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.

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%.

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.

Molecular Imprinting Fibrous Membranes of Poly(acrylonitrile-co-acrylic acid) Prepared by Electrospinning

IntroductionOver the past few decades, molecular imprinting has been described as a technology for preparing ＂molecular doors＂ which can be matched to ＂template keys＂. It has been found to be a simple and effective approach to introduce specific recognition sites into synthetic polymers, namely, to create molecular imprinting polymers Remarkable features such as stability, ease of preparation and low cost, have made molecular imprinting polymers particularly attractive in chemical sensors, catalysis, drug delivery, and dedicated separations. Practical applications of molecular imprinting polymers require accessible sites, fast mass transfer, and quick binding. However, present techniques used to prepare molecular imprinting polymers most often result in materials exhibiting a high affinity and selectivity but a low capacity and poor site accessibility for the target molecules. It is also very difficult to remove the imprinted molecules located in these molecular imprinting polymers because the highly cross-linked structures do not allow the templates to move freely. To some extent, combining molecular imprinting technology with membrane separation and surface imprinting can overcome the shortcomings, such as mass transfer limitations and non-quantitative recovery of the template molecules seen for imprinted materials fabricated by conventional bulk methods. In that ease, it appears to us that molecular imprinting polymers with high surface area to volume ratios are particularly desirable for largescale applications. Eleetrospun nano and ultrafine fibrous membranes are the most suitable materials due to advantages such as： （1） large specific surfaces, providing relatively high imprinting sites per unit mass; （2） fine porous structures, resulting in the accessibility of imprinting sites and low diffusion resistance necessary for high efficiency; and （3） easy recoverability from practical operation or applicability for continuous usages. Therefore, in this work, we prepared a unique kind of imprinted material--molecularly imprinted fibrous membranes of poly （ acrylonitrile-co-acrylic acid） fabricated by means of an electrospinning process.

Adsorption and degradation of norfloxacin by a novel molecular imprinting magnetic Fenton-like catalyst

In this study,a novel magnetically separable adsorbent,molecular imprinting magnetic γ-Fe_2O_3/crosslinked chitosan composites(MIPs),were prepared by a microemulsion process.Adsorption and Fenton-like oxidative degradation of a model pharmaceutical pollutant norfloxacin(NOR) by using MIPs were investigated.Various characterization methods were used to study the properties of MIPs,and it is suggested that the hydroxyl groups are the main adsorption sites for NOR.MIPs present better selective adsorption for NOR than its reference antibiotic sulfadiazine.The NOR adsorption data can be well fitted by Langmuir isotherm model and pseudosecond-order kinetic model.The optimum pH range for NOR adsorption is 7-10.In addition,the MIP-catalyzed Fenton-like system(MIPs/H_2O_2) exhibits remarkably faster removal rate for NOR than the case of γ-Fe_2O_3/H_2O_2.The result indicates that MIPs will be a good functional material in decontamination of pharmaceutical wastewaters since MIPs can be magnetically recycled after the treatment.

Molecular Imprinting Technique and Its Application in Food Industry

As a novel technique, molecular imprinting technique are attracting more and more attention in recent years, due to its specific recognition function to im- printed molecules. This paper firstly introduced this technique from its history, princi- ple, classification and methods, and then reviewed the application in food industry, and presented possible future research orientations.

Molecular Imprinting of (R)-(+)-α-Methylbenzylamine for Chiral Stationary Phase

A new type of molecular imprinting stationary phase was prepared by using R- (+)-α -methylbenzy lamine as the print molecule. Experiments of high performance liquid chromatography show that the new stationary phase has high enantio-selectivity and discriminates (R, S) -(± )- α -methylbenzylamine successful ly with α value of 1. 67

Computer Simulation and Experimental Investigations of Phenobarbital Molecular Imprinting System

The interaction process between the phenobarbital（PHN） and acrylamide（AM） was studied using the M062X/6-31G（d,p） method. The PHN and AM were used as the template and functional monomer,respectively. The molecular electrostatic potential（MEP） was simulated for predicting the reactive sites. The atoms in molecules theory helped to reveal the imprinting mechanism and optimize the molar ratios for PHN and AM. The molecular imprinted polymers（MIPs） containing PHN were synthesized through the precipitation polymerization. The diameter range of the obtained MIPs was from 150 to 390 nm. According to the computational results,MIPs with the molar ratio of PHN and AM equal to 1：6 showed high selective adsorption for PHN. The apparent maximum adsorption quantity（Q_（max）） of MIPs toward PHN was 7.9 mg/g,and the Qmax of nonimprinted polymer microspheres（NIPs） was 3.2 mg/g. Herein,the studies can provide theoretical and experimental references for the controllable fabrication of MIPs.

Simultaneous Chiral Separation Using a Combinatorial Molecular Imprinting Phase

Molecular imprinting chiral stationary phase against Cbz-L-Serine (Cbz-L-Ser) and Cbz-L-Alaine (Cbz-L-Ala) were prepared utilizing acrylamide + 2-vinylpyridine as combined basic functional monomers. Cross-selectivity was used to obtain simultaneous chiral separations of Cbz-DL-Ser and Cbz-DL-Ala by connecting two columns packed with Cbz-L-Ser and Cbz-L-Ala imprinted chiral stationary phase, respectively.

