Electroactive molecularly imprinted polymer nanoparticles for selective glyphosate determination.

Redox-active molecularly imprinted polymer nanoparticles selective for glyphosate, MIP-Gly NPs, were devised, synthesized, and subsequently integrated onto platinum screen-printed electrodes (Pt-SPEs) to fabricate a chemosensor for selective determination of glyphosate (Gly) without the need for redox probe in the test solution. That was because, ferrocenylmethyl methacrylate was added to the polymerization mixtures during the NPs synthesis so that the resulting MIP-Gly NPs contained covalently immobilized ferrocenyl moieties as the reporting redox ingredient, conferring these NPs with electroactive properties. MIP-Gly NPs of four different compositions were evaluated. The herein described approach represents a simple and effective way to endow MIP NPs with electrochemical reporting capabilities with neither the need to functionalize them post-synthesis nor to use electrochemical mediators present in the tested solution during the analyte determinations. MIP-Gly NPs synthesized using allylamine and squaramide-based monomers appeared most selective to Gly. The Pt-SPEs modified with MIP-Gly NPs were characterized with differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). Changes in the DPV peak originating from the oxidation of the ferrocenyl moieties in these MIP-Gly NPs served as the analytical signal. The DPV limit of detection and the linear dynamic concentration range for Gly were 3.7 pM and 25 pM-500 pM, respectively. Moreover, the selectivity of the fabricated chemosensors was sufficiently high to determine Gly successfully in spiked river water samples.

Post-imprinting modification: electrochemical and scanning electrochemical microscopy studies of a semi-covalently surface imprinted polymer.

Herein we described a post-imprinting modification of the imprinted molecular cavities for electrochemical sensing of a target protein. Imprinted molecular cavities were generated by following the semi-covalent surface imprinting approach. These mesoporous cavities were modified with a ferrocene 'electrochemical' tracer for electrochemical transduction of the target protein recognition. Electrochemical sensors prepared after post-imprinting modification showed a linear response in the concentration range of 0.5 to 50 µM. Chemosensors fabricated based on capacitive impedimetric transduction demonstrated that imprinted molecular cavities without post-imprinting modification showed better selectivity. Scanning electrochemical microscopy (SECM) was used for the surface characterization of imprinted molecular cavities modified with ferrocene electrochemical tracers. SECM analysis performed in the feedback mode monitor changes in the surface state of the ferrocene-modified polymer film. The kinetics of the mediator regeneration was almost 1.8 times higher on the non-imprinted surface versus the post-imprinting modified molecular imprinted polymer.

In-Capillary Photodeposition of Glyphosate-Containing Polyacrylamide Nanometer-Thick Films.

The present research reports on in-water, site-specific photodeposition of glyphosate (GLP)-containing polyacrylamide (PAA-GLP) nanometer-thick films (nanofilms) on an inner surface of fused silica (fused quartz) microcapillaries presilanized with trimethoxy(octen-7-yl)silane (TMOS). TMOS was chosen because of the vinyl group presence in its structure, enabling its participation in the (UV light)-activated free-radical polymerization (UV-FRP) after its immobilization on a fused silica surface. The photodeposition was conducted in an aqueous (H2O/ACN; 3:1, v/v) solution, using UV-FRP (λ = 365 nm) of the acrylamide (AA) functional monomer, the N,N'-methylenebis(acrylamide) (BAA) cross-linking monomer, GLP, and the azobisisobutyronitrile (AIBN) UV-FRP initiator. Acetonitrile (ACN) was used as the porogen and the solvent to dissolve monomers and GLP. Because of the micrometric diameters of microcapillaries, the silanization and photodeposition procedures were first optimized on fused silica slides. The introduction of TMOS, as well as the formation of PAA and PAA-GLP nanofilms, was determined using atomic force microscopy (AFM), scanning electron microscopy with energy-dispersive X-ray (SEM-EDX) spectroscopy, and confocal micro-Raman spectroscopy. Particularly, AFM and SEM-EDX measurements determined nanofilms' thickness and GLP content, respectively, whereas in-depth confocal (micro-Raman spectroscopy)-assisted imaging of PAA- and PAA-GLP-coated microcapillary inner surfaces confirmed the successful photodeposition. Moreover, we examined the GLP impact on polymer gelation by monitoring hydration in a hydrogel and a dried powder PAA-GLP. Our study demonstrated the usefulness of the in-capillary micro-Raman spectroscopy imaging and in-depth profiling of GLP-encapsulated PAA nanofilms. In the future, our simple and inexpensive procedure will enable the fabrication of polymer-based microfluidic chemosensors or adsorptive-separating devices for GLP detection, determination, and degradation.

