This paper describes a novel concept of producing energy efficient ”Maroon enriched natural gas “ and then Pink hydrogen” from any hydrocarbon base. The key idea is the extraction of hydrogen from water in addition to that from the hydrocarbon in an optimal fashion. This has the benefit of higher water vapor to CO2 exhaust ratio than conventional carbonaceous fuels when generating energy via combustion, a prudent step in achieving Netzero goals in a shorter time, and creating energy independence in most places.. The process of production makes concentrated CO₂ available for use and or sequestration. The process also maximizes use of renewable electricity in hydrogen generation, and maximizes use of existing infrastructure, with a minimum capital cost by energy recycle in the process. The process design applies sound thermodynamic principles which evolved during the nineteenth century, and mimics the geochemical processes going on in some of the natural 'colorless hydrogen'.

The present paper deals with the investigation, at conceptual level, of the performance of short-medium-range aircraft with hydrogen propulsion. The attention is focused on the relationship between figures of merit related to transport capability, such as passenger capacity and flight range, and the parameters which drive the design of liquid hydrogen tanks and their integration with a given aircraft geometry. The reference aircraft chosen for such purpose is a box-wing short-medium-range airplane, object of study within a previous European research project called PARSIFAL, capable to cut the fuel consumption per passenger-kilometre up to 22%. By adopting a retrofitting approach, non-integral pressure vessels are sized to fit into the fuselage of the reference aircraft, under the assumption that the main aerodynamic, flight mechanic and structural characteristics are not affected. A parametric model is introduced to generate a wide variety of fuselage-tank cross-section layouts, from a single tank with the maximum diameter compatible with a catwalk corridor to multiple tanks located in the cargo deck , and an assessment work-flow is implemented to perform the structural sizing of the tanks and analyse their thermodynamic behaviour during the mission. This latter is simulated with a time-marching approach that couples the fuel request from engines with the thermodynamics of the hydrogen in the tanks, which is constantly subject to evaporation and, depending on the internal pressure, vent-ed-out in gas form. Each model is presented in detail in the paper and results are provided through sensitivity analyses to both the technology parameters of the tanks and the geometric parameters influencing their integration. The guidelines resulting from the analyses indicate that light materials, such as the Aluminium alloy AA2219 for tanks’ structure and polystyrene foam for the insulation, should be selected. Preferred values are also indicted for the aspect ratios of the vessel components, i.e. central tube and endcaps, as well as suggestions for the integration layout to be adopted depending on the desired trade-off between passenger capacity, as for the case of multiple tanks in the cargo deck, and achievable flight ranges, as for the single tank in the section.

Despite significant research efforts, the question of whether rising atmospheric CO₂ concentrations (C_a) affect leaf respiration remains unanswered. Here, I reanalyse published hydrogen isotope abundances in starch glucose of sunflower leaves. I report that, as C_a increases from 450 to 1500 ppm, respiration by the oxidative pentose phosphate pathway in chloroplasts increases from 0 to ≈ 5% relative to net carbon assimilation. This is consistent with known regulatory properties of the pathway. Summarising recent reports of metabolic fluxes in plant leaves, a picture emerges in which mitochondrial processes are distinctly less important for overall respiration than the oxidative pentose phosphate pathways in chloroplasts and the cytosol. Regulatory properties of these pathways are consistent with observations of lower-than-expected stimulations of photosynthesis in response to increasing C_a. Reported advances in understanding leaf respiratory mechanisms may enable modelling and prediction of respiration effects (inter alia) on biosphere-atmosphere CO₂ exchange and plant performance under climate change.

We explore the importance of curvature in carbonaceaous species transformation and stability, using laser-induced vaporisation to evaporate and ionise a source of curved polyaromatic hydrocarbons: carbon nanobelts. Collision impacts between species cause mass loss and the resultant ions are catalogued via mass-spectrometry. To interpret the mass spectra, we perform a series of “in-silico” simulated systematic hydrogen-loss studies using density functional theory (DFT) modelling, sequentially removing hydrogen atoms using thermodynamic stability as a selection for subsequent dehydrogenation. In an initial sequence of H2 removal, the rings are maintained through stable carbyne chain and pentagon-chain formation, giving rise to circular strained dehydrobenzoannulene species. The chains subsequently break, releasing CH and C2. While theoretical closed-cage routes are identified, they are not observed experimentally. The results can serve as a useful guide to high-energy impact conditions observed in some astrochemical environments.

The North Sea Offshore Grid concept has been envisioned as a promising alternative to: 1) ease the integration of offshore wind and onshore energy systems, and 2) increase the cross-border capacity between the North Sea region countries at low cost. In this paper we explore the techno-economic benefits of the North Sea Offshore Grid using two case studies: a power-based offshore grid, where only investments in power assets are allowed (i.e. offshore wind, HVDC/HVAC interconnectors); and a power-and-hydrogen offshore grid, where investments in offshore hydrogen assets are also permitted (i.e. offshore electrolysers, new hydrogen pipelines and retrofitted natural gas pipelines). We compare these scenario results with a business as usual scenario, in which offshore wind is connected radially to the shore and no offshore grid is deployed. All scenarios are run with the IESA-NS model, without any specific technology ban and under open optimization. This paper also presents a novel methodology, combining Geographic Information Systems and Energy System Models, to cluster offshore spatial data and define meaningful offshore regions and offshore hub locations. This novel methodology is applied to the North Sea region to define nine offshore clusters taking into account offshore spatial claims, and identifying suitable areas for single-use and multi-use of space for renewable energy purposes. The scenario results show that the deployment of an offshore grid provides relevant cost savings, ranging from 1% to 4.1% of relative cost decrease (2.3 bn € to 8.7 bn €) in the power-based, and ranging from 2.8% to 7% of relative cost decrease (6 bn € to 14.9 bn €) in the power-and-hydrogen based. In the most extreme scenario (H2) an offshore grid permits to integrate 283 GW of HVDC connected offshore wind and 196 GW of HVDC meshed interconnectors. Even in the most conservative scenario (P1) the offshore grid integrates 59 GW of HVDC connected offshore wind capacity and 92 GW of HVDC meshed interconnectors. When allowed, the deployment of offshore electrolysis is considerable, ranging from 61 GW to 96 GW, with capacity factors of around 30%. Finally, we also find that, when imported hydrogen is available at 2 €/kg (including production and transport costs), large investments in an offshore grid are not optimal anymore. In contrast, at import costs over 4 €/kg imported hydrogen is not competitive.

The present is a study of the CFD simulations intended to simulate the emissions of pollutants that are generated after the combustion of proposed alternative aircraft fuels (Hydrogen, Ethanol and Methane) to compare with the emissions generated after the combustion of Kerosene and Benzene in a 2D cylindrical combustion chamber. Given that air traffic is a main contributor to not only 3% of man-made greenhouse effects but also of the generation of smog over heavy air traffic urban areas generating an impact on the air quality and the population of those areas.

Martensitic steels are used at a wide range of strength levels in environments which expose them to hydrogen or water vapor over a large range of partial pressures and temperatures. Hydrogen can cause catastrophic failures under many seemingly benign conditions. The effect of hydrogen on the dimension stability of high strength martensitic steels under such conditions has been poorly understood, and existing models do not seem to adequately account for it. Experiments were conducted to measure the variation in volume due to the uptake of hydrogen of such steels under near-ambient conditions, and the results were compared to theoretical estimates derived from the density of defects acting as hydrogen traps. Based on these results a new model for hydrogen embrittlement was developed. The hydrogen lattice dilation (HLD) model isolates volume expansion as a primary driver of hydrogen embrittlement. It provides and distinguishes two modes of failure acceleration: the fast, brittle, stress-intensity independent cracking under higher static crack loading, and a slower, highly stress-intensity dependent tearing mode at lower stress intensity. The relationship between the two is explained, as is how hydrogen absorption by defects accounts for the crack threshold and crack velocity of each.

CONTEXT– Energy is widely involved in human activity and corresponding emissions of SOX, NOX and CO2 from energy generation processes affect global climate change. Clean fuels are desired by society because of their reduced greenhouse gas emissions. Hydrogen is once such candidate fuel. Much hydrogen is produced from fossil fuel, with biomass being an alternative process. OBJECTIVE– The project compared the environmental impact of hydrogen production by natural gas steam reforming vs. biomass gasification. METHOD–Environmental impact was calculated from the input and output data from life cycle inventory analysis. The impact assessment was focused on greenhouse gas emission, acidification, and eutrophication. Models of the two processes were developed and analysed in OpenLCA. The agribalyse database was used to connect inventory flow data to environmental impacts. FINDINGS– For all three metrics, biomass gasification had lower impacts than natural gas steam reforming, sometimes by large margins. For biomass gasification the silica sand production contributes most to all three impact categories, whereas for natural gas steam reforming it is the LPG extraction.

The physicalchemistry properties and crystal structure of were nano-ZrO₂+3mol.%Y₂O₃ determined. The kinetics of the formation of H₂ as a result of the decomposition of H₂O on the surface of nano-ZrO₂+3mol.%Y₂O₃ was studied. Effects of adsorption and desorption process on ZrO₂+3 mol.%Y₂O₃ nanoparticles were studied at different (T=400÷1000⁰C) temperature. The study of H₂ in thermal processes at nano-ZrO₂+3 mol.%Y₂O₃ system increased. Such an increase in H₂ generation in comparison with a pure H₂O as thermal processes had formedactive centers for H₂O decomposition on the surface of the catalyst at the expense of δ-electrons emitted on the surface of nano-ZrO₂+3 mol.%Y₂O₃. This showed that the dimensions of the studied nanoscale particles systems are comparable to the free running distance of energy carriers generated by of nano-ZrO₂+3 mol.%Y₂O₃ as a result of thermal processes. These results are promising for hydrogen generation by waer spliting in near future.

Prereactive complexes in noncovalent organocatalysis are sensitive to the relative chirality of the binding partners and to hydrogen bond isomerism. Both effects are present when a transiently chiral alcohol docks on a chiral α-hydroxy ester, turning such 1:1 complexes into elementary, non-reactive model systems for chirality induction in the gas phase. With the help of linear infrared and Raman spectroscopy in supersonic jet expansions, conformational preferences are investigated for benzyl alcohol in combination with methyl lactate, also exploring p-chlorination of the alcohol and the achiral homolog methyl glycolate to identify potential London dispersion and chirality effects on the energy sequence. Three of the four combinations prefer barrierless complexation via the hydroxy group of the ester (association). In contrast, the lightest complex shows predominantly insertion into the intramolecular hydrogen bond, like the analogous lactate and glycolate complexes of methanol. The experimental findings are rationalized with computations and a uniform helicality induction in the alcohol by the lactate is predicted, independent on insertion into or association with the internal lactate hydrogen bond. p-Chlorination of benzyl alcohol has a stabilizing effect on association, because the insertion motif prevents a close contact between the chlorine and the hydroxy ester. After simple anharmonicity and substitution corrections, the B3LYP-D3 approach offers a fairly systematic description of the known spectroscopic data on alcohol complexes with α-hydroxy esters.

The crystals, C11H4BrF5N2S, (I), 1-((4-bromothiophen-2-yl)methylene)-2-(perfluorophenyl)hydrazine and C12H6BrF5N2S, (II), 1-((4-bromo-5-methylthiophen-2-yl)methylene)-2-(perfluorophenyl)hydrazine are molecules with two rings and hydrazone part like a centre of the molecule. The compounds have been synthesized and characterized by elemental, spectroscopic (¹H-NMR) analysis. The crystal structures of the solid phase were determined by single crystal X-ray diffraction method. They crystallize in the monoclinic space group with Z = 4 and Z = 2 molecules per unit-cell. The compound (I) crystallizes as a racemate in the centrosymmetric space group and the compound (II) crystallizes as a non-racemate in the non-centrosymmetric space group. The “absolute configuration and conformation for bond values” were derived from the anomalous dispersion (ad) for (II). The crystal structures are revealed diverse non-covalent interactions such as intra- and interhydrogen bonding, π-ring···π-ring, C-H···π-ring and they were investigated. The expected stereochemistry of hydrazones atoms C7, N2 and N1 were confirmed for (I) and (II). The hole molecule of the (I), and (II) possesses “a boat conformation” like a 6-membered ring. The results of the single crystal studies are reproduced with the help of Hirshfeld surface study and Gaussian software.

The choice of effective biocides used for routine hospital practice should consider the role of disinfectants in the maintenance and development of local resistome and how they might affect antibiotic resistance gene transfer within the hospital microbial population. Currently, there is little understanding of how different biocides contribute to eDNA release that may contribute to gene transfer and subsequent environmental retention. Here we investigated how different biocides affected the release of eDNA from mature biofilms of two opportunistic model strains Pseudomonas aeruginosa ATCC 27853 (PA) and Staphylococcus aureus ATCC 25923 (SA) and contribute to the hospital resistome in the form of surface and water contaminants and dust particles. The effect of four groups of biocides including alcohols, hydrogen peroxide, quaternary ammonium compounds, and polymeric guanidines were evaluated using PA and SA biofilms. Most biocides, except for PHMG-Cl and 70% ethanol, caused substantial eDNA release and PHMG-Cl was found to block biofilm development when used at concentrations of 0.5% and 0.1%. This might be associated with the formation of DNA-PHMG-Cl complexes as PHMG-Cl is predicted to bind to AT base pairs by molecular docking assays. PHMG-Cl was found to bind high molecular DNA and plasmid DNA and continued to inactivate DNA on surfaces even after four weeks. PHMG-Cl also effectively inactivated biofilm-associated antibiotic resistance gene eDNA released by a pan-drug-resistant Klebsiella strain which demonstrates the potential of PHMG-Cl as a new surface-active agent to combat the spread of antibiotic resistance in hospital settings.

In the article, were checked influences of microaeration, pH, and VSS (Volatile Suspended Solid) for sour cab-bage anaerobic digestion. Results fermentation of sour cabbage under the condition of small oxygen addition are presented in this research can be classified as dark fermentation or hydrogenotrophic anaerobic digestion. The investigations were carried out for two concentrations 5 g VSS /L and 10 g VSS /L of sour cabbage at pH 6.0. The oxygen flow rates (OFR) for 5 g VSS /L were in the range of 0.53 to 3.3 mL/h for obtaining 2% to 8% of oxygen. In cases of low pH and microaeration, ethylene production was observed at a level below 0.05% in biogas. The highest volume of hydrogen for 5 g VSS/L was obtained for flow rate 0.58 O2 mL/h, giving hydrogen concentration in biogas in the range of 0 to 20%. For VSS 5 g/L and oxygen flow rate 0.58 mL/h; 0.021 L of hydrogen is produced per gram of VSS. In this case, VSS 10 g/L and oxygen flow rate 1.4 mL/h at pH 6.0, 0.03 L of hydrogen is generated per gram. Microaeration from 0.58 mL/h to 0.87 mL/h was propitious for hydrogen production at 5 g VSS/L of sour cabbage and 1.4 mL/h for 10 g/L. Another relevant factor is the volatile suspended solid factor of sour cabbage that caused optimal hydrogen production at VSS 89.32%.

