Computationally assisted design of molecularly imprinted polymers for the detection of estrone

doi:10.21203/rs.3.rs-1356623/v1

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Computationally assisted design of molecularly imprinted polymers for the detection of estrone

https://doi.org/10.21203/rs.3.rs-1356623/v1

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posted 21 Feb, 2022

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Computer simulations are widely used for the selection of conditions for the synthesis of molecularly imprinted polymers and can rapidly reduce the experimental cycle time and save labor and materials. Here, estrone molecularly imprinted polymers (E1-MIPs) were designed at the M062X/6-311+G(d,p) level with itaconic acid (IA) as the functional monomer. The imprinted molar ratio between E1 and IA was optimized, cross-linkers and solvents were screened, and the nature of interactions between E1 and IA was explored. The simulated results showed that pentaerythritol triacrylate was the best cross-linker and methylbenzene was the best solvent. Meanwhile, when the imprinted molar ratio between E1 and IA was 1:4, the E1-IA complex owned the largest amount of hydrogen bonds, the lowest binding energy, and the strongest stability. The bonding situation of the E1-IA complex was studied using the atoms in molecules analysis. Finally, the study of E1 selectivity using quartz crystal microbalance sensors verified the correctness of theoretical predictions. The computer simulations and experimental studies could provide theoretical guidance for the selection of imprinted molar ratios, cross-linkers, and solvents to synthesize of E1-MIPs. It also could provide important references and directions for the accurate and rapid detection of E1 in water bodies.

estrone

molecularly imprinted polymers

detection

computational design

Table 1 The structure parameters of E1 using different methods with different basis sets 6-311+G(d,p) (Ⅰ) and 6-31G(d,p) (Ⅱ)

Species	B3LYP		CAM-B3LYP		LC-WPBE		M062X		PBEPBE		ωB97XD		Exp.
Species	Ⅰ	Ⅱ	Ⅰ	Ⅱ	Ⅰ	Ⅱ	Ⅰ	Ⅱ	Ⅰ	Ⅱ	Ⅰ	Ⅱ
						R (nm)
C9-O19	0.1207	0.1212	0.1203	0.1207	0.1202	0.1207	0.1201	0.1206	0.1217	0.1222	0.1203	0.1208	0.1200
C8-C9	0.1539	0.1542	0.1530	0.1534	0.1525	0.1529	0.1535	0.1537	0.1541	0.1546	0.1533	0.1536	0.1541
C7-C8	0.1546	0.1547	0.1540	0.1541	0.1534	0.1536	0.1542	0.1543	0.1546	0.1547	0.1540	0.1542	0.1620
C5-C10	0.1552	0.1552	0.1543	0.1544	0.1536	0.1537	0.1544	0.1543	0.1552	0.1553	0.1545	0.1546	0.1550
C6-C7	0.1539	0.1543	0.1534	0.1536	0.1529	0.1531	0.1536	0.1536	0.1542	0.1544	0.1534	0.1536	0.1488
C12-O20	0.1371	0.1368	0.1365	0.1362	0.1361	0.1359	0.1363	0.1361	0.1375	0.1372	0.1362	0.1360	0.1388
C12-C11	0.1393	0.1397	0.1388	0.1391	0.1386	0.1390	0.1391	0.1394	0.1400	0.1404	0.1390	0.1393	0.1426
C14-C13	0.1400	0.1401	0.1395	0.1395	0.1392	0.1394	0.1397	0.1397	0.1413	0.1407	0.1396	0.1397	0.1426
						Φ/°
C5-C6-C7	104.33	104.33	104.31	104.32	104.28	104.32	104.36	104.38	104.31	104.32	104.43	104.44	104.09
C7-C8-C9	105.99	105.87	105.74	105.77	105.86	105.78	105.75	105.67	106.12	105.99	105.90	105.82	101.53
C11-C12-C13	119.45	119.33	119.49	119.38	119.42	119.30	119.52	119.42	119.39	119.25	119.42	119.32	122.32
C14-C13-C12	121.32	121.36	121.26	121.30	121.19	121.28	121.20	121.23	121.38	121.42	121.27	121.29	118.93
C2-C1-C11	122.53	122.53	122.49	122.49	122.32	122.54	122.39	122.39	122.58	122.58	122.47	122.47	124.16
C5-C4-C3	110.95	110.95	110.75	110.77	110.52	110.60	110.42	110.44	110.81	110.83	110.56	110.59	109.38
C5-C6-C17	112.34	112.32	112.24	112.22	112.09	112.09	111.95	111.94	112.25	112.24	112.14	112.11	111.34

Table 2 Relevant parameters of the complexes formed from E1 and IA with different imprinted ratios

Imprinted ratios between E1 and IA	Actions sites	Bond length (nm)	Amount of hydrogen bonds	△E₁ (kJ/mol)
1:1	O49—H50---O20	0.1838	2	-31.73
1:1	C11—H33---O48	0.2396	2	-31.73
1:2	C10—H32---O48	0.2422	5	-76.24
	C4—H39---O48	0.2539
	O49—H50---O19	0.1761
	C11—H33---O70	0.2393
	O71—H72---O20	0.1848
1:3	C10—H32---O48	0.2421	7	-114.52
	C4—H39---O48	0.2551
	O49—H50---O19	0.1802
	C11—H33---O70	0.2355
	O71—H72---O20	0.1858
	C8—H21---O78	0.2319
	O79—H80---O19	0.1796
1:4	C10—H32---O48	0.2455	8	-141.55
	C4—H39---O48	0.2552
	O49—H50---O19	0.1801
	C8—H21---O78	0.2312
	O79—H80---O19	0.1792
	O20—H42---O63	0.1927
	O64—H65---O20	0.1880
	C7—H28---O93	0.2563

Table 3 ΔE₃ values of different solvents and corresponding hydrogen bond length

Solvent	Hydrogen bond length (nm)	ΔE₃ (kJ/mol)
Solvent	C11—H33┅O48	ΔE₃ (kJ/mol)
H₂O	0.2447	-59.37
ACN	0.2447	-57.82
MT	0.2447	-54.92
THF	0.2435	-48.02
TL	0.2412	-28.33

Table 4 Solubility of the reaction components and adsorption capacity of E1-MIPs in different solvents

Solvent	Solubility of reaction components	Adsorption capacity of MIPs Q/(mg/L)
H₂O	Insoluble	—
ACN	Easily soluble	2.02
MT	Easily soluble	2.58
THF	Slightly soluble	—
TL	Insoluble	—

Table 5 The hydrogen bond lengths, ρ(r)_bcp, ▽²ρ(r)_bcp, and E_H values of complex formed from E1 and IA

Molar ratios	Actions sites	Hydrogen bond length (nm)	ρ(r)_bcp (a.u.)	▽²ρ(r)_bcp (a.u.)	E_H (kJ/mol)
1:1	O49—H50┅O20	0.1838	0.0304	0.1229	-35.58
1:1	C11—H33┅O48	0.2396	0.0105	0.0353	-8.27

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Computationally assisted design of molecularly imprinted polymers for the detection of estrone

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