Search results for: hydrogen engine

Authors: Mohammad Moezzibadi, Isabelle Charpentier, Adrien Wanko, Robert Mosé

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The calibration of hydrodynamic parameters for subsurface constructed wetlands (CWs) is a sensitive process since highly non-linear equations are involved in unsaturated flow modeling. CW systems are engineered systems designed to favour natural treatment processes involving wetland vegetation, soil, and their microbial flora. Their significant efficiency at reducing the ecological impact of urban runoff has been recently proved in the field. Numerical flow modeling in a vertical variably saturated CW is here carried out by implementing the Richards model by means of a mixed hybrid finite element method (MHFEM), particularly well adapted to the simulation of heterogeneous media, and the van Genuchten-Mualem parametrization. For validation purposes, MHFEM results were compared to those of HYDRUS (a software based on a finite element discretization). As van Genuchten-Mualem soil hydrodynamic parameters depend on water content, their estimation is subject to considerable experimental and numerical studies. In particular, the sensitivity analysis performed with respect to the van Genuchten-Mualem parameters reveals a predominant influence of the shape parameters α, n and the saturated conductivity of the filter on the piezometric heads, during saturation and desaturation. Modeling issues arise when the soil reaches oven-dry conditions. A particular attention should also be brought to boundary condition modeling (surface ponding or evaporation) to be able to tackle different sequences of rainfall-runoff events. For proper parameter identification, large field datasets would be needed. As these are usually not available, notably due to the randomness of the storm events, we thus propose a simple, robust and low-cost numerical method for the inverse modeling of the soil hydrodynamic properties. Among the methods, the variational data assimilation technique introduced by Le Dimet and Talagrand is applied. To that end, a variational data assimilation technique is implemented by applying automatic differentiation (AD) to augment computer codes with derivative computations. Note that very little effort is needed to obtain the differentiated code using the on-line Tapenade AD engine. Field data are collected for a three-layered CW located in Strasbourg (Alsace, France) at the water edge of the urban water stream Ostwaldergraben, during several months. Identification experiments are conducted by comparing measured and computed piezometric head by means of the least square objective function. The temporal variability of hydrodynamic parameter is then assessed and analyzed.

Keywords: automatic differentiation, constructed wetland, inverse method, mixed hybrid FEM, sensitivity analysis

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

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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: Antonio J. Melendez-Martinez

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Beyond their role as natural colorants, some carotenoids are provitamins A and may be involved in health-promoting biological actions and contribute to reducing the risk of developing non-communicable diseases, including several types of cancer, cardiovascular disease, eye conditions, skin disorders or metabolic disorders. Given the versatility of carotenoids, the COST-funded European network to advance carotenoid research and applications in agro-food and health (EUROCAROTEN) is aimed at promoting health through the diet and increasing well-being by means. Stakeholders from 38 countries participate in this network, and one of its main objectives is to promote research on little-studied carotenoids. In this contribution, recent advances of our research group and collaborators in the study of two such understudied carotenoids, namely phytoene and phytofluene, the colorless carotenoids, are outlined. The study of these carotenoids is important as they have been largely neglected despite they are present in our diets, fluids, and tissues, and evidence is accumulating that they may be involved in health-promoting actions. More specifically, studies on their levels in diverse tomato and orange varieties were carried out as well as on their potential bioavailability from different dietary sources. Furthermore, the potential effect of these carotenoids on an animal model subjected to oxidative stress was evaluated. The tomatoes were grown in research greenhouses, and some of them were subjected to regulated deficit irrigation, a sustainable agronomic practice. The citrus samples were obtained from an experimental field. The levels of carotenoids were assessed using HPLC according to routine methodologies followed in our lab. Regarding the potential bioavailability (bioaccessibility) studies, different products containing colorless carotenoids, like fruits, juices, were subjected to simulated in vitro digestions, and their incorporation into mixed micelles was assessed. The effect of the carotenoids on oxidative stress was evaluated on the Caenorhabditis elegans model. For that purpose, the worms were subjected to oxidative stress by means of a hydrogen peroxide challenge. In relation to the presence of colorless carotenoids in tomatoes and orange varieties, it was observed that they are widespread in such products and that there are mutants with very high quantities of them, for instance, the Cara Cara or Pinalate mutant oranges. The studies on their bioaccessibility revealed that, in general, phytoene and phytofluene are more bioaccessible than other common dietary carotenoids, probably due to their distinctive chemical structure. About the in vivo antioxidant capacity of phytoene and phytofluene, it was observed that they both exerted antioxidant effects at certain doses. In conclusion, evidence on the importance of phytoene and phytofluene as dietary easily bioavailable and antioxidant carotenoids has been obtained in recent studies from our group, which can be important shortly to innovate in health-promotion through the development of functional foods and related products.

Keywords: carotenoids, health, functional foods, nutrition, phytoene, phytofluene

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Authors: O. R. Razanakoto, L. Temple

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Living in a least developed country, the Malagasy society has a weak capacity to internalize progress, including health concerns. Since the arrival in the fifteenth century of Arabic script, called Sorabe, that was mainly dedicated to the aristocracy, until the colonial era beginning at the end of the nineteenth century and that has popularized the current usual script of the occidental civilization, the upcoming manuscripts that deal with apparent scientific or at least academic issue have been slowly established. So that, the Malagasy communities’ way of life is not well documented yet to allow a precise understanding of the major concerns, reason, and purpose of the existence of the farmers that compose them. A question arises, according to literature, how does Malagasy community that is dominated by agrarian society conceive the conservation of its wellbeing? This study aims to emphasize the scope and the limits of the « One Health » concept or of the Health Integrated Approach (HIA) that evolves at global scale, with regard to the specific context of local Malagasy smallholder farms. It is expected to identify how this society represents linked risks and the mechanisms between human health, animal health, plant health, and ecosystem health within the last 100 years. To do so, the framework to conduct systematic review for agricultural research has been deployed to access available literature. This task has been coupled with the reading of articles that are not indexed by online scientific search engine but that mention part of a history of agriculture and of farmers in Madagascar. This literature review has informed the interactions between human illnesses and those affecting animals and plants (breeded or wild) with any unexpected event (ecological or economic) that has modified the equilibrium of the ecosystem, or that has disturbed the livelihoods of agrarian communities. Besides, drivers that may either accentuate or attenuate the devasting effects of these illnesses and changes were revealed. The study has established that the reasons of human worries are not only physiological. Among the factors that regulate global health, food system and contemporary medicine have helped to the improvement of life expectancy from 55 to 63 years in Madagascar during the last 50 years. However, threats to global health are still occurring. New human or animal illnesses and livestock / plant pathology or enemies may also appear, whereas ancient illnesses that are supposed to have disappeared may be back. This study has highlighted how much important are the risks associated to the impact of unmanaged externalities that weaken community’s life. Many risks, and also solutions, come from abroad and have long term effects even though those happen as punctual event. Thus, a constructivist strategy is suggested to the « One Health » global concept throughout the record of local facts. This approach should facilitate the exploration of methodological pathways and the identification of relevant indicators for research related to HIA.

Keywords: agrarian system, health integrated approach, history, madagascar, resilience, risk

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Authors: B. S. Muddukrishna, Karthik Aithal, Aravind Pai

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Introduction: Preparation of binary cocrystals of Etraverine (ETR) by using Tartaric Acid (TAR) as a conformer was the main focus of this study. Etravirine is a Class IV drug, as per the BCS classification system. Methods: Cocrystals were prepared by slow evaporation technique. A mixture of total 500mg of ETR: TAR was weighed in molar ratios of 1:1 (371.72mg of ETR and 128.27mg of TAR). Saturated solution of Etravirine was prepared in Acetone: Methanol (50:50) mixture in which tartaric acid is dissolved by sonication and then this solution was stirred using a magnetic stirrer until the solvent got evaporated. Shimadzu FTIR – 8300 system was used to acquire the FTIR spectra of the cocrystals prepared. Shimadzu thermal analyzer was used to achieve DSC measurements. X-ray diffractometer was used to obtain the X-ray powder diffraction pattern. Shake flask method was used to determine the equilibrium dynamic solubility of pure, physical mixture and cocrystals of ETR. USP buffer (pH 6.8) containing 1% of Tween 80 was used as the medium. The pure, physical mixture and the optimized cocrystal of ETR were accurately weighed sufficient to maintain the sink condition and were filled in hard gelatine capsules (size 4). Electrolab-Tablet Dissolution tester using basket apparatus at a rotational speed of 50 rpm and USP phosphate buffer (900 mL, pH = 6.8, 37 ˚C) + 1% Tween80 as a media, was used to carry out dissolution. Shimadzu LC-10 series chromatographic system was used to perform the analysis with PDA detector. An Hypersil BDS C18 (150mm ×4.6 mm ×5 µm) column was used for separation with mobile phase comprising of a mixture of ace¬tonitrile and phosphate buffer 20mM, pH 3.2 in the ratio 60:40 v/v. The flow rate was 1.0mL/min and column temperature was set to 30°C. The detection was carried out at 304 nm for ETR. Results and discussions: The cocrystals were subjected to various solid state characterization and the results confirmed the formation of cocrystals. The C=O stretching vibration (1741cm-1) in tartaric acid was disappeared in the cocrystal and the peak broadening of primary amine indicates hydrogen bond formation. The difference in the melting point of cocrystals when compared to pure Etravirine (265 °C) indicates interaction between the drug and the coformer which proves that first ordered transformation i.e. melting endotherm has disappeared. The difference in 2θ values of pure drug and cocrystals indicates the interaction between the drug and the coformer. Dynamic solubility and dissolution studies were also conducted by shake flask method and USP apparatus one respectively and 3.6 fold increase in the dynamic solubility were observed and in-vitro dissolution study shows four fold increase in the solubility for the ETR: TAR (1:1) cocrystals. The ETR: TAR (1:1) cocrystals shows improved solubility and dissolution as compared to the pure drug which was clearly showed by solid state characterization and dissolution studies.

