Particle size characterization of titanium dioxide in sunscreen products using sedimentation field-flow fractionation–inductively coupled plasma–mass spectrometry

Sedimentation field-flow fractionation–inductively coupled plasma–mass spectrometry (SdFFF-ICP-MS) was successfully applied to investigate particle size distribution of titanium dioxide (TiO₂) in sunscreen samples after hexane extraction to remove organic components from the samples. Three brands of sunscreen products of various sun protection factor (SPF) value were used as samples. Different particle size distribution profiles were observed for sunscreen samples of various brands and SPF values; however, the particle size distributions of titanium dioxide in most sunscreen samples investigated in this work were larger than 100 nm. The titanium dioxide concentrations were higher for the products of higher SPF values. By comparing the results obtained from online SdFFF-ICP-MS and those from the off-line ICP-MS determination of titanium after acid digestion, ICP-MS was found to effectively atomize and ionize the titanium dioxide particle without the need for acid digestion of the samples. Therefore, the online coupling between SdFFF and ICP-MS could be effectively used to provide quantitative information of titanium dioxide concentrations across particle size distribution profiles.     

Liquid crystalline formulations containing modified surface TiO2 nanoparticles obtained by sol–gel process

Titanium dioxide (TiO₂) is an inorganic compound used as sunscreen in cosmetic/pharmaceutical formulations as a way to prevent the skin cancer. In this work we have used surface modified titania nanoparticles obtained by thermo-reversible sol?Cgel transition showing transparency in the range of temperature typical for sunscreen use (between 20 and 45?°C). The goal of this work was to develop and characterize liquid crystalline cosmetic formulations containing surface modified titania nanoparticles. We have analyzed the citotoxicity of the nanoparticles, their zeta potential and the liquid crystalline phase behavior of the formulations. The violet crystal assay has shown no citotoxicity associated to the presence of surface modified groups on the two cell lines tested, human keratinocytes and fibroblasts, presenting more than 70% of cell viability for all analyzed nanoparticles. The zeta potential measurements revealed a negative charged surface for TiO₂ nanoparticles at pH values in the range of 6.5?C7.0, preventing the aggregation and maintaining the final transparency of the liquid crystalline sunscreen formulations. The polarized light microscopy, associated to SAXS, have shown the presence of liquid crystalline phases both with and without TiO₂ nanoparticles. The charged surface of TiO₂ nanoparticles maintains the stability of the formulations and the liquid crystalline structure. This renders this system a good candidate for being used simultaneously as sunscreen and as controlled release system of anti cancer drugs.     

Development and evaluation of microencapsulated sunscreen

The aim of the present study was to carry out stability tests and in vitro sun protection factor (SPF) evaluations of formulations containing free or microencapsulated chemical sun filters to improve their use. To this end, three formulations were developed and subjected to stability studies. The most stable formulation was chosen as a vehicle for free and microencapsulated chemical sun filters, and subjected to further stability studies and in vitro SPF assays. The SPF values were approximately 12 and 11 for formulations containing free and encapsulated sun filters, respectively, and both types were stable under stress. Chemical sun filters can be microencapsulated, which may aid in generating innovative sunscreen formulations.     

Neutral desorption extractive electrospray ionization mass spectrometry for fast screening sunscreen agents in cream cosmetic products

High throughput analysis of sunscreen agents present in cream cosmetic has been demonstrated, typically 2 samples per minute, using neutral desorption extractive electrospray ionization mass spectrometry (ND-EESI-MS) without sample pretreatment. For the targeted compounds such as 4-Aminobenzoic acid and oxybenzone, ND-EESI-MS method provided linear signal responses in the range of 1-100 ppb. Limits of detection (LOD) of the method were estimated at sub-ppb levels for the analytes tested. Reasonable relative standard deviation (RSD = 8.4-16.0%) was obtained as a result of 10 independent measurements for commercial cosmetics samples spiked with each individual sunscreen agents at 1-10 ppb. Acceptable recoveries were achieved in the range of 87-116% for direct analysis of commercial cream cosmetic samples. The experimental data demonstrate that ND-EESI-MS is a useful tool for high throughput screening of sunscreen agents in highly viscous cream cosmetic products, with the capability to obtain quantitative information of the analytes.     

