离子色谱-串联质谱法检测酒类产品中10种有机酸

doi:10.3724/SP.J.1123.2022.01020

摘要/Abstract

摘要：

建立了一种离子色谱-串联质谱(IC-MS/MS)测定白酒、黄酒、干红葡萄酒3种酒类样品中10种有机酸含量的方法。白酒样品氮吹后,经去离子水稀释,用IC-MS/MS分析检测;干红葡萄酒样品和黄酒样品,对比不同固相萃取小柱净化能力,最终选择石墨化炭黑固相萃取小柱进行净化,经去离子水稀释,用IC-MS/MS分析检测。选用高容量、强亲水性的Dionex IonPac^TM AS11-HC型阴离子分析柱进行分离,以淋洗液自动发生器在线产生的KOH水溶液为淋洗液,进行梯度淋洗。淋洗液经抑制器抑制后直接进入电喷雾电离串联质谱(ESI-MS/MS),采用负离子模式电离,多反应监测(MRM)模式检测,外标法定量。在该实验条件下:草酸、富马酸、马来酸、苹果酸、酒石酸、柠檬酸、奎尼酸和乌头酸在0.05~2 mg/L范围内线性关系良好;琥珀酸在0.05~5 mg/L范围内线性关系良好;乳酸在0.05~10 mg/L范围内线性关系良好(相关系数r²>0.99)。10种有机酸的检出限(S/N=3)在1.0~8.0 μg/L范围内,定量限(S/N=10)在3.5~26.5 μg/L范围内,在3个不同浓度的添加水平下,平均回收率在83.0%~112.1%之间,相对标准偏差≤9.1%,满足检测要求。该方法前处理简单,不使用有机溶剂,不需进行衍生化处理,测定快速、准确,灵敏度高,适用于3种酒类样品中10种有机酸的定量分析,为酒类食品的风味及品质测定提供方法支持。

关键词: 离子色谱-串联质谱, 有机酸, 白酒, 黄酒, 干红葡萄酒

Abstract:

A method was developed for the determination of 10 organic acids in liquor, yellow rice wine, and dry red wine by ion chromatography-triple quadrupole mass spectrometry (IC-MS/MS). First, the liquor samples were diluted with deionized water, degassed with nitrogen, and analyzed by IC-MS/MS. Then, the yellow rice wine and dry red wine samples were purified with different solid-phase extraction cartridges. Finally, the GCB solid-phase extraction cartridge was selected for purification, diluted with deionized water, and analyzed by IC-MS/MS. The samples were separated using a Dionex IonPac AS11-HC anion analysis column with high capacity and strong hydrophilicity, with an KOH aqueous solution as the eluent, which was produced by an automatic generator for gradient elution. After being suppressed using a suppressor, the eluent was injected directly into the electrospray ionization tandem mass spectrometry (ESI-MS/MS), ionized in negative ion mode, detected in multiple reaction monitoring (MRM) mode, and quantified using an external standard method. Oxalic acid, fumaric acid, maleic acid, malic acid, tartaric acid, citric acid, quinic acid, and aconitic acid showed good linear relationships in the range of 0.05-2 mg/L. Succinic acid and lactic acid showed good linearities in the range of 0.05-5 mg/L and 0.05-10 mg/L, respectively. The correlation coefficients (r²) were >0.99. The limits of detection (LODs) and limits of quantification (LOQs) were 1.0-8.0 μg/L and 3.5-26.5 μg/L, respectively. The average recoveries ranged from 83.0% to 112.1%, and the relative standard deviations (RSDs) were <9.1% in spiked samples at three levels. The proposed method allowed easy pretreatment without using organic solvents or derivatization processing. Overall, the proposed method is accurate, rapid, sensitive, and it is suitable for the qualitative and quantitative analyses of the 10 organic acids in three wine samples. Moreover, it can be used for the determination of flavor and quality of alcoholic products.

