Recent Advances in High-Rate Solar-Driven Interfacial Evaporation.

Recent advances in solar-driven interfacial evaporation (SDIE) have led to high evaporation rates that open promising avenues for practical utilization in freshwater production and industrial application for pollutant and nutrient concentration, and resource recovery. Breakthroughs in overcoming the theoretical limitation of 2D interfacial evaporation have allowed for developing systems with high evaporation rates. This study presents a comprehensive review of various evaporator designs that have achieved pure evaporation rates beyond 4 kg m-2 h-1, including structural and material designs allowing for rapid evaporation, passive 3D designs, and systems coupled with alternative energy sources of wind and joule heating. The operational mechanisms for each design are outlined together with discussion on the current benefits and areas for improvement. The overarching challenges encountered by SDIE concerning the feasibility of direct integration into contemporary practical settings are assessed, and issues relating to sustaining elevated evaporation rates under diverse environmental conditions are addressed.

4-Chloroisocoumarins as Chlamydial Protease Inhibitors and Anti-Chlamydial Agents.

4-Chloroisocoumarin compounds have broad inhibitory properties against serine proteases. Here, we show that selected 3-alkoxy-4-chloroisocoumarins preferentially inhibit the activity of the conserved serine protease High-temperature requirement A of Chlamydia trachomatis. The synthesis of a new series of isocoumarin-based scaffolds has been developed, and their anti-chlamydial properties were investigated. The structure of the alkoxy substituent was found to influence the potency of the compounds against High-temperature requirement A, and modifications to the C-7 position of the 3-alkoxy-4-chloroisocoumarin structure attenuate anti-chlamydial properties.

Organic impurity profiling of 3,4-methylenedioxyamphetamine (MDA) synthesised from helional.

The organic impurity profile of 3,4-methylenedioxyamphetamine (MDA) synthesised from helional via the "twodogs" method was examined to identify route-specific and condition-specific impurities. The synthesis used a condensation reaction, followed by a Beckmann rearrangement, then Hofmann rearrangement, and then conversion to a hydrochloride salt. Two chlorinating agents were investigated for the Hofmann rearrangement reaction, trichloroisocyanuric acid (TCCA) and sodium hypochlorite. Three route-specific impurities were identified in MDA using TCCA, and two of these impurities were condition-specific such that the impurities that formed were dependent on the alcohol used as solvent. Three additional impurities were identified as non-route-specific as they have previously been identified in MDA synthesised from 3,4-methylenedioxycinnamic acid or piperonal. These non-route-specific impurities were also identified in MDA synthesised using sodium hypochlorite. No impurities were detected in MDA hydrochloride. This study identified route- and condition-specific organic impurities in MDA synthesised via the "twodogs" synthetic route using helional as starting material. The results in this study provide further understanding into the illicit synthesis of MDA and highlight the expanding nature of precursors used for illicit drug manufacture. It provides valuable information to decision makers to enact legislative measures and restrict precursors of concern.

The fate of organic species upon sintering of thiol-stabilised gold nanoparticles under different atmospheric conditions.

Understanding and controlling the sintering behavior of gold nanoparticles is important for applications such as printed electronics, catalysis and sensing that utilise these materials. Here we examine the processes by which thiol-protected gold nanoparticles thermally sinter under a variety of atmospheres. We find that upon sintering, the surface-bound thiyl ligands exclusively form the corresponding disulfide species when released from the gold surface. Experiments conducted using air, hydrogen, nitrogen, or argon atmospheres revealed no significant differences between the temperatures of the sintering event nor on the composition of released organic species. When conducted under high vacuum, the sintering event occurred at lower temperatures compared to ambient pressures in cases where the resulting disulfide had relatively high volatility (dibutyl disulfide). Hexadecylthiol-stabilized particles exhibited no significant differences in the temperatures of the sintering event under ambient pressures compared to high vacuum conditions. We attribute this to the relatively low volatility of the resultant dihexadecyl disulfide product.

Highly stable gold nanolayer membrane for efficient solar water evaporation under a harsh environment.