高效液相色谱法测定化妆品中的12种紫外吸收剂

建立了高效液相色谱同时测定化妆品中12种紫外吸收剂含量的方法。样品用甲醇提取,高速离心,过滤,以SB-C8柱(250 mm×4.6 mm, 5 μm)为分离色谱柱,甲醇和0.1%(v/v)甲酸水溶液为流动相,梯度洗脱,以311 nm为检测波长进行定性、定量分析。该方法前处理简单、易操作,12种紫外吸收剂分离效果良好;在1.0～500 mg/L范围内呈线性关系,相关系数大于0.9995;方法检出限为0.002～0.1 mg/L;实际样品中的加标回收率为97.4%～107.5%,相对标准偏差为1.54%～4.98%。该方法简便、准确,能够满足化妆品中紫外吸收剂的检测要求。     

Alternative methods to evaluate the protective ability of sunscreen against photo-genotoxicity

Numerous epidemiological investigations show that sunlight is carcinogenic to humans and that the use of sunscreen may be effective in decreasing the risk of skin cancer. The biological activity of a sunscreen is evaluated by its ability to protect human skin from erythema as represented by a Sun Protection Factor (SPF). We propose that the sunscreen's protective effect against sunlight-induced genotoxicity, including mutation, should also be taken into account. In this study we examined the protective ability of sunscreens against natural sunlight and UV-induced genotoxicity in Drosophila somatic cells. We prepared three kinds of sunscreen samples, each with an SPF value of 20, 40 or 60 and compared their protective activities with commercial sunscreens. When a sunscreen of SPF 20, 40 or 60 was pasted on the plastic cover of a petri dish in which Drosophila larvae were exposed to the sun or UV lamps, genotoxicity decreased as the SPF of the sunscreen increased, relative to levels of genotoxicity observed in samples without sunscreen. However, the protective abilities of sunscreens were unexpectedly not so different from each other. To reveal the relationship between the protective activity of sunscreen and the wavelength of light with which larvae were irradiated through the sunscreen, we measured the transmittance of light through the petri dish cover on which the sunscreen was pasted. Effective protection was demonstrated by removing components of light whose wavelengths were below 315 nm. We suggest, that the measurement of anti-genotoxic activity and the determination of the wavelengths of light transmitted through the sunscreen should be an alternative method for evaluating the effectiveness of a sunscreen.     

Reapplication improves the amount of sunscreen, not its regularity, under real life conditions

The sun protection factor (SPF) of sunscreens is determined using samples applied with a thickness of 2 mg cm(-2). Sunscreen users, however, typically apply sunscreen nonuniformly and in smaller amounts. The objective of our study was to verify whether sunscreen reapplication increases the amount and regularity of the product on the skin. Volunteers were asked to apply an SPF 6 sunscreen on their forearms and reapply it 30 min later on one forearm. Tape-strips were used to collect five samples from two different sites on each forearm. The concentration of benzophenone-3 in the samples was measured and the total amount of sunscreen was estimated using high-performance liquid chromatography. The median amount of sunscreen film was 0.43 mg cm(-2) (0.17-1.07) after one application and 0.95 mg cm(-2) (0.18-1.91) after two applications (P = 0.002). No significant difference was found in the film uniformity. Though sunscreen reapplication increases the amount of product on the skin, levels are still lower than the recommended amount, confirming that the protection level is less than the product-stated SPF. Our results are the first in the literature to support the recommendation for reapplying sunscreens. Based on our results, we recommend that sunscreens be labeled using qualitative measures.     

