Search results for: hydrogen absorbing materials

Authors: Francesca Gullo, Paola Palmero, Massimo Messori

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Transparent wood is considered a promising structural material for the development of environmentally friendly, energy-efficient engineered components. To obtain transparent wood from natural wood materials two approaches can be used: i) bottom-up and ii) top-down. Through the second method, the color of natural wood samples is lightened through a chemical bleaching process that acts on chromophore groups of lignin, such as the benzene ring, quinonoid, vinyl, phenolics, and carbonyl groups. These chromophoric units form complex conjugate systems responsible for the brown color of wood. There are two strategies to remove color and increase the whiteness of wood: i) lignin removal and ii) lignin bleaching. In the lignin removal strategy, strong chemicals containing chlorine (chlorine, hypochlorite, and chlorine dioxide) and oxidizers (oxygen, ozone, and peroxide) are used to completely destroy and dissolve the lignin. In lignin bleaching methods, a moderate reductive (hydrosulfite) or oxidative (hydrogen peroxide) is commonly used to alter or remove the groups and chromophore systems of lignin, selectively discoloring the lignin while keeping the macrostructure intact. It is, therefore, essential to manipulate nanostructured wood by precisely controlling the nanopores in the cell walls by monitoring both chemical treatments and process conditions, for instance, the treatment time, the concentration of chemical solutions, the pH value, and the temperature. The elimination of wood light scattering is the second step in the fabrication of transparent wood materials, which can be achieved through two-step approaches: i) the polymer impregnation method and ii) the densification method. For the polymer impregnation method, the wood scaffold is treated with polymers having a corresponding refractive index (e.g., PMMA and epoxy resins) under vacuum to obtain the transparent composite material, which can finally be pressed to align the cellulose fibers and reduce interfacial defects in order to have a finished product with high transmittance (>90%) and excellent light-guiding. However, both the solution-based bleaching and the impregnation processes used to produce transparent wood generally consume large amounts of energy and chemicals, including some toxic or pollutant agents, and are difficult to scale up industrially. Here, we report a method to produce optically transparent wood by modifying the lignin structure with a chemical reaction at room temperature using small amounts of hydrogen peroxide in an alkaline environment. This method preserves the lignin, which results only deconjugated and acts as a binder, providing both a strong wood scaffold and suitable porosity for infiltration of biobased polymers while reducing chemical consumption, the toxicity of the reagents used, polluting waste, petroleum by-products, energy and processing time. The resulting transparent wood demonstrates high transmittance and low thermal conductivity. Through the combination of process efficiency and scalability, the obtained materials are promising candidates for application in the field of construction for modern energy-efficient buildings.

Keywords: bleached wood, energy-efficient components, hydrogen peroxide, transparent wood, wood composites

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Authors: Hamadi Cherif, Christophe Coquelet, Paolo Stringari, Denis Clodic, Laura Pellegrini, Stefania Moioli, Stefano Langè

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Biogas is a promising technology which can be used as a vehicle fuel, for heat and electricity production, or injected in the national gas grid. It is storable, transportable, not intermittent and substitutable for fossil fuels. This gas produced from the wastewater treatment by degradation of organic matter under anaerobic conditions is mainly composed of methane and carbon dioxide. To be used as a renewable fuel, biogas, whose energy comes only from methane, must be purified from carbon dioxide and other impurities such as water vapor, siloxanes and hydrogen sulfide. Purification of biogas for this application particularly requires the removal of hydrogen sulfide, which negatively affects the operation and viability of equipment especially pumps, heat exchangers and pipes, causing their corrosion. Several methods are available to eliminate hydrogen sulfide from biogas. Herein, reactive absorption in structured packed column by means of chemical absorption in aqueous sodium hydroxide solutions is considered. This study is based on simulations using Aspen Plus™ V8.0, and comparisons are done with data from an industrial pilot plant treating 85 Nm3/h of biogas which contains about 30 ppm of hydrogen sulfide. The rate-based model approach has been used for simulations in order to determine the efficiencies of separation for different operating conditions. To describe vapor-liquid equilibrium, a γ/ϕ approach has been considered: the Electrolyte NRTL model has been adopted to represent non-idealities in the liquid phase, while the Redlich-Kwong equation of state has been used for the vapor phase. In order to validate the thermodynamic model, Henry’s law constants of each compound in water have been verified against experimental data. Default values available in Aspen Plus™ V8.0 for the properties of pure components properties as heat capacity, density, viscosity and surface tension have also been verified. The obtained results for physical and chemical properties are in a good agreement with experimental data. Reactions involved in the process have been studied rigorously. Equilibrium constants for equilibrium reactions and the reaction rate constant for the kinetically controlled reaction between carbon dioxide and the hydroxide ion have been checked. Results of simulations of the pilot plant purification section show the influence of low temperatures, concentration of sodium hydroxide and hydrodynamic parameters on the selective absorption of hydrogen sulfide. These results show an acceptable degree of accuracy when compared with the experimental data obtained from the pilot plant. Results show also the great efficiency of sodium hydroxide for the removal of hydrogen sulfide. The content of this compound in the gas leaving the column is under 1 ppm.

