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Enantioselective Analysis of Naproxen Using Chiral Molecular Imprinting Polymers Based Thin-Layer Chromatography

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Enantioselective Analysis of Naproxen Using Chiral Molecular Imprinting Polymers Based Thin-Layer Chromatography http://www.e-polymers.org e-Polymers 2013, no. 017 ISSN 1618-7229 Enantioselective analysis of naproxen using chiral molecular imprinting polymers based thin-layer chromatography Fengyun Huangfu,1 Bing Wang,2* Juanjuan Shan,2 Zhiliang Zhang2 1 Textile Auxiliaries Company Ltd. of Tianjin Polytechnic University, Tianjin 300160 2 State Key Laboratory of Hollow Fiber Membrane Materials and Processes (Tianjin Polytechnic University), School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160, China; tel: 086- 022-8395-5113; fax: 086-022- 8395-5113; e-mail: [email protected]. cn (Received: 31 January, 2012; published: 30 May, 2013) Abstract: This paper describes a rational design and testing of molecularly imprinted polymers (MIPs) as chiral stationary phases of thin-layer chromatography (TLC) for enantiomeric purity of naproxen. Using D-naproxen as template, MIPs with particle size between 10~90 μm were prepared by precipitation polymerization in acetonitrile/methanol mixed solvent. The interactions between functional monomers and template were verified by UV absorption spectrometry. The morphology, particle size distribution and specific surface area of MIPs were also observed by scanning electron microscopy, particle size distribution meter and liquid nitrogen adsorption instrument, respectively. Binding capacities of MIPs had been studied by equilibrium binding assay. Preparation conditions of TLC and impact of acetic acid content on the separation of enantiomers were investigated. The results indicated that when acetic acid content was 4%, the racemates of templates were completely separated, and the chiral separation factor α was 1.58. Introduction Naproxen(Npx, Fig.1), as a non-steroidal anti-inflammatory drug, is widely used to relieve pain and inflammation. This compound exists as enatiomers, in which the efficacy of D-naproxen (D-Npx) is 28 times larger than L-naproxen (L-Npx). And L- Npx causes some unwanted side effects. So it is meaningful to separate the naproxen enantiomers. CH3 CH3 C COOH C COOH H H H3C H3C O O L Npx D Npx Fig. 1. The molecular structure of Npx enantiomers. 1 Molecular imprinting is a very useful method for the generation of polymer based on molecular recognition, which has been applied in various fields such as those of separations, sensors and catalysis [1-4]. The technique involves the polymerization of crosslinker and functional monomer in the presence of template. Then extraction of template leaves behind selective cavities which are complementary to the template in size, shape and chemical functionality. Therefore molecularly imprinted polymers (MIPs) are able to rebind the template with high affinity and specificity. As a result of its notable features, such as predictable elution order, high separation selectivity, good physical and chemical stability, etc., MIPs prepared by this technique could be used as a kind of novel chiral stationary phases in chromatographic chiral separations fields (HPLC, TLC, etc.) [5-8]. Compared with the HPLC, TLC possesses several advantages such as simplicity, rapidity, low cost and simultaneous detectability, and its combination with the molecular imprinting technique will provide simple, sensitive and rapid methods for analysis and characterization of enantiomers of optically active compounds. For this purpose, the first report on the employment of MIP as a TLC stationary phase was made by Kriz et al., involving the successful separation of enantiomers of amino acid derivatives [9], which proves the possibility of the MIPs as chiral stationary phases in TLC. And using this method, S. Roongnapa [10] and F. Rong [11] successfully completed the chiral resolution of the racemates of four kinds of adrenalines and three kinds of mandelic acids, respectively. Conventional MIPs have been synthesized by bulk polymerization. The copolymers then suffered grinding which is time-consuming. And the copolymers prepared have low capacity and poor site accessibility to template because the tedious grinding process of bulk polymerization may destroy some imprinting sites. On the contrary precipitation polymerization has overcome these shortcomings. Taking all these comments in mind, this paper describes MIPs as stationary phase of TLC to the determination of enantiomers of naproxen were synthesized using the method of precipitation polymerization. The preparation conditions of TLC and the impact of acetic acid content in the development system on the separation of enantiomers were systematically investigated. This method provides a rapid, sensitive and convenient way of analyzing and determining the enantiomers of chiral compounds. Results and discussion In this study the selected