基于金属有机骨架材料的磁固相萃取与高效液相色谱-紫外检测法分析饮料和方便面中4种防腐剂

doi:10.3724/SP.J.1123.2019.06014

摘要/Abstract

摘要：

通过简单的搅拌共混方式制备了磁性氨基功能化的金属有机骨架化合物（MOFs）材料，得到的复合材料磁性和热稳定性良好，比表面积大，被用于不同极性防腐剂（苯甲酸、山梨酸、对羟基苯甲酸丙酯和对羟基苯甲酸丁酯）的萃取。优化磁固相萃取及解吸条件后，将解吸液引入高效液相色谱-紫外检测分析仪器，采用Purospher^® STAR LP C18色谱柱（250 mm×4.6 mm，5 μm）分离，以甲醇-10 mmol/L醋酸铵水溶液（50：50，v/v）为流动相进行梯度洗脱。结果表明，目标防腐剂的检出限为0.51~1.89 μg/L；苏打水、维生素饮料和方便面面饼中目标防腐剂的加标回收率为72.2%~109%。该方法简单快速，准确可靠，适用于饮料和食品中不同极性防腐剂的分析，为食品安全及质量监控提供了有效的技术有段。

关键词: 高效液相色谱, 磁固相萃取, 金属有机骨架化合物, 防腐剂, 饮料, 方便面

Abstract:

Magnetic amino functionalized metal-organic frameworks (MOFs) were prepared by a simple stirring and blending process. The obtained composites had good magnetic and thermal stability with a large specific surface area, and were used for the extraction of four preservatives with different polarities (benzoic acid, sorbic acid, propyl p-hydroxybenzoate and butyl p-hydroxybenzoate) in soda water, vitamin beverage and instant noodle cake samples. After optimizing the conditions for magnetic solid phase extraction (MSPE) and desorption, the four preservatives were analysed by a high performance liquid chromatography-ultraviolet detection (HPLC-UV) method. The analytes were separated on a Purospher^® STAR LP C18 column (250 mm×4.6 mm, 5 μm). Methanol and 10 mmol/L ammonium acetate aqueous solution (50:50, v/v) were used as the mobile phases with gradient elution. The limits of detection of the four preservatives were 0.51-1.89 μg/L. The recoveries of the target preservatives were 72.2%-109% in the soda water, vitamin beverage and instant noodle cake samples. The method is simple, rapid, accurate and reliable, and is suitable for the analysis of preservatives with different polarities in beverages and foods. The method can provide an effective technology for food safety and quality control.

Key words: high performance liquid chromatography (HPLC), magnetic solid phase extraction (MSPE), metal-organic frameworks (MOFs), preservatives, beverages, instant noodles

肖作为, 何蔓, 陈贝贝, 胡斌. 基于金属有机骨架材料的磁固相萃取与高效液相色谱-紫外检测法分析饮料和方便面中4种防腐剂[J]. 色谱, 2020, 38(1): 127-136.

XIAO Zuowei, HE Man, CHEN Beibei, HU Bin. Analysis of four preservatives in beverages and instant noodle samples by high performance liquid chromatography-ultraviolet detection coupled with magnetic solid phase extraction based on metal-organic frameworks[J]. Chinese Journal of Chromatography, 2020, 38(1): 127-136.

图/表 10

图1 6种防腐剂的化学结构

Fig. 1 Chemical structures of the six preservatives

图2 Fe3O4@SiO2@UiO-66-NH2的(a)透射电镜(TEM)图、(b)磁滞回线、(c)XRD图、(d)热重曲线和(e)氮气吸附/脱附曲线

Fig. 2 (a) Transmission electron microscopy (TEM) image, (b) magnetic hysteresis loops, (c) X-ray diffraction (XRD) spectra, (d) thermal gravity (TG) curves and (e) N2 adsorption/desorption isotherms of Fe3O4@SiO2@UiO-66-NH2

图3 溶液pH值对目标防腐剂(200 μg/L)萃取率的影响(n=3)

Fig. 3 Effect of pH values of solution on the extraction efficiencies of the target preservatives (200 μg/L) (n=3) Conditions: sample volume, 10 mL; extraction time, 20 min; desorption solvent, methanol (MeOH)-10 mmol/L NaOH (50:50, v/v); desorption time, 20 min; desorption volume, 0.5 mL.

图4 不同解吸溶液对目标防腐剂(200 μg/L)萃取率的影响(n=3)

Fig. 4 Effect of the different desorption solutions on the extraction efficiencies of the target preservatives (200 μg/L) (n=3) Conditions: sample volume, 10 mL; pH value of solution, 3.5; extraction time, 20 min; desorption time, 15 min; desorption volume, 0.5 mL.

图5 不同体积分数的甲醇对目标防腐剂(200 μg/L)萃取率的影响

Fig. 5 Effect of the different volume fractions of MeOH on the extraction efficiencies of the target preservatives (200 μg/L) (n=3) Conditions: sample volume, 10 mL; pH value of solution, pH=3.5; extraction time, 20 min; desorption time, 15 min; desorption volume, 0.5 mL.

