Nowadays, concern over skin cancer has been growing more and more, especially in tropical countries where the incidence of UVA/B radiation is higher. The correct use of sunscreen is the most efficient way to prevent the development of this disease. The ingredients of sunscreen can be organic and/or inorganic sun filters. Inorganic filters present some advantages over organic filters, such as photostability, non-irritability and broad spectrum protection. Nevertheless, inorganic filters have a whitening effect in sunscreen formulations owing to the high refractive index, decreasing their esthetic appeal. Many techniques have been developed to overcome this problem and among them, the use of nanotechnology stands out. The estimated amount of nanomaterial in use must increase from 2000 tons in 2004 to a projected 58000 tons in 2020. In this context, this article aims to analyze critically both the different features of the production of inorganic filters (synthesis routes proposed in recent years) and the permeability, the safety and other characteristics of the new generation of inorganic filters.
An organic UV absorber, cinnamic acid, was intercalated into the interlayer gallery of layered yttrium hydroxynitrate (LYH) via the anion-exchange reaction. The complete replacement of interlayer nitrate by cinnamate was confirmed by thermogravimetric analysis of the obtained intercalation compound (cin-LYH). FT-IR spectra and powder X-ray diffraction patterns before and after intercalation reaction of LYH provided an information on the interaction of cinnamate anions with the inorganic host layer. Measured chemical composition and interlayer distance of cin-LYH and van der Waals dimensions of cinnamate proposed partially interdigitated bilayer arrangement of cinnamate anions in the interlayer space of LYH. The intercalation of cinnamate into the inorganic LYH layers highly improved its thermal stability in comparison with pure cinnamic acid. The comparison of reflectance spectra of pure cinnamic acid and cin-LYH before and after exposure to solar-simulated radiation showed that the to photoisomerization of cinnamate accompanied with a significant change of the molecular packing is not facilitated in the interlayer space of LYH. In contrast, only a slight variation in width and position of absorption band indicated no strong interaction between aromatic groups of cinnamate in the interlayer space of LYH. Quartz glasses coated with cin-LYH could be readily obtained by a simple dip-coating method in colloidal solutions and showed effective UV-filtering ability particularly in UV-B region (280–320 nm) without significant loss of the transparency of quartz glass. The release studies revealed that the interlayer space of LYH is effective for the retention of cinnamate for long time and this release reaching an equilibrium state at low concentration is suitable for long-term UV-screening service.
The objective of the present study was to develop, characterize and evaluate the clinical efficacy of topical formulations containing or not active substances and UV-filters, separate and in combination. To this end a stable formulation was developed to which four aqueous active substances and four lipophilic UV-filters were added. The formulations were then submitted to microscopic characterization by light microscopy, to particle size measurement, and to macroscopic characterization by rheology and texture analysis. Finally, a clinical efficacy study was conducted to determine the effect of the formulations on the skin after application for 1 h. The formulation containing UV-filters showed a high polydisperse microstructure and a large amount of liquid crystals. The formulations containing active substances showed higher resistance to deformation, compression and penetration tests. Regarding spreadability, formulations containing UV filters alone or in combination with active substances showed higher resistance to spreading. This behavior was associated with greater clinical efficacy in terms of stratum corneum water content, protection of the skin barrier function and skin surface brightness. It was demonstrated that the efficacy of the formulation is mainly associated with its structure and the way it interacts with the skin surface. Finally, this study showed that the mixture of these ingredients for the development of multifunctional sunscreens improves the performance of the formulations.
This article presents a monolithic extraction unit with integrated stirring using carbon nanohorns and methacrylate-based compounds as monomers. The hybrid monolithic material was prepared by thermal polymerization at 70 °C for 24 h, and was applied for the extraction of UV-filters from waters and human urine samples. To achieve the integrated stirring unit, the monolith was grown over an ironware. Variables dealing with the polymerization mixture composition and the microextraction procedure were studied in depth. The resulting hybrid monolithic polymer was also characterized by scanning electron microscopy (SEM) and nitrogen intrusion porosimetry. The target analytes were quantified by UPLC-DAD, and the limits of detection were between 1 and 10 μg/L. The precision of the method (inter extraction units) expressed as relative standard deviation ranged from 5.4% and 7.9%. Also, relative recoveries values of the analyte spiked to swimming pool water and urine samples varied in the interval 72–124 and 71–114%, respectively.
