Optimization of an Ultrasound-Assisted Extraction Technique and the Effectiveness of the Sunscreen Components Isolated from Bletilla striata.

Bletilla striata is the dried tuber of B. striata (Thund.) Reichb.f., which has antibacterial, anti-inflammatory, anti-tumor, antioxidant and wound healing effects. Traditionally, it has been used for hemostasis therapy, as well as to treat sores, swelling and chapped skin. In this study, we used the ultraviolet (UV) absorbance rate of B. striata extracts as the index, and the extraction was varied with respect to the solid-liquid ratio, ethanol concentration, ultrasonic time and temperature in order to optimize the extraction process for its sunscreen components. The main compounds in the sunscreen ingredients of Baiji (B. striata) were analyzed using ultra-high-performance liquid chromatography combined with quadrupole time-of-flight tandem mass spectrometry. The sunscreen properties were subsequently evaluated in vitro using the 3M tape method. The results show that the optimal extraction conditions for the sunscreen components of B. striata were a solid-liquid ratio of 1:40 (g/mL), an ethanol concentration of 50%, an ultrasonic time of 50 min and a temperature of 60 °C. A power of 100 W and an ultrasonic frequency of 40 Hz were used throughout the experiments. Under these optimized conditions, the UV absorption rate of the isolated sunscreen components in the UVB region reached 84.38%, and the RSD was 0.11%. Eighteen compounds were identified, including eleven 2-isobutyl malic acid glucose oxybenzyl esters, four phenanthrenes, two bibenzyl and one α-isobutylmalic acid. An evaluation of the sunscreen properties showed that the average UVB absorption values for the sunscreen samples from different batches of B. striata ranged from 0.727 to 1.201. The sunscreen ingredients of the extracts from B. striata had a good UV absorption capacity in the UVB area, and they were effective in their sunscreen effects under medium-intensity sunlight. Therefore, this study will be an experimental reference for the extraction of sunscreen ingredients from the B. striata plant, and it provides evidence for the future development of B. striata as a candidate cosmetic raw material with UVB protection properties.

Biotechnological Production of the Sunscreen Pigment Scytonemin in Cyanobacteria: Progress and Strategy.

Scytonemin is a promising UV-screen and antioxidant small molecule with commercial value in cosmetics and medicine. It is solely biosynthesized in some cyanobacteria. Recently, its biosynthesis mechanism has been elucidated in the model cyanobacterium Nostoc punctiforme PCC 73102. The direct precursors for scytonemin biosynthesis are tryptophan and p-hydroxyphenylpyruvate, which are generated through the shikimate and aromatic amino acid biosynthesis pathway. More upstream substrates are the central carbon metabolism intermediates phosphoenolpyruvate and erythrose-4-phosphate. Thus, it is a long route to synthesize scytonemin from the fixed atmospheric CO2 in cyanobacteria. Metabolic engineering has risen as an important biotechnological means for achieving sustainable high-efficiency and high-yield target metabolites. In this review, we summarized the biochemical properties of this molecule, its biosynthetic gene clusters and transcriptional regulations, the associated carbon flux-driving progresses, and the host selection and biosynthetic strategies, with the aim to expand our understanding on engineering suitable cyanobacteria for cost-effective production of scytonemin in future practices.

Anti-Photoaging and Potential Skin Health Benefits of Seaweeds.

The skin health benefits of seaweeds have been known since time immemorial. They are known as potential renewable sources of bioactive metabolites that have unique structural and functional features compared to their terrestrial counterparts. In addition, to the consciousness of green, eco-friendly, and natural skincare and cosmetics products, their extracts and bioactive compounds such as fucoidan, laminarin, carrageenan, fucoxanthin, and mycosporine like amino acids (MAAs) have proven useful in the skincare and cosmetic industries. These bioactive compounds have shown potential anti-photoaging properties. Furthermore, some of these bioactive compounds have been clinically tested and currently available in the market. In this contribution, the recent studies on anti-photoaging properties of extracts and bioactive compounds derived from seaweeds were described and discussed.

