16 research outputs found

    Co-axial heterostructures integrating palladium/titanium dioxide with carbon nanotubes for efficient electrocatalytic hydrogen evolution

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    Considering the depletion of fossil-fuel reserves and their negative environmental impact, new energy schemes must point towards alternative ecological processes. Efficient hydrogen evolution from water is one promising route towards a renewable energy economy and sustainable development. Here we show a tridimensional electrocatalytic interface, featuring a hierarchical, co-axial arrangement of a palladium/titanium dioxide layer on functionalized multi-walled carbon nanotubes. The resulting morphology leads to a merging of the conductive nanocarbon core with the active inorganic phase. A mechanistic synergy is envisioned by a cascade of catalytic events promoting water dissociation, hydride formation and hydrogen evolution. The nanohybrid exhibits a performance exceeding that of stateof- the-art electrocatalysts (turnover frequency of 15000 H2 per hour at 50mVoverpotential). The Tafel slope of B130mV per decade points to a rate-determining step comprised of water dissociation and formation of hydride. Comparative activities of the isolated components or their physical mixtures demonstrate that the good performance evolves from the synergistic hierarchical structure

    ESA ∆DOR enhancement: agencies interoperability, wideband and low-SNR functionality

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    Delta Differential One-way Ranging (ADOR) is a powerful method used for navigation of interplanetary probes. It provides a direct measurement of the angular position of a spacecraft using interferometric techniques to obtain the difference in the arrival time of a spacecraft signal received at two ground stations, using an ICRF (International Celestial Reference Frame) quasar as a reference. In 2005, Sapienza University of Rome undertook the development of a ADOR correlator for the European Space Agency, expanding the tools available for the operation of European planetary and astrometric missions. Since its delivery, the correlator has been successfully used for the orbit determination of Venus Express and Rosetta. In a later release the correlator's capabilities were expanded to accept data acquired not only at ESA's ESTRACK stations, but also at VLBI and NASA's Deep Space Network antennae. In 2011 ESA and Sapienza University have undertaken further enhancements of the correlator, by expanding the accepted data formats, extending the total spanned bandwidth and enabling the correlation of very-low SNR signals. The new Raw Data Exchange Format, RDEF, established by the Consultative-Committee for Space Data Systems (CCSDS) in order to increase the ADOR interoperability between different agencies has been implemented in the correlator. This enhancement will allow the direct processing of data acquired by different agencies. The second additional functionality provided an improved determination of the quasar and spacecraft delay by increasing the spanned bandwidth of the recorded signal. Due to current hardware limitations, the bandwidth at ESTRACK stations is currently limited to 28 MHz. ESA is planning to use three LDC (L-band Down-Converter) to acquire different portion of the signal spectrum, and route the signal to up to three IFMS receivers (Intermediate Frequency Modulation System). With this configuration the total spanned bandwidth could be increased up to 220 MHz at Ka-band. The enhanced version of the correlator is capable of handling this new configuration and take advantage of the wider bandwidth. Finally, a third enhancement enabled the correlation of narrowband, low-SNR, spacecraft signals. Although the correlator can operate in several modes, the processing of the spacecraft signal is currently carried out by means of a master phase locked loop (PLL) on the carrier and slave PLLs on the telemetry harmonics. A new PLL-free algorithm for the spacecraft data correlation allows the processing of low-SNR signals (up to 1 dBHz). Such weak signals cannot be tracked by a standard PLL (hardware or software)

    Molecular Identification of Albumin and Hsp70 as Cytosolic Anandamide-Binding Proteins

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    The cellular uptake and the intracellular synthesis/degradation of anandamide are crucial steps for controlling its extracellular level and the duration of its activity. Although the biosynthesis and breakdown of anandamide are well understood, little is known about the mechanisms underlying its intracellular transport. Here, we investigated the presence of a potential carrier-mediated trafficking of anandamide within the cytosol, using a biotinylated analog as a tool to catch by affinity chromatography anandamide-interacting proteins. The identity of two of these anandamide-binding proteins, Hsp70 and serum albumin, was determined by mass spectrometry, confirmed by western blotting and confocal microscopy, and further validated through an anandamide-binding assay. These findings suggest that the trafficking of anandamide from the plasma membrane to the internal compartments of a cell occur via a non-vesicular mechanism mediated by cytosolic carriers

    μSPE followed by HPLC–MS/MS for the determination of series D and E resolvins in biological matrices

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    tThe critical role of acute inflammatory processes is recognized in many chronic diseases; a key point inmolecular mechanisms of acute inflammation resolution is represented by a new group of pro-resolvinglipid mediators that include distinct families of molecules: lipoxins, resolvins, protectins and maresins,collectively termed “specialized pro-resolving mediators” (SPMs). In particular, resolvins are active in thepicogram to nanogram dose range, whereby they can directly modulate a plethora of anti-inflammatoryresponses. The presented method proposes an analytical protocol able to extract and to quantify 6 dif-ferent resolvins from 3 different matrices (plasma, cells and exudates). The method, validated accordingto the EMA guideline for bioanalysis, exhibited good precision (1%–20%) and accuracy (2%–20%). In par-ticular, the combination of two different sample preparation techniques, Liquid-Liquid Extraction (LLE)and micro-Solid Phase Extraction (SPE), applied for the first on this class of molecules, used for theextraction and clean-up respectively, led to high enrichment factor (20 fold) and consequently a highsensitivity (LOQ between 1 and 38 pg mL−1); moreover the validation data proved the versatility of SPEas clean-up tool as it was capable to manage huge enrichment factor without negatively affect accuracyand precision of analysis

