馨肤白/壳聚糖皮克林乳液的制备及美白活性评价

doi:10.3969/j.issn.2097-2806.2025.11.002

摘要/Abstract

摘要：

用溶胶-凝胶法制备壳聚糖纳米颗粒，以PDMS为油相，高速剪切得壳聚糖皮克林乳液（CS-PE），其中壳聚糖颗粒占乳液总质量0.4%，水油比4∶4。再经高速剪切制得负载馨肤白377 （PR）的CS-PE （称其PR CS-PE），其包封率为97.2%±0.2%，载药量为2.3%±0.01%。PR CS-PE的DPPH和ABTS自由基清除率分别为77.4%和93.8%，表明其具有良好的抗氧化性。Franz体外透皮实验结果表明PR CS-PE中PR为缓慢释放。此外PR CS-PE可有效抑制斑马鱼黑色素的生成，具有良好的美白活性。斑马鱼胚胎发育和细胞毒性实验结果表明负载有馨肤白的壳聚糖皮克林乳液配方与纯PR相比，毒性降低，表明馨肤白/壳聚糖皮克林乳液在化妆品领域具有潜在的应用价值。

关键词: 壳聚糖纳米颗粒, 皮克林乳液, 馨肤白, 斑马鱼, 细胞毒性

Abstract:

Chitosan nanoparticles （（212.2±3.2） nm） were synthesized via sol-gel method by adjusting the pH of the chitosan solution. Using polydimethylsiloxane （PDMS） as the oil phase, a chitosan-based Pickering emulsion （CS-PE） was prepared by high-speed shear homogenization, with solid particle mass fraction of 0.4% and water-to-oil volume ratio of 4∶4. Phenylethyl resorcinol （PR） was subsequently loaded into the emulsion to form the PR-loaded CS-PE （PR CS-PE）. The encapsulation efficiency and drug loading of PR in PR CS-PE were determined to be 97.2%±0.2% and 2.3%±0.01%, respectively. The radical scavenging rates of PR CS-PE for 2, 2-diphenyl-1-picrylhydrazyl （DPPH） and 2, 2′-azinobis（3-ethylbenzothiazoline-6-sulfonic acid）（ABTS） were measured to be 77.4% and 93.8%, respectively, indicative of significant antioxidant activity. The results of Franz diffusion cell test indicated that the PR within the emulsion exhibited sustained release behavior. Furthermore, PR CS-PE could effectively inhibit the melanogenesis in zebrafish models, suggesting notable skin-whitening efficacy. Results of the zebrafish embryonic development and cytotoxicity assay indicated that the PR-loaded chitosan-based Pickering emulsion exhibited lower toxicity compared with free PR. These findings suggest the potential application of the PR/chitosan Pickering emulsion in cosmetics.

Key words: chitosan nanoparticle, Pickering emulsion, phenylethyl resorcinol, zebrafish, cytotoxicity

中图分类号:

O648.2

严秋思, 毕晖, 董文心, 邹爱华. 馨肤白/壳聚糖皮克林乳液的制备及美白活性评价[J]. 日用化学工业（中英文）, 2025, 55(11): 1378-1387.

Qiusi Yan, Hui Bi, Wenxin Dong, Aihua Zou. Preparation and skin-whitening activity evaluation of phenylethyl resorcinol/chitosan Pickering emulsion[J]. China Surfactant Detergent & Cosmetics, 2025, 55(11): 1378-1387.