In Vitro and In Vivo Photoprotective Effects of (-)-Loliode Isolated from the Brown Seaweed, Sargassum horneri.

Skin is the largest organ of humans. Overexposure to ultraviolet (UV) is the primary environmental factor that causes skin damage. The compound, (-)-loliode, isolated from the brown seaweed Sargassum horneri, showed strong antioxidant and anti-inflammatory activities in in vitro and in vivo models. To further explore the potential of (-)-loliode in cosmetics, in the present study, we investigated the photoprotective effect of (-)-loliode in vitro in skin cells and in vivo in zebrafish. The results indicated that (-)-loliode significantly reduced intracellular reactive oxygen species (ROS) level, improved cell viability, and suppressed apoptosis of UVB-irradiated human keratinocytes. In addition, (-)-loliode remarkably attenuated oxidative damage, improved collagen synthesis, and inhibited matrix metalloproteinases expression in UVB-irradiated human dermal fibroblasts. Furthermore, the in vivo test demonstrated that (-)-loliode effectively and dose-dependently suppressed UVB-induced zebrafish damage displayed in decreasing the levels of ROS, nitric oxide, lipid peroxidation, and cell death in UVB-irradiated zebrafish. These results indicate that (-)-loliode possesses strong photoprotective activities and suggest (-)-loliode may an ideal ingredient in the pharmaceutical and cosmeceutical industries.

Seasonal Variation of Mycosporine-Like Amino Acids in Three Subantarctic Red Seaweeds.

UV-absorbing compounds, such as mycosporine-like amino acids (MAAs), are a group of secondary metabolites present in many marine species, including red seaweeds. In these organisms, the content and proportion of the composition of MAAs vary, depending on the species and several environmental factors. Its high cosmetic interest calls for research on the content and composition of MAAs, as well as the dynamics of MAAs accumulation in seaweeds from different latitudes. Therefore, this study aimed to survey the content of UV-absorbing MAAs in three Subantarctic red seaweeds during a seasonal cycle. Using spectrophotometric and HPLC techniques, the content and composition of MAAs of intertidal Iridaea tuberculosa, Nothogenia fastigiate, and Corallina officinalis were assessed. Some samples were also analyzed using high-resolution mass spectrometry coupled with HPLC-ESI-MS in order to identify more precisely the MAA composition. I. tuberculosa exhibited the highest MAA values (above 1 mg g-1 of dried mass weight), while C. officinalis showed values not exceeding 0.4 mg g-1. Porphyra-334 was the main component in N. fastigiata, whereas I. tuberculosa and C. officinalis exhibited a high content of palythine. Both content and composition of MAAs varied seasonally, with high concentration recorded in different seasons, depending on the species, i.e., winter (I. tuberculosa), spring (N. fastigiata), and summer (C. officinalis). HPLC-ESI-MS allowed us to identify seven different MAAs. Two were recorded for the first time in seaweeds from Subantarctic areas (mycosporine-glutamic acid and palythine-serine), and we also recorded an eighth UV-absorbing compound which remains unidentified.

Protective Effect of a Fucose-Rich Fucoidan Isolated from Saccharina japonica against Ultraviolet B-Induced Photodamage In Vitro in Human Keratinocytes and In Vivo in Zebrafish.

A fucose-rich fucoidan was purified from brown seaweed Saccharina japonica, of which the UVB protective effect was investigated in vitro in keratinocytes of HaCaT cells and in vivo in zebrafish. The intracellular reactive oxygen species levels and the viability of UVB-irradiated HaCaT cells were determined. The results indicate that the purified fucoidan significantly reduced the intracellular reactive oxygen species levels and improved the viability of UVB-irradiated HaCaT cells. Furthermore, the purified fucoidan remarkably decreased the apoptosis by regulating the expressions of Bax/Bcl-xL and cleaved caspase-3 in UVB-irradiated HaCaT cells in a dose-dependent manner. In addition, the in vivo UV protective effect of the purified fucoidan was investigated using a zebrafish model. It significantly reduced the intracellular reactive oxygen species level, the cell death, the NO production, and the lipid peroxidation in UVB-irradiated zebrafish in a dose-dependent manner. These results suggest that purified fucoidan has a great potential to be developed as a natural anti-UVB agent applied in the cosmetic industry.

