纳米氧化锆沉积硅胶色谱固定相的制备及亲水作用色谱行为

doi:10.7503/cjcu20190158

摘要/Abstract

摘要：

采用液相沉积法(LPD)制备了纳米氧化锆沉积硅胶色谱固定相(ZrO₂/SiO₂), 并将其应用于亲水作用色谱分离中. 考察并比较了ZrO₂/SiO₂、硅胶(SiO₂)和氧化锆(ZrO₂) 3种色谱固定相在不同有机调节剂比例、不同pH值及不同盐浓度的流动相条件下的色谱行为. 结果表明, 制备的ZrO₂/SiO₂色谱柱不仅具有SiO₂色谱柱高柱效的优点, 表面沉积的纳米氧化锆还能有效屏蔽硅羟基, 有利于碱性物质的保留和分离, 表现出良好的亲水作用色谱性能. 将ZrO₂/SiO₂色谱柱用于4种脱氧核苷和5种碱性化合物的分离, 均得到了较好的效果, 展现出其作为色谱固定相良好的应用前景.

关键词: 液相沉积法, 氧化锆, 亲水作用色谱, 保留机理

Abstract:

ZrO₂ nanoparticles were deposited on silica by LPD method and the resulting ZrO₂/SiO₂ was employed as stationary phase in hydrophilic-interaction liquid chromatography. The chromatographic perfor-mance of three columns packed with SiO₂, ZrO₂/SiO₂ and ZrO₂ were compared. The results showed that the column packed with ZrO₂/SiO₂ not only had the advantages of high column efficiency like the SiO₂ column, but also the deposited zirconia nanoparticles on the silica surface could shield the silicon hydroxyl group effectively, which benefit for the retention and separation of alkaline substances and showed good hydrophilic-interaction chromatographic performance. Effective separation of 4 deoxynucleosides and 5 basic compounds was achieved on ZrO₂/SiO₂ column in the hydrophilic-interaction liquid chromatography(HILIC) mode.

Key words: Liquid phase deposition(LPD), Zirconia, Hydrophilic-interaction liquid chromatography, Retention mechanism

中图分类号:

O657

TrendMD:

余琼卫, 郑凤, 方凯敏, 冯钰锜. 纳米氧化锆沉积硅胶色谱固定相的制备及亲水作用色谱行为. 高等学校化学学报, 2019, 40(9): 1857.

YU Qiongwei, ZHENG Feng, FANG Kaimin, FENG Yuqi. Preparation of Zirconia Deposited Silica Stationary Phase and Its Application to Hydrophilic-interaction Liquid Chromatography^†. Chem. J. Chinese Universities, 2019, 40(9): 1857.

图/表 11

Fig.1 SEM images of SiO2(A) and ZrO2/SiO2(B), EDX images of SiO2(C) and ZrO2/SiO2(D)

Fig.2 N2 adsorption-desorption isotherms of SiO2(a) and ZrO2/SiO2(b)

Table 1 Surface area, pore volume and pore diameter of SiO2 and ZrO2/SiO2

Sample	Surface area/<break/>(m₂·g_-1)	Pore volume/<break/>(cm₃·g_-1)	Pore diameter/<break/>nm
SiO₂	287	1.1	11
ZrO₂/SiO₂	260	1.0	11
ZrO₂	14	0.07	18

Fig.3 Pore size distribution of SiO2 and ZrO2/SiO2

Fig.4 Plots of k and theoretical plate numbers vs. H2O volume fraction in mobile phase(A) SiO2; (B) ZrO2/SiO2; (C) ZrO2; (D) theoretical plate numbers of tested analytes on different columns.Mobile phase: ACN-20 mmol/L NH4Ac(pH=6.8); flow rate: 1.0 mL/min; UV detection wavelength: 254 nm.