Key words: ion chromatography-tandem mass spectrometry (IC-MS/MS), organic acids, liquor, yellow rice wine, dry red wine

中图分类号:

O658

穆瑛琦, 吴奕萱, 王逍, 胡利明, 柯润辉. 离子色谱-串联质谱法检测酒类产品中10种有机酸[J]. 色谱, 2022, 40(12): 1128-1135.

MU Yingqi, WU Yixuan, WANG Xiao, HU Liming, KE Runhui. Determination of 10 organic acids in alcoholic products by ion chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(12): 1128-1135.

图/表 9

参考文献

[1]	Kim N, Jeon J, Chen R, et al. Chem Eng Res Des, 2022, 178: 267
[2]	Yu F, Chen C, Chen S N, et al. Food Control, 2022, 132: 1
[3]	Volschenk H, Van H J J, Viljoen M B. S Afr J Enol Vitic, 2017, 27(2): 123
[4]	Zeravik J, Fohlerova Z, Milovanivic M, et al. Food Chem, 2016, 194: 432
[5]	Alicia R, Magdalena F, Tomasz C, et al. TrAC-Trends Anal Chem, 2019, 120: 115630
[6]	Justyna D K. Food Anal Methods, 2015, 8(9): 2356
[7]	Coelho E M, Padilha C S, Miskinis G A, et al. J Food Compos Anal, 2017, 66: 160
[8]	Shirai N. J Oleo Sci, 2019, 68(12): 1271
[9]	Barbas C, Moraes E P, Villaseñor A. J Pharmaceut Biomed, 2011, 55(4): 823
[10]	Robles A D, Fabjanowicz M, Płotka W J, et al. Molecules, 2019, 24(23): 4376
[11]	AliAbadi M H S, Karami R, Kobarfard F, et al. J Food Compos Anal, 2021, 105: 104223
[12]	Pang M, Cai S L, Liu Q. Food Safety and Quality Detection Technology, 2019, 10(6): 1588
[12]	庞敏, 蔡松铃, 刘茜. 食品安全质量检测学报, 2019, 10(6): 1588
[13]	Jiang Y, Dong D, He H Y, et al. Journal of Fruit Science. DOI: 10.13925/j.cnki.gsxb.20210427
[13]	蒋莹, 董丹, 何红英, 等. 果树学报. DOI: 10.13925/j.cnki.gsxb.20210427
[14]	Zhou Y F, Xu S, Yang Y H, et al. Food Science and Technology, 2021, 46(5): 254
[14]	周宇飞, 徐帅, 杨益欢, 等. 食品科技, 2021, 46(5): 254
[15]	Zhao X Y, Qu F, Mou S F. Chinese Journal of Chromatography, 2017, 35(3): 223
[15]	赵新颖, 屈锋, 牟世芬. 色谱, 2017, 35(3): 223
[16]	Ni C Z, Zhu B H, Wang N N, et al. Food Chem, 2016, 194: 555
[17]	Xiong Z Y, Dong Y, Zhou H B, et al. Food Anal Methods, 2014, 7(9): 1908
[18]	Li J B, Hao F R, Tian F, et al. Journal of Chinese Mass Spectrometry Society, 2013, 34(2): 65
[18]	李佳斌, 郝斐然, 田芳, 等. 质谱学报, 2013, 34(2): 65
[19]	Wang Y H, Shen X M, Ma L, et al. Liquor Making, 2016, 43(1): 43
[19]	王银辉, 沈小梅, 马雷, 等. 酿酒, 2016, 43(1): 43
[20]	Ali K, Maltese F, Toepfer P, et al. J Biomol Nmr, 2011, 49: 255
[21]	Luo M Y, Lü B, Shen G B, et al. Chinese Journal of Analytical Chemistry, 2015, 43(10): 1569
[21]	罗明艳, 吕蓓, 沈国滨, 等. 分析化学, 2015, 43(10): 1569
[22]	Liu X Y, Wang Y, Cong H L, et al. J Chromatogr A, 2021, 1653: 462313
[23]	Song J, Du L J, Yao Y T, et al. Physical Testing and Chemical Analysis (Part B: Chemical Analysis), 2018, 54(1): 97
[23]	宋洁, 杜利君, 姚亚婷, 等. 理化检验(化学分册), 2018, 54(1): 97
[24]	Tang P, Shan Q M G, Wang L, et al. Food Science, 2020, 41(17): 315
[24]	唐平, 山其木格, 王丽, 等. 食品科学, 2020, 41(17): 315

