Development of rapid, sensitive and selective fluorimetric method for determination of 1-naphthalene acetic acid in cucumber by using magnetite-molecularly imprinted polymer.

In this study, a novel method based on the determination of 1-naphthalene acetic acid with the usage of magnetite-molecularly imprinted polymer prior to fluorimetric detection has been developed. Magnetite-molecularly imprinted polymer has been used for the first time as selective adsorbent for the determination of 1-naphthalene acetic acid. The adsorption capacity of the synthesized polymer was found to be 2.18 ±â€¯0.36 mg g-1 (n = 3). Limit of detection (LOD) and limit of quantification (LOQ) of the method were found to be 0.75 and 2.50 µg L-1, respectively. Linearity of the calibration graph for the proposed method was observed within the range of 20-700 µg L-1. The proposed method seems to be rapid where the detection procedure for 1-naphthalene acetic acid can be completed within a total time of 1 h. The same imprinted polymer can be used for the determination of 1-naphthalene acetic acid with quantitative sorption and recovery values repeatedly for at least ten times. The effects of some potential organic interferences were investigated. Proposed method has been successfully applied to determine 1-naphthalene acetic acid in cucumber, where the recoveries of the spiked samples were found to be in the range of 93.7-104.5%. Characterization of the synthesized polymer was also evaluated. By combining the high capacity, cheapness, reusability and selectivity of the magnetic adsorbent with the dynamic calibration range, rapidity, simplicity, and sensitivity of fluorimetry, the proposed method seems to be an ideal method for the determination of trace levels of 1-naphthalene acetic acid.

Cost-effective imprinting to minimize consumption of template in room-temperature ionic liquid for fast purification of chlorogenic acid from the extract of E. ulmoides leaves.

One of the main challenges in large-scale applications of molecularly imprinted polymers (MIPs) is the significant amount of template needed in polymer preparation. A new strategy based on room-temperature ionic liquids (RTILs) was suggested to solve this problem by reducing the amount of template in the polymerization recipe. The MIP was synthesized with a mixture of dimethyl sulfoxide and RTIL (1-butyl-3-methylimidazolium tetrafluoroborate) as porogen, in which chlorogenic acid (CGA) was used as template, 4-vinylpyridine (4-VP) as functional monomer, and ethylene glycol dimethacrylate (EDMA) as cross-linker. The influence of polymerization variables, including CGA concentrations, and the ratio of 4-VP to EDMA on imprinting effect were investigated comprehensively. Moreover, the properties involving the column permeability, the number of binding sites, and the polymer morphology of the CGA-MIP monoliths were studied thoroughly. The MIP monolith had an excellent column permeability (1.53 × 10-13 m2) and allowed an ultra-fast on-line SPE, which dramatically shortens the separation time (< 10 min) and improves the separation efficiency. At high flow velocity (5.0 mL min-1), 50 µL of the extract from Eucommia ulmoides leaves can be loaded directly on the CGA-MIP monoliths and CGA with high purity can be obtained with a recovery of 89.01 ± 0.05%. As a conclusion, the resulting RTIL-induced approach of preparing MIP may be an effective tool in fabricating MIP in a low-cost way. Graphical abstract ᅟ.

Rapid, low temperature synthesis of molecularly imprinted covalent organic frameworks for the highly selective extraction of cyano pyrethroids from plant samples.

New imine-linked molecularly imprinted covalent organic frameworks (MICOFs) were successfully prepared, using fenvalerate as the dummy template. Schiff base reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-triformylphloroglucinol was rapidly achieved at room temperature, using Sc(OTf)3 as the catalyst. The surface groups and morphologies of MICOFs were assessed by Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller surface area analysis, and scanning electron microscopy. The MICOFs exhibited high selectivity toward four structurally similar cyano pyrethroids, including fenvalerate, flucythrinate, ß-cyfluthrin and λ-cyhalothrin. A method based on solid phase extraction using MICOFs coupled to high performance liquid chromatography was established for the determination of cyano pyrethroids in plant samples. Linearity in the range 0.1-200 ng g-1, with correlation coefficients of 0.9981-0.9993, was obtained for the four cyano pyrethroids. Detection limits and quantification limits were in the range 0.011-0.018 ng g-1 and 0.036-0.060 ng g-1, respectively. Recoveries at three spiked levels ranged from 94.3% to 102.7%. The developed method is thus a promising technique for the selective extraction of cyano pyrethroids from complex matrices.

A novel molecularly imprinted electrochemical sensor based on graphene quantum dots coated on hollow nickel nanospheres with high sensitivity and selectivity for the rapid determination of bisphenol S.

