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Sample records for molecularly imprinted polypyrrole

  1. Electropolymerized Molecularly Imprinted Polypyrrole Film for Sensing of Clofibric Acid

    PubMed Central

    Schweiger, Bianca; Kim, Jungtae; Kim, Young Jun; Ulbricht, Mathias

    2015-01-01

    Piezoelectric quartz crystals and analogous gold substrates were electrochemically coated with molecularly imprinted polypyrrole films for pulsed amperometric detection (PAD) of clofibric acid, a metabolite of clofibrate. Cyclic voltammetry data obtained during polymerization and deposited weight estimations revealed a decrease of the polymerization rate with increasing clofibric acid concentration. XPS measurements indicated that clofibric acid could be removed after imprinting with an aqueous ethanol solution, which was further optimized by using PAD. Zeta potential and contact angle measurements revealed differences between molecularly imprinted (MIP) and non-imprinted polymer (NIP) layers. Binding experiments with clofibric acid and other substances showed a pronounced selectivity of the MIP for clofibric acid vs. carbamazepine, but the response of MIP and NIP to 2,4-dichlorophenoxyacetic acid was higher than that for clofibric acid. A smooth surface, revealed by AFM measurements, with roughness of 6–8 nm for imprinted and non-imprinted layers, might be a reason for an excessively low density of specific binding sites for clofibric acid. Furthermore, the decreased polymerization rate in the presence of clofibric acid might not result in well-defined polymer structures, which could be the reason for the lower sensitivity. PMID:25730487

  2. Electrochemical sensor for sulfadimethoxine based on molecularly imprinted polypyrrole: study of imprinting parameters.

    PubMed

    Turco, Antonio; Corvaglia, Stefania; Mazzotta, Elisabetta

    2015-01-15

    The present work describes the development of a simple and cost-effective electrochemical sensor for sulfadimethoxine (SDM) based on molecularly imprinted overoxidized polypyrrole (PPy). An all electrochemical approach is used for sensor fabrication and application consisting in molecularly imprinted polymer (MIP) galvanostatic deposition on a gold electrode and its overoxidation under different experimental conditions and in SDM amperometric detection. Several parameters influencing the imprinting effect are critically discussed and evaluated. A key role of the electrolyte used in electropolymerization (tetrabuthylammonium perchlorate and lithium perchlorate) has emerged demonstrating its effect on sensing performances of imprinted PPy and, related to this, on its morphology, as highlighted by atomic force microscopy (AFM). The effect of different overoxidation conditions in removing template is evaluated by analyzing MIP films before and after the treatment by X-ray photoelectron spectroscopy (XPS) also evidencing the correlation between MIP chemical structure and its rebinding ability. MIP-template interaction is verified also by Fourier Transform Infrared (FT-IR) spectroscopy. Under the selected optimal conditions, MIP sensor shows a linear range from 0.15 to 3.7 mM SDM, a limit of detection of 70 μM, a highly reproducible response (RSD 4.2%) and a good selectivity in the presence of structurally related molecules. SDM was determined in milk samples spiked at two concentration levels: 0.2 mM and 0.4 mM obtaining a satisfactory recovery of (97±3)% and (96±8)%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. A surface acoustic wave sensor functionalized with a polypyrrole molecularly imprinted polymer for selective dopamine detection.

    PubMed

    Maouche, Naima; Ktari, Nadia; Bakas, Idriss; Fourati, Najla; Zerrouki, Chouki; Seydou, Mahamadou; Maurel, François; Chehimi, Mohammed Mehdi

    2015-11-01

    A surface acoustic wave sensor operating at 104 MHz and functionalized with a polypyrrole molecularly imprinted polymer has been designed for selective detection of dopamine (DA). Optimization of pyrrole/DA ratio, polymerization and immersion times permitted to obtain a highly selective sensor, which has a sensitivity of 0.55°/mM (≈ 550 Hz/mM) and a detection limit of ≈ 10 nM. Morphology and related roughness parameters of molecularly imprinted polymer surfaces, before and after extraction of DA, as well as that of the non imprinted polymer were characterized by atomic force microscopy. The developed chemosensor selectively recognized dopamine over the structurally similar compound 4-hydroxyphenethylamine (referred as tyramine), or ascorbic acid,which co-exists with DA in body fluids at a much higher concentration. Selectivity tests were also carried out with dihydroxybenzene, for which an unexpected phase variation of order of 75% of the DA one was observed. Quantum chemical calculations, based on the density functional theory, were carried out to determine the nature of interactions between each analyte and the PPy matrix and the DA imprinted PPy polypyrrole sensing layer in order to account for the important phase variation observed during dihydroxybenzene injection.

  4. Voltammetric Behaviour of Sulfamethoxazole on Electropolymerized-Molecularly Imprinted Overoxidized Polypyrrole.

    PubMed

    Ozkorucuklu, Sabriye Perçin; Sahin, Yücel; Alsancak, Güleren

    2008-12-18

    In this work, preparation of a molecularly imprinted polymer (MIP) film and its recognition properties for sulfamethoxazolewere investigated. The overoxidized polypyrrole (OPPy) film was prepared by the cyclic voltammetric deposition of pyrrole (Py) in the presence of supporting electrolyte (tetrabutylammonium perchlorate-TBAP) with and without a template molecule (sulfamethoxazole) on a pencil graphite electrode (PGE). The voltammetric behaviour of sulfamethoxazole on imprinted and non-imprinted (NIP) films was investigated by differential pulse voltammetry (DPV) in Britton-Robinson (BR) buffer solutions prepared in different ratio of acetonitrile-water binary mixture, between the pH 1.5 and 7.0. The effect of the acetonitrile-water ratio and pH, monomer and template concentrations, electropolymerization cycles on the performance of the MIP electrode was investigated and optimized. The MIP electrode exhibited the best reproducibility and highest sensitivity. The results showed that changing acetonitrile-water ratio and pH of BR buffer solution changes the oxidation peak current values. The highest anodic signal of sulfamethoxazole was obtained in BR buffer solution prepared in 50% (v/v) acetonitrile-water at pH 2.5. The calibration curve for sulfamethoxazole at MIP electrode has linear region for a concentration range of 25.10(-3) to 0.75 mM (R²=0.9993). The detection limit of sulfamethoxazole was found as 3.59.10(-4) mM (S/N=3). The same method was also applied to determination of sulfamethoxazole in commercial pharmaceutical samples. Method precision (RSD87%) were satisfactory. The proposed method is simple and quick. The polypyrrole (PPy) electrodes have low response time, good mechanical stability and are disposable simple to construct.

  5. Voltammetric Behaviour of Sulfamethoxazole on Electropolymerized-Molecularly Imprinted Overoxidized Polypyrrole

    PubMed Central

    Özkorucuklu, Sabriye Perçin; Şahin, Yücel; Alsancak, Güleren

    2008-01-01

    In this work, preparation of a molecularly imprinted polymer (MIP) film and its recognition properties for sulfamethoxazole were investigated. The overoxidized polypyrrole (OPPy) film was prepared by the cyclic voltammetric deposition of pyrrole (Py) in the presence of supporting electrolyte (tetrabutylammonium perchlorate-TBAP) with and without a template molecule (sulfamethoxazole) on a pencil graphite electrode (PGE). The voltammetric behaviour of sulfamethoxazole on imprinted and non-imprinted (NIP) films was investigated by differential pulse voltammetry (DPV) in Britton-Robinson (BR) buffer solutions prepared in different ratio of acetonitrile-water binary mixture, between the pH 1.5 and 7.0. The effect of the acetonitrile-water ratio and pH, monomer and template concentrations, electropolymerization cycles on the performance of the MIP electrode was investigated and optimized. The MIP electrode exhibited the best reproducibility and highest sensitivity. The results showed that changing acetonitrile-water ratio and pH of BR buffer solution changes the oxidation peak current values. The highest anodic signal of sulfamethoxazole was obtained in BR buffer solution prepared in 50% (v/v) acetonitrile-water at pH 2.5. The calibration curve for sulfamethoxazole at MIP electrode has linear region for a concentration range of 25.10-3 to 0.75 mM (R2=0.9993). The detection limit of sulfamethoxazole was found as 3.59.10-4 mM (S/N=3). The same method was also applied to determination of sulfamethoxazole in commercial pharmaceutical samples. Method precision (RSD<1%) and recoveries (>87%) were satisfactory. The proposed method is simple and quick. The polypyrrole (PPy) electrodes have low response time, good mechanical stability and are disposable simple to construct. PMID:27873996

  6. Ultrasensitive dopamine sensor based on novel molecularly imprinted polypyrrole coated carbon nanotubes.

    PubMed

    Qian, Tao; Yu, Chenfei; Zhou, Xi; Ma, Peipei; Wu, Shishan; Xu, Lina; Shen, Jian

    2014-08-15

    A novel electrochemical sensor using the molecularly imprinted (MIP) oxygen-containing polypyrrole (PPy) decorated carbon nanotubes (CNTs) composite was proposed for in vivo detection of dopamine (DA). The prepared sensor exhibits a remarkable sensitivity of (16.18μA/μM) with a linear range of 5.0×10(-11)-5.0×10(-6)M and limit of detection as low as 1.0×10(-11)M in the detection of DA, which might be due to the plenty cavities for binding DA through π-π stacking between aromatic rings and hydrogen bonds between amino groups of DA and oxygen-containing groups of the novel PPy. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Voltammetric Determination of Flunixin on Molecularly Imprinted Polypyrrole Modified Glassy Carbon Electrode

    PubMed Central

    Radi, Abd-Elgawad; Abd El-Ghany, Nadia; Wahdan, Tarek

    2016-01-01

    A novel electrochemical sensing approach, based on electropolymerization of a molecularly imprinted polypyrrole (MIPpy) film onto a glassy carbon electrode (GCE) surface, was developed for the detection of flunixin (FXN). The sensing conditions and the performance of the constructed sensor were assessed by cyclic, differential pulse and (DPV) square wave voltammetry (SWV). The sensor exhibited high sensitivity, with linear responses in the range of 5.0 to 50.0 µM with detection limits of 1.5 and 1.0 µM for DPV and SWV, respectively. In addition, the sensor showed high selectivity towards FXN in comparison to other interferents. The sensor was successfully utilized for the direct determination of FXN in buffalo raw milk samples. PMID:27242945

  8. Voltammetric Determination of Flunixin on Molecularly Imprinted Polypyrrole Modified Glassy Carbon Electrode.

    PubMed

    Radi, Abd-Elgawad; Abd El-Ghany, Nadia; Wahdan, Tarek

    2016-01-01

    A novel electrochemical sensing approach, based on electropolymerization of a molecularly imprinted polypyrrole (MIPpy) film onto a glassy carbon electrode (GCE) surface, was developed for the detection of flunixin (FXN). The sensing conditions and the performance of the constructed sensor were assessed by cyclic, differential pulse and (DPV) square wave voltammetry (SWV). The sensor exhibited high sensitivity, with linear responses in the range of 5.0 to 50.0 µM with detection limits of 1.5 and 1.0 µM for DPV and SWV, respectively. In addition, the sensor showed high selectivity towards FXN in comparison to other interferents. The sensor was successfully utilized for the direct determination of FXN in buffalo raw milk samples.

  9. Xanthine microsensor based on polypyrrole molecularly imprinted film modified carbon fiber microelectrodes.

    PubMed

    Liu, Bin; Wang, Xiao-Li; Lian, Hui-Ting; Sun, Xiang-Ying

    2013-09-15

    A molecularly imprinted polymers (MIPs) microsensor was presented as a carbon fiber microelectrode (CFME) coating for specifically recognizing xanthine (Xan). The polymeric film was obtained based on the imprinted procedure of electropolymerization of pyrrole in the presence of the template molecule Xan by cyclic voltammetry, and template was removed by magnetic stirring. Under the optimum conditions, a satisfactory molecularly binding selectivity of Xan was obtained from the MIPs microsensor with an imprinting factor (IF) of 6.63 and a linear response to concentration in certain ranges. The ranges are from 4.0 × 10⁻⁶ to 6.0 × 10⁻⁵ M and from 8.0 × 10⁻⁵ to 2.0 × 10⁻³ M with a detection limit of 2.5 × 10⁻⁷ M. Meanwhile, good stability (relative standard deviation [RSD] = 3.2%, n = 10) and reproducibility (RSD = 2.0%, n = 10) were observed, and recoveries ranging from 96.9 to 102.5% were calculated when applied to Xan determination in real blood serum samples.

  10. Electrochemical sensor based on molecularly imprinted film at polypyrrole-sulfonated graphene/hyaluronic acid-multiwalled carbon nanotubes modified electrode for determination of tryptamine.

    PubMed

    Xing, Xianrong; Liu, Su; Yu, Jinghua; Lian, Wenjing; Huang, Jiadong

    2012-01-15

    An imprinted electrochemical sensor based on polypyrrole-sulfonated graphene (PPy-SG)/hyaluronic acid-multiwalled carbon nanotubes (HA-MWCNTs) for sensitive detection of tryptamine was presented. Molecularly imprinted polymers (MIPs) were synthesized by electropolymerization using tryptamine as the template, and para-aminobenzoic acid (pABA) as the monomer. The surface feature of the modified electrode was characterized by cyclic voltammetry (CV). The proposed sensor was tested by chronoamperometry. Several important parameters controlling the performance of the molecularly imprinted sensor were investigated and optimized. The results showed that the PPy-SG composites films showed improved conductivity and electrochemical performances. HA-MWCNTs bionanocomposites could enhance the current response evidently. The good selectivity of the sensor allowed three discriminations of tryptamine from interferents, which include tyramine, dopamine and tryptophan. Under the optimal conditions, a linear ranging from 9.0×10(-8) mol L(-1) to 7.0×10(-5) mol L(-1) for the detection of tryptamine was observed with the detection limit of 7.4×10(-8) mol L(-1) (S/N=3). This imprinted electrochemical sensor was successfully employed to detect tryptamine in real samples.

  11. Nanostructure conducting molecularly imprinted polypyrrole film as a selective sorbent for benzoate ion and its application in spectrophotometric analysis of beverage samples.

    PubMed

    Manbohi, Ahmad; Shamaeli, Ehsan; Alizadeh, Naader

    2014-07-15

    The benzoate anion was selectively extracted by electrochemically controlled solid-phase microextraction (EC-SPME) using a electro-synthesised nanostructure conducting molecularly imprinted polypyrrole (CMIP) film that imprinted for benzoate ions (template ion). The sorbent behaviors of CMIP were characterised using spectrophotometry analysis. The effect of pH, uptake and released times and potentials, template ion concentration, and interference were investigated, and experimental conditions optimised. The film exhibited excellent selectivity in the presence of potential interference from anions including salicylate, sorbate, citrate, phosphate, acetate and chloride ions. The calibration graph was linear (R(2)⩾ 0.993) in the range 1.1 × 10(-5)-5.5 × 10(-4) mol L(-1) and detection limit was 5.2 × 10(-6) mol L(-1). The relative standard deviation was less than 4.5% (n=3). The CMIP film, as a solid-phase micro-extraction absorbent, was applied for the selective clean up and quantification of benzoate in beverage samples using the EC-SPME-spectrophotometric method. The results were in agreement with those obtained using HPLC analysis. This method has a good selectivity and mechanical stability and is disposable simple to construct. However, HPLC method is more selective for determination of benzoate in some food products which have interference compounds such as vanilla and flavoring agents. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. Spectrophotometric determination of fluoxetine by molecularly imprinted polypyrrole and optimization by experimental design, artificial neural network and genetic algorithm.

    PubMed

    Nezhadali, Azizollah; Motlagh, Maryam Omidvar; Sadeghzadeh, Samira

    2017-09-13

    A selective method based on molecularly imprinted polymer (MIP) solid-phase extraction (SPE) using UV-Vis spectrophotometry as a detection technique was developed for the determination of fluoxetine (FLU) in pharmaceutical and human serum samples. The MIPs were synthesized using pyrrole as a functional monomer in the presence of FLU as a template molecule. The factors that affecting the preparation and extraction ability of MIP such as amount of sorbent, initiator concentration, the amount of monomer to template ratio, uptake shaking rate, uptake time, washing buffer pH, take shaking rate, Taking time and polymerization time were considered for optimization. First a Plackett-Burman design (PBD) consists of 12 randomized runs were applied to determine the influence of each factor. The other optimization processes were performed using central composite design (CCD), artificial neural network (ANN) and genetic algorithm (GA). At optimal condition the calibration curve showed linearity over a concentration range of 10(-7)-10(-8)M with a correlation coefficient (R(2)) of 0.9970. The limit of detection (LOD) for FLU was obtained 6.56×10(-9)M. The repeatability of the method was obtained 1.61%. The synthesized MIP sorbent showed a good selectivity and sensitivity toward FLU. The MIP/SPE method was used for the determination of FLU in pharmaceutical, serum and plasma samples, successfully. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Synthesis of molecularly imprinted polypyrrole as an adsorbent for solid-phase extraction of warfarin from human plasma and urine.

    PubMed

    Peyrovi, Moazameh; Hadjmohammadi, Mohammadreza

    2015-11-01

    The aim of this work was to develop a method for the clean-up and preconcentration of warfarin from biological sample employing a new molecularly imprinted polymer (MIP) as a selective adsorbent for solid-phase extraction (SPE). This MIP was synthesized using warfarin as a template, pyrrole as a functional monomer and vinyl triethoxysilane as a cross-linker. The molar ratio of 1:4:20 (template-functional monomer-cross-linker) showed the best results. Nonimprinted polymers (NIPs) were prepared and treated with the same method, but in the absence of warfarin. The prepared polymer was characterized by Fourier transmission infrared spectrometry and scanning electron microscopy. An adsorption process (SPE) for the removal of warfarin using the fabricated MIPs and NIPs was evaluated under various conditions. Effective parameters on warfarin extraction, for example, type and volume of elution solvent, pH of sample solution, breakthrough volume and maximum loading capacity, were studied. The limits of detection were in the range of 0.0035-0.0050 µg mL(-1). Linearity of the method was determined in the range of 0.0165-10.0000 µg mL(-1) for plasma and 0.0115-10.0000 µg mL(-1) for urine with coefficients of determination (R(2)) ranging from 0.9975 to 0.9985. The recoveries for plasma and urine samples were >95%.

  14. Simultaneous analysis of non-steroidal anti-inflammatory drugs using electrochemically controlled solid-phase microextraction based on nanostructure molecularly imprinted polypyrrole film coupled to ion mobility spectrometry.

    PubMed

    Ameli, Akram; Kalhor, Hamideh; Alizadeh, Naader

    2013-06-01

    A simple, rapid, and highly sensitive method for simultaneous analysis of anti-inflammatory drugs (naproxen, ibuprofen, and mefenamic acid) in diluted human serum was developed using the electrochemically controlled solid-phase microextraction coupled to ion mobility spectrometry. A conducting molecularly imprinted polymer film based on polypyrrole was synthesized for the selective uptake and release of drugs. The film was prepared by incorporation of a template molecule (naproxen) during the electropolymerization of pyrrole onto a platinum electrode using cyclic voltammetry method. The measured ion mobility spectrometry intensity was related to the concentration of analytes taken up into the films. The calibration graphs (naproxen, ibuprofen, and mefenamic acid) were linear in the range of 0.1-30 ng/mL and detection limits were 0.07-0.37 ng/mL and relative standard deviation was lower than 6%. On the basis of the results obtained in this work, the conducting molecularly imprinted polymer films as absorbent have been applied in the electrochemically controlled solid-phase microextraction and ion mobility spectrometry system for the selective clean-up and quantification of trace amounts of anti-inflammatory drugs in human serum samples. Scanning electron microscopy has confirmed the nano-structure morphology of the polypyrrole film.

  15. Rapid degradation of Congo red by molecularly imprinted polypyrrole-coated magnetic TiO2 nanoparticles in dark at ambient conditions.

    PubMed

    Wei, Shoutai; Hu, Xiaolei; Liu, Hualong; Wang, Qiang; He, Chiyang

    2015-08-30

    A novel molecularly imprinted polymer (MIP)-coated magnetic TiO2 nanocomposite was prepared, using methyl orange (MO) as the dummy template and pyrrole as functional monomer, for degradation of Congo red (CR). The nanocomposite was characterized by Fourier transform infrared spectroscopy, thermo-gravimetric analysis, X-ray diffraction, transmission electron microscopy, and vibrating sample magnetometer. The imprinting efficiency of the imprinted nanoparticles was investigated by static binding test, and their degradation ability toward CR was also studied. Moreover, the effects of pH, temperature, dissolved oxygen and oscillation rate on degradation rate of CR were investigated. Results showed that the imprinted nanocomposite had higher adsorption ability for MO compared with the non-imprinted one. Moreover, it could degrade CR rapidly in dark at room temperature and atmospheric pressure and could be recycled easily by a magnet with a good reusability. A degradation mechanism was proposed according to LC-MS analysis of degradation products of CR. The new imprinted nanoparticles showed high catalytic activity at ambient conditions without light illumination and additional chemicals, and therefore, it can be potentially applied to the rapid, "green" and low-cost degradation of CR in industrial printing and dyeing wastewater.

  16. Molecular Imprinting

    NASA Astrophysics Data System (ADS)

    Dufaud, V.; Bonneviot, L.

    Our senses of smell and taste are able to recognise molecules selectively, to the point where they can even discriminate between different chiral states. This property, called molecular recognition, is essential to all forms of life [1]. It is based on the principle of a specific interaction between a receptor or host and a target molecule, which will be identified among a multitude of others, then selectively adsorbed. If the host is endowed with reactive functions, the attached molecule may be transported or transformed. Enzymes are the archetypal host molecules exploiting the idea of molecular recognition. Their complexation sites comprise a hydrophobic pocket with definite shape within which amino acid residues are located in a precisely defined way. The combined effect of these different characteristics underlies not only the affinity for some specific substrate, but also the transformation of this substrate into the desired product [2]. In fact, the phenomena actually brought into play are much more involved, being made up of an ensemble of physicochemical events that act together in a cooperative way, either simultaneously or sequentially, and in which the molecular processes are difficult to follow in detail.

  17. Molecularly Imprinted Ionomers

    DTIC Science & Technology

    2002-04-05

    ion selective electrodes and ion selective optical sensors using a modified version of the molecular imprinting technique. The modification is a...materials may be the means to realize this goal. An additional application of metal ion imprinted polymers is as sensors . The ability to detect a...been shown to have dramatic effects on polymer properties. The benefits of ionic crosslinking on molecular imprinting are two-fold. First, ionic

  18. Molecularly Imprinted Biodegradable Nanoparticles.

    PubMed

    Gagliardi, Mariacristina; Bertero, Alice; Bifone, Angelo

    2017-01-10

    Biodegradable polymer nanoparticles are promising carriers for targeted drug delivery in nanomedicine applications. Molecu- lar imprinting is a potential strategy to target polymer nanoparticles through binding of endogenous ligands that may promote recognition and active transport into specific cells and tissues. However, the lock-and-key mechanism of molecular imprinting requires relatively rigid cross-linked structures, unlike those of many biodegradable polymers. To date, no fully biodegradable molecularly imprinted particles have been reported in the literature. This paper reports the synthesis of a novel molecularly- imprinted nanocarrier, based on poly(lactide-co-glycolide) (PLGA) and acrylic acid, that combines biodegradability and molec- ular recognition properties. A novel three-arm biodegradable cross-linker was synthesized by ring-opening polymerization of glycolide and lactide initiated by glycerol. The resulting macromer was functionalized by introduction of end-functions through reaction with acryloyl chloride. Macromer and acrylic acid were used for the synthesis of narrowly-dispersed nanoparticles by radical polymerization in diluted conditions in the presence of biotin as template molecule. The binding capacity of the imprinted nanoparticles towards biotin and biotinylated bovine serum albumin was twentyfold that of non-imprinted nanoparti- cles. Degradation rates and functional performances were assessed in in vitro tests and cell cultures, demonstrating effective biotin-mediated cell internalization.

  19. Molecularly Imprinted Biodegradable Nanoparticles

    NASA Astrophysics Data System (ADS)

    Gagliardi, Mariacristina; Bertero, Alice; Bifone, Angelo

    2017-01-01

    Biodegradable polymer nanoparticles are promising carriers for targeted drug delivery in nanomedicine applications. Molecu- lar imprinting is a potential strategy to target polymer nanoparticles through binding of endogenous ligands that may promote recognition and active transport into specific cells and tissues. However, the lock-and-key mechanism of molecular imprinting requires relatively rigid cross-linked structures, unlike those of many biodegradable polymers. To date, no fully biodegradable molecularly imprinted particles have been reported in the literature. This paper reports the synthesis of a novel molecularly- imprinted nanocarrier, based on poly(lactide-co-glycolide) (PLGA) and acrylic acid, that combines biodegradability and molec- ular recognition properties. A novel three-arm biodegradable cross-linker was synthesized by ring-opening polymerization of glycolide and lactide initiated by glycerol. The resulting macromer was functionalized by introduction of end-functions through reaction with acryloyl chloride. Macromer and acrylic acid were used for the synthesis of narrowly-dispersed nanoparticles by radical polymerization in diluted conditions in the presence of biotin as template molecule. The binding capacity of the imprinted nanoparticles towards biotin and biotinylated bovine serum albumin was twentyfold that of non-imprinted nanoparti- cles. Degradation rates and functional performances were assessed in in vitro tests and cell cultures, demonstrating effective biotin-mediated cell internalization.

  20. Molecularly Imprinted Biodegradable Nanoparticles

    PubMed Central

    Gagliardi, Mariacristina; Bertero, Alice; Bifone, Angelo

    2017-01-01

    Biodegradable polymer nanoparticles are promising carriers for targeted drug delivery in nanomedicine applications. Molecu- lar imprinting is a potential strategy to target polymer nanoparticles through binding of endogenous ligands that may promote recognition and active transport into specific cells and tissues. However, the lock-and-key mechanism of molecular imprinting requires relatively rigid cross-linked structures, unlike those of many biodegradable polymers. To date, no fully biodegradable molecularly imprinted particles have been reported in the literature. This paper reports the synthesis of a novel molecularly- imprinted nanocarrier, based on poly(lactide-co-glycolide) (PLGA) and acrylic acid, that combines biodegradability and molec- ular recognition properties. A novel three-arm biodegradable cross-linker was synthesized by ring-opening polymerization of glycolide and lactide initiated by glycerol. The resulting macromer was functionalized by introduction of end-functions through reaction with acryloyl chloride. Macromer and acrylic acid were used for the synthesis of narrowly-dispersed nanoparticles by radical polymerization in diluted conditions in the presence of biotin as template molecule. The binding capacity of the imprinted nanoparticles towards biotin and biotinylated bovine serum albumin was twentyfold that of non-imprinted nanoparti- cles. Degradation rates and functional performances were assessed in in vitro tests and cell cultures, demonstrating effective biotin-mediated cell internalization. PMID:28071745

  1. Molecularly imprinted membranes.

    PubMed

    Trotta, Francesco; Biasizzo, Miriam; Caldera, Fabrizio

    2012-07-19

    Although the roots of molecularly imprinted polymers lie in the beginning of 1930s in the past century, they have had an exponential growth only 40-50 years later by the works of Wulff and especially by Mosbach. More recently, it was also proved that molecular imprinted membranes (i.e., polymer thin films) that show recognition properties at molecular level of the template molecule are used in their formation. Different procedures and potential application in separation processes and catalysis are reported. The influences of different parameters on the discrimination abilities are also discussed.

  2. Molecularly Imprinted Membranes

    PubMed Central

    Trotta, Francesco; Biasizzo, Miriam; Caldera, Fabrizio

    2012-01-01

    Although the roots of molecularly imprinted polymers lie in the beginning of 1930s in the past century, they have had an exponential growth only 40–50 years later by the works of Wulff and especially by Mosbach. More recently, it was also proved that molecular imprinted membranes (i.e., polymer thin films) that show recognition properties at molecular level of the template molecule are used in their formation. Different procedures and potential application in separation processes and catalysis are reported. The influences of different parameters on the discrimination abilities are also discussed. PMID:24958291

  3. Clickable molecularly imprinted nanoparticles.

    PubMed

    Xu, Changgang; Ye, Lei

    2011-06-07

    Terminal alkynyl and azide groups are introduced on the surface of molecularly imprinted core-shell nanoparticles using precipitation polymerization. These clickable groups enable simple nanoparticle conjugation and surface modification under mild reaction conditions, opening new opportunities for nanoparticle-based assays and chemical sensing.

  4. Electrochemical preparation of a molecularly imprinted polypyrrole modified pencil graphite electrode for the determination of phenothiazine in model and real biological samples.

    PubMed

    Nezhadali, Azizollah; Rouki, Zohreh; Nezhadali, Mohammad

    2015-11-01

    A sensitive electrochemical sensor for determination of phenothiazine (PTZ) was introduced based on molecularly imprinted polymer (MIP) film. A computational study was performed to evaluate the template-monomer geometry and interaction energy in the prepolymerization mixture. The electrode was prepared during electropolymerization of pyrrole (Py) on a pencil graphite electrode (PGE) by cyclic voltammetry (CV) technique. The quantitative measurements were performed using differential pulse voltammetry (DPV) in Britton-Robinson (BR) buffer solutions using 60% (v/v) acetonitrile-water (ACN/H2O) binary solvent. The effect of important parameters like pH, monomer concentration, number of cycles, etc on the efficiency of MIP electrode was optimized and the calibration curve was plotted at optimal conditions. Two dynamic linear ranges of 1-300 µmol L(-1) and 0.5-10 mmol L(-1) were observed. The detection limit (based on S/N=3) of PTZ was obtained 3×10(-7) mol L(-1). The MIP/PGE has been successfully applied as a selective sensor for fast and accurate determination of PTZ in some model and real biological samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Molecular imprinting: perspectives and applications.

    PubMed

    Chen, Lingxin; Wang, Xiaoyan; Lu, Wenhui; Wu, Xiaqing; Li, Jinhua

    2016-04-21

    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).

  6. Molecularly imprinted materials: synthesis, properties, applications

    NASA Astrophysics Data System (ADS)

    Lisichkin, Georgii V.; Krutyakov, Yu A.

    2006-10-01

    This review is devoted to the method of molecular imprinting. The physicochemical fundamentals and mechanisms of covalent and non-covalent molecular imprinting aimed at the development of organic polymeric sorbents capable of molecular recognition are considered. Attention is focused on the preparation of molecular imprints on mineral supports. The mechanisms of molecular recognition in adsorption are discussed. Application fields of materials with molecular imprints are briefly surveyed.

  7. Molecular imprinting in sol-gel matrix.

    PubMed

    Gupta, Radha; Kumar, Ashok

    2008-01-01

    Molecular imprinting is a newly developed methodology which provides molecular assemblies of desired structures and properties and is being increasingly used for several applications such as in separation processes, microreactors, immunoassays and antibody mimics, catalysis, artificial enzymes, biosensor recognition elements and bio- and chemo-sensors. The ambient processing conditions and versatility of the sol-gel process makes sol-gel glassy matrix suitable for molecular imprinting. The progress of sol-gel based molecular imprinted polymers (MIPs) for various applications can be seen from the growing number of publications. The main focus of the review is molecular imprinting in sol-gel matrix and applications of molecular imprinted sol-gel derived materials for the development of sensors. Combining sol-gel process with molecular imprinting enables to procure the sensors with greater sensitivity and selectivity necessary for sensing applications. The merits, problems, challenges and factors affecting molecular imprinting in sol-gel matrix have been discussed. Considerable attention has been drawn on recent developments like use of organically modified silane precursors (ORMOSILS) for the synthesis of hybrid molecular imprinted polymers (HMIPs) and applying surface sol-gel process for molecular imprinting. The development of molecular imprinted sol-gel nanotubes for biochemical separation and bio-imprinting is a new advancement and is under progress. Templated xerogels and molecularly imprinted sol-gel films provide a good platform for various sensor applications.

  8. Molecularly Imprinted Materials: Towards the Next Generation

    DTIC Science & Technology

    2002-04-05

    SCINTILLATION POLYMERS : A NEW SENSOR CONCEPT Although molecularly imprinted polymers ( MIPs ) often display high binding affinity and specificity mimicking... sensors have been demonstrated over the past years. In general, molecular imprinting can be defined as a process of target directed synthesis of...efficiency. For these reasons imprinted polymer beads are preferable. Although the well-established suspension and dispersion polymerization methods

  9. Molecularly imprinted polymer sensor arrays.

    PubMed

    Shimizu, Ken D; Stephenson, Clifton J

    2010-12-01

    The sensor array format has proved an effective method of transforming sensors of modest selectivity into highly selective and discriminating sensors. The primary challenge in developing new sensor arrays is collecting together a sufficient number of recognition elements that possess different binding affinities for the analytes of interest. In this regard, the use of molecularly imprinted polymers (MIPs) as the recognition elements in sensor arrays has a number of unique advantages. MIPs can be rapidly and inexpensively prepared with different selectivities and tuned with different selectivity patterns via the choice of templates in the imprinting process. The array format also helps compensate for the low selectivities and high cross-reactivities of MIP sensors. These attractive qualities of MIP sensor arrays have been demonstrated in recent examples, which have established the viability and generality of the approach. In particular, the versatility of the imprinting process enables MIP sensor arrays to be tailored to specific analytes. MIP sensor arrays have also shown surprisingly broad utility, as even analytes that were not used as templates in the imprinting process can be effectively discriminated.

  10. Molecular Imprinting of Macromolecules for Sensor Applications

    PubMed Central

    Saylan, Yeşeren; Yilmaz, Fatma; Özgür, Erdoğan; Derazshamshir, Ali; Yavuz, Handan; Denizli, Adil

    2017-01-01

    Molecular recognition has an important role in numerous living systems. One of the most important molecular recognition methods is molecular imprinting, which allows host compounds to recognize and detect several molecules rapidly, sensitively and selectively. Compared to natural systems, molecular imprinting methods have some important features such as low cost, robustness, high recognition ability and long term durability which allows molecularly imprinted polymers to be used in various biotechnological applications, such as chromatography, drug delivery, nanotechnology, and sensor technology. Sensors are important tools because of their ability to figure out a potentially large number of analytical difficulties in various areas with different macromolecular targets. Proteins, enzymes, nucleic acids, antibodies, viruses and cells are defined as macromolecules that have wide range of functions are very important. Thus, macromolecules detection has gained great attention in concerning the improvement in most of the studies. The applications of macromolecule imprinted sensors will have a spacious exploration according to the low cost, high specificity and stability. In this review, macromolecules for molecularly imprinted sensor applications are structured according to the definition of molecular imprinting methods, developments in macromolecular imprinting methods, macromolecular imprinted sensors, and conclusions and future perspectives. This chapter follows the latter strategies and focuses on the applications of macromolecular imprinted sensors. This allows discussion on how sensor strategy is brought to solve the macromolecules imprinting. PMID:28422082

  11. Molecular Imprinting of Macromolecules for Sensor Applications.

    PubMed

    Saylan, Yeşeren; Yilmaz, Fatma; Özgür, Erdoğan; Derazshamshir, Ali; Yavuz, Handan; Denizli, Adil

    2017-04-19

    Molecular recognition has an important role in numerous living systems. One of the most important molecular recognition methods is molecular imprinting, which allows host compounds to recognize and detect several molecules rapidly, sensitively and selectively. Compared to natural systems, molecular imprinting methods have some important features such as low cost, robustness, high recognition ability and long term durability which allows molecularly imprinted polymers to be used in various biotechnological applications, such as chromatography, drug delivery, nanotechnology, and sensor technology. Sensors are important tools because of their ability to figure out a potentially large number of analytical difficulties in various areas with different macromolecular targets. Proteins, enzymes, nucleic acids, antibodies, viruses and cells are defined as macromolecules that have wide range of functions are very important. Thus, macromolecules detection has gained great attention in concerning the improvement in most of the studies. The applications of macromolecule imprinted sensors will have a spacious exploration according to the low cost, high specificity and stability. In this review, macromolecules for molecularly imprinted sensor applications are structured according to the definition of molecular imprinting methods, developments in macromolecular imprinting methods, macromolecular imprinted sensors, and conclusions and future perspectives. This chapter follows the latter strategies and focuses on the applications of macromolecular imprinted sensors. This allows discussion on how sensor strategy is brought to solve the macromolecules imprinting.

  12. Astrobiological Molecularly Imprinted Polymer Sensors

    NASA Astrophysics Data System (ADS)

    Izenberg, N. R.; Murray, G. M.; van Houten, K. A.; Hofstra, A. A.

    2005-12-01

    Development of Molecularly Imprinted Polymer (MIP) sensors for astrobiology is intended to provide a new class of microlaboratory sensors compatible with other life or biomarker detection. Molecular imprinting is a process for making selective binding sites in synthetic polymers. The process may be approached by designing the recognition site or by simply choosing monomers that may have favorable interactions with the imprinting molecule. We are working to apply this methodology to astrobiology for development of a reliable, low cost, low mass, low power consumption sensor technology for quantitative in-situ analysis of biochemistry, biomarkers, and other indicators of astrobiological importance. Specific goals of the project are: 1) To develop a general methodology and specific methods for MIP-based sensor construction. The overall methodology will guide procedures for design and testing of any desired sensor. Specific methods will be applied to key families and specific species of astrobiological interest, i.e., alkanes (and Polycyclic aromatic hydrocarbons - PAHs), amino acids, steroids, and hopanes; 2) To construct and characterize the general family and specific species sensors. We will test for accuracy, precision, interferences, and limitations of the sensor against blanks, standards, and known terrestrial biological environment samples. Additional testing will determine sturdiness and longevity of sensors after exposure to transit conditions (launch and space environment), and at potential target environments (pressure, temperature, pH, etc.); and 3) To construct and demonstrate the combination of multiple sensors into a viable prototype instrument, and roadmap the expansion of potential instrument capabilities and exploration of the ultimate environmental limitations of the technology, and the necessary changes and additions to create a mission-ready instrument. Initial work has resulted successful detection of aqueous alanine (D and L) with simple MIP

  13. Molecularly Imprinted Membranes: Past, Present, and Future.

    PubMed

    Yoshikawa, Masakazu; Tharpa, Kalsang; Dima, Ştefan-Ovidiu

    2016-10-12

    More than 80 years ago, artificial materials with molecular recognition sites emerged. The application of molecular imprinting to membrane separation has been studied since 1962. Especially after 1990, such research has been intensively conducted by membranologists and molecular imprinters to understand the advantages of each technique with the aim of constructing an ideal membrane, which is still an active area of research. The present review aims to be a substantial, comprehensive, authoritative, critical, and general-interest review, placed at the cross section of two broad, interconnected, practical, and extremely dynamic fields, namely, the fields of membrane separation and molecularly imprinted polymers. This review describes the recent discoveries that appeared after repeated and fertile collisions between these two fields in the past three years, to which are added the worthy acknowledgments of pioneering discoveries and a look into the future of molecularly imprinted membranes. The review begins with a general introduction in membrane separation, followed by a short theoretical section regarding the basic principles of mass transport through a membrane. Following these general aspects on membrane separation, two principles of obtaining polymeric materials with molecular recognition properties are reviewed, namely, molecular imprinting and alternative molecular imprinting, followed the methods of obtaining and practical applications for the particular case of molecularly imprinted membranes. The review continues with insights into molecularly imprinted nanofiber membranes as a promising, highly optimized type of membrane that could provide a relatively high throughput without a simultaneous unwanted reduction in permselectivity. Finally, potential applications of molecularly imprinted membranes in a variety of fields are highlighted, and a look into the future of membrane separations is offered.

  14. Electrochemical Molecular Imprinted Sensors Based on Electrospun Nanofiber and Determination of Ascorbic Acid.

    PubMed

    Zhai, Yunyun; Wang, Dandan; Liu, Haiqing; Zeng, Yanbo; Yin, Zhengzhi; Li, Lei

    2015-01-01

    In this study, electrochemical molecularly imprinted sensors were fabricated and used for the determination of ascorbic acid (AA). Nanofiber membranes of cellulose acetate (CA)/multi-walled carbon nanotubes (MWCNTs)/polyvinylpyrrolidone (PVP) (CA/MWCNTs/PVP) were prepared by electrospinning technique. After being transferred to a glass carbon electrode (GC), the nanofiber interface was further polymerized with pyrrole through electrochemical cyclic voltammetry (CV) technique. Meanwhile, target molecules (such as AA) were embedded into the polypyrrole through the hydrogen bond. The effects of monomer concentration (pyrrole), the number of scan cycles and scan rates of polymerization were optimized. Differential pulse voltammetry (DPV) tests indicated that the oxidation current of AA (the selected target) were higher than that of the structural analogues, which illustrated the selective recognition of AA by molecularly imprinted sensors. Simultaneously, the molecularly imprinted sensors had larger oxidation current of AA than non-imprinted sensors in the processes of rebinding. The electrochemical measurements showed that the molecularly imprinted sensors demonstrated good identification behavior for the detection of AA with a linear range of 10.0 - 1000 μM, a low detection limit down to 3 μM (S/N = 3), and a recovery rate range from 94.0 to 108.8%. Therefore, the electrochemical molecularly imprinted sensors can be used for the recognition and detection of AA without any time-consuming elution. The method presented here demonstrates the great potential for electrospun nanofibers and MWCNTs to construct electrochemical sensors.

  15. Molecularly Imprinted Nanomaterials for Sensor Applications

    PubMed Central

    Irshad, Muhammad; Iqbal, Naseer; Mujahid, Adnan; Afzal, Adeel; Hussain, Tajamal; Sharif, Ahsan; Ahmad, Ejaz; Athar, Muhammad Makshoof

    2013-01-01

    Molecular imprinting is a well-established technology to mimic antibody-antigen interaction in a synthetic platform. Molecularly imprinted polymers and nanomaterials usually possess outstanding recognition capabilities. Imprinted nanostructured materials are characterized by their small sizes, large reactive surface area and, most importantly, with rapid and specific analysis of analytes due to the formation of template driven recognition cavities within the matrix. The excellent recognition and selectivity offered by this class of materials towards a target analyte have found applications in many areas, such as separation science, analysis of organic pollutants in water, environmental analysis of trace gases, chemical or biological sensors, biochemical assays, fabricating artificial receptors, nanotechnology, etc. We present here a concise overview and recent developments in nanostructured imprinted materials with respect to various sensor systems, e.g., electrochemical, optical and mass sensitive, etc. Finally, in light of recent studies, we conclude the article with future perspectives and foreseen applications of imprinted nanomaterials in chemical sensors. PMID:28348356

  16. Astrobiological molecularly imprinted polymer sensors

    NASA Astrophysics Data System (ADS)

    Izenberg, Noam R.; Murrray, George M.; Pilato, Robert S.; Baird, Lance M.; Levin, Scott M.; Van Houten, Kelly A.

    2009-06-01

    The purpose of the Astrobiological MIP Sensor (AMS) Project is to develop reliable, low-cost, low-mass, low-power consumption detection technologies for in situ analysis of biochemical markers, and other indicators of astrobiological importance. To this end, we are investigating the potential role that molecularly imprinted polymers (MIP) could serve in the recognition of pre-biotic and biotic compounds in planetary, astrobiological and geochemical mission profiles. While MIPs are effective molecular recognition tools, a signal transduction method must be developed so that the recognition of analytes can be realized. In the course of this study, surface plasmon resonance (SPR) will be the detection method of the MIP recognition event. In addition, MIP-coated SPR substrates were subjected to vibration, temperature and radiation testing to demonstrate that they could withstand the rigors of space travel. The methods developed in this study require capture of the biomarkers onto the SPR sensor chip, followed by addition of a MIP. It is the binding of the MIP to the SPR bound analyte that amplifies the SPR signal associated with binding of the low molecular weight analyte. The MIPs, developed in this study are water-soluble processable star polymers while the SPR device used was SensíQ™ by Nomatics. Proof-of-principal experiments were first demonstrated using amino biotin.

  17. Molecularly Imprinted Polymers: Present and Future Prospective

    PubMed Central

    Vasapollo, Giuseppe; Sole, Roberta Del; Mergola, Lucia; Lazzoi, Maria Rosaria; Scardino, Anna; Scorrano, Sonia; Mele, Giuseppe

    2011-01-01

    Molecular Imprinting Technology (MIT) is a technique to design artificial receptors with a predetermined selectivity and specificity for a given analyte, which can be used as ideal materials in various application fields. Molecularly Imprinted Polymers (MIPs), the polymeric matrices obtained using the imprinting technology, are robust molecular recognition elements able to mimic natural recognition entities, such as antibodies and biological receptors, useful to separate and analyze complicated samples such as biological fluids and environmental samples. The scope of this review is to provide a general overview on MIPs field discussing first general aspects in MIP preparation and then dealing with various application aspects. This review aims to outline the molecularly imprinted process and present a summary of principal application fields of molecularly imprinted polymers, focusing on chemical sensing, separation science, drug delivery and catalysis. Some significant aspects about preparation and application of the molecular imprinting polymers with examples taken from the recent literature will be discussed. Theoretical and experimental parameters for MIPs design in terms of the interaction between template and polymer functionalities will be considered and synthesis methods for the improvement of MIP recognition properties will also be presented. PMID:22016636

  18. Molecularly imprinted polymers: present and future prospective.

    PubMed

    Vasapollo, Giuseppe; Sole, Roberta Del; Mergola, Lucia; Lazzoi, Maria Rosaria; Scardino, Anna; Scorrano, Sonia; Mele, Giuseppe

    2011-01-01

    Molecular Imprinting Technology (MIT) is a technique to design artificial receptors with a predetermined selectivity and specificity for a given analyte, which can be used as ideal materials in various application fields. Molecularly Imprinted Polymers (MIPs), the polymeric matrices obtained using the imprinting technology, are robust molecular recognition elements able to mimic natural recognition entities, such as antibodies and biological receptors, useful to separate and analyze complicated samples such as biological fluids and environmental samples. The scope of this review is to provide a general overview on MIPs field discussing first general aspects in MIP preparation and then dealing with various application aspects. This review aims to outline the molecularly imprinted process and present a summary of principal application fields of molecularly imprinted polymers, focusing on chemical sensing, separation science, drug delivery and catalysis. Some significant aspects about preparation and application of the molecular imprinting polymers with examples taken from the recent literature will be discussed. Theoretical and experimental parameters for MIPs design in terms of the interaction between template and polymer functionalities will be considered and synthesis methods for the improvement of MIP recognition properties will also be presented.

  19. Molecularly imprinted polymers with multi-functionality.

    PubMed

    Ye, Lei

    2016-03-01

    Molecular imprinting is a very powerful synthetic method for preparation of robust materials with pre-designed molecular selectivity. Molecularly imprinted polymers (MIPs) are attractive substitutes for antibodies in many analytical and bioanalytical applications, e.g. for development of biosensors and for drug assays. In addition to selective molecular binding, new functions are being added to MIPs to make the synthetic materials responsive to different environmental conditions, making it possible to modulate the binding and release of different molecular targets and to simplify affinity separation. Introduction of signal-transduction functionality into MIPs also brings in new, more easily operated chemical sensors for detection and quantification of important analytical targets.

  20. Molecular imprinting of bulk, microporous silica

    NASA Astrophysics Data System (ADS)

    Katz, Alexander; Davis, Mark E.

    2000-01-01

    Molecular imprinting aims to create solid materials containing chemical functionalities that are spatially organized by covalent or non-covalent interactions with imprint (or template) molecules during the synthesis process. Subsequent removal of the imprint molecules leaves behind designed sites for the recognition of small molecules, making the material ideally suited for applications such as separations, chemical sensing and catalysis. Until now, the molecular imprinting of bulk polymers and polymer and silica surfaces has been reported, but the extension of these methods to a wider range of materials remains problematic. For example, the formation of substrate-specific cavities within bulk silica, while conceptually straightforward, has been difficult to accomplish experimentally. Here we describe the imprinting of bulk amorphous silicas with single aromatic rings carrying up to three 3-aminopropyltriethoxysilane side groups; this generates and occupies microporosity and attaches functional organic groups to the pore walls in a controlled fashion. The triethoxysilane part of the molecules' side groups is incorporated into the silica framework during sol-gel synthesis, and subsequent removal of the aromatic core creates a cavity with spatially organized aminopropyl groups covalently anchored to the pore walls. We find that the imprinted silicas act as shape-selective base catalysts. Our strategy can be extended to imprint other functional groups, which should give access to a wide range of functionalized materials.

  1. A capacitive sensor for 2,4-D determination in water based on 2,4-D imprinted polypyrrole coated pencil electrode

    NASA Astrophysics Data System (ADS)

    Prusty, Arun Kumar; Bhand, Sunil

    2017-03-01

    A capacitive sensor for 2,4-dichloro phenoxy acetic acid(2,4-D) determination in drinking water has been developed using molecularly imprinted polypyrrole on pencil graphite electrode (PGE). Molecular imprinted polymer (MIP) coated PGE was prepared by electropolymerization of pyrrole via chronopotentiometry in the presence of 2,4-D as the template molecule. The prepared electrodes were characterized by field emission gun-scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). The capacitance change of MIP electrode was measured in the presence of 2,4-D using EIS. The developed capacitive sensor exhibited a linear range 0.06-1.25 µg l-1 2,4-D with limit of detection of 0.02 µg l-1 and good selectivity towards 2,4-D in water with recovery from 92 to 110%. The results suggest the viable applicability of the MIP/PGE based sensor for the determination of the 2,4-D in water samples.

  2. Dynamic assembly of molecularly imprinted polymer nanoparticles.

    PubMed

    Gong, Haiyue; Hajizadeh, Solmaz; Jiang, Lingdong; Ma, Huiting; Ye, Lei

    2017-09-11

    Manipulation of specific binding and recycling of materials are two important aspects for practical applications of molecularly imprinted polymers. In this work, we developed a new approach to control the dynamic assembly of molecularly imprinted nanoparticles by surface functionalization. Molecularly imprinted polymer nanoparticles with a well-controlled core-shell structure were synthesized using precipitation polymerization. The specific binding sites were created in the core during the first step imprinting reaction. In the second polymerization step, epoxide groups were introduced into the particle shell to act asan intermediate linker to immobilize phenylboronic acids, as well as to introduce cis-diol structures on surface. The imprinted polymer nanoparticles modified with boronic acid and cis-diol structures maintained high molecular binding specificity, and the nanoparticles could be induced to form dynamic particle aggregation that responded to pH variation and chemical stimuli. The possibility of modulating molecular binding and nanoparticle assembly in a mutually independent fashion can be exploited in a number of applications where repeated use of precious nanoparticles is needed. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Molecularly imprinted polymers for bioanalytical sample preparation.

    PubMed

    Gama, Mariana Roberto; Bottoli, Carla Beatriz Grespan

    2017-02-01

    Molecularly imprinted polymers (MIP) are stable polymers with molecular recognition abilities, provided by the presence of a template during their synthesis, and are excellent materials with high selectivity for sample preparation in bioanalytical methods. This short review discusses aspects of MIP preparation and its applications as a sorbent material in pharmaceutical and biomedical analysis. MIP in different extraction configurations, including classical solid-phase extraction, solid-phase microextraction, magnetic molecularly imprinted solid-phase extraction, microextraction by packed sorbent and solid-phase extraction in pipette tips, are used to illustrate the good performance of this type of sorbent for sample preparation procedures of complex matrices, especially prior to bioanalytical approaches.

  4. Plastic Antibodies: Molecular Recognition with Imprinted Polymers

    ERIC Educational Resources Information Center

    Rushton, Gregory T.; Furmanski, Brian; Shimizu, Ken D.

    2005-01-01

    Synthetic polymers are prepared and tested in a study for their molecular recognition properties of an adenine derivative, ethyl adenine-9-acetate (EA9A), within two laboratory periods. The procedure introduces undergraduate chemistry students to noncovalent molecular imprinting as well as the analytical techniques for assessing their recognition…

  5. Plastic Antibodies: Molecular Recognition with Imprinted Polymers

    ERIC Educational Resources Information Center

    Rushton, Gregory T.; Furmanski, Brian; Shimizu, Ken D.

    2005-01-01

    Synthetic polymers are prepared and tested in a study for their molecular recognition properties of an adenine derivative, ethyl adenine-9-acetate (EA9A), within two laboratory periods. The procedure introduces undergraduate chemistry students to noncovalent molecular imprinting as well as the analytical techniques for assessing their recognition…

  6. Fluorescence Anisotropy Studies of Molecularly Imprinted Polymers

    SciTech Connect

    Chen, Yin-Chu; Wang, Zheming; Yan, Mingdi; Prahl, Scott A.

    2006-01-01

    A molecularly imprinted polymer (MIP) is a biomimetic material that can be used as a biochemical sensing element. We studied the steady-state and time-resolved fluorescence and fluorescence anisotropy of anthracene imprinted polyurethane. We compared MIPs with imprinted analytes present, MIPs with the imprinted analytes extracted, MIPs with rebound analytes, non-imprinted control polymers (non-MIPs), and non-MIPs bound with analytes to understand MIP’s binding behavior. MIPs and non-MIPs had similar steady-state fluorescence anisotropy in the range of 0.11–0.24. Anthracene rebound in MIPs and non-MIPs had a fluorescence lifetime _=0.64 ns and a rotational correlation time _F =1.2–1.5 ns, both of which were shorter than that of MIPs with imprinted analytes present (_=2.03 ns and _F =2.7 ns). The steady-state anisotropy of polymer solutions increased exponentially with polymerization time and might be used to characterize the polymerization extent in-situ.

  7. Molecularly imprinted polymers for biomedical and biotechnological applications

    NASA Astrophysics Data System (ADS)

    Dmitrienko, E. V.; Pyshnaya, I. A.; Martyanov, O. N.; Pyshnyi, D. V.

    2016-05-01

    This survey covers main advances in the preparation and application of molecularly imprinted polymers which are capable of specific recognition of biologically active compounds. The principles underlying the production of highly efficient and template-specific molecularly imprinted polymers are discussed. The focus is on the imprinting of highly structured macromolecular and supramolecular templates. The existing and potential applications of molecularly imprinted polymers in various fields of chemistry and molecular biology are considered. The bibliography includes 261 references.

  8. Selective Binding of Organophosphate Pesticides Using Molecular Imprinted Polymers

    DTIC Science & Technology

    2005-10-01

    MIPs . SELECTIVE BINDING OF ORGANOPHOSPHATE PESTICIDES USING MOLECULAR IMPRINTED POLYMERS . *Ali M. Saboori...Maryland 20910-7500. ABSTRACT Molecular Imprinted Polymers ( MIPs ) have been used for recognition and binding of different compounds. We are...INTRODUCTION Molecular Imprinted Polymers ( MIPs ) are highly cross-linked polymers , which are formed by cross- linking monomer in

  9. Molecular imprinted polymers as drug delivery vehicles.

    PubMed

    Zaidi, Shabi Abbas

    2016-09-01

    This review is aimed to discuss the molecular imprinted polymer (MIP)-based drug delivery systems (DDS). Molecular imprinted polymers have proved to possess the potential and also as a suitable material in several areas over a long period of time. However, only recently it has been employed for pharmaceuticals and biomedical applications, particularly as drug delivery vehicles due to properties including selective recognition generated from imprinting the desired analyte, favorable in harsh experimental conditions, and feedback-controlled recognitive drug release. Hence, this review will discuss their synthesis, the reason they are selected as drug delivery vehicles and for their applications in several drug administration routes (i.e. transdermal, ocular and gastrointestinal or stimuli-reactive routes).

  10. A Formaldehyde Sensor Based on Molecularly-Imprinted Polymer on a TiO₂ Nanotube Array.

    PubMed

    Tang, Xiaohui; Raskin, Jean-Pierre; Lahem, Driss; Krumpmann, Arnaud; Decroly, André; Debliquy, Marc

    2017-03-24

    Today, significant attention has been brought to the development of sensitive, specific, cheap, and reliable sensors for real-time monitoring. Molecular imprinting technology is a versatile and promising technology for practical applications in many areas, particularly chemical sensors. Here, we present a chemical sensor for detecting formaldehyde, a toxic common indoor pollutant gas. Polypyrrole-based molecularly-imprinted polymer (PPy-based MIP) is employed as the sensing recognition layer and synthesized on a titanium dioxide nanotube array (TiO₂-NTA) for increasing its surface-to-volume ratio, thereby improving the sensor performance. Our sensor selectively detects formaldehyde in the parts per million (ppm) range at room temperature. It also shows a long-term stability and small fluctuation to humidity variations. These are attributed to the thin fishnet-like structure of the PPy-based MIP on the highly-ordered and vertically-aligned TiO₂-NTA.

  11. Monolithic molecularly imprinted cryogel for lysozyme recognition.

    PubMed

    Rabieizadeh, Mohammadmahdi; Kashefimofrad, Seyed Mohammadreza; Naeimpoor, Fereshteh

    2014-10-01

    The application of molecularly imprinted polymers in the selective adsorption of macromolecules such as proteins by monolithic protein-imprinted columns requires a macroporous structure, which can be provided by cryogelation at low temperature in which the formation of ice crystals gives a porous structure to the molecularly imprinted polymer. In this study, we applied this technique to synthesize lysozyme-imprinted polyacrylamide cryogels containing 8% w/v of total monomers and 0.3% w/v of lysozyme. The synthesized cryogel was sponge-like and elastic with very fast swelling and reshaping properties, showing a swelling ratio of 24.5 ± 3 and gel fraction yield of about 72%. It showed an imprinting effect of 1.58 and a separation factor of 1.37 for cytochrome c as the competing protein. Adsorption studies on the cryogel revealed that it follows the Langmuir isotherm, with a maximum theoretical adsorption capacity of 36.3 mg lysozyme per gram of cryogel. Additionally, it was shown that a salt-free rebinding solution at low flow rate and pH = 7.0 is favorable for lysozyme rebinding. This kind of monolithic column promises a wide range of application in separation of various biomolecules due to its preparation simplicity, good rebinding characteristics, and macroporosity.

  12. Molecular Imprinting Techniques Used for the Preparation of Biosensors

    PubMed Central

    Ertürk, Gizem; Mattiasson, Bo

    2017-01-01

    Molecular imprinting is the technology of creating artificial recognition sites in polymeric matrices which are complementary to the template in their size, shape and spatial arrangement of the functional groups. Molecularly imprinted polymers (MIPs) and their incorporation with various transducer platforms are among the most promising approaches for detection of several analytes. There are a variety of molecular imprinting techniques used for the preparation of biomimetic sensors including bulk imprinting, surface imprinting (soft lithography, template immobilization, grafting, emulsion polymerization) and epitope imprinting. This chapter presents an overview of all of these techniques with examples from particular publications. PMID:28165419

  13. Molecular Imprinting Techniques Used for the Preparation of Biosensors.

    PubMed

    Ertürk, Gizem; Mattiasson, Bo

    2017-02-04

    Molecular imprinting is the technology of creating artificial recognition sites in polymeric matrices which are complementary to the template in their size, shape and spatial arrangement of the functional groups. Molecularly imprinted polymers (MIPs) and their incorporation with various transducer platforms are among the most promising approaches for detection of several analytes. There are a variety of molecular imprinting techniques used for the preparation of biomimetic sensors including bulk imprinting, surface imprinting (soft lithography, template immobilization, grafting, emulsion polymerization) and epitope imprinting. This chapter presents an overview of all of these techniques with examples from particular publications.

  14. Molecular Imprinting Applications in Forensic Science.

    PubMed

    Yılmaz, Erkut; Garipcan, Bora; Patra, Hirak K; Uzun, Lokman

    2017-03-28

    Producing molecular imprinting-based materials has received increasing attention due to recognition selectivity, stability, cast effectiveness, and ease of production in various forms for a wide range of applications. The molecular imprinting technique has a variety of applications in the areas of the food industry, environmental monitoring, and medicine for diverse purposes like sample pretreatment, sensing, and separation/purification. A versatile usage, stability and recognition capabilities also make them perfect candidates for use in forensic sciences. Forensic science is a demanding area and there is a growing interest in molecularly imprinted polymers (MIPs) in this field. In this review, recent molecular imprinting applications in the related areas of forensic sciences are discussed while considering the literature of last two decades. Not only direct forensic applications but also studies of possible forensic value were taken into account like illicit drugs, banned sport drugs, effective toxins and chemical warfare agents in a review of over 100 articles. The literature was classified according to targets, material shapes, production strategies, detection method, and instrumentation. We aimed to summarize the current applications of MIPs in forensic science and put forth a projection of their potential uses as promising alternatives for benchmark competitors.

  15. Molecular Imprinting Applications in Forensic Science

    PubMed Central

    Yılmaz, Erkut; Garipcan, Bora; Patra, Hirak K.; Uzun, Lokman

    2017-01-01

    Producing molecular imprinting-based materials has received increasing attention due to recognition selectivity, stability, cast effectiveness, and ease of production in various forms for a wide range of applications. The molecular imprinting technique has a variety of applications in the areas of the food industry, environmental monitoring, and medicine for diverse purposes like sample pretreatment, sensing, and separation/purification. A versatile usage, stability and recognition capabilities also make them perfect candidates for use in forensic sciences. Forensic science is a demanding area and there is a growing interest in molecularly imprinted polymers (MIPs) in this field. In this review, recent molecular imprinting applications in the related areas of forensic sciences are discussed while considering the literature of last two decades. Not only direct forensic applications but also studies of possible forensic value were taken into account like illicit drugs, banned sport drugs, effective toxins and chemical warfare agents in a review of over 100 articles. The literature was classified according to targets, material shapes, production strategies, detection method, and instrumentation. We aimed to summarize the current applications of MIPs in forensic science and put forth a projection of their potential uses as promising alternatives for benchmark competitors. PMID:28350333

  16. A Path to Soluble Molecularly Imprinted Polymers

    PubMed Central

    Verma, Abhilasha; Murray, George M.

    2011-01-01

    Molecular imprinting is a technique for making a selective binding site for a specific chemical. The technique involves building a polymeric scaffold of molecular complements containing the target molecule. Subsequent removal of the target leaves a cavity with a structural “memory” of the target. Molecularly imprinted polymers (MIPs) can be employed as selective adsorbents of specific molecules or molecular functional groups. In addition, sensors for specific molecules can be made using optical transduction through lumiphores residing in the imprinted site. We have found that the use of metal ions as chromophores can improve selectivity due to selective complex formation. The combination of molecular imprinting and spectroscopic selectivity can result in sensors that are highly sensitive and nearly immune to interferences. A weakness of conventional MIPs with regard to processing is the insolubility of crosslinked polymers. Traditional MIPs are prepared either as monoliths and ground into powders or are prepared in situ on a support. This limits the applicability of MIPs by imposing tedious or difficult processes for their inclusion in devices. The size of the particles hinders diffusion and slows response. These weaknesses could be avoided if a means were found to prepare individual macromolecules with crosslinked binding sites with soluble linear polymeric arms. This process has been made possible by controlled free radical polymerization techniques that can form pseudo-living polymers. Modern techniques of controlled free radical polymerization allow the preparation of block copolymers with potentially crosslinkable substituents in specific locations. The inclusion of crosslinkable mers proximate to the binding complex in the core of a star polymer allows the formation of molecularly imprinted macromolecules that are soluble and processable. Due to the much shorter distance for diffusion, the polymers exhibit rapid responses. This paper reviews the methods

  17. Studies on molecular recognition of thymidines with molecularly imprinted polymers

    NASA Astrophysics Data System (ADS)

    Chen, Zhen-He; Luo, Ai-Qin; Sun, Li-Quan

    2009-07-01

    Molecularly imprinted polymers (MIPs) with excellent molecular recognition ability have been used in chemical sensors, chromatographic separation and biochemical analyses. Thymidine is an important part of DNA for biomolecular recognition and the intermediate of many medicines. The polymers imprinted with the template of thymidine and 5'-Otosylthymidine have been prepared, using a non-proton solvent, acetonitrile as the porogen. Direct imprinting with thymidine could not form strong molecular interaction sites in this system. Relative MIPs were obtained by bulk polymerization and their adsorption capacities were investigated. The adsorption capacities of MIP (P2) and nonimprinted polymer (P20) for thymidine are 0.120 mg•g-1and 0.103 mg•g-1, respectively. The imprinting factor is 1.17. As 5'-O-tosylthymidine is more soluble than thymidine moiety in acetonitrile and give rise to more sites of molecular recognition. The results demonstrated that the imprinted polymers were able to bind and recognize thymidine moderately in acetonitrile. MIPs imprinted with 5'-O-tosylthymidine like nature enzymes displayed some recognition ability to its analogues. The insoluble derivatives in the non-proton solvent can be an effective template to prepare efficient imprinting recognition sites.

  18. Molecularly imprinted polymers for biomolecular recognition.

    PubMed

    Molinelli, Alexandra; Janotta, Markus; Mizaikoff, Boris

    2005-01-01

    Molecular imprinting of polymers is a concept for the synthetic formation of structurally organized materials providing binding sites with molecular selectivity. Compared to biological receptors, these polymeric recognition systems have the advantage of superior chemical and mechanical stability with potential applications in areas such as biomimetic catalysis and engineering, biomedical analysis, sensor technology, or the food industry. In particular, molecularly imprinted polymers (MIPs) providing selectivity for biorelated molecules are gaining substantial importance. In this context, a self-assembly approach for the synthesis of imprinted polymers against the flavonol quercetin is presented, which is exemplary for the biologically relevant group of flavonoid compounds. The creation of synthetic selective recognition sites for this biomolecule is demonstrated by comparing the separation capabilities of imprinted and nonimprinted polymer particles for several structurally related molecules via high-performance liquid chromatography experiments. The developed quercetin-MIP enables selective extraction of quercetin even from complex mixtures, demonstrating the potential for designing biomimetic recognition materials with improved selectivity for biomolecules with tunable functionality at a nanoscale.

  19. Molecularly imprinted polymers for some reactive dyes.

    PubMed

    Okutucu, Burcu; Akkaya, Alper; Pazarlioglu, Nurdan Kasikara

    2010-01-01

    Depending upon their structure, azo- and anthraquinonic dyes are the two major classes and together represent 90% of all organic colorants. Adsorption of dye molecules onto a sorbent can be an effective, low-cost method of color removal. Most of the techniques used for removal of dyes are of high production cost, and the regeneration also makes them uneconomical. There is much interest in the development of cheaper and effective newer materials for use as adsorbents. Molecular imprinting is a new kind of materials that can be alternative adsorbents. In this study, molecularly imprinted polymers of three textile dyes (Cibacron Orange P-4R, Cibacron Red P-4B, Cibacron Black PSG) were prepared. Methacrylic acid was used as a monomer for red and orange dyes and acrylamide was used for black dye. Methanol:acetonitrile was used as a porogen. The selective recognition ability of the molecularly imprinted polymers was studied by an equilibrium-adsorption batch method. The adsorption data are for Cibacron Black PSG 65% and nonimprinted polymer (NIP) 25%; Cibacron Red P-4B 72% and NIP 18%; and Cibacron Orange P-4R 45% and NIP 10%, respectively. Dye-imprinted polymers were used as a solid-phase extraction material for selective adsorption from wastewater of textile factory.

  20. Membrane separations using molecularly imprinted polymers.

    PubMed

    Ulbricht, Mathias

    2004-05-05

    This review presents an overview on the promising field of molecularly imprinted membranes (MIM). The focus is onto the separation of molecules in liquid mixtures via membrane transport selectivity. First, the status of synthetic membranes and membrane separation technology is briefly summarized, emphasizing the need for novel membranes with higher selectivities. Innovative principles for the preparation of membranes with improved or novel functionality include self-assembly or supramolecular aggregation as well as the use of templates. Based on a detailed analysis of the literature, the main established preparation methods for MIM are outlined: simultaneous membrane formation and imprinting, or preparation of imprinted composite membranes. Then, the separation capability of MIM is discussed for two different types, as a function of their barrier structure. Microporous MIM can continuously separate mixtures based on facilitated diffusion of the template, or they can change their permeability in the presence of the template ("gate effect"). Macroporous MIM can be developed towards molecule-specific membrane adsorbers. Emerging further combinations of molecularly imprinted polymers (MIPs), especially MIP nanoparticles or microgels, with membranes and membrane processes are briefly outlined as well. Finally, the application potential for advanced MIM separation technologies is summarized.

  1. [Spectroscopic Study of Salbutamol Molecularly Imprinted Polymers].

    PubMed

    Ren, Hui-peng; Guan, Yu-yu; Dai, Rong-hua; Liu, Guo-yan; Chai, Chun-yan

    2016-02-01

    In order to solve the problem of on-site rapid detection of salbutamol residues in feed and animal products, and develop a new method of fast detection of salbutamol on the basis of the molecular imprinting technology, this article uses the salbutamol (SAL) working as template molecule, methacrylic acid (MAA) working as functional monomer. On this basis, a new type of core-shell type salbutamol molecularly imprinted polymers were prepared with colloidal gold particles as triggering core. Superficial characteristics of the MIPs and the related compounds were investigated by ultraviolet (UV) spectra and infrared (IR) spectra, Raman spectra, Scanning electron microscopy (SEM) respectively. The results indicated that a stable hydrogen bonding complex has been formed between the carboxyl groups of SAL and MA with a matching ratio of 1:1. The complex can be easily eluted by the reagent containing hydrogen bonding. The chemical binding constant K reaches -0.245 x 10⁶ L² · mol⁻². The possible binding sites of the hydrogen bonding was formed between the hydrogen atoms of -COOH in MA and the oxygen atoms of C==O in SAL. IR and Raman spectrum showed that, compared with MA, a significant red shift of -OH absorption peak was manifested in MIPs, which proved that SAL as template molecule occurred a specific bond between MA. Red shift of stretching vibration absorption peak of C==O was also detected in the un-eluted MIPs and obvious energy loss happened, which demonstrated a possible binding sites is SAL intramolecular of C==O atom of oxygen. If the hydrogen atoms of -COOH in MA wanted to generate hydrogen bond. However, the shapes of absorption peak of other functional groups including C==C, C==O, and -OH were very similar both in MIPs and NIPs. Specific cavities were formed after the template molecules in MIPs were removed. It was proved by the adsorption experiment that the specific sites in these cavities highly match with the chemical and space structure of SAL

  2. Enhanced removal of bilirubin on molecularly imprinted titania film.

    PubMed

    Yang, Zheng-peng; Yan, Jin-long; Zhang, Chun-jing; Luo, Shu-qiong

    2011-10-01

    Titania film imprinted by bilirubin molecule at the surface of quartz crystal was prepared using molecular imprinting and surface sol-gel process. The molecularly imprinted titania film was characterized by FTIR spectra, and the interaction between bilirubin and imprinted film was investigated using quartz crystal microbalance (QCM) technique. Compared with pure titania film, the molecularly imprinted titania film exhibits a much higher adsorption capacity for the target molecule, and the adsorption kinetic parameter estimated from the in situ frequency measurement is about 1.6×10(8) M(-1), which is ten times higher than that obtained on pure titania film. The photocatalytic measurements indicate that the bilirubin adsorbed on molecularly imprinted titania film can be completely removed under UV illumination. Moreover, our study indicates that the molecularly imprinted titania film possesses a better stability and reusability.

  3. Development of a Molecularly Imprinted Biomimetic Electrode

    PubMed Central

    Kindschy, Lisa M.; Alocilja, Evangelyn C.

    2007-01-01

    The technique of molecular imprinting produces artificial receptor sites in a polymer that can be used in a biomimetic sensor. This research extends previous studies of a molecularly imprinted polymer (MIP) biomimetic sensor for the small drug theophylline. The presence of theophylline in the biomimetic sensor was monitored by analyzing the peak currents from cyclic voltammetry experiments. The functional working range of the MIP modified electrode was 2 - 4 mM theophylline. The concentration of theophylline that resulted in the best signal was 3 mM. The MIP sensor showed no response to the structurally related molecule caffeine, and therefore was selective to the target analyte theophylline. This research will provide the foundation for future studies that will result in durable biomimetic sensors that can offer a viable alternative to current sensors.

  4. Nanoscale molecularly imprinted polymers and method thereof

    DOEpatents

    Hart, Bradley R.; Talley, Chad E.

    2008-06-10

    Nanoscale molecularly imprinted polymers (MIP) having polymer features wherein the size, shape and position are predetermined can be fabricated using an xy piezo stage mounted on an inverted microscope and a laser. Using an AMF controller, a solution containing polymer precursors and a photo initiator are positioned on the xy piezo and hit with a laser beam. The thickness of the polymeric features can be varied from a few nanometers to over a micron.

  5. Computationally Designed Molecularly Imprinted Materials

    NASA Astrophysics Data System (ADS)

    Pavel, Dumitru; Lagowski, Jolanta; Faid, Karim

    2004-03-01

    Molecular dynamics simulations were carried out for different molecular systems in order to predict the binding affinities, binding energies, binding distances and the active site groups between the simulated molecular systems and different bio-ligands (theophylline and its derivatives), which have been designed and minimized using molecular simulation techniques. The first simulated molecular systems consisted of a ligand and functional monomer, such as methacrylic acid and its derivatives. For each pair of molecular systems, (10 monomers with a ligand and 10 monomers without a ligand) a total energy difference was calculated in order to estimate the binding energy between a ligand and the corresponding monomers. The analysis of the simulated functional monomers with ligands indicates that the functional group of monomers interacting with ligands tends to be either COOH or CH2=CH. The distances between the ligand and monomer, in the most stable cases as indicated above, are between 2.0-4.5 Å. The second simulated molecular systems consisted of a ligand and a polymer. The polymers were obtained from monomers that were simulated above. And similar to monomer study, for each pair of molecular systems, (polymer with a ligand and polymer without a ligand) a total energy difference was calculated in order to estimate the binding energy between ligand and the corresponding polymer. The binding distance between the active site of a polymer and a ligand will also be discussed.