Keywords: biogas, hydrogen sulfide, reactive absorption, sodium hydroxide, structured packed column

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Authors: Chia-Jung Chang, Sheng-Che Chen, Ming-Long Yeh, Chih-Wei Wang, Chih-Han Chang

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Introduction and Motivation: In recent years, magnesium alloy is used to be a kind of medical biodegradable materials. Magnesium is an essential element in the body and is efficiently excreted by the kidneys. Furthermore, the mechanical properties of magnesium alloy is closest to human bone. However, in some cases magnesium alloy corrodes so quickly that it would release hydrogen on surface of implant. The other product is hydroxide ion, it can significantly increase the local pH value. The above situations may have adverse effects on local cell functions. On the other hand, nowadays magnesium alloy corrode too fast to maintain the function of implant until the healing of tissue. Therefore, much recent research about magnesium alloy has focused on controlling the corrosion rate. The in vitro corrosion behavior of magnesium alloys is affected by many factors, and pH value is one of factors. In this study, we will study on the influence of pH value on the corrosion behavior of magnesium alloy by the Micro-CT (micro computed tomography) and other instruments.Material and methods: In the first step, we make some guiding plates for specimens of magnesium alloy AZ91 by Rapid Prototyping. The guiding plates are able to be a standard for the degradation of specimen, so that we can use it to make sure the position of specimens in the CT image. We can also simplify the conditions of degradation by the guiding plates.In the next step, we prepare the solution with different pH value. And then we put the specimens into the solution to start the corrosion test. The CT image, surface photographs and weigh are measured on every twelve hours. Results: In the primary results of the test, we make sure that CT image can be a way to quantify the corrosion behavior of magnesium alloy. Moreover we can observe the phenomenon that corrosion always start from some erosion point. It’s possibly based on some defect like dislocations and the voids with high strain energy in the materials. We will deal with the raw data into Mass Loss (ML) and corrosion rate by CT image, surface photographs and weigh in the near future. Having a simple prediction, the pH value and degradation rate will be negatively correlated. And we want to find out the equation of the pH value and corrosion rate. We also have a simple test to simulate the change of the pH value in the local region. In this test the pH value will rise to 10 in a short time. Conclusion: As a biodegradable implant for the area with stagnating body fluid flow in the human body, magnesium alloy can cause the increase of local pH values and release the hydrogen. Those may damage the human cell. The purpose of this study is finding out the equation of the pH value and corrosion rate. After that we will try to find the ways to overcome the limitations of medical magnesium alloy.

Keywords: magnesium alloy, biodegradable materials, corrosion, micro-CT

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Authors: Shu-Bo Yang, Wei Wu, Yuan-Heng Liu

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This research aims to design a heat-exchanger type of methanol reformer coupled with a preheating design in gPROMS® environment. The endothermic methanol steam reforming reaction (MSR) and the exothermic preferential oxidation reaction (PROX) occur in the inner tube and the outer tube of the reformer, respectively. The effective heat transfer manner between the inner and outer tubes is investigated. It is verified that the countercurrent-flow type reformer provides the higher hydrogen yield than the cocurrent-flow type. Since the hot spot temperature appears in the outer tube, an improved scheme is proposed to suppress the hot spot temperature by splitting the excess air flowing into two sites. Finally, an optimization algorithm for maximizing the hydrogen yield is employed to determine optimal operating conditions.

Keywords: methanol reformer, methanol steam reforming, optimization, simulation

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Authors: T. Ghatauray, J. Ingram, P. Holborn

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The transition from a ‘carbon rich’ fossil fuel dependent to a ‘sustainable’ and ‘renewable’ hydrogen based society will see the deployment of hydrogen fuel cells (HFC) in transport applications and in the generation of heat and power for buildings, as part of a decentralised power network. Many deployments will be low power HFCs for domestic combined heat and power (CHP) and commercial ‘transportable’ HFCs for environmental situations, such as lighting and telephone towers. For broad commercialisation of small fuel cells to be achieved there needs to be significant confidence in their safety in both domestic and environmental applications. Low power HFCs are housed in protective steel enclosures. Standard enclosures have plain rectangular ventilation openings intended for thermal management of electronics and not the dispersion of a buoyant gas. Degradation of the HFC or supply pipework in use could lead to a low-level leak and a build-up of hydrogen gas in the enclosure. Hydrogen’s wide flammable range (4-75%) is a significant safety concern, with ineffective enclosure ventilation having the potential to cause flammable mixtures to develop with the risk of explosion. Mechanical ventilation is effective at managing enclosure hydrogen concentrations, but drains HFC power and is vulnerable to failure. This is undesirable in low power and remote installations and reliable passive ventilation systems are preferred. Passive ventilation depends upon buoyancy driven flow, with the size, shape and position of ventilation openings critical for producing predictable flows and maintaining low buoyant gas concentrations. With environmentally sited enclosures, ventilation openings with pressed horizontal and angled louvres are preferred to protect the HFC and electronics inside. There is an economic cost to adding louvres, but also a safety concern. A question arises over whether the use of pressed louvre vents impairs enclosure passive ventilation performance, when compared to same opening area plain vents. Comparison small enclosure (0.144m³) tests of same opening area pressed louvre and plain vents were undertaken. A displacement ventilation arrangement was incorporated into the enclosure with opposing upper and lower ventilation openings. A range of vent areas were tested. Helium (used as a safe analogue for hydrogen) was released from a 4mm nozzle at the base of the enclosure to simulate a hydrogen leak at leak rates from 1 to 10 lpm. Helium sensors were used to record concentrations at eight heights in the enclosure. The enclosure was otherwise empty. These tests determined that the use of pressed and angled louvre ventilation openings on the enclosure impaired the passive ventilation flow and increased helium concentrations in the enclosure. High-level stratified buoyant gas layers were also found to be deeper than with plain vent openings and were within the flammable range. The presence of gas within the flammable range is of concern, particularly as the addition of the fuel cell and electronics in the enclosure would further reduce the available volume and increase concentrations. The opening area of louvre vents would need to be greater than equivalent plain vents to achieve comparable ventilation flows or alternative schemes would need to be considered.