Interfacial solar water evaporation has attracted tremendous attention for sunlight harvesting for water purification. However, salt formation and stability of the photothermal materials (PTMs) remain a challenge that need addressing before bringing this technology to real-world applications. In this work, a nanoscale thin film of gold (Au) on a polytetrafluoroethylene (PTFE) membrane has been prepared using a magnetic sputtering technique. The fabricated membrane displays a robust mechanical strength and chemical stability arising from the adhesiveness of the thin film Au nanolayer on the PTFE membrane as well as the chemical inertness of the noble metal PTM. The Au nanolayer/PTFE membrane with cellulose sponge substrate resulted in an evaporation rate of 0.88 kg m-2 h-1 under 1 sun intensity. Remarkable salt ion rejection of 99.9% has been obtained, meeting the required standard for drinking water. Moreover, the membrane exhibited excellent stability and reusability in natural seawater and high salinity brine (150 g/L) and even in severe conditions (acidic, basic, and oxidized). No noticeable salt formation was observed on the evaporator surface after the tests. These findings reveal promising prospects for using a magnetron sputtering technique to fabricate a stable photothermal membrane for seawater and high salinity brine desalination.

A long-life lithium-oxygen battery via a molecular quenching/mediating mechanism.

The advancement of lithium-oxygen (Li-O2) batteries has been hindered by challenges including low discharge capacity, poor energy efficiency, severe parasitic reactions, etc. We report an Li-O2 battery operated via a new quenching/mediating mechanism that relies on the direct chemical reactions between a versatile molecule and superoxide radical/Li2O2. The battery exhibits a 46-fold increase in discharge capacity, a low charge overpotential of 0.7 V, and an ultralong cycle life >1400 cycles. Featuring redox-active 2,2,6,6-tetramethyl-1-piperidinyloxy moieties bridged by a quenching-active perylene diimide backbone, the tailor-designed molecule acts as a redox mediator to catalyze discharge/charge reactions and serves as a reusable superoxide quencher to chemically react with superoxide species generated during battery operation. The all-in-one molecule can simultaneously tackle issues of parasitic reactions associated with superoxide radicals, singlet oxygen, high overpotentials, and lithium corrosion. The molecular design of multifunctional additives combining various capabilities opens a new avenue for developing high-performance Li-O2 batteries.

Organic impurity profiling of 3,4-methylenedioxymethamphetamine (MDMA) synthesised from catechol and eugenol via 4-allylcatechol.

This work examines organic impurity profiles of 3,4-methylenedioxymethamphetamine (MDMA) that has been synthesised from the "pre-precursors" catechol (1,2-dihydroxybenzene) and eugenol, via a safrole intermediate. MDMA was synthesised from the catechol- and eugenol-derived safrole intermediate via two routes, which resulted in the synthesis of MDMA from catechol via two routes (Route 1A and 1B) and from eugenol via two routes (Route 2A and 2B). Twelve organic impurities were identified in MDMA synthesised via Routes 1A and 1B, and eleven organic impurities were identified in MDMA synthesised via Routes 2A and 2B. Route specific organic impurities were identified in MDMA that indicated the "pre-precursors" catechol and eugenol were used in the respective synthetic routes. Route specific organic impurities were also identified in MDMA that indicated the route used to synthesise safrole from the "pre-precursor" and the route used to synthesise MDMA from safrole. Thus, the use of the "pre-precursors" catechol and eugenol and the synthetic route utilised could be ascertained by the organic impurity profiling of MDMA under the conditions used here.

Natural Hydrogels Applied in Photodynamic Therapy.

Natural hydrogels are three-dimensional (3D) water-retaining materials with a skeleton consisting of natural polymers, their derivatives or mixtures. Natural hydrogels can provide sustained or controlled drug release and possess some unique properties of natural polymers, such as biodegradability, biocompatibility and some additional functions, such as CD44 targeting of hyaluronic acid. Natural hydrogels can be used with photosensitizers (PSs) in photodynamic therapy (PDT) to increase the range of applications. In the current review, the pertinent design variables are discussed along with a description of the categories of natural hydrogels available for PDT.

