Selective removal of 2,4-dichlorophenoxyacetic acid from water by molecularly-imprinted amino-functionalized silica gel sorbent

A molecularly-imprinted amino-functionalized sorbent for selective removal of 2,4-dichlorophenoxyacetic acid （2,4-D） was prepared by a surface imprinting technique in combination with a sol-gel process. The 2,4-D-imprinted amino-functionalized silica sorbent was characterized by FT-IR, nitrogen adsorption and static adsorption experiments. The selectivity of the sorbent was investigated by a batch competitive binding experiment using an aqueous 2,4-D and 2,4-dichlorophenol （2,4-DCP） mixture or using an aqueous 2,4-D and 2,4- dichlorophenylacetic acid （DPAC） mixture. The largest selectivity coefficient for 2,4-D in the presence of 2,4-DCP was found to be over 18, the largest relative selectivity coefficient between 2,4-D and 2,4-DCP over 9. The static uptake capacity and selectivity coefficient of the 2,4-D-imprinted functionalized sorbent are higher than those of the non-imprinted sorbent. The imprinted functionalized silica gel sorbent offered a fast kinetics for the extraction/stripping of 2,4-D, 73% of binding capacity （200 mg/L 2,4-D onto 20 mg of imprinted sorbent） was obtained within 5 min and the adsorbed 2,4-D can be easily stripped by the mixture solution of ethanol and 6 mol/L HC1 （V：V =1：1）. In a test of five extraction/stripping cycles, the adsorption capacity of the sorbent was all above 93% of that of the fresh sorbent. Experimental result showed the potential of molecularly-imprinted amino-functionalized sorbent for selective removal of 2,4-D.

Preparation of Molecular Imprinted Copolymer Membrane for Uracil Recognition

Uracil molecular imprinted membrane was prepared by phase inversion technique with [P(AN-co-MAA)] copolymer. SEM photograph shows that the resultant membrane has a typical ultrafiltration structure with Water Volume Flux of 3.7?0-5m3/m2穝, and uracil substrate permeation experiment shows that the resultant membrane can bind uracil into its structure, and shows a binding equilibrium.

Molecularly imprinted nanoparticles and their releasing properties, bio-distribution as drug carriers

Molecular imprinted nanoparticles(MINPs) can memorize the shape and functional group positions complementary to template, which account for the large drug loading capacity and slow drug release behavior as drug carriers. We synthesized MINPs via precipitation polymerization with vinblastine(VBL) as a model drug, and investigated the drug loading,releasing property in vitro and bio-distribution in vivo. The obtained MINPs, from 300 to 450 nm,had smooth surface and favorable dispersibility. The entrapment efficacy and drug loading capacity of VBL loaded MINPs(MINPs-VBL) were 83.25% and 8.72% respectively. In PBS(pH 7.4),MINPs-VBL showed sustained release behavior. The cumulative release percentage reached about 70% during 216 h and no burst release was observed. The releasing behavior of MINPsVBL in vitro conformed to the first-order kinetics model. MINPs-VBL and commercially available vinblastine sulfate injection(VBL injection) were injected via tail vein of SD rats respectively to investigate the bio-distribution. MINPs-VBL group showed higher concentration of VBL in tissues and serum than VBL injection group after 60 min, and the drug level in liver was the highest. MINPs-VBL exhibited liver targeting trend to some extent, which was based on the evaluation of drug targeting index(DTI) and drug selecting index(DSI).

Tetracycline selective electrode based on molecularly imprinted polymer particles

Tetracycline selective electrode using molecularly imprinted polymer particles as quasi-ionophore was constructed the first time, and its performance was carefully characterized. Due to the specific recognition of tetracycline by the particles, the selectivity coefficients for routine interferences were less than 10-4. Benefited from the absence of tetracycline in the sensitive membrane and the optimized composition of the inner filling solution, the limit of detection of the electrode was reduced to about 2.5 × 10^-8 mol/ L. It exhibited a good electrode slope 57.6 mV/decade near the theoretical Nernstian one, with a wide linear working range from 6.0 × 10^-8 to 1.0 × 10^-3 mol/L. The fabricated electrode should be used in pH 2--4, response time of which was less than 200 s when the concentration of tetracycline was higher than 1.0 × 10^-6 mol/L and no more than 30 min at the concentration of 1.0 × 10^-8 mol/L.