Keywords: dynamic solubility, Etraverine, in vitro dissolution, slurry method

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Authors: Ligang Wang, Theodoros Damartzis, Stefan Diethelm, Jan Van Herle, François Marechal

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Biogas production from anaerobic digestion of organic sludge from wastewater treatment as well as various urban and agricultural organic wastes is of great significance to achieve a sustainable society. Two upgrading approaches for cleaned biogas can be considered: (1) direct H₂ injection for catalytic CO₂ methanation and (2) CO₂ separation from biogas. The first approach usually employs electrolysis technologies to generate hydrogen and increases the biogas production rate; while the second one usually applies commercially-available highly-selective membrane technologies to efficiently extract CO₂ from the biogas with the latter being then sent afterward for compression and storage for further use. A straightforward way of utilizing the captured CO₂ is on-site catalytic CO₂ methanation. From the perspective of system complexity, the second approach may be questioned, since it introduces an additional expensive membrane component for producing the same amount of methane. However, given the circumstance that the sustainability of the produced biogas should be retained after biogas upgrading, renewable electricity should be supplied to drive the electrolyzer. Therefore, considering the intermittent nature and seasonal variation of renewable electricity supply, the second approach offers high operational flexibility. This indicates that these two approaches should be compared based on the availability and scale of the local renewable power supply and not only the technical systems themselves. Solid-oxide electrolysis generally offers high overall system efficiency, and more importantly, it can achieve simultaneous electrolysis of CO₂ and H₂O (namely, co-electrolysis), which may bring significant benefits for the case of CO₂ separation from the produced biogas. When taking co-electrolysis into account, two additional upgrading approaches can be proposed: (1) direct steam injection into the biogas with the mixture going through the SOE, and (2) CO₂ separation from biogas which can be used later for co-electrolysis. The case study of integrating SOE to a wastewater treatment plant is investigated with wind power as the renewable power. The dynamic production of biogas is provided on an hourly basis with the corresponding oxygen and heating requirements. All four approaches mentioned above are investigated and compared thermo-economically: (a) steam-electrolysis with grid power, as the base case for steam electrolysis, (b) CO₂ separation and co-electrolysis with grid power, as the base case for co-electrolysis, (c) steam-electrolysis and CO₂ separation (and storage) with wind power, and (d) co-electrolysis and CO₂ separation (and storage) with wind power. The influence of the scale of wind power supply is investigated by a sensitivity analysis. The results derived provide general understanding on the economic competitiveness of SOE for sustainable biogas upgrading, thus assisting the decision making for biogas production sites. The research leading to the presented work is funded by European Union’s Horizon 2020 under grant agreements n° 699892 (ECo, topic H2020-JTI-FCH-2015-1) and SCCER BIOSWEET.

Keywords: biogas upgrading, solid-oxide electrolyzer, co-electrolysis, CO₂ utilization, energy storage

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Authors: Quentin C.P. Bourgogne, Vanessa Bouchart, Pierre Chevrier, Emmanuel Dattoli

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This study presents an experimental and theoretical work conducted on a PolyPhenylene Sulfide reinforced with 40%wt of short glass fibers (PPS GF40) and its matrix. Thermoplastics are widely used in the automotive industry to lightweight automotive parts. The replacement of metallic parts by thermoplastics is reaching under-the-hood parts, near the engine. In this area, the parts are subjected to high temperatures and are immersed in cooling liquid. This liquid is composed of water and glycol and can affect the mechanical properties of the composite. The aim of this work was thus to quantify the evolution of mechanical properties of the thermoplastic composite, as a function of temperature and liquid aging effects, in order to develop a reliable design of parts. An experimental campaign in the tensile mode was carried out at different temperatures and for various glycol proportions in the cooling liquid, for monotonic and cyclic loadings on a neat and a reinforced PPS. The results of these tests allowed to highlight some of the main physical phenomena occurring during these solicitations under tough hydro-thermal conditions. Indeed, the performed tests showed that temperature and liquid cooling aging can affect the mechanical behavior of the material in several ways. The more the cooling liquid contains water, the more the mechanical behavior is affected. It was observed that PPS showed a higher sensitivity to absorption than to chemical aggressiveness of the cooling liquid, explaining this dominant sensitivity. Two kinds of behaviors were noted: an elasto-plastic type under the glass transition temperature and a visco-pseudo-plastic one above it. It was also shown that viscosity is the leading phenomenon above the glass transition temperature for the PPS and could also be important under this temperature, mostly under cyclic conditions and when the stress rate is low. Finally, it was observed that soliciting this composite at high temperatures is decreasing the advantages of the presence of fibers. A new phenomenological model was then built to take into account these experimental observations. This new model allowed the prediction of the evolution of mechanical properties as a function of the loading environment, with a reduced number of parameters compared to precedent studies. It was also shown that the presented approach enables the description and the prediction of the mechanical response with very good accuracy (2% of average error at worst), over a wide range of hydrothermal conditions. A temperature-humidity equivalence principle was underlined for the PPS, allowing the consideration of aging effects within the proposed model. Then, a limit of improvement of the reachable accuracy was determinate for all models using this set of data by the application of an artificial intelligence-based model allowing a comparison between artificial intelligence-based models and phenomenological based ones.

Keywords: aging, analytical modeling, mechanical testing, polymer matrix composites, sequential model, thermomechanical

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Authors: Saheed A. Adekola, Mabel A. Charles-Davies, Ridwan A. Adekola

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Background: Testosterone is a known androgenic and anabolic steroid, primarily secreted in the testes. It plays an important role in the development of testes and prostate and has a range of biological actions. There is evidence that exposure to mixed chemicals in the workplace leads to the generation of free radicals and inadequate antioxidants leading to oxidative stress, which may serve as an early indicator of a pathophysiologic state. Based on findings, testosterone shows direct antioxidant effects by increasing the activities of antioxidant enzymes like glutathione peroxidase, thus indirectly contributing to antioxidant capacity. Objective: To evaluate the antioxidant role of testosterone as well as the relationship between testosterone and oxidative stress biomarkers in males exposed to mixed chemicals in the automobile repair community. Methods: The study included 43 participants aged 22- 60years exposed to mixed chemicals (EMC) from the automobile repair community. Forty (40) apparently healthy, unexposed, age-matched controls were recruited after informed consent. Demographic, sexual and anthropometric characteristics were obtained from pre-test structured questionnaires using standard methods. Blood samples (10mls) were collected from each subject into plain bottles and sera obtained were used for biochemical analyses. Serum levels of testosterone and luteinizing hormone (LH) were determined by enzyme immunoassay method, EIA (Immunometrics UK.LTD). Levels of total antioxidant capacity (TAC), total plasma peroxide (TPP), Malondialdehyde (MDA), hydrogen peroxide (H2O2), glutathione peroxide (GPX), superoxide dismutase (SOD), glutathione-S-transferase (GST), and reduced glutathione (GSH) were determined using spectrophotometric methods respectively. Results obtained were analyzed using the Student’s t-test and Chi-square test for quantitative variables and qualitative variables respectively. Multiple regression was used to find associations and relationships between the variables. Results: Significant higher concentrations of TPP, MDA, OSI, H2O2 and GST were observed in EMC compared with controls (p < 0.001). Within EMC, significantly higher levels of testosterone, LH and TAC were observed in eugonadic when compared with hypogonadic participants (p < 0.001). Diastolic blood pressure, waist circumference, waist height ratio and waist hip ratio were significantly higher in participants EMC compared with the controls. Sexual history and dietary intake showed that the controls had normal erection during sex and took more vegetables in their diet which may therefore be beneficial. Conclusion: The significantly increased levels of total antioxidant capacity in males exposed to mixed chemicals despite their exposure may probably reflect the contributory antioxidant role testosterone that prevents oxidative stress.

