Imprinted micelles for chiral recognition in water: shape, depth, and number of recognition sites

Abstract

Chiral molecular recognition is important to biology, separation, and asymmetric catalysis. Because there is no direct correlation between the chiralities of the host and the guest, it is difficult to design a molecular receptor for a chiral guest in a rational manner. By cross-linking surfactant micelles containing chiral template molecules, we obtained chiral nanoparticle receptors for a number of 4-hydroxyproline derivatives. Molecular imprinting allowed us to transfer the chiral information directly from the guest to host, making the molecular recognition between the two highly predictable. Hydrophobic interactions between the host and the guest contributed strongly to the enantio- and diastereoselective differentiation of these compounds in water, whereas ion-pair interactions, which happened near the surface of the micelle, were less discriminating. The chiral recognition could be modulated by turning the size and shape of the binding pockets.

A Bait‐and‐Switch Method for the Construction of Artificial Esterases for Substrate‐Selective Hydrolysis

“…A bulkier template such as 10 , however, could not fit into the binding site imprinted from the less bulky 7 . This type of behavior has been observed previously in MINP binding and is consistent with the strong templating effect of the micellar imprinting . As will be shown below, the selectivity was also transferred into catalysis.…”

Binding-promoted chemical reaction in the nanospace of a binding site: effects of environmental constriction

“…This was an expected result from molecular imprinting and consistent with many studies we have done using micellar imprinting. [23][24][25][26][35][36][37] In DMF, however, the opposite became true, with 6 bound much more strongly than 5. It is not exactly clear why there was The titrations were performed in duplicates and the numbers given were averages of the two runs.…”

“…Please do not adjust margins Please do not adjust margins such a reversal but the result suggests that hydrophobic interactions in water were essential for the excellent selectivity observed in our previous MINP bindings. [23][24][25][26][35][36][37] Formation of micelles and the interactions between the template and the micelle in water both have strong hydrophobic contributions. Hydrophobic interactions, however, are eliminated in DMF.…”

Molecularly Imprinted Solid Phase Extraction Aiding the Analysis of Disease Biomarkers

“…Figure 4. Preparation of molecularly imprinted nanoparticles by surface-core double cross-linking of a template-containing micelle of cross-linkable surfactant.Reproduced from Ref [76]. with permission from The Royal Society of Chemistry.…”