Buffer-catalyzed perhydrolysis of aryl esters enables non-oxidative and enzyme-free H2O2 detection in food.

Accurate detection of residual H2O2 in food is essential for safety compliance, yet conventional methods rely on its oxidative reactivity and are susceptible to redox-active interferents. We report an alternative strategy based on perhydrolysis of activated aryl esters, which is enabled by common biological buffers as general base catalysts under near-neutral conditions. Mechanistic studies, including kinetics, product identification, and DFT calculations, reveal a concerted asynchronous pathway without a discrete HOO- intermediate. This oxidation-independent mechanism supports two practical assays: a fluorogenic FDA assay for trace quantification (LOD 1.3 μM) and a chromogenic NPA assay for rapid screening (LOD 7.3 μM). The FDA assay gave recoveries of 80-120% in spiked samples, while the NPA assay serves as a screening tool for moderate-to-high peroxide levels. They also outperform a standard HRP-based assay in complex matrices. This work establishes buffer-catalyzed perhydrolysis as a practical platform for interference-resistant H2O2 monitoring in food safety.