A photoprotective formulation was developed with an increased sunprotection factor (SPF), compared to a conventional nanoemulsion, but having the same concentration of three molecular sunscreens, namely ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, and ethylhexyl methoxycinnamate. The sunscreen mixture was incorporated into nanostructured lipid carriers (NLCs). The ability of nine different solid lipids to yield stable aqueous NLC suspensions was assessed. After the production by hot high pressure homogenization, the NLC were analyzed in terms of particle size, physical state, particle shape, ultraviolet absorbance and stability. The particle size for all NLC was around 200 nm after production. The NLC suspension with carnauba wax had superior UV absorbance, NLC from bees wax showed similar efficiency as the reference emulsion. The NLC formulations were incorporated into hydrogel formulations and the SPF was measured. This study demonstrated that approximately 45% higher SPF values could be obtained when the organic UV filters were incorporated into carnauba wax NLC, in comparison to the reference nanoemulsion and bees wax NLC. The data showed that the synergistic effect of NLC and incorporated sunscreens depends not only on the solid state of the lipid but also on its type.
The safety and efficacy assessment of nanomaterials is a major concern of industry and academia. These materials, due to their nanoscale size, can have chemical, physical, and biological properties that differ from those of their larger counterparts. The encapsulation of natural ingredients can provide marked improvements in sun protection efficacy. This strategy promotes solubility enhancement of flavonoids and yields an improved active ingredient with innovative physical, physicochemical and functional characteristics. Rutin, a flavonoid, has chemical and functional stability in topical vehicles exerting a synergistic effect in association with ultraviolet (UV) filters. However, the solubility of rutin is a limiting factor. Additionally, this bioactive compound does not have tendency to permeate across the . As an alternative to common synthetic based sunscreens, rutin-entrapped gelatin nanoparticles were designed. The present study investigated the pre-clinical safety of gelatin nanoparticles (GNPs) using an method and also assessed the clinical safety and efficacy of the association of GNPs with three commonly used chemical UV filters (ethylhexyl dimethyl PABA, ethylhexyl methoxycinnamate and methoxydibenzoylmethane). The non-irritant and adequate safety profile under sun-exposed skin conditions of the nanomaterials and the emulsions qualified the products for clinical efficacy assays. The results indicated that the GNPs increased the antioxidant protection of the emulsions developed. However, the presence of rutin in the nanosized material did not enhance performance on the SPF test. In conclusion, these findings characterized the nanomaterials as an innovative platform for multifunctional bioactive sunscreens.
The increased awareness of protection against UV radiation damages has led to a rise in the use of topically applied chemical sunscreen agents and to an increased need of innovative carriers designed to achieve the highest protective effect and reduce the toxicological risk resulting from the percutaneous absorption of these substances. In this paper, nanostructured lipid carriers (NLC) and nanoemulsions (NE) were formulated to optimize the topical application of different and widespread UVA or UVB sun filters (ethyl hexyltriazone (EHT), diethylamino hydroxybenzoyl hexyl benzoate (DHHB), bemotrizinol (Tinosorb S), octylmethoxycinnamate (OMC) and avobenzone (AVO)). The preparation and stability parameters of these nanocarriers have been investigated concerning particle size and zeta potential. The release pattern of the sunscreens from NLC and NE was evaluated in vitro, determining their percutaneous absorption through excised human skin. Additional in vitro studies were performed in order to evaluate, after UVA radiation treatment, the spectral stability of the sunfilters once formulated in NLC or NE. From the results obtained, when incorporated in NLC, the skin permeation abilities of the sun filter were drastically reduced, remaining mainly on the surface of the skin. The photostability studies showed that EHT, DHHB and Tinosorb S still retain their photostability when incorporated in these carriers, while OMC and AVO were not photostable as expected. However, no significant differences in terms of photoprotective efficacy between the two carriers were observed.
