Search results for: corrosion kinetics

Authors: Zoi Konsoula

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The increasing prevalence of Alzheimer’s disease (AD) and diabetes mellitus (DM) constitutes them major global health problems. Recently, the inhibition of key enzyme activity is considered a potential treatment of both diseases. Specifically, inhibition of acetylcholinesterase (AChE), the key enzyme involved in the breakdown of the neurotransmitter acetylcholine, is a promising approach for the treatment of AD, while inhibition of α-amylase retards the hydrolysis of carbohydrates and, thus, reduces hyperglycemia. Unfortunately, commercially available AChE and α-amylase inhibitors are reported to possess side effects. Consequently, there is a need to develop safe and effective treatments for both diseases. In the present study, pomegranate peel (PP) was extracted using various solvents of increasing polarity, while two extraction methods were employed, the conventional maceration and the ultrasound assisted extraction (UAE). The concentration of bioactive phytoconstituents, such as total phenolics (TPC) and total flavonoids (TFC) in the prepared extracts was evaluated by the Folin-Ciocalteu and the aluminum-flavonoid complex method, respectively. Furthermore, the anti-neurodegenerative and anti-hyperglycemic activity of all extracts was determined using AChE and α-amylase inhibitory activity assays, respectively. The inhibitory activity of the extracts against AChE and α-amylase was characterized by estimating their IC₅₀ value using a dose-response curve, while galanthamine and acarbose were used as positive controls, respectively. Finally, the kinetics of AChE and α-amylase in the presence of the most inhibitory potent extracts was determined by the Lineweaver-Burk plot. The methanolic extract prepared using the UAE contained the highest amount of phytoconstituents, followed by the respective ethanolic extract. All extracts inhibited acetylcholinesterase in a dose-dependent manner, while the increased anticholinesterase activity of the methanolic (IC₅₀ = 32 μg/mL) and ethanolic (IC₅₀ = 42 μg/mL) extract was positively correlated with their TPC content. Furthermore, the activity of the aforementioned extracts was comparable to galanthamine. Similar results were obtained in the case of α-amylase, however, all extracts showed lower inhibitory effect on the carbohydrate hydrolyzing enzyme than on AChE, since the IC₅₀ value ranged from 84 to 100 μg/mL. Also, the α-amylase inhibitory effect of the extracts was lower than acarbose. Finally, the methanolic and ethanolic extracts prepared by UAE inhibited both enzymes in a mixed (competitive/noncompetitive) manner since the Kₘ value of both enzymes increased in the presence of extracts, while the Vmax value decreased. The results of the present study indicate that PP may be a useful source of active compounds for the management of AD and DM. Moreover, taking into consideration that PP is an agro-industrial waste product, its valorization could not only result in economic efficiency but also reduce the environmental pollution.

Keywords: acetylcholinesterase, Alzheimer’s disease, α-amylase, diabetes mellitus, pomegranate

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Authors: Rio Hirakawa, Christian Gundlach, Sven Hartwig

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In recent years, the use of aluminium has further expanded and is expected to replace steel in the future as vehicles become lighter and more recyclable in order to reduce greenhouse gas (GHG) emissions and improve fuel economy. In line with this, structures and components are becoming increasingly multi-material, with different materials, including aluminium, being used in combination to improve mechanical utility and performance. A common method of assembling dissimilar materials is mechanical fastening, but it has several drawbacks, such as increased manufacturing processes and the influence of substrate-specific mechanical properties. Adhesive bonding and fusion bonding are methods that overcome the above disadvantages. In these two joining methods, surface pre-treatment of the substrate is always necessary to ensure the strength and durability of the joint. Previous studies have shown that laser surface treatment improves the strength and durability of the joint. Yan et al. showed that laser surface treatment of aluminium alloys changes α-Al2O3 in the oxide layer to γ-Al2O3. As γ-Al2O3 has a large specific surface area, is very porous and chemically active, laser-treated aluminium surfaces are expected to undergo physico-chemical changes over time and adsorb moisture and organic substances from the air or storage atmosphere. The impurities accumulated on the laser-treated surface may be released at the adhesive and bonding interface by the heat input to the bonding system during the joining phase, affecting the strength and durability of the joint. However, only a few studies have discussed the effect of such storage periods on laser-treated surfaces. This paper, therefore, investigates the ageing of laser-treated aluminium alloy surfaces through thermal analysis, electrochemical analysis and microstructural observations.AlMg3 of 0.5 mm and 1.5 mm thickness was cut using a water-jet cutting machine, cleaned and degreased with isopropanol and surface pre-treated with a pulsed fibre laser at 1060 nm wavelength, 70 W maximum power and 55 kHz repetition frequency. The aluminium surface was then analysed using SEM, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and cyclic voltammetry (CV) after storage in air for various periods ranging from one day to several months TGA and FTIR analysed impurities adsorbed on the aluminium surface, while CV revealed changes in the true electrochemically active surface area. SEM also revealed visual changes on the treated surface. In summary, the changes in the laser-treated aluminium surface with storage time were investigated, and the final results were used to determine the appropriate storage period.

Keywords: laser surface treatment, pre-treatment, adhesion, bonding, corrosion, durability, dissimilar material interface, automotive, aluminium alloys

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Authors: Rajat Dhawan, Hitendra K. Malik

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Electronegative plasmas comprising electrons, positive ions, and negative ions are advantageous for their expanding applications in industries. In plasma cleaning, plasma etching, and plasma deposition process, electronegative plasmas are preferred because of relatively less potential developed on the surface of the material under investigation. Also, the presence of negative ions avoid the irregularity in etching shapes and also enhance the material working during the fabrication process. The interaction of metallic conducting surface with plasma becomes mandatory to understand these applications. A metallic conducting probe immersed in a plasma results in the formation of a thin layer of charged species around the probe called as a sheath. The density of the ions embedded on the surface of the material and the sheath thickness are the important parameters for the surface-plasma interaction. Sheath thickness will give rise to the information of affected plasma region due to conducting surface/probe. The knowledge of the density of ions in the sheath region is advantageous in plasma nitriding, and their temperature is equally important as it strongly influences the thickness of the modified layer during surface plasma interaction. In the present work, we considered a negatively biased metallic probe immersed in a warm electronegative plasma. For this system, we adopted the continuity equation and momentum transfer equation for both the positive and negative ions, whereas electrons are described by Boltzmann distribution. Finally, we use the Poisson’s equation. Here, we assumed the spherical geometry for small probe radius. Poisson’s equation reveals the behaviour of potential surrounding a conducting metallic probe along with the use of the continuity and momentum transfer equations, with the help of proper boundary conditions. In turn, it gives rise to the information about the density profile of charged species and most importantly the thickness of the sheath. By keeping in mind, the well-known Bohm-Sheath criterion, all calculations are done. We found that positive ion density decreases with an increase in positive ion temperature, whereas it increases with the higher temperature of the negative ions. Positive ion density decreases as we move away from the center of the probe and is found to show a discontinuity at a particular distance from the center of the probe. The distance where discontinuity occurs is designated as sheath edge, i.e., the point where sheath ends. These results are beneficial for industrial applications, as the density of ions embedded on material surface is strongly affected by the temperature of plasma species. It has a drastic influence on the surface properties, i.e., the hardness, corrosion resistance, etc. of the materials.

Keywords: electronegative plasmas, plasma surface interaction positive ion density, sheath thickness

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Authors: Sofia Lazareva, Artem Smolentsev

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Fluorescent photochromic materials collect strong interest due to their possible application in organic photonics such as optical logic systems, optical memory, visualizing sensors, as well as characterization of polymers and biological systems. In photochromic fluorescence switching systems the emission of fluorophore is modulated between ‘on’ and ‘off’ via the photoisomerization of photochromic moieties resulting in effective resonance energy transfer (FRET). In current work, we have studied both photochromic and fluorescent properties of several diarylethenes. It was found that coloured forms of these compounds are not fluorescent because of the efficient intramolecular energy transfer. Spectral and photochromic parameters of investigated substances have been measured in five solvents having different polarity. Quantum yields of photochromic transformation A↔B ΦA→B and ΦB→A as well as B isomer extinction coefficients were determined by kinetic method. It was found that the photocyclization reaction quantum yield of all compounds decreases with the increase of solvent polarity. In addition, the solvent polarity is revealed to affect fluorescence significantly. Increasing of the solvent dielectric constant was found to result in a strong shift of emission band position from 450 nm (nhexane) to 550 nm (DMSO and ethanol) for all three compounds. Moreover, the emission intensive in polar solvents becomes weak and hardly detectable in n-hexane. The only one exception in the described dependence is abnormally low fluorescence quantum yield in ethanol presumably caused by the loss of electron-donating properties of nitrogen atom due to the protonation. An effect of the protonation was also confirmed by the addition of concentrated HCl in solution resulting in a complete disappearance of the fluorescent band. Excited state dynamics were investigated by ultrafast optical spectroscopy methods. Kinetic curves of excited states absorption and fluorescence decays were measured. Lifetimes of transient states were calculated from the data measured. The mechanism of ring opening reaction was found to be polarity dependent. Comparative analysis of kinetics measured in acetonitrile and hexane reveals differences in relaxation dynamics after the laser pulse. The most important fact is the presence of two decay processes in acetonitrile, whereas only one is present in hexane. This fact supports an assumption made on the basis of steady-state preliminary experiments that in polar solvents occur stabilization of TICT state. Thus, results achieved prove the hypothesis of two channel mechanism of energy relaxation of compounds studied.