This paper extends the application of the ROTASE model for the formation of spiral arms of disc galaxies, questions and confusions from readers about this model are addressed. The optical trail effect behind the spiral arm rotation is the natural consequence of the model. The morphologies of ring-galaxies are classified into four categories: type I: single ring; type II: 8-shaped double ring; type III: 8-shaped double ring wrapped by a larger outer ring; type IV: single ring without spiral and bar. All four types of ring galaxies can be described by the ROTASE model. The ROTASE model predicts that the false impression of spiral arm rotating ahead of the galactic bar in the galaxy MCG+00-04-051 will change with time, it will look like a normal galaxy with about 30° to 40° bar rotation in the future and the galactic bar ends will look like rotating ahead of the spiral arms with further 10 ° to 15 °bar rotation. The formation of one arm galaxies is due to X-matter at one side of supermassive black hole is much stronger than other side. More evidence is found to support the explanation of the formation and the evolution of the Hoag’s object. The possible evolution of spiral pattern of galaxies is illustrated by UGC 6093. The winding of the Milky Way could be tighter in the future based on the ROTASE model.

Epilepsy is a heterogenous neurological disorder characterized by recurrent unprovoked seizures, mitochondrial stress, and neurodegeneration. Hydrogen sulfide (H2S), a gasotransmitter, promotes mitochondrial function and biogenesis, elicits neuromodulation and neuroprotection, and may acutely suppress seizures. A major gap in knowledge remains in understanding the role of mitochondrial dysfunction and progressive changes in H2S levels following acute seizures and during epileptogenesis. We thus sought to quantify changes in H2S and its methylated metabolite (MeSH) via LC-MS/MS subsequent to acute maximal electroshock and 6 Hz 44 mA seizures in mice, as well as in the corneal kindled mouse model of chronic seizures. Plasma H2S was acutely reduced after a maximal electroshock seizure. H2S or MeSH levels in whole brain homogenate and expression of related genes in corneal kindled mice were not altered. However, plasma H2S and MeSH levels were significantly lower during kindling, but not after established kindling. Morever, we demonstrated a time-dependent increase in expression of mitochondrial membrane integrity-related proteins, Opa1, Mfn2, Drp1, and Mff during kindling, which did not correlate with gene expression. Taken together, short-term reductions in plasma H2S could be a novel biomarker for seizures. Future studies should further define the role of H2S and mitochondrial stress in epilepsy.

The structural, elastic, anisotropic elastic, electronic, vibrational and properties of the Perovskite type Hydrides RbXH3 (X = Be, Ca, Mg) were performed via Vienna Ab – initio Simulation Pac-kage (VASP) based on Density Functional Theory (DFT). Our results have exhibited a well-agreement with previous calculations and experiments for each compound. In order to de-termine physical properties of RbXH3 has been used the Generalized Gradient Approximation (GGA) with Perdew-Burke-Ernzerhof (PBE) functional at this study. Present compounds were found to be mechanically stable as well as their gravimetric hydrogen storage capacities has been investigated. The Perovskite type Hydrides RbBeH3 and RbMgH3 has an indirect bandgap of 0.274 eV and 2.209 eV while RbCaH3 has a direct bandgap of 3.274 eV respectively and therefo-re these compounds has shown a semiconductor behaviour at equilibrium. Besides directional dependence of anisotropic properties was visualized by representing them with maximum - mi-nimum points..

Integrated photovoltaic-fuel cell (IPVFC) systems, amongst other integrated energy generation methodologies are renewable and clean energy technologies that have received diverse research and development attentions over the last few decades due to their potential applications in a hydrogen economy. This article systematically updates the state-of-the-art of IPVFC systems and provides critical insights into the research and development gaps needed to be filled/addressed to advance these systems towards full commercialisation. The design methodologies, renewable energy-based microgrid and off-grid applications, energy management strategies, optimisations and the prospects as self-sustaining power source were covered. IPVFC systems could play an important role in the upcoming hydrogen economy since they depend on solar hydrogen which has almost zero emissions during operation. Highlighted herein are the progresses as well as the technical challenges requiring research efforts to solve to realise numerous potential applications of IPVFC systems such as in unmanned aerial vehicles, hybrid electric vehicles, agricultural applications, telecommunications, desalination, synthesis of ammonia, boats, buildings, and distributed microgrid applications.

Isobaric ions having the same mass-to-charge ratio cannot be separately identified by mass spectrometry (MS) alone, but this limitation can be overcome using hydrogen-deuterium exchange (HDX) in microdroplets. Because isobaric ions may contain a varied number of exchangeable sites and different types of functional groups, each one produces a unique MS spectral pattern after droplet spray HDX without the need for MS/MS experiments or introduction of ion mobility measurements. As an example of the power of this approach, isobaric ions in urinary metabolic profiles are identified and used to distinguish between healthy individuals and those having bladder cancer.

As fossil-fueled heating in the building sector is responsible for 16 % of Germanys total CO2 emissions, it is of great importance to use climate-neutral alternatives for the decarbonization of this sector. Options for the climate-neutral heating of buildings include electricity or hydrogen as energy carriers, both explicitly considered by German policy. In this paper, bottom-up studies are conducted to investigate the role of hydrogen for the climate-neutral energy supply of ten selected residential buildings in comparison to electricity-based systems. Based on a selection of as different typical buildings as possible for single- (SFH) and multi-family houses (MFH) of different construction years, demand profiles are simulated for each building and the respective cost-optimal supply system is determined. For the construction of this system, the electricity-based technologies available are electric heater and heat pump as well as the hydrogen-based technologies hydrogen boiler and fuel cell combined heat and power (CHP) system. Based on the results of the optimization, sensitivity analyses are performed. These analyses aim to identify threshold values of the hydrogen price for the use of hydrogen in building energy systems as well as to make the quantities of hydrogen consumed visible.The identified threshold values show the significant role of hydrogen-operated CHP in MFH if the hydrogen price reaches 0.17 €/kWh_H2 in 2050 at an electricity price of 0.31 €/kWh_el. So, hydrogen-based energy systems represent an economically viable alternative to electricity-based systems with heat pumps. We identify electricity to hydrogen price ratios for the economically viable use of hydrogen in the examined buildings that range from 1.67 to 2.82. According to these ratios, the economically reasonable use of hydrogen in buildings can be derived. For the individual building groups for the year 2050, a ratio of 2.5 can be determined for SFH and 1.8 for MFH, that is favored by the use of CHP which also supplies electricity to the buildings. However, the role hydrogen will finally play in German residential buildings in the future depends to a large extent on political decisions on distribution issues and price signals.

Hydrogen used as an energy carrier can provide an important route to the decarbonization of energy supplies. However, realizing this opportunity requires a significant increase in both production and transportation capacity. Part of the increase in transportation capacity could be provided by the shipping of liquid hydrogen, but this introduces an energy-intensive liquefaction step into the supply-chain. The energy required for liquefaction can be reduced by developing improved process designs, but since all low-temperature processes are affected by the available heat-sink temperature, local ambient conditions will also affect the energy penalty. This work studies how the energy consumption associated with liquefaction varies with heat-sink temperature through the optimization of design parameters for a typical next-generation hydrogen liquefaction process. The results show that energy consumption increases by around 20%, across the cooling temperature range 5 to 50 °C. Considering just the range 20 to 30 °C there is a 5% increase, illustrating the significant impact ambient temperature can have on energy consumption.

Recently, it was reported that the physical cross-linking exhibited by some biopolymers could provide multiple benefits to biomedical applications. In particular, grafting thermoresponsive polymers onto biopolymers may enhance the degradability or offer other features, as ther-mothickening behavior. Thus, different interactions will affect the different hydrogen bonds and interactions from the physical cross-linking of CMC, the lower critical solution temperatures (LCSTs), and the presence of the ions. This work focuses on the study of blends composed of poly(N-isopropylacrylamide), poly(N-ethylacrylamide), and carboxymethyl cellulose in water and water/methanol. The molecular features, the thermoresponsive behavior, and gelation phenomena are deeply studied. The ratio defined by both homopolymers will alter the final properties and the gelation of the final structures, showing that the presence of the hydrophilic groups modifies the number and contributions of the diverse hydrogen bonds.

This review proposes an overview on the use of organic functionalized carbon nanostructures (CNSs) into solar energy conversion schemes. Our attention has focused in particular on the contribution given by organic chemistry to the development of new hybrid materials that find application in dye sensitized solar cells (DSSC), organic photovoltaics (OPV), perovskite solar cells (PSC) and also in photocatalytic fuel production, focusing in particular on the most recent literature. The request for new materials able to accompany the green energy transition that are abundant, low cost, with low toxicity, from renewable sources has further increased the interest in CNSs that meet all these requirements. The inclusion of an organic molecule, thanks to both covalent and non-covalent interactions, into a CNS, leads to the development of a completely new hybrid material able of combining and improving the properties of both starting materials. Besides the numerical data, which unequivocally state the positive effect of the new hybrid material, we hope that these examples can be inspiring for further research in the field of photoactive materials from an organic point of view.

Phenol is added to acetophenone (methyl phenyl ketone) and to six of its halogenated derivatives in a supersonic jet expansion to determine the hydrogen bonding preference of the cold and isolated 1:1 complexes by linear infrared spectroscopy. Halogenation is found to have a pronounced effect on the docking site in this intermolecular ketone balance experiment. The spectra unambiguously decide between competing variants of phenyl group stacking due to their differences in hydrogen bond strength. Structures where the phenyl group interaction strongly distorts the hydrogen bond are more difficult to quantify in the experiment. For unsubstituted acetophenone, phenol clearly prefers the methyl side despite a predicted sub-kJ/mol advantage which is nearly independent of zero point vibrational energy, turning this complex into a challenging benchmark system for electronic structure methods which include long range dispersion interactions in some way.

Clausius’ virial theorem set a basis for relating kinetic energy in a body of independent material particles to its potential energy, pointing to their complementary role with respect to the second law of maximum entropy. In action mechanics, expressing the entropy of ideal gases as a capacity factor for sensible heat or enthalpy plus the configurational work to sustain the relative translational, rotational and vibrational action yields algorithms for estimating chemical reaction rates and positions of equilibrium. All properties of state including entropy, work potential as Helmholtz and Gibbs energies and activated transition state reaction rates can be estimated, using easily accessible molecular properties, such as atomic weights, bond lengths, moments of inertia and vibrational frequencies. Understanding how Clausius’ virial theorem balances the internal kinetic energy with field potential energy justifies partitioning between thermal and statistical properties of entropy, yielding a more complete view of the evolutionary nature of the second law of thermodynamics. The ease of performing these operations is illustrated by three important chemical gas phase reactions, the reversible dissociation of the hydrogen molecules, lysis of water to hydrogen and oxygen and the reversible formation of ammonia from nitrogen and hydrogen. Employing the ergal also introduced by Clausius to define the reversible internal work to overcome molecular interactions plus the configurational internal work of negative Gibbs energy as a function of volume or pressure may provide a practical guide for managing risk in industrial processes and climate change at the global scale.

Clairton, Pennsylvania, is home to the largest coke works facility in the United States (US). On 24 December 2018, a large fire occurred at this facility and damaged pollution control equipment. Although repairs were not completed for several months, production continued at pre-fire capacity and daily emissions increased by 24 to 35 times, with multiple exceedances of monitored levels of outdoor air pollution (OAP). The aim of this study was to objectively evaluate the impact of this industrial incident and resultant OAP exceedances on asthma morbidity. We assessed pre-fire and post-fire rate ratios (RR) of outpatient and emergency department (ED) visits for asthma exacerbations among nearby adult residents. Pre-fire versus post-fire RRs increased for both visit types: RR = 1.82 (95% CI: 1.30, 2.53; p < 0.001) and 1.84 (95% CI: 1.05, 3.22; p = 0.032) for outpatient and ED visits, respectively. Additionally, total visit rates increased on days with OAP exceedances: RR = 2.47 (95% CI: 1.52, 4.01; p < 0.0001), 1.58 (95% CI: 1.00, 2.48; p = 0.048) and 1.79 (95% CI: 1.27, 2.54; p = 0.001) for PM_2.5, SO₂, and H₂S exceedance days, respectively. These results show a near doubling of acute visits for asthma exacerbations in nearby adult residents during this industrial incident and underscore the need for prompt remediation and public notification of OAP exceedances to prevent adverse health impacts.

We present a critical analysis of the mechanism of reversible hydrogen evolution reaction based on thermodynamics of hydrogen processes considering atomic and ionic species as intermediates. Clear distinction between molecular hydrogen evolution/oxidation (H$_2$ER and H$_2$OR) and atomic hydrogen evolution/oxidation (HER and HOR) reactions is made. It is suggested that the main reaction describing reversible H$_2$ER and H$_2$OR in acidic and basic solutions is: $\ce{H3O^+} + 2e^- \xrightleftharpoons{\mathrm{({H}_{2}^{+}})_{ad}} \ce{H2} + \ce{OH^-}$, which proceeds via the formation of hydrogen molecular ion as intermediate and its potential is $E^{0}$ = 0.414~V (at the standard Hydrogen electrode SHE scale). We analyse experimentally reported data with models which provide \emph{quantitative} match (R.J.Kriek et al., Electrochem. Sci. Adv. e2100041 (2021)). The experimentally observed slope of $\lg(Current)$ vs. $Potential$ equal to $\approx 30$~mV/dec corroborates the presented model of H$_2$ER/H$_2$ER based on \ce{H2$^+$} as intermediate.

