Lartia Rémy, Allain Clémence, Bordeau Guillaume, Schmidt Falk, Fiorini-Debuisschert Céline, Charra Fabrice, Teulade-Fichou Marie-Paule
Institut Curie, CNRS UMR-176, bat 110, Centre Universitaire, 91405 Orsay Cedex, France,
J Org Chem. 2008 Mar 7;73(5):1732-44. doi: 10.1021/jo702002y. Epub 2008 Feb 2.
A versatile synthetic strategy to access a set of highly fluorescent pi-conjugated triphenylamines bearing a functional linker at various positions on one phenyl ring is described. These compounds were designed for large two-photon absorption (2PA) and in particular for labeling of biomolecules. The monoderivatized trisformylated or trisiodinated intermediates described herein allow introduction of a large variety of electron-withdrawing groups required for large 2PA as well as a panel of chemical functions suitable for coupling to biomolecules. The monoderivatized three-branched compounds and in particular the benzothiazole (TP-3Bz) series show remarkable linear (high extinction coefficients and high quantum yield) and nonlinear (high 2-photon cross sections) optical properties. Interestingly the presence of functional side chains does not disturb the two-photon absorption. Finally, monoderivatized two-branched derivatives also appear to be valuable candidates. Altogether the good optical properties of the new derivatizable pi-conjugated TPA combined with their small size and their compatibility with bioconjugation protocols suggest that they represent a new chemical class of labels potentially applicable for the tracking of biomolecules using two-photon scanning microscopy.
本文描述了一种通用的合成策略，用于制备一系列在一个苯环的不同位置带有功能连接基的高荧光π共轭三苯胺。这些化合物被设计用于实现大的双光子吸收（2PA），特别是用于生物分子的标记。本文所述的单衍生化三醛基化或三碘化中间体允许引入大2PA所需的多种吸电子基团以及适合与生物分子偶联的一系列化学官能团。单衍生化的三分支化合物，特别是苯并噻唑（TP-3Bz）系列，表现出显著的线性（高消光系数和高量子产率）和非线性（高双光子截面）光学性质。有趣的是，功能性侧链的存在并不干扰双光子吸收。最后，单衍生化的双分支衍生物似乎也是有价值的候选物。总之，新的可衍生化π共轭TPA的良好光学性质，结合其小尺寸以及与生物共轭方案的兼容性，表明它们代表了一类新的化学标记物，有可能适用于使用双光子扫描显微镜追踪生物分子。