Keywords: diarylethenes, fluorescence switching, FRET, photochromism, TICT state

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Authors: Shiva Shakori Poshteh

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Lung cancer is a highly prevalent and devastating disease, representing a significant global health concern with profound implications for healthcare systems and society. Its high incidence, mortality rates, and late-stage diagnosis contribute to its formidable nature. To address these challenges, nanoparticle-based drug delivery has emerged as a promising therapeutic strategy. Curcumin (CUR), a natural compound derived from turmeric, has garnered attention as a potential nanomedicine for lung cancer treatment. Nanoparticle formulations of CUR offer several advantages, including improved drug delivery efficiency, enhanced stability, controlled release kinetics, and targeted delivery to lung cancer cells. CUR exhibits a diverse array of effects on cancer cells. It induces apoptosis by upregulating pro-apoptotic proteins, such as Bax and Bak, and downregulating anti-apoptotic proteins, such as Bcl-2. Additionally, CUR inhibits cell proliferation by modulating key signaling pathways involved in cancer progression. It suppresses the PI3K/Akt pathway, crucial for cell survival and growth, and attenuates the mTOR pathway, which regulates protein synthesis and cell proliferation. CUR also interferes with the MAPK pathway, which controls cell proliferation and survival, and modulates the Wnt/β-catenin pathway, which plays a role in cell proliferation and tumor development. Moreover, CUR exhibits potent antioxidant activity, reducing oxidative stress and protecting cells from DNA damage. Utilizing CUR as a standalone treatment is limited by poor bioavailability, lack of targeting, and degradation susceptibility. Nanoparticle-based delivery systems can overcome these challenges. They enhance CUR’s bioavailability, protect it from degradation, and improve absorption. Further, Nanoparticles enable targeted delivery to lung cancer cells through surface modifications or ligand-based targeting, ensuring sustained release of CUR to prolong therapeutic effects, reduce administration frequency, and facilitate penetration through the tumor microenvironment, thereby enhancing CUR’s access to cancer cells. Thus, nanoparticle-based CUR delivery systems promise to improve lung cancer treatment outcomes. This article provides an overview of lung cancer, explores CUR nanoparticles as a treatment approach, discusses the benefits and challenges of nanoparticle-based drug delivery, and highlights prospects for CUR nanoparticles in lung cancer treatment. Future research aims to optimize these delivery systems for improved efficacy and patient prognosis in lung cancer.

Keywords: lung cancer, curcumin, nanomedicine, nanoparticle-based drug delivery

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Authors: Misagh Ghobadi, Rich Crane, Karen Hudson-Edwards, Clemens Vinzenz Ullmann

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Lithium is recognized as the critical energy metal of the 21st century, comparable in importance to coal in the 19th century and oil in the 20th century, often termed 'white gold'. Current global demand for lithium, estimated at 0.95-0.98 million metric tons (Mt) of lithium carbonate equivalent (LCE) annually in 2024, is projected to rise to 1.87 Mt by 2027 and 3.06 Mt by 2030. Despite anticipated short-term stability in supply and demand, meeting the forecasted 2030 demand will require the lithium industry to develop an additional capacity of 1.42 Mt of LCE annually, exceeding current planned and ongoing efforts. Brine resources constitute nearly 65% of global lithium reserves, underscoring the importance of exploring lithium recovery from underutilized sources, especially geothermal brines. However, conventional lithium extraction from brine deposits faces challenges due to its time-intensive process, low efficiency (30-50% lithium recovery), unsuitability for low lithium concentrations (<300 mg/l), and notable environmental impacts. Addressing these challenges, direct lithium extraction (DLE) methods have emerged as promising technologies capable of economically extracting lithium even from low-concentration brines (>50 mg/l) with high recovery rates (75-98%). However, most studies (70%) have predominantly focused on synthetic brines instead of native (natural/real), with limited application of these approaches in real-world case studies or industrial settings. This study aims to bridge this gap by investigating a geothermal brine sample collected from a real case study site in the UK. A Mn-based lithium-ion sieve (LIS) adsorbent was synthesized and employed to selectively extract lithium from the sample brine. Adsorbents with a Li:Mn molar ratio of 1:1 demonstrated superior lithium selectivity and adsorption capacity. Furthermore, the pristine Mn-based adsorbent was modified through transition metals doping, resulting in enhanced lithium selectivity and adsorption capacity. The modified adsorbent exhibited a higher separation factor for lithium over major co-existing cations such as Ca, Mg, Na, and K, with separation factors exceeding 200. The adsorption behaviour was well-described by the Langmuir model, indicating monolayer adsorption, and the kinetics followed a pseudo-second-order mechanism, suggesting chemisorption at the solid surface. Thermodynamically, negative ΔG° values and positive ΔH° and ΔS° values were observed, indicating the spontaneity and endothermic nature of the adsorption process.

Keywords: adsorption, critical minerals, DLE, geothermal brines, geochemistry, lithium, lithium-ion sieves

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Authors: Chiao-Cheng Huang, Pei-Te Chiueh, Ya-Hsuan Liou

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Chromium-contaminated wastewater from electroplating industrial activity has been a long-standing environmental issue, as it can degrade surface water quality and is harmful to soil ecosystems. The traditional method of treating chromium-contaminated wastewater has been to use chemical coagulation processes. However, this method consumes large amounts of chemicals such as sulfuric acid, sodium hydroxide, and sodium bicarbonate in order to remove chromium. However, a series of new methods for treating chromium-containing wastewater have been developed. This study aimed to compare the environmental impact of four different lab scale chromium removal processes: 1.) chemical coagulation process (the most common and traditional method), in which sodium metabisulfite was used as reductant, 2.) electrochemical process using two steel sheets as electrodes, 3.) reduction by iron-copper bimetallic powder, and 4.) photocatalysis process by TiO2. Each process was run in the lab, and was able to achieve 100% removal of chromium in solution. Then a Life Cycle Assessment (LCA) study was conducted based on the experimental data obtained from four different case studies to identify the environmentally preferable alternative to treat chromium wastewater. The model used for calculating the environmental impact was TRACi, and the system scope includes the production phase and use phase of chemicals and electricity consumed by the chromium removal processes, as well as the final disposal of chromium containing sludge. The functional unit chosen in this study was the removal of 1 mg of chromium. Solution volume of each case study was adjusted to 1 L in advance and the chemicals and energy consumed were proportionally adjusted. The emissions and resources consumed were identified and characterized into 15 categories of midpoint impacts. The impact assessment results show that the human ecotoxicity category accounts for 55 % of environmental impact in Case 1, which can be attributed to the sulfuric acid used for pH adjustment. In Case 2, production of steel sheet electrodes is an energy-intensive process, thus contributed to 20 % of environmental impact. In Case 3, sodium bicarbonate is used as an anti-corrosion additive, which results mainly in 1.02E-05 Comparative Toxicity Unit (CTU) in the human toxicity category and 0.54E-05 (CTU) in acidification of air. In Case 4, electricity consumption for power supply of UV lamp gives 5.25E-05 (CTU) in human toxicity category, 1.15E-05 (kg Neq) in eutrophication. In conclusion, Case 3 and Case 4 have higher environmental impacts than Case 1 and Case 2, which can be attributed mostly to higher energy and chemical consumption, leading to high impacts in the global warming and ecotoxicity categories.

Keywords: chromium, lab scale, life cycle assessment, wastewater

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Authors: Opemiposi Adegbulu

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The research investigates the existence of a public interest consideration or rationale for the management of directors’ conflicts of interest within large public corporations. This is conducted through extensive literature review and theories on the definition of conflicts of interest, the firm and purposes of the fiduciary duty of loyalty under which the management of these conflicts of interest find their foundation. Conflicts of interest is an elusive, diverse and engaging subject, a cross-cutting problem of governance which involves all levels of governance, ranging from local to global, public to corporate or financial sectors. It is a common issue that affects corporate governance and corporate culture, having a negative impact on the reputation of corporations and their trustworthiness. It is clear that addressing this issue is imperative for good governance of corporations as they are increasingly becoming and are powerful global economies with significant power and influence in the society. Similarly, the bargaining power of these powerful corporations has been recognised by international organisations such as the UN and the OECD. This is made evident by the increasing calls and push for greater responsibility of these corporations for environmental and social disasters caused by their corporate activities and their impact in various parts of the world. Equally, in the US, the Sarbanes-Oxley Act like other legislation and regulatory efforts made to manage conflicts of interest linked to corporate governance, in many countries indicates that there is a (global) public interest in the maintenance of the orderly functioning of commerce. Consequently, the governance of these corporations is tremendously pivotal to the society as it touches upon a key aspect of the good functioning of society. This is because corporations, particularly large international corporations can be said to be the plumbing of the global economy. This study will employ theoretical, doctrinal and comparative methods. The research will make use largely of theory-guided methodology and theoretical framework – theories of the firm, public interest, regulation, conflicts of interest in general, directors’ conflicts of interest and corporate governance. Although, the research is intended to be narrowed down to the topic of conflicts of interest in corporate governance, the subject of company directors’ duty of loyalty and the management of conflicts of interest, an examination of the history, origin and typology of conflicts of interest in general will be carried out in order to identify some specific challenges to understanding and identifying these conflicts of interest; origin, diverging theories, psychological barrier to definition, similarities with public sector conflicts of interest due to the notions of corrosion of trust, the effect on decision-making and judgment, “being in a particular kind of situation”, etc. The result of this research will be useful and relevant in the identification of the rationale for the management of directors’ conflicts of interest, contributing to the understanding of conflicts of interest in the private sector and the significance of public interest in corporate governance of large corporations.