Health Properties and Composition of Honeysuckle Berry Lonicera caerulea L. An Update on Recent Studies.

Lonicera caerulea L., also known as haskap or honeysuckle berry, is a fruit commonly planted in eastern Europe, Canada and Asia. The fruit was registered as a traditional food from a third country under European Union regulations only on December 2018. It is resistant to cold, pests, various soil acidities and diseases. However, its attractiveness is associated mostly with its health properties. The fruit shows anticancer, anti-inflammatory, and antioxidant activity-important factors in improving health. These features result from the diverse content of phytochemicals in honeysuckle berries with high concentrations of phytocompounds, mainly hydroxycinnamic acids, hydroxybenzoic acids, flavanols, flavones, isoflavones, flavonols, flavanones and anthocyanins but also iridoids, present in the fruit in exceptional amounts. The content and health properties of the fruit were identified to be dependent on cultivar, genotype and the place of harvesting. Great potential benefits of this nutritious food are its ability to minimize the negative effects of UV radiation, diabetes mellitus and neurodegenerative diseases, and to exert hepato- and cardioprotective activity.

Ganoderma lucidum polysaccharide inhibits UVB-induced melanogenesis by antagonizing cAMP/PKA and ROS/MAPK signaling pathways.

Ultraviolet (UV)-induced pigmentation is very common in clinical practice, but the current treatments are rarely effective, accompanied by some side effects. Ganoderma lucidum polysaccharide (GLP) is a natural antioxidant with no toxic side effects, which can antagonize UVB-induced fibroblast photo aging. The study aims to explore the role of GLP in inhibiting UVB-induced melanogenesis and its possible mechanism. The expression of melanogenesis genes such as microphthalmia-associated transcription factor (MITF), tyrosine (TYR), tyrosinase related protein 1 (TYRP1), tyrosinase related protein 2 (TYRP2), ras-related protein Rab-27A (Rab27A), and Myosin shows an upward trend after exposure of B16F10 and PIG1 cells to UVB irradiation, but GLP can downregulate the expression of genes related to UVB-induced melanogenesis. GLP can inhibit UVB-activated protein kinase A (PKA) and mitogen-activated protein kinase (MAPK) signaling pathways. Besides, GLP protects mitochondria from UVB damage and inhibits reactive oxygen species (ROS) production. Also, UVB-induced cyclic adenosine monophosphate (cAMP) can be inhibited. It has been found in the experiments of UVB-induced skin pigmentation in zebrafish that GLP is capable of inhibiting UVB-induced skin pigmentation. Meanwhile, it can greatly relieve erythema reaction in guinea pig skin caused by high-dosage UVB irradiation. In conclusion, this study shows that GLP can inhibit UVB-induced melanogenesis by antagonizing cAMP/PKA and ROS/MAPK signaling pathways and is a potential natural safe whitening sunscreen additive.

UVA and UVB Photoprotective Capabilities of Topical Formulations Containing Mycosporine-like Amino Acids (MAAs) through Different Biological Effective Protection Factors (BEPFs).

The safety and stability of synthetic UV-filters and the procedures for evaluating the photoprotective capability of commercial sunscreens are under continuous review. The influence of pH and temperature stressors on the stability of certain Mycosporine-like amino acids (MAAs) isolated at high purity levels was examined. MAAs were highly stable at room temperature during 24 h at pH 4.5⁻8.5. At 50 °C, MAAs showed instability at pH 10.5 while at 85 °C, progressive disappearances were observed for MAAs through the studied pH range. In alkaline conditions, their degradation was much faster. Mycosporine-serinol and porphyra-334 (+shinorine) were the most stable MAAs under the conditions tested. They were included in four cosmetically stable topical sunscreens, of which the Sun Protection Factor (SPF) and other Biological Effective Protection Factors (BEPFs) were calculated. The formulation containing these MAAs showed similar SPF and UVB-BEPFs values as those of the reference sunscreen, composed of synthetic UV absorbing filters in similar percentages, while UVA-BEPFs values were slightly lower. Current in vitro data strongly suggest that MAAs, as natural and safe UV-absorbing and antioxidant compounds, have high potential for protection against the diverse harmful effects of solar UV radiation. In addition, novel complementary in vitro tests for evaluation of commercial sunscreens efficacy are proposed.