气相色谱-质谱法测定化妆品中13种防晒剂

防晒剂广泛应用于化妆品中,是目前化妆品监管的重点。建立了同时测定化妆品中13种防晒剂的气相色谱-质谱(GC-MS)方法。化妆品样品经二氯甲烷提取后,涡旋超声后稀释。采用程序升温模式,经HP-5ms毛细管色谱柱(30 m×250 μm×0.25 μm)在30 min内对13种防晒剂实现分离,经电子轰击(EI)源电离后采用选择离子监测模式(SIM)扫描测定,外标法定量。比较了6种常用有机溶剂的基质效应和平均回收率,二氯甲烷的基质效应弱,平均回收率较高。13种防晒剂在相应的线性范围内线性关系良好,相关系数均大于0.998,检出限(LOD, S/N=3)为0.04~0.63 mg/g,定量限(LOQ, S/N=10)为0.12~2.10 mg/g。实验选取了两种基质,在3个水平下验证方法的回收率和精密度,13种防晒剂在霜类基质中的加标回收率为88.7%~103.6%,相对标准偏差(RSD, n=6)为1.7%~4.9%,在乳类基质中的加标回收率为88.4%~102.3%, RSD(n=6)为1.2%~3.9%。美白类化妆品常添加防晒剂成分,为监管盲区,采用该方法检测了5批含有防晒剂的美白类化妆品,其所含5种防晒剂的含量为0.8%~5.2%,符合相关要求。该方法操作简单,灵敏度高,回收率好,测定的13种防晒剂均为我国《化妆品安全技术规范》2015版规定的常用的限用组分,可以用于各类化妆品中13种防晒剂的定性定量测定,为市场监管和实验室检测提供新的技术支持。     

Penetration Study of Formulated Nanosized Titanium Dioxide in Models of Damaged and Sun‐Irradiated Skins

Inorganic ultraviolet filters such as titanium dioxide (TiO₂), safe to use on healthy skin, are often applied on compromised and irradiated skin. The aim of this study was to evaluate in vitro the cutaneous penetration of TiO₂ nanoparticles (≥ 20 nm primary size), included in a sunscreen, in intact, damaged, irradiated, and damaged/irradiated pigskin. Cutaneous penetration and localization of TiO₂ after a 24‐h sunscreen application were investigated quantitatively using inductively coupled plasma‐mass spectrometry, and qualitatively using transmission electron microscopy (TEM). Elemental identity of the nanoparticles was evaluated by TEM‐coupled Energy Dispersive X‐ray analysis (TEM‐EDX). In intact and damaged/irradiated skins, 102.35 ± 4.20% and 102.84 ± 5.67% of the titanium deposited, respectively, were found at the surface and stratum corneum (SC), whereas only 0.19 ± 0.15% and 0.39 ± 0.39% were found in the viable epidermis and dermis and no titanium was detected in the receptor fluid. TEM‐EDX analysis confirmed the presence of titanium in the aggregates formed by TiO₂ at the SC surface, as already characterized in the sunscreen formulation. TiO₂ nanoparticles included in a sunscreen thus remain in the uppermost layers of the SC, whether in intact skin or in compromised and/or skin exposed to simulated solar radiation.     

高效液相色谱法同时测定防晒类化妆品中15种紫外线吸收剂

建立了一种反相高效液相色谱同时测定防晒类化妆品中15种紫外线吸收剂的分析方法。化妆水、乳液、膏霜和蜡质样品中首先加入四氢呋喃(含2 g/L氢氧化铵),涡旋、振荡、混匀(若蜡质样品仍分散不完全,可超声振荡加热至50 ℃),再加入80%(v/v)甲醇水溶液振荡混匀、超声提取、离心、过滤后,采用XTerra MS C₁₈柱分离,经水(含0.1%(v/v)甲酸)和甲醇(含0.1%(v/v)甲酸)梯度洗脱,以二极管阵列检测器检测,检测波长为280 nm和311 nm,外标法定量。实验中对不同基质类型样品的前处理条件(样品分散溶剂、萃取溶剂和萃取时间等)进行了重点优化。结果表明,15种紫外线吸收剂在各自的线性范围内呈良好的线性关系(r²≥0.9991),方法的定量限为1.2~5.1 μg/g,在低、中、高3个添加水平下的回收率为84.2%~100.7%,相对标准偏差(RSD)为0.9%~9.5%。该分析方法分离效果好、灵敏度高、定量准确,可用于防晒类化妆品的实际检测。     

In Vivo Evaluation of the Photoprotective Efficacy of O1/W/O2 Multiple Emulsions with Andiroba Oil (Carapa guianensis)

Stable multiple emulsions containing andiroba oil and sunscreen have been formulated. These were prepared using the two-step procedure. The formulations were characterized and their stability over the time was evaluated by centrifugation, macroscopic, and microscopic analyses, and rheological measurements. The photoprotective efficacy of the O/W and O₁/W/O₂ containing or not andiroba oil was evaluated by in vivo sun protection factor determination according to the FDA method. The formulations exhibited good stability during 30 days after preparation at different temperatures. These presented pseudoplastic flow behaviour and thixotropy. The increase of in vivo SPF value was not observed when andiroba oil was incorporated into emulsions containing ethylhexyl methoxycinnamate. These multiple emulsions can be utilized as an interesting topical vehicle.     