Keywords: mixed chemicals, oxidative stress, antioxidant, hypogonadism testosterone

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Authors: Ali Kadir, O. Anwar Beg

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Thermal barrier coatings are among the most popular methods for providing corrosion protection in high temperature applications including aircraft engine systems, external spacecraft structures, rocket chambers etc. Many different materials are available for such coatings, of which ceramics generally perform the best. Motivated by these applications, the current investigation presents detailed finite element simulations of coating stress analysis for a 3- dimensional, 3-layered model of a test sample representing a typical gas turbine component scenario. Structural steel is selected for the main inner layer, Titanium (Ti) alloy for the middle layer and Silicon Carbide (SiC) for the outermost layer. The model dimensions are 20 mm (width), 10 mm (height) and three 1mm deep layers. ANSYS software is employed to conduct three types of analysis- static structural, thermal stress analysis and also computational fluid dynamic erosion/corrosion analysis (via ANSYS FLUENT). The specified geometry which corresponds to corrosion test samples exactly is discretized using a body-sizing meshing approach, comprising mainly of tetrahedron cells. Refinements were concentrated at the connection points between the layers to shift the focus towards the static effects dissipated between them. A detailed grid independence study is conducted to confirm the accuracy of the selected mesh densities. To recreate gas turbine scenarios; in the stress analysis simulations, static loading and thermal environment conditions of up to 1000 N and 1000 degrees Kelvin are imposed. The default solver was used to set the controls for the simulation with the fixed support being set as one side of the model while subjecting the opposite side to a tabular force of 500 and 1000 Newtons. Equivalent elastic strain, total deformation, equivalent stress and strain energy were computed for all cases. Each analysis was duplicated twice to remove one of the layers each time, to allow testing of the static and thermal effects with each of the coatings. ANSYS FLUENT simulation was conducted to study the effect of corrosion on the model under similar thermal conditions. The momentum and energy equations were solved and the viscous heating option was applied to represent improved thermal physics of heat transfer between the layers of the structures. A Discrete Phase Model (DPM) in ANSYS FLUENT was employed which allows for the injection of continuous uniform air particles onto the model, thereby enabling an option for calculating the corrosion factor caused by hot air injection (particles prescribed 5 m/s velocity and 1273.15 K). Extensive visualization of results is provided. The simulations reveal interesting features associated with coating response to realistic gas turbine loading conditions including significantly different stress concentrations with different coatings.

Keywords: thermal coating, corrosion, ANSYS FEA, CFD

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Authors: Md. Hafezur Rahaman, Mohd. Maniruzzaman, Md. Shadiqul Islam, Md. Masud Rana

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With the growth of environmental awareness, enormous researches are running to develop the next generation materials based on sustainability, eco-competence, and green chemistry to preserve and protect the environment. Due to biodegradability and biocompatibility, poly (L-lactic acid) (PLLA) has a great interest in ecological and medical applications. Also, cellulose is one of the most abundant biodegradable, renewable polymers found in nature. It has several advantages such as low cost, high mechanical strength, biodegradability and so on. Recently, an immense deal of attention has been paid for the scientific and technological development of α-cellulose based composite material. PLLA could be used for grafting of cellulose to improve the compatibility prior to the composite preparation. Here it is quite difficult to form a bond between lower hydrophilic molecules like PLLA and α-cellulose. Dimmers and oligomers can easily be grafted onto the surface of the cellulose by ring opening or polycondensation method due to their low molecular weight. In this research, α-cellulose extracted from jute fiber is grafted with oligo(D-lactic acid) (ODLA) via graft polycondensation reaction in presence of para-toluene sulphonic acid and potassium persulphate in toluene at 130°C for 9 hours under 380 mmHg. Here ODLA is synthesized by ring opening polymerization of D-lactides in the presence of stannous octoate (0.03 wt% of lactide) and D-lactic acids at 140°C for 10 hours. Composites of PLLA with ODLA grafted α-cellulose are prepared by solution mixing and film casting method. Confirmation of grafting was carried out through FTIR spectroscopy and SEM analysis. A strongest carbonyl peak of FTIR spectroscopy at 1728 cm⁻¹ of ODLA grafted α-cellulose confirms the grafting of ODLA onto α-cellulose which is absent in α-cellulose. It is also observed from SEM photographs that there are some white areas (spot) on ODLA grafted α-cellulose as compared to α-cellulose may indicate the grafting of ODLA and consistent with FTIR results. Analysis of the composites is carried out by FTIR, SEM, WAXD and thermal gravimetric analyzer. Most of the FTIR characteristic absorption peak of the composites shifted to higher wave number with increasing peak area may provide a confirmation that PLLA and grafted cellulose have better compatibility in composites via intermolecular hydrogen bonding and this supports previously published results. Grafted α-cellulose distributions in composites are uniform which is observed by SEM analysis. WAXD studied show that only homo-crystalline structures of PLLA present in the composites. Thermal stability of the composites is enhanced with increasing the percentages of ODLA grafted α-cellulose in composites. As a consequence, the resultant composites have a resistance toward the thermal degradation. The effects of length of the grafted chain and biodegradability of the composites will be studied in further research.

Keywords: α-cellulose, composite, graft polycondensation, oligo(D-lactic acid), poly(L-lactic acid)

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Authors: Ruslin, R. E. Kartasasmita, M. S. Wibowo, S. Ibrahim

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An aphrodisiac is a substance contained in food or drug that can arouse sexual instinct and increase pleasure while working, these substances derived from plants, animals, and minerals. When consuming substances that have aphrodisiac activity and duration can improve the sexual instinct. The natural aphrodisiac effect can be obtained through plants, animals, and minerals. Leonurine compound has aphrodisiac activity, these compounds can be isolated from plants of Leonurus Sp, Sundanese people is known as deundereman, this plant is empirical has aphrodisiac activity and based on the isolation of active compounds from plants known to contain compounds leonurine, so that the compound is expected to have activity aphrodisiac. Leonurine compound can be isolated from plants or synthesized chemically with material dasa siringat acid. Leonurine compound can be obtained commercial and derivatives of these compounds can be synthesized in an effort to increase its activity. This study aims to obtain derivatives leonurine better aphrodisiac activity compared with the parent compound, modified the structure of the compounds in the form leonurin guanidino butyl ester group with butyl amin and bromoetanol. ArgusLab program version 4.0.1 is used to determine the binding energy, hydrogen bonds and amino acids involved in the interaction of the compound PDE5 receptor. The in vivo test leonurine compounds and derivatives as an aphrodisiac ingredients and hormone testosterone levels using 27 male rats Wistar strain and 9 female mice of the same species, ages ranged from 12 weeks rats weighing + 200 g / tail. The test animal is divided into 9 groups according to the type of compounds and the dose given. Each treatment group was orally administered 2 ml per day for 5 days. On the sixth day was observed male rat sexual behavior and taking blood from the heart to measure testosterone levels using ELISA technique. Statistical analysis was performed in this study is the ANOVA test Least Square Differences (LSD) using the program Statistical Product and Service Solutions (SPSS). Aphrodisiac efficacy of the leonurine compound and its derivatives have proven in silico and in vivo test, the in silico testing leonurine derivatives have smaller binding energy derivatives leonurine so that activity better than leonurine compounds. Testing in vivo using rats of wistar strain that better leonurine derivative of this compound shows leonurine that in silico studies in parallel with in vivo tests. Modification of the structure in the form of guanidine butyl ester group with butyl amin and bromoethanol increase compared leonurine compound for aphrodisiac activity, testosterone derivatives of compounds leonurine experienced a significant improvement especial is 1RD compounds especially at doses of 100 and 150 mg/bb. The results showed that the compound leonurine and its compounds contain aphrodisiac activity and increase the amount of testosterone in the blood. The compound test used in this study acts as a steroid precursor resulting in increased testosterone.

Keywords: aphrodisiac dysfunction erectile leonurine 1-RD 2-RD, dysfunction, erectile leonurine, 1-RD 2-RD

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Authors: Valentin Père, Mathieu Milhé, Fabien Baillon, Jean-Louis Dirion

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Microgrids offer potential solutions to meet the need for local grid stability and increase isolated networks autonomy with the integration of intermittent renewable energy production and storage facilities. In such a context, sizing production and storage for a given network is a complex task, highly depending on input data such as power load profile and renewable resource availability. This work aims at developing an operating cost computation methodology for different microgrid designs based on the use of deep reinforcement learning (RL) algorithms to tackle the optimal operation problem in stochastic environments. RL is a data-based sequential decision control method based on Markov decision processes that enable the consideration of random variables for control at a chosen time scale. Agents trained via RL constitute a promising class of Energy Management Systems (EMS) for the operation of microgrids with energy storage. Microgrid sizing (or design) is generally performed by minimizing investment costs and operational costs arising from the EMS behavior. The latter might include economic aspects (power purchase, facilities aging), social aspects (load curtailment), and ecological aspects (carbon emissions). Sizing variables are related to major constraints on the optimal operation of the network by the EMS. In this work, an islanded mode microgrid is considered. Renewable generation is done with photovoltaic panels; an electrochemical battery ensures short-term electricity storage. The controllable unit is a hydrogen tank that is used as a long-term storage unit. The proposed approach focus on the transfer of agent learning for the near-optimal operating cost approximation with deep RL for each microgrid size. Like most data-based algorithms, the training step in RL leads to important computer time. The objective of this work is thus to study the potential of Batch-Constrained Q-learning (BCQ) for the optimal sizing of microgrids and especially to reduce the computation time of operating cost estimation in several microgrid configurations. BCQ is an off-line RL algorithm that is known to be data efficient and can learn better policies than on-line RL algorithms on the same buffer. The general idea is to use the learned policy of agents trained in similar environments to constitute a buffer. The latter is used to train BCQ, and thus the agent learning can be performed without update during interaction sampling. A comparison between online RL and the presented method is performed based on the score by environment and on the computation time.

