Preparation of ECB Molecularly Imprinted Film Fluorescent Sensor for Detection of Traditional Chinese Herbal Medicine†

doi:10.7503/cjcu20180814

Abstract

Abstract:

Using Ebracteolata compound B(ECB) extracted from the root of Euphorbia Fischeriana steud as template molecule, 7-diethylamine coumarin-3-allyl terminal compounds(DCAC) synthesized by condensation reaction between 7-diethylamine coumarin-3-carboxylic acid and 3-bromopropene as fluorescent monomer, acrylamide as the functional monomer, ethylene glycol dimethacrylate as the crosslinking agent, azodiisobutyronitrile as the initiator, the molecularly imprinted fluorescent film sensor with strong cyan fluorescence was achieved through the free radical polymerization, which could selectively assemble ECB. The adsorption performance of the film showed that the linear range of ECB was 1.00—50.00 μmol/L. The cyan fluorescence(489 nm) quenching response of the film was shown obviously with the increasing concentration of ECB. The sensor could be used to detect the low concentration of ECB, with a detection limit to 0.29 μmol/L. The imprinting factor was 3.58, obviously higher than the analogues(2-methoxy-4-hydroxybenzoic acid, gallic acid and 3,3'-diacetyl-4,4'-dimethoxy-2,2',6,6'-tetrahydroxydiphenylmethane). The sensor with excellent reusability has been successfully applied to detect the content of ECB in Euphorbia fischeriana Steud.

Key words: Ebracteolata compound B, Molecularly imprinted film, Coumarin, Fluorescenc sensor

CLC Number:

O658

TrendMD:

MA Yukun, WANG Haijun, GUO Mengyan. Preparation of ECB Molecularly Imprinted Film Fluorescent Sensor for Detection of Traditional Chinese Herbal Medicine^†[J]. Chem. J. Chinese Universities, 2019, 40(7): 1381.

Figures/Tables 16

Scheme 1 Synthetic routes of fluorescent monomer DCAC

Scheme 2 Structures of ECB and three other similar compoundsECB: Ebracteolata Compound B; MHBA: 2-hydroxy-6-methoxyacetopheonone; GA: 3,5-trithydroxybenzoic acid; DDTPM: 3,3’-diacetyl-4,4’-dimethoxy-2,2’,6,6’-tetrahydroxydiphenylmethane.

Fig.1 Ultrahigh performance liquid chromatography of ECB

Scheme 3 Synthesis of FL-MIF sensor and the proposed quenching mechanism on the basis of energy transfer(ET)

Fig.2 FTIR spectra of FL-MIF(a), FL-NIF(b), DCAC(c) and ECB(d)

Fig.3 SEM images of FL-MIF with different manification

Fig.4 Fluorescence emission spectra of samples a. DCAC; b. DACCA; c. FL-NIF; d. FL-MIF, before washing; e. FL-MIF, after washing.

Fig.5 Dynamic adsorption curves of FL-MIF(a) and FL-NIF(b) toward ECB

Fig.6 Static adsorption curves of FL-MIF(a) and FL-NIF(b) toward ECB

Fig.7 Fluorescence responses of FL-MIF(A) and FL-NIF(B) with the increasing concentration of ECBInsets: Stern-Volmer curves.

Fig.8 Stern-Volmer curves of FL-MIF(A) and FL-NIF(B) for analogues

Fig.9 Stern-Volmer quenching constant diagram of FL-MIF and FL-NIF for analogues

Fig.10 Fluorescence intensity contrast diagram of FL-MIF for ECB with different ratio of competitors

Fig.11 Regeneration of FL-MIF

Fig.12 Fluorescence spectra of FL-MIF with different content of ECB in sample 1cstandard/(μmol·L-1): a. 0; b. 5; c. 10; d. 15.

Table 1 Detection results of the ECB contents in Euphorbia fischeriana Steud from different habitats

No.	Source	ECB content/(μmol·g^-1)
No.	Source	FL-MIF	HPLC
1	Medicine Garden of Qiqihar Medical University	1.09	1.11
2	Jiefang Township, Yi’an County, Qiqihar	1.85	1.81
3	Dajiazi Mountain, Nianzishan District, Qiqihar	1.29	1.30
4	Green grassland, Dulbert County, Daqing	1.92	1.91
5	Chabaqi Township, Arong Banner, Hulunbuir	2.44	2.47

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