Correction: Alopecia areata patients show deficiency of FOXP3+CD39+ T regulatory cells and clonotypic restriction of Treg TCRß-chain, which highlights the immunopathological aspect of the disease.

[This corrects the article DOI: 10.1371/journal.pone.0210308.].

Alopecia areata patients show deficiency of FOXP3+CD39+ T regulatory cells and clonotypic restriction of Treg TCRß-chain, which highlights the immunopathological aspect of the disease.

Alopecia areata (AA) is a hair loss disorder resulting from an autoimmune reaction against hair follicles. T-helper 1 cells are a major contributor to this disorder, but little is known about the role of T-regulatory cells (Tregs) in AA. Here, we analysed the distribution of circulating Treg subsets in twenty AA patients with active hair loss and fifteen healthy subjects by flow cytometry. The Treg suppressor HLA-DR+ subpopulation was significantly reduced in the patients (P<0.001) and there were significantly fewer cells expressing CD39 among the CD4+CD25+Foxp3+ Treg subpopulation in patients (P = 0.001). FOXP3 CD39 Treg cells were also reduced in hair follicles; by 75% in non-lesional skin and 90% in lesional skin, when compared to control healthy skin. To further characterise Treg cells in AA; Tregs (CD4+CD25+FOXP3+) were investigated for their TCRß sequence. PCR products analysed by Next Generation Sequencing techniques, showed that all frequent public clonotypes in AA Tregs were also present in controls at relatively similar frequencies, excepting two public clonotypes: CATSRDEGGLDEKLFF (V15 D1 J1-4) and CASRDGTGPSNYGYTF (V2 D1 J1-2), which were exclusively present in controls. This suggests that these Treg clonotypes may have a protective effect and that they may be an exciting subject for future therapeutic applications.

Genome-wide association study in frontal fibrosing alopecia identifies four susceptibility loci including HLA-B*07:02.

Frontal fibrosing alopecia (FFA) is a recently described inflammatory and scarring type of hair loss affecting almost exclusively women. Despite a dramatic recent increase in incidence the aetiopathogenesis of FFA remains unknown. We undertake genome-wide association studies in females from a UK cohort, comprising 844 cases and 3,760 controls, a Spanish cohort of 172 cases and 385 controls, and perform statistical meta-analysis. We observe genome-wide significant association with FFA at four genomic loci: 2p22.2, 6p21.1, 8q24.22 and 15q2.1. Within the 6p21.1 locus, fine-mapping indicates that the association is driven by the HLA-B*07:02 allele. At 2p22.1, we implicate a putative causal missense variant in CYP1B1, encoding the homonymous xenobiotic- and hormone-processing enzyme. Transcriptomic analysis of affected scalp tissue highlights overrepresentation of transcripts encoding components of innate and adaptive immune response pathways. These findings provide insight into disease pathogenesis and characterise FFA as a genetically predisposed immuno-inflammatory disorder driven by HLA-B*07:02.

A versatile functionalized ionic liquid to boost the solution-mediated performances of lithium-oxygen batteries.

Due to the high theoretical specific energy, the lithium-oxygen battery has been heralded as a promising energy storage system for applications such as electric vehicles. However, its large over-potentials during discharge-charge cycling lead to the formation of side-products, and short cycle life. Herein, we report an ionic liquid bearing the redox active 2,2,6,6-tetramethyl-1-piperidinyloxy moiety, which serves multiple functions as redox mediator, oxygen shuttle, lithium anode protector, as well as electrolyte solvent. The additive contributes a 33-fold increase of the discharge capacity in comparison to a pure ether-based electrolyte and lowers the over-potential to an exceptionally low value of 0.9 V. Meanwhile, its molecule facilitates smooth lithium plating/stripping, and promotes the formation of a stable solid electrolyte interface to suppress side-reactions. Moreover, the proportion of ionic liquid in the electrolyte influences the reaction mechanism, and a high proportion leads to the formation of amorphous lithium peroxide and a long cycling life (> 200 cycles). In particular, it enables an outstanding electrochemical performance when operated in air.