Keywords: batch-constrained reinforcement learning, control, design, optimal

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Authors: Loganathan Kumaresan, Velusamy Chidambaram, Arumugam Velayutham Karthikeyani, Alex Cheru Pulikottil, Madhusudan Sau, Gurpreet Singh Kapur, Sankara Sri Venkata Ramakumar

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Environmentally driven regulations throughout the world stipulate dramatic improvements in the quality of transportation fuels and refining operations. The exhaust gases like CO, NOx, and SOx from stationary sources (e.g., refinery) and motor vehicles contribute to a large extent for air pollution. The refining industry is under constant environmental pressure to achieve more rigorous standards on sulphur content in the fuel used in the transportation sector and other off-gas emissions. Fluid catalytic cracking unit (FCCU) is a major secondary process in refinery for gasoline and diesel production. CO-combustion promoter additive and gasoline sulphur reduction (GSR) additive are catalytic systems used in FCCU to assist the combustion of CO to CO₂ in the regenerator and regulate sulphur in gasoline faction respectively along with main FCC catalyst. Effectiveness of these catalysts is governed by the active metal used, its dispersion, the type of base material employed, and retention characteristics of additive in FCCU such as attrition resistance and density. The challenge is to have a high-density microsphere catalyst support for its retention and high activity of the active metals as these catalyst additives are used in low concentration compare to the main FCC catalyst. The present paper discusses in the first part development of high dense microsphere of nanocrystalline alumina by hydro-thermal method for CO combustion promoter application. Performance evaluation of additive was conducted under simulated regenerator conditions and shows CO combustion efficiency above 90%. The second part discusses the efficacy of a co-precipitation method for the generation of the active crystalline spinels of Zn, Mg, and Cu with aluminium oxides as an additive. The characterization and micro activity test using heavy combined hydrocarbon feedstock at FCC unit conditions for evaluating gasoline sulphur reduction activity are studied. These additives were characterized by X-Ray Diffraction, NH₃-TPD & N₂ sorption analysis, TPR analysis to establish structure-activity relationship. The reaction of sulphur removal mechanisms involving hydrogen transfer reaction, aromatization and alkylation functionalities are established to rank GSR additives for their activity, selectivity, and gasoline sulphur removal efficiency. The sulphur shifting in other liquid products such as heavy naphtha, light cycle oil, and clarified oil were also studied. PIONA analysis of liquid product reveals 20-40% reduction of sulphur in gasoline without compromising research octane number (RON) of gasoline and olefins content.

Keywords: hydrothermal, nanocrystalline, spinel, sulphur reduction

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Authors: Sakshi Piplani, Ajit Kumar

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Valproic acid (VPA) is the first synthetic therapeutic agent used to treat epileptic disorders, which account for affecting nearly 1% world population. Teratogenicity caused by VPA has prompted the search for next generation drug with better efficacy and lower side effects. Recent studies have posed HDAC8 as direct target of VPA that causes the teratogenic effect in foetus. We have employed molecular dynamics (MD) and docking simulations to understand the binding mode of VPA and their analogues onto HDAC8. A total of twenty 3D-structures of human HDAC8 isoforms were selected using BLAST-P search against PDB. Multiple sequence alignment was carried out using ClustalW and PDB-3F07 having least missing and mutated regions was selected for study. The missing residues of loop region were constructed using MODELLER and energy was minimized. A set of 216 structural analogues (>90% identity) of VPA were obtained from Pubchem and ZINC database and their energy was optimized with Chemsketch software using 3-D CHARMM-type force field. Four major neurotransmitters (GABAt, SSADH, α-KGDH, GAD) involved in anticonvulsant activity were docked with VPA and its analogues. Out of 216 analogues, 75 were selected on the basis of lower binding energy and inhibition constant as compared to VPA, thus predicted to have anti-convulsant activity. Selected hHDAC8 structure was then subjected to MD Simulation using licenced version YASARA with AMBER99SB force field. The structure was solvated in rectangular box of TIP3P. The simulation was carried out with periodic boundary conditions and electrostatic interactions and treated with Particle mesh Ewald algorithm. pH of system was set to 7.4, temperature 323K and pressure 1atm respectively. Simulation snapshots were stored every 25ps. The MD simulation was carried out for 20ns and pdb file of HDAC8 structure was saved every 2ns. The structures were analysed using castP and UCSF Chimera and most stabilized structure (20ns) was used for docking study. Molecular docking of 75 selected VPA-analogues with PDB-3F07 was performed using AUTODOCK4.2.6. Lamarckian Genetic Algorithm was used to generate conformations of docked ligand and structure. The docking study revealed that VPA and its analogues have more affinity towards ‘hydrophobic active site channel’, due to its hydrophobic properties and allows VPA and their analogues to take part in van der Waal interactions with TYR24, HIS42, VAL41, TYR20, SER138, TRP137 while TRP137 and SER138 showed hydrogen bonding interaction with VPA-analogues. 14 analogues showed better binding affinity than VPA. ADMET SAR server was used to predict the ADMET properties of selected VPA analogues for predicting their druggability. On the basis of ADMET screening, 09 molecules were selected and are being used for in-vivo evaluation using Danio rerio model.

Keywords: HDAC8, docking, molecular dynamics simulation, valproic acid

Procedia PDF Downloads 221

Authors: Milu T. Cherian, Sergio C. Chai, Morgan A. Casal, Taosheng Chen

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This study aims to use CINPA1, a recently discovered small-molecule inhibitor of the xenobiotic receptor CAR (constitutive androstane receptor) for understanding the binding modes of CAR and to guide CAR-mediated gene expression profiling studies in human primary hepatocytes. CAR and PXR are xenobiotic sensors that respond to drugs and endobiotics by modulating the expression of metabolic genes that enhance detoxification and elimination. Elevated levels of drug metabolizing enzymes and efflux transporters resulting from CAR activation promote the elimination of chemotherapeutic agents leading to reduced therapeutic effectiveness. Multidrug resistance in tumors after chemotherapy could be associated with errant CAR activity, as shown in the case of neuroblastoma. CAR inhibitors used in combination with existing chemotherapeutics could be utilized to attenuate multidrug resistance and resensitize chemo-resistant cancer cells. CAR and PXR have many overlapping modulating ligands as well as many overlapping target genes which confounded attempts to understand and regulate receptor-specific activity. Through a directed screening approach we previously identified a new CAR inhibitor, CINPA1, which is novel in its ability to inhibit CAR function without activating PXR. The cellular mechanisms by which CINPA1 inhibits CAR function were also extensively examined along with its pharmacokinetic properties. CINPA1 binding was shown to change CAR-coregulator interactions as well as modify CAR recruitment at DNA response elements of regulated genes. CINPA1 was shown to be broken down in the liver to form two, mostly inactive, metabolites. The structure-activity differences of CINPA1 and its metabolites were used to guide computational modeling using the CAR-LBD structure. To rationalize how ligand binding may lead to different CAR pharmacology, an analysis of the docked poses of human CAR bound to CITCO (a CAR activator) vs. CINPA1 or the metabolites was conducted. From our modeling, strong hydrogen bonding of CINPA1 with N165 and H203 in the CAR-LBD was predicted. These residues were validated to be important for CINPA1 binding using single amino-acid CAR mutants in a CAR-mediated functional reporter assay. Also predicted were residues making key hydrophobic interactions with CINPA1 but not the inactive metabolites. Some of these hydrophobic amino acids were also identified and additionally, the differential coregulator interactions of these mutants were determined in mammalian two-hybrid systems. CINPA1 represents an excellent starting point for future optimization into highly relevant probe molecules to study the function of the CAR receptor in normal- and pathophysiology, and possible development of therapeutics (for e.g. use for resensitizing chemoresistant neuroblastoma cells).

Keywords: antagonist, chemoresistance, constitutive androstane receptor (CAR), multi-drug resistance, structure activity relationship (SAR), xenobiotic resistance

Procedia PDF Downloads 262

Authors: Gizem Kayar, Ramazan Bakir, M. Ilkay Koşar, Ceren U. Gencer, Alperen Ayyildiz

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Anatomy classes are crucial for general education of medical students, whereas learning anatomy is quite challenging and requires memorization of thousands of structures. In traditional teaching methods, learning materials are still based on books, anatomy mannequins, or videos. This results in forgetting many important structures after several years. However, more interactive teaching methods like virtual reality, augmented reality, gamification, and motion sensors are becoming more popular since such methods ease the way we learn and keep the data in mind for longer terms. During our study, we designed a virtual reality based digital head anatomy platform to investigate whether a fully interactive anatomy platform is effective to learn anatomy and to understand the level of teaching and learning optimization. The Head is one of the most complicated human anatomy structures, with thousands of tiny, unique structures. This makes the head anatomy one of the most difficult parts to understand during class sessions. Therefore, we developed a fully interactive digital tool with 3D model marking, quiz structures, 2D/3D puzzle structures, and VR support so as to integrate the power of VR and gamification. The project has been developed in Unity game engine with HTC Vive Cosmos VR headset. The head anatomy 3D model has been selected with full skeletal, muscular, integumentary, head, teeth, lymph, and vein system. The biggest issue during the development was the complexity of our model and the marking of it in the 3D world system. 3D model marking requires to access to each unique structure in the counted subsystems which means hundreds of marking needs to be done. Some parts of our 3D head model were monolithic. This is why we worked on dividing such parts to subparts which is very time-consuming. In order to subdivide monolithic parts, one must use an external modeling tool. However, such tools generally come with high learning curves, and seamless division is not ensured. Second option was to integrate tiny colliders to all unique items for mouse interaction. However, outside colliders which cover inner trigger colliders cause overlapping, and these colliders repel each other. Third option is using raycasting. However, due to its own view-based nature, raycasting has some inherent problems. As the model rotate, view direction changes very frequently, and directional computations become even harder. This is why, finally, we studied on the local coordinate system. By taking the pivot point of the model into consideration (back of the nose), each sub-structure is marked with its own local coordinate with respect to the pivot. After converting the mouse position to the world position and checking its relation with the corresponding structure’s local coordinate, we were able to mark all points correctly. The advantage of this method is its applicability and accuracy for all types of monolithic anatomical structures.