  6. Molecular Recognition Effects in Atomistic Models of Imprinted Polymers

    PubMed Central

    Dourado, Eduardo M. A.; Herdes, Carmelo; van Tassel, Paul R.; Sarkisov, Lev

    2011-01-01

    In this article we present a model for molecularly imprinted polymers, which considers both complexation processes in the pre-polymerization mixture and adsorption in the imprinted structures within a single consistent framework. As a case study we investigate MAA/EGDMA polymers imprinted with pyrazine and pyrimidine. A polymer imprinted with pyrazine shows substantial selectivity towards pyrazine over pyrimidine, thus exhibiting molecular recognition, whereas the pyrimidine imprinted structure shows no preferential adsorption of the template. Binding sites responsible for the molecular recognition of pyrazine involve one MAA molecule and one EGDMA molecule, forming associations with the two functional groups of the pyrazine molecule. Presence of these specific sites in the pyrazine imprinted system and lack of the analogous sites in the pyrimidine imprinted system is directly linked to the complexation processes in the pre-polymerization solution. These processes are quite different for pyrazine and pyrimidine as a result of both enthalpic and entropic effects. PMID:21954325

  7. Molecular recognition effects in atomistic models of imprinted polymers.

    PubMed

    Dourado, Eduardo M A; Herdes, Carmelo; van Tassel, Paul R; Sarkisov, Lev

    2011-01-01

    In this article we present a model for molecularly imprinted polymers, which considers both complexation processes in the pre-polymerization mixture and adsorption in the imprinted structures within a single consistent framework. As a case study we investigate MAA/EGDMA polymers imprinted with pyrazine and pyrimidine. A polymer imprinted with pyrazine shows substantial selectivity towards pyrazine over pyrimidine, thus exhibiting molecular recognition, whereas the pyrimidine imprinted structure shows no preferential adsorption of the template. Binding sites responsible for the molecular recognition of pyrazine involve one MAA molecule and one EGDMA molecule, forming associations with the two functional groups of the pyrazine molecule. Presence of these specific sites in the pyrazine imprinted system and lack of the analogous sites in the pyrimidine imprinted system is directly linked to the complexation processes in the pre-polymerization solution. These processes are quite different for pyrazine and pyrimidine as a result of both enthalpic and entropic effects.

  8. Molecularly Imprinted Filtering Adsorbents for Odor Sensing

    PubMed Central

    Shinohara, Sho; Chiyomaru, You; Sassa, Fumihiro; Liu, Chuanjun; Hayashi, Kenshi

    2016-01-01

    Versatile odor sensors that can discriminate among huge numbers of environmental odorants are desired in many fields, including robotics, environmental monitoring, and food production. However, odor sensors comparable to an animal’s nose have not yet been developed. An animal’s olfactory system recognizes odor clusters with specific molecular properties and uses this combinatorial information in odor discrimination. This suggests that measurement and clustering of odor molecular properties (e.g., polarity, size) using an artificial sensor is a promising approach to odor sensing. Here, adsorbents composed of composite materials with molecular recognition properties were developed for odor sensing. The selectivity of the sensor depends on the adsorbent materials, so specific polymeric materials with particular solubility parameters were chosen to adsorb odorants with various properties. The adsorption properties of the adsorbents could be modified by mixing adsorbent materials. Moreover, a novel molecularly imprinted filtering adsorbent (MIFA), composed of an adsorbent substrate covered with a molecularly imprinted polymer (MIP) layer, was developed to improve the odor molecular recognition ability. The combination of the adsorbent and MIP layer provided a higher specificity toward target molecules. The MIFA thus provides a useful technique for the design and control of adsorbents with adsorption properties specific to particular odor molecules. PMID:27886070

  9. Development of Improved Crosslinking Monomers for Molecularly Imprinted Materials

    DTIC Science & Technology

    2002-04-05

    Molecular imprinting involves the self-assembled complexation of a substrate to functional monomers to form a pre- polymer complex which is "locked-in" to...on the design of crosslinking monomers for molecular imprinting , we have developed new classes of crosslinked polymers to optimize the performance of...of the design, synthesis, polymerization and performance of these new crosslinking monomers for molecularly imprinted polymers will be reported

  10. Molecular Imprinting of Polymeric Core-Shell Nanoparticles

    DTIC Science & Technology

    2002-04-05

    UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADP013604 TITLE: Molecular Imprinting of Polymeric Core-Shell Nanoparticles...Soc. Symp. Proc. Vol. 723 © 2002 Materials Research Society M3.2 MOLECULAR IMPRINTING OF POLYMERIC CORE-SHELL NANOPARTICLES Natalia P~rez Moral and...rebinding was performed in an organic solvent. INTRODUCTION Molecularly imprinted polymers ( MIPs ) address the need for robust, simple, fast and efficient

  11. Micro and nanofabrication of molecularly imprinted polymers.

    PubMed

    Bompart, Marc; Haupt, Karsten; Ayela, Cédric

    2012-01-01

    Molecularly imprinted polymers (MIPs) are tailor-made receptors that possess the most important feature of biological antibodies and receptors - specific molecular recognition. They can thus be used in applications where selective binding events are of importance, such as chemical sensors, biosensors and biochips. For the development of microsensors, sensor arrays and microchips based on molecularly imprinted polymers, micro and nanofabrication methods are of great importance since they allow the patterning and structuring of MIPs on transducer surfaces. It has been shown that because of their stability, MIPs can be easily integrated in a number of standard microfabrication processes. Thereby, the possibility of photopolymerizing MIPs is a particular advantage. In addition to specific molecular recognition properties, nanostructured MIPs and MIP nanocomposites allow for additional interesting properties in such sensing materials, for example, amplification of electromagnetic waves by metal nanoparticles, magnetic susceptibility, structural colors in photonic crystals, or others. These materials will therefore find applications in particular for chemical and biochemical detection, monitoring and screening.

  12. A molecular-imprint nanosensor for ultrasensitive detection of proteins

    NASA Astrophysics Data System (ADS)

    Cai, Dong; Ren, Lu; Zhao, Huaizhou; Xu, Chenjia; Zhang, Lu; Yu, Ying; Wang, Hengzhi; Lan, Yucheng; Roberts, Mary F.; Chuang, Jeffrey H.; Naughton, Michael J.; Ren, Zhifeng; Chiles, Thomas C.

    2010-08-01

    Molecular imprinting is a technique for preparing polymer scaffolds that function as synthetic receptors. Imprinted polymers that can selectively bind organic compounds have proven useful in sensor development. Although creating synthetic molecular-imprinting polymers that recognize proteins remains challenging, nanodevices and nanomaterials show promise in this area. Here, we show that arrays of carbon-nanotube tips with an imprinted non-conducting polymer coating can recognize proteins with subpicogram per litre sensitivity using electrochemical impedance spectroscopy. We have developed molecular-imprinting sensors specific for human ferritin and human papillomavirus derived E7 protein. The molecular-imprinting-based nanosensor can also discriminate between Ca2+-induced conformational changes in calmodulin. This ultrasensitive, label-free electrochemical detection of proteins offers an alternative to biosensors based on biomolecule recognition.

  13. A Formaldehyde Sensor Based on Molecularly-Imprinted Polymer on a TiO2 Nanotube Array

    PubMed Central

    Tang, Xiaohui; Raskin, Jean-Pierre; Lahem, Driss; Krumpmann, Arnaud; Decroly, André; Debliquy, Marc

    2017-01-01

    Today, significant attention has been brought to the development of sensitive, specific, cheap, and reliable sensors for real-time monitoring. Molecular imprinting technology is a versatile and promising technology for practical applications in many areas, particularly chemical sensors. Here, we present a chemical sensor for detecting formaldehyde, a toxic common indoor pollutant gas. Polypyrrole-based molecularly-imprinted polymer (PPy-based MIP) is employed as the sensing recognition layer and synthesized on a titanium dioxide nanotube array (TiO2-NTA) for increasing its surface-to-volume ratio, thereby improving the sensor performance. Our sensor selectively detects formaldehyde in the parts per million (ppm) range at room temperature. It also shows a long-term stability and small fluctuation to humidity variations. These are attributed to the thin fishnet-like structure of the PPy-based MIP on the highly-ordered and vertically-aligned TiO2-NTA. PMID:28338635

  14. Photoelectrochemical sensor for pentachlorophenol on microfluidic paper-based analytical device based on the molecular imprinting technique.

    PubMed

    Sun, Guoqiang; Wang, Panpan; Ge, Shenguang; Ge, Lei; Yu, Jinghua; Yan, Mei

    2014-06-15

    Combining microfluidic paper-based analytical device (μ-PAD) and the molecular imprinting technique, a visible light photoelectrochemical (PEC) sensing platform for the detection of pentachlorophenol (PCP) was established on gold nanoparticles (AuNPs) decorated paper working electrode using polypyrrole-functionalized ZnO nanoparticles. Ascorbic acid (AA) was exploited as an efficient and nontoxic electron donor for scavenging photogenerated holes under mild solution medium and facilitating the generation of stable photocurrent. The microfluidic molecular imprinted polymer-based PEC analytical origami device is developed for the detection of PCP in the linear range from 0.01 ng mL(-1) to 100 ng mL(-1) with a low detection limit of 4 pg mL(-1). This disposable microfluidic PEC origami device would provide a new platform for sensitive, specific, and multiplex assay in public health, environmental monitoring, and the developing world.

  15. Small organic molecular imprinted materials: their preparation and application.

    PubMed

    Jiang, Xiaoman; Jiang, Na; Zhang, Haixia; Liu, Mancang

    2007-09-01

    Molecular imprinting is a technique for preparing polymeric materials that are capable of recognizing and binding the desired molecular target with a high affinity and selectivity. The materials can be applied to a wide range of target molecules, even those for which no natural binder exists or whose antibodies are difficult to raise. The imprinting of small organic molecules (e.g., pharmaceuticals, pesticides, amino acids, steroids, and sugars) is now almost routine. In this review, we pay special attention to the synthesis and application of molecular imprinted polymer (MIPs) imprinted with small organic molecules, including herbicides, pesticides, and drugs. The advantages, applications, and recent developments in small organic molecular imprinted technology are highlighted.

  16. A Molecularly Imprinted Polymer with Incorporated Graphene Oxide for Electrochemical Determination of Quercetin

    PubMed Central

    Sun, Si; Zhang, Mengqi; Li, Yijun; He, Xiwen

    2013-01-01

    The molecularly imprinted polymer based on polypyrrole film with incorporated graphene oxide was fabricated and used for electrochemical determination of quercetin. The electrochemical behavior of quercetin on the modified electrode was studied in detail using differential pulse voltammetry. The oxidation peak current of quercetin in B-R buffer solution (pH = 3.5) at the modified electrode was regressed with the concentration in the range from 6.0 × 10−7 to 1.5 × 10−5 mol/L (r2 = 0.997) with a detection limit of 4.8 × 10−8 mol/L (S/N = 3). This electrode showed good stability and reproducibility. In the above mentioned range, rutin or morin which has similar structures and at the same concentration as quercetin did not interfere with the determination of quercetin. The applicability of the method for complex matrix analysis was also evaluated. PMID:23698263

  17. A molecularly imprinted polymer with incorporated graphene oxide for electrochemical determination of quercetin.

    PubMed

    Sun, Si; Zhang, Mengqi; Li, Yijun; He, Xiwen

    2013-04-25

    The molecularly imprinted polymer based on polypyrrole film with incorporated graphene oxide was fabricated and used for electrochemical determination of quercetin. The electrochemical behavior of quercetin on the modified electrode was studied in detail using differential pulse voltammetry. The oxidation peak current of quercetin in B-R buffer solution (pH = 3.5) at the modified electrode was regressed with the concentration in the range from 6.0 × 10(-7) to 1.5 × 10(-5) mol/L (r2 = 0.997) with a detection limit of 4.8 × 10(-8) mol/L (S/N = 3). This electrode showed good stability and reproducibility. In the above mentioned range, rutin or morin which has similar structures and at the same concentration as quercetin did not interfere with the determination of quercetin. The applicability of the method for complex matrix analysis was also evaluated.

  18. A contemporary approach for design and characterization of fiber-optic-cortisol sensor tailoring LMR and ZnO/PPY molecularly imprinted film.

    PubMed

    Usha, Sruthi P; Shrivastav, Anand M; Gupta, Banshi D

    2017-01-15

    A fiber optic salivary cortisol sensor using a contemporary approach of lossy mode resonance and molecular imprinting of nanocomposites of zinc oxide (ZnO) and polypyrrole (PPY) is structured and depicted for the concentration range of 0-10(-6)g/ml of cortisol prepared in artificial saliva. Components of polymer preparation and the nanocomposite of polymer with ZnO are optimized for realizing the molecular imprinted layer of the sensor. Nanocomposite having 20% of ZnO in PPY is found to give highest sensitivity of the sensor. The sensor reports the best limit of detection ever reported with better stability, repeatability and response time. Lossy mode resonance based salivary cortisol sensor using nanocomposite molecular imprinted layer reported first time boosts the specificity of the sensor. The implementation of sensor over optical fiber adds up other advantages such as real time and online monitoring along with remote sensing abilities which makes the sensor usable for nonintrusive clinical applications.

  19. Molecularly imprinted polymers for alpha-tocopherol delivery.

    PubMed

    Puoci, Francesco; Cirillo, Giuseppe; Curcio, Manuela; Iemma, Francesca; Parisi, Ortensia Ilaria; Castiglione, Mariarosaria; Picci, Nevio

    2008-05-01

    Biomedical applications of antioxidants have increased dramatically since the link between human diseases and oxidative stress was established. This paper focuses on alpha -tocopherol and on the possibility of employing molecularly imprinted polymers as a controlled release device for alpha-tocopherol in gastrointestinal simulating fluids. Polymers were synthesized using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linker. Considerable differences in recognition characteristics between imprinted and non-imprinted polymers, both in organic and in aqueous media, were observed. Imprinted polymers bound much more alpha-tocopherol and showed a controlled/sustained drug release capacity in gastrointestinal simulating fluids.

  20. Molecularly imprinted polymers: synthetic receptors in bioanalysis.

    PubMed

    Tse Sum Bui, Bernadette; Haupt, Karsten

    2010-11-01

    Molecularly imprinted polymers (MIPs) are tailor-made synthetic materials possessing specific cavities designed for a target molecule. Since they recognise their target analyte with affinities and selectivities comparable to those of antibody-antigen, enzyme-substrate and ligand-receptor interactions, they are often referred to as synthetic receptors or plastic antibodies. In this review, we describe the great potential and recent developments of MIPs in affinity separations, with emphasis on their application to the solid-phase extraction (SPE) of analytes from complex matrices. Research efforts made in this field to obtain water-compatible polymers for their applicability in aqueous environments are described. We particularly discuss problems encountered in the use of MIPs in SPE and the attempts carried out to improve their efficiency.

  1. Molecularly imprinted nanotubes for enantioselective drug delivery and controlled release.

    PubMed

    Yin, Junfa; Cui, Yue; Yang, Gengliang; Wang, Hailin

    2010-11-07

    Molecularly imprinted nanotubes for enantioselective drug delivery and controlled release are fabricated by the combination of template synthesis and ATRP grafting. The release of R-propranolol from the imprinted nanotubes in rats is restricted while the release of pharmacologically active S-enantiomer is greatly promoted.

  2. Molecularly Imprinted Intelligent Scaffolds for Tissue Engineering Applications.

    PubMed

    Neves, Mariana I; Wechsler, Marissa E; Gomes, Manuela E; Reis, Rui L; Granja, Pedro L; Peppas, Nicholas A

    2017-02-01

    The development of molecularly imprinted polymers (MIPs) using biocompatible production methods enables the possibility to further exploit this technology for biomedical applications. Tissue engineering (TE) approaches use the knowledge of the wound healing process to design scaffolds capable of modulating cell behavior and promote tissue regeneration. Biomacromolecules bear great interest for TE, together with the established recognition of the extracellular matrix, as an important source of signals to cells, both promoting cell-cell and cell-matrix interactions during the healing process. This review focuses on exploring the potential of protein molecular imprinting to create bioactive scaffolds with molecular recognition for TE applications based on the most recent approaches in the field of molecular imprinting of macromolecules. Considerations regarding essential components of molecular imprinting technology will be addressed for TE purposes. Molecular imprinting of biocompatible hydrogels, namely based on natural polymers, is also reviewed here. Hydrogel scaffolds with molecular memory show great promise for regenerative therapies. The first molecular imprinting studies analyzing cell adhesion report promising results with potential applications for cell culture systems, or biomaterials for implantation with the capability for cell recruitment by selectively adsorbing desired molecules.

  3. Tools for fluorescent molecularly imprinted polymers.

    PubMed

    Rathbone, Daniel L; Bains, Ajeet

    2005-01-15

    A linear co-polymer of hexyl acrylate and quinine acrylate was prepared anchored to cellulose filtration membranes. These were used to probe quenching of the tethered fluorophore by test compounds in solution for the validation of imprinted polymer fluorescence studies. The results are compared with simple solution phase quenching studies and also for two membrane-bound imprinted polymers containing the same fluorophore.

  4. Fluorescense Anisotropy Studies of Molecularly Imprinted Polymer Sensors

    SciTech Connect

    Chen, Yin-Chu; Wang, Zheming; Yan, Mingdi; Prahl, Scott A.

    2005-08-03

    Molecularly imprinted polymers (MIPs) are used as recognition elements in biochemical sensors. In a fluorescence-based MIP sensor system, it is difficult to distinguish the analyte fluorescence from the background fluorescence of the polymer itself. We studied steady-state fluorescence anisotropy of anthracene imprinted in a polymer (polyurethane) matrix. Vertically polarized excitation light was incident on MIP films coated on silicon wafers; vertically and horizontally polarized emission was measured. We compared the fluorescence anisotropy of MIPs with imprinted molecules, MIPs with the imprinted molecules extracted, MIPs with rebound molecules, and nonimprinted control polymers (without binding cavities). It is shown that differences in fluorescence anisotropy between the polymers and imprinted fluorescent molecules may provide a means to discriminate the fluorescence of analyte from that of the background polymer.

  5. Synthetic strategies for the generation of molecularly imprinted organic polymers.

    PubMed

    Mayes, A G; Whitcombe, M J

    2005-12-06

    Molecular imprinting is a method of inducing molecular recognition properties in synthetic polymers in response to the presence of a template species during formation of the three-dimensional structure of the polymer. The molecularly imprinted polymers (MIPs) prepared in this way have been termed "plastic antibodies" and combine the robustness of the polymer scaffold with binding properties more readily associated with biological receptors. Smart polymers of this type may find applications in drug delivery, controlled release and monitoring of drug and metabolite concentrations. In this review the main synthetic strategies used in the preparation of imprinted organic polymers are described in terms of the chemical principles used in the templating step. These are illustrated with examples taken from the literature and are classified as covalent, semi-covalent, non-covalent, metal-mediated and non-polar. Finally strategies for the selection of monomers, optimisation and modification of the properties of imprinted polymers are reviewed.

  6. Molecular crowding-based imprinted monolithic column for capillary electrochromatography.

    PubMed

    Zong, Hai-Yan; Liu, Xiao; Liu, Zhao-Sheng; Huang, Yan-Ping

    2015-03-01

    Molecular crowding is a new approach to stabilizing binding sites and improving molecular recognition. In this work, the concept was applied to the preparation of imprinted monolithic columns for CEC. The imprinted monolithic column was synthesized using a mixture of d-zopiclone (d-ZOP)(template), methacrylic acid, ethylene glycol dimethacrylate, and poly(methyl methacrylate) (PMMA) (molecular crowding agent). The resulting PMMA-based imprinted capillary was able to separate ZOP enantiomers in CEC mode. The resolution of enantiomer separation achieved on the d-ZOP-imprinted monolithic column was up to 2.09. Some polymerization factors, such as template-monomer molar ratio, functional monomer-cross-linker molar ratio and the composition of the porogen, on the imprinting effect of resulting molecularly imprinted polymer (MIP) monolithic column were systematically investigated. Chromatographic parameters, including pH values, the content of acetonitrile and the salt concentration on chiral separation were also studied. The results indicated the addition of PMMA resulted in MIPs with superior retention properties and excellent selectivity for d-ZOP, as compared to the MIPs prepared without addition of the crowding-inducing agent. The results revealed that molecular crowding is an effective method for the preparation of a highly efficient MIP stationary phase for chiral separation in CEC.

  7. Chemical microsensors with molecularly imprinted sensitive layers

    NASA Astrophysics Data System (ADS)

    Dickert, Franz L.; Greibl, Wolfgang; Sikorski, Renatus; Tortschanoff, Matthias; Weber, K.; Bulst, W. E.; Fischerauer, G.

    1998-12-01

    The bottleneck in the development of chemical sensors is the design of the coatings for chemical recognition of the analyte. One pronounced method is to tailor supramolecular cavities for different analytes. Polyfunctional linkers or the embedding of these materials in a polymeric matrix can improve stability and response time of the sensor. An even more favorable method to synthesize chemically sensitive layers is realized by molecular imprinting, since a rigid polymer can be generated directly on the transducer of interest and may be included in its production process. The analyte of interest acts as a template during the polymerization process and is evaporated or extracted by suitable solvents. Due to the cavities formed this polymer enriches analyte molecules, which can be detected by mass- sensitive devices such as QMB or SAW resonators or by optical measurements. This procedure allows both the detection of polycyclic aromatic hydrocarbons (PAHs) with fluorescence or mass sensitive devices. If the print PAHs are varied the polymers are tuned to the desired analyte. The enrichment of solvent vapors or other uncolored specimen by the layer can also be followed by the embedding of carbenium ions used as optical labels.

  8. Molecularly Imprinted Polymer Based Sensor for the Detection of Theophylline

    NASA Astrophysics Data System (ADS)

    Braga, Guilherme S.; Paterno, Leonardo G.; Fonseca, Fernando J.; del Valle, Manel

    2011-11-01

    A molecularly imprinted polymer (MIP) impedance-based sensor was employed to detect theophylline in distilled water. To evaluate its sensibility, impedance measurements were carried out in a diluted solution of theophylline (1 mM) and distilled water using MIP and NIP (reference non-imprinted polymer) sensors. MIP showed higher sensitivity to theophylline than the NIP. This feature shows their suitability for developing an electronic tongue system for determination of methylxanthines.

  9. Quantitative prediction of imprinting factor of molecularly imprinted polymers by artificial neural network

    NASA Astrophysics Data System (ADS)

    Nantasenamat, Chanin; Naenna, Thanakorn; Ayudhya, Chartchalerm Isarankura Na; Prachayasittikul, Virapong

    2005-07-01

    Artificial neural network (ANN) implementing the back-propagation algorithm was applied for the calculation of the imprinting factors (IF) of molecularly imprinted polymers (MIP) as a function of the computed molecular descriptors of template and functional monomer molecules and mobile phase descriptors. The dataset used in our study were obtained from the literature and classified into two distinctive datasets on the basis of the polymer's morphology, irregularly sized MIP and uniformly sized MIP datasets. Results revealed that artificial neural network was able to perform well on datasets derived from uniformly sized MIP ( n=23, r=0.946, RMS=2.944) while performing poorly on datasets derived from irregularly sized MIP ( n=75, r=0.382, RMS=6.123). The superior performance of the uniformly sized MIP dataset over the irregularly sized MIP dataset could be attributed to its more predictable nature owing to the consistency of MIP particles, uniform number and association constant of binding sites, and minimal deviation of the imprinted polymers. The ability to predict the imprinting factor of imprinted polymer prior to performing actual experimental work provide great insights on the feasibility of the interaction between template-functional monomer pairs.

  10. Characterization of the Binding Properties of Molecularly Imprinted Polymers.

    PubMed

    Ansell, Richard J

    2015-01-01

    The defining characteristic of the binding sites of any particular molecularly imprinted material is heterogeneity: that is, they are not all identical. Nonetheless, it is useful to study their fundamental binding properties, and to obtain average properties. In particular, it has been instructive to compare the binding properties of imprinted and non-imprinted materials. This chapter begins by considering the origins of this site heterogeneity. Next, the properties of interest of imprinted binding sites are described in brief: affinity, selectivity, and kinetics. The binding/adsorption isotherm, the graph of concentration of analyte bound to a MIP versus concentration of free analyte at equilibrium, over a range of total concentrations, is described in some detail. Following this, the techniques for studying the imprinted sites are described (batch-binding assays, radioligand binding assays, zonal chromatography, frontal chromatography, calorimetry, and others). Thereafter, the parameters that influence affinity, selectivity and kinetics are discussed (solvent, modifiers of organic solvents, pH of aqueous solvents, temperature). Finally, mathematical attempts to fit the adsorption isotherms for imprinted materials, so as to obtain information about the range of binding affinities characterizing the imprinted sites, are summarized.

  11. Bio-Mimetic Sensors Based on Molecularly Imprinted Membranes

    PubMed Central

    Algieri, Catia; Drioli, Enrico; Guzzo, Laura; Donato, Laura

    2014-01-01

    An important challenge for scientific research is the production of artificial systems able to mimic the recognition mechanisms occurring at the molecular level in living systems. A valid contribution in this direction resulted from the development of molecular imprinting. By means of this technology, selective molecular recognition sites are introduced in a polymer, thus conferring it bio-mimetic properties. The potential applications of these systems include affinity separations, medical diagnostics, drug delivery, catalysis, etc. Recently, bio-sensing systems using molecularly imprinted membranes, a special form of imprinted polymers, have received the attention of scientists in various fields. In these systems imprinted membranes are used as bio-mimetic recognition elements which are integrated with a transducer component. The direct and rapid determination of an interaction between the recognition element and the target analyte (template) was an encouraging factor for the development of such systems as alternatives to traditional bio-assay methods. Due to their high stability, sensitivity and specificity, bio-mimetic sensors-based membranes are used for environmental, food, and clinical uses. This review deals with the development of molecularly imprinted polymers and their different preparation methods. Referring to the last decades, the application of these membranes as bio-mimetic sensor devices will be also reported. PMID:25196110

  12. Bio-mimetic sensors based on molecularly imprinted membranes.

    PubMed

    Algieri, Catia; Drioli, Enrico; Guzzo, Laura; Donato, Laura

    2014-07-30

    An important challenge for scientific research is the production of artificial systems able to mimic the recognition mechanisms occurring at the molecular level in living systems. A valid contribution in this direction resulted from the development of molecular imprinting. By means of this technology, selective molecular recognition sites are introduced in a polymer, thus conferring it bio-mimetic properties. The potential applications of these systems include affinity separations, medical diagnostics, drug delivery, catalysis, etc. Recently, bio-sensing systems using molecularly imprinted membranes, a special form of imprinted polymers, have received the attention of scientists in various fields. In these systems imprinted membranes are used as bio-mimetic recognition elements which are integrated with a transducer component. The direct and rapid determination of an interaction between the recognition element and the target analyte (template) was an encouraging factor for the development of such systems as alternatives to traditional bio-assay methods. Due to their high stability, sensitivity and specificity, bio-mimetic sensors-based membranes are used for environmental, food, and clinical uses. This review deals with the development of molecularly imprinted polymers and their different preparation methods. Referring to the last decades, the application of these membranes as bio-mimetic sensor devices will be also reported.

  13. Molecularly imprinted sol-gel nanotubes membrane for biochemical separations.

    PubMed

    Yang, Huang-Hao; Zhang, Shu-Qiong; Yang, Wei; Chen, Xiao-Lan; Zhuang, Zhi-Xia; Xu, Jin-Gou; Wang, Xiao-Ru

    2004-04-07

    In this study, we report a simple procedure for applying molecular imprinting functional groups to the inner surfaces of the template-synthesized sol-gel nanotubes for chemical separation of estrone. The silica nanotubes were synthesized within the pores of nanopore alumina template membranes using a sol-gel method by simultaneous hydrolysis of a silica monomer-imprinted molecule complex and tetraethoxysilane (TEOS). A covalent imprinting strategy was employed by generating a sacrificial spacer through the reaction of the isocyanate group of 3-(triethoxysilyl)propyl isocyanate and a phenol moiety of estrone to form a thermally cleavable urethane bond. This allowed us to remove the imprinted estrone by simple thermal reaction and to simultaneously introduce functional groups into the cavity formed by the silica nanotubes. Experiments indicated that estrone could be bound selectively by such an approach and have a binding affinity of 864 +/- 137 (n = 3).

  14. Nanoscale molecular-switch devices fabricated by imprint lithography

    NASA Astrophysics Data System (ADS)

    Chen, Yong; Ohlberg, Douglas A. A.; Li, Xuema; Stewart, Duncan R.; Stanley Williams, R.; Jeppesen, Jan O.; Nielsen, Kent A.; Stoddart, J. Fraser; Olynick, Deirdre L.; Anderson, Erik

    2003-03-01

    Nanoscale molecular-electronic devices comprising a single molecular monolayer of bistable [2]rotaxanes sandwiched between two 40-nm metal electrodes were fabricated using imprint lithography. Bistable current-voltage characteristics with high on-off ratios and reversible switching properties were observed. Such devices may function as basic elements for future ultradense electronic circuitry.

  15. Chitosan in Molecularly-Imprinted Polymers: Current and Future Prospects.

    PubMed

    Xu, Long; Huang, Yun-An; Zhu, Qiu-Jin; Ye, Chun

    2015-08-07

    Chitosan is widely used in molecular imprinting technology (MIT) as a functional monomer or supporting matrix because of its low cost and high contents of amino and hydroxyl functional groups. The various excellent properties of chitosan, which include nontoxicity, biodegradability, biocompatibility, and attractive physical and mechanical performances, make chitosan a promising alternative to conventional functional monomers. Recently, chitosan molecularly-imprinted polymers have gained considerable attention and showed significant potential in many fields, such as curbing environmental pollution, medicine, protein separation and identification, and chiral-compound separation. These extensive applications are due to the polymers' desired selectivity, physical robustness, and thermal stability, as well as their low cost and easy preparation. Cross-linkers, which fix the functional groups of chitosan around imprinted molecules, play an important role in chitosan molecularly-imprinted polymers. This review summarizes the important cross-linkers of chitosan molecularly-imprinted polymers and illustrates the cross-linking mechanism of chitosan and cross-linkers based on the two glucosamine units. Finally, some significant attempts to further develop the application of chitosan in MIT are proposed.

  16. Chitosan in Molecularly-Imprinted Polymers: Current and Future Prospects

    PubMed Central

    Xu, Long; Huang, Yun-An; Zhu, Qiu-Jin; Ye, Chun

    2015-01-01

    Chitosan is widely used in molecular imprinting technology (MIT) as a functional monomer or supporting matrix because of its low cost and high contents of amino and hydroxyl functional groups. The various excellent properties of chitosan, which include nontoxicity, biodegradability, biocompatibility, and attractive physical and mechanical performances, make chitosan a promising alternative to conventional functional monomers. Recently, chitosan molecularly-imprinted polymers have gained considerable attention and showed significant potential in many fields, such as curbing environmental pollution, medicine, protein separation and identification, and chiral-compound separation. These extensive applications are due to the polymers’ desired selectivity, physical robustness, and thermal stability, as well as their low cost and easy preparation. Cross-linkers, which fix the functional groups of chitosan around imprinted molecules, play an important role in chitosan molecularly-imprinted polymers. This review summarizes the important cross-linkers of chitosan molecularly-imprinted polymers and illustrates the cross-linking mechanism of chitosan and cross-linkers based on the two glucosamine units. Finally, some significant attempts to further develop the application of chitosan in MIT are proposed. PMID:26262607

  17. Molecularly imprinted polymers as the future drug delivery devices.

    PubMed

    Luliński, Piotr

    2013-01-01

    In recent years, the investigations of new drug delivery systems have been directed on the development of some "intelligent" drug delivery devices that are able to directly respond to the patient's individual needs. New drug delivery systems should maximize the efficiency of administrated therapeutic agents and improve the patient's quality of life. Introduction of the new drug delivery devices is an important scientific goal, which could be achieved by combining new technologies and intelligent biomaterials. Molecular imprinting technology has a high potential for the preparation of optimized drug delivery forms. Here, molecularly imprinted polymers (MIPs) are promising new materials for such purposes, but their application in this field is nowadays at a developing stage. In this review, the principles of molecular imprinting and the recognition-release mechanisms of polymeric matrices are discussed. The potential application of molecularly imprinted materials as the future drug delivery systems with various administering routes (transdermal, ocular or oral) are presented, and some future prospects for the imprinted polymers are outlined.

  18. Spectroscopic studies of the molecular imprinting self-assembly process.

    PubMed

    Svenson, J; Andersson, H S; Piletsky, S A; Nicholls, I A

    1998-01-01

    A method for the rapid estimation of the extent of complex formation in molecular imprinting prepolymerization mixtures is described. By the use of a UV spectroscopy titration procedure, apparent binding constants for such self-assembly processes have been obtained. This method was used for comparison of the interactions between a dipeptide template (N-acetyl-L-phenylalaninyl-L-tryptophanyl methyl ester) and the functional monomer methacrylic acid, and the monomer analogues acetic acid and trifluoroacetic acid. The importance of template-monomer association during the molecular imprinting prepolymerization phase is discussed with respect to the systems studied.

  19. Application of molecularly imprinted polymers in wastewater treatment: a review.

    PubMed

    Huang, Dan-Lian; Wang, Rong-Zhong; Liu, Yun-Guo; Zeng, Guang-Ming; Lai, Cui; Xu, Piao; Lu, Bing-An; Xu, Juan-Juan; Wang, Cong; Huang, Chao

    2015-01-01

    Molecularly imprinted polymers are synthetic polymers possessing specific cavities designed for target molecules. They are prepared by copolymerization of a cross-linking agent with the complex formed from a template and monomers that have functional groups specifically interacting with the template through covalent or noncovalent bonds. Subsequent removal of the imprint template leaves specific cavities whose shape, size, and functional groups are complementary to the template molecule. Because of their predetermined selectivity, molecularly imprinted polymers (MIPs) can be used as ideal materials in wastewater treatment. Especially, MIP-based composites offer a wide range of potentialities in wastewater treatment. This paper reviews the latest applications of MIPs in wastewater treatment, highlights the development of MIP-based composites in wastewater, and offers suggestions for future success in the field of MIPs.

  20. Capacitive Biosensors and Molecularly Imprinted Electrodes

    PubMed Central

    Ertürk, Gizem; Mattiasson, Bo

    2017-01-01

    Capacitive biosensors belong to the group of affinity biosensors that operate by registering direct binding between the sensor surface and the target molecule. This type of biosensors measures the changes in dielectric properties and/or thickness of the dielectric layer at the electrolyte/electrode interface. Capacitive biosensors have so far been successfully used for detection of proteins, nucleotides, heavy metals, saccharides, small organic molecules and microbial cells. In recent years, the microcontact imprinting method has been used to create very sensitive and selective biorecognition cavities on surfaces of capacitive electrodes. This chapter summarizes the principle and different applications of capacitive biosensors with an emphasis on microcontact imprinting method with its recent capacitive biosensor applications. PMID:28218689

  1. Capacitive Biosensors and Molecularly Imprinted Electrodes.

    PubMed

    Ertürk, Gizem; Mattiasson, Bo

    2017-02-17

    Capacitive biosensors belong to the group of affinity biosensors that operate by registering direct binding between the sensor surface and the target molecule. This type of biosensors measures the changes in dielectric properties and/or thickness of the dielectric layer at the electrolyte/electrode interface. Capacitive biosensors have so far been successfully used for detection of proteins, nucleotides, heavy metals, saccharides, small organic molecules and microbial cells. In recent years, the microcontact imprinting method has been used to create very sensitive and selective biorecognition cavities on surfaces of capacitive electrodes. This chapter summarizes the principle and different applications of capacitive biosensors with an emphasis on microcontact imprinting method with its recent capacitive biosensor applications.

  2. Holographic molecularly imprinted polymers for label-free chemical sensing.

    PubMed

    Fuchs, Yannick; Soppera, Olivier; Mayes, Andrew G; Haupt, Karsten

    2013-01-25

    Holographic molecularly imprinted polymer films for the use in chemical sensors are obtained in one step through photopolymerization with interfering laser beams. This results in hierarchical structuring at four length scales: micrometer-scale patterning of millimeter- to centimeter- size polymer objects with holographic optical properties, exhibiting nanometer-scale porosity and specific molecular recognition properties at the molecular scale through self-assembly. Specific binding of the target analyte testosterone is measured by diffraction analysis.

  3. Quantum-dots-encoded-microbeads based molecularly imprinted polymer.

    PubMed

    Liu, Yixi; Liu, Le; He, Yonghong; He, Qinghua; Ma, Hui

    2016-03-15

    Quantum dots encoded microbeads have various advantages such as large surface area, superb optical properties and the ability of multiplexing. Molecularly imprinted polymer that can mimic the natural recognition entities has high affinity and selectivity for the specific analyte. Here, the concept of utilizing the quantum dots encoded microbeads as the supporting material and the polydopamine as the functional monomer to form the core-shell molecular imprinted polymer was proposed for the first time. The resulted imprinted polymer can provide various merits: polymerization can complete in aqueous environment; fabrication procedure is facile and universal; the obvious economic advantage; the thickness of the imprinting layer is highly controllable; polydopamine coating can improve the biocompatibility of the quantum dot encoded microbeads. The rabbit IgG binding and flow cytometer experiment result showed the distinct advantages of this strategy: cost-saving, facile and fast preparation procedure. Most importantly, the ability for the multichannel detection, which makes the imprinted polydopamine modified encoded-beads very attractive in protein pre-concentration, recognition, separation and biosensing. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Molecularly imprinted polymers for 5-fluorouracil release in biological fluids.

    PubMed

    Puoci, Francesco; Iemma, Francesca; Cirillo, Giuseppe; Picci, Nevio; Matricardi, Pietro; Alhaiqu, Franco

    2007-04-18

    The aim of this work was to investigate the possibility of employing Molecularly Imprinted Polymers (MIPs) as a controlled release device for 5-fluorouracil (5-FU) in biological fluids, especially gastrointestinal ones, compared to Non Imprinted Polymers (NIPs). MIPs were synthesized using methacrylic acid (MAA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinking agent. The capacity of the polymer to recognize and to bind the template selectively in both organic and aqueous media was evaluated. An in vitro release study was performed both in gastrointestinal and in plasma simulating fluids. The imprinted polymers bound much more 5-Fu than the corresponding non-imprinted ones and showed a controlled/sustained drug release, with MIPs release rate being indeed much more sustained than that obtained from NIPs. These polymers represent a potential valid system for drug delivery and this study indicates that the selective binding characteristic of molecularly imprinted polymers is promising for the preparation of novel controlled release drug dosage form.

  5. Molecularly Imprinted Polymers and Highly Porous Materials in Sensing Applications

    DTIC Science & Technology

    2007-04-01

    materials with applications in synthesis and catalysis”, Tetrahedron 59, 2025- 2057 (2003). 4. J. J. Becker and M.R. Gagne , “Exploiting the synergy...Dong Min Wu, Nicolas Fang, Xiang Zhang, Joseph Roberts , and Kenneth J. Shea, “Functional Molecularly Imprinted Polymer Microstructures Fabricated Using

  6. PREPARATION AND CHARACTERIZATION OF MOLECULARLY IMPRINTED ELECTROPOLYMERIZED CARBON ELECTRODES

    EPA Science Inventory

    Molecularly imprinted polymers (MIP) selective for fluorescein, rhodamine or 2,4-dichlorophenoxyacetic acid (2,4-D) were electropolymerized onto graphite electrodes using an aqueous solution equimolar in resorsinol/ortho-phenylenediamine and in the presence of the template mole...

  7. PREPARATION AND CHARACTERIZATION OF MOLECULARLY IMPRINTED ELECTROPOLYMERIZED CARBON ELECTRODES

    EPA Science Inventory

    Molecularly imprinted polymers (MIP) selective for fluorescein, rhodamine or 2,4-dichlorophenoxyacetic acid (2,4-D) were electropolymerized onto graphite electrodes using an aqueous solution equimolar in resorsinol/ortho-phenylenediamine and in the presence of the template mole...

  8. Molecularly imprinted polymers (MIPs): sensing, an explosive new opportunity?

    PubMed

    McCluskey, Adam; Holdsworth, Clovia I; Bowyer, Michael C

    2007-10-21

    Our group is currently developing in-field detection systems alongside the Australian Federal Police Forensic Services utilising molecularly imprinted polymers as the recognition elements. This review looks at MIP synthesis and our perceptions of future directions from an Australian and forensic perspective.

  9. Investigation of imprinting parameters and their recognition nature for quinine-molecularly imprinted polymers

    NASA Astrophysics Data System (ADS)

    He, Jian-feng; Zhu, Quan-hong; Deng, Qin-ying

    2007-08-01

    A series of molecularly imprinted polymers (MIPs) was prepared using quinine as the template molecules by bulk polymerization. The presence of monomer-template solution complexes in non-covalent MIPs systems has been verified by both fluorescence and UV-vis spectrometric detection. The influence of different synthetic conditions (porogen, functional monomer, cross-linkers, initiation methods, monomer-template ratio, etc.) on recognition properties of the polymers was investigated. Scatchard analysis revealed that two classes of binding sites were formed in the imprinted polymer. The corresponding dissociation constants were estimated to be 45.00 μmol l -1 and 1.42 mmol l -1, respectively, by utilizing a multi-site recognition model. The binding characteristics of the imprinted polymers were explored in various solvents using equilibrium binding experiments. In the organic media, results suggested that polar interactions (hydrogen bonding, ionic interactions, etc.) between acidic monomer/polymer and template molecules were mainly responsible for the recognition, whereas in aqueous media, hydrophobic interactions had a remarkable non-specific contribution to the overall binding. The specificity of MIP was evaluated by rebinding the other structurally similar compounds. The results indicated that the imprinted polymers exhibited an excellent stereo-selectivity toward quinine.

  10. Production of abiotic receptors by molecular imprinting of proteins.

    PubMed

    Braco, L; Dabulis, K; Klibanov, A M

    1990-01-01

    When a protein is dissolved in a concentrated aqueous solution of a multifunctional organic compound, freeze-dried, and washed with an anhydrous organic solvent to remove the ligand, the resultant "imprinted" protein preparation binds up to 30-fold more of the template compound in anhydrous solvents than the nonimprinted protein in the same solvent (and both proteins in water). These artificial receptors exhibit marked ligand selectivity as well as stability in anhydrous media. This phenomenon of molecular imprinting, demonstrated for several unrelated proteins and ligands, may be helpful in the development of unique bioadsorbents and, potentially, new biocatalysts.

  11. Production of abiotic receptors by molecular imprinting of proteins.

    PubMed Central

    Braco, L; Dabulis, K; Klibanov, A M

    1990-01-01

    When a protein is dissolved in a concentrated aqueous solution of a multifunctional organic compound, freeze-dried, and washed with an anhydrous organic solvent to remove the ligand, the resultant "imprinted" protein preparation binds up to 30-fold more of the template compound in anhydrous solvents than the nonimprinted protein in the same solvent (and both proteins in water). These artificial receptors exhibit marked ligand selectivity as well as stability in anhydrous media. This phenomenon of molecular imprinting, demonstrated for several unrelated proteins and ligands, may be helpful in the development of unique bioadsorbents and, potentially, new biocatalysts. Images PMID:2153288

  12. Guiding Molecular Motors with Nano-Imprinted Structures

    NASA Astrophysics Data System (ADS)

    Bunk, Richard; Carlberg, Patrick; Månsson, Alf; Nicholls, Ian A.; Omling, Pär; Sundberg, Mark; Tågerud, Sven; Montelius, Lars

    2005-05-01

    This work, for the first time, demonstrates that nano-imprinted samples, with 100 nm wide polymer lines, can act as guides for molecular motors consisting of motor proteins actin and myosin. The motor protein function was characterized using fluorescence microscopy and compared to actomyosin motility on non-structured nitrocellulose surfaces. Our results open for further use of the nano-imprint technique in the production of disposable chips for bio-nanotechnological applications and miniaturized biological test systems. We discuss how the nano-imprinted motor protein assay system may be optimized and also how it compares to previously tested assay systems involving low-resolution UV-lithography and low throughput but high-resolution electron beam lithography.

  13. Molecular imprinted polymers for separation science: a review of reviews.

    PubMed

    Cheong, Won Jo; Yang, Song Hee; Ali, Faiz

    2013-02-01

    Molecular imprinted polymer is an artificial receptor made by imprinting molecules of a template in a polymer matrix followed by removing the template molecules via thorough washing to give the permanent template grooves. They show favored affinity to the template molecule compared to other molecules, and this property is the basic driving force for such diverse application of this techniques. Such techniques have been increasingly employed in a wide scope of applications such as chromatography, sample pretreatment, purification, catalysts, sensors, and drug delivery, etc., mostly in bioanalytical areas. A major part of them is related to development of new stationary phases and their application in chromatography and sample pretreatment. Embodiments of molecular imprinted polymer materials have been carried out in a variety of forms such as irregularly ground particles, regular spherical particles, nanoparticles, monoliths in a stainless steel or capillary column, open tubular layers in capillaries, surface attached thin layers, membranes, and composites, etc. There have been numerous review articles on molecular imprinted polymer issues. In this special review, the reviews in recent ca. 10 years will be categorized into several subgroups according to specified topics in separation science, and each review in each subgroup will be introduced in the order of date with brief summaries and comments on new developments and different scopes of prospects. Brief summaries of each categories and conclusive future perspectives are also given.

  14. Determination of fusaric acid in maize using molecularly imprinted SPE clean-up

    USDA-ARS?s Scientific Manuscript database

    A new liquid chromatography method to detect fusaric acid in maize is reported based on molecularly imprinted polymer solid phase extraction clean-up (MISPE) using mimic-templated molecularly-imprinted polymers. Picolinic acid was used as a toxin analog for imprinting polymers during a thermolytic s...

  15. Molecular mechanisms of memory in imprinting.

    PubMed

    Solomonia, Revaz O; McCabe, Brian J

    2015-03-01

    Converging evidence implicates the intermediate and medial mesopallium (IMM) of the domestic chick forebrain in memory for a visual imprinting stimulus. During and after imprinting training, neuronal responsiveness in the IMM to the familiar stimulus exhibits a distinct temporal profile, suggesting several memory phases. We discuss the temporal progression of learning-related biochemical changes in the IMM, relative to the start of this electrophysiological profile. c-fos gene expression increases <15 min after training onset, followed by a learning-related increase in Fos expression, in neurons immunopositive for GABA, taurine and parvalbumin (not calbindin). Approximately simultaneously or shortly after, there are increases in phosphorylation level of glutamate (AMPA) receptor subunits and in releasable neurotransmitter pools of GABA and taurine. Later, the mean area of spine synapse post-synaptic densities, N-methyl-D-aspartate receptor number and phosphorylation level of further synaptic proteins are elevated. After ∼ 15 h, learning-related changes in amounts of several synaptic proteins are observed. The results indicate progression from transient/labile to trophic synaptic modification, culminating in stable recognition memory. Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.

  16. Molecular mechanisms of memory in imprinting

    PubMed Central

    Solomonia, Revaz O.; McCabe, Brian J.

    2015-01-01

    Converging evidence implicates the intermediate and medial mesopallium (IMM) of the domestic chick forebrain in memory for a visual imprinting stimulus. During and after imprinting training, neuronal responsiveness in the IMM to the familiar stimulus exhibits a distinct temporal profile, suggesting several memory phases. We discuss the temporal progression of learning-related biochemical changes in the IMM, relative to the start of this electrophysiological profile. c-fos gene expression increases <15 min after training onset, followed by a learning-related increase in Fos expression, in neurons immunopositive for GABA, taurine and parvalbumin (not calbindin). Approximately simultaneously or shortly after, there are increases in phosphorylation level of glutamate (AMPA) receptor subunits and in releasable neurotransmitter pools of GABA and taurine. Later, the mean area of spine synapse post-synaptic densities, N-methyl-d-aspartate receptor number and phosphorylation level of further synaptic proteins are elevated. After ∼15 h, learning-related changes in amounts of several synaptic proteins are observed. The results indicate progression from transient/labile to trophic synaptic modification, culminating in stable recognition memory. PMID:25280906

  17. Nanostructured conducting molecularly imprinted polymer for selective uptake/release of naproxen by the electrochemically controlled sorbent.

    PubMed

    Ameli, Akram; Alizadeh, Naader

    2012-09-15

    A conducting molecularly imprinted polymer (CMIP) film, based on polypyrrole, was electrosynthesized for selective uptake/release and determination of naproxen. The film was prepared by incorporation of a template anion (naproxen) during the electropolymerization of pyrrole into a platinum electrode using the cyclic voltammetry method. Overoxidized polypyrrole films with cavities complementary to the template were used as a potential-induced selective recognition element in the solid-phase sorbent. Various important fabricating factors, which control the performance of the CMIP film, were investigated using fluorescence spectroscopy. The measured fluorescence intensities of released solutions were related to the concentrations of naproxen taken up into the films. Several key parameters such as applied potential and time for uptake and release were varied to achieve the optimal sorption procedure. The film template with naproxen exhibited excellent selectivity over some interference. The calibration graphs were linear in the ranges of 5 × 10⁻⁸ to 3 × 10⁻⁷ mol ml⁻¹ and 7 × 10⁻⁶ to 8 × 10⁻⁴ mol ml⁻¹, and the limit of detection was 1 × 10⁻⁸ mol ml⁻¹. The CMIP films, as the electrochemically controlled solid-phase sorbent, were applied for the selective cleanup and quantification of trace amounts of naproxen from physiological samples. Scanning electron microscopy confirmed the nanostructure morphology of the films. Copyright © 2012 Elsevier Inc. All rights reserved.

  18. A sensitive and selective molecularly imprinted sensor combined with magnetic molecularly imprinted solid phase extraction for determination of dibutyl phthalate.

    PubMed

    Zhang, Zhaohui; Luo, Lijuan; Cai, Rong; Chen, Hongjun

    2013-11-15

    A highly sensitive and selective molecularly imprinted (MIP) sensor combined with magnetic molecularly imprinted solid phase extraction (MMISPE) was developed for the determination of dibutyl phthalate (DBP) in complex matrixes. The magnetic molecularly imprinted polymer (MMIP) was synthesized as solid phase extraction (SPE) sorbet to extract DBP from complex matrixes and as sensing element to improve the selectivity of the imprinted sensor. The morphologies of MMIP and MIP-sensor were characterized by using scanning electron microscope (SEM) and transmission electron microscopy (TEM). The electrochemical performances of MIP-sensor were investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The conditions of preconcentration, elution and electrochemical determination were studied in detail. Under the optimized experimental conditions, the response currents of the MIP-sensor exhibited a linear relationship towards DBP concentrations ranging from 1.0 × 10(-8)g/L to 1.0 × 10(-3)g/L. The limit of detection of the MMIP-sensor coupled with the MMISPE was calculated as 0.052 ng/L. The MMIP-sensor coupled with the MMISPE was applied to detect DBP in complex samples successfully.

  19. Molecular receptors in metal oxide sol-gel materials prepared via molecular imprinting

    DOEpatents

    Sasaki, Darryl Y.; Brinker, C. Jeffrey; Ashley, Carol S.; Daitch, Charles E.; Shea, Kenneth J.; Rush, Daniel J.

    2000-01-01

    A method is provided for molecularly imprinting the surface of a sol-gel material, by forming a solution comprised of a sol-gel material, a solvent, an imprinting molecule, and a functionalizing siloxane monomer of the form Si(OR).sub.3-n X.sub.n, wherein n is an integer between zero and three and X is a functional group capable of reacting with the imprinting molecule, evaporating the solvent, and removing the imprinting molecule to form the molecularly imprinted metal oxide sol-gel material. The use of metal oxide sol-gels allows the material porosity, pore size, density, surface area, hardness, electrostatic charge, polarity, optical density, and surface hydrophobicity to be tailored and be employed as sensors and in catalytic and separations operations.

  20. Molecularly Imprinted Polymers: Thermodynamic and Kinetic Considerations on the Specific Sorption and Molecular Recognition.

    PubMed

    Li, Songjun; Huang, Xing; Zheng, Mingxia; Li, Wuke; Tong, Kejun

    2008-04-23

    This article presents a work aiming at thermodynamically and kinetically interpreting the specific sorption and recognition by a molecularly imprinted polymer. Using Boc-L-Phe-OH as a template, the imprinted material was prepared. The result indicates that the prepared polymer can well discriminate the imprint species from its analogue (Boc-D-Phe-OH), so as to adsorb more for the former but less for the latter. Kinetic analysis indicates that this specific sorption, in nature, can be a result of a preferential promotion. The imprint within the polymer causes a larger adsorption rate for the template than for the analogue. Thermodynamic study also implies that the molecular induction from the specific imprint to the template is larger than to the analogue, which thus makes the polymer capable of preferentially alluring the template to bind.

  1. Magnetic molecularly imprinted polymer for aspirin recognition and controlled release

    NASA Astrophysics Data System (ADS)

    Kan, Xianwen; Geng, Zhirong; Zhao, Yao; Wang, Zhilin; Zhu, Jun-Jie

    2009-04-01

    Core-shell structural magnetic molecularly imprinted polymers (magnetic MIPs) with combined properties of molecular recognition and controlled release were prepared and characterized. Magnetic MIPs were synthesized by the co-polymerization of methacrylic acid (MAA) and trimethylolpropane trimethacrylate (TRIM) around aspirin (ASP) at the surface of double-bond-functionalized Fe3O4 nanoparticles in chloroform. The obtained spherical magnetic MIPs with diameters of about 500 nm had obvious superparamagnetism and could be separated quickly by an external magnetic field. Binding experiments were carried out to evaluate the properties of magnetic MIPs and magnetic non-molecularly imprinted polymers (magnetic NIPs). The results demonstrated that the magnetic MIPs had high adsorption capacity and selectivity to ASP. Moreover, release profiles and release rate of ASP from the ASP-loaded magnetic MIPs indicated that the magnetic MIPs also had potential applications in drug controlled release.

  2. Nanocoax-based molecular imprint polymer for electrochemical biosensor

    NASA Astrophysics Data System (ADS)

    Rizal, Binod; Archibald, Michelle; Simko, Laura; Connolly, Timothy; Shepard, Stephen; Burns, Michael; Chiles, Thomas; Naughton, Michael

    2013-03-01

    We have used molecular imprint polymerization (MIP) on planar, nanopillar, and nanocoax structures to fabricate label-free, all-electronic electrochemical biosensors with high selectivity and sensitivity. MIP-based films of ~ 7 nm thickness are formed on gold-coated surfaces by electropolymerization of a solution containing phenol and a target protein (streptavidin, at 100 μg/ml, or 1 nanomole concentration) and subsequent removal of exposed target protein, leaving behind its molecular imprint. With its molecular memory, MIP subsequently specifically recognizes and binds target protein with attomolar sensitivity, detected via differential pulse voltammetry. We will discuss and compare the results of MIP for different proteins on planar, nanopillar, and nanocoax structures, along with their respective ultimate sensitivities. Supported by the NIH grants NCI CA137681 and NIAID AI100216.

  3. Chiral recognition applications of molecularly imprinted polymers: a critical review.

    PubMed

    Maier, Norbert M; Lindner, Wolfgang

    2007-09-01

    Molecular imprinting technology offers the unique opportunity to tailor chiral stationary phases with predefined chiral recognition properties by employing the enantiomers of interest as binding-site-forming templates. Added advantages, such as ease of preparation, chemical robustness, low-cost production, and the possibility of shaping molecularly imprinted polymers (MIPs) in various self-supporting formats, render them attractive materials for a broad range of chiral recognition applications. In this review a critical overview on recent developments in the field of MIP-based chiral recognition applications is given, focusing on separation techniques and molecular sensing. Inherent limitations associated with the use of enantioselective MIP materials in high-performance separation techniques are outlined, including binding site heterogeneity and slow mass transfer characteristics. The prospects of MIP materials as versatile recognition elements for the design of enantioselective sensor systems are highlighted.

  4. Low cross-linked molecularly imprinted monolithic column prepared in molecular crowding conditions.

    PubMed

    Mu, Li-Na; Wang, Xian-Hua; Zhao, Liang; Huang, Yan-Ping; Liu, Zhao-Sheng

    2011-12-23

    Molecular crowding is a new approach to promoting molecular imprinting more efficiently. In this work, this concept was applied to the preparation of low cross-linked imprinted polymers in the presence of an immobilised template for stabilizing binding sites and improving molecular recognition. An imprinted monolithic column was synthesized using a mixture of 2,4-diamino-6-methyl-1,3,5-triazine (template), 2,4-diamino-6-(methacryloyloxy) ethyl-1,3,5-triazine (polymerisable template), methacrylic acid, ethylene glycol dimethacrylate, and polystyrene (molecular crowding agent). Some polymerization factors, such as template-monomer molar ratio, the composition of the porogen and crosslinking density, on the imprinting effect of resulting MIP monolith were systematically investigated. The results indicated that the imprinted monolithic columns prepared in the presence of molecular crowding agent retained affinity and specificity for template even when prepared with a level of cross-linker as low as 9%. Moreover, a stoichiometric displacement model for retention was successfully applied to evaluate the interaction between the solute and the stationary phase. Compared with the low cross-linked MIP prepared by conventional polymerization, the molecular crowding-based low cross-linked monolithic MIPs showed higher selectivity. The results suggested that molecular crowding is a powerful strategy to increase the effect of molecular imprinting at a low level of crosslinker.

  5. Caffeine electrochemical sensor using imprinted film as recognition element based on polypyrrole, sol-gel, and gold nanoparticles hybrid nanocomposite modified pencil graphite electrode.

    PubMed

    Rezaei, Behzad; Khalili Boroujeni, Malihe; Ensafi, Ali A

    2014-10-15

    In the present study, a novel sensitive and selective nanocomposite imprinted electrochemical sensor for the indirect determination of caffeine has been prepared. The imprinted sensor was fabricated on the surface of pencil graphite electrode (PGE) via one-step electropolymerization of the imprinted polymer composed of conductive polymer, sol-gel, gold nanoparticles (AuNPs), and caffeine. Due to such combination like the thin film of molecularly imprinted polymer (MIP) with specific binding sites, the sensor responded quickly to caffeine. AuNPs were introduced for the enhancement of electrical response by facilitating charge transfer processes of [Fe(CN)6](3-)/[Fe(CN)6](4-) which was used as an electrochemical active probe. The fabrication process of the sensor was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Several important parameters controlling the performance of the sensor were investigated and optimized. The imprinted sensor has the advantages of high porous surface structure, inexpensive, disposable, excellent stability, good reproducibility and repeatability. The linear ranges of the MIP sensor were in the range from 2.0 to 50.0 and 50.0 to 1000.0 nmol L(-1), with the limit of detection (LOD) of 0.9 nmol L(-1) (S/N=3). Furthermore, the proposed method was successfully intended for the determination of caffeine in real samples (urine, plasma, tablet, green tea, energy and soda drink).

  6. Computational design and multivariate optimization of an electrochemical metoprolol sensor based on molecular imprinting in combination with carbon nanotubes.

    PubMed

    Nezhadali, Azizollah; Mojarrab, Maliheh

    2016-06-14

    This work describes the development of an electrochemical sensor based on a new molecularly imprinted polymer for detection of metoprolol (MTP) at ultra-trace level. The polypyrrole (PPy) was electrochemically synthesized on the tip of a pencil graphite electrode (PGE) which modified whit functionalized multi-walled carbon nanotubes (MWCNTs). The fabrication process of the sensor was characterized by cyclic voltammetry (CV) and the measurement process was carried out by differential pulse voltammetry (DPV). A computational approach was used to screening functional monomers and polymerization solvent for rational design of molecularly imprinted polymer (MIP). Based on computational results, pyrrole and water were selected as functional monomer and polymerization solvent, respectively. Several significant parameters controlling the performance of the MIP sensor were examined and optimized using multivariate optimization methods such as Plackett-Burman design (PBD) and central composite design (CCD). Under the selected optimal conditions, MIP sensor was showed a linear range from 0.06 to 490 μmol L(-1) MTP, a limit of detection of 2.88 nmol L(-1), a highly reproducible response (RSD 3.9%) and a good selectivity in the presence of structurally related molecules. Furthermore, the applicability of the method was successfully tested with determination of MTP in real samples (tablet, and serum).

  7. Molecularly imprinted polymers for histamine recognition in aqueous environment.

    PubMed

    Trikka, Foteini A; Yoshimatsu, Keiichi; Ye, Lei; Kyriakidis, Dimitrios A

    2012-11-01

    Molecularly imprinted polymers (MIP) for histamine using methacrylic acid were developed and recognition mechanisms were thoroughly characterized for the first time in this study. The binding affinity of imprinted polymer with structurally related compounds was studied in organic and aqueous media, at various conditions. In organic media, MIP was found to bind histamine two and six times more than ranitidine and fluoxetine, respectively, whereas higher selectivity was observed in the case of dimentidene or disodium cromoglycate. The specific binding sites of MIP recognized histamine over L-histidine in aqueous conditions, while higher affinity for histamine compared to ranitidine, disodium cromoglycate, putrescine and to a putrescine analogue was observed. A combination of NMR and UV spectroscopy analyses for investigation of imprinting and recognition properties revealed that strong specific interactions between the functional monomer and histamine in the prepolymerization and in the aqueous solutions were probably responsible for histamine recognition. The preparation of histamine MIPs and elucidation of imprinting and recognition mechanism may serve as useful insight for future application of MIPs.

  8. [Molecularly imprinted polymers in electro analysis of proteins].

    PubMed

    Shumyantseva, V V; Bulko, T V; Baychorov, I Kh; Archakov, A I

    2015-01-01

    In the review the main approaches to creation of recognition materials capable of competing with biological specific receptors, (polymeric analogs of antibodies or molecularly imprinted polymers, MIP) for the electro analysis of functionally significant proteins such as a myoglobin, troponin T, albumin, human ferritin, calmodulin are considered. The main types of monomers for MIP fabrication, and methods for MIP/protein interactions, such as a surface plasmon resonance (SPR), nanogravimetry with use of the quartz crystal resonator (QCM), spectral and electrochemical methods are discussed. Experimental data on electrochemical registration of a myoglobin using MIP/electrode are presented. For a development of electrochemical sensor systems based on MIPs, o-phenylenediamine (1,2-diaminobenzene was used as a monomer. It was shown that the imprinting factor Imax(MIP)/Imax(NIP), calculated as a myoglobin signal ratio when embedding in MIP to a myoglobin signal when embedding in the polymer received without molecular template (NIP) corresponds 2-4.

  9. An electrochemical sensor for phenylephrine based on molecular imprinting.

    PubMed

    Yao, Liuduan; Tang, Youwen; Zeng, Weipeng; Huang, Zhaofa

    2009-09-01

    Molecularly imprinted polymers (MIPs) were applied as molecular recognition elements to an electrochemical sensor for phenylephrine. A MIPs membrane was created on a glassy carbon electrode. SEM revealed a gradual change on the morphology of modified electrodes as the ratios of function monomer and cross-linking varied. When the ratio was 4:40, the surface morphology between the imprinted electrode (M-electrode) and the control electrode (N-electrode) became unambiguously different. This artificial receptor exhibited high selectivity for the template compared to closely related analogue. The response of the sensor varied in different concentration range might due to the heterogeneity of the MIPs membrane. This sensor was also used to determine phenylephrine in tablet samples.

  10. Optimization, evaluation, and characterization of molecularly imprinted polymers.

    PubMed

    Spivak, David A

    2005-12-06

    The underlying mechanisms for molecular recognition exhibited by the imprinting effect can be attributed to two processes. The pre-organization of complementary functional groups in the polymer by the template and the formation of a shape-selective cavity that is complementary to the template. However, measurements of binding and selectivity combine all effects contributing to molecular recognition in MIPs into one figure of merit. If the two molecules being compared are not enantiomers, then there are other factors which contribute to differential binding such as size or different partitioning effects due to differences in polarity, hydrophobicity, ionization state or shape and/or conformational effects. The best probe for the imprinting effect is therefore an enantiomeric pair. Therefore, the first section of this article discusses enantioselective optimization of polymerization, the second section will review methods employed for evaluation of MIPs and the last section will cover materials science methods used to characterize the physical properties of MIP materials.

  11. Direct writing of molecularly imprinted microstructures using a nanofountain pen

    NASA Astrophysics Data System (ADS)

    Belmont, Anne-Sophie; Sokuler, Mordechai; Haupt, Karsten; Gheber, Levi A.

    2007-05-01

    Molecularly imprinted polymers (MIPs) constitute a very appealing avenue to parallel sensors of a multitude of small target molecules due to their stability, relative ease of preparation, and their ability to recognize targets for which natural capture molecules do not exist. The authors present here a way of arraying MIP structures with micrometer dimensions, using nanofountain pen, and demonstrate their functionality using a fluorescent template molecule.

  12. Absolute configuration determination using enantiomeric pairs of molecularly imprinted polymers.

    PubMed

    Meador, Danielle S; Spivak, David A

    2014-03-07

    A new method for determination of absolute configuration (AC) is demonstrated using an enantiomeric pair of molecularly imprinted polymers, referred to as "DuoMIPs". The ratio of HPLC capacity factors (k') for the analyte on each of the DuoMIPs is defined as the γ factor and can be used to determine AC when above 1.2. A mnemonic based on the complementary binding geometry of the DuoMIPs was used to aid in understanding and prediction of AC.

  13. Highly Selective Fluorescent Sensing of Proteins Based on a Fluorescent Molecularly Imprinted Nanosensor

    PubMed Central

    Deng, Qiliang; Wu, Jianhua; Zhai, Xiaorui; Fang, Guozhen; Wang, Shuo

    2013-01-01

    A fluorescent molecularly imprinted nanosensor was obtained by grafting imprinted polymer onto the surface of multi-wall carbon nanotubes and post-imprinting treatment with fluorescein isothiocyanate (FITC). The fluorescence of lysozyme-imprinted polymer (Lys-MIP) was quenched more strongly by Lys than that of nonimprinted polymer (NIP), which indicated that the Lys-MIP could recognize Lys. The resulted imprinted material has the ability to selectively sense a target protein, and an imprinting factor of 3.34 was achieved. The Lys-MIP also showed selective detection for Lys among other proteins such as cytochrome C (Cyt C), hemoglobin (HB) and bovine serum albumin (BSA) due to the imprinted sites in the Lys-MIP. This approach combines the high selectivity of surface molecular imprinting technology and fluorescence, and converts binding events into detectable signals by monitoring fluorescence spectra. Therefore, it will have further applications for Lys sensing. PMID:24077318

  14. Template synthesized molecularly imprinted polymer nanotube membranes for chemical separations.

    PubMed

    Wang, Hai-Juan; Zhou, Wen-Hui; Yin, Xiao-Fei; Zhuang, Zhi-Xia; Yang, Huang-Hao; Wang, Xiao-Ru

    2006-12-20

    In this report, we describe the synthesis of a molecularly imprinted polymer (MIP) nanotube membrane, using a porous anodic alumina oxide (AAO) membrane by surface-initiated atom transfer radical polymerization (ATRP). The use of a MIP nanotube membrane in chemical separations gives the advantage of high affinity and selectivity. Furthermore, because the molecular imprinting technique can be applied to different kinds of target molecules, ranging from small organic molecules to peptides and proteins, such MIP nanotube membranes will considerably broaden the application of nanotube membranes in chemical separations and sensors. This report also shows that the ATRP route is an efficient procedure for the preparation of molecularly imprinted polymers. Furthermore, the ATRP route works well in its formation of MIP nanotubes within a porous AAO membrane. The controllable nature of ATRP allows the growth of a MIP nanotube with uniform pores and adjustable thickness. Thus, using the same route, it is possible to tailor the synthesis of MIP nanotube membranes with either thicker MIP nanotubes for capacity improvement or thinner nanotubes for efficiency improvement.

  15. Characterization of QCM sensor surfaces coated with molecularly imprinted nanoparticles.

    PubMed

    Reimhult, Kristina; Yoshimatsu, Keiichi; Risveden, Klas; Chen, Si; Ye, Lei; Krozer, Anatol

    2008-07-15

    Molecularly imprinted polymers (MIPs) are gaining great interest as tailor-made recognition materials for the development of biomimetic sensors. Various approaches have been adopted to interface MIPs with different transducers, including the use of pre-made imprinted particles and the in situ preparation of thin polymer layers directly on transducer surfaces. In this work we functionalized quartz crystal microbalance (QCM) sensor crystals by coating the sensing surfaces with pre-made molecularly imprinted nanoparticles. The nanoparticles were immobilized on the QCM transducers by physical entrapment in a thin poly(ethylene terephthalate) (PET) layer that was spin-coated on the transducer surface. By controlling the deposition conditions, it was possible to gain a high nanoparticle loading in a stable PET layer, allowing the recognition sites in nanoparticles to be easily accessed by the test analytes. In this work, different sensor surfaces were studied by micro-profilometry and atomic force microscopy and the functionality was evaluated using quartz crystal microbalance with dissipation (QCM-D). The molecular recognition capability of the sensors were also confirmed using radioligand binding analysis by testing their response to the presence of the test compounds, (R)- and (S)-propranolol in aqueous buffer.

  16. Optimization of Molecularly Imprinted Polymers of Serotonin for Biomaterial Applications.

    PubMed

    Khurshid, Shahana S; Schmidt, Christine E; Peppas, Nicholas A

    2011-01-01

    We prepared molecularly imprinted polymers (MIPs) of serotonin (5-hydroxytryptamine or 5-HT), a neurotransmitter and mood modulator, using a combination of neutral (methacrylamide or acrylamide) and positively charged (methacrylic acid) functional monomers. Water, PBS, acidified methanol and sodium dodecyl sulfate were compared as rinsing solvents for the removal of serotonin from the MIPs. Methacrylamide MIPs rinsed in acidified methanol (92% serotonin removal) produced the highest imprinting factor (3.1) in equilibrium batch rebinding experiments using a combination of 2% water and 98% MeCN as the rebinding solvent. For the first time, these MIPs were assessed for cytocompatibility using mouse mesencephalon neural progenitor cells (NPC) and NIH 3T3 fibroblasts. Although MIP particles decreased NPC viability to <70%, MIP particles did not significantly reduce fibroblast viability when incorporated into a hyaluronic acid biomaterial. MIP microparticles were incorporated into a cross-linked hyaluronic acid biomaterial to present one way in which molecularly imprinted polymers may be used in vivo in future biomaterials or biosensors applications.

  17. Consequences of Morphology on Molecularly Imprinted Polymer-Ligand Recognition

    PubMed Central

    Rosengren, Annika M.; Karlsson, Björn C. G.; Nicholls, Ian A.

    2013-01-01

    The relationship between molecularly imprinted polymer (MIP) morphology and template-rebinding over a series of warfarin-imprinted methacrylic acid co(ethylene dimethacrylate) polymers has been explored. Detailed investigations of the nature of template recognition revealed that an optimal template binding was obtained with polymers possessing a narrow population of pores (~3–4 nm) in the mesopore size range. Importantly, the warfarin-polymer rebinding analyses suggest strategies for regulating ligand binding capacity and specificity through variation of the degree of cross-linking, where polymers prepared with a lower degree of cross-linking afford higher capacity though non-specific in character. In contrast, the co-existence of specific and non-specific binding was found in conjunction with higher degrees of cross-linking and resultant mesoand macropore size distributions. PMID:23303280

  18. Molecularly imprinted polymer-assisted refolding of lysozyme.

    PubMed

    Haruki, Mitsuru; Konnai, Yoshihiro; Shimada, Ayumi; Takeuchi, Hirofumi

    2007-01-01

    For production of active proteins using heterologous expression systems, refolding of proteins from inclusion bodies often creates a bottleneck due to its poor yield. In this study, we show that molecularly imprinted polymer (MIP) toward native lysozyme promotes the folding of chemically denatured lysozyme. The MIP, which was prepared with 1 M acrylamide, 1 M methacrylic acid, 1 M 2-(dimethylamino)ethyl methacrylate, and 5 mg/mL lysozyme, successfully promoted the refolding of lysozyme, whereas the non-imprinted polymer did not. The refolding yield of 90% was achieved when 15 mg of the MIP was added to 0.3 mg of the unfolded lysozyme. The parallel relationship between the refolding yield and the binding capacity of the MIP suggests that MIP promotes refolding through shifting the folding equilibrium toward the native form by binding the refolded protein.

  19. A Molecularly Imprinted Polymer (MIP)-Coated Microbeam MEMS Sensor for Chemical Detection

    DTIC Science & Technology

    2015-09-01

    ARL-RP-0536 ● SEP 2015 US Army Research Laboratory A Molecularly Imprinted Polymer (MIP)- Coated Microbeam MEMS Sensor for...ARL-RP-0536 ● SEP 2015 US Army Research Laboratory A Molecularly Imprinted Polymer (MIP)- Coated Microbeam MEMS Sensor for Chemical...TITLE AND SUBTITLE A Molecularly Imprinted Polymer (MIP)-Coated Microbeam MEMS Sensor for Chemical Detection 5a. CONTRACT NUMBER 5b. GRANT NUMBER

  20. Studies on the Process of Formation, Nature and Stability of Binding Sites in Molecularly Imprinted Polymers

    DTIC Science & Technology

    2002-04-05

    MIPs in dynamic applications such as in chromatography, membrane separation or in chemical sensors . 93 In non-covalent molecular imprinting this...6 8 10 Molecular Radius (rm) - - MIP DCM - NIP DCM Figure 6. Pore size distributions obtained from ISEC measurements on an ametryn imprinted polymer ...unger.chemie.uni- mainz.de) ’ Polymer Research Unit, Material Ireland, Trinity College Dublin, Ireland ABSTRACT In Molecular Imprinting the nature of the

  1. Computational Optimization and Characterization of Molecularly Imprinted Polymers

    NASA Astrophysics Data System (ADS)

    Terracina, Jacob J.

