UPLC-MS/MS法测定中药牙膏中21种指标成分

doi:10.3969/j.issn.2097-2806.2026.03.015

Abstract

Abstract:

An ultra-high performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） method was established to simultaneously determine 21 characteristic components derived from 14 traditional Chinese medicines （TCMs） in TCM formula toothpaste. The toothpaste samples were ultrasonically extracted with 80% methanol. Separation was achieved on a BEH C₁₈ column （100 mm×2.1 mm, 1.7 μm）, employing a gradient elution with 0.1% formic acid aqueous solution and acetonitrile as mobile phases. The 21 characteristic components from TCM materials were simultaneously identified using multiple reaction monitoring （MRM） with electrospray ionization in both positive and negative modes. Quantification was carried out by the matrix-matching external standard method. The 21 characteristic components exhibit good linearity between peak areas and concentrations, with correlation coefficients all above 0.99. The limits of detection range from 0.2 ng/mL to 4.8 ng/mL. The limits of quantification range from 0.5 ng/mL to 14.5 ng/mL. The average recoveries at three different spiked levels are between 88.3% and 121.0%. The RSDs range from 0.9% to 12.6% （n=6）. The established method was applied to the detection of 38 real samples from commercially available TCM formula toothpaste. The developed method is specific, sensitive, accurate, and highly efficient. It is suitable for simultaneous determination of these 21 characteristic components in TCM formula toothpaste. This work provides a technical reference for investigating the material basis and efficacy of TCM extracts in TCM formula toothpaste, and it offers support for the standardization and regulation of the toothpaste market.

Key words: UPLC-MS/MS, toothpaste, traditional Chinese medicine extracts, characteristic components

CLC Number:

TQ658

Hui Lu,Yiwen Huang,Li Ren,Linling Lu,Bin Zhang. Determination of 21 characteristic components in Chinese medicine formula toothpaste by UPLC-MS/MS[J].China Surfactant Detergent & Cosmetics, 2026, 56(3): 392-399.

Figures/Tables 7

Tab.1

Tab.2

Fig.1

Fig.2

Tab.3

Tab.4

Tab.5

References 18

[1]	仲楠, 魏家艳, 张国玉, 等. 中草药抑菌抗炎活性成分在功效型牙膏中的应用研究[J]. 华西药学杂志, 2025, 40 (2) : 222-226.
[2]	Naghsh N, Mazrooei F, Hosseini A, et al. Effects of propolis-based herbal toothpaste on dentine hypersensitivity[J]. International Dental Journal, 2024, 74(3):559-565.
[3]	Adam F A, Mohd N, Rani H, et al. An effective anti-plaque and anti-gingivitis toothpaste: A systematic review & meta-analysis of randomized control clinical trials[J]. Journal of Herbal Medicine, 2023, 40: 100677.
[4]	林昊, 张赞, 谢鹏, 等. HPLC测定两面针中药牙膏中的毛两面针素[J] .华西药学杂志, 2024, 39 (2) : 205-208.
[5]	叶蓉姿, 聂明霞, 王亚茹, 等. 超高效液相色谱-串联质谱法测定牙膏中的异嗪皮啶[J]. 广东化工, 2022, 49 (24) : 234-236.
[6]	中华人民共和国工业和信息化部. [S]. 北京: 中国轻工业出版社, 2014.
[7]	杨培, 谭建华, 李慧勇, 等. 超高效液相色谱法同时测定牙膏中5种植物源活性成分[J]. 分析测试学报, 2019, 38 (1) : 92-96.
[8]	管弋铦, 韩和平, 李利伟. HPLC法测定牙膏中厚朴酚与和厚朴酚含量前处理方法的优化[J]. 口腔护理用品工业, 2022, 32 (6) : 28-30.
[9]	赖焕华, 宋佳, 陈华龙, 等. 高效液相色谱法同时测定牙膏中六种清热解毒植物成分[J]. 广东化工, 2023, 50 (17) : 147-150.
[10]	Xiao G P, Yuan L, Liao D D, et al. Implementation of gas chromatography tandem mass spectrometry for the analysis of six high boiling point polyhydric alcohols in cosmetics and toothpaste based on precolumn derivatization[J]. Journal of Pharmaceutical and Biomedical Analysis, 2025, 252: 116503.
[11]	吴晓云, 高天阳, 谢强胜, 等. 气相色谱-质谱法测定牙膏中7种薄荷类化学成分[J]. 化学分析计量, 2024, 33 (9) : 74-79.
[12]	税钿, 夏泽敏, 聂明霞, 等. 超高效液相色谱-串联质谱法同时测定牙膏中三七皂苷和人参皂苷[J]. 口腔护理用品工业, 2023, 33(5) : 7-11.
[13]	刘亦菲, 刘兆薇, 任一冉, 等. 蒲公英化学成分、药理作用研究进展及质量标志物预测分析[J]. 中华中医药学刊, 2024, 42 (8) : 132-141.
[14]	张孝莹, 祁纪鸽, 苏世家, 等. UHPLC-MS/MS法同时测定枳实薤白桂枝汤中10种成分[J]. 天津中医药, 2023, 40 (7) : 910-915.
[15]	李忠, 吴杨, 聂金菊, 等. 基体匹配-电感耦合等离子体质谱法测定钆喷酸葡胺中24种元素杂质[J]. 中国医药工业杂志, 2022, 53(9) : 1311-1317.
[16]	黄炜东. UPLC-MS/MS法测定美白化妆品中10种植物原料指标性成分[J]. 日用化学工业(中英文), 2025, 55 (4) : 531-538.
[17]	李鑫玉, 褚佳豪, 王甜甜, 等. BBD法提取芦荟苷工艺的优化及稳定性分析[J]. 北京石油化工学院学报, 2022, 30 (4) : 13-18.
[18]	张强, 崔君, 顾华, 等. 化妆品中芦荟苷的测定及其稳定性的研究[J]. 日用化学工业, 2019, 49 (3) : 199-202.

