基于复合表面活性剂提取的SP-ICP-MS法测定油包水防晒剂中纳米氧化锌

doi:10.3969/j.issn.2097-2806.2026.08.015

摘要/Abstract

摘要：

建立了一种基于十二烷基硫酸钠（SDS）与聚乙二醇-聚丙二醇（25/30）共聚物（PEG-PPG-25/30）复合表面活性剂提取的超声辅助结合单颗粒电感耦合等离子体质谱（Single particle-inductively coupled plasma-mass spectrometry，SP-ICP-MS）的分析方法，用于同步测定油包水（W/O）型防晒霜中纳米氧化锌（ZnONPs）的粒径分布及颗粒数量。该复合分散体系通过静电排斥与空间位阻的协同作用，有效破解了W/O乳液的稳定结构，显著提升了ZnONPs的提取效率与分散稳定性。通过对pH值、超声时间及稀释倍数等关键参数的系统优化，确定最佳分析条件为：pH为7.0、超声处理时间为30 min、颗粒数量在1.6×10⁸~1.2×10⁹ 颗粒数/L范围内。方法学验证结果显示，ZnONPs标准物质的测定值与参考值高度一致；方法的粒径检出限为7 nm，颗粒数量检出限为2.34×10³ 颗粒数/L，加标回收率为109.7%±3.5%，且ZnONPs标准物质的测定值与参考值高度吻合，显示出优异的准确性、灵敏度与重现性。该研究为解决复杂基质中纳米颗粒的提取与准确定量难题提供了可靠的前处理策略。所建立的方法操作简便、分析快速，适用于W/O型防晒产品中ZnONPs的高精度、高灵敏度检测。

关键词: 单颗粒-电感耦合等离子质谱, 氧化锌纳米颗粒, 表面活性剂, 防晒剂

Abstract:

A method for analysis of oil-in-water （W/O） sunscreen formulations containing nano zinc oxide （ZnONPs） was established. The mixture of sodium dodecyl sulfate （SDS） and polyethylene glycol-polypropylene glycol copolymer （PEG-PPG-25/30） was used for extraction, and then the extracted sample was analyzed by ultrasound-assisted single particle inductively coupled plasma mass spectrometry （SP-ICP-MS）. This method enabled the determination of particle size distribution and particle number concentration of ZnONPs. The surfactant-polymer mixture could effectively break the stable structure of W/O emulsions through synergistic effects of electrostatic repulsion and steric hindrance, thus significantly enhancing the extraction efficiency and dispersion stability of ZnONPs. Key parameters such as pH value, ultrasonic treatment time, and dilution factor were optimized, and the optimized analytical conditions were as follows: pH of 7.0, ultrasonic processing for 30 min, and a range of particle testing concentration from 1.6×10⁸ to 1.2×10⁹ particles/L. Results of methodological validation indicated that the measured values for ZnONP standard materials were highly consistent with reference values; specifically, the detection limit for particle size was 7 nm while the detection limit for particle number concentration was 2.34×10³ particles/L. The spiked recovery was found to be 109.7%±3.5%, further confirming the excellent accuracy, sensitivity, and reproducibility in measurement. This work provided a reliable pre-treatment strategy to address challenges associated with extracting and accurately quantifying nanoparticles in complex matrices. The established method was straightforward in operation and rapid in analysis, making it suitable for high-precision and high-sensitivity detection of ZnONPs in W/O sunscreen products.

Key words: single particle inductively coupled plasma mass spectrometry, zinc oxide nanoparticle, surfactant, sunscreen

中图分类号:

TQ423

宋玉函, 徐羽翀, 杨阳, 张雪青, 刘真, 冯敬敬. 基于复合表面活性剂提取的SP-ICP-MS法测定油包水防晒剂中纳米氧化锌[J]. 日用化学工业（中英文）, 2026, 56(8): 1111-1117.

Yuhan Song, Yuchong Xu, Yang Yang, Xueqing Zhang, Zhen Liu, Jingjing Feng. Dtermination of ZnO nanoparticles in water-in-oil sunscreen by SP-ICP-MS based on extraction with a surfactant-polymer mixture[J]. China Surfactant Detergent & Cosmetics, 2026, 56(8): 1111-1117.