    Molecularly imprinted polymers (MIPs) are a class of materials containing sites capable of selectively binding to the imprinted target molecule. Computational chemistry techniques were used to study the effect of different fabrication parameters (the monomer-to-target ratios, pre-polymerization solvent, temperature, and pH) on the formation of the MIP binding sites. Imprinted binding sites were built in silico for the purposes of better characterizing the receptor - ligand interactions. Chiefly, the sites were characterized with respect to their selectivities and the heterogeneity between sites. First, a series of two-step molecular mechanics (MM) and quantum mechanics (QM) computational optimizations of monomer -- target systems was used to determine optimal monomer-to-target ratios for the MIPs. Imidazole- and xanthine-derived target molecules were studied. The investigation included both small-scale models (one-target) and larger scale models (five-targets). The optimal ratios differed between the small and larger scales. For the larger models containing multiple targets, binding-site surface area analysis was used to evaluate the heterogeneity of the sites. The more fully surrounded sites had greater binding energies. Molecular docking was then used to measure the selectivities of the QM-optimized binding sites by comparing the binding energies of the imprinted target to that of a structural analogue. Selectivity was also shown to improve as binding sites become more fully encased by the monomers. For internal sites, docking consistently showed selectivity favoring the molecules that had been imprinted via QM geometry optimizations. The computationally imprinted sites were shown to exhibit size-, shape-, and polarity-based selectivity. This represented a novel approach to investigate the selectivity and heterogeneity of imprinted polymer binding sites, by applying the rapid orientation screening of MM docking to the highly accurate QM-optimized geometries. Next

  2. Fluorescence measurements of activity associated with a molecularly imprinted polymer imprinted to dipicolinic acid

    NASA Astrophysics Data System (ADS)

    Anderson, John; Pestov, Dmitry; Fischer, Robert L.; Webb, Stanley; Tepper, Gary C.

    2004-03-01

    Steady state and lifetime fluorescence measurements were acquired to measure the binding activity associated with molecularly imprinted polymer (MIP) microparticles imprinted to dipicolinic acid. Dipicolinic acid is a unique compound associated with the sporulation phase of spore-forming bacteria (e.g., genus Bacillus and Clostridium). Vinylic monomers were polymerized in a dimethylformamide solution containing the dipicolinic acid as a template. The resulting MIP was then pulverized and size selected into small microscale particles. Samplers were adapted incorporating the MIP particles within a dialyzer (500 MW). Tests were run on replicate samples of biologically active cultures representing both stationary phase and sporulation post fermentation products in standard media. The permeability of the membrane permitted diffusion of lighter molecular weight constituents from media effluents to enter the dialyzer chamber and contact the MIP. Extractions of the media were measured using steady state and lifetime fluorescence. Results showed dramatic steady state fluorescence changes as a function of excitation, emission and intensity and an estimated lifetime of 5.8 ns.

  3. Molecularly Imprinted Polymers Used as Optical Waveguides for the Detection of Fluorescent Analytes

    DTIC Science & Technology

    2002-04-05

    molecular sieves. Fabrication of MIP waveeuides Fabrication of polymer waveguides utilized the soft lithography technique of micromolding in...UNCLASSIFIED Defense Technical Information Center Compilation Part Notice ADP013610 TITLE: Molecularly Imprinted Polymers Used as Optical Waveguides...TITLE: Materials Research Society Symposium Proceedings. Volume 723. Molecularly Imprinted Materials - Sensors and Other Devices. Symposia Held in

  4. Ordered macroporous quercetin molecularly imprinted polymers: Preparation, characterization, and separation performance.

    PubMed

    Feng, Yonggang; Liu, Qin; Ye, Lifang; Wu, Quanzhou; He, Jianfeng

    2017-02-01

    Ordered macroporous molecularly imprinted polymers were prepared by a combination of the colloidal crystal templating method and the molecular imprinting technique by using SiO2 colloidal crystal as the macroporogen, quercetin as the imprinting template, acrylamide as the functional monomer, ethylene glycol dimethacrylate as the cross-linker and tetrahydrofuran as the solvent. Scanning electron microscopy and Brunauer-Emmett-Teller measurements show that the ordered macroporous molecularly imprinted polymers have a more regular macroporous structure, a narrower pore distribution and a greater porosity compared with the traditional bulk molecularly imprinted polymers. The kinetic and isothermal adsorption behaviors of the polymers were investigated. The results indicate that the ordered macroporous molecularly imprinted polymers have a faster intraparticle mass transfer process and a higher adsorption capacity than the traditional bulk molecularly imprinted polymers. The ordered macroporous molecularly imprinted polymers were further employed as a sorbent for a solid-phase extraction. The results show that the ordered macroporous molecularly imprinted polymers can effectively separate quercetin from the Gingko hydrolysate.

  5. Molecularly imprinted silica-silver nanowires for tryptophan recognition

    NASA Astrophysics Data System (ADS)

    Díaz-Faes López, T.; Díaz-García, M. E.; Badía-Laíño, R.

    2014-10-01

    We report on silver nanowires (AgNWs) coated with molecularly imprinted silica (MIP SiO2) for recognition of tryptophan (Trp). The use of AgNWs as a template confers an imprinted material with adequate mechanical strength and with a capability of recognizing Trp due to its nanomorphology when compared to spherical microparticles with a similar surface-to-volume ratio. Studies on adsorption isotherms showed the MIP-SiO2-AgNWs to exhibit homogeneous affinity sites with narrow affinity distribution. This suggests that the synthesized material behaves as a 1D nanomaterial with a large area and small thickness with very similar affinity sites. Trp release from MIP-SiO2-AgNWs was demonstrated to be dominated by the diffusion rate of Trp as controlled by the specific interactions with the imprinted silica shell. Considering these results and the lack of toxicity of silica sol-gel materials, the material offers potential in the field of drug or pharmaceutical controlled delivery, but also in optoelectronic devices, electrodes and sensors.

  6. Cocaine abuse determination by ion mobility spectrometry using molecular imprinting.

    PubMed

    Sorribes-Soriano, A; Esteve-Turrillas, F A; Armenta, S; de la Guardia, M; Herrero-Martínez, J M

    2017-01-20

    A cocaine-based molecular imprinted polymer (MIP) has been produced by bulk polymerization and employed as selective solid-phase extraction support for the determination of cocaine in saliva samples by ion mobility spectrometry (IMS). The most appropriate conditions for washing and elution of cocaine from MIPs were studied and MIPs were characterized in terms of analyte binding capacity, reusability in water and saliva analysis, imprinting factor and selectivity were established and compared with non-imprinted polymers. The proposed MIP-IMS method provided a LOD of 18μgL(-1) and quantitative recoveries for blank saliva samples spiked from 75 to 500μgL(-1) cocaine. Oral fluid samples were collected from cocaine consumers and analysed by the proposed MIP-IMS methodology. Results, ranging from below the LOD to 51±2mgL(-1), were statistically comparable to those obtained by a confirmatory gas chromatography-mass spectrometry method. Moreover, results were compared to a qualitative lateral flow immunoassay procedure providing similar classification of the samples. Thus, MIP-IMS can be considered an useful alternative that provided fast, selective and sensitive results with a cost affordable instrumentation that does not require skilled operators. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Molecularly imprinted cryogel for L-glutamic acid separation.

    PubMed

    Aydoğan, Cemil; Andaç, Muge; Bayram, Engin; Say, Rıdvan; Denizli, Adil

    2012-01-01

    A molecular recognition based L-glutamic acid (L-GLU) imprinted cryogel was prepared for L-GLU separation via chromatographic applications. The novel functional monomer N-methacryloyl-(L)-glutamic acid-Fe(3+) (MAGA-Fe(3+) ) was synthesized to be complex with L-GLU. The L-GLU imprinted cryogel was prepared by free radical polymerization under semifrozen conditions in the presence of a monomer-template complex MAGA-Fe(3+) -L-GLU. The binding mechanism of MAGA-Fe(3+) and L-GLU was characterized by Fourier transform infrared (FTIR) spectroscopy in detail. FTIR analyses on the synthesized MAGA-Fe(3+) -GLU complex reveals bridging bidentate and monodentate binding modes of Fe(3+) in complex with the carboxylate groups of the glutamate residues. The template L-GLU could be reversibly detached from the cryogel to form the template cavities using a 100 mM solution of HNO(3) . The amount of adsorbed L-GLU was detected using the phenyl isothiocyanate method. The L-GLU adsorption capacity of the cryogel decreased drastically from 11.3 to 6.4 μmol g(-1) as the flow rate increased from 0.5 to 4.0 mL min(-1) . The adsorption onto the L-GLU imprinted cryogel was highly pH dependent due to electrostatic interaction between the L-GLU and MAGA-Fe(3+) . The PHEMAGA-Fe(3+) -GLU cryogel exhibited high selectivity to the corresponding guest amino acids (i.e., D-GLU, L-ASN, L-GLN, L-, and D-ASP). Finally, the L-GLU imprinted cryogel was recovered and reused many times, with no significant decrease in their adsorption capacities.

  8. Comparison of binding behavior for molecularly imprinted polymers prepared by hierarchical imprinting or Pickering emulsion polymerization.

    PubMed

    Giovannoli, Cristina; Passini, Cinzia; Anfossi, Laura; Nardo, Fabio Di; Spano, Giulia; Maurino, Valter; Baggiani, Claudio

    2015-10-01

    The aim of this study was the evaluation of the binding performances and selectivity of molecularly imprinted beads prepared toward several penicillins (i) by hierarchical bulk polymerization in the pores of template-grafted silica microbeads (hMIPs) and (ii) by Pickering emulsion polymerization in the presence of template-decorated silica nanobeads (pMIPs). 6-Aminopenicillanic acid was chosen as the common fragmental mimic template. Both approaches produced micron-sized polymeric beads with good recognition properties toward the target ligands whereas the selectivity pattern appeared quite different. The polymer prepared by the Pickering emulsion approach showed binding properties similar to imprinted beads prepared by hierarchical approach. Equilibrium binding constants changed their values from 0.1-0.2 × 10(6) (hMIPs) to 0.2-0.6 × 10(6) M(-1) (pMIPs), while the binding site densities changed from 3.7-4.8 (hMIPs) to 0.3-0.55 μmol/g (pMIPs). Compared to the hierarchical polymerization, Pickering emulsion polymerization represents a more practical approach when a template mimic needs to be used.

  9. From 3D to 2D: A Review of the Molecular Imprinting of Proteins

    PubMed Central

    Turner, Nicholas W.; Jeans, Christopher W.; Brain, Keith R.; Allender, Christopher J.; Hlady, Vladimir; Britt, David W.

    2008-01-01

    Molecular imprinting is a generic technology that allows for the introduction of sites of specific molecular affinity into otherwise homogeneous polymeric matrices. Commonly this technique has been shown to be effective when targeting small molecules of molecular weight <1500, while extending the technique to larger molecules such as proteins has proven difficult. A number of key inherent problems in protein imprinting have been identified, including permanent entrapment, poor mass transfer, denaturation, and heterogeneity in binding pocket affinity, which have been addressed using a variety of approaches. This review focuses on protein imprinting in its various forms, ranging from conventional bulk techniques to novel thin film and monolayer surface imprinting approaches. PMID:17137293

  10. Micromolding in Capillaries for the Generation of Molecularly Imprinted Polymer Filaments and Microstructures

    DTIC Science & Technology

    2002-04-05

    to define the shape and size of the imprinted polymers . This article describes the processes leading to the fabrication of free-standing MIP ...recognition and interactions play central roles in these applications. Molecular imprinting , a technique for the synthesis of polymeric materials with analyte...generate molecularly imprinted polymer ( MIP ) microstructures on devices should open new possibilities towards the development of miniaturized systems for

  11. Molecularly imprinted polymers for on-line extraction techniques.

    PubMed

    Moein, Mohammad M; Abdel-Rehim, Mohamed

    2015-01-01

    Recent years have seen an increasing interest in the use of molecularly imprinted polymers (MIPs) as a sorbent for different extraction methods and this is due to its high selectivity. The MIP is designed to show specificity for the analyte of interest. Moreover, MIPs show physical robustness, resistance to high temperatures and pressures, and stability in the presence of acids, bases and a wide range of organic solvents. In the present article, various novel sample preparation techniques which MIPs applied as sorbent and on-line connected with analytical instruments were highlighted and discussed. The future aspects of MIPs as well were described.

  12. Molecular Imprinting Technology in Quartz Crystal Microbalance (QCM) Sensors

    PubMed Central

    Emir Diltemiz, Sibel; Keçili, Rüstem; Ersöz, Arzu; Say, Rıdvan

    2017-01-01

    Molecularly imprinted polymers (MIPs) as artificial antibodies have received considerable scientific attention in the past years in the field of (bio)sensors since they have unique features that distinguish them from natural antibodies such as robustness, multiple binding sites, low cost, facile preparation and high stability under extreme operation conditions (higher pH and temperature values, etc.). On the other hand, the Quartz Crystal Microbalance (QCM) is an analytical tool based on the measurement of small mass changes on the sensor surface. QCM sensors are practical and convenient monitoring tools because of their specificity, sensitivity, high accuracy, stability and reproducibility. QCM devices are highly suitable for converting the recognition process achieved using MIP-based memories into a sensor signal. Therefore, the combination of a QCM and MIPs as synthetic receptors enhances the sensitivity through MIP process-based multiplexed binding sites using size, 3D-shape and chemical function having molecular memories of the prepared sensor system toward the target compound to be detected. This review aims to highlight and summarize the recent progress and studies in the field of (bio)sensor systems based on QCMs combined with molecular imprinting technology. PMID:28245588

  13. Molecular Imprinting Technology in Quartz Crystal Microbalance (QCM) Sensors.

    PubMed

    Emir Diltemiz, Sibel; Keçili, Rüstem; Ersöz, Arzu; Say, Rıdvan

    2017-02-24

    Molecularly imprinted polymers (MIPs) as artificial antibodies have received considerable scientific attention in the past years in the field of (bio)sensors since they have unique features that distinguish them from natural antibodies such as robustness, multiple binding sites, low cost, facile preparation and high stability under extreme operation conditions (higher pH and temperature values, etc.). On the other hand, the Quartz Crystal Microbalance (QCM) is an analytical tool based on the measurement of small mass changes on the sensor surface. QCM sensors are practical and convenient monitoring tools because of their specificity, sensitivity, high accuracy, stability and reproducibility. QCM devices are highly suitable for converting the recognition process achieved using MIP-based memories into a sensor signal. Therefore, the combination of a QCM and MIPs as synthetic receptors enhances the sensitivity through MIP process-based multiplexed binding sites using size, 3D-shape and chemical function having molecular memories of the prepared sensor system toward the target compound to be detected. This review aims to highlight and summarize the recent progress and studies in the field of (bio)sensor systems based on QCMs combined with molecular imprinting technology.

  14. [Preparation and evaluation of novel mesoporous molecular sieve of baicalin surface molecularly imprinted polymers].

    PubMed

    Gu, Xia-li; He, Hong-liang; Shi, Li-ying; Gao, Yan-kun; Chen, Li-na

    2015-05-01

    Taking mesoporous molecular sieve MCM-41 as a substrate, baicalin (BA) as template, acrylamide (AM) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, ethanol as solvent, under thermal polymerization initiator of azobis isobutyronitrilo (AIBN) , a kind of selective recognition of baicalin surface molecularly imprinted polymer was synthesized. The surface morphologies and characteristics of the MIPs were characterized by infrared spectroscopy (IR) and transmission electron microscope (TEM). The adsorption properties of polymer microsphere for the template were tested by the dynamic adsorption equilibrium experiments and static adsorption equilibrium experiments. The experiment showed that the imprinting process was successfully and the well-ordered one-dimensional pore structure of MCM-41 was still preserved. Furthermore, molecularly imprinted polymers had higher selective ability for BA, then provided a new method for the efficient separation and enrichment of baicalin active ingredients from medicinal plants Scutellaria baicalensis.

  15. Enhanced adsorption of atrazine from aqueous solution by molecularly imprinted TiO2 film

    NASA Astrophysics Data System (ADS)

    Zhang, Chunjing; Yan, Jinlong; Zhang, Chunxiao; Yang, Zhengpeng

    2012-07-01

    TiO2 film imprinted by atrazine molecule at the surface of quartz crystal was prepared using molecular imprinting and surface sol-gel process. The molecularly imprinted TiO2 film was characterized by scanning electron microscopy and cyclic voltammetry, and the atrazine adsorption was investigated by quartz crystal microbalance (QCM) technique. In comparison with non-imprinted TiO2 film, the molecularly imprinted TiO2 film exhibits high selectivity for atrazine, better reversibility and a much higher adsorption capacity for the target molecule, the adsorption equilibrium constant estimated from the in situ frequency measurement is about 6.7 × 104 M-1, which is thirteen times higher than that obtained on non-imprinted TiO2 film.

  16. Binding characteristics of molecularly imprinted polymers based on fungicides in hydroalcoholic media.

    PubMed

    Bitar, Manal; Bou-Maroun, Elias; Lerbret, Adrien; Ouaini, Naim; Cayot, Philippe

    2015-10-01

    An iprodione-imprinted polymer was prepared by copolymerization of methacrylamide and ethylene glycol dimethacrylate using a noncovalent imprinting approach. Methacrylamide was chosen using molecular dynamics simulations. To concentrate iprodione from hydro-alcoholic solutions, batch sorption of iprodione on the imprinted polymer were conducted. The equilibrium time for iprodione sorption is 20 min, and the corresponding kinetic mechanism follows the pseudo-second order indicating a strong interaction between iprodione and the imprinted polymer. Langmuir, Freundlich, and Dubinin-Radushkevich models were used to fit the isotherm of iprodione sorption. The imprinted polymer was found to be more efficient than the nonimprinted polymer for the uptake of iprodione, as revealed by its higher adsorption energy, affinity, and capacity. Finally, a selectivity study was conducted on the imprinted and the nonimprinted polymers to sorb three fungicides. It shows that the imprinted polymer could be used as a preconcentration phase in a multiresidue analysis of fungicides in hydroalcoholic medium.

  17. Selective enrichment and separation of phosphotyrosine peptides by thermosensitive molecularly imprinted polymers.

    PubMed

    Yang, Xiaoqing; Xia, Yan

    2016-01-01

    Novel thermosensitive molecularly imprinted polymers were successfully prepared using the epitope imprinting approach in the presence of the mimic template phenylphosphonic acid, the functional monomer vinylphosphonic acid-Ti(4+) , the temperature-sensitive monomer N-isopropylacrylamide and the crosslinker N,N'-methylenebisacrylamide. The ratio of the template/thermosensitive monomers/crosslinker was optimized, and when the ratio was 2:2:1, the prepared thermosensitive molecularly imprinted polymers had the highest imprinting factor. The synthetic thermosensitive molecularly imprinted polymers were characterized by Fourier transform infrared spectroscopy to reveal the combination and elution processes of the template. Then, the adsorption capacity and thermosensitivity was measured. When the temperature was 28°C, the imprinting factor was the highest. The selectivity and adsorption capacity of the thermosensitive molecularly imprinted polymers for phosphotyrosine peptides from a mixture of three tailor-made peptides were measured by high-performance liquid chromatography. The results showed that the thermosensitive molecularly imprinted polymers have good selectivity for phosphotyrosine peptides. Finally, the imprinted hydrogels were applied to specifically adsorb phosphotyrosine peptides from a sample mixture containing phosphotyrosine and a tryptic digest of β-casein, which demonstrated high selectivity. After four rebinding cycles, 78.9% adsorption efficiency was still retained.

  18. Binding capacity of molecularly imprinted polymers and their nonimprinted analogs.

    PubMed

    Dorkó, Zsanett; Szakolczai, Anett; Verbić, Tatjana; Horvai, George

    2015-12-01

    Molecularly imprinted polymers bind their target compounds at binding sites. The binding sites are typically based on some type of functional group, such as carboxyl group. The total amount of such functional groups and their distribution into available and unavailable groups is not well known. The total binding capacity is usually indirectly determined from adsorption isotherms, which are measured much below the theoretical binding capacity. This work shows that in a variety of differently prepared, methacrylic acid based molecularly imprinted and nonimprinted polymers, all carboxylic groups used for the polymer synthesis are retained in the polymer, 80-90% of them can be accessed by strong bases and essentially the same amount can be used for adsorption of weak bases. This high level of adsorption can only be achieved, however, if the adsorbed weak base is strong enough, if the polymer is sufficiently elastic and if the solvent does not compete too strongly for the binding sites. These results may explain why the maximum binding capacities obtained from isotherm measurements are usually not equal to the total amount of available binding sites. This study confirms the usefulness of nonimprinted polymers at high loadings.

  19. Molecularly-imprinted polymer sensors: realising their potential.

    PubMed

    Uzun, Lokman; Turner, Anthony P F

    2016-02-15

    In parallel with recent developments in communications, nanotechnology and materials sciences, there has been extraordinary growth in the area of biosensors, with almost half of the total number of papers ever published (1962-2015) appearing in the last five-years (2010-2015). Molecular imprinting offers a route to the creation of specific and selective cavities in a 3D-polymeric network, which are complementary not only to the size and shape of a target species, but also provide interaction points and a coordination sphere around the template molecule. Given the challenges facing biosensor technologists, it is natural that this approach to create potentially highly stable synthetic ligands as an alternative to, or to compliment natural receptors, should emerge as a key line of interdisciplinary research. Despite the profuse amount of recent literature on molecularly-imprinted polymers (MIPs) and some limited commercial activity, these promising materials still need to overcome some limitations before taking their place in analytical market. In this review, we have focused on the most promising advances in MIP-based biosensors to illustrate how close to market they really are. We present our material under five main sections covering computational design, polymerisation strategies, material combinations, recent sensor designs and manufacturing issues. Each section provides technical details and evaluates the effect on sensor performance.

  20. Fluorescent monomers: "bricks" that make a molecularly imprinted polymer "bright".

    PubMed

    Wan, Wei; Wagner, Sabine; Rurack, Knut

    2016-03-01

    Molecularly imprinted polymers (MIPs) are potent and established recognition phases in separation and enrichment applications. Because of their robustness, versatility and format adaptability, they also constitute very promising sensing phases, especially when the active sensing element is directly integrated into the MIP. Fluorescent MIPs incorporating fluorescent monomers are perhaps the best developed and most successful approach here. This article reviews the state of the art in this field, discussing the pros and cons of the use of fluorescent dye and probe derivatives as such monomers, the different molecular interaction forces for template complexation, signalling modes and a variety of related approaches that have been realized over the years, including Förster resonance energy transfer processes, covalent imprinting, postmodification attachment of fluorescent units and conjugated polymers as MIPs; other measurement schemes and sensing chemistries that use MIPs and fluorescence interrogation to solve analytical problems (fluorescent competitive assays, fluorescent analytes, etc.) are not covered here. Throughout the article, photophysical processes are discussed to facilitate understanding of the effects that can occur when one is planning for a fluorescence response to happen in a constrained polymer matrix. The article concludes with a concise assessment of the suitability of the different formats for sensor realization.

  1. Xerogel-based molecularly imprinted polymers for explosives detection

    NASA Astrophysics Data System (ADS)

    Holthoff, Ellen L.; Stratis-Cullum, Dimitra N.; Hankus, Mikella E.

    2010-04-01

    Molecularly imprinted polymers (MIPs) can be utilized as artificial recognition elements for target chemical analytes of interest. Molecular imprinting involves arranging polymerizable functional monomers around a template followed by polymerization and template removal. The selectivity for the target analyte is based on the spatial orientation of the binding site and covalent or noncovalent interactions between the functional monomer and the analyte. The polymer materials of particular interest are sol-gel-derived xerogels. To allow for increased target recognition, the xerogel has specific functional groups, which allow for polymer interactions with the template molecule (and target analyte). In a sensor format, the recognition event is monitored with some form of transduction. MIP technology is still in its infancy and limitations such as non-specific binding may be overcome utilizing surface enhanced Raman scattering (SERS) as an integrated transduction method for enhanced sensor performance. The objective of the present work is to create a sensitive and selective MIP-SERS sensing platform for 2,4,6-trinitrotoluene (TNT).

  2. Molecularly imprinted polymers as recognition materials for electronic tongues.

    PubMed

    Huynh, Tan-Phat; Kutner, Wlodzimierz

    2015-12-15

    For over three decades now, molecularly imprinted polymers (MIPs) have successfully been used for selective chemical sensing because the shape and size of their imprinted molecular cavities perfectly matched those of the target analyte molecules. Moreover, orientation of recognizing sites of these cavities corresponded to those of the binding sites of the template molecules. In contrast, electronic tongue (e-tongue) is usually an array of low-affinity recognition units. Its selectivity is based on recognition pattern or multivariate analysis. Merging these two sensing devices led to a synergetic hybrid sensor, an MIP based e-tongue. Fabrication of these e-tongues permitted simultaneous sensing and discriminating several analytes in complex solutions of many components so that these arrays compensated for limitation in cross-reactivity of MIPs. Apparently, analytical signals generated by MIP-based e-tongues, compared to those of ordinary sensor arrays, were more reliable where a unique pattern or 'fingerprint' for each analyte was generated. Additionally, several transduction platforms (from spectroscopic to electrochemical) engaged in constructing MIP-based e-tongues, found their broad and flexible applications. The present review critically evaluates achievements in recent developments of the MIP based e-tongues for chemosensing. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Enhancement of selective separation on molecularly imprinted monolith by molecular crowding agent.

    PubMed

    Wang, Xian-Hua; Dong, Qian; Ying, Ling-Ling; Chi, Shuai-Shuai; Lan, Yao-Han; Huang, Yan-Ping; Liu, Zhao-Sheng

    2017-01-01

    In this study, a new molecularly imprinted polymer chiral stationary phase (MIP-CSP) was prepared utilizing molecular crowding agent for improvement the selective separation ability. S-amlodipine (S-AML), methacrylic acid (MAA), ethylene glycol dimethacrylate (EDMA), and polymethyl methacrylate (PMMA) were selected as template, functional monomer, cross-linker, and molecular crowding agent, respectively. The composition of formulas for MIP-CSP was optimized, and the permeability and structural feature of resultant MIP-CSP were characterized. The effect of mobile-phase composition, including ionic strength, pH, and organic modifier content, was investigated for achieving the selective separation of rac-amlodipine (rac-AML) on MIP-CSP. The baseline separation of rac-AML was achieved with resolution of 1.58, whereas no selective separation was observed on the imprinted monolith without molecular crowding agent. The perturbation chromatography method was successfully applied to evaluate the recognition mechanism of templates on MIP-CSP. The retention time of S-AML detected in typical analytical conditions was obviously greater than the time of negative peak derived from perturbation, which indicated the retention of template may be due to the imprinted cavities on MIP-CSP. Additionally, the result of Van't Hoff analysis indicated that the chiral separation of rac-AML on MIP-CSP was an entropy-driven process, which supported the molecular imprinting theory. These results reveal that molecular crowding is a potential strategy for preparation of MIP-CSP with excellent selective separation ability. Graphical Abstract Improvement of chiral separation on molecularly imprinted monolith by molecular crowding condition.

  4. Affinity sensor based on immobilized molecular imprinted synthetic recognition elements.

    PubMed

    Lenain, Pieterjan; De Saeger, Sarah; Mattiasson, Bo; Hedström, Martin

    2015-07-15

    An affinity sensor based on capacitive transduction was developed to detect a model compound, metergoline, in a continuous flow system. This system simulates the monitoring of low-molecular weight organic compounds in natural flowing waters, i.e. rivers and streams. During operation in such scenarios, control of the experimental parameters is not possible, which poses a true analytical challenge. A two-step approach was used to produce a sensor for metergoline. Submicron spherical molecularly imprinted polymers, used as recognition elements, were obtained through emulsion polymerization and subsequently coupled to the sensor surface by electropolymerization. This way, a robust and reusable sensor was obtained that regenerated spontaneously under the natural conditions in a river. Small organic compounds could be analyzed in water without manipulating the binding or regeneration conditions, thereby offering a viable tool for on-site application.

  5. Monolithic molecularly imprinted polymeric capillary columns for isolation of aflatoxins.

    PubMed

    Szumski, Michał; Grzywiński, Damian; Prus, Wojciech; Buszewski, Bogusław

    2014-10-17

    Monolithic molecularly imprinted polymers extraction columns have been prepared in fused-silica capillaries by UV or thermal polymerization in a two-step process. First, a poly-(trimethylolpropane trimethacrylate) (polyTRIM) core monolith was synthesized either by UV or thermal polymerization. Then it was grafted with the mixture of methacrylic acid (MAA) as a functional monomer, ethylene dimethacrylate (EDMA) as a cross-linking agent, 5,7-dimethoxycoumarin (DMC) as an aflatoxin-mimicking template, toluene as a porogen solvent and 2,2-azobis-(2-methylpropionitrile) (AIBN) as an initiator of the polymerization reaction. Different thermal condition of the photografting and different concentrations of the grafting mixture were tested during polymerization. The extraction capillary columns were evaluated in the terms of their hydrodynamic and chromatographic properties. Retention coefficients for aflatoxin B1 and DMC were used for assessment of the selectivity and imprinting factor. The obtained results indicate that the temperature of photografting and concentration of the grafting mixture are key parameters that determine the quality of the prepared MIPs. From the MIP columns characterized by the highest permeability the column of the highest imprinting factor was applied for isolation of aflatoxins B1, B2, G1 and G2 from the model aqueous sample followed by on-line chromatographic separation. The process was performed using a micro-MISPE-microLC-LIF system of a novel design, which allowed for detection of the eluates from the sample preparation part as well as from the chromatographic separation. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Molecular imprinting of proteins emerging as a tool for protein recognition.

    PubMed

    Takeuchi, Toshifumi; Hishiya, Takayuki

    2008-07-21

    This article gives the recent developments in molecular imprinting for proteins. Currently bio-macromolecules such as antibodies and enzymes are mainly employed for protein recognition purposes. However, such bio-macromolecules are sometimes difficult to find and/or produce, therefore, receptor-like synthetic materials such as protein-imprinted polymers have been intensively studied as substitutes for natural receptors. Recent advances in protein imprinting shown here demonstrate the possibility of this technique as a future technology of protein recognition.

  7. [Application of molecularly imprinted technology for separation of PGG from Guizhi Fuling capsule].

    PubMed

    Song, Ya-ling; Wang, Xue-jing; Ni, Fu-yong; Gu, Rui; Zhao, Yi-wu; Huang, Wen-zhe; Wang, Zhen-zhong; Xu, Xiao-jie; Xiao, Wei

    2015-03-01

    1,2,3,4,6-penta-O-galloyl-D-glucose (PGG) is one of the main active compounds of Guizhi Fuling capsule. Molecularly imprinted polymers (MIP) have high affinity toward template molecules synthesized by molecularly imprinted technology for its specific combined sites, which can overcome the shortcoming of traditional separation methods, such as complex operation, low efficiency, using large quantity of solvent and environmental pollution. In this paper, surface molecularly imprinted polymer (SMIP) was prepared by surface imprinting with PGG as the template molecule. Its adsorption capacity was measured by the scatchard equation. The separation of PGG from Guizhi Fuling capsule at preparatived scale was achieved with molecularly imprinted polymer as stationary phase and the purity was 90.2% by HPLC. This method can be used to prepare PGG from Guizhi Fuling capsule with large capacity and is easy to operate. It provides a new method for efficient separation and purification for other natural products.

  8. Sensitive determination of citrinin based on molecular imprinted electrochemical sensor

    NASA Astrophysics Data System (ADS)

    Atar, Necip; Yola, Mehmet Lütfi; Eren, Tanju

    2016-01-01

    In this report, a novel molecular imprinted voltammetric sensor based on glassy carbon electrode (GCE) modified with platinum nanoparticles (PtNPs) involved in a polyoxometalate (H3PW12O40, POM) functionalized reduced graphene oxide (rGO) was prepared for the determination of citrinin (CIT). The developed surfaces were characterized by using scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) method. CIT imprinted GCE was prepared via electropolymerization process of 80.0 mM pyrrole as monomer in the presence of phosphate buffer solution (pH 6.0) containing 20.0 mM CIT. The linearity range and the detection limit of the developed method were calculated as 1.0 × 10-12-1.0 × 10-10 M and 2.0 × 10-13 M, respectively. In addition, the voltammetric sensor was applied to rye samples. The stability and selectivity of the voltammetric sensor were also reported.

  9. Molecularly imprinted solid phase extraction of fluconazole from pharmaceutical formulations.

    PubMed

    Manzoor, S; Buffon, R; Rossi, A V

    2015-03-01

    This work encompasses a direct and coherent strategy to synthesise a molecularly imprinted polymer (MIP) capable of extracting fluconazole from its sample. The MIP was successfully prepared from methacrylic acid (functional monomer), ethyleneglycoldimethacrylate (crosslinker) and acetonitrile (porogenic solvent) in the presence of fluconazole as the template molecule through a non-covalent approach. The non-imprinted polymer (NIP) was prepared following the same synthetic scheme, but in the absence of the template. The data obtained from scanning electronic microscopy, infrared spectroscopy, thermogravimetric and nitrogen Brunauer-Emmett-Teller plot helped to elucidate the structural as well as the morphological characteristics of the MIP and NIP. The application of MIP as a sorbent was demonstrated by packing it in solid phase extraction cartridges to extract fluconazole from commercial capsule samples through an offline analytical procedure. The quantification of fluconazole was accomplished through UPLC-MS, which resulted in LOD≤1.63×10(-10) mM. Furthermore, a high percentage recovery of 91±10% (n=9) was obtained. The ability of the MIP for selective recognition of fluconazole was evaluated by comparison with the structural analogues, miconazole, tioconazole and secnidazole, resulting in percentage recoveries of 51, 35 and 32%, respectively.

  10. Detection of organophosphorus compounds using a molecularly imprinted photonic crystal.

    PubMed

    Liu, Feng; Huang, Shuyue; Xue, Fei; Wang, Yifei; Meng, Zihui; Xue, Min

    2012-02-15

    A label free molecularly imprinted photonic crystal (MIPC) was developed to detect the degradation product of nerve agents. Mono-dispersed poly-methyl methacrylate colloidal particles with the diameter of 280 nm were used to fabricate a closely packed colloidal crystal array (CCA), and a methyl phosphonic acid (MPA) imprinted hydrogel was prepared within the CCA using 2-hydroxyethyl-methacrylate and N-isopropylacrylamide as monomers, ethyleneglycol dimethacrylate and N, N'-methylenebisacrylamide as cross-linkers, a mixture of n-octanol and acetonitrile as porogen. The diffraction intensity of the MIPC decreased significantly upon the MPA adsorption with a limit of detection (LOD) of 10(-6) molL(-1). Furthermore, the diffraction intensity decreased and blue shifted with the increase of temperature, decreased and red shifted with the increase of ionic strength. At higher pH, the diffraction intensity increased without obvious diffraction shift. The MIPC provides an indirect path to detect nerve agents (Sarin, Soman, VX and R-VX) by monitoring the MPA released from the hydrolysis of nerve agents, with LODs of 3.5 × 10(-6) molL(-1), 2.5 × 10(-5) molL(-1), 7.5 × 10(-5) molL(-1) and 7.5 × 10(-5) molL(-1) for Sarin, Soman, VX and R-VX, respectively.

  11. Molecularly Imprinted Polymers with DNA Aptamer Fragments as Macromonomers.

    PubMed

    Zhang, Zijie; Liu, Juewen

    2016-03-01

    Molecularly imprinted polymers (MIPs) are produced in the presence of a template molecule. After removing the template, the cavity can selectively rebind the template. MIPs are attractive functional materials with a low cost and high stability, but traditional MIPs often suffer from low binding affinity. This study employs DNA aptamer fragments as macromonomers to improve MIPs. The DNA aptamer for adenosine was first split into two halves, fluorescently labeled, and copolymerized into MIPs. With a fluorescence quenching assay, the importance of imprinting was confirmed. Further studies were carried out using isothermal titration calorimetry (ITC). Compared to the mixture of the free aptamer fragments, their MIPs doubled the binding affinity. Each free aptamer fragment alone cannot bind adenosine, whereas MIPs containing each fragment are effective binders. We further shortened one of the aptamer fragments, and the DNA length was pushed to as short as six nucleotides, yielding MIPs with a dissociation constant of 27 μM adenosine. This study provides a new method for preparing functional MIP materials by combining high-affinity biopolymer fragments with low-cost synthetic monomers, allowing higher binding affinity and providing a method for signaling binding based on DNA chemistry.

  12. An innovative approach to molecularly imprinted capillaries for polar templates by grafting polymerization.

    PubMed

    Giovannoli, Cristina; Passini, Cinzia; Baravalle, Patrizia; Anfossi, Laura; Giraudi, Gianfranco; Baggiani, Claudio

    2012-06-01

    Molecularly imprinted polymers have been successfully used as selective stationary phases in capillary electrophoresis. Notwithstanding, this technique suffers from several drawbacks as the loss of molecular recognition properties in aqueous media and the lack of feasibility for imprinted systems directed towards highly polar templates soluble in aqueous environments only. Thus, the preparation of imprinted polymers for highly polar, water-soluble analytes, represents a challenge. In this work, we present an innovative approach to overcome these drawbacks. It is based on a surface molecular imprinting technique that uses preformed macromonomers as both functional recognition elements and cross-linking agents. A poly-2-hydroxyethyl-co-methacrylic acid linear polymer was grafted from the surface of silica capillaries. The grafted polymer was exhaustively esterified with methacrylic anhydride to obtain polyethylendimethacrylate-co-methacrylic acid linear chains. Then, as a proof of concept, an adequate amount of a very polar template like penicillin V was added in a hydro-organic mixture, and a thin layer of imprinted polymer was obtained by cross-linking the polymer linear chains. The binding behaviour of the imprinted and non-imprinted capillaries was evaluated in different separation conditions in order to assess the presence of template selectivity and molecular recognition effects. The experimental results clearly show that this innovative kind of imprinted material can be easily obtained in very polar polymerization environments and that it is characterized by enhanced molecular recognition properties in aqueous buffers and good selectivity towards the template and strictly related molecules.

  13. Molecularly imprinted ultrathin graphitic carbon nitride nanosheets-Based electrochemiluminescence sensing probe for sensitive detection of perfluorooctanoic acid.

    PubMed

    Chen, Sihua; Li, Aimin; Zhang, Lizhi; Gong, Jingming

    2015-10-08

    Driven by the urgent demand for the determination of low level perfluorooctanoic acid (PFOA) present in environment, a novel electrochemiluminescence (ECL) sensor has been first developed for the detection of PFOA using the molecularly imprinted polypyrrole modified two-dimensional ultrathin g-C3N4 (utg-C3N4) nanosheets as a cathodic ECL emitter with S2O8(2-) as coreactant. The prepared molecularly imprinted polymer (MIP) functionalized utg-C3N4 nanosheets (MIP@utg-C3N4) exhibit a stable and significantly amplified ECL signal. It is found that the targets of PFOA could be efficiently oxidized by the electro-generated strong oxidants of SO4(-) (from the reduction of coreactant S2O8(2-)), thus leading to a low yield of the excited utg-C3N4 (g-C3N4*) and finally a decrease in ECL signal. Based on this, a highly sensitive and selective MIP@utg-C3N4-based signal-off ECL sensor is developed for sensing PFOA. Such a newly designed ECL sensor exhibits highly linear over the PFOA concentration in two ranges, from 0.02 to 40.0 ng mL(-1) and 50.0-400.0 ng mL(-1). The detection limit (S/N = 3) is estimated to be 0.01 ng mL(-1) (i.e. 0.01 ppb), comparable to the results obtained by using well-established liquid chromatography-tandem mass spectrometry (LC-MS/MS). Toward practical applications, this low-cost and sensitive assay was successfully applied to measure PFOA in real water samples, showing fine applicability for the detection of PFOA in real samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Nicotine molecularly imprinted polymer: synergy of coordination and hydrogen bonding.

    PubMed

    Huynh, Tan-Phat; B K C, Chandra; Sosnowska, Marta; Sobczak, Janusz W; Nesterov, Vladimir N; D'Souza, Francis; Kutner, Wlodzimierz

    2015-02-15

    Two new bis(2,2'-bithienyl)methane derivatives, one with the zinc phthalocyanine substituent (ZnPc-S16) and the other with the 2-hydroxyethyl substituent (EtOH-S4), were synthesized to serve as functional monomers for biomimetic recognition of nicotine (Nic) by molecular imprinting. Formation of a pre-polymerization complex of the Nic template with ZnPc-S16 and EtOH-S4 was confirmed by both the high negative Gibbs free energy gain, ΔG = -115.95 kJ/mol, calculated using the density functional theory at the B3LYP/3-21G* level, and the high stability constant, Ks = 4.67 × 10(5) M(-1), determined by UV-vis titration in chloroform. A solution of this complex was used to deposit a Nic-templated molecularly imprinted polymer (MIP-Nic) film on an Au electrode of a quartz crystal resonator of EQCM by potentiodynamic electropolymerization. The imprinting factor was as high as ~9.9. Complexation of the Nic molecules by the MIP cavities was monitored with X-ray photoelectron spectroscopy (XPS), as manifested by a negative shift of the binding energy of the Zn 2p3/2 electron of ZnPc-S16 after Nic templating. For sensing applications, simultaneous chronoamperometry (CA) and piezoelectric microgravimetry (PM) measurements were performed under flow-injection analysis conditions. The limit of detection of the CA and PM chemosensing was as low as 40 and 12 µM, respectively. Among them, the CA chemosensing was more selective to the cotinine and myosmine interferences due to the 1.10 V vs. Ag/AgCl discriminating potential of nicotine electro-oxidation applied. Differences in selectivity to the analyte and interferences were interpreted by modeling complexation of Nic and, separately, each of the interferences with a "frozen" MIP-Nic molecular cavity. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. Preliminary evaluation of molecular imprinting of 5-fluorouracil within hydrogels for use as drug delivery systems.

    PubMed

    Singh, Baljit; Chauhan, Nirmala

    2008-09-01

    Molecular imprinting is a new and rapidly evolving technique used to create synthetic receptors and it possesses great potential in a number of applications in the life sciences. Keeping in mind the therapeutic importance of 5-fluorouracil (5-FU) and the technological significance of molecular imprinting polymers, the present study is an attempt to synthesize 2-hydroxyethylmetacrylate- and acrylic acid-based 5-FU imprinted hydrogels. For the synthesis of these hydrogels, N,N'-methylenebisacrylamide was used as a crosslinker, ammonium persulfate as an initiator and N,N,N',N'-tetramethylethylenediamine as an accelerator. Both molecular imprinted polymers (MIPs) and non-imprinted polymers were synthesized at the optimum crosslinker concentration obtained from swelling studies and used to study their recognition affinity, their swelling and the in vitro release dynamics of the drug. It was observed from this study that the recognition affinity of MIPs is increased when these are synthesized in a high concentration template solution.

  16. Molecularly Imprinted Polymers for Ochratoxin A Extraction and Analysis

    PubMed Central

    Yu, Jorn C. C.; Lai, Edward P. C.

    2010-01-01

    Molecularly imprinted polymers (MIPs) are considered as polymeric materials that mimic the functionality of antibodies. MIPs have been utilized for a wide variety of applications in chromatography, solid phase extraction, immunoassays, and sensor recognition. In this article, recent advances of MIPs for the extraction and analysis of ochratoxins are discussed. Selection of functional monomers to bind ochratoxin A (OTA) with high affinities, optimization of extraction procedures, and limitations of MIPs are compared from different reports. The most relevant examples in the literature are described to clearly show how useful these materials are. Strategies on MIP preparation and schemes of analytical methods are also reviewed in order to suggest the next step that would make better use of MIPs in the field of ochratoxin research. The review ends by outlining the remaining issues and impediments. PMID:22069649

  17. Molecularly Imprinted Polymer Nanoparticles for Formaldehyde Sensing with QCM.

    PubMed

    Hussain, Munawar; Kotova, Kira; Lieberzeit, Peter A

    2016-06-30

    Herein, we report on molecularly imprinted polymers (MIPs) for detecting formaldehyde vapors in air streams. A copolymer thin film consisting of styrene, methacrylic acid, and ethylene glycol dimethacrylate on quartz crystal microbalance (QCM) yielded a detection limit of 500 ppb formaldehyde in dry air. Surprisingly, these MIPs showed specific behavior when tested against a range of volatile organic compounds (VOCs), such as acetaldehyde, methanol, formic acid, and dichloromethane. Despite thus being a suitable receptor in principle, the MIPs were not useful for measurements at 50% humidity due to surface saturation by water. This was overcome by introducing primary amino groups into the polymer via allyl amine and by changing the coating morphology from thin film to nanoparticles. This led to the same limit of detection (500 ppb) and selectivity as before, but at the real-life conditions of 50% relative humidity.

  18. Adsorption of β-sitosterol on molecularly imprinted polymer

    NASA Astrophysics Data System (ADS)

    Soekamto, N. H.; Fauziah, St.; Taba, P.; Amran, M. B.

    2017-04-01

    Molecularly Imprinted Polymer (MIP) has been synthesized using methacrylate acid (MAA) as a monomer with hydroxyl and carbonyl functional groups that can react with ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, and β-sitosterol as a template molecule. After the template was removed from the polymer, MIP_TFMAA was obtained. The MIP was used to adsorb β-sitosterol. The amount of β-sitosterol in solution after the adsorption was determined by HPLC. The results showed that the MIP was able to adsorb well the β-sitosterol at a pH 7 and the contact time of 90 min. The kinetic adsorption data obtained for β-sitosterol followed the pseudo-second-order model and consistent with the model of Feundlich isothermal with the adsorption capacity of 1.05 mg/g. The MIP was selective on β-sitosterol because it was able to adsorb β-sitosterol better than cholesterol.

  19. Volatile phenols depletion in red wine using molecular imprinted polymers.

    PubMed

    Teixeira, Rafaela; Dopico-García, Sonia; Andrade, Paula B; Valentão, Patrícia; López-Vilariño, José M; González-Rodríguez, Victoria; Cela-Pérez, Concepción; Silva, Luís R

    2015-12-01

    Wines can be modified by microorganisms during the ageing process, by producing off-flavours like volatile phenols (VP), leading to their deterioration, with great economic losses. The development of methods to recover wines affected by unwanted VP became an important target. Molecular imprinted polymers (MIPs) are synthetic materials with artificially-generated recognition sites for selective extraction of organic compounds from different matrices. In this work, two MIPs to remove unwanted VP from wines were developed and their effects were evaluated. Volatile compounds were determined by GC-FID and GC-IT/MS and phenolic compounds (non-coloured and anthocyanins) by HPLC-DAD. The treatment with MIP-4EG and MIP-4EP significantly reduced the content of 4-ethylguaiacol and 4-ethylphenol, respectively. Nevertheless, the changes observed in wine non-coloured and coloured phenolics and sensorial analysis indicate that their specificity and selectivity regarding off-flavours still needs to be improved.

  20. Molecularly Imprinted Polymer Nanoparticles for Formaldehyde Sensing with QCM

    PubMed Central

    Hussain, Munawar; Kotova, Kira; Lieberzeit, Peter A.

    2016-01-01

    Herein, we report on molecularly imprinted polymers (MIPs) for detecting formaldehyde vapors in air streams. A copolymer thin film consisting of styrene, methacrylic acid, and ethylene glycol dimethacrylate on quartz crystal microbalance (QCM) yielded a detection limit of 500 ppb formaldehyde in dry air. Surprisingly, these MIPs showed specific behavior when tested against a range of volatile organic compounds (VOCs), such as acetaldehyde, methanol, formic acid, and dichloromethane. Despite thus being a suitable receptor in principle, the MIPs were not useful for measurements at 50% humidity due to surface saturation by water. This was overcome by introducing primary amino groups into the polymer via allyl amine and by changing the coating morphology from thin film to nanoparticles. This led to the same limit of detection (500 ppb) and selectivity as before, but at the real-life conditions of 50% relative humidity. PMID:27376287

  1. Molecularly imprinted polymers for ochratoxin a extraction and analysis.

    PubMed

    Yu, Jorn C C; Lai, Edward P C

    2010-06-01

    Molecularly imprinted polymers (MIPs) are considered as polymeric materials that mimic the functionality of antibodies. MIPs have been utilized for a wide variety of applications in chromatography, solid phase extraction, immunoassays, and sensor recognition. In this article, recent advances of MIPs for the extraction and analysis of ochratoxins are discussed. Selection of functional monomers to bind ochratoxin A (OTA) with high affinities, optimization of extraction procedures, and limitations of MIPs are compared from different reports. The most relevant examples in the literature are described to clearly show how useful these materials are. Strategies on MIP preparation and schemes of analytical methods are also reviewed in order to suggest the next step that would make better use of MIPs in the field of ochratoxin research. The review ends by outlining the remaining issues and impediments.

  2. Review of the recent progress in photoresponsive molecularly imprinted polymers containing azobenzene chromophores.

    PubMed

    Wei, Yu-bo; Tang, Qian; Gong, Cheng-bin; Lam, Michael Hon-Wah

    2015-11-05

    Photoresponsive molecularly imprinted polymers (PMIPs) containing azobenzene have received wide research attention in recent years and made notable achievements. This article reviews the recent developments on PMIPs containing azobenzene. Topics include the following: (i) brief introduction of azobenzene, molecularly imprinted polymers, and PMIPs containing azobenzene; (ii) progress in functional monomers, cross-linkers, and polymerization conditions; (iii) preparation methods, properties, applications, as well as advantages and disadvantages of conventional PMIPs; (iv) substrate, preparation method, and applications of photoresponsive surface molecularly imprinted polymers; and (v) some perspectives for further development of PMIPs containing azobenzene.

  3. Mechanisms underlying molecularly imprinted polymer molecular memory and the role of crosslinker: resolving debate on the nature of template recognition in phenylalanine anilide imprinted polymers.

    PubMed

    Olsson, Gustaf D; Karlsson, Björn C G; Shoravi, Siamak; Wiklander, Jesper G; Nicholls, Ian A

    2012-02-01

    A series of molecular dynamics simulations of prepolymerization mixtures for phenylalanine anilide imprinted co-(ethylene glycol dimethacrylate-methacrylic acid) molecularly imprinted polymers have been employed to investigate the mechanistic basis for template selective recognition in these systems. This has provided new insights on the mechanisms underlying template recognition, in particular the significant role played by the crosslinking agent. Importantly, the study supports the occurrence of template self-association events that allows us to resolve debate between the two previously proposed models used to explain this system's underlying recognition mechanisms. Moreover, the complexity of the molecular level events underlying template complexation is highlighted by this study, a factor that should be considered in rational molecularly imprinted polymer design, especially with respect to recognition site heterogeneity.

  4. [Special influence of molecular imprinting technology on traditional Chinese medicine theories].

    PubMed

    Xia, Zan-Shao; He, Fu-Yuan; Deng, Kai-Wen; Liu, Wen-Long; Shi, Ji-Lian; Tang, Yu

    2013-04-01

    To investigate the influence of molecular imprinting phenomena of traditional Chinese medicines (TCMs) on basic theories of TCMs according to current situations of molecular imprinting technology and experimental studies. Fundamental principles of molecular imprinting theory were followed to analyze the material basis for TCM molecules to generate the imprinting phenomena, in order to find other material basis with more direct efficacy in line with the requirements of basic theories and modernization of TCMs. Compared with single-component structures, TCMs and their compound components could create super-molecular compounds through complexation, composition, chelation, inclusion, neutralization, self-assembly and chemical reaction. The material basis of TCMs was super-molecular compounds including single ingredients, and there was an inter-molecule imprinting phenomenon. Therefore, special attention should be paid to inter-super-molecule imprinting actions in studies on TCM property, quality control, processing, drug preparation and pharmacology. The compatibility of TCM compounds could significantly change the action. The material basis of TCMs is super-molecular compounds based on single molecular groups. Super-molecules and molecular groups act rules, which is another difference between TCM compounds and single molecular drugs.

  5. Fingerprint-imprinted polymer: rational selection of peptide epitope templates for the determination of proteins by molecularly imprinted polymers.

    PubMed

    Bossi, Alessandra M; Sharma, Piyush S; Montana, Luca; Zoccatelli, Gianni; Laub, Orgad; Levi, Raphael

    2012-05-01

    The pool of peptides composing a protein allows for its distinctive identification in a process named fingerprint (FP) analysis. Here, the FP concept is used to develop a method for the rational preparation of molecularly imprinted polymers (MIPs) for protein recognition. The fingerprint imprinting (FIP) is based on the following: (1) the in silico cleavage of the protein sequence of interest with specific agents; (2) the screening of all the peptide sequences generated against the UniProtKB database in order to allow for the rational selection of distinctive and unique peptides (named as epitopes) of the target protein; (3) the selected epitopes are synthesized and used as templates for the molecular imprinting process. To prove the principle, NT-proBNP, a marker of the risk of cardiovascular events, was chosen as an example. The in silico analysis of the NT-proBNP sequence allowed us to individuate the peptide candidates, which were next used as templates for the preparation of NT-pro-BNP-specific FIPs and tested for their ability to bind the NT-proBNP peptides in complex samples. Results indicated an imprinting factor, IF, of ~10, a binding capacity of 0.5-2 mg/g, and the ability to rebind 40% of the template in a complex sample, composed of the whole digests of NT-proBNP.

  6. Core-shell nanostructured molecular imprinting fluorescent chemosensor for selective detection of atrazine herbicide.

    PubMed

    Liu, Renyong; Guan, Guijian; Wang, Suhua; Zhang, Zhongping

    2011-01-07

    To convert the binding events on molecularly imprinted polymers (MIPs) into physically detectable signals and to extract the templates completely are the great challenges in developing MIP-based sensors. In this paper, a core-shell nanostructure was employed in constructing the MIP chemosensor for the improvements of template extraction efficiency and imprinted sites accessibility. Vinyl-substituted zinc(II) protoporphyrin (ZnPP) was used as both fluorescent reporter and functional monomer to synthesize atrazine-imprinted polymer shell at silica nanoparticle cores. The template atrazine coordinates with the Lewis acid binding site Zn of ZnPP to form a complex for the molecular imprinting polymerization. These imprinted sites are located in polymer matrix of the thin shells (~8 nm), possessing better accessibility and lower mass-transfer resistance for the target molecules. The fluorescence properties of ZnPP around the imprinted sites will vary upon rebinding of atrazine to these imprinted sites, realizing the conversion of rebinding events into detectable signals by monitoring fluorescence spectra. This MIP probe showed a limit of detection (LOD) of about 1.8 μM for atrazine detection. The core-shell nanostructured MIP method not only improves the sensitivity, but also shows high selectivity for atrazine detection when compared with the non-molecular imprinted counterparts.

  7. Characterization of molecularly imprinted polymer nanoparticles by photon correlation spectroscopy.

    PubMed

    Malm, Björn; Yoshimatsu, Keiichi; Ye, Lei; Krozer, Anatol

    2014-12-01

    We follow template-binding induced aggregation of nanoparticles enantioselectively imprinted against (S)-propranolol, and the non-imprinted ones, using photon correlation spectroscopy (dynamic light scattering). The method requires no separation steps. We have characterized binding of (R,S)-propranolol to the imprinted polymers and determined the degree of non-specificity by comparing the specific binding with the results obtained using non-imprinted nanoparticles. Using (S)-propranolol as a template for binding to (S)-imprinted nanoparticle, and (R)-propranolol as a non-specific control, we have determined range of concentrations where chiral recognition can be observed. By studying aggregation induced by three analytes related to propranolol, atenolol, betaxolol, and 1-amino-3-(naphthalen-1-yloxy)propan-2-ol, we were able to determine which parts of the template are involved in the specific binding, discuss several details of specific adsorption, and the structure of the imprinted site.

  8. Biomimetic estimation of glucose using non-molecular and molecular imprinted polymer nanosponges.

    PubMed

    Deshmukh, Kiran; Tanwar, Yuveraj Singh; Shende, Pravin; Cavalli, Roberta

    2015-10-15

    The aim of the present work was to develop biomimetics for glucose estimation using molecularly and non-molecularly imprinted polymers of pyromellitic dianhydride crosslinked β-cyclodextrin based nanosponges. The ionic association of glucose phosphate to nanosponges by polymerization reaction and removal of glucose created molecular imprinted polymer (MIP)-nanosponges with affinity for glucose binding. Particle size, zeta potential, glucose binding studies and FTIR were used to characterize molecular and non-molecular imprinted polymer (NIP) nanosponges. Particle size of the nanosponges was found in the range of 450.81±5.33 nm to 550.63±8.14 nm with low polydispersity index. MIP-nanosponges retained a relatively large population of pores in the nano-range, while NIP was related to the nonporous materials with weak interaction and had poor tendency to aggregate. Nanosponges showed the variation in binding capacities and specificities; and also exhibited a similar degree of swelling. Moreover electrostatic force of attraction and cavities specific fitting of glucose in MIP-nanosponges might be due to advance selectivity and affinity for glucose. FTIR study showed glucose molecules might be entered into the selective binding cavities, which were created by the extraction of template molecules It is concluded that nanosized MIP-nanosponges have advantages over conventional NIP due to diffusion of template in the formed cavity as of its high surface area.

  9. Characterization of molecularly imprinted polymers using a new polar solvent titration method.

    PubMed

    Song, Di; Zhang, Yagang; Geer, Michael F; Shimizu, Ken D

    2014-07-01

    A new method of characterizing molecularly imprinted polymers (MIPs) was developed and tested, which provides a more accurate means of identifying and measuring the molecular imprinting effect. In the new polar solvent titration method, a series of imprinted and non-imprinted polymers were prepared in solutions containing increasing concentrations of a polar solvent. The polar solvent additives systematically disrupted the templation and monomer aggregation processes in the prepolymerization solutions, and the extent of disruption was captured by the polymerization process. The changes in binding capacity within each series of polymers were measured, providing a quantitative assessment of the templation and monomer aggregation processes in the imprinted and non-imprinted polymers. The new method was tested using three different diphenyl phosphate imprinted polymers made using three different urea functional monomers. Each monomer had varying efficiencies of templation and monomer aggregation. The new MIP characterization method was found to have several advantages. To independently verify the new characterization method, the MIPs were also characterized using traditional binding isotherm analyses. The two methods appeared to give consistent conclusions. First, the polar solvent titration method is less susceptible to false positives in identifying the imprinting effect. Second, the method is able to differentiate and quantify changes in binding capacity, as measured at a fixed guest and polymer concentration, arising from templation or monomer aggregation processes in the prepolymerization solution. Third, the method was also easy to carry out, taking advantage of the ease of preparing MIPs.

  10. Removal of Toxic Mercury from Petroleum Oil by Newly Synthesized Molecularly-Imprinted Polymer

    PubMed Central

    Khairi, Nor Ain Shahera; Yusof, Nor Azah; Abdullah, Abdul Halim; Mohammad, Faruq

    2015-01-01

    In recent years, molecularly-imprinted polymers (MIPs) have attracted the attention of several researchers due to their capability for molecular recognition, easiness of preparation, stability and cost-effective production. By taking advantage of these facts, Hg(II) imprinted and non-imprinted copolymers were prepared by polymerizing mercury nitrate stock solution (or without it) with methacrylic acid (MAA), 2-hydroxyl ethyl methacrylate (HEMA), methanol and ethylene glycol dimethacrylate (EGDMA) as the monomer, co-monomer solvent (porogen) and cross-linker, respectively. Thus, the formed Hg(II) imprinted polymer was characterized by using Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), Brunauer, Emmett and Teller (BET) and thermal gravimetric analysis (TGA). The separation and preconcentration characteristics of Hg(II) imprinted polymer were investigated by solid phase extraction (SPE) procedures, and an optimal pH of 7 was investigated as ideal. The specific surface area of the Hg(II) imprinted polymer was found to be 19.45 m2/g with a size range from 100 to 140 µm in diameter. The maximum adsorption capacity was observed to be 1.11 mg/g of Hg(II) imprinted beads with 87.54% removal of Hg(II) ions within the first 5 min. The results of the study therefore confirm that the Hg(II) imprinted polymer can be used multiple times without significantly losing its adsorption capacity. PMID:26006226

  11. Magnetic-graphene based molecularly imprinted polymer nanocomposite for the recognition of bovine hemoglobin.

    PubMed

    Guo, Junxia; Wang, Yuzhi; Liu, Yanjin; Zhang, Cenjin; Zhou, Yigang

    2015-11-01

    The protein imprinted technique combining surface imprinting and nanomaterials has been an attractive strategy for recognition and rapid separation of proteins. In this work, magnetic-graphene (MG) was chosen as the supporting substrate for the magnetic nanomaterials, which served to absorb the targeting imprinting molecules, bovine hemoglobin (BHb). Acryl amide (AAm) with a high affinity to BHb and N,N'- methylenebisacrylamide (MBA) were selected as the functional monomer and cross-linking agent, respectively. After in-situ polymerization, the proposed magnetic-graphene based molecularly imprinted polymer (MG-MIP) was obtained with a further extraction step of imprinted BHb. Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), raman spectroscopy(RS), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM) were employed to characterize the resulted MG-MIP. The maximum adsorption capability (Qmax) was determined by Langmuir Isotherm Plots and was 186.73 mg/g for imprinted nanomaterials (MIP) with an imprinting factor of 1.96. The selectivity of MG-MIP was investigated by using several proteins that are different in molecular mass and isoelectric points as the reference. The results showed that the shape memory effect of imprinted cavities, the size of proteins and the charge effect of proteins were the major factors for the selective recognition. The proposed method was also employed to specifically capture BHb from a binary protein mixture.

  12. Removal of toxic mercury from petroleum oil by newly synthesized molecularly-imprinted polymer.

    PubMed

    Khairi, Nor Ain Shahera; Yusof, Nor Azah; Abdullah, Abdul Halim; Mohammad, Faruq

    2015-05-08

    In recent years, molecularly-imprinted polymers (MIPs) have attracted the attention of several researchers due to their capability for molecular recognition, easiness of preparation, stability and cost-effective production. By taking advantage of these facts, Hg(II) imprinted and non-imprinted copolymers were prepared by polymerizing mercury nitrate stock solution (or without it) with methacrylic acid (MAA), 2-hydroxyl ethyl methacrylate (HEMA), methanol and ethylene glycol dimethacrylate (EGDMA) as the monomer, co-monomer solvent (porogen) and cross-linker, respectively. Thus, the formed Hg(II) imprinted polymer was characterized by using Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), Brunauer, Emmett and Teller (BET) and thermal gravimetric analysis (TGA). The separation and preconcentration characteristics of Hg(II) imprinted polymer were investigated by solid phase extraction (SPE) procedures, and an optimal pH of 7 was investigated as ideal. The specific surface area of the Hg(II) imprinted polymer was found to be 19.45 m2/g with a size range from 100 to 140 µm in diameter. The maximum adsorption capacity was observed to be 1.11 mg/g of Hg(II) imprinted beads with 87.54% removal of Hg(II) ions within the first 5 min. The results of the study therefore confirm that the Hg(II) imprinted polymer can be used multiple times without significantly losing its adsorption capacity.

  13. Preparation of melamine molecularly imprinted polymer by computer-aided design.

    PubMed

    Wang, Yan; Liu, Jun-Bo; Tang, Shan-Shan; Jin, Rui-Fa

    2015-08-01

    Melamine was chosen as template, methacrylic acid was chosen as functional monomer, and divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethylacrylate were chosen as cross-linking agents, respectively. The WB97XD/6-31G(d, p) method was used to calculate the geometry optimization of the different imprinting ratios, the action sites, the bonding situation, and the optimization of the cross-linking agents. The nature of the imprinting effect was also studied by the atoms in molecules theory. The theoretical results showed that melamine interacts with methacrylic acid by hydrogen bonding, and the melamine molecularly imprinted polymers with a molar ratio of 1:6 have the most hydrogen bonds and the most stable structure. Divinylbenzene is the best cross-linking agent for the melamine molecularly imprinted polymers. The melamine molecularly imprinted polymers were synthesized by precipitation polymerization. The results showed that the maximum adsorption capacity for molecularly imprinted polymers towards melamine is 19.84 mg/g, and the adsorption quantity of the polymers to melamine is obviously higher than that of cyromazine, cyanuric acid, and trithiocyanuric in milk. This study could provide theoretical and experimental references for the screening of the imprinting ratio and the cross-linking agent for the given template and monomer system. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Molecular imprinting: a tool of modern chemistry for the preparation of highly selective monolithic sorbents

    NASA Astrophysics Data System (ADS)

    Vlakh, E. G.; Korzhikov, V. A.; Hubina, A. V.; Tennikova, T. B.

    2015-09-01

    Characteristic features of the synthesis of molecularly imprinted polymer systems used as sorbents for separation of complex mixtures into components are discussed. The data about the molecules imprinted in monoliths of various natures and shapes are integrated. Examples of application of new-generation separating media are discussed. Data on the utilization of the molecular imprinting principle for the fabrication of supermacroporous monolithic cryogels specific to particular molecules, which is important for the design of smart biomaterials, are analyzed. The bibliography includes 293 references.

  15. Molecular imprinting sensor based on quantum weak measurement.

    PubMed

    Li, Dongmei; He, Qinghua; He, Yonghong; Xin, Meiguo; Zhang, Yilong; Shen, Zhiyuan

    2017-03-10

    A new type of sensing protocol, based on a high precision metrology of quantum weak measurement, was first proposed for molecularly imprinted polymers (MIP) sensor. The feasibility, sensitivity and selectivity of weak measurement based MIP (WMMIP) sensor were experimentally demonstrated with bovine serum albumin (BSA). Weak measurement system exhibits high sensitivity to the optical phase shift corresponding to the refractive index change, which is induced by the specific capture of target protein molecules with its recognition sites. The recognition process can be finally characterized by the central wavelength shift of output spectra through weak value amplification. In our experiment, we prepared BSA@MIP with modified reversed-phase microemulsion method, and coated it on the internal surface of measuring channels assembled into the Mach-Zehnder (MZ) interferometer based optical weak measurement system. The design of this home-built optical system makes it possible to detect analyte in real time. The dynamic process of the specific adsorption and concentration response to BSA from 5×10(-4) to 5×10(-1)μg/L was achieved with a limit of detection (LOD) of 8.01×10(-12)g/L. This WMMIP shows superiority in accuracy, fast response and low cost. Furthermore, real-time monitoring system can creatively promote the performance of MIP in molecular analysis.

  16. Improving the imprinting effect by optimizing template:monomer:cross-linker ratios in a molecularly imprinted polymer for sulfadimethoxine.

    PubMed

    Tom, Lou Ann; Schneck, Nicole A; Walter, Carla

    2012-11-15

    Four non-covalently prepared molecularly imprinted polymers (MIPs) for sulfadimethoxine (SDM) were prepared using different ratios of SDM template, methacrylic acid monomer, and ethylene glycol dimethacrylate cross-linker. The imprinting factor (IF) was calculated by comparing the retention of SDM on the imprinted polymer with a comparable non-imprinted polymer. The template:monomer:cross-linker ratio of 1:6:20 resulted in an IF of 3.94 which is higher than found in previous studies. A significant decrease in IF to 0.89 when template:cross-linker ratio was 1:40 contradicts most literature where higher cross-linker concentration improves selectivity. IF was 4.36 when 20% water was added to the acetonitrile HPLC mobile phase during evaluation. Retention of SDM increased as water concentration changed as: 20, 40, 0, 60 and 70%, indicating a combination of shape recognition, hydrogen bonding and hydrophobic interactions contributing to retention of analyte. The MIP has the potential for use in SPE for purification and concentration of SDM and with further optimization, possibly direct HPLC analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Molecularly imprinted polymers prepared using protein-conjugated cleavable monomers followed by site-specific post-imprinting introduction of fluorescent reporter molecules.

    PubMed

    Suga, Yusuke; Sunayama, Hirobumi; Ooya, Tooru; Takeuchi, Toshifumi

    2013-10-04

    Molecularly imprinted polymers were prepared using a protein-conjugated disulfide cleavable monomer. After removing the protein by disulfide reduction, a thiol-reactive fluorophore was introduced into the thiol residue located only inside the imprinted cavity, resulting in specific transduction of the binding events into fluorescence spectral change.

  18. Development of ocular drug delivery systems using molecularly imprinted soft contact lenses.

    PubMed

    Tashakori-Sabzevar, Faezeh; Mohajeri, Seyed Ahmad

    2015-05-01

    Recently, significant advances have been made in order to optimize drug delivery to ocular tissues. The main problems in ocular drug delivery are poor bioavailability and uncontrollable drug delivery of conventional ophthalmic preparations (e.g. eye drops). Hydrogels have been investigated since 1965 as new ocular drug delivery systems. Increase of hydrogel loading capacity, optimization of drug residence time on the ocular surface and biocompatibility with the eye tissue has been the main focus of previous studies. Molecular imprinting technology provided the opportunity to fulfill the above-mentioned objectives. Molecularly imprinted soft contact lenses (SCLs) have high potentials as novel drug delivery systems for the treatment of eye disorders. This technique is used for the preparation of polymers with specific binding sites for a template molecule. Previous studies indicated that molecular imprinting technology could be successfully applied for the preparation of SCLs as ocular drug delivery systems. Previous research, particularly in vivo studies, demonstrated that molecular imprinting is a versatile and effective method in optimizing the drug release behavior and enhancing the loading capacity of SCLs as new ocular drug delivery systems. This review highlights various potentials of molecularly imprinted contact lenses in enhancing the drug-loading capacity and controlling the drug release, compared to other ocular drug delivery systems. We have also studied the effects of contributing factors such as the type of comonomer, template/functional monomer molar ratio, crosslinker concentration in drug-loading capacity, and the release properties of molecularly imprinted hydrogels.

  19. Synthesis and Characterization of Molecular Imprinting Polymer Microspheres of Piperine: Extraction of Piperine from Spiked Urine.

    PubMed

    Roland, Rachel Marcella; Bhawani, Showkat Ahmad

    2016-01-01

    Molecularly imprinted polymer (MIP) microspheres for Piperine were synthesized by precipitation polymerization with a noncovalent approach. In this research Piperine was used as a template, acrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and 2,2'-azobisisobutyronitrile (AIBN) as an initiator and acetonitrile as a solvent. The imprinted and nonimprinted polymer particles were characterized by using Fourier transform infrared spectroscopy (FT-IR) and Scanning Electron Microscopy (SEM). The synthesized polymer particles were further evaluated for their rebinding efficiency by batch binding assay. The highly selected imprinted polymer for Piperine was MIP 3 with a composition (molar ratio) of 0.5 : 3 : 8, template : monomer : cross-linker, respectively. The MIP 3 exhibits highest binding capacity (84.94%) as compared to other imprinted and nonimprinted polymers. The extraction efficiency of highly selected imprinted polymer of Piperine from spiked urine was above 80%.

  20. Tetracycline speciation during molecular imprinting in xerogels results in class-selective binding.

    PubMed

    Mojica, Elmer-Rico E; Autschbach, Jochen; Bright, Frank V; Aga, Diana S

    2011-02-21

    The creation of tetracycline (TC) responsive molecularly imprinted xerogels (MIXs) was investigated using electronic absorbance, liquid chromatography-ion-trap mass spectrometry (LC-ITMS), and first-principles theory. Experimental results show that the template molecule converts to its epimer, 4-epitetracycline (ETC), during the imprinting process. Additionally, end capping of the MIX surface silanols transforms TC into anhydrotetracycline (ATC) and 4-epianhydrotetracycline (EATC). Hence, despite aiming to imprint for a single analyte (TC), one simultaneously imprints for up to four analogs (TC, ETC, EATC and ATC) within a MIX. Binding studies using LC-MS showed the binding of the prepared xerogels with the four analogs. In some formulations, preferential uptake of ETC, EATC and ATC relative to the template molecule (TC) was observed. Computations of the interaction energies between silane monomers and the four analogs reveal that ETC, EATC and ATC have higher interaction energies and are more likely to be imprinted in comparison to TC.

  1. Synthesis and Characterization of Molecular Imprinting Polymer Microspheres of Piperine: Extraction of Piperine from Spiked Urine

    PubMed Central

    Roland, Rachel Marcella

    2016-01-01

    Molecularly imprinted polymer (MIP) microspheres for Piperine were synthesized by precipitation polymerization with a noncovalent approach. In this research Piperine was used as a template, acrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and 2,2′-azobisisobutyronitrile (AIBN) as an initiator and acetonitrile as a solvent. The imprinted and nonimprinted polymer particles were characterized by using Fourier transform infrared spectroscopy (FT-IR) and Scanning Electron Microscopy (SEM). The synthesized polymer particles were further evaluated for their rebinding efficiency by batch binding assay. The highly selected imprinted polymer for Piperine was MIP 3 with a composition (molar ratio) of 0.5 : 3 : 8, template : monomer : cross-linker, respectively. The MIP 3 exhibits highest binding capacity (84.94%) as compared to other imprinted and nonimprinted polymers. The extraction efficiency of highly selected imprinted polymer of Piperine from spiked urine was above 80%. PMID:28018704

  2. Surface plasmon resonance sensor based on magnetic molecularly imprinted polymers amplification for pesticide recognition.

    PubMed

    Yao, Gui-Hong; Liang, Ru-Ping; Huang, Chun-Fang; Wang, Ying; Qiu, Jian-Ding

    2013-12-17

    We reported here a method to enhance detection sensitivity in surface plasmon resonance (SPR) spectroscopy integrated with a surface molecular imprinting recognition system and employing magnetic molecular imprinting polymer nanoparticles for amplifying SPR response. The proposed magnetic molecular imprinting polymer was designed by self-polymerization of dopamine on the Fe3O4 NPs surface in weak base aqueous solution in the presence of template chlorpyrifos (CPF). The imprinted Fe3O4@polydopamine nanoparticles (Fe3O4@PDA NPs) were characterized by Fourier transform infrared spectroscopy, UV-vis absorption spectroscopy, and transmission electron microscopy. The biosensor showed a good linear relationship between the SPR angle shift and the chlorpyrifos concentration over a range from 0.001 to 10 μM with a detection limit of 0.76 nM. A significant increase in sensitivity was therefore afforded through the use of imprinted Fe3O4@PDA NPs as an amplifier, and meanwhile, the imprinted Fe3O4@PDA NPs had an excellent recognition capacity to chlorpyrifos over other pesticides. The excellent sensitivity and selectivity and high stability of the designed biosensor make this magnetic imprinted Fe3O4@PDA NP an attractive recognition element for various SPR sensors for detecting pesticide residuals and other environmentally deleterious chemicals.

  3. Magnetic deep eutectic solvents molecularly imprinted polymers for the selective recognition and separation of protein.