Keywords: enclosure, fuel cell, helium, hydrogen safety, louvre vent, passive ventilation

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Authors: Ali Haratian, Soroosh Emami Meybodi

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Using viable microbial cultures within hydrocarbon reservoirs so as to the enhancement of oil recovery through metabolic activities is exactly what we recognize as microbial enhanced oil recovery (MEOR). In similar to many other processes in industries, there are some cons and pros following with MEOR. The creation of sulfides such as hydrogen sulfide as a result of injecting the sulfate-containing seawater into hydrocarbon reservoirs in order to maintain the required reservoir pressure leads to production and growth of sulfate reducing bacteria (SRB) approximately near the injection wells, turning the reservoir into sour; however, SRB is not considered as the only microbial process stimulating the formation of sulfides. Along with SRB, thermochemical sulfate reduction or thermal redox reaction (TSR) is also known to be highly effective at resulting in having extremely concentrated zones of ?2S in the reservoir fluids eligible to cause corrosion. Owing to extent of the topic, more information on the formation of ?₂S is going to be put finger on. Besides, confronting the undesirable production of sulfide species in the reservoirs can lead to serious operational, environmental, and financial problems, in particular the transporting pipelines. Consequently, conjuring up reservoir souring control strategies on the way production of oil and gas is the only way to prevent possible damages in terms of environment, finance, and manpower which requires determining the compound’s reactivity, origin, and partitioning behavior. This article is going to provide a comprehensive review of progress made in this field and the possible advent of new strategies in this technologically advanced world of the petroleum industry.

Keywords: corrosion, hydrogen sulfide, NRB, reservoir souring, SRB

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Authors: Jigar Shaileshumar Halpati, Aravind Kumar Chandiran

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Vacancy ordered double perovskites (VOPs) have been significantly attracting researchers due to their chemical structure diversity and interesting optoelectronic properties. Some VOPs have been recently reported to be suitable photoelectrodes for photoelectrochemical water-splitting reactions due to their high stability and panchromatic absorption. In this work, we systematically synthesized mixed tetravalent VOPs based on Cs₂RuₘPt₁-ₘX₆ (X = Cl-, Br-) and reported their structural, optical, electrochemical and photoelectrochemical properties. The structural characterization confirms that the mixed tetravalent site intermediates formed their own phases. The parent materials, as well as their intermediates, were found to be stable in ambient conditions for over 1 year and also showed incredible stability in harsh pH media ranging from pH 1 to pH 11. Moreover, these materials showed panchromatic absorption with onset up to 1000 nm depending upon the mixture stoichiometry. The extraordinary stability and excellent absorption properties make them suitable materials for photoelectrochemical water-splitting applications. PEC studies of these series of materials showed a high water oxidation photocurrent of 0.56 mA cm-² for Cs₂Ru₀.₅Pt₀.₅Cl₆. Fundamental investigation from photoelectrochemical reactions revealed that the intrinsic ruthenium-based VOP showed enhanced hole transfer to the electrolyte, while the intrinsic platinum-based VOP showed higher photovoltage. The mix of these end members at the tetravalent site showed a synergic effect of reduced charge transfer resistance from the material to the electrolyte and increased photovoltage, which led to increased PEC performance of the intermediate materials.

Keywords: solar water splitting, photo electrochemistry, photo absorbers, material characterization, device characterization, green hydrogen

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Authors: Patrizia Frontera, Anastasia Macario, Sebastiano Candamano, Fortunato Crea, Pierluigi Antonucci

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The increasing of the world energy demand makes today biomass an attractive energy source, based on the minimizing of CO2 emission and on the global warming reduction purposes. Recently, COP-21, the international meeting on global climate change, defined the roadmap for sustainable worldwide development, based on low-carbon containing fuel. Hydrogen is an energy vector able to substitute the conventional fuels from petroleum. Ethanol for hydrogen production represents a valid alternative to the fossil sources due to its low toxicity, low production costs, high biodegradability, high H2 content and renewability. Ethanol conversion to generate hydrogen by a combination of partial oxidation and steam reforming reactions is generally called auto-thermal reforming (ATR). The ATR process is advantageous due to the low energy requirements and to the reduced carbonaceous deposits formation. Catalyst plays a pivotal role in the ATR process, especially towards the process selectivity and the carbonaceous deposits formation. Bimetallic or trimetallic catalysts, as well as catalysts with doped-promoters supports, may exhibit high activity, selectivity and deactivation resistance with respect to the corresponding monometallic ones. In this work, NiMoCo/GDC, NiMoCu/GDC and NiMoRe/GDC (where GDC is Gadolinia Doped Ceria support and the metal composition is 60:30:10 for all catalyst) have been prepared by impregnation method. The support, Gadolinia 0.2 Doped Ceria 0.8, was impregnated by metal precursors solubilized in aqueous ethanol solution (50%) at room temperature for 6 hours. After this, the catalysts were dried at 100°C for 8 hours and, subsequently, calcined at 600°C in order to have the metal oxides. Finally, active catalysts were obtained by reduction procedure (H2 atmosphere at 500°C for 6 hours). All sample were characterized by different analytical techniques (XRD, SEM-EDX, XPS, CHNS, H2-TPR and Raman Spectorscopy). Catalytic experiments (auto-thermal reforming of ethanol) were carried out in the temperature range 500-800°C under atmospheric pressure, using a continuous fixed-bed microreactor. Effluent gases from the reactor were analyzed by two Varian CP4900 chromarographs with a TCD detector. The analytical investigation focused on the preventing of the coke deposition, the metals sintering effect and the sulfur poisoning. Hydrogen productivity, ethanol conversion and products distribution were measured and analyzed. At 600°C, all tri-metallic catalysts show the best performance: H2 + CO reaching almost the 77 vol.% in the final gases. While NiMoCo/GDC catalyst shows the best selectivity to hydrogen whit respect to the other tri-metallic catalysts (41 vol.% at 600°C). On the other hand, NiMoCu/GDC and NiMoRe/GDC demonstrated high sulfur poisoning resistance (up to 200 cc/min) with respect to the NiMoCo/GDC catalyst. The correlation among catalytic results and surface properties of the catalysts will be discussed.

