ABSTRACT We report an autocatalytic molecular amplification system based on the double masking of benzoquinones with boronate ester protecting groups (i.e., diboronate ester probes). This design extends a previously described redox cross‐catalytic (RCC) reaction scheme, in which hydrogen peroxide (H 2 O 2 ) and quinones are exponentially co‐generated through coupled catalytic loops. The double protection aims to enhance the chemical stability of the diboronate probes while preserving their ability to undergo autocatalytic deprotection. Through kinetic modeling and experimental validation, we demonstrate that complete deprotection to the corresponding quinones can occur even under substoichiometric H 2 O 2 conditions, thereby sustaining autocatalytic behavior. Comparative studies of symmetric and asymmetric diboronate probes reveal how molecular structure and electronic effects control the kinetics of each deprotection step and so the overall amplification efficiency. Finally, we show that these doubly protected systems enable efficient responses to H 2 O 2 across more than two orders of magnitude in concentration (from µM to sub‐millimolar range) and within minutes, while providing improved probe stability and tunable reactivity. This work offers mechanistic insights and design principles for next‐generation autocatalytic redox amplification systems with enhanced analytical performance.
Hui et al. (Fri,) studied this question.