Hyaluronic acid/tannic acid hydrogel sunscreen with excellent anti-UV, antioxidant, and cooling effects.

Excessive exposure to UV radiation is one of the major factors that causes skin aging, erythema, burns, and skin cancer. Recently, the usage of sunscreens for skin protection has increased because the amount of UV radiation reaching the Earth's surface has increased owing to the destruction of the ozone layer that blocks UV radiation. Hydrogels with a three-dimensional network structure exhibit physical and chemical properties that are similar to those of the extracellular matrix in the human body, a high water content, flexibility, and biocompatibility. Therefore, they are applied in a wide range of fields, such as in cosmetics, medicines, and pharmaceuticals. However, conventional hydrogel-based sunscreens have drawbacks such as complicated process conditions, high cost, and low biocompatibility. In this study, a novel hydrogel-type sunscreen with excellent UV protection and cooling effects was prepared by a very simple process using two natural materials, hyaluronic acid (HA) and tannic acid (TA). The HA/TA hydrogels exhibited broad-spectrum UV protection in the UVA and UVB regions (280-360 nm). In addition, they showed excellent adhesion to the skin surface, antioxidative activity, cooling effect, and high moisture content, demonstrating great application potential as a hydrogel-type sunscreen.

Cerium oxide nanoparticles: green synthesis using Banana peel, cytotoxic effect, UV protection and their photocatalytic activity.

Nanomaterials, as an active ingredient, have been widely deployed in various science and technological applications with zinc and titanium oxides nanoparticles being commonly applied in sunscreens. On similar lines, cerium oxide nanoparticles (CeO2-NPs) were synthesized using Musa sapientum peel extract, to investigate its cytotoxic effects, UV protection and photocatalytic activity. The synthesized nanoparticles were identified through Raman, Powder X-ray Diffraction (PXRD), Fourier-Transform Infrared spectroscopy (FT-IR), Transmission Electron Microscopy (TEM), Field Emission Scanning Electron Microscopy (FESEM) and Energy-Dispersive Spectroscopy (EDX). FESEM results showed that the size of synthesized nanoparticles is in the range 4-13 nm. Their cytotoxic activity revealed a non-toxic behavior in concentrations below 500 µg/mL on lung (A549) cell lines. The Sun protection factor (SPF) was estimated approximately ~ 40 for synthesized CeO2-NPs. The survey of photocatalytic activity showed that synthesized nanoparticles can remove 81.7% of AO7 in 180 min under visible light.

Investigation of calcium silicate as a natural clay-based sunblock: Formulation and characterization.

BACKGROUND: Sunlight exposure causes several types of health issues to humans, and in particular, it affects especially the skin. Among the most common harmful issues developed by UV exposure are erythema, pigmentation, and lesions in DNA, which may lead to cancer. These long-term effects can be minimized with the use of sunscreen. OBJECTIVE: The use of commercial UV filters causes severe side effects such as skin allergy and whitening of the skin. Therefore, in this study the effectiveness of Ca2 SiO4 , a compound abundantly present in the soils of certain South Asian regions, has been the first time explored as UV filter. This compound leaves a low amount of white residue on the skin and is highly stable. METHOD: The comparative study of a cosmetic formulation having 5% Ca2 SiO4 , and other formulations containing 5% TiO2 and 5% ZnO as inorganic UV filters, was performed to evaluate the physical and chemical stability. RESULT: The zeta potential and chemical stability of formulations containing these different UV filters were investigated by using UV-Vis spectroscopy, FTIR-ATR, and X-ray diffraction. Results indicated Ca2 SiO4 as a promising innovative UV filter with an SPF value of 37.94. One of the reasons is its low interaction with organic filter, that is, PABA, as compared to commercial ZnO and TiO2 inorganic UV filters. Biological absorption in organs was studied by ICP-MS on model mice. CONCLUSION: It also has a low photocatalytic activity; thus, formation of radicals is minimum. Moreover, Ca2 SiO4 showed a recognized ability to leave a low amount of white residue on the skin combined with great stability.

The Involvement of Xanthone and (E)-Cinnamoyl Chromophores for the Design and Synthesis of Novel Sunscreening Agents.

