Giger Autumn I, Voldrich Jaiden C, Michel Brian W
Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado 80210, United States.
J Am Chem Soc. 2025 Apr 9;147(14):11654-11661. doi: 10.1021/jacs.5c00854. Epub 2025 Mar 27.
Amplified sensing offers the potential for high sensitivity; however, the vast majority of molecular strategies involve stoichiometric detection and signal transduction, including numerous recent examples of systems inspired by transition-metal-catalyzed reactions. Activation of latent precatalysts by a target analyte represents an attractive strategy for detecting low-concentration species. Analyte amplification represents another attractive approach, akin to PCR-based assays. Here we report an autocatalytic detection system based on the ethylene activation of Ru-I2 olefin metathesis precatalysts. Signal transduction is amplified by both catalytic ring closing metathesis of profluorescent substrates and ethylene propagation to activate additional units of catalyst. High sensitivity is observed as a result of this dual-mode amplified detection of ethylene. Detection of endogenous ethylene from fruit and oxidation-decomposition of polyunsaturated fatty acids via lipid peroxides is demonstrated.
放大传感具有实现高灵敏度的潜力;然而,绝大多数分子策略都涉及化学计量检测和信号转导,包括许多近期受过渡金属催化反应启发的系统实例。目标分析物对潜在前催化剂的激活是检测低浓度物质的一种有吸引力的策略。分析物放大是另一种有吸引力的方法,类似于基于聚合酶链式反应(PCR)的检测方法。在此,我们报道了一种基于Ru-I2烯烃复分解前催化剂的乙烯活化的自催化检测系统。信号转导通过荧光底物的催化闭环复分解以及乙烯的传播来激活额外的催化剂单元而得到放大。由于这种乙烯的双模式放大检测,实现了高灵敏度。本文展示了对水果中内源性乙烯的检测以及通过脂质过氧化物对多不饱和脂肪酸的氧化分解。