Epigallocatechin-3 Gallate Inhibits STAT-1/JAK2/IRF-1/HLA-DR/HLA-B and Reduces CD8 MKG2D Lymphocytes of Alopecia Areata Patients.

BACKGROUND: Alopecia areata (AA) is associated with Interferon- γ (IFN-γ) mediated T-lymphocyte dysfunction and increased circulating Interleukine-17 (IL-17) levels. Epigallocatechin-3-gallate (EGCG) specifically inhibits IFN-γ pathways and unlike Janus Kinase 1 and 2 (JAK1/JAK2) inhibitors (tofacitinib, ruxolitinib), EGCG is safer, more cost-effective, and is a topically active agent. Our objective is to test the mode of action of EGCG in vitro and ex vivo using HaCat, Jurkat cell lines, and peripheral blood mononuclear cells (PBMCs) of AA patients and healthy controls (HCs), respectively. METHODS: distribution of T helper cells (Th1, Th17), and cytotoxic cells (CD8) in PBMCs isolated from 30 AA patients and 30 HCs was investigated by flowcytomterty. In vitro treatment of HaCat and Jurkat cells with 40 µm EGCG for 48 h was performed to measure the level of phosphorylation of signal transducer and activator of transcription protein STAT1, and replicated in ex vivo model using PBMCs of AA patients. RESULTS: Interestingly, 40 µm EGCG is capable of completely inhibiting phosphorylation of STAT1 after 48 h in HaCat and Jurkat cells and ex vivo in PBMCs of AA patients. Based on QPCR data, the action of EGCG on p-STAT1 seems to be mediated via downregulation of the expression of JAK2 but not JAK1 leading to the inhibition of human leukocyte antigens (HLA-DR and HLA-B) expression probably via IRF-1. On the other hand, AA patients have significantly increased levels of Th1, Th17, and CD8 cells and the production of IFN-γ and IL-17 by PBMCs in AA patients was significantly higher compared to HC; p = 0.008 and p = 0.006, respectively. Total numbers of CD8+ cells were not significantly different between treated and untreated samples. However, CD8+ cells with positive Natural killer group 2 member D (NKG2D) transmembrane receptor (CD8+ NKG2D+ subset) was significantly reduced when PBMCs were treated with 20 µm EGCG for 48 h. CONCLUSION: These results suggest that EGCG has a synergistic action that inhibits expression of HLA-DR and HLA-B molecules via the IFN-γ pathway to maintain immune privilege in HF; also it reduces CD8+ NKG2D+ subset.

Whole Genome Sequencing in an Acrodermatitis Enteropathica Family from the Middle East.

We report a family from Tabuk, Saudi Arabia, previously screened for Acrodermatitis Enteropathica (AE), in which two siblings presented with typical features of acral dermatitis and a pustular eruption but differing severity. Affected members of our family carry a rare genetic variant, p.Gly512Trp in the SLC39A4 gene which encodes a zinc transporter; disease is thought to result from zinc deficiency. Similar mutations have been reported previously; however, the variable severity within cases carrying the p.Gly512Trp variant and in AE overall led us to hypothesise that additional genetic modifiers may be contributing to the disease phenotype. Therefore whole genome sequencing was carried out in five family members, for whom material was available to search for additional modifiers of AE; this included one individual with clinically diagnosed AE. We confirmed that the p.Gly512Trp change in SLC39A4 was the only candidate homozygous change which was sufficiently rare (ExAC allele frequency 1.178e-05) and predicted deleterious (CADD score 35) to be attributable as a fully penetrant cause of AE. To identify other genes which may carry relevant genetic variation, we reviewed the relevant literature and databases including Gene Ontology Consortium, GeneMANIA, GeneCards, and MalaCards to identify zinc transporter genes and possible interacting partners. The affected individual carried variants in RECQL4 and GPAA1 genes with ExAC allele frequency <0.01 and CADD score >10. p.Gly512Trp is highly likely to be the pathogenic variant in this family. This variant was previously detected in a Tunisian proband with perfect genotype-phenotype segregation suggestive of pathogenicity. Further research is required in this area due to small sample size, but attention should be given to RECQL4 and GPAA1 to understand their role in the skin disease.