序号	化合物	纯度/%	分子式	母离子（m/z）	子离子（m/z）	CE/eV	DP/V	t_R/min	加合离子
1	异嗪皮啶	99.9	C₁₁H₁₀O₅	223.1	190.1^*/162.1	30/35	60	7.68	[M+H]⁺
2	迷迭香酸	99.6	C₁₈H₁₆O₈	359.1	160.9^*/196.8	-22/-22	-60	11.06	[M-H]^-
3	氯化两面针碱	91.0	C₂₁H₁₈NO₄Cl	348.0	332.2^*/304.2	44/45	60	14.28	[M-Cl]⁺
4	绿原酸	96.3	C₁₆H₁₈O₉	353.1	191.1^*/85.0	-22/-55	-40	3.11	[M-H]^-
5	木犀草苷	98.1	C₂₁H₂₀O₁₁	447.1	284.8^*/327.1	-35/-30	-160	8.50	[M-H]^-
6	人参皂苷Rg₁	97.0	C₄₂H₇₂O₁₄	845.5	799.5^*/637.5	-35/-45	-60	13.55	[M+HCOO]^-
7	人参皂苷Rb₁	93.8	C₅₄H₉₂O₂₃	1 153.6	1 107.6^*/945.5	-30/-60	-60	15.68	[M+HCOO]^-
8	三七皂苷R₁	97.8	C₄₇H₈₀O₁₈	977.5	931.2^*/637.1	-30/-60	-60	12.68	[M+HCOO]^-
9	黄芩苷	97.2	C₂₁H₁₈O₁₁	445.1	269.1^*/175.0	-24/-15	-60	12.79	[M-H]^-
10	小檗碱	91.0	C₂₀H₁₇NO₄	336.1	320.2^*/292.1	40/40	70	13.61	[M+H]⁺
11	黄连碱	94.0	C₁₉H₁₃NO₄	320.1	292.1^*/262.1	40/46	40	11.08	[M+H]⁺
12	丹皮酚	99.9	C₉H₁₀O₃	167.1	121.0^*/149.0	20/27	20	15.75	[M+H]⁺
13	芦荟苷	94.8	C₂₁H₂₂O₉	419.1	239.2^*/211.0	18/32	30	12.60	[M+H]⁺
14	厚朴酚	99.2	C₁₈H₁₈O₂	265.1	247.1^*/204.0	-30/-50	-120	18.59	[M-H]^-
15	和厚朴酚	99.8	C₁₈H₁₈O₂	265.1	223.7^*/249.9	-30/-30	-140	18.31	[M-H]^-
16	紫丁香苷	94.3	C₁₇H₂₄O₉	395.1	232.0^*/185.1	32/26	160	3.04	[M+Na]⁺
17	长梗冬青苷	93.8	C₃₆H₅₈O₁₀	695.3	487.2^*/649.4	-35/-25	-120	15.87	[M+HCOO]^-
18	儿茶素	96.6	C₁₅H₁₄O₆	289.1	245.1^*/203.1	-20/-26	-100	3.15	[M-H]^-
19	咖啡酸	99.7	C₉H₈O₄	179.0	135.1^*/107.1	-20/-40	-40	4.09	[M-H]^-
20	紫堇灵	98.3	C₂₁H₂₁NO₅	368.1	289.2^*/319.2	36/28	60	12.93	[M+H]⁺
21	（R, S） -告依春	100.0	C₅H₇NOS	130.0	69.9^*/95.9	10/12	20	2.88	[M+H]⁺

