Preparation of Zirconia Deposited Silica Stationary Phase and Its Application to Hydrophilic-interaction Liquid Chromatography†

doi:10.7503/cjcu20190158

Abstract

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

CLC Number:

O657

TrendMD:

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

Figures/Tables 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)

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.

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.

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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