Selectivity Of Molecularly Imprinted Polymer Research Articles

Development of antibody-engineered molecularly imprinted polymers for selective capture of aflatoxin B1 from starchy food and medicinal materials

Molecularly imprinted polymers(MIPs) have been widely used as selective recognition materials for analysis and detection of mycotoxins, such as aflatoxin B1(AFB1). However, little attention was given to investigate key factors that affecting selectivity and specificity of MIPs, such as functional monomers and imprinted cavity compatibility. Inspired by the recognition of antibody to antigen, we designed and employed amino acids as functional monomers with multiple interaction sites via hydrogen bonding and aromatic π-π stacking, meanwhile, synthesized structurally matched alternative template, 5,7-dimethoxycyclopentenone [2,3-c]coumarin(DMPC) to prepare MIPs via silica surface grafting. The adsorption of antibody-engineered MIPs was enhanced significantly compared to that of MIPs prepared by conventional functional monomers and dummy templates for selective capture of AFB1. And the specific recognition sites of MIPs left by DMPC conferred the most remarkable selectivity toward AFB1 among aflatoxins. The mechanism and contribution of functional groups and imprinted cavities for selective adsorption of AFB1 were elucidated, providing a different approach to improving functional monomers and templates in MIPs. The solid phase extraction cartridges packed DMPC-ATry-MIPs@SiO2 were used for enrichment of AFB1 in Lotus seeds and Coix seeds. The recoveries were 94.48–112.90 % and 83.32–116.04 % respectively, even after being used five times repeatedly. The cartridges could replace expensive and low-reusability immunoaffinity columns in the analysis and detection of AFB1 in real samples, providing a kind of promising sample pretreatment materials for trace analysis in food and drugs.

Innovative approaches to suppress non-specific adsorption in molecularly imprinted polymers for sensing applications

Molecularly imprinted polymers (MIPs) are synthetic antibodies developed to bind selectively with specific molecules. They function through a particular recognition process involving their cavities and functional groups. Nevertheless, functional groups located outside these cavities are the main cause of non-specific molecule binding, thus reducing the effectiveness of MIPs in sensing applications. This work focused on enhancing the selectivity and performance of MIPs through electrostatic modification with surfactants. The study investigates the use of two surfactants, namely sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB), to eliminate non-specific adsorption in MIPs. The binding isotherms of the target molecule sulfamethoxazole (SMX) on MIPs and non-imprinted polymers (NIPs) were analyzed, showing higher adsorption capacity of MIPs due to the specific cavities. The modification with SDS or CTAB effectively eliminated non-specific adsorption in MIPs. The kinetic adsorption behavior further demonstrated the efficacy of MIP+--SDS/CTAB in the selective adsorption of SMX. Calibration curves showcase the methodology's analytical capabilities, achieving low limit of detection for SMX 6 ng mL−1 using MIP +-SDS. The stability study confirmed that the developed MIP +/--SDS/CTAB remains stable even at high temperatures, demonstrating its suitability for on-site applications. The methodology was successfully applied to detect SMX in milk and water samples, achieving promising recoveries. Overall, the electrostatic modification of MIPs with surfactants emerges as a valuable strategy for enhancing selectivity and performance in target molecule recognition and detection.

A MOF-doped molecularly imprinted polymer/MOF hybrid gel incorporating with pH-buffering sodium acrylate for practical detoxification of organophosphorus nerve agents

The fatal toxicity of organophosphorus nerve agents (ONAs) and the realistic condition of chemical attack occurring place trigger the urgent need to develop catalyst materials with degrading ability under the natural environment without bulk water and bases. Here, we strategically design a molecularly imprinted polymer (MIP)/MOF hybrid catalyst material by integrating enzyme-mimic MIP with Zr-MOF UiO-66-NH2 which demonstrate promising catalytic performance for degradation of ONAs. Furthermore, sodium acrylate functions as a hydrophilic and alkaline functional unit together with pyridine-amidoxime based functional monomers (PAAO) to copolymerize into molecularly imprinted polymeric network. The basic sodium carboxylate groups were installed near the active sites to provide appropriate alkaline microenvironment, non-bulk water and acid buffer capacity for the catalysis in pure water. The resultant MIP/MOF composite catalyst demonstrate outstanding catalytic activities in both liquid and solid phase hydrolysis of ONAs. Specifically, the half-life of liquid phase hydrolysis catalyzed by MIP/UiO-66-NH2-0.5 achieves 9.4 min for diethyl-4-nitrophenyl phosphate (DENP) and 10 min for dimethyl 4-nitrophenyl phosphate (DMNP), and solid-state hydrolysis present rapid degradation efficiency with a half-life of 28.6 min. In addition, composite catalyst MIP-Ag/UiO-66-NH2-0.5 that retains substrate selectivity of MIP, enables the simultaneous degradation of two types of organophosphorus substrates (phosphate and thiophosphate) by MIP and MOF in a synergistic way. Summarily, this work displays promising potential of MIP/MOF hybrid enzyme-like catalyst as effective and practical material for the practical protection and detoxification of organophosphorus nerve agents.

