## 3 Results and Discussion  
Scheme 1 illustrates the preparation of the zinc-containing nanoparticle catalyst (i.e., **NP-Zn**). The surface- and core-cross-linking of the micelles were monitored by \({}^{1}\)H NMR spectroscopy (Figure S1). The resulting **NP-Zn** was characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM) for its particle size (Figures S2-S5). We initially used **1a** as the substrate to evaluate the hydrolytic activity of **NP-Zn** but found that the compound hydrolyzes too quickly under our experimental conditions (pH 7 at 25 \({}^{\circ}\)C). We then employed a less reactive substrate (**1b**) to evaluate the performance of our catalyst. Figure 1a shows the reaction rates for the hydrolysis of **1b** in aqueous buffer over pH 6.5-9.5. The background hydrolysis in the buffer is slow below pH 8 and increases steadily above pH 8. This is consistent with base-promoted hydrolysis of the carbonate with a higher concentration of hydroxide under more basic conditions [48]. The presence of the (unpolymerized) zinc-containing **FM** in the solution makes very little difference in the hydrolysis rate, while both NINP and **NP-Zn** speed up the hydrolysis strongly. The  
largest rate acceleration by the nanoparticles over the background hydrolysis occurs over pH 6.5-7.5. Cationic micelles are known to help deprotonation of water near the micelle surface by their electric potentials. The surface of the micelles of cetyltrimethylammonium bromide (CTAB), for example, has a local pH of 9.5 when the bulk solution is neutral [49]. The effect of the electric potential is stronger when the micelle is cross-linked [50]. Thus, the higher reactivity of **1b** in the presence of cross-linked cationic micelles (NINP) is not surprising. A more important question is whether **NP-Zn** is able to catalyze the hydrolysis of diaryl carbonates, as hypothesized in Scheme 1. The molecularly imprinted catalyst (**NP-Zn**) is only slightly more active as a catalyst than the control NINP in Figure 1a. These nanoparticles were prepared with 1 equivalent of DVB to surfactant **3**. This amount of DVB is the maximum that can be solubilized by **3** in water and has been shown to be critical to the integrity of the imprinted site [37]. Given that the substrate is large and hydrophobic, its entrance into the active site and the exit of the hydrolyzed product (i.e., the corresponding phenol **2b**) might be hindered by the rigid polymer network. To increase the flexibility of the cross-linked micelle, we prepared **NP-Zn** and NINP with half of the amount of DVB (0.5 equiv to **3**). To our delight, the imprinted catalyst shows significant improvements in its activity (compare the green lines in Figure 1a,b), while the corresponding NINP displays little change over that prepared with 1 equiv DVB (compare the magenta lines in Figure 1a,b). Figure 2a compares the initial velocity (\(V_{0}\)) for the catalytic hydrolysis of **1b** by **NP-Zn** and NINP prepared with 0.5 equiv DVB. Importantly, the hydrolysis by **NP-Zn** exhibits a saturation behavior, typical of enzymes (solid square data points). The data fits well to the Michaelis-Menten model, affording a \(k_{\text{cat}}\) of (39.5 \(\pm\) 0.6) \(\times\) 10\({}^{-3}\) s\({}^{-1}\) and a \(K_{\text{M}}\) of 64.4 \(\pm\) 3.0 \(\upmu\)M (Table 1, entry 1). In contrast, no saturation in catalysis is observed for the hydrolysis by NINP (empty square data points), suggesting that a different catalytic mechanism is involved. The reaction by NINP displays a slower and a faster region, and more efficient catalysis is achieved only at high substrate concentrations (>300 \(\upmu\)M). Below 200 \(\upmu\)M of **1b**, **NP-Zn** is clearly a better catalyst for the hydrolysis than NINP.