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参考文献 43

[1]	Zhang Y, Sil B C, Kung C P, et al. Characterization and topical delivery of phenylethyl resorcinol[J]. Int J Cosmet Sci, 2019, 41 (5) : 479-488. doi: 10.1111/ics.v41.5
[2]	Schmaus G, Vielhaber G, Jacobs K, et al. 4- (1-phenylethyl) 1, 3-benzenediol: A new highly potent lightening agent[J]. J Cosmet Sci, 2006, 57 (2) : 197-198.
[3]	Sorg O, Kasraee B, Salomon D, et al. The combination of a retinoid, a phenolic agent and an antioxidant improves tolerance while retaining an optimal depigmenting action in reconstructed epidermis[J]. Dermatology, 2013, 227 (2) : 150-156. doi: 10.1159/000353578
[4]	于承仟, 徐学刚, 李远宏. 苯乙基间苯二酚的研究应用进展[J]. 中国皮肤性病学杂志, 2020, 34 (6) : 692-695.
[5]	Amnuaikit T, Limsuwan T, Khongkow P, et al. Vesicular carriers containing phenylethyl resorcinol for topical delivery system; liposomes, transfersomes and invasomes[J]. Asian J Pharm Sci, 2018, 13 (5) : 472-484. doi: 10.1016/j.ajps.2018.02.004 pmid: 32104421
[6]	Köpke D, Muller R H, Pyo S M. Phenylethyl resorcinol smartlipids for skin brightening-increased loading & chemical stability[J]. Eur J Pharm Sci, 2019, 137: 104992. doi: 10.1016/j.ejps.2019.104992
[7]	Kim B S, Na Y G, Choi J H, et al. The improvement of skin whitening of phenylethyl resorcinol by nanostructured lipid carriers[J]. Nanomaterials (Basel), 2017, 7 (9) : 241: 1-13. doi: 10.3390/nano7010001
[8]	Demina P A, Bukreeva T V. Pickering emulsion stabilized by commercial titanium dioxide nanoparticles in the form of rutile and anatase[J]. Nanotechnologies in Russia, 2018, 13 (7/8) : 425-429. doi: 10.1134/S1995078018040043
[9]	Tan J S J, Wong S L Y, Chen Z. Preparation of Janus titanium dioxide particles via ultraviolet irradiation of Pickering emulsions[J]. Advanced Materials Interfaces, 2020, 1901961.
[10]	Bao Y, Zhang Y, Liu P, et al. Novel fabrication of stable Pickering emulsion and latex by hollow silica nanoparticles[J]. Journal of Colloid and Interface Science, 2019, 553: 83-90. doi: S0021-9797(19)30681-2 pmid: 31195217
[11]	Gálvez-Vergara A, Fresco-Cala B, Cárdenas S. Switchable Pickering emulsions stabilized by polystyrene-modified magnetic nanoparticles[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020, 606.
[12]	Li W, Suzuki T, Minami H. The interface adsorption behavior in a Pickering emulsion stabilized by cylindrical polystyrene particles[J]. J Colloid Interface Sci, 2019, 552: 230-235. doi: 10.1016/j.jcis.2019.05.058
[13]	Bouhoute M, Taarji N, de Oliveira Felipe L, et al. Microfibrillated cellulose from argania spinosa shells as sustainable solid particles for O/W Pickering emulsions[J]. Carbohydr Polym, 2021, 251: 116990. doi: 10.1016/j.carbpol.2020.116990
[14]	Shi A, Feng X, Wang Q, et al. Pickering and high internal phase Pickering emulsions stabilized by protein-based particles: A review of synthesis, application and prospective[J]. Food Hydrocolloids, 2020, 109: 106117. doi: 10.1016/j.foodhyd.2020.106117
[15]	Zhu F. Starch based Pickering emulsions: Fabrication, properties, and applications[J]. Trends in Food Science & Technology, 2019, 85: 129-137.
[16]	Zhai X, Lin D, Liu D, et al. Emulsions stabilized by nanofibers from bacterial cellulose: New potential food-grade Pickering emulsions[J]. Food Res Int, 2018, 103: 12-20. doi: S0963-9969(17)30711-1 pmid: 29389597
[17]	Tiong A C Y, Tan I S, Foo H C Y, et al. Macroalgae-derived regenerated cellulose in the stabilization of oil-in-water Pickering emulsions[J]. Carbohydr Polym, 2020, 249: 116875. doi: 10.1016/j.carbpol.2020.116875
[18]	Jia Y, Zheng M, Xu Q, et al. Rheological behaviors of Pickering emulsions stabilized by tempo-oxidized bacterial cellulose[J]. Carbohydr Polym, 2019, 215: 263-271. doi: 10.1016/j.carbpol.2019.03.073
[19]	Ahmed R, Wang M, Qi Z, et al. Pickering emulsions based on the pH-responsive assembly of food-grade chitosan[J]. ACS Omega, 2021, 6 (28) : 17915-17922. doi: 10.1021/acsomega.1c01490 pmid: 34308026
[20]	Terescenco D, Hucher N, Picard C, et al. Sensory perception of textural properties of cosmetic Pickering emulsions[J]. Int J Cosmet Sci, 2020, 42 (2) : 198-207. doi: 10.1111/ics.v42.2
[21]	Almajidi Y Q, Gupta J, Sheri F S, et al. Advances in chitosan-based hydrogels for pharmaceutical and biomedical applications: A comprehensive review[J]. Int J Biol Macromol, 2023, 253 (6) : 127278.
[22]	Meng W, Sun H, Mu T, et al. Chitosan-based Pickering emulsion: A comprehensive review on their stabilizers, bioavailability, applications and regulations[J]. Carbohydr Polym, 2023, 304: 120491. doi: 10.1016/j.carbpol.2022.120491