This paper aims at addressing the exploitation of solid-state carriers for hydrogen storage, with attention paid both to the technical aspects, through a wide review of the available integrated systems, and to the social aspects, through a preliminary overview of the connected impacts from a gender perspective. As for the technical perspective, carriers to be used for solid-state hydrogen storage for various applications can be classified into two classes: metal and complex hydrides. Related crystal structures and corresponding hydrogen sorption properties are reviewed and discussed. Fundamentals of thermodynamics of hydrogen sorption evidences the key role of the enthalpy of reaction, which determines the operating conditions (i.e. temperatures and pressures). In addition, it rules the heat to be removed from the tank during hydrogen absorption and to be delivered to the tank during hydrogen desorption. Suitable values for the enthalpy of hydrogen sorption reaction for operating conditions close to ambient (i.e. room temperature and 1-10 bar of hydrogen) are close to 30 kJ·molH2 1. The kinetics of hydrogen sorption reaction is strongly related to the microstructure and to the morphology (i.e. loose powder or pellets) of the carriers. Usually, kinetics of hydrogen sorption reaction is rather fast, and the thermal management of the tank is the rate determining step of the processes. As for the social perspective, various scenarios for the applications in different socio-economic contexts of solid-state hydrogen storage technologies are described. As it occurs with the exploitation of other renewables innovative technologies, a wide consideration of the social factors connected to these processes is needed to assess the extent to which a specific innovation might produce positive or negative impacts in the recipient socio-economic system and to explore the potential role of the social components and dynamics in fostering the diffusion of the innovation itself. Attention has been addressed to the gender perspective, in view of the enhancement of hydrogen-related energy storage systems, intended both in terms of the role of women in triggering the exploitation of hydrogen-based storage as well as to the impact of this innovation in their current conditions, at work and in daily life.

Cystathionine gamma-lyase (CSE) is an essential Hydrogen sulphide (H2S)-producing enzyme that regulates diverse processes related to cardiovascular function. It is crucial to understand how exogenous H2S regulates CSE expression in vascular endothelial cells during hypoxia. We examined the regulatory effect of 100 μM H2S on the transcription and expression of CSE in HUVECs during hypoxia by luciferase assay, Western blotting, and quantitative RT-qPCR. Exogenous H2S influenced the promoter activity of CSE in HUVECs during hypoxia. Compared with 0 μM H2S, 100 μM H2S decreased the mRNA expression of CSE in HUVECs. Compared with 0 μM H2S, 100 μM H2S decreased the protein expression of CSE in HUVECs after 2 h of hypoxia. These findings suggest that vascular endothelial cells can respond to changes in H2S concentration in the blood during hypoxia.

In this work we explored how solvents can affect olefin oxidation reactions catalyzed by MCM-bpy-Mo catalysts and whether their control can be made with those players. The results of this study evidenced that polar and apolar aprotic solvents modulated the reactions in different ways. Experimental data showed that acetonitrile (aprotic polar) could hinder largely the reaction rate whereas toluene (aprotic apolar) did not. In both cases product selectivity at isoconversion was not affected. Further insights were obtained by means of neutron diffraction experiments, which confirmed the kinetic data allowing to propose a model based on substrate-solvent crosstalk by means of hydrogen bonding. In addition, the model was also validated in the ring-opening reaction (overoxidation) of styrene oxide towards benzaldehyde, which progressed when toluene was the solvent (reaching 31% styrene oxide conversion) but was strongly hindered when acetonitrile was used instead (reaching only 7% conversion), due to the establishment of H-bonds in the latter. Although this model was confirmed and validated for olefin oxidation reactions, it can be envisaged that it may also be applied to other catalytic reaction systems where reaction control is critical, while widening its use.

Photosynthesis is a pivotal process that determines the synthesis of carbohydrates required for sustaining growth under normal or stress situation. Stress exposure reduces the photosynthetic potential owing to the excess synthesis of reactive oxygen species that disturb the proper functioning of photosynthetic apparatus. This decreased photosynthesis is associated with disturbances in carbohydrate metabolism resulting in reduced growth under stress. We evaluated the importance of melatonin in reducing heat stress-induced severity in wheat plants (Triticum aestivum L.). The plants were subjected to 25 ˚C (optimum temperature) or 40 ˚C (heat stress) for 15 days at 6 hours time duration and then developed the plants for 30 days. Heat stress led to oxidative stress with increased production of TBARS and H2O2 content and reduced accrual of total soluble sugars, starch and carbohydrate metabolism enzymes which are reflected in reduced photosynthesis. Application of melatonin not only reduced oxidative stress through lowering TBARS and H2O2 content, through augmenting the activity of antioxidative enzymes but also increased the photosynthesis in plant and carbohydrate metabolism that is needed to provide energy and carbon skeleton to the developing plant under stress. However, the increase in these parameters with melatonin was mediated via hydrogen sulfide (H2S), as the inhibition of H2S by hypotaurine (HT; H2S inhibitor) reversed the ameliorative effect of melatonin. This suggests a crosstalk of melatonin and H2S in protecting heat stress-induced photosynthetic inhibition via regulation of carbohydrate metabolism.

The role of plant growth-promoting rhizobacteria (PGPR) on enhancing tolerance of plants to abiotic stresses is well reported, but the effects of RGPRs on plants under salinity stress are not widely studied in the literature. Our study aimed to investigate the effect of Halomonas sp. and Azotobacter sp. on antioxidant activity, secondary metabolites, and biochemicals changes of purple basil under salinity stress conditions. The applied salt concentrations in this study were 50, 100, and 150 mM sodium chloride (NaCl). Salinity stress had a negative effect on plant growth parameters. Moreover, a reduction in some of the osmolytes and oxidative stress markers was observed. Inoculated plants ameliorated the oxidative damage by reducing the hydrogen peroxide (H2O2) contents and by increasing osmolytes (proline, total proteins, and soluble sugars), antioxidant enzymes activities (catalase, ascorbate peroxidase) and secondary metabolites (flavonoids). Overall, among treatments, plants inoculated with Azotobacter showed a better impact on physiological attributes to alleviate the adverse effects of 150 mM NaCl salinity stress on basil growth.

Three ternary mixtures composed by choline chloride (ChCl), ethylene glycol (EG) and a second hydrogen bond donor (HBD) as ethanol (A), 2-propanol (B), and glycerol (C) were studied in terms of composition related to the band gap energy (BGE). A Design of Experiments (DoE) approach, and in particular a Simple Lattice three-components design, was employed for determining the variation of the BGE upon the composition of each system. UV-VIS analysis and subsequent Tauc plot methodology provided the data requested from the DoE and multivariate statistical analysis revealed a drop of the BGE in correspondence to specific binary compositions for systems A and B. In particular, a BGE of 3.85 eV was registered for the mixtures ChCl/EtOH (1:1), and ChCl/2-propanol (1:1), which represents one of the lowest values ever observed for these systems.

Ferric oxide containing waterworks sludge can be used to reduce formation of hydrogen sulfide during anaerobic digestion. The ferric compound is reduced biochemically in the digester and forms insoluble pyrite in digester sludge. Often virgin ferric chloride is used to solve the hydrogen sulfide problem. Since 2013, Sydvatten AB has supplied a growing number of digestion plants in Sweden with ferric containing dewatered waterworks sludge from the drinking water treatment plant Ringsjöverket to limit the formation of hydrogen sulfide. At the waterworks, ferric chloride is added to enhance coagulation of organic matter from the source water. The sludge formed in this process is dewatered and landfilled, but also recycled in the biogas production in order to reduce the hydrogen sulfide concentration. In this study, the use of sludge, for hydrogen sulfide removal in digesters, was technically and economically evaluated from cases studies from 13 full-scale digesters in Sweden. Compared with use of fresh ferric chloride, the operational costs are reduced up to 50 % by using sludge. The quality of the sludge is high and its content on metals is low or very low, especially when compared with requirements from different certification standards on biosolid reuse applied in Sweden. An addition of waterworks sludge containing iron to a digester for removal of dissolved hydrogen sulfide is a technically and economic good alternative when producing biogas. It is also one step closer to a circular economy, when replacing use of virgin chemicals with the by-product waterworks sludge which saves energy, material and reduces the carbon foot-print of the waterworks.

The 2-oxoglutarate dehydrogenase complex (OGDHc) is a key enzyme in the TCA cycle and represents one of the major regulators of mitochondrial metabolism through NADH and reactive oxygen species levels. The OGDHc impacts cell metabolic and cell signaling pathways through the coupling of 2-oxoglutarate metabolism to gene transcription related to tumor cell proliferation and aging. DHTKD1 is a gene encoding 2-oxoadipate dehydrogenase (E1a), which functions in the L-lysine degradation pathway. The potentially damaging variants in DHTKD1 have been associated to the (neuro) pathogenesis of several diseases. Evidence was obtained for the formation of a hybrid complex between the OGDHc and E1a, suggesting a potential cross talk between the two metabolic pathways and raising fundamental questions about their assembly. Here we reviewed the recent findings and advances in understanding of protein-protein interactions in OGDHc and 2-oxoadipate dehydrogenase complex (OADHc), an understanding that will create a scaffold to help design approaches to mitigate the effects of diseases associated with dysfunction of the TCA cycle or lysine degradation. A combination of biochemical, biophysical and structural approaches such as chemical cross-linking MS and cryo-EM appears particularly promising to provide vital information for the assembly of 2-oxo acid dehydrogenase complexes, their function and regulation.

At present, the world is at the peak of production of traditional fossil fuels. Much of the resources that humanity has been consuming (oil, coal and natural gas) are coming to an end. The human being faces a future that must necessarily go through a paradigm shift, which includes a progressive movement towards increasingly less polluting and energetically viable resources. In this sense, nanotechnology has a transcendental role in this change. For decades, new materials capable of being used in energy processes have been synthesized that undoubtedly will be the cornerstone of the future development of the planet. In this review, we report on the current progress in the synthesis and use of one-dimensional (1D) nanostructured materials (specifically nanowires, nanofibers, nanotubes and nanorods), with compositions based on oxides, nitrides, or metals, for applications related to energy. Due to its extraordinary surface-volume relationship, tunable thermal and transport properties, and its high surface area, these 1D nanostructures have become fundamental elements for the development of energy processes. The most relevant 1D nanomaterials, their different synthesis procedures, and useful methods for assembling 1D nanostructures in functional devices will be presented. Applications in relevant topics such as optoelectronic and photochemical devices, hydrogen production or energy storage, among others, will be discussed. The present review concludes with a forecast on the directions towards which future research could be directed on this class of nanostructured materials.

The Residential and Industrial zones as is, rely heavily, if not exclusively, on Hydrocarbons. Hydrocarbon thermal machinery such as Spark Ignition-Compression Ignition engines, Gasoline-Diesel generators, Coal-Lignite gasifiers, residential diesel-powered heating systems, Pyrolysis units and so on, are commonly met all around the planet. Such technology practically oxidizes Hydrocarbons to produce either heat, steam or useful mechanical work depending on the application, though energy losses are not, by any means, insignificant. Advanced material processing is an industrial sector who’s energy demand is significant and it is important for the general public to come to terms with the fact that by implementing Hydrogen technology to power such plant while at the same time improving the energy equilibrium of houses(advanced materials), communities would be taking major steps towards Climate Change effects debilitation. The downside of Hydrocarbon thermochemical exploitation can be described by the limited resources-reserves and the gaseous pollutant emissions (CO2, CO, NOx, SOx). In recent years, the Industrial zone as a whole has began taking a turn towards Electrification without having established the necessary infrastructure to support such a transition. Indicatively, at current rate of production, dead Lithium-Ion batteries are projected to reach as high as 11,000 metric tons by 2030, yet there is no recycling scheme in place, not to mention the prospect of that number rising even more, given the recent e-mobility trend. As it pertains to Electrification, such powertrains-machinery require electricity and a battery. Electricity production is mainly achieved through Coal-Lignite gasification, Batteries require metals, among others, for manufacturing, meaning that up-on mining, local water resources are contaminated, another very important ‘aspect’ of Lithium(per say) mining is that child labor is often associated with such processes, a truly despicable act. All of the above paint a crystal-clear picture as to how ‘environmentally friendly’ reckless-rushed Electrification really is. Climate Change is up-on us and it’s effects on the planet are obvious, the most important of which is glacier melting due to rising of the global Temperature. The COVID-19 crisis is a sign of what could come from glacier melting could as ice contains potentially harmful-toxic to humans, biological entities that are sure to be introduced to the general public if we were to continue exploiting mineral resources. Purpose of this paper is to provide a general overview of the technology around Hydrogen.

The compound, C27H23N3 (1), crystallizes in the triclinic system of the P-1 space group. The unit cell comprises a dimer of 1, in which the monomers are linked by two complementary hydrogen bonds between N1 and H1-C1 of another molecule. The dimers form chains along the a-axis through intermolecular interactions between the N2 acceptor atoms and C17 donors from molecules in the nearest neighbouring dimer. These interactions form extended sheets of the dimers of 1, along the ab plane. The quinolinylmeth-2-yl groups of 1 lie in almost orthogonal planes and their N1/2(q) donor atoms being away from the apical amino N3 atom.

In this article, it is proposed to use aluminum breakage scraps to obtain Green Hydrogen through the aluminum-water reaction with caustic soda as a catalyst. From this exothermic reaction, both hydrogen and the heat generated can be used. Due to the low price of aluminum chips, this allows us to produce Green hydrogen below the current price that is obtained using renewable energy sources and electrolyzers. On the other hand, we have developed a process that is sustainable since it is obtained as alumina and caustic soda waste that can be reused. This alumina obtained, once filtered, has high purity which allows us to produce high-quality primary aluminum without the need to use bauxite and reducing the production of red sludge. A comparative study-analysis has been carried out of two of the types of forms in which the most common aluminum is presented in the industry to analyze which one performs better by studying key factors such as the hydrogen produced, and the waste generated during the process. Finally, the mathematical model has been defined to be able to control the flow based on different key parameters such as temperature, molarity, and geometry. Undoubtedly, the study that we present represents a milestone for the recovery of metallic aluminum waste and may be of great interest to industries that use aluminum in their processes, such as recuperators, but also the vehicle or aerospace industry.