Excessive UV exposure contributes to several pathological conditions like skin burns, erythema, premature skin aging, photodermatoses, immunosuppression, and skin carcinogenesis. Effective protection from UV radiation may be achieved with the use of sunscreens containing UV filters. Currently used UV filters are characterized by some limitations including systemic absorption, endocrine disruption, skin allergy induction, and cytotoxicity. In the research centers all over the world new molecules are developed to improve the safety, photostability, solubility, and absorption profile of new derivatives. In our study, we designed and synthesized seventeen novel molecules by combining in the structures two chromophores: xanthone and (E)-cinnamoyl moiety. The ultraviolet spectroscopic properties of the tested compounds were confirmed in chloroform solutions. They acted as UVB or UVA/UVB absorbers. The most promising compound 9 (6-methoxy-9-oxo-9H-xanthen-2-yl)methyl (E)-3-(2,4-dimethoxyphenyl)acrylate) absorbed UV radiation in the range 290-369 nm. Its photoprotective activity and functional photostability were further evaluated after wet milling and incorporation in the cream base. This tested formulation with compound 9 possessed very beneficial UV protection parameters (SPFin vitro of 19.69 ± 0.46 and UVA PF of 12.64 ± 0.32) which were similar as broad-spectrum UV filter tris-biphenyl triazine. Additionally, compound 9 was characterized by high values of critical wavelength (381 nm) and UVA/UVB ratio (0.830) thus it was a good candidate for broad-spectrum UV filter and it might protect skin against UVA-induced photoaging. Compound 9 were also shown to be photostable, non-cytotoxic at concentrations up to 50 µM when tested on five cell lines, and non-mutagenic in Ames test. It also possessed no estrogenic activity, according to the results of MCF-7 breast cancer model. Additionally, its favorable lipophilicity (miLogP = 5.62) does not predispose it to penetrate across the skin after topical application.

Synthesis and Characterization of Nanostructured Lipid Nanocarriers for Enhanced Sun Protection Factor of Octyl p-methoxycinnamate.

Sunlight is important to health, but higher exposure to radiation causes early aging of the skin and skin damage that can lead to skin cancers. This study aimed at producing a stable octyl p-methoxycinnamate (OMC)-loaded nanostructured lipid carrier (NLC) sunscreen, which can help in the photoprotective effect. NLC was produced by emulsification-sonication method and these systems were composed of myristyl myristate (MM), caprylic capric triglyceride (CCT), Tween® 80 (TW), and soybean phosphatidylcholine (SP) and characterized by dynamic light scattering (DLS), zeta potential (ZP) measurement, atomic force microscopy (AFM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and in vitro release studies. Pre-formulation studies were performed changing TW concentrations and no differences were found at concentrations of 1.0 and 2.0%. Two selected formulations were designed and showed an average size of 91.5-131.7, polydispersity index > 0.2, and a negative value of ZP. AFM presented a sphere-like morphology and SEM showed ability to form a thin film. DSC exhibited that the incorporation of OMC promoted reduction of enthalpy due to formation of a more amorphous structure. Drug release shows up to 55.74% and 30.57%, and this difference could be related to the presence of SP in this formulation that promoted a more amorphous structure; the release mechanism study indicated Fickian diffusion and relaxation. Sun protection factor (SPF) evaluation was performed using NLC and presented values around 40, considerably higher than those observed in the literature. The developed formulations provide a beneficial alternative to conventional sunscreen formulations.

Development of agri-biomass based lignin derived zinc oxide nanocomposites as promising UV protectant-cum-antimicrobial agents.