    5-Lipoxygenase-dependent apoptosis of human lymphocytes in the International Space Station: data from the ROALD experiment

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    The functional adaptation of the immune system to the surrounding environment is also a fundamental issue in space. It has been suggested that a decreased number of lymphocytes might be a cause of immunosuppression, possibly due to the induction of apoptosis. Early activation of 5-lipoxygenase (5-LOX) might play a central role in the initiation of the apoptotic program. The goal of the role of apoptosis in lymphocyte depression (ROALD) experiment, flown on the International Space Station as part of the BIO-4 mission of the European Space Agency, was to ascertain the induction of apoptosis in human lymphocytes under authentic microgravity, and to elucidate the possible involvement of 5-LOX. Our results demonstrate that exposure of human lymphocytes to microgravity for 48 h onboard the ISS remarkably increased apoptotic hallmarks such as DNA fragmentation (∼3-fold compared to ground-based controls) and cleaved–poly (ADP-ribose) polymerase (PARP) protein expression (∼3-fold), as well as mRNA levels of apoptosis-related markers such as p53 (∼3-fold) and calpain (∼4-fold); these changes were paralleled by an early increase of 5-LOX activity (∼2-fold). Our findings provide a molecular background for the immune dysfunction observed in astronauts during space missions, and reveal potential new markers to monitor health status of ISS crew members

    Effects of Rare Phytocannabinoids on the Endocannabinoid System of Human Keratinocytes

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    The decriminalization and legalization of cannabis has paved the way for investigations into the potential of the use of phytocannabinoids (pCBs) as natural therapeutics for the treatment of human diseases. This growing interest has recently focused on rare (less abundant) pCBs that are non-psychotropic compounds, such as cannabigerol (CBG), cannabichromene (CBC), Δ9-tetrahydrocannabivarin (THCV) and cannabigerolic acid (CBGA). Notably, pCBs can act via the endocannabinoid system (ECS), which is involved in the regulation of key pathophysiological processes, and also in the skin. In this study, we used human keratinocytes (HaCaT cells) as an in vitro model that expresses all major ECS elements in order to systematically investigate the effects of CBG, CBC, THCV and CBGA. To this end, we analyzed the gene and protein expression of ECS components (receptors: CB1, CB2, GPR55, TRPV1 and PPARα/γ/δ; enzymes: NAPE-PLD, FAAH, DAGLα/β and MAGL) using qRT-PCR and Western blotting, along with assessments of their functionality using radioligand binding and activity assays. In addition, we quantified the content of endocannabinoid(-like) compounds (AEA, 2-AG, PEA, etc.) using UHPLC-MS/MS. Our results demonstrated that rare pCBs modulate the gene and protein expression of distinct ECS elements differently, as well as the content of endocannabinoid(-like) compounds. Notably, they all increased CB1/2 binding, TRPV1 channel stimulation and FAAH and MAGL catalytic activity. These unprecedented observations should be considered when exploring the therapeutic potential of cannabis extracts for the treatment of human skin diseases

    Characterization of biotin-anandamide, a novel tool for the visualization of anandamide accumulation

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    Anandamide (N-arachidonoylethanolamide; AEA) acts as an endogenous agonist ofboth cannabinoid and vanilloid receptors. During the last two decades, itsmetabolic pathways and biological activity have been investigated extensively andrelatively well characterized. In contrast, at present, the effective nature and mechanism of AEA transport remain controversial and still unsolved issues. Here, we report the characterization of a biotinylated analog of AEA (b-AEA) that hasthe same lipophilicity of the parent compound. In addition, by means ofbiochemical assays and fluorescence microscopy, we show that b-AEA is accumulatedinside the cells in a way superimposable on that of AEA. Conversely, b-AEA doesnot interact or interfere with the other components of the endocannabinoidsystem, such as type-1 and type-2 cannabinoid receptors, vanilloid receptor, AEA synthetase (N-acylphosphatidylethanolamine-hydrolyzing phospholipase D), or AEAhydrolase (fatty acid amide hydrolase). Together, our data suggest that b-AEAcould be a very useful probe for visualizing the accumulation and intracellulardistribution of this endocannabinoid.[...

    Liquorice Toxicity: A Comprehensive Narrative Review

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    Background: Renowned since ancient times for its medical properties, liquorice is nowadays mainly used for flavoring candies or soft drinks. Continuous intake of large amounts of liquorice is a widely known cause of pseudo-hyperaldosteronism leading to hypertension and hypokalemia. These manifestations are usually mild, although in some cases may generate life-threatening complications, i.e., arrhythmias, muscle paralysis, rhabdomyolysis, and coma. In addition, liquorice has an important estrogenic-like activity. Methods: We summarized the current knowledge about liquorice and reviewed 104 case reports in both the English and Italian languages from inception to June 2023 concerning complications due to an excess of liquorice intake. Results: In contrast to most published data, female sex and old age do not appear to be risk factors. However, hypertension and electrolyte imbalance (mainly hypokalemia) are prevalent features. The detection of glycyrrhetinic acid in blood is very uncommon, and the diagnosis is essentially based on an accurate history taking. Conclusions: Although there is not a significant mortality rate, liquorice toxicity often requires hospitalization and therefore represents a significant health concern. Major pharmaceutical drug regulatory authorities should solicit public awareness about the potentially dangerous effects caused by excessive use of liquorice
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