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The emission of potentially harmful compounds, including polycyclic aromatic hydrocarbons (PAHs), and the resulting air pollution is a serious problem in modern cities. It is therefore important to develop mitigation strategies, such as "smart" planting of trees that act as sinks for PAHs. However, the intra-individual (within-tree) variability in leaf PAH concentrations remains unknown. In this paper, we studied 15 ornamental apple trees (Malus × moerlandsii 'Profusion') growing on a main street in a medium-sized city in Galicia (NW Spain). We determined the PAH concentrations at 12 canopy positions in each tree (2 orientations and 2 distances from the trunk at 3 heights), measured various ecological traits (specific leaf area [SLA], δ 13 C, stomatal density, fatty acid contents and leaf hairiness) and analyzed the variability in traits within the canopy in relation to PAH concentrations. We observed high intra-individual variability in the PAH concentrations and the leaf traits. Statistical analyses revealed that leaf height was the main source of variability both in the PAH concentrations and in the traits, mainly due to the leaf morphology, particularly to the SLA. Therefore, the ideal vegetation to remove PAHs would be high leaf biomass trees, not too tall and with a high proportion of shade leaves., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Adult stem cells play a crucial role in tissue homeostasis and repair through multiple mechanisms. In addition to being able to replace aged or damaged cells, stem cells provide signals that contribute to the maintenance and function of neighboring cells. In the lung, airway basal stem cells also produce cytokines and chemokines in response to inhaled irritants, allergens, and pathogens, which affect specific immune cell populations and shape the nature of the immune response. However, direct cell-to-cell signaling through contact between airway basal stem cells and immune cells has not been demonstrated. Recently, a unique population of intraepithelial airway macrophages (IAMs) has been identified in the murine trachea. Here, we demonstrate that IAMs require Notch signaling from airway basal stem cells for maintenance of their differentiated state and function. Furthermore, we demonstrate that Notch signaling between airway basal stem cells and IAMs is required for antigen-induced allergic inflammation only in the trachea where the basal stem cells are located whereas allergic responses in distal lung tissues are preserved consistent with a local circuit linking stem cells to proximate immune cells. Finally, we demonstrate that IAM-like cells are present in human conducting airways and that these cells display Notch activation, mirroring their murine counterparts. Since diverse lung stem cells have recently been identified and localized to specific anatomic niches along the proximodistal axis of the respiratory tree, we hypothesize that the direct functional coupling of local stem cell-mediated regeneration and immune responses permits a compartmentalized inflammatory response.

Hydroalcoholic gels or hand sanitisers have become essential products to prevent and mitigate the transmission of COVID-19. Depending on their use, they can be classified as cosmetics (cleaning the skin) or biocides (with antimicrobial effects). The aim of this work was to determine sixty personal care products frequently found in cosmetic formulations, including fragrance allergens, synthetic musks, preservatives and plasticisers, in hydroalcoholic gels and evaluate their compliance with the current regulation. A simple and fast analytical methodology based on solid-phase microextraction followed by gas chromatography-tandem mass spectrometry (SPME-GC-MS/MS) was validated and applied to 67 real samples. Among the 60 target compounds, 47 of them were found in the analysed hand sanitisers, highlighting the high number of fragrance allergens (up to 23) at concentrations of up to 32,458 μg g -1 . Most of the samples did not comply with the labelling requirements of the EU Regulation No 1223/2009, and some of them even contained compounds banned in cosmetic products such as plasticisers. Method sustainability was also evaluated using the metric tool AGREEPrep, demonstrating its greenness.

Infections caused by multidrug-resistant bacteria are becoming increasingly frequent and sometimes difficult to treat due to the limited number of antibiotics active against them. In addition, they can spread between countries and/or continents, which is a problem of great relevance worldwide. It is, therefore, urgent to find alternatives to treat infections caused by multidrug-resistant bacteria. This study aimed at exploring a possible therapeutic alternative in the fight against antibiotic resistance. Based on the known antibacterial capacity of polyphenols, we tested the antimicrobial activity of a polyphenolic extract of Albariño white grape marc on clinical strains since research on such bacteria has been very scarce until now. First, the extract was obtained using a medium-scale ambient temperature (MSAT) system, which is an efficient and sustainable extractive method. The determinations of the polyphenolic content of the extract and its antioxidant capacity showed good results. Using chromatographic and mass spectrometric tools, 13 remarkable polyphenols were detected in the extract. The antibacterial activity of our grape marc extract against nineteen clinical strain isolates, some of which are multidrug-resistant, was evaluated by means of the calculation of half of the maximum inhibitory concentration (IC50) and the value of the minimum bactericidal concentrations (MBCs). In conclusion, the extract showed effectiveness against all clinical strains tested, regardless of their level of antibiotic resistance, and shows promise in the fight against antibiotic resistance.

The content of bioactive compounds in four brown and one red algae from the Adriatic Sea ( Dictyota dichotoma , Gongolaria barbata, Ericaria amentacea , Sargassum hornschuchii and Ellisolandia elongata ) is explored. The efficiency of two different extraction methods viz. ultrasound-assisted extraction (UAE) and matrix solid-phase dispersion (MSPD) to obtain the extracts rich in phenolic compounds was compared. The effect of the extraction solvent to modulate the phenolic profile was assessed. In general, the mixture ethanol/water in an isovolumetric proportion showed the best results. The total phenolic content (TPC) and antioxidant activity (AA), as well as the individual polyphenolic profile, were evaluated for five target algae. TPC values ranged between 0.2 mg GAE/g (for E. elongata ) and 38 mg GAE/g (for S. hornschuchii ). Regarding the quantification of individual polyphenols by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis, the presence of a high number of hydroxybenzoic acid derivatives (mainly of 3- and 4-hydroxybenzoic acids) in all species was noted. In G. barbata their concentrations reached up to 500 mg/kg. IC 50 values (ABTS assay) ranged between 44 mg/L (for S. hornschuchii ) and 11,040 mg/L (for E. elongata ). This work contributes to the in-depth characterization of these little-explored algae, showing their potential as a natural source of phenolic compounds.