Keywords: catalysts, ceria, ethanol, gadolinia, hydrogen, Nickel

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Authors: Renata Josipovic, Ante Cvitkovic

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Particulate matter belongs to pollutants that can lead to respiratory problems or premature death due to exposure (long-term, short-term) to these substances, all depending on the severity of the effects. The importance of the study is to determine whether the existing climatic conditions in the period from January 1st to August 31st, 2018 increased the number of emergency interventions in Slavonski Brod with regard to pollutants hydrogen sulfide and particles less than 10 µm (PM10) and less than 2.5 µm (PM2.5). Analytical data of the concentration of pollutants are collected from the Croatian Meteorological and Hydrological Service, which monitors the operation of two meteorological stations in Slavonski Brod, as well as climatic conditions. Statistics data of emergency interventions were collected from the Emergency Medicine Department of Slavonski Brod. All data were compared (air pollution, emergency interventions) according to climatic conditions (air humidity and air temperature) and statistically processed. Statistical significance, although weak positive correlation PM2.5 (correlation coefficient 0.147; p = 0.036), determined PM10 (correlation coefficient 0.122; p = 0.048), hydrogen sulfide (correlation coefficient 0.141; p = 0.035) with max. temperature (correlation coefficient 0.202; p = 0.002) with number of interventions. The association between mean air humidity was significant but negative (correlation coefficient - 0.172; p = 0.007). The values of the influence of air pressure are not determined. As the problem of air pollution is very complex, coordinated action at many levels is needed to reduce air pollution in Slavonski Brod and consequences that can affect human health.

Keywords: emergency interventions, human health, hydrogen sulfide, particulate matter

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Authors: K. B. Vinay, K. G. Vismay, S. Kasturirengan, G. A. Vivek

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Cryosorption pumps are considered to be safe, quiet and ultra-high vacuum production pumps which have their application from Semiconductor industries to ITER [International Thermonuclear Experimental Reactor] units. The principle of physisorption of gases over highly porous materials like activated charcoal at cryogenic temperatures (below -1500°C) is involved in determining the pumping speed of gases like Helium, Hydrogen, Argon and Nitrogen. This paper aims at providing detailed overview of development of Cryosorption pump which is the modern ultra-high vacuum pump and characterization of different activated charcoal materials that optimizes the performance of the pump. Different grades of charcoal were tested in order to determine the pumping speed of the pump and were compared with commercially available Varian cryopanel. The results for bare panel, bare panel with adhesive, cryopanel with pellets, and cryopanel with granules were obtained and compared. The comparison showed that cryopanel adhered with small granules gave better pumping speeds than large sized pellets.

Keywords: adhesive, cryopanel, granules, pellets

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Authors: Heval Serhat Uluk, Sam M. Dakka, Kuldeep Singh, Richard Jefferson-Loveday

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The carbon footprint of the aviation sector in total measured 3.8% in 2017, and it is expected to triple by 2050. New combustion approaches and fuel types are necessary to prevent this. This paper will focus on using propane, methane, and hydrogen as fuel replacements for kerosene and implement a trapped vortex combustor design to increase efficiency. Reacting simulations were conducted for axisymmetric trapped vortex combustor to investigate the static pressure drop, combustion efficiency and pattern factor for various cavity aspect ratios for 0.3, 0.6 and 1 and air mass flow rates for 14 m/s, 28 m/s and 42 m/s. Propane, methane and hydrogen are used as alternative fuels. The combustion model was anchored based on swirl flame configuration with an emphasis on high fidelity of boundary conditions with favorable results of eddy dissipation model implementation. Reynolds Averaged Navier Stokes (RANS) k-ε model turbulence model for the validation effort was used for turbulence modelling. A grid independence study was conducted for the three-dimensional model to reduce computational time. Preliminary results for 24 m/s air mass flow rate provided a close temperature profile inside the cavity relative to the experimental study. The investigation will be carried out on the effect of air mass flow rates and cavity aspect ratio on the combustion efficiency, pattern factor and static pressure drop in the combustor. A comparison study among pure methane, propane and hydrogen will be conducted to investigate their suitability for trapped vortex combustors and conclude their advantages and disadvantages as a fuel replacement. Therefore, the study will be one of the milestones to achieving 2050 zero carbon emissions or reducing carbon emissions.

Keywords: computational fluid dynamics, aerodynamic, aerospace, propulsion, trapped vortex combustor

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Authors: Hilary Rutto

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Leaching with acids are the most commonly reagents used to remove copper ions from its copper ores. It is important that the process conditions are optimized to improve the leaching efficiency. In the present study the effects of pH, oxidizing agent (hydrogen peroxide), stirring speed, solid to liquid ratio and acid concentration on the leaching of copper ions from it ore were investigated using a pH Stat apparatus. Copper ions were analyzed at the end of each experiment using Atomic Absorption (AAS) machine. Results showed that leaching efficiency improved with an increase in acid concentration, stirring speed, oxidizing agent, pH and decreased with an increase in the solid to liquid ratio.

Keywords: leaching, copper, oxidizing agent, pH stat apparatus

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Authors: R. Ziaie Moayed, H. Keshavarz Hedayati

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Over recent years, due to increased population and increased waste production, groundwater protection has become more important, therefore, designing engineered barrier systems such as landfill liners to prevent the entry of leachate into groundwater should be done with greater accuracy. These measures generally involve the application of low permeability soils such as clays. Bentonite is a natural clay with low permeability which makes it a suitable soil for using in liners. Also zeolite with high cation exchange capacity can help to reduce of hazardous materials risk. Bentonite expands when wet, absorbing as much as several times its dry mass in water. This property may effect on some structural properties of soil such as shear strength. In present study, shear strength parameters are determined by both leachates polluted and not polluted bentonite-amended zeolite soil with mixing rates (B/Z) of 5%-10% and 20% with unconfined compression test to obtain the differences. It is shown that leachate presence causes reduction in resistance in general.

