Fe3 C/Fe Decorated N-doped Carbon Derived from Tetrabutylammonium tetrachloroferrate Complex as Bifunctional Electrocatalysts for ORR, OER and Zn-Air Batteries in Alkaline Medium.

The emergence of non-precious metal-based robust and economic bifunctional oxygen electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is crucial for the rational design of commercial rechargeable Zn-air batteries (RZAB) with safe energy conversion and storage systems. Herein, a facile strategy to fabricate a cost-efficient, bifunctional oxygen electrocatalyst Fe3 C/Fe decorated N doped carbon (FeC-700, the catalyst prepared at carbinization temperature of 700 °C) with a unique structure has been developed by carbonization of a single source precursor, tetrabutylammonium tetrachloroferrate(III) complex. The ORR and OER activity revealed excellent performance (ΔE=0.77 V) of the FeC-700 electrocatalyst, comparable to commercial Pt/C and RuO2, respectively. The designed temperature-tuneable structure provided sufficiently accessible active sites for the continuous passage of electrons by shortening the mass transfer pathway, leading to extremely durable electrocatalysts with high ECSA and amazing charge transfer performance. Remarkably, the assembled Zn-air batteries with the FeC-700 catalyst as the bifunctional air electrode delivers gratifying charging-discharging ability with an impressive power density of 134 mW cm-2 with a long lifespan, demonstrating prodigious possibilities for practical application.

Correction: Highly active spherical amorphous MoS2: facile synthesis and application in photocatalytic degradation of rose bengal dye and hydrogenation of nitroarenes.

[This corrects the article DOI: 10.1039/C5RA19442C.].

Impact of the transition to digital pathology in a clinical setting on histopathologists in training: experiences and perceived challenges within a UK training region.

AIMS: With increasing utility of digital pathology (DP), it is important to consider the experiences of histopathologists in training, particularly in view of the varied access to DP across a training region and the consequent need to remain competent in reporting on glass slides (GS), which is also relevant for the Fellowship of the Royal College of Pathologists part 2 examination. Understanding the impact of DP on training is limited but could aid development of guidance to support the transition. We sought to investigate the perceptions of histopathologists in training around the introduction of DP for clinical diagnosis within a training region, and the potential training benefits and challenges. METHODS: An anonymous online survey was circulated to 24 histopathologists in training within a UK training region, including a hospital which has been fully digitised since summer 2020. RESULTS: 19 of 24 histopathologists in training responded (79%). The results indicate that DP offers many benefits to training, including ease of access to cases to enhance individual learning and teaching in general. Utilisation of DP for diagnosis appears variable; almost half of the (10 of 19) respondents with DP experience using it only for ancillary purposes such as measurements, reporting varying levels of confidence in using DP clinically. For those yet to undergo the transition, there was a perceived anxiety regarding digital reporting despite experience with DP in other contexts. CONCLUSIONS: The survey evidences the need for provision of training and support for histopathologists in training during the transition to DP, and for consideration of their need to maintain competence and confidence with GS reporting.

The Potential of Artificial Intelligence to Detect Lymphovascular Invasion in Testicular Cancer.

Testicular cancer is the most common cancer in men aged from 15 to 34 years. Lymphovascular invasion refers to the presence of tumours within endothelial-lined lymphatic or vascular channels, and has been shown to have prognostic significance in testicular germ cell tumours. In non-seminomatous tumours, lymphovascular invasion is the most powerful prognostic factor for stage 1 disease. For the pathologist, searching multiple slides for lymphovascular invasion can be highly time-consuming. The aim of this retrospective study was to develop and assess an artificial intelligence algorithm that can identify areas suspicious for lymphovascular invasion in histological digital whole slide images. Areas of possible lymphovascular invasion were annotated in a total of 184 whole slide images of haematoxylin and eosin (H&E) stained tissue from 19 patients with testicular germ cell tumours, including a mixture of seminoma and non-seminomatous cases. Following consensus review by specialist uropathologists, we trained a deep learning classifier for automatic segmentation of areas suspicious for lymphovascular invasion. The classifier identified 34 areas within a validation set of 118 whole slide images from 10 patients, each of which was reviewed by three expert pathologists to form a majority consensus. The precision was 0.68 for areas which were considered to be appropriate to flag, and 0.56 for areas considered to be definite lymphovascular invasion. An artificial intelligence tool which highlights areas of possible lymphovascular invasion to reporting pathologists, who then make a final judgement on its presence or absence, has been demonstrated as feasible in this proof-of-concept study. Further development is required before clinical deployment.