Recycled tire crumb rubber (RTCR) surfaces contain harmful and carcinogenic substances, which can be ingested by the users of these facilities, mainly athletes and children. In this work, the potential in-vitro oral bioaccessibility of eighteen polycyclic aromatic hydrocarbons (PAHs) from RTCR employed as infill in synthetic football fields was studied in human synthetic body fluids (saliva, gastric, duodenal and bile), prepared according the Unified Bioaccessibility Method. Solid-phase extraction (SPE) using commercial sorbents and a new green material based on cork (cork industry by-product) were used to isolate the bioaccessible PAHs before gas chromatography-tandem mass spectrometry analysis. The method was optimized and validated attending the analytical figures of merit. The feasibility of cork biosorbent for the extraction of the compounds was demonstrated, as well as the suitability of the UBM method to perform the digestion with good precision. The application to real samples collected from football fields demonstrated the presence of 17 of the 18 target PAHs in the biofluids. Most volatile PAHs such as NAP, ACY, ACE, FLU, PHN and ANC, achieved the highest bioaccessibility percentage levels. The carcinogenic B[a]P was detected in 75 % of the samples at concentrations up to 2.5 ng g -1 (bioaccessible fraction). Children exposure assessment was carried out to identify potential risk. Other hazardous and environmentally problematic compounds such as N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPD-quinone), recently related with the dead of coho salmon, and hexamethoxymethylmelamine (HMMM), among others, were also detected. This is the first study in which the bioaccesibility from real crumb rubber samples of 15 out of the 16 PAHs considered as priority pollutants by the United States Environmental Protection Agency (EPA) and the presence of 6PPD-quinone and HMMM in the bioaccessible fractions is reported., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The genus Ulex comprises thirteen accepted species of perennial shrubs in the family Fabaceae. In Galicia (Spain) many of these are considered spontaneous colonizing species, which are easy to establish and maintain. Among them, Ulex gallii Planch. is used in traditional medicine for the same anti-infective, hypotensive and diuretic purposes as Ulex europaeus L., which is the most studied species. Likewise, some studies have described the antitumoral properties of several species. However, there are few scientific studies that justify the use of Ulex gallii Planch. and nothing has been reported about its composition to date. In our study, the entire plant was extracted with methanol and the crude extract was subjected to liquid phase extraction with distinct solvents, yielding three fractions: hexane (H), dichloromethane (D) and methanol (M), which were subsequently fractionated. The dichloromethane (D5, D7 and D8) and methanol (M4) sub-fractions showed antiproliferative activity on A549 (lung cancer) and AGS (stomach cancer) cell lines, and caspase 3/7 activity assessment and DNA quantification were also performed. Targeted analysis via UHPLC-QToF, in combination with untargeted analysis via MS-Dial, MS-Finder and Global Natural Products Social Molecular Networking (GNPS), allowed us to tentatively identify different metabolites in these sub-fractions, mostly flavonoids, that might be involved in their antiproliferative activity.

The terrestrial environment is one of the main recipients of plastic waste. However, limited research has been performed on soil contamination by plastics and even less assessing the effects of nanoplastics (NPls). Behind the potential toxicity caused per se, NPls are recognized vectors of other environmental harmful contaminants. Therefore, the main aim of the present study is to understand whether the toxicity of an industrial chemical (bisphenol A - BPA) and a pharmaceutical (diphenhydramine - DPH) changes in the presence of polystyrene NPls to the terrestrial invertebrate Folsomia candida. Assessed endpoints encompassed organismal (reproduction, survival and behavior) and biochemical (neurotransmission and oxidative stress) levels. BPA or DPH, 28 d single exposures (1 to 2000 mg/kg), induce no effect on organisms' survival. In terms of reproduction, the calculated EC50 (concentration that causes 50% of the effect) and determined LOEC (lowest observed effect concentration) were higher than the environmental concentrations, showing that BPA or DPH single exposure may pose no threat to the terrestrial invertebrates. Survival and reproduction effects of BPA or DPH were independent on the presence of NPls. However, for avoidance behavior (48 h exposure), the effects of the tested mixtures (BPA + NPls and DPH + NPls) were dependent on the NPls concentration (at 0.015 mg/kg - interaction: no avoidance; at 600 mg/kg - no interaction: avoidance). Glutathione S-transferase activity increased after 28 d exposure to 100 mg/kg DPH + 0.015 mg/kg NPls (synergism). The increase of lipid peroxidation levels found after the exposure to 0.015 mg/kg NPls (a predicted environmental concentration) was not detected in the mixtures (antagonism). The results showed that the effects of the binary mixtures were dependent on the assessed endpoint and the tested concentrations. The findings of the present study show the ability of NPls to alter the effects of compounds with different natures and mechanisms of toxicity towards soil organisms, showing the importance of environmental risk assessment considering mixtures of contaminants., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Apples and apple-based products are particularly interesting due to being a good source of polyphenols in an everyday diet. Recently there has been increased interest in the preservation of traditional apple varieties due to studies that suggest that traditional apple varieties have a higher content of polyphenols and antioxidant activity compared to commercial varieties. This study shows that traditional apple varieties contain higher concentration of polyphenolic compounds than conventional ones, such as chlorogenic acid (1.29-456 mg/kg dw), catechin (0.70-312 mg/kg dw), epicatechin (1.75-244 mg/kg dw), procyanidin B1 + B2 (4.08-358 mg/kg dw) and quercetin-3-glucoside (0.96-231 mg/kg dw). This research underlies the great potential of traditional apple varieties as a source of natural antioxidants and polyphenolics., Competing Interests: The authors declare no conflict of interest.

A scalable procedure with minimum energy requirements, MSAT (Medium Scale Ambient Temperature), in combination with solvents generally recognized as safe (GRAS), has been optimized to obtain polyphenolic extracts from white grape ( Vitis vinifera ) marc. The solvents considered were propylene glycol (Pg), ethanol (Et), and ethyl lactate (Lc), as well as their respective hydro-organic mixtures. In a first approach, the operating parameters were optimized through a response surface matrix: extraction solvent volume (range 10-150 mL), marc mass (range 20-200 g) and marc/dispersant mass ratio (range 0.5-2 g⋅g -1 ), using the total polyphenol content (TPC) and the antioxidant activity (AA) of the extracts as response parameters. The highest TPC (5,918 mgGAE⋅L -1 ) and AA (44 mmolTE⋅L -1 ) values were obtained using 200 g marc and 100 mL solvent. Regarding the type of solvent, a better response was reached with Lc > Et > Pg > H 2 O obtaining a polyphenol concentration of 252 mg⋅L -1 for the hydro-organic isovolumetric ratio of ethyl lactate. In addition, the stability of the extracts was studied for 62 days. The effect of factors such as temperature, light exposure, and oxidative reactivity was evaluated. The bioactivity indices showed no changes with the storage conditions of the extracts in the first month of analysis, after which 75% of the antioxidant activity as the concentration of the polyphenolic profile (204 mg⋅L -1 ) remains. The absence of reactive oxygen and the cooling of the extract (4°C) were the most determining factors ( p < 0.05) in modulating the stability of the total polyphenolic profile., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Castillo, Celeiro, Rubio, Bañobre, Otero-Otero, Garcia-Jares and Lores.)

