PDA-TiO<sub>2</sub>杂化纳米粒子的制备及其防晒应用

黎赛瑶; 汪洋; 李婷; 东为富

doi:10.14133/j.cnki.1008-9357.20210104001

PDA-TiO₂杂化纳米粒子的制备及其防晒应用

doi: 10.14133/j.cnki.1008-9357.20210104001

江南大学化学与材料工程学院，合成与生物胶体教育部重点实验室，江苏无锡 214122

基金项目: 国家自然科学基金（21975108）

详细信息

作者简介:
黎赛瑶（1994—），女，硕士研究生，主要研究方向为复合纳米粒子的紫外屏蔽性。E-mail：18230306627@163.com

通讯作者:
东为富，E-mail：wfdong@jiangnan.edu.cn

中图分类号: O63
计量
- 文章访问数: 544
- HTML全文浏览量: 329
- PDF下载量: 79
- 被引次数: 0
出版历程
- 收稿日期: 2021-01-04
- 网络出版日期: 2021-03-05
- 刊出日期: 2021-07-08

Preparation of PDA-TiO₂ Hybrid Nanoparticles and Their Application in Sun Protection

Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China

摘要

摘要: 采用溶胶凝胶法制备二氧化钛（TiO₂）前驱体，将其与盐酸多巴胺共混后制备聚多巴胺-TiO₂（PDA-TiO₂）杂化纳米粒子。在PDA与TiO₂的协同作用下，PDA-TiO₂粒子具有高效的防紫外线性能。利用红外光谱、X射线光电子能谱、扫描电镜、透射电镜、紫外-可见光吸收光谱、热失重曲线以及皮肤渗透实验对纳米粒子的基本结构与性能进行了一系列表征。结果表明：以PDA-TiO₂杂化纳米粒子作为唯一功效成分制备的防晒霜，其防晒系数（SPF）达到33.7；PDA具有良好的生物黏附性，能有效防止PDA-TiO₂杂化纳米粒子渗透皮肤，确保了其使用安全性。
- 聚多巴胺 /
- 二氧化钛 /
- 紫外屏蔽 /
- 生物黏附性 /
- 防晒霜
Abstract: Organic filters in conventional sunscreens generally have poor photo stability and can easily penetrate through stratum corneum and dermis into the blood vessel, thus causing potential health-threatening issues. Polydopamine (PDA) nanoparticles can be formed by self-polymerization of dopamine. Inspired by its excellent anti-ultraviolet, free radical scavenging and adhesion properties, the titanium dioxide (TiO₂) precursor is prepared by the sol-gel method and blended with dopamine hydrochloride to prepare PDA-TiO₂ hybrid nanoparticles. Infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet-visible absorption spectroscopy (UV-Vis), thermogravimetric analysis (TGA) and skin penetration experiments were used to characterize the basic structures and properties of nanoparticles. Under the synergistic effect of PDA and TiO₂, the particles have highly efficient UV protection. By simply adjusting the reaction material ratio, it was found that the more dopamine content, the better UV absorption effect was obtained, and it showed better UV absorption performance than small particle size PDA. Therefore, PDA-TiO₂(1/10) (m (DA)∶m(TiO₂)=1∶10) had the best UV absorption effect. The PDA-TiO₂ (1/10) was introduced as the sole active ingredient to formulating sunscreen, whose sun protection factor (SPF) values could reach 33.7, which can meet daily sun protection needs. Most importantly, PDA had good bioadhesion and can effectively prevent the penetration of PDA-TiO₂ hybrid nanoparticles. The thickness of the stratum corneum of the human body was about 15—20 μm. Upon comparing the PDA-TiO₂ with commercially available benzophenone small molecule sunscreens, it was found that the skin permeability of PDA-TiO₂ was significantly reduced. The penetration depth was 9—17 μm, mainly distributed in the upper and middle parts of the stratum corneum of the skin. It is not easy to enter the human body and will not pose a potential threat to skin health. The commercially available benzophenone sunscreen small molecules had a skin penetration of 18—35 μm, indicating that they penetrate the stratum corneum to reach the living epidermis and enter the human body. Therefore, the prepared nanoparticles have excellent UV resistance and biocompatibility, ensuring their excellent performance and safe use in sunscreens.
- polydopamine /
- titanium dioxide /
- UV-shielding /
- bioadhesion /
- sunscreen