In this paper, a novel molecularly imprinted electrochemical sensor (MIECS) based on a glassy carbon electrode (GCE) modified with graphene quantum dots (GQDs) coated on hollow nickel nanospheres (hNiNS) for the rapid determination of bisphenol S (BPS) was proposed for the first time. HNiNS and GQDs as electrode modifications were used to enlarge the active area and electron-transport ability for amplifying the sensor signal, while molecularly imprinted polymer (MIP) film was electropolymerized by using pyrrole as monomer and BPS as template to detect BPS via cyclic voltammetry (CV). Scanning electron microscope (SEM), energy-dispersive spectrometry (EDS), CV and differential pulse voltammetry (DPV) were employed to characterize the fabricated sensor. Experimental conditions, such as molar ratio of monomer to template, electropolymerization cycles, pH, incubation time and elution time were optimized. The DPV response of the MIECS to BPS was obtained in the linear range from 0.1 to 50µM with a low limit of detection (LOD) of 0.03µM (S/N = 3) under the optimized conditions. The MIECS exhibited excellent response towards BPS with high sensitivity, selectivity, good reproducibility, and stability. In addition, the proposed MIECS was also successfully applied for the determination of BPS in the plastic samples with simple sample pretreatment.

Cost-effective imprinting combining macromolecular crowding and a dummy template for the fast purification of punicalagin from pomegranate husk extract.

The combination of molecular crowding and virtual imprinting was employed to develop a cost-effective method to prepare molecularly imprinted polymers. By using linear polymer polystyrene as a macromolecular crowding agent, an imprinted polymer recognizable to punicalagin had been successfully synthesized with punicalin as the dummy template. The resulting punicalin-imprinted polymer presented a remarkable selectivity to punicalagin with an imprinting factor of 3.17 even at extremely low consumption of the template (template/monomer ratio of 1:782). In contrast, the imprinted polymer synthesized without crowding agent, did not show any imprinting effect at so low template amount. The imprinted polymers made by combination of molecular crowding and virtual imprinting can be utilized for the fast separation of punicalagin from pomegranate husk extract after optimizing the protocol of solid-phase extraction with the recovery of 85.3 ± 1.2%.

Removal of probable human carcinogenic polycyclic aromatic hydrocarbons from contaminated water using molecularly imprinted polymer.

A molecularly imprinted polymer (MIP) adsorbent for carcinogenic polycyclic aromatic hydrocarbons (PAHs) was prepared using a non-covalent templating technique. MIP particles sized from 2 to 5 microm were synthesized in acetonitrile by using six PAHs mix as a template, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. When compared with the non-imprinted polymer (NIP), the MIP showed an excellent affinity towards PAHs in aqueous solution with binding capacity (B(max)) of 687 microg g(-1)MIP, imprinting effect of 6, and a dissociation constant of 24 microM. The MIP exhibited significant binding affinity towards PAHs even in the presence of environmental parameters such as dissolved organic matter (COD) and total dissolved inorganic solids (TDS), suggesting that this material may be appropriate for removal of carcinogenic PAHs. The feasibility of removing PAHs from water by the MIP demonstrated using groundwater spiked with PAHs. In addition, the MIP reusability without any deterioration in performance was demonstrated at least ten repeated cycles.

Molecularly imprinted monolith in-tube solid-phase microextraction coupled with HPLC/UV detection for determination of 8-hydroxy-2'-deoxyguanosine in urine.

Urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG) has been widely used as a biomarker of oxidative DNA damage. Measurements of 8-OHdG in urinary samples are challenging owing to the low level of 8-OHdG and the complex matrix. In this study, a novel molecularly imprinted polymer (MIP) monolithic column was synthesized with guanosine as a dummy template which was used as the medium for in-tube solid-phase microextraction (SPME). In-tube SPME coupled with HPLC/UV detection for extraction and determination of urinary 8-OHdG was developed. The synthesized MIP monolithic column exhibited high extraction efficiency owing to its greater phase ratio with convective mass transfer and inherent selectivity. The enrichment factor for 8-OHdG was found to be 76 and the limits of detection and quantification of the method for urinary samples were 3.2 nmol/L (signal-to-noise ratio 3) and 11 nmol/L (signal-to-noise ratio 10), respectively. The MIP(')s selectivity also made the sample preparation procedure and chromatographic separation much easier. The linear range of the proposed method was from 0.010 to 5.30 micromol/L (r = 0.9997), with a relative standard deviation of 1.1-6.8%, and the recovery for spiked urine samples was 84 +/- 3%. The newly developed method was successfully applied to determine urinary samples of healthy volunteers, coking plant workers, and cancer patients. The 8-OHdG level in cancer patients was significantly higher than that in healthy people.