Functionalized Cochlear Implant Electrode for Intracochlear Histamine Detection via Molecularly Imprinted Polymer Coating

By coating the electrodes of a cochlear implant (CI) electrode array with a powdered form of molecularly imprinted polymer (MIP), a straightforward process to functionalize existing electrodes to selectively detect histamine is demonstrated. Detection is based on non‐Faradaic impedance spectroscopy, omitting the need for a reference electrode or redox mediators, and fitting to a 5‐element equivalent electronic circuit. Proof‐of‐concept measurements on three functionalized cochlear implants in three human cadaveric cochleae indicate a level of detection of 200 nM of histamine in albumin‐based artificial perilymph following a sigmoid dose‐response trend up to 10 mM. This sensitivity enables quantized and localized analysis of histamine‐mediated inflammation immediately following the CI operation. The selectivity and adaptability of MIPs opens possibilities to detect a wide spectrum of inflammation markers inside the human cochlea and could be used for fast mid‐ or postoperative intervention to improve the medical implant's outcome.

A novel carbonized polymer dots-based molecularly imprinted polymer with superior affinity and selectivity for oxytetracycline removal

Molecularly imprinted polymers (MIPs) synthesized from chain functional monomers are restricted by spatial extension and exhibit relatively poor affinity and selectivity; this results in unsatisfactory applications in complex media. In this study, we prepared unique spherical carbonized polymer dots (CPDs-OH) via the incomplete carbonization of 1-allyl-3-vinylimidazolium bromide and ethylene glycol, and used it as a functional monomer to prepare a newly imprinted polymer (CPDs-OH@MIP) in aqueous media. As a result, the CPDs-OH@MIP exhibited effective recognition of oxytetracycline with an impressive imprinting factor of 6.17, surpassing MIPs prepared with chain functional monomers (1–3). Furthermore, CPDs-OH@MIP exhibited excellent adsorption for oxytetracycline (278.52 mg g−1) and achieved equilibrium in 30 min, with stronger resistance to coexisting cations, anions, and humic acid. Compared to other MIPs and adsorbents, the recognition performance of CPDs-OH@MIP improved 2–4 times; this polymer could remove >92.1% of oxytetracycline in real water samples with at least 10 cycle times. CPDs-OH@MIP prepared using the special spherical monomer forms a denser structure with fewer nonimprinted regions and precisely imprinted sites, remarkably improving the affinity and selectivity of MIPs combined via hydrogen bonds and electrostatic and π-π interactions. Our proposed strategy provides an effective basis for breakthroughs in the practical application of MIPs.

Molecularly imprinted photoelectrochemical sensing platform based on g-C3N4/MOFs photoresponsive oxidase mimic for norfloxacin detection

A molecularly imprinted photoelectrochemical sensor was successfully designed for sensitive detection of norfloxacin (NOR) based on poly (o-phenylenediamine) (PoPD) sensitized g-C3N4/Zr-MOFs(Fe) composite. Herein g-C3N4/Zr-MOFs(Fe) heterojunction composite was explored as photoresponsive oxidase mimic and photoactive material for the purpose of enhancing photoelectrochemical performances. In addition, PoPD molecularly imprinted polymers (MIPs) were introduced not only to act as the recognition element for selective performance, but also to possess photosensitive effect, which enhanced the photocurrent of sensor. SEM, element mapping method, XRD, UV–Vis and electrochemical impedance spectroscopy were employed for the characterization of the structural, chemical composition, optical and electrical properties of g-C3N4/Zr-MOFs(Fe) composite. Thanks to the photoresponsive oxidase mimic property and the selectivity of MIPs, the as-prepared sensor presented a good linear range of from 1.0 × 10−8 mol/L to 2.0 × 10−6 mol/L with NOR and a limit of detection of 5.7 × 10−9 mol/L. Moreover, the sensor platform has been proved to have excellent selectivity and real sample application.