Keywords: conflicts of interest, corporate governance, corporate law, directors duty of loyalty, public interest

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Authors: M. François, L. Sigot, C. Vallières

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Volatile Organic Compounds (VOCs) are a real health issue, particularly in domestic indoor environments. Among these VOCs, acetaldehyde is frequently monitored in dwellings ‘air, especially due to smoking and spontaneous emissions from the new wall and soil coverings. It is responsible for respiratory complaints and is classified as possibly carcinogenic to humans. Adsorption processes are commonly used to remove VOCs from the air. Metal-Organic Frameworks (MOFs) are a promising type of material for high adsorption performance. These hybrid porous materials composed of metal inorganic clusters and organic ligands are interesting thanks to their high porosity and surface area. The HKUST-1 (also referred to as MOF-199) is a copper-based MOF with the formula [Cu₃(BTC)₂(H₂O)₃]n (BTC = benzene-1,3,5-tricarboxylate) and exhibits unsaturated metal sites that can be attractive sites for adsorption. The objective of this study is to investigate the impact of HKUST-1 pretreatment on acetaldehyde adsorption. Thus, dynamic adsorption experiments were conducted in 1 cm diameter glass column packed with 2 cm MOF bed height. MOF were sieved to 630 µm - 1 mm. The feed gas (Co = 460 ppmv ± 5 ppmv) was obtained by diluting a 1000 ppmv acetaldehyde gas cylinder in air. The gas flow rate was set to 0.7 L/min (to guarantee a suitable linear velocity). Acetaldehyde concentration was monitored online by gas chromatography coupled with a flame ionization detector (GC-FID). Breakthrough curves must allow to understand the interactions between the MOF and the pollutant as well as the impact of the HKUST-1 humidity in the adsorption process. Consequently, different MOF water content conditions were tested, from a dry material with 7 % water content (dark blue color) to water saturated state with approximately 35 % water content (turquoise color). The rough material – without any pretreatment – containing 30 % water serves as a reference. First, conclusions can be drawn from the comparison of the evolution of the ratio of the column outlet concentration (C) on the inlet concentration (Co) as a function of time for different HKUST-1 pretreatments. The shape of the breakthrough curves is significantly different. The saturation of the rough material is slower (20 h to reach saturation) than that of the dried material (2 h). However, the breakthrough time defined for C/Co = 10 % appears earlier in the case of the rough material (0.75 h) compared to the dried HKUST-1 (1.4 h). Another notable difference is the shape of the curve before the breakthrough at 10 %. An abrupt increase of the outlet concentration is observed for the material with the lower humidity in comparison to a smooth increase for the rough material. Thus, the water content plays a significant role on the breakthrough kinetics. This study aims to understand what can explain the shape of the breakthrough curves associated to the pretreatments of HKUST-1 and which mechanisms take place in the adsorption process between the MOF, the pollutant, and the water.

Keywords: acetaldehyde, dynamic adsorption, HKUST-1, pretreatment influence

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Authors: Joël Passicousset, David Gilbert, Chloé Chervier-Legourd, Emmanuel Caron-Garant, Didier Labarre

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Living soil agriculture tries to reconciliate food production while improving soil health, soil biodiversity, soil fertility and more generally attenuating the inherent environmental drawbacks induced by modern agriculture. Using appropriate organic materials as soil amendments has a role to play in the aim of increasing the soil organic matter, improving soil fertility, sequestering carbon, and diminishing the dependence on both mineral fertilizer and pesticides. Insect farming consists in producing insects that can be used as a rich-in-protein and entomo-based food. Usually, detritivores are chosen, thus they can be fed with food wastes, which contributes to circular economy while producing low-carbon food. This process also produces frass, made of insect feces, exuvial material, and non-digested fibrous material, that have valuable fertilizer and biostimulation properties. But frass, used as a sole fertilizer on a crop may be not completely adequate for plants’ needs. This is why this project considers black soldier fly (termed BSF, one of the three main insect species grown commercially) frass as a complementary fertilizer, both in organic and in conventional contexts. Three kinds of experiments are made to understand the behaviour of fertilizer treatments based on frass incorporation. Lab-scale mineralization experiments suggest that BSF frass alone mineralizes more slowly than chicken manure alone (CM), but at a ratio of 90% CM-10% BSF frass, the mineralization rate of the mixture is higher than both frass and CM individually. For example, in the 7 days following the fertilization with same nitrogen amount introduced among treatments, around 80% of the nitrogen content supplied through 90% CM-10% BSF frass fertilization is present in the soil under mineral forms, compared to roughly 60% for commercial CM fertilization and 45% with BSF-frass. This suggests that BSF frass contains a more recalcitrant form of organic nitrogen than CM, but also that BSF frass has a highly active microbiota that can increase CM mineralization rate. Consequently, when progressive mineralization is needed, pure BSF-frass may be a consistent option from an agronomic aspect whereas, for specific crops that require spikes of readily available nitrogen sources (like cranberry), fast release 90CM-10BSF frass biofertilizer are more appropriate. Field experiments on cranberry suggests that, indeed, 90CM-10BSF frass is a potent candidate for organic cranberry production, as currently, organic growers rely solely on CM, whose mineralization kinetics are known to imperfectly match plant’s needs, which is known to be a major reason that sustains the current yield gap between conventional and organic cranberry sectors.

Keywords: soil mineralization, biofertilizer, BSF-frass, chicken manure, soil functions, nitrogen, soil microbiota

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Authors: Ranjita Ghoshmoulick, Aswathi Madhavan, Subhavna Juneja, Prasenjit Sen, Jaydeep Bhattacharya

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Type 2 diabetes mellitus (T2DM) is a very complex and multifactorial metabolic disease where the blood sugar level goes up. One of the major consequence of this elevated blood sugar is the formation of AGE (Advance Glycation Endproducts), from a series of chemical or biochemical reactions. AGE are detrimental because it leads to severe pathogenic complications. They are a group of structurally diverse chemical compounds formed from nonenzymatic reactions between the free amino groups (-NH2) of proteins and carbonyl groups (>C=O) of reducing sugars. The reaction is known as Maillard Reaction. It starts with the formation of reversible schiff’s base linkage which after sometime rearranges itself to form Amadori Product along with dicarbonyl compounds. Amadori products are very unstable hence rearrangement goes on until stable products are formed. During the course of the reaction a lot of chemically unknown intermediates and reactive byproducts are formed that can be termed as Early Glycation Products. And when the reaction completes, structurally stable chemical compounds are formed which is termed as Advanced Glycation Endproducts. Though all glycation products have not been characterized well, some fluorescence compounds e.g pentosidine, Malondialdehyde (MDA) or carboxymethyllysine (CML) etc as AGE and α-dicarbonyls or oxoaldehydes such as 3-deoxyglucosone (3-DG) etc as the intermediates have been identified. In this work Gold NanoParticle (GNP) was used as an optical indicator of glycation products. To achieve faster glycation kinetics and high AGE accumulation, fructose was used instead of glucose. Hemoglobin A0 (HbA0) was fructosylated by in-vitro method. AGE formation was measured fluorimetrically by recording emission at 450nm upon excitation at 350nm. Thereafter this fructosylated HbA0 was fractionated by column chromatography. Fractionation separated the proteinaceous substance from the AGEs. Presence of protein part in the fractions was confirmed by measuring the intrinsic protein fluorescence and Bradford reaction. GNPs were synthesized using the templates of chromatographically separated fractions of fructosylated HbA0. Each fractions gave rise to GNPs of varying color, indicating the presence of distinct set of glycation products differing structurally and chemically. Clear solution appeared due to settling down of particles in some vials. The reactive groups of the intermediates kept the GNP formation mechanism on and did not lead to a stable particle formation till Day 10. Whereas SPR of GNP showed monotonous colour for the fractions collected in case of non fructosylated HbA0. Our findings accentuate the use of GNPs as a simple colorimetric sensing platform for the identification of intermediates of glycation reaction which could be implicated in the prognosis of the associated health risk due to T2DM and others.