Apples and apple-based products are among the most consumed fruits around the world. However, they are susceptible to infection with the fungi Penicilium expansum . In addition to the reduction of apple quality, secondary metabolism of this fungus produces a mycotoxin patulin that has a negative effect on human health. Currently, there is no available research in the literature on the resistance of Croatian traditional apple cultivars to contamination with P. expansum , and consequently, on the patulin content in apples and apple juice produced from those apples. Although the mechanism of apple resistance to fungal diseases has not yet been sufficiently investigated, some studies have shown that polyphenolic compounds have some impact on fungi growth. In order to contribute with new knowledge, this research deals with monitoring the growth of P. expansum on apples, patulin detection by LC/MS-MS, determination of polyphenol profile by validated HPLC method, and determining the effect of polyphenolic compounds on fungi growth and patulin production during apple storage. The results of this study have shown that Croatian traditional apple cultivars harvested from family farm Horvatić contain higher concentration of polyphenolic compounds and higher antioxidant activity. At the same time, they showed more resistance to infection by P. expansum than conventional ones. The higher content of dihydrochalcones and flavanols encouraged the biosynthesis of patulin in examined cultivars. However, the higher content of non-flavonoids such as 2-6 dimethoxybenzoic acid, 4-hydroxycinnamic acid and chlorogenic acid leads to decrease in content of patulin. In conclusion, it seems that content of polyphenols and patulin production are correlated.

Because of the coronavirus pandemic, hydroalcoholic gels have become essential products to prevent the spread of COVID-19. This research aims to develop a simple, fast and sustainable microextraction methodology followed by gas chromatography tandem mass spectrometry (GC-MS/MS) to analyze simultaneously 60 personal care products (PCPs) including fragrances allergens, synthetic musks, preservatives and plasticizers in hand sanitizers. Micro-matrix-solid-phase dispersion (μMSPD) and solid-phase microextraction (SPME) were compared with the aim of obtaining high sensitivity and sample throughput. SPME demonstrated higher efficiency being selected as sample treatment. Different dilutions of the sample in ultrapure water were assessed to achieve high sensitivity but, at the same time, to avoid or minimize matrix effect. The most critical parameters affecting SPME (fibre coating, extraction mode and temperature) were optimized by design of experiments (DOE). The method was successfully validated in terms of linearity, precision and accuracy, obtaining recovery values between 80 and 112% for most compounds with relative standard deviation (RSD) values lower than 10%. External calibration using standards prepared in ultrapure water demonstrated suitability due to the absence of matrix effect. Finally, the simple, fast and high throughput method was applied to the analysis of real hydroalcoholic gel samples. Among the 60 target compounds, 39 of them were found, highlighting the high number of fragrance allergens, at concentrations ranging between 0.01 and 217 μg g -1 . Most of the samples were not correctly labelled attending cosmetic Regulation (EU) No 1223/2009, and none of them followed the World Health Organization (WHO) recommendation for hand sanitizers formulation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

A fast, efficient, and simple air sampling methodology was developed to study a high number of volatile and semivolatile organic compounds in air above tire rubber materials and surfaces made of recycled tire rubber. The proposed method, based on active sampling (solid-phase extraction, SPE) using a small quantity of sorbent material (25 mg) followed by solid-phase microextraction (SPME) and gas chromatography-tandem mass spectrometry analysis, was developed with the aim of determining 40 organics substances including polycyclic aromatic hydrocarbons (PAHs), plasticizers, antioxidants, and vulcanization agents. An experimental design was carried out to study the influence of main factors such as type of SPME fibre, solvent addition, headspace volume, stirring, as well as the factor interactions. Method performance showed good linearity in a broad concentration range (0.05 to 200 ng m -3 , for most compounds), with coefficients of determination (R 2 ) higher than 0.9900. Whole method precision (≤ 16 %) and accuracy were also satisfactory, obtaining quantitative recoveries (mean values between 80 and 110 % in most cases). Limits of detection and quantification have also been calculated, yielding values of sub ng m -3 for most compounds. The validated method was applied to outdoor and indoor air environments including playgrounds, football pitches and warehouses showing the presence of most target compounds in the samples achieving high levels for some PAHs (concentrations up to 51 ng m -3 ), benzothiazole (BTZ), diisobutyl- dibutyl- and di-(2-ethylhexyl)- phthalate, among others, reaching concentrations up to hundreds of ng m -3 (BTZ). This is the first time that the combination of techniques SPE and SPME is applied for these families of chemicals, and it is also the first time that this approach is proposed for the simultaneous multiclass compound extraction of substances of different chemical families. The whole sampling and extraction procedure is performed in a short period of time (61 min) allowing high throughput. The elimination of the use of organic solvents and waste generation by using only 25 mg of sorbent and a SPME fibre than are both reused makes the method sustainable and in consonance with the principles of the green chemistry. The method can be implemented in any routine lab and easily automated using a SPME autosampler., Competing Interests: Declaration of Competing Interest The authors declare they have no known competing financial interest or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Author(s). Published by Elsevier B.V. All rights reserved.)