Assessment of Molecularly Imprinted Polymers as Selective Solid-Phase Extraction Sorbents for the Detection of Cloxacillin in Drinking and River Water.

This paper describes a new methodology for carrying out quantitative extraction of cloxacillin from drinking and river water samples using a molecularly imprinted polymer (MIP) as a selective sorbent for solid-phase extraction (MISPE). Several polymers were synthesized via thermal polymerization using cloxacillin as a template, methacrylic acid (MAA) as a functional monomer, ethyleneglycoldimethacrylate (EGDMA) as a cross-linker and different solvents as porogens. Binding characteristics of the adequate molecularly imprinted and non-imprinted (NIP) polymers were evaluated via batch adsorption assays following the Langmuir and Freundlich isotherms and Scatchard assays. The parameters related to the extraction approach were studied to select the most appropriate polymer for cloxacillin determination. Using the optimized MIP as the SPE sorbent, a simple sample treatment methodology was combined with high-performance liquid chromatography (HPLC) to analyze cloxacillin residues in drinking and river water. Under the optimum experimental conditions, the MISPE methodology was validated using spiked samples. The linearity for cloxacillin was assessed within the limits of 0.05-1.5 µg L-1 and the recovery percentage was higher than 98% (RSD < 4%). The limits of detection and limits of quantification were 0.29 and 0.37 µg L-1 and 0.8 and 0.98 µg L-1 for drinking and river water, respectively. The selectivity of MIP against other ß-lactam antibiotics with similar structures (oxacillin, cefazoline, amoxicillin and penicillin V) was studied, obtaining a good recovery higher than 85% for all except cefazoline. The proposed MISPE-HPLC methodology was successfully applied for the detection of cloxacillin in drinking water from Canal de Isabel II (Madrid) and river water from the Manzanares River (Madrid).

Fabrication and application of molecularly imprinted polymer doped carbon dots coated silica stationary phase

Facing the difficulties in chromatographic separation of polar compounds, this investigation devotes to developing novel stationary phase. Molecularly imprinted polymers (MIPs) have aroused wide attention, owing to their outstanding selectivity, high stability, and low cost. In this work, a novel stationary phase based on carbon dots (CDs), MIP layer, and silica beads was synthesized to exploit high selectivity of MIPs, excellent physicochemical property of CDs, and outstanding chromatographic performances of silica microspheres simultaneously. The MIP doped CDs coated silica (MIP-CDs/SiO2) stationary phase was systematically characterized by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area measurement, and carbon elemental analysis. Furthermore, the chromatographic performance of the MIP-CDs/SiO2 column was thoroughly assessed by using a wide variety of compounds (including nucleosides, sulfonamides, benzoic acids, and some other antibiotics). Meanwhile, the separation efficiency of the MIP-CDs/SiO2 stationary phase was superior to other kinds of stationary phases (e.g. nonimprinted NIP-CDs/SiO2, MIP/SiO2, and C18–SiO2). The results demonstrated that MIP-CDs/SiO2 column exhibited best performance in terms of chromatographic separation. For all tested compounds, the resolution value was not less than 1.60, and the column efficiency of MIP-CDs/SiO2 for thymidine was 22,740 plates/m. The results further indicate that the MIP-CDs/SiO2 column can combine the good properties of MIP, CDs, with those of silica microbeads. Therefore, the developed MIP-CDs/SiO2 stationary phase can be applied in the separation science and chromatography-based techniques.