Agri-biomass derived lignin is one of the most abundant natural nontoxic organic polymers. However, a major portion of lignin is underutilized, which is being left in the fields or thrown into rivers, causing waste accumulation. Utilization of the low-cost biomass-derived lignin serves a dual purpose by reducing agri-waste and by converting it into value-added materials. Here we describe the valorization of agri-biomass based lignin via its direct utilization in the green and one-step synthesis of zinc oxide nanocomposites. Lignin offered an easy and sustainable synthesis of nanocomposites in a water-ethanol mixture without the need to use any toxic material. The lignin derived nanomaterials showed excellent potential as antioxidant, UV-blocking and antimicrobial agents due to the synergistic effect of lignin and zinc oxide. Further, these nanocomposites were incorporated as an additive into a commonly used body cream to impart UV-blocking and antimicrobial properties. This one-step, cost-effective and green synthesis technique of lignin derived zinc oxide nanocomposites not only contributes to agro-waste reduction, but at the same time helps in the production of value-added materials.

Fabrication of TiO2/Zn2TiO4/Ag nanocomposite for synergic effects of UV radiation protection and antibacterial activity in sunscreen.

A systematic and detailed study has been designed and conducted, taking into account some of the proposed benefits such as increased efficiency, transparency, unique texture, protection of active ingredient and higher consumer compliance of cosmetics containing nano-sized metal oxides. The objective of the present study was to develop novel sunscreen cream containing a TiO2/Zn2TiO4/Ag nanocomposite for enhanced UV radiation protection and antibacterial activity. In this study, TiO2/Zn2TiO4/Ag nanocomposite was prepared using sol-gel method and characterized by FESEM, EDX, XRD, TGA, UV-vis spectrophotometry, and FTIR techniques. Different sunscreen creams were formulated by incorporating the nanocomposite and TiO2 nanoparticles and the Sun Protection Factor (SPF) against ultraviolet radiation and antibacterial activity were examined. The antibacterial activity of synthesized TiO2/Zn2TiO4/Ag nanocomposite was investigated against gram positive (S. aureus) and gram negative (Escherichia coli). TiO2/Zn2TiO4/Ag nanocomposite has a higher protective factor compared to TiO2 nanoparticles. The results show that the average particle sizes of the synthesized nanoparticles are on a scale below 100 nm. The energy gap of the TiO2/Zn2TiO4/Ag nanocomposite was 3.01 eV which is close to the energy gap of the pure TiO2 nanoparticles. The nanocomposite presents higher UV absorption than the pure TiO2 nanoparticles. According to MIC test, minimum inhibitory concentration for this nanocomposite was 10 mg/ml. According to the MTT test, up to 0.3 µg/ml of this nanocomposite was found not to be susceptible to toxicity and almost 79.5 % of the cells exposed to nanoparticles had vital activities. In fact, TiO2/Zn2TiO4/Ag nanocomposite addition to cream was considered, not only to achieve the best protection over the whole UV range but also to take advantage of any synergistic effects of them in sunscreens.

Molecular modeling as a design tool for sunscreen candidates: a case study of bemotrizinol.

Sunscreen-based photoprotection is an important strategy to prevent photoaging and skin cancer. Among the effective and modern sunscreens, triazine compounds are known as an important class based on their physical-chemical properties, such as photostability and UV broad-spectrum absorption (UVA and UVB). Molecular modeling and quantum mechanical calculations approaches can be helpful to orientate the design of sunscreens. Herein, a case study is presented to demonstrate the importance of the molecular modeling as a design tool for promising sunscreen candidates based on the synthesis research previously described of bemotrizinol, a broad-spectrum photostable organic UV filter present in many sunscreens products. Time-dependent density functional theory (TD-DFT) calculations performed in gas phase on the isolated organic UV filters proved to reproduce the experimental UV absorption, guiding the choice of the most efficient candidate as sunscreen. The present work highlights the importance of molecular modeling as an effective tool to support synthesis research, increasing the possibility of obtaining promising compounds with reduced costs and effluent production. Graphical abstractA case study to demonstrate the importance of the molecular modeling as a design tool for promising sunscreen candidates is presented. The method proved to be a valuable tool to reproduce the experimental UV absorption and to determinate the most efficient molecule as sunscreen among the candidates.

Interkingdom Genetic Mix-and-Match To Produce Novel Sunscreens.