Metabolites of Tobacco- and E-Cigarette-Related Nitrosamines Can Drive Cu2+-Mediated DNA Oxidation.

Nitrosamine metabolites resulting from cigarette smoking and E-cigarette (E-cig) vaping cause DNA damage that can lead to genotoxicity. While DNA adducts of metabolites of nitrosamines 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and N-nitrosonornicotine (NNN) are well-known tobacco-related cancer biomarkers, only a few studies implicate NNN and NNK in DNA oxidation in humans. NNK and NNN were found in the urine of E-cigarette users who never smoked cigarettes. This paper proposes the first chemical pathways of DNA oxidation driven by NNK and NNN metabolites in redox reactions with Cu2+ and NADPH leading to reactive oxygen species (ROS). A microfluidic array with thin films of DNA and metabolic enzymes that make metabolites of NNN and NNK in the presence of Cu2+ and NADPH was used to estimate relative rates of DNA oxidation. Detection by electrochemiluminescence (ECL) employed a new ECL dye [Os(tpy-benz-COOH)2]2+ that is selective for and sensitive to the primary DNA oxidation product 8-oxo-7,8-dihydro-2-deoxyguanosine (8-oxodG) in DNA. Enzyme-DNA films on magnetic beads were used to produce nitrosamine metabolites that enter ROS-forming redox cycles with Cu2+ and NADPH, and liquid chromatography-mass spectrometry (LC-MS) was used to quantify 8-oxodG and identify metabolites. ROS were detected by optical sensors. Metabolites of NNK and NNN + Cu2+ + NADPH generated relatively high rates of DNA oxidation. Lung is the exposure route in smoking and vaping, human lung tissue contains Cu2+ and NADPH, and lung microsomal enzymes gave the highest rates of DNA oxidation in this study. Also, E-cigarette vapor contains 6-fold more copper than that in cigarette smoke, which could exacerbate DNA oxidation.

An overview of COVID-19 for diagnostic pathologists: clinicopathological correlation and diagnostic techniques.

The emergence of COVID-19 as a global pandemic has led to a rapid focus on understanding its pathobiology. The constellation of clinical, histological and laboratory findings seen in these patients is similar to other forms of viral pneumonia, but somewhat distinctive aspects exist which may raise the index of suspicion for this disease. The pathological findings are not limited to the respiratory system; cardiovascular, gastrointestinal and renal abnormalities have also been described. Establishing a link between the clinical features and macroscopic and microscopic findings is not only important for the practicing autopsy pathologist, but also for understanding of the disease as a whole. Furthermore, context-sensitive interpretation of diagnostic tests is essential. This article aims to review understanding of clinicopathological correlation in COVID-19, as well as clarifying the role of current diagnostic techniques.

One Step Synthesis of a Gold/Ordered Mesoporous Carbon Composite Using a Hard Template Method for Electrocatalytic Oxidation of Methanol and Colorimetric Determination of Glutathione.

Ordered mesoporous carbon-supported gold nanoparticles (Au/OMC) have been fabricated in one step through a hard template method using gold nanoparticle-intercalated mesoporous silica (GMS) to explore two different catalytic properties, for example, electrocatalytic oxidation of methanol and colorimetric determination of glutathione (GSH). The catalytically inert but conducting nature of mesoporous carbon (OMC) and promising catalytic activity of gold nanoparticles (AuNPs) has inspired us to synthesize Au/OMC. The as-prepared Au/OMC catalyst was characterized by powder X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray analysis-elemental mapping, and X-ray photoelectron spectroscopy. The characterization results indicate that AuNPs are uniformly distributed on the surface of OMC. The conducting-OMC framework with a high surface area of Au/OMC provides superior transport of electrons through the porous surface of carbon matrix and resulted in its high efficiency and stability as an electrocatalyst for the oxidation of methanol in comparison to CMK-3, SBA-15, and GMS in alkaline medium. The efficiency of Au/OMC toward methanol oxidation in alkaline medium is much higher in comparison to that in acidic medium. The lower value of I f/I b in the acidic medium in comparison to that in the alkaline medium clearly indicates that the oxidation process with Au/OMC as a catalyst is much more superior in alkaline medium with better tolerance toward the accumulation of intermediate CO species on the active surface area. Furthermore, the Au/OMC catalyst is successfully utilized for the detection and quantification of GSH spectrophotometrically with a limit of detection value of 0.604 nM.