imprinted molecule (Npx) and functional monomer (AM) were expected to form a stable supramolecular complex via the non-covalent self- assembly process, which would impact electronic energy levels in the imprinted molecular. The UV-vis spectrum of Npx and AM with different ratios is described in Fig. 2. As shown in Fig. 2, with the increasing concentration of functional monomer (AM), the absorption wavelength between 220 nm and 270 nm of D-Npx showed a redshift, and the absorption intensity decreased significantly. It indicated that some strong inter-molecular forces occurred between Npx and AM. On the basis of molecular structures of Naproxen (Npx with the methoxyl and carbonyl groups) and acrylamide (AA with the amide group), it could be deduced that hydrogen bonding might play a key role between them and a template-functional monomer complex formed via the molecular self-assembly process, in which the electron cloud distribution and density 2 of big pi (π) bond on naphthalene are transformed. This is the result of changes in the ultraviolet spectrum of Npx. So we deduced that the synthesis route and recognition mechanism of the imprinted polymer were as follows (Fig. 3) 3.0 2.5 2.0 1.5 Abs 1.0 0.5 0.0 200 250 300 350 400 nm Fig. 2. UV–vis spectra of Npx samples with different molar ratios of Npx to AM. CH3 CH3 C OH C O C OH H C AA H3C O H O H2N H3C O O O NH2 GDMA / DVB CH3 C OH C O H O Adsorption H3C O O H2N H2N O NH2 Elution O NH2 Fig. 3. Synthesis route of the imprinted polymer and its recognition mechanism. The adsorption isotherms drawn from the experimental data are shown in Fig. 4. As shown in Fig. 4, the adsorption of polymers (P1, P2) adhered to the rules of monolayer adsorption of the Langmuir model [12]. From the comparison of the three binding isotherms of P1, NP and P2, with increasing initial concentration of D-Npx, the adsorption capacities of the polymers (P1, P2) to D-Npx increased. However, the combination amount of D-Npx on P1 was always greater than those on NP and P2 obviously. Also, it was saturated in a high concentration range. Thus, P1 showed a better binding ability. During the experiments, the total pore volume and specific surface area of polymer 3 P1 were measured using multi-point BET method. The values are 0.1132cm /g and 2 99.64m /g respectively, which are higher than those of polymer P2 with a total pore volume of 0.0678cm3/g and a specific surface area 55.32m2/g, and higher than those of polymer NP with a total pore volume of 0.0171 cm3/g and a specific surface area 3 0.9457 m2/g. These results suggest that MIPs are porous materials, the pore volume and specific surface area of polymer P2 are smaller than those of polymer P1, the reason is that part of the imprinted holes were destroyed during the grinding process. While for polymer NP, because of the absence of imprinted cavities, its pore volume and specific surface area are relatively much less. 70 P1 60 -1 50 g P2 mol 40 Q/ 30 20 NP 10 0 0 1 2 3 4 5 c/mmolL-1 Fig. 4. Adsorption (Q) of P1, P2 and NP to the D-Npx with different initial concentration. Fig. 5. SEM images of P1 with different magnification. 30 100 80 20 ) % ) 60 % on ( ( q 40 10 Q 20 0 0 0 20 40 60 80 100120140160180200 diameter ( mm) Fig. 6. Particle size distributions of P1. Compared synthesis process of the three kinds of polymers, we can see that many specific structure holes with fixed three-dimensional shape and position of functional groups matching to D-Npx formed during the synthetically process in presence of 4 imprinted molecule. These imprinted holes with active binding site in them caused a good ability to bind the imprinted molecules on the MIPs. Fig. 5 was the SEM of P1 particles with different magnification. It can be seen that MIP particles showed agglomerates of random irregular particles in the morphology. And as shown in Fig. 6, its particle size distribution was between the 10 ~ 90 μm, and the median particle size was about 36 μm. In this experiment, two kinds of binder were investigated for the preparation of the TLC plates. The tendency of the polymer to swell in acetonitrile and water made it difficult to manufacture the plates in these solvents unless a binder was found which was strong enough not to allow the coating forming cracks as it dried due to polymer shrinking. A small amount of ethanol was used to increase the wet ability of the particles. Plaster of Paris was found to be a suitable binder when water was used as solvent. When using methyl cellulose as the binder, the prepared TLC plates showed poor mechanical properties and emerged cracks after drying. Tab. 1. Effect of the particle size of MIPs and binder amount on the physical properties of TLC. Size distribution of Binder/MIPs Crack Mechanical TLC MIPs [µm] [w/w] formation stability Ⅰ 1:1 no good 15~38.5 Ⅱ 1:2 yes bad Ⅲ 1:1 no good 38.5~74 Ⅳ 1:2 no good Ⅴ 15~74 1:1 no good Coatings were made with three different size distributions of MIP particles (as shown in Tab.
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