[23]	Bhutto R A, Wang M, Iqbal S, et al. Curcumin-loaded Pickering emulsion stabilized by pH-induced self-aggregated chitosan particles: Effects of degree of deacetylation and molecular weight[J]. Food Hydrocolloids, 2024, 147: 109422. doi: 10.1016/j.foodhyd.2023.109422
[24]	Saiki P, Mello-Andrade F, Gomes T, et al. Sediment toxicity assessment using zebrafish (Danio rerio) as a model system: Historical review, research gaps and trends[J]. Sci Total Environ, 2021, 793: 148633. doi: 10.1016/j.scitotenv.2021.148633
[25]	董思颖, 陈亮, 张璐, 等. 基于斑马鱼实验模型评价人参玫瑰膏改善气血健康作用[J]. 时珍国医国药, 2021, 32 (9) : 2295-2298.
[26]	Bai L, Huan S, Xiang W, et al. Pickering emulsions by combining cellulose nanofibrils and nanocrystals: Phase behavior and depletion stabilization[J]. Green Chemistry, 2018, 20 (7) : 1571-1582. doi: 10.1039/C8GC00134K
[27]	Ye F, Miao M, Cui S W, et al. Characterisations of oil-in-water Pickering emulsion stabilized hydrophobic phytoglycogen nanoparticles[J]. Food Hydrocolloids, 2018, 76: 78-87. doi: 10.1016/j.foodhyd.2017.05.003
[28]	Mession J L, Assifaoui A, Lafarge C, et al. Protein aggregation induced by phase separation in a pea proteins-sodium alginate-water ternary system[J]. Food Hydrocolloids, 2012, 28 (2) : 333-343. doi: 10.1016/j.foodhyd.2011.12.022
[29]	Argatov I, Iantchenko A, Kocherbitov V. How to define the storage and loss moduli for a rheologically nonlinear material? A constructive review of nonlinear rheological measures[J]. Continuum Mechanics and Thermodynamics, 2017, 29: 1375-1387. doi: 10.1007/s00161-017-0584-8
[30]	Costa A L R, Gomes A, Cunha R L. One-step ultrasound producing O/W emulsions stabilized by chitosan particles[J]. Food Research International, 2018, 107: 717-725. doi: S0963-9969(18)30150-9 pmid: 29580539
[31]	Ahmed Bhutto R, Hira Bhutto N U A, Wang M, et al. Curcumin-loaded Pickering emulsion stabilized by pH-induced self-aggregated chitosan particles: Effects of degree of deacetylation and molecular weight[J]. Food Hydrocolloids, 2024, 147: 109422. doi: 10.1016/j.foodhyd.2023.109422
[32]	Lv H, Wang Z, An J, et al. Preparation and emulsifying properties of carbon-based Pickering emulsifier[J]. Processes, 2023, 11: 1070. doi: 10.3390/pr11041070
[33]	Elmastas M, Turkekul I, Ozturk L, et al. Antioxidant activity of two wild edible mushrooms (Morchella vulgaris and Morchella esculanta) from north turkey[J]. Combinatorial Chemistry & High Throughput Screening, 2006, 9 (6) : 443-448.
[34]	Chen W, Pan H, Sheng Y, et al. Pickering emulsion stabilized by sugarcane leaf polyphenols-zein covalent nanoparticles for curcumin delivery: In-vitro and inhibition of oxidative hemolytic activity evaluation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 687: 133539. doi: 10.1016/j.colsurfa.2024.133539
[35]	Woo K, Shih J, Fraser S E. Fate maps of the zebrafish embryo[J]. Curr Opin Genet Dev, 1995, 5 (4) : 439-443. pmid: 7580134
[36]	Brönnimann D, Annese T, Gorr T A, et al. Splitting of circulating red blood cells as an in vivo mechanism of erythrocyte maturation in developing zebrafish, chick and mouse embryos[J]. J Exp Biol, 2018, 221 (15) : jeb184564-jeb184576.
[37]	Jong J L, Zon L I. Use of the zebrafish system to study primitive and definitive hematopoiesis[J]. Annu Rev Genet, 2005, 39: 481-501. pmid: 16285869
[38]	Caro M, Iturria I, Martinez-Santos M, et al. Zebrafish dives into food research: Effectiveness assessment of bioactive compounds[J]. Food Funct, 2016, 7 (6) : 2615-2623. doi: 10.1039/c6fo00046k pmid: 27109696
[39]	Behar R Z, Luo W, Lin S C, et al. Distribution, quantification and toxicity of cinnamaldehyde in electronic cigarette refill fluids and aerosols[J]. Tob Control, 2016, 25 (S2) : ii94-ii102.
[40]	Stockert J C, Horobin R W, Colombo L L, et al. Tetrazolium salts and formazan products in cell biology: Viability assessment, fluorescence imaging, and labeling perspectives[J]. Acta Histochem, 2018, 120 (3) : 159-167. doi: S0065-1281(17)30474-9 pmid: 29496266
[41]	管淑玉. 黑色素相关研究中动物模型的应用进展[J]. 中国实验动物学报, 2009, 17 (6) : 475-477.
[42]	Zhang J, Chambers I, Yun S, et al. Hrg1 promotes heme-iron recycling during hemolysis in the zebrafish kidney[J]. PLoS Genet, 2018, 14 (9) : e1007665.
[43]	Logan D W, Burn S F, Jackson I J. Regulation of pigmentation in zebrafish melanophores[J]. Pigment Cell Res, 2006, 19 (3) : 206-213. doi: 10.1111/pcr.2006.19.issue-3