Sunscreen-containing skincare products protect the skin from damage caused by sun exposure. However, many of them contain oxybenzone and/or octinoxate, which have been reported to be toxic to juvenile coral and to cause coral bleaching. Thus, there is a growing need for new sunscreen compounds that are less harmful to the environment. Here, we report an engineered biosynthetic pathway employing genes from a vertebrate and two Gram-(+) bacteria that forms novel sunscreen compounds with hybrid structures of gadusol and mycosporine-like amino acids, both of which are found in marine environments. These compounds, named gadusporines, have unique UV absorbance at 340 nm, expanding the range of mycosporine- and gadusol-based sunscreen products. The synthesis of gadusporines in Streptomyces coelicolor establishes a platform for the design and production of novel sunscreens.

Synthesis and evaluation of 1,3,5-triazine derivatives as sunscreens useful to prevent skin cancer.

The incidence of skin cancers such as non-melanoma skin cancer and malignant melanoma has increased in the last few years mainly because of chronic exposure to ultraviolet (UV) radiation. Sunscreens protect the skin against harmful UV radiations; however, some limitations of these products justify the discovery of new UV filters. Novel 1,3,5-triazine derivatives (12a-h) obtained by the optimization of prototype resveratrol were synthesized and characterized. All compounds exhibited sun protection factor (SPF) and UVA protection factor (UVAPF) in the range of 3-17 and 3-13, respectively. These values were superior to resveratrol and the UV filter ethylhexyl triazone (EHT) currently available on the market. In addition, all compounds demonstrated in vitro antioxidant activity and thermal stability with the decomposition at temperatures above 236 °C. In conclusion, the novel 1,3,5-triazine derivatives have emerged as new UV filters with antioxidant effect useful to prevent skin cancer.

Using Nature's polyenes as templates: studies of synthetic xanthomonadin analogues and realising their potential as antioxidants.

Two truncated analogues of the polyenyl photoprotective xanthomonadin pigments have been synthesised utilising an iterative Heck-Mizoroki (HM)/iododeboronation cross coupling approach and investigated as models of the natural product photoprotective agents in bacteria. Despite the instability of these types of compounds, both analogues proved to be sufficiently stable to allow isolation, spectroscopic analysis and biological studies of their photoprotective behaviour which showed that despite their shorter polyene chain length, they retained the ability to protect bacteria from photochemical damage; i.e. incorporation of one compound into E. coli provided photoprotective activity against singlet oxygen analogous to the natural photoprotective mechanisms employed by Xanthomonas bacteria, answering key questions about what minimal functionality is required to impart photoprotection, potentially leading to new classes of photoprotective and antioxidants compounds.

Indole derivatives as multifunctional drugs: Synthesis and evaluation of antioxidant, photoprotective and antiproliferative activity of indole hydrazones.

Two series of indole derivatives 4-17, 20-22 were easily prepared and assayed for their radical-scavenging ability. Arylidene-1H-indole-2-carbohydrazones showed different extent antioxidant activity in DPPH, FRAP and ORAC assays. Good antioxidant activity is related to the number and position of hydroxyl groups on the arylidene moiety as well as to the presence of methoxy or 4-(diethylamino) group. On the contrary low antioxidant activity is showed by the isomeric 1H-indol-2-yl(methylene)-benzohydrazides. Furthermore, hydrazones 4-17 showed photoprotective capacities with satisfactory in vitro SPF as compared to the commercial PBSA sunscreen filter. The indole 16 and 17, showing the best antioxidant and photoprotective profile, were included in different formulation and their topical release was evaluated. Varying the formulation composition, it was possible to optimize skin adsorption and solubility of the active indole in the formulation. The antiproliferative effect of the hydrazones 4-17 was tested on human erythroleukemia K562 and melanoma Colo-38 cells. Hydrazones 11, 16 and 17 showed growth inhibition at sub micromolar concentrations on both cell lines. These results indicate indole hydrazones as potential multifunctional molecules especially in the treatment of neoplastic diseases being the good antioxidant properties of 16 and 17 correlated to their high antiproliferative activity.

ZnO:SBA-15 Nanocomposites for Potential Use in Sunscreen: Preparation, Properties, Human Skin Penetration and Toxicity.

