Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 2150

World Academy of Science, Engineering and Technology

[Chemical and Molecular Engineering]

Online ISSN : 1307-6892

2150 Asymmetric Organocatalytic Synthesis of Unnatural Amino Acids and Their Application in Foldamer Design

Authors: Alexander J. A. Cobb

Abstract:

The primary interest of our group has been the development of asymmetric synthetic methodology – primarily using organocatalysis. Partly by design and partly through serendipity, unnatural amino acids have been a prevalent target in our studies. We have developed a variety of methods - from making cyclic gamma-systems with very high enantioselectivity through to acyclic delta amino acids – themselves dipeptide mimics. Recent focus has been on utilising some of our novel amino acid monomers towards the construction of unnatural peptides with the ability to fold into discrete structures such as helices. Known as ‘foldamers’ the ultimate aim of our work is to design these constructs to have some kind of function – starting, of course, with their potential use as asymmetric catalysts in their own right, with the hope of transferring stereogenic information via the chirality of the helix itself.

Keywords: Amino Acids, bifunctional organocatalysts, foldamers, secondary amino catalysis

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2149 Bringing the World to Net Zero Carbon Dioxide by Sequestering Biomass Carbon

Authors: Jeffrey A. Amelse

Abstract:

Many corporations aspire to become Net Zero Carbon Carbon Dioxide by 2035-2050. This paper examines what it will take to achieve those goals. Achieving Net Zero CO₂ requires an understanding of where energy is produced and consumed, the magnitude of CO₂ generation, and proper understanding of the Carbon Cycle. The latter leads to the distinction between CO₂ and biomass carbon sequestration. Short reviews are provided for prior technologies proposed for reducing CO₂ emissions from fossil fuels or substitution by renewable energy, to focus on their limitations and to show that none offer a complete solution. Of these, CO₂ sequestration is poised to have the largest impact. It will just cost money, scale-up is a huge challenge, and it will not be a complete solution. CO₂ sequestration is still in the demonstration and semi-commercial scale. Transportation accounts for only about 30% of total U.S. energy demand, and renewables account for only a small fraction of that sector. Yet, bioethanol production consumes 40% of U.S. corn crop, and biodiesel consumes 30% of U.S. soybeans. It is unrealistic to believe that biofuels can completely displace fossil fuels in the transportation market. Bioethanol is traced through its Carbon Cycle and shown to be both energy inefficient and inefficient use of biomass carbon. Both biofuels and CO₂ sequestration reduce future CO₂ emissions from continued use of fossil fuels. They will not remove CO₂ already in the atmosphere. Planting more trees has been proposed as a way to reduce atmospheric CO₂. Trees are a temporary solution. When they complete their Carbon Cycle, they die and release their carbon as CO₂ to the atmosphere. Thus, planting more trees is just 'kicking the can down the road.' The only way to permanently remove CO₂ already in the atmosphere is to break the Carbon Cycle by growing biomass from atmospheric CO₂ and sequestering biomass carbon. Sequestering tree leaves is proposed as a solution. Unlike wood, leaves have a short Carbon Cycle time constant. They renew and decompose every year. Allometric equations from the USDA indicate that theoretically, sequestrating only a fraction of the world’s tree leaves can get the world to Net Zero CO₂ without disturbing the underlying forests. How can tree leaves be permanently sequestered? It may be as simple as rethinking how landfills are designed to discourage instead of encouraging decomposition. In traditional landfills, municipal waste undergoes rapid initial aerobic decomposition to CO₂, followed by slow anaerobic decomposition to methane and CO₂. The latter can take hundreds to thousands of years. The first step in anaerobic decomposition is hydrolysis of cellulose to release sugars, which those who have worked on cellulosic ethanol know is challenging for a number of reasons. The key to permanent leaf sequestration may be keeping the landfills dry and exploiting known inhibitors for anaerobic bacteria.

Keywords: biomass, Carbon Dioxide, sequestration, leaves, net zero

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2148 Comparison of Two Different Methods for Peptide Synthesis

Authors: Klaudia Chmielewska, Krystyna Dzierzbicka, Iwona Inkielewicz-Stepniak

Abstract:

Carnosine, an endogenous peptide consisting of β-alanine and L-histidine has a variety of functions to mention: antioxidant, antiglycation, and reducing the toxicity of metal ions. It has therefore been proposed to act as a therapeutic agent for many pathological states, although its therapeutic index is limited by quick enzymatic cleavage. To overcome this limitation, there’s an urge to create new derivatives which might become less potent to hydrolysis, while preserving the therapeutic effect. The poster summarizes the efficiency of two peptide synthesis methods, which were: (1) the mixed anhydride with isobutyl chloroformate and N-methylmorpholine (NMM) and (2) carbodiimide - mediated coupling method via appropriate reagent condensing, here – CDI. The methods were used to obtain dipeptides which were the derivatives of carnosine. Obtained dipeptides were made in the form of methyl esters and their structures will be confirmed 1H NMR, 13C NMR, MS and elemental analysis techniques. Later on, they will be analyzed for their antioxidant properties, in comparison to carnosine.

