高效液相色谱法同时测定口腔护理牙膏中10种磺胺类物质含量

doi:10.3969/j.issn.2097-2806.2025.01.016

摘要/Abstract

摘要： 建立了高效液相色谱法（HPLC）同时检测牙膏中10种磺胺类物质的方法。选用0.1%甲酸-甲醇（体积比90:10）作为牙膏样品溶液的提取溶剂，提取方法为20 ℃水浴超声提取20 min。流动相：A为0.1%甲酸，B为甲醇。柱温20 ℃；进样量10 μL，流速1.0 mL/min；检测波长为270 nm。方法学考察结果显示，10种磺胺类物质的精密度RSD范围为0.90%~1.49%，稳定性RSD范围为0.61%~1.42%，重复性RSD范围为0.94%~1.42%，所有RSD均<2.0%。10种磺胺类物质在1~100 mg/L质量浓度范围内呈良好的线性关系，相关系数为0.999 1~0.999 8。10种磺胺类物质的平均回收率范围为91.99%~110.82%，RSD为0.93%~2.03%。应用本方法检测了20种牙膏中10种磺胺类物质的含量，均未检出。本研究建立的HPLC同时测定10种磺胺类物质的方法具有良好的精密度、稳定性、重复性和准确性，适用于检测牙膏中磺胺类物质。

关键词: 高效液相色谱法, 牙膏, 磺胺类物质

Abstract:

A method for simultaneous determination of 10 sulfonamides in the toothpaste by high performance liquid chromatography （HPLC） was established. 0.1% formic acid aqueous solution-methanol （volume ratio of 90:10） was used as the extraction solvent for the toothpaste sample solution, and the extraction method was ultrasonic extraction for 20 min in a 20 ℃ water bath. The HPLC conditions were as follows: The mobile phase: A was 0.1% formic acid aqueous solution, and B was methanol. The column temperature was 20 ℃; the injection volume was 10 μL, and the flow rate was 1.0 mL/min; the detection wavelength was 270 nm. The results of methodological investigation showed that the precision RSD of the 10 sulfonamides ranged from 0.90% to 1.49%, the stability RSD ranged from 0.61% to 1.42%, and the repeatability RSD ranged from 0.94% to 1.42%, and all RSDs were<2.0%. The 10 sulfonamides showed good linear relationship in the mass concentration range of 1-100 mg/L, with the correlation coefficients of 0.999 1-0.999 8. The average recovery rate of the 10 sulfonamides ranged from 91.99% to 110.82%, and the RSD ranged from 0.93% to 2.03%. This detection method was used to detect the content of the 10 sulfonamides in 20 toothpastes, and none of the 10 sulfonamides were detected in these 20 toothpastes. The HPLC method established in this work for simultaneous determination of 10 sulfonamides had good precision, stability, repeatability and accuracy, which was suitable for the detection of sulfonamides in toothpastes.

Key words: high performance liquid chromatography, toothpaste, sulfonamide

中图分类号:

TQ658

董振花, 王美艳, 路文博, 刘建东, 王子健, 陈超. 高效液相色谱法同时测定口腔护理牙膏中10种磺胺类物质含量[J]. 日用化学工业（中英文）, 2025, 55(1): 125-130.

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.

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参考文献 19

[1]	罗成江, 陈慧华, 林仙军, 等. UPLC和HPLC法检测猪肉中磺胺类药物残留的比较[J]. 中国兽药杂志, 2012, 46 (4) : 25-28.
[2]	林红英, 沈子龙, 陆桂萍. HPLC法测定牛奶中磺胺二甲基嘧啶残留量[J]. 中国药科大学学报, 2006, 37 (2) : 191-192.
[3]	陈吉之, 闫超. 饲料中9种磺胺类药物的HPLC法快速分离与检测[J]. 中国医药工业杂志, 2015, 46 (8) : 892-894.
[4]	Apaydın S, Török M. Sulfonamide derivatives as multi-target agents for complex diseases[J]. Bioorg. Med. Chem. Lett., 2019, 29 (16) : 2042-2050.
[5]	洪蕾洁, 石璐, 张亚雷, 等. 固相萃取-高效液相色谱法同时测定水体中的10种磺胺类抗生素[J]. 环境科学, 2012, 33 (2) : 652-657.
[6]	Karadağlıoğlu Ö, Ulusoy N, Başer K H C, et al. Antibacterial activities of herbal toothpastes combined with essential oils against streptococcus mutans[J]. Pathogens, 2019, 8 (1) : 20.
[7]	Hajishengallis G, Chavakis T, Hajishengallis E, et al. Neutrophil homeostasis and inflammation: novel paradigms from studying periodontitis[J]. J. Leukoc. Biol., 2015, 98 (4) : 539-548.
[8]	Schmidt J C, Bux M, Filipuzzi-Jenny E, et al. Influence of time, toothpaste and saliva in the retention of Streptococcus mutans and Streptococcus sanguinis on different toothbrushes[J]. J. Appl. Oral. Sci., 2014, 22 (3) : 152-158.
[9]	Filoche S K, Anderson S A, Sissons C H. Biofilm growth of lactobacillus species is promoted by actinomyces species and streptococcus mutans[J]. Oral. Microbiol. Immunol., 2004, 19 (5) : 322-326.
[10]	Smith A J, Jackson M S, Bagg J. The ecology of Staphylococcus species in the oral cavity[J]. J. Med. Microbiol., 2001, 50 (11) : 940-946. doi: 10.1099/0022-1317-50-11-940 pmid: 11699589
[11]	Anderson A C, Jonas D, Huber I, et al. Enterococcus faecalis from food, clinical specimens, and oral sites: prevalence of virulence factors in association with biofilm formation[J]. Front Microbiol., 2015, 6: 1534. doi: 10.3389/fmicb.2015.01534 pmid: 26793174
[12]	Liao W, Ning Y, Zhang Y, et al. Determination of sulfonamides in milk and egg samples by HPLC with mesoporous polymelamine-formaldehyde as magnetic solid-phase extraction adsorbent[J]. J. Sep. Sci., 2021, 44 (24) : 4402-4411.
[13]	Yao T, Du K. Simultaneous determination of sulfonamides in milk: In-situ magnetic ionic liquid dispersive liquid-liquid microextraction coupled with HPLC[J]. Food Chem., 2020, 331: 127342.
[14]	张岩, 马晓斐, 吕品, 等. 液相色谱-串联质谱法同时测定牙膏中16种磺胺类药物残留[J]. 质谱学报, 2013, 34 (4) : 239-246. doi: 10.7538/zpxb.2013.34.04.0239
[15]	Khuluza F, Kigera S, Jähnke R W, et al. Use of thin-layer chromatography to detect counterfeit sulfadoxine/pyrimethamine tablets with the wrong active ingredient in Malawi[J]. Malar. J., 2016, 15: 215.
[16]	Ning Y, Ye Y, Liao W, et al. Triazine-based porous organic polymer as pipette tip solid-phase extraction adsorbent coupled with HPLC for the determination of sulfonamide residues in food samples[J]. Food Chem., 2022, 397: 133831.
[17]	Pashaei R, Dzingelevičienė R, Abbasi S, et al. Determination of 15 human pharmaceutical residues in fish and shrimp tissues by high-performance liquid chromatography-tandem mass spectrometry[J]. Environ. Monit. Assess., 2022, 194 (5) : 325.
[18]	林海丹, 谢守新, 冯德雄, 等. 动物源性食品中磺胺类药物残留的固相萃取-高效液相色谱法测定[J]. 分析测试学报, 2003, 22 (1) : 94-96.
[19]	孙晶玮, 赵新淮. 牛奶中多种磺胺类抗生素残留的HPLC快速分析[J]. 食品科学, 2007, 28 (6) : 256-259.

