Preparation of Photoirradiation Molecular Imprinting Polymer for Selective Separation of Branched Cyclodextrins.
ABSTRACT: In the present study, photoirradiation molecularly imprinted polymer (MIP) with azobenzene was used as a functional monomer for the selective separation of the branched cyclodextrins. The functional monomer 4-methacryloyloxy azobenzene (MAA) and the molecular template 6-O-?-d-maltosyl-?-cyclodextrin (G2-?-CD) were implemented for the molecular imprinting. The core-shell structure of photoirradiation MIP was visualized by the transmission electron microscopy (TEM). With Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA), we identified that G2-?-CD was imprinted into the polymer and removed from the MIP. The binding association constant (Ka) and the maximum number of the binding site (Nmax) were 1.72 × 10? M-1 and 7.93 ?mol·g-1 MIP, respectively. With alternate irradiation at 365 and 440 nm light, the prepared MIP reversibly released and rebound to the G2-?-CD, which resulted in the nearly zero amount of G2-?-CD in the solution. The HPLC results indicated that the purity of G2-?-CD could reach 90.8% after going through MIP. The main finding of our study was that the photoirradiation of MIP was an easy and effective method for the selective separation of the branched cyclodextrins.
Project description:This work describes methacrylic acid functionalized ?-cyclodextrin (MAA-?CD) as a novel functional monomer in the preparation of molecular imprinted polymer (MIP MAA-?CD) for the selective removal of 2,4-dichlorophenol (2,4-DCP). The polymer was characterized using Fourier Transform Infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) and Field Emission Scanning Electron Microscopy (FESEM) techniques. The influence of parameters such as solution pH, contact time, temperature and initial concentrations towards removal of 2,4-DCP using MIP MAA-?CD have been evaluated. The imprinted material shows fast kinetics and the optimum pH for removal of 2,4-DCP is pH 7. Compared with the corresponding non-imprinted polymer (NIP MAA-?CD), the MIP MAA-?CD exhibited higher adsorption capacity and outstanding selectivity towards 2,4-DCP. Freundlich isotherm best fitted the adsorption equilibrium data of MIP MAA-?CD and the kinetics followed a pseudo-second-order model. The calculated thermodynamic parameters showed that adsorption of 2,4-DCP was spontaneous and exothermic under the examined conditions.
Project description:A monolithic imprinted atenolol column was constructed by in situ polymerisation using a methacrylic acid monomer and a 1?:?1 (v/v) porogen of propanol: toluene with two template: monomer: crosslinker combinations, namely, MIP 1 (1?:?4?:?20) and MIP 2 (1?:?5?:?20). Physical characterisation of the monolithic columns consisted of permeability testing, Fourier transform infrared (FTIR) testing, surface area analysis (SAA), and scanning electron microscopy (SEM). The permeability value of four monolithic columns was in the good category: MIP 1 (24.01 mD), NIP 1 (56.43 mD), MIP 2 (23.03 mD), and NIP 2 (14.47 mD). The polymerisation process of these four monolithic imprinted columns was carried out perfectly, as shown by the absence of vinyl groups (1000?cm-1 and 900?cm-1) during FTIR testing. Based on SAA testing, the pores of the four polymers were classified as mesopores. The best monolithic column was MIP 1, as seen from the intercolumn and intracolumn reproducibility values and a % RSD <2.0%. The MIP 1 column was selective towards atenolol, as seen from the selectivity factor, imprinting factor (IF), and resolution (Rs) values. The IF values of MIP 1 were atenolol (204.62), metoprolol (3.36), and propranolol (1.27). The Rs value between atenolol and the analogue compounds was 7.23. The MIP 1 column can be used for the analysis of atenolol in blood serum samples with an average percentage recovery rate of 94.88?±?4.43%.
Project description:To fabricate molecularly imprinted polymer nanospheres via click reaction, five different clickable compounds were synthesized and two types of click reactions (azide-alkyne and thiol-yne) were explored. It was found that molecularly imprinted polymer nanospheres could be successfully synthesized via thiol-yne click reaction using 3,5-diethynyl-pyridine (1) as the monomer, tris(3-mercaptopropionate) (tri-thiol, 5) as the crosslinker, and hypericin as the template (MIP⁻NSHs). The click polymerization completed in merely 4 h to produce the desired MIP⁻NSHs, which were characterized by FTIR, SEM, DLS, and BET, respectively. The reaction conditions for adsorption capacity and selectivity towards hypericin were optimized, and the MIP⁻NSHs synthesized under the optimized conditions showed a high adsorption capacity (Q = 6.03 μmol•g-1) towards hypericin. The imprinting factors of MIP⁻NSHs towards hypericin, protohypericin, and emodin were 2.44, 2.88, and 2.10, respectively.