Monocrotophos Molecularly Imprinted Microspheres Prepared by Precipitation Polymerization in Acetonitrile

Molecularly imprinted microspheres (MIP) for monocrotophos have been prepared by precipitation polymerization in acetonitrile (ACN) 60℃,24 h,using methacrylic acid (MAA),ethylene glycol dimethacrylate (EGDMA) and 2, 2-azobisiobutyronitrile (AIBN) as functional monomer,cross-linker and initiator,respectively.The recognition mechanism was elucidated by UV-vis spectra and computer modeling.Equilibrium binding experiment was employed to investigate the rebinding properties,Scatchard analysis showed that specific binding sites formed in the imprinted microspheres,and there were two kinds of binding sites,one was high binding sites,the other was low binding sites.This microspheres can be useful affinity absorbent used for organophosphorus pesticides separation and purification in food and environmental analysis.

Separation and Enrichment of Melamine in Feed by a New Molecularly Imprinted Solid-phase Extraction Column

[ Objective] The research aimed to develop a new molecular imprinting solid-phase extraction column for the separation and enrichment of melamine in feed. [ Method] The molecular imprinting polymer of melamine was prepared by mass polymerization method. This polymer was used as filler to prepare molecular imprinting polymer solid-phase extraction（MIP-SPE） column of melamine. The solid-phase extraction conditions were optimized and melamine content in concentrated solution was determined by using HPLC. [ Result] Melamine eould be separated selectively from feed and enriehed by self-made MIP-SPE column. It could wipe off complex matrix from feed and the addition recovery rate was 95%. The contrast experiment between MIP-SPE column and NMIP-SPE （ non-imprinted polymer- solid phase extraction） column showed that the extraction efficiency of the former was obviously higher than the latter. [ Conclusion] The home-made MIP- SPE column could be used to separate and enrich melamine in feed efficiently, with a broad application prospect.

Molecular Imprinted Membrane with High Flux by Surface Photo-grafting Copolymerization

Molecular imprinted polymer membranes (MIM) combine the merits of molecular imprint and membrane technology. In this work, a very thin of imprinted polymer that can specifically and selectively absorb the basic template (adenine) was grafted on the surface of polyvinylidene fluoride membrane by photo-grafting copolymerization. Because the molecular imprinted polymer is grafted on the surface of the matrix membrane without blocking the membrane pores, the resultant MIMs have high flux as microfiltration membrane (0.26 mol·m^-2·h^-1 of template and flux for distilled water was 3.6 ml·mim^-1·cm^-2 at 0.8 MPa). Moreover, the MIMs can absorb/desorb template molecules rapidly. Usually, it only takes several minutes for MIMs to absorb more than 75% of the template (adenine) in aqueous solution. And the influences of the type and amount of the functional monomers, the amount of the cross-linker on the absorption capability are discussed to determine the optimal preparation conditions。

Development of a competitive format sorbent assay for the determination of parathion in water using molecular imprinted polymer as specific sorbent carrier

A rapid,simple,and reliable competitive molecular imprinted polymer sorbent assay（MIPSA） was developed and validated for measurement of parathion in water samples.This assay employed a molecular imprinted polymer（MIP） that was synthesized with non-covalent imprinting method as capture reagent and p-aminoparathion conjugate of horseradish peroxidase（para-HRP） as an enzyme label.The assay depended on a competitive binding reaction between the enzyme conjugate and analyte for the binding sites of the MIP.The optimized analysis conditions of 10 ng mL-1 para-HRP and 10 mg mL-1 polymer were found.The assay was acceptable to detect parathion in water samples under the optimized conditions,with a limit of detection of 50 ng mL-1.Mean analytical recoveries of added parathion in water samples ranged from 101.2%to 105%.The precision of the assay was satisfactory; relative standard deviation ranged from 4.3%to 6%.

Molecularly Imprinted Polymers with Bi-functional Monomers of Polymerizable Cyclodextrin Derivatives and 2-(Diethylamino)-ethyl Methacrylate for Recognition of Norfloxacin in Aqueous Media

A molecularly imprinted polymer was synthesized using 2-（diethylamino）ethylmethacry -late（DEM） and bismethacryloyl-β-cyclodextrin（BMA-β-CD） as bi-functional monomers and norfloxacin（NOF） as a template. The results of equilibrium binding experiments indicated that the polymer has affinity and specificity for NOF in aqueous media, and that its selective recognition ability for the template was higher than that of the imprinted polymers synthesized with a single functional monomer （BMA-β-CD or DEM）.