In situ study of the precursor conversion reactions during solventless synthesis of Co9S8, Ni3S2, Co and Ni nanowires.

Synthesis of Co9S8, Ni3S2, Co and Ni nanowires by solventless thermolysis of a mixture of metal(ii) acetate and cysteine in vacuum is reported. The simple precursor system enables the nanowire phase to be tuned from pure metal (Co or Ni) to metal sulfide (Co9S8, Ni3S2) by varying the relative concentration of the metal(ii) acetate. The growth environment facilitates new insights through in situ characterization using field-emission scanning electron microscopy (FESEM) and thermogravimetric analysis with gas chromatography-mass spectrometry (TGA-GC-MS). Direct observation by FESEM shows the temperature at which nanowire growth occurs and suggests adatoms are incorporated into the base of the growing nanowire. TGA-GC-MS reveals the rates of precursor decomposition and identity of the volatilized ligand fragments during heat-up and at the nanowire growth temperature. Our results constitute a new approach for the selective fabrication of high quality Co9S8 and Ni3S2 nanowires and more importantly provides new understanding of precursor decomposition reactions that support symmetry-breaking growth in nanocrystals by heat-up synthesis.

Meta-Analysis of Autoimmune Regulator-Regulated Genes in Human and Murine Models: A Novel Human Model Provides Insights on the Role of Autoimmune Regulator in Regulating STAT1 and STAT1-Regulated Genes.

Autoimmune regulator (AIRE) regulates promiscuous expression of tissue-restricted antigens in medullary epithelial cells (mTEC) of the thymus. To understand the diverse effects of AIRE, it is crucial to elucidate the molecular mechanisms underlying the process of AIRE-regulated gene expression. In this study, we generated a recombinant AIRE expression variant of the TEC 1A3 human cell line, TEC 1A3 AIREhi, to determine genes targeted by AIRE, and using microarray analysis, we identified 482 genes showing significant differential expression (P < 0.05; false discovery rate <5%), with 353 upregulated and 129 downregulated by AIRE expression. Microarray data were validated by quantitative PCR, confirming the differential expression of 12 known AIRE-regulated genes. Comparison of AIRE-dependent differential expression in our cell line model with murine datasets identified 447 conserved genes with a number of transcription regulatory interactions, forming several key nodes, including STAT1, which had over 30 interactions with other AIRE-regulated genes. As STAT1 mutations cause dominant chronic mucocutaneous candidiasis and decreased STAT1 levels in monocytes of autoimmune polyglandular syndrome 1 (APS-1) patients, it was important to further characterize AIRE-STAT1 interactions. TEC 1A3AIREhi were treated with the STAT1 phosphorylation inhibitors fludarabine and LLL3 showed that phosphorylated STAT1 (p-STAT1) was not responsible for any of the observed differential expression. Moreover, treatment of TEC 1A3 AIREhi with STAT1 shRNA did not induce any significant variation in the expression of unphosphorylated STAT1 (U-STAT1) downstream genes, suggesting that these genes were directly regulated by AIRE but not via U-STAT1. The novel model system we have developed provides potential opportunities for further analysis of the pathogenesis of (APS-1) and the wider roles of the AIRE gene.

Genome-Wide Analysis of Circulating Cell-Free DNA Copy Number Detects Active Melanoma and Predicts Survival.

