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.     

Phosphonate electrochemical recognition by molecularly imprinted deposited film

In this paper, thin films of titanium oxide imprinted with O,O-dimethyl-(2,4-dichlorophenoxyacetoxyl)(3′-nitrobenyl) methinephosphonate (Phi-NO₂) were prepared via liquid phase deposition (LPD) method on a glassy carbon electrode. The imprinted molecular in the films was removed by treatment with immersion in CH₂Cl₂. X-ray diffraction (XRD) and electrochemical methods were introduced to show the evidence of the molecular imprinting phenomenon. It was also found that the recognition ability of the sensor depended on the substituents associated with tridimensional structures of the nitro-compounds. Under the optimized condition, the sensor showed better sensitivity, selectivity and reproducibility to the imprinted molecule and the linear relationship between the current and the concentration of analyte in the range of 0.1-50 μM was obtained. LPD proved to be a powerful method for imprinting titanium oxide thin sense films.     

分子印迹技术在样品前处理中的应用

分子印迹聚合物具有选择性高、稳定性好及制备简单的特点,可用于生物、医药、环境样品等复杂基体中痕量分析物的高选择性分离与富集,因此在样品前处理中的应用特别引人关注.本文介绍了分子印迹技术的基本原理,综述了分子印迹技术在样品前处理中应用的研究进展.     

Biomimetic piezoelectric quartz sensor for caffeine based on a molecularly imprinted polymer

A piezoelectric quartz sensor coated with molecularly imprinted polymer (MIP) for caffeine was developed. The MIP was prepared by co-polymerizing methacrylic acid (MAA) and ethylene glycol dimethacrylate (EDMA) in the presence of azobis(isobutyronitrile) as initiator, caffeine as template molecule, and chloroform as solvent. The MIP suspension in polyvinyl chloride/tetrahydrofuran (6:2:1 w/w/v) solution was spin coated onto the surface of the electrode of a 10 MHz AT-cut quartz crystal. The sensor exhibited a linear relationship between the frequency shift and caffeine concentration in the range of 1×10^–7 mg mL^–1 up to 1x10^–3 mg mL^–1 [correlation coefficient (r)=0.9935] in a stopped flow measurement mode. It has a sensitivity of about 24 Hz/ln(concentration, mg mL^–1). A steady-state response was achieved in less than 10 min. The performance characteristic of the sensor shows a promising and inexpensive alternative method of detecting caffeine. Surface studies were carried out for the reagent phase of the sensor using SEM, AFM, and XPS analysis in order to elucidate the imprinting of the caffeine molecule. The SEM micrograph, AFM image, and XPS spectra confirmed the removal of caffeine by Soxhlet extraction in the imprinting process and the rebinding of caffeine to the MIP sensing layer during measurement.     

Optical sensor materials for the detection of amines in organic solvents

A new optical polymer-based sensor was developed, which is able to recognize amines in organic solvents with high sensitivity. Thin polymer membranes were prepared and investigated, which contain a chromogenic functional dye (reactand) that shows a significant colour change during a reversible chemical reaction with the analyte. For that purpose the azo dye 4-trifluoroacetyl-4′-[N-(methacryloxyethyl)-N-(ethyl)amino]-azobenzene (CR-465) was synthesized, which contains a trifluoroacetyl moiety (receptor for interaction with amines) and in addition, a polymerizable methacrylate group. The methacrylate group links the dye covalently to the polymer matrix and the receptor recognizes the analyte via covalent binding. For immobilisation of the dye cross-linked methacrylate polymers with different composition were used. The highly cross-linked polymer network was stable against most organic solvents and exhibited enhanced stability against mechanical strain compared to plasticized PVC. The sensitivity of the reaction between the analyte and the dye was tailored by the choice of the solvent in which the analysis of the sensor layer was performed, with equilibrium constants for 1-butylamine ranging from 80 to 2000 M⁻¹ in chloroform and DMSO, respectively. In toluene as the solvent, sensor layers typically exhibited equilibrium constants of 100 M⁻¹ for 1-butylamine, 1300 M⁻¹ for 1,4-diaminobutane and 20,000 M⁻¹ for tris-(2-aminoethyl)amine. We have also investigated the cross-linked sensor layers with respect to molecular imprinting and did not find any enhancement in selectivity through imprinting in the presence of different analyte molecules.     