Electrochemically Synthesized Polyacrylamide Gel and Core-Shell Nanoparticles for 3D Cell Culture Formation.

Biocompatible polyacrylamide gel and core-shell nanoparticles (NPs) were synthesized using a one-step electrochemically initiated gelation. Constant-potential electrochemical decomposing of ammonium persulfate initiated the copolymerization of N-isopropyl acrylamide, methacrylic acid, and N,N'-methylenebisacrylamide monomers. This decomposing potential and monomers' concentrations were optimized to prepare gel NPs and thin gel film-grafted core-shell NPs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) imaging confirmed the gel NP formation. The lyophilized gel NPs and core-shell NPs were applied to support the three-dimensional (3D) cell culture. In all, core-shell NPs provided superior support for complex 3D tissue structures.

Ni(OH)2-Type Nanoparticles Derived from Ni Salen Polymers: Structural Design toward Functional Materials for Improved Electrocatalytic Performance.

Herein, we report the potential-driven electrochemical transformation carried out in basic media of two Ni2+ salen polymers, (poly(NiSalen)s), abbreviated as poly(meso-NiSaldMe) and poly(NiSaltMe). These two polymers, with different configurations of methyl substituents on the imine bridge, were used as precursors for the preparation of electrocatalytically active nickel hydroxide [Ni(OH)2]-type nanoparticles (NPs) anchored in the polymeric matrix as poly[SalenNi(OH)2]. The use of potentiodynamic and potentiostatic electropolymerization conditions for the deposition of polymeric precursors allowed us to control the molecular architecture of poly(NiSalen)s and NPs derived from them. Thus, we obtained different arrangements of NPs embedded in morphologically different poly(Salen) matrixes, indicating their electrocatalytic activity toward ethanol to different extents. Moreover, we found a direct relationship between the electrochemical stability of the poly(NiSalen) precursors operating in the organic solvent-based electrolyte solutions and the easiness of their transformation into Ni(OH)2 NPs operating in the aqueous alkaline media. Poly(NiSalen)s and Ni(OH)2-type NPs were characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy.

Molecularly imprinted polymer-based extended-gate field-effect transistor (EG-FET) chemosensor for selective determination of matrix metalloproteinase-1 (MMP-1) protein.

A conducting molecularly imprinted polymer (MIP) film was integrated with an extended-gate field-effect transistor (EG-FET) transducer to determine epitopes of matrix metalloproteinase-1 (MMP-1) protein biomarker of idiopathic pulmonary fibrosis (IPF) selectively. Most suitable epitopes for imprinting were selected with Basic Local Alignment Search Tool software. From a pool of MMP-1 epitopes, the two, i.e., MIAHDFPGIGHK and HGYPKDIYSS, the relatively short ones, most promising for MMP-1 determination, were selected, mainly considering their advantageous outermost location in the protein molecule and stability against aggregation. MIPs templated with selected epitopes of the MMP-1 protein were successfully prepared by potentiodynamic electropolymerization and simultaneously deposited as thin films on electrodes. The chemosensors, constructed of MIP films integrated with EG-FET, proved useful in determining these epitopes even in a medium as complex as a control serum. The limit of detection for the MIAHDFPGIGHK and HGYPKDIYSS epitope was ∼60 and 20 nM, respectively. Moreover, the chemosensors selectively recognized whole MMP-1 protein in the 50-500 nM concentration range in buffered control serum samples.

Electrochemically Initiated Synthesis of Polyacrylamide Microgels and Core-shell Particles.