In this work, kinetics of the reaction between 5,10,15,20-tetrakis(N-methylpyridium-4-yl)porphyrin and Ni2+ species were investigated in aqueous solution at 25 ±1 ºC in I = 0.10 M (NaNO3). Speciation of Ni2+ was carried out in I = 0.10 M (NaNO3) in order to provide the distribution of the Ni2+ species with different solution pH. The experimental data have been compared with the speciation diagram constructed from the values of hydrolysis constants of Ni2+ ion. Speciation data showed that the hexaaquanickel(II), [Ni(H2O)6]2+, ions take place in hydrolysis reactions through formation of [Ni(OH2)6-n(OH)n]2-n species with solution pH. Based on the speciation of Ni2+ and pH dependent rate constants, rate expression can be written as: d[Ni(TMPyP)4+]/dt = (k1[Ni2+(aq)] + k2[Ni(OH)+(aq)] + k3[Ni(OH)2o(aq)] + k4[Ni(OH)3-(aq)])[H2TMPyP4+], where k1, k2, k3 and k4 were found to be k1 = (0.62 ± 0.22) × 10-2; k2 = (3.60 ± 0.40) × 10-2; k3 = (2.09 ± 0.52) × 10-2, k4 = (0.53 ± 0.04) × 10-2 M-1s-1 at 25 ±1 °C, respectively. Kinetic results showed that monohydroxo, [Ni(H2O)5(OH)]+, is the most reactive among the [Ni(OH2)6-n(OH)n]2-n species. The enhanced reactivity has been ascribed to the formation of hydrogen bonding between oxygen atom of hydroxyl group of the [Ni(H2O)5(OH)]+ species and the pyrrolic hydrogen atom of the [H2TMPyP]4+. The rate of formation of [Ni(II)TMPyP]4+ complex was to be 3.99 × 10-2 M-1s-1 in I = 0.10 M, NaNO3 (25 ± 1 ºC). Ionic strength effect on the reaction rate is suggested that the net charge of the tetracationic porphyrin is to be +3.6 on the basis of Brønsted-Bjerrum equation. The UV-Vis and fluorescence data revealed that [Ni(II)TMPyP]4+ and H2(TMPyP)4+ interact with DNA, and UV-Vis results suggest that Ni(II)-porphyrin and free base porphyrin interact with DNA via outside binding with self-stacking and intercalation, respectively. Mechanism of kinetics of formation of the [Ni(II)TMPyP]4+ complex in aqueous medium is discussed. An investigation of application of the [Ni(II)TMPyP]4+ complex along with other metalloporphyrins such as Zn2+-, Ru2+-, Pt2+-, [Au(III)TMPyP]5+ as anti-COVID-19 agents is now in progress under international collaboration.

this review summarizes current knowledge of the hydrogen sulfide role in cardiovascular system, the proposed mechanisms of its action and the prospects for its applicability in the treatment of cardiovascular diseases. Hydrogen sulfide was recently recognized as gasotransmitter – simple signaling molecule which freely penetrates the cell membrane and regulates a number of biological functions. In humans endogenous H2S is generated via enzymatic and non-enzymatic pathways and its content varies in different tissues and is strictly regulated. In cardiovascular system H2S is produced by myocardial, vascular and blood cells and regulates a number of vital functions. Numerous experimental data prove that endogenously generated as well as exogenously administered H2S exerts a wide range of actions in cardiovascular system, including vasodilator/vasoconstrictor effects, regulation of blood pressure, pro-apoptotic and anti-proliferative effects in the vascular smooth muscle cells, influence on angiogenesis and erythropoiesis, myocardial cytoprotection in ischemia-reperfusion injury, oxygen sensing, inhibition of platelet aggregation and blood coagulation, modification of erythrocyte microrheological properties (aggregability and deformability). Understanding of molecular mechanisms of H2S action and molecular crosstalk between H2S, NO, and CO is essential for the development of its diagnostic and therapeutic potential.

The study aimed to elucidate the optimum level of elemental sulfur, fresh cassava root (FCR), and urea and their effect on gas production, ruminal fermentation, thiocyanate concentration, and in vitro degradability. A 3×2×4 in a completely randomized design were conducted. Factor A was level of sulfur at 0%, 1%, and 2% of concentrate dry matter (DM), factor B was level of urea at 2% and 4% of concentrate DM, and factor C was level of the FCR at 0, 200, 300, and 400 mg of the total substrate. The study found that elemental sulfur, urea, and FCR had no interaction effect on the kinetics of gas, ruminal fermentation, hydrogen cyanide (HCN), and in vitro degradability. Elemental sulfur supplementation (P<0.05) significantly increased the gas produced from an insoluble fraction (b), in vitro DM degradability and either neutral detergent fiber or acid detergent fiber degradability, and propionate (C3) concentration while decreased the ruminal HCN concentration. Urea levels showed a (P<0.05) significant increase of the potential extent of gas production, ruminal NH3-N, and total volatile fatty acid (VFA). FCR supplementation (P<0.05) significantly increased the gas produced from an immediate soluble fraction (a), gas produced from insoluble fraction, gas production rate constant, total VFA, C3 concentration, and HCN while decreased ruminal pH, acetate, and butyrate concentration. It could be concluded that 2% elemental sulfur, 4% urea, and 300 mg FCR showed a greater effect on gas production, ruminal fermentation, and HCN reduction.

We investigated effects of molecular hydrogen (H2) supplementation on acid-base status, pulmonary gas exchange responses, and local muscle oxygenation during incremental exercise. Eighteen healthy, trained subjects in a randomized, double-blind, crossover design received H2-rich calcium powder (HCP) (1500 mg/day, containing 2.544 µg/day of H2) or H2-depleted placebo (1500 mg/day) for 3 consecutive days. They performed cycling incremental exercise starting at 20-watts work rate, increasing by 20 watts/2 min until exhaustion. Breath-by-breath pulmonary ventilation (VE) and CO2 output (VCO2) were measured and muscle deoxygenation (deoxy[Hb + Mb]) was determined via time-resolved-NIRS in the vastus lateralis (VL) and rectus femoris (RF). Blood gases' pH, lactate, and HCO3− concentrations were measured at rest and 120-, 200-, and 240-watt work rates. At rest, the HCP group had significantly lower VE, VCO2, and higher HCO3−, PCO2 versus placebo. During exercise, a significant pH decrease and greater HCO3− continued until 240-watts work rate in HCP. The VE was significantly lower in HCP versus placebo, but HCP did not affect the gas exchange status of VCO2 or oxygen uptake (VO2). HCP increased absolute values of deoxy[Hb + Mb] at the RF but not VL. Thus, HCP-induced hypoventilation would lead to lower pH and secondarily impaired balance between O2 delivery and utilization in the local RF during exercise, suggesting that HCP supplementation, which increases the at-rest antioxidant potential, affects the lower ventilation and pH status during incremental exercise. HPC induced a significantly lower O2 delivery/utilization ratio in the RF but not the VL, which may be because these regions possess inherently different vascular/metabolic control properties, perhaps related to fiber-type composition.

This work focuses on the support effect on the performances of Co-based catalysts for the acetic acid steam reforming. SBA-15, a well ordered hexagonal mesoporous silica structure, and CeO2 have been selected as the supports, with the impact of chromium addition also being investigated. Better acetic acid steam reforming performances have been recorded for CeO2 compared to SBA-15 supported catalysts and, in particular, the 7Co/CeO2 catalyst showed the highest values of acetic acid conversions with enhanced H2 yields below 480°C, in comparison to the other investigated catalytic formulations. In addition, more pronounced coke depositions and acetone concentrations have been obtained with CeO2 supported catalysts, due to the tendency of ceria to catalyse the ketonization reaction. Chromium addition to Co/SBA-15 catalysts led to an enhancement in the activity towards acetic acid steam reforming, while on CeO2 supported catalysts no improvement in the catalysts activity was observed; however, on both SBA-15 and CeO2 supported catalysts, Cr addition reduced the amount of coke deposited on the catalysts surface.

Covid-19 pandemic lockdown has slow down the world economic system. The pandemic has cleared the roads, close factories and grounded planes causing severe economic challenges. The damaging impact of the pandemic amid lockdown has been a blessing in guise for the environment because of significant drop in pollution level as transport and industrial sectors shutdown. Transport and industrial sectors are major contributors to environmental degradation through various emissions as a result of fossil fuel consumption. Energy consumed by transport and industrial sectors will have to shift to viable, readily available, economically and environmentally friendly with no carbon build up post Covid-19 pandemic. Hydrogen energy remains the best alternative option technologies containing green house gas emission and pollutions of several forms. Hydrogen holds the potential to provide a clean, reliable, renewable and economical source of energy for meeting the growing and unending global energy needs post pandemic. The present paper explores the economic feasibility and potential of hydrogen to serve as a competitive fuel option post pandemic. In this paper, the role of hydrogen as an energy carrier hydrogen economy structure, potential of hydrogen economy, hydrogen production methods, hydrogen application and the economic and environmental importance of hydrogen as a viable fuel option post covid-19 pandemic were discussed. There will be a surge in demand and investment for hydrogen economy post Covid-19.

Production and transport of reactive species through plasma-liquid interactions plays a significant role in multiple applications in biomedicine, environment, and agriculture. We experimentally investigated the transport mechanisms of hydrogen peroxide H2O2 and ozone O3, as the typical plasma species, into water. We measured the solvation of gaseous H2O2 and O3 in airflow into water bulk vs. electrosprayed microdroplets while changing the gas and water flow rates, applied voltage that determines the gas-liquid interface area, and treatment time. The solvation rate of H2O2 and O3 increased with the treatment time and the gas-liquid interface area. The total surface area of the electrosprayed microdroplets was larger than that of the bulk, but their lifetime was much shorter. We estimated that only microdroplets with diameters below ~ 40 µm could achieve the saturation by O3 during their lifetime, while the saturation by H2O2 was impossible due to its depletion from air. Besides the short-lived flying microdroplets, the longer-lived bottom microdroplets substantially contributed to H2O2 and O3 solvation in water electrospray. This study contributes to a better understanding of the gaseous H2O2 and O3 transport into water as a function of different parameters and will lead to design optimization of the plasma-liquid interaction systems.

This work communicates the connection of measured shadowgraphs from optically induced air breakdown with emission spectroscopy in selected gas mixtures. Laser-induced optical breakdown is generated using 850 mJ and 170 mJ, 6-ns pulses at a wavelength of 1064 nm, the shadowgraphs are recorded using time-delayed 5-ns pulses at a wavelength of 532 nm and a digital camera, and emission spectra are recorded for typically a dozen of discrete time-delays from optical breakdown by employing an intensified charge-coupled device. The symmetry of the breakdown event can be viewed as close-to spherical symmetry for time-delays of several 100 ns. Spectroscopic analysis explores well-above hypersonic expansion dynamics using primarily the diatomic molecule cyanide and atomic hydrogen emission spectroscopy. Analysis of the air breakdown and selected gas breakdown events permits the use of Abel inversion for inference of the expanding species distribution. Typically, species are prevalent at higher density near the hypersonically expanding shockwave, measured by tracing cyanide and a specific carbon atomic line. Overall, recorded air breakdown shadowgraphs are indicative of laser-plasma expansion in selected gas mixtures, and optical spectroscopy delivers analytical insight into plasma expansion phenomena.

Arylsulfatase and β-glucuronidase are two important enzymes in human, which play important role on dynamic equilibrium of steroidal estrogens. This work probably for the first time reported that hydrogen peroxide (H2O2), hypochlorite and peracetic acid (PAA) could effectively inhibit the activities of arylsulfatase and/or β-glucuronidase. The 50 percent of inhibitions (IC50) of H2O2, and PAA on arylsulfatase were found to be 142.90±9.00, 91.83±10.01, and 43.46±2.92 μM, respectively. The corresponding respective IC50 of hypochlorite and PAA on β-glucuronidase were 704.90±41.40 and 23.26±0.82 μM, while H2O2 showed no inhibition on β-glucuronidase. It was further revealed that the inhibition of hypochlorite on both arylsulfatase and β-glucuronidase was irreversible. On the contrary, the inhibition by H2O2 and PAA was reversible. Moreover, it was found that the inhibitions of arylsulfatase and/or β-glucuronidase by these three chemicals were pH-dependent, among which the inhibition by H2O2 was competitive and non-competitive for PAA. In general, H2O2 and hypochlorite can be endogenously produced in human, which suggested that the two compounds are potential endocrine disruption compounds (EDCs) as they can cause endocrine disruption via inhibition of arylsulfatase and β-glucuronidase. This work further indicated that any agent that can induce production of H2O2 or hypochlorite in human is potential EDC, which explains why some EDCs with very weak or no estrogenic potency can cause endocrine disruption that confirmed in epidemiological studies.

Specific aquaporins (AQP), called peroxyporins, play a relevant role in controlling H2O2 permeability and ensure reactive oxygen species wasting during oxidative stress. Another target involved in oxidative stress is the Sigma1 Receptor (S1R), since its activation is triggered by oxidative or endoplasmic reticulum stress. Herein we evaluated the effect of S1R modulators on AQP-dependent water permeability in the presence and in the absence of oxidative stress. Applying stopped-flow light scattering and fluorescent probe methods, water and hydrogen peroxide permeability in Hela cells have been studied. Results evidenced that S1R agonists can restore water permeability in heat-stressed cells and the co-administration with a S1R antagonist totally counteracted the ability to restore the water permeability. All compounds except one were able to counteract the oxidative stress of HeLa cells specifically knocked down for S1R. Taken together, our results support the hypothesis that the investigated compounds act as dual aquaporin and Sigma1 receptor (DAS) modulators. The finding that small molecules can modulate both AQP and S1R opens a new direction toward the identification of innovative drugs able to regulate cell survival during oxidative stress in pathologic conditions, like cancer and degenerative diseases.

This study evaluates the production of biohydrogen from agro industrial waste. The worldwide energy demand is increasing exponentially and the reserves of fossil fuels are depleting, the combustion of fossil fuels has the effect on environment because of CO2 emission. Hydrogen generation market size is forecast to cross 180 billion by 2024, according to a new research report by global market. For the production of biohydrogen. we had chosen groundnut shell as our source, using Tween80 as a surfactant we had undergone pre-treatment studies for (10min,20min,30min,40min,50min) we had estimated the content of cellulose, protein, carbohydrates at (1%,2%,3%,4%,5%) and obtained the optimum value in the form of graph. The production of hydrogen is done by using the rumen fluid of the cow and the quantity of the hydrogen produced by this process is identified by using the analytical instrument Gas Chromatography.