Table 2 Correlation coefficients of the tested analytes on three columns using Eqs.(1)—(3)

Tested analyte	Correlation coefficient on SiO₂			Correlation coefficient on ZrO₂/SiO₂			Correlation coefficient on ZrO₂
Tested analyte	Eq.(1)	Eq.(2)	Eq.(3)	Eq.(1)	Eq.(2)	Eq.(3)	Eq.(1)	Eq.(2)	Eq.(3)
Deoxycytidine	0.9179	0.9537	0.9999	0.8947	0.9866	0.9987	0.9397	0.9980	0.9984
Deoxyadenosine	0.9147	0.9179	0.9998	0.8883	0.9839	0.9981	0.9771	0.98840	0.9934
Cytosine	0.9015	0.9147	0.9998	0.8546	0.9670	0.9926	0.9693	0.9988	0.9987
Adenine	0.8936	0.9015	0.9999	0.8662	0.9751	0.9987	0.9670	0.9919	0.9930
Guanine	0.9090	0.8936	0.9998	0.8781	0.9801	0.9985	0.9207	0.9948	0.9991

Fig.5 Effects of mobile phase pH values on retention factors(k) and symmetry factors of tested analytes(A) SiO2; (B) ZrO2/SiO2; (C) ZrO2; (D) effect of pH on the symmetry factor of tested analytes on SiO2 column; (E) effect of pH on the symmetry factor of tested analytes on ZrO2/SiO2 column. Mobile phase: ACN-20 mmol/L NH4Ac(80∶20, volume ratio). Flow rate: 1.0 mL/min; UV detection wavelength: 254 nm. (A)—(C) a. Proparanolol; b. berberine; c. melamine; d. deoxycytidine; e. adenine; f. benzoic acid; g. p-nitrobenzoic acid. (D) and (E) a. Propranolo; b. berberine; c. deoxycytidine; d. adenine.

Fig.6 Influence of NH4Ac concentration on the retention factor(k) and symmetry factors of tested analytes(A) SiO2; (B) ZrO2/SiO2; (C) ZrO2; (D) effect of NH4Ac concentration on the symmetry factor of tested analytes on SiO2column; (E) effect of NH4Ac concentration on the symmetry factor of tested analytes on ZrO2/SiO2 column. Mobile phase: ACN-NH4Ac(pH=6.8)(80∶20, volume ratio). Flow rate: 1.0 mL/min; UV detection wavelength: 254 nm.

Table 3 Comparison of reported ZrO2 stationary phases on retention mechanism and application

ZrO₂related stationary phase	Interaction mechanism	Application	Ref.
Zirconia-based stationary phase cellulose	Ion-exchange interaction	Drug control	[45]
Tris(3,5-dimethylphenylcarbamate)-coatedzirconia		Chiral compounds	[46]
Octadecyl coated zirconia stationary phase	Ion-exchange interaction	Parabens	[47]
N-Methylimidazolium functionalized ZrO₂/SiO₂-4	Ion-exchange interaction	Inorganic and organic anions	[48]
Adenosine 5'-monophosphate modified ZrO₂/SiO₂	Hydrogen-bonding, electrostatic and <br/>ion-exchange interaction	Acidic compounds	[49]
ZrO₂/SiO₂	Adsorption and partition	Polar compounds	This work

Fig.7 Separation of four deoxynucleosides on ZrO2/SiO2 columnMobile phase: ACN-20 mmol/L NH4Ac(pH=6.8)(80∶20, volume ratio). Flow rate: 1.0 mL/min; UV detection wavelength: 254 nm. Peak 1: thymidine; peak 2: 2'-deoxyadenosine; peak 3: 2'-deoxyguanosine; peak 4: 2'-deoxycytidine.

Fig.8 Separation of several basic analytes on ZrO2/SiO2 columnMobile phase: ACN-20 mmol/L NH4Ac(pH=6.8)(80∶20, volume ratio). Flow rate: 1.0 mL/min; UV detection wavelength: 254 nm. Peak 1: theophylline; peak 2: melamine; peak 3: ractopamine; peak 4 clenbuterol; peak 5: terbutaline.

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