Keywords: bentonite, leachate, shear strength parameters, unconfined compression test

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Authors: Tami A. Ulhiza, Noor I. M. Puad, Azlin S. Azmi, Mohd. I. A. Malek

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High amount of chemical oxygen demand (COD) in starchy waste can be harmful to the environment. In common practice, starch processing wastewater is discharged to the river without proper treatment. However, starchy waste still contains complex sugars and organic acids. By the right pretreatment method, the complex sugar can be hydrolyzed into more readily digestible sugars which can be utilized to be converted into more valuable products. At the same time, the global demand of energy is inevitable. The continuous usage of fossil fuel as the main source of energy can lead to energy scarcity. Hydrogen is a renewable form of energy which can be an alternative energy in the future. Moreover, hydrogen is clean and carries the highest energy compared to other fuels. Biohydrogen produced from waste has significant advantages over chemical methods. One of the major problems in biohydrogen production is the raw material cost. The carbohydrate-rich starchy wastes such as tapioca, maize, wheat, potato, and sago wastes is a promising candidate to be used as a substrate in producing biohydrogen. The utilization of those wastes for biohydrogen production can provide cheap energy generation with simultaneous waste treatment. Therefore this paper aims to review variety source of starchy wastes that has been widely used to synthesize biohydrogen. The scope includes the source of waste, the performance in yielding hydrogen, the pretreatment method and the type of culture that is suitable for starchy waste.

Keywords: biohydrogen, dark fermentation, renewable energy, starchy waste

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Authors: Dara Satyadileep, Abdallah S. Berrouk

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Selective absorption of Hydrogen Sulphide (H2S) using methyldiethanol amine (MDEA) has become a point of interest as means of minimizing capital and operating costs of gas sweetening plants. This paper discusses the prominence of optimum design of column internals to best achieve H2S selectivity using MDEA. To this end, a kinetics-based process simulation model has been developed for a commercial gas sweetening unit. Trends of sweet gas H2S & CO2 contents as function of fraction active area (and hence residence time) have been explained through analysis of interdependent heat and mass transfer phenomena. Guidelines for column internals design in order to achieve desired degree of H2S selectivity are provided. Also the effectiveness of various operating conditions in achieving H2S selectivity for an industrial absorber with fixed internals is investigated.

Keywords: gas sweetening, H2S selectivity, methyldiethanol amine, process simulation, residence time

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Authors: Ionela-Daniela Carja, Diana Serbezeanu, Tachita Vlad-Bubulac, Corneliu Hamciuc

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Nowadays, epoxy materials are extensively used in ever more areas and under ever more demanding environmental conditions due to their remarkable combination of properties, light weight and ease of processing. However, these materials greatly increase the fire risk due to their flammability and possible release of toxic by-products as a result of their chemical composition which consists mainly from carbon and hydrogen atoms. Therefore, improving the fire retardant behaviour to prevent the loss of life and property is of particular concern among government regulatory bodies, consumers and manufacturers alike. Modification of epoxy resins with organophosphorus compounds, as reactive flame retardants or additives, is the key to achieving non-flammable advanced epoxy materials. Herein, a detailed characterization of fire behaviour for a series of phosphorus-containing epoxy thermosets is reported. A carefully designed phosphorus flame retardant additive was simply blended with a bifunctional bisphenol-A based epoxy resin. Further thermal cross-linking in the presence of various aminic hardeners led to eco-friendly flame retardant epoxy resins. The type of hardener, concentration of flame retardant additive, compatibility between the components of the mixture, char formation and morphology, thermal stability, flame retardant mechanisms were investigated. It was found that even a very low content of phosphorus introduced into the epoxy matrix increased the limiting oxygen index value to about 30%. In addition, the peak of the heat release rate value decreased up to 45% as compared to the one of the neat epoxy system. The main flame retardant mechanism was the condensed-phase one as revealed by SEM and XPS measurements.

Keywords: condensed-phase mechanism, eco-friendly phosphorus flame retardant, epoxy resin, thermal stability

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Authors: Qiming Wang

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Dynamic polymer networks (DPNs) crosslinked by dynamic bonds have received intensive attention because of their special crack-healing capability. Diverse DPNs have been synthesized using a number of dynamic bonds, including dynamic covalent bond, hydrogen bond, ionic bond, metal-ligand coordination, hydrophobic interaction, and others. Despite the promising success in the polymer synthesis, the fundamental understanding of their self-healing mechanics is still at the very beginning. Especially, a general analytical model to understand the interfacial self-healing behaviors of DPNs has not been established. Here, we develop polymer-network based analytical theories that can mechanistically model the constitutive behaviors and interfacial self-healing behaviors of DPNs. We consider that the DPN is composed of interpenetrating networks crosslinked by dynamic bonds. bonds obey a force-dependent chemical kinetics. During the self-healing process, we consider the The network chains follow inhomogeneous chain-length distributions and the dynamic polymer chains diffuse across the interface to reform the dynamic bonds, being modeled by a diffusion-reaction theory. The theories can predict the stress-stretch behaviors of original and self-healed DPNs, as well as the healing strength in a function of healing time. We show that the theoretically predicted healing behaviors can consistently match the documented experimental results of DPNs with various dynamic bonds, including dynamic covalent bonds (diarylbibenzofuranone and olefin metathesis), hydrogen bonds, and ionic bonds. We expect our model to be a powerful tool for the self-healing community to invent, design, understand, and optimize self-healing DPNs with various dynamic bonds.