Keywords: advance glycation endproducts, glycation, gold nano particle, sensor

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Authors: Sarah Crawford, Gerry Lesley

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This research is a pre-clinical assessment of anti-cancer effects of novel non-steroidal diethyl stilbestrol-like estrogen analogs in estrogen-receptor positive/ progesterone-receptor positive human breast cancer microtumors of MCF 7 cell line. Tamoxifen analog formulation (Tam A1) was used as a single agent or in combination with therapeutic concentrations of 4-hydroxytamoxifen, currently used as a long-term treatment for the prevention of breast cancer recurrence in women with estrogen receptor positive/ progesterone receptor positive malignancies. At concentrations ranging from 30-50 microM, Tam A1 induced microtumor disaggregation and cell death. Incremental cytotoxic effects correlated with increasing concentrations of Tam A1. Live tumor microscopy showed that microtumos displayed diffuse borders and substrate-attached cells were rounded-up and poorly adherent. A complete cytotoxic effect was observed using 40-50 microM Tam A1 with time course kinetics similar to 4-hydroxytamoxifen. Combined treatment with TamA1 (30-50 microM) and 4-hydroxytamoxifen (10-15 microM) induced a highly cytotoxic, synergistic combined treatment response that was more rapid and complete than using 4-hydroxytamoxifen as a single agent therapeutic. Microtumors completely dispersed or formed necrotic foci indicating a highly cytotoxic combined treatment response. Moreover, breast cancer microtumors treated with both 4-hydroxytamoxifen and Tam A1 displayed lower levels of long-term post-treatment regrowth, a critical parameter of primary drug resistance, than observed for 4-hydroxytamoxifen when used as a single agent therapeutic. Tumor regrowth at 6 weeks post-treatment with either single agent 4-hydroxy tamoxifen, Tam A1 or a combined treatment was assessed for the development of drug resistance. Breast cancer cells treated with both 4-hydroxytamoxifen and Tam A1 displayed significantly lower levels of post-treatment regrowth, indicative of decreased drug resistance, than observed for either single treatment modality. The preclinical data suggest that combined treatment involving the use of tamoxifen analogs may be a novel clinical approach for long-term maintenance therapy in patients with estrogen-receptor positive/progesterone-receptor positive breast cancer receiving hormonal therapy to prevent disease recurrence. Detailed data on time-course, IC50 and tumor regrowth assays post- treatment as well as a proposed mechanism of action to account for observed synergistic drug effects will be presented.

Keywords: 4-hydroxytamoxifen, tamoxifen analog, drug-resistance, microtumors

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Authors: Rabindranath Jana, Biswajit Maity, Keka Rana

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The most promising clean energy source is the fuel cell, since it does not generate toxic gases and other hazardous compounds. Again the direct methanol fuel cell (DMFC) is more user-friendly as it is easy to be miniaturized and suited as energy source for automobiles as well as domestic applications and portable devices. And unlike the hydrogen used for some fuel cells, methanol is a liquid that is easy to store and transport in conventional tanks. The most important part of a fuel cell is its membrane. Till now, an overall efficiency for a methanol fuel cell is reported to be about 20 ~ 25%. The lower efficiency of the cell may be due to the critical factors, e.g. slow reaction kinetics at the anode and methanol crossover. The oxidation of methanol is composed of a series of successive reactions creating formaldehyde and formic acid as intermediates that contribute to slow reaction rates and decreased cell voltage. Currently, the investigation of new anode catalysts to improve oxidation reaction rates is an active area of research as it applies to the methanol fuel cell. Surprisingly, there are very limited reports on nanostructured membranes, which are rather simple to manufacture with different tuneable compositions and are expected to allow only the proton permeation but not the methanol due to their molecular sizing effects and affinity to the membrane surface. We have developed a nanostructured fuel cell membrane from polydimethyl siloxane rubber (PDMS), ethylene methyl co-acrylate (EMA) and multi-walled carbon nanotubes (MWNTs). The effect of incorporating different proportions of f-MWNTs in polymer membrane has been studied. The introduction of f-MWNTs in polymer matrix modified the polymer structure, and therefore the properties of the device. The proton conductivity, measured by an AC impedance technique using open-frame and two-electrode cell and methanol permeability of the membranes was found to be dependent on the f-MWNTs loading. The proton conductivity of the membranes increases with increase in concentration of f-MWNTs concentration due to increased content of conductive materials. Measured methanol permeabilities at 60oC were found to be dependant on loading of f-MWNTs. The methanol permeability decreased from 1.5 x 10-6 cm²/s for pure film to 0.8 x 10-7 cm²/s for a membrane containing 0.5wt % f-MWNTs. This is due to increasing proportion of f-MWNTs, the matrix becomes more compact. From DSC melting curves it is clear that the polymer matrix with f-MWNTs is thermally stable. FT-IR studies show good interaction between EMA and f-MWNTs. XRD analysis shows good crystalline behavior of the prepared membranes. Significant cost savings can be achieved when using the blended films which contain less expensive polymers.

Keywords: fuel cell membrane, polydimethyl siloxane rubber, carbon nanotubes, proton conductivity, methanol permeability

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Authors: Augustus K. Lebechi, Kenneth I. Ozoemena

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Rechargeable zinc-air batteries (RZABs) have been described as one of the most viable next-generation ‘beyond-the-lithium-ion’ battery technologies with great potential for renewable energy storage. It is safe, with a high specific energy density (1086 Wh/kg), environmentally benign, and low-cost, especially in resource-limited African countries. For widespread commercialization, the sluggish oxygen reaction kinetics pose a major challenge that impedes the reversibility of the system. Hence, there is a need for low-cost and highly active bifunctional electrocatalysts. Manganese oxide catalysts on carbon conducting additives remain the best couple for the realization of such low-cost RZABs. In this work, hausmannite Mn₃O₄ nanoparticles were synthesized through the annealing method from commercial electrolytic manganese dioxide (EMD), multi-walled carbon nanotubes (MWCNTs) were synthesized via the chemical vapor deposition (CVD) method and carbon nanofibers (CNFs) were synthesized via the electrospinning process with subsequent carbonization. Both Mn₃O₄ catalysts and the carbon conducting additives (MWCNT and CNF) were thoroughly characterized using X-ray powder diffraction spectroscopy (XRD), scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and X-ray photoelectron spectroscopy (XPS). Composite electrocatalysts (Mn₃O₄/CNT and Mn₃O₄/CNF) were investigated for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in an alkaline medium. Using the established electrocatalytic modalities for evaluating the electrocatalytic performance of materials (including double layer, electrochemical active surface area, roughness factor, specific current density, and catalytic stability), CNFs proved to be the most efficient conducting additive material for the Mn₃O₄ catalyst. From the DFT calculations, the higher performance of the CNFs over the MWCNTs is related to the ability of the CNFs to allow for a more favorable distribution of the d-electrons of the manganese (Mn) and enhanced synergistic effect with Mn₃O₄ for weaker adsorption energies of the oxygen intermediates (O*, OH* and OOH*). In a proof-of-concept, Mn₃O₄/CNF was investigated as the air cathode for rechargeable zinc-air battery (RZAB) in a micro-3D-printed cell configuration. The RZAB showed good performance in terms of open circuit voltage (1.77 V), maximum power density (177.5 mW cm-2), areal-discharge energy and cycling stability comparable to Pt/C (20 wt%) + IrO2. The findings here provide fresh physicochemical perspectives on the future design and utility of CNFs for developing manganese-based RZABs.

Keywords: bifunctional electrocatalyst, oxygen evolution reaction, oxygen reduction reactions, rechargeable zinc-air batteries.

Procedia PDF Downloads 45

Authors: Suman Som, Abhijit Maity, Sunil B. Daschakraborty, Sujit Chaudhuri, Manik Pradhan

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Background: Helicobacter pylori is a common and important human pathogen and the primary cause of peptic ulcer disease and gastric cancer. Currently H. pylori infection is detected by both invasive and non-invasive way but the diagnostic accuracy is not up to the mark. Aim: To set up an optimal diagnostic cut-off value of 13C-Urea Breath Test to detect H. pylori infection and evaluate a novel c-PDR methodology to overcome of inconclusive grey zone. Materials and Methods: All 83 subjects first underwent upper-gastrointestinal endoscopy followed by rapid urease test and histopathology and depending on these results; we classified 49 subjects as H. pylori positive and 34 negative. After an overnight, fast patients are taken 4 gm of citric acid in 200 ml water solution and 10 minute after ingestion of the test meal, a baseline exhaled breath sample was collected. Thereafter an oral dose of 75 mg 13C-Urea dissolved in 50 ml water was given and breath samples were collected upto 90 minute for 15 minute intervals and analysed by laser based high precisional cavity enhanced spectroscopy. Results: We studied the excretion kinetics of 13C isotope enrichment (expressed as δDOB13C ‰) of exhaled breath samples and found maximum enrichment around 30 minute of H. pylori positive patients, it is due to the acid mediated stimulated urease enzyme activity and maximum acidification happened within 30 minute but no such significant isotopic enrichment observed for H. pylori negative individuals. Using Receiver Operating Characteristic (ROC) curve an optimal diagnostic cut-off value, δDOB13C ‰ = 3.14 was determined at 30 minute exhibiting 89.16% accuracy. Now to overcome grey zone problem we explore percentage dose of 13C recovered per hour, i.e. 13C-PDR (%/hr) and cumulative percentage dose of 13C recovered, i.e. c-PDR (%) in exhaled breath samples for the present 13C-UBT. We further explored the diagnostic accuracy of 13C-UBT by constructing ROC curve using c-PDR (%) values and an optimal cut-off value was estimated to be c-PDR = 1.47 (%) at 60 minute, exhibiting 100 % diagnostic sensitivity , 100 % specificity and 100 % accuracy of 13C-UBT for detection of H. pylori infection. We also elucidate the gastric emptying process of present 13C-UBT for H. pylori positive patients. The maximal emptying rate found at 36 minute and half empting time of present 13C-UBT was found at 45 minute. Conclusions: The present study exhibiting the importance of c-PDR methodology to overcome of grey zone problem in 13C-UBT for accurate determination of infection without any risk of diagnostic errors and making it sufficiently robust and novel method for an accurate and fast non-invasive diagnosis of H. pylori infection for large scale screening purposes.