UV Protection by Natural Products: C. myrrha Oil Versus Sunscreen.

Exposure to various types of ultraviolet (UV) radiation from the sun has been linked to skin cancer. Use of sunscreen can reduce the damaging and carcinogenic effects of UV radiation. However, multiple chemicals in sunscreen can trigger allergic responses, making people less inclined to use sunscreen. Thus, finding natural, plant-based alternatives to sunscreen with similar efficacy has become an important area of research. Myrrh oil, extracted from the shrub Commiphora myrrha, has been used in the treatment of topical wounds and studies have shown that it may provide protection against solar radiation. This study sought to further investigate if C. myrrha oil can confer protection against UV radiation. A UV-sensitive strain of Saccharomyces cerevisiae was grown in petri dishes with one half covered by aluminum foil and the other half covered by clear polyethylene food wrap. The polyethylene half was treated with either SPF 15 or SPF 30 sunscreen, C. myrrha oil or a combination of C. myrrha oil and either sunscreen. The plates were exposed to sunlight. Colony death was quantified using visual estimation. While UV blocking by C. myrrha oil alone was not as effective as that by the synthetic sunscreen, the 1:1 combination of C. myrrha oil and SPF 15 sunblock was significantly more effective than SPF 15 sunblock alone to prevent S. cerevisiae death. These data suggest that naturally-based sunscreens supplemented with synthetic UV deterrents may provide a more holistic approach to prevent UV-induced skin damage. J Drugs Dermatol. 2018;17(8):905-907.

Elicited ROS Scavenging Activity, Photoprotective, and Wound-Healing Properties of Collagen-Derived Peptides from the Marine Sponge Chondrosia reniformis.

Recently, the bioactive properties of marine collagen and marine collagen hydrolysates have been demonstrated. Although there is some literature assessing the general chemical features and biocompatibility of collagen extracts from marine sponges, no data are available on the biological effects of sponge collagen hydrolysates for biomedical and/or cosmetic purposes. Here, we studied the in vitro toxicity, antioxidant, wound-healing, and photoprotective properties of four HPLC-purified fractions of trypsin-digested collagen extracts-marine collagen hydrolysates (MCHs)-from the marine sponge C. reniformis. The results showed that the four MCHs have no degree of toxicity on the cell lines analyzed; conversely, they were able to stimulate cell growth. They showed a significant antioxidant activity both in cell-free assays as well as in H2O2 or quartz-stimulated macrophages, going from 23% to 60% of reactive oxygen species (ROS) scavenging activity for the four MCHs. Finally, an in vitro wound-healing test was performed with fibroblasts and keratinocytes, and the survival of both cells was evaluated after UV radiation. In both experiments, MCHs showed significant results, increasing the proliferation speed and protecting from UV-induced cell death. Overall, these data open the way to the use of C. reniformis MCHs in drug and cosmetic formulations for damaged or photoaged skin repair.

Prasiolin, a new UV-sunscreen compound in the terrestrial green macroalga Prasiola calophylla (Carmichael ex Greville) Kützing (Trebouxiophyceae, Chlorophyta).

