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.

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.

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.

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.

Preparation and Cyclic Voltammetry Characterization Of Cu-dipyridyl Imprinted Polymer

Polymer capable of specific binding to Cu-dipyridyl complex was prepared by molecular imprinting technology. The binding specificity of the polymer to the template (Cu-dipyridyl complex) was investigated by cyclic voltametric scanning using the carbon paste electrode modified by polymer particles in phosphate buffer solution. Factors that influence rebinding of the imprinted polymer were explored. The result demonstrated that the cyclic voltammetry was an efficient approach to explore interactions between template and imprinted polymers.

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.

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.

Molecularly Imprinted Polymer for Solid-Phase Extraction of Ecteinascidin 743 from Sea Squirt

Ecteinascidin 743 from sea squirt is one of the most original anti-tumoral activity compounds, as proven by the Natural Cancer Institute. Ecteinascidin 743 could be obtained with traditional liquid extraction, but it should be purified and separated from the extract. A molecularly imprinted solid-phase extraction procedure was developed for the selective separation. Ecteinascidin 743 was used as the template and the polymer was synthesized in a methanol environment. Water and n-hexane as the washing solvents can eliminate most of the interference. Good linearity and low relative standard deviations （less than 4.39%）justify its continuing development.

Fe-doped TiO_2/SiO_2 nanofibrous membranes with surface molecular imprinted modification for selective photodegradation of 4-nitrophenol

In this study, Fe-doped TiO2/SiO2 （Fe@TS） nanofibrous membranes with molecular imprinted modification, were fabricated by a combination of sol-gel process, electrospinning, calcination and liquid phase deposition techniques, The precursor sol was prepared from one-pot condensation of poly （vinylpyrrolidone）, ferric chloride hexahydrate, tetraethyl orthosilicate and titanium n-butoxide in the mixture solvents of N,N-dimethylformamide and ethyl alcohol. Fibrous membrane wasthen fabricated by electrospinning, followed by calcination to form the Fe@TS composite. The physicochemical properties of Fe@TS were characterized. Thereafter, 4-nitrophenol （4NP） was used as the template to deposit onto nanofibrous Fe@TS membranes, with a thin layer of molecular imprinted polymer in liquid phase. The photodegradation capabilities of 4NP and methyl orange wereexamined in both single and binary systems. The results demonstrated that molecular imprinted Fe@TS membranes exhibited excellent selectivity for photodegradation of 4NP.

Preparation of Thermosensitive Hollow Imprinted Microspheres via Combining Distillation Precipitation Polymerization and Thiol-ene Click Chemistry

Hollow molecular imprinted polymer microspheres were prepared by distillation precipitation polymerization with(S)-(+)-ibuprofen(S-IBF)as template molecule and acrylamide(AM)as functional monomer.Using the silicon dioxide(SiO_(2),180 nm)modified by 3-(trimethoxysilyl)propyl methacrylate(MPS)as the template micro-spheres,the molecular imprinted shells were coated on successfully(SiO_(2)@MIPs).The thermosensitive SiO_(2)@MIPs-PNIPAM core-shell microspheres were subsequently prepared by grafting the PNIPAM chains(M_(n)=1.21×10^(4)g/mol,polydispersity index=1.30),which were prepared by reversible addition-fragmentation chain transfer(RAFT)polymerization,on the surface of SiO_(2)@MIPs microspheres via the thiol-ene click chemistry.The grafting density of PNIPAM brushes on the SiO_(2)@MIPs microspheres was about 0.18 chains/nm^(2).After HF etching,the hollow imprinted microspheres were finally obtained.For thermosensitivity analysis,the phase transition temperatures of multifunctional nanoparticles were measured by DSL at 25℃and 45℃respectively,and the sizes of the microspheres changed by about 35 nm.The modified microspheres presented excellent controlled release property to S-IBF,moreover about half amount of the adsorptions passed into acetonitrile-water solution through the specific holes of imprinted shell at 25℃under vibration.

Adsorption Isotherms of Quercetin and Catechin Compounds on Quercetin-MIP

A molecular imprinted polymer（MIP） was prepared with quereetin as the template and methaerylie acid（MAA） as the functional monomer. Aeetonitrile and methanol were used as the porogen with ethylene glycol dimethaerylate （EGDMA） as the erosslinker and 2,2＇-azobis （ isobutyronitrile ） （ AIBN ） as the initiator. The experimental parameters of the equilibrium isotherms were estimated via linear and nonlinear regression analyses. The linear equadon as the functions of the adsorption concentration of the single compound in its solution and the competitive adsorption of the single compound in its mixed compounds solution was then expressed, and the adsorption equilibrium data were correlated to Langmuir and Freundlich isotherm models. The mixture compounds show competitive adsorption on the specific binding sites of quereetin-MIP. Furthermore, the competitive Langmnir isotherms were applied to the mixture compounds. The adsorption concentrations of quercetin, （＋）eatechin（＋C）, and （-）epieateehin（EC） on the quercetin molecular imprinted polymer were compared. The quercetin-imprinted polymer shows extraordinarily higher adsorption ability for quercetin than for the two eateehin compounds that were also assessed.

Novel polymer system for molecular imprinting polymer against amino acid derivatives

Molecular imprinting polymers (MIPs) against N-Cbz-L-Tyr were prepared utilizing different polymer systems and evaluated in HPLC mode. It was found that MIP utilizing cocktail functional monomers, acrylamide + 2-vinylpyridine showed better molecular recognition and better separation ability for the template molecule than those utilizing other functional monomers. MIP utilizing trimethylolpropane trimethacrylate as cross-linker showed higher load capacity and separation factor than those utilizing ethylene glycol dimethacrylate as cross-linker. Increasing the concentration of competing solvent, acetic acid weakened me ionic interaction and hydrogen bonding between the analyte and the functional monomers, 2-vinylpyridine and acrylamide, when me template enantiomer was separated by HPLC. Therefore increasing of the concentration of acetic acid leads to decreasing of capacity factor, separation factor and resolution.