图6 解吸体积对(a)萃取率和(b)富集倍数的影响(n=3)

Fig. 6 Effect of desorption volumes on the (a) extraction efficiencies and (b) enrichment factors (n=3) Conditions: sample volume, 25 mL; pH value of solution, pH 3.5; extraction time, 10 min; desorption solvent, MeOH-10 mmol/L NaOH (50/50, v/v); desorption time, 20 min.

表1 4种防腐剂的线性范围、相关系数、检出限、定量限、相对标准偏差和富集倍数

Table 1 Linear ranges, correlation coefficients (r), LODs, LOQs, RSDs and enrichment factors (EFs) of the four preservatives

Analyte	Linear range/(μg/L)	r	LOD/(μg/L)	LOQ/(μg/L)	RSDs (n=7)/%		EF
Analyte	Linear range/(μg/L)	r	LOD/(μg/L)	LOQ/(μg/L)	Intra-day	Inter-day	EF
BA	2-2000	0.9998	0.51	1.60	3.8	3.3	40.2
SA	2-1000	0.9976	0.65	2.28	5.5	7.4	19.1
PP	10-1000	0.9982	1.89	5.35	3.5	7.8	6.3
BP	5-1000	0.9961	1.29	4.02	2.1	6.7	15.9

表2 本方法与其他方法的比较

Table 2 Comparison of the proposed method with other methods

Method	Analytes	Samples	Extraction time/min	LOD/ (μg/L)	Recovery/ %	Ref.
DLLME: dispersive liquid liquid microextraction; CLC: capillary liquid chromatography; HKUST-1: a kind of MOFs materials; d- μ SPE: dispersive micro-solid-phase extraction; CME: capillary microextraction; SCSE: stir cake sorptive extraction; PDMS: polydimethylsiloxane; SBSE: stir bar sorptive extraction; MSPE: magnetic solid phase extraction.
DLLME-CLC-MS	MP, EP, PP, BP	human urine, serum	20	7-11	95.2-107	[34]
HKUST-1-d-μSPE-HPLC-UV	MP, EP, PP, BP	cosmetic creams, human urine	5	0.1-0.6	63.7-121	[22]
Monolith-CME-HPLC-UV	BA, SA	soft drinks	5	0.9-1.2	84.4-106	[18]
Monolith-SCSE-HPLC-UV	BA, SA	juices, soft drinks	180	0.16-1.03	96.1-104	[6]
PDMS-SPE-GC-FID	BA, SA, MP, EP, PP	soft drinks, yogurts, sauces	45	2-200	92-106	[12]
Dual phase-dual SBSE-HPLC-UV	BA, SA, MP, EP, PP, BP	cola, orange juice, herb tea	40	0.6-2.7	74.6-119	[21]
UiO-66-NH₂-MSPE-HPLC-UV	BA, SA, PP, BP	beverages, instant noodles	10	0.51-1.89	59.2-109	this work

表3 饮料样品和方便面中目标防腐剂的分析结果(n=3)

Table 3 Analytical results of the four preservatives in the beverage and instant noodles samples (n=3)

Compound	Added/ (μg/L)	Soda water		Vitamin beverage		Instant noodles
Compound	Added/ (μg/L)	Found/ (μg/L)	Recovery/ %	Found/ (μg/L)	Recovery/ %	Found/ (μg/L)	Recovery/ %
ND: not detected; -: no data.
BA	0	ND	-	ND	-	ND	-
	5.00	4.11±0.3	82.3	3.67±0.2	73.4	4.68±0.2	93.6
	25.0	24.9±1.2	99.6	20.3±1.4	81.2	24.2±1.0	96.6
	50.0	47.9±1.7	95.7	44.7±2.2	89.4	51.3±2.1	103
SA	0	ND	-	ND	-	ND	-
	5.00	4.57±0.2	91.5	3.61±0.4	72.2	4.3±0.2	85.9
	25.0	27.3±0.9	109	20.0±1.3	80.1	23.6±1.5	94.3
	50.0	53.5±1.9	107	42.9±1.7	85.8	46.9±1.6	93.9
PP	0	ND	-	ND	-	ND	-
	10.0	7.46±0.8	74.6	7.55±0.5	75.5	8.01±0.2	80.1
	50.0	39.7±1.5	79.3	37.5±1.2	74.9	43.2±2.2	86.4
	100	84.6±3.9	84.6	80.2±2.3	80.2	83.5±4.1	83.5
BP	0	ND	-	ND	-	ND	-
	10.0	8.79±0.4	87.9	8.25±0.6	82.5	9.78±0.4	97.8
	50.0	48.2±1.0	96.5	43.7±1.5	87.3	47.2±1.6	94.3
	100	89.1±4.2	89.1	94.2±6.4	94.2	89.2±5.3	89.2

图7 苏打水、维生素饮料和方便面中4种防腐剂的色谱图

Fig. 7 Chromatograms of the four preservatives in the soda, vitamin beverage and instant noodles samples a. original sample obtained by direct injection; b. original sample obtained by MSPE; c. spiked sample obtained by MSPE (25 μg/L for BA and SA, 50 μg/L for PP and BP).

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