Advanced catalytic performance of amorphous MoS2 for degradation/reduction of organic pollutants in both individual and simultaneous fashion.

A cluster [(S2)2Mo(S2)2Mo(S2)2], has been used to synthesise molybdenum sulfide microparticles (MPs) by solvothermal treatments under inert environment. During synthesis, surfactants i.e. oleylamine and dodecanthiol take part in chief role in shaping the morphology of MPs into ultrathin nano-fibre, and nano-rod. MPs have been characterized by X-ray diffraction analysis, energy dispersive X-ray spectroscopy, transmission electron microscopy and UV-vis spectroscopic techniques. The optical spectral data reveals a simultaneous presence of direct and indirect band gap in both MoS2. The material emerges as an effective catalyst towards the mineralization of different cationic dyes (rhodamine B and methylene blue) and anionic dye (rosebngal). These MPs have also been effectively used for the simultaneous degradations of different dyes in the same reaction mixture which make further highlighted the catalytic performances of MoS2. The above kinetics of the decomposition processes were examined and found to follow the pseudo-first-order reaction model. The plausible mechanism has been explained by comparing the position of conduction band levels of MoS2 (measured by Mott-schotky and touc's plot) and potential value of borohydride. We have also investigated the active species behind the degradation of dyes by using different scavengers. The new catalyst was also effective for the degradation of mixture of dyes to the same extent as it was in case of individual.

Single source precursor driven phase selective synthesis of Au-CuGaS2 heteronanostructures: an observation of plasmon enhanced photocurrent efficiency.

The design of new functional metal-semiconductor heteronanostructures with improved photovoltaic efficiencies has drawn significant attention because of their unprecedented properties and potential applications. Herein, we report a phase selective synthesis of ternary CuGaS2 (wurtzite and tetragonal) by simple solution based thermal decomposition of a new binuclear single molecular precursor [Ga(acda)3Cu(PPh3)2]NO3 (acda = 2-aminocyclopentene-1-dithiocarboxylic acid, PPh3 = triphenylphosphine) where the phase selectivity has been achieved easily by changing the combination of surface active agents. Furthermore, we have extended our approach to develop a well-controlled synthetic strategy for the preparation of a Au-CuGaS2 heteronanocomposite with both the phases. A detailed microscopic study reveals that during heterostructure synthesis, an epitaxial junction has been formed at the interface of ternary CuGaS2 and metallic Au. To find out the influence of this epitaxial connectivity on the properties, we have studied the photocurrent and photoresponse behavior of the material and compared them with that of bare CuGaS2. For both the wurtzite and tetragonal phases, the Au-CuGaS2 twin structure exhibits a plasmon enhanced superior charge transport ability and an abruptly high photocurrent density compared to that of pure CuGaS2. Due to efficient charge separation by strong plasmon-exciton coupling at the interface, Au-CuGaS2 can be used as a potential candidate for photoelectrochemical applications.

iNKT Cells Induce FGF21 for Thermogenesis and Are Required for Maximal Weight Loss in GLP1 Therapy.

