Molecular imprinted polymer of methacrylic acid functionalised ?-cyclodextrin for selective removal of 2,4-dichlorophenol.
ABSTRACT: 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: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:Surface imprinting is an effective and simple method to fabricate and retain imprinted templates and recognizable nanocavities after template extraction. The imprinted effects can be controlled depending on the surface morphological changes. In general, a planar film has a limited area compared to a structured film with relatively higher surface-to-volume (S/V) ratio (A/A0), leading to the conventional sensing response upon the functionality of monomers in a fixed chemical composition. To increase the limited sensing properties and develop simple fabrication of porous arrays on a large area, we herein demonstrate the 2,4-dichlorophenoxyacetic acid (2,4-D, herbicide)-imprinted porous thin film lithographically patterned using photopolymerization and silica colloidal array as a master mold, derived by a unidirectional rubbing method. The resonant frequency changes with respect to the adsorption of 2,4-D molecules on a template-extracted porous poly(MAA-co-EGDMA) (MIP) film in a 10-1 mM aqueous solution of 2,4-D for 1 h, and when compared to the planar MIP film, the higher sensing response (?f = -283 ± 7 Hz ? 1543 ± 38 ng/cm2) appears on the porous MIP film due to the specific recognition toward the more accessible templated cavities of the structured porous array, indicating an imprinting effect (If) value of 3.5. In addition, a higher selectivity for 2,4-D was also displayed on the porous MIP film compared to other herbicides. From these results, it was revealed that these improved sensing properties can be determined from the effects of various parameters (template functionality, film structuring, hydroxyl groups of silica colloids, etc.).
Project description:In the recent decade, deep eutectic solvents (DESs) have occupied a strategic place in green chemistry research. This paper discusses the application of DESs as functionalization agents for multi-walled carbon nanotubes (CNTs) to produce novel adsorbents for the removal of 2,4-dichlorophenol (2,4-DCP) from aqueous solution. Also, it focuses on the application of the feedforward backpropagation neural network (FBPNN) technique to predict the adsorption capacity of DES-functionalized CNTs. The optimum adsorption conditions that are required for the maximum removal of 2,4-DCP were determined by studying the impact of the operational parameters (i.e., the solution pH, adsorbent dosage, and contact time) on the adsorption capacity of the produced adsorbents. Two kinetic models were applied to describe the adsorption rate and mechanism. Based on the correlation coefficient (R2) value, the adsorption kinetic data were well defined by the pseudo second-order model. The precision and efficiency of the FBPNN model was approved by calculating four statistical indicators, with the smallest value of the mean square error being 5.01 × 10-5. Moreover, further accuracy checking was implemented through the sensitivity study of the experimental parameters. The competence of the model for prediction of 2,4-DCP removal was confirmed with an R2 of 0.99.
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: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.
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: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).
Project description:Herein, a novel method for molecularly imprinted polymers (MIPs) using methacrylic acid functionalized beta-cyclodextrin (MAA-?-CD) monomer is presented, which was designed as a potential water-compatible composite for the controlled release of atropine (ATP). The molecularly imprinted microspheres with pH-sensitive characteristics were fabricated using thermally-initiated precipitation polymerization, employing ATP as a template molecule. The effects of different compounds and concentrations of cross-linking agents were systematically investigated. Uniform microspheres were obtained when the ratio between ATP, MAA-?-CD, and trimethylolpropane trimethacrylate (TRIM) was 1:4:20 (mol/mol/mol) in polymerization system. The ATP loading equilibrium data was best suited to the Freundlich and Langmuir isotherm models. The in vitro drug release study was assessed under simulated oral administration conditions (pH 1.5 and 7.4). The potential usefulness of MIPs as drug delivery devices are much better than non-molecularly imprinted polymers (NIPs). The study shows that the prepared polymers are a pH stimuli-responsive system, which controlled the release of ATP, indicating the potential applications in the field of drug delivery.
Project description:In this study, thermo-responsive molecularly imprinted hydrogels (T-MIHs) were developed as an effective potential adsorbent for selectively adsorption phenol from wastewater. During the process, N-isopropyl acrylamide (NIPAm) was used as thermal responsive monomer. The obtained materials were characterized in detail by fourier transform infrared (FT-IR) spectrometer, scanning electron microscope (SEM), and thermo gravimetric analysis (TGA). A series of static adsorption studies were performed to investigate the kinetics, specific adsorption equilibrium, and selective recognition ability of phenol. Reversible adsorption and release of phenol were realized by changing temperatures. Three type of phenols, namely 3-chlorophenols (3-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) were selected as model analytes to evaluate the selective recognition performance of T-MIHs. The T-MIHs have good selectivity, temperature response, and reusability, making them ideal in applying in the controlled separation and release of phenol pollutants.
Project description:Molecularly imprinted polymers (MIPs) have proven to be particularly effective chemical probes for the molecular recognition of proteins, DNA, and viruses. Here, we started from a filamentous bacteriophage to synthesize a multi-functionalized MIP for detecting the acidic pharmaceutic clofibric acid (CA) as a chemical pollutant. Adsorption and quartz crystal microbalance with dissipation monitoring experiments showed that the phage-functionalized MIP had a good binding affinity for CA, compared with the non-imprinted polymer and MIP. In addition, the reusability of the phage-functionalized MIP was demonstrated for at least five repeated cycles, without significant loss in the binding activity. The results indicate that the exposed amino acids of the phage, together with the polymer matrix, create functional binding cavities that provide higher affinity to acidic pharmaceutical compounds.