Keywords: anatomy, e-learning, virtual reality, 3D model marking

Procedia PDF Downloads 68

Authors: Semenov Matvei, Stoporev Andrey, Pavelyev Roman, Varfolomeev Mikhail

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Gas hydrates are host-guest compounds. Guest molecules can be low molecular weight components of associated petroleum gas (C1-C4 hydrocarbons), carbon dioxide, hydrogen sulfide, and nitrogen. Gas hydrates have a number of unique properties that make them interesting from a technological point of view, for example, for storing hydrocarbon gases in solid form under moderate thermobaric conditions. The hydrate form of gas has a number of advantages, including a significant gas content in the hydrate, relative safety and environmental friendliness of the process. Such technology could be especially useful in cold regions, where hydrate production, storage and transportation can be more energy efficient. Recently, new developments have been proposed that seek to reduce the number of steps to obtain the finished hydrate, for example, using a pressing device/screw inside the reactor. However, the energy consumption required for the hydrate formation process remains a challenge. Thus, the goal of the current work is to study the patterns and mechanisms of the hydrate formation process using small additions of hydrate formation promoters under static conditions. The study of these aspects will help solve the problem of accelerated production of gas hydrates with minimal energy consumption. Currently, new compounds have been developed that can accelerate the formation of methane hydrate with a small amount of promoter in water, not exceeding 0.1% by weight. To test the influence of promoters on the process of hydrate formation, standard experiments are carried out under dynamic conditions with stirring. During such experiments, the time at which hydrate formation begins (induction period), the temperature at which formation begins (supercooling), the rate of hydrate formation, and the degree of conversion of water to hydrate are assessed. This approach helps to determine the most effective compound in comparative experiments with different promoters and select their optimal concentration. These experimental studies made it possible to study the features of the formation of associated petroleum gas hydrate from promoter solutions under static conditions. Phase transformations were studied using high-pressure micro-differential scanning calorimetry under various experimental conditions. Visual studies of the growth mode of methane hydrate depending on the type of promoter were also carried out. The work is an extension of the methodology for studying the effect of promoters on the process of associated petroleum gas hydrate formation in order to identify new ways to accelerate the formation of gas hydrates without the use of mixing. This work presents the results of a study of the process of associated petroleum gas hydrate formation using high-pressure differential scanning micro-calorimetry, visual investigation, gas chromatography, autoclaves study and stability data. It was found that the synthesized compounds multiply the conversion of water into hydrate under static conditions up to 96% due to a change in the growth mechanism of associated petroleum gas hydrate.

Keywords: gas hydrate, gas storage, promotor, associated petroleum gas

Procedia PDF Downloads 35

Authors: Mauro Cristeche

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This paper approaches the intervention of the American State in the social arena and the modeling of the rights system from the Argentinian experience, by observing the characteristics of its federal budgetary system, the evolution of social public spending and welfare programs in recent years, labor and poverty statistics, and the changes on the labor market structure. The analysis seeks to combine different methodologies and sources: in-depth interviews with specialists, analysis of theoretical and mass-media material, and statistical sources. Among the results, it could be mentioned that the tendency to state interventionism (what has been called ‘nationalization of social life’) is quite evident in the United States, and manifests itself in multiple forms. The bibliography consulted, and the experts interviewed pointed out this increase of the state presence in historical terms (beyond short-term setbacks) in terms of increase of public spending, fiscal pressure, public employment, protective and control mechanisms, the extension of welfare policies to the poor sectors, etc. In fact, despite the significant differences between both countries, the United States and Argentina have common patterns of behavior in terms of the aforementioned phenomena. On the other hand, dissimilarities are also important. Some of them are determined by each country's own political history. The influence of political parties on the economic model seems more decisive in the United States than in Argentina, where the tendency to state interventionism is more stable. The centrality of health spending is evident in America, while in Argentina that discussion is more concentrated in the social security system and public education. The biggest problem of the labor market in the United States is the disqualification as a consequence of the technological development while in Argentina it is a result of its weakness. Another big difference is the huge American public spending on Defense. Then, the more federal character of the American State is also a factor of differential analysis against a centralized Argentine state. American public employment (around 10%) is comparatively quite lower than the Argentinian (around 18%). The social statistics show differences, but inequality and poverty have been growing as a trend in the last decades in both countries. According to public rates, poverty represents 14% in The United States and 33% in Argentina. American public spending is important (welfare spending and total public spending represent around 12% and 34% of GDP, respectively), but a bit lower than Latin-American or European average). In both cases, the tendency to underemployment and disqualification unemployment does not assume a serious gravity. Probably one of the most important aspects of the analysis is that private initiative and public intervention are much more intertwined in the United States, which makes state intervention more ‘fuzzy’, while in Argentina the difference is clearer. Finally, the power of its accumulation of capital and, more specifically, of the industrial and services sectors in the United States, which continues to be the engine of the economy, express great differences with Argentina, supported by its agro-industrial power and its public sector.

Keywords: state intervention, welfare policies, labor market, system of rights, United States of America

Procedia PDF Downloads 106

Authors: Domenico Carmelo Mongelli

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The context is that of great uncertainty in the 27 countries belonging to the European Union which has adopted an epochal measure: the elimination of internal combustion engines for the traction of road vehicles starting from 2035 with complete replacement with electric vehicles. If on the one hand there is great concern at various levels for the unpreparedness for this change, on the other the Scientific Community is not preparing accurate studies on the problem, as the scientific literature deals with single aspects of the issue, moreover addressing the issue at the level of individual countries, losing sight of the global implications of the issue for the entire EU. The aim of the research is to fill these gaps: the technological, plant engineering, environmental, economic and employment aspects of the energy transition in question are addressed and connected to each other, comparing the current situation with the different scenarios that could exist in 2035 and in the following years until total disposal of the internal combustion engine vehicle fleet for the entire EU. The methodologies adopted by the research consist in the analysis of the entire life cycle of electric vehicles and batteries, through the use of specific databases, and in the dynamic simulation, using specific calculation codes, of the application of the results of this analysis to the entire EU electric vehicle fleet from 2035 onwards. Energy balance sheets will be drawn up (to evaluate the net energy saved), plant balance sheets (to determine the surplus demand for power and electrical energy required and the sizing of new plants from renewable sources to cover electricity needs), economic balance sheets (to determine the investment costs for this transition, the savings during the operation phase and the payback times of the initial investments), the environmental balances (with the different energy mix scenarios in anticipation of 2035, the reductions in CO2eq and the environmental effects are determined resulting from the increase in the production of lithium for batteries), the employment balances (it is estimated how many jobs will be lost and recovered in the reconversion of the automotive industry, related industries and in the refining, distribution and sale of petroleum products and how many will be products for technological innovation, the increase in demand for electricity, the construction and management of street electric columns). New algorithms for forecast optimization are developed, tested and validated. Compared to other published material, the research adds an overall picture of the energy transition, capturing the advantages and disadvantages of the different aspects, evaluating the entities and improvement solutions in an organic overall picture of the topic. The results achieved allow us to identify the strengths and weaknesses of the energy transition, to determine the possible solutions to mitigate these weaknesses and to simulate and then evaluate their effects, establishing the most suitable solutions to make this transition feasible.

Keywords: engines, Europe, mobility, transition

Procedia PDF Downloads 38

Authors: Anna Demian, Levi Howard, L. Ng, Leslie Simon, Mark Dragon, A. Desai, Timothy Devlantes, W. David Freeman

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Introduction: Out-of-hospital cardiac arrest (OHCA) can carry a high mortality. For survivors, the most common complication is hypoxic-ischemic brain injury (HIBI). Rarely, lumbosacral spinal cord and/or other spinal cord artery ischemia can occur due to anatomic variation and variable mean arterial pressure after the return of spontaneous circulation. We present a case of an OHCA survivor who later woke up with bilateral leg weakness with preserved sensation (ASIA grade B, L2 level). Methods: We describe a clinical, radiographic, and laboratory presentation, as well as a National Library of Medicine (NLM) search engine methodology, characterizing incidence/prevalence of this entity is discussed. A 70-year-old male, a longtime smoker, and alcohol user, suddenly collapsed at a bar surrounded by friends. He had complained of chest pain before collapsing. 911 was called. EMS arrived, and the patient was in pulseless electrical activity (PEA), cardiopulmonary resuscitation (CPR) was initiated, and the patient was intubated, and a LUCAS device was applied for continuous, high-quality CPR in the field by EMS. In the ED, central lines were placed, and thrombolysis was administered for a suspected Pulmonary Embolism (PE). It was a prolonged code that lasted 90 minutes. The code continued with the eventual return of spontaneous circulation. The patient was placed on an epinephrine and norepinephrine drip to maintain blood pressure. ECHO was performed and showed a “D-shaped” ventricle worrisome for PE as well as an ejection fraction around 30%. A CT with PE protocol was performed and confirmed bilateral PE. Results: The patient woke up 24 hours later, following commands, and was extubated. He was found paraplegic below L2 with preserved sensation, with hypotonia and areflexia consistent with “spinal shock” or anterior spinal cord syndrome. MRI thoracic and lumbar spine showed a conus medullaris level spinal cord infarction. The patient was given IV steroids upon initial discovery of cord infarct. NLM search using “cardiac arrest” and “spinal cord infarction” revealed 57 results, with only 8 review articles. Risk factors include age, atherosclerotic disease, and intraaortic balloon pump placement. AoA (Artery of Adamkiewicz) anatomic variation along with existing atherosclerotic factors and low perfusion were also known risk factors. Conclusion: Acute paraplegia from anterior spinal cord infarction of the AoA territory after cardiac arrest is rare. Larger prospective, multicenter trials are needed to examine potential interventions of hypothermia, lumbar drains, which are sometimes used in aortic surgery to reduce ischemia and/or other neuroprotectants.