Keywords: 13C-Urea breath test, c-PDR methodology, grey zone, Helicobacter pylori

Procedia PDF Downloads 287

Authors: A. Alzahrani, G. Arnold, W. Wang

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Background: Stroke commonly occurs in middle-aged and elderly populations, and the diagnosis of early stroke is still difficult. Patients who have suffered a stroke have different balance and gait patterns from healthy people. Advanced techniques of motion analysis have been routinely used in the clinical assessment of cerebral palsy. However, so far, little research has been done on the direct diagnosis of early stroke patients using motion analysis. Objectives: The aim of this study was to investigate whether patients with stroke have different balance and gait from healthy people and which biomechanical parameters could be used to predict and diagnose potential patients who are at a potential risk to stroke. Methods: Thirteen patients with stroke were recruited as subjects whose gait and balance was analysed. Twenty normal subjects at the matched age participated in this study as a control group. All subjects’ gait and balance were collected using Vicon Nexus® to obtain the gait parameters, kinetic, and kinematic parameters of the hip, knee, and ankle joints in three planes of both limbs. Participants stood on force platforms to perform a single leg balance test. Then, they were asked to walk along a 10 m walkway at their comfortable speed. Participants performed 6 trials of single-leg balance for each side and 10 trials of walking. From the recorded trials, three good ones were analysed using the Vicon Plug-in-Gait model to obtain gait parameters, e.g., walking speed, cadence, stride length, and joint parameters, e.g., joint angle, force, moments, etc. Result: The temporal-spatial variables of Stroke subjects were compared with the healthy subjects; it was found that there was a significant difference (p < 0.05) between the groups. The step length, speed, cadence were lower in stroke subjects as compared to the healthy groups. The stroke patients group showed significantly decreased in gait speed (mean and SD: 0.85 ± 0.33 m/s), cadence ( 96.71 ± 16.14 step/min), and step length (0.509 ± 017 m) in compared to healthy people group whereas the gait speed was 1.2 ± 0.11 m/s, cadence 112 ± 8.33 step/min, and step length 0.648 ± 0.43 m. Moreover, it was observed that patients with stroke have significant differences in the ankle, hip, and knee joints’ kinematics in the sagittal and coronal planes. Also, the result showed that there was a significant difference between groups in the single-leg balance test, e.g., maintaining single-leg stance time in the stroke patients showed shorter duration (5.97 ± 6.36 s) in compared to healthy people group (14.36 ± 10.20 s). Conclusion: Our result showed that there are significantly differences between stroke patients and healthy subjects in the various aspects of gait analysis and balance test, as a consequences of these findings some of the biomechanical parameters such as joints kinematics, gait parameters, and single-leg stance balance test could be used in clinical practice to predict and diagnose potential patients who are at a high risk of further stroke.

Keywords: gait analysis, kinetics, kinematics, single-leg stance, Stroke

Procedia PDF Downloads 127

Authors: A. N. Kurbanova, G. K. Sugurbekova, N. K. Akhmetov

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The asphaltenes are heavy fraction of crude oil. Asphaltenes on oilfield is known for its ability to plug wells, surface equipment and pores of the geologic formations. The present research is devoted to the deasphalting of crude oil as the initial stage refining oil. Solvent deasphalting was conducted by extraction with organic solvents (cyclohexane, carbon tetrachloride, chloroform). Analysis of availability of metals was conducted by ICP-MS and spectral feature at deasphalting was achieved by FTIR. High contents of asphaltenes in crude oil reduce the efficiency of refining processes. Moreover, high distribution heteroatoms (e.g., S, N) were also suggested in asphaltenes cause some problems: environmental pollution, corrosion and poisoning of the catalyst. The main objective of this work is to study the effect of deasphalting process crude oil to improve its properties and improving the efficiency of recycling processes. Experiments of solvent extraction are using organic solvents held in the crude oil JSC “Pavlodar Oil Chemistry Refinery. Experimental results show that deasphalting process also leads to decrease Ni, V in the composition of the oil. One solution to the problem of cleaning oils from metals, hydrogen sulfide and mercaptan is absorption with chemical reagents directly in oil residue and production due to the fact that asphalt and resinous substance degrade operational properties of oils and reduce the effectiveness of selective refining of oils. Deasphalting of crude oil is necessary to separate the light fraction from heavy metallic asphaltenes part of crude oil. For this oil is pretreated deasphalting, because asphaltenes tend to form coke or consume large quantities of hydrogen. Removing asphaltenes leads to partly demetallization, i.e. for removal of asphaltenes V/Ni and organic compounds with heteroatoms. Intramolecular complexes are relatively well researched on the example of porphyinous complex (VO2) and nickel (Ni). As a result of studies of V/Ni by ICP MS method were determined the effect of different solvents-deasphalting – on the process of extracting metals on deasphalting stage and select the best organic solvent. Thus, as the best DAO proved cyclohexane (C6H12), which as a result of ICP MS retrieves V-51.2%, Ni-66.4%? Also in this paper presents the results of a study of physical and chemical properties and spectral characteristics of oil on FTIR with a view to establishing its hydrocarbon composition. Obtained by using IR-spectroscopy method information about the specifics of the whole oil give provisional physical, chemical characteristics. They can be useful in the consideration of issues of origin and geochemical conditions of accumulation of oil, as well as some technological challenges. Systematic analysis carried out in this study; improve our understanding of the stability mechanism of asphaltenes. The role of deasphalted crude oil fractions on the stability asphaltene is described.

Keywords: asphaltenes, deasphalting, extraction, vanadium, nickel, metalloporphyrins, ICP-MS, IR spectroscopy

Procedia PDF Downloads 227

Authors: P. D. Pedrosa, J. M. A. Rebello, M. P. Cindra Fonseca

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Duplex stainless steels (DSS) exhibit a biphasic microstructure consisting of austenite and delta ferrite. Their high resistance to oxidation, and corrosion, even in H2S containing environments, allied to low cost when compared to conventional stainless steel, are some properties which make this material very attractive for several industrial applications. However, several of these industrial applications imposes cyclic loading to the equipments and in consequence fatigue damage needs to be a concern. A well-known way of improving the fatigue life of a component is by introducing compressive residual stress in its surface. Shot peening is an industrial working process which brings the material directly beneath component surface in a high mechanical compressive state, so inhibiting fatigue crack initiation. However, one must take into account the fact that the cyclic loading itself can reduce and even suppress these residual stresses, thus having undesirable consequences in the process of improving fatigue life by the introduction of compressive residual stresses. In the present work, shot peening was used to introduce residual stresses in several DSS samples. These were thereafter submitted to three different fatigue regimes: low, medium and high cycle fatigue. The evolution of the residual stress during loading were then examined on both surface and subsurface of the samples. It was used the DSS UNS S31803, with microstructure composed of 49% austenite and 51% ferrite. The treatment of shot peening was accomplished by the application of blasting in two Almen intensities of 0.25 and 0.39A. The residual stresses were measured by X-ray diffraction using the double exposure method and a portable equipment with CrK radiation and the (211) diffracting plane for the austenite phase and the (220) plane for the ferrite phase. It is known that residual stresses may arise when two regions of the same material experienced different degrees of plastic deformation. When these regions are separated in respect to each other on a scale that is large compared to the material's microstructure they are called macro stresses. In contrast, microstresses can largely vary over distances which are small comparable to the scale of the material's microstructure and must balance zero between the phases present. In the present work, special attention will be paid to the measurement of residual microstresses. Residual stress measurements were carried out in test pieces submitted to low, medium and high-cycle fatigue, in both longitudinal and transverse direction of the test pieces. It was found that after shot peening, the residual microstress is tensile in the austenite and compressive in the ferrite phases. It was hypothesized that the hardening behavior of the austenite after shot peening was probably due to its higher nitrogen content. Fatigue cycling can effectively change this stress state but this effect was found to be dependent of the shot peening intensity was well as the fatigue range.