No.	Compound	Retention time/min	Parent ion (m/z)	Product ion (m/z)	Cone voltage/V	Collision energy/eV
1	quinic acid	11.56	191.1	85.1^*	38	21
				59.1		23
2	lactic acid	13.94	89.1	45.1^*	22	11
				43.1		10
3	succinic acid	23.95	117.1	73.0^*	19	12
				99.1		11
4	malic acid	23.97	133.1	115.0^*	19	12
				71.0		16
5	tartaric acid	24.35	149.0	87.0^*	20	12
				73.0		16
6	maleic acid	24.85	115.1	71.1^*	15	15
				27.1		10
7	fumaric acid	25.94	115.1	71.0^*	17	9
				27.0		11
8	oxalic acid	26.17	89.1	43.0^*	20	12
				45.1		11
9	citric acid	28.36	191.0	87.0^*	18	12
				111.0		20
10	aconitic acid	30.75	173.0	85.1^*	12	7
				129.1		11

No.	Compound	Retention time/min	Parent ion (m/z)	Product ion (m/z)	Cone voltage/V	Collision energy/eV
1	quinic acid	11.56	191.1	85.1^*	38	21
				59.1		23
2	lactic acid	13.94	89.1	45.1^*	22	11
				43.1		10
3	succinic acid	23.95	117.1	73.0^*	19	12
				99.1		11
4	malic acid	23.97	133.1	115.0^*	19	12
				71.0		16
5	tartaric acid	24.35	149.0	87.0^*	20	12
				73.0		16
6	maleic acid	24.85	115.1	71.1^*	15	15
				27.1		10
7	fumaric acid	25.94	115.1	71.0^*	17	9
				27.0		11
8	oxalic acid	26.17	89.1	43.0^*	20	12
				45.1		11
9	citric acid	28.36	191.0	87.0^*	18	12
				111.0		20
10	aconitic acid	30.75	173.0	85.1^*	12	7
				129.1		11

No.	Compound	Linear range/(mg/L)	Linear equation	r²	LOD/(μg/L)	LOQ/(μg/L)
1	quinic acid	0.05-2	Y=3.71×10⁵X+1.97×10⁴	0.9939	4.0	12.5
2	lactic acid	0.05-10	Y=3.30×10⁴X+3.08×10³	0.9955	8.0	26.5
3	succinic acid	0.05-5	Y=2.70×10⁵X+5.52×10⁴	0.9957	1.5	5.0
4	malic acid	0.05-2	Y=4.49×10⁵X+3.16×10⁴	0.9925	1.5	5.0
5	tartaric acid	0.05-2	Y=2.56×10⁵X+1.22×10⁴	0.9964	1.0	3.5
6	maleic acid	0.05-2	Y=6.56×10⁵X+1.00×10⁴	0.9960	1.5	5.0
7	fumaric acid	0.05-2	Y=2.75×10⁵X+1.72×10⁴	0.9930	3.5	12.0
8	oxalic acid	0.05-2	Y=2.28×10⁴X+3.78×10³	0.9942	3.5	12.0
9	citric acid	0.05-2	Y=2.53×10⁵X+9.34×10³	0.9988	3.0	10.0
10	aconitic acid	0.05-2	Y=4.15×10⁵X+1.29×10⁴	0.9951	4.0	13.5