Keywords: cardiac arrest, spinal cord infarction, artery of Adamkiewicz, paraplegia

Procedia PDF Downloads 170

Authors: Biswaranjan D. Mohapatra, Ipsha Hota, Swarna P. Mantry, Nibedita Behera, Kumar S. K. Varadwaj

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Designing highly active and low-cost oxygen evolution (2H₂O → 4H⁺ + 4e⁻ + O₂) electrocatalyst is one of the most active areas of advanced energy research. Some precious metal-based electrocatalysts, such as IrO₂ and RuO₂, have shown excellent performance for oxygen evolution reaction (OER); however, they suffer from high-cost and low abundance which limits their applications. Recently, layered double hydroxides (LDHs), composed of layers of divalent and trivalent transition metal cations coordinated to hydroxide anions, have gathered attention as an alternative OER catalyst. However, LDHs are insulators and coupled with carbon materials for the electrocatalytic applications. Graphene covalently doped with nitrogen has been demonstrated to be an excellent electrocatalyst for energy conversion technologies such as; oxygen reduction reaction (ORR), oxygen evolution reaction (OER) & hydrogen evolution reaction (HER). However, they operate at high overpotentials, significantly above the thermodynamic standard potentials. Recently, we reported remarkably enhanced catalytic activity of benzoate or 1-pyrenebutyrate functionalized N-doped graphene towards the ORR in alkaline medium. The molecular and heteroatom co-doping on graphene is expected to tune the electronic structure of graphene. Therefore, an innovative catalyst architecture, in which LDHs are anchored on aromatic acid functionalized ‘N’ doped graphene may presumably boost the OER activity to a new benchmark. Herein, we report fabrication of Co₂Fe-LDH on aromatic acid (AA) functionalized ‘N’ doped reduced graphene oxide (NG) and studied their OER activities in alkaline medium. In the first step, a novel polyol method is applied for synthesis of AA functionalized NG, which is well dispersed in aqueous medium. In the second step, Co₂Fe LDH were grown on AA functionalized NG by co-precipitation method. The hybrid samples are abbreviated as Co₂Fe LDH/AA-NG, where AA is either Benzoic acid or 1, 3-Benzene dicarboxylic acid (BDA) or 1, 3, 5 Benzene tricarboxylic acid (BTA). The crystal structure and morphology of the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). These studies confirmed the growth of layered single phase LDH. The electrocatalytic OER activity of these hybrid materials was investigated by rotating disc electrode (RDE) technique on a glassy carbon electrode. The linear sweep voltammetry (LSV) on these catalyst samples were taken at 1600rpm. We observed significant OER performance enhancement in terms of onset potential and current density on Co₂Fe LDH/BTA-NG hybrid, indicating the synergic effect. This exploration of molecular functionalization effect in doped graphene and LDH system may provide an excellent platform for innovative design of OER catalysts.

Keywords: π-π functionalization, layered double hydroxide, oxygen evolution reaction, reduced graphene oxide

Procedia PDF Downloads 179

Authors: Trevor Malambo Simbayi, Diane Hildebrandt, Tonderayi Matambo

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The rapid growth of population in recent decades has resulted in an increased need for energy to meet human activities. As energy demands increase, the need for other sources of energy other than fossil fuels, increases in turn. Furthermore, environmental concerns such as global warming due to the use of fossil fuels, depleting fossil fuel reserves and the rising cost of oil have contributed to an increased interest in renewables sources of energy. Biogas is a renewable source of energy produced through the process of anaerobic digestion (AD) and it offers a two-fold solution; it provides an environmentally friendly source of energy and its production helps to reduce the amount of organic waste taken to landfills. This research seeks to address the waste management problem caused by an aquatic weed called water hyacinth (Eichhornia crassipes) at the Hartbeespoort (Harties) Dam in the North West Province of South Africa, through biogas production of the weed. Water hyacinth is a category 1 invasive species and it is deemed to be the most problematic aquatic weed. This weed is said to double its size in the space of five days. Eutrophication in the Hartbeespoort Dam has manifested itself through the excessive algae bloom and water hyacinth infestation. A large amount of biomass from water hyacinth and algae are generated per annum from the two hundred hectare surface area of the dam exposed to the sun. This biomass creates a waste management problem. Water hyacinth when in full bloom can cover nearly half of the surface of Hartbeespoort Dam. The presence of water hyacinth in the dam has caused economic and environmental problems. Economic activities such as fishing, boating, and recreation, are hampered by the water hyacinth’s prolific growth. This research proposes the use of water hyacinth as a feedstock or substrate for biogas production in order to find an economic and environmentally friendly means of waste management for the communities living around the Hartbeespoort Dam. In order to achieve this objective, water hyacinth will be collected from the dam and it will be mechanically pretreated before anaerobic digestion. Pretreatment is required for lignocellulosic materials like water hyacinth because such materials are called recalcitrant solid materials. Cow manure will be employed as a source of microorganisms needed for biogas production to occur. Once the water hyacinth and the cow dung are mixed, they will be placed in laboratory anaerobic reactors. Biogas production will be monitored daily through the downward displacement of water. Characterization of the substrates (cow manure and water hyacinth) to determine the nitrogen, sulfur, carbon and hydrogen, total solids (TS) and volatile solids (VS). Liquid samples from the anaerobic digesters will be collected and analyzed for volatile fatty acids (VFAs) composition by means of a liquid gas chromatography machine.

Keywords: anaerobic digestion, biogas, waste management, water hyacinth

Procedia PDF Downloads 168

Authors: Sibgha Noreen, Muhammad Salim Akhter, Seema Mahmood

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Salt stress is an abiotic stress that causes a heavy toll on growth and development and also reduces the productivity of arable and horticultural crops. Globally, a quarter of total arable land has fallen prey to this menace, and more is being encroached because of the usage of brackish water for irrigation purposes. Though barley is categorized as salt-tolerant crop, but cultivars show a wide genetic variability in response to it. In addressing salt stress, silicon nutrition would be a facile tool for enhancing salt tolerant to sustain crop production. A greenhouse study was conducted to evaluate the response of barley (Hordeum vulgare L.) cultivars to silicon nutrition under salt stress. The treatments included [(a) four barley cultivars (Jou-87, B-14002, B-14011, B-10008); (b) two salt levels (0, 200 mM, NaCl); and (c) two silicon levels (0, 200ppm, K2SiO3. nH2O), arranged in a factorial experiment in a completely randomized design with 16 treatments and repeated 4 times. Plants were harvested at 15 days after exposure to different experimental salinity and silicon foliar conditions. Results revealed that various physiological and biochemical attributes differed significantly (p<0.05) in response to different treatments and their interactive effects. Cultivar “B-10008” excelled in biological yield, chlorophyll constituents, antioxidant enzymes, and grain yield compared to other cultivars. The biological yield of shoot and root organs was reduced by 27.3 and 26.5 percent under salt stress, while it was increased by 14.5 and 18.5 percent by exogenous application of silicon over untreated check, respectively. The imposition of salt stress at 200 mM caused a reduction in total chlorophyll content, chl ‘a’ , ‘b’ and ratio a/b by 10.6,16.8,17.1 and 7.1, while spray of 200 ppm silicon improved the quantum of the constituents by 10.4,12.1,10.2,10.3 over untreated check, respectively. The quantum of free amino acids and protein content was enhanced in response to salt stress and the spray of silicon nutrients. The amounts of superoxide dismutase, catalases, peroxidases, hydrogen peroxide, and malondialdehyde contents rose to 18.1, 25.7, 28.1, 29.5, and 17.6 percent over non-saline conditions under salt stress. However, the values of these antioxidants were reduced in proportion to salt stress by 200 ppm silicon applied as rooting medium on barley crops. The salt stress caused a reduction in the number of tillers, number of grains per spike, and 100-grain weight to the amount of 29.4, 8.6, and 15.8 percent; however, these parameters were improved by 7.1, 10.3, and 9.6 percent by foliar spray of silicon over untreated crop, respectively. It is concluded that the barley cultivar “B-10008” showed greater tolerance and adaptability to saline conditions. The yield of barley crops could be potentiated by a foliar spray of 200 ppm silicon at the vegetative growth stage under salt stress.