BACKGROUND: A substantial number of melanoma patients develop local or metastatic recurrence, and early detection of these is vital to maximise benefit from new therapies such as inhibitors of BRAF and MEK, or immune checkpoints. This study explored the use of novel DNA copy-number profiles in circulating cell-free DNA (cfDNA) as a potential biomarker of active disease and survival. PATIENTS AND METHODS: Melanoma patients were recruited from oncology and dermatology clinics in Sheffield, UK, and cfDNA was isolated from stored blood plasma. Using low-coverage whole-genome sequencing, we created copy-number profiles from cfDNA from 83 melanoma patients, 44 of whom had active disease. We used scoring algorithms to summarize copy-number aberrations and investigated their utility in multivariable logistic and Cox regression analyses. RESULTS: The copy-number aberration score (CNAS) was a good discriminator of active disease (odds ratio, 3.1; 95% CI, 1.5-6.2; P = 0.002), and CNAS above or below the 75th percentile remained a significant discriminator in multivariable analysis for active disease (P = 0.019, with area under ROC curve of 0.90). Additionally, mortality was higher in those with CNASs above the 75th percentile than in those with lower scores (HR, 3.4; 95% CI, 1.5-7.9; P = 0.005), adjusting for stage of disease, disease status (active or resected), BRAF status, and cfDNA concentration. CONCLUSIONS: This study demonstrates the potential of a de novo approach utilizing copy-number profiling of cfDNA as a biomarker of active disease and survival in melanoma. Longitudinal analysis of copy-number profiles as an early marker of relapsed disease is warranted.

From Lead(II) Dithiocarbamate Precursors to a Fast Response PbS Positive Temperature Coefficient Thermistor.

PbS submicron crystals were formed by thermolysis of two different lead dithiocarbamate complexes. These precursors were readily synthesized and fully characterized, and in situ synchrotron powder diffraction experiments were performed to characterize their decomposition. The structure and purity of resultant PbS was examined using scanning electron and transmission electron microscopies, powder X-ray diffraction, and infrared spectroscopy. Submicron crystalline PbS was used to create a new PbS thermistor with excellent sensitivity and an ultrarapid thermal response time.

Photomechanical photochromism in a cetyltrimethylammonium isopolytungstate.

The photochromic properties of a hybrid compound comprised of the surfactant cation cetyltrimethylammonium [(C16H33)N(CH3)3]+ (CTA+) and the isopolytungstate anion [H2W12O40]6- is investigated. The compound, which has the nominal formula (CTA)7[H2W12O40]Cl·2H2O, changes from white to blue when exposed to UV radiation. The sample returns to the bleached state if stored in the dark-ambient. Application of XPS indicates that the coloring species are WV and WIV. The CTA+ component is found by XPS and FTIR to undergo progressive and irreversible oxidation during this cycle. Examination of FTIR suggests that the changes occur at multiple sites across the amphiphile. Surprisingly, the photochromic cycle is correlated with changes in the X-ray diffraction pattern, indicating partially reversible changes in the ordering of the Keggin ions and their spacing. In particular, application of the UV radiation causes the progressive accumulation of strain in the [001] direction. This is due to permanent oxidative changes in the CTA+ accumulating from cycle to cycle, resulting in an increase in interlamellar-distance due to less interdigitation of the chains. This provides a controllable photomechanical response.

Photocatalysis of estrone in water and wastewater: Comparison between Au-TiO2 nanocomposite and TiO2, and degradation by-products.

Gold-modified TiO2 (Au-TiO2) photocatalysts were utilised for the degradation of estrone (E1), a major endocrine disrupting chemical in water and wastewater. Au-TiO2 catalysts were synthesised by a deposition-precipitation method with gold loadings of 0-8% (wt%). The Au-TiO2 nanocomposite exhibited superior activity compared to P25 TiO2 under UVA (λ=365nm), cool white (λ>420nm) and green (λ=523nm) light emitting diodes (LEDs), for treating 1mgl-1 of E1. The 4wt% Au loading was found to produce the best photocatalytic activity with a rate constant of 2.44±0.36h-1, compared to 0.06±0.01h-1 for P25 TiO2, under visible light. In total 4 by-products were identified, one from negative ionization mode (m/z=269) and three from positive ionization mode (m/z=287) during photocatalysis, which were also degraded with time by Au-TiO2. For different water matrices, the photodegradation rate of E1 decreased in the order: ultrapure water>synthetic wastewater≈wastewater effluent from membrane bio-reactor. Overall, 4wt% Au-TiO2 demonstrated superior performance compared to P25 TiO2 in water and wastewater.