Simulation and Preparation of Molecular Imprinting System with Atrazine as Template

In this work, atrazine functions as a template molecule, and trifluoromethacrylic acid （TFMAA）, methacrylic acid （MAA）, methyl methacrylate （MMA）, and acrylamide （AM） serve as functional monomers, respectively. By using density functional theory （DFT）, the computational approach was carried out to simulate the self-assembly system of template and functional monomer. The geometry optimization, action sites, binding energies, and molecular imprinting mechanism of complexes with different functional monomers in different proportions were predicted. The simulation results showed that atrazine and the functional monomers interacted through hydrogen bond. Among the 4 functional monomers, the imprinted complex formed by TFMAA and atrazine with a ratio of （1：6） has the lowest binding energy and the best imprinting effect. Then, the microspheres of molecularly imprinted polymer （MIPs） were prepared by precipitating polymerization using atrazine as the template molecule and TFMAA as the functional monomer. The microspheres were observed by scanning electron microscopy （SEM）. The results showed that atrazine MIP microspheres had average particle size of 400 nm, which was greater than the non-imprinted polymeric microspheres （NIPs）. Dynamic adsorption experiments of MIPs showed that the adsorption reaction reached balance after 200 min. Analysis of the Scatchard plot revealed that the binding sites of MIPs to atrazine were equal class under the studied concentration range. The dissociation constant （Kd） and apparent maximum adsorption quantity （Qmax） of MIPs were 3.6×10^-5 mol/L and 4.83μmol/g, respectively. The study of selective adsorption between atrazine and metribuzin showed that imprinted microspheres had high selectivity for the template molecule atrazine.

Molecular imprinting of protein by coordinate interaction

In this article, a novel strong interaction by forming complex between bovine serum albumin （BSA） and copper ion was utilized for the preparation of molecular imprinted bydrogel in aqueous solution. Results show that the inclusion of copper ion in preparation can bridge the template BSA and functional monomers together and improve the imprinting effect compared to the polymer made without copper ion added. High selectivity factor and large adsorption capacity are also observed for the obtained BSA-imprinted hydrogel.

Template-Monomer Interaction in Molecular Imprinting: Is the Strongest the Best?

Molecularly imprinted polymers (MIPs) represent a new class of materials possessing high selectivity and affinity for the target molecule. They have been utilized as sensors, catalysts, sorbents for solid-phase extraction, stationary phase for liquid chromatography, mimics of enzymes, receptors, and antibodies. In this research, molecular imprinted polymers (MIPs) for luteolin were prepared using acrylamide, 4-vinylpyridine and 1-allyl-piperazine as functional monomers and ethylene glycol dimethacrylate as cross-linker by non-covalent imprinting method. UV-visible spectra were used to evaluate the interaction strength between the template and the monomers. The composites of the polymers were calculated from elementary analysis. The porous properties of the imprinted polymers have been determined from nitrogen adsorption-desorption isotherms. The imprinting efficiency of the prepared MIPs was evaluated by selective adsorption for luteolin and its structural analogues. Although the interaction strength of monomers to the template was in the order 1-ALPP > 4-VP > AA, the binding affinity of the imprinted polymers towards luteolin was in the order MIP 2 > MIP 3 > MIP 1. Our results demonstrated that the imprinting efficiency was depending not only on the interaction strength between the template and the monomer, but also on the fidelity in transferring the complex into the polymer.

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.

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.

Solid-phase Extraction of β-Sitosterol from Oldenlandia diffusa Using Molecular Imprinting Polymer

The β-sitosterol imprinted polymer was prepared for selective extraction and analysis of β-sitosterol from Old-enlandia diffusa （0. diffusa） followed by HPLC with UV detection. The imprinted polymers show high affinity and selectivity to β-sitosterol. Using this molecularly imprinted polymer （MIP） cartridge as solid-phase extraction （SPE） material, the interferences could be quickly washed out and β-sitosterol was selectively retained and enriched. HPLC analysis method was used to evaluate the characteristics of this MIP material. At the condition of mobile phase composed of MeOH/H20/H3PO4 （99/1/0.1, V/V/V, pH=6.0） and the flow rate of 1.0 mL·min -1, a good linear relationship was demonstrated when the concentrations of β-sitosterol were in the range of 0.50--100.0 μg·mL-1. The recoveries ranged from 75.3% to 86.5% and the inter-day and intra-day relative standard deviations were less than 5%. This developed HPLC method was proved to be acceptable for extraction offl-sitosterol from O. diffusa.

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.

A Novel Molecular Imprinted Polymers-Based Lateral Flow Strip for Sensitive Detection of Thiodiglycol

Traditional detection of thiodiglycol(TDG),a metabolic marker for sulfur mustard poisoning,requires not only professional operators,but also expensive reagents and large instruments.Herein,we developed a novel molecular imprinted polymers(MIPs)-based lateral flow assay(LFA)strategy for the quick,sensitive,and selective detection of TDG.Gold nanoparticles(Au NPs),MIPs,and metallothioneins(MTs)were respectively loaded on the conjugate pad,test line(T line)and control line(C line).After adding TDG,Au NPs on the conjugate pad reacted with TDG through the Au-S bond first.Then,under the action of capillary force,the conjugates of TDG and Au NPs were trapped by the MIPs as they traveled to the T line,and the residual Au NPs bound with the MTs on the C line,exhibiting two obvious red bands on T line and C line,respectively.In contrast,a single red band could be observed on C line without TDG.This method exhibited a wide linear range from 10.0 pg/m L to 10,000.0 ng/m L and its limit of detection(LOD)was as low as 0.41 pg/m L.This method was successfully utilized to detect TDG in human urine,presenting significant potential in the point-of-care testing of TDG in clinical samples of the sulfur mustard poisoning patients.

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.