Project description:Cyclodextrins (CDs) were used in the present study for the ring-opening oligomerization (ROO) of l-lactide (LA) in order to synthesize biodegradable products with possible applications in pharmaceutical and medical fields. The practical importance of ROO reactions may reside in the possibility of synthesizing novel CD derivatives with high purity due to the dual role played by CDs, the role of the initiator through the hydroxylic groups, and the role of the catalyst by monomer inclusion in the CD cavity. The analyzed compounds were CDs modified with oligolactides obtained through ROO reactions of l-lactide in dimethylformamide. The resulting CD isomeric mixtures were investigated using classical characterization techniques such as gel permeation chromatography and nuclear magnetic resonance. Moreover, advanced mass spectrometry (MS) techniques were employed for the determination of the average number of monomer units attached to the cyclodextrin and the architecture of the derivatives (if the monomer units were attached as a single chain or as multiple chains). Thus, fragmentation studies effectuated on two different instruments (ESI Q-TOF and MALDI TOF) allowed us to correlate the size of the oligolactide chains attached to the CD with the observed fragmentation patterns.
Project description:The formation of effective and precise linkages in bottom-up or top-down processes is important for the development of self-assembled materials. Self-assembly through molecular recognition events is a powerful tool for producing functionalized materials. Photoresponsive molecular recognition systems can permit the creation of photoregulated self-assembled macroscopic objects. Here we demonstrate that macroscopic gel assembly can be highly regulated through photoisomerization of an azobenzene moiety that interacts differently with two host molecules. A photoregulated gel assembly system is developed using polyacrylamide-based hydrogels functionalized with azobenzene (guest) or cyclodextrin (host) moieties. Reversible adhesion and dissociation of the host gel from the guest gel may be controlled by photoirradiation. The differential affinities of ?-cyclodextrin or ?-cyclodextrin for the trans-azobenzene and cis-azobenzene are employed in the construction of a photoswitchable gel assembly system.
Project description:A novel electrochemical sensor based on electropolymerized ion imprinted poly (o-phenylenediamine) PoPD/electrochemical reduced graphene (ERGO) composite on glass carbon electrode (GCE) was fabricated for selective and sensitive determination of trace Cd(II) in water. ERGO was first deposited on the surface of GCE by electrochemical cyclic voltammetry (CV) scanning to enhance the electron transport activity at electrode surface. The ion imprinted polymer (IIP) of imprinted PoPD was then in situ electropolymerized on ERGO via CV scanning with oPD as functional monomer and Cd(II) ions as template, following removal of the template using electrochemical peroxidation method. The obtained imprinted PoPD/RERGO composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray energy spectroscopy (EDS) for the observation of their morphologies and components. The electrochemical behavior of the imprinted PoPD/ERGO/GCE was performed by CV and SWASV. The fabricated sensor of the imprinted PoPD/ERGO/GCE showed a good selectivity toward target Cd(II) ions in the presence of other heavy metal ions. Under the optimized experimental conditions, the sensor exhibited a good linear relationship between SWASV stripping peak values and Cd(II) concentration in the range of 1 to 50 ng/mL, with the limit of detection as 0.13 ng/mL (S/N = 3). The proposed electrochemical sensor of imprinted PoPD/ERGO/GCE was successfully applied for trace Cd(II) determination in real water samples.
Project description:Molecularly imprinted polymer (MIP) and magnetic molecularly imprinted polymer (mag-MIP) for solid extraction and pre-concentration of quercetin have been successfully prepared by thermal polymerization method using quercetin (Q) as a template, acrylamide (AA) as a functional monomer, and ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent. The MIP and mag-MIP were successfully applied in analysis of quercetin by mass spectrometry (MS) methods. To perform ambient plasma ionization experiments, a setup consisting of the heated crucible, a flowing atmospheric-pressure afterglow (FAPA) plasma ion source, and amaZon SL ion trap (Bruker, Bremen, Germany) was used. The heated crucible with programmable temperature allowed desorption of the analytes from MIPs structure which resulted in their direct introduction into the ion stream. The results of Q-MIP/Q-mag-MIP and FAPA-MS measurements were compared with those of the analysis of quercetin by the ESI-MS method without extractions and pre-concentration of analytes on polymers. Limits of detection (LOD) for quercetin solutions in both positive and negative ESI-MS were established at 10-8 M and 10-7 M, respectively. The linearity (R2 = 0.9999) of the proposed analytical procedure for quercetin determination in positive ions was provided in the range between 10-4 M and 10-7 M. Moreover, the same parameters were established for FAPA-MS in positive ions, reaching LOD at 0.005 mg/gMIP and the linearity of the method in the range of 0.015-0.075 mg/gMIP with the correlation coefficient value R2 = 0.9850.