样品名称	DPPH乙醇溶液/mL	PR CS-PE乳液/mL	PE乳液/ mL	PR-TW80乳液/mL	TW80乳液/ mL	PR乙醇乳液/ mL	乙醇/ mL
DPPH乙醇溶液（A₀）	2	0	0	0	0	0	0
PR CS-PE乳液（A₁）	2	2	0	0	0	0	0
PR CS-PE乳液（A₂）	0	2	0	0	0	0	2
PE乳液（A₁）	2	0	2	0	0	0	0
PE乳液（A₂）	0	0	2	0	0	0	2
PR-TW80乳液（A₁）	2	0	0	2	0	0	0
PR-TW80乳液（A₂）	0	0	0	2	0	0	2
TW80乳液（A₁）	2	0	0	0	2	0	0
TW80乳液（A₂）	0	0	0	0	2	0	2
PR乙醇溶液（A₁）	2	0	0	0	0	2	0
PR乙醇溶液（A₂）	0	0	0	0	0	2	2

名称	PR CS-PE乳液/mL	CS-PE乳液/mL	PR乙醇溶液/mL	乙醇/mL	ABTS母液/mL
PR CS-PE乳液（A₁）	1	0	0	0	3
CS-PE乳液（A₁）	0	1	0	0	3
PR乙醇溶液（A₁）	0	0	1	0	3
乙醇（A₁）	0	0	0	1	3