Although there are several works in the literature that study the presence of pharmaceuticals and personal care products (PPCPs) in surface waters, the vast majority focus their attention on pharmaceuticals and little information is found about personal care products (PCPs). Therefore, this study focused, for the first time, on the monitoring of five classes of PCPs - fragrance allergens, synthetic musks, phthalates, antioxidants, and ultraviolet-filters - in the surface water of four small-size typically pollution-impacted Portuguese rivers (Ave, Leça, Antuã and Cértima). A solid-phase microextraction (SPME) followed by gas chromatography - tandem mass spectrometry (GC-MS/MS) protocol was employed to analyse surface water samples collected in two seasonal campaigns - summer and winter (34 samples per season). A total of 22 out of 37 target PCPs were detected concomitantly at least once in one sampling point, being the most frequently detected α-isomethyl ionone, galaxolide, tonalide and cashmeran. The highest concentrations were confirmed for diethylhexyl phthalate (610.6 ng L -1 ), galaxolide (379.2 ng L -1 ), geraniol (290.9 ng L -1 ), linalool (271.2 ng L -1 ), benzophenone-3 (254.1 ng L -1 ) and citronellol (200.2 ng L -1 ). Leça River, traversing the more densely urban and industrialized area, had the highest levels of contaminants, which were also found in the sampling points located downstream of wastewater treatment plants discharge points. In general, higher levels were detected in summer, when the river flows are lower. Hazard quotients were determined and octocrylene, tonalide, and geraniol presented values above 1 in some sampling sites, which may indicate an ecotoxicological risk to the aquatic environment. The results presented suggest that these three PCPs should be included as priority pollutants in environmental monitoring schemes in surface waters, due to their high detection, persistence, and potential adverse effects., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Social and environmental concern about the use of crumb rubber from end-of-life car tires in the construction of different sport and recreational facilities is increasing due to the presence of hazardous compounds. The aim of this research was the assessment of 42 organic chemicals, including polycyclic aromatic hydrocarbons (PAHs), phthalates, adipates, antioxidants and vulcanisation agents in a large number of infill samples (91) from synthetic turf football pitches of diverse characteristics and geographical origin. Samples were taken worldwide, in 17 countries on 4 continents, to show the global dimension of this problem. Ultrasound assisted extraction was employed to extract the target compounds, followed by gas chromatography coupled to tandem-mass spectrometry (UAE-GC-MS/MS). Seventy-eight crumb rubber samples as well as thirteen samples of alternatives materials, such as cork granulates, thermoplastic elastomers and coconut fibre, were analyzed. The results highlight the presence of all target PAH in most rubber samples at concentrations up to μg g -1 , including the eight ECHA (European Chemicals Agency) PAHs considered as carcinogenic, and anthracene (ANC), pyrene (PYR) and benzo[ghi]perylene (B[ghi]P), catalogued as substances of very high concern (SVHC). Endocrine disruptors such as some plasticizers (mainly phthalates), and other compounds like benzothiazole (BTZ) and 2-mercaptobenzothiazole (MBTZ) were found reaching the mg g -1 level. This confirms the presence of the hazardous substances in the recycled crumb rubber samples collected all around the world. Three crumb rubber samples exceeded the limit of 20 μg g -1 for the sum of the eight ECHA PAHs. Regarding the chemical composition of other infill alternatives, cork appears to be adequate, while the thermoplastic elastomers contained high levels of some plasticizers. In addition, the plastic infill as well as the crumb rubber both are microplastics. Microplastics are considered contaminants of emerging concern since they do not biodegrade and remain in the environment for a long time., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

An extraction method was designed and scaled up to produce multicomponent polyphenolic extracts from blueberries ( Vaccinium corymbosum ) of three different varieties. The process was specifically drawn up to comply with green chemistry principles. Extracts were obtained for the direct assessment of their antimicrobial and antiadhesive activities, and their direct use in the control of infections caused by concerning multidrug-resistant nosocomial pathogens. Analytical characterization was performed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Similar qualitative profiles were obtained in the three studied varieties with some significant quantitative differences. Up to 22 different polyphenols were identified with a clear predominance of anthocyani(di)ns followed by flavanols, non-flavonoids, and far behind by flavan-3-ols and procyanidins. The individual content of the main polyphenols was also discussed. A pilot scale extract has been also produced as a proof-of-concept, showing that scaling-up triples the content of bioactive phytochemicals. The effect of the polyphenolic extracts was analyzed against seven multidrug-resistance bacterial species by performing biofilm formation and growth and killing curves assays. All the studied varieties showed antibacterial and antiadhesive activities, being the extract containing the highest concentration of bioactive polyphenols, the most active with a high bactericidal effect.

Honey is a natural product well known for its beneficial properties. It contains phytochemicals, a wide class of nutraceuticals found in plants, including compounds with highly demonstrated antimicrobial and antioxidant capacities as phenolic compounds and flavonoids. The main goal of this work is the development of a miniaturized and environmentally friendly methodology to obtain the phenolic profile of Galician honeys (Northwest Spain) from different varieties such as honeydew, chestnut, eucalyptus, heather, blackberry and multi-floral. The total phenolic content (TPC) and antioxidant activity (AA) were also evaluated. As regards sample preparation, miniaturized vortex (VE) and ultrasound assisted extraction (UAE) employing aqueous-based solvents were performed. Individual quantification of 41 target phenolic compounds was carried out by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Results revealed the presence of 25 phenolic compounds in the 91 analyzed samples, reaching concentrations up to 252 µg g -1 . Statistical tools such as analysis of variance (ANOVA) and principal component analysis (PCA) were employed to obtain models that allowed classifying the different honeys according to their botanical origin. Obtained results, based on TPC, AA and ∑phenolic compounds showed that significant differences appeared depending on the honey variety, being several of the identified phenol compounds being responsible of the main differentiation.

The use of cosmetics and personal care products is increasing worldwide. Their high matrix complexity, together with the wide range of products currently marketed under different forms imply a challenge for their analysis, most of them requiring a sample pre-treatment step before analysis. Classical sample preparation methodologies involve large amounts of organic solvents as well as multiple steps resulting in large time consumption. Therefore, in recent years, the trends have been moved towards the development of simple, sustainable, and environmentally friendly methodologies in two ways: (i) the miniaturization of conventional procedures allowing a reduction in the consumption of solvents and reagents; and (ii) the development and application of sorbent- and liquid-based microextraction technologies to obtain a high analyte enrichment, avoiding or significantly reducing the use of organic solvents. This review provides an overview of analytical methodology during the last ten years, placing special emphasis on sample preparation to analyse cosmetics and personal care products. The use of liquid-liquid and solid-liquid extraction (LLE, SLE), ultrasound-assisted extraction (UAE), solid-phase extraction (SPE), pressurized liquid extraction (PLE), matrix solid-phase extraction (MSPD), and liquid- and sorbent-based microextraction techniques will be reviewed. The most recent advances and future trends including the development of new materials and green solvents will be also addressed.

Nowadays concern exists about the safety for both football players and the environment of recycled tire rubber used as infill in synthetic turf football pitches. In this study 40 target compounds, including polycyclic aromatic hydrocarbons (PAHs), plasticizers, antioxidants and vulcanization agents were determined in 50 synthetic football pitches of diverse characteristics to estimate environmental risks. This is the first study of crumb rubber sport facilities in Portugal. Analyses were performed by ultrasound-assisted extraction followed by gas chromatography-tandem mass spectrometry (UAE-GC-MS/MS). To evaluate the transfer of the target chemicals from the crumb rubber to the runoff water, water leachates collected from several football pitches were analyzed by solid-phase microextraction (SPME-GC-MS/MS). In addition, lab-scale runoff simulation experiments were performed to assess whether a persistent inflow of the target compounds from the football pitches into the runoff water wcould exist. Results revealed the presence of most of the target PAHs in crumb rubber at total concentrations up to 57 μg g -1 , next to a high number of plasticizers and vulcanization agents. Runoff water collected from the football pitches contained up to 13 PAHs as well as other chemicals of environmental concern. In addition, continuous leaching of chemicals from the crumb rubber to the surrounding water was demonstrated. The transfer of target chemicals into the runoff water poses a potential risk for the aquatic environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The wide range and complexity of cosmetic formulations currently available on the market poses a challenge from an analytical point of view. In addition, during cosmetics manufacture, impurities coming from raw materials or formed by reaction of different organic compounds present in the formulation may be present. Their identification is mandatory to assure product quality and consumer health. In this work, micro-matrix solid-phase dispersion (μMSPD) is proposed as a multi-target sample preparation strategy to analyze a wide number of unexpected families of compounds including polycyclic aromatic hydrocarbons (PAHs), pesticides, plasticizers, nitrosamines, alkylphenols (APs), and alkylphenol ethoxylates (APEOs). Analytical determination was performed by gas chromatography-mass spectrometry (GC-MS) for the determination of 51 target compounds in a single run, whereas liquid chromatography tandem mass spectrometry (LC-MS/MS) was employed for the analysis of six APs and APEOs. Both methodologies were successfully validated in terms of linearity, accuracy, and precision in leave-on and rinse-off cosmetics. Limits of detection (LODs) were calculated in the low ng g -1 , showing their suitability to determine trace levels of impurities and banned compounds with different chemical natures, providing useful tools to cosmetic control laboratories and companies.