The study experimentally investigated a novel approach for producing hydrogen from methane cracking in dielectric barrier discharge catalytic plasma reactor using a nanocatalyst. Plasma-catalytic methane (CH4) cracking was undertaken in a dielectric barrier discharge (DBD) catalytic plasma reactor using Ni/MgAl2O4. The Ni/MgAl2O4 was synthesised through co-precipitation followed customised hydrothermal method. The physicochemical properties of the catalyst were examined using X-ray diffraction (XRD), scanning electron microscopy - energy dispersive X-ray spectrometry (SEM-EDX) and thermogravimetric analysis (TGA). The Ni/MgAl2O4 shows a porous structure spinel MgAl2O4 and thermal stability. In the catalytic-plasma methane cracking, the Ni/MgAl2O4 shows 80% of the maximum conversion of CH4 with H2 selectivity 75%. Furthermore, the stability of the catalyst was encouraging 16 hours with CH4 conversion above 75%, and the selectivity of H2 was above 70%. This is attributed to the synergistic effect of the catalyst and plasma. The plasma-catalytic CH4 cracking is a promising technology for the simultaneous H2 and carbon nanotubes (CNTs) production for energy storage applications.

There is a marked momentum towards the use of clean hydrogen energy as an alternative for fossil fuels. Renewable energies such as solar and wind are being used to generate hydrogen from the water hydrolysis process. Indeed, this approach stores renewable energies in the form of combustible hydrogen for other energy uses. The other alternative that could be economically more cost-effective at the current technology stage is to explore the natural “Hydrogen System” where the natural hydrogen is generated and accumulated within the earth system, the same that stands for a “Petroleum System”. The Discovery of a large accumulation of relatively pure natural hydrogen (H2) in Mali has triggered the opportunity of searching for natural hydrogen accumulations in other countries. The generation of hydrogen from a circular depression in Mali and some other countries is linked to the presence of geologically very old iron-rich basement rocks. Solid-liquid redox reactions between iron-rich minerals and groundwater that split water are a possible source of H2 in deep basement rocks. It is believed that the hydrogen degassing may be detected by surface topographic circular to sub-circular shallow depressions. Chemical processes such as dissolution by hydrogen are considered to play the main role in the formation of the circular depressions through preferential vertical hydrogen migration channel. Archean iron-rich Yilgarn Craton that covers a vast area of Western Australia (WA) contains abundant iron-rich mafic-ultramafic rocks. The craton reveals many surficial circular depressions visible through satellite images. The area has abundant fault systems and is blanketed with Eocene sedimentary rocks containing high-quality reservoir rocks. All these characteristics seem to provide most of the required elements, such as hydrogen source, migration pathway, and reservoir rock for a “Hydrogen System” in this area.

The beginnings of redox biology are recalled with special emphasis on formation, metabolism and function of reactive oxygen and nitrogen species in mammalian systems. The review covers the early history of heme peroxidases and the metabolism of hydrogen peroxide, the discovery of selenium as integral part of glutathione peroxidases, which expanded the scope of the field to other hydroperoxides including lipid hydroperoxide, the discovery of superoxide dismutases and superoxide radicals in biological systems and their role in host defense, tissue damage, metabolic regulation and signaling, the identification of the endothelial-derived relaxing factor as the nitrogen monoxide radical and its physiological and pathological implications. The article highlights the perception of hydrogen peroxide and other hydroperoxides as signaling molecules, which marks the beginning of the flourishing fields of redox regulation and redox signaling. Final comments describe the development of the redox language. In the 18th and 19th century, it was highly individualized and hard to translate into modern terminology. In the 20th century, the redox language co-developed with the chemical terminology and became clearer. More recently, the introduction and inflationary use of poorly defined terms has unfortunately impaired the understanding of redox events in biological systems.

Environmental impact associated with odor and gaseous emissions from animal manure is one of the challenges for communities, farmers, and regulatory agencies. Microbe-based manure additives treatments are marketed and used by farmers for mitigation of emissions. However, their performance is difficult to assess objectively. Thus, comprehensive, practical, and low-cost treatments are still in demand. We have been advancing such treatments based on physicochemical principles. The objective of this research was to test the effect of the surficial application of a thin layer (¼"; 6.3 mm) of biochar on the mitigation of gaseous emissions (as the percent reduction, % R) from swine manure. Two types of biochar were tested: highly alkaline and porous (HAP) biochar made from corn stover and red oak (RO), both with different pH and morphology. Three 30-day trials were conducted with a layer of HAP and RO (2.0 & 1.65 kg∙m^-2, respectively) applied on manure surface, and emissions of ammonia (NH₃), hydrogen sulfide (H₂S), greenhouse gases (GHG), and odorous volatile organic compounds (VOCs) were measured. The manure and biochar type and properties had an impact on the mitigation effect and its duration. RO significantly reduced NH₃ (19-39%) and p-cresol (66-78%). H₂S was mitigated (16~23%), but not significantly for all trials. Significant (66~78%) reductions for p-cresol were observed for all trials. The phenolic VOCs had relatively high % R in most trials but not significantly for all trials. HAP reduced NH₃ (4~21%) and H₂S (2~22%), but not significantly for all trials. Significant % R for p-cresol (91~97%) and skatole (74~95%) were observed for all trials. The % R for phenol and indole ranged from (60~99%) & (29~94%) but was not significant for all trials. The impact on GHGs, isobutyric acid, and the odor was mixed with some mitigation and generation effects. However, larger-scale experiments are needed to understand how biochar properties and the dose and frequency of application can be optimized to mitigate odor and gaseous emissions from swine manure. The lessons learned can also be applicable to surficial biochar treatment of gaseous emissions from other waste and area sources.

In light of the latest trends in global installed capacities, the importance of variable renewable energy sources (VRES) to future energy supply systems is evident. Despite this, the inherent intermittency of VRES remains an obstacle to their widespread adoption. Green hydrogen is often suggested as an energy carrier that can account for this in a sustainable manner. In the analysis, a robust European energy system in the context of 2050 and with 100% VRES energy supply is designed through an iterative minimal cost-optimization approach that ensures robust security of supply over 38 weather-year scenarios (1980-2017). The impact of spatial VRES variability is factored in by defining exclusive VRES groups within each optimization region and, from this, it can be seen that higher numbers of groups in each region offer cheap electricity generation locations to the optimizer and thus decrease the total annual cost of the system. Beyond this, the robust system design and impact of inter-annual variability is identified by iteratively combining the installed capacities of different system designs obtained by applying 38 historical weather years. The robust system design outlined here has significantly lower capacities in comparison to the maximum regional capacities obtained in the first round of optimization.

Korea Atomic Energy Research Institute (KAERI) established a multi-dimensional hydrogen analysis system to evaluate a hydrogen release, distribution, and combustion in the containment of a nuclear power plant using MAAP, GASFLOW, and COM3D. KAERI developed the COM3D analysis methodology on the basis of the COM3D validation results against the experiments of ENACCEF and THAI. The proposed analysis methodology accurately predicts the peak overpressure with an error range of approximately ±10% using the Kawanabe turbulent flame speed model. KAERI performed a hydrogen flame acceleration analysis using the multi-dimensional hydrogen analysis system for a severe accident initiated by a station blackout (SBO) under the assumption of 100% metal-water reaction in the reactor pressure vessel for evaluating an overpressure buildup in the Advanced Power Reactor 1400 MWe (APR1400). The COM3D calculation results using the established analysis methodology showed that the calculated peak pressure in the containment was much lower than the fracture pressure of the APR1400 containment. This calculation result may have resulted from a large air volume of the containment, a reduced hydrogen concentration owing to passive auto-catalytic recombiners installed in the containment, and a lot of stem presence during the hydrogen flame acceleration in the containment. Therefore, we can know that the current design of the APR1400 containment maintains its integrity when the flame acceleration occurs during the severe accident initiated by the SBO accident.

In this study, we report a detailed experimental and theoretical investigation of three glycols, namely ethane-1,2-diol, 2-methoxyethan-1-ol and 1,2-dimethoxy ethane. For the first time, the X-Ray spectra of the latter two liquids was measured at room temperature, and they were compared with the newly measured spectrum of ethane-1,2-diol. The experimental diffraction patterns were interpreted very satisfactorily with molecular dynamics calculations, and suggest that in liquid ethane-1,2-diol most molecules are found in gauche conformation, with intramolecular hydrogen bond between the two hydroxyl groups. Intramolecular H-bonds are established in the mono-alkylated diol, but the interaction is weaker. The EDXD study also evidences strong intermolecular hydrogen-bond interactions, with short O···O correlations in both systems, while longer methyl-methyl interactions are found in 1,2-dimethoxy ethane. X-Ray studies are complemented by micro Raman investigations at room temperature and at 80°C, that confirm the conformational analysis predicted by X-Ray experiments and simulations.

Semisolid casting can provide excellent castings, but the nature of the pore-forming mechanisms has not been properly clarified. In the current communication, it was suggested that hydrogen precipitated during slurry making might have a decisive role in the formation of both gas and shrinkage porosity. Intensive stirring at the end of the slurry making process may act as a degassing step. Without the intense stirring, structures of primary slurry particles form around the hydrogen pores, strongly affecting pore formation and feeding during the intensification stage.

The influence of distant London dispersion forces on the docking preference of alcohols of different size between the two lone electron pairs of the carbonyl group in pinacolone is explored by infrared spectroscopy of the OH stretching fundamental in supersonic jet expansions of 1:1 solvate complexes. Experimentally, no pronounced tendency of the alcohol to switch from the methyl to the bulkier tert-butyl side with increasing size is found. In all cases, methyl docking dominates by at least a factor of two, whereas DFT-optimized structures suggest a very close balance for the larger alcohols, once corrected by CCSD(T) relative electronic energies. Together with inconsistencies when switching from a C4 to a C5 alcohol, this points at deficiencies of the investigated B3LYP and in particular TPSS functionals even after dispersion correction, which cannot be blamed on zero point energy effects. The search for density functionals which describe the harmonic frequency shift, the structural change and the energy difference between the docking isomers of larger alcohols to unsymmetric ketones in a satisfactory way is open.

A brand-new approach to the understanding of breast cancer (BC) is urgently needed. In this contribution, the etiology, pathogenesis, and treatment of this disease is approached from the new pH-centric anticancer paradigm. Only this Unitarian perspective based upon that the hydrogen ion (H+) dynamics of cancer, allows understanding and integrating the many dualisms, confusions, and paradoxes of the disease. The new H+-related wide range model can embrace under a unique frame of mind the many aspects of the disease and at the same time therapeutically interfere with most, if not with all, the hallmarks of cancer known to date. The pH-related armamentarium available for the treatment of BC here reviewed may be beneficial for all types and stages of the disease. In this vein, we have attempted a mega synthesis of traditional and new knowledge in the different areas of breast cancer research and treatment based upon the wide range approach afforded by the hydrogen ion dynamics of cancer. The concerted utilization of a pH-related drugs nowadays available for the treatment of breast cancer is advanced.

Susceptibility of four blood orange cultivars (‘Moro’, ‘Tarocco’, ‘Sanguinello’ and ‘Sanguine’) to chilling injury (CI) was studied. Antioxidant enzymes, physiological and biochemical changes were measured monthly at 2 and 5 °C plus 2 days at 20 °C for shelf life. At 2 °C, CI symptoms were higher than at 5 °C, and ‘Moro’ and ‘Tarocco’ had significantly higher CI than ‘Sanguinello’ and ‘Sanguine’. ‘Moro’ and ‘Tarocco’ had the highest electrolyte leakage, malondialdehyde, H2O2 and polyphenol oxidase activity and lower phenylalanine ammonia-lyase compared with ‘Sanguinello’ and ‘Sanguine’. The scanning electron microscopy micrographs revealed that ‘Moro’ and ‘Taroco’ showed severe fractures in the flavedo due to CI. ‘Sanguinello’ and ‘Sanguine’ were more tolerant to CI due to an increase of catalase, ascorbate peroxidase and superoxide dismutase, which could prevent the loss of membrane integrity and alleviate CI symptoms. The order of susceptibility of cultivars to CI was ‘Moro’> ‘Tarocco’> ‘Sanguine’> ‘Sanguinello’.

A super-porous hybrid platform can offer significantly increased number of reaction sites for the analytes and thus can offer advantages in the biosensor applications. In this work, a significantly improved sensitivity and selectivity of hydrogen peroxide (H2O2) cancer sensor is demonstrated by a super-porous hybrid CuO/Pt NP platform. The super-porous hybrid platform is fabricated by a physiochemical approach combining the physical vapor deposition of Pt NPs and electrochemical deposition of super-porous CuO structures by adopting a dynamic hydrogen bubble technique. Under an optimized condition, the hybrid CuO/Pt biosensor demonstrates a very high sensitivity of 2,205 µA/mM∙cm2 and a low limit of detection (LOD) of 140 nM with a wide range of H2O2 detection. This is meaningfully improved performance as compared to the CuO-based H2O2 sensors as well as to the previously reported metal oxide based H2O2 sensors. The hybrid CuO/Pt platform exhibits excellent selectivity against other interfering molecules such as glucose, fructose, dopamine, and ascorbic acid. Due to the synergetic effect of highly porous CuO structures and underlying Pt NPs, the CuO/Pt architecture offers extremely abundant active sites for the H2O2 reduction and electron transfer pathways.

Abstract: The biological process of photosynthesis was critical in catalyzing the oxygenation of Earth’s atmosphere 2.5 billion years ago, changing the course of development of life on Earth. Recently, the fields of applied and synthetic photosynthesis have utilized the light-driven protein-pigment supercomplexes central to photosynthesis for the photocatalytic production of fuel and other various valuable products. The reaction center Photosystem I is of particular interest in applied photosynthesis due to its high stability post-purification, non-geopolitical limitation, and its ability to generate the greatest reducing power found in Nature. These remarkable properties have been harnessed for the photocatalytic production of a number of valuable products in the applied photosynthesis research field. These primarily include photocurrents and molecular hydrogen as fuels. The use of artificial reaction centers to generate substrates and reducing equivalents to drive non-photoactive enzymes for valuable product generation has been a long-standing area of interest of the synthetic photosynthesis research field. In this review, we cover advances in these areas and further speculate synthetic and applied photosynthesis as photocatalysts for the generation of valuable products.

The KID (Koopmans in DFT) procedure usually applies in organic molecules of the closed–shell type. We used the KID procedure in an open–shell system for the first time to choose the most suitable density functional to compute global and local reactivity descriptors coming from the Conceptual Density–Functional Theory. From a set of 18 density functionals spread from the second until the fourth rung of the Jacob’s ladder: BP86, B97-D, BLYP, CAM-B3LYP, M06-L, M11-L, MN12-L, B3LYP, PBE0, N12-SX, M06-2X, M11, MN12-SX, CAM-B3LYP, LC-ωHPBE, ωB97X-D, APFD, MN15 and MN15-L, we concluded that CAM-B3LYP provides the best outcome.