反相高效液相色谱法测定化妆品中的防晒剂

用反相高效液相色谱法在２０ｍｉｎ内同时测定化妆品中１１种防晒剂。色谱柱为ＹＷＧ－Ｃ１８柱,流动相为甲醇－四氢呋喃－水－高氯酸（２００２００１６００．１,Ｖ／Ｖ）,检测波长为３１１ｎｍ。报告了对１０３种防晒化妆品测定的结果。     

Determination of benzophenones in a cosmetic matrix by supercritical fluid extraction and capillary electrophoresis

Benzophenones are common additives in commercial sunscreen products. These UV absorbers were extracted by supercritical fluid extraction (SFE), and then analyzed by capillary zone electrophoresis (CZE) and high-performance liquid chromatography. This study was applied to identify the contents of benzophenones in cosmetic matrix, and simultaneously, to investigate the behavior of migration in CZE. Adding non-ionic surfactant (Tween 20) to optimize the separation in the CZE operation improves resolution. In SFE, we chose carbon dioxide with 2.5% modifier of 10% aqueous phosphoric acid-MeOH (1:1) as the supercritical fluid. Real recoveries of up to 92% with relative standard deviations of less than 4.0% were achieved. These analytical techniques were also applied to assay benzophenones for ten commercial sunscreen cosmetics. We found benzophenone 3 was the most commonly used sunscreen additive in Taiwan.     

Particulate sol–gel synthesis and optical and electrical properties of CeO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> nanocomposite

CeO₂/TiO₂ nanocomposite was synthesized by particulate sol–gel method. The X-ray diffractogram shows the presence of cubic CeO₂ and anatase TiO₂ in the composite. The high resolution scanning electron micrographs reveal the nanoparticulate nature of the prepared composite. The composite absorbs UV light and exhibits near-band gap emission corresponding to TiO₂ and deep level emission due to crystal defects. The Nyquist plot displays two semicircular arcs indicating the material heterogeneity. The physicochemical characteristics of the synthesized nanocomposite are in favour of its application as an ingredient of sunscreen formulations; under UV light the photocatalytic activity of CeO₂/TiO₂ composite, tested through the degradation of rhodamine B, is very much less than that by pristine anatase TiO₂. Reduced adsorption of moisture by the nanocomposite is a possible reason for the observed very low photocatalytic activity.     

Photoprotective nanoemulsions containing microbial carotenoids and buriti oil: Efficacy and safety study

Photoprotective nanoemulsions are able to attenuate skin damage from overexposure to the sun, thus avoiding the immediate effects caused by ultraviolet radiation. The global cosmetics market understands that there is a demand and greater acceptance by consumers for formulations containing natural products compatible with the skin. Consequently, there is an increasingly need to develop such products that are safe and effective. Furthermore, there is a growing interest in nanoemulsions (NE) in the pharmaceutical industry, due the versatility of incorporating lipophilic substances into cosmetic formulations. In the present work, oil-in-water photoprotective nanoemulsions containing microbial carotenoids, buriti oil and chemical filters were developed and characterized. The essential physical properties of the droplets, the transmission electronic microscopy (TEM), the sun protection factor (SPF) as well as the stability of the formulations were determined. In vitro phototoxicity was evaluated using Balb 3 T3 with relative cell viability estimated by Neutral Red Uptake, with the Photo Irritation Factor (PIF) and the Medium Photo Effect Factor (MPF) as the measurement parameters. Nanoemulsion 3 (NE3) showed spherical morphology with an average droplet size of 142.11 ± 0.92 nm and polydispersity index (PDI) of 0.198 ± 0.017. This nanoemulsion containing microbial carotenoids and buriti oil exhibited a SPF of 36 ± 1.5. Neutral Red Uptake revealed that the cells kept their viability even after irradiation and those nanoemulsions containing the microbial carotenoids and buriti oil were not phototoxic. The addition of microbial carotenoids and buriti oil in nanoemulsions was positive in increasing the mean SPF values compared to the control formulation.     