An effective, quick, and sustainable air analysis method was developed to analyze 41 volatiles and semivolatile organic compounds present in tire rubber and crumb rubber materials. The proposed method, based on active sampling using a sorbent material followed by an ultrasound assisted extraction, was developed with the aim of obtaining a fast and simple procedure to determine polycyclic aromatic hydrocarbons, plasticizers, antioxidants, and vulcanization agents in air. A small amount of sorbent (25 mg) was used, and the analytes were recovered in only 1 mL of solvent. An experimental design was applied to study the influence of main factors such as type of sorbent and type of solvent, extraction technique (ultrasound-assisted extraction and vortex extraction), extraction time, as well as the factor interactions. Under optimal conditions, no breakthrough occurs in the studied interval (up to 4 m 3 ). Linearity was demonstrated in a wide concentration range. Accuracy of the total sampling-extraction analysis was evaluated obtaining satisfactory recoveries as well as good precision. The method was successfully applied to different outdoor and indoor air environments, including a recycled rubber synthetic turf football pitch., (© 2021 Wiley-VCH GmbH.)

Chronic, sustained exposure to stressors can profoundly affect tissue homeostasis, although the mechanisms by which these changes occur are largely unknown. Here we report that the stress hormone corticosterone-which is derived from the adrenal gland and is the rodent equivalent of cortisol in humans-regulates hair follicle stem cell (HFSC) quiescence and hair growth in mice. In the absence of systemic corticosterone, HFSCs enter substantially more rounds of the regeneration cycle throughout life. Conversely, under chronic stress, increased levels of corticosterone prolong HFSC quiescence and maintain hair follicles in an extended resting phase. Mechanistically, corticosterone acts on the dermal papillae to suppress the expression of Gas6, a gene that encodes the secreted factor growth arrest specific 6. Restoring Gas6 expression overcomes the stress-induced inhibition of HFSC activation and hair growth. Our work identifies corticosterone as a systemic inhibitor of HFSC activity through its effect on the niche, and demonstrates that the removal of such inhibition drives HFSCs into frequent regeneration cycles, with no observable defects in the long-term.

Crumb rubber obtained from scrap tires is greatly employed for the construction of different facilities for sport, recreational and other uses. However, in recent years the concern about their safety and the related adult and children exposure to these surfaces is growing. This study aims a thorough chemical characterization encompassing 42 hazardous compounds, including polycyclic aromatic hydrocarbons (PAHs), phthalates, adipates, antioxidants and vulcanization agents in a wide range of crumb rubber from different surfaces. For the extraction of the target compounds, a method based on ultrasound-assisted extraction followed by gas chromatography-tandem mass spectrometry (UAE-GC-MS/MS) has been validated. Forty crumb rubber samples coming from synthetic turf football pitches, outdoor and indoor playgrounds, urban pavements, commercial tiles and granulates, and scrap tires, were analyzed. In addition, green alternative materials, such as sand and artificial turf based on cork granulate infill were included to compare the levels of the target compounds with those of crumb rubber. Most of the analyzed recycled surfaces meet the recent limits proposed by the European Commission for rubber granulates and mulches, although they exceed in several cases the maximum levels allowed for rubber consumer products. Besides, most of the other target compounds, including several of them considered as endocrine disruptors, were detected in the analyzed samples, reaching parts per million concentrations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In this study, green extraction methods-high voltage electrical discharges (HVED), pulsed electric field (PEF), and ultrasound-assisted extraction (UAE)-were compared in terms of extraction yield of total and individual polyphenolic compounds, as well as the antioxidant capacity of blueberry pomace extracts. All extractions were performed with methanol- and ethanol-based solvents. The highest total polyphenols content (TPC) (10.52 mg of gallic acid equivalent (GAE) per g of dry weight (dw)) and antioxidant activity (AA) (0.83 mmol TE/g dw) were obtained by PEF-assisted extraction in the ethanol-based solvent after 100 pulses and 20 kV/cm, which corresponds to an energy input of 41.03 kJ/kg. A total of eighteen individual polyphenols were identified in all investigated blueberry pomace extracts by high-performance liquid chromatography with the diode-array detector (HPLC-DAD) and liquid chromatography electrospray ionization tandem mass spectrometric (LC-(HESI)-MS/MS). The highest anthocyanin (1757.32 µg/g of dw) and flavanol (297.86 µg/g of dw) yields were obtained in the methanol-based solvent, while the highest phenolic acid (625.47 µg/g of dw) and flavonol (157.54 µg/g of dw) yields were obtained in the ethanol-based solvent by PEF-assisted extraction at the energy input of 41.03 kJ/kg. These results indicated that PEF is a promising green extraction method which can improve the blueberry pomace's polyphenol extraction yield.