Keywords: salt stress, silicon nutrition, chlorophyll constituents, antioxidant enzymes, barley crop

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Authors: Mohamed A. Baba, Gazy Rodowan, Brigita Abakevičienė, Sigitas Tamulevičius, Bartlomiej Lemieszek, Sebastian Molin, Tomas Tamulevičius

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Solid oxide fuel cells (SOFC) efficiently convert hydrogen to energy without producing any disturbances or contaminants. The core of the cell is electrolyte. For improving the performance of electrolyte-supported cells, it is desirable to extend the available exchange surface area by micro-structuring of the electrolyte with laser-based micromachining. This study investigated the electrochemical performance of cells micro machined using a femtosecond laser. Commercial ceramic SOFC (Elcogen, AS) with a total thickness of 400 μm was structured by 1030 nm wavelength Yb: KGW fs-laser Pharos (Light Conversion) using 100 kHz repetition frequency and 290 fs pulse length light by scanning with the galvanometer scanner (ScanLab) and focused with a f-Theta telecentric lens (SillOptics). The sample height was positioned using a motorized z-stage. The microstructures were formed using a laser spiral trepanning in Ni/YSZ anode supported membrane at the central part of the ceramic piece of 5.5 mm diameter at active area of the cell. All surface was drilled with 275 µm diameter holes spaced by 275 µm. The machining processes were carried out under ambient conditions. The microstructural effects of the femtosecond laser treatment on the electrolyte surface were investigated prior to the electrochemical characterisation using a scanning electron microscope (SEM) Quanta 200 FEG (FEI). The Novo control Alpha-A was used for electrochemical impedance spectroscopy on a symmetrical cell configuration with an excitation amplitude of 25 mV and a frequency range of 1 MHz to 0.1 Hz. The fuel cell characterization of the cell was examined on open flanges test setup by Fiaxell. Using nickel mesh on the anode side and au mesh on the cathode side, the cell was electrically linked. The cell was placed in a Kittec furnace with a Process IDentifier temperature controller. The wires were connected to a Solartron 1260/1287 frequency analyzer for the impedance and current-voltage characterization. In order to determine the impact of the anode's microstructure on the performance of the commercial cells, the acquired results were compared to cells with unstructured anode. Geometrical studies verified that the depth of the -holes increased linearly according to laser energy and scanning times. On the other hand, it reduced as the scanning speed increased. The electrochemical analysis demonstrates that the open circuit voltage OCV values of the two cells are equal. Further, the modified cell's initial slope reduces to 0.209 from 0.253 of the unmodified cell, revealing that the surface modification considerably decreases energy loss. Plus, the maximum power density for the cell with the microstructure and the reference cell respectively, are 1.45 and 1.16 Wcm⁻².

Keywords: electrochemical performance, electrolyte-supported cells, laser micro-structuring, solid oxide fuel cells

Procedia PDF Downloads 44

Authors: Iordana Neamtu, Aurica P. Chiriac, Loredana E. Nita, Mihai Asandulesa, Elena Butnaru, Nita Tudorachi, Alina Diaconu

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In the last decade, the attention of many researchers is focused on the synthesis of innovative “intelligent” copolymer structures with great potential for different uses. This considerable scientific interest is stimulated by possibility of the significant improvements in physical, mechanical, thermal and other important specific properties of these materials. Functionalization of polymer in synthesis by designing a suitable composition with the desired properties and applications is recognized as a valuable tool. In this work is presented a comparative study of the properties of the new copolymers poly(maleic anhydride maleic-co-3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane) and poly(itaconic-anhydride-co-3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane) obtained by radical polymerization in dioxane, using 2,2′-azobis(2-methylpropionitrile) as free-radical initiator. The comonomers are able for generating special effects as for example network formation, biodegradability and biocompatibility, gel formation capacity, binding properties, amphiphilicity, good oxidative and thermal stability, good film formers, and temperature and pH sensitivity. Maleic anhydride (MA) and also the isostructural analog itaconic anhydride (ITA) as polyfunctional monomers are widely used in the synthesis of reactive macromolecules with linear, hyperbranched and self & assembled structures to prepare high performance engineering, bioengineering and nano engineering materials. The incorporation of spiroacetal groups in polymer structures improves the solubility and the adhesive properties, induce good oxidative and thermal stability, are formers of good fiber or films with good flexibility and tensile strength. Also, the spiroacetal rings induce interactions on ether oxygen such as hydrogen bonds or coordinate bonds with other functional groups determining bulkiness and stiffness. The synthesized copolymers are analyzed by DSC, oscillatory and rotational rheological measurements and dielectric spectroscopy with the aim of underlying the heating behavior, solution viscosity as a function of shear rate and temperature and to investigate the relaxation processes and the motion of functional groups present in side chain around the main chain or bonds of the side chain. Acknowledgments This work was financially supported by the grant of the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, project number PN-II-132/2014 “Magnetic biomimetic supports as alternative strategy for bone tissue engineering and repair’’ (MAGBIOTISS).

Keywords: Poly(maleic anhydride-co-3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5)undecane); Poly(itaconic anhydride-co-3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5)undecane); DSC; oscillatory and rotational rheological analysis; dielectric spectroscopy

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Authors: Cecilia Sosa, Fernanda Figueroa, Leonardo Calzada

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Biosphere reserves (BR) are considered as the main strategy for biodiversity and ecosystems conservation. Mexican BR are mainly inhabited by rural communities who strongly depend on forests and their resources. Even though the dual objective of conservation and development has been sought in BR, land cover change is a common process in these areas, while most rural communities are highly marginalized, partly as a result of restrictions imposed by conservation to the access and use of resources. Achieving ecosystems conservation and social development face serious challenges. Factors such as financial support for development projects (public/private), environmental conditions, infrastructure and regional economic conditions might influence both land use change and wellbeing. Examining the temporal trends of conservation and development in BR is central for the evaluation of outcomes for these conservation strategies. In this study, we analyzed changes in primary vegetation cover (as a proxy for conservation) and the index of marginalization (as a proxy for development) in Mexican BR (2000-2015); we also explore the influence of various factors affecting these trends, such as conservation-development projects financial support (public or private), geographical distribution in ecoregions (as a proxy for shared environmental conditions) and in economic zones (as a proxy for regional economic conditions). We developed a spatial analysis at the municipal scale (2,458 municipalities nationwide) in ArcGIS, to obtain road densities, geographical distribution in ecoregions and economic zones, the financial support received, and the percent of municipality area under protection by protected areas and, particularly, by BR. Those municipalities with less than 25% of area under protection were regarded as part of the protected area. We obtained marginalization indexes for all municipalities and, using MODIS in Google Earth Engine, the number of pixels covered by primary vegetation. We used a linear mixed model in RStudio for the analysis. We found a positive correlation between the marginalization index and the percent of primary vegetation cover per year (r=0.49-0.5); i.e., municipalities with higher marginalization also show higher percent of primary vegetation cover. Also, those municipalities with higher area under protection have more development projects (r=0.46) and some environmental conditions were relevant for percent of vegetation cover. Time, economic zones and marginalization index were all important. Time was particularly, in 2005, when both marginalization and deforestation decreased. Road densities and financial support for conservation-development projects were irrelevant as factors in the general correlation. Marginalization is still being affected by the conservation strategies applied in BR, even though that this management category considers both conservation and development of local communities as its objectives. Our results suggest that roads densities and support for conservation-development projects have not been a factor of poverty alleviation. As better conservation is being attained in the most impoverished areas, we face the dilemma of how to improve wellbeing in rural communities under conservation, since current strategies have not been able to leave behind the conservation-development contraposition.

Keywords: deforestation, local development, marginalization, protected areas

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Authors: Iris Vural Gursel, Andrea Ramirez

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Effective utilization of lignin is an important mean for developing economically profitable biorefineries. Current literature suggests that large amounts of lignin will become available in second generation biorefineries. New conversion technologies will, therefore, be needed to carry lignin transformation well beyond combustion to produce energy, but towards high-value products such as chemicals and transportation fuels. In recent years, significant progress on catalysis has been made to improve transformation of lignin, and new catalytic processes are emerging. In this work, a techno-economic assessment of two of these novel conversion routes and comparison with more established lignin pyrolysis route were made. The aim is to provide insights into the potential performance and potential hotspots in order to guide the experimental research and ease the commercialization by early identifying cost drivers, strengths, and challenges. The lignin conversion routes selected for detailed assessment were: (non-catalytic) lignin pyrolysis as the benchmark, direct hydrodeoxygenation (HDO) of lignin and hydrothermal lignin depolymerisation. Products generated were mixed oxygenated aromatic monomers (MOAMON), light organics, heavy organics, and char. For the technical assessment, a basis design followed by process modelling in Aspen was done using experimental yields. A design capacity of 200 kt/year lignin feed was chosen that is equivalent to a 1 Mt/y scale lignocellulosic biorefinery. The downstream equipment was modelled to achieve the separation of the product streams defined. For determining external utility requirement, heat integration was considered and when possible gasses were combusted to cover heating demand. The models made were used in generating necessary data on material and energy flows. Next, an economic assessment was carried out by estimating operating and capital costs. Return on investment (ROI) and payback period (PBP) were used as indicators. The results of the process modelling indicate that series of separation steps are required. The downstream processing was found especially demanding in the hydrothermal upgrading process due to the presence of significant amount of unconverted lignin (34%) and water. Also, external utility requirements were found to be high. Due to the complex separations, hydrothermal upgrading process showed the highest capital cost (50 M€ more than benchmark). Whereas operating costs were found the highest for the direct HDO process (20 M€/year more than benchmark) due to the use of hydrogen. Because of high yields to valuable heavy organics (32%) and MOAMON (24%), direct HDO process showed the highest ROI (12%) and the shortest PBP (5 years). This process is found feasible with a positive net present value. However, it is very sensitive to the prices used in the calculation. The assessments at this stage are associated with large uncertainties. Nevertheless, they are useful for comparing alternatives and identifying whether a certain process should be given further consideration. Among the three processes investigated here, the direct HDO process was seen to be the most promising.