The surge in skin cancer cases across the globe has forced the scientific community to develop solutions to protect humans against the ill effects of ultraviolet (UV) radiation. Nowadays, functionalized cotton textiles are employed to protect humans against UV radiation. In this context, nanostructured ZnO modified cotton fabrics towards the enhancement of ultraviolet protection factor (UPF) as well as to develop wearable gas sensors have been developed. The surface of carbon cellulosic fabric was modified by sol-gel and sputter seed layer-coated sol-gel techniques. ZnO grown fabrics were characterized using X-ray Diffractometer (XRD), Field Emission Scanning Electron Microscope (FE-SEM), Thermogravimetric Analysis (TGA), X-ray Photoelectron Spectrometer (XPS) and Fourier Transform Infrared Spectrometer (FTIR). Subsequently, UV-blocking and gas sensing properties of the modified textile samples were investigated. The seed layer initiated sol-gel modified cotton fabric showed a maximum UV protection factor (UPF) of 378. Also, room temperature gas-sensing performance of the functionalized cotton fabric towards volatile organic compounds such as acetaldehyde, ammonia and ethanol vapours was investigated.
Zinc oxide (ZnO) nanoparticles are commonly used in sunscreens for their UV-filtering properties. Their growing use can lead to their release into ecosystems, raising question about their toxicity. Effects of these engineered nanomaterials (ENMs) on cyanobacteria, which are important primary producers involved in many biogeochemical cycles, are unknown. In this study, we investigated by several complementary approaches the toxicological effects of two marketed ZnO-ENMs (coated and uncoated) on the model cyanobacteria Synechococcus elongatus PCC 7942. It was shown that despite the rapid adsorption of ENMs on cell surface, toxicity is mainly due to labile Zn released by ENMs. Zn dissipates cell membrane potential necessary for both photosynthesis and respiration, and induces oxidative stress leading to lipid peroxidation and DNA damages. It leads to global downregulation of photosystems, oxidative phosphorylation, and transcription/translation machineries. This also translates into significant decrease of intracellular ATP content and cell growth inhibition. However, there is no major loss of pigments and even rather an increase in exposed cells compared to controls. A proposed way to reduce the environmental impact of Zn would be the improvement of the coating stability to prevent solubility of ZnO-ENMs.
Magnetic solid-phase extraction is one of the most promising new extraction methods for liquid samples before ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis. Several types of materials, including carbonaceous ones, have been prepared for this purpose. In this paper, for the first time, the preparation, characterization, and sorption capability of Fe3O4-graphitized carbon black (mGCB) composite toward some compounds of environmental interest were investigated. The synthesized mGCB consisted of micrometric GCB particles with 55 m(2) g(-1) surface area bearing some carbonyl and hydroxyl functionalities and the surface partially decorated by Fe3O4 microparticles. The prepared mGCB was firstly tested as an adsorbent for the extraction from surface water of 50 pollutants, including estrogens, perfluoroalkyl compounds, UV filters, and quinolones. The material showed good affinity to many of the tested compounds, except carboxylates and glucoronates; however, some compounds were difficult to desorb. Ten UV filters belonging to the chemical classes of benzophenones and p-aminobenzoates were selected, and parameters were optimized for the extraction of these compounds from surface water before UHPLC-MS/MS determination. Then, the method was validated in terms of linearity, trueness, intra-laboratory precision, and detection and quantification limits. In summary, the method performance (trueness, expressed as analytical recovery, 85-114%; RSD 5-15%) appears suitable for the determination of the selected compounds at the level of 10-100 ng L-1, with detection limits in the range of 1-5 ng L-1. Finally, the new method was compared with a published one, based on conventional solid-phase extraction with GCB, showing similar performance in real sample analysis.