During stoppers production, large amounts of cork by-products (CBPs) are generated, being used as low-value material. This project aims to turn CBPs into smart, natural and sustainable materials (sorbent) for solid-phase extraction (SPE) of pesticides from water. The study describes the use of CBPs for the extraction of 17 fungicides (metalaxyl, cyprodinil, tolylfluanid, procymidone, folpet, fludioxonil, myclobutanil, kresoxim methyl, iprovalicarb, benalaxyl, trifloxystrobin, fenhexamid, tebuconazole, iprodione, pyraclostrobin, azoxystrobin and dimethomorph) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis. The most critical parameters affecting SPE were optimized by experimental design methodology. Under the optimal conditions, the method was successfully validated in terms of linearity, repeatability, and intermediate precision. Fungicide recovery was assessed in different real water samples including river, fountain, rainwater and spring water at 3 concentration levels (0.1, 0.5 and 10 µg L -1 ). Recoveries ranged between 70-118% with RSD values lower than 20%, and matrix effects were not observed. Finally, the method was applied to samples from irrigation, rain, and river water, all collected in vineyards areas, revealing the presence of 10 of the 17 fungicides, at concentration up to hundreds of µg L -1 . The use of CBPs seems to be a promising low-cost and ecofriendly alternative to be employed as sorbent in SPE techniques to extract fungicides from the aquatic environment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Piloerection (goosebumps) requires concerted actions of the hair follicle, the arrector pili muscle (APM), and the sympathetic nerve, providing a model to study interactions across epithelium, mesenchyme, and nerves. Here, we show that APMs and sympathetic nerves form a dual-component niche to modulate hair follicle stem cell (HFSC) activity. Sympathetic nerves form synapse-like structures with HFSCs and regulate HFSCs through norepinephrine, whereas APMs maintain sympathetic innervation to HFSCs. Without norepinephrine signaling, HFSCs enter deep quiescence by down-regulating the cell cycle and metabolism while up-regulating quiescence regulators Foxp1 and Fgf18. During development, HFSC progeny secretes Sonic Hedgehog (SHH) to direct the formation of this APM-sympathetic nerve niche, which in turn controls hair follicle regeneration in adults. Our results reveal a reciprocal interdependence between a regenerative tissue and its niche at different stages and demonstrate sympathetic nerves can modulate stem cells through synapse-like connections and neurotransmitters to couple tissue production with demands., Competing Interests: Declaration of Interests A provisional patent application has been filed by the President and Fellows of Harvard College based on this work., (Copyright © 2020 Elsevier Inc. All rights reserved.)

A rapid environmental pollution screening and monitoring workflow based on fabric phase sorptive extraction-gas chromatography-tandem mass spectrometry (FPSE-GC-MS/MS) is proposed for the first time for the analysis of 17 widespread used fungicides (metalaxyl, cyprodinil, tolylfluanid, procymidone, folpet, fludioxonil, myclobutanil, kresoxim methyl, iprovalicarb, benalaxyl, trifloxystrobin, fenhexamid, tebuconazole, iprodione, pyraclostrobin, azoxystrobin and dimethomorph) in environmental waters. The most critical parameters affecting FPSE, such as sample volume, matrix pH, desorption solvent and time, and ionic strength were optimized by statistical design of experiment to obtain the highest extraction efficiency. Under the optimized conditions, the proposed FPSE-GC-MS/MS method was validated in terms of linearity, repeatability, reproducibility, accuracy and precision. To assess matrix effects, recovery studies were performed employing different water matrices including ultrapure, fountain, river, spring, and tap water at 4 different concentration levels (0.1, 0.5, 1 and 5 µg/L). Recoveries were quantitative with values ranging between 70-115%, and relative standard deviation values lower than 14%. Limits of quantification were at the low ng/L for all the target fungicides. Finally, the validated FPSE-GC-MS/MS method was applied to real water samples, revealing the presence of 11 out of the 17 target fungicides., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The mechanism of phytotoxicity of citral was probed in Arabidopsis thaliana using RNA-Seq and in silico binding analyses. Inhibition of growth by 50% by citral downregulated transcription of 9156 and 5541 genes in roots and shoots, respectively, after 1 h. Only 56 and 62 genes in roots and shoots, respectively, were upregulated. In the shoots, the downregulation increased at 3 h (6239 genes downregulated, vs 66 upregulated). Of all genes affected in roots at 1 h (time of greatest effect), 7.69% of affected genes were for nucleic acid binding functions. Genes for single strand DNA binding proteins (SSBP) WHY1, WHY 2 and WHY3 were strongly downregulated in the shoot up until 12 h after citral exposure. Effects were strong in the root at just 1 h after the treatment and then at 12 and 24 h. Similar effects occurred with the transcription factors MYC-2, ANAC and SCR-SHR, which were also significantly downregulated for the first hour of treatment, and downregulation occurred again after 12 and 24 h treatment. Downregulation of ANAC in the first hour of treatment was significantly (P < 0.0001) decreased more than eight times compared to the control. In silico molecular docking analysis suggests binding of citral isomers to the SSBPs WHY1, WHY2, and WHY3, as well as with other transcription factors such as MYC-2, ANAC and SCR-SHR. Such effects could account for the profound and unusual effects of citral on downregulation of gene transcription., (© 2019 Scandinavian Plant Physiology Society.)

A novel method based on fabric phase sorptive extraction (FPSE) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been validated for the simultaneous determination of 11 UV filters (ethylhexyl salicylate, benzyl salicylate, homosalate, benzophenone-3, isoamylmethoxycinnamate, 4-methylbenzylidenecamphor, methyl anthranilate, etocrylene, 2-ethylhexylmethoxycinnamate, 2-ethylhexyl p -dimethylaminobenzoate, and octocrylene), in natural and recreational waters. Major experimental parameters affecting FPSE procedure have been optimized to obtain the highest extraction efficiency. Different types and sizes of sol-gel coated FPSE media, sample volume, extraction time, and type and volume of desorption solvent were evaluated. The optimal conditions involved the use of a (2.0 × 2.5) cm 2 FPSE device with PDMS based coating for the extraction of 20 mL of water for 20 min. The quantitative desorption of the target compounds was performed with 0.5-1 mL of ethyl acetate. The method was satisfactorily validated in terms of linearity, precision, repeatability and reproducibility. Recovery studies were performed at different concentration levels in real water matrices to show its suitability, obtaining mean values about 90% and satisfactory precision. LODs were at the low ng L -1 in all cases. Finally, the validated FPSE-GC-MS/MS method was applied to different real samples, including environmental water (lake, river, seawater) and recreational water (swimming-pool), where 8 out of the 11 studied compounds were detected at concentrations between 0.12-123 μg L -1 . FPSE is proposed as an efficient and simple alternative to other extraction and microextraction techniques for the analysis of UV filters in waters. Since no matrix effects were observed, quantification could be carried out by conventional calibration with standard solutions, without the need to perform the complete FPSE procedure, thus allowing a higher throughput in comparison with other microextraction techniques., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2019 Published by Elsevier B.V.)