    PubMed

    Liu, Yanjin; Wang, Yuzhi; Dai, Qingzhou; Zhou, Yigang

    2016-09-14

    A novel and facile magnetic deep eutectic solvents (DES) molecularly imprinted polymers (MIPs) for the selective recognition and separation of Bovine hemoglobin (BHb) was prepared. The new-type DES was adopted as the functional monomer which would bring molecular imprinted technology to a new direction. The amounts of DES were optimized. The obtained magnetic DES-MIPs were characterized with fourier transform infrared spectrometry (FT-IR), thermogravimetric analysis (TGA), field emission scanning electron microscope (FESEM), dynamic light scattering (DLS), elemental analysis and vibrating sample magnetometer (VSM). The results suggested that the imprinted polymers were successfully formed and possessed a charming magnetism. The maximum adsorption capability (Qmax) and dissociation constant (KL) were analyzed by Langmuir isotherms (R(2) = 0.9983) and the value were estimated to be 175.44 mg/g and 0.035 mg/mL for the imprinted particles. And the imprinted particles showed a high imprinting factor of 4.77. In addition, the magnetic DES-MIPs presented outstanding recognition specificity and selectivity so that it can be utilized to separate template protein from the mixture of proteins and real samples. Last but not least, the combination of deep eutectic solvents and molecular imprinted technology in this paper provides a new perspective for the recognition and separation of proteins. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Novel molecularly imprinted polymer prepared by nanoattapulgite as matrix for selective solid-phase extraction of diethylstilbestrol.

    PubMed

    Zhao, Chuande; Ji, Yongsheng; Shao, Yongliang; Jiang, Xiaoman; Zhang, Haixia

    2009-10-30

    Using nanoattapulgite as matrix, both diethylstilbestrol surface molecularly imprinted polymer and non-imprinted polymer were synthesized in this work. Compared with each other, the diethylstilbestrol surface molecularly imprinted polymer is superior to non-imprinted polymer in adsorption capacity, selectivity and mass transfer property. The maximum static adsorption capacities of diethylstilbestrol surface molecularly imprinted polymer, non-imprinted polymer and nanoattapulgite for diethylstilbestrol was 105.14, 78.54 and 28.50 mg g(-1), respectively. As the packing material of solid-phase extraction, the diethylstilbestrol surface molecularly imprinted polymer has been applied to concentrating diethylstilbestrol in pond water and fish samples. A corresponding analytical method to determine diethylstilbestrol has been developed. The limit of detection for diethylstilbestrol in pond water sample and fish samples were 3 microg L(-1) and 15 microg kg(-1).

  5. Molecular imprinted photonic crystal hydrogels for the rapid and label-free detection of imidacloprid.

    PubMed

    Wang, Xuan; Mu, Zhongde; Liu, Ran; Pu, Yuepu; Yin, Lihong

    2013-12-15

    A novel sensor for the rapid and label-free detection of imidacloprid was developed based on the combination of a colloidal crystal templating method and a molecular imprinting technique. The molecular imprinted photonic hydrogel film was prepared with methacrylic acid as monomers, ethylene glycol dimethylacrylate as cross-linkers and imidacloprid as imprinting template molecules. When the colloidal crystal template and the molecularly imprinted template was removed, the resulted MIPH film possessed a highly ordered three-dimensional macroporous structure with nanocavities. The response of the MIPH film to imidacloprid in aqueous solution can be detected through a readable Bragg diffraction red shift. When the concentration of imidacloprid increased from 10(-13) to 10(-7) g/mL, the Bragg diffraction peak shifted from 551 to 589 nm, while there were no obvious peak shifts for thiamethoxam and acetamiprid. This sensor which comprises of no label techniques and expensive instruments has potential application for the detection of trace imidacloprid.

  6. Towards analysis of mykotoxins in beverages with molecularly imprinted polymers for deoxynivalenol and zearalenone.

    PubMed

    Weiss, R; Mizaikoff, B

    2002-03-01

    Due to ease of use and generally cost effective production molecularly imprinted polymers offer the possibility generating highly selective separation and enrichment materials. Therefore, they are considered a serious competitor to conventional biological agents such as antibodies, proteins and cells for affinity separations. Molecular imprinting applied in the present study is based on non-covalent self-assembly of the template with functional monomers prior to polymerization. Free radical polymerization with a cross-linking monomer is stabilizing (freezing) these template-functional monomer complexes, resulting in a mechanically and thermally stable polymer. After template extraction, rebinding may take place via non-covalent interactions.Selective polymeric phases intended for use in solid-phase extraction of deoxynivalenol (DON) and zearalenone (ZON) from beverages have been prepared [1]. Using crystalline deoxynivalenol, zearalenone and quercetin, molecularly imprinted polymers (MIPs) have been developed by a non-covalent imprinting approach via photo initiated addition polymerization. Prepared polymers are based on 4-vinylpyridine (4-VP) as functional monomer and ethylenglycoldimethacrylat (EDMA) as crosslinking monomer. Selectivity of generated molecularly imprinted polymers has been investigated by application of prepared MIPs as stationary phase in high pressure liquid chromatography (HPLC) experiments. Retention and elution behavior of template compounds were determined and compared. Achieved results promise future application of molecularly imprinted polymers as highly selective matrix for clean-up and enrichment of deoxynivalenol and zearalenone from natural sources such as grains and beer.

  7. Preparation of a novel molecularly imprinted polymer for the highly selective extraction of baicalin.

    PubMed

    Liu, Xiao; Zhang, Wenpeng; Chen, Zilin

    2015-12-01

    The selective extraction of baicalin is important to its quality control especially when the matrices are complicated. In this work, a novel molecularly imprinted polymer was prepared for the selective extraction of baicalin in herbs. The molecularly imprinted polymer was synthesized by the copolymerization of 4-vinyl pyridine and ethylene glycol dimethacrylate in the presence of baicalin by a precipitation polymerization method. After the optimization of parameters for molecularly imprinted polymer preparation, including the functional monomer, porogen, sampling solvent, and washing solvent, good selectivity was obtained, with an imprinting factor of about 4, which is much better than that achieved by the bulk-polymerization method. The performances of the prepared molecularly imprinted polymers were systematically investigated, including adsorption kinetics, isotherm experiment, and Scatchard analysis. On the basis of the good adsorptive capability of the prepared molecularly imprinted polymer, it was also applied for the pretreatment of baicalin in Scutellaria baicalensis Georgi. The result showed that most of the matrices were removed and baicalin was selectively enriched.

  8. Electrochemical sensors based on magnetic molecularly imprinted polymers: A review.

    PubMed

    Yáñez-Sedeño, Paloma; Campuzano, Susana; Pingarrón, José M

    2017-04-01

    Participation of magnetic component in molecularly imprinted polymers (MIPs) has facilitated enormously the incorporation of these polymeric materials on electrode surfaces allowing the design of electrochemical sensors with very attractive analytical characteristics in terms of simplicity, reproducibility, low fabrication cost, high sensitivity and selectivity and rapid assay time. The magnetically susceptible resultant MIPs (MMIPs) allowed a simple and fast elution of the template molecules from MMIPs, are easily and faster collected without filtration, centrifugation or other complex operations and are also faster assembled and removed from the electrode surface by simply using an external magnetic field. A wide range of different (nano)materials such as gold nanoparticles (AuNPs), graphene oxide, single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs) as well as different electrode modifiers (ionic liquids (ILs) and surfactants/dispersants) have been incorporated into the MMIPs to improve the analytical performance of the resulting electrochemical sensors which have demonstrated great promise for determination of relevant analytes in environmental, food and clinical analyses.

  9. Quartz crystal microbalance sensor for organic vapor detection based on molecularly imprinted polymers.

    PubMed

    Fu, Yi; Finklea, Harry O

    2003-10-15

    Molecularly imprinted polymers on quartz crystal microbalances (QCM) are examined for their ability to detect vapors of small organic molecules with greater sensitivity and selectivity than the traditional amorphous polymer coatings. Hydroquinone and phenol serve as noncovalently bound templates that generate shape-selective cavities in a poly(acrylic) or poly(methacrylic) polymer matrix. The imprinted polymers are immobilized on the piezoelectric crystal surface via a precoated poly(isobutylene) layer. The behavior of the imprinted polymer films is characterized by the dynamic and steady-state response of the QCM frequency to pulses of organic vapors in dry air. The apparent partition coefficients are determined for imprinted and nonimprinted polymers prepared by two synthetic methods and for varying mole ratios of template to monomer. The hydroquinone-imprinted polymers and, to a lesser extent, the phenol-imprinted polymers exhibit greater sensitivity and higher selectivity than the nonimprinted polymers toward organic vapors that are structurally related to the templates. These results indicate that molecularly imprinted polymers are promising for the development of selective piezoelectric sensors for organic vapor detection.

  10. Molecularly imprinted titania nanoparticles for selective recognition and assay of uric acid

    NASA Astrophysics Data System (ADS)

    Mujahid, Adnan; Khan, Aimen Idrees; Afzal, Adeel; Hussain, Tajamal; Raza, Muhammad Hamid; Shah, Asma Tufail; uz Zaman, Waheed

    2015-06-01

    Molecularly imprinted titania nanoparticles are su ccessfully synthesized by sol-gel method for the selective recognition of uric acid. Atomic force microscopy is used to study the morphology of uric acid imprinted titania nanoparticles with diameter in the range of 100-150 nm. Scanning electron microscopy images of thick titania layer indicate the formation of fine network of titania nanoparticles with uniform distribution. Molecular imprinting of uric acid as well as its subsequent washing is confirmed by Fourier transformation infrared spectroscopy measurements. Uric acid rebinding studies reveal the recognition capability of imprinted particles in the range of 0.01-0.095 mmol, which is applicable in monitoring normal to elevated levels of uric acid in human blood. The optical shift (signal) of imprinted particles is six times higher in comparison with non-imprinted particles for the same concentration of uric acid. Imprinted titania particles have shown substantially reduced binding affinity toward interfering and structurally related substances, e.g. ascorbic acid and guanine. These results suggest the possible application of titania nanoparticles in uric acid recognition and quantification in blood serum.

  11. Determination of clenbuterol in pork and potable water samples by molecularly imprinted polymer through the use of covalent imprinting method.

    PubMed

    Tang, Yiwei; Lan, Jianxing; Gao, Xue; Liu, Xiuying; Zhang, Defu; Wei, Liqiao; Gao, Ziyuan; Li, Jianrong

    2016-01-01

    A novel molecularly imprinted polymer (MIP) for efficient separation and concentration of clenbuterol (CLB) was synthesized by covalent imprinting approach using CLB derivative as functional monomer. The MIPs synthesized were characterized by scanning electron microscope, nitrogen adsorption analysis, Fourier transform infrared spectrometer, and thermo-gravimetric analysis. The binding experimental results showed that the MIPs synthesized had fast adsorption kinetic (20 min at 25 mg L(-1)), high adsorption capacity and specific recognition ability for the analyte. In addition, the MIPs synthesized were successfully used as solid-phase sorbent for CLB sample preparation to be analyzed by high performance liquid chromatography with ultraviolet detector. Under optimized experimental conditions, the linear range of the calibration curve was 5-80 μg L(-1) (R(2) = 0.9938). The proposed method was also applied to the analysis of CLB in pork and potable water samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Determination of melamine in aquaculture feed samples based on molecularly imprinted solid-phase extraction.

    PubMed

    Lian, Ziru; Liang, Zhenlin; Wang, Jiangtao

    2015-10-01

    This research highlights the application of highly efficient molecularly imprinted solid-phase extraction for the preconcentration and analysis of melamine in aquaculture feed samples. Melamine-imprinted polymers were synthesized employing methacrylic acid and ethylene glycol dimethacrylate as functional monomer and cross-linker, respectively. The characteristics of obtained polymers were evaluated by scanning electron microscopy, Fourier transform infrared spectroscopy and binding experiments. The imprinted polymers showed an excellent adsorption ability for melamine and were applied as special solid-phase extraction sorbents for the selective cleanup of melamine. An off-line molecularly imprinted solid-phase extraction procedure was developed for the separation and enrichment of melamine from aquaculture feed samples prior to high-performance liquid chromatography analysis. Optimum molecularly imprinted solid-phase extraction conditions led to recoveries of the target in spiked feed samples in the range 84.6-96.6% and the relative standard deviation less than 3.38% (n = 3). The aquaculture feed sample was determined, and there was no melamine found. The results showed that the molecularly imprinted solid-phase extraction protocols permitted the sensitive, uncomplicated and inexpensive separation and pre-treatment of melamine in aquaculture feed samples.

  13. A Novel Methodology for Metal Ion Separation Based on Molecularly Imprinting

    SciTech Connect

    Zuo, Xiaobin; Mosha, Donnati; Hassan, Mansour M.; Givens, Richard S.; Busch, Daryle H.

    2004-03-31

    The siderophore-based extraction of iron from the soil by bacteria is proposed as a model for a new separation methodology labeled the soil poutice, a molecular device that would selectively retrieve the complex of a targeted metal ion. In this report we described the synthesis and characterization of molecularly imprinted polymers and their application in the specific recognition of macrocyclic metal complexes. The imprinting is based on non-covalent interactions such as hydrogen bonding, electrostatic attractions and minor metal-ligand coordination. Good rebinding capacity for the imprinting metal complex was observed in acetonitrile as well as in water. The polymers are resistant to strong acids and oxidizing agents and showed an increase of rebinding capacity during cycles of reuse. The imprinting procedure, combined with the previously known selective chelation of macrocyclic ligands, supports the feasibility of a new methodology that can be used to extract waste metal ions effectively and selectively from soils and ground water.

  14. Design of molecularly imprinted polymers for diphenylamine sensing.

    PubMed

    Granado, V L V; Rudnitskaya, A; Oliveira, J A B P; Gomes, M T S R

    2012-05-30

    A series of the polymers imprinted with diphenylamine (DPA) and respective non imprinted polymers were synthesized using precipitation polymerization. Synthesized polymers were characterized by Fourier Transform Infra-Red spectroscopy with Total Attenuated Reflectance (FTIR-ATR), Scanning Electron Microscopy (SEM) and equilibrium batch re-binding experiments. Influence of the synthesis conditions, namely monomer/template ratio and reaction duration, on the polymer binding capacity and selectivity towards aromatic compounds was investigated. Binding behavior of MIP was described using Freundlich isotherm. Significance of the effects of the synthesis conditions on the polymer properties was evaluated using ANOVA. MIPs synthesized at different conditions, which displayed different properties (binding capacity and selectivity), and respective non-imprinted polymers were employed for the fabrication of the potentiometric sensors. While sensors prepared using imprinted polymers had higher sensitivity and selectivity compared to the ones containing non-imprinted polymer, no difference was observed between sensors containing different imprinted polymers. No correspondence between polymers' characteristics obtained in the equilibrium re-binding studies and potentiometric behavior of the sensors based on the same polymers was observed. Therefore, equilibrium re-binding studies cannot be used for predicting sensor behavior.

  15. Preparation and evaluation of a novel molecularly imprinted polymer coating for selective extraction of indomethacin from biological samples by electrochemically controlled in-tube solid phase microextraction.

    PubMed

    Asiabi, Hamid; Yamini, Yadollah; Seidi, Shahram; Ghahramanifard, Fazel

    2016-03-24

    In the present work, an automated on-line electrochemically controlled in-tube solid-phase microextraction (EC-in-tube SPME) coupled with HPLC-UV was developed for the selective extraction and preconcentration of indomethacin as a model analyte in biological samples. Applying an electrical potential can improve the extraction efficiency and provide more convenient manipulation of different properties of the extraction system including selectivity, clean-up, rate, and efficiency. For more enhancement of the selectivity and applicability of this method, a novel molecularly imprinted polymer coated tube was prepared and applied for extraction of indomethacin. For this purpose, nanostructured copolymer coating consisting of polypyrrole doped with ethylene glycol dimethacrylate was prepared on the inner surface of a stainless-steel tube by electrochemical synthesis. The characteristics and application of the tubes were investigated. Electron microscopy provided a cross linked porous surface and the average thickness of the MIP coating was 45 μm. Compared with the non-imprinted polymer coated tubes, the special selectivity for indomethacin was discovered with the molecularly imprinted coated tube. Moreover, stable and reproducible responses were obtained without being considerably influenced by interferences commonly existing in biological samples. Under the optimal conditions, the limits of detection were in the range of 0.07-2.0 μg L(-1) in different matrices. This method showed good linearity for indomethacin in the range of 0.1-200 μg L(-1), with coefficients of determination better than 0.996. The inter- and intra-assay precisions (RSD%, n = 3) were respectively in the range of 3.5-8.4% and 2.3-7.6% at three concentration levels of 7, 70 and 150 μg L(-1). The results showed that the proposed method can be successfully applied for selective analysis of indomethacin in biological samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Solvent-Responsive Molecularly Imprinted Nanogels for Targeted Protein Analysis in MALDI-TOF Mass Spectrometry.

    PubMed

    Bertolla, Maddalena; Cenci, Lucia; Anesi, Andrea; Ambrosi, Emmanuele; Tagliaro, Franco; Vanzetti, Lia; Guella, Graziano; Bossi, Alessandra Maria

    2017-03-01

    Molecular imprinted poly(acrylamido)-derivative nanogels have shown their selectivity to bind the protein human serum transferrin (HTR) and also showed their capability for instantaneous solvent-induced modification upon the addition of acetonitrile. Integrated to matrix-assisted laser desorption/ionization time-of-flight mass analysis the HTR-imprinted solvent-responsive nanogels permitted the determination of HTR straight from serum and offered novel perspectives in targeted protein analysis.

  17. Molecularly imprinted polymers-curcuminoids and its application for solid phase extraction

    NASA Astrophysics Data System (ADS)

    Wulandari, Meyliana; Amran, M. B.; Lopez, A. B. Descalzo; Urraca, J. L.; Moreno-Bondi, M. C.

    2014-03-01

    Molecularly Imprinted Polymers (MIPs) for the selective recognition properties of curcumin (CUR), a cancer chemopreventive agent were obtained by a non-covalent imprinting approach with bisdemetoxycurcumin (BDMC) as the template molecule. The double bond of BDMC has been reduced in order not to be involved in polymerization and make the template molecules easy to be eluted. Several functional monomers have been evaluated to maximize the interactions with the template molecule during polymerization. MIPs prepared by bulk of N-(2-aminoethyl) metacrylamid hydrochlorideas functional monomer, ethylene glycol dimethacrylate as crosslinker, 2,2'-azobis (2'4-dimethyl valeronitril) as initiator and acetonitrile as porogen. Non-imprinted polymer (NIP) have been also synthesized for reference purposes. UV-vis spectroscopy has been used to predict the template to functional monomer ratio which indicates the formation of 2:1 complexes between monomer and curcumin and the association constants (K11 = 2529 μM and K12 = 1960.75 μM in acetonitrile). The capacity and imprinting factor have been evaluated as stationary phases in high-pressure liquid chromatography to CUR and BDMC. The binding properties and the homogeneity of the binding sites of the different polymers have been studied by Freundlich isotherm modeling and weight average affinity and number of binding sites. One of the foremost applications of molecular imprinting has been in molecularly imprinted solid phase extraction and it has the ability to separate and preconcentrate between closely related compounds in curcuminoids.

  18. Molecularly imprinted polymers: an analytical tool for the determination of benzimidazole compounds in water samples.

    PubMed

    Cacho, Carmen; Turiel, Esther; Pérez-Conde, Concepción

    2009-05-15

    Molecularly imprinted polymers (MIPs) for benzimidazole compounds have been synthesized by precipitation polymerization using thiabendazole (TBZ) as template, methacrylic acid as functional monomer, ethyleneglycol dimethacrylate (EDMA) and divinylbenzene (DVB) as cross-linkers and a mixture of acetonitrile and toluene as porogen. The experiments carried out by molecularly imprinted solid phase extraction (MISPE) in cartridges demonstrated the imprint effect in both imprinted polymers. MIP-DVB enabled a much higher breakthrough volume than MIP-EDMA, and thus was selected for further experiments. The ability of this MIP for the selective recognition of other benzimidazole compounds (albendazole, benomyl, carbendazim, fenbendazole, flubendazole and fuberidazole) was evaluated. The obtained results revealed the high selectivity of the imprinted polymer towards all the selected benzimidazole compounds. An off-line analytical methodology based on a MISPE procedure has been developed for the determination of benzimidazole compounds in tap, river and well water samples at concentration levels below the legislated maximum concentration levels (MCLs) with quantitative recoveries. Additionally, an on-line preconcentration procedure based on the use of a molecularly imprinted polymer as selective stationary phase in HPLC is proposed as a fast screening method for the evaluation of the presence of benzimidazole compounds in water samples.

  19. Synthesis and evaluation of molecularly imprinted silica gel for 2-hydroxybenzoic Acid in aqueous solution.

    PubMed

    Raof, Siti Farhana Abdul; Mohamad, Sharifah; Abas, Mhd Radzi

    2013-03-14

    A molecularly imprinted silica gel sorbent for selective removal of 2-Hydroxybenzoic acid (2-HA) was prepared by a surface imprinting technique with a sol-gel process. The 2-HA molecularly imprinted silica gel (2-HA-MISG) sorbent was evaluated by various parameters, including the influence of pH, static, kinetic adsorption and selectivity experiments. The optimum adsorption capacity to the 2-HA appeared to be around pH 2 by the polymer. Morevoer, the imprinted sorbent displayed fast uptake kinetics, obtained within 20 min. The adsorption capacity of the 2-HA-MISG (76.2 mg g-1) was higher than that of the non-imprinted silica gel (NISG) (42.58 mg g-1). This indicates that the 2-HA-MISG offers a higher affinity for 2-HA than the NISG. The polymer displays good selectivity and exhibits good reusability. Experimental results show the potential of molecularly imprinted silica sorbent for selective removal of 2-HA.

  20. Synthesis and Evaluation of Molecularly Imprinted Silica Gel for 2-Hydroxybenzoic Acid in Aqueous Solution

    PubMed Central

    Abdul Raof, Siti Farhana; Mohamad, Sharifah; Abas, Mhd Radzi

    2013-01-01

    A molecularly imprinted silica gel sorbent for selective removal of 2-Hydroxybenzoic acid (2-HA) was prepared by a surface imprinting technique with a sol-gel process. The 2-HA molecularly imprinted silica gel (2-HA-MISG) sorbent was evaluated by various parameters, including the influence of pH, static, kinetic adsorption and selectivity experiments. The optimum adsorption capacity to the 2-HA appeared to be around pH 2 by the polymer. Morevoer, the imprinted sorbent displayed fast uptake kinetics, obtained within 20 min. The adsorption capacity of the 2-HA-MISG (76.2 mg g−1) was higher than that of the non-imprinted silica gel (NISG) (42.58 mg g−1). This indicates that the 2-HA-MISG offers a higher affinity for 2-HA than the NISG. The polymer displays good selectivity and exhibits good reusability. Experimental results show the potential of molecularly imprinted silica sorbent for selective removal of 2-HA. PMID:23493059

  1. Comparison of monofunctional and multifunctional monomers in phosphate binding molecularly imprinted polymers.

    PubMed

    Wu, Xiangyang; Goswami, Kisholoy; Shimizu, Ken D

    2008-01-01

    In this study, molecularly imprinted polymers (MIPs) prepared using a multifunctional and a monofunctional monomer were compared with respect to their affinities, selectivities, and imprinting efficiencies for organophosphates. This is of interest because multifunctional monomers have higher affinities than traditional monofunctional monomers for their target analytes and thus should yield MIPs with higher affinities and selectivities. However, polymers containing multifunctional monomer may also have a higher number of unselective, non-templated binding sites. This increase in background binding sites could lead to a decrease in the magnitude of the imprinting effect and in the selectivity of the MIP. Therefore, phosphate selective imprinted and non-imprinted polymers (NIPs) were prepared using a novel multifunctional triurea monomer. The binding properties of these polymers were compared with polymers prepared using a monofunctional monourea monomer. The binding affinities and selectivities of the monomers, imprinted polymers, and NIPs were characterized by NMR titration, binding uptake studies, and binding isotherms. MIPs prepared with the triurea monomer showed higher binding affinity and selectivity for the diphenylphosphate anion in organic solvents than the MIPs prepared with the monofunctional monomer. Surprisingly, the binding properties of the NIPs revealed that the polymers prepared using the multifunctional and monofunctional monomers were very similar in affinity and selectivity. Thus, the multifunctional monomers increase not only the affinity of the MIP but also enhance the imprinting effect.

  2. The binding of metal ions to molecularly-imprinted polymers.

    PubMed

    Perera, Rukshan; Ashraf, Syed; Mueller, Anja

    2017-04-01

    Imprinting polymerization is a flexible method to make resins specific for different compounds. Imprinting polymerization involves the polymerization of the resin in the presence of a template, here cadmium ions or arsenate. The template is then removed by washing, leaving specific binding sites in the resin. In water treatment, the removal of toxic metal ions is difficult due to the limited affinity of these ions to ion exchange resins. Imprinting polymerization of ion-exchange resins is used to develop resins with high capacity and some selectivity for cadmium ions or arsenate for water treatment that still function as general ion-exchange resins. A minimum binding capacity of 325 meq/g was achieved for cadmium ions. Competition experiments elucidate the type of bonds present in the imprinting complex. The capacity and bond types for the cadmium ions and arsenate were contrasted. In the case of cadmium, metal-ligand bonds provide significant specificity of binding, although significant binding also occurs to non-specific surface sites. Arsenate ions are larger than cadmium ions and can only bind via ionic and hydrogen bonds, which are weaker than metal-ligand bonds. This results in lower specificity for arsenate. Additionally, diffusion into the resin is a limiting factor due to the larger size of the arsenate ion. These data elucidate the bonds formed between metal ions and the imprinting sites as well as other parameters that increase the capacity for heavy metals and arsenate.

  3. Determination of glyphosate in foodstuff by one novel chemiluminescence-molecular imprinting sensor

    NASA Astrophysics Data System (ADS)

    Zhao, Peini; Yan, Mei; Zhang, Congcong; Peng, Ruixue; Ma, Dongsheng; Yu, Jinghua

    2011-05-01

    A novel chemiluminescence (CL) sensor for the determination of glyphosate (GLY) was made up based on molecularly imprinted polymer (MIP). The molecularly imprinted microspheres (MIMs) with a small dimension which possess extremely high surface-to-volume ratio were synthesized using precipitation polymerization with GLY as template. And then the MIMs were modified on glass sheets, which were placed at the bottom of wells of microplate as the recognizer. Subsequently, a highly selective and high throughput chemiluminescence (CL)-molecular imprinting (MI) sensor for detection of GLY was achieved. Influencing factors were investigated and optimized in detail. The method can perform 96 independent measurements sequentially in 10 min and the limit of detection (LOD) for GLY was 0.046 μg mL -1. The relative standard deviation (RSD) for 11 parallel measurements of GLY was 4.68%. The results show that CL-MI sensor can become a useful analytical technology for quick molecular recognition.

  4. Enrichment of (E)-resveratrol from peanut byproduct with molecularly imprinted polymers.

    PubMed

    Schwarz, Lachlan J; Danylec, Basil; Yang, Yuanzhong; Harris, Simon J; Boysen, Reinhard I; Hearn, Milton T W

    2011-04-27

    Molecularly imprinted solid phase extraction (MISPE) has been employed to isolate and concentrate bioactive polyphenols from peanut press waste. To this end, a molecularly imprinted polymer (MIP) templated with the phytoalexin (E)-resveratrol has been prepared via self-assembly with the functional monomer 4-vinylpyridine (4VP) in a 1:3 molar ratio. Subsequent molecular interrogation of the MIP binding sites demonstrated preferential structural selectivity for (E)-resveratrol with respect to other structurally related naturally occurring compounds. This selectivity was subsequently exploited to achieve substantial sample cleanup of peanut press waste under aqueous conditions with significant enrichment of (E)-resveratrol (>60 fold) requiring minimal sample preparation.

  5. Selective extraction of proteins and other macromolecules from biological samples using molecular imprinted polymers.

    PubMed

    Stevenson, Derek; El-Sharif, Hazim F; Reddy, Subrayal M

    2016-11-01

    The accurate determination of intact macromolecules in biological samples, such as blood, plasma, serum, urine, tissue and feces is a challenging problem. The increased interest in macromolecules both as candidate drugs and as biomarkers for diagnostic purposes means that new method development approaches are needed. This review charts developments in the use of molecularly imprinted polymers first for small-molecular-mass compounds then for proteins and other macromolecules. Examples of the development of molecularly imprinted polymers for macromolecules are highlighted. The two main application areas to date are sensors and separation science, particularly SPE. Examples include peptides and polypeptides, lysozyme, hemoglobin, ovalbumin, bovine serum albumin and viruses.

  6. Selective adsorption of micro ciprofloxacin by molecularly imprinted functionalized polymers appended onto ZnS.

    PubMed

    Zhang, Xiaojie; Gao, Xiaoyan; Huo, Pengwei; Yan, Yongsheng

    2012-09-01

    Molecularly imprinted polymers (MIPs) for selective removal of ciprofloxacin (CIP) was prepared by a surface imprinting technique. The MIPs was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). The selectivity of the sorbent was investigated by a batch competitive binding experiment using aqueous CIP and gatifloxacin, CIP and chloramphenicol, and CIP and tetracycline mixtures, respectively. The static uptake capacity and selectivity coefficient of the MIPs are higher than those of the non-imprinted sorbent. The imprinted functionalized sorbent offered a fast kinetics for the extraction of CIP, which was obtained within 12 min. In a test of five extraction cycles, the adsorption capacity of the sorbent was above 92% of that of the fresh sorbent. Experimental results showed the potential of MIPs for selectivity removal of CIP.

  7. Molecularly imprinted polymers based drug delivery devices: a way to application in modern pharmacotherapy. A review.

    PubMed

    Luliński, Piotr

    2017-07-01

    This review presents the current status of molecularly imprinted polymers (MIPs) for drug delivery, in particular the studies that focus on biocompatibility, cytotoxicity, and in vitro or in vivo behavior of MIPs. It also shows the limitations that hamper the introduction of MIPs to pharmacotherapy and prevent this class of polymers from commercialization. MIPs are promising materials in the construction of drug delivery devices because they can provide improved delivery profiles or longer release times and deliver the drugs in the feedback regulated way, which is extremely important in modern pharmacotherapy. Here, a brief overview of the imprinting process and a concise description of drug release mechanisms from the imprinted materials will be presented followed by the discussion of potential MIP drug delivery devices for ocular, dermal, intravenous and oral routes of administration. Finally, future prospects for imprinted drug delivery forms will be outlined. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Atomic-Scale Friction in Direct Imprinting Process: Molecular Dynamics Simulation

    NASA Astrophysics Data System (ADS)

    Hsieh, Chih-Wei; Sung, Cheng-Kuo

    2007-09-01

    This paper investigates the mechanisms of the atomic-scale friction in the metal direct imprinting process by utilizing the molecular dynamics (MD) simulation, which is different from the ones during the scratching process conducted at a constant indenting depth. The relationships between the force and the imprinting depth are acquired first to realize the imprinting force and the demolding forces during the entire process, and also to confirm the substrate effect. To understand the effects of velocity on the process, various processing velocities are analyzed. Moreover, the surface of the mold is demarcated into three regions, namely, the bottom, the corner, and the sidewall surfaces, for the purpose of characterizing the different frictional mechanisms. The simulation results show that the trends of the frictional forces, growing with the imprinting depth, are similar in those regions, but their frictional mechanisms induced by the slip, substrate effect and bonding situations, respectively, are obviously different. The transferred results are also affected by frictional behavior.

  9. A Nanosensor for Explosives Detection Based on Molecularly Imprinted Polymers (MIPs) and Surfaced-enhanced Raman Scattering (SERS)

    DTIC Science & Technology

    2010-03-01

    Imprinted Polymers ( MIPs ) and Surfaced- enhanced Raman Scattering (SERS) Ellen Holthoff and Dimitra Stratis-Cullum Sensors and Electron Devices...for target chemical analytes of interest. Essentially, one creates a molecular “memory” within the imprinted polymer matrix. In a sensor format, the...A Nanosensor for Explosives Detection Based on Molecularly Imprinted Polymers ( MIPs ) and Surfaced- enhanced Raman Scattering (SERS) by Ellen

  10. Fundamental studies of molecularly imprinted polymers and atropisomers

    NASA Astrophysics Data System (ADS)

    Rushton, Gregory T.

    Three distinct research goals governed the work presented herein. First, methods for characterizing the binding properties of molecularly imprinted polymers (MIPs) were investigated and reported upon. We found that although the heterogeneous nature of these materials produced highly concentration-dependent adsorption behavior, there was a dearth of analytical methods that had been previously applied that accommodated this feature. The merits of the Freundlich Isotherm in describing MIP binding properties was evaluated and found to be useful under most conditions tested. Based on this and other previous work, we also presented a more qualitative approach to analyzing MIPs using log-log isotherms. The advantage of this method was that the most important properties to a researcher, the polymer's capacity and selectivity, were easily evaluated through a visual inspection of the log-log isotherm. This approach avoided the necessity of assuming and applying a particular binding model to the isotherm before a determination of the material's utility could be assessed. When this analysis was applied to a MIP for (+)-cinchonine in aqueous and organic media, the results indicated that diastereoselectivity was achieved under both conditions. Second, host-guest interactions between a N,N'-diaryl naphthalene diimide atropisomer and a variety of organic molecules were investigated to determine the relationship between the strength of the complex formed and the rotational barrier about a Caryl-Nimide bond. We found that the barrier was sensitive to both the identity and the concentration of guest which afforded fine control over the rotational freedom of the system. This control was exploited in the design of a reversible molecular brake. Finally, two laboratory investigations based upon the these research projects were developed for use in undergraduate chemistry courses. The first was designed for a polymer course where the students investigate the binding properties of an ethyl

  11. Acetylsalicylic acid electrochemical sensor based on PATP-AuNPs modified molecularly imprinted polymer film.

    PubMed

    Wang, Zhihua; Li, Hui; Chen, Jing; Xue, Zhonghua; Wu, Bowan; Lu, Xiaoquan

    2011-09-15

    A novel electrochemical sensor based on molecularly imprinted polymer film has been developed for aspirin detection. The sensitive film was prepared by co-polymerization of p-aminothiophenol (p-ATP) and HAuCl(4) on the Au electrode surface. First, p-ATP was self-assembled on the Au electrode surface by the formation of Au-S bonds. Then, the acetylsalicylic acid (ASA) template was assembled onto the monolayer of p-ATP through the hydrogen-bonding interaction between amino group (p-ATP) and oxygen (ASA). Finally, a conductive hybrid membrane was fabricated at the surface of Au electrode by the co-polymerization in the mixing solution containing additional p-ATP, HAuCl(4) and ASA template. Meanwhile, the ASA was spontaneously imprinted into the poly-aminothiophenol gold nanoparticles (PATP-AuNPs) complex film. The amount of imprinted sites at the PATP-AuNPs film significantly increases due to the additional replenishment of ASA templates. With the significant increasing of imprinted sites and doped gold nanoparticles, the sensitivity of the molecular imprinted polymer (MIP) electrode gradually increased. The molecularly imprinted sensor was characterized by electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV), and cyclic voltammetry (CV). The linear relationships between current and logarithmic concentration were obtained in the range from 1 nmol L(-1) to 0.1 μmol L(-1) and 0.7 μmol L(-1) to 0.1 mmol L(-1). The detection limit of 0.3 nmol L(-1) was achieved. This molecularly imprinted sensor for the determination of ASA has high sensitivity, good selectivity and reproducibility, with the testing in some biological fluids also has good selectivity and recovery. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

  12. Surface-imprinted nanostructured layer-by-layer film for molecular recognition of theophylline derivatives.

    PubMed

    Niu, Jia; Liu, Zhihua; Fu, Long; Shi, Feng; Ma, Hongwei; Ozaki, Yukihiro; Zhang, Xi

    2008-10-21

    In this article we report the introduction of the cooperativity of various specific interactions combined with photo-cross-linking of the interlayers to yield binding sites that can realize better selectivity and imprinting efficiency of a surface molecularly imprinted LbL film (SMILbL), thus providing a new approach toward fabrication of nanostructured molecularly imprinted thin films. It involves preassembly of poly(acrylic acid) (PAA) conjugated of the theophylline residue template via a disulfide bridge, denoted as PAAtheo 15, in solution, and layer-by-layer (LbL) assembly of PAAtheo 15 and a positively charged photoreactive diazo resin (DAR) to form multilayer thin film with designed architecture. After photo-cross-linking of the film and template removal, binding sites specific to 7-(beta-hydroxyethyl)theophylline (Theo-ol) molecules are introduced within the film. Binding assay demonstrates that the SMILbL has a high selectivity of SMILbL to Theo-ol over caffeine. A control experiment demonstrates that the selectivity of SMILbL derives from nanostructured recognition sites among the layers. The imprinting amount per unit mass of the film can be 1 order of magnitude larger than that of the conventional bulk molecular imprinting systems. As this concept of construction SMILbL can be easily extended to the other molecules by the following similar protocol: its applications in building many other different molecular recognition systems are greatly anticipated.

  13. Molecular imprinted polymer for solid-phase extraction of flavonol aglycones from Moringa oleifera extracts.

    PubMed

    Pakade, Vusumzi; Cukrowska, Ewa; Lindahl, Sofia; Turner, Charlotta; Chimuka, Luke

    2013-02-01

    Molecular imprinted polymer produced using quercetin as the imprinting compound was applied for the extraction of flavonol aglycones (quercetin and kaempferol) from Moringa oleifera methanolic extracts obtained using heated reflux extraction method. Identification and quantification of these flavonols in the Moringa extracts was achieved using high performance liquid chromatography with ultra violet detection. Breakthrough volume and retention capacity of molecular imprinted polymer SPE was investigated using a mixture of myricetin, quercetin and kaempferol. The calculated theoretical number of plates was found to be 14, 50 and 8 for myricetin, quercetin and kaempferol, respectively. Calculated adsorption capacities were 2.0, 3.4 and 3.7 μmol/g for myricetin, quercetin and kaempferol, respectively. No myricetin was observed in Moringa methanol extracts. Recoveries of quercetin and kaempferol from Moringa methanol extracts of leaves and flowers ranged from 77 to 85% and 75 to 86%, respectively, demonstrating the feasibility of using the developed molecularly imprinted SPE method for quantitative clean-up of both of these flavonoids. Using heated reflux extraction combined with molecularly imprinted SPE, quercetin concentrations of 975 ± 58 and 845 ± 32 mg/kg were determined in Moringa leaves and flowers, respectively. However, the concentrations of kaempferol found in leaves and flowers were 2100 ± 176 and 2802 ± 157 mg/kg, respectively.

  14. Molecularly imprinted magnetic nanoparticles for the micro solid-phase extraction of thiabendazole from citrus samples.

    PubMed

    García-Fernández, Miguel; Díaz-Álvarez, Myriam; Martín-Esteban, Antonio

    2017-06-01

    The preparation of molecularly imprinted core-shell magnetic nanoparticles and their subsequent use in the solid-phase extraction of thiabendazole from citrus sample extracts is described. Molecularly imprinted core-shell magnetic nanoparticles were prepared by the precipitation copolymerization of the imprinting polymerization mixture on the surface of vinyl-modified silica magnetic nanoparticles and were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The obtained molecularly imprinted core-shell magnetic nanoparticles exhibited a high selectivity for thiabendazole and were easily collected and separated by an external magnetic field without additional centrifugation or filtration steps. Under optimum conditions, a magnetic molecularly imprinted solid-phase extraction method was developed allowing the extraction of thiabendazole from citrus sample extracts and final determination by high-performance liquid chromatography with fluorescence detection. The detection limit was 0.2 mg/kg, far lower than the maximum residue limit established within the European Union for thiabendazole in citrus samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. An optical reflected device using a molecularly imprinted polymer film sensor.

    PubMed

    Wu, Nan; Feng, Liang; Tan, Yiyong; Hu, Jiming

    2009-10-19

    A novel and highly selective optical sensor with molecularly imprinted polymer (MIP) film was fabricated and investigated. The optical sensor head employing a medium finesse molecularly imprinted polymer film has been fabricated and characterised. A blank polymer and formaldehyde imprinted polymer were using methacrylic acid as the functional monomer and the ethylene glycol dimethacrylate as a crosslinker. The transduction mechanism is discussed based on the changes of optical intensity of molecularly imprinted polymer film acting as an optical reflected sensor. Template molecules, which diffused into MIP, could cause film density, and refractive index change, and then induce measurable optical reflective intensity shifts. Based on the reflective intensity shifts, an optical reflection detection of formaldehyde was achieved by illuminating MIP with a laser beam. For the same MIP, the reflective intensity shift was proportional to the amount of template molecule. This optical sensor, based on an artificial recognition system, demonstrates long-time stability and resistance to harsh chemical environments. As the research moves forward gradually, we establish the possibilities of quantitative analysis primly, setting the groundwork to the synthesis of the molecular imprinted optical fiber sensor. The techniques show good reproducibility and sensitivity and will be of significant interest to the MIP community.

  16. Molecular imprinted polymer-coated optical fiber sensor for the identification of low molecular weight molecules.

    PubMed

    Lépinay, Sandrine; Ianoul, Anatoli; Albert, Jacques

    2014-10-01

    A biomimetic optical probe for detecting low molecular weight molecules (maltol, 3-hydroxy-2-methyl-4H-pyran-4-one, molecular weight of 126.11 g/mol), was designed, fabricated, and characterized. The sensor couples a molecular imprinted polymer (MIP) and the Bragg grating refractometry technology into an optical fiber. The probe is fabricated first by inscribing tilted grating planes in the core of the fiber, and then by photopolymerization to immobilize a maltol imprinted MIP on the fiber cladding surface over the Bragg grating. The sensor response to the presence of maltol in different media is obtained by spectral interrogation of the fiber transmission signal. The results showed that the limit of detection of the sensor reached 1 ng/mL in pure water with a sensitivity of 6.3 × 10(8)pm/M. The selectivity of the sensor against other compounds and its reusability were also studied experimentally. Finally, the unambiguous detection of concentrations as little as 10nM of maltol in complex media (real food samples) by the MIP-coated tilted fiber Bragg grating sensor was demonstrated.

  17. Enantioseparations by high-performance liquid chromatography using molecularly imprinted polymers.

    PubMed

    Spivak, David A

    2013-01-01

    Molecularly imprinted polymers (MIPs) are becoming increasingly useful as chromatographic adsorbents for molecular separations, especially chiral separations, because they can be tailored to specifically recognize the target molecule including its stereochemistry. Traditionally formed MIPs (as described here) are stable under ambient conditions for years, take only days to make, and use relatively inexpensive components, with the possible exception of the template in some cases which can be reused after it is removed from the polymer to keep costs down. In addition to providing experimental details for typical synthetic methods to fabricate MIPs and pack them into HPLC columns, this chapter also gives an overview of the concepts of molecular imprinting method and discusses important factors for designing an effective imprinted polymer.

  18. Surface engineering: molecularly imprinted affinity membranes by photograft polymerization

    NASA Astrophysics Data System (ADS)

    Matuschewski, Heike; Sergeyeva, Tatiana A.; Bendig, Juergen; Piletsky, Sergey A.; Ulbricht, Matthies; Schedler, Uwe

    2001-02-01

    Commercial polymer microfiltration membranes were surface-modified with a graft copolymer of a functional monomer and a crosslinker in the presence of a template (triazine-herbicide). As result, membranes covered with a thin layer of imprinted polymer (MIP) selective to the template were obtained. The influence of the polymerization conditions on membrane recognition properties was studied by membranes

  19. Molecularly-Imprinted Material Made by Template-Directed Synthesis

    DTIC Science & Technology

    1999-07-30

    Biotech, 16, 468-475 (1997); Davis et al, "Rational Catalyst Design via Imprinted 3 Nanostructured Materials" Chem. Mater. 8 (1996) pp 1820-1839. and Wulff...acrylate, methyl methacrylate, olefins, pyrrole , saccharides, silanes, styrene, isocyanates, vinyl acetate, vinyl chloride, etc. Mixed materials may

  20. Effectively designed molecularly imprinted polymers for selective extraction of glabridin from Glycyrrhiza glabra L. residues by screening the library of non-imprinted polymers.

    PubMed

    Chen, Lingxiao; Ji, Wenhua; Duan, Wenjuan; Wang, Xiao; Gao, Qianshan; Geng, Yanling; Huang, Luqi

    2014-08-15

    Molecularly imprinted polymers (MIPs) with high selectivity and affinity to glabridin were designed based on the screening results of the library of non-imprinted polymers (NIPs). The NIP library contained 48 polymers that were polymerized with the combinations of different functional monomers, cross-linkers, and porogenic solvents. The distribution coefficient (k) values were used to estimate the affinity of NIPs to glabridin. The corresponding MIPs of the best three NIPs were prepared. After evaluating the imprinting effects and selectivity of the three MIPs, the performance of the best MIP as solid phase extraction sorbent was investigated. Glabridin with percent recovery of 83 was obtained from the extract of Glycyrrhiza glabra L. (G. glabra L.) residues by molecularly imprinted solid phase extraction (MISPE). Thus, this material can be successfully used for the extraction and purification of glabridin from G. glabra L. residues. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. A novel strategy to improve the sensitivity of antibiotics determination based on bioelectrocatalysis at molecularly imprinted polymer film electrodes.

    PubMed

    Lian, Wenjing; Liu, Shuang; Wang, Lei; Liu, Hongyun

    2015-11-15

    A new strategy for the sensitive detection of kanamycin (KA) and other antibiotics based on molecularly imprinted polymer (MIP) and bioelectrocatalysis was developed in the present study. The KA-polypyrrole MIP films were electropolymerized on the surface of pyrolytic graphite (PG) electrodes, with pyrrole (PY) serving as the monomer and KA as the template. Because KA is electro-inactive, electroactive K3[Fe(CN)6] was used as the probe in the cyclic voltammetric (CV) measurements. The difference of the CV reduction peaks of K3[Fe(CN)6] at electrodes between the MIP films after KA removal and KA-rebinding MIP films could thus be used to determine KA quantitatively. When horseradish peroxidase (HRP) and H2O2 were added into the testing solution, the detection sensitivity of the system was greatly amplified because the electrochemical reduction of H2O2 could be catalyzed by HRP and mediated by K3[Fe(CN)6]. With the bioelectrocatalysis amplification, the limit of detection (LOD) for KA fell as low as 28 nM, approximately two orders of magnitude lower than that for the MIP films in the absence of enzymatic catalysis. The strategy demonstrated the generality. Not only KA but also other antibiotics, such as oxytetracycline (OTC), could be determined by this method. More significantly, in addition to the K3[Fe(CN)6]-HRP-H2O2 system, other bioelectrocatalysis systems, such as Fc(COOH)2-GOD-glucose (Fc(COOH)2=ferrocenedicarboxylic acid, GOD=glucose oxidase), could also be used to amplify the CV signal and realize the sensitive detection of KA for the MIP film system, thereby illustrating the great potential and prospects of the strategy.

  2. Mimicking Biological Delivery Through Feedback-Controlled Drug Release Systems Based on Molecular Imprinting

    PubMed Central

    Kryscio, David R.; Peppas, Nicholas A.

    2015-01-01

    Intelligent drug delivery systems (DDS) are able to rapidly detect a biological event and respond appropriately by releasing a therapeutic agent; thus, they are advantageous over their conventional counterparts. Molecular imprinting is a promising area that generates a polymeric network which can selectively recognize a desired analyte. This field has been studied for a variety of applications over a long period of time, but only recently has it been investigated for biomedical and pharmaceutical applications. Recent work in the area of molecularly imprinted polymers in drug delivery highlights the potential of these recognitive networks as environmentally responsive DDS that can ultimately lead to feedback controlled recognitive release systems. PMID:26500352

  3. Molecularly imprinted polymers: compromise between flexibility and rigidity for improving capture of template analogues.

    PubMed

    Pardo, Antonelle; Mespouille, Laetitia; Dubois, Philippe; Blankert, Bertrand; Duez, Pierre

    2014-03-17

    New synthetic strategies for molecularly imprinted polymers (MIPs) were developed to mimic the flexibility and mobility exhibited by receptor/enzyme binding pockets. The MIPs were prepared by bulk polymerization with quercetin as template molecule, acrylamide as functional monomer, ethylene glycol dimethacrylate as cross-linker, and THF as porogen. The innovative grafting of specific oligoethylene glycol units onto the imprinted cavities allowed MIPs to be obtained that exhibit extended selectivity towards template analogues. This synthetic strategy gives promising perspectives for the design of molecular recognition of molecules based on a congruent pharmacophore, which should be of interest for drug development.

  4. Lipoate-based imprinted self-assembled molecular thin films for biosensor applications.

    PubMed

    Tappura, Kirsi; Vikholm-Lundin, Inger; Albers, Willem M

    2007-01-15

    Lipoate derivatives were used for the formation of imprinted self-assembled molecular thin films for the recognition of morphine. A large collection of lipoate derivatives was screened by molecular dynamics simulations in various solvents. A set of ligands showing favourable interactions with morphine in aqueous environment was selected for synthesis. Morphine-imprinted layers were then produced on gold substrates in mixed monolayers with morphine added as the template. The binding of ligands and morphine to gold, as well as the association/dissociation of morphine to the formed layers were studied with Surface Plasmon Resonance. Imprinted factors were highly variable and were dependent on ligand/morphine mixing ratio, lipoate derivative and monolayer preparation method. The imprinted factors were as high as 100 and 600 for one of the ligands. The results show that the simulations are able to provide correct information of the relative strengths of the molecular interactions between the ligand and morphine molecules in different solutions. The liquid phase simulations are, however, not able to predict the imprinted factors (i.e. distinguish between specific and non-specific binding), because the specificity is not formed before self-assembly on the surface.

  5. Molecularly imprinted shells from polymer and xerogel matrices on polystyrene colloidal spheres.

    PubMed

    Guan, Guijian; Liu, Renyong; Mei, Qingsong; Zhang, Zhongping

    2012-04-10

    We have devised a facile and general methodology for the synthesis of various molecularly imprinted shells at the surface of polystyrene (PS) colloidal spheres to recognize the explosive compound 2,4,6-trinitrotoluene (TNT). PS spheres with surface-functionalized carboxyl-group layers could direct a selective imprinting polymerization on their surface through the hydrogen-bonding interactions between surface carboxyl groups and amino monomers. Meanwhile, homogeneous polymerization in the solution phase was completely prevented by stepwise polymerization. The overall process led to the formation of monodisperse molecularly imprinted core-shell microspheres, and was very successful in the preparation of organic polymer and inorganic xerogel shells. Furthermore, greater capacity and faster binding kinetics towards target species were achieved, because surface-imprinted sites ensured the complete removal of templates, good accessibility to target molecules, and low mass-transfer resistance. The results reported herein, concerning the production of high-quality molecularly imprinted products, could also form the basis for the formulation of a new strategy for the fabrication of various functional coating layers on colloidal spheres with potential applications in the fields of separations and chemical sensing.

  6. Biomimetic sensor based on molecularly imprinted polymer with nitroreductase-like activity for metronidazole detection.

    PubMed

    Gu, Yue; Yan, Xiaoyi; Li, Cong; Zheng, Bo; Li, Yaru; Liu, Weilu; Zhang, Zhiquan; Yang, Ming

    2016-03-15

    The utility of molecularly imprinted polymer (MIP) as electrochemical sensor often suffers from its limited catalytic efficiency. Here, we proposed an alternative approach by combining the concept of MIP with the use of mimetic enzyme. A metronidazole imprinted polymer with nitroreductase-like activity was successfully achieved via an electrochemical method, where melamine served two purposes: functional monomer of MIP and component of mimetic enzyme. During the imprinting process, the redox-active center, which is responsible for catalysis, was introduced into the imprinted cavities. Accordingly, the imprinted polymer, having both catalysis centers and recognition sites, exhibited enhanced electrocatalytic activity and selectivity. The sensing performances of this metronidazole imprinted biomimetic sensor were evaluated in detail. Results revealed that the response to metronidazole was linear in the concentration range of 0.5-1000 μM, and the detection limit was 0.12 μM (S/N=3). In addition, we applied the proposed sensor to detect metronidazole in an injection solution and the results implied its feasibility for practical application. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Facile synthesis of polydopamine-coated molecularly imprinted silica nanoparticles for protein recognition and separation.

    PubMed

    Xia, Zhiwei; Lin, Zian; Xiao, Yun; Wang, Ling; Zheng, Jiangnan; Yang, Huanghao; Chen, Guonan

    2013-09-15

    Surface imprinting over nanostructured matrices is an effective solution to overcome template removal and achieve high binding capacity. In this work, a facile method was developed for synthesis of polydopamine-coated molecularly imprinted silica nanoparticles (PDA-coated MIP silica NPs) based on self-polymerization of dopamine (DA) on the surface of silica NPs in the presence of template protein. Transmission electronic microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) showed that PDA layers were successfully attached on the surface of silica NPs and the corresponding thickness was about 5nm, which enabled the MIP silica NPs to have fast binding kinetics and high binding capacity. Under the aqueous media, the imprinted silica NPs showed much higher binding affinity toward template than non-imprinted (NIP) silica NPs. The protein recognition properties were examined by single-protein or competitive batch rebinding experiments and rebinding kinetics study, validating that the imprinted silica NPs have high selectivity for the template. The resultant BHb-MIP silica NPs could not only selectively separate BHb from the protein mixture, but also specifically deplete high-abundance BHb from cattle whole blood. In addition, the stability and regeneration were also investigated, which indicated that the imprinted silica NPs had excellent reusability. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. Preparation and characterization of erythromycin molecularly imprinted polymers based on distillation-precipitation polymerization.

    PubMed

    Liu, Jiang; Li, Le; Tang, Hui; Zhao, Feilang; Ye, Bang-Ce; Li, Yingchun; Yao, Jun

    2015-09-01

    Erythromycin-imprinted polymers with excellent recognition properties were prepared by an innovative strategy called distillation-precipitation polymerization. The interaction between erythromycin and methacrylic acid was studied by ultraviolet absorption spectroscopy, and the as-prepared materials were characterized by Fourier-transform infrared spectroscopy and scanning electron microscopy. Moreover, their binding performances were evaluated in detail by static, kinetic and selective sorption tests. It was found that the molecularly imprinted polymers afforded good morphology, monodispersity, and high adsorption capacity when the fraction of the monomers was 7 vol% in the whole reaction system, and the adsorption data for imprinted polymers correlated well with the Langmuir model. The maximum capacity of the imprinted and the non-imprinted polymers for adsorbing erythromycin is 44.03 and 19.95 mg/g, respectively. The kinetic studies revealed that the adsorption process fitted a pseudo-second-order kinetic model. Furthermore, the imprinted polymers display higher affinity toward erythromycin, compared with its analogue roxithromycin.

  9. Miniaturized molecularly imprinted polymer extraction method for the gas chromatographic analysis of flavonoids.

    PubMed

    Nolvachai, Yada; Kulsing, Chadin; Boysen, Reinhard I; Hearn, Milton T W; Marriott, Philip J

    2014-04-01

    In this study, the use of monolithic molecularly imprinted polymers in a micropipette tip format allowing the simple and fast extraction of flavonoids from standard solutions and a black tea sample is demonstrated. The imprinted polymer employed quercetin, methacrylic acid or 4-vinylpyridine, and ethylene glycol dimethacrylate as template, functional monomer, and cross-linker, respectively. Surface morphologies of the quercetin-imprinted polymers and the corresponding nonimprinted polymers were characterized by SEM. Extraction of flavonoid standards was performed to evaluate the selectivity and recovery with these imprinted and nonimprinted polymers. Flavonoid compositions in aliquots eluted from the tips were identified using fast GC with flame ionization detection. Maximum specific capacities of 0.2, 5.7, and 16.0 mg/g for catechin, morin, and quercetin, respectively, were obtained with the imprinted polymer prepared with methacrylic acid, with the corresponding recoveries of 99.8, 98.8, and 95.4%, respectively. Efficient extraction by the quercetin-imprinted polymer of epicatechin, catechin, and quercetin from an apple-flavored black tea sample was achieved, with GC-MS employed for compound identification for both the tea and extracted samples.

  10. Highly selective and sensitive analysis of dopamine by molecularly imprinted stir bar sorptive extraction technique coupled with complementary molecularly imprinted polymer sensor.

    PubMed

    Prasad, Bhim Bali; Srivastava, Amrita; Tiwari, Mahavir Prasad

    2013-04-15

    This paper reports a combination of molecularly imprinted stir bar sorptive extraction and complementary molecularly imprinted polymer-sensor for the analysis of dopamine as a biomarker of several neurodegenerative diseases occurred at ultra trace level. This exploited iniferter initiated polymerization via "surface grafting-from" approach onto magnetic stir bar (for sorptive extraction) and multiwalled carbon nanotubes-ceramic electrode (for detection). Such hyphenation helped dual pre-concentration of dopamine in aqueous, biological and pharmaceutical samples. This enabled high sensitivity to achieve the stringent limit [limit of detection: 4.9ngL(-1), RSD=2.4%, S/N=3, cerebrospinal fluid] of clinical detection, without any problems of non-specific contributions and cross-reactivity.

  11. Synthesis, characterization, and ab initio theoretical study of a molecularly imprinted polymer selective for biosensor materials.

    PubMed

    Jacob, Rebecca; Tate, Margaret; Banti, Yididya; Rix, Colin; Mainwaring, David E

    2008-01-17

    Despite the complex phenomena involved in encoding template molecule information within stable synthetic polymers to yield selective and efficient molecular recognition processes, molecularly imprinted polymers (MIP) are increasingly finding broad areas of application. Molecular interactions, both during the polymerization of the functional monomers in the presence of the template and during the processes of specific recognition after template removal, are key determinants of an effective MIP. Covalent and noncovalent template imprinting have been employed to achieve specific recognition sites. In the present study, a molecularly imprinted biocompatible polymer, having a high capacity and affinity for the dye template, nickel(II) phthalocyanine tetrasulfonic acid, has been prepared. UV-visible spectroscopy, FTIR spectroscopy, and ICP analysis were used to investigate the aspects of the synthesis, binding capacity, and adsorption kinetics of the system. Poly(allylamine) cross-linked with epichlorohydrin has been used to represent an amino-functional receptor. Binding isotherms and capacities were correlated with the degree of template removal. Kinetic studies of binding allowed diffusion mechanisms to be evaluated for the fine particulate MIP. Ab initio molecular orbital calculations were performed using Hartree-Fock, MP2, and density functional theory methods to determine the most likely mechanisms of molecular imprinting. Suitable theoretical models have been constructed to mimic the interactions between the template molecule and the polymer. Simulation of the vibrational spectra was also undertaken to make meaningful assignments to experimentally determined spectral bands resulting from these template MIP receptor interactions.

  12. Molecularly imprinted polymers with synthetic dummy templates for the preparation of capsaicin and dihydrocapsaicin from chili peppers.

    PubMed

    Ma, Xiuli; Ji, Wenhua; Chen, Lingxiao; Wang, Xiao; Liu, Jianhua; Wang, Xueyong

    2015-01-01

    In this work, dummy molecularly imprinted polymers with high selectivity and affinity to capsaicin and dihydrocapsaicin are designed using N-vanillylnonanamide as a dummy template. The performance of dummy molecularly imprinted polymers and nonimprinted polymers was evaluated using adsorption isotherms, adsorption kinetics, and selective recognition capacity. Dummy molecularly imprinted polymers were found to exhibit good site accessibility, taking just 20 min to achieve adsorption equilibrium; they were also highly selective toward capsaicin and dihydrocapsaicin. We successfully used dummy molecularly imprinted polymers as a specific sorbent for selectively enriching capsaicin and dihydrocapsaicin from chili pepper samples. In a scaled-up experiment, the selective recovery of capsaicinoids was calculated to be 77.8% using solid-phase extraction. To the best of our knowledge, this is the first example of the use of N-vanillylnonanamide as a dummy template in molecularly imprinted polymers to simultaneously enrich capsaicin and dihydrocapsaicin.

  13. Solid-phase extraction of esculetin from the ash bark of Chinese traditional medicine by using molecularly imprinted polymers.

    PubMed

    Hu, Shu-Guo; Li, Li; He, Xi-Wen

    2005-01-07

    A molecularly imprinted polymer solid-phase extraction method is used to extract esculetin from the ash bark of Chinese traditional medicine. Ratio of ethanol and water as washing solution were investigated. Data of accumulative adsorption on molecularly imprinted polymers from the continuous loading experiment suggests that there are two different kinds of recognition sites in molecularly imprinted polymers. By selecting the washing and eluting solution a scheme was designed to separate esculetin and its analogues including esculin, coumarin, 7-methoxylcoumarin and daphnetin. Finally, by applying the revised scheme esculetin was extracted from the ash bark of Chinese traditional medicine that was purchased from two big drugstores, respectively, with both molecularly imprinted polymers and non-molecularly imprinted polymers.

  14. Determination of ractopamine in pork using a magnetic molecularly imprinted polymer as adsorbent followed by HPLC.

    PubMed

    Tang, Yiwei; Gao, Jingwen; Liu, Xiuying; Lan, Jianxing; Gao, Xue; Ma, Yong; Li, Min; Li, Jianrong

    2016-06-15

    A new magnetic molecularly imprinted polymers (MMIPs) for separation and concentration of ractopamine (RAC) were prepared using surface molecular imprinting technique with methacryloyl chloride as functional monomer and RAC as template. The MMIPs were characterized using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, and vibrating sample magnetometer. The results of re-binding experiments indicated that the MMIPs had fast adsorption kinetics and could reach binding equilibrium within 20 min, and the adsorption capacity of the MMIPs was 2.87-fold higher than that of the corresponding non-imprinted polymer. The selectivity of the MMIPs was evaluated according to its recognition to RAC and its analogues. The synthesized MMIPs were successfully applied to extraction, followed by high performance liquid chromatography to determine RAC in real food samples. Spiked recoveries ranged from 73.60% to 94.5%, with relative standard deviations of <11.17%.

  15. Convenient solid phase extraction of cephalosporins in milk using a molecularly imprinted polymer.

    PubMed

    Quesada-Molina, Carolina; Claude, Bérengère; García-Campaña, Ana M; del Olmo-Iruela, Monsalud; Morin, Philippe

    2012-11-15

    In this paper, a molecularly imprinted polymer (MIP) for cephalosporin molecules (cephalexin (CFL) and cephapirin (CFP)), was prepared by non covalent molecular imprinting approach and applied to solid phase extraction (SPE). For MIP synthesis, a tributylammonium cefadroxil salt (TBA-CFD) was used as template with methacrylic acid and ethylene glycol dimethacrylate as monomer and cross-linker, respectively, in acetone-methanol 92/8 (v/v) mixture. The selectivity of MIP versus non imprinted polymer (NIP) was confirmed for CFL, CFD and CFP in standard solutions as well as in milk samples. The efficiency of the synthesized MIP was evaluated by means of the application of the proposed MIP-SPE procedure to spiked milk samples previous to the HPLC method for the detection of cephalosporins. The MIP-SPE recoveries were higher than 60% for the three target analytes in spiked milk.

  16. Selective adenosine-5'-monophosphate uptake by water-compatible molecularly imprinted polymer.

    PubMed

    Breton, Florent; Delépée, Raphaël; Jégourel, Damien; Deville-Bonne, Dominique; Agrofoglio, Luigi A

    2008-06-02

    Molecularly imprinted polymers (MIPs) were prepared for adenosine-5'-monophosphate (AMP), a substrate of AMP-activated protein kinase. The template molecule was formed by the vinylphenylboronate diester of adenosine on which 5'-free hydroxide was protected by tert-butyldimethylsilyl group in order to mimic the steric hindrance of the phosphate moiety of AMP. Molecular imprinting was performed by complexing acrylamide and the template in a highly cross-linked polymer. MIPs were tested in batch experiments with aqueous samples of nucleotides and a number of parameters were investigated. The use of tetrabutylammonium hydroxide (TBAH) was necessary to obtain a rebinding of nucleotides on MIP. The adsorption of AMP was optimal in 5 mM ammonium acetate buffer solution pH 9.5 for 30 min, with 30 mM of TBAH. The imprinted polymer was selective for AMP towards others nucleotides or deoxi analogues.

  17. Emergence of molecular recognition phenomena in a simple model of imprinted porous materials

    NASA Astrophysics Data System (ADS)

    Dourado, Eduardo M. A.; Sarkisov, Lev

    2009-06-01

    Polymerization in the presence of templates, followed by their consequent removal, leads to structures with cavities capable of molecular recognition. This molecular imprinting technology has been employed to create porous polymers with tailored selectivity for adsorption, chromatographic separations, sensing, and other applications. Performance of these materials crucially depends on the availability of highly selective binding sites. This parameter is a function of a large number of processing conditions and is difficult to control. Furthermore, the nature of molecular recognition processes in these materials is poorly understood to allow a more systematic design. In this work we propose a simple model of molecularly imprinted polymers mimicking the actual process of their formation. We demonstrate that a range of molecular recognition effects emerge in this model and that they are consistent with the experimental observations. The model also provides a wealth of information on how binding sites form and function in the imprinted structures. It demonstrates the capability to assess the role of various processing conditions in the final properties of imprinted materials, and therefore it can be used to provide some qualitative insights on the optimal values of processing parameters.

  18. Electrochemical sensor based on magnetic molecularly imprinted nanoparticles modified magnetic electrode for determination of Hb.

    PubMed

    Sun, Binghua; Ni, Xinjiong; Cao, Yuhua; Cao, Guangqun

    2017-05-15

    A fast and selective electrochemical sensor for determination of hemoglobin (Hb) was developed based on magnetic molecularly imprinted nanoparticles modified on the magnetic glassy carbon electrode. The nanoparticles Fe3O4@SiO2 with a magnetic core and a molecularly imprinted shell had regular structures and good monodispersity. Hb could be determined directly by electrochemical oxidization with the modified electrode. A magnetic field increased electrochemical response to Hb by two times. Imprinting Hb on the surface of Fe3O4@SiO2 shortened the response time within 7min. Under optimum conditions, the imprinting factor toward the non-imprinted sensor was 2.8, and the separation factor of Hb to horseradish peroxidase was 2.6. The oxidation peak current had a linear relationship with Hb concentration ranged from 0.005mg/ml to 0.1mg/ml with a detection limit (S/N =3) of 0.0010mg/ml. The sensors were successfully applied to analysis of Hb in whole blood samples with recoveries between 95.7% and 105%.

  19. Synthesis of molecularly imprinted polymer with 7-chloroethyl-theophylline-immobilized silica gel as template and its molecular recognition function

    NASA Astrophysics Data System (ADS)

    Zhang, Yuhui; Tong, Aijun; Li, Longdi

    2004-01-01

    By reaction of 7-chloroethyl-theophylline with aminopropylsilanized silica gel we synthesized a 7-chloroethyl-theophylline-immobilized silica gel as template molecule and prepared a molecularly imprinted polymer (MIP-Si), which had special recognition sites to 7-chloroethyl-theophylline. A conventional molecularly imprinted polymer (MIP) using 7-chloroethyl-theophylline as template was also prepared for comparison. Binding abilities to 7-chloroethyl-theophylline and its structural analogs revealed that the MIP-Si shows much higher binding speed and much more binding capacity than the MIP does.

  20. Molecular dynamics approaches to the design and synthesis of PCB targeting molecularly imprinted polymers: interference to monomer-template interactions in imprinting of 1,2,3-trichlorobenzene.

    PubMed

    Cleland, Dougal; Olsson, Gustaf D; Karlsson, Björn C G; Nicholls, Ian A; McCluskey, Adam

    2014-02-07

    The interactions between each component of the pre-polymerisation mixtures used in the synthesis of molecularly imprinted polymers (MIP) specific for 1,2,3,4,5-pentachlorobenzene (1) and 1,2,3-trichlorobenzene (2) were examined in four molecular dynamics simulations. These simulations revealed that the relative frequency of functional monomer-template (FM-T) interactions was consistent with results obtained by the synthesis and evaluation of the actual MIPs. The higher frequency of 1 interaction with trimethylstyrene (TMS; 54.7%) than 1 interaction with pentafluorostyrene (PFS; 44.7%) correlated with a higher imprinting factor (IF) of 2.1 vs. 1.7 for each functional monomer respectively. The higher frequency of PFS interactions with 2 (29.6%) than TMS interactions with 2 (1.9%) also correlated well with the observed differences in IF (3.7) of 2 MIPs imprinted using PFS as the FM than the IF (2.8) of 2 MIPs imprinted using TMS as the FM. The TMS-1 interaction dominated the molecular simulation due to high interaction energies, but the weaker TMS-2 resulted in low interaction maintenance, and thus lower IF values. Examination of the other pre-polymerisation mixture components revealed that the low levels of TMS-2 interaction was, in part, due to interference caused by the cross linker (CL) ethyleneglycol dimethylacrylate (EGDMA) interactions with TMS. The main reason was, however, attributed to MeOH interactions with TMS in both a hydrogen bond and perpendicular configuration. This positioned a MeOH directly above the π-orbital of all TMS for an average of 63.8% of MD2 creating significant interference to π-π stacking interactions between 2 and TMS. These findings are consistent with the deviation from the 'normal' molecularly imprinted polymer synthesis ratio of 1 : 4 : 20 (T : FM : CL) of 20 : 1 : 29 and 15 : 6 : 29 observed with 2 and TMS and PFS respectively. Our molecular dynamics simulations correctly predicted the high level

  1. "Bite-and-Switch" approach using computationally designed molecularly imprinted polymers for sensing of creatinine.

    PubMed

    Subrahmanyam, S; Piletsky, S A; Piletska, E V; Chen, B; Karim, K; Turner, A P

    2001-12-01

    A method for the selective detection of creatinine is reported, which is based on the reaction between polymerised hemithioacetal, formed by allyl mercaptan, o-phthalic aldehyde, and primary amine leading to the formation of fluorescent isoindole complex. This method has been demonstrated previously for the detection of creatine using creatine-imprinted molecularly imprinted polymers (MIPs) Since MIPs created using traditional methods were unable to differentiate between creatine and creatinine, a new approach to the rational design of a molecularly imprinted polymer (MIP) selective for creatinine was developed using computer simulation. A virtual library of functional monomers was assigned and screened against the target molecule, creatinine, using molecular modelling software. The monomers giving the highest binding score were further tested using simulated annealing in order to mimic the complexation of the functional monomers with template in the monomer mixture. The result of this simulation gave an optimised MIP composition. The computationally designed polymer demonstrated superior selectivity in comparison to the polymer prepared using traditional approach, a detection limit of 25 microM and good stability. The "Bite-and-Switch" approach combined with molecular imprinting can be used for the design of assays and sensors, selective for amino containing substances.

  2. Fiber optic profenofos sensor based on surface plasmon resonance technique and molecular imprinting.

    PubMed

    Shrivastav, Anand M; Usha, Sruthi P; Gupta, Banshi D

    2016-05-15

    A successful approach for the fabrication and characterization of an optical fiber sensor for the detection of profenofos based on surface plasmon resonance (SPR) and molecular imprinting is introduced. Molecular imprinting technology is used for the creation of three dimensional binding sites having complementary shape and size of the specific template molecule over a polymer for the recognition of the same. Binding of template molecule with molecularly imprinted polymer (MIP) layer results in the change in the dielectric nature of the sensing surface (polymer) and is identified by SPR technique. Spectral interrogation method is used for the characterization of the sensing probe. The operating profenofos concentration range of the sensor is from 10(-4) to 10(-1)µg/L. A red shift of 18.7 nm in resonance wavelength is recorded for this profenofos concentration range. The maximum sensitivity of the sensor is 12.7 nm/log (µg/L) at 10(-4)µg/L profenofos concentration. Limit of detection (LOD) of the sensor is found to be 2.5×10(-6)µg/L. Selectivity measurements predict the probe highly selective for the profenofos molecule. Besides high sensitivity due to SPR technique and selectivity due to molecular imprinting, proposed sensor has numerous other advantages like immunity to electromagnetic interference, fast response, low cost and capability of online monitoring and remote sensing of analyte due to the fabrication of the probe on optical fiber. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. First steps towards conformationally selective artificial lectins: the chair-boat discrimination by molecularly imprinted polymers.

    PubMed

    de Talancé, Vincent Lemau; Massinon, Olivier; Baati, Rachid; Wagner, Alain; Vincent, Stéphane P

    2012-11-07

    A series of molecularly imprinted polymers (MIPs) were prepared in the presence of a synthetic galactoside locked in a (1,4)B boat conformation. This study demonstrates that, depending on the polymerisation technique, an organic material can selectively bind a carbohydrate in a biologically relevant boat conformation.

  4. Detection of nicotine based on molecularly imprinted TiO2-modified electrodes.

    PubMed

    Wu, Cheng-Tar; Chen, Po-Yen; Chen, Jian-Ging; Suryanarayanan, Vembu; Ho, Kuo-Chuan

    2009-02-02

    Amperometric detection of nicotine (NIC) was carried out on a titanium dioxide (TiO(2))/poly(3,4-ethylenedioxythiophene) (PEDOT)-modified electrode by a molecular imprinting technique. In order to improve the conductivity of the substrate, PEDOT was coated onto the sintered electrode by in situ electrochemical polymerization of the monomer. The sensing potential of the NIC-imprinted TiO(2) electrode (ITO/TiO(2)[NIC]/PEDOT) in a phosphate-buffered saline (PBS) solution (pH 7.4) containing 0.1M KCl was determined to be 0.88 V (vs. Ag/AgCl/saturated KCl). The linear detection range for NIC oxidation on the so-called ITO/TiO(2)[NIC]/PEDOT electrode was 0-5mM, with a sensitivity and limit of detection of 31.35 microA mM(-1)cm(-2) and 4.9 microM, respectively. When comparing with the performance of the non-imprinted one, the sensitivity ratio was about 1.24. The sensitivity enhancement was attributed to the increase in the electroactive area of the imprinted electrode. The at-rest stability of the ITO/TiO(2)[NIC]/PEDOT electrode was tested over a period of 3 days. The current response remained about 85% of its initial value at the end of 2 days. The ITO/TiO(2)[NIC]/PEDOT electrode showed reasonably good selectivity in distinguishing NIC from its major interferent, (-)-cotinine (COT). Moreover, scanning electrochemical microscopy (SECM) was employed to elucidate the surface morphology of the imprinted and non-imprinted electrodes using Fe(CN)(6)(3-)/Fe(CN)(6)(4-) as a redox probe on a platinum tip. The imprinted electrode was further characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR).

