Peptide-Binding Nanoparticle Materials with Tailored Recognition Sites for Basic Peptides

J of Molecular Recognition

2018

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Molecular recognition in water is an important challenge in supramolecular chemistry. Surface‐core double cross‐linking of template‐containing surfactant micelles by the click reaction and free radical polymerization yields molecularly imprinted nanoparticles (MINPs) with guest‐complementary binding sites. An important property of MINP‐based receptors is the surface‐cross‐linking between the propargyl groups of the surfactants and a diazide cross‐linker. Decreasing the number of carbons in between the two azides enhanced the binding affinity of the MINPs, possibly by keeping the imprinted binding site more open prior to the guest binding. The depth of the binding pocket can be controlled by the distribution of the hydrophilic/hydrophobic groups of the template and was found to influence the binding in addition to electrostatic interactions between oppositely charged MINPs and guests. Cross‐linkers with an alkoxyamine group enabled two‐stage double surface‐cross‐linking that strengthened the binding constants by an order of magnitude, possibly by expanding the binding pocket of the MINP into the polar region. The binding selectivity among very similar isomeric structures also improved.

Section: Resultsmentioning

confidence: 84%

“…The DLS size(~5 nm with ligand 3) has been confirmed by transmission electron microscopy. 48,49 The characterization data are found in the Supporting Information of the paper.…”

Section: Design and Synthesis Of Materialsmentioning

confidence: 99%

Tuning surface‐cross‐linking of molecularly imprinted cross‐linked micelles for molecular recognition in water

Zhang

J of Molecular Recognition

2018

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“…Despite the great progress that has been made in supramolecular chemistry in the last decades, it has been difficult to create enzyme‐like artificial catalysts with controllable substrate selectivity . Micellar imprinting has become a powerful technique to generate strong and selective receptors for many types of molecules including small‐molecule drugs, carbohydrates, and peptides . Through the bait‐and‐switch method shown in this work, we can quickly convert these receptors into highly specific catalysts with enzyme‐like kinetics and substrate selectivity.…”

Section: Discussionmentioning

confidence: 99%

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

2019

Chemistry A European J

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Outcomes of chemical reactions are generally dominated by the intrinsic reactivities of reaction partners, but enzymes frequently override such constraints to transform less reactive molecules in the presence of more reactive ones. Despite the attractivenesso fs uch catalysis, it is difficult to build synthetic catalysts with these features. Micellar imprinting is ap owerful method to create template-complementary binding sites inside protein-sized water-soluble nanoparticles. When ap hotocleavable functional monomer was used to bind two phosphonate/phosphate templates as transition-statea nalogues, active sites with predetermined size and shape were formedi nside doubly cross-linked micelles throughm olecular imprinting. Postmodification replaced the binding group with ac atalytic pyridyl group, formingh ighly selectivea rtificial esterases. The catalysts displayed enzyme-like kineticsa nd turnover numbers that were in the hundreds. Thes electivityo ft he catalysts, derived from the substrate-complementary imprinted active sites, enabledt ransformation of less reactive esters in the presence of more reactiveo nes.[a] Dr.Scheme2.Preparation of DMAP-containinga )MINP-A and b) MINP-B for the selective hydrolysis of activatedester PNPH 4 and BNPC 11,respectively.

“…Our method allows one to create an analyte-specific binding site with a nearby environmentally sensitive fluorescent probe. Our MINPs have been shown to detect peptides with very similar side chains, 26,27,33 as well as mono-and oligosaccharides. 34,35 Integration of the fluorescent sensing mechanism demonstrated in this work potentially can afford selective sensors for many important biomolecules.…”

Section: Fluorescent Nanoparticle Sensors With Tailor-made Recognitiomentioning

confidence: 95%

“…The DLS size has been confirmed by transmission electron microscopy (TEM). 26,27 With MINP 4 (i.e., MINP prepared with compound 4) in hand, we studied different methods to hydrolyze the imine bond. Although the imine was located inside the hydrophobic core of the cross-linked micelle, 6 M HCl at 95 °C was found to cleave the fluorescent naphthyl group (along with the adamentyl).…”

Section: Fluorescent Nanoparticle Sensors With Tailor-made Recognitiomentioning

confidence: 99%

Fluorescent nanoparticle sensors with tailor-made recognition units and proximate fluorescent reporter groups

Xing

2018

New J. Chem.

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