A methodology based on solid-phase microextraction (SPME) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed for the simultaneous analysis of different families of personal care products (PCPs) including fragrance allergens, synthetic musks, phthalates, antioxidants and UV filters in continental waters. The main parameters affecting SPME procedure were optimized by an ANOVA study. The final selected conditions comprised the use of 10 mL of sample with 20% (w/v) of sodium chloride (NaCl), polydimtehylsiloxane/divinylbenzene (PDMS/DVB) fiber and 20 min of extraction time at 100 °C in the head-space mode. Good linearity (R 2 >0.9925), quantitative recoveries (>79%), and precision (RSD < 15%) were achieved for all compounds under the optimal conditions. Limits of quantification (LOQs) at the sub and low ng L -1 were obtained. The validated methodology was successfully applied to the analysis of river water samples from the North Portuguese coast allowing the determination of five different families of PCPs, including a total of 43 compounds in a single chromatographic run within 23 min., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Three different by-products from the Eucalyptus wood industry have been exhaustively characterized to find compounds with antioxidant properties. The industrial process to manufacture Eucalyptus greenboards is distinguished by using just wood and water, which converts the generated by-products in a highly attractive source of bioactive compounds that are originally in the raw material. The studied by-products were: the screw water, derived from the washing of the wood chips; the condensates, obtained after the evaporation and further condensation of the screw water; and finally, the concentrate of eucalyptus. For all of them and for their derived organic extracts, the total polyphenols content (TPC) and antioxidant activity (AA) have been evaluated. The chromatographic fingerprints, based on gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-tandem mass spectrometry (LC-MS/MS) have been obtained to identify the main extractable organic wood components. Besides, solid-phase microextraction (SPME) has been employed to characterize the most volatile compounds. Significant differences were observed for the chromatographic profiles of the studied by-products. Up to 48 and 30 different compounds were identified in the screw water, and condensate by-products, respectively; whereas the highest number of compounds, up to 72, have been identified in the organic extracts derived from the concentrate of Eucalyptus, highlighting the presence of monoterpenes, sesquiterpenes, polyphenols, and other bioactive compounds with antioxidant properties. Therefore, these by-products could be exploited to obtain natural extracts with added value which could be reused in the food, cosmetic or pharmaceutical industry, reducing the environmental impact of the industrial activity., Competing Interests: The authors declare no conflicts of interest

Different photodegradation strategies were assessed to remove 21 multiclass organic ultraviolet (UV) filters including benzophenone-, camphor-, and p-aminobenzoic acid- derivatives, methoxycinnamates, and salicylates, among others, from the aquatic environment. Direct photolysis under UVA (λ = 365 nm) and UVC (λ = 254 nm) radiations and advanced oxidation processes (AOPs) based on heterogeneous UVA/TiO 2 photocatalysis and the UVC/H 2 O 2 system were applied for the degradation tests. LC-MS/MS and SPME-GC-MS/MS were employed for the monitoring of the target compound degradations. UVC photolysis provided the highest removal efficiency for most of the studied UV filters with degradation yields higher than 90% after 60 min of light exposure in ultrapure water. This radiation was also applied to different real water matrices (river, sea, and swimming-pool water), showing that the degradation yield was dependent on the water matrix, being more difficult the removal of the target compounds in waters with high organic matter content. In an attempt to accelerate the degradation of the studied compounds in this kind of water matrices, the use of a powerful UVC/H 2 O 2 system improvement the reaction kinetics, showing degradation > 90% for most of the studied UV filters. Besides, up to 19 photoproducts could be identified by HRMS., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In vivo delivery of genome-modifying enzymes holds significant promise for therapeutic applications and functional genetic screening. Delivery to endogenous tissue stem cells, which provide an enduring source of cell replacement during homeostasis and regeneration, is of particular interest. Here, we use a sensitive Cre/lox fluorescent reporter system to test the efficiency of genome modification following in vivo transduction by adeno-associated viruses (AAVs) in tissue stem and progenitor cells. We combine immunophenotypic analyses with in vitro and in vivo assays of stem cell function to reveal effective targeting of skeletal muscle satellite cells, mesenchymal progenitors, hematopoietic stem cells, and dermal cell subsets using multiple AAV serotypes. Genome modification rates achieved through this system reached >60%, and modified cells retained key functional properties. This study establishes a powerful platform to genetically alter tissue progenitors within their physiological niche while preserving their native stem cell properties and regulatory interactions., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

The cosmetic industry currently focuses on products with magnified or exaggerated effects or extremely long-lasting characteristics. There are also a number of related commercial products for which the regulatory framework is far from clear; they are called 'borderline', and the European authorities only recommend which regulations they need to comply with. In any case, all these products must be safe under reasonable conditions of use in accordance with the applicable laws in force in the European Union (EU) framework. In this context, adequate analytical methodology is needed to evaluate the degree of compliance. Ultrasound Assisted Extraction (UAE) procedures for the analysis of 70 cosmetic ingredients have therefore been developed in this work. Moreover, for cosmetics with plastic applicators, a Supported-UAE (Sup-UAE) method was also opportunely optimized to check if a partial transfer of plasticizers to the cosmetics-and thereby to the consumers-could happen. In a survey of 50 commercial products (30 'extreme' and 20 'borderline'), the methods afforded mean recoveries of about 100% and RSD values lower than 5% for UAE and 10% for Sup-UAE, and with detection limits far below the legal requirements, for all the target compounds, thereby demonstrating their analytical suitability. Results are discussed in detail for phthalates, fragrances (musks and allergens) and some frequent preservatives. Additionally, a labelling study was performed to check if the consumer is correctly and fully informed. Graphical abstract ᅟ.

A solvent-free method based on solid-phase microextraction (SPME) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous determination of eleven fungicides at trace levels in different types of waters. Several experimental SPME parameters such as temperature, fibre coating, and SPME mode, were optimized in order to obtain the highest extraction efficiency. Under the optimal conditions, 100 °C, polyacrilate fibre (PA) and direct-immersion mode, the method was validated showing good linearity, repeatability and reproducibility. Recovery studies were carried out in four different real water matrices and at three concentration levels (20, 200 and 2000 ng L -1 ), with overall recovery values between 92 and 104% and relative standard deviations (RSD) about 10%. Limits of detection (LODs) at the low ng L -1 were obtained. The method demonstrated its suitability for the determination of fungicides in real water samples using external calibration for quantification purposes as well as for photodegradation studies at low concentration levels., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Due to the high concern generated in the last years about the safety of recycled tire rubber used for recreational sports surfaces, this study aims at evaluating the presence of forty organic compounds including polycyclic aromatic hydrocarbons (PAHs), phthalates, adipates, vulcanisation additives and antioxidants in recycled tire crumb of synthetic turf football fields. Ultrasound Assisted Extraction (UAE) was successfully employed to extract the target compounds from the crumb rubber, and analysis was performed by gas chromatography-mass spectrometry (GC-MS). The transfer of the target chemicals from the crumb rubber to the runoff water and to the air above the rubber surface has also been evaluated employing solid-phase microextraction (SPME). Samples from fifteen football fields were analysed, and the results revealed the presence of 24 of the 40 target compounds, including 14 of the 16 EPA PAHs, with total concentrations up to 50 μg g -1 . Heavy metals such as Cd, Cr and Pb were also found. A partial transfer of organic compounds to the air and runoff water was also demonstrated. The analysis of rain water collected directly from the football field, showed the presence of a high number of the target compounds at concentrations reaching above 100 μg L -1 . The environmental risk arising from the burning of crumb rubber tires has been assessed, as well, analysing the crumb rubber, and the air and water in contact with this material, showing a substantial increase both of the number and concentration of the hazardous chemicals., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The mode of action and phytotoxic potential of scopoletin, a natural compound belonging to the group of coumarins, has been evaluated in detail. Analysis conducted by light and electron transmission microscopy showed strong cell and tissue abnormalities on treated roots, such as cell wall malformations, multi-nucleated cells, abnormal nuclei and tissue disorganization. Scopoletin compromised root development by inducing wrong microtubule assembling, mitochondrial membrane depolarization and ultimate cell death, in a way similar to auxin herbicides. The structural similarities of the natural compound scopoletin and the auxin herbicide 2,4-D, as well as the ability of scopoletin to fit into the auxin-binding site TIR1, were analyzed, suggesting that the phytotoxic activity of scopoletin matches with that exhibited by auxinic herbicides., (Copyright © 2017 Elsevier GmbH. All rights reserved.)

