIPY核心的反应可用于调整吸收和发射波长、斯托克斯位移、光稳定性、量子产率、水溶性以及引入共轭功能。所提出的合成方法将得到扩展的，β, β '-苯并引信和8取代的BODIPYs。在本项目中，主要策略是：1)在BODIPY的β， β '-吡啶位置上开发苯并化，以及在3,5位置上进行功能化，以增加BODIPY核心的共轭pi系统，刚性和水溶性；2)通过计算建模和合成aza-BODIPY研究在8位置上引入氮原子。3)通过各种亲核试剂的取代研究硼中心的功能化。该项目利用计算方法来辅助目标设计和模拟BODIPY的机制和性质，并探索BODIPYs和aza-BODIPYs的合成和功能化的新方法。

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Maria da Graça H. Vicente of the Department of Chemistry at Louisiana State University, in collaboration with Associate Professor Petia Bobadova-Parvanova of the Department of Chemistry at Rockhurst University, will develop a new class of fluorescent dyes for use in biological applications, such as in bioimaging, biosensing, and bioanalyses. The goal of this research is to design, synthesize and then investigate the photophysical 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 the new fluorescent dyes and their conjugates, involving 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; reactions of the basic BODIPY core can be used for the tuning of the absorption and emission wavelengths, Stokes' shifts, photostability, quantum yields, water-solubility, and for introduction of functionality for conjugation. The proposed syntheses will afford pi-extended, beta, beta'-benzo-fuzed and 8-substituted BODIPYs. In this project, the main strategies are 1) to develop the use of benzo-annelation at the beta, beta'-pyrrolic positions of the BODIPY, as well as functionalizations of the 3,5-positions to increase the conjugated pi-system, rigidity, and water-solubility of the BODIPY core, 2) to investigate the introduction of a nitrogen atom at the 8-position via computational modeling and the synthesis of aza-BODIPYs, and 3) investigate the functionalization at the boron center via substitutions using various nucleophiles. 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 functionalizations of BODIPYs and aza-BODIPYs.