Accelerated development procedure for molecularly imprinted polymers using membrane filterplates.

A novel technique for the synthesis and testing of large numbers of molecularly imprinted polymers is described requiring much less time than the commonly used miniMIP approach. Instead of vials, the polymers are synthesized on the surface of microfiltration membranes in multiwell filterplates. The thin polymeric films enable accelerated template removal. The MIP development procedure is thereby shortened to two days. Performance of the system was demonstrated by creating a combinatorial library of MIPs selective for cimetidine, an antiulcer drug. The polymer composition has been optimized. An experimental design combined with a multivariate analysis (i.e., response surface modeling) was used to minimize the number of experiments in the optimization process. The highest imprinting factor was obtained using a MAA/EDMA/template molar ratio of 3.5:19.5:1.

A systematic approach to forming micro-contact imprints of creatine kinase.

A systematic approach has been used to form molecular imprints of creatine kinase (CK) using micro-contact imprinting. Using thermocalorimetry data, we selected poly(ethylene glycol) 400 dimethacrylate (PEG400DMA) as our crosslinker, on the basis that it would be expected to have minimal specific recognition when incorporated into the imprinted polymer. The functional monomer used, methacrylic acid (MAA), was chosen from a panel of six candidates on the basis of it giving the highest differential affinity with respect to a non-imprinted polymer. A polymer formed with 5% MAA and 95% PEG400DMA showed excellent imprint recognition, with CK binding to the imprinted material being 2.05 +/- 0.07 x 10(-10) mol cm(-2) compared to 9.1 +/- 4.5 x 10(-12) mol cm(-2) control binding. The imprinted polymers (approximate thickness 22.6 mum as measured by Alpha-step) showed clear two-phase binding with maximum absorption achieved after approximately 2 hours. Data extracted from Scatchard plots showed the K(d) for the high affinity binding site population to be 2.56 x 10(-10) M and the binding site population to be 1.97 x 10(-10) mol cm(-2), corresponding data for low affinity binding sites shows the K(d) = 3.27 x 10(-9) M and the binding site population to be 2.32 x 10(-10) mol cm(-2). Re-binding the molecularly imprinted polymers (MIPs) with non-template proteins, namely myoglobin, human serum albumin (HSA) and immunoglobulin G (Ig G), showed these proteins to have comparatively little affinity for the CK imprinted films. The percentage re-binding figures, relative to CK binding, were: 18.7, 3.5, and 3.5 for myoglobin, HSA, and Ig G respectively. This pattern of binding was maintained in competitive binding protocols with two proteins in solution at equal concentrations, where the percentage re-binding figures, relative to CK binding (4.5 +/- 0.06 x 10(-10) mol cm(-2)), were 17.2, 4.5, and 2.9 for myoglobin, HSA, and Ig G respectively. The presence of multiple competing analytes in undiluted human serum did not significantly decrease template protein recognition. Finally, we used circular dichroism to monitor protein denaturation, and showed that the denatured template protein loses a significant proportion (76.8%) of its MIP affinity after being heated at 80 degrees C for 10 minutes.

Ultratrace analysis of uracil and 5-fluorouracil by molecularly imprinted polymer brushes grafted to silylated solid-phase microextraction fiber in combination with complementary molecularly imprinted polymer-based sensor.

Main inborn errors of metabolism diagnosable through uracil (Ura) analysis and the therapeutic monitoring of toxic 5-fluorouracil (5FU) in dihydro pyrimidine dehydrogenase (DPD) deficient patients require a sensitive, reproducible, selective and accurate method. In this work, an artificial receptor in the format of molecularly imprinted polymer (MIP) brush 'grafted to' the surface of sol-gel immobilized on cost-effective homemade solid-phase microextraction (SPME) fibers, individually imprinted with either of Ura and 5FU, was used in combination with a voltammetric sensor duly modified with the same MIP. This combination provided up to 10- and 8.4-fold preconcentrations of Ura and 5FU, respectively, which was more than sufficient for achieving stringent detection limits in the primitive diagnosis of uracil disorders and fluoropyrimidine toxicity in DPD-deficient patients. The proposed method permits the assessment of Ura and 5FU plasma concentrations with detection limits pf 0.0245 and 0.0484 ng mL(-1) (RSD = 1.0-2.5%, S/N = 3), respectively, without any problems of non-specific false-positives and cross-reactivities in complicated matrices of biological samples.