  5. Preparation of highly selective solid-phase extractants for Cibacron reactive dyes using molecularly imprinted polymers.

    PubMed

    Al-Degs, Yahya S; Abu-Surrah, Adnan S; Ibrahim, Khalid A

    2009-02-01

    Selective polymeric extractants were prepared for preconcentration of Cibacron reactive red dye, a dye that is often applied with Cibacron reactive blue and Cibacron reactive yellow for dyeing of fabrics. The best extractant was fabricated (in chloroform) using methacrylic acid (as monomer), ethylene glycol dimethacrylate (as crosslinker), AIBN (as initiator for polymerization), and red dye as template molecule, with a molar stoichiometric ratio of 8.0:40.0:2.5:0.63, respectively. The structure of the molecularly imprinted polymer (MIP) was robust, and resisted dissolution up to 260 degrees C. Compared with the un-imprinted polymer, the imprinted product has a large specific surface area which improved its adsorption capacity. The effect of imprinting was obvious from the adsorption capacity measured at pH 4 for red dye (the imprinted molecule), which was increased from 24.0 to 79.3 mg g(-1) after imprinting. Equilibrium adsorption studies revealed that the dye-imprinted-polymer enables efficient extraction of red dye even in the presence of blue and yellow dyes which have similar chemical natures to the red dye. The selectivity coefficients S (red dye/dye), were 13.9 and 17.1 relative to the yellow and blue dyes, respectively. The MIP was found to be effective for red dye preconcentration, with a preconcentration factor of 100, from tap water and treated textile wastewater. The factors affecting extraction of red dye by the MIP were studied and optimized. Under the optimized extraction conditions, red dye was selectively quantified in the presence of other competing dyes at a concentration of 20 microg L(-1) from different water systems with satisfactory recoveries (91-95%) and RSD values (approximately 5.0%).

  6. Designing and preparation of cytisine alkaloid surface-imprinted material and its molecular recognition characteristics

    NASA Astrophysics Data System (ADS)

    Gao, Baojiao; Bi, Concon; Fan, Li

    2015-03-01

    Based on molecular design, a cytisine surface-imprinted material was prepared using the new surface-imprinting technique of "pre-graft polymerizing and post-imprinting". The graft-polymerization of glycidyl methacrylate (GMA) on the surfaces of micron-sized silica gel particles was first performed with a surface-initiating system, preparing the grafted particles PGMA/SiO2. Subsequently, a polymer reaction, the ring-opening reaction of the epoxy groups of the grafted PGMA, was conducted with sodium 2,4-diaminobenzene sulfonate (SAS) as reagent, resulting in the functional grafted particles SAS-PGMA/SiO2. The adsorption of cytisine on SAS-PGMA/SiO2 particles reached saturation via strong electrostatic interaction between the sulfonate groups of SAS-PGMA/SiO2 particles and the protonated N atoms in cytisine molecule. Finally, cytisine surface-imprinting was successfully carried out with glutaraldehyde as crosslinker, obtaining cytisine surface-imprinted material MIP-SASP/SiO2. The binding and recognition characteristics of MIP-SASP/SiO2 towards cytisine were investigated in depth. The experimental results show that there is strong electrostatic interaction between particles and cytisine molecules, and on this basis, cytisine surface-imprinting can be smoothly performed. The surface-imprinted MIP-SASP/SiO2 has special recognition selectivity and excellent binding affinity for cytisine, and the selectivity coefficients of MIP-SASP/SiO2 particles for cytisine relative to matrine and oxymatrine, which were used as two contrast alkaloids, are 9.5 and 6.5, respectively.

  7. Molecular imprinted magnetic nanoparticles for controlled delivery of mitomycin C.

    PubMed

    Türkmen, Deniz; Bereli, Nilay; Çorman, M Emin; Shaikh, Huma; Akgöl, Sinan; Denizli, Adil

    2014-10-01

    Controlled drug delivery system is a technique which has considerable recent potential in the fields of pharmacy and medicine. Mitomycin C is commonly used drug in the treatment of superficial bladder and breast cancers. In the present study, mitomycin C-imprinted magnetic poly(hydroxyethyl methacrylate)-based nanoparticles (MIMNs) were prepared using surfactant free emulsion polymerization for controlled delivery of mitomycin C. The MIMNs were characterized by fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, electron spin resonance, and elemental analysis. The average particle diameter of MIMNs was about 200 nm.

  8. Quality control of automotive engine oils with mass-sensitive chemical sensors--QCMs and molecularly imprinted polymers.

    PubMed

    Dickert, F L; Forth, P; Lieberzeit, P A; Voigt, G

    2000-04-01

    Molecularly imprinted polyurethanes were used as sensor materials for monitoring the degradation of automotive engine oils. Imprinting with characteristic oils permits the analysis of these complex mixtures without accurately knowing their composition. Mass-sensitive quartz crystal microbalances (QCMs) coated with such layers exhibit mass effects in addition to frequency shifts caused by viscosity, which can be compensated by an uncoated quartz or a non-imprint layer. Incorporation of degradation products into the imprinted coatings is a bulk phenomenon, which is proven by variation of the sensor layer height. Therefore, the resulting sensor effects are determined by the degradation products in the oil.

  9. A quartz crystal microbalance sensor based on mussel-inspired molecularly imprinted polymer.

    PubMed

    Zhou, Wen-Hui; Tang, Shui-Fen; Yao, Qiu-Hong; Chen, Fa-Rong; Yang, Huang-Hao; Wang, Xiao-Ru

    2010-10-15

    In this work, we describe a simple, inexpensive and fast method for the generation of molecularly imprinted polymer (MIP) film on quartz crystal microbalance (QCM) crystals using mussel-inspired polymer. Commonly known as a neurotransmitter, dopamine is also a small-molecule mimic of the adhesive proteins of mussels. Polymerization of dopamine in the presence of template molecule (1,3,5-pentanetricarboxylic acid, an analogue of domoic acid, in this case) could produce an adherent molecularly imprinted polydopamine film coating on QCM crystals. Advantages, such as high hydrophilicity, high biocompatibility and controllable thickness, make this molecularly imprinted polydopamine film an attractive recognition element for sensors. Selective rebinding of domoic acid on mussel-inspired molecularly imprinted polymer (m-MIP) coated crystal was observed as a frequency shift quantified by piezoelectric microgravimetry with the QCM system. The decreasing frequency shows a good linear relationship with the concentration of domoic acid. The quantitation limit of domoic acid was 5 ppb with the linear range of 0-100 ppb. The QCM sensor has high selectivity and was able to distinguish domoic acid from its analogous p-phthalic acid and o-phthalic acid owing to the molecular imprinting effect. In addition, the practical analytical performance of the sensor was examined by evaluating the detection of domoic acid in mussel extracts with satisfactory results. It is envisaged that m-MIP could be suitable as recognition element for sensors and the proposed m-MIP QCM sensor could be employed to detect analyte of interest in complex matrices. Copyright © 2010 Elsevier B.V. All rights reserved.

  10. A Cascade-Reaction Nanoreactor Composed of a Bifunctional Molecularly Imprinted Polymer that Contains Pt Nanoparticles.

    PubMed

    Wang, Jiao; Zhu, Maiyong; Shen, Xiaojuan; Li, Songjun

    2015-05-11

    This study was aimed at addressing the present challenge of cascade reactions, namely, how to furnish the catalysts with desired and hierarchical catalytic ability. This issue was addressed by constructing a cascade-reaction nanoreactor made of a bifunctional molecularly imprinted polymer containing acidic catalytic sites and Pt nanoparticles. The acidic catalytic sites within the imprinted polymer allowed one specified reaction, whereas the encapsulated Pt nanoparticles were responsible for another coupled reaction. To that end, the unique imprinted polymer was fabricated by using two well-coupled templates, that is, 4-nitrophenyl acetate and 4-nitrophenol. The catalytic hydrolysis of the former compound at the acidic catalytic sites led to the formation of the latter compound, which was further reduced by the encapsulated Pt nanoparticles to 4-aminophenol. Therefore, this nanoreactor demonstrated a catalytic-cascade ability. This protocol opens up the opportunity to develop functional catalysts for complicated chemical processes.

  11. Preparation and characterization of novel molecularly imprinted polymers based on thiourea receptors for nitrocompounds recognition.

    PubMed

    Athikomrattanakul, Umporn; Katterle, Martin; Gajovic-Eichelmann, Nenad; Scheller, Frieder W

    2011-04-15

    Molecularly imprinted polymers (MIPs) for the recognition of nitro derivatives are prepared from three different (thio)urea-bearing functional monomers. The binding capability of the polymers is characterized by a batch binding experiment. The imprinting factors and affinity constants (K) of the imprinted polymers exhibit the same tendency as the binding constants (K(a)) of the functional monomers to the target substance in solution. Not only nitrofurantoin is efficiently bound by these MIPs but also a broad spectrum of other nitro compounds is bound with at the intermediate level, addressing that these (thio)urea-based monomers can be utilized to prepare a family of MIPs for various nitro compounds, which can be applied as recognition elements in separation and analytical application.

  12. Preparation of electrochemical sensor for lead(II) based on molecularly imprinted film

    NASA Astrophysics Data System (ADS)

    Wang, Zhihua; Qin, Yaxin; Wang, Chu; Sun, Lijun; Lu, Xiaole; Lu, Xiaoquan

    2012-01-01

    A high selective voltammetric sensor for Pb2+ was introduced. The feasibility of utilizing strong interactions between Schiff bases and metal ion to prepare the molecularly imprinted polymers (MIPs) electrochemical sensor for Pb2+ in aqueous solutions was studied. Some parameters affecting sensor response were optimized and then a calibration curve was plotted. A dynamic linear range of 3.00 × 10-7 to 5.00 × 10-5 mol/L was obtained. The redox process of Pb2+ on the imprinted electrode is controlled by surface reaction. The stability and the life of imprinted membrane were improved by storing into diluted Pb2+ ion solution. The proposed method was applied to determination of Pb2+ in the Yellow River.

  13. Molecular imprinted nanoelectrodes for ultra sensitive detection of ovarian cancer marker.

    PubMed

    Viswanathan, Subramanian; Rani, Chinnakkaruppanan; Ribeiro, Susana; Delerue-Matos, Cristina

    2012-03-15

    The relentless discovery of cancer biomarkers demands improved methods for their detection. In this work, we developed protein imprinted polymer on three-dimensional gold nanoelectrode ensemble (GNEE) to detect epithelial ovarian cancer antigen-125 (CA 125), a protein biomarker associated with ovarian cancer. CA 125 is the standard tumor marker used to follow women during or after treatment for epithelial ovarian cancer. The template protein CA 125 was initially incorporated into the thin-film coating and, upon extraction of protein from the accessible surfaces on the thin film, imprints for CA 125 were formed. The fabrication and analysis of the CA 125 imprinted GNEE was done by using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) techniques. The surfaces of the very thin, protein imprinted sites on GNEE are utilized for immunospecific capture of CA 125 molecules, and the mass of bound on the electrode surface can be detected as a reduction in the faradic current from the redox marker. Under optimal conditions, the developed sensor showed good increments at the studied concentration range of 0.5-400 U mL(-1). The lowest detection limit was found to be 0.5 U mL(-1). Spiked human blood serum and unknown real serum samples were analyzed. The presence of non-specific proteins in the serum did not significantly affect the sensitivity of our assay. Molecular imprinting using synthetic polymers and nanomaterials provides an alternative approach to the trace detection of biomarker proteins.

  14. Electrochemical sensor based on chlorohemin modified molecularly imprinted microgel for determination of 2,4-dichlorophenol.

    PubMed

    Zhang, Jin; Lei, Jianping; Ju, Huangxian; Wang, Chaoying

    2013-07-05

    A newly designed molecularly imprinted polymer (MIP) was synthesized and successfully utilized as a recognition element of an amperometric sensor for 2,4-dichlorophenol (2,4-DCP) detection. The MIP with a well-defined structure could imitate the dehalogenative function of the natural enzyme chloroperoxidase for 2,4-DCP. Imprinted sensor was fabricated in situ on a glassy carbon electrode surface by drop-coating the 2,4-DCP imprinted microgel suspension and chitosan/Nafion mixture. Under optimized conditions, the sensor showed a linear response in the range of 5.0-100 μmol L(-1) with a detection limit of 1.6 μmol L(-1). Additionally, the imprinted sensor demonstrated higher affinity to target 2,4-DCP over competitive chlorophenolic compounds than non-imprinted sensor. It also exhibited good stability and acceptable repeatability. The proposed sensor could be used for the determination of 2,4-DCP in water samples with the recoveries of 96.2-111.8%, showing a promising potential in practical application.

  15. Molecularly imprinted polymers as drug delivery systems for the sustained release of glycyrrhizic acid.

    PubMed

    Cirillo, Giuseppe; Parisi, Ortensia Ilaria; Curcio, Manuela; Puoci, Francesco; Iemma, Francesca; Spizzirri, Umile Gianfranco; Picci, Nevio

    2010-05-01

    The aim was to synthesize molecularly imprinted polymers (MIPs) with high recognition properties towards glycyrrhizic acid and to evaluate the performance of these materials to act as base excipients in glycyrrhizic acid sustained release in gastrointestinal simulating fluids. MIPs were synthesized using methacrylic acid (MAA) as acidic, 2-(dimethylamino)ethyl methacrylate (DMAEMA) as basic, and 2-hydroxyethylmethacrylate (HEMA) as neutral functional monomers, while ethylene glycol dimethacrylate (EGDMA) was chosen as a crosslinking agent. The imprinting effect was evaluated by binding experiments using glycyrrhizic acid and glycyrrhetic acid (analogue molecule) solutions and in-vitro release studies were performed in gastrointestinal simulating fluids. Good recognition and selectivity properties were found in all the synthesized materials in both ethanol and ethanol-water mixture. The release from non-imprinted polymers was indeed higher at acidic pH, while a slower release was observed in MIPs' case, because of the presence of imprinted cavities in the polymeric structure. The stronger capacity of MAA to interact by hydrogen bonds with the template makes MAA-containing MIPs the most effective materials in both rebinding and release experiments. The release tests confirm the applicability of imprinted polymer for glycyrrhizic acid sustained release in gastrointestinal simulating fluids.

  16. Syntheses of steroid-based molecularly imprinted polymers and their molecular recognition study with spectrometric detection

    NASA Astrophysics Data System (ADS)

    Dong, He; Tong, Ai-jun; Li, Long-di

    2003-01-01

    Recognition of five steroid compounds, β-estradiol, ethynylestradiol, estradiolbenzoate, testosterone and methyltestosterone were studied using a synthesized molecularly imprinted polymer (MIP). When β-estradiol was used as the template molecule, the polymer was synthesized with methacrylic acid (MAA) as the functional monomer and ethylene glycol dimethacrylate (EGDMA) as the cross linking agent through non-covalent interactions. It is found that the kind of porogen solvent and the polymerization conditions greatly affected the binding ability of a MIP to a certain molecule. Releasing of the template was performed by continuous extraction with methanol containing 10% acetic acid in a Soxhlet extractor. Our results indicated that such carefully synthesized MIP showed specific affinity toward β-estradiol in the adsorption process.

  17. Preparation of lysozyme molecularly imprinted polymers and purification of lysozyme from egg white.

    PubMed

    Wang, Xuejiao; Dong, Shaohua; Bai, Quan

    2014-06-01

    Molecular imprinting as a promising and facile separation technique has received much attention because of its high selectivity for target molecules. In this study, lysozyme molecularly imprinted polymers (Lys-MIPs) were successfully prepared by the entrapment method with lysozyme as the template molecule, acrylamide as the functional monomer and N,N-methylenebisacrylamide as the cross-linker. The removal of the template lysozyme from the molecularly imprinted polymers was investigated in detail by two methods. The synthesized Lys-MIPs were characterized by scanning electron microscopy and Fourier transform-infrared, and the adsorption capacity, selectivity and reproducibility of the Lys-MIPs were also evaluated. The maximum adsorption capacity reached 94.8 mg/g, which is twice that of nonmolecularly imprinted polymers, and satisfactory selectivity and reproducibility were achieved. Using the Lys-MIP column, lysozyme could be separated completely from egg white, with purity close to 100% and mass recovery of 98.2%. This illustrated that the synthesized Lys-MIPs had high specific recognition and selectivity to the template lysozyme when they were applied to a mixture of protein standards and a real sample.

  18. Surface Plasmon Resonance-Based Fiber Optic Sensors Utilizing Molecular Imprinting

    PubMed Central

    Gupta, Banshi D.; Shrivastav, Anand M.; Usha, Sruthi P.

    2016-01-01

    Molecular imprinting is earning worldwide attention from researchers in the field of sensing and diagnostic applications, due to its properties of inevitable specific affinity for the template molecule. The fabrication of complementary template imprints allows this technique to achieve high selectivity for the analyte to be sensed. Sensors incorporating this technique along with surface plasmon or localized surface plasmon resonance (SPR/LSPR) provide highly sensitive real time detection with quick response times. Unfolding these techniques with optical fiber provide the additional advantages of miniaturized probes with ease of handling, online monitoring and remote sensing. In this review a summary of optical fiber sensors using the combined approaches of molecularly imprinted polymer (MIP) and the SPR/LSPR technique is discussed. An overview of the fundamentals of SPR/LSPR implementation on optical fiber is provided. The review also covers the molecular imprinting technology (MIT) with its elementary study, synthesis procedures and its applications for chemical and biological anlayte detection with different sensing methods. In conclusion, we explore the advantages, challenges and the future perspectives of developing highly sensitive and selective methods for the detection of analytes utilizing MIT with the SPR/LSPR phenomenon on optical fiber platforms. PMID:27589746

  19. Surface Plasmon Resonance-Based Fiber Optic Sensors Utilizing Molecular Imprinting.

    PubMed

    Gupta, Banshi D; Shrivastav, Anand M; Usha, Sruthi P

    2016-08-29

    Molecular imprinting is earning worldwide attention from researchers in the field of sensing and diagnostic applications, due to its properties of inevitable specific affinity for the template molecule. The fabrication of complementary template imprints allows this technique to achieve high selectivity for the analyte to be sensed. Sensors incorporating this technique along with surface plasmon or localized surface plasmon resonance (SPR/LSPR) provide highly sensitive real time detection with quick response times. Unfolding these techniques with optical fiber provide the additional advantages of miniaturized probes with ease of handling, online monitoring and remote sensing. In this review a summary of optical fiber sensors using the combined approaches of molecularly imprinted polymer (MIP) and the SPR/LSPR technique is discussed. An overview of the fundamentals of SPR/LSPR implementation on optical fiber is provided. The review also covers the molecular imprinting technology (MIT) with its elementary study, synthesis procedures and its applications for chemical and biological anlayte detection with different sensing methods. In conclusion, we explore the advantages, challenges and the future perspectives of developing highly sensitive and selective methods for the detection of analytes utilizing MIT with the SPR/LSPR phenomenon on optical fiber platforms.

  20. Exploiting β-cyclodextrin in molecular imprinting for achieving recognition of benzylparaben in aqueous media.

    PubMed

    Asman, Saliza; Mohamad, Sharifah; Sarih, Norazilawati Muhamad

    2015-02-06

    The molecularly imprinted polymer (MIP) based on methacrylic acid functionalized β-cyclodextrin (MAA-β-CD) monomer was synthesized for the purpose of selective recognition of benzylparaben (BzP). The MAA-β-CD monomer was produced by bridging a methacrylic acid (MAA) and β-cyclodextrin (β-CD) using toluene-2,4-diisocyanate (TDI) by reacting the -OH group of MAA and one of the primary -OH groups of β-CD. This monomer comprised of triple interactions that included an inclusion complex, π-π interaction, and hydrogen bonding. To demonstrate β-CD performance in MIPs, two MIPs were prepared; molecularly imprinted polymer-methacrylic acid functionalized β-cyclodextrin, MIP(MAA-β-CD), and molecularly imprinted polymer-methacrylic acid, MIP(MAA); both prepared by a reversible addition fragmentation chain transfer polymerization (RAFT) in the bulk polymerization process. Both MIPs were characterized using the Fourier Transform Infrared Spectroscopy (FTIR), Field Emission Scanning Electron Microscopy (FESEM), and Brunauer-Emmett-Teller (BET). The presence of β-CD not only influenced the morphological structure, it also affected the specific surface area, average pore diameter, and total pore volume of the MIP. The rebinding of the imprinting effect was evaluated in binding experiments, which proved that the β-CD contributed significantly to the enhancement of the recognition affinity and selective adsorption of the MIP.

  1. Exploiting β-Cyclodextrin in Molecular Imprinting for Achieving Recognition of Benzylparaben in Aqueous Media

    PubMed Central

    Asman, Saliza; Mohamad, Sharifah; Muhamad Sarih, Norazilawati

    2015-01-01

    The molecularly imprinted polymer (MIP) based on methacrylic acid functionalized β-cyclodextrin (MAA-β-CD) monomer was synthesized for the purpose of selective recognition of benzylparaben (BzP). The MAA-β-CD monomer was produced by bridging a methacrylic acid (MAA) and β-cyclodextrin (β-CD) using toluene-2,4-diisocyanate (TDI) by reacting the –OH group of MAA and one of the primary –OH groups of β-CD. This monomer comprised of triple interactions that included an inclusion complex, π–π interaction, and hydrogen bonding. To demonstrate β-CD performance in MIPs, two MIPs were prepared; molecularly imprinted polymer-methacrylic acid functionalized β-cyclodextrin, MIP(MAA-β-CD), and molecularly imprinted polymer-methacrylic acid, MIP(MAA); both prepared by a reversible addition fragmentation chain transfer polymerization (RAFT) in the bulk polymerization process. Both MIPs were characterized using the Fourier Transform Infrared Spectroscopy (FTIR), Field Emission Scanning Electron Microscopy (FESEM), and Brunauer-Emmett-Teller (BET). The presence of β-CD not only influenced the morphological structure, it also affected the specific surface area, average pore diameter, and total pore volume of the MIP. The rebinding of the imprinting effect was evaluated in binding experiments, which proved that the β-CD contributed significantly to the enhancement of the recognition affinity and selective adsorption of the MIP. PMID:25667978

  2. Molecularly imprinted polymeric micro- and nano-particles for the targeted delivery of active molecules.

    PubMed

    Gagliardi, Mariacristina; Mazzolai, Barbara

    2015-01-01

    Molecular imprinting (MI) represents a strategy to introduce a 'molecular memory' in a polymeric system obtaining materials with specific recognition properties. MI particles can be used as drug delivery systems providing a targeted release and thus reducing the side effects. The introduction of molecular recognition properties on a polymeric drug carrier represents a challenge in the development of targeted delivery systems to increase their efficiency. This review will summarize the limited number of drug delivery MI particles described in the literature along with an overview of potential solutions for a larger exploitation of MI particles as targeted drug delivery carriers. Molecularly imprinted drug carriers can be considered interesting candidates to significantly improve the efficiency of a controlled drug treatment.

  3. Preparation of mixed molecularly imprinted polymer magnetic nanoparticles and its application in separation of Chinese traditional medicine

    NASA Astrophysics Data System (ADS)

    Xie, Yihui; Ma, Yajuan; Bai, Wenting; Zhu, Xiaofang; Liu, Min; Huang, Liping

    2017-08-01

    A mixed imprinted polymer which can rapidly adsorb all flavonoids from raspberry extract was prepared and recycled. The hybrid molecular surface imprinted polymers were prepared by using quercetin as the template molecule and Fe3O4 magnetic nanospheres as the carrier. The molecular imprinting polymer was prepared by using the "initial template molecule, molecularly imprinted polymer, mixed template molecule, molecularly imprint ted polymers (MIPS)". The adsorption performance and durability of the hybrid molecularly imprinted polymers were investigated by using the fingerprints of the ethyl acetate fraction of raspberry as an index. The adsorption of flavonoids from raspberry extract, lindenoside, cis-lindenin, quercetin, kaempferol and other flavonoids was completely adsorbed by mixed molecular-imprinted polymer, and the other components were basically adsorbed. When Mix-IMPs were repeatedly used 10 times, the fingerprints showed that the content and content of flavonoids were basically the same. The experimental results show that Mix-IMPs has good adsorption performance, can be recycled and used for rapid enrichment of flavonoids in raspberry.

  4. Polymeric Colloidal Nanostructures Fabricated via Highly Controlled Convective Assembly and Their Use for Molecular Imprinting.

    PubMed

    Yang, Jin Chul; Park, Jin Young

    2016-03-23

    In this work, the formation of various polystyrene (PS) colloidal structures on striped PS patterns is demonstrated based on a simple and novel convective assembly method that controls the electrostatic interactions between the PS colloidal particles and sodium dodecyl sulfate (SDS). Under the optimal conditions (different withdrawal speeds, channel dimensions, suspension concentrations, etc.), highly ordered structures such as highly close-packed, zigzag, and linear colloidal aggregates are observed. In addition, these colloidal arrangements are used for development of molecularly imprinted polymer (MIP) sensors with highly improved sensing properties. Using PDMS replicas, three hemispherical poly(methacrylic acid-ethylene glycol dimethacrylate) (poly(MAA-EGDMA)) MIP films, including planar MIP and non-imprinted polymer (NIP) films, are photopolymerized for detection of trace atrazine in an aqueous solution. From gravimetric quartz crystal microbalance (QCM) measurements, a non-close-packed MIP film exhibits highest sensing response (Δf = 932 Hz) to atrazine detection among hemispherical MIP films and shows 6.5-fold higher sensing response than the planar MIP film. In addition, the sensitivity of the MIP sensor is equivalent to -119 Hz/(mol L(-1)). From the ratio of slopes of the calibration curves for the hemispherical MIP and NIP films, the imprinting factor (If) is as high as 11.0. The hemispherical MIP film also shows excellent selectivity in comparison with the sensing responses of other analogous herbicides. As a result, this molecular surface imprinting using PS colloidal arrays is highly efficient for herbicide detection.

  5. Molecularly imprinted microparticles in lipid-based formulations for sustained release of donepezil.

    PubMed

    Ruela, André Luís Morais; de Figueiredo, Eduardo Costa; de Araújo, Magali Benjamim; Carvalho, Flávia Chiva; Pereira, Gislaine Ribeiro

    2016-10-10

    Donepezil is a drug administered for Alzheimer's disease treatment, and it is a potential template molecule for imprinted microparticles. The precipitation polymerization technique allows the synthesis of spherical imprinted microparticles, and the intermolecular interactions among drug and molecularly imprinted polymers (MIPs) play a promising role for delineating drug delivery systems. Once that donepezil is a poorly-water soluble compound, lipid based-formulations (LBFs) may enhance its oral administration. Based on this, LBFs are useful vehicles to incorporate imprinted microparticles synthesized by precipitation polymerization. In these formulations, the drug dissolved in lipids is accessible to adsorbate in the polymers, and the hydrophobic environment of lipids increases the molecular recognition of MIPs. The formulations based on MIPs using pure oleic acid as vehicle prolong the in vitro release of donepezil up to several hours by a Fickian diffusion mechanism, and it provides a multiphasic release pattern related to the heterogeneity of the binding sites. The modulation of donepezil release from MIPs-based formulations using oil vehicles may contribute to decrease its side effects, possibly regulating its absorption rate in the gastrointestinal tract. These systems represent a novel technological platform to prolong the delivery not only for donepezil, but also for a variety of therapeutics. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Molecularly imprinted capillary electrochromatography for selective determination of thiabendazole in citrus samples.

    PubMed

    Cacho, Carmen; Schweitz, Leif; Turiel, Esther; Pérez-Conde, Concepción

    2008-02-01

    In this work, the suitability of the combination of molecular imprinting and capillary electrochromatography (MIP-CEC) to be used as powerful tool in environmental or food analysis has been for the first time studied and successfully demonstrated. A molecularly imprinted monolith (MIM) has been synthesised and evaluated as stationary phase for the selective determination of the fungicide thiabendazole (TBZ) in citrus samples by non-aqueous capillary electrochromatography. The influence of the mobile phase composition, the voltage of the power supply and the separation temperature on the recognition of TBZ by the imprinted polymer has been evaluated, and the imprint effect in the MIM was clearly demonstrated. Once optimum recognition conditions were established, other variables affecting mechanical properties and chromatographic performance of MIM were adjusted using computational approach. The high selectivity achieved by the MIP-CEC developed procedure allowed unambiguous detection and quantification of TBZ in citrus samples by direct injection of the crude sample extracts, without any previous clean-up, in less than 6 min. The developed method was properly validated and the calculated detection limits were below the established maximum residue limits (MRLs), clearly demonstrating the suitability of the method to be used for the control of the selected fungicide.

  7. Preparation of diclofenac-imprinted polymer beads for selective molecular separation in water.

    PubMed

    Zhou, Tongchang; Kamra, Tripta; Ye, Lei

    2017-01-13

    Molecular imprinting technique is an attractive strategy to prepare materials for target recognition and rapid separation. In this work, a new type of diclofenac (DFC)-imprinted polymer beads was synthesized by Pickering emulsion polymerization using 2-(dimethylamino)ethyl methacrylate as the functional monomer. The selectivity and capacity of the molecularly imprinted polymers (MIPs) were investigated in aqueous solution. Equilibrium binding results show that the MIPs have a high selectivity to bind DFC in a wide range of pH values. Moreover, in liquid chromatography experiment, the imprinted polymer beads were packed into column to investigate the binding selectivity under nonequilibrium conditions. The retention time of DFC on the MIP column is significantly longer than its structural analogues. Also, retention of DFC on the MIP column was significantly longer than on the nonimprinted polymer column under aqueous condition. As the new MIP beads can be used to achieve direct separation of DFC from water, the synthetic method and the affinity beads developed in this work opened new possibilities for removing toxic chemicals from environmental and drinking water.

  8. Optical sensing of phenylalanine in urine via extraction with magnetic molecularly imprinted poly(ethylene-co-vinyl alcohol) nanoparticles

    NASA Astrophysics Data System (ADS)

    Hsu, Chung-Yi; Lee, Mei-Hwa; Thomas, James L.; Shih, Ching-Ping; Hung, Tzu-Lin; Whang, Thou-Jen; Lin, Hung-Yin

    2015-07-01

    Incorporation of superparamagnetic nanoparticles into molecularly imprinted polymers (MIPs) is useful for both bioseparations and for concentration and sensing of biomedically relevant target molecules in physiological fluids, through the application of a magnetic field. In this study, we combined the separation and concentration of a target (phenylalanine) in urine, using magnetic molecularly imprinted polymeric composite nanoparticles, with optical sensing, to improve assay sensitivity. This target is important as a catecholamine precursor, and as an important amino acid constituent of proteins. Poly(ethylene-co-vinyl alcohol)s were imprinted with target molecules, and showed a high imprinting effectiveness (target binding compared with binding to non-imprinted polymer particles.) Fluorescence spectrophotometry was used to measure binding of the target, and also binding of possible interfering compounds. These measurements suggest that functional groups on phenylalanine dominate the selectivity of the synthesized MIPs. Finally, the composite nanoparticles were used to separate and sense the target molecule in urine by Raman scattering microscopy.

  9. Nanostructured conducting molecularly imprinted polymer for selective extraction of salicylate from urine and serum samples by electrochemically controlled solid-phase micro-extraction.

    PubMed

    Ameli, Akram; Alizadeh, Naader

    2011-11-30

    Overoxidized polypyrrole (OPPy) films templated with salicylate (SA) have been utilized as conducting molecular imprinted polymers (CMIPs) for potential-induced selective solid-phase micro-extraction processes. Various important fabrication factors for controlling the performance of the OPPy films have been investigated using fluorescence spectrometry. Several key parameters such as applied potential for uptake, release, pH of uptake and release solution were varied to achieve the optimum micro-extraction procedure. The film template with SA exhibited excellent selectivity over some interference. The calibration graphs were linear in the ranges of 5×10(-8) to 5×10(-4) and 1.2×10(-6) to 5×10(-4)mol mL(-1) and the detection limit was 4×10(-8) mol L(-1). The OPPy film as the solid-phase micro-extraction absorbent has been applied for the selective clean-up and quantification of trace amounts of SA from physiological samples. The results of scanning electron microscopy (SEM) have confirmed the nano-structure morphologies of the films. Copyright © 2011 Elsevier B.V. All rights reserved.

  10. Synthesis of hydrophilic and conductive molecularly imprinted polyaniline particles for the sensitive and selective protein detection.

    PubMed

    Luo, Jing; Huang, Jing; Wu, Yunan; Sun, Jun; Wei, Wei; Liu, Xiaoya

    2017-08-15

    In this work, a novel kind of water-dispersible molecular imprinted conductive polyaniline particles was prepared through a facile and efficient macromolecular co-assembly of polyaniline with amphiphilic copolymer, and applied as the molecular recognition element to construct protein electrochemical sensor. In our strategy, an amphiphilic copolymer P(AMPS-co-St) was first synthesized using 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and styrene (St) as monomer, which could co-assemble with PANI in aqueous solution to generate PANI particles driven by the electrostatic interaction. During this process, ovalbumin (OVA) as template protein was added and trapped into the PANI NPs particles owing to their interactions, resulting in the formation of molecular imprinted polyaniline (MIP-PANI) particles. When utilizing the MIP-PANI particles as recognition element, the resultant imprinted PANI sensor not only exhibited good selectivity toward template protein (the imprinting factor α is 5.31), but also a wide linear range over OVA concentration from 10(-11) to 10(-6)mgmL(-1) with a significantly lower detection limit of 10(-12)mgmL(-1), which outperformed most of reported OVA detecting methods. In addition, an ultrafast response time of less than 3min has also been demonstrated. The superior performance is ascribed to the water compatibility, large specific surface area of PANI particles and the electrical conductivity of PANI which provides a direct path for the conduction of electrons from the imprinting sites to the electrode surface. The outstanding sensing performance combined with its facile, quick, green preparation procedure as well as low production cost makes the MIP-PANI particles attractive in specific protein recognition and sensing. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Potentiometric Sensors Based on Surface Molecular Imprinting: Detection of Cancer Biomarkers and Viruses

    SciTech Connect

    Wang, Y.; Zhang, Z; Jain, V; Yi, J; Mueller, S; Sokolov, J; Liu, Z; Levon, K; Rigas, B; Rafailovich, M

    2010-01-01

    The continuing discovery of cancer biomarkers necessitates improved methods for their detection. Molecular imprinting using artificial materials provides an alternative to the detection of a wide range of substances. We applied surface molecular imprinting using self-assembled monolayers to design sensing elements for the detection of cancer biomarkers and other proteins. These elements consist of a gold-coated silicon chip onto which hydroxyl-terminated alkanethiol molecules and template biomolecule are co-adsorbed, where the thiol molecules are chemically bound to the metal substrate and self-assembled into highly ordered monolayers, the biomolecules can be removed, creating the foot-print cavities in the monolayer matrix for this kind of template molecules. Re-adsorption of the biomolecules to the sensing chip changes its potential, which can be measured potentiometrically. We applied this method to the detection of carcinoembryonic antigen (CEA) in both solutions of purified CEA and in the culture medium of a CEA-producing human colon cancer cell line. The CEA assay, validated also against a standard immunoassay, was both sensitive (detection range 2.5-250 ng/mL) and specific (no cross-reactivity with hemoglobin; no response by a non-imprinted sensor). Similar results were obtained for human amylase. In addition, we detected virions of poliovirus in a specific manner (no cross-reactivity to adenovirus, no response by a non-imprinted sensor). Our findings demonstrate the application of the principles of molecular imprinting to the development of a new method for the detection of protein cancer biomarkers and to protein-based macromolecular structures such as the capsid of a virion. This approach has the potential of generating a general assay methodology that could be highly sensitive, specific, simple and likely inexpensive.

  12. Syntheses of molecularly imprinted polymers: Molecular recognition of cyproheptadine using original print molecules and azatadine as dummy templates.

    PubMed

    Feás, X; Seijas, J A; Vázquez-Tato, M P; Regal, P; Cepeda, A; Fente, C

    2009-01-12

    The use of custom-made polymeric materials with high selectivities as target molecules in solid-phase extraction (SPE), known as molecularly imprinted solid-phase extraction (MISPE), is becoming an increasingly important sample preparation technique. However, the potential risk of leakage of the imprinting molecules during the desorption phase has limited application. The use of a mimicking template, called a dummy molecular imprinting polymer (DMIP), that bears the structure of a related molecule and acts as a putative imprinting molecule may provide a useful solution to this problem. In the current study, cyproheptadine (CPH) and azatadine (AZA) were used as templates in the development of an MIP and DMIP for acrylic acid and methacrylic acid monomers. Our results indicate that DMIPs have equal recognition of CPH, avoiding the problem of leakage of original template during the desorption phase relative to MIPs synthesized in presence of the print molecule CPH. Examination of the surface structure of the two polymer products by SEM shows appreciable differences in structural morphology and function of the monomers employed. These results are well supplemented by data obtained for swelling ratios and solvent uptake. Molecular modelling of CPH and AZA suggests that both substrates are similar in shape and volume.

  13. An innovative approach to prepare hypericin molecularly imprinted pearls using a "phyto-template".

    PubMed

    Florea, Ana-Mihaela; Iordache, Tanța-Verona; Branger, Catherine; Ghiurea, Marius; Avramescu, Sorin; Hubca, Gheorghe; Sârbu, Andrei

    2016-01-01

    In this paper, an innovative method that uses hypericin "phyto-template" molecules is being applied herein for the first time to produce molecularly imprinted polymer (MIP) pearls able to selectively retain hypericin from Hypericum Perforatum L primary extracts. For this purpose, the wet phase inversion method was preferred for preparing the hypericin-MIP pearls for several reasons referring to economical benefits but also due to the fact that hypericin "phyto-template" molecules can be generated along with the phase inversion of the copolymer. Practically, the precursor poly(acrylonitrile-co-methacrylic acid) solution was mixed with a purified and concentrated naphtodianthrone phyto-extract (consisting only of hypericin and pseudo-hypericin). In the subsequent phase inversion step hypericin was trapped in the copolymer droplets, as a result to its poor solubility in the inversion water bath, and further served as "phyto-template" in the imprinting step. This in situ repartition of hypericin and pseudo-hypericin was sustained by HPLC-DAD chromatograms which recorded only the presence of hypericin during the extraction stage of imprinted pearls. Batch rebinding measurements, all together, validated the efficiency of this innovative imprinting procedure. The hypericin rebinding of imprinted pearls was quantitative (up to 318 µg/L) and approximately 5 times more specific relative to the blank pearls. Competitive re-binding revealed a more selective behaviour of imprinted pearls for hypericin when the up-take was measured against pseudohypericin (selectivity coefficient above 4.50). Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Molecularly imprinted polymer grafted to porous polyethylene frits: a new selective solid-phase extraction format.

    PubMed

    Barahona, Francisco; Turiel, Esther; Martín-Esteban, Antonio

    2011-10-07

    In this paper, a novel format for selective solid-phase extraction based on a molecularly imprinted polymer (MIP) is described. A small amount of MIP has been synthesized within the pores of commercial polyethylene (PE) frits and attached to its surface using benzophenone (BP), a photo-initiator capable to start the polymerisation from the surface of the support material. Key properties affecting the obtainment of a proper polymeric layer, such as polymerisation time and kind of cross-linker were optimised. The developed imprinted material has been applied as a selective sorbent for cleaning extracts of thiabendazole (TBZ), as model compound, from citrus samples. The use of different solvents for loading the analyte in the imprinted frits was investigated, as well as the binding capacity of the imprinted polymer. Imprinted frits showed good selectivity when loads were performed using toluene and a linear relationship was obtained for the target analyte up to 1000 ng of loaded analyte. Prepared composite material was applied to the SPE of TBZ in real samples extracts, showing an impressive clean-up ability. Calibrations showed good linearity in the concentration range of 0.05-5.00 μg g(-1), referred to the original solid sample, and the regression coefficients obtained were greater than 0.996. The calculated detection limit was 0.016 μg g(-1), low enough to satisfactory analysis of TBZ in real samples. RSDs at different spiking levels ranged below 15% in all the cases and imprinted frits were reusable without loss in their performance.

  15. Molecularly imprinted fluorescent hollow nanoparticles as sensors for rapid and efficient detection λ-cyhalothrin in environmental water.

    PubMed

    Wang, Jixiang; Qiu, Hao; Shen, Hongqiang; Pan, Jianming; Dai, Xiaohui; Yan, Yongsheng; Pan, Guoqing; Sellergren, Börje

    2016-11-15

    Molecularly imprinted fluorescent polymers have shown great promise in biological or chemical separations and detections, due to their high stability, selectivity and sensitivity. In this work, molecularly imprinted fluorescent hollow nanoparticles, which could rapidly and efficiently detect λ-cyhalothrin (a toxic insecticide) in water samples, was reported. The molecularly imprinted fluorescent sensor showed excellent sensitivity (the limit of detection low to 10.26nM), rapid detection rate (quantitative detection of λ-cyhalothrin within 8min), regeneration ability (maintaining good fluorescence properties after 8 cycling operation) and appreciable selectivity over several structural analogs. Moreover, the fluorescent sensor was further used to detect λ-cyhalothrin in real samples form the Beijing-Hangzhou Grand Canal Water. Despite the relatively complex components of the environmental water, the molecularly imprinted fluorescent hollow nanosensor still showed good recovery, clearly demonstrating the potential value of this smart sensor nanomaterial in environmental monitoring. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Imprinting of Molecular Recognition Sites on Nanostructures and Its Applications in Chemosensors.

    PubMed

    Guan, Guijian; Liu, Bianhua; Wang, Zhenyang; Zhang, Zhongping

    2008-12-15

    Biological receptors including enzymes, antibodies and active proteins have been widely used as the detection platform in a variety of chemo/biosensors and bioassays. However, the use of artificial host materials in chemical/biological detections has become increasingly attractive, because the synthetic recognition systems such as molecularly imprinted polymers (MIPs) usually have lower costs, higher physical/chemical stability, easier preparation and better engineering possibility than biological receptors. Molecular imprinting is one of the most efficient strategies to offer a synthetic route to artificial recognition systems by a template polymerization technique, and has attracted considerable efforts due to its importance in separation, chemo/biosensors, catalysis and biomedicine. Despite the fact that MIPs have molecular recognition ability similar to that of biological receptors, traditional bulky MIP materials usually exhibit a low binding capacity and slow binding kinetics to the target species. Moreover, the MIP materials lack the signal-output response to analyte binding events when used as recognition elements in chemo/biosensors or bioassays. Recently, various explorations have demonstrated that molecular imprinting nanotechniques may provide a potential solution to these difficulties. Many successful examples of the development of MIP-based sensors have also been reported during the past several decades. This review will begin with a brief introduction to the principle of molecular imprinting nanotechnology, and then mainly summarize various synthesis methodologies and recognition properties of MIP nanomaterials and their applications in MIP-based chemosensors. Finally, the future perspectives and efforts in MIP nanomaterials and MIP-based sensors are given.

  17. Imprinting of Molecular Recognition Sites on Nanostructures and Its Applications in Chemosensors

    PubMed Central

    Guan, Guijian; Liu, Bianhua; Wang, Zhenyang; Zhang, Zhongping

    2008-01-01

    Biological receptors including enzymes, antibodies and active proteins have been widely used as the detection platform in a variety of chemo/biosensors and bioassays. However, the use of artificial host materials in chemical/biological detections has become increasingly attractive, because the synthetic recognition systems such as molecularly imprinted polymers (MIPs) usually have lower costs, higher physical/chemical stability, easier preparation and better engineering possibility than biological receptors. Molecular imprinting is one of the most efficient strategies to offer a synthetic route to artificial recognition systems by a template polymerization technique, and has attracted considerable efforts due to its importance in separation, chemo/biosensors, catalysis and biomedicine. Despite the fact that MIPs have molecular recognition ability similar to that of biological receptors, traditional bulky MIP materials usually exhibit a low binding capacity and slow binding kinetics to the target species. Moreover, the MIP materials lack the signal-output response to analyte binding events when used as recognition elements in chemo/biosensors or bioassays. Recently, various explorations have demonstrated that molecular imprinting nanotechniques may provide a potential solution to these difficulties. Many successful examples of the development of MIP-based sensors have also been reported during the past several decades. This review will begin with a brief introduction to the principle of molecular imprinting nanotechnology, and then mainly summarize various synthesis methodologies and recognition properties of MIP nanomaterials and their applications in MIP-based chemosensors. Finally, the future perspectives and efforts in MIP nanomaterials and MIP-based sensors are given. PMID:27873989

  18. The Application of Template Selectophores for the Preparation of Molecularly Imprinted Polymers.

    PubMed

    Danylec, Basil; Schwarz, Lachlan J; Harris, Simon J; Boysen, Reinhard I; Hearn, Milton T W

    2015-09-23

    Molecularly imprinted polymers are versatile materials with wide application scope for the detection, capture and separation of specific compounds present in complex feed stocks. A major challenge associated with their preparation has been the need to sacrifice one mole equivalent of the template molecule to generate the complementary polymer cavities that selectively bind the target molecule. Moreover, template molecules can often be difficult to synthesise, expensive or lack stability. In this study, we describe a new approach, directed at the use of synthetic selectophores, chosen as readily prepared and low cost structural analogues with recognition groups in similar three-dimensional arrangements as found in the target molecule. To validate the approach, a comparative study of selectophores related to the polyphenolic compound (E)-resveratrol has been undertaken using traditional and green chemical synthetic approaches. These molecular mimic compounds were employed as polymer templates and also as binding analytes to interrogate the recognition sites associated with the molecularly imprinted polymers. Importantly, the study confirms that the use of selectophores has the potential to confer practical advantages, including access to more efficient methods for selection and preparation of suitable template molecules with a broader range of molecular diversity, as well as delivering imprinted polymers capable of recognizing the target compound and structurally related products.

  19. Synthesis and computational investigation of molecularly imprinted nanospheres for selective recognition of alpha-tocopherol succinate

    PubMed Central

    Piacham, Theeraphon; Nantasenamat, Chanin; Isarankura-Na-Ayudhya, Chartchalerm; Prachayasittikul, Virapong

    2013-01-01

    Molecularly imprinted polymers (MIPs) are macromolecular matrices that can mimic the functional properties of antibodies, receptors and enzymes while possessing higher durability. As such, these polymers are interesting materials for applications in biomimetic sensor, drug synthesis, drug delivery and separation. In this study, we prepared MIPs and molecularly imprinted nanospheres (MINs) as receptors with specific recognition properties toward tocopherol succinate (TPS) in comparison to tocopherol (TP) and tocopherol nicotinate (TPN). MIPs were synthesized using methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as crosslinking agent and dichloromethane or acetronitrile as porogenic solvent under thermal-induced polymerization condition. Results indicated that imprinted polymers of TPS-MIP, TP-MIP and TPN-MIP all bound specifically to their template molecules at 2 folds greater than the non-imprinted polymers. The calculated binding capacity of all MIP was approximately 2 mg per gram of polymer when using the optimal rebinding solvent EtOH:H2O (3:2, v/v). Furthermore, the MINs toward TPS and TP were prepared by precipitation polymerization that yielded particles that are 200-400 nm in size. The binding capacities of MINs to their templates were greater than that of the non-imprinted nanospheres when using the optimal rebinding solvent EtOH:H2O (4:1, v/v). Computer simulation was performed to provide mechanistic insights on the binding modalities of template-monomer complexes. In conclusion, we had successful prepared MIPs and MINs for binding specifically to TP and TPS. Such MIPs and MINs have great potential for industrial and medical applications, particularly for the selective separation of TP and TPS. PMID:26622214

  20. Acetic and Acrylic Acid Molecular Imprinted Model Silicone Hydrogel Materials for Ciprofloxacin-HCl Delivery

    PubMed Central

    Hui, Alex; Sheardown, Heather; Jones, Lyndon

    2012-01-01

    Contact lenses, as an alternative drug delivery vehicle for the eye compared to eye drops, are desirable due to potential advantages in dosing regimen, bioavailability and patient tolerance/compliance. The challenge has been to engineer and develop these materials to sustain drug delivery to the eye for a long period of time. In this study, model silicone hydrogel materials were created using a molecular imprinting strategy to deliver the antibiotic ciprofloxacin. Acetic and acrylic acid were used as the functional monomers, to interact with the ciprofloxacin template to efficiently create recognition cavities within the final polymerized material. Synthesized materials were loaded with 9.06 mM, 0.10 mM and 0.025 mM solutions of ciprofloxacin, and the release of ciprofloxacin into an artificial tear solution was monitored over time. The materials were shown to release for periods varying from 3 to 14 days, dependent on the loading solution, functional monomer concentration and functional monomer:template ratio, with materials with greater monomer:template ratio (8:1 and 16:1 imprinted) tending to release for longer periods of time. Materials with a lower monomer:template ratio (4:1 imprinted) tended to release comparatively greater amounts of ciprofloxacin into solution, but the release was somewhat shorter. The total amount of drug released from the imprinted materials was sufficient to reach levels relevant to inhibit the growth of common ocular isolates of bacteria. This work is one of the first to demonstrate the feasibility of molecular imprinting in model silicone hydrogel-type materials. PMID:28817033

  1. Synthesis and computational investigation of molecularly imprinted nanospheres for selective recognition of alpha-tocopherol succinate.

    PubMed

    Piacham, Theeraphon; Nantasenamat, Chanin; Isarankura-Na-Ayudhya, Chartchalerm; Prachayasittikul, Virapong

    2013-01-01

    Molecularly imprinted polymers (MIPs) are macromolecular matrices that can mimic the functional properties of antibodies, receptors and enzymes while possessing higher durability. As such, these polymers are interesting materials for applications in biomimetic sensor, drug synthesis, drug delivery and separation. In this study, we prepared MIPs and molecularly imprinted nanospheres (MINs) as receptors with specific recognition properties toward tocopherol succinate (TPS) in comparison to tocopherol (TP) and tocopherol nicotinate (TPN). MIPs were synthesized using methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as crosslinking agent and dichloromethane or acetronitrile as porogenic solvent under thermal-induced polymerization condition. Results indicated that imprinted polymers of TPS-MIP, TP-MIP and TPN-MIP all bound specifically to their template molecules at 2 folds greater than the non-imprinted polymers. The calculated binding capacity of all MIP was approximately 2 mg per gram of polymer when using the optimal rebinding solvent EtOH:H2O (3:2, v/v). Furthermore, the MINs toward TPS and TP were prepared by precipitation polymerization that yielded particles that are 200-400 nm in size. The binding capacities of MINs to their templates were greater than that of the non-imprinted nanospheres when using the optimal rebinding solvent EtOH:H2O (4:1, v/v). Computer simulation was performed to provide mechanistic insights on the binding modalities of template-monomer complexes. In conclusion, we had successful prepared MIPs and MINs for binding specifically to TP and TPS. Such MIPs and MINs have great potential for industrial and medical applications, particularly for the selective separation of TP and TPS.

  2. Electroanalysis of myoglobin based on electropolymerized molecularly imprinted polymer poly-o-phenylenediamine and carbon nanotubes/screen printed electrode.

    PubMed

    Shumyantseva, V V; Bulko, T V; Sigolaeva, L V; Kuzikov, A V; Archakov, A I

    2016-05-01

    Electroanalysis of myoglobin as a marker of acute myocardial infarction by means of screenprinted electrodes modified with multiwalled carbon nanotubes and polymeric artificial antibodies is developed. Plastic antibodies to myoglobin (molecularly imprinted polymers, MIPs) based on o-phenylenediamine were produced by electropolymerization. Molecular imprinting technology in biosensor analysis was used as alternative to natural receptors (namely, antibodies) and demonstrated high sensitivity (1.5 × 10(-2) A/nmol of myoglobin) and selectivity.

  3. Molecularly imprinted films of acrylonitrile/methyl methacrylate/acrylic acid terpolymers: influence of methyl methacrylate in the binding performance of L-ephedrine imprinted films.

    PubMed

    Brisbane, Carrie; McCluskey, Adam; Bowyer, Michael; Holdsworth, Clovia I

    2013-05-07

    Molecularly imprinted polymeric films (MIPFs) highly selective to 1R,2S(-)ephedrine (L-ephedrine, EPD) were produced by phase inversion post-polymerization imprinting on poly(acrylonitrile-co-methyl methacrylate-co-acrylic acid) (PAMA) terpolymers. The inclusion of methyl methacrylate (MMA) to the polymer formulation resulted in enhanced EPD selectivity which appears to be dictated by polymer composition to achieve the necessary balance between polymer rigidity and porosity. Substitution of MMA with methyl acrylate, ethyl acrylate and n-butyl acrylate resulted in a loss of EPD selectivity and EPD entrapment within the polymer matrix not observed in PAMA MIPFs. MMA, by virtue of its methyl group, is able to provide the scaffolding and rigidity necessary for stability and preservation of imprinted cavities within the PAMA MIPF leading to high EPD selectivity.

  4. Selective cholesterol adsorption by molecular imprinted polymeric nanospheres and application to GIMS.

    PubMed

    Inanan, Tülden; Tüzmen, Nalan; Akgöl, Sinan; Denizli, Adil

    2016-11-01

    Molecular imprinted polymers (MIPs) are tailor-made materials with selective recognition to the target. The goals of this study were to prepare cholesterol imprinted polymeric nanospheres (CIPNs) and optimize their adsorption parameters and also to use CIPNs for adsorption of cholesterol (CHO), which is an important physiological biomacromolecule, from gastrointestinal mimicking solution (GIMS). Pre-polymerization complex was prepared using CHO as template and N-methacryloylamido-(l)-phenylalanine methyl ester (MAPA). This complex was polymerized with 2-hydroxyethyl methacrylate (HEMA). CHO was removed by MeOH and tetrahydrofuran (THF). Adsorption studies were performed after chacterization studies to interrogate the effects of time, initial concentration, temperature, and ionic strength on CHO adsorption onto CIPNs. Maximum adsorption capacity (714.17mg/g) was higher than that of cholesterol imprinted polymers in literature. Pseudo-second-order kinetics and Langmuir isotherm fitted best with the adsorption onto CIPNs. 86% of adsorbed cholesterol was desorbed with MeOH:HAc (80:20, v/v) and CIPNs were used in adsorption-desorption cycle for 5-times with a decrease as 12.28%. CHO analogues; estron, estradiol, testosterone, and progesterone were used for competitive adsorption. The relative selectivity coefficients of CINPs for cholesterol/estron and cholesterol/testosterone were 3.84 and 10.47 times greater than the one of non-imprinted polymeric nanospheres (NIPNs) in methanol, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Polydopamine-based superparamagnetic molecularly imprinted polymer nanospheres for efficient protein recognition.

    PubMed

    Lan, Fang; Ma, Shaohua; Yang, Qi; Xie, Liqin; Wu, Yao; Gu, Zhongwei

    2014-11-01

    A new strategy for synthesis of superparamagnetic molecularly imprinted polymer nanospheres (MIPNSs) for efficient protein recognition is described here. Homogeneous hydroxyl group functionalized Fe3O4/polymethyl methacrylate (PMMA) composite nanospheres were prepared using improved miniemulsion polymerization. Uniform superparamagnetic MIPNSs were obtained via self-polymerization of dopamine (DA) on the surface of Fe3O4/PMMA composite nanospheres in the presence of lysozyme (lyz) template. The as-synthesized Fe3O4/PMMA/PDA MIPNSs had average diameters of 180 nm, high saturation magnetization and a good magnetic response. The lyz-imprinted Fe3O4/PMMA/PDA MIPNSs exhibited specific recognition and efficient adsorption capacity toward lyz template. The amount of lyz adsorbed onto the lyz-imprinted Fe3O4/PMMA/PDA MIPNSs was about 4 times greater than that of the Fe3O4/PMMA/PDA non-imprinted polymer nanospheres (NIPNSs) and about 14, 5, and 5 times greater than that of BSA, BHb, and cyt C, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Synthesis and evaluation of a selective molecularly imprinted polymer for the contraceptive drug levonorgestrel.

    PubMed

    Khorrami, Afshin Rajabi; Mehrseresht, Shima

    2008-05-15

    A molecularly imprinted polymer (MIP) has been prepared using levonorgestrel (LEV) as template. The polymer was synthesised in a non-covalent approach using methacrylic acid (MAA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linking monomer via a free radical polymerization. An equivalent blank polymer was also synthesised in the absence of the template compound. Batch adsorption experiments were used to evaluate the binding affinity of the imprinted polymer. After packing MIP into a stainless steel column (150 mm x 4.6 mm i.d.), retention and elution of the template and related compounds were evaluated by high-performance liquid chromatography (HPLC). This LEV imprinted polymer was further applied for selective solid phase extraction (SPE) of LEV from human serum. It was confirmed that the binding ability of the prepared MIP for LEV was essentially sufficient in the presence of other compounds coexisting in serum sample. Therefore, as a selective and efficient solid phase material, LEV imprinted polymer has a high potential application in analysis of this steroidal hormone in clinical purposes.

  7. Comparison of the thermodynamic properties of particulate and monolithic columns of molecularly imprinted copolymers

    SciTech Connect

    Kim, Hyunjung; Guiochon, Georges A

    2005-01-01

    A variety of polymerization techniques can be used to prepare molecularly imprinted copolymers (MIPs) for the purpose of the separation of enantiomers by HPLC. Unfortunately, the lack of thermodynamic and kinetic data characterizing the imprinted polymers prepared by these different techniques prevents the rational choice of the one most suited for a specific application. We investigated and compared the thermodynamic properties of copolymers imprinted for Fmoc-l-tryptophan and prepared by two different methods. The first was an in situ polymerization method that gives monolithic columns (monolithic MIPs), the second, a traditional method giving bulk MIPs. Examination of the thermodynamic properties on these two different MIPs showed that three types of binding sites coexist on their surface. The highest energy sites adsorb only the imprinted molecule or template. Most of the intermediate energy sites adsorb both the template and its antipode, although part of them may adsorb only the template. Finally, the lowest energy sites provide nonselective interactions of both the template and its antipode. On the nonimprinted copolymer, there are only two types of sites. The high-energy sites have a slightly lower energy that the intermediate sites of the MIPs, and the low-energy sites have properties close to those of the lowest energy sites on the MIPs. The monolithic MIPs have fewer nonselective sites than the bulk MIPs. However, the polar porogen that is needed to prepare the monolithic MIPs negatively affects the enantiomeric separation.

  8. Differential fluorescence from molecularly imprinted polymers containing europium ions as a transducer element

    NASA Astrophysics Data System (ADS)

    Pestov, Dmitry; Anderson, John; Tepper, Gary

    2006-10-01

    Molecularly imprinted polymers (MIPs) have the potential to provide a unique combination of high chemical selectivity and environmental stability and are, therefore, being widely studied in chemical sensor applications. Optical interrogation of the MIP-chemical interaction is very convenient for the detection of fluorescent compounds, but is problematic for the detection of non-fluorescent species. Doping MIPs with Eu3+ is one approach that can facilitate the optical detection of non-fluorescent species. Eu3+ has absorption in the near UV and the doped MIP can, therefore, be excited with a commercially available laser diode at 375nm. In the present paper MIPs doped with Eu3+ and imprinted to methyl salicylate (MES), a chemical warfare agent simulant, were prepared in the form of a thin film on a quartz substrate. Non-imprinted (Blank) polymer films were also prepared using the same imprinting procedure, but without introducing the MES template. Both polymers were tested to MES and the structurally similar compound methyl 3,5-dimethylbenzoate (DMB) in hexane. For MES, the fluorescence intensity of the MIP was significantly stronger than for the Blank, while for the methyl 3,5-dimethylbenzoate, the Blank polymer exhibited the stronger fluorescence signal. A portable chemical sensor employing differential fluorescence from MIP/Blank polymer pairs is under development and allows target discrimination without the need for spectroscopic analysis of the emission spectra.

  9. Synthesis of porous molecularly imprinted polymers for selective adsorption of glutathione

    NASA Astrophysics Data System (ADS)

    Song, Renyuan; Hu, Xiaoling; Guan, Ping; Li, Ji; Qian, Liwei; Wang, Chaoli; Wang, Qiaoli

    2015-03-01

    An effective approach overcome the classical deficiencies of biomolecules molecularly imprinted polymers (MIPs), that is, low binding capacity and slow mass transfer rate, is proposed. With glutathione (GSH) as target molecule, porous imprinted layers were fabricated according to our newly developed method the introduction of a mixture of acetontrile and dimethylsulfoxide as porogen in surface-initiated polymerization systems. The resultant MIPs particles exhibited a large surface area could remarkably improve the imprinting effect in relation to a significantly increased imprinting factor and mass transfer rate, compared to the MIPs prepared by using aqueous solution as solvent. The batch static binding tests were carried out to evaluate the adsorption kinetics, adsorption isotherms and selective recognition of the MIPs particles. The binding behavior followed the pseudo-second order kinetic model, revealing that the process was chemically carried out. Two binding isotherm models were applied to analyze equilibrium data, obtaining the best description by Langmuir isotherm model. In addition, the selective of separation and extraction of GSH from a mixture of GSH and its structural analogs could be achieved on the MIPs solid-phase extraction cartridge, indicating that the possibility for the separation and enrichment of the template from complicated matrices.

  10. Surface plasmon resonance based optical fiber riboflavin sensor by using molecularly imprinted gel

    NASA Astrophysics Data System (ADS)

    Verma, Roli; Gupta, Banshi D.

    2013-05-01

    We report the fabrication and characterization of surface plasmon resonance (SPR) based optical fiber riboflavin/vitamin B2 sensor using combination of colloidal crystal templating and molecularly imprinted gel. The sensor works on spectral interrogation method. The operating range of the sensor lies from 0 μg/ml to 320 μg/ml, the suitable amount of intakes of riboflavin recommended for different age group. The SPR spectra show blue shift with increasing concentration of riboflavin, which is due to the interaction of riboflavin molecule over specific binding sites caused by molecular imprinting. The present sensor has many advantageous features such as fast response, small probe size, low cost and can be used for remote/online monitoring.

  11. Chemical Sensors Based on Molecularly Imprinted Sol-Gel Materials †

    PubMed Central

    Mujahid, Adnan; Lieberzeit, Peter A.; Dickert, Franz L.

    2010-01-01

    The sol-gel technique is earning the worldwide attention of researchers in the field of material science, due to its versatility in synthesizing inorganic ceramic materials at mild conditions. High purity, homogeneity, controlled porosity, stable temperature and nanoscale structuring are the most remarkable features offered by this method for generating highly sensitive and selective matrices to incorporate analyte molecules. The crafting of sol-gel sensors through molecular imprinting has put great influence on the development of innovative chemical sensors, which can be seen from the growing number of publications in this field. The review provides a brief overview of sol-gel sensor applications, and discusses the contribution of molecular imprinting in exploring the new world of sensors.

  12. Automated Protein Biomarker Analysis: on-line extraction of clinical samples by Molecularly Imprinted Polymers

    PubMed Central

    Rossetti, Cecilia; Świtnicka-Plak, Magdalena A.; Grønhaug Halvorsen, Trine; Cormack, Peter A.G.; Sellergren, Börje; Reubsaet, Léon

    2017-01-01

    Robust biomarker quantification is essential for the accurate diagnosis of diseases and is of great value in cancer management. In this paper, an innovative diagnostic platform is presented which provides automated molecularly imprinted solid-phase extraction (MISPE) followed by liquid chromatography-mass spectrometry (LC-MS) for biomarker determination using ProGastrin Releasing Peptide (ProGRP), a highly sensitive biomarker for Small Cell Lung Cancer, as a model. Molecularly imprinted polymer microspheres were synthesized by precipitation polymerization and analytical optimization of the most promising material led to the development of an automated quantification method for ProGRP. The method enabled analysis of patient serum samples with elevated ProGRP levels. Particularly low sample volumes were permitted using the automated extraction within a method which was time-efficient, thereby demonstrating the potential of such a strategy in a clinical setting. PMID:28303910

  13. Molecular imprinting polymers and their composites: a promising material for diverse applications.

    PubMed

    Zaidi, Shabi Abbas

    2017-02-28

    Molecular imprinted polymerization is considered one of the most useful preparation strategies to obtain highly selective polymeric materials called molecular imprinted polymers (MIPs). It has attracted a tremendous amount of interest in the last decade. Consequently, MIPs have been employed in a variety of applications including chromatographic separation, sensors and biosensors fabrication, drug delivery, proteomic analysis and plastic antibody synthesis, etc. The hybridization of the excellent features of MIPs and nanomaterials has further fueled the intensity of research in this area. A good number of works have been reported on MIP-nanomaterial composites in last few years covering all types of applications. In this review, we discuss the basic fundamentals of MIPs, nanomaterials and their combined applications. As a proof of concept, we included selective works published from 2012 to 2016.

  14. Molecular imprinting science and technology: a survey of the literature for the years 2004-2011.

    PubMed

    Whitcombe, Michael J; Kirsch, Nicole; Nicholls, Ian A

    2014-06-01

    Herein, we present a survey of the literature covering the development of molecular imprinting science and technology over the years 2004-2011. In total, 3779 references to the original papers, reviews, edited volumes and monographs from this period are included, along with recently identified uncited materials from prior to 2004, which were omitted in the first instalment of this series covering the years 1930-2003. In the presentation of the assembled references, a section presenting reviews and monographs covering the area is followed by sections describing fundamental aspects of molecular imprinting including the development of novel polymer formats. Thereafter, literature describing efforts to apply these polymeric materials to a range of application areas is presented. Current trends and areas of rapid development are discussed.

  15. Automated Protein Biomarker Analysis: on-line extraction of clinical samples by Molecularly Imprinted Polymers

    NASA Astrophysics Data System (ADS)

    Rossetti, Cecilia; Świtnicka-Plak, Magdalena A.; Grønhaug Halvorsen, Trine; Cormack, Peter A. G.; Sellergren, Börje; Reubsaet, Léon

    2017-03-01

    Robust biomarker quantification is essential for the accurate diagnosis of diseases and is of great value in cancer management. In this paper, an innovative diagnostic platform is presented which provides automated molecularly imprinted solid-phase extraction (MISPE) followed by liquid chromatography-mass spectrometry (LC-MS) for biomarker determination using ProGastrin Releasing Peptide (ProGRP), a highly sensitive biomarker for Small Cell Lung Cancer, as a model. Molecularly imprinted polymer microspheres were synthesized by precipitation polymerization and analytical optimization of the most promising material led to the development of an automated quantification method for ProGRP. The method enabled analysis of patient serum samples with elevated ProGRP levels. Particularly low sample volumes were permitted using the automated extraction within a method which was time-efficient, thereby demonstrating the potential of such a strategy in a clinical setting.

  16. Computational simulation and preparation of fluorescent magnetic molecularly imprinted silica nanospheres for ciprofloxacin or norfloxacin sensing.

    PubMed

    Gao, Bo; He, Xin-Ping; Jiang, Yang; Wei, Jia-Tong; Suo, Hui; Zhao, Chun

    2014-12-01

    A magnetic molecularly imprinted fluorescent sensor for the sensitive and convenient determination of ciprofloxacin or norfloxacin in human urine was synthesized and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, ultraviolet/visible spectroscopy, and fluorescence spectroscopy. Both cadmium telluride quantum dots and ferroferric oxide nanoparticles are introduced into the polymer for the rapid separation and detection of the target molecules. The synthesized molecularly imprinted polymers were applied to detect ciprofloxacin or its structural analog norfloxacin in human urine with the detection limit 130 ng/mL. A computational study was developed to evaluate the template-monomer geometry and interaction energy in the polymerization mixture to determine the reaction molar ratio of the template and monomer molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Preparation of molecularly imprinted polymers for the detection of aromatic hydrocarbons.

    PubMed

    Hwang, Min-Jin; Shim, Wang-Geun; Yang, Chang Yel; Moon, Hee

    2011-08-01

    In this study, the molecularly imprinted polymers (MIPs) are designed to improve their sensitivity and selectivity for specific aromatic hydrocarbons such as benzene, toluene, and xylene isomers. The MIPs based on methyl acrylate (MA) monomer are prepared using toluene and ethylene glycol dimetacrylate (EGDMA) as a template and a cross linking agent, respectively. The binding sites on the MIPs are characterized by using Fourier transform infrared spectrometry (FT-IR), nitrogen adsorption isotherms, and transmission electron microscopy (TEM). The selective behaviors of the MIPs are evaluated by their adsorption properties on a gravimetric apparatus. It is found that the performance is strongly influenced by the composition ratios of cross-linker, functional monomer, and template molecule. The molecular recognition ability can be assessed on the basis of an imprinting effect. The results indicate that the prepared MIPs can be used for the aromatic hydrocarbon sensor materials with high sensitivity and selectivity.

  18. Molecularly imprinted protein recognition thin films constructed by controlled/living radical polymerization.

    PubMed

    Sasaki, Shogo; Ooya, Tooru; Kitayama, Yukiya; Takeuchi, Toshifumi

    2015-02-01

    We demonstrated the synthesis of molecularly imprinted polymers (MIPs) with binding affinity toward a target protein, ribonuclease A (RNase) by atom transfer radical polymerization (ATRP) of acrylic acid, acrylamide, and N,N'-methylenebisacrylamide in the presence of RNase. The binding activity of the MIPs was evaluated by surface plasmon resonance (SPR) of the MIP thin layers prepared on the gold-coated sensor chips. The MIPs prepared by ATRP (MIP-ATRP) had a binding affinity toward RNase with larger binding amount compared to MIPs prepared by conventional free radical polymerization methods (MIP-RP). Moreover, protein selectivity was evaluated using reference proteins (cytochrome c, myoglobin, and α-lactalbumin) and was confirmed in MIP-ATRP of optimum film thickness determined experimentally to be 15-30 nm; however, protein selectivity was not achieved in all MIP-RP. We have shown that ATRP is powerful technique for preparing protein recognition materials by molecular imprinting.

  19. A molecularly imprinted sensor based on an electrochemiluminescent membrane for ultratrace doxycycline determination.

    PubMed

    Li, Shuhuai; Li, Jianping; Lin, Qingyu; Wei, Xiaoping

    2015-07-07

    A new molecularly imprinted sensor was developed based on an electroluminescent molecularly imprinted polymer (MIP) membrane and used for doxycycline determination. The MIP was prepared by electropolymerization of pyrogallol doped with alizarin red. An electrochemiluminescence (ECL) signal was produced by the oxidation of the poly-pyrogallol polymer and reaction with alizarin red. The luminescence intensity was enhanced by doxycycline molecules which were re-adsorbed in cavities in MIP due to the energy transfer of the doxycycline oxidized intermediate to alizarin red. The changes of ECL intensities were linear with the concentrations of doxycycline in the range of 2 × 10(-10) to 5 × 10(-8) mol L(-1). The detection limit was 5.17 × 10(-11) mol L(-1). This method was utilized to determine doxycycline residuals in fish muscles with satisfactory results.

  20. Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection.

    PubMed

    Sergeyeva, T A; Slinchenko, O A; Gorbach, L A; Matyushov, V F; Brovko, O O; Piletsky, S A; Sergeeva, L M; Elska, G V

    2010-02-05

    Portable biomimetic sensor devices for the express control of phenols content in water were developed. The synthetic binding sites mimicking active site of the enzyme tyrosinase were formed in the structure of free-standing molecularly imprinted polymer membranes. Molecularly imprinted polymer membranes with the catalytic activity were obtained by co-polymerization of the complex Cu(II)-catechol-urocanic acid ethyl ester with (tri)ethyleneglycoldimethacrylate, and oligourethaneacrylate. Addition of the elastic component oligourethaneacrylate provided formation of the highly cross-linked polymer with the catalytic activity in a form of thin, flexible, and mechanically stable membrane. High accessibility of the artificial catalytic sites for the interaction with the analyzed phenol molecules was achieved due to addition of linear polymer (polyethyleneglycol Mw 20,000) to the initial monomer mixture before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) were formed. The cross-linked component of the semi-IPN was represented by the highly cross-linked catalytic molecularly imprinted polymer, while the linear one was represented by polyethyleneglycol Mw 20,000. Extraction of the linear polymer from the fully formed semi-IPN resulted in formation of large pores in the membranes' structure. Concentration of phenols in the analyzed samples was detected using universal portable device oxymeter with the oxygen electrode in a close contact with the catalytic molecularly imprinted polymer membrane as a transducer. The detection limit of phenols detection using the developed sensor system based on polymers-biomimics with the optimized composition comprised 0.063 mM, while the linear range of the sensor comprised 0.063-1 mM. The working characteristics of the portable sensor devices were investigated. Storage stability of sensor systems at room temperature comprised 12 months (87%). As compared to traditional methods of phenols

  1. Preparation of a novel drug sensor using a molecular imprinted polymer approach

    NASA Astrophysics Data System (ADS)

    Wren, Stephen P.; Nguyen, T. Hien; Gascoine, Paul; Lacey, Dick; Sun, Tong; Grattan, Kenneth T. V.

    2013-05-01

    A chemical sensor for the detection of cocaine has been developed, based on a molecularly imprinted polymer (MIP) containing a fluorescein moiety as the signalling group. The fluorescent MIP was formed and covalently attached to the distal end of an optical fibre. The sensor exhibited an increase in fluorescence intensity in response to cocaine in an aqueous acetonitrile mixture. Selectivity for cocaine over codeine has been demonstrated.

  2. Liquid crystal alignment with a molecular template of imprinted polymer layer during phase separation

    NASA Astrophysics Data System (ADS)

    Kim, Hak-Rin; Jung, Jong-Wook; Lee, You-Jin; Kim, Jae-Hoon

    2006-03-01

    We developed a liquid crystal (LC) alignment method using a molecular template of an imprinted polymer layer during polymerization-induced phase separation. Our results showed that the nematic ordering of LC is transferred to the polymer chain ordering during an anisotropic phase separation, which produces an anisotropic azimuthal surface anchoring. Using in-plane field treatment during phase separation, a twisted nematic cell is demonstrated.