MAIN CONCLUSION: We introduced a novel combination of chromatographic techniques for the purification and analysis of a new UV-sunscreen mycosporine-like amino acid (MAA) in the terrestrial green alga Prasiola calophylla. Prasiola calophylla (Carmichael ex Greville) Kützing (Trebouxiophyceae, Chlorophyta) is a typical member of terrestrial algal communities in temperate Europe, where it regularly experiences various stress conditions including strong diurnal and seasonal fluctuations in ultraviolet radiation (UVR). As a photoprotective mechanism Prasiola species and other related Trebouxiophycean taxa synthesize a mycosporine-like amino acid (MAA) as natural sunscreen whose chemical structure was unknown so far. In the present study a new methodological approach is described for the isolation, purification and structural elucidation of this novel sunscreen in P. calophylla. The new compound exhibits an absorption maximum at 324 nm (in the short ultraviolet-A), a molecular weight of 333 and a molecular extinction coefficient of 12.393 M(-1) cm(-1), and could be identified as N-[5,6 hydroxy-5(hydroxymethyl)-2-methoxy-3-oxo-1-cycohexen-1-yl] glutamic acid using one- and two-dimensional (1)H and (13)C-NMR spectroscopy. As trivial name for this novel MAA we suggest 'prasiolin'. The ecologically essential function of prasiolin for UVR-protection in terrestrial algae of the Trebouxiophyceae is discussed.

A Multifunctional and Possible Skin UV Protectant, (3R)-5-Hydroxymellein, Produced by an Endolichenic Fungus Isolated from Parmotrema austrosinense.

Lichens are considered a great bio-resource because they produce large numbers of secondary metabolites with many biological activities; however, they have not been cultivated under artificial conditions to date. As a result, lichen substances from natural sources are limited and have not been widely utilized in commercial applications. Accordingly, interest in lichen-associated fungi, especially endogenic fungi, has increased. Ultraviolet (UV) radiation in sunlight is harmful to human health, resulting in demand for effective UV filtering agents for use in sunscreen. In this study, we purified (3R)-5-hydroxymellein, which has UVA absorption activity, from the secondary metabolites of an endolichenic fungus (ELF000039). The antioxidant properties were then assessed by in vitro tests. The antioxidant activity of (3R)-5-hydroxymellein was high when compared to the recognized antioxidants ascorbic acid (ASA) and butyl hydroxyl anisole (BHA). Moreover, the compound exhibited no cytotoxicity toward mouse melanoma cell lines, B16F1 and B16F10, or the normal cell line, HaCaT. Furthermore, (3R)-5-hydroxymellein recovered the damage caused by UVB irradiation and inhibited melanin synthesis. Taken together, these results suggest that (3R)-5-hydroxymellein could have an interesting and vital profile to go further development as a multifunctional skin UV protectant.

Double dispersant-assisted ionic liquid dispersive liquid-liquid microextraction coupled with capillary electrophoresis for the determination of benzophenone-type ultraviolet filters in sunscreen cosmetic product.

In this work, double dispersant-assisted ionic liquid dispersive liquid-liquid microextraction coupled with micellar electrokinetic chromatography was developed to determine four UV filters (benzophenone, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-methoxybenzophenone). 1-Hexyl-3-methylimidazolium hexafluorophosphate was used as the extraction solvent. The main novelty of the present work was that acetonitrile-Triton X-114 was used as double disperser solvent. Parameters affected the extraction efficiency were investigated and optimized. Under the optimum conditions, enrichment factors were in the range of 25.3-40.5. The limits of detection and quantitation, calculated at a S/N of three and ten, were 3.9-6.7 ng/mL and 13.0-22.3 ng/mL. The linearity of the method was in the range of 0.02-2 µg/mL for 2, 4-dihydroxybenzophenone and 4-hydroxybenzophenone, 0.01-2 µg/mL for benzophenone and 2-hydroxy-4-methoxybenzophenone, with correlation coefficient (R(2)) of 0.9984-0.9991. The proposed method was successfully applied to the determination of four benzophenone-type UV filters in six kinds of sunscreen cosmetic products, with yielded relative recoveries ranging from 80.2 to 117.7%.

Blackberry extract inhibits UVB-induced oxidative damage and inflammation through MAP kinases and NF-κB signaling pathways in SKH-1 mice skin.