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参考文献 15

[1]	Smijs T G, Pavel S. Titanium dioxide and zinc oxide nanoparticles in sunscreens: focus on their safety and effectiveness[J]. Nanotechnology, Science and Applications, 2011, 4: 95-112. doi: 10.2147/NSA.S19419 pmid: 24198489
[2]	Ulrike B, Lauren B, Qasim C, et al. The SCCS scientific advice on the safety of nanomaterials in cosmetics[J]. Regulatory Toxicology and Pharmacology, 2021, 126: 105046. doi: 10.1016/j.yrtph.2021.105046
[3]	Snežana S, Jelica P. Safety of cosmetic products in the light of European legislation: Cosmetic Regulation (EC) No 1223/2009[J]. Arhiv za Farmaciju, 2018, 68(5): 911-933. doi: 10.5937/ArhFarm1805911S
[4]	Chen Q, Zhang Z, Su Z, et al. Correlation of cosmetic nanomaterials attributes and their efficacy[J]. China Surfactant Detergent & Cosmetics, 2024, 54(5): 588-595.
[5]	Meng Z W, Zheng L N, Fang H, et al. Single particle inductively coupled plasma time-of-flight mass spectrometry: a powerful tool for the analysis of nanoparticles in the environment[J]. Processes, 2023, 11(4): 1237.
[6]	Francisco L, Javier J, Eduardo B, et al. Selective identification, characterization and determination of dissolved silver (i) and silver nanoparticles based on single particle detection by inductively coupled plasma mass spectrometry[J]. Journal of Analytical Atomic Spectrometry, 2011, 26(7): 1362-1371. doi: 10.1039/c0ja00098a
[7]	Bengt F, Lucian F, Barry H, et al. Advanced tools for the safety assessment of nanomaterials[J]. Nature Nanotechnology, 2018, 13(7): 537-543. doi: 10.1038/s41565-018-0185-0 pmid: 29980781
[8]	Beatrice B, Stefano C, Oreste S, et al. ICP-MS based methods to characterize nanoparticles of TiO₂ and ZnO in sunscreens with focus on regulatory and safety issues[J]. Science of the Total Environment, 2018, 630: 922-930. doi: 10.1016/j.scitotenv.2018.02.166
[9]	Wang Y F, Hou B F, Cao X L, et al. Interaction between polymer and anionic/nonionic surfactants and its mechanism of enhanced oil recovery[J]. Journal of Dispersion Science and Technology, 2017, 39(8): 1178-1184. doi: 10.1080/01932691.2017.1386112
[10]	Zhang X, Servos M R, Liu J. Ultrahigh nanoparticle stability against salt, pH, and solvent with retained surface accessibility via depletion stabilization[J]. Journal of the American Chemical Society, 2012, 134(24): 9910-9913. doi: 10.1021/ja303787e pmid: 22646098
[11]	Jiang J H, Pi J, Cai J Y, et al. The advancing of zinc oxide nanoparticles for biomedical applications[J]. Bioinorganic Chemistry and Applications, 2018, Article ID 1062562: 1-18.
[12]	Mittal A K, Bhaumik J, Kumar S, et al. Biosynthesis of silver nanoparticles: elucidation of prospective mechanism and therapeutic potential[J]. Journal of Colloid and Interface Science, 2014, 415: 39-47. doi: 10.1016/j.jcis.2013.10.018 pmid: 24267328
[13]	Wang X G, Sun T S, Zhu Z, et al. Roles of pH, cation valence, and ionic strength in the stability and aggregation behavior of zinc oxide nanoparticles[J]. Journal of Environmental Management, 2020, 267: 110656. doi: 10.1016/j.jenvman.2020.110656
[14]	Wang G K, Yang Y X. Infection of different ultra audible frequency and temperature to dispersive property of ZnO nanometre granule[J]. Progress in Textile Science & Technology, 2005 (2): 3.
[15]	Laborda F, Bolea E, Jimenez-Lamana J. Single particle ICPMS: a powerful tool for nano-analysis[J]. Analytical Chemistry, 2013, 86(5): 2270-2278. doi: 10.1021/ac402980q

分散剂	颗粒数量/ （颗粒数/L）	平均颗粒数量/ （颗粒数/L）	粒径/ nm	平均粒径/ nm	加标回收率/%
Triton X-100-1	1.50×10⁶	4.15×10⁶	55	60	103.28±2.6
Triton X-100-2	4.40×10⁵		55
Triton X-100-3	1.80×10⁶		74
Triton X-100-4	1.90×10⁷		44
Triton X-100-5	8.80×10⁵		84
Triton X-100-6	1.30×10⁶		49
SDS-1	4.70×10⁶	5.82×10⁶	44	50	102.5±3.0
SDS-2	5.40×10⁶		56
SDS-3	3.80×10⁶		52
SDS-4	5.40×10⁶		47
SDS-5	9.70×10⁶		56
SDS-6	5.90×10⁶		47
PEG-PPG-25/30-1	7.30×10⁷	7.53×10⁷	55	51	108.30±4.1
PEG-PPG-25/30-2	7.40×10⁷		50
PEG-PPG-25/30-3	8.20×10⁷		52
PEG-PPG-25/30-4	7.60×10⁷		50
PEG-PPG-25/30-5	7.70×10⁷		49
PEG-PPG-25/30-6	7.00×10⁷		48
SDS+PEG-PPG- 25/30-1	1.70×10⁹	1.77×10⁹	36	35	109.7±3.5
SDS+PEG-PPG- 25/30-2	1.70×10⁹		37
SDS+PEG-PPG- 25/30-3	1.70×10⁹		35
SDS+PEG-PPG- 25/30-4	1.90×10⁹		34
SDS+PEG-PPG- 25/30-5	1.70×10⁹		36
SDS+PEG-PPG- 25/30-6	1.90×10⁹		33