Molecularly imprinted polymers-isolated AuNP-enhanced CdTe QD fluorescence sensor for selective and sensitive oxytetracycline detection in real water samples

A molecularly imprinted polymers (MIPs)-isolated AuNP-enhanced fluorescence sensor, AuNP@MIPs-CdTe QDs, was developed for highly sensitive and selective detection of oxytetracycline (OTC) in aqueous medium. The developed sensor combined the advantages of strong fluorescence signal of metal-enhanced fluorescence (MEF), high selectivity of MIPs, and stability of CdTe QDs. The MIPs shell with specific recognition served as an isolation layer to adjust the distance between AuNP and CdTe QDs to optimize the MEF system. The sensor demonstrated the detection limit as low as 5.22 nM (2.40 μg/L) for a concentration range of 0.1–3.0 μM OTC and good recovery rates of 96.0–103.0% in real water samples. In addition, high specificity recognition for OTC over its analogs was achieved with an imprinting factor of 6.10. Molecular dynamics (MD) simulation was utilized to simulate the polymerization process of MIPs and revealed H-bond formation as the mainly binding sites of APTES and OTC, and finite-difference time-domain (FDTD) analysis was employed to obtain the distribution of electromagnetic field (EM) for AuNP@MIPs-CdTe QDs. The experimental results combined with theoretical analyses not only provided a novel MIP-isolated MEF sensor with excellent detection performance for OTC but also established a theoretical basis for the development of a new generation of sensors.

Molecularly imprinted polymer preparations for selective detection of C‐reactive protein: Thermodynamic and kinetic studies

AbstractC‐reactive protein (CRP) is a member of the pentraxin protein group. CRP is considered an acute‐phase protein produced by the liver during inflammation in various diseases limited to pathogenic infections. It is very important that serum CRP concentration can be measured quickly, reliably and easily. Therefore, a three‐dimensional crosslinked molecularly imprinted polymer (MIP) with selective recognition sites for CRP was synthesized (CRP‐MIP) and characterization analyzes (scanning electron microscopy, Fourier transform infrared, and thermogravimetric analysis) were performed. The binding abilities of the synthesized polymers by adsorption of CRP in aqueous solution were evaluated in detail and compared with the abilities of an unprinted polymer (CRP‐NIP) used as a reference. It was found that the MIP prepared by the printing effect selectively adsorbed the template molecule CRP. For this effect, the selectivity of MIP toward CRP and various positive acute‐phase reactants such as α1‐antitrypsin and α1‐acid glycoprotein was evaluated and high selectivity toward CRP was obtained. CRP‐MIP was used to remove CRP from crude human serum, and the recovery was up to 91%. Adsorption process of CRP from aqueous solutions on polymeric adsorbents; equilibrium was evaluated in terms of kinetic and thermodynamic conditions and the necessary parameters to describe the process were calculated under these conditions. Adsorption data: the pseudo‐first order kinetic model, the pseudo‐second order kinetic model, the Elovich kinetic model and the intraparticle diffusion model were studied and the thermodynamic parameters ΔG°, ΔH°, and ΔS° were calculated.

Molecularly Imprinted Solid Phase Extraction Strategy for Quinic Acid.

Quinic acid (QA) and its ester conjugates have been subjected to in-depth scientific investigations for their antioxidant properties. In this study, molecularly imprinted polymers (MIPs) were used for selective extraction of quinic acid (QA) from coffee bean extract. Computational modelling was performed to optimize the process of MIP preparation. Three different functional monomers (allylamine, methacrylic acid (MAA) and 4-vinylpyridine (4-VP)) were tested for imprinting. The ratio of each monomer to template chosen was based on the optimum ratio obtained from computational studies. Equilibrium rebinding studies were conducted and MIP C, which was prepared using 4-VP as functional monomer with template to monomer ratio of 1:5, showed better binding performance than the other prepared MIPs. Accordingly, MIP C was chosen to be applied for selective separation of QA using solid-phase extraction. The selectivity of MIP C towards QA was tested versus its analogues found in coffee (caffeic acid and chlorogenic acid). Molecularly imprinted solid-phase extraction (MISPE) using MIP C as sorbent was then applied for selective extraction of QA from aqueous coffee extract. The applied MISPE was able to retrieve 81.918 ± 3.027% of QA with a significant reduction in the amount of other components in the extract.