AIM: We evaluated the effects of the incorporation of zinc oxide (ZnO) nanoparticles in a mesoporous matrix, aiming to improve the textural, structural and morphological properties and verify their safety so that they can be applied in sunscreen cosmetics. MATERIALS AND METHODS: ZnO nano-particles were incorporated into an ordered mesoporous silica matrix known as Santa Barbara Amorphous-15 (SBA-15), using post-synthesis methodology. The resulting nanocomposites were characterized using X-ray diffraction, small angle X-ray scattering, N2 adsorption-desorption isotherms, Fourier transform infrared spectroscopy, scanning electron microscopy and predicted in vitro sun protector factor (SPF) estimation. Effectiveness and safety were evaluated by antimicrobial activity, in vitro cell toxicity and non-invasive multi-photon tomography with fluorescence lifetime imaging. RESULTS: The structure of the nanocomposites was similar to that of SBA-15, with little perturbation caused by ZnO incorporation. Nanocomposites had an increased in vitro SPF, reduced cytotoxic activity and favourable antimicrobial properties compared to ZnO. ZnO:SBA-15 nanocomposites exhibited no measurable toxicity when applied to human skin in vivo. CONCLUSION: Due to their suitable physicochemical properties and improved safety compared to bare ZnO nanoparticles, the ZnO:SBA-15 nanocomposites show promise for use in cosmetic applications.

Benzofuran hydrazones as potential scaffold in the development of multifunctional drugs: Synthesis and evaluation of antioxidant, photoprotective and antiproliferative activity.

New benzofuranhydrazones 3-12 were easily prepared and assayed for their radical-scavenging ability. Hydrazones 3-12 showed different extent antioxidant activity in DPPH, FRAP and ORAC assays. Good antioxidant activity is related to the number and position of hydroxyl groups on the arylidene moiety. High antioxidant activity is showed by the 2-hydroxy-4-(diethylamino)benzylidene derivative 11. Furthermore, hydrazones 3-12 showed photoprotective capacities with satisfactory in vitro SPF as compared to the commercial PBSA sunscreen filter. The antiproliferative effects of the hydrazones 3-12 was tested on erythroleukemia K562 and Colo-38 melanoma human cells. All the compounds showed growth inhibition in the micromolar to sub micromolar concentration range. If taken together these results points to benzofuran hydrazones as potential multifunctional molecules especially in the treatment of neoplastic diseases being the good antioxidant properties of 5, 7 and 11 correlated to their high antiproliferative activity.

Skin protection efficacy from UV irradiation and skin penetration property of polysaccharide-benzophenone conjugates as a sunscreen agent.

Sunscreen materials have been developed to protect skin from UV radiation. However, many organic sunscreen materials are small molecules and absorbed into human skin after topical application and lead to systemic side effects. To improve the adverse effects of conventional sunscreen materials, we designed a sunscreen agent using an organic sunscreen material and a polymer. Dioxybenzone, an organic sunscreen compound is selected and polymerized with natural polymer pullulan. Polymerization not only provides a long polymer backbone to dioxybenzone, but also keeps the distance between benzene rings of the dioxybenzone and prevents reduction of photoabsorption intensity. UV/vis spectrophotometry confirmed that dioxybenzone-pullulan polymer (DOB-PUL) and dioxybenzone (DOB) demonstrated similar UV absorption. To measure the accumulation of sunscreen materials on skin, Franz diffusion cell was used to confirm the accumulation of DOB and lack of penetration of DOB-PUL. Most importantly, DOB showed higher plasma concentration after multiple applications compared to that of DOB-PUL.

Metabolic engineering of Corynebacterium glutamicum for production of sunscreen shinorine.

Ultraviolet-absorbing chemicals are useful in cosmetics and skin care to prevent UV-induced skin damage. We demonstrate here that heterologous production of shinorine, which shows broad absorption maxima in the UV-A and UV-B region. A shinorine producing Corynebacterium glutamicum strain was constructed by expressing four genes from Actinosynnema mirum DSM 43827, which are responsible for the biosynthesis of shinorine from sedoheptulose-7-phosphate in the pentose phosphate pathway. Deletion of transaldolase encoding gene improved shinorine production by 5.2-fold. Among the other genes in pentose phosphate pathway, overexpression of 6-phosphogluconate dehydrogenase encoding gene further increased shinorine production by 60% (19.1 mg/L). The genetic engineering of the pentose phosphate pathway in C. glutamicum improved shinorine production by 8.3-fold in total, and could be applied to produce the other chemicals derived from sedoheptulose-7-phosphate.

