巴比妥印迹聚合物的理论设计与实验性能评价

doi:10.7503/cjcu20140393

摘要/Abstract

摘要：

借助于Gaussian 09程序, 运用杂化密度泛函M062X方法, 以巴比妥(BAR)为印迹分子, 分别以甲基丙烯酸(MAA)、丙烯酰胺(AM)、 4-乙烯基吡啶(4-Vpy)及N,N'-亚甲基双丙烯酰胺(MBAD)为功能单体, 模拟计算了BAR与不同功能单体间的相互作用, 用氢键与结合能(ΔE)优化最佳功能单体. 计算结果表明, MAA与印迹分子氢键数目最多, 键长最短, ΔE最小, 作用力最强, 且最佳反应摩尔比为1∶6. 采用沉淀聚合法合成BAR与MAA的分子印迹聚合物(MIPs)纳米微球, 并对MIPs进行表征. 结果表明, 与AM, 4-Vpy及MBAD相比, MAA与BAR形成的复合物稳定性与选择吸附性更高; 乙腈致孔剂中合成的MIPs微球平均粒径为190 nm, 分散性良好. Scatchard分析表明, 在所研究的浓度范围内MIPs对BAR的结合位点是等价的, 其离解平衡常数K_d与最大表观吸附量Q_max分别为63.3 mg/L和17.5 mg/g; 热力学研究表明, BAR-MIPs对BAR的吸附为放热过程; BAR-MIPs对BAR的吸附量明显高于其对1,3-二甲基巴比妥酸(DMBA)、 2-硫代巴比妥酸(TMB)和戊巴比妥钠(PBS)的吸附量, 表现出较强的特异性吸附能力.

关键词: 巴比妥, 功能单体, 分子印迹聚合物, 模拟, 选择性吸附

Abstract:

On the basis of the density functional theory of M062X, we performed the interaction processes between the barbital(BAR) and different functional monomers by Gaussian 09 software. The functional monomers are methacrylic acid(MAA), acrylamide(AM), 4-vinylpyridine(4-Vpy), and N,N'-methylenebisa-crylamide(MBAD), respectively. The excellent functional monomer was optimized according to the hydrogen bond and binding energies(ΔE). The calculation results indicated that the number of hydrogen bonds was the largest, the bond length was the shortest, the ΔE was the lowest, and the interaction was the strongest between the MAA and the template molecule when the molar ratio of reaction for BAR-MAA was 1∶6. The molecular imprinted polymer microspheres(MIPs) composed of the BAR and MAA was synthesized by precipitation polymerization. The results showed that the stability and selective adsorption for MAA and BAR were the highest compared with the AM, 4-Vpy and MBAD. The average diameters of BAR-MIPs synthesized in acetonitrile was 190 nm. Analysis of the Scatchard plot revealed that the binding sites of BAR-MIPs to BAR were equal class under the studied concentration range, the dissociation constant(K_d) and apparent maximum adsorption quantity(Q_max) of BAR-MIPs were 63.3 mg/L and 17.5 mg/g, respectively. The thermodynamic study indicated that the adsorption of BAR-MIPs to BAR was an exothermic process, and the adsorption effect was better under the 293 K. The study of selective adsorption showed that BAR-MIPs had higher selectivity for BAR than that for 1,3-dimethyl barbituric acid(DMBA), 2-thiobarbituric acid(TMB), and pelltobarbitalum natricum(PBS). The studies can provide theoretical and experimental bases for the BAR molecular imprinted system, such as the selection of functional monomers, the optimization of reaction ratios, and the prediction of adsorption performance.

Key words: Barbital, Functional monomer, Molecular imprinting polymer, Simulation, Selective adsorption

中图分类号:

O641.3
O631

TrendMD:

苏婷婷, 刘俊渤, 唐珊珊, 靳瑞发. 巴比妥印迹聚合物的理论设计与实验性能评价. 高等学校化学学报, 2014, 35(10): 2146.

SU Tingting, LIU Junbo, TANG Shanshan, JIN Ruifa. Theoretical Design and Experimental Performance Research on Barbital Imprinting Polymer^†. Chem. J. Chinese Universities, 2014, 35(10): 2146.

