油酸甾醇酯液晶的合成、微胶囊化及其防晒配方应用

doi:10.3969/j.issn.2097-2806.2025.11.006

摘要/Abstract

摘要：

本研究旨在合成具有液晶特性的油酸甾醇酯，并通过微胶囊化技术提升其稳定性和紫外阻隔性能。油酸甾醇酯通过植物甾醇与油酸酯化反应制备，采用红外光谱（FTIR）和质谱（MS）表征其分子结构，利用偏光显微镜（POM）、热重分析（TGA）、差示扫描量热法（DSC）、广角与小角X射线散射（WAXS、SAXS）表征其液晶行为，并测定其紫外阻隔性能。为提升液晶结构的稳定性，利用乳液聚合法将其微胶囊化。针对包含液晶、液晶微胶囊和纳米二氧化钛的防晒配方进行SPF值测试。结果显示，油酸甾醇酯表现出典型的胆甾相液晶行为及UVA强紫外吸收；且微胶囊化进一步提升了其稳定性和紫外阻隔性能，SPF测试表明，含有液晶微胶囊的配方SPF值达到7.01，高于含纳米二氧化钛的配方（SPF=6.23），且显著优于含未包裹液晶的配方（SPF=2.65），说明液晶微胶囊有效保护了液晶结构，维持了其紫外阻隔性能。本研究表明，微胶囊化的油酸甾醇酯在防晒配方中具有应用潜力，能够提供更高的稳定性与高效的紫外防护性能，展示出在创新化妆品产品中的应用前景。

关键词: 植物甾醇, 液晶, 微胶囊化, 紫外吸收, 防晒配方, SPF测试

Abstract:

This study reports the synthesis of oleic acid sterol ester with liquid crystalline properties and its enhanced stability and UV-blocking performance through microencapsulation. Oleic acid sterol ester was synthesized via the esterification of phytosterol and oleic acid, whose structure was characterized using Fourier-transform infrared spectroscopy （FTIR） and mass spectrometry （MS）. Its liquid crystalline behavior was confirmed via the polarized optical microscopy （POM）, thermogravimetric analysis （TGA）, differential scanning calorimetry （DSC）, wide-angle X-ray scattering （WAXS）, and small-angle X-ray scattering （SAXS）. UV absorption tests were conducted to assess the UV-blocking performance of the oleic acid sterol ester liquid crystals. To improve the stability of its liquid crystalline structure, the oleic acid sterol ester was encapsulated into microcapsules through the emulsion polymerization. SPF measurements were performed on the sunscreen formulations containing liquid crystal microcapsules. The oleic acid sterol ester displayed cholesteric liquid crystalline behavior and strong UVA absorption, which indicates its suitability as a natural UV absorber. Microencapsulation further enhanced its stability and UV-blocking properties. SPF testing showed that the formulations with microcapsules achieved an SPF value of 7.01, which surpasses the nano titanium dioxide （SPF=6.23） and significantly outperform the unencapsulated liquid crystal formulations （SPF=2.65）. This study highlights the potential of microencapsulated oleic acid sterol ester as a novel UV absorber in the sunscreen formulations, offers the enhanced stability and effective UV protection, and showcases its application potential in the innovative cosmetic products.

Key words: phytosterol, liquid crystals, microencapsulation, UV absorption, sunscreen formulations, SPF testing

中图分类号:

TQ658

柳旭泽, 许倡, 林良良, 许虎君. 油酸甾醇酯液晶的合成、微胶囊化及其防晒配方应用[J]. 日用化学工业（中英文）, 2025, 55(11): 1408-1418.

Xuze Liu, Chang Xu, Liangliang Lin, Hujun Xu. Synthesis and microencapsulation of oleic acid sterol ester liquid crystals for its application in sunscreen formulations[J]. China Surfactant Detergent & Cosmetics, 2025, 55(11): 1408-1418.