序号	中药提取物	指标成分
1	草珊瑚	异嗪皮啶、迷迭香酸
2	两面针	氯化两面针碱
3	金银花	绿原酸、木犀草苷
4	三七（田七）	人参皂苷Rg₁、人参皂苷Rb₁、三七皂苷R₁
5	黄芩	黄芩苷
6	黄连	盐酸小檗碱、盐酸黄连碱
7	牡丹皮	丹皮酚
8	芦荟	芦荟苷
9	厚朴	厚朴酚、和厚朴酚
10	救必应	紫丁香苷、长梗冬青苷
11	茶	儿茶素
12	蒲公英	咖啡酸
13	苦地丁	紫堇灵
14	板蓝根（菘蓝根）	（R, S） -告依春

序号	化合物	基质效应^*	线性范围/ （ng/mL）	r	检出限/ （ng/mL）	定量限/ （ng/mL）
1	异嗪皮啶	0.47	0.5~26.7	0.998 5	0.2	0.5
2	迷迭香酸	1.05	10.4~517.9	0.999 9	3.4	10.4
3	氯化两面针碱	0.90	1.0~48.4	0.999 6	0.3	1.0
4	绿原酸	1.13	10.7~532.9	0.998 2	3.6	10.7
5	木犀草苷	1.02	10.0~501.9	1.000 0	3.4	10.0
6	人参皂苷Rg₁	1.00	2.6~130.3	0.999 9	0.9	2.6
7	人参皂苷Rb₁	0.91	10.5~526.7	0.999 7	3.5	10.5
8	三七皂苷R₁	0.98	11.7~585.8	0.999 6	3.9	11.7
9	黄芩苷	1.12	5.0~248.6	1.000 0	1.7	5.0
10	盐酸小檗碱	0.97	0.5~23.9	0.999 9	0.2	0.5
11	盐酸黄连碱	0.97	0.5~25.4	1.000 0	0.2	0.5
12	丹皮酚	0.91	5.5~275.8	0.999 6	1.8	5.5
13	芦荟苷	0.86	2.0~99.5	1.000 0	0.7	2.0
14	厚朴酚	1.04	6.4~321.4	0.999 8	2.1	6.4
15	和厚朴酚	0.95	1.4~67.7	0.999 8	0.4	1.4
16	紫丁香苷	0.60	5.0~251.0	0.999 7	1.7	5.0
17	长梗冬青苷	0.97	5.3~264.5	0.996 3	1.8	5.3
18	儿茶素	1.03	10.4~521.3	0.999 9	3.5	10.4
19	咖啡酸	1.01	14.5~723.8	0.996 4	4.8	14.5
20	紫堇灵	1.01	0.6~32.2	0.999 7	0.2	0.6
21	（R,S） -告依春	0.81	6.4~319.0	0.998 9	2.1	6.4

