Preparation of Melamine Molecular Imprinted Polymer by Computer Aided Design†

doi:10.7503/cjcu20141077

Abstract

Abstract:

Melamine(MAM) was chosen as the template molecule and acrylamide(AM), methacrylic acid(MAA), N,N'-methylenebisacrylamide(MBA), itaconic acid(IA) were as the function monomers, the ethylene glycol dimethacrylate(EGDMA), trimethacrylate(TRIM), and divinylbenzene(DVB) were as the cross-linking agents, respectively. Long-range correction method of quantum chemistry density functional theory was used to simulate and discuss the bonding site, the number of hydrogen bonds, imprinted ratio of the stable complex, and the reaction mechanism. The optimizations of function monomers and the cross-linking agents were according to the bond energy(ΔE). The nature of the imprinting effect was also studied by the atoms in molecules(AIM) theory. The results indicate that MAM and the four monomers have interaction to form imprinted polymers via the hydrogen bonds, and the molar ratio is 1∶6. The MIPs synthesized using IA as monomer owns the lowest bond energy, and the complex configuration is the most stable. The DVB as cross-linking agent with the highest binding energy in comparison with the TRIM and EGDMA is the best one for MAM-MIPs. In addition, the MAM-MIPs were prepared by precipitation polymerization to study the adsorption capacity characteristics. The results show that the MAM-MIPs(molar ratio=1∶6) synthesized with IA as monomer and DVB as cross-linking agent have the best binding capacity. The average diameter of MAM-MIPs is 195 nm. The analysis of the Scatchard plot reveals that the binding sites of MAM-MIPs to MAM are equal class under the studied concentration range, the apparent maximum adsorption quantity(Q_max) is 20.79 mg/g, the dissociation constant(K_d) is 58.82 mg/L. The adsorption quantity of MIPs to MAM is obviously higher than that of cyromazine(CYR), cyanuric acid(CYA), and trithiocyanuric(TRI) in milk, which shows better specific absorption capacity. The studies can provide theoretical and experimental basis for screen of the functional monomer, the imprinting ratio, and cross-linking agent for the preparation of MAM-MIPs.

Key words: Melamine, Molecularly imprinted polymer, Functional monomer, Cross-linking agent, Computer simulation

CLC Number:

O641.3
O631

TrendMD:

WANG Yan, LIU Junbo, TANG Shanshan, JIN Ruifa, CHANG Haibo. Preparation of Melamine Molecular Imprinted Polymer by Computer Aided Design^†[J]. Chem. J. Chinese Universities, 2015, 36(5): 945.

Figures/Tables 13

References 26

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Species	B3LYP		PBE1PBE		LC-wPBE		WB97XD		Exp.^[15]
Species	Ⅰ	Ⅱ	Ⅰ	Ⅱ		Ⅰ	Ⅱ	Ⅰ	Ⅱ
N2—C3	0.1343	0.1343	0.1339	0.1339	0.1335	0.1335	0.1339	0.1339	0.1336
N2—C1	0.1344	0.1343	0.1339	0.1399	0.1335	0.1335	0.1339	0.1339	0.1345
N5—C1	0.1344	0.1343	0.1339	0.1399	0.1335	0.1355	0.1339	0.1339	0.1338
N5—C4	0.1344	0.1344	0.1339	0.1339	0.1335	0.1356	0.1339	0.1339	0.1345
N6—C3	0.1343	0.1343	0.1339	0.1399	0.1335	0.1355	0.1339	0.1339	0.1336
N6—C4	0.1344	0.1343	0.1339	0.1399	0.1335	0.1355	0.1339	0.1339	0.1347
N13—C3	0.1362	0.1361	0.1356	0.1355	0.1359	0.1360	0.1353	0.1354	0.1351
N10—C1	0.1361	0.1362	0.1355	0.1356	0.1359	0.1359	0.1354	0.1353	0.1336
N7—C4	0.1361	0.1361	0.1355	0.1355	0.1359	0.1360	0.1353	0.1354	0.1327

Species	B3LYP		PBE1PBE		LC-wPBE		WB97XD		Exp.^[15]
Species	Ⅰ	Ⅱ	Ⅰ	Ⅱ		Ⅰ	Ⅱ	Ⅰ	Ⅱ
N2—C3	0.1343	0.1343	0.1339	0.1339	0.1335	0.1335	0.1339	0.1339	0.1336
N2—C1	0.1344	0.1343	0.1339	0.1399	0.1335	0.1335	0.1339	0.1339	0.1345
N5—C1	0.1344	0.1343	0.1339	0.1399	0.1335	0.1355	0.1339	0.1339	0.1338
N5—C4	0.1344	0.1344	0.1339	0.1339	0.1335	0.1356	0.1339	0.1339	0.1345
N6—C3	0.1343	0.1343	0.1339	0.1399	0.1335	0.1355	0.1339	0.1339	0.1336
N6—C4	0.1344	0.1343	0.1339	0.1399	0.1335	0.1355	0.1339	0.1339	0.1347
N13—C3	0.1362	0.1361	0.1356	0.1355	0.1359	0.1360	0.1353	0.1354	0.1351
N10—C1	0.1361	0.1362	0.1355	0.1356	0.1359	0.1359	0.1354	0.1353	0.1336
N7—C4	0.1361	0.1361	0.1355	0.1355	0.1359	0.1360	0.1353	0.1354	0.1327