Herein, we developed a simple procedure for synthesizing micrometer-sized microgel particles as a suspension in an aqueous solution and thin films deposited as shells on different inorganic cores. A sufficiently high constant potential was applied to the working electrode to commence the initiator decomposition that resulted in gelation. Under hydrodynamic conditions, this initiation allowed preparing different morphology microgels at room temperature. Importantly, neither heating nor UV-light illumination was needed to initiate the polymerization. Moreover, thin films of the cross-linked gel were anchored on different core substrates, including silica and magnetic nanoparticles. Scanning electron microscopy and transmission electron microscopy imaging confirmed the microgel particles' and films' irregular shape and porous structure. Energy-dispersive X-ray spectroscopy indicated that the core coating with the microgel film was successful. Dynamic light scattering measured the micrometer size of gel particles with different combinations of acrylic monomers. Thermogravimetric analysis and the first-derivative thermogravimetric analysis revealed that the microgels' thermal stability of different compositions was different. Fourier-transform infrared and 13C NMR spectroscopy showed successful copolymerization of the main, functional, and cross-linking monomers.

Oriented Immobilization of Protein Templates: A New Trend in Surface Imprinting.

In this Review, we have summarized recent trends in protein template imprinting. We emphasized a new trend in surface imprinting, namely, oriented protein immobilization. Site-directed proteins were assembled through specially selected functionalities. These efforts resulted in a preferably oriented homogeneous protein construct with decreased protein conformation changes during imprinting. Moreover, the maximum functionality for protein recognition was utilized. Various strategies were exploited for oriented protein immobilization, including covalent immobilization through a boronic acid group, metal coordinating center, and aptamer-based immobilization. Moreover, we have discussed the involvement of semicovalent as well as covalent imprinting. Interestingly, these approaches provided additional recognition sites in the molecular cavities imprinted. Therefore, these molecular cavities were highly selective, and the binding kinetics was improved.

Hexagonally Packed Macroporous Molecularly Imprinted Polymers for Chemosensing of Follicle-Stimulating Hormone Protein.

Homogenous nanostructuration of molecularly imprinted polymer (MIP) films for follicle-stimulating hormone (FSH)-sensing was achieved by using optimized colloidal crystals as a hard mold. Introduction of a heating step after assembling colloidal crystals of silica beads promoted their adhesion. Thus, precise assembling of beads was not disturbed during further multisteps of surface imprinting, and crack-free hexagonal packing was maintained. Scanning electron microscopy imaging confirmed hexagonal packing of silica colloidal crystals as well as homogenous nanostructuration in MIP films. FSH immobilization over silica beads and later its derivatization with electroactive functional monomers was confirmed by X-ray photoelectron spectroscopy analysis. The nanostructured molecular recognition films prepared in this way were combined with an electrochemical transducer in order to design a capacitive impedimetry-based chemosensing system. It was tested for the determination of FSH in the range from 0.1 fM to 100 pM in 10 mM 2-(N-morpholino) ethane sulfonic acid buffer (pH = 4.2). The detection limit of the chemosensor was 0.1 fM, showing a high selectivity with respect to common protein interferences as well as other protein hormones of the gonadotropin family.

Facile Fabrication of Surface-Imprinted Macroporous Films for Chemosensing of Human Chorionic Gonadotropin Hormone.

We present an improved approach for the preparation of highly selective and homogeneous molecular cavities in molecularly imprinted polymers (MIPs) via the combination of surface imprinting and semi-covalent imprinting. Toward that, first, a colloidal crystal mold was prepared via the Langmuir-Blodgett (LB) technique. Then, human chorionic gonadotropin (hCG) template protein was immobilized on the colloidal crystal mold. Later, hCG derivatization with electroactive functional monomers via amide chemistry was performed. In a final step, optimized potentiostatic polymerization of 2,3'-bithiophene enabled depositing an MIP film as the macroporous structure. This synergistic strategy resulted in the formation of molecularly imprinted cavities exclusively on the internal surface of the macropores, which were accessible after dissolution of silica molds. The recognition of hCG by the macroporous MIP film was transduced with the help of electric transducers, namely, extended-gate field-effect transistors (EG-FET) and capacitive impedimetry (CI). These readout strategies offered the ability to create chemosensors for the label-free determination of the hCG hormone. Other than the simple confirmation of pregnancy, hCG assay is a common tool for the diagnosis and follow-up of ectopic pregnancy or trophoblast tumors. Concentration measurements with these EG-FET and CI-based devices allowed real-time measurements of hCG in the range of 0.8-50  and 0.17-2.0 fM, respectively, in 10 mM carbonate buffer (pH = 10). Moreover, the selectivity of chemosensors with respect to protein interferences was very high.