Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, University of Notre Dame, Notre Dame, IN 46556, USA.
Org Biomol Chem. 2021 Apr 14;19(14):3213-3219. doi: 10.1039/d1ob00306b. Epub 2021 Mar 24.
Targeted fluorescent molecular probes are useful for cell microscopy, diagnostics, and biological imaging. An emerging discovery paradigm is to screen libraries of fluorescent molecules and identify hit compounds with interesting targeting properties. However, a current limitation with this approach is the lack of fluorescent molecular scaffolds that can produce libraries of probe candidates with three dimensional globular shape, chiral centers, and constrained conformation. This study evaluated a new probe scaffold called squaraine figure-eight (SF8), a self-threaded molecular architecture that is comprised of an encapsulated deep-red fluorescent squaraine dye, surrounding tetralactam macrocycle, and peripheral loops. Easy synthetic variation of the loops produced four chiral isomeric SF8 probes, with the same log P values. Cell microscopy showed that subtle changes in the loop structure led to significant differences in intracellular targeting. Most notably, a comparison of enantiomeric probes revealed a large difference in mitochondrial accumulation, very likely due to differences in affinity for a chiral biomarker within the organelle. A tangible outcome of the research is a probe candidate that can be: (a) developed further as a bright and photostable, deep-red fluorescent probe for mitochondrial imaging, and (b) used as a molecular tool to identify the mitochondrial biomarker for selective targeting. It will be straightforward to expand the SF8 probe chemical space and produce structurally diverse probe libraries with high potential for selective targeting of a wide range of biomarkers.
靶向荧光分子探针在细胞显微镜、诊断和生物成像方面非常有用。一种新兴的发现范式是筛选荧光分子文库,并鉴定具有有趣靶向特性的命中化合物。然而,这种方法目前的局限性在于缺乏能够产生具有三维球状形状、手性中心和受限构象的探针候选物文库的荧光分子支架。本研究评估了一种称为方酸八元环(SF8)的新型探针支架,这是一种自穿分子架构,由包裹的深红色荧光方酸染料、四元内酰胺大环和外围环组成。环的简单合成变化产生了四个手性异构 SF8 探针,具有相同的 logP 值。细胞显微镜显示,环结构的细微变化导致细胞内靶向性的显著差异。最值得注意的是,对对映体探针的比较揭示了线粒体积累的巨大差异,很可能是由于对细胞器内手性生物标志物的亲和力不同所致。研究的一个实际成果是可以进一步开发作为明亮和光稳定的深红色荧光探针用于线粒体成像的探针候选物,以及用作分子工具来鉴定用于选择性靶向的线粒体生物标志物。扩展 SF8 探针化学空间并产生具有高选择性靶向广泛生物标志物潜力的结构多样的探针文库将非常简单。