Preparation and Properties Characterization of Intelligent Molecularly Imprinted Polymer Based on Diles-Alder Reaction†

doi:10.7503/cjcu20170522

Abstract

Abstract:

Using activated epoxy group-containing silica gel as the carrier, the modification of β-cyclodextrin as functional monomer, and the indole-3-acetic acid(IAA) as template molecule, by Diels-Alder(DA) reaction with diene, a grafted furan-type diene was polymerized and crosslinked to obtain a molecularly imprinted polymer(DA-MIP). The structure of raw material, intermediates and the molecularly imprinted polymer was characterized by Fourier transform infrared spectroscopy(FTIR), cross polarization magic angle spinning ¹³C nuclear magnetic resonance spectroscopy(CP/MAS ¹³C NMR) and scanning electron microscope(SEM). The thermo-sensitivities were tested by differential scanning calorimetry(DSC) and thermal gravimetric analysis(TG), adsorption performance and adsorption properties of the products were detected by adsorption experiment. The results showed the DA-MIP shows a good heat-reactivity. DA-MIP does not show the role of identification of IAA at low temperature(60 ℃), but display specific identification of IAA at high temperature(140 ℃), and showed obvious temperature sensitivity. Its temperature control is affected by environmental stimuli. The repetitive adsorption experiment of MIP show that the recovery rate is 84%. The results show that the MIP have a good reuse performance.

Key words: DA-molecularly imprinted polymer, Temperature sensitivity and specific recognition for indole-3-acetic, Thermal performance, Adsorption property, Intelligence material

CLC Number:

O631
O647.33

TrendMD:

GUO Ming, ZHANG Xinge, ZENG Chuchu, YIN Xinxin. Preparation and Properties Characterization of Intelligent Molecularly Imprinted Polymer Based on Diles-Alder Reaction^†[J]. Chem. J. Chinese Universities, 2018, 39(3): 566.

Figures/Tables 16

Scheme 1 Synthetic routes of DA-molecularly imprinted polymer

Scheme 2 Synthetic routes of molecularly imprinted polymer

Scheme 3 Synthetic route of DA-molecularly imprinted polymer

Fig.1 FTIR spectra of silica(a), silica-KH-560(b), MIP(c) and DA-MIP(d)

Fig.2 CP/MAS 13C NMR spectra of β-CD-furan(A), modified silica(B),no elution spectroscopy(C) and DA-MIP(D)

Fig.3 SEM images of MIP(A), DA-MIP(B) and rDA-MIP(C)

Fig.4 TG curves of silica(a), silica-KH560-β-CD-furan(b), DA-MIP(c) and MIP(d)

Fig.5 FTIR spectra of DA-molecularly imprinted polymer with increasing temperatureTemperature/℃: a. 80; b. 90; c. 100; d. 110; e. 120; f. 130; g. 140; h. 150; i. 160; j. 170; k. 180.

Fig.6 DSC healing traces of DA-molecularly imprinted polymer

Table 1 Standard curve equations of IAA, IBA and 3-ICA in methanol

Substrate	Equation	R	SD	N	P
IAA	y=0.3134+3.6203x	0.9979	0.7375	5	<0.0001
IBA	y=0.0662+5.5632x	0.9988	0.4886	5	<0.0001
3-ICA	y=0.0694+6.9997x	0.9979	0.7375	5	<0.0001

Fig.7 Standard curves of IAA(a), IBA(b) and 3-ICA(c) in methanol

Fig.8 Adsorption isotherm of MIP(a), NMIP(b), DA-MIP(c) and rDA-MIP(d) on IAA

Table 2 Isothermal adsorption equation of MIP, NMIP, DA-MIP and rDA-MIP on IAA

Sample	Equation	R	SD	N	P
IAA	y=-9.3+206.7x-152.8x²	0.9931	0.4513	5	<0.0001
DA-IAA	y=8.7+35.7x-36.3x²	0.9905	0.1324	5	<0.0001
rDA-IAA	y=3.6+80.1x-65.1x²	0.9965	0.2361	5	<0.0001
NIAA	y=-2.7+122.7x-31.0x²	0.9987	0.2421	5	<0.0001

Fig.9 Adsorption of MIP, NMIP, DA-MIP and rDA-MIP on IAA(a), IBA(b) and 3-ICA(c)

Table 3 Adsorption capacity and imprinting factor of MIP, NMIP, DA-MIP and rDA-MIP on IAA , IBA and 3-ICA

Sample	α_MIP	β_MIP	α_rDA-MIP	β_rDA-MIP	α_DA-MIP	β_DA-MIP
IAA	3.44	2.45	3.19	2.19	1.58	0.58
IBA	1.17	0.17	1.04	0.04	1.01	0.07
3-ICA	1.28	1.28	0.28	1.07	0.07	0.07

Fig.10 Reusability adsorption of MIP on IAA

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