Hydrogen gas is seeping from the sedimentary basin of São Franciso, Brazil. The seepages of H₂ are accompanied by helium whose isotopes reveal a strong crustal signature. Geophysical data indicates that this intra-cratonic basin is characterized by i) a relatively high geothermal gradient, ii) deep faults delineating a horst and graben structure and affecting the entire sedimentary sequence, iii) an archean to paleoproterozoïc basements enriched in radiogenic elements and displaying mafic and ultramafic units, and iv) a possible karstic reservoir located 400 m below the surface. The high geothermal gradient could be due to a thin lithosphere enriched in radiogenic elements, which can also contribute to a massive radiolysis process of water at depth, releasing an important amount of H₂. Alternatively, ultramafic rocks that may have generated H₂ during their serpentinization are also documented in the basement. The seismic profiles show that the faults seen at the surface are deeply rooted in the basement, and can drain deep fluids to shallow depths in a short time scale. The carbonate reservoirs within the Bambuí group which forms the main part of the sedimentary layers are crossed by the fault system and represent good candidates for temporary H₂ accumulation zones. The formation by chemical dissolution of sinkholes located at 400 m depth might explain the presence of sub-circular depressions seen at the surface. These sinkholes might control the migration of gas from temporary storage reservoirs in the upper layer of the Bambuí formation to the surface. The very high fluxes of H₂ escaping out of these structures which have been recently documented are, however, in disagreement with the newly developed H₂ production model in the Precambrian continental crust. They either question the validity of these models or the measurement methodology.

With the decline in fossil fuels, hydrogen-based alternatives provide a reliable and clean source for sustainable energy generation. In these endeavors, photochemical splitting for hydrogen production through tandem cells has been the source of much theoretical and experimental research in science. Much focus has been placed on interfacial band gap engineering as one of the most promising routes in the generation of hydrogen.This present work explores sputtering of n-silicon to form the active electrode in a n-Si | n-TiO₂ tandem cell and investigates the effect of variations in sputtering and post sputtering treatment parameters (rapid thermal annealing and long cycle annealing) for successful deposition of crystalline Silicon. The samples were successfully characterized via Raman Spectroscopy, X-ray Diffraction and Optical Transmission Spectroscopy to ascertain prevalent crystalline order and optical band gap, under different sputtering and post-sputtering conditions. Relevant conclusions were drawn to ascertain the best possible deposition parameters of n-Si for photocatalytic water splitting.

For some decades, the scientific community has been looking for alternatives to the use of fossil fuels that allow the planet's sustainable and environmentally friendly development. To do this, attempts have been made to mimic some processes that occur in nature, among which the photosystem-II stands out, which allows water splitting operating with different steps to generate oxygen and hydrogen. This research presents promising results using synthetic catalysts, which try to simulate some natural processes, and which are based on Au@ZnO-graphene compounds. These catalysts were prepared by incorporating different amounts of gold nanoparticles (1 wt.%, 3 wt.%, 5 wt.%, 10 wt.%) and graphene (1 wt.%) on the surface of synthesized zinc oxide nanowires (ZnO NWs), and zinc oxide nanoparticles (ZnO NPs), along with a commercial form (commercial ZnO) for comparison purposes. The highest amount of hydrogen (1,127 µmol/hg) was reported by ZnO NWs with a gold and graphene loadings of 10 wt.% and 1 wt.%, respectively, under irradiation at 400 nm. Quantities of 759 µmol / hg and 709 µmol / hg were obtained with catalysts based on ZnO NPs and commercial ZnO, respectively. The photocatalytic activity of all composites increased with respect to the bare semiconductors, being 2.5 times higher in ZnO NWs, 8.8 times for ZnO NPs and 7.5 times for commercial ZnO. The high photocatalytic activity of the catalysts is attributed, mainly, to the synergism between the different amount of gold and graphene incorporated, and the surface area of the composites.

Hydrogenases are iron-sulfur enzymes that catalyze proton reduction and H₂ oxidation with outstanding efficiency. They are considered blueprints for the design of transition metal complexes, e.g. as heterogenous catalysts in the context of H₂ production from water. Moreover, hydrogenases are biological model systems for metal hydride chemistry and proton-coupled electron transfer. Depending on the composition of the active site cofactor, [NiFe]-hydrogenases are distinguished from [FeFe]-hydrogenases. The former binds a hetero bimetallic nickel/iron site, embedded in the protein by four cysteine ligands. The later, by contrast, carries a homo bimetallic iron/iron site attached to the protein by only a single cysteine. Carbon monoxide and cyanide ligands (CO/CN) at the active site facilitated detailed investigations of hydrogenase catalysis by infrared spectroscopy, owing to strong signals and redox-dependent frequency shifts. However, the details of proton transfer have not been addressed experimentally.We found that specific redox state transitions in [NiFe]- and [FeFe]-hydrogenase can be triggered by visible light to record extremely sensitive ‘light-minus-dark’ infrared difference spectra monitoring key amino acid residues as shown in the ToC figure. As these transitions are coupled to protonation changes, our data allowed investigating dynamic hydrogen-bonding changes that go well beyond the resolution of protein crystallography. In [NiFe]-hydrogenase, photolysis of the bridging hydride ligand in the ‘Ni-C’ state was followed by rapid accumulation of the ‘Ni-SI_a’ state and/or ‘Ni-L’ state. Infrared difference spectra in various isotopic media clearly indicated the formation of a protonated cysteine residue as well as hydrogen-bonding changes involving the COOH group of a glutamic acid residue and a ‘dangling water’ molecule. These findings are in excellent agreement with crystallographic analyses of [NiFe]-hydrogenase in the Ni-R state and allowed devising a molecular precise model of catalytic proton transfer. In [FeFe]-hydrogenase, an external redox dye was used to accumulate the ‘Hred’ state over the oxidized resting state ‘Hox’. Infrared difference spectra of wild-type enzyme and numerous amino acid variants indicated hydrogen-bonding changes involving the COOH groups of two glutamic acid residues. Moreover, we noted the deprotonation of an arginine residue. Crystallographic analyses of [FeFe]-hydrogenase in the Hox state failed to explain the rapid proton transfer due to a ‘breach’ in the succession of residues. To this end, our findings facilitated a molecular precise model of ‘discontinued’ proton transfer.The comparison of catalytic proton transfer in bimetallic hydrogenases emphasizes the role of the outer coordination sphere. We suggest that the stable protonation of a nickel-ligating cysteine in [NiFe]-hydrogenase has a crucial influence on the preferred direction of proton flow and catalysis (i.e., H₂ oxidation). On the contrary, proton transfer in [FeFe]-hydrogenase involves an adjacent cysteine as a relay group that promotes both proton release and proton uptake. We presume that this causes the notable bidirectionality of [FeFe]-hydrogenase. These observations must guide the design of biomimetic compounds for the production or consumption of H₂.

Hydrogen sulfide and ammonia are always a concern in the livestock industries, especially when farmers try to clear their manure storage pits. Agitation of manure can cause dangerously high concentrations of harmful agents such as H₂S and NH₃ to be emitted into the air. Biochar has the ability to sorb these gases. We hypothesized that applying biochar on top of manure can create an effective barrier to protect farmers and animals from exposure to NH₃ and H₂S. In this study, two kinds of biochar were tested, highly alkaline, and porous (HAP, pH 9.2) biochar made from corn stover and red oak biochar (RO, pH 7.5). Two scenarios of (6 mm) 0.25” and (12 mm) 0.5” thick layers of biochar treatments were topically applied to the manure and tested on a pilot-scale setup, simulating a deep pit storage. Each setup experienced 3-min of agitation using a transfer pump, and measurements of the concentrations of NH₃ and H₂S were taken in real-time and measured until the concentration stabilized after the sharp increase in concentration due to agitation. The results were compared with the control in the following 3 situations: 1. The maximum (peak) flux 2. Total emission from the start of agitation until the concentration stabilized, and 3. The total emission during the 3 min of agitation. For NH₃, 0.5” HAP biochar treatment significantly (p<0.05) reduced maximum flux by 63.3%, overall total emission by 70%, and total emissions during the 3-min agitation by 85.2%; 0.25” HAP biochar treatment significantly (p<0.05) reduced maximum flux by 75.7%, overall, total emission by 74.5%, and total emissions during the 3-min agitation by 77.8%. 0.5” RO biochar treatment significantly reduced max by 8.8%, overall total emission by 52.9%, and total emission during 3-min agitation by 56.8%; 0.25” RO biochar treatment significantly reduced max by 61.3%, overall total emission by 86.1%, and total emission during 3-min agitation by 62.7%. For H₂S, 0.5” HAP biochar treatment reduced the max by 42.5% (p=0.125), overall total emission by 17.9% (p=0.290), and significantly reduced the total emission during 3-min agitation by 70.4%; 0.25” HAP treatment reduced max by 60.6% (p=0.058), and significantly reduced overall and 3-min agitation’s total emission by 64.4% and 66.6%, respectively. 0.5” RO biochar treatment reduce the max flux by 23.6% (p=0.145), and significantly reduced overall and 3-min total emission by 39.3% and 62.4%, respectively; 0.25” RO treatment significantly reduced the max flux by 63%, overall total emission by 84.7%, and total emission during 3-min agitation by 67.4%.

Even 20 years after the first crystal structures of [FeFe]-hydrogenase have been published, several aspects of biological hydrogen turnover are heatedly discussed. In this perspective, we give an overview on how the diversity of naturally occurring and artificially prepared, semi-synthetic [FeFe]-hydrogenases deepens our understanding of hydrogenase chemistry. In parallel, we cover new results from biophysical techniques that go beyond the scope of conventional electrochemistry, X-ray diffraction, EPR, and FTIR spectroscopy. Taking into account both proton transfer and electron transfer as well as the notorious sensitivity of [FeFe]-hydrogenases towards carbon monoxide, the discussion further touches upon the molecular proceedings of biological hydrogen turnover.

Based on detection of elliptic particle tracks, $\simeq 137^2 n^2$ bigger than Bohr-Sommerfeld electron orbits, indicating the possible detection of superluminal electrons masquerading as magnetic monopoles, a new structure emerges leading to: (i) a new set of seven elementary lengths; (ii) replacement of the usual motion (Lorentz) transformations by scale transformations between $v^2<c^2$ and $v^2>c^2$ frames; (iii) equivalence of charge between $v^2<c^2$ and $v^2>c^2$ frames based on the Dirac-Schwinger quantization condition; (iv) a relativistic foundation for the Dirac-Schwinger quantization condition; (v) a possible cause of charge quantization; and (vi) the prospect of symmetry in Maxwell's equations. If the elliptic particle tracks are viewed as a magnification of electron orbits, the effect is suggestive of a spacetime distortion such as those predicted in general relativistic theories.

Durability and performance of electrochemical energy converters such as fuel cells and electrolysers are not only dependent on the properties and the quality of the used materials. They strongly depend on operation conditions. Variations in external parameters, such as flow, pressure, temperature and, obviously, load can lead to significant local changes of current density, even local transients. The segmented cell technology was developed with the purpose to gain insight into local operation conditions in electrochemical cells, during operation. The operando measurement of the local current density and temperature distribution allows effective improvement of operation conditions, mitigation of potentially critical events and assessment of the performance of new materials. The segmented cell, which can replace a regular bipolar plate in the current state of the technology, can be used as monitoring tool and for targeted developments. This article gives an overview over the development and applications for proton exchange membrane fuel cell of this technology, such as water management or fault recognition. Recent advancements towards locally resolved monitoring of humidity and to current distributions in electrolysers are outlined.

The purpose of this study is to check out the involvement of entropy in Mpemba effect. Provided that preheating of the water the cooling duration is reduced, we theoretically show that water gains more entropy when warmed and re-cooled to the original temperature.

Hydrogen evolution reaction (HER) is one of the most important reaction in electrochemistry. This is not only because it is the simplest way to produce high purity hydrogen and the fact that it is the side reaction in many other technologies. HER actually shaped current electrochemistry because it was in focus of active research for so many years (and it still is). The number of catalysts investigated for HER is immense, and it is impossible to overview them all. In fact, it seems that the complexity of the field overcomes the complexity of HER. The aim of this review is to point out some of the latest developments in HER catalysis, current directions and some of the missing links between a single crystal, nanosized supported catalysts and, recently emerging, single atom catalysts for HER

The present study focuses on the synthesis, characterization, and investigation of a p-n heterojunction photocatalysis. Titanium dioxide (TiO2) can’t alone induce the photocatalytic water splitting due to its wide bandgap, which decreases its catalytic activity in the visible light. To make redshift of absorptivity for the TiO2, Nickel (Ni)-doped Graphene (rGO) supported TiO2 was synthesized. Several characterization techniques have been employed to validate the composition and the light absorption ability of the prepared photocatalysts including TEM, SEM, EDS, XRD, XPS, and UV-Vis spectroscopy. The characterization revealed successful doping of the Ni and TiO2 on the rGO nanosheet. Moreover, the UV-Vis spectroscopy indicated a significant shift of light absorption toward the visible spectrum. The photon-induced evolution of H2 was remarkably enhanced using the prepared Ni-rGO/TiO2 nanocomposite. Furthermore, the optimum ratio of rGO: TiO2: Ni in the hybrids was 10:1:4, while the higher Ni ratio would decrease the photocatalytic activity. The stability of the photocatalyst was also verified during 8 cycles of photocatalytic reactions. The kinetic study revealed the nature of the integrated reaction and the controlling step governing the reaction sequence. .

The threats of climate change and the sustainable supply of clean energy are global challenges that require an international approach to the energy supply. Utilizing the wind and solar energy potential of regions where these renewable sources are especially viable to produce hydrogen by means of water electrolysis represents an attractive option to counter the above-mentioned challenges. Within the scope of this techno economic analysis of a worldwide hydrogen supply infrastructure based on renewable energy, selected regions are assessed on the basis of their wind or solar energy potential. In contrast to established analyses of hydrogen infrastructures, this paper introduces a worldwide allocation approach to the supply hydrogen from strong wind and solar regions to different demand regions on the premise of a global supply cost minimum. The allocation results show a significant dependence of hydrogen export volumes and the oversea transport distances of potential trading partners. Hence, the transnational trading flows of hydrogen derived from wind and solar energy are concentrated in continental regions.