Keywords: residual stresses, fatigue, duplex steel, shot peening

Procedia PDF Downloads 203

Authors: Franciele L. Bernard, Felipe Dalla Vecchia, Barbara B. Polesso, Jose A. Donato, Marcus Seferin, Rosane Ligabue, Jailton F. do Nascimento, Sandra Einloft

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The increasing level of carbon dioxide concentration in the atmosphere related to fossil fuels processing and utilization are contributing to global warming phenomena considerably. Carbon capture and storage (CCS) technologies appear as one of the key technologies to reduce CO2 emissions mitigating the effects of climate change. Absorption using amines solutions as solvents have been extensively studied and used in industry for decades. However, solvent degradation and equipment corrosion are two of the main problems in this process. Poly (ionic liquid) (PIL) is considered as a promising material for CCS technology, potentially more environmentally friendly and lesser energy demanding than traditional material. PILs possess a unique combination of ionic liquids (ILs) features, such as affinity for CO2, thermal and chemical stability and adjustable properties, coupled with the intrinsic properties of the polymer. This study investigated new Poly (ionic liquid) (PIL) based on polyurethanes with different ionic liquids cations and its potential for CO2 capture. The PILs were synthesized by the addition of diisocyante to a difunctional polyol, followed by an exchange reaction with the ionic Liquids 1-butyl-3-methylimidazolium chloride (BMIM Cl); tetrabutylammonium bromide (TBAB) and tetrabutylphosphonium bromide (TBPB). These materials were characterized by Fourier transform infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance (1H-NMR), Atomic force microscopy (AFM), Tensile strength analysis, Field emission scanning electron microscopy (FESEM), Thermogravimetric analysis (TGA), Differential scanning calorimetry (DSC). The PILs CO2 sorption capacity were gravimetrically assessed in a Magnetic Suspension Balance (MSB). It was found that the ionic liquids cation influences in the compounds properties as well as in the CO2 sorption. The best result for CO2 sorption (123 mgCO2/g at 30 bar) was obtained for the PIL (PUPT-TBA). The higher CO2 sorption in PUPT-TBA is probably linked to the fact that the tetraalkylammonium cation having a higher positive density charge can have a stronger interaction with CO2, while the imidazolium charge is delocalized. The comparative CO2 sorption values of the PUPT-TBA with different ionic liquids showed that this material has greater capacity for capturing CO2 when compared to the ILs even at higher temperature. This behavior highlights the importance of this study, as the poly (urethane) based PILs are cheap and versatile materials.

Keywords: capture, CO2, ionic liquids, ionic poly(urethane)

Procedia PDF Downloads 219

Authors: Dongwoo Kang, Yunsung Yoo, Injun Kim, Jongin Lee, Jinwon Park

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Since industrial revolution, energy usage by human-beings has been drastically increased resulting in the enormous emissions of carbon dioxide into the atmosphere. High concentration of carbon dioxide is well recognized as the main reason for the climate change by breaking the heat equilibrium of the earth. In order to decrease the amount of carbon dioxide emission, lots of technologies have been developed. One of the methods is to capture carbon dioxide after combustion process using liquid type absorbents. However, for some nations, captured carbon dioxide cannot be treated and stored properly due to their geological structures. Also, captured carbon dioxide can be leaked out when crust activities are active. Hence, the method to convert carbon dioxide as stable and useful products were developed. It is usually called CCU, that is, Carbon Capture and Utilization. There are several ways to convert carbon dioxide into useful substances. For example, carbon dioxide can be converted and used as fuels such as diesel, plastics, and polymers. However, these types of technologies require lots of energy to make stable carbon dioxide into a reactive one. Hence, converting it into metal carbonates salts have been studied widely. When carbon dioxide is captured by alkanolamine-based liquid absorbents, it exists as ionic forms such as carbonate, carbamate, and bicarbonate. When adequate metal ions are added, metal carbonate salt can be produced by ionic reaction with fast reaction kinetics. However, finding metal sources can be one of the problems for this method to be commercialized. If natural resources such as calcium oxide were used to supply calcium ions, it is not thought to have the economic feasibility to use natural resources to treat carbon dioxide. In this research, high concentrated industrial wastewater produced from refined salt production facility have been used as metal supplying source, especially for calcium cations. To ensure purity of final products, calcium ions were selectively separated in the form of gypsum dihydrate. After that, carbon dioxide is captured using alkanolamine-based absorbents making carbon dioxide into reactive ionic form. And then, high purity calcium carbonate salt was produced. The existence of calcium carbonate was confirmed by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) images. Also, carbon dioxide loading curves for absorption, conversion, and desorption were provided. Also, in order to investigate the possibility of the absorbent reuse, reabsorption experiments were performed either. Produced calcium carbonate as final products is seemed to have potential to be used in various industrial fields including cement and paper making industries and pharmaceutical engineering fields.

Keywords: alkanolamine, calcium carbonate, climate change, seawater, industrial wastewater

Procedia PDF Downloads 170

Authors: Sherif Fakher

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Hydrogen has been gaining a lot of global attention as an uprising contributor in the energy sector. Labeled as an energy carrier, hydrogen is used in many industries and can be used to generate electricity via fuel cells. Blue hydrogen involves the production of hydrogen from hydrocarbons using different processes that emit CO₂. However, the CO₂ is captured and stored. Hence, very little environmental damage occurs during the hydrogen production process. This research investigates the ability to use different catalysts for the production of hydrogen from different hydrocarbon sources, including coal, oil, and gas, using a two-step Aquathermolysis reaction. The research presents the results of experiments conducted to evaluate different catalysts and also highlights the main advantages of this process over other blue hydrogen production methods, including methane steam reforming, autothermal reforming, and oxidation. Two methods of hydrogen generation were investigated including partial oxidation and aquathermolysis. For those two reactions, the reaction kinetics, thermodynamics, and medium were all investigated. Following this, experiments were conducted to test the hydrogen generation potential from both methods. The porous media tested were sandstone, ash, and prozzolanic material. The spent oils used were spent motor oil and spent vegetable oil from cooking. Experiments were conducted at temperatures up to 250 C and pressures up to 3000 psi. Based on the experimental results, mathematical models were developed to predict the hydrogen generation potential at higher thermodynamic conditions. Since both partial oxidation and aquathermolysis require relatively high temperatures to undergo, it was important to devise a method by which these high temperatures can be generated at a low cost. This was done by investigating two factors, including the porous media used and the reliance on the spent oil. Of all the porous media used, the ash had the highest thermal conductivity. The second step was the partial combustion of part of the spent oil to generate the heat needed to reach the high temperatures. This reduced the cost of the heat generation significantly. For the partial oxidation reaction, the spent oil was burned in the presence of a limited oxygen concentration to generate carbon monoxide. The main drawback of this process was the need for burning. This resulted in the generation of other harmful and environmentally damaging gases. Aquathermolysis does not rely on burning, which makes it the cleaner alternative. However, it needs much higher temperatures to run the reaction. When comparing the hydrogen generation potential for both using gas chromatography, aquathermolysis generated 23% more hydrogen using the same volume of spent oil compared to partial oxidation. This research introduces the concept of using spent oil for hydrogen production. This can be a very promising method to produce a clean source of energy using a waste product. This can also help reduce the reliance on freshwater for hydrogen generation which can divert the usage of freshwater to other more important applications.

Keywords: blue hydrogen production, catalytic aquathermolysis, direct carbon dioxide capture, CCUS

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Authors: Kumaran Letchmanan, Shou-Cang Shen, Wai Kiong Ng

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Postoperative implant-associated infections in soft tissues and bones remain a serious complication in orthopaedic surgery, which leads to impaired healing, re-implantation, prolong hospital stay and increase cost. Drug-loaded implants with sustained release of antibiotics at the local site are current research interest to reduce the risk of post-operative infections and osteomyelitis, thus, minimize the need for follow-up care and increase patient comfort. However, the improved drug release of the drug-loaded bone cements is usually accompanied by a loss in mechanical strength, which is critical for weight-bearing bone cement. Recently, more attempts have been undertaken to develop techniques to enhance the antibiotic elution as well as preserve the mechanical properties of the bone cements. The present study investigates the potential influence of addition of mesoporous silica nanoparticles (MSN) on the in vitro drug release kinetics of gentamicin (GTMC), along with the mechanical properties of bone cements. Simplex P was formulated with MSN and loaded with GTMC by direct impregnation. Meanwhile, Simplex P with water soluble poragen (xylitol) and high loading of GTMC as well as commercial bone cement CMW Smartset GHV were used as controls. MSN-formulated bone cements are able to increase the drug release of GTMC by 3-fold with a cumulative release of more than 46% as compared with other control groups. Furthermore, a sustained release could be achieved for two months. The loaded nano-sized MSN with uniform pore channels significantly build up an effective nano-network path in the bone cement facilitates the diffusion and extended release of GTMC. Compared with formulations using xylitol and high GTMC loading, incorporation of MSN shows no detrimental effect on biomechanical properties of the bone cements as no significant changes in the mechanical properties as compared with original bone cement. After drug release for two months, the bending modulus of MSN-formulated bone cements is 4.49 ± 0.75 GPa and the compression strength is 92.7 ± 2.1 MPa (similar to the compression strength of Simplex-P: 93.0 ± 1.2 MPa). The unaffected mechanical properties of MSN-formulated bone cements was due to the unchanged microstructures of bone cement, whereby more than 98% of MSN remains in the matrix and supports the bone cement structures. In contrast, the large portions of extra voids can be observed for the formulations using xylitol and high drug loading after the drug release study, thus caused compressive strength below the ASTM F541 and ISO 5833 minimum of 70 MPa. These results demonstrate the potential applicability of MSN-functionalized poly(methyl methacrylate)-based bone cement as a highly efficient, sustained and local drug delivery system with good mechanical properties.