Extensive exposure of solar ultraviolet-B (UVB) radiation to skin induces oxidative stress and inflammation that play a crucial role in the induction of skin cancer. Photochemoprevention with natural products represents a simple but very effective strategy for the management of cutaneous neoplasia. In this study, we investigated whether blackberry extract (BBE) reduces chronic inflammatory responses induced by UVB irradiation in SKH-1 hairless mice skin. Mice were exposed to UVB radiation (100 mJ/cm(2)) on alternate days for 10 weeks, and BBE (10% and 20%) was applied topically a day before UVB exposure. Our results show that BBE suppressed UVB-induced hyperplasia and reduced infiltration of inflammatory cells in the SKH-1 hairless mice skin. BBE treatment reduced glutathione (GSH) depletion, lipid peroxidation (LPO), and myeloperoxidase (MPO) in mouse skin by chronic UVB exposure. BBE significantly decreased the level of pro-inflammatory cytokines IL-6 and TNF-α in UVB-exposed skin. Likewise, UVB-induced inflammatory responses were diminished by BBE as observed by a remarkable reduction in the levels of phosphorylated MAP Kinases, Erk1/2, p38, JNK1/2 and MKK4. Furthermore, BBE also reduced inflammatory mediators such as cyclooxygenase-2 (COX-2), prostaglandin E2 (PGE2), and inducible nitric oxide synthase (iNOS) levels in UVB-exposed skin. Treatment with BBE inhibited UVB-induced nuclear translocation of NF-κB and degradation of IκBα in mouse skin. Immunohistochemistry analysis revealed that topical application of BBE inhibited the expression of 8-oxo-7, 8-dihydro-2'-deoxyguanosine (8-oxodG), cyclobutane pyrimidine dimers (CPD), proliferating cell nuclear antigen (PCNA), and cyclin D1 in UVB-exposed skin. Collectively, these data indicate that BBE protects from UVB-induced oxidative damage and inflammation by modulating MAP kinase and NF-κB signaling pathways.

A novel two-dimensional liquid-chromatography method for online prediction of the toxicity of transformation products of benzophenones after water chlorination.

Benzophenone-type UV filters (BPs) are ubiquitous in the environment. Transformation products (TPs) of BPs with suspected toxicity are likely to be produced during disinfection of water by chlorination. To quickly predict the toxicity of TPs, in this study, a novel two-dimensional liquid-chromatography (2D-LC) method was established in which the objective of the first dimension was to separate the multiple components of the BPs sample after chlorination, using a reversed-phase liquid-chromatography mode. A biochromatographic system, i.e. bio-partitioning micellar chromatography with the polyoxyethylene (23) lauryl ether aqueous solution as the mobile phase, served as the second dimension to predict the toxicity of the fraction from the first dimension on the basis of the quantitative retention-activity relationships (QRARs) model. Six BPs, namely 2,4-dihydroxybenzophenone, oxybenzone, 4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2,2'-dihydroxy-4-methoxybenzophenone, were the target analytes subjected to chlorination. The products of these BPs after chlorination were directly injected to the 2D-LC system for analysis. The results indicated that most TPs may be less toxic than their parent chemicals, but some may be more toxic, and that intestinal toxicity of TPs may be more obvious than blood toxicity. The proposed method is time-saving, high-throughput, and reliable, and has great potential for predicting toxicity or bioactivity of unknown and/or known components in a complex sample. Graphical Abstract The scheme for the 2D-LC online prediction of toxicity of the transformation products of benzophenone-type UV filters after chlorination.

Development of piperic acid derivatives from Piper nigrum as UV protection agents.