The photodegradation behaviour for nine widespread fungicides (benalaxyl, cyprodinil, dimethomorph, fenhexamide, iprovalicarb, kresoxim-methyl, metalaxyl, myclobutanil and tebuconazole) was evaluated in different types of water. Two different systems, direct UV photolysis and UVC/H 2 O 2 advanced oxidation process (AOP), were applied for the photodegradation tests. For the monitoring of the target compound degradation, a method based on direct injection liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed. Several fungicide photodegradation by-products were tentatively identified by high-resolution mass spectrometry (HRMS) as well. For the photolysis studies, the efficiency of different types of radiation, UVC (λ = 254 nm) and UVA (λ = 365 nm), was compared. UVC photolysis provided the highest removal with a complete degradation for fenhexamide and kresoxim-methyl, and percentages between 48 and 78% for the other compounds, excluding iprovalicarb and myclobutanil with removals <35%, after 30 min of irradiation. Besides, the photodegradation tests were performed with different initial concentrations of fungicides, and the efficiency of two photoreactor systems was compared. In all cases, the kinetics followed pseudo-first order, and the half-life times could also be calculated. The addition of H 2 O 2 under UVC light allowed an improvement of the reaction kinetics, especially for the most recalcitrant fungicides, obtaining in all cases removals higher than 82% in less than 6 min. Finally, in order to evaluate the suitability of the proposed systems, both UVC photolysis and UVC/H 2 O 2 system were tested in different real water matrices (wastewater, tap water, swimming pool water and river water), showing that the UVC/H 2 O 2 system had the highest removal efficiency in less than 6 min, for all water samples.

UV filters are a class of emerging contaminants that are widely used in personal care products (PCPs) and that can be detected at low concentrations in the aquatic environment (ngL -1 ). Sensitive modern analytical methods are then mandatory to accurately analyze them. A methodology based on solid-phase-microextraction (SPME), considered as a 'Green Chemistry' technique, followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in environmental and recreational waters. In-vial low-cost derivatization was carried out to improve chromatographic performance of phenolic compounds. The extraction parameters (fiber coating, extraction mode, and salt addition) were optimized by means of experimental designs in order to achieve reliable conditions. Finally, the SPME-GC-MS/MS method was validated in terms of linearity, accuracy and precision with LODs in the low ngL -1 level. Its application to the analysis of 28 different samples including sea, river, spa, swimming pool, and aquapark waters, enabled the detection of 11 target UV filters at concentration levels up to 540μgL -1 , highlighting the presence of OCR in all analyzed samples and of 2EHMC (proposed to be considered as priority pollutant) in 79% of them., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Growth and regeneration of one tissue within an organ compels accommodative changes in the surrounding tissues. However, the molecular nature and operating logic governing these concurrent changes remain poorly defined. The dermal adipose layer expands concomitantly with hair follicle downgrowth, providing a paradigm for studying coordinated changes of surrounding lineages with a regenerating tissue. Here, we discover that hair follicle transit-amplifying cells (HF-TACs) play an essential role in orchestrating dermal adipogenesis through secreting Sonic Hedgehog (SHH). Depletion of Shh from HF-TACs abrogates both dermal adipogenesis and hair follicle growth. Using cell type-specific deletion of Smo, a gene required in SHH-receiving cells, we found that SHH does not act on hair follicles, adipocytes, endothelial cells, and hematopoietic cells for adipogenesis. Instead, SHH acts directly on adipocyte precursors, promoting their proliferation and their expression of a key adipogenic gene, peroxisome proliferator-activated receptor γ (Pparg), to induce dermal adipogenesis. Our study therefore uncovers a critical role for TACs in orchestrating the generation of both their own progeny and a neighboring lineage to achieve concomitant tissue production across lineages., (© 2016 Zhang et al.; Published by Cold Spring Harbor Laboratory Press.)

The skin epidermis is constantly renewed by epidermal stem cells. In a recent Science paper, Rompolas et al. utilize live imaging to track epidermal stem cells over their lifetimes. Their findings provide new insights into epidermal stem cell behaviors and unravel how newly generated cells are integrated into pre-existing tissues., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Cosmetic products placed on the market and their ingredients, must be safe under reasonable conditions of use, in accordance to the current legislation. Therefore, regulated and allowed chemical substances must meet the regulatory criteria to be used as ingredients in cosmetics and personal care products, and adequate analytical methodology is needed to evaluate the degree of compliance. This article reviews the most recent methods (2005-2015) used for the extraction and the analytical determination of the ingredients included in the positive lists of the European Regulation of Cosmetic Products (EC 1223/2009): comprising colorants, preservatives and UV filters. It summarizes the analytical properties of the most relevant analytical methods along with the possibilities of fulfilment of the current regulatory issues. The cosmetic legislation is frequently being updated; consequently, the analytical methodology must be constantly revised and improved to meet safety requirements. The article highlights the most important advances in analytical methodology for cosmetics control, both in relation to the sample pretreatment and extraction and the different instrumental approaches developed to solve this challenge. Cosmetics are complex samples, and most of them require a sample pretreatment before analysis. In the last times, the research conducted covering this aspect, tended to the use of green extraction and microextraction techniques. Analytical methods were generally based on liquid chromatography with UV detection, and gas and liquid chromatographic techniques hyphenated with single or tandem mass spectrometry; but some interesting proposals based on electrophoresis have also been reported, together with some electroanalytical approaches. Regarding the number of ingredients considered for analytical control, single analyte methods have been proposed, although the most useful ones in the real life cosmetic analysis are the multianalyte approaches., (Copyright © 2016 Elsevier B.V. All rights reserved.)