Keywords: self-healing polymers, dynamic covalent bonds, hydrogen bonds, ionic bonds

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Authors: C. Hall, J. Ramos, V. Ramasamy

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Hydrocarbon-based fuel vehicles are a major contributor to air pollution due to harmful emissions produced, leading to a demand for cleaner fuel types. A leader in this pursuit is hydrogen, with its application in vehicles producing zero harmful emissions and the only by-product being water. To compete with the performance of conventional vehicles, hydrogen gas must be stored on-board of vehicles in cylinders at high pressures (35–70 MPa) and have a short refueling duration (approximately 3 mins). However, the fast-filling of hydrogen cylinders causes a significant rise in temperature due to the combination of the negative Joule-Thompson effect and the compression of the gas. This can lead to structural failure and therefore, a maximum allowable internal temperature of 85°C has been imposed by the International Standards Organization. The technological solution to tackle the issue of rapid temperature rise during the refueling process is to decrease the temperature of the gas entering the cylinder. Pre-cooling of the gas uses a heat exchanger and requires energy for its operation. Thus, it is imperative to determine the least amount of energy input that is required to lower the gas temperature for cost savings. A validated universal thermodynamic model is used to identify an energy-efficient pre-cooling strategy. The model requires negligible computational time and is applied to previously validated experimental cases to optimize pre-cooling requirements. The pre-cooling characteristics include the location within the refueling timeline and its duration. A constant pressure-ramp rate is imposed to eliminate the effects of rapid changes in mass flow rate. A pre-cooled gas temperature of -40°C is applied, which is the lowest allowable temperature. The heat exchanger is assumed to be ideal with no energy losses. The refueling of the cylinders is modeled with the pre-cooling split in ten percent time intervals. Furthermore, varying burst durations are applied in both the early and late stages of the refueling procedure. The model shows that pre-cooling in the later stages of the refuelling process is more energy-efficient than early pre-cooling. In addition, the efficiency of pre-cooling towards the end of the refueling process is independent of the pressure profile at the inlet. This leads to the hypothesis that pre-cooled gas should be applied as late as possible in the refueling timeline and at very low temperatures. The model had shown a 31% reduction in energy demand whilst achieving the same final gas temperature for a refueling scenario when pre-cooling was applied towards the end of the process. The identification of the most energy-efficient refueling approaches whilst adhering to the safety guidelines is imperative to reducing the operating cost of hydrogen refueling stations. Heat exchangers are energy-intensive and thus, reducing the energy requirement would lead to cost reduction. This investigation shows that pre-cooling should be applied as late as possible and for short durations.

Keywords: cylinder, hydrogen, pre-cooling, refueling, thermodynamic model

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Authors: Peter Kus, Anna Ostroverkh, Yurii Yakovlev, Yevheniia Lobko, Roman Fiala, Ivan Khalakhan, Vladimir Matolin

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Hydrogen economy is a concept of low-emission society which harvests most of its energy from renewable sources (e.g., wind and solar) and in case of overproduction, electrochemically turns the excess amount into hydrogen, which serves as an energy carrier. Proton exchange membrane water electrolyzers (PEMWE) are the backbone of this concept. By fast-response electricity to hydrogen conversion, the PEMWEs will not only stabilize the electrical grid but also provide high-purity hydrogen for variety of fuel cell powered devices, ranging from consumer electronics to vehicles. Wider commercialization of PEMWE technology is however hindered by high prices of noble metals which are necessary for catalyzing the redox reactions within the cell. Namely, platinum for hydrogen evolution reaction (HER), running on cathode, and iridium for oxygen evolution reaction (OER) on anode. Possible way of how to lower the loading of Pt and Ir is by using conductive high-surface nanostructures as catalyst supports in conjunction with thin-film catalyst deposition. The presented study discusses unconventional technique of membrane electron assembly (MEA) preparation. Noble metal catalysts (Pt and Ir) were magnetron sputtered in very low loadings onto the surface of porous sublayers (located on gas diffusion layer or directly on membrane), forming so to say localized three-phase boundary. Ultrasonically sprayed corrosion resistant TiC-based sublayer was used as a support material on anode, whereas magnetron sputtered nanostructured etched nitrogenated carbon (CNx) served the same role on cathode. By using this configuration, we were able to significantly decrease the amount of noble metals (to thickness of just tens of nanometers), while keeping the performance comparable to that of average state-of-the-art catalysts. Complex characterization of prepared supported catalysts includes in-cell performance and durability tests, electrochemical impedance spectroscopy (EIS) as well as scanning electron microscopy (SEM) imaging and X-ray photoelectron spectroscopy (XPS) analysis. Our research proves that magnetron sputtering is a suitable method for thin-film deposition of electrocatalysts. Tested set-up of thin-film supported anode and cathode catalysts with combined loading of just 120 ug.cm⁻² yields remarkable values of specific current. Described approach of thin-film low-loading catalyst deposition might be relevant when noble metal reduction is the topmost priority.

Keywords: hydrogen economy, low-loading catalyst, magnetron sputtering, proton exchange membrane water electrolyzer

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Authors: Fatima Zohra Zeggai, Benjamin Carbonnier, Aïcha Hachemaoui, Ahmed Yahiaoui, Samia Mahouche-Chergui, Zakaria Salmi

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A series of polyaniline (PANI)/modified Montmorillonite (MMT) Clay nanocomposite materials have been successfully prepared by In-Situ polymerization in the presence of modified MMT-Clay or Diazonium-MMT-Clay. The obtained nanocomposites were characterized and compared by various physicochemical techniques. The presence of physicochemical interaction, probably hydrogen bonding, between clay and polyaniline, which was confirmed by FTIR, UV-Vis Spectroscopy. The electrical conductivity of neat PANI and a series of the obtained nanocomposites were also studied by cyclic voltammograms.

Keywords: polyaniline, clay, nanocomposites, in-situ polymerization, polymers conductors, diazonium salt

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Authors: Udit Mohanty, Mari Lundstrom

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Electrochemical investigation by cyclic voltammetry was conducted to explore the polarization behavior of reactions occurring in nickel electrowinning in presence of cationic impurities such as Ca2+ (0-100 mg/L), Na+ (1-10 g/L) and Mg2+ (10-100 mg/L). A comparative study was devised between industrial and synthetic electrolytes to observe the shift in the nucleation overpotentials of nickel deposition, dissolution and hydrogen evolution reactions at the cathode and anode respectively. Significant polarization of cathodic reactions were observed with concentrations of Na ≥ 8g /L and Ca ≤ 40 mg /L in the synthetic electrolytes. Nevertheless, a progressive increase in the concentration of Ca, Mg and Na in the industrial electrolyte demonstrated a depolarization behavior in the cathodic reactions related to nickel deposition and/or hydrogen evolution. Synergistic effect of Ca with Mg and Na in both the industrial and synthetic electrolytes induced a notable depolarization effect, also reflected in the peak currents.