Preparation and Selectivity of Molecularly Imprinted Polymer Coating on the Micro Pore Membrane of Polytetrafluoroethylene

In order to obtain mechanically stable membrane for practical application, the imprinted polymer was synthesized in the pores of polyfluoromembrane, the binding and transport ability of the membrane were studied.

Molecularly Imprinted Polymer for Theophylline Retention and Molecular Recognition Properties in Capillary Electrochromatography

Molecular imprinting of theophylline in poly (methacrylic acid- ethylene dimethacrylate) as CEC stationary phases was synthesized by an in situ photo-initiated polymerization reaction. The effect of electrolyte pH on xanthine derivatives and the stability of MIP column performance were investigated. the relative standard deviation (D RS) of migration time of five consecutive runs on MIP column was in the range of 2.2%–3.1%. The reproducibility of migration time column to column of M(A) was in the range of 3.8%–4.9%. The highest column efficiency was more than 140 000 plates per meter. The MIP capillaries had showed better selective for theophylline, which comparing with the reference column. The urine sample was separated by spiked 5×10?4 mol·L?1 theophylline. Key words capillary electrochromatography - molecular imprinting polymers - theophylline CLC number O 657.8 Foundation item: Supported by the National Nature Science Foundation of China (20375028) and the Research Fund for the National High Technology Development “863” of China (2002AA2Z2004)Biography: Cai Ling-shuang (1968-), female, Associate professor, Ph. D, research direction: separation science.

Selective recognition in molecularly imprinted polymer and its chromatographic characterization for cinchonine

A molecularly imprinting polymer (MIP) was synthesized via bulk polymerization under different conditions using anti-ague drug cinchonine (CN) as template. Infrared spectra (IR) results show that the template CNand functional monomer α-methyl acrylic acid (MAA) formed complexes before polymerization and the structure of complexes was simulated by Hyperchem. The results indicate that there are hydrogen bond or ionic bond between functional monomer and template molecule in acetonitrile solution. The MIP made in cold-initiated photo-polymerization has higher separation performance than that in the therm-initiated polymerization. The separation of the isomers CN and cinchonidine (CD) can be successfully obtained when its separate factor α reaches 1.82. Scatchard analysis suggests that the MIP recognizing CN with two classes of binding sites. The partition coefficient Kd, 1 and apparent maximum number nmax, 1 of binding sites with high affinity are 131.43 μmol/L and 58. 90 μmol/g, respectively,while Kd, 2 and nmax, 2 of binding sites with low affinity are 2.32 mmol/L and 169.08 mmol/g, respectively.

RECENT ADVANCES IN THE PREPARATION OF MOLECULARLY IMPRINTED POLYMERS VIA CONTROLLED RADICAL POLYMERIZATION TECHNIQUES

Molecular imprinting technique is a simple and efficient method for the preparation of polymer materials (i.e., molecularly imprinted polymers, MIPs) with tailor-made recognition sites for certain target molecules. The resulting MIPs have proven to be versatile synthetic receptors due to their high specific recognition ability, favorable mechanical, thermal and chemical stability, and ease of preparation. Recent years have witnessed significant progress in the synthesis and applications of MIPs. This review focus on the recent developments and advances in the preparation of MIPs via various controlled radical polymerization techniques.

MOLECULAR IMPRINTED POLYMERS——Novel Polymer Adsorbents

Molecular imprinted polymers (MIPs) are novel functional polymer materials and known as specific adsorbents for the template molecules. These novel functional polymers have promised potential applications in racemic resolution, sensor, chromatography, adsorptive separation and other fields. This review exhibits the approach for preparing MIPs, the features of MIPs obtained by different routes and the characteristics of adsorptive separations with MIPs. The molecular recognition mechanism and the idea of the present possibilities and limitations of molecular imprinting polymerization are discussed as well.

Fabrication of Molecularly Imprinted Electrospun Nanofibers with Mono-amidoxime Functional Ligand for Efficient Decontamination of Toxic Organophosphates