序号	化合物	加入量/ （μg/g）	平均回收率/%	RSD/%
1	异嗪皮啶	0.016，0.037，0.107	101.7，105.1，109.8	6.1，6.3，1.8
2	迷迭香酸	0.311，0.725，2.072	100.3，102.2，111.2	1.3，2.5，1.5
3	氯化两面针碱	0.029，0.068，0.194	108.6，95.5，99.1	4.4，8.8，12.6
4	绿原酸	0.320，0.746，2.131	88.3，97.1，109.3	4.9，2.4，1.4
5	木犀草苷	0.301，0.703，2.008	103.1，105.0，111.8	2.2，2.7，1.1
6	人参皂苷Rg₁	0.078，0.182，0.521	102.0，105.1，112.7	3.1，4.6，1.9
7	人参皂苷Rb₁	0.316，0.737，2.107	111.4，111.1，115.8	4.9，4.8，4.8
8	三七皂苷R₁	0.351，0.820，2.343	100.3，109.3，119.8	2.3，2.9，1.2
9	黄芩苷	0.149，0.348，0.994	104.1，104.0，113.0	2.7，1.4，3.0
10	小檗碱	0.014，0.033，0.096	108.8，104.0，106.6	3.8，2.1，2.1
11	黄连碱	0.015，0.036，0.102	102.9，102.2，109.1	2.3，2.7，4.7
12	丹皮酚	0.166，0.386，1.103	103.9，105.5，114.8	3.2，2.5，1.6
13	芦荟苷	0.060，0.139，0.398	100.7，101.5，111.6	2.4，1.3，1.2
14	厚朴酚	0.193，0.450，1.286	91.5，112.2，119.0	3.2，1.6，2.7
15	和厚朴酚	0.041，0.095，0.271	88.7，96.8，111.9	6.9，3.2，2.5
16	紫丁香苷	0.151，0.351，1.004	114.3，112.6，121.0	7.5，4.8，3.6
17	长梗冬青苷	0.159，0.370，1.058	121.0，108.5，101.6	5.6，7.6，4.6
18	儿茶素	0.313，0.730，2.085	101.6，106.0，114.6	2.0，2.4，0.9
19	咖啡酸	0.434，1.013，2.895	91.1，96.1，102.7	4.4，1.5，2.2
20	紫堇灵	0.019，0.045，0.129	96.6，104.0，114.5	3.2，1.5，1.6
21	（R,S） -告依春	0.191，0.447，1.276	90.0，109.0，116.2	4.5，4.3，2.3

序号	中药提取物	化合物	含量/(μg/g)	总批数	检出批数
1	草珊瑚	异嗪皮啶	0.089~0.590	3	3
1	草珊瑚	迷迭香酸	0.146	3	3
2	两面针	氯化两面针碱	2.209~4.689	5	4
3	金银花（忍冬花）	绿原酸	0.042~1.550	5	4
3	金银花（忍冬花）	木犀草苷	0.016~0.025	5	4
4	三七（田七）	人参皂苷Rg₁	25.17~586.27	8	7
		人参皂苷Rb₁	41.19~637.39
		三七皂苷R₁	3.96~586.29
5	黄芩	黄芩苷	391.98~1 528.25	7	6
6	黄连	盐酸小檗碱	15.32	1	1
6	黄连	盐酸黄连碱	< LOQ	1	1
7	牡丹皮	丹皮酚	114.14~203.14	3	3
8	芦荟	芦荟苷	未检出	6	0
9	厚朴	厚朴酚	2.12	1	1
9	厚朴	和厚朴酚	2.22	1	1
10	救必应	紫丁香苷	0.284~292.39	3	3
10	救必应	长梗冬青苷	286.83~1 035.59	3	3
11	茶	儿茶素	0.071~0.124	5	3
12	蒲公英	咖啡酸	0.535~5.807	7	7
13	苦地丁	紫堇灵	0.243~3.106	6	6
14	板蓝根（菘蓝根）	（R, S） -告依春	0.210~0.882	6	5

Determination of 21 characteristic components in Chinese medicine formula toothpaste by UPLC-MS/MS

RichHTML

PDF (PC)