  3. Theoretical and experimental research on the self-assembled system of molecularly imprinted polymers formed by salbutamol and methacrylic acid.

    PubMed

    Jun-Bo, Liu; Yang, Shi; Shan-Shan, Tang; Rui-Fa, Jin

    2015-03-01

    The quantum chemical method was applied for screening functional monomers in the rational design of salbutamol-imprinted polymers. Salbutamol was the template molecule, and methacrylic acid was the single functional monomer. The LC-WPBE/6-31G(d,p) method was used to investigate the geometry optimization, active sites, natural bond orbital charges, binding energies of the imprinted molecule, and solvation energy. The mechanism of action between salbutamol and methacrylic acid was also discussed. The theoretical results show that salbutamol interacts with functional monomers by hydrogen bonds, and the salbutamol-imprinted polymers with a ratio of 1:4 (salbutamol/methacrylic acid) in acetonitrile had the highest stability. The salbutamol-imprinted polymers were prepared by precipitation polymerization. The experimental results indicated that the maximum adsorption capacity for salbutamol toward molecularly imprinted polymers was 7.33 mg/g, and the molecularly imprinted polymers had a higher selectivity for salbutamol than for norepinephrine and terbutaline sulfate. Herein, the studies can provide theoretical and experimental references for the salbutamol molecular imprinted system.

  4. Clinical spectrum and molecular diagnosis of Angelman and Prader-Willi syndrome patients with an imprinting mutation

    SciTech Connect

    Saitoh, S.; Cassidy, S.B.; Conroy, J.M.

    1997-01-20

    Recent studies have identified a new class of Prader-Willi syndrome (PWS) and Angelman syndrome (AS) patients who have biparental inheritance, but neither the typical deletion nor uniparental disomy (UPD) or translocation. However, these patients have uniparental DNA methylation throughout 15q11-q13, and thus appear to have a mutation in the imprinting process for this region. Here we describe detailed clinical findings of five AS imprinting mutation patients (three families) and two PWS imprinting mutation patients (one new family). All these patients have essentially the classical clinical phenotype for the respective syndrome, except that the incidence of microcephaly is lower in imprinting mutation AS patients than in deletion AS patients. Furthermore, imprinting mutation AS and PWS patients do not typically have hypopigmentation, which is commonly found in patients with the usual large deletion. Molecular diagnosis of these cases is initially achieved by DNA methylation analyses of the DN34/ZNF127, PW71 (D15S63), and SNRPN loci. The latter two probes have clear advantages in the simple molecular diagnostic analysis of PWS and AS patients with an imprinting mutation, as has been found for typical deletion or UPD PWS and AS cases. With the recent finding of inherited microdeletions in PWS and AS imprinting mutation families, our studies define a new class of these two syndromes. The clinical and molecular identification of these PWS and AS patients has important genetic counseling consequences. 49 refs., 4 figs., 3 tabs.

  5. Surface molecularly imprinted silica for selective solid-phase extraction of biochanin A, daidzein and genistein from urine samples.

    PubMed

    Chrzanowska, Anna M; Poliwoda, Anna; Wieczorek, Piotr P

    2015-05-01

    Selective molecularly imprinted silica polymer (SiO2MIP) for extraction of biochanin A, daidzein and genistein was synthesized using the surface molecular imprinting technique with the silica gel as a support. Biochanin A (BCA) was used as a template, 3-aminopropyltriethoxysilane (APTES) as a functional monomer, and tetraethoxysilicane (TEOS) as a cross-linker. Non-imprinted polymer with the sol-gel process (SiO2NIP) was also prepared for comparison. The synthesized polymers were characterized by Fourier transform infrared spectrometry (FTIR), scanning electron microscopy (SEM) and a standard Brunauer-Emett-Teller (BET) and Barret-Joyner-Halenda (BJH) analysis. The obtained results indicated the structural differences between imprinted and non-imprinted polymers. Finally, the SiO2MIP and SiO2NIP were adopted as the adsorbents of solid phase extraction for isolation and preconcentration of biochanin A and its structural analogues-daidzein and genistein from aqueous and urine samples. The performance analysis revealed that SiO2MIP displayed better affinity to the three investigated isoflavones compared with SiO2NIP. The recoveries of spiked samples for studied analytes ranged from 65.7% to 102.6% for molecularly imprinted silica polymer and 8.9-16.0% for non-imprinted sorbents.

  6. Metal ion mediated molecularly imprinted polymer for selective capturing antibiotics containing beta-diketone structure.

    PubMed

    Qu, Shanshan; Wang, Xiaobo; Tong, Changlun; Wu, Jianmin

    2010-12-24

    A new molecularly imprinted polymer (MIP) targeting to quinolones (Qs) and tetracyclines (TCs) was synthesized using itaconic acid (ITA) and ciprofloxacin (CIP) as a functional monomer and template molecule, respectively. Factors affecting the overall performance of MIP were investigated, and the results showed that Fe(3+) ion play a vital role in the formation of MIP with high molecular imprinting effect. Meanwhile, the chelating ability of monomer, species of template molecule, as well as the molar ratio of monomer and template also contribute to the performance of the obtained MIP. Cyclic voltammetry verified that, with the participation of Fe(3+) ions, a ternary complex of ITA-Fe(3+)-CIP could be formed before polymerization. Compared with conventional MIP prepared from commonly used monomer, methacrylic acid (MAA), the new MIP show significantly enhanced molecular imprinting effect and higher capacity for specific adsorption of target compounds as revealed by static and dynamic binding experiments. The MIP was successfully used as solid-phase extraction (SPE) adsorbent for enriching a broad spectrum of antibiotics containing beta-diketone structure from surface water sample. HPLC detection showed that high recovery rate (78.6-113.6%) was found in these spiked antibiotics, whereas recovery rate for the non structurally related drugs, epinephrine (EP) and dopamine (DOPA), was very low (4.7-7.6%) on the MIP cartridges. The results demonstrate that the MIP prepared by the strategy proposed in this work, could specifically target to a series of structurally related antibiotics containing beta-diketone structure.

  7. Configuration control on the shape memory stiffness of molecularly imprinted polymer for specific uptake of creatinine

    NASA Astrophysics Data System (ADS)

    Ang, Qian Yee; Zolkeflay, Muhammad Helmi; Low, Siew Chun

    2016-04-01

    In this study, sol-gel processing was proposed to prepare a creatinine (Cre)-imprinted molecularly imprinted polymer (MIP). The intermolecular interaction constituted by the cross-linkers, i.e., 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) and aluminium ion (Al3+), was studied and compared in order to form a confined matrix that promises the effectiveness of molecular imprinting. In view of the shape recognition, the hydrogen bonded Cre-AMPS did not demonstrate good recognition of Cre, with Cre binding found only at 5.70 ± 0.15 mg g-1 of MIP. Whilst, MIP cross-linked using Al3+ was able to attain an excellent Cre adsorption capacity of 19.48 ± 0.64 mg g-1 of MIP via the stronger ionic interaction of Cre-Al3+. Based on the Scatchard analysis, a higher Cre concentration in testing solution required greater driving force to resolve the binding resistance of Cre molecules, so as to have a precise Cre binding with shape factor. The molecular recognition ability of Cre-MIP in present work was shape-specific for Cre as compared to its structural analogue, 2-pyrrolidinone (2-pyr), by an ideal selectivity coefficient of 6.57 ± 0.10. In overall, this study has come up with a practical approach on the preparation of MIP for the detection of renal dysfunction by point-of-care Cre testing.

  8. Integrating Nanostructured Artificial Receptors with Whispering Gallery Mode Optical Microresonators via Inorganic Molecular Imprinting Techniques

    PubMed Central

    Hammond, G. Denise; Vojta, Adam L.; Grant, Sheila A.; Hunt, Heather K.

    2016-01-01

    The creation of label-free biosensors capable of accurately detecting trace contaminants, particularly small organic molecules, is of significant interest for applications in environmental monitoring. This is achieved by pairing a high-sensitivity signal transducer with a biorecognition element that imparts selectivity towards the compound of interest. However, many environmental pollutants do not have corresponding biorecognition elements. Fortunately, biomimetic chemistries, such as molecular imprinting, allow for the design of artificial receptors with very high selectivity for the target. Here, we perform a proof-of-concept study to show how artificial receptors may be created from inorganic silanes using the molecular imprinting technique and paired with high-sensitivity transducers without loss of device performance. Silica microsphere Whispering Gallery Mode optical microresonators are coated with a silica thin film templated by a small fluorescent dye, fluorescein isothiocyanate, which serves as our model target. Oxygen plasma degradation and solvent extraction of the template are compared. Extracted optical devices are interacted with the template molecule to confirm successful sorption of the template. Surface characterization is accomplished via fluorescence and optical microscopy, ellipsometry, optical profilometry, and contact angle measurements. The quality factors of the devices are measured to evaluate the impact of the coating on device sensitivity. The resulting devices show uniform surface coating with no microstructural damage with Q factors above 106. This is the first report demonstrating the integration of these devices with molecular imprinting techniques, and could lead to new routes to biosensor creation for environmental monitoring. PMID:27314397

  9. Visualizing BPA by molecularly imprinted ratiometric fluorescence sensor based on dual emission nanoparticles.

    PubMed

    Lu, Hongzhi; Xu, Shoufang

    2017-06-15

    Construction of ratiometric fluorescent probe often involved in tedious multistep preparation or complicated coupling or chemical modification process. The emergence of dual emission fluorescent nanoparticles would simplify the construction process and avoids the tedious chemical coupling. Herein, we reported a facile strategy to prepare ratiometric fluorescence molecularly imprinted sensor based on dual emission nanoparticles (d-NPs) which comprised of carbon dots and gold nanoclusters for detection of Bisphenol A (BPA). D-NPs emission at 460nm and 580nm were first prepared by seed growth co-microwave method using gold nanoparticles as seeds and glucose as precursor for carbon dots. When they were applied to propose ratiometric fluorescence molecularly imprinted sensor, the preparation process was simplified, and the sensitivity of sensor was improved with detection limit of 29nM, and visualizing BPA was feasible based on the distinguish fluorescence color change. The feasibility of the developed method in real samples was successfully evaluated through the analysis of BPA in water samples with satisfactory recoveries of 95.9-98.9% and recoveries ranging from 92.6% to 98.6% in canned food samples. When detection BPA in positive feeding bottles, the results agree well with those obtained by accredited method. The developed method proposed in this work to prepare ratiometric fluorescence molecularly imprinted sensor based on dual emission nanoparticles proved to be a convenient, reliable and practical way to prepared high sensitive and selective fluorescence sensors.

  10. Catalytically active polymers obtained by molecular imprinting and their application in chemical reaction engineering.

    PubMed

    Brüggemann, O

    2001-08-01

    Molecular imprinting is a way of creating polymers bearing artificial receptors. It allows the fabrication of highly selective plastics by polymerizing monomers in the presence of a template. This technique primarily had been developed for the generation of biomimetic materials to be used in chromatographic separation, in extraction approaches and in sensors and assays. Beyond these applications, in the past few years molecular imprinting has become a tool for producing new kinds of catalysts. For catalytic applications, the template must be chosen, so that it is structurally comparable with the transition state (a transition state analogue, TSA) of a reaction, or with the product or substrate. The advantage of using these polymeric catalysts is obvious: the backbone withstands more aggressive conditions than a bio material could ever survive. Results are presented showing the applicability of a molecularly imprinted catalyst in different kinds of chemical reactors. It is demonstrated that the catalysts can be utilized not only in batch but also in continuously driven reactors and that their performance can be improved by means of chemical reaction engineering.

  11. Preparation and evaluation of molecularly imprinted polymer liquid chromatography column for the separation of Cathine enantiomers

    PubMed Central

    Balamurugan, Krishnamoorthy; Gokulakrishnan, Kannan; Prakasam, Tangirala

    2011-01-01

    In this study molecular imprinting technology was employed to prepare a specific affinity sorbent for the resolution of Cathine, a chiral drug product. The molecularly imprinted polymer (MIP) was prepared by non-covalent molecular imprinting with either (+) or (−)-Cathine (threo-2-amino-1-hydroxy-1-phenyl propane; norpseudoephedrine) as the template. Methacrylic acid and ethylene glycol di-methacrylate were copolymerized in the presence of the template molecule. The bulk polymerization was carried out in chloroform with 2,2′-azobisisobutyronitrile as the initiator, at 5 °C and under UV radiation. The resulting MIP was ground into powders, which were slurry packed into analytical columns. After removal of template molecules, the MIP-packed columns were found to be effective for the resolution of (±)-Cathine racemates. The separation factor for the enantiomers ranged between 1.5 and 2.4 when the column was packed with MIP prepared with (+)-Cathine as the template. A separation factor ranging from 1.6 to 2.9 could be achieved from the column packed with MIP, prepared with (−)-Cathine as the template. Although the separation factor was higher with that previously obtained from reversed-phase column chromatography following derivatization with a chiral agent, elution peaks were broader due to the heterogeneity of binding sites on MIP particles and the possible non-specific interaction. PMID:23960776

  12. Molecularly Imprinted Composite Membranes for Selective Detection of 2-Deoxyadenosine in Urine Samples

    PubMed Central

    Scorrano, Sonia; Mergola, Lucia; Di Bello, Maria Pia; Lazzoi, Maria Rosaria; Vasapollo, Giuseppe; Del Sole, Roberta

    2015-01-01

    An important challenge for scientific research is the production of artificial systems able to mimic the recognition mechanisms occurring at the molecular level in living systems. A valid contribution in this direction resulted from the development of molecular imprinting. In this work, a novel molecularly imprinted polymer composite membrane (MIM) was synthesized and employed for the selective detection in urine samples of 2-deoxyadenosine (2-dA), an important tumoral marker. By thermal polymerization, the 2-dA-MIM was cross-linked on the surface of a polyvinylidene-difluoride (PVDF) membrane. By characterization techniques, the linking of the imprinted polymer on the surface of the membrane was found. Batch-wise guest binding experiments confirmed the absorption capacity of the synthesized membrane towards the template molecule. Subsequently, a time-course of 2-dA retention on membrane was performed and the best minimum time (30 min) to bind the molecule was established. HPLC analysis was also performed to carry out a rapid detection of target molecule in urine sample with a recovery capacity of 85%. The experiments indicated that the MIM was highly selective and can be used for revealing the presence of 2-dA in urine samples. PMID:26086824

  13. Integrating Nanostructured Artificial Receptors with Whispering Gallery Mode Optical Microresonators via Inorganic Molecular Imprinting Techniques.

    PubMed

    Hammond, G Denise; Vojta, Adam L; Grant, Sheila A; Hunt, Heather K

    2016-06-15

    The creation of label-free biosensors capable of accurately detecting trace contaminants, particularly small organic molecules, is of significant interest for applications in environmental monitoring. This is achieved by pairing a high-sensitivity signal transducer with a biorecognition element that imparts selectivity towards the compound of interest. However, many environmental pollutants do not have corresponding biorecognition elements. Fortunately, biomimetic chemistries, such as molecular imprinting, allow for the design of artificial receptors with very high selectivity for the target. Here, we perform a proof-of-concept study to show how artificial receptors may be created from inorganic silanes using the molecular imprinting technique and paired with high-sensitivity transducers without loss of device performance. Silica microsphere Whispering Gallery Mode optical microresonators are coated with a silica thin film templated by a small fluorescent dye, fluorescein isothiocyanate, which serves as our model target. Oxygen plasma degradation and solvent extraction of the template are compared. Extracted optical devices are interacted with the template molecule to confirm successful sorption of the template. Surface characterization is accomplished via fluorescence and optical microscopy, ellipsometry, optical profilometry, and contact angle measurements. The quality factors of the devices are measured to evaluate the impact of the coating on device sensitivity. The resulting devices show uniform surface coating with no microstructural damage with Q factors above 10⁶. This is the first report demonstrating the integration of these devices with molecular imprinting techniques, and could lead to new routes to biosensor creation for environmental monitoring.

  14. Development and application of novel clonazepam molecularly imprinted coatings for stir bar sorptive extraction.

    PubMed

    Li, Xiaoxu; Mei, Xiaoliang; Xu, Lei; Shen, Xin; Zhu, Wanying; Hong, Junli; Zhou, Xuemin

    2016-04-15

    The molecularly imprinted magnetic stir bar coatings were created based on graft-functional Fe3O4 nanoparticles with magnetic field-induced self-assembly. The magnetic complex including clonazepam as template, the graft-functional Fe3O4 nanoparticles and methacrylic acid as monomers was pre-assembled through π-π interaction and hydrogen bonding, then was directionally adsorbed on the surface of magnetic stir bar under the magnetic induction. The molecularly imprinted coating with well-ordered structure was generated by one-step copolymerization based on the cross linking of ethylene glycol dimethacrylate. The molecularly imprinted coating with multiple recognition sites could be manufactured and applied in polar solvents, and showed superior selectivity and fast binding kinetics for benzodiazepines. The analytes in herbal health foods, treated by stir bar sorptive extraction, were determined by HPLC-UV. Good linearity was observed in the range of 0.01-2 μg mL(-1). The content of clonazepam in the herbal health foods was found to be 44 ng g(-1), and the average recoveries were 89.8-103.3% with a relative standard deviation (RSD) <6.5%, demonstrating the successful application in real sample analysis.

  15. [Spectroscopy study on the selectively distinguishing cefalexin with the molecular imprinted polymer].

    PubMed

    Jiang, Yu-xiang; Pang, Dao-lin; He, Qiang; Lai, Cheng-yue; Zheng, Huai-li; Li, Fang

    2011-07-01

    Molecular imprinted polymers of cefalexin (CFL) were prepared by non-covalent molecular imprinting technique in the present paper. Using CFL as template molecule, acrylamide (AM) or methacrylic acid (MAA) as functional monomer, ethylene dimethacrylate (EGDMA) as cross-linker, AIBN as initiator and methanol as porogen agent, different molecularly imprinted polymers (MIPs) of CFL were synthesized by bulk or suspension polymerization as synthetic method. The intermolecular action between AM and CFL was investigated by UV and IR spectrophotometric analysis, and the results indicated that polymerizing functional monomer AM could bond effectively with template molecule CFL. By using UV spectrophotometric analysis method, it was found that the MIP prepared with AM-EGDMA by bulk polymerization showed the highest binding capacity for CFL. Test of selective adsorption made clear that the MIP represented more excellent identification property to CFL than to cefadroxol and ampicillin. The MIPs were used as solid-phase extraction sorbent for extraction and enrichment of CFL in actual samples. And the recoveries for CFL extraction were found to be 99.3%-99.7% (n=3), demonstrating the feasibility of the prepared MIPs for CFL extraction.

  16. Computational prediction and experimental selectivity coefficients for hydroxyzine and cetirizine molecularly imprinted polymer based potentiometric sensors.

    PubMed

    Azimi, Abolfazl; Javanbakht, Mehran

    2014-02-17

    In spite of the increasing usages number of molecularly imprinted polymers (MIPs) in many scientific applications, the theoretical aspects of participating intra molecular forces are not fully understood. This work investigates effects of the electrostatic force, the Mulliken charge and the role of cavity's backbone atoms on the selectivity of MIPs. Moreover, charge distribution, which is a computational parameter, was proposed for the prediction of the selectivity coefficients of MIP-based sensors. In the computational approaches and experimental study, methacrylic acid (MAA) was chosen as the functional monomer and ethylene glycol dimethacrylate (EGDMA) as the cross linker for hydroxyzine and cetirizine imprinted polymers. Ab initio, DFT B3LYP method was carried out on molecular optimization. With regard to results obtained from molecules optimization and hydrogen bonding properties, possible configurations of 1:n (n≤5) template/monomer complexes were designed and optimized. The binding energy for each complex in gas phase was calculated. Depending on the most stable configuration, hydroxyzine and cetirizine imprinted polymer models were designed. The calculations including the porogen were also investigated. The theoretical charge distributions for the template and some potential interfering molecules were calculated. The results showed a correlation between the selectivity coefficients and the theoretical charge distributions. The results surprisingly show that charge distribution based model was able to predict the selectivity coefficients of MIP based potentiometric sensors.

  17. A molecularly imprinted polymer (MIP)-coated microbeam MEMS sensor for chemical detection

    NASA Astrophysics Data System (ADS)

    Holthoff, Ellen L.; Li, Lily; Hiller, Tobias; Turner, Kimberly L.

    2015-05-01

    Recently, microcantilever-based technology has emerged as a viable sensing platform due to its many advantages such as small size, high sensitivity, and low cost. However, microcantilevers lack the inherent ability to selectively identify hazardous chemicals (e.g., explosives, chemical warfare agents). The key to overcoming this challenge is to functionalize the top surface of the microcantilever with a receptor material (e.g., a polymer coating) so that selective binding between the cantilever and analyte of interest takes place. Molecularly imprinted polymers (MIPs) can be utilized as artificial recognition elements for target chemical analytes of interest. Molecular imprinting involves arranging polymerizable functional monomers around a template molecule followed by polymerization and template removal. The selectivity for the target analyte is based on the spatial orientation of the binding site and covalent or noncovalent interactions between the functional monomer and the analyte. In this work, thin films of sol-gel-derived xerogels molecularly imprinted for TNT and dimethyl methylphosphonate (DMMP), a chemical warfare agent stimulant, have demonstrated selectivity and stability in combination with a fixed-fixed beam microelectromechanical systems (MEMS)-based gas sensor. The sensor was characterized by parametric bifurcation noise-based tracking.

  18. Molecularly imprinted polymer microspheres for optical measurement of ultra trace nonfluorescent cyhalothrin in honey.

    PubMed

    Gao, Lin; Li, Xiuying; Zhang, Qi; Dai, Jiangdong; Wei, Xiao; Song, Zhilong; Yan, Yongsheng; Li, Chunxiang

    2014-08-01

    In this study, we first present a general protocol for making fluorescent molecularly imprinted polymer microspheres via precipitation polymerisation. We first prepared the fluorescent molecularly imprinted polymer microspheres upon copolymerisation of acrylamide with a small quantity of allyl fluorescein in the presence of cyhalothrin to form recognition sites without doping. The as-synthesised microspheres exhibited spherical shape, high fluorescence intensity and highly selective recognition. Under optical conditions, polymer microspheres were successfully applied to selectively and sensitively detect cyhalothrin, and a linear relationship could be obtained covering the lower concentration range of 0-1.0nM with a correlation coefficient of 0.9936 described by the Stern-Volmer equation. A lower limit of detection was found to be 0.004nM. The results of practical detection suggested that the developed method was satisfactory for determination of cyhalothrin in honey samples. This study therefore demonstrated the potential of molecularly imprinted polymers for detection of cyhalothrin in food.

  19. Ion-exchange molecularly imprinted polymer for the extraction of negatively charged acesulfame from wastewater samples.

    PubMed

    Zarejousheghani, Mashaalah; Schrader, Steffi; Möder, Monika; Lorenz, Pierre; Borsdorf, Helko

    2015-09-11

    Acesulfame is a known indicator that is used to identify the introduction of domestic wastewater into water systems. It is negatively charged and highly water-soluble at environmental pH values. In this study, a molecularly imprinted polymer (MIP) was synthesized for negatively charged acesulfame and successfully applied for the selective solid phase extraction (SPE) of acesulfame from influent and effluent wastewater samples. (Vinylbenzyl)trimethylammonium chloride (VBTA) was used as a novel phase transfer reagent, which enhanced the solubility of negatively charged acesulfame in the organic solvent (porogen) and served as a functional monomer in MIP synthesis. Different molecularly imprinted polymers were synthesized to optimize the extraction capability of acesulfame. The different materials were evaluated using equilibrium rebinding experiments, selectivity experiments and scanning electron microscopy (SEM). The most efficient MIP was used in a molecularly imprinted-solid phase extraction (MISPE) protocol to extract acesulfame from wastewater samples. Using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) analysis, detection and quantification limits were achieved at 0.12μgL(-1) and 0.35μgL(-1), respectively. Certain cross selectivity for the chemical compounds containing negatively charged sulfonamide functional group was observed during selectivity experiments. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Dummy molecularly imprinted mesoporous silica prepared by hybrid imprinting method for solid-phase extraction of bisphenol A.

    PubMed

    Yu, Dan; Hu, Xiaolei; Wei, Shoutai; Wang, Qiang; He, Chiyang; Liu, Shaorong

    2015-05-29

    A novel hybrid dummy imprinting strategy was developed to prepare a mesoporous silica for the solid-phase extraction (SPE) of bisphenol A (BPA). A new covalent template-monomer complex (BPAF-Si) was first synthesized with 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF) as the template. The imprinted silica was obtained through the gelation of BPAF-Si with tetraethoxysilane and the subsequent removal of template by thermal cleavage, and then it was characterized by FT-IR spectroscopy, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption-desorption isotherms. Results showed that the new silica had micron-level particle size and ordered mesoporous structure. The static binding test verified that the imprinted silica had much higher recognition ability for BPA than the non-imprinted silica. The imprinted silica also showed high extraction efficiencies and high enrichment factor for SPE of BPA. Using the imprinted silica, a SPE-HPLC-UV method was developed and successfully applied for detecting BPA in BPA-spiked tap water and lake water samples with a recovery of 99-105%, a RSD of 2.7-5.0% and a limit of detection (S/N=3) of 0.3ng/mL. The new imprinted silica avoided the interference of the residual template molecules and reduced the non-specific binding sites, and therefore it can be utilized as a good sorbent for SPE of BPA in environmental water samples.

  1. Binding behaviour of molecularly imprinted polymers prepared by a hierarchical approach in mesoporous silica beads of varying porosity.

    PubMed

    Baggiani, Claudio; Baravalle, Patrizia; Giovannoli, Cristina; Anfossi, Laura; Passini, Cinzia; Giraudi, Gianfranco

    2011-04-08

    One of the most interesting methods for preparing molecularly imprinted polymers with controlled morphology consists in filling the pores of silica beads with an imprinting mixture, polymerizing it and dissolving the support, leaving porous imprinted beads that are the "negative image" of the silica beads. The main advantage of such an approach consists in the easy preparation of spherical imprinted polymeric particles with narrow diameter and pore size distribution, particularly indicated for chromatographic applications. In this approach it has been shown that the resulting morphology of polymeric beads depends essentially on the porosity and surface properties of the silica beads that act as microreactors for the thermopolymerization process. Anyway, it is not yet clear if the porosity of the silica beads influences the binding properties of the resulting imprinted beads. In this paper, we report the effect of different porosities of the starting mesoporous silica beads on the resulting binding properties of imprinted polymers with molecular recognition properties towards the fungicide carbendazim. The morphological properties of the imprinted beads prepared through this hierarchical approach were measured by nitrogen adsorption porosimetry and compared with a reference imprinted material prepared by bulk polymerization. The chromatographic behaviour of HPLC columns packed with the imprinted materials were examined by eluting increasing amounts of carbendazim and extracting the binding parameters through a peak profiling approach. The experimental results obtained show that the resulting binding properties of the imprinted beads are strongly affected by the polymerization approach used but not by the initial porosity of the silica beads, with the sole exception of the binding site density, which appears to be inversely proportional to them. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. Novel surface dummy molecularly imprinted silica as sorbent for solid-phase extraction of bisphenol A from water samples.

    PubMed

    Hu, Xiaolei; Wu, Xiao; Yang, Fanfan; Wang, Qiang; He, Chiyang; Liu, Shaorong

    2016-01-01

    A novel surface molecularly imprinted silica composite was prepared by a dummy-template imprinting strategy for the solid-phase extraction (SPE) of bisphenol A (BPA). 2,2-Bis(4-hydroxyphenyl) hexafluoropropane (BPAF) was chosen as the template molecule, and a hybrid technique was used for imprinting procedure. The imprinted silica was characterized by FT-IR spectroscopy, scanning electron microscope, thermo-gravimetric analysis, and nitrogen adsorption-desorption isotherms. The static binding test verified that the imprinted silica had much higher recognition ability for BPA than the non-imprinted silica, and the kinetic adsorption test presented the fast binding kinetics of the surface imprinted silica for BPA. When used as a SPE sorbent, the imprinted silica showed high extraction efficiencies and high enrichment factor for BPA. Based on the imprinted silica, a SPE-HPLC-UV method was developed and successfully applied to the detection of BPA in BPA-spiked lake water, tap water and drinking water samples with a high recovery of 97.3-106.0%, a RSD of 1.2-3.8% (n=3) and a limit of detection (S/N=3) of 0.3 ng/mL. The analysis results of a certified BPA sample also demonstrated the reliability of present method. The new surface dummy molecularly imprinted silica completely avoided the interference of the residual template molecules and greatly improved the binding kinetic of the target molecules. Therefore, it can be used as a good sorbent for SPE of BPA in environmental water samples.

  3. Preparation of boronate-functionalized molecularly imprinted monolithic column with polydopamine coating for glycoprotein recognition and enrichment.

    PubMed

    Lin, Zian; Wang, Juan; Tan, Xiaoqing; Sun, Lixiang; Yu, Ruifang; Yang, Huanghao; Chen, Guonan

    2013-12-06

    A novel imprinting strategy using reversible covalent complexation of glycoprotein was described for creating glycoprotein-specific recognition cavities on boronate-functionalized monolithic column. Based on it, a molecularly imprinted monolithic column was prepared by self-polymerization of dopamine (DA) on the surface of 4-vinylphenylboronic acid (VPBA)-based polymeric skeletons after reversible immobilization of horseradish peroxidase (HRP). Due to the combination of boronate affinity and surface imprinting of DA, the stable and accessible recognition sites in the as-prepared imprinted monolith could be obtained after the removal of the template, which facilitated the rebinding of the template and provided good reproducibility and lifetime of use. The recognition behaviors of proteins on the bare VPBA-based, HRP-imprinted and nonimprinted monolithic columns were evaluated in detail and the results showed that the HRP-imprinted monolith exhibited higher recognition ability toward the template than another two monolithic columns. Not only nonglycoproteins but also glycoproteins can be well separated with the HRP-imprinted monolith. In addition, the feasibility of the HRP-imprinted monolith, adopted as an in-tube solid phase microextraction (in-tube SPME), was further assessed by selective extraction and enrichment of HRP from human serum. The good results demonstrated its potential in glycoproteome analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Molecularly imprinted layer-coated monodisperse spherical silica microparticles toward affinity-enrichment of isoflavonoid glycosides from Radix puerariae.

    PubMed

    Luo, Jing; Zhang, Liying; Chen, Danjun; Wang, Peng; Zhao, Jiawei; Peng, Yan; Du, Shuhu; Zhang, Zhongping

    2012-06-21

    This paper reports the preparation of puerarin (PR) imprinted layer-coated silica microparticles toward selective recognition of PR and fast affinity-enrichment of the main isoflavonoid glycosides from the crude extract of Radix puerariae. Before the preparation, quantum mechanics (QM) method was applied to identify three kinds of common functional monomers capable of interaction with PR and then predicted optimal functional monomer (acrylamide, AA) and the relative molar ratio of template to functional monomer (PR/AA, 1:4). The obtained PR-imprinted silica microparticles were evaluated by transmission electron microscope (TEM) and rebinding experiments, exhibiting good morphology and high binding affinity to PR. Meanwhile, the rebinding amount of the imprinted microparticles to PR was nearly 2.1-folds that of non-imprinted microparticles. When the PR-imprinted microspheres were used as packing materials for solid-phase extraction, the recovery yields of PR, daidzin (DD) and genistin (GS) were simultaneously up to 90% by one-step extraction from the crude extract of Radix puerariae. Additionally, the PR-imprinted microparticles could be re-used for at least 5 times without losing any extraction efficiency. These results indicate that the PR-imprinted microparticles have highly selective adsorption capabilities to PR, DD and GS from the crude extract of Radix puerariae. The method of molecularly imprinted polymers (MIPs) coupled with solid-phase extraction (SPE) provides a good solution of the enrichment and separation of active extracts from complicated traditional Chinese medicine (TCM) with certain structures.

  5. Molecularly imprinted nanopatterns for the recognition of biological warfare agent ricin.

    PubMed

    Pradhan, Santwana; Boopathi, M; Kumar, Om; Baghel, Anuradha; Pandey, Pratibha; Mahato, T H; Singh, Beer; Vijayaraghavan, R

    2009-11-15

    Molecularly imprinted polymer (MIP) for biological warfare agent (BWA) ricin was synthesized using silanes in order to avoid harsh environments during the synthesis of MIP. The synthesized MIP was utilized for the recognition of ricin. The complete removal of ricin from polymer was confirmed by fluorescence spectrometer and SEM-EDAX. SEM and EDAX studies confirmed the attachment of silane polymer on the surface of silica gel matrix. SEM image of Ricin-MIP exhibited nanopatterns and it was found to be entirely different from the SEM image of non-imprinted polymer (NIP). BET surface area analysis revealed more surface area (227 m(2)/g) for Ricin-MIP than that of NIP (143 m(2)/g). In addition, surface area study also showed more pore volume (0.5010 cm(3)/g) for Ricin-MIP than that of NIP (0.2828 cm(3)/g) at 12 nm pore diameter confirming the presence of imprinted sites for ricin as the reported diameter of ricin is 12 nm. The recognition and rebinding ability of the Ricin-MIP was tested in aqueous solution. Ricin-MIP rebound more ricin when compared to the NIP. Chromatogram obtained with Ricin-MIP exhibited two peaks due to imprinting, however, chromatogram of NIP exhibited only one peak for free ricin. SDS-PAGE result confirmed the second peak observed in chromatogram of Ricin-MIP as ricin peak. Ricin-MIP exhibited an imprinting efficiency of 1.76 and it also showed 10% interference from the structurally similar protein abrin.

  6. Molecularly imprinted polymer for specific extraction of hypericin from Hypericum perforatum L. herbal extract.

    PubMed

    Li, Zhaozhou; Qin, Cuili; Li, Daomin; Hou, Yuze; Li, Songbiao; Sun, Junjie

    2014-09-01

    The molecularly imprinted polymers (MIPs) were prepared by an oxidation-reduction polymerization system using a non-covalent molecularly imprinting strategy with hypericin as the template, acrylamide as the functional monomer and pentaerythritol triacrylate as the cross-linker in the porogen of acetone. The UV spectrum revealed that a cooperative hydrogen-bonding complex between hypericin and acrylamide might be formed at the ratio of 1:6 in the prepolymerized system. Two classes of the binding sites were produced in the resulting hypericin-imprinted polymer with the dissociation constants of 16.61μgL(-1) and 69.35μgL(-1), and the affinity binding sites of 456.53μgg(-1) and 603.06μgg(-1), respectively. The synthesized MIPs were characterized by scanning electron microscope, thermogravimetric and differential thermal analysis. High-performance liquid chromatography was used to investigate the adsorption and recognition properties of the MIPs. Selective binding of the template molecule was demonstrated in comparison to the analog pseudohypericin. After the Hypericum perforatum L. plant being air dried and finely ground, an extract was prepared by shaking the powder in a methanol-water solution (80:20, v/v), vacuum filtration though a Büchner funnel, liquid-liquid extraction with ethyl ether and ethyl acetate, and evaporating on a rotary evaporator until dry. With the sorbents of the optimized MIPs, a molecularly imprinted solid-phase extraction (MISPE) procedure was developed for enrichment and separation of hypericin from the Hypericum extract in the presence of interfering substances. The selective extraction of hypericin from herbal medicine was achieved with the recovery of 82.30%. The results showed that MISPE can be a useful tool for specific isolation and effective clean-up of target compounds from natural products. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Carbon paste electrode modified with duplex molecularly imprinted polymer hybrid film for metronidazole detection.

    PubMed

    Xiao, Ni; Deng, Jian; Cheng, Jianlin; Ju, Saiqin; Zhao, Haiqing; Xie, Jin; Qian, Duo; He, Jun

    2016-07-15

    A novel electrochemical sensor based on duplex molecularly imprinted polymer (DMIP) hybrid film modified carbon paste electrode (CPE) has been developed for highly sensitive and selective determination of metronidazole (MNZ). A conductive poly(anilinomethyltriethoxysilane) film is firstly electrodeposited on the surface of a CPE, and then a molecularly imprinted polysiloxane (MIPS) membrane is covalently covered on the film via sol-gel process. The as-constructed DMIP hybrid film, combining the advantages of MIPS and conducting MIP, can make feasible the direct and efficient signal transformation between the target analyte and the transducer, as well as enhance the imprinting recognition capability, mass transfer efficiency and the detection sensitivity. Under optimized conditions, the reduction peak currents of MNZ are linear to MNZ concentrations in the range from 4.0×10(-7) to 2.0×10(-4) molL(-1) with a detection limit of 9.1×10(-8)molL(-1). The RSD values vary from 2.9% to 4.7% for intra-day and from 3.4% to 4.2% for inter-day precision. The DMIP-based sensor has been successfully applied for the determination of MNZ in biological and pharmaceutical samples. The accuracy and reliability of the method is further confirmed by high performance liquid chromatography. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Molecularly imprinted calixarene fiber for solid-phase microextraction of four organophosphorous pesticides in fruits.

    PubMed

    Li, Jing-Wen; Wang, Yu-Long; Yan, Shan; Li, Xiu-Juan; Pan, Si-Yi

    2016-02-01

    Calixarene was used as a functional monomer to fabricate a molecularly imprinted polymer (MIP) by sol-gel technique for solid-phase microextraction (SPME) of parathion-methyl and its structural analogs. The MIP-coated fiber possessed excellent thermal and chemical stability as well as high extraction capacity. Its selectivity and possible recognition mechanism were investigated. The similarities in molecular shape and functional group play a key role in the selective recognition of the imprinted material. Any changes to the structure of the template would decrease the imprinting factor. A comparison of MIP-SPME was made with liquid-liquid extraction coupled with gas chromatography for the determination of organophosphorus pesticides (OPPs) in fruits. Much lower limits of detection and better recoveries were achieved by SPME in spiked apple and pineapple samples. The experiment demonstrates that the proposed method using the calixarene MIP fiber was more suitable for selective determination of trace OPPs in those fruit samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Molecularly imprinted polymers as the extracted sorbents of clenbuterol ahead of liquid chromatographic determination*

    PubMed Central

    Lay, Sovichea; Yu, Hai-ning; Hu, Bao-xiang; Shen, Sheng-rong

    2016-01-01

    A pre-treatment methodology for clenbuterol hydrochloride (CLEN) isolation and enrichment in a complex matrix environment was developed through exploiting molecularly imprinted polymers (MIPs). CLEN-imprinted polymers were synthesized by the combined use of ally-β-cyclodextrin (ally-β-CD) and methacrylic acid (MAA), allyl-β-CD and acrylonitrile (AN), and allyl-β-CD and methyl methacrylate (MMA) as the binary functional monomers. MAA-linked allyl-β-CD MIPs (M-MAA) were characterized by Fourier transform-infrared (FT-IR) spectroscopy and a scanning electron microscope (SEM). Based upon the results, M-MAA polymers generally proved to be an excellent selective extraction compared to its references: AN-linked allyl-β-CD MIPs (M-AN) and MMA-linked allyl-β-CD MIPs (M-MMA). M-MAA polymers were eventually chosen to run through a molecularly imprinted solid-phase extraction (MISPE) micro-column to enrich CLEN residues spiked in pig livers. A high recovery was achieved, ranging from 91.03% to 96.76% with relative standard deviation (RSD) ≤4.45%. PMID:27256680

  10. Molecularly imprinted core-shell magnetic nanoparticles for selective extraction of triazines in soils.

    PubMed

    Patiño-Ropero, María José; Díaz-Álvarez, Myriam; Martín-Esteban, Antonio

    2017-04-01

    In this work, a propazine-imprinted polymer was synthesized on the surface of modified magnetic nanoparticles to be used in the solid-phase extraction of triazines in soil samples. The effect of different solvents on the selective extraction of target analytes was assessed to establish the optimum rebinding conditions. The obtained magnetic molecularly imprinted particles exhibited high selectivity for triazines and were easily collected and separated by an external magnetic field without additional centrifugation or filtration steps. Under optimum conditions, a magnetic molecularly imprinted solid-phase extraction method was developed allowing the extraction of several triazines (desisopropylatrazine, desethylatrazine, simazine, atrazine, and propazine) from soil samples and their subsequent final determination by high-performance liquid chromatography with diode-array detection. Recoveries for the triazines studied were within the range 5.4% to 40.6%, with relative standard deviations lower than 7.0% (n = 3). The detection limits were within 0.1 to 3 ng g(-1) , depending upon the triazine and the type of soil used. Copyright © 2016 John Wiley & Sons, Ltd.

  11. Fullerene derived molecularly imprinted polymer for chemosensing of adenosine-5'-triphosphate (ATP).

    PubMed

    Sharma, Piyush S; Dabrowski, Marcin; Noworyta, Krzysztof; Huynh, Tan-Phat; Kc, Chandra B; Sobczak, Janusz W; Pieta, Piotr; D'Souza, Francis; Kutner, Wlodzimierz

    2014-09-24

    For molecular imprinting of oxidatively electroactive analytes by electropolymerization, we used herein reductively electroactive functional monomers. As a proof of concept, we applied C60 fullerene adducts as such for the first time. For that, we derivatized C60 to bear either an uracil or an amide, or a carboxy addend for recognition of the adenosine-5'-triphosphate (ATP) oxidizable analyte with the ATP-templated molecularly imprinted polymer (MIP-ATP). Accordingly, the ATP complex with all of the functional monomers formed in solution was potentiodynamically electropolymerized to deposit an MIP-ATP film either on an Au electrode of the quartz crystal resonator or on a Pt disk electrode for the piezoelectric microgravimetry (PM) or capacitive impedimetry (CI) determination of ATP, respectively, under the flow-injection analysis (FIA) conditions. The apparent imprinting factor for ATP was ∼4.0. After extraction of the ATP template, analytical performance of the resulting chemosensors, including detectability, sensitivity, and selectivity, was characterized. The limit of detection was 0.3 and 0.03mM ATP for the PM and CI chemosensor, respectively. The MIP-ATP film discriminated structural analogues of ATP quite well. The Langmuir, Freundlich, and Langmuir-Freundlich isotherms were fitted to the experimental data of the ATP sorption and sorption stability constants appeared to be nearly independent of the adopted sorption model.

  12. Molecularly imprinted polymer microspheres for solid-phase extraction of protocatechuic acid in Rhizoma homalomenae.

    PubMed

    Chen, Fang-Fang; Wang, Guo-Ying; Shi, Yan-Ping

    2011-10-01

    Molecularly imprinted polymers (MIPs) had been prepared by precipitation polymerization method using acrylamide as the functional monomer, ethylene glycol dimethacrylate as the cross-linker, acetonitrile as the porogen solvent and protocatechuic acid (PA), one of phenolic acids, as the template molecule. The MIPs were characterized by scanning electron microscopy and Fourier transform infrared, and their performance relative to non-imprinted polymers was assessed by equilibrium binding experiments. Six structurally similar phenolic acids, including p-hydroxybenzoic acid, gallic acid, salicylic acid, syringic acid, vanillic acid, ferulic acid were selected to assess the selectivity and recognition capability of the MIPs. The MIPs were applied to extract PA from the traditional Chinese medicines as a solid-phase extraction sorbent. The resultant cartridge showed that the MIPs have a good extraction performance and were able to selectively extract almost 82% of PA from the extract of Rhizoma homalomenae. Thus, the proposed molecularly imprinted-solid phase extraction-high performance liquid chromatography method can be successfully used to extract and analyse PA in traditional Chinese medicines.

  13. Molecularly imprinted polymers for sample preparation and biosensing in food analysis: Progress and perspectives.

    PubMed

    Ashley, Jon; Shahbazi, Mohammad-Ali; Kant, Krishna; Chidambara, Vinayaka Aaydha; Wolff, Anders; Bang, Dang Duong; Sun, Yi

    2017-05-15

    Molecularly imprinted polymers (MIPs) are biomimetics which can selectively bind to analytes of interest. One of the most interesting areas where MIPs have shown the biggest potential is food analysis. MIPs have found use as sorbents in sample preparation attributed to the high selectivity and high loading capacity. MIPs have been intensively employed in classical solid-phase extraction and solid-phase microextraction. More recently, MIPs have been combined with magnetic bead extraction, which greatly simplifies sample handling procedures. Studies have consistently shown that MIPs can effectively minimize complex food matrix effects, and improve recoveries and detection limits. In addition to sample preparation, MIPs have also been viewed as promising alternatives to bio-receptors due to the inherent molecular recognition abilities and the high stability in harsh chemical and physical conditions. MIPs have been utilized as receptors in biosensing platforms such as electrochemical, optical and mass biosensors to detect various analytes in food. In this review, we will discuss the current state-of-the-art of MIP synthesis and applications in the context of food analysis. We will highlight the imprinting methods which are applicable for imprinting food templates, summarize the recent progress in using MIPs for preparing and analysing food samples, and discuss the current limitations in the commercialisation of MIPs technology. Finally, future perspectives will be given. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Preparation of the high purity gingerols from ginger by dummy molecularly imprinted polymers.

    PubMed

    Ji, Wenhua; Ma, Xiuli; Zhang, Jinghua; Xie, Hongkai; Liu, Feng; Wang, Xiao

    2015-03-27

    In this work, a dummy molecularly imprinted polymers (MIPs) were developed as the selective sorbents for preparation of the high purity gingerols from ginger for the first time. The dummy template molecule with similar structural skeleton to gingerols, N-vanillylnonanamide, has been designed and synthesized. The performance of the MIPs and non-imprinted polymers (NIPs) were evaluated including selective recognition capacity, adsorption isotherm, and adsorption kinetics. Optimization of various parameters affecting dummy molecular imprinted solid phase extraction (MISPE), such as the type and flow rate of the loading solvent, the composition and volume of the eluting solvent, and the composition and volume of the washing solvent were investigated. Gingerols with the percent recovery of 80 and the percent purity of 99.1 were obtained from the extracts of ginger by MISPE. Besides, gingerols obtained by MISPE had more powerful activity of eliminating free radical compared with extracts before extraction with the MISPE column. Application of MIPs with a high affinity toward three gingerols provides a novel method for obtaining a group of compounds which have likely active groups from natural products.

  15. Introduction of selectivity and specificity to graphene using an inimitable combination of molecular imprinting and nanotechnology.

    PubMed

    Roy, Ekta; Patra, Santanu; Tiwari, Ashutosh; Madhuri, Rashmi; Sharma, Prashant K

    2017-03-15

    Recently, the nanostructured modified molecularly imprinting polymer has created a great attention in research field due to its excellent properties such as high surface to volume ratio, low cost, and easy preparation/handling. Among the nanostructured materials, the carbonaceous material such as 'graphene' has attracted the tremendous attention of researchers owing to their fascinating electrical, thermal and physical properties. In this review article, we have tried to explore as well as compile the role of graphene-based nanomaterials in the fabrication of imprinted polymers. In other words, herein the recent efforts made to introduce selectivity in graphene-based nanomaterials were tried collected together. The major concern of this review article is focused on the sensing devices fabricated via a combination of graphene, graphene@nanoparticles, graphene@carbon nanotubes and molecularly imprinted polymers. Additionally, the combination of graphene and quantum dots was also included to explore the fluorescence properties of zero-band-gap graphene. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Development of andrographolide molecularly imprinted polymer for solid-phase extraction

    NASA Astrophysics Data System (ADS)

    Yin, Xiaoying; Liu, Qingshan; Jiang, Yifan; Luo, Yongming

    2011-06-01

    A method employing molecularly imprinted polymer (MIP) as selective sorbent for solid-phase extraction (SPE) to pretreat samples was developed. The polymers were prepared by precipitation polymerization with andrographolide as template molecule. The structure of MIP was characterized and its static adsorption capacity was measured by the Scatchard equation. In comparison with C 18-SPE and non-imprinted polymer (NIP) SPE column, MIP-SPE column displays high selectivity and good affinity for andrographolide and dehydroandrographolide for extract of herb Andrographis paniculata ( Burm.f.) Nees (APN). MIP-SPE column capacity was 11.9 ± 0.6 μmol/g and 12.1 ± 0.5 μmol/g for andrographolide and dehydroandrographolide, respectively and was 2-3 times higher than that of other two columns. The precision and accuracy of the method developed were satisfactory with recoveries between 96.4% and 103.8% (RSD 3.1-4.3%, n = 5) and 96.0% and 104.2% (RSD 2.9-3.7%, n = 5) for andrographolide and dehydroandrographolide, respectively. Various real samples were employed to confirm the feasibility of method. This developed method demonstrates the potential of molecularly imprinted solid phase extraction for rapid, selective, and effective sample pretreatment.

  17. Molecular Imprinting of Silica Nanoparticle Surfaces via Reversible Addition-Fragmentation Polymerization for Optical Biosensing Applications

    NASA Astrophysics Data System (ADS)

    Oluz, Zehra; Nayab, Sana; Kursun, Talya Tugana; Caykara, Tuncer; Yameen, Basit; Duran, Hatice

    Azo initiator modified surface of silica nanoparticles were coated via reversible addition-fragmentation polymerization (RAFT) of methacrylic acid and ethylene glycol dimethacrylate using 2-phenylprop 2-yl dithobenzoate as chain transfer agent. Using L-phenylalanine anilide as template during polymerization led molecularly imprinted nanoparticles. RAFT polymerization offers an efficient control of grafting process, while molecularly imprinted polymers shows enhanced capacity as sensor. L-phenylalanine anilide imprinted silica particles were characterized by X-Ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM). Performances of the particles were followed by surface plasmon resonance spectroscopy (SPR) after coating the final product on gold deposited glass substrate against four different analogous of analyte molecules: D-henylalanine anilide, L-tyrosine, L-tryptophan and L-phenylalanine. Characterizations indicated that silica particles coated with polymer layer do contain binding sites for L-phenylalanine anilide, and are highly selective for the molecule of interest. This project was supported by TUBITAK (Project No:112M804).

  18. Implementation of molecularly imprinted polymer beads for surface enhanced Raman detection.

    PubMed

    Kamra, Tripta; Zhou, Tongchang; Montelius, Lars; Schnadt, Joachim; Ye, Lei

    2015-01-01

    Molecularly imprinted polymers (MIPs) have a predesigned molecular recognition capability that can be used to build robust chemical sensors. MIP-based chemical sensors allow label-free detection and are particularly interesting due to their simple operation. In this work we report the use of thiol-terminated MIP microspheres to construct surfaces for detection of a model organic analyte, nicotine, by surface enhanced Raman scattering (SERS). The nicotine-imprinted microspheres are synthesized by RAFT precipitation polymerization and converted into thiol-terminated microspheres through aminolysis. The thiol groups on the MIP surface allow the microspheres to be immobilized on a gold-coated substrate. Three different strategies are investigated to achieve surface enhanced Raman scattering in the vicinity of the imprinted sites: (1) direct sputtering of gold nanoparticles, (2) immobilization of gold colloids through the MIP's thiol groups, and (3) trapping of the MIP microspheres in a patterned SERS substrate. For the first time we show that large MIP microspheres can be turned into selective SERS surfaces through the three different approaches of assembly. The MIP-based sensing surfaces are used to detect nicotine to demonstrate the proof of concept. As synthesis and surface functionalization of MIP microspheres and nanoparticles are well established, the methods reported in this work are handy and efficient for constructing label-free chemical sensors, in particular for those based on SERS detection.

  19. Novel hybrid probe based on double recognition of aptamer-molecularly imprinted polymer grafted on upconversion nanoparticles for enrofloxacin sensing.

    PubMed

    Liu, Xiuying; Ren, Jing; Su, Lihong; Gao, Xue; Tang, Yiwei; Ma, Tao; Zhu, Lijie; Li, Jianrong

    2017-01-15

    A novel luminescent "double recognition" method for the detection of enrofloxacin (ENR) is developed to overcome some of the challenges faced by conventional molecularly imprinting. Biotinylated ENR aptamers immobilised on upconversion nanoparticles (UCNPs) surface are implemented to capture and concentrate ENR as the first imprinting recognition safeguard. After correct folding of the aptamer upon the existing targets, polymerization of methacrylic acid monomers around the ENR-aptamer complexes to interact with the residual functional groups of ENR by using molecularly imprinting techniques is the second imprinting recognition safeguard. The "double recognition" imprinting cavities are formed after removal of ENR, displaying recognition properties superior to that of aptamer or traditional molecularly imprinting alone. Another interest of this method is simultaneous molecular recognition and signal conversion by fabricating the "double recognition" receptor on to the surface of UCNPs to form a hybrid sensing system of apta-MIP/UCNPs. The proposed sensing method is applied to measure ENR in different fish samples. Good recoveries between 87.05% and 96.24%, and relative standard deviation (RSD) values in the range of 1.19-4.83% are obtained, with the limits of detection and quantification of 0.04 and 0.12ng/mL, respectively. It indicates that the sensing method is feasible for the quantification of target ENRs in real samples, and show great potential for wide-ranging application in bioassays. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Molecularly imprinted polymers based on SBA-15 for selective solid-phase extraction of baicalein from plasma samples.

    PubMed

    He, Hongliang; Gu, Xiaoli; Shi, Liying; Hong, Junli; Zhang, Hongjuan; Gao, Yankun; Du, Shuhu; Chen, Lina

    2015-01-01

    Highly selective molecularly imprinted mesoporous silica polymer (SBA-15@MIP) for baicalein (BAI) extraction was synthesized using a surface molecular imprinting technique on the SBA-15 supporter. Computational simulation was used to predict the optimal functional monomer for the rational design of SBA-15@MIP. Meanwhile, high adsorption capacity was obtained when a suitable yield of molecularly imprinted polymers (MIPs) layer was grafted onto the surface of SBA-15. Characterization and performance tests of the obtained polymer revealed that SBA-15@MIP possessed a highly ordered mesoporous structure, reached saturated adsorption within 60 min, and exhibited higher sorption capacity to the target molecule BAI compared with non-imprinted mesoporous silica polymer (SBA-15@NIP) and SBA-15. Finally, SBA-15@MIP was successfully applied to solid-phase extraction (SPE) coupled with high-performance liquid chromatography and ultraviolet detection (HPLC-UV) for the determination of trace BAI in plasma samples. Mean recoveries of BAI through the molecularly imprinted solid-phase extraction (MISPE) sorbent, non-imprinted solid-phase extraction (NISPE) sorbent, and SBA-15 solid-phase extraction (SBA-15-SPE) sorbent were 94.4, 22.7, and 10.7 %, respectively, and the relative standard deviations were 2.9, 2.6, and 3.6 %, respectively. These results reveal that SBA-15@MIP as a SPE sorbent has good applicability to selectively separate and enrich trace BAI from complex samples.

  1. Molecularly imprinted polymers as analyte sequesters and selective surfaces for easy ambient sonic-spray ionization.

    PubMed

    Figueiredo, Eduardo Costa; Sanvido, Gustavo Braga; Arruda, Marco Aurélio Zezzi; Eberlin, Marcos Nogueira

    2010-04-01

    The use of a molecularly imprinted polymer (MIP) as a selective surface for ambient mass spectrometry is demonstrated. The MIP is used to sequester target analytes from urine and easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to be able to efficiently desorb the analytes from the MIP surface and then transfer them in protonated forms to the gas phase for MS analysis. A set of five phenothiazines (chlorpromazine, perphenazine, triflupromazine, thioridazine and prochlorperazine) were chosen from a proof-of-principle class of drug samples. A chlorpromazine-imprinted methacrylic polymer was synthesized and used to prepare a MIP probe. The MIP-EASI-MS technique using acidified methanol as solvent has been shown to allow quantification of all five drugs in urine with LOQ of ca. 1 micromol L(-1).

  2. Titania-based molecularly imprinted polymer for sulfonic acid dyes prepared by sol-gel method.

    PubMed

    Li, Man; Li, Rong; Tan, Jin; Jiang, Zi-Tao

    2013-03-30

    A novel titania-based molecularly imprinted polymer (MIP) was synthesized through sol-gel process with sunset yellow (Sun) as template, without use of functional monomer. MIP was used as a solid-phase extraction material for the isolation and enrichment of sulfonic acid dyes in beverages. The results showed that MIP exhibited better selectivity, higher recovery and adsorption capacity for the sulfonic acid dyes compared to the non-imprinted polymer (NIP). MIP presented highest extraction selectivity to Sun when pH less than or equal to 3. The adsorption capacity was 485.9 mg g(-1), which was larger than that of NIP (384.7 mg g(-1)). The better clean-up ability demonstrated the capability of MIP for the isolation and enrichment of sulfonic acid dyes in complicated food samples. The mean recoveries for the sulfonic acid dyes on MIP were from 81.9% to 97.2% in spiked soft drink.

  3. Tert-butylhydroquinone recognition of molecular imprinting electrochemical sensor based on core-shell nanoparticles.

    PubMed

    Zhao, Peini; Hao, Jingcheng

    2013-08-15

    One novel electrochemistry-molecular imprinting sensor for determining tert-butylhydroquinone (TBHQ) in foodstuff was developed. TBHQ-imprinted core-shell nanoparticles (TICSNs) were fabricated using silica nanoparticles as core material. The silica nanoparticles were modified with (3-chloropropyl) trimethoxysilan and polyethylenimine, respectively, and polymerised to form the TICSNs with ethylene glycol dimethacrylate as cross-linker. The specific core-shell structure demonstrates extremely high specific surface area which greatly increases the effective binding sites and improves the recognition capability for model molecules. Under the optimal conditions, the linear range of the calibration curve was 0.1-50.0 mg kg(-1) with the detection limit of 0.27 mg kg(-1). The sensor has been successfully applied to the determination of TBHQ in food samples and achieved high sensitivity and selectivity. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Selective removal of diclofenac from contaminated water using molecularly imprinted polymer microspheres.

    PubMed

    Dai, Chao-Meng; Geissen, Sven-Uwe; Zhang, Ya-Lei; Zhang, Yong-Jun; Zhou, Xue-Fei

    2011-06-01

    A molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template. Binding characteristics of the MIP were evaluated using equilibrium binding experiments. Compared to the non-imprinted polymer (NIP), the MIP showed an outstanding affinity towards DFC in an aqueous solution with a binding site capacity (Q(max)) of 324.8 mg/g and a dissociation constant (K(d)) of 3.99 mg/L. The feasibility of removing DFC from natural water by the MIP was demonstrated by using river water spiked with DFC. Effects of pH and humic acid on the selectivity and adsorption capacity of MIP were evaluated in detail. MIP had better selectivity and higher adsorption efficiency for DFC as compared to that of powdered activated carbon (PAC). In addition, MIP reusability was demonstrated for at least 12 repeated cycles without significant loss in performance, which is a definite advantage over single-use activated carbon.

  5. Preliminary investigations into surface molecularly imprinted nanoparticles for Helicobacter pylori eradication

    PubMed Central

    Han, Jiaying; Sun, Yinjing; Hou, Jiapeng; Wang, Yuyan; Liu, Yu; Xie, Cao; Lu, Weiyue; Pan, Jun

    2015-01-01

    This paper reports investigations into the preparation and characterization of surface molecularly imprinted nanoparticles (SMINs) designed to adhere to Helicobacter pylori (H. pylori). Imprinted nanoparticles were prepared by the inverse microemulsion polymerization method. A fraction of Lpp20, an outer membrane protein of H. pylori known as NQA, was chosen as template and modified with myristic acid to facilitate its localization on the surface of the nanoparticles. The interaction between these SMINs with the template NQA were evaluated using surface plasmon resonance (SPR), change in zeta potential and fluorescence polarization (FP). The results were highly consistent in demonstrating a preferential recognition of the template NQA for SMINs compared with the control nanoparticles. In vitro experiments also indicate that such SMINs are able to adhere to H. pylori and may be useful for H. pylori eradication. PMID:26713273

  6. Guided folding takes a start from the molecular imprinting of structured epitopes.

    PubMed

    Cenci, L; Guella, G; Andreetto, E; Ambrosi, E; Anesi, A; Bossi, A M

    2016-08-25

    A biomimetic route towards assisted folding was explored. Molecularly imprinted polymeric nanoparticles (MIP NPs), i.e. biomimetics with entailed molecular recognition properties made by a template assisted synthesis, were prepared to target a structured epitope: the cystine containing peptide CC9ox, which corresponds to the apical portion of the β-hairpin hormone Hepcidin-25. The structural selection was achieved by the MIP NPs; moreover, the MIP NPs demonstrated favouring the folding of the linear random peptide (CC9red) into the structured one (CC9ox), anticipating the future role of the MIP NPs as in situ nanomachines to counteract folding defects.

  7. Imprints of the molecular-orbital geometry on the high-harmonic ellipticity.

    PubMed

    Qin, Meiyan; Zhu, Xiaosong; Liu, Kunlong; Zhang, Qingbin; Lu, Peixiang

    2012-08-27

    The influence of the orbital symmetry on the ellipticity of the high-order harmonics is investigated. It is found that the ellipticity maps have distinct shapes for the molecular orbitals with different symmetry. Our analysis shows that the feature of the harmonic ellipticity map is essentially determined by the nodal structure of the nonsymmetric orbital. The results indicate that the molecular-orbital geometry is imprinted on the ellipticity of the high-order harmonics, which invites the use of ellipticity measurements as a probe of the orbital structure for polar molecules.

  8. Polypyrrole, Formation and Use

    DTIC Science & Technology

    2005-01-01

    transformer en un matériau robuste. Parmi les matériaux présentant un tel intérêt, on retrouve des peintures au polypyrrole, des composites moulés... peintures au polypyrrole, des composites moulés par injection de type polypyrrole/poly(chlorure de vinyle) et des tissus et des fibres enduits de polypyrrole

  9. Selective solid-phase extraction using molecular imprinted polymer sorbent for the analysis of florfenicol in food samples.

    PubMed

    Sadeghi, Susan; Jahani, Moslem

    2013-11-15

    A molecularly imprinted polymer (MIP) for the selective solid phase extraction (SPE) of florfenicol (FF) was prepared using FF as template and 4-vinyl pyridine (4-VP) as functional monomer. For comparison, non-imprinted polymer (NIP) was synthesized in the absence of FF. The synthesized polymers were characterised by infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and differential thermal analysis (DTA). A molecularly imprinted solid phase extraction (MISPE) procedure was performed in column method by spectrophotometry detection technique. The prepared FF-MIP showed higher adsorption capacity than the non-imprinted polymer (NIP) and the maximum static adsorption capacities of FF on the MIP and the NIP were 4.32 and 2.88mgg(-1), respectively. Kinetics of the adsorption was fast and the adsorption equilibrium was achieved in 30min. The accuracy of the developed method was satisfactory for determination of FF in fish, chicken meat and honey samples.

  10. Molecular imprinting-based separation methods for selective analysis of fluoroquinolones in soils.

    PubMed

    Turiel, Esther; Martín-Esteban, Antonio; Tadeo, José Luis

    2007-11-23

    Molecularly imprinted polymers (MIPs) for fluoroquinolone antibiotics (FQs) have been synthesised in one single preparative step by precipitation polymerisation using ciprofloxacin (CIP) as template. Combinations of methacrylic acid (MAA) or 4-vinylpyridine (VP) as functional monomers, ethylene glycol dimethacrylate as crosslinker and dichloromethane, methanol, acetonitrile or toluene as porogens were tested. The experiments carried out by molecularly imprinted solid-phase extraction (MISPE) in cartridges did not allow to detect any imprint effect in the VP-based polymers whereas it was clearly observed in the MAA-based polymers. Among them, the MIP prepared in methanol using MAA as monomer showed the best performance and was chosen for further experiments. The ability of the selected MIP for the selective recognition of other widely used FQs (enoxacin, norfloxacin, danofloxacin and enrofloxacin) and quinolones (Qs) (cinoxacin, flumequine, nalidixic acid and oxolinic acid) was evaluated. The obtained results revealed the high selectivity of the obtained polymer, which was able to distinguish between FQs, that were recognised and retained onto the MIP cartridge, and Qs, which were washed out during loading and washing steps. The MIP was then packed into a stainless steel column (50mmx4.6mm i.d.) and evaluated as chromatography column for screening of FQs in soil samples. The mobile phase composition, flow rate, and the elution profile were then optimised in order to improve peak shape without sacrifying imprinting factor. Finally, under optimised conditions, soil samples spiked with CIP or with a mixture of fluoroquinolones in concentration of 0.5microgg(-1) were successfully analysed by the developed MIP-based procedures.

  11. Importance of gene duplication in the evolution of genomic imprinting revealed by molecular evolutionary analysis of the type I MADS-box gene family in Arabidopsis species.

    PubMed

    Yoshida, Takanori; Kawabe, Akira

    2013-01-01

    The pattern of molecular evolution of imprinted genes is controversial and the entire picture is still to be unveiled. Recently, a relationship between the formation of imprinted genes and gene duplication was reported in genome-wide survey of imprinted genes in Arabidopsis thaliana. Because gene duplications influence the molecular evolution of the duplicated gene family, it is necessary to investigate both the pattern of molecular evolution and the possible relationship between gene duplication and genomic imprinting for a better understanding of evolutionary aspects of imprinted genes. In this study, we investigated the evolutionary changes of type I MADS-box genes that include imprinted genes by using relative species of Arabidopsis thaliana (two subspecies of A. lyrata and three subspecies of A. halleri). A duplicated gene family enables us to compare DNA sequences between imprinted genes and its homologs. We found an increased number of gene duplications within species in clades containing the imprinted genes, further supporting the hypothesis that local gene duplication is one of the driving forces for the formation of imprinted genes. Moreover, data obtained by phylogenetic analysis suggested "rapid evolution" of not only imprinted genes but also its closely related orthologous genes, which implies the effect of gene duplication on molecular evolution of imprinted genes.

  12. Synthesis of surface molecularly imprinted polymer and the selective solid phase extraction of imidazole from its structural analogs.

    PubMed

    Zhu, Guifen; Fan, Jing; Gao, Yanbu; Gao, Xia; Wang, Jianji

    2011-05-30

    A surface molecularly imprinted polymer (MIP) was synthesized by using imidazole as the template and modified silica particles as the support material. The static adsorption, solid phase extraction (SPE) and high-performance liquid chromatography (HPLC) experiments were performed to investigate the adsorption properties and selective recognition characteristics of the polymer for imidazole and its structural analogs. It was shown that the maximum binding capacities of imidazole on the MIP and the non-imprinted polymer (NIP) were 312 and 169 μmol g(-1), respectively. The adsorption was fast and the adsorption equilibrium was achieved in 30 min. The binding process could be described by pseudo-second order kinetics. Compared with the corresponding non-imprinted polymer, the molecularly imprinted polymer exhibited much higher adsorption performance and selectivity for imidazole. The selective separation of imidazole from a mixture of 1-hexyl-3-methylimidazolium bromide ([C(6)mim][Br]) and 2,4-dichlorophenol could be achieved on the MIP-SPE column. The recoveries of imidazole and [C(6)mim][Br] were 97.6-102.7% and 12.2-17.3%, respectively, but 2,4-dichlorophenol could not be retained on the column. The surface molecularly imprinted polymer presented here may find useful application as a solid phase absorbent to separate trace imidazole in environmental water samples. This may also form the basis for our research program on the preparation and application of alkyl-imidazolium imprinted polymers. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Novel molecularly imprinted polymers based on multiwalled carbon nanotubes with bifunctional monomers for solid-phase extraction of rhein from the root of kiwi fruit.

    PubMed

    Chen, Xing; Zhang, Zhaohui; Yang, Xiao; Liu, Yunan; Li, Jiaxing; Peng, Mijun; Yao, Shouzhuo

    2012-09-01

    A novel molecularly imprinted polymers based on multiwalled carbon nanotubes synthesized by precipitate polymerization was applied as a selective sorbent for separation and determination of rhein (4,5-dihydroxyanthraquinone-2-carboxylic acid) from the root of kiwi fruit samples coupled with high performance liquid chromatography (HPLC). The molecularly imprinted polymers were prepared with methacrylic acid and 4-vinylpyridine as bifunctional monomers. The chemical structure of the molecularly imprinted polymers was characterized by Fourier transform infrared spectrometer. The equilibrium rebinding experiment and competitive adsorption experiment showed that these imprinted polymers exhibited good adsorption ability toward rhein. The Langmuir adsorption equilibrium constant, K(m) , and theoretical maximum adsorption capacity, Q(m) , were estimated to be 0.43 and 6.77 mg g(-1) , respectively. Compared with molecularly imprinted polymers prepared with methacrylic acid or 4-vinylpyridine solely, the molecularly imprinted polymers synthesized with bifunctional monomers showed enhanced molecular imprinting effect and higher adsorption capacity for the template rhein. The performances of the molecularly imprinted polymers utilized as solid phase extraction sorbent were investigated in detail. The molecularly imprinted polymers prepared by the method proposed in this work could successfully apply to extraction and determination of rhein from the root of kiwi fruit samples coupled with HPLC.

  14. Oxytetracycline recovery from aqueous media using computationally designed molecularly imprinted polymers.

    PubMed

    Rodríguez-Dorado, Rosalía; Carro, Antonia M; Chianella, Iva; Karim, Kal; Concheiro, Angel; Lorenzo, Rosa A; Piletsky, Sergey; Alvarez-Lorenzo, Carmen

    2016-09-01

    Polymers for recovery/removal of the antimicrobial agent oxytetracycline (OTC) from aqueous media were developed with use of computational design and molecular imprinting. 2-Hydroxyethyl methacrylate, 2-acrylamide-2-methylpropane sulfonic acid (AMPS), and mixtures of the two were chosen according to their predicted affinity for OTC and evaluated as functional monomers in molecularly imprinted polymers and nonimprinted polymers. Two levels of AMPS were tested. After bulk polymerization, the polymers were crushed into particles (200-1000 μm). Pressurized liquid extraction was implemented for template removal with a low amount of methanol (less than 20 mL in each extraction) and a few extractions (12-18 for each polymer) in a short period (20 min per extraction). Particle size distribution, microporous structure, and capacity to rebind OTC from aqueous media were evaluated. Adsorption isotherms obtained from OTC solutions (30-110 mg L(-1)) revealed that the polymers prepared with AMPS had the highest affinity for OTC. The uptake capacity depended on the ionic strength as follows: purified water > saline solution (0.9 % NaCl) > seawater (3.5 % NaCl). Polymer particles containing AMPS as a functional monomer showed a remarkable ability to clean water contaminated with OTC. The usefulness of the stationary phase developed for molecularly imprinted solid-phase extraction was also demonstrated. Graphical Abstract Selection of functional monomers by molecular modeling renders polymer networks suitable for removal of pollutants from contaminated aqueous environments, under either dynamic or static conditions.

  15. Synthesis and characterization of a molecularly imprinted polymer for the determination of spiramycin in sheep milk.

    PubMed

    García Mayor, M A; Paniagua González, G; Garcinuño Martínez, R M; Fernández Hernando, P; Durand Alegría, J S

    2017-04-15

    A series of molecularly imprinted polymers (MIPs) comprising reactionary sites which are complementary to macrolide antibiotic spiramycin (SPI) were synthetized by noncovalent bulk polymerization technique. MIPs were synthesized under different polymerization process and their recognition efficiency was evaluated in binding studies in comparison with non-imprinted polymers. The best MIP was morphologically characterized and equilibrium assays were carried out. The MIP was evaluated as a sorbent for extraction and preconcentration of SPI from aqueous and sheep milk samples, and an off-line MISPE method followed by high-performance liquid chromatography with UV diode-array detection was established. Good linearity were obtained for SPI in a range of 24-965μgkg(-1) and the average recoveries at three spiked levels in milk samples were higher than 90% (RSD<5%). Limit of quantification was 24.1μgkg(-1). Cross-reactivity studies from other macrolides with similar structure were tested. The optimum imprinted polymer showed a good selectivity and affinity for SPI, demonstrating the potential of the proposed MISPE for rapid, sensitive and effective sample pretreatment for selective determination of SPI in sheep milk samples.

  16. Extraction of melamine from milk using a magnetic molecularly imprinted polymer.

    PubMed

    Anirudhan, T S; Christa, J; Deepa, J R

    2017-07-15

    A novel magnetic molecularly imprinted polymer (MMIP) for the preconcentration of melamine, a non-protein nitrogen food additive from complex matrices was synthesized and characterized using FT-IR, XRD, SEM and VSM techniques. Surface imprinting was done on vinyltrimethoxysilane coated Fe3O4 (Fe3O4-VTMS) using 2-acrylamido-2-methylpropane sulfonic acid (AMPS), N,N'-methylenebisacrylamide (MBA) and potassium persulfate (KPS) as functional monomer, crosslinker and initiator respectively. Saturation magnetization value obtained for MMIP was 1.72emug(-1). Binding studies showed that MMIP exhibits good recognition to melamine compared to magnetic non imprinted polymer (MNIP). The optimum pH for the binding of melamine was found to be 4.5. Binding process was very fast and pseudo-second-order model fitted well with the kinetic data. Binding isotherm followed Langmuir isotherm model of monolayer adsorption with a maximum melamine binding efficiency of 62.25mgg(-1). The HPLC-UV analysis results revealed the applicability of MMIP in solid phase extraction and determination of melamine from milk samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Molecularly Imprinted Polymer Microspheres Containing Photoswitchable Spiropyran-Based Binding Sites

    PubMed Central

    2013-01-01

    A versatile approach for the preparation of photoswitchable molecularly imprinted polymers (MIPs) is proposed where the selective recognition and the photoresponsive function are assumed by two different monomers. As a proof of concept, MIP microspheres were synthesized by precipitation polymerization for recognizing terbutylazine, a triazine-type herbicide. Formation of the selective binding sites was based upon H-bonding interactions between the template and the functional monomer methacrylic acid, whereas a polymerizable spiropyran unit was incorporated into the polymer matrix to provide light-controllable characteristics. A trifunctional monomer, trimethylolpropane trimethacrylate, was used as a cross-linker. The imprinted particles exhibited considerable morphological differences compared to their nonimprinted counterparts as observed by scanning electron microscopy. The imprinting effect was confirmed by equilibrium rebinding studies. The photoresponsiveness of the polymer particles was visualized by fluorescence microscopy and further characterized by spectroscopy. The template binding behavior could be regulated by alternating UV and visible light illumination when analyte release and uptake was observed, respectively. Binding isotherms fitted by the Freundlich model revealed the photomodulation of the number of binding sites and their average affinity. This facile synthetic approach may give an attractive starting point to endow currently existing highly selective MIPs with photoswitchable properties, thereby extending the scope of spiropyran-based photoresponsive smart materials. PMID:23961698

  18. New molecularly-imprinted polymer for carnitine and its application as ionophore in potentiometric selective membranes.