No.	Compound	Linear range/(mg/L)	Linear equation	r²	LOD/(μg/L)	LOQ/(μg/L)
1	quinic acid	0.05-2	Y=3.71×10⁵X+1.97×10⁴	0.9939	4.0	12.5
2	lactic acid	0.05-10	Y=3.30×10⁴X+3.08×10³	0.9955	8.0	26.5
3	succinic acid	0.05-5	Y=2.70×10⁵X+5.52×10⁴	0.9957	1.5	5.0
4	malic acid	0.05-2	Y=4.49×10⁵X+3.16×10⁴	0.9925	1.5	5.0
5	tartaric acid	0.05-2	Y=2.56×10⁵X+1.22×10⁴	0.9964	1.0	3.5
6	maleic acid	0.05-2	Y=6.56×10⁵X+1.00×10⁴	0.9960	1.5	5.0
7	fumaric acid	0.05-2	Y=2.75×10⁵X+1.72×10⁴	0.9930	3.5	12.0
8	oxalic acid	0.05-2	Y=2.28×10⁴X+3.78×10³	0.9942	3.5	12.0
9	citric acid	0.05-2	Y=2.53×10⁵X+9.34×10³	0.9988	3.0	10.0
10	aconitic acid	0.05-2	Y=4.15×10⁵X+1.29×10⁴	0.9951	4.0	13.5

Compound	Liquor			Yellow rice wine			Dry red wine
Compound	Spiked/(mg/L)	Recovery/%	RSD/%	Spiked/(mg/L)	Recovery/%	RSD/%	Spiked/(mg/L)	Recovery/%	RSD/%
Quinic acid	0.1	96.0	5.6	0.1	95.7	5.8	0.1	108.8	5.8
	0.2	102.0	2.3	0.2	99.2	1.9	0.2	95.5	6.4
	0.5	105.4	3.3	0.5	101.4	2.7	0.5	102.4	3.1
Lactic acid	1	110.2	3.7	1.0	99.8	5.9	1.0	103.9	1.8
	2	98.9	4.1	2.0	105.2	1.6	2.0	102.4	2.3
	4	99.3	2.9	4.0	101.8	4.9	4.0	105.8	5.6
Succinic acid	0.1	103.1	3.5	0.1	104.6	1.3	0.1	98.7	2.6
	0.2	107.0	4.3	0.2	89.5	2.3	0.2	96.5	0.5
	0.5	108.4	5.4	0.5	96.4	6.7	0.5	95.0	2.3
Malic acid	0.1	112.0	4.8	0.1	100.5	4.4	0.1	88.2	5.4
	0.2	105.0	3.7	0.2	97.8	4.9	0.2	87.0	6.2
	0.5	107.8	4.2	0.5	103.7	5.8	0.5	106.2	2.8
Tartaric acid	0.1	94.0	6.3	0.1	102.3	7.2	0.1	93.2	1.8
	0.2	101.0	6.0	0.2	97.8	5.5	0.2	84.1	8.9
	0.5	96.2	5.8	0.5	101.1	4.9	0.5	101.6	3.7
Maleic acid	0.1	84.4	3.1	0.1	104.2	1.3	0.1	98.3	3.7
	0.2	105.3	6.8	0.2	99.7	6.3	0.2	102.4	4.1
	0.5	98.8	5.1	0.5	107.2	4.7	0.5	89.2	4.9
Fumaric acid	0.1	105.0	3.4	0.1	99.0	3.3	0.1	105.3	1.6
	0.2	111.5	2.4	0.2	107.2	3.7	0.2	93.0	2.1
	0.5	100.6	2.6	0.5	101.3	8.5	0.5	111.6	4.1
Oxalic acid	0.1	101.1	3.7	0.1	101.0	4.7	0.1	107.0	2.1
	0.2	96.5	5.6	0.2	103.5	6.2	0.2	107.5	3.6
	0.5	102.4	8.0	0.5	98.4	5.8	0.5	98.0	2.1
Citric acid	0.1	88.2	7.4	0.1	90.3	3.9	0.1	106.8	5.1
	0.2	97.5	4.7	0.2	93.6	4.2	0.2	90.5	4.5
	0.5	101.2	6.2	0.5	100.7	3.8	0.5	83.0	6.8
Aconitic acid	0.1	94.2	5.8	0.1	103.0	4.3	0.1	112.1	9.0
	0.2	108.5	3.6	0.2	90.5	5.6	0.2	91.2	9.1
	0.5	91.2	5.9	0.5	92.8	4.4	0.5	104.1	7.2