图/表 14

参考文献 23

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Species	6-31G(d,p)	6-31++G(d,p)	6-311G(d)	Expt.^[18]
C1—N2/nm	0.1386	0.1385	0.1385	0.1376
N2—C3/nm	0.1385	0.1385	0.1384	0.1376
C3—C4/nm	0.1522	0.1523	0.1521	0.1514
C1—O9/nm	0.1206	0.1208	0.1199	0.1213
C3—O11/nm	0.1209	0.1211	0.1203	0.1213
N2—H8/nm	0.1013	0.1014	0.1012	0.0939
N6—H7/nm	0.1013	0.1014	0.1012	0.0939
C4—C12/nm	0.1544	0.1546	0.1544	0.1541
C12—C22/nm	0.1526	0.1527	0.1526	0.1514
C1—N2—C3/(°)	127.7	127.4	127.8	126.5
N2—C3—C4/(°)	117.4	117.7	117.4	118.3
C3—C4—C5/(°)	115.1	114.7	115.2	115.8
C4—C5—N6/(°)	117.4	117.7	117.4	118.3
C5—N6—C1/(°)	127.7	127.4	127.8	126.4
N6—C1—N2/(°)	114.4	114.7	114.3	114.6
C12—C4—C5/(°)	107.8	107.9	107.8	109.6
C4—C12—C22/(°)	114.3	113.3	113.3	114.8

Species	6-31G(d,p)	6-31++G(d,p)	6-311G(d)	Expt.^[18]
C1—N2/nm	0.1386	0.1385	0.1385	0.1376
N2—C3/nm	0.1385	0.1385	0.1384	0.1376
C3—C4/nm	0.1522	0.1523	0.1521	0.1514
C1—O9/nm	0.1206	0.1208	0.1199	0.1213
C3—O11/nm	0.1209	0.1211	0.1203	0.1213
N2—H8/nm	0.1013	0.1014	0.1012	0.0939
N6—H7/nm	0.1013	0.1014	0.1012	0.0939
C4—C12/nm	0.1544	0.1546	0.1544	0.1541
C12—C22/nm	0.1526	0.1527	0.1526	0.1514
C1—N2—C3/(°)	127.7	127.4	127.8	126.5
N2—C3—C4/(°)	117.4	117.7	117.4	118.3
C3—C4—C5/(°)	115.1	114.7	115.2	115.8
C4—C5—N6/(°)	117.4	117.7	117.4	118.3
C5—N6—C1/(°)	127.7	127.4	127.8	126.4
N6—C1—N2/(°)	114.4	114.7	114.3	114.6
C12—C4—C5/(°)	107.8	107.9	107.8	109.6
C4—C12—C22/(°)	114.3	113.3	113.3	114.8

Complex	Action site	R/nm	ρ(r)	▽²ρ(r)	Complex	Action site	R/nm	ρ(r)	▽²ρ(r)
BAR-MAA(1∶6)	O35…H8—N2	0.1764	0.0371	0.1186	BAR-4-Vpy(1∶3)	C56—H62…O10	0.2325	0.0125	0.0381
	O36—H37…O11	0.1783	0.0340	0.1111	BAR-MBAD	N27—H45…O11	0.1979	0.0224	0.0723
	O47…H7—N6	0.1718	0.0416	0.1311	(1∶4)	O36…H8—N2	0.1752	0.0354	0.1270
	O48—H49…O9	0.1785	0.0339	0.1113		N48—H66…O10	0.2147	0.0159	0.0474
	O60—H61…O10	0.1889	0.0258	0.0906		O57…H7—N6	0.1717	0.0353	0.1386
	O72—H73…O11	0.1792	0.0309	0.1151		N70—H88…O10	0.1908	0.0266	0.0868
	O84—H85…O9	0.1897	0.0257	0.0825		N90—H108…O11	0.2323	0.0126	0.0450
	O96—H97…O10	0.1847	0.0293	0.0972	BAR-MAA-MBAD	O36…H8—N2	0.1767	0.0350	0.1185
BAR-AM(1∶6)	O27…H8—N2	0.1838	0.0322	0.0962	(1∶1∶2)	N27—H45…O11	0.1989	0.0219	0.0710
	N28—H29…O11	0.2017	0.0212	0.0656		N49—H67…O10	0.2089	0.0178	0.0599
	O37…H7—N6	0.1705	0.0340	0.1328		O78—H79…O9	0.1732	0.0385	0.1253
	N38—H39…O10	0.1986	0.0233	0.0688		O77…H7—N6	0.1782	0.0356	0.1156
	N49—H50…O9	0.2008	0.0215	0.0713	BAR-MAA-AM	O27…H8—N2	0.1729	0.0411	0.1263
	N58—H59…O9	0.2120	0.0174	0.0528	(1∶1∶3)	O28—H29…O11	0.1958	0.0245	0.0733
	N68—H69…O11	0.2184	0.0155	0.0519		O37…H7—N6	0.1794	0.0350	0.1088
	N78—H79…O10	0.2126	0.0174	0.0519		O38—H39…O10	0.1942	0.0252	0.0765
BAR-4-Vpy(1∶3)	N31…H8—N2	0.1742	0.0485	0.1081		O56—H57…O9	0.1750	0.0363	0.1217
	N46…H7—N6	0.1750	0.0476	0.1069		O60—H61…O9	0.2073	0.0186	0.0577