HTML全文

图 1 样品的红外光谱图

Figure 1. FT-IR spectra of samples

下载: 全尺寸图片幻灯片

图 2 TiO₂和PDA-TiO₂杂化纳米粒子的XPS谱图

Figure 2. XPS spectra of TiO₂ and PDA-TiO₂ hybrid nanoparticles

下载: 全尺寸图片幻灯片

图 3 样品的SEM（a, b, c）和TEM（d, e, f）图

Figure 3. SEM （a, b, c） and TEM （d, e, f） images of samples

下载: 全尺寸图片幻灯片

图 4 PDA和PDA-TiO₂的紫外-可见光吸收谱图

Figure 4. UV-Vis absorption spectra of PDA and PDA-TiO₂

下载: 全尺寸图片幻灯片

图 5 PDA-TiO₂的热失重曲线

Figure 5. TGA curves of PDA-TiO₂

下载: 全尺寸图片幻灯片

图 6 苯酮类小分子防晒剂与PDA-TiO₂在（左）光学显微镜和（右）荧光显微镜下的皮肤渗透性

Figure 6. Skin permeability of benzophenone small molecule sunscreen and PDA-TiO₂ under （left） optical microscope and （right） fluorescence microscope

下载: 全尺寸图片幻灯片

表 1 防晒霜的配方

Table 1. Formulation of sunscreen

Phase	Name	w/%
Oil phase	Octadecanol	3.0
	Beewax	1.0
	Simethicone	1.5
	Mono-fatty acid glycerides	3.5
	Stearyl alcohol polyether-2/21	3.0
Water phase	Glycerinum	3.0
	Kalam-940	0.3
	PDA-TiO₂	5～25

下载: 导出CSV

表 2 掺入PDA-TiO₂防晒霜的SPF

Table 2. SPF value of sunscreen with PDA-TiO₂

Sample	SPF
Sample	w（PDA-TiO₂）=5%	w（PDA-TiO₂）=10%	w（PDA-TiO₂）=15%	w（PDA-TiO₂）=25%
PDA-TiO₂（1/10）	8.2±1.3	12.3±1.2	21.4±2.5	33.7±2.9
PDA-TiO₂（1/20）	4.2±1.1	6.6±1.7	13.5±1.8	21.2±3.2
PDA-TiO₂（1/30））	2.6±0.9	4.8±1.3	10.2±2.3	14.6±2.1

下载: 导出CSV

参考文献(22)