Replacing carbon by hydrogen is a huge step towards reducing CO₂ emissions in the iron- and steel-making industry. The reduction of iron oxides using hydrogen plasma smelting reduction as an alternative to conventional steel-making routes has been studied at Montanuniversitaet Leoben, Austria. The aim of this work was to study the slag formation during the reduction process and the reduction behaviour of iron oxides. Furthermore, the reduction behaviour of iron ore during continuous feeding was assessed. Mixtures of iron ore and calcined lime with a basicity of 0, 0.8, 1.6, 2.3, and 2.9 were melted and reduced by hydrogen. The off-gas composition was measured during the operations to calculate the process parameters. The reduction parameters, namely the degree of reduction, degree of hydrogen utilisation, produced iron, and slag, are presented. The results of the batch-charged experiments showed that at the beginning of the reduction process, the degree of hydrogen utilisation was high, and then, it decreased over the operation time. In contrast, during the continuous-feeding experiment, the degree of hydrogen utilisation could be kept approximately constant. The highest degrees of reduction and hydrogen utilisation were obtained upon the application of a slag with a basicity of 2.3. The experiment showed that upon the continuous feeding of iron ore, the best conditions for the reduction process using hydrogen could be applied.

With a relatively small population, Russia accesses huge oil, natural gas, coal and uranium resources, and hosts advanced nuclear energy, oil and natural gas industries. However, the combined effect of today’s low cost electricity generation via photovoltaic modules, water and wind turbines and similarly low cost storage in Li-ion battery and solar hydrogen obtained via water electrolysis will have a profound impact on Russia’s energy and automotive industries.

Three-dimensional structure of six closely related hydrogenases from purple bacteria has been modeled by combining template-based and ab initio modeling approach. The results lead to conclusion that there should be 4Fe3S-cluster in the structure of these enzymes. Thus, these hydrogenases could drive attention for exploring their oxygen tolerance and practical applicability in hydrogen fuel cells. Analysis of 4Fe3S-cluster's microenvironment showed intragroup heterogeneity. Possible function of the C-terminal part of the small subunit in membrane binding has been discussed. Comparison of the built models with existing hydrogenases of the same subgroup (membrane-bound oxygen-tolerant hydrogenases) has been carried out. Analysis of intramolecular interactions in the large subunits showed statistically reliable differences in number of hydrophobic interactions and number of ionic interactions. Molecular tunnels were mapped in the models and compared with structures from PDB. Protein-protein docking showed that these enzymes could exchange electrons in oligomeric state, which is important for oxygen-tolerant hydrogenases. Molecular docking with model electrode compounds showed mostly the same results as with hydrogenases from E.coli, H. marinus, R. eutropha, S. enterica; some interesting results were shown in case of HupSL from Rba. sphaeroides and Rvx. gelatinosus.

In this paper we review dynamics and roughness of bonds in proteins on example of albumin, that is important from the physiological point of view. We have performed computer simulations of albumin chain. Statistics were collected by performing many simulations realizations for each experimental setting. We concentrate on hydrogen bonds, cation-π and π- π interactions and NP contacts. Histograms of hydrogen bonds length are positively skewed in contrary to histograms of interactions and HP contacts that are negatively skewed. Scaling exponents of power spectra of energies of bonds / interactions /contacts are in range -0.2 to -0.5 and significantly differ between various hydrogen bonds or interactions. Varying scaling of such spectra can be used to classify between distinct bonds or contacts. Concerning particular amino-acids, largest amount of HBO H20 bonds are between Glutamate (GLU) amino-acids and water particle, while large amount of HBO bonds are formed with Lysine (LYS). For HP contacts the mayor role plays Phenylalanine (PHE) and Leucine (LEU) amino-acids. From decay curves HBO H2O bonds decays in fastest rate, while HBO bonds and HP contacts at slowest rate. We present as well decay curves of bonds formed by particular amino-acids, that gives interesting results.

Despite all efforts, the treatment of breast cancer (BC) cannot be considered to be a success story. The advances in surgery, chemotherapy and radiotherapy have not been sufficient. Indeed, the accumulated experience clearly indicates that new perspectives and non-main stream approaches are needed to better characterize the etiopathogenesis and treatment of this disease. This contibution deals with how the new pH-centric anticancer paradigm plays a fundamental role in reaching a more integral understanding of the etiology, etiopathogenesis and treatment of this multifactorial disease. For the first time the armamentarium available for the treatment of the different types and phases of BC is approached here from a Unitarian perspective based upon the hydrogen ion dynamics of cancer. The wide-ranged pH-related molecular, biochemical and metabolic model is able to embrace most the fields and subfields of breast cancer pathology. This single and integrated approach allows to advance a unidirectional program to treatment. Further efforts in this line are likely to first improve the therapeutics of each subtype of this tumor, then every phase of the disease and finally every individual patient.

As a dominant mangrove species, Kandelia obovata is distributed in an intertidal marsh with an active H₂S release. Whether H₂S participates in the salt tolerance of mangrove plant is still ambiguous although increasing evidence have demonstrated that H₂S functions in plant responses to multiple abiotic stresses. In this study, as an H₂S donor, NaHS was used to investigate the regulatory mechanism of H₂S on salt tolerance of K. obovata seedlings using a combined physiological and proteomic analysis. The results showed that the reduction in photosynthesis (Pn) caused by 400 mM NaCl was recovered by the addition of NaHS (200 μM). Furthermore, the application of H₂S enhanced the quantum efficiency of PSII and the membrane lipid stability, implying that H₂S is beneficial to the survival of K. obovata seedlings under high salinity. We further identified 37 differentially expressed proteins by proteomic approaches under salinity and NaHS treatment. Among them, the proteins related to photosynthesis, primary metabolism, stress response and hormone biosynthesis were primarily enriched. The physiological and proteomic results highlighted that exogenous H₂S up-regulated photosynthesis and energy metabolism to help K. obovata to cope with high salinity. Specifically, H₂S increased photosynthetic electron transfer, chlorophyll biosynthesis and carbon fixation in K. obovata leaves under salt stress. Furthermore, the abundances of other proteins related to metabolic pathway, such as antioxidation (APX, CSD2, PDX1), protein synthesis (HSP, Cpn 20), nitrogen metabolism (GS2, GS1:1), glycolysis (PGK, TPI), AsA-GSH cycle were increased by H₂S under high salinity. These findings provide new insights into the roles of H₂S in the adaptations of mangrove plant K. obovata to high salinity environment.

This research paper presents a new application of electroactive polyimide doped with gold nanoparticles (PI/AuNPs) as a chemiresistor sensor for detecting hydrogen sulfide gas. The synthesis of PI/AuNPs was done in a simple 3-step process of polymerization using the as prepared amine-capped aniline trimer (ACAT), followed by imidization, and doping. Spectral analyses via FTIR, LC-MS and ¹H-NMR confirmed the formation of amine-capped aniline trimer with a MW of 288 g mol^-1. Comparison of ACAT, BSAA, and PI FTIR spectra showed successful polymerization of the last, while XRD validated the incorporation of metal nanoparticles onto the polymer matrix showing characteristic diffraction peaks corresponding to gold. Furthermore, TEM, and FE-SEM revealed the presence of well-dispersed Au nanoparticles with an average diameter of about 60nm. The electroactive PI/AuNPs-based sensor showed a sensitivity of 0.29% ppm^-1 H₂S at a linear concentration range of 50 to 300 ppm H₂S (r = 0.9777). The theoretical limit of detection was found at 0.142 ppm or 142 ppb H₂S gas. The sensor provided a stable response reading at an average response time of 43±5 seconds, which was easily recovered after an average time of 99±5 seconds. The sensor response was highly repeatable and reversible with RSD values of 8.88%, and 8.60%, respectively. Compared with the performance of the conventional conducting polyaniline also doped with gold nanoparticles (PANI/AuNPs), the fabricated electroactive PI/AuNPs exhibited improved sensing performance making it a potential candidate in monitoring H₂S in the environment and for work-related safety.

In this paper, the columnar supramolecular aggregates of photosensitive star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core and azobenzene arms are analysed theoretically applying a combination of computer simulation techniques. Without a light stimulus, the trans-stars build one-dimensional columns of stacked molecules during the first stage of the noncovalent association. These columnar aggregates represent the structural elements of more complex experimentally observed morphologies -- fibers, spheres, gels and others. Upon UV light exposure, the azobenzene arms isomerise from thermodynamically stable planar trans- to a metastable kinked cis-state influencing the aggregate morphology. Here, we determine the most favourable mutual orientations of the \textit{trans}-stars in the stack in terms of (i) the pi-pi distance between the cores lengthwise the aggregate, (ii) the star slipped displacements and (iii) the rotation promoting the helical twist and chirality of the aggregate by calculating the binding energy diagrams using density functional theory. The model predictions are further compared with available experimental data. The intermolecular forces responsible for the stability of the stacks made of trans-azobenzene stars in crystals are quantified using Hirshfeld surface analysis. Finally, to characterize the self-assembly mechanism of such stars in solution, we calculate the hydrogen bond lengths, the normalized dipole moment and the binding energies as the functions of the columnar length using molecular dynamics trajectories, and conclude about the cooperative nature of this process.

In this study the processes taking place on the surfaces of nanostructurized Cu/CuO and Cu/CuO/Pd electrodes at different potential, $E$, values in the solutions of 0.1 M KOH in H$_2$O and D$_2$O (heavy water) were probed by the surface enhanced Raman spectroscopy (SERS) and analysis of electrochemical reactions occurring under experimental conditions is presented. Bands of the SERS spectra of Cu/CuO/Pd electrode observed in the range of $E$ values from +0.3~V to 0 V~(SHE) at 1328 - 1569~cm$^{-1}$ are consistent with the existence of species which are adsorbed or weakly bound to the surface with the energy of interaction close to 15 - 21~kJ mol$^{-1}$. These bands can be attributed to the ad(ab)sorbed (H$_3$O$^+$)$\rm{_{ad}}$, (H$_2^+$)$\rm{_{ab}}$ and (H$_2^+$)$\rm{_{ad}}$ ions as intermediates in reversible HER/HOR processes taking place on Cu/CuO/Pd electrode. There was no isotopic effect observed; this is consistent with a dipole nature of electron-ion pair formation of adsorbed (H$_3$O$^+$)$\rm{_{ad}}$ and (H$_2^+$)$\rm{_{ad}}$ or (D$_3$O$^+$)$\rm{_{ad}}$ and (D$_2^+$)$\rm{_{ad}}$. In accordance with literature data SERS bands at 125-146~cm$^{-1}$ and $\sim 520-565$~cm$^{-1}$ were assigned to Cu(I) and Cu(II) oxygen species. These findings corroborate the mechanism of cascading reduction of water.

Glucose-sensitive films were prepared by the layer-by-layer (LbL) deposition of poly(ethyleneimine) (H-PEI) solution and DNA solution (containing glucose oxidase (GOx)). H-PEI/DNA+GOx multilayer films were constructed using electrostatic interactions. The (H-PEI/DNA+GOx)5 film was then partially decomposed by hydrogen peroxide (H2O2). The mechanism for the decomposition of the LbL film was considered to involve a more reactive oxygen species (ROS) that was formed by the reaction of hemin and H2O2, which then caused nonspecific DNA cleavage. GOx present in the LbL films reacts with glucose to generate hydrogen peroxide. Therefore, decomposition of the H-PEI/DNA+GOx)5 film was observed when the thin film was immersed in a glucose solution. A (H-PEI/DNA+GOx)5 film exposed to a glucose solution for periods of 24, 48 72, and 96 h indicated decomposition of the film increased with the time. The rate of LbL film decomposition increased with the glucose concentration. At pH and ionic strength close to physiological conditions, it was possible to slowly decompose the LbL film at a sub-millimolar glucose concentration.

A laser-based hydrogen (H₂) sensor using wavelength modulation spectroscopy (WMS) was developed for contactless measurements of molecular hydrogen. The sensor uses a distributed feedback (DFB) laser to target the H₂ quadrupole absorption line at 2121.8 nm. The H₂ absorption line exhibits weak collisional broadening and strong collisional narrowing effects. Both effects were investigated by comparing measurements of the absorption linewidth with detailed models using different line profiles that include collisional narrowing effects. The collisional broadening and narrowing parameters were determined for pure hydrogen as well as for hydrogen in nitrogen and air. Performance of the sensor was evaluated and the sensor applicability for H₂ measurements in a range of 0- 10 %v of H₂ was demonstrated. A precision of 0.02 %v was achieved with 1 meter of absorption pathlength (0.02 %v∙m) and 1 s of integration time. For the optimum averaging time of 20 s a precision of 0.005 %v∙m was achieved. A good linear relationship between H₂ concentration and the sensor response was observed. A simple and robust transmitter-receiver configuration of the sensor allows in-situ installations in harsh industrial environments.

An amorphous silicon carbide (SiC) membrane with H2 permeance of 1.2E-7 mol･m^-2･s^-1･Pa^-1 and excellent H₂/CO₂ selectivity of 2600 at 673 K was successfully synthesized on a Ni-gamma-alumina-coated alpha-alumina porous support by counter diffusion chemical vapor deposition (CDCVD) using silacycrobutane (SCB) at 788 K. The dominant permeation mechanism for He and H₂ in the temperature range 323-673 K was activated diffusion. The SiC active layer was formed in Ni-gamma-Al₂O₃ intermediate layer. The thermal expansion coefficients mismatch between SiC active layer and Ni-gamma-Al₂O₃-coated alpha-Al₂O₃ porous support was eased by the low decomposition temperature of SiC source and membrane structure.

Graphite carbon nitride (g-C3N4) supported PtNi alloy nanoparticles (NPs) were fabricated via a facile and simple impregnation and chemical reduction method and explored their catalytic performance towards hydrogen evolution from ammonia borane (AB). Interestingly, the resultant Pt_0.5Ni₀.5/g-C₃N₄ catalyst affords superior performance, including 100% conversion, 100% H₂ selectivity, yielding the extraordinary initial total turnover frequency (TOF) of 250.8 mol_H2 min^-1 (mol_Pt)^-1 for hydrogen evolution from AB at 10 °C, a relatively low activation energy of 38.09 kJ mol⁻¹, and a remarkable reusability (at least 10 times), which surpass most of the noble metal heterogeneous catalysts. This notably improved activity is attributed to the charge interaction between PtNi NPs and g-C₃N₄ support. Especially, the nitrogen-containing functional groups on g-C₃N₄, serving as the anchoring sites for PtNi NPs, may be beneficial for becoming a uniform distribution and decreasing the particle size for the NPs. Our work not only provides a cost-effective route for constructing high-performance catalysts towards the hydrogen evolution of AB but also prompts the utilization of g-C₃N₄ in energy fields.

