面膜中荧光增白剂的透皮吸收特性及对皮肤刺激性的实验研究

doi:10.3969/j.issn.1001-1803.2022.03.014

摘要/Abstract

摘要：

为了研究含脂溶性荧光增白剂（FWAs）面膜的透皮吸收特性及其对皮肤刺激性,采用改良的Franz透皮扩散池,以离体雄性大鼠腹部皮肤为模型,通过高效液相色谱-三重四极杆液质联用法测定接收液中5种吡唑啉型荧光增白剂的含量,计算其不同透皮时间段的累计渗透量,并对试验终期皮肤中FWAs的贮留量进行检测;按《化妆品安全技术规范》（2015年版）中皮肤刺激性实验要求,采用家兔进行皮肤刺激性试验。结果显示,5种脂溶性FWAs呈现良好的线性关系,相关系数（r²）均大于0.999,检出限为0.5~10.0 pg,定量限为2.0~30.0 pg,平均回收率和相对标准偏差分别为95.2%~102.1%和1.8%~4.2%。面膜中的脂溶性荧光增白剂C.I.162有较强的透皮能力可以进入皮下,在0~36 h内透皮扩散符合零级动力学方程;而C.I.135、C.I.185、C.I.367、C.I.368四种FWAs短期内均被皮肤吸收而未透过皮肤。结果提示,脂溶性FWAs较易迁移到皮肤的角质层或皮下,对哺乳动物皮肤没有刺激作用。

关键词: 面膜, 荧光增白剂, 透皮吸收, 皮肤刺激性, 高效液相色谱-三重四极杆液质联用法

Abstract:

In order to study the transdermal absorption characteristics and skin irritation of the fluorescent whitening agents （FWAs） in the facial mask, the content of 5 pyrazoline fat-soluble FWAs in the receiving solution was determined by high performance liquid chromatography triple quadrupole liquid chromatography mass spectrometry （HPLC-MS/MS） with the modified Franz transdermal diffusion cell and the abdominal skin of male rats in vitro. The cumulative penetration amount of 5 pyrazoline fat-soluble FWAs at different time points was calculated, and the FWAs remained in the skin was detected at the end of the experiment. The skin irritation test was carried out using rabbits according to the requirements of skin irritation test in “Safety and Technical Standards for Cosmetics” （2015 Edition）. The results show that there is good linear relationship between the five fat-soluble FWAs determined by HPLC-MS/MS in their respective concentration ranges. The correlation coefficients （r ²） are all greater than 0.999. The detection limits are 0.5-10.0 pg and the lower limits of quantification are 2.0-30.0 pg. The average recoveries and relative standard deviations are 95.2%-102.1% and 1.8%-4.2%, respectively. The liposoluble FWAs C.I.162 in the mask could penetrate into the skin, and the transdermal diffusion within 0-36 h is in accordance with zero order kinetics equation. C.I.135, C.I.185, C.I.367 and C.I.368 are absorbed in the skin but not through the skin in a short period. Skin irritation test shows that 5 pyrazoline liposoluble FWAs in facial mask have no irritation on rabbit skin. It is suggested that the fat-soluble FWAs are easy to migrate to the stratum corneum or subcutaneous layer of the skin and have no iiritating effect on mammalian skin.

Key words: facial mask, fluorescent whitening agents （FWAs）, transdermal absorption, skin irritation, HPLC-MS/MS

中图分类号:

TQ658

张虹艳,石晓峰,王小乔,刘兴国,刘亚鹏,李赟. 面膜中荧光增白剂的透皮吸收特性及对皮肤刺激性的实验研究[J]. 日用化学工业, 2022, 52(3): 322-327.

Zhang Hongyan,Shi Xiaofeng,Wang Xiaoqiao,Liu Xingguo,Liu Yapeng,Li Yun. Study on transdermal absorption and skin irritation of fluorescent whitening agents in facial mask[J]. China Surfactant Detergent & Cosmetics, 2022, 52(3): 322-327.

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化合物	分子量/Da	母离子（m/z）	子离子（m/z）	锥孔电压/eV	碰撞能量/eV	极性
C.I.135	290.3	291.3	77.0^*	133	29	正离子
C.I.135	290.3	291.3	107.0	133	61	正离子
C.I.162	241.2	242.3	185.1^*	118	21	正离子
C.I.162	241.2	242.3	127.0	118	41	正离子
C.I.185	318.3	319.4	65.0^*	153	33	正离子
C.I.185	318.3	319.4	226.0	153	53	正离子
C.I.367	362.4	363.4	270.1^*	148	37	正离子
C.I.367	362.4	363.4	65.0	148	61	正离子
C.I.368	428.5	429.5	77.0^*	113	45	正离子
C.I.368	428.5	429.5	107.0	113	73	正离子

化合物	保留时间/min	线性方程	相关系数（r²）	线性范围/（μg/L）	检出限/pg	定量限/pg
C.I.135	5.49	Y=2 563X-220	0.999 1	1~100	0.5	2.0
C.I.162	4.15	Y=3 051X-224	0.999 2	1~100	1.0	3.0
C.I.185	5.52	Y=1 735X-150	0.999 6	1~100	0.5	2.0
C.I.367	6.96	Y=7 473X-1 489	0.999 6	1~100	0.5	2.0
C.I.368	7.32	Y=993X-284	0.999 5	1~100	10.0	30.0

透皮时间/h	透皮率/%	误差/%
0	0	0
3	0.44	7.8
6	1.10	6.4
12	2.22	4.7
24	4.73	2.6
36	7.57	2.1
48	8.40	2.4

皮肤反应	反应程度	得分/分
红斑和焦痂形成	无红斑	0
	轻微红斑（勉强可见）	1
	明显红斑	2
	中度-重度红斑	3
	严重红斑（紫红色）至轻微焦痂形成	4
水肿形成	无水肿	0
	轻微水肿（勉强可见）	1
	轻度水肿（皮肤隆起轮廓清楚）	2
	中度水肿（皮肤隆起约1 mm）	3
	重度水肿（皮肤隆起超过1 mm,范围扩大）	4