图/表 14

参考文献 34

[1]	Chen L, Wang J X, Wu X W, et al. Boosting the effectiveness of UV filters and sunscreen formulations using photostable, non-toxic inorganic platelets[J]. Chemical Communications, 2024, 8: 1039-1042.
[2]	Najafabadi A H, Soheilifar M H, Masoudi-Khoram N. Exosomes in skin photoaging: biological functions and therapeutic opportunity[J]. Cell Communication and Signaling, 2024, 22 (1) : 32.
[3]	Shin S H, Lee Y H, Rho N K, et al. Skin aging from mechanisms to interventions: focusing on dermal aging[J]. Frontiers in Physiology, 2023, 14: 1195272. doi: 10.3389/fphys.2023.1195272
[4]	Karmali R A, Safai B. Ultraviolet-evoked prostaglandin biosynthesis in varying stages of keratinocyte differentiation in guinea pig skin[J]. Prostaglandins Leukotrienes and Medicine, 1984, 15 (3) : 277-286. doi: 10.1016/0262-1746(84)90127-6
[5]	Poon F, Kang S, Chien A L. Mechanisms and treatments of photoaging[J]. Photodermatology, Photoimmunology & Photomedicine, 2015, 31 (2) : 65-74.
[6]	Jin S G, Padron F, Pfeifer G P. UVA radiation, DNA damage, and melanoma[J]. ACS Omega, 2022, 7 (37) : 32936-32948. doi: 10.1021/acsomega.2c04424
[7]	Mu J, Chen H, Ye M, et al. Acacetin resists UVA photoaging by mediating the SIRT3/ROS/MAPKs pathway[J]. Journal of Cellular and Molecular Medicine, 2022, 26 (16) : 4624-4628. doi: 10.1111/jcmm.v26.16
[8]	Hoang M, Qureshi A, Oancea E, et al. Furocoumarins potentiate UVA-induced DNA damage in skin melanocytes[J]. Biochemical And Biophysical Research Communications, 2023, 684: 149066. doi: 10.1016/j.bbrc.2023.09.094
[9]	Wakefield G, Stott J. Photostabilization of organic UV-absorbing and anti-oxidant cosmetic components in formulations containing micronized manganese-doped titanium oxide[J]. International Journal of Cosmetic Science, 2006, 57 (5) : 385-395.
[10]	Kullberg S A, Hylwa S A. The versatile UV absorber drometrizole: Expanding from the realm of cosmetics to feminine sanitary products[J]. Contact Dermatitis, 2020, 83 (6).
[11]	Sahoo D K, Mohanty P, Biswal H S, et al. Conformers influence on UV-absorbance of avobenzone[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2024, 453: 115671. doi: 10.1016/j.jphotochem.2024.115671
[12]	Liu H M, Ma X Y, Zhao Y H. Preparation of liquid crystal emulsion and its application in cosmetics[J]. China Surfactant Detergent & Cosmetics, 2022, 52 (7) : 762-769.
[13]	Zhao Y, Shi Z, Lang T, et al. Research of nanofibres loaded with ultraviolet absorber to increase the wavewidth of cholesteric liquid crystals[J]. Optical Materials, 2023, 137: 113545. doi: 10.1016/j.optmat.2023.113545
[14]	Pathak G, Hegde G, Prasad V. Octadecylamine-capped CdSe/ZnS quantum dot dispersed cholesteric liquid crystal for potential display application: Investigation on photoluminescence and UV absorbance[J]. Liquid Crystals, 2021, 48 (4) : 579-587. doi: 10.1080/02678292.2020.1799085
[15]	Rapalli V K, Waghule T, Hans N, et al. Insights of lyotropic liquid crystals in topical drug delivery for targeting various skin disorders[J]. Journal of Molecular Liquids, 2020, 315: 113771. doi: 10.1016/j.molliq.2020.113771
[16]	Puglia C, Bonina F. In vivo spectrophotometric evaluation of skin barrier recovery after topical application of soybean phytosterols[J]. International Journal of Cosmetic Science, 2008, 31: 217-224.
[17]	Rocha V Z, Ras R T, Gagliardi A C, et al. Effects of phytosterols on markers of inflammation: A systematic review and meta-analysis[J]. Atherosclerosis, 2016, 248: 76-83. doi: 10.1016/j.atherosclerosis.2016.01.035 pmid: 26987068
[18]	Shen M, Yuan L, Zhang J, et al. Phytosterols: Physiological functions and potential application[J]. Foods, 2024, 13 (11) : 1754.
[19]	Vigne S, Pot C. Implication of oxysterols and phytosterols in aging and human diseases[J]. Implication of Oxysterols and Phytosterols in Aging and Human Diseases, 2023: 231-260.