Honey is a complex sweet food stuff with well-established antimicrobial and antioxidant properties. It has been used for millennia in a variety of applications, but those most noteworthy include treatment of surface wounds, burns and inflammation. A variety of substances in honey have been suggested as the key component to its antimicrobial potential; polyphenolic compounds, hydrogen peroxide, methylglyoxal and bee-defensin 1. These components vary greatly across honey samples due to botanical origin, geographical location and the individual bee. The use of medical grade honey, Medihoney and Revamil, in the treatment of surface wounds and burns has been seen to improve the healing process, reduce healing time, reduce scarring and prevent microbial contamination. Therefore, medical grade honeys should be used for these treatments and reduce the demand for antibiotic usage. In this review, we aim to outline the constituents of honey and how they affect the antibiotic potential of honeys in a clinical setting.

Photoelectrochemical systems have the potential to contribute to de-carbonation of the energy system because solar energy can be directly converted to hydrogen which can be burnt without the release of greenhouse gases. However, meaningful deployment of photoelectrochemical (PEC) technology in the global energy system, even when highly efficient scaled up devices become available, shall only be a reality when their safe and reliable operation can be guaranteed over serveral years of service life. The first part of the review discusses the importance of hermetic sealing of up scaled PEC device provided by the casing and sealing joints from a reliability and risk perspective. The second part of the review presents a survey of fully functional devices and early demonstrators and uses this to establish the extent to which the state of the art in PEC device design address the issue of hermetic sealing. The survey revealed that current material choices and sealing techniques are still unsuitable for scale –up and commercialization. Accordingly, we examined possible synergies with related photovoltaic and electrochemical devices that have been commericalised and derived therefrom, recommendations for future research routes that could accelerate the development of hermetic sealings of PEC devices.

Background: Catalase is a vital antioxidant enzyme that dismutates H₂O₂ into water and molecular oxygen. Many protocols have been developed to measure catalase enzyme activity. Spectrophotometric methods are the most common assays that used to assess catalase enzyme activity. Methods: Because the rate-limiting step during catalase enzyme activity depends upon the dissociation of hydrogen peroxide, the developed assay measures the reaction between a hydroquinone/anilinium sulfate/ammonium molybdate reagent and Unreacted Hydrogen Peroxide, which results in the production of a purple, disubstituted quinone compound with a maximum absorbance value at 550 nm. Results: To clarify the precision of the developed method, the coefficients of variation were determined to be 2.6% and 4.7% for within run measurements and between run measurements, respectively. This method returned results that correlated well (r = 0.9982) with the results returned using the peroxovanadate method to assess catalase enzyme activity. Additionally, we examined the use of the newly developed hydroquinone assay to measure catalase enzyme activity in liver and bacterial homogenate samples. Conclusion: These results demonstrated that this assay can be used for scientific research and routine health applications because it is inexpensive, simple, accurate, and rapid. This method is suitable for use in clinical pathology laboratories because it is simple and produces precise and reproducible results.

The role of hydrogen in a future energy system with a high share of variable renewable energy sources (VRES) is regarded as crucial in order to balance fluctuations in electricity generation. These fluctuations can be compensated for by flexibility measures such as the expansion of transmission, flexible generation, larger back-up capacity and storage. Salt cavern storage is the most promising technology due to its large storage capacity, followed by pumped hydro storage. For the underground storage of chemical energy carriers such as hydrogen, salt caverns offer the most promising option owing to their low investment cost, high sealing potential and low cushion gas requirement. This paper provides a suitability assessment of European subsurface salt structures in terms of size, land eligibility and storage capacity. Two distinct cavern volumes of 500,000 m³ and 750,000 m³ are considered, with preference being given for salt caverns over bedded salt deposits and salt domes. The storage capacities of individual caverns are estimated on the basis of thermodynamic considerations based on site-specific data. The results are analyzed using three different scenarios: onshore and offshore salt caverns, only onshore salt caverns and only onshore caverns within 50 km of the shore. The overall technical storage potential across Europe is estimated at 84.8 PWh_H2, 27% of which constitutes only onshore locations. Furthermore, this capacity decreases to 7.3 PWh_H2 with a limitation of 50 km distance from shore. In all cases, Germany has the highest technical storage potential, with a value of 9.4 PWh_H2, located onshore only in salt domes in the north of the country. Moreover, Norway has 7.5 PWh_H2 of storage potential for offshore caverns, which are all located in the subsurface of the North Sea Basin.

The transition towards a renewable energy system is essential in order to reduce greenhouse gas emissions. The increase in the share of variable renewable energy sources (VRES), which mainly comprise wind and solar energy, necessitates storage technologies by which the intermittency of VRES can be compensated for. Although hydrogen has been envisioned to play a significant role as a promising alternative energy carrier in a future European VRES-based energy concept, the optimal design of this system remains uncertain. In this analysis, a hydrogen infrastructure is posited that would meet the electricity and hydrogen demand for a 100% renewable energy-based European energy system in the context of 2050. The overall system design is optimized by minimizing the total annual cost. Onshore and offshore wind energy, open-field photovoltaics (PV), rooftop PV and hydro energy, as well as biomass, are the technologies employed for electricity generation. The electricity generated is then either transmitted through the electrical grid or converted into hydrogen by means of electrolyzers and then distributed through hydrogen pipelines. Battery, hydrogen vessels and salt caverns are considered as potential storage technologies. In the case of a lull, stored hydrogen can be re-electrified to generate electricity to meet demand during that time period. For each location, eligible technologies are introduced, as well as their maximum capacity and hourly demand profiles, in order to build the optimization model. In addition, a generation time series for VRES has been exogenously derived for the model. The generation profiles of wind energy have been investigated in detail by considering future turbine designs with high spatial resolution. In terms of salt cavern storage, the technical potential for hydrogen storage is defined in the system as the maximum allowable capacity per region. Whether or not a technology is installed in a region, the hourly operation of these technologies, as well as the cost of each technology, are obtained within the optimization results. It is revealed that a 100 percent renewable energy system is feasible and would meet both electricity demand and hydrogen demand in Europe.

Reducing emissions from the iron and steel industry is essential to achieve the Paris climate goals. A new system to reduce the carbon footprint of steel production is proposed in this article by coupling hydrogen direct reduction of iron ore (H-DRI) and natural gas pyrolysis on liquid metal surface inside a bubble column reactor. If grid electricity from EU is used, the emissions would be 435 kg CO₂/tls without considering methane leakage from the extraction, storage and transport of natural gas. Solid carbon, produced as a by-product of natural gas decomposition, finds applications in many industrial sectors, including as a replacement for coal in coke ovens. Specific energy consumption (SEC) of the proposed system is approximately 6.3 MWh per ton of liquid steel(tls). It is higher than other competing technologies, 3.48 MWh/tls for water electrolysis based DRI, and, 4.3-4.5 MWh/tls for natural gas based DRI and blast furnace-basic oxygen furnace (BF-BOF) respectively. Utilization of large quantities of natural gas, where the carbon remains unused, is the major reason for high SEC. Preliminary analysis of the system revealed that it has the potential to compete with existing technologies to produce CO₂ free steel, if renewable electricity is used. Further studies on the kinetics of the bubble column reactor, H-DRI shaft furnace, design and sizing of components, along with building of industrial prototypes are required to improve the understanding of the system performance.

Satterthwaite and Toepke (1970 Phys. Rev. Lett. 25 741) discovered that Th₄H₁₅-Th₄D₁₅ superhydrides exhibit superconductivity and have no isotope effect. The latter is fundamental contradiction with the concept of electron-phonon mediated superconductivity of Bardeen-Cooper-Schrieffer (BCS) theory. Soon after this work, Stritzker and Buckel (1972 Zeitschrift für Physik A Hadrons and nuclei 257 1-8) reported that superconductors in PdH_x-PdD_x system exhibit reverse isotope effect. Yussouff et al (1995 Solid State Communications 94 549) extended this finding on PdH_x-PdD_x-PdT_x system. Recent interest to hydrogen- and deuterium-rich superconductors is based on the discovery of near-room-temperature superconductivity in highly-compressed H₃S (Drozdov et al. 2015 Nature 525 73) and LaH₁₀ (Somayazulu et al 2019 Phys. Rev. Lett. 122 027001). To date, there is no clarity about isotope effect in H₃S-D₃S system, because thorough examination of available experimental data reported by Drozdov et al (2015 Nature 525 73) shows that H₃S-D₃S system perhaps has reverse isotope effect. In attempt to reaffirm/disprove our primary idea that the mechanism for near-room-temperature superconductivity in hydrogen-rich superconductors is not BCS electron-phonon interaction, we analyse the upper critical field data, B_c2(T), in Th₄H₁₅-Th₄D₁₅ phases (Satterthwaite and Toepke 1970 Phys. Rev. Lett. 25 741) and two recently discovered high-pressure hydrogen-rich phases of ThH₉ and ThH₁₀ (Semenok et al 2019 arXiv:1902.10206). As the result, it is found that all known to date thorium super-hydrides/deuterides are unconventional superconductors which have T_c/T_F ratios within a range of 0.008 < T_c/T_F < 0.120, where T_c is the superconducting transition temperature and T_F is the Fermi temperature.

In this paper, we consider the temporal development of the optical density of the H$_\alpha$ spectral line in a hydrogen laser induced plasma. This is achieved by using the so-called duplication method in which the spectral line is re-imaged onto itself and the ratio of the spectral line with it duplication is taken to its measurement without the duplication. We asses the temporal development of the self-absorption of the H$_\alpha$ line by tracking the decay of duplication ratio from its ideal value of 2. We show that when 20% loss is considered along the duplication optical path length, the ratio is 1.8 and decays to a value of 1.25 indicating an optically thin plasma grows in optical density to an optical depth of 1.16 by 400 ns in the plasma decay for plasma initiation conditions using Nd:YAG laser radiation at 120 mJ per pulse in a 1.11$\times10^{5}$ Pa hydrogen/nitrogen gas mixture environment. We also go on to correct the H$_\alpha$ line profiles for the self-absorption impact using two methods. We show that a method in which the optical depth is directly calculated from the duplication ratio is equivalent to standard methods of self-absorption correction when only relative corrections to spectral emissions are needed.

To achieve efficient and durable consolidation of weathered sandstone, the selection of a suitable consolidant is essential. To reasonably assess the suitability of different formulations, it is fundamental to compare their performance as a consolidant within a substrate, which reliably models the properties of deteriorated material. As a test substrate, the sandstone from quarries in Mšené in central Bohemia was selected, for its developed porosity and relatively low mechanical strength. To obtain relevant comparison of their application potential, both commercial (Remmers KSE OH and Surfapore) and self-developed consolidants were included. To test the long-term stability of each consolidant, the stone was subjected to accelerated weathering. The characterization of texture properties was based on the physical sorption of nitrogen and krypton, mercury intrusion porosimetry and water uptake. While the mechanical properties in microscale were determined by nanoindentation, the mechanical strength in macroscale before and after consolidation was measured by drilling resistance. Both commercial exhibited good mechanical performance with reasonable durability. The performance of our developed samples was comparable or, in some cases, superior. Very interesting were the consolidants containing TiO2 and ZnO nanoparticles, the former exhibiting comparable degree of consolidation and durability as commercial ones, with additional photocatalytic function, the latter unusually high increase in the mechanical strength, even after the weathering test. The diammonium hydrogen phosphate based consolidant showed exceptional durability in the weathering test, which makes it a promising product not only for carbonate but also sandstone materials.

The noble metals palladium and silver find use in many high performance applications, and their alloys (PdAg), known for more than sixty years, are industrially important, finding use in many fields including hydrogen purification and separation, numerous facets of catalysis, and in fuel cells. In recent years, interest in these materials has grown significantly, particularly in energy generating applications and due to their performance as solid-state chemical sensors for a range of small molecules. PdAg thin films can be prepared using traditional physical methods such as cold rolling, or more modern and controllable chemical or physical deposition techniques such as electrodeposition or chemical vapour deposition. Despite the wide-reaching uses of PdAg, several recent advancements in materials preparation, such as additive manufacturing, better known as 3-D printing, remain unexplored for this material due to the differing chemistries of the two elements. In this review, we explore the manufacturing methods commonly employed for the preparation of PdAg thin films, the common and niche applications of these materials, and opportunities for the future development of these two aspects, with an emphasis on how preparation of thin films can utilise additive manufacturing approaches.

By using hydrogen quench continuous annealing technology, Stelco Inc. has developed a suite of Advanced High Strength Steel (AHSS) grades with tensile strength greater than 1000MPa to meet standard automotive specifications and for unique customer requirements. These grades were optimized by correlating chemical composition and processing parameters with microstructures and mechanical properties. Dual-Phase 980 (Stelco trademarked STELMAXTM 980DP), Multi-Phase 1180 (STELMAXTM 1180MP), Martensitic Steel 1300 (STELMAXTM 1300M) and 1500 (STELMAXTM 1500M) products met strength and formability requirements with excellent flatness and surface quality. Hydrogen quench continuous annealing technology not only ensures all developed AHSS grades have consistent mechanical properties across the entire strip length (from strip head to tail) and width (from edge to edge), but also produces high product yield compared with other continuous annealing processes.

The limited information available on the structure of complexes involving transcription factors and cognate DNA response elements represents a major obstacle in the quest to understand their mechanism of action at the molecular level. We implemented a concerted structural proteomics approach, which combined hydrogen-deuterium exchange (HDX), quantitative protein-protein and protein-nucleic acid cross-linking (XL), and homology analysis, to model the structure of the complex between the full-length DNA binding domain (DBD) of FOXO4 and its DNA binding element (DBE). The results confirmed that FOXO4-DBD assumes the characteristic forkhead topology shared by these types of transcription factors, but its binding mode differs significantly from those of other members of the family. The results showed that the binding interaction stabilized regions that were rather flexible and disordered in the unbound form. Surprisingly, the conformational effects were not limited only to the interface between bound components but extended also to distal regions that may be essential to recruiting additional factors to the transcription machinery. In addition to providing valuable new insights into the binding mechanism, this project provided an excellent evaluation of the merits of structural proteomics approaches in the investigation of systems that arematerial not directly amenable to traditional high-resolution techniques.