Molecular Imprinting in Sol-Gel Materials: Recent Developments and Applications

Since its inception five decades ago, imprinted sol-gel materials went practically unnoticed, until in the 1970s the conceptual introduction of molecular imprinting in synthetic polymers triggered a new interest in this field. The recent growth in interest in organic–inorganic hybrid materials prepared by sol-gel chemistry and the development of a variety of new strategies for imprinting polymeric matrices have led to a growing activity in what became known as molecularly imprinted sol-gel materials. This paper intends to give an overview of recent progress in molecular imprinting in sol-gel matrices, the potential analytical applications of these tailor-made materials and their limitations, with the aim of drawing attention to useful information and to enhancing interest in this practically unexplored but promising field.     

Molecular imprinting in ultrathin titania gel films via surface sol-gel process

Recent progresses of molecular imprinting in metal oxide matrices were summarized. Application of the surface sol-gel process to mixtures of organic carboxylic acids and titanium alkoxide provides ultrathin layers of titania gel (10-20 nm thick), in which molecule-sized cavities are kept intact upon removal of the organic templates. The imprinted cavity reflects the structural and functional features of the template molecule, and the enantioselective imprinting of dipeptide isomers is observed. Robustness and flexibility of the ultrathin titania layer is demonstrated by the formation of interconnected titania hollow structures. Possible practical applications and unsolved problems of this technique are discussed.     

Chiral separation of 1,1'-bi-2-naphthol and its analogue on molecular imprinting monolithic columns by HPLC

Two molecular imprinting polymer (MIP) monolithic columns with (S)-(-)-1,1'-bi-2-naphthol and (R)-(+)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol as the templating molecules, respectively, have been prepared by in situ polymerization using 4-vinylpyridine and ethylene dimethacrylate as functional monomer and cross-linker, respectively. The columns with good flow-through properties were obtained by changing the molar ratio of the functional monomer and the template molecule. The effects of mobile-phase composition on separation of enantiomers were systematically investigated. The results indicate that hydrophobic interaction in aqueous solution and hydrogen-bonding interaction in ACN between the enantiomers and polymers could play important roles in the retention and resolution. The effects of chromatographic conditions, such as flow rate, column temperature, sample loading, on the enantioseparation were also studied. Further, these two MIP columns show a cross-reactivity.     

Preparation of a novel molecularly imprinted polymer using a water-soluble crosslinking agent

A molecularly imprinted polymer was prepared using a water-soluble crosslinking agent. An ionic complex was utilized as the assembly for the template molecule and the functional monomer, and water as porogenic solvent during preparation of the imprinted polymer. The results of chromatographic evaluations for the prepared polymer suggested that the polymer had much lower hydrophobicity compared with usual octadecyl group bonded silica or the usual molecular imprinted polymer prepared from ethyleneglycol dimethacrylate, and the selective recognition ability for template molecule in the completely aqueous condition.     

Adsorption isotherms of a molecular imprinted polymer prepared in the presence of a polymerisable template: Indirect evidence of the formation of template clusters in the binding site

The current opinion about molecular imprinted polymers (MIPs) is that their molecular recognition properties are due to the presence of nanocavities formed during a polymerization process developed in the presence of a template molecule. According to this principle, the shape of these nanocavities is complementary to that of the template and non-covalent interactions are established between the binding site and a single template molecule. Nevertheless, there are some experimental indications that the real molecular recognition mechanism involves clusters of template molecules being packed into the binding site. Recently, it has been proposed that template molecules covalently linked to the binding site can act as nucleation points, enhancing the formation of these molecular clusters.We have tested this hypothesis by studying the adsorption isotherms of polymers prepared by imprinting them with 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Three different polymers were considered: P0, prepared without the template, P1, whose template was represented by 2,4,5-T molecules, and P2, whose template was 1/3 constituted by the polymerisable 2-(2,4,5-trichlorophenoxyacetoxy)-ethylmethacrylate (2,4,5-TEMA) and 2/3 by 2,4,5-T. The polymers were prepared by thermoinduced polymerization of template mixtures, 4-vinylpyridine and ethylene dimethacrylate. The crushed polymers were packed into HPLC columns and frontal chromatographic runs were performed by eluting the columns with a mobile phase containing variable amounts of 2,4,5-T.The experimental adsorption isotherms were fitted by using several isotherm models, and the Freundlich-Langmuir model was found to give the best fitting in terms of F-test. All the models considered showed a significant difference between the affinity constant values measured for the polymer P1 and P2, with a higher value for the polymer P2 (for Freundlich-Langmuir model: polymer P1, k=(2.00±0.43)×10⁴ M⁻¹; polymer P2, k=(1.93±0.0535)×10⁵ M⁻¹; ratio P2/P1, 9.65±2.09). Such experimental results support the hypothesis that a polymer prepared with a limited amount of template covalently attached to the binding site shows an increased affinity for the template itself.