To understand the influence of the pH on the rate of autocatalysis (as illustrated in Figure ), one has to start by identifying the rate constants that a priori are the most strongly pH dependent. On account of the two pKas of the 1,4-NQH2 (pKa,1 = 9.48 and pKa,2 = 11.02, see SI), the rate constants k0, kco,1 and k3 are clearly much pH sensitive than the other rate constants of the model (since this is HO2 -the reactive species involved in the oxidative cleavage of boronates, the constants k are also pH dependent but to a lesser extent than k0, kco,1 and k3). Therefore, if we consider kco,1 and k3 (k0 is not taken into account for the same reason as previously) are mainly responsible for the pH dependency of the autocatalysis rate, this should be verifiable through the simulation of the H2O2 calibration curve. From the two pKas of the 1,4-NQH2, we can calculate the values of kco,1 and k3 at pH 9.5, which are 6.6 × 10 6 M -1 •s - 1 and 4.7 × 10 6 M -1 •s -1 , respectively (see SI). The theoretical H2O2 calibration curve (orange line in Figure ) determined using these new values of kco,1 and k3 (while keeping the other rate constants the same as previously at pH 8.5) finally agrees quite well with the experimental plot at pH 9.5 (black squares in Figure ). This result confirms the key role played by both kco,1 and k3 in the pH-rate dependence of the autocatalysis. A better fit to the data would certainly be obtained by increasing slightly the two deprotection rate constants are also expected to rise with the pH. This kinetic analysis also explains the better detection limit obtained by increasing the pH (Figure ). Indeed, if we admit that the NADH autoxidation (kns) (which determines the nonspecific response of the system and thus the LOD) varies less rapidly with the pH than the overall rate of autocatalysis (varying predominantly with the pH through kco,1 and k3), then we can understand why the LOD is 10-fold improved when the pH is increased from 8.5 to 9.5.