磺胺类物质	精密度RSD/%	稳定性RSD/%	重复性RSD/%
磺胺苯吡唑	1.25	1.17	1.24
磺胺对甲氧嘧啶	1.49	1.32	1.04
磺胺二甲异噁唑	0.90	1.08	1.14
磺胺甲基嘧啶	1.36	0.61	1.08
磺胺甲基异噁唑	1.22	1.32	1.22
磺胺甲噻二唑	1.30	1.26	1.09
磺胺间二甲氧嘧啶	1.43	1.42	0.94
磺胺氯哒嗪	0.93	0.97	1.14
磺胺嘧啶	1.28	1.39	0.93
磺胺噻唑	1.34	1.01	1.42

磺胺类物质	线性方程	线性范围/（mg/L）	相关系数
磺胺苯吡唑	y=327.635 5x+69.317 0	1~100	0.999 6
磺胺对甲氧嘧啶	y=318.326 9x-98.772 4	1~100	0.999 3
磺胺二甲异噁唑	y=272.157 2x+65.650 5	1~100	0.999 5
磺胺甲基嘧啶	y=369.479 4x+54.489 7	1~100	0.999 7
磺胺甲基异噁唑	y=265.533 7x-111.266 7	1~100	0.999 3
磺胺甲噻二唑	y=294.039 7x+68.886 1	1~100	0.999 1
磺胺间二甲氧嘧啶	y=358.172 9x+58.514 4	1~100	0.999 5
磺胺氯哒嗪	y=241.435 8x-149.028 4	1~100	0.999 8
磺胺嘧啶	y=264.006 2x-47.793 1	1~100	0.999 4
磺胺噻唑	y=307.947 8x+117.400 9	1~100	0.999 2

磺胺类物质	加入量/（mg/kg）	实测量/（mg/g）	回收率/%	RSD/%	平均回收率/%	平均RSD/%
磺胺苯吡唑	1	1.13	112.95	2.08	104.02	2.03
	10	11.02	110.19	1.82
	50	44.46	88.93	2.09
磺胺对甲氧嘧啶	1	1.10	109.57	2.16	96.25	1.86
	10	8.83	88.30	1.81
	50	45.45	90.89	1.42
磺胺二甲异噁唑	1	0.92	92.13	2.33	104.91	1.31
	10	12.18	121.78	1.72
	50	50.40	100.81	1.52
磺胺甲基嘧啶	1	0.99	99.19	1.19	96.76	1.83
	10	8.66	86.63	2.06
	50	52.22	104.45	2.12
磺胺甲基异噁唑	1	1.16	116.19	1.91	107.91	1.40
	10	12.22	122.16	1.69
	50	42.69	85.37	1.73
磺胺甲噻二唑	1	1.07	107.18	1.60	107.42	1.49
	10	11.98	119.78	1.79
	50	47.64	95.28	2.14
磺胺间二甲氧嘧啶	1	1.14	113.69	1.55	103.80	0.93
	10	10.64	106.37	1.90
	50	45.67	91.34	1.63
磺胺氯哒嗪	1	0.82	81.55	2.06	91.99	1.58
	10	10.62	106.24	1.94
	50	44.09	88.18	1.45
磺胺嘧啶	1	1.15	115.22	2.27	110.82	1.40
	10	11.43	114.30	2.17
	50	51.46	102.93	2.01
磺胺噻唑	1	1.01	101.43	2.03	99.40	1.70
	10	9.64	96.40	2.59
	50	50.19	100.37	2.36