[1]	GU Y, HAN J, JIANG C, et al. Biomarkers, oxidative stress and autophagy in skin aging [J]. Ageing Research Reviews,2020,59:101036. doi: 10.1016/j.arr.2020.101036
[2]	ERHAED H, HERBERT H. UV-radiation-sources, wavelength, environment [J]. Journal der Deutschen Dermatologischen Gesellschaft,2005,3 (Suppl 2):S3-S10.
[3]	SURJADINATA B, JACOBO D, CISNEROS L. UVA, UVB and UVC light enhances the biosynthesis of phenolic antioxidants in fresh-cut carrot through a synergistic effect with wounding [J]. Molecules,2017,22(4):668-681. doi: 10.3390/molecules22040668
[4]	HERRLING T, JUNG K, FUCHS J. The role of melanin as protector against free radicals in skin and its role as free radical indicator in hair [J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2008,69(5):1429-1435. doi: 10.1016/j.saa.2007.09.030
[5]	ZOU W, GONZALEZ A, JAMPAIAH D, et al. Skin color-specific and spectrally-selective naked-eye dosimetry of UVA, B and C radiations [J]. Nature Communications,2018,9(1):3743-3753. doi: 10.1038/s41467-018-06273-3
[6]	VELASCO M V R, SARRUF F D, SALGADO-SANTOS I M N, et al. Broad spectrum bioactive sunscreens [J]. International Journal of Pharmaceutics,2008,363(1-2):50-57. doi: 10.1016/j.ijpharm.2008.06.031
[7]	KULLAVANIJAYA P, LIM H W. Photoprotection [J]. Journal of the American Academy of Dermatology,2005,52(6):937-958. doi: 10.1016/j.jaad.2004.07.063
[8]	GARLAND C F, GARLAND F C, GORHAM E D. Could sunscreens increase melanoma risk? [J]. American Journal of Public Health,1992,82(4):614-625. doi: 10.2105/AJPH.82.4.614
[9]	WESTERDAHL J, INGVAR C, MASBCK A, et al. Sunscreen use and malignant melanoma [J]. International Journal of Cancer,2000,87(1):145-150. doi: 10.1002/1097-0215(20000701)87:1<145::AID-IJC22>3.0.CO;2-3
[10]	曹妍, 骆丹. 防晒化妆品中的纳米技术 [J]. 中国美容医学杂志,2006,15(10):1206-1208. CAO Y, LUO D. Nanotechnology in sun-screening cosmetics [J]. Chinese Journal of Aesthetic Medicine,2006,15(10):1206-1208.
[11]	GIACOMONI P U, TETA L, NAJDEK L. Sunscreens: The impervious path from theory to practice [J]. Photochemical & Photobiological Sciences Official Journal of the European Photochemistry Association & the European Society for Photobiology,2010,9(4):524-529.
[12]	WU P, LEE Y, KUO Y, et al. Development of octyl methoxy cinnamates (OMC)/silicon dioxide (SiO₂) nanoparticles by sol-gel emulsion method [J]. Nanomaterials,2017,7(12):434-444. doi: 10.3390/nano7120434
[13]	ZAYAT M, GARCIA-PAREGO P, LEVY D. Preventing UV-light damage of light sensitive materials using a highly protective UV-absorbing coating [J]. Chemical Society Reviews,2007,36(8):1270-1281. doi: 10.1039/b608888k
[14]	WANG Y, LI T, MA P, et al. Simultaneous enhancements of UV-shielding properties and photostability of poly(vinyl alcohol) via incorporation of sepia eumelanin [J]. ACS Sustainable Chemistry & Engineering,2016,4(4):2252-2258.
[15]	GOLLAVILLI H, HEGDE A R, MANAGULI R S, et al. Naringin nano-ethosomal novel sunscreen creams: Development and performance evaluation [J]. Colloids and Surfaces B: Biointerfaces,2020,193:111122-111134. doi: 10.1016/j.colsurfb.2020.111122
[16]	BANERJEE I, DE M, DEY G, et al. A peptide-modified solid lipid nanoparticle formulation of paclitaxel modulates immunity and outperforms dacarbazine in a murine melanoma model [J]. Biomaterials Science,2019,7(3):1161-1178. doi: 10.1039/C8BM01403E
[17]	李晓燕, 刘志洪, 蔡汝秀. 黑色素对羟基自由基清除活性的研究 [J]. 四川大学学报(自然科学版),2003,40(6):1132-1136. LI X Y, LIU Z H, CAI R X. Study on scavenging activity of melanin to hydroxyl radical [J]. Journal of Sichuan University (Natural Science Edition),2003,40(6):1132-1136.
[18]	WANG L, DAI W, YANG M, et al. Cell membrane mimetic copolymer coated polydopamine nanoparticles for combined pH-sensitive drug release and near-infrared photothermal therapeutic [J]. Colloids and Surfaces B: Biointerfaces,2019,176:1-8. doi: 10.1016/j.colsurfb.2018.12.057
[19]	LEE S H, BAE I, LEE E, et al. Glucose exerts an anti-melanogenic effect by indirect inactivation of tyrosinase in melanocytes and a human skin equivalent [J]. International Journal of Molecular Sciences,2020,21(5):1736-1749. doi: 10.3390/ijms21051736
[20]	ROY S, VAN HAI L, KIM H C, et al. Preparation and characterization of synthetic melanin-like nanoparticles reinforced chitosan nanocomposite films [J]. Carbohydrate Polymers,2020,231:115729-115740. doi: 10.1016/j.carbpol.2019.115729
[21]	SEVER M J, WEISSER J T, MONAHAN J, et al. Metal-mediated cross-linking in the generation of a marine-mussel adhesive [J]. Angewandte Chemie International Edition,2004,43(4):448-450. doi: 10.1002/anie.200352759
[22]	潘兵. 基于聚多巴胺的超疏水通用制备方法研究[D]. 江西: 南昌航空大学, 2014. PAN B. Universal strategies to fabricate superhydrophobic sufaces on different substrates based on polydopamine [D]. Jiangxi: Nanchang Hangkong University, 2014.