Keywords: antibiotics, biomechanical properties, bone cement, sustained release

Procedia PDF Downloads 243

Authors: Oubelkacem Yacine, El Bast Hassan, El Bakkali Abdelmajid, Lamhasni Taibi, Ettakni Mahmoud, Ait Lyazidi Saadia, Haddad Mustapha, Ben-Ncer Abdelouahed, El Ferrane Mohammed, Boufarra Abdelkrim

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The present work relates to an on-site and completely non-invasive investigation of one of the most famous west Mediterranean Torah Scroll housed at the National Library of the Kingdom of Morocco. The scroll is 26 m long and consists of 143 parchment sheets of 59 cm x 19 cm, exhibiting only black writings; it is of unknown age. The artifact has been restored by the curator staff of the library. The investigation exploring separately the parchment support and the writing black ink aims at: i) the examination of the parchment conservation/degradation state, ii) the identification of the black ink and iii) the identification of the parchment handcrafting materials. For this purpose, the analyses have been based on combining all of elemental XRF and structural Raman, ATR-FT Infrared Red and Fiber Optical Reflectance spectroscopies, in addition to chroma-metric and pH measurements. pH measurements showing values around 6.5 are in concordance with the absence of any visual corrosion related to the parchment acidity. However, on the basis of the relative intensities and frequency shift of amid I (AI) and amid II (AII) vibrational bands of the collagen, ATR-FTIR spectra revealed diffuse hydrolysis and gelatinization of the parchment writing support; diffuse and non-homogeny degradation by gelatinization has been also confirmed by the IG gelatinization index deduced from the NIR bands on the FOR spectra. This IG index, defined as the ratio I (6860 cm-1) / I (6685 cm-1), ranges in the interval 0.98 – 1 and highlights collagen degradation at the molecular level. Sequentially Shifted Excitation Raman measurements (SSERS) crossed to X-ray fluorescence (XRF) ones on the black writings revealed that the black ink used is an iron-copper gall one, while FOR spectra are typical of pure metal gall inks. These later reflectance measurements exclude, thus, any intentional addition of carbon black to the ink recipe. Moreover, no lead white had been used while pre-drawing the writing lines. On another side, ATR-FTIR measurements highlighted the presence of oxalates as ink degradation products. Considering the parchment handcrafting, the combination of XRF and ATR-FTIR measurements led to the assumption that this writing support had been prepared according to ancient Middle East practices; the parchment infrared fingerprint seems identical to that of the Dead Sea scroll. The present multi-technical analyses are the first ones performed on an ancient Judaic written parchment of Morocco; it is under furthering. The investigation will be extended to other parchments belonging to the Jewish Cultural Heritage Museum of Morocco in Casablanca.

Keywords: torah scroll, parchment, black ink, non-invasive analyses, XRF/ATR-FTIR/RAMAN/FORS

Procedia PDF Downloads 70

Authors: Yanheng Zhang, Lu Feng, Yilan Kang, Donghui Fu, Qian Zhang, Qiu Li, Wei Qiu

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Diamond-reinforced Ni matrix composite has been widely applied in engineering for coating large-area structural parts owing to its high hardness, good wear resistance and corrosion resistance compared with those features of pure nickel. The mechanical properties of Ni-diamond composite coating can be promoted by the high incorporation and uniform distribution of diamond particles in the nickel matrix, while the distribution features of particles are affected by electrodeposition process parameters, especially the additives in the plating bath. Glycine has been utilized as an organic additive during the preparation of pure nickel coating, which can effectively increase the coating hardness. Nevertheless, to author’s best knowledge, no research about the effects of glycine on the Ni-diamond co-deposition has been reported. In this work, the diamond reinforced Ni nanocomposite coatings were fabricated by a co-electrodeposition technique from a modified Watt’s type bath in the presence of glycine. After preparation, the SEM morphology of the composite coatings was observed combined with energy dispersive X-ray spectrometer, and the diamond incorporation was analyzed. The surface morphology and roughness were obtained by a three-dimensional profile instrument. 3D-Debye rings formed by XRD were analyzed to characterize the nickel grain size and orientation in the coatings. The average coating thickness was measured by a digital micrometer to deduce the deposition rate. The microhardness was tested by automatic microhardness tester. The friction coefficient and wear volume were measured by reciprocating wear tester to characterize the coating wear resistance and cutting performance. The experimental results confirmed that the presence of glycine effectively improved the surface morphology and roughness of the composite coatings. By optimizing the glycine concentration, the incorporation of diamond particles was increased, while the nickel grain size decreased with increasing glycine. The hardness of the composite coatings was increased as the glycine concentration increased. The friction and wear properties were evaluated as the glycine concentration was optimized, showing a decrease in the wear volume. The wear resistance of the composite coatings increased as the glycine content was increased to an optimum value, beyond which the wear resistance decreased. Glycine complexation contributed to the nickel grain refinement and improved the diamond dispersion in the coatings, both of which made a positive contribution to the amount and uniformity of embedded diamond particles, thus enhancing the microhardness, reducing the friction coefficient, and hence increasing the wear resistance of the composite coatings. Therefore, additive glycine can be used during the co-deposition process to improve the mechanical properties of protective coatings.

Keywords: co-electrodeposition, glycine, mechanical properties, Ni-diamond nanocomposite coatings

Procedia PDF Downloads 110

Authors: Feiyu Yang, Chunfang Ni, Rong Wang, Yun Zou, Wenbin Liu, Chenggong Zhang, Fenjin Sun, Chun Wang

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Cocaine is the most frequently used illegal drug globally, with the global annual prevalence of cocaine used ranging from 0.3% to 0.4 % of the adult population aged 15–64 years. Growing consumption trend of abused cocaine and drug crimes are a great concern, therefore urine sample testing has become an important noninvasive sampling whereas cocaine and its metabolites (COCs) are usually present in high concentrations and relatively long detection windows. However, direct analysis of urine samples is not feasible because urine complex medium often causes low sensitivity and selectivity of the determination. On the other hand, presence of low doses of analytes in urine makes an extraction and pretreatment step important before determination. Especially, in gathered taking drug cases, the pretreatment step becomes more tedious and time-consuming. So developing a sensitive, rapid and high-throughput method for detection of COCs in human body is indispensable for law enforcement officers, treatment specialists and health officials. In this work, a new automated magnetic dispersive solid-phase extraction (MDSPE) sampling method followed by high performance liquid chromatography-mass spectrometry (HPLC-MS) was developed for quantitative enrichment of COCs from human urine, using prepared magnetic nanoparticles as absorbants. The nanoparticles were prepared by silanizing magnetic Fe3O4 nanoparticles and modifying them with divinyl benzene and vinyl pyrrolidone, which possesses the ability for specific adsorption of COCs. And this kind of magnetic particle facilitated the pretreatment steps by electromagnetically controlled extraction to achieve full automation. The proposed device significantly improved the sampling preparation efficiency with 32 samples in one batch within 40mins. Optimization of the preparation procedure for the magnetic nanoparticles was explored and the performances of magnetic nanoparticles were characterized by scanning electron microscopy, vibrating sample magnetometer and infrared spectra measurements. Several analytical experimental parameters were studied, including amount of particles, adsorption time, elution solvent, extraction and desorption kinetics, and the verification of the proposed method was accomplished. The limits of detection for the cocaine and cocaine metabolites were 0.09-1.1 ng·mL-1 with recoveries ranging from 75.1 to 105.7%. Compared to traditional sampling method, this method is time-saving and environmentally friendly. It was confirmed that the proposed automated method was a kind of highly effective way for the trace cocaine and cocaine metabolites analyses in human urine.