Keywords: cationic impurities, cyclic voltammetry, electrowinning, nickel, polarization

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Authors: Parth Mehta, Vedasri Bai Khavala, Prabhu Rajagopal, Tiju Thomas

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There is an increasing need for alternative clean fuels, and hydrogen (H₂) has long been considered a promising solution with a high calorific value (142MJ/kg). However, the storage of H₂ and expensive processes for its generation have hindered its usage. Sodium borohydride (NaBH₄) can potentially be used as an economically viable means of H₂ storage. Thus far, there have been attempts to optimize the life of NaBH₄ (half-life) in aqueous media by stabilizing it with sodium hydroxide (NaOH) for various pH values. Other reports have shown that H₂ yield and reaction kinetics remained constant for all ratios of H₂O to NaBH₄ > 30:1, without any acidic catalysts. Here we highlight the importance of pH and H₂O: NaBH₄ ratio (80:1, 40:1, 20:1 and 10:1 by weight), for NaBH₄ stabilization (half-life reaction time at room temperature) and corrosion minimization of H₂ reactor components. It is interesting to observe that at any particular pH>10 (e.g., pH = 10, 11 and 12), the H₂O: NaBH₄ ratio does not have the expected linear dependence with stability. On the contrary, high stability was observed at the ratio of 10:1 H₂O: NaBH₄ across all pH>10. When the H₂O: NaBH₄ ratio is increased from 10:1 to 20:1 and beyond (till 80:1), constant stability (% degradation) is observed with respect to time. For practical usage (consumption within 6 hours of making NaBH₄ solution), 15% degradation at pH 11 and NaBH₄: H₂O ratio of 10:1 is recommended. Increasing this ratio demands higher NaOH concentration at the same pH, thus requiring a higher concentration or volume of acid (e.g., HCl) for H₂ generation. The reactions are done with tap water to render the results useful from an industrial standpoint. The observed stability regimes are rationalized based on complexes associated with NaBH₄ when solvated in water, which depend sensitively on both pH and NaBH₄: H₂O ratio.

Keywords: hydrogen, sodium borohydride, stability optimization, H₂O:NaBH₄ ratio

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Authors: Pelin Altay, Ahmed El-Shafei, Peter J. Hauser, Nevin Cigdem Gursoy

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Exceedingly high temperatures are used (around 95 °C) to perform hydrogen peroxide bleaching of cotton fabrics in textile industry, which results in high energy consumption and also gives rise to significant fiber damage. Activated bleach systems have the potential to produce more efficient bleaching through increased oxidation rates with reducing energy cost, saving time and causing less fiber damage as compared to conventional hot peroxide bleaching. In this study, a cationic bleach activator was synthesized using caprolactam as a leaving group and triethylamine as a cationic group to establish an activated peroxide system for low temperature bleaching. Cationic bleach activator was characterized by FTIR, 1H NMR and mass spectrometry. The bleaching performance of the prototype cationic bleach activator was evaluated and optimizing the bleach recipe was performed.

Keywords: bleach activator, cotton bleaching, hydrogen peroxide bleaching, low temperature bleaching

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Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

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Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO Hydrodeoxygenation, DFT, liquid fuels, XPS, XTL

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Authors: Nassima Sotehi

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This article presents experimental and numerical results concerning the thermal properties of the porous materials used as heat insulator in the buildings sector. Initially, the thermal conductivity of three types of studied walls (classic concrete, concrete with cork aggregate and polystyrene concrete) was measured in experiments by the method of the boxes. Then a numerical modeling of the heat and mass transfers which occur within porous materials was applied to these walls. This work shows the influence of the presence of water in building materials on their thermophysical properties, as well as influence of the nature of materials and dosage of fibers introduced within these materials on the thermal and mass transfers.

Keywords: modeling, porous media, thermal materials, thermal properties

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Authors: R. F. Vieira, S. A. Figueiredo, O. M. Freitas, V. F. Domingues, C. Delerue-Matos

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The presence of sulphur compounds like hydrogen sulphide and mercaptans is one of the reasons for waste-water treatment and waste management being associated with odour emissions. In this context having a quantifying method for these compounds helps in the optimization of treatment with the goal of their elimination, namely biofiltration processes. The aim of this study was the development of a method for quantification of odorous gases in waste treatment plants air samples. A method based on head space solid phase microextraction (HS-SPME) coupled with gas chromatography - flame photometric detector (GC-FPD) was used to analyse H2S and Metil Mercaptan (MM). The extraction was carried out with a 75-μm Carboxen-polydimethylsiloxane fiber coating at 22 ºC for 20 min, and analysed by a GC 2010 Plus A from Shimadzu with a sulphur filter detector: splitless mode (0.3 min), the column temperature program was from 60 ºC, increased by 15 ºC/min to 100 ºC (2 min). The injector temperature was held at 250 ºC, and the detector at 260 ºC. For calibration curve a gas diluter equipment (digital Hovagas G2 - Multi Component Gas Mixer) was used to do the standards. This unit had two input connections, one for a stream of the dilute gas and another for a stream of nitrogen and an output connected to a glass bulb. A 40 ppm H2S and a 50 ppm MM cylinders were used. The equipment was programmed to the selected concentration, and it automatically carried out the dilution to the glass bulb. The mixture was left flowing through the glass bulb for 5 min and then the extremities were closed. This method allowed the calibration between 1-20 ppm for H2S and 0.02-0.1 ppm and 1-3.5 ppm for MM. Several quantifications of air samples from inlet and outlet of a biofilter operating in a waste management facility in the north of Portugal allowed the evaluation the biofilters performance.

