## 4 Conclusions  
Molecular imprinting in cross-linked micelles affords a facile method to prepare hydrolytic nanzymes for aromatic carbonates. An aromatic thiourea template resembles the substrate in size/shape and uses its sulfur atom to coordinate to a zinc-containing functional monomer. Double cross-linking of cross-linkable micelles containing the above template-FM complex produces water-soluble nanoparticles as enzyme mimics in a straightforward fashion. Our study reveals that the zinc cofactor is able to accelerate the hydrolysis of aromatic carbonates substantially, with a rate acceleration of \(1\times 10^{6}\) for diphenyl carbonate, a nonideal substrate. The involvement of the molecularly imprinted site for the catalysis is supported by the strong reactivity of the _para_-substituted substrate **1c** and the low reactivity of the mismatched isomeric **1d**. Mechanistic studies support that the most likely mechanism for the hydrolysis comes from local hydroxide generated by the ac  
Figure 3: (**a**) Hammett \(\alpha\)–\(\rho\) correlation in the hydrolysis of _para_-substituted diaryl carbonates catalyzed by (**a**) **NP-Zn** and (**b**) NINP. Reaction rate constants were measured in 25 mM HEPES buffer (pH 7.0) at 25 \({}^{\circ}\)C. [carbonates] = 25 \(\upmu\)M. [**NP-Zn**] = [NINP] = 5 \(\upmu\)M. \(\sigma\) values p-NO\({}_{2}\), 0.78; p-CH\({}_{3}\)CO, 0.52; p-CHO, 0.22; p-H, 0.00; p-CH\({}_{3}\), -0.17. The nanoparticles were prepared using 0.5 equiv of DVB. tive site zinc cofactor. For more reactive carbonates (e.g., **1b**), the cationic micelle can also generate hydroxide ions near the micelle surface by its electric potential, which contribute to the hydrolysis at high substrate concentrations. These doubly cross-linked micellar catalysts have extraordinary abilities to tolerate high temperatures [22], organic solvents [59], and adverse pH conditions [60]. As mentioned earlier, the current catalyst **NP-Zn** is unable to accommodate (a segment of) the BPA-PC chain and is only designed to hydrolyze the small molecule substrates. The designability of the molecularly imprinted catalysts, however, should enable a catalyst for hydrolyzing the polymer using more elaborate template molecules. This work has begun in our laboratory and will be reported in due course. The following supporting information can be downloaded at [[https://www.mdpi.com/article/10.3390/nano15030169/s1](https://www.mdpi.com/article/10.3390/nano15030169/s1)]([https://www.mdpi.com/article/10.3390/nano15030169/s1](https://www.mdpi.com/article/10.3390/nano15030169/s1)), Figure S1: Monitoring of the surface- and the core-cross-linking of the micelles of **3** during the molecular imprinting by \({}^{1}\)H NMR spectroscopy; Figure S2: Distribution of the hydrodynamic diameters of the nanoparticles in water as determined by DLS for alkynyl-SCM (surface-cross-linked micelle); Figure S3: Distribution of the hydrodynamic diameters of the nanoparticles in water as determined by DLS for surface functionalized SCM (surface-cross-linked micelle); Figure S4: Distribution of the hydrodynamic diameters of the nanoparticles in water as determined by DLS for **NP-Zn**; Figure S5: Bright-field TEM image of typical molecularly imprinted nanoparticles; Figure S6: Lineweaver-Burk plot of the hydrolysis of **1b** by NINP in a 25 mM HEPES buffer (pH 7.0) at 25 \({}^{\circ}\)C; Figure S7: Lineweaver-Burk plot of the hydrolysis of **1c** by **NP-Zn** in a 25 mm HEPES buffer (pH 7.0) containing 25 vol % methanol; Table S1: Pseudo-first-order rate constants and solvent kinetic isotope effects of the hydrolysis of compound **1b** catalyzed by **NP-Zn** at 25 \({}^{\circ}\)C.  
Conceptualization, Y.Z. ; investigation, T.T.B. ; writing--original draft preparation, Y.Z. ; writing--review and editing, T.T.B. and Y.Z. ; supervision, Y.Z. ; project administration, Y.Z. ; funding acquisition, Y.Z. All authors have read and agreed to the published version of the manuscript. This research was funded by NSF, grant number CHE-2246635.