Preparation of arctiin moleculary imprinted polymers with 4-vinylpyridine and Allyl-β-cyclodextrin as binary monomers under molecular crowding conditions

This paper reported a feasible method to prepare molecularly imprinted polymer (MIPs) using 4-vinylpyridine (4-VP) and Allyl-β-cyclodextrin (β-CD) as binary functional monomer in the presence of polystyrene (PS). This is the first time that a surrounding of macromolecular crowding was established to improve the imprinting effect of cyclodextrins as monomer in organic solvents. The morphological and characteristics of the polymers with macromolecular crowding reagents were investigated by scanning electron microscope (SEM), fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and nitrogen adsorption experiments. The MIPs were synthesized with 4-VP and β-CD as binary functional monomers, a series of experiments were conducted to compare with the control groups. Furthermore, the selectivity of MIP for analogues experiment showed that the β-CD/4-VP MIP has higher specific recognition for arctiin than β-CD/4-VP NIP. A purification method by β-CD/4-VP MIPs coupled with macromolecular crowding reagents was developed for extraction arctiin from Arctium lappa L. In the MIP-SPE process, the optimal washing and eluting reagents are methanol/water (5:5) and methanol/acid (9:1), respectively. When using the β-CD/4-VP MIPs as SPE absorbent, the mean recoveries for arctiin were 87% with purity of 95%. All the results indicate that this synthetic method using 4-VP and β-CD as binary functional monomers in the presence of PS is a promising method for the preparation of selective adsorbents for arctiin analysis in Arctium lappa L.

Selective enrichment of microbiota-derived tryptophan metabolites in mouse faeces based on molecularly imprinted solid-phase extraction for HPLC analysis

Gut microbiota-derived tryptophan (TRP) metabolites, especially the indole derivatives, function as critical modulators of intestinal immune function and integrity via modulating the aryl hydrocarbon receptor pathway. Selective enrichment of these indole metabolites in biological samples is important for quantitative determination by routine methods such as HPLC. Here, we report a molecularly imprinted polymer (MIP) for solid-phase extraction (SPE) of TRP-derived indole metabolites from faeces of mice. The MIP was synthesized by surface polymerization by using indole-3-acetic acid (IAA) and acrylamide after cross-linking by ethylene glycol dimethacrylate (EGDMA) and initialed by 2′,2-azobisisobutyronitrile (AIBN). The MIPs were then characterized by transmission electron microscope (TEM) and fourier transform infrared spectroscopy (FTIR), and the adsorption capacity, selectivity and reusability of MIPs were systematically evaluated. Results showed that IAA-MIPs showed a uniformly distributed nanoshell layer with a thin shell thickness of 26 nm. The IAA-MIPs could selectively adsorb IAA, indole-3-propionic acid (IPA), and indole-3-lactic acid (ILA) in a mixed solution that also contains TRP and tyrosine. The adsorption capacity of IAA-MIPs only slightly decreased with the increase of recycling use. As purification material for SPE, the IAA-imprinted polymers (IAA-MIPs) were successfully applied to extract IAA, IPA, and ILA from normal and colitis mice for HPLC determination. Collectively, these surface molecularly imprinted polymers could find extensive use to selective enrichment of microbiota-derived indole metabolites in biological samples.

Raman Studies on Surface-Imprinted Polymers to Distinguish the Polymer Surface, Imprints, and Different Bacteria.

Molecularly imprinted polymers (MIPs) are widely used as robust biomimetic recognition layers in sensing devices targeting a wide variety of analytes including microorganisms such as bacteria. Assessment of imprinting success and selectivity toward the target is of great importance in MIP quality control. We generated Escherichia coli-imprinted poly(styrene-co-DVB) as a model system for bacteria-imprinted polymers via surface imprinting using a glass stamp with covalently immobilized E. coli. Confocal Raman Microscopy was successfully employed to visualize bacteria, imprints, and polymer and to distinguish them from each other. The method has proven highly feasible for assessing if imprinting had been successful. In addition, we developed a method for selectivity investigation of bacteria MIPs based on combining Confocal Raman Microscopy and Partial Least Squares Discriminant Analysis (PLS-DA). The Raman spectra of E. coli and Bacillus cereus were acquired on E. coli-imprinted poly(styrene-co-DVB) and used to establish a PLS-DA model for differentiating between the bacteria species. Model validation demonstrated a correct classification of 95% of Raman spectra, indicating sufficient accuracy of the model for future use in MIP selectivity studies. Simultaneous differentiation of 3 bacteria species (E. coli, B. cereus, and Lactococcus lactis) on E. coli-imprinted poly(styrene-co-DVB) proved more difficult, which might be due to the limited depth resolution of the confocal Raman microscope resulting in the presence of interfering signals from the polymer substrate. It might be possible to overcome this obstacle by selective enhancement of the Raman signals originating from bacteria surfaces, such as tip enhanced Raman spectroscopy.