Species	B3LYP		PBE1PBE		LC-wPBE		WB97XD		Exp.^[15]
Species	Ⅰ	Ⅱ	Ⅰ	Ⅱ		Ⅰ	Ⅱ	Ⅰ	Ⅱ
C3—N2—C1	113.45	113.56	113.29	113.42	113.54	113.75	113.61	113.76	114.11
C1—N5—C4	113.45	113.55	113.29	113.43	113.54	113.76	113.62	113.76	114.64
C3—N6—C4	113.45	113.56	113.29	113.42	113.54	113.75	113.61	113.75	114.74
N2—C3—N6	126.56	126.32	126.70	126.34	126.46	126.30	126.58	126.28	125.92
N2—C3—N13	116.71	116.81	116.73	116.82	116.79	116.88	116.71	116.88	117.55
N6—C3—N13	116.71	116.79	116.76	116.81	116.75	116.86	116.70	116.86	116.52
N10—C1—N5	116.73	116.80	116.74	116.81	116.78	116.86	116.70	116.85	117.41
N10—C1—N2	116.71	116.89	116.73	116.81	116.76	116.86	116.72	116.91	116.87
N5—C1—N2	126.54	126.25	126.72	126.43	126.46	126.31	126.58	126.22	125.72
N7—C4—N5	116.72	116.86	116.65	116.73	116.77	116.86	116.70	116.87	118.03
N7—C4—N6	116.72	116.86	116.64	116.73	116.77	116.89	116.70	116.86	117.22
N5—C4—N6	126.55	126.24	126.70	126.43	126.46	126.31	126.59	126.25	124.76

Species	B3LYP		PBE1PBE		LC-wPBE		WB97XD		Exp.^[15]
Species	Ⅰ	Ⅱ	Ⅰ	Ⅱ		Ⅰ	Ⅱ	Ⅰ	Ⅱ
C3—N2—C1	113.45	113.56	113.29	113.42	113.54	113.75	113.61	113.76	114.11
C1—N5—C4	113.45	113.55	113.29	113.43	113.54	113.76	113.62	113.76	114.64
C3—N6—C4	113.45	113.56	113.29	113.42	113.54	113.75	113.61	113.75	114.74
N2—C3—N6	126.56	126.32	126.70	126.34	126.46	126.30	126.58	126.28	125.92
N2—C3—N13	116.71	116.81	116.73	116.82	116.79	116.88	116.71	116.88	117.55
N6—C3—N13	116.71	116.79	116.76	116.81	116.75	116.86	116.70	116.86	116.52
N10—C1—N5	116.73	116.80	116.74	116.81	116.78	116.86	116.70	116.85	117.41
N10—C1—N2	116.71	116.89	116.73	116.81	116.76	116.86	116.72	116.91	116.87
N5—C1—N2	126.54	126.25	126.72	126.43	126.46	126.31	126.58	126.22	125.72
N7—C4—N5	116.72	116.86	116.65	116.73	116.77	116.86	116.70	116.87	118.03
N7—C4—N6	116.72	116.86	116.64	116.73	116.77	116.89	116.70	116.86	117.22
N5—C4—N6	126.55	126.24	126.70	126.43	126.46	126.31	126.59	126.25	124.76

Molecular	Atom	q_i(n+1)	q_i(n-1)	q_i(n)	f(r)⁺	f(r)^-	f ²(r)
MAM	H8	0.215	0.357	0.298	-0.083	-0.059	-0.024
	H9	0.215	0.358	0.298	-0.083	-0.060	-0.023
	H11	0.238	0.357	0.299	-0.061	-0.062	-0.001
	H12	0.238	0.359	0.299	-0.061	-0.060	-0.001
	H14	0.238	0.359	0.299	-0.061	-0.060	-0.001
	H15	0.238	0.359	0.299	-0.061	-0.060	-0.001
	N2	-0.574	-0.501	-0.566	-0.008	-0.065	0.057
	N5	-0.575	-0.398	-0.567	-0.008	-0.169	0.161
	N6	-0.575	-0.501	-0.567	-0.008	-0.066	0.058
AM	H8	0.213	0.379	0.302	-0.089	-0.077	-0.012
	O10	-0.675	-0.230	-0.505	-0.170	-0.275	0.105
Molecular	Atom	q_i(n+1)	q_i(n-1)	q_i(n)	f(r)⁺	f(r)^-	f ²(r)
MAA	H11	0.236	0.418	0.343	-0.107	-0.075	-0.032
	O9	-0.665	-0.141	-0.486	-0.179	-0.345	0.166
MBA	H15	0.241	0.351	0.299	-0.058	-0.052	-0.006
	H18	0.240	0.354	0.298	-0.058	-0.056	-0.002
	O11	-0.613	-0.431	-0.532	-0.081	-0.101	0.020
	O10	-0.586	-0.448	-0.544	-0.042	-0.096	0.054
IA	H10	0.283	0.392	0.347	-0.064	-0.045	-0.019
	H13	0.267	0.399	0.342	-0.075	-0.057	-0.018
	O7	-0.512	-0.407	-0.478	-0.034	-0.071	0.037
	O8	-0.532	-0.287	-0.458	-0.074	-0.171	0.097