    PubMed

    Moret, Joséphine; Moreira, Felismina T C; Almeida, Sofia A A; Sales, M Goreti F

    2014-10-01

    Carnitine (CRT) is a biological metabolite found in urine that contributes in assessingseveral disease conditions, including cancer. Novel quick screening procedures for CRT are therefore fundamental. This work proposes a novel potentiometric device where molecularly imprinted polymers (MIPs) were used as ionophores. The host-tailored sites were imprinted on a polymeric network assembled by radical polymerization of methacrylic acid (MAA) and trimethylpropane trimethacrylate (TRIM). Non-imprinted polymers (NIPs) were produced as control by removing the template from the reaction media. The selective membrane was prepared by dispersing MIP or NIP particles in plasticizer and poly(vinyl chloride), PVC, and casting this mixture over a solid contact support made of graphite. The composition of the selective membrane was investigated with regard to kind/amount of sensory material (MIP or NIP), and the need for a lipophilic additive. Overall, MIP sensors with additive exhibited the best performance, with near-Nernstian response down to ~1×10(-4)mol L(-1), at pH5, and a detection limit of ~8×10(-5)mol L(-1). Suitable selectivity was found for all membranes, assessed by the matched potential method against some of the most common species in urine (urea, sodium, creatinine, sulfate, fructose and hemoglobin). CRT selective membranes including MIP materials were applied successfully to the potentiometric determination of CRT in urine samples.

  19. [Preparation and characterization of core-shell structural magnetic molecularly imprinted polymers for nafcillin].

    PubMed

    Chen, Langxing; Liu, Yuxing; He, Xiwen; Zhang, Yukui

    2015-05-01

    The uniform core-shell nanostructured magnetic molecularly imprinted polymers (MIPs) were synthesized using antibiotic nafcillin as a template. In this protocol, the magnetite nanoparticles (NPs) were synthesized by the solvothermal reaction firstly. Subsequently, the vinyl groups were grated onto silica-modified Fe3O4 surface by 3-methacryloyloxypropyltrimethoxysilane via sol-gel method. Finally, the nafcillin-MIPs film was formed on the surface of Fe3O4 @ SiO2 by the copolymerization of vinyl end group with functional monomer, methacrylic acid, cross-linking agent, ethylene glycol dimethacrylate, the initiator azo-bis-isobutyronitrile and template molecule. The morphological and magnetic characteristics of the MIPs were characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and vibrating sample magnetometer. The obtained spherical magnetic MIPs with diameters of about 320 nm had good monodispersity. The static binding experiment was carried out to evaluate the properties of magnetic MIPs and non imprinted polymers (NIPs). The results demonstrated that the magnetic MIPs had high adsorption capacity to template and good selectivity. The imprinting factor and the maximum adsorption capacity of Fe3O4 @ MIPs to nafcillin were 2.46 and 50.7 mg/g, respectively. It is expected that the prepared magnetic MIPs could be used for the enrichment of nafcillin in complex samples.

  20. Molecularly imprinted polymer doped with Hectorite for selective recognition of sinomenine hydrochloride.

    PubMed

    Zhang, W; Fu, H L; Li, X Y; Zhang, H; Wang, N; Li, W; Zhang, X X

    2016-01-01

    In this work, a new and facile method was introduced to prepare molecularly imprinted polymers (MIPs) based on nano clay hectorite (Hec) for sinomenine hydrochloride (SM) analysis. Hec was firstly dissolved in distilled water in order to swell adequately, followed by a common precipitation polymerization with SM as the template, methacrylic acid as monomer, ethylene glycol dimethacrylate as a crosslinker and 2,2-azobisisobutyronitrile as an initiator. Hec@SM-MIPs were characterized by Fourier transform infrared spectrometer, transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. The maximum binding capacity of Hec@SM-MIPs, SM-MIPs and non-imprinted polymers (NIPs) (Hec@NIPs) was 57.4, 16.8 and 11.6 mg/g, respectively. The reason for this result may be that Hec@SM-MIPs have more binding sites and imprinted cavities for template molecule. Equilibrium data were described by the Langmuir and Freundlich isotherm models. The results showed that the Hec@SM-MIPs adsorption data correlated better with the Langmuir equation than the Freundlich equation under the studied concentration range. In vitro drug release experiment, Hec@SM-MIPs have a better ability to control SM release than SM-MIPs. Therefore, Hec@SM-MIPs were successfully applied to extraction of SM and used as the materials for drug delivery system.

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

    PubMed

    Krupadam, Reddithota J; Khan, Muntazir S; Wate, Satish R

    2010-02-01

    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.

  2. Molecularly Imprinted Polymers for Selective Extraction of Oblongifolin C from Garcinia yunnanensis Hu.

    PubMed

    Wang, Liping; Fu, Wenwei; Shen, Yunhui; Tan, Hongsheng; Xu, Hongxi

    2017-03-23

    Molecularly imprinted polymers (MIPs) were synthesized and applied for the selective extraction of oblongifolin C (OC) from fruit extracts of Garcinia yunnanensis Hu. A series of experiments and computational approaches were employed to improve the efficiency of screening for optimal MIP systems in the study. The molar ratio (1:4) was eventually chosen based on the comparison of the binding energy of the complexes between the template (OC) and the functional monomers using density functional theory (DFT) at the RI-PBE-D3-gCP/def2-TZVP level of theory. The binding characterization and the molecular recognition mechanism of MIPs were further explained using the molecular modeling method along with NMR and IR spectra data. The reusability of this approach was demonstrated in over 20 batch rebinding experiments. A mass of 140.5 mg of OC (>95% purity) was obtained from the 5 g extracts, with 2 g of MIPs with the best binding properties, through a gradient elution program from 35% to 70% methanol-water solution. At the same time, another structural analog, 46.5 mg of guttiferone K (GK) (>88% purity), was also obtained by the gradient elution procedure. Our results showed that the structural analogs could be separated from the crude extracts by the molecularly imprinted solid-phase extraction (MISPE) using a gradient elution procedure for the first time.

  3. Optimisation and production of a molecular-imprinted-polymer for the electrochemical determination of triacetone triperoxide (TATP)

    NASA Astrophysics Data System (ADS)

    Mamo, S. K.; Gonzalez-Rodriguez, J.

    2014-10-01

    Triacetone triperoxide (TATP) explosive is one of the most common components of improvised explosive devices which can be prepared from commercially readily available reagents with easier synthetic procedure that is available over the internet. Molecularly imprinted polymer electrochemical sensors can offer highly selective determination of several classes of compounds from wide range of sample matrices in parts per billion levels. Highly sensitive and selective molecularly imprinted polymer electrochemical sensor has been developed for determination of TATP in acetonitrile. Molecular imprinting has been performed via electro-polymerization on to glassy carbon, gold, silver and platinum electrode surface by cyclic voltammetry from a solution of pyrrole functional monomer, TATP template, and LiClO4 supporting electrolyte. Quantitative differential pulse voltammetric measurements of TATP, with LiClO4 supporting electrolyte, were performed using the molecularly imprinted polymer modified and bare glassy carbon electrodes in a potential range of -2.0V to +1.0 V (vs. Ag/AgCl). Three-factor two-level factorial design has been used to optimize the monomer concentration at 0.1 mol L-1, template concentration at 100 mmol L-1, and the number of cyclic voltammetry scan cycles to 10 cycles, using differential pulse voltammetric current intensity as response variable. The molecularly imprinted polymer modified glassy carbon electrode demonstrated superior selectivity for TATP in the presence of PETN, RDX, HMX, and TNT.

  4. Design of a molecular imprinting biosensor with multi-scale roughness for detection across a broad spectrum of biomolecules.

    PubMed

    Yu, Yingjie; Zhang, Qi; Chang, Chung-Chueh; Liu, Ying; Yang, Zhenhua; Guo, Yichen; Wang, Yantian; Galanakis, Dennis K; Levon, Kalle; Rafailovich, Miriam

    2016-10-07

    The molecular imprinting technique has tremendous applications in artificial enzymes, bioseparation, and sensor devices. In this study, a novel molecular imprinting (MI) biosensor platform was developed for the detection of a broad range of biomolecules with different sizes. Previously this method has been applied to 2D molecular imprinting, where the height of the self-assembled monolayer (SAM) of around 2 nm limited the maximum dimensions of the molecule that can be imprinted to create template-shaped cavities. In order to match the size of the imprinted molecules with the height of the SAM, we propose a model for 3D molecular imprinting where the analyte is sequestered within a niche created by the surface roughness. The SAM is assembled on the walls of the niche, forming a 3D pattern of the analyte uniquely molded to its contour. Surfaces with multi-scale roughness were prepared by evaporation of gold onto electropolished (smooth) and unpolished (rough) Si wafers, where the native roughness was found to have a normal distribution centered around 5 and 90 nm respectively. Our studies using molecules with size ranging on a nanometer scale, from proteins of a few nanometers to bacteria of hundreds of nanometers, showed that when the size of the analyte matched the roughness range of the gold surface, the molecular imprinting process was optimized for the best biosensing performance. After optimization, the MI biosensor platform enabled the identification and quantification of a broad range of biomolecules with great discrimination abilities. Hemoglobin under different pH values and several mutated fibrinogen molecules can also be well differentiated through the test.

  5. Utilization of theoretical studies of the imprinting ratio to guide experimental research into the molecular imprinted polymers formed using enrofloxacin and methacrylic acid.

    PubMed

    Liu, Junbo; Dai, Zhengqiang; Li, Bo; Tang, Shanshan; Jin, Ruifa

    2014-10-01

    Computational approaches have been suggested as rational and fast methods for optimizing imprinting ratios. The B3LYP/6-31 g(d,p) level was applied to simulate the self-assembled system of molecularly imprinted polymers (MIPs) formed by enrofloxacin (ENRO) and methacrylic acid (MAA). Geometry optimization, the bonding situation, and the binding energies involved were studied to determine the impact of varying the imprinting ratio on the recognition characteristics. These theoretical results showed that the compound with an ENRO:MAA ratio of 1:7 had the lowest binding energy and the most stable structure. MIPs with different imprinting ratios of ENRO to MAA were then prepared in order to study the binding capacities of the polymers experimentally. The experimental and theoretically calculated results for these polymers were found to be consistent with each other. In dynamic adsorption experiments on the MIPs, the adsorption reaction was observed to reach a balanced state after 120 min. Analysis of the Scatchard plot revealed that the dissociation constant (K d) and the apparent maximum binding capacity (Q max) of MIPs with high-affinity sites were 451.67 mg/L and 42.23 mg/g, respectively, whereas the dissociation constant and apparent maximum binding capacity of MIPs with low-affinity sites were 883.39 mg/L and 73.15 mg/g, respectively. The quantity of ENRO adsorbed onto the MIPs was considerably higher than the quantities of ciprofloxacin (CIP) and ofloxacin (OFL) adsorbed, indicating that these MIPs have a much higher specific absorption capacity than the corresponding non-imprinted polymers.

  6. A comparison of the performance of molecularly imprinted polymer nanoparticles for small molecule targets and antibodies in the ELISA format.

    PubMed

    Smolinska-Kempisty, Katarzyna; Guerreiro, Antonio; Canfarotta, Francesco; Cáceres, César; Whitcombe, Michael J; Piletsky, Sergey

    2016-11-24

    Here we show that molecularly imprinted polymer nanoparticles, prepared in aqueous media by solid phase synthesis with immobilised L-thyroxine, glucosamine, fumonisin B2 or biotin as template, can demonstrate comparable or better performance to commercially produced antibodies in enzyme-linked competitive assays. Imprinted nanoparticles-based assays showed detection limits in the pM range and polymer-coated microplates are stable to storage at room temperature for at least 1 month. No response to analyte was detected in control experiments with nanoparticles imprinted with an unrelated template (trypsin) but prepared with the same polymer composition. The ease of preparation, high affinity of solid-phase synthesised imprinted nanoparticles and the lack of requirement for cold chain logistics make them an attractive alternative to traditional antibodies for use in immunoassays.

  7. A comparison of the performance of molecularly imprinted polymer nanoparticles for small molecule targets and antibodies in the ELISA format

    NASA Astrophysics Data System (ADS)

    Smolinska-Kempisty, Katarzyna; Guerreiro, Antonio; Canfarotta, Francesco; Cáceres, César; Whitcombe, Michael J.; Piletsky, Sergey

    2016-11-01

    Here we show that molecularly imprinted polymer nanoparticles, prepared in aqueous media by solid phase synthesis with immobilised L-thyroxine, glucosamine, fumonisin B2 or biotin as template, can demonstrate comparable or better performance to commercially produced antibodies in enzyme-linked competitive assays. Imprinted nanoparticles-based assays showed detection limits in the pM range and polymer-coated microplates are stable to storage at room temperature for at least 1 month. No response to analyte was detected in control experiments with nanoparticles imprinted with an unrelated template (trypsin) but prepared with the same polymer composition. The ease of preparation, high affinity of solid-phase synthesised imprinted nanoparticles and the lack of requirement for cold chain logistics make them an attractive alternative to traditional antibodies for use in immunoassays.

  8. Subpicomolar sensing of delta-opioid receptor ligands by molecular-imprinted polymers using plasmon-waveguide resonance spectroscopy.

    PubMed

    Devanathan, Savitha; Salamon, Zdzislaw; Nagar, Anoop; Narang, Subhash; Schleich, Donald; Darman, Paul; Hruby, Victor; Tollin, Gordon

    2005-04-15

    Here we report, for the first time, the formation of a biomimetic covalently imprinted polymeric sensor for a target ligand, the delta-opioid G-protein coupled receptor agonist DPDPE, which reproducibly exhibits subpicomolar binding affinity in an aqueous environment. In addition to having a well-defined and homogeneous binding site, the imprinted polymer template is quite stable to storage in both the dry and wet states and has at least 6 orders of magnitude higher affinities than exhibited by similar peptide-based molecular-imprinted polymers (MIPs) thus far. A highly sensitive optical detection methodology, plasmon-waveguide resonance spectroscopy, was employed, capable of measuring binding in real time and discriminating between ligand molecules, without requiring labeling protocols (fluorophores or radioisotopes). The DPDPE-imprinted polymer showed a broad structure-activity relationship profile, not unlike that found for protein receptors. Such sensitivity and robustness of MIPs suggests potential applications ranging from biowarfare agent detection to pharmaceutical screening.

  9. A comparison of the performance of molecularly imprinted polymer nanoparticles for small molecule targets and antibodies in the ELISA format

    PubMed Central

    Smolinska-Kempisty, Katarzyna; Guerreiro, Antonio; Canfarotta, Francesco; Cáceres, César; Whitcombe, Michael J.; Piletsky, Sergey

    2016-01-01

    Here we show that molecularly imprinted polymer nanoparticles, prepared in aqueous media by solid phase synthesis with immobilised L-thyroxine, glucosamine, fumonisin B2 or biotin as template, can demonstrate comparable or better performance to commercially produced antibodies in enzyme-linked competitive assays. Imprinted nanoparticles-based assays showed detection limits in the pM range and polymer-coated microplates are stable to storage at room temperature for at least 1 month. No response to analyte was detected in control experiments with nanoparticles imprinted with an unrelated template (trypsin) but prepared with the same polymer composition. The ease of preparation, high affinity of solid-phase synthesised imprinted nanoparticles and the lack of requirement for cold chain logistics make them an attractive alternative to traditional antibodies for use in immunoassays. PMID:27883023

  10. Molecularly imprinted polymer monolith containing magnetic nanoparticles for the stir-bar sorptive extraction of triazines from environmental soil samples.

    PubMed

    Díaz-Álvarez, Myriam; Turiel, Esther; Martín-Esteban, Antonio

    2016-10-21

    In this work, novel molecularly imprinted stir-bars based upon the entrapment of modified magnetic nanoparticles within an imprinted polymer monolith is developed for stir-bar sorptive extraction (SBSE). Firstly, magnetic nanoparticles were surface modified with oleic acid followed by encapsulation inside a silica network. Then, vinyl-groups were grafted onto the particles surface for the subsequent copolymerization with the imprinting polymerization mixture using a glass vial insert as a mold. As a result, the obtained imprinted monolith presented magnetic properties allowing its use as magnetic stir-bar. Variables affecting both polymer morphology (i.e., amount of magnetic nanoparticles, polymerization time) and binding-elution conditions of target analytes (i.e., solvents, time) was carefully optimized. Optimum imprinted stir-bars were evaluated for the SBSE of triazines in soil sample extracts. Recoveries, at 16ngg(-1) concentration level, ranged from 2.4 to 8.7% with relative standard deviations lower than 15% (n=3). Although low recoveries were obtained, the high selectivity provided by the new molecularly imprinted stir-bars allowed reaching detection limits below 7.5ngg(-1) by liquid chromatography coupled to UV detection.

  11. Effect of minimizing amount of template by addition of macromolecular crowding agent on preparation of molecularly imprinted monolith.

    PubMed

    Sun, Guang-Ying; Zhong, Dan-Dan; Li, Xiang-Jie; Luo, Yu-Qing; Ba, Hang; Liu, Zhao-Sheng; Aisa, Haji Akber

    2015-09-01

    One of the main challenges in the preparation of molecularly imprinted polymers (MIPs) is the substantial initial amount of template needed because of the requirement of high load capacities for most applications. A new strategy of macromolecular crowding was suggested to solve this problem by reducing the amount of template in the polymerization recipe. In a ternary porogenic system of polystyrene (PS) (crowding agent), tetrahydrofuran, and toluene, an imprinted monolithic column with high porosity and good permeability was synthesized using a mixture of ellagic acid (template), acrylamide, and ethylene glycol dimethacrylate. The effect of polymerization factors, including monomer-template molar ratio and the molecular weight and concentration of PS, on the imprinting effect of the resulting MIP monoliths was systematically investigated. At a high ratio of monomer-template (120:1), the greatest imprinting factor of 32.4 was obtained on the MIP monolith with the aid of macromolecular crowding agent. The PS-based imprinted monolith had imprinting even at the extremely high ratio of functional monomer to template of 1510:1. Furthermore, an off-line solid-phase extraction based on the ground MIP was conducted, and the purification recovery of ellagic acid from pomegranate-rind extract was up to 80 %. In conclusion, this approach based on macromolecular crowding is simple, and is especially valuable for those applications of MIP preparation for which a rare template is used.

  12. Molecularly Imprinted Plasmonic Substrates for Specific and Ultrasensitive Immunoassay of Trace Glycoproteins in Biological Samples.

    PubMed

    Muhammad, Pir; Tu, Xueying; Liu, Jia; Wang, Yijia; Liu, Zhen

    2017-04-05

    Assays of glycoproteins hold significant biological importance and clinical values, for which immunoassay has been the workhorse tool. As immunoassays are associated with disadvantages such as poor availability of high-specificity antibodies, limited stability of biological reagents, and tedious procedure, innovative alternatives that can overcome these drawbacks are highly desirable. Plasmonic immunosandwich assay (PISA) has emerged as an appealing alternative to immunoassay for fast and sensitive determination of trace glycoproteins in biosamples. Plasmonic substrates play key roles in PISA, not only in determining the specificity but also in greatly influencing the detection sensitivity. Herein, we report a new type of molecularly imprinted plasmonic substrates for rapid and ultrasensitive PISA assay of trace glycoproteins in complex real samples. The substrates were fabricated from glass slides, first coated with self-assembled monolayer (SAM) of gold nanoparticles (AuNPs) and then molecularly imprinted with organo-siloxane polymer in the presence of template glycoproteins. The prepared molecularly imprinted substrates exhibited not only a significant plasmonic effect but also excellent binding properties, ensuring the sensitivity as well as the specificity of the assay. Alkaline phosphatase (ALP) and α-fetoprotein (AFP), glycoproteins that are routinely used as disease markers in clinical diagnosis, were used as representative targets. The limit of detection (LOD) was 3.1 × 10(-12) M for ALP and 1.5 × 10(-14) M for AFP, which is the best among the PISA approaches reported. The sample volume required was only 5 μL, and the total time required was within 30 min for each assay. Specific and ultrasensitive determination of ALP and AFP in human serum was demonstrated. Because many disease biomarkers are glycoproteins, the developed PISA approach holds great promise in disease diagnostics.

  13. Determination of theophylline in serum by molecularly imprinted solid-phase extraction with pulsed elution.

    PubMed

    Mullett, W M; Lai, E P

    1998-09-01

    The technique of molecular imprinting is used to produce an extensively cross-linked poly(methacrylic acid-co-ethylene dimethacrylate) material that contains theophylline as a print molecule. After Soxhlet extraction of the theophylline, binding sites are formed in the polymer with complementary size, shape, and positioning of chemical functionalities. The molecularly imprinted polymer's (MIP) high theophylline selectivity, chemical stability, and physically robust nature make it an ideal stationary-phase material in columns for HPLC separation of theophylline from other structurally related drug compounds. Mobile-phase tests confirm that a retention mechanism typical of normal-phase chromatography governs the separation, and selectivity of the MIP column can be controlled by a combination of the mobile phase and the sample solvent. Under optimal conditions, the MIP column functions like a solid-phase sorbent for theophylline extraction. Rapid elution of the bound theophylline can be accomplished in a pulsed format through injection of 20 μL of a solvent that has the proper polarity and protic nature to disrupt the electrostatic interactions and hydrogen bonding between theophylline and binding sites. A concentration detection limit of 120 ng/mL is obtained using direct UV absorption detection at 270 nm, which corresponds to a mass detection limit of 2.4 ng. This new technique, molecularly imprinted solid-phase extraction with pulsed elution (MISPE-PE), permits on-line preconcentration of theophylline from a large volume of dilute sample solution. Using a sample volume of 300 μL, a 40 ng/mL standard solution produces a detectable peak signal. Application of MISPE-PE in serum analysis further demonstrates the high capability of the MIP column to selectively isolate theophylline from other matrix components for fast, accurate determination.

  14. Detection of template binding to molecularly imprinted polymers by Raman microspectroscopy

    NASA Astrophysics Data System (ADS)

    Kantarovich, Keren; Belmont, Anne-Sophie; Haupt, Karsten; Bar, Ilana; Gheber, Levi A.

    2009-05-01

    We report on sensitive and specific detection and quantification of a template in a molecularly imprinted polymer (MIP) using Raman microspectroscopy. The β-blocking drug S-propranolol and its enantiomer, R-propranolol, were used as target molecules since the selectivity of this MIP is well established and serves as an appropriate validation standard. Specific peaks originating in the template were identified in the Raman spectrum, allowing quantification of bound target molecule. We demonstrate that label-free monitoring can be achieved from volumes as small as 1 μm3 of MIP, based on a single identifying peak.

  15. Theoretical investigation on functional monomer and solvent selection for molecular imprinting of tramadol

    NASA Astrophysics Data System (ADS)

    Fonseca, Matheus C.; Nascimento, Clebio S.; Borges, Keyller B.

    2016-02-01

    The purpose of this Letter was to study for the first time the interaction process of tramadol (TRM) with distinct functional monomers (FM) in the formation of molecular imprinted polymer (MIP), using density functional theory (DFT) calculations at B3LYP/6-31G(d,p). As result we were able to establish that the best MIP synthesis conditions are obtained with acrylic acid as FM in 1:3 molar ratio and with chloroform as solvent. This condition presented the lowest stabilization energy for the pre-polymerization complexes. Besides, the intermolecular hydrogen bonds found between the template molecule and functional monomers play a primary role to the complex stability.

  16. Isotherm charts for material selection and method development with molecularly imprinted polymers and other sorbents.

    PubMed

    Dorkó, Zsanett; Tamás, Barbara; Horvai, George

    2017-01-01

    A simple and efficient method is presented for assessing molecularly imprinted polymers (MIP) and other sorbents from the point of view of practical applications. The adsorption isotherms of the compounds, which need to be separated or detected in an application, are constructed from a small number of measured points on a log-log chart and then are compared graphically. Despite its simplicity and robustness this method reveals the information needed for optimal selection between MIPs and alternative sorbents. The design of separation or detection methods with MIPs is also supported by the proposed graphical isotherm comparison. Many experimental isotherms are presented supporting the proposed method.

  17. Formation of target-specific binding sites in enzymes: solid-phase molecular imprinting of HRP

    NASA Astrophysics Data System (ADS)

    Czulak, J.; Guerreiro, A.; Metran, K.; Canfarotta, F.; Goddard, A.; Cowan, R. H.; Trochimczuk, A. W.; Piletsky, S.

    2016-05-01

    Here we introduce a new concept for synthesising molecularly imprinted nanoparticles by using proteins as macro-functional monomers. For a proof-of-concept, a model enzyme (HRP) was cross-linked using glutaraldehyde in the presence of glass beads (solid-phase) bearing immobilized templates such as vancomycin and ampicillin. The cross-linking process links together proteins and protein chains, which in the presence of templates leads to the formation of permanent target-specific recognition sites without adverse effects on the enzymatic activity. Unlike complex protein engineering approaches commonly employed to generate affinity proteins, the method proposed can be used to produce protein-based ligands in a short time period using native protein molecules. These affinity materials are potentially useful tools especially for assays since they combine the catalytic properties of enzymes (for signaling) and molecular recognition properties of antibodies. We demonstrate this concept in an ELISA-format assay where HRP imprinted with vancomycin and ampicillin replaced traditional enzyme-antibody conjugates for selective detection of templates at micromolar concentrations. This approach can potentially provide a fast alternative to raising antibodies for targets that do not require high assay sensitivities; it can also find uses as a biochemical research tool, as a possible replacement for immunoperoxidase-conjugates.Here we introduce a new concept for synthesising molecularly imprinted nanoparticles by using proteins as macro-functional monomers. For a proof-of-concept, a model enzyme (HRP) was cross-linked using glutaraldehyde in the presence of glass beads (solid-phase) bearing immobilized templates such as vancomycin and ampicillin. The cross-linking process links together proteins and protein chains, which in the presence of templates leads to the formation of permanent target-specific recognition sites without adverse effects on the enzymatic activity. Unlike

  18. Glucose optical fibre sensor based on a luminescent molecularly imprinted polymer

    NASA Astrophysics Data System (ADS)

    Elosua, C.; Wren, S. P.; Sun, T.; Arregui, F. J.; Grattan, Kenneth T. V.

    2015-09-01

    An optrode able to detect glucose dissolved in water has been implemented. The device is based on the luminescence emission of a Molecularly Imprinted Polymer synthesized specifically for glucose detection, therefore its intensity changes in presence of glucose. This sensing material is attached onto a cleaved ended polymer-clad optical fibre and it is excited by light via 1x2 fibre coupler. The reflected fluorescence signal increases when it is immersed into glucose solutions and recovers to the baseline when it is dipped in ultrapure water. This reversible behaviour indicates the measurement repeatability of using such a glucose sensor.

  19. Molecular imprinting of AMP by an ionic-noncovalent dual approach.

    PubMed

    Breton, Florent; Delépée, Raphaël; Agrofoglio, Luigi A

    2009-10-01

    In order to mimic recognition properties of adenylate kinase, molecularly imprinted polymers (MIPs) were prepared for adenosine 5'-monophosphate (AMP), a substrate of the enzyme. Different functional monomers interacting with the phosphate moiety were tested, and the MIP giving the best specific binding of AMP was composed with one equivalent of 2-(dimethylamino)ethyl methacrylate and ten equivalents of acrylamide compared to AMP. Packed into solid phase cartridge, this polymer showed similar characteristics than the enzyme, since it was specific for AMP toward other nucleotides.

  20. Synthesis of molecular imprinted polymer modified TiO{sub 2} nanotube array electrode and their photoelectrocatalytic activity

    SciTech Connect

    Lu Na; Chen Shuo; Wang Hongtao; Quan Xie Zhao Huimin

    2008-10-15

    A tetracycline hydrochloride (TC) molecularly imprinted polymer (MIP) modified TiO{sub 2} nanotube array electrode was prepared via surface molecular imprinting. Its surface was structured with surface voids and the nanotubes were open at top end with an average diameter of approximately 50 nm. The MIP-modified TiO{sub 2} nanotube array with anatase phase was identified by XRD and a distinguishable red shift in the absorption spectrum was observed. The MIP-modified electrode also exhibited a high adsorption capacity for TC due to its high surface area providing imprinted sites. Photocurrent was generated on the MIP-modified photoanode using the simulated solar spectrum and increased with the increase of positive bias potential. Under simulated solar light irradiation, the MIP-modified TiO{sub 2} nanotube array electrode exhibited enhanced photoelectrocatalytic (PEC) activity with the apparent first-order rate constant being 1.2-fold of that with TiO{sub 2} nanotube array electrode. The effect of the thickness of the MIP layer on the PEC activity was also evaluated. - Graphical abstract: A tetracycline hydrochloride molecularly imprinted polymer modified TiO{sub 2} nanotube array electrode was prepared via surface molecular imprinting. It showed improved response to simulated solar light and higher adsorption capability for tetracycline hydrochloride, thereby exhibiting increased PEC activity under simulated solar light irradiation. The apparent first-order rate constant was 1.2-fold of that on TiO{sub 2} nanotube array electrode.

  1. Development of molecularly imprinted microspheres for the fast uptake of 4-cumylphenol from water and soil samples.

    PubMed

    Narula, Priyanka; Kaur, Varinder; Singh, Raghubir; Kansal, Sushil Kumar

    2014-11-01

    Molecularly imprinted microspheres containing binding sites for the extraction of 4-cumylphenol have been prepared for the first time. The imprinted microspheres were synthesized by a precipitation method using 4-cumylphenol as a template molecule, methacrylic acid as a functional monomer and divinylbenzene-80 as a cross-linker for polymer network formation. The formation and the morphology of molecularly imprinted microspheres were well characterized using infrared spectroscopy, thermogravimetric studies, and scanning electron microscopy. The Brunauer-Emmett-Teller analysis revealed the high surface area of the sorbent indicating formation of molecularly imprinted microspheres. The developed microspheres were employed as a sorbent for the solid-phase extraction of 4-cumylphenol and showed fast uptake kinetics. The sorption parameters were optimized to achieve efficient sorption of the template molecule, like pH, quantity of molecularly imprinted microspheres, time required for equilibrium set-up, sorption kinetics, and adsorption isotherm. A standard method was developed to analyze the sorbed sample quantitatively at 279 nm using high-performance liquid chromatography with diode array detection. It was validated by determining target analyte from synthetic samples, bottled water, spiked tap water, and soil samples. The prepared material is a selective and robust sorbent with good reusability.

  2. Selective recognition of Triamterene in biological samples by molecularly imprinted monolithic column with a pseudo template employed.

    PubMed

    Zhao, Xiao-Yun; Zhang, Hong-Wu; Liang, Zhen-Jie; Shu, Ya-Ping; Liang, Yong

    2013-05-01

    Melamine (MAM) was employed as a pseudo template to prepare a molecularly imprinted polymer monolithic column which presents the ability of selective recognition to Triamterene (TAT), whose structure was similar to that of MAM. Methacrylic acid and ethylene glycol dimethacrylate were applied as functional monomer and cross-linker, respectively, during the in situ polymerization process. Chromatographic behaviors were evaluated, the results indicated that the molecularly imprinted polymer monolithic column possessed excellent affinity and selectivity for TAT, and the imprinting factor was high up to 3.99 when 7:3 of ACN/water v/v was used as mobile phase. In addition, the dissociation constant and the binding sites were also determined by frontal chromatography as 134.31 μmol/L and 132.28 μmol/g, respectively, which demonstrated that the obtained molecularly imprinted polymer monolith had a high binding capacity and strong affinity ability to TAT. Furthermore, biological samples could be directly injected into the column and TAT was enriched with the optimized mobile phase. These assays gave recovery values higher than 91.60% with RSD values that were always less than 3.5%. The molecularly imprinted monolithic column greatly simplified experiment procedure and can be applied to preconcentration, purification, and analysis of TAT in biological samples.

  3. A novel molecularly imprinted sensor for selectively probing imipramine created on ITO electrodes modified by Au nanoparticles.

    PubMed

    Xu, Xiaoli; Zhou, Guoliang; Li, Huixiang; Liu, Qian; Zhang, Song; Kong, Jilie

    2009-04-15

    A sensitive molecularly imprinted electrochemical sensor was created for selective detection of a tricyclic antidepressant imipramine by combination of Au nanoparticles (Au-NPs) with a thin molecularly imprinted film. The sensor was fabricated onto the indium tin oxide (ITO) electrode via stepwise modification of Au-NPs by self-assembly and a thin film of molecularly imprinted polymers (MIPs) via sol-gel technology. It was observed that the molecularly imprinted film displayed excellent selectivity towards the target molecule imipramine. Meanwhile, the introduced Au-NPs exhibited noticeable catalytic activities towards imipramine oxidation, which remarkably enhanced the sensitivity of the imprinted film. Due to such combination, the as-prepared sensor responded quickly to imipramine, within only 1 min of incubation. The differential voltammetric anodic peak current was linear to the logarithm of imipramine concentration in the range from 5.0x10(-6) to 1.0x10(-3) mol L(-1), and the detection limits obtained was 1.0x10(-9) mol L(-1). This method proposed was successfully applied to the determination of imipramine in drug tablets, and proven to be reliable compared with conventional UV method. These results reveal that such a sensor fulfills the selectivity, sensitivity, speed and simplicity requirements for imipramine detection, and provides possibilities of clinical application in physiological fluids.

  4. Molecularly imprinted microspheres as SPE sorbent for selective extraction of four Sudan dyes in catsup products.

    PubMed

    Qiao, Fengxia; Geng, Yuru; He, Changqing; Wu, Yupei; Pan, Pengyu

    2011-10-01

    A highly selective molecularly imprinted solid-phase extraction (MISPE) coupled with high performance liquid chromatography (HPLC) ultraviolet-visible detection was developed for the simultaneous isolation and determination of four Sudan dyes (I, II, III and IV) in catsup products. The novel molecularly imprinted microspheres (MIM) were synthesized by aqueous suspension polymerization using phenylamine and naphthol as template, which showed high affinity to Sudan dyes in aqueous solution. In order to develop a selective extraction protocol for simultaneous determination the four Sudan dyes from catsup products, the molecular recognition properties of MIM as a SPE sorbent were evaluated. Under the optimized condition, good linearity was obtained from 0.01 to 2.5 μg g(-1) (r(2)≥ 0.9990) with the relative standard deviations of less than 3.4%. This proposed MISPE-HPLC procedure eliminated the effect of template leakage on quantitative analysis and could be applied to direct determination of four Sudan dyes in complicated food samples.

  5. AN IMPRINT OF MOLECULAR CLOUD MAGNETIZATION IN THE MORPHOLOGY OF THE DUST POLARIZED EMISSION

    SciTech Connect

    Soler, J. D.; Netterfield, C. B.; Fissel, L. M.; Hennebelle, P.; Martin, P. G.; Miville-Deschenes, M.-A.

    2013-09-10

    We describe a morphological imprint of magnetization found when considering the relative orientation of the magnetic field direction with respect to the density structures in simulated turbulent molecular clouds. This imprint was found using the Histogram of Relative Orientations (HRO), a new technique that utilizes the gradient to characterize the directionality of density and column density structures on multiple scales. We present results of the HRO analysis in three models of molecular clouds in which the initial magnetic field strength is varied, but an identical initial turbulent velocity field is introduced, which subsequently decays. The HRO analysis was applied to the simulated data cubes and mock-observations of the simulations produced by integrating the data cube along particular lines of sight. In the three-dimensional analysis we describe the relative orientation of the magnetic field B with respect to the density structures, showing that: (1) the magnetic field shows a preferential orientation parallel to most of the density structures in the three simulated cubes, (2) the relative orientation changes from parallel to perpendicular in regions with density over a critical density n{sub T} in the highest magnetization case, and (3) the change of relative orientation is largest for the highest magnetization and decreases in lower magnetization cases. This change in the relative orientation is also present in the projected maps. In conjunction with simulations, HROs can be used to establish a link between the observed morphology in polarization maps and the physics included in simulations of molecular clouds.

  6. Surface-enhanced Raman scattering sensor for theophylline determination by molecular imprinting on silver nanoparticles.

    PubMed

    Liu, Ping; Liu, Renyong; Guan, Guijian; Jiang, Changlong; Wang, Suhua; Zhang, Zhongping

    2011-10-21

    A surface-enhanced Raman scattering (SERS)-based sensor for the determination of theophylline (THO) has been developed by imprinting the target molecules on the surface of silver nanoparticles. The desired recognition sites are generated after template removal and homogeneous distribution on the silver nanoparticles that have been incorporated within polymer matrix by the in situ reduction of theophylline-silver complexes, providing molecular recognition ability and SERS active surfaces. The theophylline molecules, complementary to the shape, size, and functionality of the recognition cavities, can selectively bind to the recognition sites at the surface of silver nanoparticles driven by the formation of hydrogen bonding and surface coordination. It has been demonstrated that the SERS signals of the theophylline molecules captured on the surface of the silver nanoparticles have a good reproducibility and a dose-response relationship to the target analytes, showing the potential for reliable identification and quantification of the bioactive compound. The molecular imprinting-based SERS sensor, like antibodies or enzymes, also possesses the ability to distinguish theophylline from the closely related structure caffeine due to the variations of molecular size and shape as well as the different affinity to silver ions.

  7. Computational approach to the rational design of molecularly imprinted polymers for voltammetric sensing of homovanillic acid.

    PubMed

    Diñeiro, Yolanda; Menéndez, M Isabel; Blanco-López, M Carmen; Lobo-Castañón, M Jesús; Miranda-Ordieres, Arturo J; Tuñón-Blanco, Paulino

    2005-10-15

    A methodology based on density functional theory calculations for the design of molecularly imprinted polymers (MIPs) is described. The method allows the rational choice of the most suitable monomer and polymerization solvent among a set of chemicals traditionally used in MIP formulations for the molecular imprinting of a given template. It is based on the comparison of the stabilization energies of the prepolymerization adducts between the template and different functional monomers. The effect of the polymerization solvent is included using the polarizable continuum model. A voltammetric sensor for homovanillic acid was constructed using different MIPs as recognition element, confirming that the solvent (toluene) and functional monomer (methacrylic acid) selected according to the theoretical predictions lead to the most efficient molecular recognition sensing phase. With the voltammetric sensor prepared using the MIP designed according to the theoretical predictions, a linear response for concentrations of homovanillic acid between 5 x 10(-8) and 1 x 10(-5) M can be obtained. The limit of detection is 7 x 10(-9) M. The selectivity obtained for homovanillic acid over other structurally related compounds buttresses the validity of this strategy of design.

  8. Extended release of high molecular weight hydroxypropyl methylcellulose from molecularly imprinted, extended wear silicone hydrogel contact lenses.

    PubMed

    White, Charles J; McBride, Matthew K; Pate, Kayla M; Tieppo, Arianna; Byrne, Mark E

    2011-08-01

    Symptoms of contact lenses induced dry eye (CLIDE) are typically treated through application of macromolecular re-wetting agents via eye drops. Therapeutic soft contact lenses can be formulated to alleviate CLIDE symptoms by slowly releasing comfort agent from the lens. In this paper, we present an extended wear silicone hydrogel contact lens with extended, controllable release of 120 kDa hydroxypropyl methylcellulose (HPMC) using a molecular imprinting strategy. A commercial silicone hydrogel lens was tailored to release approximately 1000 μg of HPMC over a period of up to 60 days in a constant manner at a rate of 16 μg/day under physiological flowrates, releasing over the entire range of continuous wear. Release rates could be significantly varied by the imprinting effect and functional monomer to template ratio (M/T) with M/T values 0, 0.2, 2.8, 3.4 corresponding to HPMC release durations of 10, 13, 23, and 53 days, respectively. Lenses had high optical quality and adequate mechanical properties for contact lens use. This work highlights the potential of imprinting in the design and engineering of silicone hydrogel lenses to release macromolecules for the duration of wear, which may lead to decreased CLIDE symptoms and more comfortable contact lenses.

  9. An ionic liquid-modified graphene based molecular imprinting electrochemical sensor for sensitive detection of bovine hemoglobin.

    PubMed

    Wang, Zonghua; Li, Feng; Xia, Jianfei; Xia, Lin; Zhang, Feifei; Bi, Sai; Shi, Guoyu; Xia, Yanzhi; Liu, Jingquan; Li, Yanhui; Xia, Linhua

    2014-11-15

    A novel kind of molecular imprinted polymers based on ionic liquid-functionalized graphene (MIPs/IL/GR) was prepared by electro-polymerization, which was applied as a molecular recognition element to modify glassy carbon electrode (GCE) to construct an electrochemical sensor (MIPs/IL/GR/GCE) for sensitive detection of bovine hemoglobin (BHb). The fabrication conditions that affect the performance of the imprinted sensor, such as pyrrole concentration, scan cycles and scan rates, have been discussed. Under the optimized conditions, the prepared molecular imprinting electrochemical sensor showed a fast rebinding dynamics, which was successfully applied to BHb detection with a wide linear range from 1.0 × 10(-10) to 1.0 × 10(-3)g/L (R=0.998) and a detection limit of 3.09 × 10(-11)g/L. Moreover, the fabricated sensor possessed a good selectivity and stability, providing a promising tool for immunoassays and clinical applications.

  10. [Recent advances and perspective in the study of the nano-reinforcing materials for molecular imprinting of proteins].

    PubMed

    Wu, Zhi-hui; Chai, Miao-ling; Hou, Jia-peng; Pan, Jun

    2015-01-01

    Molecular imprinting technique (MIT) involves the synthesis of polymer in the presence of a template to produce complementary binding sites in terms of its size, shape and functional group orientation. Such kind of polymer possesses specific recognition ability towards its template molecule. Despite the rapid development of MIT over the years, the majority of the template molecules that have been studied are small molecules, while molecular imprinting of proteins remains a significant yet challenging task due to their large size, structural flexibility and complex conformation. This review, we summarized the research findings over the past years, and discussed the nano-reinforcing materials used to prepare molecular imprinting of proteins and the perspective of these nano-reinforcing materials.

  11. Structured water and water-polymer interactions in hydrogels of molecularly imprinted polymers.

    PubMed

    Zhao, Zhi-Jian; Wang, Qi; Zhang, Li; Wu, Tao

    2008-06-26

    Recently, molecular imprinting technology has fleetly developed for applications in different fields. It shows great potential in sensor design, drug delivery, chromatography separation, catalysis, chiral synthesis, and especially in the molecular recognition field. In this work, a cubic model of a hydrogel network was developed and an infinite hydrogel backbone network was constructed for molecular dynamics simulation. The water structure and water-polymer interaction was investigated from the radial distribution function and the viewpoint of the hydrogen-bonding system. It is found that the hydrogen bonds between polymer and water strongly depress the diffusion of water molecules and enhance the structure of water in the system. The greater the network mesh size of the polymer, the weaker the structure of the water. The decreasing of the density of hydrogen bonds between polymer and water is the major factor that leads to the weakening of water structure.

  12. Paclitaxel molecularly imprinted polymer-PEG-folate nanoparticles for targeting anticancer delivery: Characterization and cellular cytotoxicity.

    PubMed

    Esfandyari-Manesh, Mehdi; Darvishi, Behrad; Ishkuh, Fatemeh Azizi; Shahmoradi, Elnaz; Mohammadi, Ali; Javanbakht, Mehran; Dinarvand, Rassoul; Atyabi, Fatemeh

    2016-05-01

    The aim of this work was to synthesize molecularly imprinted polymer-poly ethylene glycol-folic acid (MIP-PEG-FA) nanoparticles for use as a controlled release carrier for targeting delivery of paclitaxel (PTX) to cancer cells. MIP nanoparticles were synthesized by a mini-emulsion polymerization technique and then PEG-FA was conjugated to the surface of nanoparticles. Nanoparticles showed high drug loading and encapsulation efficiency, 15.6 ± 0.8 and 100%, respectively. The imprinting efficiency of MIPs was evaluated by binding experiments in human serum. Good selective binding and recognition were found in MIP nanoparticles. In vitro drug release studies showed that MIP-PEG-FA have a controlled release of PTX, because of the presence of imprinted sites in the polymeric structure, which makes it is suitable for sustained drug delivery. The drug release from polymeric nanoparticles was indeed higher at acidic pH. The molecular structure of MIP-PEG-FA was confirmed by Hydrogen-Nuclear Magnetic Resonance (H NMR), Fourier Transform InfraRed (FT-IR), and Attenuated Total Reflection (ATR) spectroscopy, and their thermal behaviors by Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). Scanning Electron Microscopy (SEM) and Photon Correlation Spectroscopy (PCS) results showed that nanoparticles have a smooth surface and spherical shape with an average size of 181 nm. MIP-PEG-FA nanoparticles showed a greater amount of intracellular uptake in folate receptor-positive cancer cells (MDA-MB-231 cells) in comparison with the non-folate nanoparticles and free PTX, with half maximal inhibitory concentrations (IC50) of 4.9 ± 0.9, 7.4 ± 0.5 and 32.8 ± 3.8 nM, respectively. These results suggest that MIP-PEG-FA nanoparticles could be a potentially useful drug carrier for targeting drug delivery to cancer cells.

  13. Selective extraction of organophosphorus nerve agent degradation products by molecularly imprinted solid-phase extraction.

    PubMed

    Le Moullec, Sophie; Bégos, Arlette; Pichon, Valérie; Bellier, Bruno

    2006-03-03

    The analysis of alkyl alkylphosphonic acids, the degradation products of V and G nerve agents as VX, Sarin or Soman, is an important task for the verification of compliance to the Chemical Weapons Convention. The detection of these contaminants at low concentration levels is often difficult in complex matrices due to the amount of interfering substances. Molecularly imprinted solid-phase extraction technique should allow a selective extraction of these compounds from complex samples, and thus make their detection easier. Two molecularly imprinted polymers (MIPs) prepared with methacrylic acid (MAA) as monomer and pinacolyl methylphosphonic acid (PMPA) as template molecule were synthesised and tested. The first polymer, MIP A, was prepared with ethylene glycol dimethacrylate (EGDMA) in dichloromethane. The second polymer, MIP B, was synthesised using trimethylolpropane trimethacrylate (TRIM) in acetonitrile. To evaluate the selectivity provided by these MIPs, the retention of the ethyl methylphosphonic acid (EMPA) target molecule was studied in parallel on a non-imprinted polymer (NIP). While MIP A does not show any difference compared to NIP A, a good selectivity was obtained for MIP B. After the optimisation of the extraction process, 60% of EMPA can be removed from the NIP B without affecting the retention on the MIP B. A recovery of extraction of 93% was then obtained on the MIP B. Its capacity was then measured and corresponds to 97 microg of EMPA per gram of MIP. Finally, the selectivity of MIP B was clearly demonstrated by applying it to the clean-up of a soil extract spiked with EMPA.

  14. Novel molecularly imprinted magnetic nanoparticles for the selective extraction of protoberberine alkaloids in herbs and rat plasma.

    PubMed

    Meng, Jiawei; Zhang, Wenpeng; Bao, Tao; Chen, Zilin

    2015-06-01

    In this work, a novel magnetic nanomaterial functionalized with a molecularly imprinted polymer was prepared for the extraction of protoberberine alkaloids. Molecularly imprinted polymers were made on the surface of Fe3 O4 nanoparticles by using berberine as template, acetonitrile/water as porogen, acrylamide as functional monomer and ethylene glycol dimethacrylate as cross-linker. The optimized molar ratio of template/functional monomer was 1:7. The polymeric magnetic nanoparticles were characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. The stability and adsorption capacity of the molecularly imprinted polymers were investigated. The molecularly imprinted polymers were used as a selective sorbent for the magnetic molecularly imprinted solid-phase extraction and determination of jatrorrhizine, palmatine, and berberine. Extraction parameters were studied including loading pH, sample volume, stirring speed, and extraction time. Finally, a magnetic molecularly imprinted solid-phase extraction coupled to high-performance liquid chromatography method was developed. Under the optimized conditions, the method showed good linear range of 0.1-150 ng/mL for berberine and 0.1-100 ng/mL for jatrorrhizine and palmatine. The limit of detection was 0.01 ng/mL for berberine and 0.02 ng/mL for jatrorrhizine and palmatine. The proposed method has been applied to determine protoberberine alkaloids in Cortex phellodendri and rat plasma samples. The recoveries ranged from 87.33-102.43%, with relative standard deviation less than 4.54% in Cortex phellodendri and from 102.22-111.15% with relative standard deviation less than 4.59% in plasma.

  15. Separation and determination of citrinin in corn using HPLC fluorescence detection assisted by molecularly imprinted solid phase extraction clean-up

    USDA-ARS?s Scientific Manuscript database

    A liquid chromatography based method to detect citrinin in corn was developed using molecularly imprinted solid phase extraction (MISPE) sample clean-up. Molecularly imprinted polymers were synthesized using 1,4-dihydroxy-2-naphthoic acid as the template and an amine functional monomer. Density func...

  16. Design of biomimetic catalysts by molecular imprinting in synthetic polymers: the role of transition state stabilization.

    PubMed

    Wulff, Günter; Liu, Junqiu

    2012-02-21

    The impressive efficiency and selectivity of biological catalysts has engendered a long-standing effort to understand the details of enzyme action. It is widely accepted that enzymes accelerate reactions through their steric and electronic complementarity to the reactants in the rate-determining transition states. Thus, tight binding to the transition state of a reactant (rather than to the corresponding substrate) lowers the activation energy of the reaction, providing strong catalytic activity. Debates concerning the fundamentals of enzyme catalysis continue, however, and non-natural enzyme mimics offer important additional insight in this area. Molecular structures that mimic enzymes through the design of a predetermined binding site that stabilizes the transition state of a desired reaction are invaluable in this regard. Catalytic antibodies, which can be quite active when raised against stable transition state analogues of the corresponding reaction, represent particularly successful examples. Recently, synthetic chemistry has begun to match nature's ability to produce antibody-like binding sites with high affinities for the transition state. Thus, synthetic, molecularly imprinted polymers have been engineered to provide enzyme-like specificity and activity, and they now represent a powerful tool for creating highly efficient catalysts. In this Account, we review recent efforts to develop enzyme models through the concept of transition state stabilization. In particular, models for carboxypeptidase A were prepared through the molecular imprinting of synthetic polymers. On the basis of successful experiments with phosphonic esters as templates to arrange amidinium groups in the active site, the method was further improved by combining the concept of transition state stabilization with the introduction of special catalytic moieties, such as metal ions in a defined orientation in the active site. In this way, the imprinted polymers were able to provide both an

  17. Molecular imprinting science and technology: a survey of the literature for the years up to and including 2003.

    PubMed

    Alexander, Cameron; Andersson, Håkan S; Andersson, Lars I; Ansell, Richard J; Kirsch, Nicole; Nicholls, Ian A; O'Mahony, John; Whitcombe, Michael J

    2006-01-01

    Over 1450 references to original papers, reviews and monographs have herein been collected to document the development of molecular imprinting science and technology from the serendipitous discovery of Polyakov in 1931 to recent attempts to implement and understand the principles underlying the technique and its use in a range of application areas. In the presentation of the assembled references, a section presenting reviews and monographs covering the area is followed by papers dealing with fundamental aspects of molecular imprinting and the development of novel polymer formats. Thereafter, literature describing attempts to apply these polymeric materials to a range of application areas is presented.

  18. Superhydrophilic molecularly imprinted polymers based on a water-soluble functional monomer for the recognition of gastrodin in water media.

    PubMed

    Ji, Wenhua; Zhang, Mingming; Wang, Daijie; Wang, Xiao; Liu, Jianhua; Huang, Luqi

    2015-12-18

    In this study, the first successfully developed superhydrophilic molecularly imprinted polymers (MIPs) for gastrodin recognition have been described. MIPs were prepared via the bulk polymerization process in an aqueous solution using alkenyl glycosides glucose (AGG) as the water-soluble functional monomer. The non-imprinted polymers (NIPs) were also synthesized using the same method without the use of the template. The dynamic water contact angles and photographs of the dispersion properties confirmed that the molecularly imprinted polymers displayed excellent superhydrophilicity. The results demonstrated that the MIPs exhibited high selectivity and an excellent imprinting effect. A molecularly imprinted solid phase extraction (MISPE) method was established. Optimization of various parameters affecting MISPE was investigated. Under the optimized conditions, a wide linear range (0.001-100.0μgmL(-1)) and low limits of detection (LOD) and quantification (LOQ) (0.03 and 0.09ngmL(-1), respectively) were achieved. When compared with the NIPs, higher recoveries (90.5% to 97.6%) of gastrodin with lower relative standard deviations values (below 6.4%) using high performance liquid chromatography were obtained at three spiked levels in three blank samples. These results demonstrated one efficient, highly selective and environmentally-friendly MISPE technique with excellent reproducibility for the purification and pre-concentration of gastrodin from an aqueous extract of Gastrodia elata roots.

  19. Synthetic approaches to parabens molecularly imprinted polymers and their applications to the solid-phase extraction of river water samples.

    PubMed

    Beltran, A; Marcé, R M; Cormack, P A G; Borrull, F

    2010-09-10

    In this paper we describe the synthesis, characterisation and use of two distinct molecularly imprinted polymers (MIPs) prepared using esters of p-hydroxybenzoic acid (parabens) as templates: one MIP was synthesised by precipitation polymerisation using a semi-covalent molecularly imprinting strategy with methyl paraben as the template/target (MIP 1); the second MIP was prepared in monolithic form through a conventional non-covalent molecular imprinting strategy, with butyl paraben as the template (MIP 2). MIP 1 recognized methyl paraben, showed cross-selectivity for other parabens analytes used in the study and higher affinity towards these compounds than did a non-imprinted control polymer. Similarly, MIP 2 demonstrated higher affinity towards paraben analytes than a non-imprinted control polymer. For the analysis of environmental water samples, a solid-phase extraction (SPE) protocol was developed using MIP 2 as sorbent, and results were compared to a SPE using a commercial sorbent (Oasis HLB). With MIP 2 as sorbent and butyl paraben as target, when percolating 500 mL of river water spiked at 1 μg L(-1) through the SPE cartridge, and using 1 mL of isopropanol as cleaning solvent, a higher recovery of butyl 4-hydroxybenzoate (butyl paraben) and a cleaner chromatogram where achievable when using the MIP compared to the commercial sorbent.

  20. A disposable microfluidic biochip with on-chip molecularly imprinted biosensors for optical detection of anesthetic propofol.

    PubMed

    Hong, Chien-Chong; Chang, Po-Hsiang; Lin, Chih-Chung; Hong, Chian-Lang

    2010-05-15

    This paper presents a disposable microfluidic biochip with on-chip molecularly imprinted biosensors for optical detection of anesthetic propofol. So far, the methods to detect anesthetic propofol in hospitals are liquid chromatography (LC), high-performance liquid chromatography (HPLC), and gas chromatography-mass spectroscopy (GC-MS). These conventional instruments are bulky, expensive, and not ease of access. In this work, a novel plastic microfluidic biochip with on-chip anesthetic biosensor has been developed and characterized for rapid detection of anesthetic propofol. The template-molecule imprinted polymers were integrated into microfluidic biochips to be used for detecting anesthetic propofol optically at 655 nm wavelength after the reaction of propofol with color reagent. Experimental results show that the sensitivity of the microfluidic biochip with on-chip molecularly imprinted polymers (MIPs) biosensor is 6.47 mV/(ppm mm(2)). The specific binding of MIP to non-imprinted polymer (NIP) is up to 456%. And the detection limit of the microsystem is 0.25 ppm with a linear detection range from 0.25 to 10 ppm. The disposable microfluidic biochip with on-chip anesthetic biosensor using molecularly imprinted polymers presented in this work showed excellent performance in separation and sensing of anesthetic propofol molecules. While compared to large-scale conventional instruments, the developed microfluidic biochips with on-chip MIP biosensors have the advantages of compact size, high sensitivity, high selectivity, low cost, and fast response.

  1. Molecular function of microtubule-associated protein 2 for filial imprinting in domestic chicks (Gallus gallus domesticus).

    PubMed

    Yamaguchi, Shinji; Katagiri, Sachiko; Aoki, Naoya; Iikubo, Eiji; Kitajima, Takaaki; Matsushima, Toshiya; Homma, Koichi J

    2011-01-01

    RNA interference (RNAi)-mediated gene-silencing can be a tool for elucidating the role of genes in the neural basis of behavioral plasticity. Previously, we reported that exogenous DNA could be successfully delivered into newly-hatched chick brains via electroporation. Here, we used this in vivo gene-transfer technique and showed that transfected microRNA vectors preferentially silence exogenous DNA expression in neuronal cells. Using this system, the up-regulation of microtubule-associated protein 2 (MAP2) accompanying filial imprinting was suppressed in vivo, which impaired the filial imprinting in chicks. In addition, the phosphorylation of MAP2 was found to increase in parallel with filial imprinting, and lithium chloride, an inhibitor of glycogen synthase kinase 3 (GSK3), was found to impair filial imprinting. Our results suggest that the regulation of MAP2 expression and its phosphorylation are required for filial imprinting and may modify microtubule stability, thereby leading to cytoskeletal reorganization during imprinting. This in vivo RNAi-mediated gene-silencing system will facilitate the analysis of gene function in the living chick brain and provides further clues regarding the molecular mechanisms underpinning avian learning. Copyright © 2010 Elsevier Ireland Ltd and the Japan Neuroscience Society. All rights reserved.

  2. Preparation of an amperometric sensor for norfloxacin based on molecularly imprinted grafting photopolymerization.

    PubMed

    Wang, Zhihua; Li, Jinshu; Liu, Xiaole; Yang, Jianming; Lu, Xiaoquan

    2013-03-01

    A sensitive amperometric sensor for norfloxacin (NF) was introduced. The receptor layer was prepared by molecularly imprinted photopolymerization of acrylamide and trimethylolpropane trimethacrylate on the surface of a gold electrode. The binding mechanism of the molecularly imprinted polymer was explored by ultraviolet (UV) and infrared (IR) spectroscopy. The chemosensor was characterized by cyclic voltammetry (CV), differential pulse voltammetry (DPV), electrochemical impedance (EI), and scanning electron microscopy (SEM). The electrode prepared by photopolymerization has a better recognition ability to template molecules than that of electropolymerization and NIP. Some parameters affecting sensor response were optimized. Norfloxacin was detected by measurements of an amperometric i-t curve. The linear relationships between current and logarithmic concentration are obtained from 1.0 × 10(-9) to 1.0 × 10(-3) mol L(-1). The detection limit of the sensor was 1.0 × 10(-10) mol L(-1). The proposed method is sensitive, simple, and cheap, and is applied to detect NF in human urine successfully.

  3. Molecularly imprinted photonic polymers as sensing elements for the creation of cross-reactive sensor arrays.

    PubMed

    Xu, Dan; Zhu, Wei; Wang, Chen; Tian, Tian; Cui, Jiecheng; Li, Jian; Wang, Hui; Li, Guangtao

    2014-12-08

    By combining molecular imprinting and colloidal crystal templating, molecularly imprinted inverse-opal photonic polymers (MIPPs) acting as sensing elements have been exploited to create sensor arrays for the first time. With this new strategy, abundant sensing elements with differential sensing abilities were easily accessible. Because of the unique hierarchical porous structure integrated in each sensing element, high sensitivity and selectivity, fast response and self-reporting (label-free) detection could be simultaneously achieved. All these fascinating features indicate that MIPPs are ideal sensing elements for creating sensor arrays. By integrating the individual sensing elements on a substrate, the formed array chip delivers better portability and high-throughput capability. As a demonstration, six kinds of contaminants were selected as analytes. The detection and discrimination of these analytes and even their mixtures in a wide range of concentrations, particularly trace amounts of analyte against a high background of other components, could be achieved, indicating the powerful capability of MIPPs-based sensor array for sensing. These results suggest that the described strategy opens a new route for sensor array creation and should find important applications in a wide range of areas.

  4. Ammonium sensing in aqueous solutions with plastic optical fiber modified by molecular imprinting

    NASA Astrophysics Data System (ADS)

    Sequeira, F.; Duarte, D.; Rudnitskaya, A.; Gomes, M. T. S. R.; Nogueira, R.; Bilro, L.

    2016-05-01

    We report the development of a low cost plastic optical fibre (POF) sensor for ammonium detection using molecularly imprinted polymers (MIP's). The cladding of a 1 mm diameter PMMA fiber is removed, in which is grafted a molecular imprinted polymer (MIP), by radical polymerization with thermal initiation, that act as a selective sensing layer. For the polymerization, 2,2'-Azobis(2-methylpropionamidine)dihydrochloride (AAPH) is used as initiator, methacrylic acid (MAA) as a monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linker, ammonium chloride (NH4Cl) as a template and 30% of ethanol in water as a solvent. The sensing method consists of an intensity based scheme. The response to different concentrations of ammonium solutions in water has been evaluated at room temperature. Solutions with (0 - 0.6) M concentration, with the corresponding refractive indexes varying between 1.3325 - 1.3387, at 25°C were used. The response of the fiber with the original cladding, and after cladding removal has been monitored and compared to the response given by the developed sensor. The response is very fast, less than 1 minute and reversible, which allows the continuum use of the sensor. Further developments are focused in optimization of MIP grafting procedure and sensor performance, in order to increase sensitivity.

  5. A highly selective molecularly imprinted electrochemiluminescence sensor for ultra-trace beryllium detection.

    PubMed

    Li, Jianping; Ma, Fei; Wei, Xiaoping; Fu, Cong; Pan, Hongcheng

    2015-04-29

    A new molecularly imprinted electrochemiluminescence (ECL) sensor was proposed for highly sensitive and selective determination of ultratrace Be(2+) determination. The complex of Be(2+) with 4-(2-pyridylazo)-resorcinol (PAR) was chosen as the template molecule for the molecularly imprinted polymer (MIP). In this assay, the complex molecule could be eluted from the MIP, and the cavities formed could then selectively recognize the complex molecules. The cavities formed could also work as the tunnel for the transfer of probe molecules to produce sound responsive signal. The determination was based on the intensity of the signal, which was proportional to the concentrations of the complex molecule in the sample solution, and the Be(2+) concentration could then be determined indirectly. The results showed that in the range of 7×10(-11 )mol L(-1) to 8.0×10(-9) mol L(-1), the ECL intensity had a linear relationship with the Be(2+) concentrations, with the limit of detection of 2.35×10(-11) mol L(-1). This method was successfully used to detect Be(2+) in real water samples.

  6. Molecularly imprinted photonic hydrogels as colorimetric sensors for rapid and label-free detection of vanillin.

    PubMed

    Peng, Hailong; Wang, Shenqi; Zhang, Zhong; Xiong, Hua; Li, Jinhua; Chen, Lingxin; Li, Yanbin

    2012-02-29

    A novel colorimetric sensor for the rapid and label-free detection of vanillin, based on the combination of photonic crystal and molecular imprinting technique, was developed. The sensing platform of molecularly imprinted photonic hydrogel (MIPH) was prepared by a noncovalent and self-assembly approach using vanillin as a template molecule. Morphology characterization by scanning electron microscope (SEM) showed that the MIPH possessed a highly ordered three-dimensional (3D) macroporous structure with nanocavities. The vanillin recognition events of the created nonocavities could be directly transferred into readable optical signals through a change in Bragg diffraction of the ordered macropores array of MIPH. The Bragg diffraction peak shifted from 451 to 486 nm when the concentration of the vanillin was increased from 10⁻¹² to 10⁻³ mol L⁻¹ within 60 s, whereas there were no obvious peak shifts for methyl and ethyl vanillin, indicating that the MIPH had high selectivity and rapid response for vanillin. The adsorption results showed that the hierarchical porous structure and homogeneous layers were formed in the MIPH with higher adsorption capacity. The application of such a label-free sensor with high selectivity, high sensitivity, high stability, and easy operation might offer a potential method for rapid real-time detection of trace vanillin.

  7. Determination of cyproheptadine in feeds using molecularly imprinted solid-phase extraction coupled with HPLC.

    PubMed

    Yang, Jianwen; Wang, Zongnan; Zhou, Tong; Song, Xuqin; Liu, Qingyong; Zhang, Yuman; He, Limin

    2015-05-15

    A novel method was developed for the determination of cyproheptadine in feeds using molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography. The polymers were prepared using cyproheptadine as a template molecule, methacrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linking agent, and dichloromethane as a solvent by bulk polymerization. Under the optimum solid-phase extraction conditions, the molecular imprinting cartridge can selectively extract and enrich cyproheptadine from a variety of feeds. Mean recoveries of cyproheptadine from four kinds of feeds spiked at 0.1, 1.0 and 10mgkg(-1) ranged from 85.5% to 96.2%, with intra-day and inter-day relative standard deviation less than 10%. The calibration curve of cyproheptadine was good linear relationship (r>0.9993) within the range of 0.1-50μgmL(-1). The limit of detection (LOD) and the limit of quantification (LOQ) were 0.04 and 0.1mgkg(-1), respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Magnetic molecularly imprinted polymer for the selective extraction of quercetagetin from Calendula officinalis extract.

    PubMed

    Ma, Run-Tian; Shi, Yan-Ping

    2015-03-01

    A new magnetic molecularly imprinted polymers (MMIPs) for quercetagetin was prepared by surface molecular imprinting method using super paramagnetic core-shell nanoparticle as the supporter. Acrylamide as the functional monomer, ethyleneglycol dimethacrylate as the crosslinker and acetonitrile as the porogen were applied in the preparation process. Fourier transform infrared spectrometer (FT-IR), X-ray diffraction (XRD) and Vibrating sample magnetometer (VSM) were applied to characterize the MMIPs, and High performance liquid chromatography (HPLC) was utilized to analyze the target analytes. The selectivity of quercetagetin MMIPs was evaluated according to their recognition to template and its analogues. Excellent binding for quercetagetin was observed in MMIPs adsorption experiment, and the adsorption isotherm models analysis showed that the homogeneous binding sites were distributed on the surface of the MMIPs. The MMIPs were employed as adsorbents in solid phase extraction for the determination of quercetagetin in Calendula officinalis extracts. Furthermore, this method is fast, simple and could fulfill the determination and extraction of quercetagetin from herbal extract. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Molecular imprint polymers as highly selective stationary phases for open tubular liquid chromatography and capillary electrochromatography.

    PubMed

    Tan, Z J; Remcho, V T

    1998-09-01

    Chiral separations employing molecular imprint polymer (MIP) stationary phases in both open tubular liquid chromatography (OT-LC) and capillary electrochromatography (OT-CEC) are demonstrated. MIPs are highly crosslinked polymers containing spatial and functionality memory of template molecules which provide a higher degree of selectivity when used as stationary phases for chromatographic separations. Thin films of molecular imprinted polymers bonded to the inner walls of 25 microm ID fused-silica capillaries were prepared using an in situ polymerization technique developed in our laboratory that allows the use of conventional fused-silica capillaries with polyimide outer coatings. The success rate in preparing such open tubular columns was about 70%. Methacrylic acid and 2-vinyl pyridine were chosen as functional monomers, and either ethylene dimethacrylate or trimethylol propane trimethacrylate was used as the crosslinker. Toluene was employed as the porogen. Effects of polymerization conditions on column preparation and chromatographic performance were studied. Enantiomeric separations of D- and L-dansyl phenylalanines were achieved in both OT-LC and OT-CEC modes with good selectivity and efficiencies. Both types of separations may be performed on the same column using a single commercial instrument.

  10. Visual detection of 2,4,6-trinitrotolune by molecularly imprinted colloidal array photonic crystal.

    PubMed

    Lu, Wei; Asher, Sanford A; Meng, Zihui; Yan, Zequn; Xue, Min; Qiu, Lili; Yi, Da

    2016-10-05

    We developed a photonic crystal (PhC) sensor for the quantification of 2,4,6-trinitrotoluene (TNT) in solution. Monodisperse (210nm in diameter) molecularly imprinted colloidal particles (MICs) for TNT were prepared by the emulsion polymerization of methyl methacrylate and acrylamide in the presence of TNT as a template. The MICs were then self-assembled into close-packed opal PhC films. The adsorption capacity of the MICs for TNT was 64mg TNT/g. The diffraction from the PhC depended on the TNT concentration in a methanol/water (3/2, v/v) potassium dihydrogen phosphate buffer solution (pH=7.0, 30mM). The limit of detection (LOD) of the sensor was 1.03μg. The color of the molecularly imprinted colloidal array (MICA) changed from green to red with an 84nm diffraction red shift when the TNT concentration increased to 20mM. The sensor response time was 3min. The PhC sensor was selective for TNT compared to similar compounds such as 2,4,6-trinitrophenol, 2,4-dinitrotoluene, 2,6-dinitrotoluene, 2-nitromesitylene, 4-nitrotoluene, 2-nitrotoluene, 1,3-dinitrobenzene, methylbenzene, 4-nitrophenol, 2-nitroaniline, 3-aminophenol and 3-nitroaniline. The sensor showed high stability with little response change after three years storage. This sensor technology might be useful for the visual determination of TNT.

  11. Preparation of magnetic superhydrophilic molecularly imprinted resins for detection of triazines in aqueous samples.

    PubMed

    Zhou, Tianyu; Ding, Jie; Ni, Ling; Yu, Jia; Li, Huiyu; Ding, Hong; Chen, Yanhua; Ding, Lan

    2017-05-12

    In this work, magnetic superhydrophilic molecularly imprinted resins (MMIRs) were prepared for the determination of triazines in aqueous samples combined HPLC-MS/MS. The amino functionalized magnetic nanoparticles were introduced into superhydrophilic molecularly imprinted resins based on one-pot condensation of resorcinol, melamine and formaldehyde. The obtained MMIRs exhibited magnetic responsiveness, superhydrophilic and selective feature. The MMIRs were directly used as adsorbents for selective enrichment and separation of six triazines in juice and lake samples under an applied magnetic field. The detection limits of triazines are in the range of 0.02-0.07μgL(-1) (except for simazine, 0.38μgL(-1)). At the spiked level (5μgL(-1)), the recoveries are in the range of 85-101% with the RSDs ≤7%. This work provided a novel and efficient approach for the detection of triazines in aqueous samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Development and application of molecularly imprinted polymers as solid-phase sorbents for erythromycin extraction.

    PubMed

    Song, Suquan; Wu, Aibo; Shi, Xizhi; Li, Rongxiu; Lin, Zhixin; Zhang, Dabing

    2008-04-01

    Six molecularly imprinted polymers (MIPs) of erythromycin (ERY) were prepared by noncovalent bulk polymerization using methacrylic acid (MAA) as the functional monomer. On the basis of binding analysis, the MIPs with 1:2 optimum ratio of template to MAA were selected for subsequent scanning electron microscopy and Brunauer-Emmett-Teller analyses, which indicated that the MIPs had more convergent porous structures than the nonimprinted polymers. The equilibrium binding experiments showed that the binding sites of MIPs were heterogeneous, with two dissociation constants of 0.005 and 0.63 mg mL(-1), respectively. Furthermore, the performance of the MIPs as solid-phase extraction (SPE) sorbents was evaluated, and the selectivity analysis showed that the MIPs could recognize ERY with moderate cross-reactivity for other macrolides. The overall investigation of molecularly imprinted SPE for cleanup and enrichment of the ERY in pig muscle and tap water confirmed the feasibility of utilizing the MIPs obtained as specific SPE sorbents for ERY extraction in real samples. [figure: see text

  13. Formation of target-specific binding sites in enzymes: solid-phase molecular imprinting of HRP.

    PubMed

    Czulak, J; Guerreiro, A; Metran, K; Canfarotta, F; Goddard, A; Cowan, R H; Trochimczuk, A W; Piletsky, S

    2016-06-07

    Here we introduce a new concept for synthesising molecularly imprinted nanoparticles by using proteins as macro-functional monomers. For a proof-of-concept, a model enzyme (HRP) was cross-linked using glutaraldehyde in the presence of glass beads (solid-phase) bearing immobilized templates such as vancomycin and ampicillin. The cross-linking process links together proteins and protein chains, which in the presence of templates leads to the formation of permanent target-specific recognition sites without adverse effects on the enzymatic activity. Unlike complex protein engineering approaches commonly employed to generate affinity proteins, the method proposed can be used to produce protein-based ligands in a short time period using native protein molecules. These affinity materials are potentially useful tools especially for assays since they combine the catalytic properties of enzymes (for signaling) and molecular recognition properties of antibodies. We demonstrate this concept in an ELISA-format assay where HRP imprinted with vancomycin and ampicillin replaced traditional enzyme-antibody conjugates for selective detection of templates at micromolar concentrations. This approach can potentially provide a fast alternative to raising antibodies for targets that do not require high assay sensitivities; it can also find uses as a biochemical research tool, as a possible replacement for immunoperoxidase-conjugates.