Fabrication of a fluorescence probe via molecularly imprinted polymers on carbazole-based covalent organic frameworks for optosensing of ethyl carbamate in fermented alcoholic beverages

Ethyl carbamate (EC), which is a group 2A carcinogen, is a byproduct formed in the alcohol fermentation process that can accumulate with heating, transportation, and storage. In this study, molecularly imprinted polymers (MIPs) on carbazole-based covalent organic frameworks (COFs) were prepared as a fluorescence probe for the optosensing of EC in fermented alcoholic beverages. The excellent optical properties of carbazole-based COFs coupled with the good adsorption and selectivity of MIPs provided fast and efficient recognition of EC. MIPs on carbazole-based COFs exhibited advantages of high efficiency, a good separation effect, fluorescence dependence, and reproducibility. A good linear relationship was obtained over the concentration range of 1–200 μg L−1, with a low limit of detection (LOD) of 0.607 μg L−1. The RSD precision and five-cycle reproducibility were lower than 4.91% and 6.38%, respectively, and the recoveries were 85.30%–109.49%. This optosensor was applied to quantify EC contents in several fermented alcoholic beverages, all of which were less than LOD. The results of the optosensors based on MIPs on carbazole-based COFs were then validated using standard gas chromatography–mass spectrometry (GC-MS), which gave results consistent with the proposed method.

Restricted Access Molecularly Imprinted Polymers for Biological Sample Preparation

Restricted access molecularly imprinted polymers (RAMIPs) have been efficiently used for the extraction of small organic molecules from untreated biological matrices (e.g. blood, plasma, serum, and milk). These materials have been obtained by modifying the external surface of conventional molecularly imprinted polymers (MIPs) with hydrophilic monomer grafting, crosslinked protein capsule or a combination of both. These sorbents aggregate the selectivity of MIPs with the ability to exclude macromolecules of restricted access materials (RAMs), being widely employed in solid phase extraction techniques, beyond their use in sensors. In this review, we discuss about the design and application of RAMIPs in biological sample preparation, emphasizing the future trends and remaining challenges of this technology for bioanalyses.

A miniaturized analytical method based on molecularly imprinted absorbents for selective extraction of (S)-1,1'-binaphthyl-2,2'-diamine and combinatorial screening of polymer precursors by computational simulation.

Chiral resolution of binaphthylamine is often a toilful conundrum in the field of analytical chemistry and biomedicine. The work puts forward a selective, sensitive, and miniaturized analytical method based on molecularly imprinted polymers (MIPs) as adsorbent for miniaturized tip solid-phase extraction (MTSPE) in the separation of binaphthylamine enantiomer. This method combines the advantages of MIPs (high selectivity), MTSPE (low consumption), and high-performance liquid chromatography (HPLC, high sensitivity). A simple synthesis methodology of MIP (P2) was conducted through bulk polymerization with (S)-(-)-1,1'-binaphthyl-2,2'-diamine (S-DABN) as template together with methacrylic acid monomer, and ethylene glycol dimethacrylate as cross-linker in proper porogen, realizing a selective recognition and efficient enrichment for S-DABN. The method exhibited appreciable linearity (0.06-1.00 mg ml-1 ), low quantification limit (0.056 mg ml-1 ), good absolute recoveries (45.70%-69.29%), and high precision (relative standard deviations ≤ 3.54%), along with low consumption (0.50ml sample solution and 25.0mg adsorbent). Based on the density functional theory, computational simulation was used to make a preliminary prediction for rational design of MIPs and gave a reasonable elaboration involving the potential mechanism of templates interacting with functional monomers. The adsorption kinetics and thermodynamics were investigated to evaluate the recombination process of substrates. In addition, the selectivity of MIPs for S-DABN was obtained by MIP-MTSPE coupled with HPLC, which supports the feasibility of this convenient design process. The proposed method was employed for selective extraction of S-DABN and exhibited promising potential in the application of chiral analysis.