Design, synthesis and biological evaluation of novel hydroxy-phenyl-1H-benzimidazoles as radical scavengers and UV-protective agents.

An ever-increasing incidence of skin neoplastic diseases is registered. Therefore, it is important to protect the skin from the UV radiation that reaches the epidermis and dermis but also to block ROS generated by them. Our attention was attracted in developing new compounds provided with both UV filtering and antioxidant capacities. To this end, 2-phenyl-1H-benzimidazole-5-sulfonic acid (PBSA), a known UV filter, was selected as lead compound for its lack of antioxidant activity, high water solubility and good safety profile. PBSA was sequentially modified introducing hydroxyls on the phenyl ring and also substituting the functional group in position 5 of the benzimidazole ring. At the end of the synthetic study, a new, very potent class of antioxidants has been obtained. Surprisingly some of the developed molecules, while devoid of significant UV-filtering activity was endowed with potent UV-filtering booster capability if associated with known commercial UVB and UVA filters.

Effect of preparation and processing conditions on UV absorbing properties of hydroxyapatite-Fe2O3 sunscreen.

The development of innovative, safe and non-photocatalytic sunscreens is urgently needed, as it is essential to have sunscreen filters offering appropriate UV protection without damaging the environment and/or generating free radicals when in contact with the skin. Hydroxyapatite (Ca10(PO4)6(OH)2, HAp) when substituted with iron has UV protection properties and is not photocatalytic; HAp was used to make a sunscreen filter by treating cod fish bones in an iron-containing solution, and then calcining them at 700°C. Here we present a systematic and advanced study on this material, to obtain a sunscreen with improved UV absorbing properties. Bones were treated with three different iron salts - Fe(II) chloride, Fe(II) lactate and Fe(III) nitrate - under various pH conditions. Results showed that Fe(II) chloride in basic pH led to the most effective iron inclusion. High energy ball milling or ultrasound were investigated to increase surface area and corresponding UV absorption; high energy ball milling treatment led to the best optical properties. The optimum powders were used to formulate UV protection creams, which showed Sun Protection Factor (SPF) values significantly superior to the control cream (up to 4.1). Moreover the critical wavelength (λcrit) was >370nm (388-389nm) and UVA/UVB ratios were very close to 1. With these properties these sunscreens can be classified as broad UV protectors. Results also showed that combining these powders with other sunscreens (i.e. titanium dioxide), a synergic effect between the different components was also observed. This investigation showed that HAp-based sunscreens of marine origin are a valid alternative to commercial products, safe for the health of the customers and, being non-photocatalytic, do not pose a threat to the environment.

Preparation of pectin/silver nanoparticles composite films with UV-light barrier and properties.

Silver nanoparticles (AgNPs) was synthesized by a green method using an aqueous extract of Caesalpinia mimosoides Lamk (CMLE) as reducing and stabilizing agents, and they were used for the preparation of pectin-based antimicrobial composite films. The AgNPs were spherical in shape with the size in the range of 20-80nm and showed the absorption peak around 500nm. The pectin/AgNPs composite film exhibited characteristic absorption peak of AgNPs at 480nm. The surface color and light transmittance of the pectin films were greatly influenced by the addition of AgNPs. The lightness of the films decreased, however, redness and yellowness of the films increased after incorporation of AgNPs. UV-light barrier property of the pectin film increased significantly with a little decrease in the transparency. Though there were no structural changes in the pectin film by the incorporation of CMLE and AgNPs as indicated by the FTIR results, the film properties such as thermal stability, mechanical strength, and water vapor barrier properties of the pectin films increased. The pectin/AgNPs nanocomposite films exhibited strong antibacterial activity against food-borne pathogenic bacteria, Escherichia coli and Listeria monocytogenes.