Keywords: biorefinery, economic assessment, lignin conversion, process design

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Authors: V. E. Messerle, O. A. Lavrichshev, A. B. Ustimenko

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Currently and in the foreseeable future (up to 2100), the global economy is oriented to the use of organic fuel, mostly, solid fuels, the share of which constitutes 40% in the generation of electric power. Therefore, the development of technologies for their effective and environmentally friendly application represents a priority problem nowadays. This work presents the results of thermodynamic and experimental investigations of plasma technology for processing of low-grade coals. The use of this technology for producing target products (synthesis gas, hydrogen, technical carbon, and valuable components of mineral mass of coals) meets the modern environmental and economic requirements applied to basic industrial sectors. The plasma technology of coal processing for the production of synthesis gas from the coal organic mass (COM) and valuable components from coal mineral mass (CMM) is highly promising. Its essence is heating the coal dust by reducing electric arc plasma to the complete gasification temperature, when the COM converts into synthesis gas, free from particles of ash, nitrogen oxides and sulfur. At the same time, oxides of the CMM are reduced by the carbon residue, producing valuable components, such as technical silicon, ferrosilicon, aluminum and carbon silicon, as well as microelements of rare metals, such as uranium, molybdenum, vanadium, titanium. Thermodynamic analysis of the process was made using a versatile computation program TERRA. Calculations were carried out in the temperature range 300 - 4000 K and a pressure of 0.1 MPa. Bituminous coal with the ash content of 40% and the heating value 16,632 kJ/kg was taken for the investigation. The gaseous phase of coal processing products includes, basically, a synthesis gas with a concentration of up to 99 vol.% at 1500 K. CMM components completely converts from the condensed phase into the gaseous phase at a temperature above 2600 K. At temperatures above 3000 K, the gaseous phase includes, basically, Si, Al, Ca, Fe, Na, and compounds of SiO, SiH, AlH, and SiS. The latter compounds dissociate into relevant elements with increasing temperature. Complex coal conversion for the production of synthesis gas from COM and valuable components from CMM was investigated using a versatile experimental plant the main element of which was plug and flow plasma reactor. The material and thermal balances helped to find the integral indicators for the process. Plasma-steam gasification of the low-grade coal with CMM processing gave the synthesis gas yield 95.2%, the carbon gasification 92.3%, and coal desulfurization 95.2%. The reduced material of the CMM was found in the slag in the form of ferrosilicon as well as silicon and iron carbides. The maximum reduction of the CMM oxides was observed in the slag from the walls of the plasma reactor in the areas with maximum temperatures, reaching 47%. The thusly produced synthesis gas can be used for synthesis of methanol, or as a high-calorific reducing gas instead of blast-furnace coke as well as power gas for thermal power plants. Reduced material of CMM can be used in metallurgy.

Keywords: gasification, mineral mass, organic mass, plasma, processing, solid fuel, synthesis gas, valuable components

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Authors: Gondrexon, Gonon, Mendil-Jakani, Mareau

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Proton Exchange Membrane Fuel Cells (PEMFCs) seems to be a promising device used for converting hydrogen into electricity. PEMFC is made of a Membrane Electrode Assembly (MEA) composed of a Proton Exchange Membrane (PEM) sandwiched by two catalytic layers. Nowadays, specific performances are targeted in order to ensure the long-term expansion of this technology. Current polymers used (perfluorinated as Nafion®) are unsuitable (loss of mechanical properties) for the high-temperature range. To overcome this issue, sulfonated polyaromatic polymers appear to be a good alternative since it has very good thermomechanical properties. However, their proton conductivity and chemical stability (oxidative resistance to H2O2 formed during fuel cell (FC) operating) are very low. In our team, we patented an original concept of hybrid membranes able to fulfill the specific requirements for PEMFC. This idea is based on the improvement of commercialized polymer membrane via an easy and processable stabilization thanks to sol-gel (SG) chemistry with judicious embeded chemical functions. This strategy is thus breaking up with traditional approaches (design of new copolymers, use of inorganic charges/additives). In 2020, we presented the elaboration and functional properties of a 1st generation of hybrid membranes with promising performances and durability. The latter was made by self-condensing a SG phase with 3(mercaptopropyl)trimethoxysilane (MPTMS) inside a commercial sPEEK host membrane. The successful in-situ condensation reactions of the MPTMS was demonstrated by measures of mass uptakes, FTIR spectroscopy (presence of C-Haliphatics) and solid state NMR 29Si (T2 & T3 signals of self-condensation products). The ability of the SG phase to prevent the oxidative degradation of the sPEEK phase (thanks to thiol chemical functions) was then proved with H2O2 accelerating tests and FC operating tests. A 2nd generation made of thiourea functionalized SG precursors (named HTU & TTU) was made after. By analysing in depth the morphologies of these different hybrids by direct space analysis (AFM/SEM/TEM) and reciprocal space analysis (SANS/SAXS/WAXS), we highlighted that both SG phase morphology and its localisation into the host has a huge impact on the PEM functional properties observed. This relationship is also dependent on the chemical function embedded. The hybrids obtained have shown very good chemical resistance during aging test (exposed to H2O2) compared to the commercial sPEEK. But the chemical function used is considered as “sacrificial” and cannot react indefinitely with H2O2. Thus, we are now working on a 3rd generation made of both sacrificial/regenerative chemical functions which are expected to inhibit the chemical aging of sPEEK more efficiently. With this work, we are confident to reach a predictive approach of the key parameters governing the final properties.

Keywords: fuel cells, ionomers, membranes, sPEEK, chemical stability

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Authors: Poojan Gharat, Haridas Pal, Sharmistha Dutta Choudhury

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Tuning photophysical properties of guest dyes through host-guest interactions involving macrocyclic hosts are the attractive research areas since past few decades, as these changes can directly be implemented in chemical sensing, molecular recognition, fluorescence imaging and dye laser applications. Excited state intramolecular proton transfer (ESIPT) is an intramolecular prototautomerization process display by some specific dyes. The process is quite amenable to tunability by the presence of different macrocyclic hosts. The present study explores the interesting effect of p-sulfonatocalix[n]arene (SCXn) and cyclodextrin (CD) hosts on the excited-state prototautomeric equilibrium of Chrysazine (CZ), a model antitumour drug. CZ exists exclusively in its normal form (N) in the ground state. However, in the excited state, the excited N* form undergoes ESIPT along with its pre-existing intramolecular hydrogen bonds, giving the excited state prototautomer (T*). Accordingly, CZ shows a single absorption band due to N form, but two emission bands due to N* and T* forms. Facile prototautomerization of CZ is considerably inhibited when the dye gets bound to SCXn hosts. However, in spite of lower binding affinity, the inhibition is more profound with SCX6 host as compared to SCX4 host. For CD-CZ system, while prototautomerization process is hindered by the presence of β-CD, it remains unaffected in the presence of γCD. Reduction in the prototautomerization process of CZ by SCXn and βCD hosts is unusual, because T* form is less dipolar in nature than the N*, hence binding of CZ within relatively hydrophobic hosts cavities should have enhanced the prototautomerization process. At the same time, considering the similar chemical nature of two CD hosts, their effect on prototautomerization process of CZ would have also been similar. The atypical effects on the prototautomerization process of CZ by the studied hosts are suggested to arise due to the partial inclusion or external binding of CZ with the hosts. As a result, there is a strong possibility of intermolecular H-bonding interaction between CZ dye and the functional groups present at the portals of SCXn and βCD hosts. Formation of these intermolecular H-bonds effectively causes the pre-existing intramolecular H-bonding network within CZ molecule to become weak, and this consequently reduces the prototautomerization process for the dye. Our results suggest that rather than the binding affinity between the dye and host, it is the orientation of CZ in the case of SCXn-CZ complexes and the binding stoichiometry in the case of CD-CZ complexes that play the predominant role in influencing the prototautomeric equilibrium of the dye CZ. In the case of SCXn-CZ complexes, the results obtained through experimental findings are well supported by quantum chemical calculations. Similarly for CD-CZ systems, binding stoichiometries obtained through geometry optimization studies on the complexes between CZ and CD hosts correlate nicely with the experimental results. Formation of βCD-CZ complexes with 1:1 stoichiometry while formation of γCD-CZ complexes with 1:1, 1:2 and 2:2 stoichiometries are revealed from geometry optimization studies and these results are in good accordance with the observed effects by the βCD and γCD hosts on the ESIPT process of CZ dye.

Keywords: intermolecular proton transfer, macrocyclic hosts, quantum chemical studies, photophysical studies

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