Isotherm and Electrochemical Properties of Atrazine Sensing Using PVC/MIP: Effect of Porogenic Solvent Concentration Ratio.

Widespread atrazine use is associated with an increasing incidence of contamination of drinking water. Thus, a biosensor using molecularly imprinted polymers (MIPs) was developed to detect the amount of atrazine in water to ensure prevention of exposure levels that could lead to reproductive effects in living organisms. In this study, the influence of the porogen on the selectivity of MIPs was investigated. The porogen plays a pivotal role in molecular imprinting as it affects the physical properties and governs the prepolymerization complex of the resulting polymer, which in turn firmly defines the recognition properties of the resulting molecularly imprinted polymer (MIP). Therefore, bulk MIPs against atrazine (Atr) were synthesized based on methacrylic acid (MAA) as a functional monomer and ethyleneglycol dimethacrylate (EGDMA) as a crosslinker; they were prepared in toluene and dimethyl sulfoxide (DMSO). The imprinting factor, binding capacity, and structural stability were evaluated using the respective porogenic solvents. Along with the characterization of the morphology of the obtained polymers via SEM and BET analysis, the kinetic and adsorption analyses were demonstrated and verified. The highest imprinting factor, binding capacity, and the highest structural stability were found to be on polymer synthesized in a medium of MAA and EGDMA, which contained 90% toluene and 10% DMSO as porogen. Moreover, the response for Atr concentrations by the PVC-based electrochemical sensor was found to be at a detection limit of 0.0049 μM (S/N = 3). The sensor proved to be an effective sensor with high sensitivity and low Limit of Detection (LOD) for Atr detection. The construction of the sensor will act as a baseline for a fully functionalized membrane sensor.

A Note about Crosslinking Density in Imprinting Polymerization.

Imprinting polymerization is an exciting technique since it leads to specific binding sites, which are the basis of a variety of applications, such as sensors, detectors, and catalysts. The specific binding sites are created using templates and then fixing the structure of the binding site with crosslinking. The literature review of imprinting polymerizations shows that the crosslinking density governs the physical properties of the resulting molecularly imprinted polymer (MIP). It is also a factor governing the capacity and the selectivity of MIPs. Reviewing polymer science data and theory, the crosslinking density commonly used in MIP synthesis is unusually high. The data reviewed here suggest that more research is needed to determine the optimal crosslinking density for MIPs.

Molecularly imprinted polymer nanoparticles-based electrochemical chemosensors for selective determination of cilostazol and its pharmacologically active primary metabolite in human plasma

Molecularly imprinted polymer (MIP) nanoparticles-based differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) chemosensors for antiplatelet drug substance, cilostazol (CIL), and its pharmacologically active primary metabolite, 3,4-dehydrocilostazol (dhCIL), selective determination in human plasma were devised, prepared, and tested. Molecular mechanics (MM), molecular dynamics (MD), and density functional theory (DFT) simulations provided the optimum structure and predicted the stability of the pre-polymerization complex of the CIL template with the chosen functional acrylic monomers. Moreover, they accounted for the MIP selectivity manifested by the molecularly imprinted cavity with the CIL molecule complex stability higher than that for each interference. On this basis, a fast and reliable method for determining both compounds was developed to meet an essential requirement concerning the personalized drug dosage adjustment. The limit of detection (LOD) at the signal-to-noise ratio of S/N = 3 in DPV and EIS determinations using the ferrocene redox probe in a “gate effect” mode was 93.5 (±2.2) and 86.5 (±4.6) nM CIL, respectively, and the linear dynamic concentration range extended from 134 nM to 2.58 μM in both techniques. The chemosensor was highly selective to common biological interferences, including cholesterol and glucose, and less selective to structurally similar dehydroaripiprazole. Advantageously, it responded to dhCIL, thus allowing for the determination of CIL and dhCIL together. The EIS chemosensor appeared slightly superior to the DPV chemosensor concerning its selectivity to interferences. The CIL DPV sorption data were fitted with Langmuir, Freundlich, and Langmuir-Freundlich isotherms. The determined sorption parameters indicated that the imprinted cavities were relatively homogeneous and efficiently interacted with the CIL molecule.