Complex	Action site	R/nm	ρ(r)	▽²ρ(r)	Complex	Action site	R/nm	ρ(r)	▽²ρ(r)
BAR-MAA(1∶6)	O35…H8—N2	0.1764	0.0371	0.1186	BAR-4-Vpy(1∶3)	C56—H62…O10	0.2325	0.0125	0.0381
	O36—H37…O11	0.1783	0.0340	0.1111	BAR-MBAD	N27—H45…O11	0.1979	0.0224	0.0723
	O47…H7—N6	0.1718	0.0416	0.1311	(1∶4)	O36…H8—N2	0.1752	0.0354	0.1270
	O48—H49…O9	0.1785	0.0339	0.1113		N48—H66…O10	0.2147	0.0159	0.0474
	O60—H61…O10	0.1889	0.0258	0.0906		O57…H7—N6	0.1717	0.0353	0.1386
	O72—H73…O11	0.1792	0.0309	0.1151		N70—H88…O10	0.1908	0.0266	0.0868
	O84—H85…O9	0.1897	0.0257	0.0825		N90—H108…O11	0.2323	0.0126	0.0450
	O96—H97…O10	0.1847	0.0293	0.0972	BAR-MAA-MBAD	O36…H8—N2	0.1767	0.0350	0.1185
BAR-AM(1∶6)	O27…H8—N2	0.1838	0.0322	0.0962	(1∶1∶2)	N27—H45…O11	0.1989	0.0219	0.0710
	N28—H29…O11	0.2017	0.0212	0.0656		N49—H67…O10	0.2089	0.0178	0.0599
	O37…H7—N6	0.1705	0.0340	0.1328		O78—H79…O9	0.1732	0.0385	0.1253
	N38—H39…O10	0.1986	0.0233	0.0688		O77…H7—N6	0.1782	0.0356	0.1156
	N49—H50…O9	0.2008	0.0215	0.0713	BAR-MAA-AM	O27…H8—N2	0.1729	0.0411	0.1263
	N58—H59…O9	0.2120	0.0174	0.0528	(1∶1∶3)	O28—H29…O11	0.1958	0.0245	0.0733
	N68—H69…O11	0.2184	0.0155	0.0519		O37…H7—N6	0.1794	0.0350	0.1088
	N78—H79…O10	0.2126	0.0174	0.0519		O38—H39…O10	0.1942	0.0252	0.0765
BAR-4-Vpy(1∶3)	N31…H8—N2	0.1742	0.0485	0.1081		O56—H57…O9	0.1750	0.0363	0.1217
	N46…H7—N6	0.1750	0.0476	0.1069		O60—H61…O9	0.2073	0.0186	0.0577

Complex	ΔE_BSSE/(kJ·mol^-1)	Complex	ΔE_BSSE/(kJ·mol^-1)
BAR-MAA	-114.51	BAR-MBAD-MAA	-46.19
BAR-AM	-63.53	BAR-MBAD	-22.05
BAR-MAA-AM	-53.49	BAR-4-Vpy	-14.44