Keywords: automatic magnetic dispersive solid-phase extraction, cocaine detection, magnetic nanoparticles, urine sample testing

Procedia PDF Downloads 185

Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

Abstract:

This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: Riya Bose, Ashok Bera, Manas R. Parida, Anirudhha Adhikari, Basamat S. Shaheen, Erkki Alarousu, Jingya Sun, Tom Wu, Osman M. Bakr, Omar F. Mohammed

Abstract:

This work reports visualization of charge carrier dynamics on the surface of copper indium gallium selenide (CIGSe) nanocrystals in real space and time using four-dimensional scanning ultrafast electron microscopy (4D S-UEM) and correlates it with the optoelectronic properties of the nanocrystals. The surface of the nanocrystals plays a key role in controlling their applicability for light emitting and light harvesting purposes. Typically for quaternary systems like CIGSe, which have many desirable attributes to be used for optoelectronic applications, relative abundance of surface trap states acting as non-radiative recombination centre for charge carriers remains as a major bottleneck preventing further advancements and commercial exploitation of these nanocrystals devices. Though ultrafast spectroscopic techniques allow determining the presence of picosecond carrier trapping channels, because of relative larger penetration depth of the laser beam, only information mainly from the bulk of the nanocrystals is obtained. Selective mapping of such ultrafast dynamical processes on the surfaces of nanocrystals remains as a key challenge, so far out of reach of purely optical probing time-resolved laser techniques. In S-UEM, the optical pulse generated from a femtosecond (fs) laser system is used to generate electron packets from the tip of the scanning electron microscope, instead of the continuous electron beam used in the conventional setup. This pulse is synchronized with another optical excitation pulse that initiates carrier dynamics in the sample. The principle of S-UEM is to detect the secondary electrons (SEs) generated in the sample, which is emitted from the first few nanometers of the top surface. Constructed at different time delays between the optical and electron pulses, these SE images give direct and precise information about the carrier dynamics on the surface of the material of interest. In this work, we report selective mapping of surface dynamics in real space and time of CIGSe nanocrystals applying 4D S-UEM. We show that the trap states can be considerably passivated by ZnS shelling of the nanocrystals, and the carrier dynamics can be significantly slowed down. We also compared and discussed the S-UEM kinetics with the carrier dynamics obtained from conventional ultrafast time-resolved techniques. Additionally, a direct effect of the state trap removal can be observed in the enhanced photoresponse of the nanocrystals after shelling. Direct observation of surface dynamics will not only provide a profound understanding of the photo-physical mechanisms on nanocrystals’ surfaces but also enable to unlock their full potential for light emitting and harvesting applications.

Keywords: 4D scanning ultrafast microscopy, charge carrier dynamics, nanocrystals, optoelectronics, surface passivation, trap states

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Authors: Liudmila Shabalinskaya, Victor Golovanov, Liudmila Milinis, Sergey Loponos, Alexander Maslov, D. O. Frolov

Abstract:

The work is devoted to the rapid laboratory diagnosis of the condition of aircraft friction units, based on the application of the nondestructive testing method by analyzing the parameters of wear particles, or tribodiagnostics. The most important task of tribodiagnostics is to develop recommendations for the selection of more advanced designs, materials and lubricants based on data on wear processes for increasing the life and ensuring the safety of the operation of machines and mechanisms. The object of tribodiagnostics in this work are the tooth gears of the central drive and the gearboxes of the gas turbine engine of the civil aviation PS-90A type, in which rolling friction and sliding friction with slip occur. The main criterion for evaluating the technical state of lubricated friction units of a gas turbine engine is the intensity and rate of wear of the friction surfaces of the friction unit parts. When the engine is running, oil samples are taken and the state of the friction surfaces is evaluated according to the parameters of the wear particles contained in the oil sample, which carry important and detailed information about the wear processes in the engine transmission units. The parameters carrying this information include the concentration of wear particles and metals in the oil, the dispersion composition, the shape, the size ratio and the number of particles, the state of their surfaces, the presence in the oil of various mechanical impurities of non-metallic origin. Such a morphological analysis of wear particles has been introduced into the order of monitoring the status and diagnostics of various aircraft engines, including a gas turbine engine, since the type of wear characteristic of the central drive and the drive box is surface fatigue wear and the beginning of its development, accompanied by the formation of microcracks, leads to the formation of spherical, up to 10 μm in size, and in the aftermath of flocculent particles measuring 20-200 μm in size. Tribodiagnostics using the morphological analysis of wear particles includes the following techniques: ferrography, filtering, and computer analysis of the classification and counting of wear particles. Based on the analysis of several series of oil samples taken from the drive box of the engine during their operating time, a study was carried out of the processes of wear kinetics. Based on the results of the study and comparing the series of criteria for tribodiagnostics, wear state ratings and statistics of the results of morphological analysis, norms for the normal operating regime were developed. The study allowed to develop levels of wear state for friction surfaces of gearing and a 10-point rating system for estimating the likelihood of the occurrence of an increased wear mode and, accordingly, prevention of engine failures in flight.

Keywords: aviation, box of drives, morphological analysis, tribodiagnostics, tribology, ferrography, filtering, wear particle

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Authors: M. N. Baig, F. N. Khan, M. Junaid

Abstract:

Titanium alloys are widely employed in aerospace, medical, chemical, and marine applications. These alloys offer many advantages such as low specific weight, high strength to weight ratio, excellent corrosion resistance, high melting point and good fatigue behavior. These attractive properties make titanium alloys very unique and therefore they require special attention in all areas of processing, especially welding. In this work, 1.6 mm thick sheets of Ti-5Al-2,5Sn, an alpha titanium (α-Ti) alloy, were welded using electron beam (EBW) and laser beam (LBW) welding processes to achieve a full penetration Bead-on Plate (BoP) configuration. The weldments were studied using polarized optical microscope, SEM, EDS and XRD. Microhardness distribution across the weld zone and smooth and notch tensile strengths of the weldments were also recorded. Residual stresses using Hole-drill Strain Measurement (HDSM) method and deformation patterns of the weldments were measured for the purpose of comparison of the two welding processes. Fusion zone widths of both EBW and LBW weldments were found to be approximately equivalent owing to fairly similar high power densities of both the processes. Relatively less oxide content and consequently high joint quality were achieved in EBW weldment as compared to LBW due to vacuum environment and absence of any shielding gas. However, an increase in heat-affected zone width and partial ά-martensitic transformation infusion zone of EBW weldment were observed because of lesser cooling rates associated with EBW as compared with LBW. The microstructure infusion zone of EBW weldment comprised both acicular α and ά martensite within the prior β grains whereas complete ά martensitic transformation was observed within the fusion zone of LBW weldment. Hardness of the fusion zone in EBW weldment was found to be lower than the fusion zone of LBW weldment due to the observed microstructural differences. Notch tensile specimen of LBW exhibited higher load capacity, ductility, and absorbed energy as compared with EBW specimen due to the presence of high strength ά martensitic phase. It was observed that the sheet deformation and deformation angle in EBW weldment were more than LBW weldment due to relatively more heat retention in EBW which led to more thermal strains and hence higher deformations and deformation angle. The lowest residual stresses were found in LBW weldments which were tensile in nature. This was owing to high power density and higher cooling rates associated with LBW process. EBW weldment exhibited highest compressive residual stresses due to which the service life of EBW weldment is expected to improve.

Keywords: Laser and electron beam welding, Microstructure and mechanical properties, Residual stress and distortions, Titanium alloys

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Authors: E. Fabre, C. Vale, E. Pereira, C. M. Silva

Abstract:

Introduction: Mercury is one of the most troublesome toxic metals responsible for the contamination of the aquatic systems due to its accumulation and bioamplification along the food chain. The 2030 agenda for sustainable development of United Nations promotes the improving of water quality by reducing water pollution and foments an enhance in wastewater treatment, encouraging their recycling and safe water reuse globally. Sorption processes are widely used in wastewater treatments due to their many advantages such as high efficiency and low operational costs. In these processes the target contaminant is removed from the solution by a solid sorbent. The more selective and low cost is the biosorbent the more attractive becomes the process. Agricultural wastes are especially attractive approaches for sorption. They are largely available, have no commercial value and require little or no processing. In this work, banana peels were tested for mercury removal from low concentrated solutions. In order to investigate the applicability of this solid, six water matrices were used increasing the complexity from natural waters to a real wastewater. Studies of kinetics and equilibrium were also performed using the most known models to evaluate the viability of the process In line with the concept of circular economy, this study adds value to this by-product as well as contributes to liquid waste management. Experimental: The solutions were prepared with Hg(II) initial concentration of 50 µg L-1 in natural waters, at 22 ± 1 ºC, pH 6, magnetically stirring at 650 rpm and biosorbent mass of 0.5 g L-1. NaCl was added to obtain the salt solutions, seawater was collected from the Portuguese coast and the real wastewater was kindly provided by ISQ - Instituto de Soldadura e qualidade (Welding and Quality Institute) and diluted until the same concentration of 50 µg L-1. Banana peels were previously freeze-drying, milled, sieved and the particles < 1 mm were used. Results: Banana peels removed more than 90% of Hg(II) from all the synthetic solutions studied. In these cases, the enhance in the complexity of the water type promoted a higher mercury removal. In salt waters, the biosorbent showed removals of 96%, 95% and 98 % for 3, 15 and 30 g L-1 of NaCl, respectively. The residual concentration of Hg(II) in solution achieved the level of drinking water regulation (1 µg L-1). For real matrices, the lower Hg(II) elimination (93 % for seawater and 81 % for the real wastewaters), can be explained by the competition between the Hg(II) ions and the other elements present in these solutions for the sorption sites. Regarding the equilibrium study, the experimental data are better described by the Freundlich isotherm (R ^ 2=0.991). The Elovich equation provided the best fit to the kinetic points. Conclusions: The results exhibited the great ability of the banana peels to remove mercury. The environmental realist conditions studied in this work, highlight their potential usage as biosorbents in water remediation processes.

Keywords: banana peels, mercury removal, sorption, water treatment

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