Adipose-resident invariant natural killer T (iNKT) cells are key players in metabolic regulation. iNKT cells are innate lipid sensors, and their activation, using their prototypic ligand α-galactosylceramide (αGalCer), induces weight loss and restores glycemic control in obesity. Here, iNKT activation induced fibroblast growth factor 21 (FGF21) production and thermogenic browning of white fat. Complete metabolic analysis revealed that iNKT cell activation induced increased body temperature, V02, VC02, and fatty acid oxidation, without affecting food intake or activity. FGF21 induction played a major role in iNKT cell-induced weight loss, as FGF21 null mice lost significantly less weight after αGalCer treatment. The glucagon-like peptide 1 (GLP-1) receptor agonist, liraglutide, also activated iNKT cells in humans and mice. In iNKT-deficient mice, liraglutide promoted satiety but failed to induce FGF21, resulting in less weight loss. These findings reveal an iNKT cell-FGF21 axis that defines a new immune-mediated pathway that could be targeted for glycemic control and weight regulation.

Enhanced photocatalytic performance of morphologically tuned Bi2S3 NPs in the degradation of organic pollutants under visible light irradiation.

Here in, morphologically tuned Bi2S3 NPs were successfully synthesized from a single-source precursor complex [Bi(ACDA)3] [HACDA=2-aminocyclopentene-1-dithiocarboxylic acid] by decomposing in various solvents using a simple solvothermal method. The as-obtained products were characterized by XRD, TEM, UV-vis spectroscopy and BET surface area measurements. Structural analyses revealed that the as-prepared Bi2S3 NPs can be tuned to different morphologies by varying various solvents and surfactants. The interplay of factors that influenced the size and morphology of the nanomaterials has been studied. Moreover, mastery over the morphology of nanoparticles enables control of their properties and enhancement of their usefulness for a given application. These materials emerged as a highly active visible light-driven photocatalyst towards degradation of methylene blue dye and the efficiencies are dependent on size and surface area of the NPs. In addition, photocatalytic degradation of highly toxic dichlorodiphenyltrichloroethane was studied using synthesized Bi2S3 NPs as catalyst and the rate of degradation has been found to be much better compared to that exhibited by commercial WO3. We believe that this new synthesis approach can be extended to the synthesis of other metal sulfide nanostructures and open new opportunities for device applications.

Th17 plasticity and its changes associated with inflammatory bowel disease.

CD4 T helper (Th) cell differentiation into distinct T cell subsets is critical to the normal function of the immune system. Until recently, the paradigm held that naïve T cells differentiated into distinct subsets under the guidance of environmental cues (e.g., cytokines) and that once polarized, these cells were committed to a particular functional state. However, the existence of transdifferentiated T cell populations, which express signature transcription factors and cytokines associated with more than one Th subset, challenges the immutability of T helper subsets and suggests that plasticity is a feature of multifaceted immune responses. How this process impacts immune dysregulation in diseases such as inflammatory bowel diseases (IBD) and the machinery that underlies this process is far from fully understood. Interleukin (IL)-17 secreting helper T (Th17) cells have been heavily implicated in tissue-specific immune pathology including murine models of IBD, human Crohn's disease and ulcerative colitis. Plasticity within this subset is suggested by the existence of IL-17 secreting cells, which, can also secrete interferon-γ, the signature cytokine for Th1 cells or, can co-express the anti-inflammatory transcription factor forkhead box p3, a signature transcription factor of regulatory T cells. In this review we mainly discuss evidence for Th17 plasticity, mechanisms, which govern it, and highlight the potential to therapeutically target this process in human IBD.

Colorimetric estimation of human glucose level using γ-Fe2O3 nanoparticles: an easily recoverable effective mimic peroxidase.

This article reports simple, green and efficient synthesis of γ-Fe2O3 nanoparticles (NPs) (maghemite) through single-source precursor approach for colorimetric estimation of human glucose level. The γ-Fe2O3 NPs, having cubic morphology with an average particle size of 30 nm, exhibited effective peroxidase-like activity through the catalytic oxidation of peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2 producing a blue-colored solution. On the basis of this colored-reaction, we have developed a simple, cheap, highly sensitive and selective colorimetric method for estimation of glucose using γ-Fe2O3/TMB/glucose-glucose oxidase (GOx) system in the linear range from 1 to 80 µM with detection limit of 0.21 µM. The proposed glucose sensor displays faster response, good stability, reproducibility and anti-interference ability. Based on this simple reaction process, human blood and urine glucose level can be monitored conveniently.