There is an urgent imperative to discover practical and efficacious artificial catalysts for the expeditious decontamination of toxic organophosphates. Herein, we propose a novel molecularly imprinted approach utilizing electrospun fiber scaffolds. Specifically, an amidoxime-based functional polymer (PMAOX) has been synthesized, which contains amidoxime groups that can act as nucleophiles and ligands for the formation of catalytic active sites. This polymer was blended with polyacrylonitrile (PAN), a well-processable material, to prepare a nanofiber mat using electrospinning techniques. Then, the amidoxime side groups on fiber surface were further cross-linked after the molecular coordination of templates to complete the molecularly imprinting process. This approach can not only enhance the content of functional molecularly imprinted polymers without affecting structural stability, but also combines surface MI technology to fully expose and leverage the advantages of active sites. The as prepared molecularly imprinted electrospun nanofibers MIF-Zn-PMAOX/PAN-6/4 catalyzes the degradation of paraoxon with a half-life of 32 min, and MIF-Ag-PMAOX/PAN catalyzes the degradation of parathion with a half-life of 18 min. The maximum catalytic rate evidence rate enhancements nearly 3700-fold of the self-hydrolysis. Thus, the mono-amidoxime based molecularly imprinted fibers demonstrate the versatility and superiority as self-detoxifying for organophosphates.

Preparation and Electrochemical Characters of Parathion Molecule Imprinted Polymeric Sensors

A sensitive, fast and low-cost molecular imprinted polymeric sensor for quantitative determination of parathion was prepared with chitosan（CS） as function matrix and parathion（PT） as template molecule via constant potential electrochemical deposition. Sensitive response was obtained with a detection limit of 1.0× 10-7 mol/L and an excellent recognition for PT was achieved due to the good memory capacity of the sensor. The developed sensor exhibited good fabrication reproducibility and acceptable stability, which provided a new promising tool for pesticide analysis.

Enantiomeric Resolution on L-Carnitine Selective Polymers Prepared by Molecular Imprinting

L-carnitine selective polymers were prepared by molecular imprinting using methacrylic acid as the functional monomer. The acid function of the monomer is expected to form hydrogen bond and ionic interactions with the amine function of the target molecule L-carnitine. The imprinted polymers were used as stationary phases in high-performance liquid chromatography (HPLC). It was shown that L-carnitine imprinted polymer exhibited a higher affinity to its template molecule, while the non-imprinted polymer had no affinity to the compounds tested. Racemic carnitine hydrochloride was efficiently resolved on the L-carnitine imprinted polymer, and the separation factor is 1.9.

Theoretical Study on the Structures and Properties of Phenobarbital Imprinted Polymers

Recently, the investigation of novel molecularly imprinted polymers（MIPs） has attracted a lot of interest and becomes a fascinating field. The phenobarbital（PHN） was taken as an imprinted molecule and the 2-vinyl-4,6-diamino-1,3,5-triazine（VDAT） was considered as a functional monomer in this study. The geometry optimization, natural bond orbital（NBO） charge, and molecular electrostatic potential（MEP） of PHN and VDAT were studied at the M062 X level belonging to one of the hybrid density functional theories. Furthermore, we discussed the bonding conditions of PHN molecular imprinted polymers（PHN-MIPs） via the hydrogen bond length and atoms in molecules（AIM） theory. The rebinding property of PHN-MIPs was also researched. The results of MEP and NBO charge analysis were coincident. The stability property was excellent when the ratio of PHN and VDAT was 1：4. Except the classic hydrogen bonds, non-classical hydrogen bonds also existed in the imprinted polymers. By simulating the rebinding energies between the pentobarbital（PNT）, barbital（BAR）, and PHN-MIPs after the elution of PHN, the rebinding property of PHN-MIPs to PHN was excellent when PNT and BAR existed all at once. This research can provide theoretical reference for the synthesis and characterization of novel PHN-MIPs.

Nano-silica particles enhanced adsorption and recognition of lysozyme on imprinted polymers gels

Molecular imprinting technology has a great potential to be used in protein separation and purification. In this work, lysozyme imprinted polyacrylamide gel was prepared with silica particles as a sacrificial template to generate macro-porosity for fast adsorption. The adsorption equilibrium time and adsorption capacity were 9 h and 56 mg/g respectively, which was 2 h less and 2.3-fold more than polymers without the sacrificial template. In order to test molecular imprinting polymers （MIPs） ＇ selectivity, bovine serum albumin （BSA） was chosen as interferent for binary adsorption tests. In addition, the adsorption selectivity was further investigated using different molar ratios of lysozyme to BSA with fixed total concentration of proteins, as well as using various total concentra- tions of proteins with an equimolar ratio of lysozyme to BSA. It has been proven that the total con- centration of proteins should be larger than 1.5 × 10^-7 mol/mL, when the molar ratio of BSA to Lyz is 1： 1, in order to effectively separate Lyz from the binary protein mixture. The macro-porous lyso- zyme molecularly imprinted polymers have less adsorption time, larger adsorption capacity, and bet- ter imprinting effect.