CONTEXT: There is a need for the discovery of novel natural and semi-synthetic sunscreen that is safe and effective. Piperine has a UV absorption band of 230-400 nm with high molar absorptivity. This compound has a high potential to be developed to sunscreen. OBJECTIVE: This study develops new UV protection compounds from piperine by using chemical synthesis. MATERIALS AND METHODS: Piperine was isolated from Piper nigrum L. (Piperaceae) fruits, converted to piperic acid by alkaline hydrolysis, and prepared as ester derivatives by chemical synthesis. The piperate derivatives were prepared as 5% o/w emulsion, and the SPF values were evaluated. The best compound was submitted to cytotoxicity test using MTT assay. RESULTS: Piperic acid was prepared in 86.96% yield. Next, piperic acid was reacted with alcohols using Steglich reaction to obtain methyl piperate, ethyl piperate, propyl piperate, isopropyl piperate, and isobutyl piperate in 62.39-92.79% yield. All compounds were prepared as 5% oil in water emulsion and measured its SPF and UVA/UVB values using an SPF-290S analyzer. The SPF values (n = 6) of the piperate derivatives were 2.68 ± 0.17, 8.89 ± 0.46, 6.86 ± 0.91, 16.37 ± 1.8, and 9.68 ± 1.71. The UVA/UVB ratios of all compounds ranged from 0.860 to 0.967. Cytotoxicity of isopropyl piperate was evaluated using human skin fibroblast cells and the IC50 was equal to 120.2 µM. DISCUSSION AND CONCLUSION: From the results, isopropyl piperate is an outstanding compound that can be developed into a UV protection agent.

Thanaka: traditional Burmese sun protection.

Limonia acidissima or Hesperethusa crenulata is a common tree in Southeast Asia. It is indigenous to the Republic of Myanmar (formerly Burma) as well as India, Sri Lanka, Java, and Pakistan. In English, the common names for Limonia acidissima are sandalwood, wood-apple, elephant-apple, monkey fruit, and curd fruit tree. The plant has a number of different names in different languages including bal or bael in Assamese, bael in Bengali, kaitha in Hindi, belingai in Malaysia, and thanaka in Burmese. Unique to the Burmese people, thanaka has been used as a cosmetic product for over 2000 years. Mention of thanaka has been traced back to ancient Burmese lyrics, and relics of equipment used by ancient royalty to grind thanaka can be found in museums.

Determination of UV filters in river water samples by in-line SPE-CE-MS.

The use of SPE coupled in-line to CE using electrospray MS detection (in-line SPE-CE-ESI-MS) was investigated for the preconcentration and separation of four UV filters: benzophenone-3, 2,2-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone and 2-phenylbenzimidazole-5-sulphonic acid. First, a CE-ESI-MS method was developed and validated using standard samples, obtaining LODs between 0.06 µg/mL and 0.40 µg/mL. For the in-line SPE-CE-ESI-MS method, three different sorbents were evaluated and compared: Oasis HLB, Oasis MCX, and Oasis MAX. For each sorbent, the main parameters affecting the preconcentration performance, such as sample pH, volume, and composition of the elution plug, and sample injection time were studied. The Oasis MCX sorbent showed the best performance and was used to validate the in-line SPE-CE-ESI-MS methodology. The LODs reached for standard samples were in the range between 0.01 and 0.05 ng/mL with good reproducibility and the developed strategy provided sensitivity enhancement factors between 3400-fold and 34 000-fold. The applicability of the developed methodology was demonstrated by the analysis of UV filters in river water samples.

Microwave-assisted extraction combined with on-line solid phase extraction followed by ultra-high-performance liquid chromatography with tandem mass spectrometric determination of benzotriazole UV stabilizers in marine sediments and sewage sludges.

Benzotriazole ultra-violet stabilisers are compounds widely used in personal care products, which can reach the environment after passing through wastewater treatment plants. In this work, we develop a novel method to evaluate the presence of seven compounds in marine sediments and sewage sludges using microwave-assisted extraction followed by a clean-up step based in on-line solid phase extraction coupled to ultra-high-performance liquid chromatography with MS/MS detection. This method allows for fast and efficient extraction from the solid matrix, subsequent automatic on-line purification and preconcentration, and analysis. For the optimised method, LOD were from 53.3 to 146 ng/kg and LOQ were in the range of 176-486 ng/kg. The method was validated for different environmental solid samples with satisfactory recoveries and relative standard deviations, between 46.1 and 83.9 and 7.8 and 15.5% (sludges) and 50.1 and 87.1% and 8.83 and 16.3% (sediments), respectively. Finally, the studied analytes were quantified in concentrations between 0.18 and 24.0 ng/g in real samples of marine sediments and sewage sludges from Gran Canaria Island (Spain).