  14. Determination triazine pesticides in cereal samples based on single-hole hollow molecularly imprinted microspheres.

    PubMed

    Zhao, Qi; Li, Huiyu; Xu, Yang; Zhang, Fengshuang; Zhao, Jiahui; Wang, Long; Hou, Juan; Ding, Hong; Li, Yi; Jin, Haiyan; Ding, Lan

    2015-01-09

    Single-hole hollow molecularly imprinted microspheres (h-MIMs) were prepared by hard template method and applied to extract six triazine pesticides in cereal samples, followed by HPLC-MS/MS detection. The synthesis mechanism of the h-MIMs has been studied. The h-MIMs exhibited bigger specific surface area and much higher binding capacity than the molecularly imprinted polymers prepared by precipitation polymerization (p-MIPs) and surface polymerization (s-MIPs). Besides, the adsorption rate of h-MIMs to prometryn was significantly higher than that of p-MIPs and s-MIPs. Owing to the hollow structure of the h-MIMs, more binding cavities were located on the inner and outer surfaces of the h-MIMs, which could facilitate the removal of template molecules from the polymers and the rebinding of the target molecules to the polymers. Under the optimal conditions, the detection limits of triazines are in the range of 0.08-0.16ngg(-1). At the spiked level (5ngg(-1)), the recoveries of triazines are in the range of 81±4% to 96±4%. The proposed method was successfully applied to determine six triazines in five cereal samples. Atrazine was found in two rice samples and a wheat sample with the contents of 5.1, 6.7 and 5.6ngg(-1), respectively. Ametryn and prometryn were found in a maize sample with the contents of 7.6 and 7.3ngg(-1), respectively.

  15. Chemiluminescence sensor for sulfonylurea herbicide using molecular imprinted microspheres as recognition element.

    PubMed

    Xie, Cheng-gen; Gao, Shan; Zhou, Han-kun; Li, Huai-fen

    2011-01-01

    Uniform molecular imprinting microspheres were prepared using precipitation polymerization with thifensulfuron-methyl (TFM) as template, acrylamide as functional monomer and ethylene glycol dimethacrylate as cross-linker. TFM could be selectively adsorbed on the molecularly imprinted polymers (MIPs) matrix through the hydrogen bonding interaction and the adsorbed TFM could be sensed by its strikingly enhancing effect on the weak chemiluminescence (CL) reaction between luminol and hydrogen peroxide. On this basis, a novel CL sensor for the determination of TFM using MIPs as recognition elements was established. The logarithm of net CL intensity (ΔI) is linearly proportional to the logarithm of TFM concentration (C) in the range from 1.0 × 10(-9) to 5.0 × 10(-5)  mol L(-1) with a detection limit of 8.3 × 10(-10)  mol L(-1) (3σ). The results demonstrated that the MIP-CL sensor was reversible and reusable and that it could strikingly improve the selectivity and sensitivity of CL analysis. Furthermore, it is suggested that the CL enhancement of luminol-H(2)O(2) by TFM might be ascribed to the enhancement effect of CO(2), which came from TFM hydrolysis in basic medium.

  16. Electrochemical sensor for dopamine based on a novel graphene-molecular imprinted polymers composite recognition element.

    PubMed

    Mao, Yan; Bao, Yu; Gan, Shiyu; Li, Fenghua; Niu, Li

    2011-10-15

    A novel composite of graphene sheets/Congo red-molecular imprinted polymers (GSCR-MIPs) was synthesized through free radical polymerization (FRP) and applied as a molecular recognition element to construct dopamine (DA) electrochemical sensor. The template molecules (DA) were firstly absorbed at the GSCR surface due to their excellent affinity, and subsequently, selective copolymerization of methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) was further achieved at the GSCR surface. Potential scanning was presented to extract DA molecules from the imprinted polymers film, and as a result, DA could be rapidly and completely removed by this way. With regard to the traditional MIPs, the GSCR-MIPs not only possessed a faster desorption and adsorption dynamics, but also exhibited a higher selectivity and binding capacity toward DA molecule. As a consequence, an electrochemical sensor for highly sensitive and selective detection of DA was successfully constructed as demonstration based on the synthesized GSCR-MIPs nanocomposites. Under experimental conditions, selective detection of DA in a linear concentration range of 1.0 × 10(-7)-8.3 × 10(-4)M was obtained, which revealed a lower limit of detection and wider linear response compared to some previously reported DA electrochemical MIPs sensors. The new DA electrochemical sensor based on GSCR-MIPs composites also exhibited excellent repeatability, which expressed as relative standard deviation (RSD) was about 2.50% for 30 repeated analyses of 20 μM DA.

  17. A nanosensor for TNT detection based on molecularly imprinted polymers and surface enhanced Raman scattering.

    PubMed

    Holthoff, Ellen L; Stratis-Cullum, Dimitra N; Hankus, Mikella E

    2011-01-01

    We report on a new sensor strategy that integrates molecularly imprinted polymers (MIPs) with surface enhanced Raman scattering (SERS). The sensor was developed to detect the explosive, 2,4,6-trinitrotoluene (TNT). Micron thick films of sol gel-derived xerogels were deposited on a SERS-active surface as the sensing layer. Xerogels were molecularly imprinted for TNT using non-covalent interactions with the polymer matrix. Binding of the TNT within the polymer matrix results in unique SERS bands, which allow for detection and identification of the molecule in the MIP. This MIP-SERS sensor exhibits an apparent dissociation constant of (2.3 ± 0.3) × 10(-5) M for TNT and a 3 μM detection limit. The response to TNT is reversible and the sensor is stable for at least 6 months. Key challenges, including developing a MIP formulation that is stable and integrated with the SERS substrate, and ensuring the MIP does not mask the spectral features of the target analyte through SERS polymer background, were successfully met. The results also suggest the MIP-SERS protocol can be extended to other target analytes of interest.

  18. Highly selective detection of oil spill polycyclic aromatic hydrocarbons using molecularly imprinted polymers for marine ecosystems.

    PubMed

    Krupadam, Reddithota J; Nesterov, Evgueni E; Spivak, David A

    2014-06-15

    Im*plications due to oil spills on marine ecosystems have created a great interest toward developing more efficient and selective materials for oil spill toxins detection and remediation. This research paper highlights the application of highly efficient molecularly imprinted polymer (MIP) adsorbents based on a newly developed functional crosslinker (N,O-bismethacryloyl ethanolamine, NOBE) for detection of highly toxic polycyclic aromatic hydrocarbons (PAHs) in seawater. The binding capacity of MIP for oil spill toxin pyrene is 35 mg/g as compared to the value of 3.65 mg/g obtained using a non-imprinted polymer (NIP). The selectivity of all three high molecular weight PAHs (pyrene, chrysene and benzo[a]pyrene) on the NOBE-MIP shows an excellent selective binding with only 5.5% and 7% cross-reactivity for chrysene and benzo[a]pyrene, respectively. Not only is this particularly significant because the rebinding solvent is water, which is known to promote non-selective hydrophobic interactions; the binding remains comparable under salt-water conditions. These selective and high capacity adsorbents will find wide application in industrial and marine water monitoring/remediation. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Preparation of Magnetic Hollow Molecularly Imprinted Polymers for Detection of Triazines in Food Samples.

    PubMed

    Wang, Aixiang; Lu, Hongzhi; Xu, Shoufang

    2016-06-22

    Novel magnetic hollow molecularly imprinted polymers (M-H-MIPs) were proposed for highly selective recognition and fast enrichment of triazines in food samples. M-H-MIPs were prepared on the basis of multi-step swelling polymerization, followed by in situ growth of magnetic Fe3O4 nanoparticles on the surface of hollow molecularly imprinted polymers (H-MIPs). Transmission electron microscopy and scanning electron microscopy confirmed the successful immobilization of Fe3O4 nanoparticles on the surface of H-MIPs. M-H-MIPs could be separated simply using an external magnet. The binding adsorption results indicated that M-H-MIPs displayed high binding capacity and fast mass transfer property and class selective property for triazines. Langmuir isotherm and pseudo-second-order kinetic models fitted the best adsorption models for M-H-MIPs. M-H-MIPs were used to analyze atrazine, simazine, propazine, and terbuthylazine in corn, wheat, and soybean samples. Satisfactory recoveries were in the range of 80.62-101.69%, and relative standard deviation was lower than 5.2%. Limits of detection from 0.16 to 0.39 μg L(-1) were obtained. When the method was applied to test positive samples that were contaminated with triazines, the results agree well with those obtained from an accredited method. Thus, the M-H-MIP-based dispersive solid-phase extraction method proved to be a convenient and practical platform for detection of triazines in food samples.

  20. Molecular imprinted polymer functionalized carbon nanotube sensors for detection of saccharides

    NASA Astrophysics Data System (ADS)

    Badhulika, Sushmee; Mulchandani, Ashok

    2015-08-01

    In this work, we report the synthesis and fabrication of an enzyme-free sugar sensor based on molecularly imprinted polymer (MIP) on the surface of single walled carbon nanotubes (SWNTs). Electropolymerization of 3-aminophenylboronic acid (3-APBA) in the presence of 10 M d-fructose and fluoride at neutral pH conditions resulted in the formation of a self-doped, molecularly imprinted conducting polymer (MICP) via the formation of a stable anionic boronic ester complex between poly(aniline boronic acid) and d-fructose. Template removal generated binding sites on the polymer matrix that were complementary to d-fructose both in structure, i.e., shape, size, and positioning of functional groups, thus enabling sensing of d-fructose with enhanced affinity and specificity over non-MIP based sensors. Using carbon nanotubes along with MICPs helped to develop an efficient electrochemical sensor by enhancing analyte recognition and signal generation. These sensors could be regenerated and used multiple times unlike conventional affinity based biosensors which suffer from physical and chemical stability.

  1. Core-shell magnetic molecularly imprinted polymers as sorbent for sulfonylurea herbicide residues.

    PubMed

    Miao, Shan Shan; Wu, Mei Sheng; Zuo, Hai Gen; Jiang, Chen; Jin, She Feng; Lu, Yi Chen; Yang, Hong

    2015-04-15

    Sulfonylurea herbicides are widely used at lower dosage for controlling broad-leaf weeds and some grasses in cereals and economic crops. It is important to develop a highly efficient and selective pretreatment method for analyzing sulfonylurea herbicide residues in environments and samples from agricultural products based on magnetic molecularly imprinted polymers (MIPs). The MIPs were prepared by a surface molecular imprinting technique especially using the vinyl-modified Fe3O4@SiO2 nanoparticle as the supporting matrix, bensulfuron-methyl (BSM) as the template molecule, methacrylic acid (MAA) as a functional monomer, trimethylolpropane trimethacrylate (TRIM) as a cross-linker, and azodiisobutyronitrile (AIBN) as an initiator. The MIPs show high affinity, recognition specificity, fast mass transfer rate, and efficient adsorption performance toward BSM with the adsorption capacity reaching up to 37.32 mg g(-1). Furthermore, the MIPs also showed cross-selectivity for herbicides triasulfuron (TS), prosulfuron (PS), and pyrazosulfuron-ethyl (PSE). The MIP solid phase extraction (SPE) column was easier to operate, regenerate, and retrieve compared to those of C18 SPE column. The developed method showed highly selective separation and enrichment of sulfonylurea herbicide residues, which enable its application in the pretreatment of multisulfonylurea herbicide residues.

  2. Determination of donepezil in serum samples using molecularly imprinted polymer nanoparticles followed by high-performance liquid chromatography with ultraviolet detection.

    PubMed

    Khansari, Mehdi Rajabnia; Bikloo, Shahrzad; Shahreza, Sara

    2016-03-01

    A molecularly imprinted polymer designed for the selective extraction of donepezil from serum samples was synthesized using a noncovalent molecular imprinting approach. The molecularly imprinted polymer was evaluated chromatographically and then its affinity for donepezil was confirmed by solid-phase extraction. The optimal conditions for solid-phase extraction were provided by cartridge conditioning using acidified water purified from a Milli-Q system, sample loading under basic aqueous conditions, clean-up using acetonitrile, and elution with methanol/tetrahydrofuran. Desirable molecular recognition properties of the molecularly imprinted polymer led to good donepezil recoveries (90-102%). The data indicated that the imprinted polymer has a perfect selectivity and affinity for donepezil and could be used for selective extraction and analysis of donepezil in human serum.

  3. Controllable synthesis of conducting polypyrrole nanostructures.

    PubMed

    Zhang, Xuetong; Zhang, Jin; Song, Wenhui; Liu, Zhongfan

    2006-01-26

    Wire-, ribbon-, and sphere-like nanostructures of polypyrrole have been synthesized by solution chemistry methods in the presence of various surfactants (anionic, cationic, or nonionic surfactant) with various oxidizing agents [ammonium persulfate (APS) or ferric chloride (FeCl3), respectively]. The surfactants and oxidizing agents used in this study have played a key role in tailoring the nanostructures of polypyrrole during the polymerization. It is inferred that the lamellar structures of a mesophase are formed by self-assembly between the cations of a long chain cationic surfactant [cetyltrimethylammonium bromide (CTAB) or dodeyltrimethylammonium bromide (DTAB)] and anions of oxidizing agent APS. These layered mesostructures are presumed to act as templates for the formation of wire- and ribbon-like polypyrrole nanostructures. In contrast, if a short chain cationic surfactant octyltrimethylammonium bromide (OTAB) or nonionic surfactant poly(ethylene glycol) mono-p-nonylphenyl ether (Opi-10) is used, sphere-like polypyrrole nanostructures are obtained, whichever of the oxidizing agents mentioned above is used. In this case, micelles resulting from self-assembly among surfactant molecules are envisaged to serve as the templates while the polymerization happens. It is also noted that, if anionic surfactant sodium dodeyl surfate (SDS) is used, no characteristic nanostructures of polypyrrole were observed. This may be attributed to the doping effect of anionic surfactants into the resulting polypyrrole chains, and as a result, micelles self-assembled among surfactant molecules are broken down during the polymerization. The effects of monomer concentration, surfactant concentration, and surfactant chain length on the morphologies of the resulting polypyrrole have been investigated in detail. The molecular structures, composition, and electrical properties of the nanostructured polypyrrole have also been investigated in this study.

  4. Magnetic molecularly imprinted polymers synthesized by surface-initiated reversible addition-fragmentation chain transfer polymerization for the enrichment and determination of synthetic estrogens in aqueous solution.

    PubMed

    Chen, Fangfang; Zhang, Jingjing; Wang, Minjun; Kong, Jie

    2015-08-01

    Magnetic molecularly imprinted polymers have attracted significant interest because of their multifunctionality of selective recognition of target molecules and rapid magnetic response. In this contribution, magnetic molecularly imprinted polymers were synthesized via surface-initiated reversible addition addition-fragmentation chain transfer polymerization using diethylstilbestrol as the template for the enrichment of synthetic estrogens. The uniform imprinted surface layer and the magnetic property of the magnetic molecularly imprinted polymers favored a fast binding kinetics and rapid analysis of target molecules. The static and selective binding experiments demonstrated a desirable adsorption capacity and good selectivity of the magnetic molecularly imprinted polymers in comparison to magnetic non-molecularly imprinted polymers. Accordingly, a corresponding analytical method was developed in which magnetic molecularly imprinted polymers were employed as magnetic solid-phase extraction materials for the concentration and determination of four synthetic estrogens (diethylstilbestrol, hexestrol, dienestrol, and bisphenol A) in fish pond water. The recoveries of these synthetic estrogens in spiked fish pond water samples ranged from 61.2 to 99.1% with a relative standard deviation of lower than 6.3%. This study provides a versatile approach to prepare well-defined magnetic molecularly imprinted polymers sorbents for the analysis of synthetic estrogens in water solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Oligonucleofide Imprinting in Aqueous Environment

    DTIC Science & Technology

    2002-04-05

    imprint molecule for various organic and aqueous polymerization formulations (Table I). The polymer ...interactions (Table 1). Table 1. Polymer formulations used to imprint adenosine dimer 1. Molecularly imprinted polymer ( MIP ) using 1% dimer 1 as template ( MIP ... MIP P3 is compared to its rebinding with non- imprinted polymer P30. Cb is the amount of dimer rebound to the polymer . Cf is the

  6. Synthesis of metronidazole-imprinted molecularly imprinted polymers by distillation precipitation polymerization and their use as a solid-phase adsorbent and chromatographic filler.

    PubMed

    Liu, Jiang; Zhang, Lu; Li Han Song, Le; Liu, Yuan; Tang, Hui; Li, Yingchun

    2015-04-01

    Metronidazole-imprinted polymers with superior recognition properties were prepared by a novel strategy called distillation-precipitation polymerization. The as-obtained polymers were characterized by Fourier-transform infrared spectroscopy, laser particle size determination and scanning electron microscopy, and their binding performances were evaluated in detail by static, kinetic and dynamic rebinding tests, and Scatchard analysis. The results showed that when the fraction of the monomers was 5 vol% in the whole reaction system, the prepared polymers afforded good morphology, monodispersity, and high adsorption capacity and excellent selectivity to the target molecule, metronidazole. The optimal binding performance is 12.41 mg/g for metronidazole just before leakage occurred and 38.51 mg/g at saturation in dynamic rebinding tests. Metronidazole-imprinted polymers were further applied as packing agents in solid-phase extraction and as chromatographic filler, both of which served for the detection of metronidazole in fish tissue. The results illustrated the recoveries of spiked samples ranged from 82.97 to 87.83% by using molecularly imprinted solid-phase extraction combined with a C18 commercial column and 93.7 to 101.2% by directly using the polymer-packed chromatographic column. The relative standard deviation of both methods was less than 6%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Clean-up of triazines in vegetable extracts by molecularly-imprinted solid-phase extraction using a propazine-imprinted polymer.

    PubMed

    Cacho, C; Turiel, E; Martín-Esteban, A; Pérez-Conde, C; Cámara, C

    2003-06-01

    An analytical methodology based on a molecularly imprinted solid-phase extraction (MISPE) procedure was developed for the determination of several triazines (atrazine, simazine, desethylatrazine (DEA), desisopropylatrazine (DIA), and propazine) in vegetable samples. A methacrylic acid-based imprinted polymer was prepared by precipitation polymerisation using propazine as template and toluene as porogen. After removal of the template by Soxhlet extraction, the optimum loading, washing, and elution conditions for MISPE of the selected triazines were established. The optimised MISPE procedure was applied to the extraction of the selected triazines in pea, potato, and corn sample extracts and a high degree of clean-up was obtained. However, some remaining interferences, non-specifically and strongly bound to the polymeric matrix, appeared in the chromatogram, preventing quantification of DIA in potatoes and DIA, DEA, and propazine in corn samples. Thus, a new clean-up protocol based on the use of a non-imprinted polymer for removal of these interferences prior to the MISPE step was developed. By following the new two-step MISPE procedure, the matrix compounds were almost completely removed, allowing the determination of all the triazines selected at concentration levels below the established maximum residue limits, making the developed procedure suitable for monitoring these analytes in vegetable samples.

  8. Potentiometric chemosensor for neopterin, a cancer biomarker, using an electrochemically synthesized molecularly imprinted polymer as the recognition unit.

    PubMed

    Sharma, Piyush Sindhu; Wojnarowicz, Agnieszka; Sosnowska, Marta; Benincori, Tiziana; Noworyta, Krzysztof; D'Souza, Francis; Kutner, Wlodzimierz

    2016-03-15

    With an established procedure of molecular imprinting, a synthetic polymer receptor for the neopterin cancer biomarker was devised and used as a recognition unit of a potentiometric chemosensor. For that, bis-bithiophene derivatized with cytosine and bithiophene derivatized with boronic acid were used as functional monomers. The open-circuit potential (OCP) based transduction under flow-injection analysis conditions (FIA) determined neopterin in the concentration range of 0.15-2.5mM with the 22 µM limit of detection (LOD) and 7.01(±0.15) mVmM(-1) sensitivity indicating its potential suitability in clinical analysis applications. The molecularly imprinted polymer (MIP) film showed an appreciable apparent imprinting factor of ~6. The chemosensor successfully discriminated the interferences including the 6-biopterin and pterin structural analogs of neopterin as well as glucose and creatinine. Moreover, it determined neopterin in synthetic serum samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Molecularly imprinted polymer of 5-methyluridine for solid-phase extraction of pyrimidine nucleoside cancer markers in urine.

    PubMed

    Jégourel, Damien; Delépée, Raphaël; Breton, Florent; Rolland, Antoine; Vidal, Richard; Agrofoglio, Luigi A

    2008-10-01

    Normal and modified urinary nucleosides represent potential biomarkers for cancer diagnosis. To selectively extract modified nucleosides, we developed a molecularly imprinted polymer (MIP) of 5-methyluridine as selective material for molecularly imprinted solid-phase extraction (MISPE). The MIPs were obtained from vinyl-phenylboronate ester derivative of the template, acrylamide and pentaerythritol triacrylate co-polymer, and were tested in batch and cartridge experiments with aqueous samples. Our results indicated that the imprinted polymer was selective for pyrimidine nucleosides with a K(d) and a B(max) of 46 microM and 18 micromol/g, respectively. Finally, a MISPE of the most common pyrimidine nucleoside cancer markers in urine sample was realized.

  10. Blood Group Typing: From Classical Strategies to the Application of Synthetic Antibodies Generated by Molecular Imprinting.

    PubMed

    Mujahid, Adnan; Dickert, Franz L

    2015-12-31

    Blood transfusion requires a mandatory cross-match test to examine the compatibility between donor and recipient blood groups. Generally, in all cross-match tests, a specific chemical reaction of antibodies with erythrocyte antigens is carried out to monitor agglutination. Since the visual inspection is no longer useful for obtaining precise quantitative information, therefore there is a wide variety of different technologies reported in the literature to recognize the agglutination reactions. Despite the classical methods, modern biosensors and molecular blood typing strategies have also been considered for straightforward, accurate and precise analysis. The interfacial part of a typical sensor device could range from natural antibodies to synthetic receptor materials, as designed by molecular imprinting and which is suitably integrated with the transducer surface. Herein, we present a comprehensive overview of some selected strategies extending from traditional practices to modern procedures in blood group typing, thus to highlight the most promising approach among emerging technologies.

  11. Development of a molecularly imprinted polymer based surface plasmon resonance sensor for theophylline monitoring

    NASA Astrophysics Data System (ADS)

    Zheng, Rui; Cameron, Brent D.

    2011-03-01

    Molecularly imprinted polymer (MIP) thin films and surface plasmon resonance (SPR) sensing technologies were combined to develop a novel sensing platform for monitoring real-time theophylline concentration, which is a compound of interest in environmental monitoring and a molecular probe for phenotyping certain cytochrome P450 enzymes. The MIPs hydrogel is easy to synthesize and provides shape-selective recognition with high affinity to specific target molecules. Different polymerization formulas were tested and optimized. The influence of the monomer sensitive factors were addressed by SPR. SPR is an evanescent wave optics based sensing technique that is suitable for real-time and label free sensing purposes. Gold nanorods (Au NRs) were uniformly immobilized onto a SPR sensing surface for the construction of a fiber optics based prism-free localized SPR (LSPR) measurement. This technique can be also applied to assess the activities of other small organic molecules by adjusting the polymerization formula, thus, this approach also has many other potential applications.

  12. Ultratrace Detection of Histamine Using a Molecularly-Imprinted Polymer-Based Voltammetric Sensor.

    PubMed

    Akhoundian, Maedeh; Rüter, Axel; Shinde, Sudhirkumar

    2017-03-21

    Rapid and cost-effective analysis of histamine, in food, environmental, and diagnostics research has been of interest recently. However, for certain applications, the already-existing biological receptor-based sensing methods have usage limits in terms of stability and costs. As a result, robust and cost-effective imprinted polymeric receptors can be the best alternative. In the present work, molecularly-imprinted polymers (MIPs) for histamine were synthesized using methacrylic acid in chloroform and acetonitrile as two different porogens. The binding affinity of the MIPs with histamine was evaluated in aqueous media. MIPs synthesized in chloroform displayed better imprinting properties for histamine. We demonstrate here histamine MIPs incorporated into a carbon paste (CP) electrode as a MIP-CP electrode sensor platforms for detection of histamine. This simple sensor format allows accurate determination of histamine in the sub-nanomolar range using an electrochemical method. The sensor exhibited two distinct linear response ranges of 1 × 10(-10)-7 × 10(-9) M and 7 × 10(-9)-4 × 10(-7) M. The detection limit of the sensor was calculated equal to 7.4 × 10(-11) M. The specificity of the proposed electrode for histamine is demonstrated by using the analogous molecules and other neurotransmitters such as serotonin, dopamine, etc. The MIP sensor was investigated with success on spiked serum samples. The easy preparation, simple procedure, and low production cost make the MIP sensor attractive for selective and sensitive detection of analytes, even in less-equipped laboratories with minimal training.

  13. Surface molecular imprinted layer-by-layer film attached to a porous membrane for selective filtration.

    PubMed

    Liu, Zhihua; Yi, Yu; Gauczinski, Jan; Xu, Huaping; Schönhoff, Monika; Zhang, Xi

    2011-10-04

    A surface molecular imprinted layer-by-layer (SMILbL) film was fabricated on a polyethersulfone (PES) porous membrane substrate for selective filtration of cations and anions. The LbL deposition procedure and the ultraviolet (UV) cross-linking of the modified membrane were monitored by attenuated total reflection-infrared (ATR-IR) spectra. The SMILbL-PES membrane with 4.5 bilayers of diazoresin (DAR)/poly(acrylic acid) complexed with 5,10,15,20-tetrakis(4-(trimethylammonio)-phenyl)-21H,23H-porphyrin tetratosylate (PAA-Por(4+)) effectively reduced the permeation velocity of Por(4+) after washing the Por(4+) template out. In comparison to a control film DAR/PAA-modified PES membrane (ConLbL-PES) in a dialysis experiment, the SMILbL-PES membrane exhibited better selectivity for permeation of 5,10,15,20-tetraphenyl-21H,23H-porphine-p,p',p″,p‴-tetrasulfonic acid tetrasodium hydrate (Por(4-)) against permeation of Por(4+). In pressure-driven transport experiments, the SMILbL-PES membrane showed a much longer blocking time for Por(4+) than for Por(4-), indicating the selective loading of Por(4+) into the SMILbL film. The surface charge of the SMILbL-PES membrane after Por(4+) loading was higher than that of other membranes, resulting in an enhanced rejection ability of the SMILbL-PES membrane to Por(4+) caused by Coulomb repulsion. A possible mechanism was proposed as follows. The binding sites generated through imprinting in the SMILbL-PES membrane enable loading of a larger amount of Por(4+). The stronger repulsion between Por(4+) and the SMILbL film may cause the main contribution to the selective rejection of Por(4+). It can be easily imagined that this concept can be extended to the construction of composite membranes from other imprinting systems. © 2011 American Chemical Society

  14. Ultratrace Detection of Histamine Using a Molecularly-Imprinted Polymer-Based Voltammetric Sensor

    PubMed Central

    Akhoundian, Maedeh; Rüter, Axel; Shinde, Sudhirkumar

    2017-01-01

    Rapid and cost-effective analysis of histamine, in food, environmental, and diagnostics research has been of interest recently. However, for certain applications, the already-existing biological receptor-based sensing methods have usage limits in terms of stability and costs. As a result, robust and cost-effective imprinted polymeric receptors can be the best alternative. In the present work, molecularly-imprinted polymers (MIPs) for histamine were synthesized using methacrylic acid in chloroform and acetonitrile as two different porogens. The binding affinity of the MIPs with histamine was evaluated in aqueous media. MIPs synthesized in chloroform displayed better imprinting properties for histamine. We demonstrate here histamine MIPs incorporated into a carbon paste (CP) electrode as a MIP-CP electrode sensor platforms for detection of histamine. This simple sensor format allows accurate determination of histamine in the sub-nanomolar range using an electrochemical method. The sensor exhibited two distinct linear response ranges of 1 × 10−10–7 × 10−9 M and 7 × 10−9–4 × 10−7 M. The detection limit of the sensor was calculated equal to 7.4 × 10−11 M. The specificity of the proposed electrode for histamine is demonstrated by using the analogous molecules and other neurotransmitters such as serotonin, dopamine, etc. The MIP sensor was investigated with success on spiked serum samples. The easy preparation, simple procedure, and low production cost make the MIP sensor attractive for selective and sensitive detection of analytes, even in less-equipped laboratories with minimal training. PMID:28335573

  15. A novel composite of molecularly imprinted polymer-coated PdNPs for electrochemical sensing norepinephrine.

    PubMed

    Chen, Jianrong; Huang, Hong; Zeng, Yanbo; Tang, Huan; Li, Lei

    2015-03-15

    A novel composite of molecularly imprinted polymer-coated palladium nanoparticles (MIP-coated PdNPs) was synthesized by sol-gel method using norepinephrine as template, phenyl trimethoxysilane as functional monomer and tetramethoxysilane as crosslinker. The combination of PdNPs and silica-based MIP endowed the composite with good electrochemical catalytic property, large surface area and template selectivity. MIP-coated PdNPs were characterized by Fourier transform infrared spectroscopy and Transmission electron microscopy. Then MIP-coated PdNPs composite was used as a recognition element in the construction of an electrochemical sensor for norepinephrine. The properties of MIP-coated PdNPs sensor such as special binding, adsorption dynamics and selective recognition ability were evaluated by differential pulse voltammetry. The results demonstrated that MIP-coated PdNPs sensor not only possessed a short response time, but also high binding capacity for norepinephrine, which enabled the imprinted sensor with higher current response than that of non-imprinted material and MIP without PdNPs. In addition, the MIP-coated PdNPs sensor exhibited selectivity for norepinephrine in comparison to other analogs. The MIP-coated PdNPs sensor had a wide linear range over norepinephrine concentration from 0.5 to 80.0μM with a detection limit of 0.1μM. The MIP-coated PdNPs sensor was proved to be a suitable sensing tool for the fast, sensitive and selective determination of norepinephrine in injection and urine samples.

  16. Novel biphasic separations utilising highly selective molecularly imprinted polymers as biorecognition solvent extraction agents.

    PubMed

    Castell, Oliver K; Allender, Christopher J; Barrow, David A

    2006-10-15

    Molecularly imprinted polymers (MIPs) represent a class of artificial receptors that promise an environmentally robust alternative to naturally occurring biorecognition elements of biosensing devices and systems. However, in general, the performance of conventional MIPs in aqueous environments is poor. In the study reported here, this limitation has been addressed by the novel application of MIPs as a solvent extraction solid phase in a biphasic solvent system. This paper describes a previously unreported use of MIPs as solvent extraction reagents, their successful application to aqueous sample media and the opportunities for utilisation of this unique system in novel biosensing and separation procedures. This study demonstrates the development of a novel biphasic solvent system utilising MIP in the extracting phase to enhance both efficiency and selectivity of a simple two phase liquid extraction. Monodisperse propranolol imprinted polymer microspheres [p(divinylbenzene-co-methacrylic acid)] were prepared by precipitation polymerisation. Initially, the affinity of the polymers for (R,S)-propranolol was assessed by established techniques whereby the MIP demonstrated greater affinity for the template than did the non-imprinted control polymer (NIP). Importantly, MIP performance was also assessed using the novel dual solvent system. The depletion of (R,S)-propranolol from the aqueous phase into the polymer containing organic phase was determined. When compared to control extractions containing no polymer the presence of MIP in the extracting solvent phase resulted in an increased extraction of (R,S)-propranolol from the aqueous phase. Importantly, this extraction was significantly greater in the presence of MIP when compared to NIP. This unique principle generates opportunities for MIP based extractions and chemical enrichments in industrial applications, offering commercial, ecological and practical advantages to traditional solvent extraction techniques. The

  17. A new molecularly imprinted polymer for selective extraction of cotinine from urine samples by solid-phase extraction.

    PubMed

    Yang, Jun; Hu, Yan; Cai, Ji-Bao; Zhu, Xiao-Lan; Su, Qing-De

    2006-02-01

    Cotinine, the main metabolite of nicotine in human body, is widely used as a biomarker for assessment of direct or passive exposure to tobacco smoke. A method for molecularly imprinted solid-phase extraction (MISPE) of cotinine from human urine has been investigated. The molecularly imprinted polymer (MIP) with good selectivity and affinity for cotinine was synthesized using cotinine as the template molecule, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. The imprinted polymer was evaluated for use as a SPE sorbent, in tests with aqueous standards, by comparing recovery data obtained using the imprinted form of the polymer and a non-imprinted form (NIP). Extraction from the aqueous solutions resulted in more than 80% recovery. A range of linearity for cotinine between 0.05 and 5 microg mL-1 was obtained by loading 1 mL blank urine samples spiked with cotinine at different concentrations in acetate buffer of pH 9.0, and by using double basic washing and acidic elution. The intra-day coefficient of variation (CV) was below 7% and inter-day CV was below 10%. This investigation has provided a reliable MISPE-HPLC method for determination of cotinine in human urine from both active smokers and passive smokers.

  18. Ligand Replacement Approach to Raman-Responded Molecularly Imprinted Monolayer for Rapid Determination of Penicilloic Acid in Penicillin.

    PubMed

    Zhang, Liying; Jin, Yang; Huang, Xiaoyan; Zhou, Yujie; Du, Shuhu; Zhang, Zhongping

    2015-12-01

    Penicilloic acid (PA) is a degraded byproduct of penicillin and often causes fatal allergies to humans, but its rapid detection in penicillin drugs remains a challenge due to its similarity to the mother structure of penicillin. Here, we reported a ligand-replaced molecularly imprinted monolayer strategy on a surface-enhanced Raman scattering (SERS) substrate for the specific recognition and rapid detection of Raman-inactive PA in penicillin. The bis(phenylenediamine)-Cu(2+)-PA complex was first synthesized and stabilized onto the surface of silver nanoparticle film that was fabricated by a bromide ion-added silver mirror reaction. A molecularly imprinted monolayer was formed by the further modification of alkanethiol around the stabilized complex on the Ag film substrate, and the imprinted recognition site was then created by the replacement of the complex template with Raman-active probe molecule p-aminothiophenol. When PA rebound into the imprinted site in the alkanethiol monolayer, the SERS signal of p-aminothiophenol exhibited remarkable enhancement with a detection limit of 0.10 nM. The imprinted monolayer can efficiently exclude the interference of penicillin and thus provides a selective determination of 0.10‰ (w/w) PA in penicillin, which is about 1 order of magnitude lower than the prescribed residual amount of 1.0‰. The strategy reported here is simple, rapid and inexpensive compared to the traditional chromatography-based methods.

  19. A sensitive molecularly imprinted polymer based quartz crystal microbalance nanosensor for selective determination of lovastatin in red yeast rice.

    PubMed

    Eren, Tanju; Atar, Necip; Yola, Mehmet Lütfi; Karimi-Maleh, Hassan

    2015-10-15

    Lovastatin (LOV) is a statin, used to lower cholesterol which has been found as a hypolipidemic agent in commercial red yeast rice. In present study, a sensitive molecular imprinted quartz crystal microbalance (QCM) sensor was prepared by fabricating a self-assembling monolayer formation of allylmercaptane on QCM chip surface for selective determination of lovastatin (LOV) in red yeast rice. To prepare molecular imprinted quartz crystal microbalance (QCM) nanosensor, LOV imprinted poly(2-hydroxyethyl methacrylate-methacryloylamidoaspartic acid) [p(HEMA-MAAsp)] nanofilm was attached on the modified gold surface of QCM chip. The non-modified and improved surfaces were characterized by using contact angle, atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy. The imprinted QCM sensor was validated according to the ICH guideline (International Conference on Harmonisation). The linearity range was obtained as 0.10-1.25 nM. The detection limit of the prepared material was calculated as 0.030 nM. The developed QCM nanosensor was successfully used to examine red yeast rice. Furthermore, the stability and repeatability of the prepared QCM nanosensor were studied. The spectacular long-term stability and repeatability of the prepared LOV-imprinted QCM nanosensor make them intriguing for use in QCM sensors. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Selective recognition and discrimination of water-soluble azo dyes by a seven-channel molecularly imprinted polymer sensor array.

    PubMed

    Long, Zerong; Lu, Yi; Zhang, Mingliang; Qiu, Hongdeng

    2014-10-01

    A seven-channel molecularly imprinted polymer sensor array was prepared and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, UV-Vis spectroscopy, and nitrogen physisorption studies. The results revealed that the imprinted polymers have distinct-binding affinities from those of structurally similar azo dyes. Analysis of the UV-Vis spectral response patterns of the seven dye analytes against the imprinted polymer array suggested that the different selectivity patterns of the array were closely connected to the imprinting process. To evaluate the effectiveness of the array format, the binding of a series of analytes was individually measured for each of the seven polymers, made with different templates (including one control polymer synthesized without the use of a template). The response patterns of the array to the selected azo dyes were processed by canonical discriminant analysis. The results showed that the molecularly imprinted array was able to discriminate each analyte with 100% accuracy. Moreover, the azo dyes in two real samples, spiked chrysoidin in smoked bean curd extract and Fanta lime soda (containing tartrazine), were successfully classified by the array.

  1. Tailoring molecularly imprinted polymer beads for alternariol recognition and analysis by a screening with mycotoxin surrogates.

    PubMed

    Abou-Hany, Rahma A G; Urraca, Javier L; Descalzo, Ana B; Gómez-Arribas, Lidia N; Moreno-Bondi, María C; Orellana, Guillermo

    2015-12-18

    Molecularly imprinted porous polymer microspheres have been prepared for selective binding of alternariol (AOH), a phenolic mycotoxin produced by Alternaria fungi. In order to lead the synthesis of recognition materials, four original AOH surrogates have been designed, prepared and characterized. They bear different number of phenol groups in various positions and different degree of O-methylation on the dibenzo[b,d]pyran-6-one skeleton. A comprehensive library of mixtures of basic, acidic or neutral monomers, with divinylbenzene or ethyleneglycol dimethacrylate as cross-linkers, were polymerized at a small scale in the presence of the four molecular mimics of the toxin molecule. This polymer screening has allowed selection of the optimal composition of the microbeads (N-(2-aminoethyl)methacrylamide, EAMA, and ethylene glycol dimethacrylate). The latter are able to bind AOH in water-acetonitrile (80:20, v/v) with an affinity constant of 109±10mM(-1) and a total number of binding sites of 35±2μmolg(-1), being alternariol monomethylether the only competitor species. Moreover, (1)H NMR titrations have unveiled a 1:2 surrogate-to-EAMA stoichiometry, the exact interaction sites and a binding constant of 1.5×10(4)M(-2). A molecularly imprinted solid phase extraction (MISPE) method has been optimized for selective isolation of the mycotoxin from aqueous samples upon a discriminating wash with 3mL of acetonitrile/water (20:80, v/v) followed by determination by HPLC with fluorescence detection. The method has been applied, in combination to ultrasound-assisted extraction, to the analysis of AOH in tomato samples fortified with the mycotoxin at five concentration levels (33-110μgkg(-1)), with recoveries in the range of 81-103% (RSD n=6). To the best of our knowledge, this is the first imprinted material capable of molecularly recognizing this widespread food contaminant. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Human imprinting anomalies in fetal and childhood growth disorders: clinical implications and molecular mechanisms.

    PubMed

    Azzi, Salah; Brioude, Fréderic; Le Bouc, Yves; Netchine, Irène

    2014-01-01

    Genomic imprinting is among the most important epigenetic mechanisms whereby expression of a subset of genes is restricted to a single parental allele. Loss of imprinting (LOI) through hypo or hyper methylation is involved in various human syndromes. These LOI occur early during development and usually impair growth. Some imprinting syndromes are the consequences of genetic anomalies, such as uniparental disomies (UPD) or copy number variations (deletion or duplications) involving the imprinted domains; others are due to LOI at the imprinting control regions (ICR) regulating each domain. Imprinting disorders are phenotypically heterogeneous, although some share various common clinical features such that diagnosis may be difficult. Multilocus imprinting defects associated with several syndromes have been increasingly reported in recent years, although there are no obvious clinical differences between monolocus and multilocus LOI patients. Subsequently, some rare mutations of transacting factors have been identified in patients with multilocus imprinting defects but they do not explain the majority of the cases; this therefore implies that other factors are involved. By contrast, no mutation of a transacting factor has yet been identified in monolocus LOI. The effect of the environment on the regulation of imprinting is clearly illustrated by studies of assisted reproductive technology (ART). The regulation of imprinting is complex and involves a huge range of genetic and environmental factors; the identification of these factors will undoubtedly help to elucidate the regulation of imprinting and contribute to the understanding of imprinting disorders. This would be beneficial for diagnostics, clinical follow up and the development of treatment guidelines.

  3. Efficient synthesis of narrowly dispersed hydrophilic and magnetic molecularly imprinted polymer microspheres with excellent molecular recognition ability in a real biological sample.

    PubMed

    Zhao, Man; Zhang, Cong; Zhang, Ying; Guo, Xianzhi; Yan, Husheng; Zhang, Huiqi

    2014-02-28

    A facile and highly efficient approach to obtain narrowly dispersed hydrophilic and magnetic molecularly imprinted polymer microspheres with molecular recognition ability in a real biological sample as good as what they show in the organic solvent-based media is described for the first time.

  4. Molecularly Imprinted Electropolymer for a Hexameric Heme Protein with Direct Electron Transfer and Peroxide Electrocatalysis.

    PubMed

    Peng, Lei; Yarman, Aysu; Jetzschmann, Katharina J; Jeoung, Jae-Hun; Schad, Daniel; Dobbek, Holger; Wollenberger, Ulla; Scheller, Frieder W

    2016-02-23

    For the first time a molecularly imprinted polymer (MIP) with direct electron transfer (DET) and bioelectrocatalytic activity of the target protein is presented. Thin films of MIPs for the recognition of a hexameric tyrosine-coordinated heme protein (HTHP) have been prepared by electropolymerization of scopoletin after oriented assembly of HTHP on a self-assembled monolayer (SAM) of mercaptoundecanoic acid (MUA) on gold electrodes. Cavities which should resemble the shape and size of HTHP were formed by template removal. Rebinding of the target protein sums up the recognition by non-covalent interactions between the protein and the MIP with the electrostatic attraction of the protein by the SAM. HTHP bound to the MIP exhibits quasi-reversible DET which is reflected by a pair of well pronounced redox peaks in the cyclic voltammograms (CVs) with a formal potential of -184.4 ± 13.7 mV vs. Ag/AgCl (1 M KCl) at pH 8.0 and it was able to catalyze the cathodic reduction of peroxide. At saturation the MIP films show a 12-fold higher electroactive surface concentration of HTHP than the non-imprinted polymer (NIP).

  5. Deep Eutectic Solvents Modified Molecular Imprinted Polymers for Optimized Purification of Chlorogenic Acid from Honeysuckle.

    PubMed

    Li, Guizhen; Wang, Wei; Wang, Qian; Zhu, Tao

    2016-02-01

    Deep eutectic solvents (DES) were synthesized with choline chloride (ChCl), and DES modified molecular imprinted polymers (DES-MIPs), DES modified non-imprinted polymers (DES-NIPs, without template), MIPs and NIPs were prepared in an identical procedure. Fourier transform infrared spectrometer (FT-IR) and field emission scanning electron microscopy (FE-SEM) were used to characterize the obtained polymers. Rebinding experiment and solid-phase extraction (SPE) were used to prove the high selectivity adsorption properties of the polymers. Box-Behnken design (BBD) with three factors was used to optimize the extraction condition of chlorogenic acid (CA) from honeysuckles. The optimum extraction conditions were found to be ultrasonic time optimized (20 min), the volume fraction of ethanol (60%) and ratio of liquid to material (15 mL g(-1)). Under these conditions, the mean extraction yield of CA was 12.57 mg g(-1), which was in good agreement with the predicted BBD model value. Purification of hawthorn extract was achieved by SPE process, and SPE recoveries of CA were 72.56, 64.79, 69.34 and 60.08% by DES-MIPs, DES-NIPs, MIPs and NIPs, respectively. The results showed DES-MIPs had potential for promising functional adsorption material for the purification of bioactive compounds.

  6. Carbon paste electrode modified molecularly imprinted polymer as a sensor for creatinine analysis by stripping voltammetry

    NASA Astrophysics Data System (ADS)

    Khasanah, M.; Darmokoesoemo, H.; Rizki, D. A.

    2017-09-01

    Modification of carbon paste electrode with molecularly imprinted polymer (CP-MIP) as a voltammetric sensor for creatinine has been developed. MIP was synthesized by reacting melamine, chloranil and creatinine with a mole ratio of 1:1:0.1. Creatinine was extracted from polymer chain by using hot water to form a specific imprinted for creatinine molecule. Carbon paste-MIP electrode was prepared by mixing activated carbon, solid paraffin, and MIP in a 45:40:15(w/w %) ratio. The optimum conditions of creatinine analysis by differential pulse stripping voltammetry (DPSV) using the developed electrode were the accumulation potential -1000 mV during 90 s at pH 5. The precision of the method for 0.1-0.5 μlg/L creatinine was 88.7-96.3%, while the detection limit of this method was 0.0315 μlg/L. The accuracy compared by spectrophotometric method was 95.3-103.6%

  7. Molecularly Imprinted Electropolymer for a Hexameric Heme Protein with Direct Electron Transfer and Peroxide Electrocatalysis

    PubMed Central

    Peng, Lei; Yarman, Aysu; Jetzschmann, Katharina J.; Jeoung, Jae-Hun; Schad, Daniel; Dobbek, Holger; Wollenberger, Ulla; Scheller, Frieder W.

    2016-01-01

    For the first time a molecularly imprinted polymer (MIP) with direct electron transfer (DET) and bioelectrocatalytic activity of the target protein is presented. Thin films of MIPs for the recognition of a hexameric tyrosine-coordinated heme protein (HTHP) have been prepared by electropolymerization of scopoletin after oriented assembly of HTHP on a self-assembled monolayer (SAM) of mercaptoundecanoic acid (MUA) on gold electrodes. Cavities which should resemble the shape and size of HTHP were formed by template removal. Rebinding of the target protein sums up the recognition by non-covalent interactions between the protein and the MIP with the electrostatic attraction of the protein by the SAM. HTHP bound to the MIP exhibits quasi-reversible DET which is reflected by a pair of well pronounced redox peaks in the cyclic voltammograms (CVs) with a formal potential of −184.4 ± 13.7 mV vs. Ag/AgCl (1 M KCl) at pH 8.0 and it was able to catalyze the cathodic reduction of peroxide. At saturation the MIP films show a 12-fold higher electroactive surface concentration of HTHP than the non-imprinted polymer (NIP). PMID:26907299

  8. Molecularly imprinted electrochemical sensor based on bioinspired Au microflowers for ultra-trace cholesterol assay.

    PubMed

    Yang, Hua; Li, Li; Ding, Yaping; Ye, Daixin; Wang, Yingzi; Cui, Shiqiang; Liao, Lanfeng

    2017-06-15

    A novel imprinted sensor for ultra-trace cholesterol (CHO) detection based on electropolymerized aminothiophenol (ATP) molecularly imprinted polymer (MIP) on a glassy carbon electrode (GCE) modified with dopamine@graphene (DGr) and bioinspired Au microflowers has been developed in this work. As the specific recognition element, the bioinspired Au microflowers were formed by Au nanoparticles (AuNPs) and wrapped by bionic polydopamine film (PDA) through electropolymerization method. These excellent biocompatible materials could capture the target CHO effectively. The morphology of the MIP modified electrode was characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM). The hydrogen-bonding interaction between templates and monomers was characterized by ultraviolet spectroscopy. Under the optimal experimental conditions, the sensor's linear response range was between 10(-18) and 10(-13) M, with a detection limit of 3.3×10(-19) M, which was much more sensitive than most available CHO detection methods in previously reports. Moreover, the MIP sensor exhibited high sensitivity for CHO, low interference, and good stability. The human serum samples analysis confirmed the applicability of this MIP sensor to quantitative analysis of ultra-trace CHO. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. H5N1 Virus Plastic Antibody Based on Molecularly Imprinted Polymers.

    PubMed

    Sangma, Chak; Lieberzeit, Peter A; Sukjee, Wannisa

    2017-01-01

    Normally, antibodies against influenza A have been prepared from viable virus or an engineered strain in certain hosts or cultured media. Two factors concerning antibody production are obvious. The obtaining antibody that is a kind of biomolecule has to be handled carefully, e.g., to be kept in a refrigerator. Furthermore, when the virus strain is highly pathogenic, such as H5N1, antibody production has to be done carefully in a high-level biosafety lab. Here, we show how to produce an antibody against H5N1 from a polymeric material using inactivated virus which can be conducted in a low-level biosafety lab. The process is based on imprinting the whole virus on a polymer surface to form molecularly imprinted polymers (MIPs). The MIPs show some properties of H5N1 antibody as they recognize H5N1 and have some important antibody activity. The H5N1 MIPs are not to be considered biomaterial, so they can be stored at room temperature and thus do not need any special care.

  10. Optimization of chitosan and β-cyclodextrin molecularly imprinted polymer synthesis for dye adsorption.

    PubMed

    Kyzas, George Z; Lazaridis, Nikolaos K; Bikiaris, Dimitrios N

    2013-01-02

    In this study, two types of novel molecularly imprinted polymers (MIPs) were prepared, for toxic and carcinogenic dyes adsorption. Substrates of the polymeric matrix of the two MIPs were β-cyclodextrin and chitosan. The conditions in the polymerization/imprinting stage and in the rebinding/adsorption step were optimized. The effect of a range of parameters (polymer, cross-linker, and initiator concentrations, reaction time and pH) on the selectivity and adsorption capacity of the dye-MIPs were investigated. Their dye rebinding properties were demonstrated by equilibrium batch experiments (fitting with Freundlich model) and their kinetic rates were exported by the pseudo-first order model. Additionally, a thermodynamic evaluation was carried out through the determination of enthalpy, entropy, and free energy. The selectivity of MIPs was elucidated by their different rebinding capabilities in a trichromatic mixture (composed of related structurally dyes). Regeneration/reuse of the dye-loaded polymers was evaluated via sequential adsorption-desorption cycles. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Preparation and evaluation of amoxicillin loaded dual molecularly imprinted nanoparticles for anti-Helicobacter pylori therapy.

    PubMed

    Wu, Zhihui; Hou, Jiapeng; Wang, Yuyan; Chai, Miaolin; Xiong, Yan; Lu, Weiyue; Pan, Jun

    2015-12-30

    This paper reports studies on preparation and evaluation of amoxicillin loaded dual molecularly imprinted nanoparticles (Amo/Dual-MIPs) designed for anti-H. pylori therapy. Both MNQA and AmoNa were chosen as templates to prepare Dual-MIPs using inverse microemulsion polymerization method. NQA was modified with myristic acid (MNQA) to become amphiphilic and assist in leaving NQA cavities on the surface of Dual-MIPs for H. pylori adhesion. AmoNa was applied to produce imprinting sites in Dual-MIPs for rebinding AmoNa to exert its anti-H. pylori effect. Batch rebinding test demonstrated a preferential rebinding effect of NQA toward the Dual-MIPs. In vivofluorescence imaging showed the prolonged residence time of Dual-MIPs in H. pylori infected mice stomachs after intragastric administration of nanoparticles.In vivo H. pylori clearance tests indicated Amo/Dual-MIPs had a better aniti-H. pylori effect than amoxicillin powder did. In conclusion, Amo/Dual-MIPs may provide an alternative drug delivery strategy for anti-H. pylori therapy.

  12. Study of the molecularly imprinted polymers for selective binding of the mono-substituted sulfonylurea herbicides.

    PubMed

    Wang, Shengli; Dong, Xiangchao; Wang, Bo; Fan, Zhijin; Luan, Linbo; Li, Yanni

    2013-04-01

    A new molecularly imprinted polymer (MIP) was synthesized for the selective extraction of mono-substituted sulfonylurea herbicides, with monosulfuron as the template and acrylamide as the functional monomer. The recognition property and affinity of the MIP for monosulfuron and its analog, monosulfuron-ester, were evaluated by equilibrium adsorption and a chromatographic study. Computer modeling, including simulated annealing and semi-empirical quantum calculation, was employed to study the recognition mechanism. The computer modeling demonstrated that monosulfuron can form multiple hydrogen bonds with methacrylic acid and acrylamide, whereas monosulfuron-ester cannot form a stable complex with these two functional monomers, which aligns with the results of the rebinding experiment. The selectivity study further demonstrated that binding sites in the MIP interact with the hydrogen in the acylamino group of mono-substituted sulfonylurea. A comparison experiment also showed that monosulfuron-imprinted MIP offers better selectivity for monosulfuron-ester than the commercial C18 high-performance liquid chromatography stationary phase material.

  13. Expanding Cancer Detection Using Molecular Imprinting for a Novel Point-of-Care Diagnostic Device

    NASA Astrophysics Data System (ADS)

    Yu, Yingjie; Rafailovich, Miriam; Wang, Yantian; Kang, Yeona; Zhang, Lingxi; Rigas, Basil; Division of Gastroenterology, School of Medicine Team

    2013-03-01

    We propose the use of a potentiometric biosensor that incorporates the efficient and specific molecular imprinting (MI) method with a self-assembled monolayer (SAM). We first tested the biosensor using carcinoembryonic antigen, CEA, a biomarker associated with pancreatic cancer. No change in detection efficiency was observed, indicating that the sensor is able to discriminate for the template analyte even in concentrated solution of similar substances. In addition, we use biosensor to discriminate normal fibrinogen and damaged fibrinogen, which is critical for the detection of bleeding disorder. Computer simulations of the protein structure were performed in order to estimate the changes in morphology and determine the sensitivity of the biosensor to conformational changes in the proteins. We found that even small changes in PH can generate rotation of the surface functional groups. Yet, the results show that only when the detection and imprinting conditions are similar, robust signals occurs. Hence we concluded that both morphology and surface chemistry play a role in the recognition.

  14. Molecular imprinting ratiometric fluorescence sensor for highly selective and sensitive detection of phycocyanin.

    PubMed

    Wang, Xiaoyan; Yu, Jialuo; Kang, Qi; Shen, Dazhong; Li, Jinhua; Chen, Lingxin

    2016-03-15

    A facile strategy was developed to prepare molecular imprinting ratiometric fluorescence sensor for highly selective and sensitive detection of phycocyanin (PC) based on fluorescence resonance energy transfer (FRET), via a sol-gel polymerization process using nitrobenzoxadiazole (NBD) as fluorescent signal source. The ratio of two fluorescence peak emission intensities of NBD and PC was utilized to determine the concentration of PC, which could effectively reduce the background interference and fluctuation of diverse conditions. As a result, this sensor obtained high sensitivity with a low detection limit of 0.14 nM within 6 min, and excellent recognition specificity for PC over its analogues with a high imprinting factor of 9.1. Furthermore, the sensor attained high recoveries in the range of 93.8-110.2% at three spiking levels of PC, with precisions below 4.7% in seawater and lake water samples. The developed sensor strategy demonstrated simplicity, reliability, rapidity, high selectivity and high sensitivity, proving to be a feasible way to develop high efficient fluorescence sensors and thus potentially applicable for ultratrace analysis of complicated matrices.

  15. Enzyme activity assay of glycoprotein enzymes based on a boronate affinity molecularly imprinted 96-well microplate.

    PubMed

    Bi, Xiaodong; Liu, Zhen

    2014-12-16

    Enzyme activity assay is an important method in clinical diagnostics. However, conventional enzyme activity assay suffers from apparent interference from the sample matrix. Herein, we present a new format of enzyme activity assay that can effectively eliminate the effects of the sample matrix. The key is a 96-well microplate modified with molecularly imprinted polymer (MIP) prepared according to a newly proposed method called boronate affinity-based oriented surface imprinting. Alkaline phosphatase (ALP), a glycoprotein enzyme that has been routinely used as an indicator for several diseases in clinical tests, was taken as a representative target enzyme. The prepared MIP exhibited strong affinity toward the template enzyme (with a dissociation constant of 10(-10) M) as well as superb tolerance for interference. Thus, the enzyme molecules in a complicated sample matrix could be specifically captured and cleaned up for enzyme activity assay, which eliminated the interference from the sample matrix. On the other hand, because the boronate affinity MIP could well retain the enzymatic activity of glycoprotein enzymes, the enzyme captured by the MIP was directly used for activity assay. Thus, additional assay time and possible enzyme or activity loss due to an enzyme release step required by other methods were avoided. Assay of ALP in human serum was successfully demonstrated, suggesting a promising prospect of the proposed method in real-world applications.

  16. Application of molecularly imprinted polymers to selective removal of clofibric acid from water.

    PubMed

    Dai, Chaomeng; Zhang, Juan; Zhang, Yalei; Zhou, Xuefei; Liu, Shuguang

    2013-01-01

    A new molecularly imprinted polymer (MIP) adsorbent for clofibric acid (CA) was prepared by a non-covalent protocol. Characterization of the obtained MIP was achieved by scanning electron microscopy (SEM) and nitrogen sorption. Sorption experimental results showed that the MIP had excellent binding affinity for CA and the adsorption of CA by MIP was well described by pseudo-second-order model. Scatchard plot analysis revealed that two classes of binding sites were formed in the MIP with dissociation constants of 7.52 ± 0.46 mg L(-1) and 114 ± 4.2 mg L(-1), respectively. The selectivity of MIP demonstrated higher affinity for CA over competitive compound than that of non-imprinted polymers (NIP). The MIP synthesized was used to remove CA from spiked surface water and exhibited significant binding affinity towards CA in the presence of total dissolved solids (TDS). In addition, MIP reusability was demonstrated for at least 12 repeated cycles without significant loss in performance.

  17. Molecularly imprinted polymers in drug delivery: state of art and future perspectives.

    PubMed

    Puoci, Francesco; Cirillo, Giuseppe; Curcio, Manuela; Parisi, Ortensia Ilaria; Iemma, Francesca; Picci, Nevio

    2011-10-01

    Molecularly imprinted polymers (MIPs) are synthetic receptors, characterized by a high selectivity for the selected template. Among the different applications of MIPs, their use as controlled/sustained drug delivery devices has been extensively explored, even though the optimization of such devices needs to be performed before they are applied in clinical practice. Within drug delivery, one of the most promising fields is the possibility to modulate the drug release profile in response to a specific external stimulus; MIPs represent potentially suitable vehicles, because of the possibility to insert a stimuli-responsive co-monomer in their structure. This review discusses recent advances in the use of external stimuli to modulate drug release, as well as the synthetic strategies devoted to increase the water compatibility of these systems, which is a base requirement for their application in biomedicine. Although it is easy to imagine imprinted polymers for biomedical applications, several aspects have to be further investigated, such as the in vivo studies, efficiency and biocompatibility. However, we think that in the next few years it will possible to see unprecedented progress in the preparation of such systems and the translational application of these intelligent structures in medicine.

  18. Preparation of molecularly imprinted polymer nanoparticles for selective removal of fluoroquinolone antibiotics in aqueous solution.

    PubMed

    Tan, Feng; Sun, Daming; Gao, Jinsuo; Zhao, Qian; Wang, Xiaochun; Teng, Fei; Quan, Xie; Chen, Jingwen

    2013-01-15

    In this study, novel molecularly imprinted polymer nanoparticles (nanoMCN@MIPs) were prepared by covalent grafting of ofloxacin-imprinted polymer onto the surface of mesoporous carbon nanoparticles (MCNs). SEM analyses indicated that the prepared nanoMCN@MIPs were almost uniform, and their geometrical mean diameter was about 230 nm. The sorption behaviors of the nanoMCN@MIPs including sorption kinetics and isotherms, effect of pH, ionic strength, and cross-reactivity were investigated in detail. The adsorption capacity of the nanoparticles for ofloxacin was 40.98 mg/g, with a selectivity factor of 2.6 compared to the nonimprinted polymer nanoparticles (nanoMCN@NIPs). The feasibility of removing fluoroquinolone antibiotics (FQs) from environmental waters with the nanoMCN@MIPs was demonstrated using sea water spiked with six typical FQs (ofloxacin, gatifloxacin, balofloxcacin, enrofloxacin, norfloxacin and sarafloxacin). The nanoMCN@MIPs could be reused at least five times with removal efficiency more than 90% except for norfloxacin. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Sensitive detection of L-5-hydroxytryptophan based on molecularly imprinted polymers with graphene amplification.

    PubMed

    Chen, Lu; Lian, Hui-Ting; Sun, Xiang-Ying; Liu, Bin

    2017-06-01

    A novel electrochemical sensor was presented for the determination of L-5-hydroxytryptophan (L-5-HTP) based on a graphene-chitosan molecularly imprinted film modified on the surface of glassy carbon electrode (GR-MIP/GCE). The morphology and composition of the imprinted film were observed in field emission scanning electron microscopy (FESEM), raman spectroscopy and fourier transform infrared (FTIR). The properties of the sensor were evaluated by electrochemical techniques. Under the optimal conditions, the peak currents of L-5-HIP were found to be linear in the concentration range of 0.05-7.0 μM, while the sensor also exhibited great features such as low detection limit of 6.0 nM (S/N = 3), superb selectivity against the structural analogues, good antidisturbance ability among coexisting components, excellent repeatability and stability. Moreover, the proposed method had been applied to the detection of L-5-HTP in human blood serum with a satisfactory recoveries ranging from 90.6% to 105.6%. Copyright © 2017. Published by Elsevier Inc.

  20. Protein crystallization and biosensor applications of hydrogel-based molecularly imprinted polymers.

    PubMed

    Reddy, Subrayal M; Phan, Quan T; El-Sharif, Hazim; Govada, Lata; Stevenson, Derek; Chayen, Naomi E

    2012-12-10

    We have characterized the imprinting capability of a family of acrylamide polymer-based molecularly imprinted polymers (MIPs) for bovine hemoglobin (BHb) and trypsin (Tryp) using spectrophotometric and quartz crystal microbalance (QCM) sensor techniques. Bulk gel characterization on acrylamide (AA), N-hydroxymethylacrylamide (NHMA), and N-isopropylacrylamide (NiPAM) gave varied selectivities when compared with nonimprinted polymers. We have also harnessed the ability of the MIPs to facilitate protein crystallization as a means of evaluating their selectivity for cognate and noncognate proteins. Crystallization trials indicated improved crystal formation in the order NiPAM

  1. Atrazine Molecular Imprinted Polymers: Comparative Analysis by Far-Infrared and Ultraviolet Induced Polymerization

    PubMed Central

    Chen, Jun; Bai, Lian-Yang; Liu, Kun-Feng; Liu, Run-Qiang; Zhang, Yu-Ping

    2014-01-01

    Atrazine molecular imprinted polymers (MIPs) were comparatively synthesized using identical polymer formulation by far-infrared (FIR) radiation and ultraviolet (UV)-induced polymerization, respectively. Equilibrium binding experiments were carried out with the prepared MIPs; the results showed that MIPuv possessed specific binding to atrazine compared with their MIPFIR radiation counterparts. Scatchard plot’s of both MIPs indicated that the affinities of the binding sites in MIPs are heterogeneous and can be approximated by two dissociation-constants corresponding to the high-and low-affinity binding sites. Moreover, several common pesticides including atrazine, cyromazine, metamitron, simazine, ametryn, terbutryn were tested to determine their specificity, similar imprinting factor (IF) and different selectivity index (SI) for both MIPs. Physical characterization of the polymers revealed that the different polymerization methods led to slight differences in polymer structures and performance by scanning electron microscope (SEM), Fourier transform infrared absorption (FT-IR), and mercury analyzer (MA). Finally, both MIPs were used as selective sorbents for solid phase extraction (SPE) of atrazine from lake water, followed by high performance liquid chromatography (HPLC) analysis. Compared with commercial C18 SPE sorbent (86.4%–94.8%), higher recoveries of atrazine in spiked lake water were obtained in the range of 90.1%–97.1% and 94.4%–101.9%, for both MIPs, respectively. PMID:24398982

  2. Quartz crystal microbalance for the detection of carbaryl using molecularly imprinted polymers as recognition element.

    PubMed

    Yao, Wei; Gao, Zhixian; Cheng, Yiyong

    2009-10-01

    A new piezoelectric quartz crystal sensor using molecularly imprinted polymers (MIPs) as recognition element has been prepared for the fast detection of carbaryl. The MIPs were prepared by precipitation polymerization in ACN, and then the polymer particles were fixed on the surface of the electrode. Computer simulation technology was employed to investigate the interaction between carbaryl and methacrylic acid (MAA) for elucidating the recognition mechanism. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to evaluate the obtained imprinted polymer particles and the MIP sensitive film coated on the electrode. The sensor developed exhibits a liner relationship between the frequency shift and carbaryl concentration in the range of 10-1000 ng/mL (y = 0.139 x + 2.99, r = 0.9981), and the detection limit was 12.5 ng/mL (S/N = 3). Furthermore, the influencing factors were investigated, and the experiments indicated that the obtained sensor has high sensitivity, excellent selectivity, good reproducibility, and reusable property.

  3. Selective extraction of nitroaromatic explosives by using molecularly imprinted silica sorbents.

    PubMed

    Lordel, Sonia; Chapuis-Hugon, Florence; Eudes, Véronique; Pichon, Valérie

    2011-01-01

    Two molecularly imprinted silicas (MISs) were synthesized and used as selective sorbents for the extraction of nitroaromatic explosives in post-blast samples. The synthesis of the MISs was carried out with phenyltrimethoxysilane as monomer, 2,4-dinitrotoluene (2,4-DNT) as template and triethoxysilane as cross-linker by a sol-gel approach in two molar ratios: 1/4/20 and 1/4/30 (template/monomer/cross-linker). Non-imprinted silica sorbents were also prepared following the same procedures without introducing the template. An optimized procedure dedicated to the selective treatment of aqueous samples was developed for both MISs for the simultaneous extraction of the template and other nitroaromatic compounds commonly used as explosives. The capacity of the MISs was measured by the extraction of increasing amounts of 2,4-DNT in pure water and is higher than 3.2 mg/g of sorbent for each MIS. For the first time, four nitroaromatic compounds were selectively extracted and determined simultaneously with extraction recoveries higher than 79%. The potential of these sorbents was then highlighted by their use for the clean-up of post-blast samples (motor oil, post-mortem blood, calcined fragments, etc.). The results were compared to those obtained using a conventional sorbent, thus demonstrating the interest of the use of these MISs as selective sorbents.

  4. Synthesis and applications of diethylstilbestrol-based molecularly imprinted polymer-coated hollow fiber tube.

    PubMed

    Liu, Meihua; Li, Meijin; Qiu, Bin; Chen, Xi; Chen, Guonan

    2010-03-17

    A novel molecularly imprinted polymer-coated polypropylene hollow fiber tube (MIP-HFT) was photoinitiated for the copolymerization of diethylstilbestrol (DES) as a template molecule, alpha-methacrylic acid as a functional monomer, and ethylene glycol dimethacrylate as a crosslinking agent. The characteristics and applications of the MIP-HFT were investigated. In order to compare its characteristics with those of a non-imprinted polymer-immersed hollow fiber tube, the selectivity of the MIP-HFT was investigated using dienestrol and hexestrol as the structural analogues of a DES template, and phenol and methylbenzene were taken as reference compounds. The MIP-HFT was employed in the HPLC analysis of spiked milk samples. The detection limits of the method were found to be in the range 2.5-3.3microgL(-1) for DES, dienestrol and hexestrol and the RSD% were in the range 6.4-8.9. The limits of quantitation were found to be in the range 8.7-9.4microgL(-1) in milk for DES, dienestrol and hexestrol, and their average recoveries were 83.7-90.6% in the spiked milk samples. The experimental results revealed that the MIP-HFT provides a good carrier for the selective adsorption of DES and its chemical structure analogs, and can be used for the preconcentration of these compounds in complicated samples. Copyright 2010 Elsevier B.V. All rights reserved.

  5. Reduced graphene oxide/molecular imprinted polymer-organic thin film transistor for amino acid detection

    NASA Astrophysics Data System (ADS)

    Halim, Nurul Farhanah AB.; Musa, Nur Hazwani; Zakaria, Zulkhairi; Von Schleusingen, Mubaraq; Ahmad, Mohd Noor; Derman, Nazree; Shakaff, Ali Yeon Md.

    2017-03-01

    This works reports the electrical performance of reduced graphene oxide (RGO)/Molecular imprinted polymer (MIP)- organic thin film transistor (OTFT) for amino-acid detection, serine. These biomimetic sensors consider MIP as man-tailored biomimetic recognition sites that play an important role in signal transduction. MIP provides recognition sites compatible with serine molecules was developed by dispersing serine with methylacrylate acid (MAA) as functional monomer and Ethylene glycol dimethylacrylate (EGDMA) as cross-linker. The imprinted polymeric were mixed with reduced graphene oxide to produced sensing layer for the sensor. RGO-MIP layer was introduced between source and drain of OTFT via spin coating as a detecting layer for serine molecules. RGO was introduced into MIP, to allow a highly conductive sensing material thus enhanced selectivity and sensitivity of the sensor. By analyzing the electrical performance of the sensors, the performances of OTFT sensor enhanced with RGO/MIP interlayer and OTFT sensor with MIP interlayer when exposed to serine analyte were obtained. The results showed that there were remarkable shifts of drain current (ID) obtained from OTFT sensor with RGO/MIP interlayer after exposed to serine analyte. Moreover, the sensitivity of OTFT sensor with RGO/MIP interlayer was nearly higher than the OTFT sensor with MIP interlayer. Hence, it proved that RGO successfully enhanced the sensing performance of OTFT sensor.

  6. Molecularly imprinted polymers for the isolation of bioactive naphthoquinones from plant extracts.

    PubMed

    Tsermentseli, Stella K; Manesiotis, Panagiotis; Assimopoulou, Andreana N; Papageorgiou, Vassilios P

    2013-11-08

    Molecularly Imprinted Polymers (MIPs) targeting shikonin, a potent antioxidant and wound healing agent, have been prepared using methacrylic acid (MAA) and 2-diethylaminoethyl methacrylate (DEAEMA) as functional monomers. An investigation of solution association between shikonin and both acidic and basic functional monomers by UV-vis titrations, suggested stronger affinity towards the basic functionality. Strong inhibition of the co-polymerisation reaction of such basic monomers was observed, but was overcome by reduction of the amount of template used during polymer synthesis. Polymer morphology was severely impacted by the template's radical scavenging behaviour as demonstrated by solid state NMR spectroscopy measurements. HPLC evaluation of the final materials in polar conditions revealed limited imprinting effects and selectivity, with the MAA polymers exhibiting marginally better performance. During application of the polymers as MI-SPE sorbents in non-polar solvents it was found that the DEAEMA based polymer was more selective towards shikonin compared to the MAA counterpart, while shikonin recoveries of up to 72% were achieved from hexane solutions of a commercial sample of shikonin, hexane extract of Alkanna tinctoria roots and a commercial pharmaceutical ointment.

  7. Quantum dots coated with molecularly imprinted polymer as fluorescence probe for detection of cyphenothrin.

    PubMed

    Ren, Xiaohui; Chen, Ligang

    2015-02-15

    A newly designed molecularly imprinted polymer (MIP) material was fabricated and successfully utilized as recognition element to develop a quantum dots (QDs) based MIP-coated composite for selective recognition of the template cyphenothrin. The MIP-coated QDs were characterized by fluorescence spectrophotometer, Fourier transform infrared spectroscopy, transmission electron microscope, dynamic light scattering and X-ray powder diffraction. The fluorescence of the coated QDs is quenched on loading the MIP with cyphenothrin, and the effect is much stronger for the MIP than for the non-imprinted polymer, which indicates the MIP could as a recognition template composite. This method can detect down to 9.0 nmol L(-1) of cyphenothrin in water, and a linear relationship has been obtained covering the concentration range of 0.1-80.0 μmol L(-1). The method has been used in the determination of cyphenothrin in water samples and gave recoveries in the range from 88.5% to 97.1% with relative standard deviations in the range of 3.1-6.2%. The present study provides a new and general strategy to fabricate inorganic-organic MIP-coated QDs with highly selective recognition ability in aqueous media and is desirable for chemical probe application.

  8. Preparation and selective adsorption of organic pollutants by an inorganic molecular imprinted polymer.

    PubMed

    Shang, Jiaobo; Song, Yanqun; Rong, Chuan; Wang, Yinghui; Wang, Liwei; Zhang, Yuanyuan; Yu, Kefu

    A novel inorganic molecular imprinted polymer (MIP) was synthesized by adding Al(3+) to the Fe/SiO2 gel with Acid Orange II (AO II) as the template. The MIP was characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy and nitrogen adsorption-desorption measurement. Compared with the non-imprinted polymer (NIP), the MIP enhanced the adsorption capacity of the target pollutants AO II. The selective adsorption capacity study indicated that the MIP adsorbed more AO II than the interferent Bisphenol A (BPA), which also has the structure of a benzene ring, thus proving the selective adsorption capacity of the MIP for template molecules AO II. In addition, the adsorption of AO II over MIP belonged to the Langmuir type and pseudo-second adsorption kinetics, and Dubinin-Radushkevich model indicates that the adsorption process of AO II over MIP and NIP are both given priority to chemical adsorption. The MIP reusability in performance was demonstrated in at least six repeated cycles.

  9. Sol-gel molecularly imprinted polymer for selective solid phase microextraction of organophosphorous pesticides.

    PubMed

    Wang, Yu-Long; Gao, Yuan-Li; Wang, Pei-Pei; Shang, Huan; Pan, Si-Yi; Li, Xiu-Juan

    2013-10-15

    A sol-gel technique was applied for the preparation of water-compatible molecularly imprinted polymer (MIP) for solid phase microextraction (SPME) using diazinon as template and polyethylene glycol as functional monomer. The MIP-coated fiber demonstrated much better selectivity to diazinon and its structural analogs in aqueous cucumber sample than in distilled water, indicating its potential in real samples. Thanks to its specific adsorption as well as rough and porous surface, the coating revealed rather larger extraction capability than the non-imprinted polymer and commercial fibers. In addition, the fiber exhibited excellent thermal (about 350°C) and chemical stability (organic and inorganic). After optimization of several parameters affecting extraction efficiency, a method based on MIP-SPME combined with gas chromatography was developed for the determination of organophosphorus pesticides (OPPs) in vegetable samples. The limits of detection for the tested OPPs were in the range of 0.017-0.77 μg kg(-1). The proposed method was applied to evaluate OPPs in spiked cucumber, green pepper, Chinese cabbage, eggplant and lettuce samples, and recoveries of 81.2-113.5% were obtained by the standard addition method with three spiking levels in each kind of vegetable.

  10. HIGHLY SELECTIVE SENSORS FOR CHEMICAL AND BIOLOGICAL WARFARE AGENTS, INSECTICIDES AND VOCS BASED ON A MOLECULAR SURFACE IMPRINTING TECHNIQUE

    EPA Science Inventory

    Abstract was given as an oral platform presentation at the