Abstract:Au nanoparticles (NPs) are functionalized with thioaniline electropolymerizable groups and (mercaptophenyl)boronic acid. The antibiotic substrates neomycin (NE), kanamycin (KA), and streptomycin (ST) include vicinal diol functionalities and, thus, bind to the boronic acid ligands. The electropolymerization of the functionalized Au NPs in the presence of NE, KA, or ST onto Au surfaces yields bisaniline-cross-linked Au NP composites that, after removal of the ligated antibiotics, provide molecularly imprinted ma… Show more
“…Generally, SPR spectroscopy measures the optical dielectric constants of thin films deposited onto noble metal-coated substrates like Au NPs or Ag NPs, which are extremely sensitive to the refractive index changes occurring within a few hundred nanometers from the sensor surface. Moreover, the SPR sensors incorporated with MIPs have been widely used to monitor protein, 623 environmental contaminants, 624 drugs 625 and food. 626 In general, the combination of SPR with electrochemistry or applying the surface-initiated ATRP for grafting polymeric films on the Au chips is a powerful analytical technique.…”
a Molecular imprinting technology (MIT), often described as a method of making a molecular lock to match a molecular key, is a technique for the creation of molecularly imprinted polymers (MIPs) with tailor-made binding sites complementary to the template molecules in shape, size and functional groups. Owing to their unique features of structure predictability, recognition specificity and application universality, MIPs have found a wide range of applications in various fields. Herein, we propose to comprehensively review the recent advances in molecular imprinting including versatile perspectives and applications, concerning novel preparation technologies and strategies of MIT, and highlight the applications of MIPs. The fundamentals of MIPs involving essential elements, preparation procedures and characterization methods are briefly outlined.Smart MIT for MIPs is especially highlighted including ingenious MIT (surface imprinting, nanoimprinting, etc.), special strategies of MIT (dummy imprinting, segment imprinting, etc.) and stimuli-responsive MIT (single/dual/ multi-responsive technology). By virtue of smart MIT, new formatted MIPs gain popularity for versatile applications, including sample pretreatment/chromatographic separation (solid phase extraction, monolithic column chromatography, etc.) and chemical/biological sensing (electrochemical sensing, fluorescence sensing, etc.). Finally, we propose the remaining challenges and future perspectives to accelerate the development of MIT, and to utilize it for further developing versatile MIPs with a wide range of applications (650 references).
“…Generally, SPR spectroscopy measures the optical dielectric constants of thin films deposited onto noble metal-coated substrates like Au NPs or Ag NPs, which are extremely sensitive to the refractive index changes occurring within a few hundred nanometers from the sensor surface. Moreover, the SPR sensors incorporated with MIPs have been widely used to monitor protein, 623 environmental contaminants, 624 drugs 625 and food. 626 In general, the combination of SPR with electrochemistry or applying the surface-initiated ATRP for grafting polymeric films on the Au chips is a powerful analytical technique.…”
a Molecular imprinting technology (MIT), often described as a method of making a molecular lock to match a molecular key, is a technique for the creation of molecularly imprinted polymers (MIPs) with tailor-made binding sites complementary to the template molecules in shape, size and functional groups. Owing to their unique features of structure predictability, recognition specificity and application universality, MIPs have found a wide range of applications in various fields. Herein, we propose to comprehensively review the recent advances in molecular imprinting including versatile perspectives and applications, concerning novel preparation technologies and strategies of MIT, and highlight the applications of MIPs. The fundamentals of MIPs involving essential elements, preparation procedures and characterization methods are briefly outlined.Smart MIT for MIPs is especially highlighted including ingenious MIT (surface imprinting, nanoimprinting, etc.), special strategies of MIT (dummy imprinting, segment imprinting, etc.) and stimuli-responsive MIT (single/dual/ multi-responsive technology). By virtue of smart MIT, new formatted MIPs gain popularity for versatile applications, including sample pretreatment/chromatographic separation (solid phase extraction, monolithic column chromatography, etc.) and chemical/biological sensing (electrochemical sensing, fluorescence sensing, etc.). Finally, we propose the remaining challenges and future perspectives to accelerate the development of MIT, and to utilize it for further developing versatile MIPs with a wide range of applications (650 references).
“…Complementary approaches for tailoring the analytical performance of MIP architectures comprise the integration of nanomaterials such as metallic nanoparticles [3], carbon nanotubes [67], quantum dots [30] and graphene [68]. Synergistic combination of the different approaches may make the MIPs to real competitors of proteins and aptamers and open up the route to new fields of applications [69].…”
Hybrid architectures which combine a MIP with an immobilized “affinity ligand” or a biocatalyst sum up the advantages of both components. In this paper, hybrid architectures combining a layer of a molecularly imprinted electropolymer with a mini‐enzyme or a self‐assembled monolayer will be presented. (i) Microperoxidase‐11 (MP‐11) catalyzed oxidation of the drug aminopyrine on a product‐imprinted sublayer: The peroxide dependent conversion of the analyte aminopyrine takes place in the MP‐11 containing layer on top of a product‐imprinted electropolymer on the indicator electrode. The hierarchical architecture resulted in the elimination of interfering signals for ascorbic acid and uric acid. An advantage of the new hierarchical structure is the separation of MIP formation by electropolymerization and immobilization of the catalyst. In this way it was for the first time possible to integrate an enzyme with a MIP layer in a sensor configuration. This combination has the potential to be transferred to other enzymes, e.g. P450, opening the way to clinically important analytes. (ii) Epitope‐imprinted poly‐scopoletin layer for binding of the C‐terminal peptide and cytochrome c (Cyt c): The MIP binds both the target peptide and the parent protein almost eight times stronger than the non‐imprinted polymer with affinities in the lower micromolar range. Exchange of only one amino acid in the peptide decreases the binding by a factor of five. (iii) MUA‐poly‐scopoletin MIP for cytochrome c: Cyt c bound to the MIP covered gold electrode exhibits direct electron transfer with a redox potential and rate constant typical for the native protein. The MIP cover layer suppresses the displacement of the target protein by BSA or myoglobin. The combination of protein imprinted polymers with an efficient electron transfer is a new concept for characterizing electroactive proteins such as Cyt c. The competition with other proteins shows that the MIP binds its target Cyt c preferentially and that molecular shape and the charge of protein determine the binding of interfering proteins.
“…Frasconi et al [142] reported a novel surface-plasmon resonance (SPR) method for detection in milk of three antibiotics having vicinal diol functionalities (neomycin, kanamycin, and streptomycin). A special ''MIP'' for the analytes was prepared by electropolymerizing the AuNPs functionalized with thioaniline groups and (mercaptophenyl)boronic acid.…”
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