Keywords: biofiltration, hydrogen sulphide, mercaptans, quantification

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Authors: Yohanes Kristianto

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The objective of this paper is to compose a sustainable supply chain that integrates product, process and networks design. An integrated life cycle assessment and techno-economic optimization is proposed that might deliver more economically feasible operations, minimizes environmental impacts and maximizes social contributions. Closed loop economy of the supply chain is achieved by reusing waste to be raw material of final products. Societal benefit is given by the supply chain by absorbing waste as source of raw material and opening new work opportunities. A case study of ethanol supply chain from rice straws is considered. The modeling results show that optimization within the scope of LCA is capable of minimizing both CO₂ emissions and energy and utility consumptions and thus enhancing raw materials utilization. Furthermore, the supply chain is capable of contributing to local economy through jobs creation. While the model is quite comprehensive, the future research recommendation on energy integration and global sustainability is proposed.

Keywords: life cycle assessment, techno-economic optimization, sustainable supply chains, closed loop economy

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Authors: Shashank Gahlaut, Chandrashekhar Sharan, J. P. Singh

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Increasing incidence of antibiotic-resistant bacteria is a big concern for the treatment of pathogenic diseases. The effect of treatment of patients with antibiotics often leads to the evolution of antibiotic resistance in the pathogens. The detection of antibiotic or antimicrobial resistant bacteria (microbes) is quite essential as it is becoming one of the big threats globally. Here we propose a novel technique to tackle this problem. We are taking a step forward to prevent the infections and diseases due to drug resistant microbes. This detection is based on some unique features of silver (a noble metal) nanorods (AgNRs) which are fabricated by a physical deposition method called thermal glancing angle deposition (GLAD). Silver nanorods are found to be highly sensitive and selective for hydrogen sulfide (H2S) gas. Color and water wetting (contact angle) of AgNRs are two parameters what are effected in the presence of this gas. H₂S is one of the major gaseous products evolved in the bacterial metabolic process. It is also known as gasotransmitter that transmits some biological singles in living systems. Nitric Oxide (NO) and Carbon mono oxide (CO) are two another members of this family. Orlowski (1895) observed the emission of H₂S by the bacteria for the first time. Most of the microorganism produce these gases. Here we are focusing on H₂S gas evolution to determine live/dead and antibiotic-resistant bacteria. AgNRs array has been used for the detection of H₂S from micro-organisms. A mobile app is also developed to make it easy, portable, user-friendly, and cost-effective.

Keywords: antibiotic resistance, hydrogen sulfide, live and dead bacteria, mobile app

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Authors: Raina J. Olsen, Andrew K. Gillespie, John W. Taylor, Cristian I. Contescu, Peter Pfeifer, James R. Morris

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While adsorbent surfaces such as graphite are known to increase the melting temperature of solid H2, this effect is normally rather small, increasing to 20 Kelvin (K) relative to 14 K in the bulk. An as-yet unidentified phase transition has been observed in a system of H2 adsorbed in a porous, locally graphitic, Saran carbon with sub-nanometer sized pores at temperatures (74-101 K) and pressures ( > 76 bar) well above the critical point of bulk H2 using hydrogen adsorption and neutron scattering experiments. Adsorption data shows a discontinuous pressure jump in the kinetics at 76 bar after nearly an hour of equilibration time, which is identified as an exothermic phase transition. This discontinuity is observed in the 87 K isotherm, but not the 77 K isotherm. At higher pressures, the measured isotherms show greater excess adsorption at 87 K than 77 K. Inelastic neutron scattering measurements also show a striking phase transition, with the amount of high angle scattering (corresponding to large momentum transfer/ large effective mass) increasing by up to a factor of 5 in the novel phase. During the course of the neutron scattering experiment, three of these reversible spectral phase transitions were observed to occur in response to only changes in sample temperature. The novel phase was observed by neutron scattering only at high H2 pressure (123 bar and 187 bar) and temperatures between 74-101 K in the sample of interest, but not at low pressure (30 bar), or in a control activated carbon at 186 bar of H2 pressure. Based on several of the more unusual observations, such as the slow equilibration and the presence of both an upper and lower temperature bound, a reasonable hypothesis is that this phase forms only in the presence of a high concentration of ortho-H2 (nuclear spin S=1). The increase in adsorption with temperature, temperatures which cross the lower temperature bound observed by neutron scattering, indicates that this novel phase is denser. Structural characterization data on the adsorbent shows that it may support a commensurate solid phase denser than those known to exist on graphite at much lower temperatures. Whatever this phase is eventually proven to be, these results show that surfaces can have a more striking effect on hydrogen phases than previously thought.

Keywords: adsorbed phases, hydrogen, neutron scattering, nuclear spin

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Authors: Jung-Feng Hsieh, Chu Ze Chen

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Curcumin is the main active compound of turmeric that can inhibit the activities of α-glucosidase and xanthine oxidase (XO). α-Glucosidase and XO inhibitors are widely used to treat patients with diabetes mellitus and gout, respectively; therefore, the objective of this research was to evaluate the inhibitory activities of curcumin and its analogs against α-glucosidase and XO. Our results demonstrated that CM-F had the strongest antioxidant activity with a half-maximal effective concentration (EC50) of 9.39 ± 0.16 μM, which was superior to vitamin E (EC50=17.03 ± 0.09 μM). CM-F also exhibited potent inhibitory activity against XO with an IC50 value of 6.14 ± 0.38 μM and enzyme kinetic results revealed competitive inhibition of XO. We also found that CM-1 and CM-2 inhibited α-glucosidase with IC50 values of 21.06 ± 0.92 μM and 5.95 ± 0.09 μM, respectively, and kinetic studies indicated that both CM-1 and CM-2 are mixed competitive inhibitors of α-glucosidase. Furthermore, docking simulation identified five hydrogen bonds between XO and CM-F; however, only one and two hydrogen bonds are involved in CM-1 and CM-2 binding to α-glucosidase, respectively. Accordingly, curcumin and its analogs have the potential to be used in the treatment of patients with diabetes mellitus and gout.

Keywords: curcumin, α-glucosidase, inhibitor, xanthine oxidase

Procedia PDF Downloads 181