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 7

References 18

Related Articles 15

Metrics

Comments

Recommended 0

[1]	Yanfang Zhou,Weihong Huo,Haixin Yang,Xuejing Chen. Simultaneous determination of 5 kinds of sweeteners in oral care toothpaste by HPLC [J]. China Surfactant Detergent & Cosmetics, 2026, 56(3): 400-406.
[2]	Huixiang Liu, Feiyan Diao, Xiaoyun Wu, Junjie Li, Chunlin Liu, Qiyan Li. Determination of 12 whitening ingredients in cosmetics using UPLC-MS/MS [J]. China Surfactant Detergent & Cosmetics, 2026, 56(1): 129-136.
[3]	Bingbing Xie, Linli Liu, Limin Fan. Simultaneous determination of 5 new preservatives in oral care toothpaste by high performance liquid chromatography [J]. China Surfactant Detergent & Cosmetics, 2026, 56(1): 122-128.
[4]	Lu Wang, Dan Ran, Hui Wang, Shaotong He, Lulu Pi, Nan Deng. Detection of pyoluteorin and pyocyanin in cosmetics using UPLC-MS/MS method [J]. China Surfactant Detergent & Cosmetics, 2025, 55(8): 1066-1071.
[5]	Xiaoting Jin, Jinsheng Li. Simultaneous determination of 6 flavonoids in grapefruit extract toothpaste by high performance liquid chromatography [J]. China Surfactant Detergent & Cosmetics, 2025, 55(7): 937-942.
[6]	Limin Fan, Meiling He, Liying Yuan, Yali Shen, Bingbing Xie, Peilin Liu. Simultaneous determination of 10 quaternary ammonium salt bactericides in oral care toothpaste by high performance liquid chromatography [J]. China Surfactant Detergent & Cosmetics, 2025, 55(7): 943-948.
[7]	Weidong Huang. Determination of 10 indicative components from plant materials in whitening cosmetics by UPLC-MS/MS [J]. China Surfactant Detergent & Cosmetics, 2025, 55(4): 531-538.
[8]	Qiuyan Zhang, Juntao Liao, Weiwei Liang, Fang Huang, Huiqin Wu, Huitai Luo. Determination of 14 thiazides in cosmetics by ultra high performance liquid chromatography-tandem mass spectrometry [J]. China Surfactant Detergent & Cosmetics, 2025, 55(1): 117-124.
[9]	Zhenhua Dong, Meiyan Wang, Wenbo Lu, Jiandong Liu, Zijian Wang, Chao Chen. Simultaneous determination of 10 sulfonamides in oral care toothpastes by high performance liquid chromatography [J]. China Surfactant Detergent & Cosmetics, 2025, 55(1): 125-130.
[10]	Changzhao Wang, Zihao Li, Yixin Wang, Yue Yang. Determination of 5 whitening agents in cosmetics using UPLC-MS/MS [J]. China Surfactant Detergent & Cosmetics, 2024, 54(7): 873-878.
[11]	Zhishan Wu, Yanchao Wang, Chengjun Jiang, Yuchen Long, Shuai Yin, Weicheng Yin. Simultaneous determination of 27 preservatives in toothpaste by high-performance liquid chromatography [J]. China Surfactant Detergent & Cosmetics, 2024, 54(12): 1515-1523.
[12]	Liangyu Zhang, Haiying Yu, Silong Li, Yaqi Jiang, Weijian Wang, Qiyan Li, Junjie Li. Study on the using status of preservatives in toothpastes based on HPLC [J]. China Surfactant Detergent & Cosmetics, 2024, 54(11): 1397-1404.
[13]	Dongxia Cao, Lei Zhou, Jiahong Li, Changqin Lin, Jinling Chen. Rapid quantitative analysis of soluble/ionic fluoride in toothpastes [J]. China Surfactant Detergent & Cosmetics, 2024, 54(1): 38-44.
[14]	Wang Jicai, Jian Ruidong, Xie Yu, Chen Xiaobin, Zhou Yi, Tan Jianhua. Study on the standardization of evaluation for the efficacy of toothpaste in extrinsic stain removal [J]. China Surfactant Detergent & Cosmetics, 2023, 53(9): 1101-1107.
[15]	Zhou Lei,Cao Dongxia,Li Jiahong,Su Nafeng,Li Wenhui. Study of different forms of fluoride in toothpaste by solid state NMR [J]. China Surfactant Detergent & Cosmetics, 2023, 53(8): 963-967.