Preparation of Quercetin Imprinted Polymer by Living Radical Polymerization and Its Application in the Composition Analysis of Zukamu Granules for Uighur Medicine†

doi:10.7503/cjcu20150357

Abstract

Abstract:

Quercetin imprinted polymer was synthesized by a reversible addition-fragmentation chain transfer(RAFT) polymerization method, combining molecular imprinting with living radical polymerization techniques, usingthe dibenzyltrithiocarbonate(DBTTC) as reversible RAFT reagent, quercetin as the imprinted compound, and the methacrylic acid(MAA), acrylamide(AM), acrylic acid(AA), 4-vinylpyridine(4-VP) and 2-vinylpyridine(2-VP) as functional monomers, ethyleneglycoldim ethacrylate(EDMA) as cross-linker and 2,2-azob isisobuty ronitrile(AIBN) as initiator.The preparation of molecular imprinted polymers(MIPs) were conducted under different experimental conditions, and the structures of the MIPs were characterized by nitrogen adsorption and scanning electron microscopy, respectively. The identify ability and separation efficiency of MIPs for quercetin were evaluated by high performance liquid chromatography(HPLC). The relationship among the polymerization conditions, structure of polymer and separation efficiency was studied, and the synthetic method and characteristics of MIPs prepared by living radical polymerization were also explored. The quercetin was separated and enriched in Zukamu Granules for Uighur medicine, using synthesized MIPs as stationary phase. The results showed that the MIPs synthesized by living radical polymerization method exhibited a better morphology, and a good adsorption efficiency for the target molecule.

Key words: Living radical polymerization, Molecular imprinted polymer, Quercetin, Zukamu granules for Uighur medicine, High performance liquid chromatography

CLC Number:

O657

TrendMD:

TURSON Mamat, DAWUT Gulbahar, EMIN Risalat, CHU Ganghui, JELIL Mahmutjan, TURHON Muhetar. Preparation of Quercetin Imprinted Polymer by Living Radical Polymerization and Its Application in the Composition Analysis of Zukamu Granules for Uighur Medicine^†[J]. Chem. J. Chinese Universities, 2015, 36(12): 2402.

Figures/Tables 11

Scheme 1 Synthesis of DBTTC

Table 1 Lengths of strong hydrogen bonds in the complex of quercetin and MAA polymer

Bond	Bond length/nm	Bond type	Bond	Bond length/nm	Bond type
O12—H28	0.112855	Covalent bond	O51—H27	0.141021	Hydrogen bond
O13—H28	0.133938	Hydrogen bond	O21—H33	0.111729	Covalent bond
O13—H46	0.137195	Hydrogen bond	O63—H33	0.137623	Hydrogen bond
O39—H25	0.155918	Hydrogen bond	O64—H70	0.110604	Covalent bond
O11—H27	0.109424	Covalent bond	O22—H70	0.137756	Hydrogen bond

Fig.1 Optimized geometries for the most stable complexes between quercetin and MAA at molar ratio of 1:3

Fig.2 Polymerization of quercetin molecularly imprinted polymer

Fig.3 Adsorption kinetics curves of MIPs synthesized by different functional monomers for quercetin a. MMA; b. AM; c. AA; d. 4-VP.

Fig.4 SEM images of MIPs P1(A), P2(B), P3(C) and P4(D)

Fig.5 Pore size distribution of MIPs P1—P6

Table 2 Synthetic conditions and structure characterizations of the MIPs

MIP	n(monomer)/n(AIBN)/n(DBTTC)	Specific surface area/(m²·g^-1)	Characteristic dimension of the globules/μm
P1	200:1:0	17.2	2—4
P2	200:1:1	20.6	2—4
P3	200:1:2	39.4	2—3
P4	200:1:3	35.1	2—3.5
P5	200:2:2	20.9	1.5—3.5
P6	200:2:0	14.9	1.5—4
P7	300:1:2	16.3	1—4
P8	150:1:2	9.23	0.2—0.5

Fig.6 Adsorption kinetics curves of MIPs and NIPs for quercetin and kaempferol a. MIP-quercetin; b. MIP-kaempferol;c. NMIP-quercetin; d. NIP-kaempferol.

Fig.7 Effects of adsorption for different synthetic conditions of MIPs for kaempferol and quercetin

Fig.8 Chromatograms of selectivity of molecularly imprinted solid extraction (A) Zukamu solution; (B) solution after extraction; (C) eluate. Peak a: quercetin; peak b: kaempferol.

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