TiOx Films Deposited by Plasma Enhanced Chemical Vapour Deposition Method in Atmospheric Dielectric Barrier Discharge Plasma

The plasma enhanced chemical vapour deposition method applying atmospheric dielectric barrier discharge (ADBD) plasma was used for TiO_x thin films deposition employing titanium (IV) isopropoxide and oxygen as reactants, and argon as a working gas. ADBD was operated in the filamentary mode. The films were deposited on glass. The films?? chemical composition, surface topography, wettability and aging were analysed, particularly the dependence between precursor and reactant concentration in the discharge atmosphere and its impact on TiO_x films properties. Titanium in films near the surface area was oxidized, the dominating species being TiO₂ and substoichiometric titanium oxides. The films exhibited contamination with carbon, as a result of atmospheric oxygen and carbon dioxide reactions with radicals in films. No relevant difference of the film surface due to oxygen concentration inside the reactor was determined. The films were hydrophilic immediately after deposition, afterwards their wettability diminished, due to chemical reactions of the film surface and chemical groups involved in the atmosphere.     

Simple Extraction and HPLC Determination of UV-A and UV-B Filters in Sunscreen Products

The determination of 11 organic UV filters, worldwide authorised in sunscreen formulations, was performed by HPLC with UV spectrophotometric detection. The filters determined were: phenylbenzimidazole sulfonic acid, benzophenone-4, benzophenone-3, 4-methylbenzylidene camphor, ethylhexyl methoxycinnamate, octocrylene, methylene bis-benzotriazolyl tetramethylbutyl phenol, butyl methoxydibenzoylmethane, bis-ethylhexyloxyphenol methoxyphenyltriazine, ethylhexyl triazone, and diethylamino hydroxybenzoyl hexyl benzoate. Three analytical methods were developed which were based on an ultrasonic extraction of the sample in methanol/1% aqueous acetic acid (70:30, v/v) or dimethylacetamide/propan-2-ol (1:1, v/v) in dependence of the water or fat-solubility of the filter, followed by HPLC separation and quantitation. HPLC was carried out using three different columns and eluting conditions. Standard calibration curves were linear for all the analytes over the concentration range 0.5–100 μg mL^?1. UV measurements were carried out at 280, 300, 310 or 360 nm with the aid of a diode array detector in dependence on the maximum absorption of each filter. Quantitative recoveries were obtained for all sunscreen compounds determined in homemade formulations. The proposed analytical procedure has been successfully applied for the analysis of commercial samples in order to check the presence of UV filters and to determine their concentration.     

Nanodisperse photocatalysts based on titanium dioxide

A new method for synthesizing amorphous ultradisperse titanium oxide particles immobilized on the surface of SiO₂ aerogel was suggested. TiO₂/SiO₂ systems containing 3–15 wt % TiO₂ were prepared. The chemical composition, structure, and morphology of the surface of the synthesized catalysts were studied by transmission electron microscopy, X-ray diffraction, and IR spectroscopy. The Brunauer-Emmett-Teller method was used to estimate the specific surface area of the samples. The photocatalytic activity of the systems was studied in the model reaction of the decomposition of methylene blue dye. The systems synthesized were found to be more active than TiO₂ Degussa P25.     

Materials Science Challenges in Skin UV Protection: A Review

UV radiation is one of the critical environmental stress factors for human skin, which can trigger various problems such as pruritus, burning, erythema, premature skin aging and skin cancer. Hence, UV protection has become an indispensable daily routine and the use of topical sunscreen products is rapidly increasing. However, there are emerging concerns over the efficiency and safety of existing chemical and physical UV filters used in consumer products. Furthermore, there is no universally approved method for assessing sun protection efficiency regardless of the immediate end user need to develop safer sunscreen products that afford broad-spectrum photoprotection. It is evident that the current organic and inorganic UV filters have significant unfavorable impacts on human, environmental, and marine safety. Therefore, effective alternative UV filters should be established. This article comprehensively reviews the properties, safety, health and ecological concerns of various UV filters including TiO₂ and ZnO nanoparticles as well as the limitations of the testing protocols and guidelines provided by major regulatory bodies. The photoreactivity of UV filters used in sunscreen remains a major challenge, and it is crucial to develop new sunscreen ingredients, which not only protect the consumer, but also the environment.