Department of Chemistry, Howard Hughes Medical Institute, University of California, Berkeley, CA 94720, USA.
Proc Natl Acad Sci U S A. 2010 Dec 14;107(50):21316-21. doi: 10.1073/pnas.1012864107. Epub 2010 Nov 29.
Living organisms produce hydrogen peroxide (H(2)O(2)) to kill invading pathogens and for cellular signaling, but aberrant generation of this reactive oxygen species is a hallmark of oxidative stress and inflammation in aging, injury, and disease. The effects of H(2)O(2) on the overall health of living animals remain elusive, in part owing to a dearth of methods for studying this transient small molecule in vivo. Here we report the design, synthesis, and in vivo applications of Peroxy Caged Luciferin-1 (PCL-1), a chemoselective bioluminescent probe for the real-time detection of H(2)O(2) within living animals. PCL-1 is a boronic acid-caged firefly luciferin molecule that selectively reacts with H(2)O(2) to release firefly luciferin, which triggers a bioluminescent response in the presence of firefly luciferase. The high sensitivity and selectivity of PCL-1 for H(2)O(2), combined with the favorable properties of bioluminescence for in vivo imaging, afford a unique technology for real-time detection of basal levels of H(2)O(2) generated in healthy, living mice. Moreover, we demonstrate the efficacy of PCL-1 for monitoring physiological fluctuations in H(2)O(2) levels by directly imaging elevations in H(2)O(2) within testosterone-stimulated tumor xenografts in vivo. The ability to chemoselectively monitor H(2)O(2) fluxes in real time in living animals offers opportunities to dissect H(2)O(2)'s disparate contributions to health, aging, and disease.
生物体产生过氧化氢 (H(2)O(2)) 以杀死入侵的病原体并进行细胞信号传递,但这种活性氧物种的异常产生是衰老、损伤和疾病中氧化应激和炎症的标志。由于缺乏研究体内这种瞬态小分子的方法,H(2)O(2)对活体动物整体健康的影响仍然难以捉摸。在这里,我们报告了 Peroxy Caged Luciferin-1 (PCL-1) 的设计、合成和体内应用,这是一种用于实时检测活体动物内 H(2)O(2)的化学选择性生物发光探针。PCL-1 是一种硼酸封端的萤火虫荧光素分子,它选择性地与 H(2)O(2)反应释放萤火虫荧光素,在存在萤火虫荧光素酶的情况下触发生物发光反应。PCL-1 对 H(2)O(2) 的高灵敏度和选择性,结合生物发光用于体内成像的有利特性,为实时检测健康、活体小鼠中产生的基础 H(2)O(2)水平提供了独特的技术。此外,我们通过直接成像体内睾酮刺激的肿瘤异种移植中 H(2)O(2)水平的升高,证明了 PCL-1 用于监测 H(2)O(2)水平生理波动的功效。能够在活体动物中实时化学选择性地监测 H(2)O(2)通量为剖析 H(2)O(2)对健康、衰老和疾病的不同贡献提供了机会。