Semi‐Covalent Surface Molecular Imprinting of Polymers by One‐Stage Mini‐emulsion Polymerization: Glucopyranoside as a Model Analyte

Abstract

This paper describes a new type of surface imprinting technique that combines the advantages of both the semi-covalent approach and one-stage miniemulsion polymerization. This process has been successfully applied for the preparation of glucose surface-imprinted nanoparticles. The selective artificial receptors for glucopyranoside were fully characterized by IR, TEM and BET analyses, and their molecular recognition abilities by binding experiments carried out in batch processes. The molecular affinity and selectivity of the glucose molecularly imprinted polymers were accurately quantified. These characteristics are essential for verification of the efficiency of the developed surface imprinting process. The imprinting effect was clearly demonstrated using the batch rebinding method. We have found that the glucose imprinted polymers produced using the optimized one-stage mini-emulsion exhibited quite fast kinetics of binding and equilibration with glucopyranoside templates, compared to polymers prepared by bulk polymerization technique, as well as extremely low levels of unspecific bindings. We also demonstrated that glucose molecular imprinted polymer (MIP) exhibited very good selectivity for its original template compared to other glycopyranoside derivatives, such as galactose. Finally, the extraction of the binding properties from isotherms of binding by fitting to the bi-Langmuir and Freundlich models allowed the determination of the affinity constant distribution of the binding sites. This imprinting protocol allowed the determination of an affinity constant (K(D)), involving exclusively H-bonding interactions, for the glucose MIP (P2C) with the best template 1, in CH3CN as the solvent system.

Strategies for Molecular Imprinting and the Evolution of MIP Nanoparticles as Plastic Antibodies—Synthesis and Applications

“…In addition, the relatively high surface areas of imprinted polymers in relation to the number of high affinity sites contribute directly to the non-specific binding observed for the template and interfering molecules [75], a feature which often hinders MIP use in applications such as sensing and separation. To improve the homogeneity of the binding sites, several successful strategies have been suggested such as the semi-covalent approach [76] and stoichiometric non-covalent imprinting [77].…”

Biorecognition and highly sensitive determination of Ribonuclease A with chemiluminescence sensor based on Fe3O4/multi-walled carbon nanotubes/SiO2-surface molecular imprinting polymer

“…Aerwards, the surface molecular imprinting technique was proposed. By attaching the biomolecule to or close to the surface of the polymer, 10,11 the mass transfer was improved and the removal rate of the biomolecule was promoted for the imprinting sites enabling easy access to the target protein molecules. 12 While expediting the pace of the polymerization in signicant measure, atom transfer radical polymerization was rst introduced for the preparation of a myoglobin surface molecular imprinting polymer (SMIP) by graing it on to a silicon surface, 13 which could be initiated at a moderate temperature and even in the presence of a small amount of oxygen.…”

Synthesis and evaluation of uniformly sized nalidixic acid–imprinted nanospheres based on precipitation polymerization method for analytical and biomedical applications

“…Because of their similarity to natural antibodies in terms of the ability of selective and strong binding to a target molecule, MIPs have been widely recognized as synthetic and robust alternatives to antibodies ("plastibodies") (Ge and Turner 2009). Thus, because of their favorable molecular recognition capability and stability at extremes of pH and temperature, ease of preparation, low cost of preparation, potential application to a wide range of target molecules, and reusability (Yang et al, 2005;He et al, 2006) have led to the development of various MIP applications in broad areas, such as ligand binding assays (Ansell, 2002), capillary electrochromatography (Priego-Capote et al, 2008;Wei et al, 2011), liquid chromatography (Kitahara et al, 2010;Moein et al, 2011), solid-phase extraction (Shi et al, 2011;Soleiman et al, 2012), sensors (Alizadeh and Akhoundian 2010;Chen et al, 2010;Moreira and Sales 2011), catalytic chemical reactions (Kirsch et al, 2009;Abbate et al, 2011), and drug delivery (Alvarez-Lorenzo et al, 2006;Costa et al, 2010).…”

“…The irregular particles generally give less binding recognition in adsorption procedure. The shape of the particles remains intrinsically irregular and the ground particles tend to extremely broad size distribution and shape distribution (Zhang et al, 2012).To streamline and optimize the production and performance of MIP particles, alternative synthetic strategies to discrete, imprinted, particulate products that obviate the need for grinding and sieving have evolved, such as suspension polymerization (Zhang et al, 2009), core-shell emulsion polymerization (Gao et al, 2011;Ma et al, 2011), and mini-emulsion polymerization (Schillemans and van Nostrum 2006;Curcio et al, 2009). Although these methods have undoubted value, the optimization of reliable experimental protocols can be lengthy, the general applicability is questionable in some cases, and residual emulsifier or stabilizer can remain adsorbed on the particles' surfaces, potentially compromising selective rebinding of molecules to the imprinted material.…”