Abstract

An innovative approach to imprinted nanoparticles (nanoMIPs) is represented by solid-phase synthesis. Since the polymeric chains grow over time and rearrange themselves around the template, the binding properties of nanoMIPs could depend on the polymerization time. Here we present an explorative study about the effect of different polymerization times on the binding properties of ciprofloxacin-imprinted nanoMIPs. The binding properties towards ciprofloxacin were studied by measuring the binding affinity constants (Keq) and the kinetic rate constants (kd, ka). Furthermore, selectivity and nonspecific binding were valued by measuring the rebinding of levofloxacin onto ciprofloxacin-imprinted nanoMIPs and ciprofloxacin onto diclofenac-imprinted nanoMIPs, respectively. The results show that different polymerization times produce nanoMIPs with different binding properties: short polymerization times (15 min) produced nanoMIPs with high binding affinity but low selectivity (Keq > 107 mol L−1, α ≈ 1); medium polymerization times (30 min–2 h) produced nanoMIPs with high binding affinity and selectivity (Keq ≥ 106 mol L−1, α < 1); and long polymerization times (>2 h) produced nanoMIPs with low binding affinity, fast dissociation kinetics and low selectivity (Keq ≤ 106 mol L−1, kdis > 0.2 min−1, α ≈ 1). The results can be explained as the combined effect of rearrangement and progressive stiffening of the polymer chains around the template molecules.

Highlights

  • Molecularly imprinted nanoparticles present several advantages with respect to bulk imprinted materials, but, when prepared by traditional methods, their usefulness is limited as the approaches are costly or require complex optimization steps, while the purification from template molecules is challenging [1,2,3]

  • To study the effect of the duration of the polymerization process, we considered ciprofloxacin-imprinted nanoMIPs prepared by persulfate/TEMED-induced radical polymerization in water at room temperature

  • The results reported in this work show that polymerization time plays a pivotal role in determining the binding properties of nanoMIPs prepared by persulfate/TEMEDinduced radical polymerization

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Summary

Introduction

Imprinted nanoparticles (nanoMIPs) present several advantages with respect to bulk imprinted materials, but, when prepared by traditional methods, their usefulness is limited as the approaches are costly or require complex optimization steps, while the purification from template molecules is challenging [1,2,3]. The preparation of nanoMIPs by solid‐ phase synthesis has proven to be suitable for small molecules [10,11,12], peptides and proteins [13,14], living cells [15] or viruses [16]. It seems to be very ver‐ satile, as the experimental conditions necessary for a successful imprinting process can be changed according to current needs in a more flexible way than the solution synth2eosfis technique [15]

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