Project description:To develop efficient materials with enhanced adsorption and selectivity for genotoxic 2-aminopyridine in water, based on magnetic chitosan (CTs) and ?-cyclodextrin (?-CD), the magnetic molecularly imprinted polymers (MMIPs) of Fe?O?-CTs@MIP and Fe?O?-MAH-?-CD@MIP were synthesized by a molecular imprinting technique using 2-aminopyridine as a template. The selective adsorption experiments for 2-aminopyridine were performed by four analogues including pyridine, aniline, 2-amino-5-chloropyridine and phenylenediamine. Results showed the target 2-aminopyridine could be selectively adsorbed and quickly separated by the synthesized MMIPs in the presence of the above structural analogues. The coexisting ions including Na?, K?, Mg2+, Ca2+, Cl- and SO?2- showed little effect on the adsorption of 2-aminopyridine. The maximum adsorption capacity of 2-aminopyridine on Fe?O?-CTs@MIP and Fe?O?-MAH-?-CD@MIP was 39.2 mg·g-1 and 46.5 mg·g-1, respectively, which is much higher than values in previous reports. The comparison result with commercial activated carbon showed the obtained MMIPs had higher adsorption ability and selectivity for 2-aminopyridine. In addition, the synthesized MMIPs exhibited excellent performance of regeneration, which was used at least five times with little adsorption capacity loss. Therefore, the synthesized MMIPs are potential effective materials in applications for selective removal and analysis of the genotoxic compound aminopyridine from environmental water.
Project description:Novel, molecularly imprinted polymers (MIPs) were developed for the highly sensitive and selective recognition of the stress marker cortisol. Oriented, homogeneous cavities with two binding sites for cortisol were fabricated by surface-initiated atom transfer radical polymerization, using a cortisol motif template molecule (TM1) which consists of a polymerizable moiety attached at the 3-carbonyl group of cortisol via an oxime linkage and an adamantane carboxylate moiety coupled with the 21-hydroxyl group. TM1 was orientationally immobilized on a ?-cyclodextrin (?-CD)-grafted gold-coated sensor chip by inclusion of the adamantane moiety of TM1, followed by copolymerization of a hydrophilic comonomer, 2-methacryloyloxyethyl phosphorylcholine, with or without a cross-linker, N,N'-methylenebisacrylamide. Subsequent cleavage of the oxime linkage leaves the imprinted cavities that contain dual binding sites-namely, the aminooxy group and ?-CD-capable of oxime formation and hydrophobic interaction, respectively. As an application, MIP-based picomolar level detection of cortisol was demonstrated by a competitive binding assay using a fluorescent competitor. Cross-linking of the MIP imparts rigidity to the binding cavities, and improves the selectivity and sensitivity significantly, reducing the limit of detection to 4.8?pM. In addition, detection of cortisol in saliva samples was demonstrated as a feasibility study.
Project description:Molecularly imprinted polymers (MIPs) mimic the binding sites of antibodies by substituting the amino acid-scaffold of proteins by synthetic polymers. In this work, the first MIP for the recognition of the diagnostically relevant enzyme butyrylcholinesterase (BuChE) is presented. The MIP was prepared using electropolymerization of the functional monomer o-phenylenediamine and was deposited as a thin film on a glassy carbon electrode by oxidative potentiodynamic polymerization. Rebinding and removal of the template were detected by cyclic voltammetry using ferricyanide as a redox marker. Furthermore, the enzymatic activity of BuChE rebound to the MIP was measured via the anodic oxidation of thiocholine, the reaction product of butyrylthiocholine. The response was linear between 50 pM and 2 nM concentrations of BuChE with a detection limit of 14.7 pM. In addition to the high sensitivity for BuChE, the sensor responded towards pseudo-irreversible inhibitors in the lower mM range.