[20]	Zhang S, Yang Y, Xing H, et al. Synthesis of phytosteryl oleate using composite catalysts[J]. CIESC Journal, 2015, 66 (8) : 3078-3083.
[21]	Meng X, Pan Q, Yang T. Synthesis of phytosteryl esters by using alumina-supported zinc oxide (ZnO/Al₂O₃) from esterification production of phytosterol with fatty acid[J]. Journal of the American Oil Chemists’ Society, 2011, 88 (1) : 143-149. doi: 10.1007/s11746-010-1654-2
[22]	Pastarnokienė L, Potapov E, Makuška R, et al. Optimization of microencapsulation of polyaspartic acid ester into UV curable epoxy-acrylate resin using Taguchi method of experimental design[J]. Journal of Applied Polymer Science, 2024, 141 (15) : e55216.
[23]	Xu D, Yang R. Efficient preparation and characterization of paraffin-based microcapsules by emulsion polymerization[J]. Journal of Applied Polymer Science, 2019, 136 (21) : 47552.
[24]	Wang L, Liu S, Luo S, et al. Advances in the preparation and application of liquid crystal microcapsules[J]. Liquid Crystals, 2024, 51 (11) : 1792-1823. doi: 10.1080/02678292.2024.2364789
[25]	Althaqafi K A, Satterthwaite J, AlShabib A, et al. Synthesis and characterisation of microcapsules for self-healing dental resin composites[J]. BMC Oral Health, 2024, 24 (1) : 109.
[26]	Zhang Y R, Liu D, Zhang Y, et al. Preparation of SiO₂-encapsulated TiO₂ composite nanoparticles and evaluation of the sunscreen performance[J]. China Surfactant Detergent & Cosmetics, 2022, 52 (1) : 28-34.
[27]	Jiang Z J. Consistency of sunscreen SPF values measured by in vivo and in vitro methods[J]. China Surfactant Detergent & Cosmetics, 2019, 49 (4) : 234-237.
[28]	Liu Z P, He X Z, Cong Y H, et al. Synthesis and characterization of two series of pressure-sensitive cholesteric liquid crystal elastomers with optical properties[J]. Liquid Crystals, 2020, 47 (1) : 143-153. doi: 10.1080/02678292.2019.1642524
[29]	Labeeb A M, Ward Y A, Fikry M. Thermal control of tunable photonic optical bandgaps in different cholesteric liquid crystals mixtures[J]. Journal of Molecular Liquids, 2021, 340: 117179. doi: 10.1016/j.molliq.2021.117179
[30]	den Adel R, Heussen P C M, Bot A. Effect of water on self-assembled tubules in β-sitosterol+γ-oryzanol-based organogels[J]. Journal of Physics: Conference Series. IOP Publishing, 2010, 247 (1) : 012025.
[31]	Hsiao B S, Chu B, Burger C. Synchrotron X-Ray scattering of polymer nanocomposites[J]. Synchrotron Radiation News, 2002, 15 (5) : 20-34.
[32]	Zhang J, Dong B, Zheng L, et al. Lyotropic liquid crystalline phases formed in ternary mixtures of 1-cetyl-3-methylimidazolium bromide/p-xylene/water: A SAXS, POM, and rheology study[J]. Journal of Colloid and Interface Science, 2008, 321 (1) : 159-165. doi: 10.1016/j.jcis.2008.01.020 pmid: 18294647
[33]	Hong H J, Nasrollahi A, Park S Y. Transparent UV-blocking photonic film based on reflection of cholesteric liquid crystals[J]. Journal of Molecular Liquids, 2021, 344: 117739. doi: 10.1016/j.molliq.2021.117739
[34]	Qu C, Wang Q, Zhang X, et al. Excellent ultraviolet-blocking properties of chiral nematic liquid crystals[J]. Photochemistry and Photobiology, 2024, 100 (1) : 33-40. doi: 10.1111/php.v100.1

	w/%
	Formulation A		Formulation B		Formulation C		Formulation D
Phase A	Stearic acid	8	Stearic acid	8	Stearic acid	8	Stearic acid	8
	Stearyl alcohol	3	Stearyl alcohol	3	Stearyl alcohol	3	Stearyl alcohol	3
	liquid crystal microcapsules	5	Oleic acid sterol ester	5	Nano titanium dioxide	5	Glyceryl monostearate	1.5
	Glyceryl monostearate	1.5	Glyceryl monostearate	1.5	Glyceryl monostearate	1.5	Glyceryl monostearate	1.5
Phase B	Glycerol	10	Glycerol	10	Glycerol	10	Glycerol	10
Phase B	Water	72.5	Water	72.5	Water	72.5	Water	77.5