Keywords: Synthesis, Method, Peptide, carnosine

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2147 Green, Smooth and Easy Electrochemical Synthesis of N-Protected Indole Derivatives

Authors: Tamer Ezzat Youssef, Sarah Fahad Alajmi

Abstract:

Here, we report a simple method for the direct conversion of 6-Nitro-1H-indole into N-substituted indoles via electrochemical dehydrogenative reaction with halogenated reagents under strongly basic conditions through N–R bond formation. The reactions have been evolved under moderate and scalable electrolytic conditions afforded N-protected indoles 3a-f. The conduct of the reactions was performed in a simple divided cell under constant current without oxidizing reagents or transition-metal catalysts. The synthesized products have been characterized via UV/Vis spectrophotometry, 1H-NMR, and FTIR spectroscopy. A possible reaction mechanism is discussed based on the N-protective products. This methodology could be applied to the synthesis of various biologically active N-substituted indole derivatives.

Keywords: Green Chemistry, heteroaromatic, organic electrosynthesis

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2146 Multi-Objective Optimization (Pareto Sets) and Multi-Response Optimization (Desirability Function) of Microencapsulation of Emamectin

Authors: Victoria Molina, José M. Troncoso, José R. Perez-Correa, Wendy Franco, Sergio Benavides, Ricardo Luna

Abstract:

Emamectin Benzoate (EB) is a crystal antiparasitic that belongs to the avermectin family. It is one of the most common treatments used in Chile to control Caligus rogercresseyi in Atlantic salmon. However, the sea lice acquired resistance to EB when it is exposed at sublethal EB doses. The low solubility rate of EB and its degradation at the acidic pH in the fish digestive tract are the causes of the slow absorption of EB in the intestine. To protect EB from degradation and enhance its absorption, specific microencapsulation technologies must be developed. Amorphous Solid Dispersion techniques such as Spray Drying (SD) and Ionic Gelation (IG) seem adequate for this purpose. Recently, Soluplus® (SOL) has been used to increase the solubility rate of several drugs with similar characteristics than EB. In addition, alginate (ALG) is a widely used polymer in IG for biomedical applications. Regardless of the encapsulation technique, the quality of the obtained microparticles is evaluated with the following responses, yield (Y%), encapsulation efficiency (EE%) and loading capacity (LC%). In addition, it is important to know the percentage of EB released from the microparticles in gastric (GD%) and intestinal (ID%) digestions. In this work, we microencapsulated EB with SOL (EB-SD) and with ALG (EB-IG) using SD and IG, respectively. Quality microencapsulation responses and in vitro gastric and intestinal digestions at pH 3.35 and 7.8, respectively, were obtained. A central composite design was used to find the optimum microencapsulation variables (amount of EB, amount of polymer and feed flow). In each formulation, the behavior of these variables was predicted with statistical models. Then, the response surface methodology was used to find the best combination of the factors that allowed a lower EB release in gastric conditions, while permitting a major release at intestinal digestion. Two approaches were used to determine this. The desirability approach (DA) and multi-objective optimization (MOO) with multi-criteria decision making (MCDM). Both microencapsulation techniques allowed to maintain the integrity of EB in acid pH, given the small amount of EB released in gastric medium, while EB-IG microparticles showed greater EB release at intestinal digestion. For EB-SD, optimal conditions obtained with MOO plus MCDM yielded a good compromise among the microencapsulation responses. In addition, using these conditions, it is possible to reduce microparticles costs due to the reduction of 60% of BE regard the optimal BE proposed by (DA). For EB-GI, the optimization techniques used (DA and MOO) yielded solutions with different advantages and limitations. Applying DA costs can be reduced 21%, while Y, GD and ID showed 9.5%, 84.8% and 2.6% lower values than the best condition. In turn, MOO yielded better microencapsulation responses, but at a higher cost. Overall, EB-SD with operating conditions selected by MOO seems the best option, since a good compromise between costs and encapsulation responses was obtained.

Keywords: Multi-objective optimization, microencapsulation, multiple decision-making criteria, Soluplus®

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2145 A Method for Harvesting Atmospheric Lightning-Energy and Utilization of Extra Generated Power of Nuclear Power Plants during the Low Energy Demand Periods

Authors: Akbar Rahmani Nejad, Pejman Rahmani Nejad, Ahmad Rahmani Nejad

Abstract:

we proposed the arresting of atmospheric lightning and passing the electrical current of lightning-bolts through underground water tanks to produce Hydrogen and restoring Hydrogen in reservoirs to be used later as clean and sustainable energy. It is proposed to implement this method for storage of extra electrical power (instead of lightning energy) during low energy demand periods to produce hydrogen as a clean energy source to store in big reservoirs and later generate electricity by burning the stored hydrogen at an appropriate time. This method prevents the complicated process of changing the output power of nuclear power plants. It is possible to pass an electric current through sodium chloride solution to produce chlorine and sodium or human waste to produce Methane, etc. however atmospheric lightning is an accidental phenomenon, but using this free energy just by connecting the output of lightning arresters to the output of power plant during low energy demand period which there is no significant change in the design of power plant or have no cost, can be considered completely an economical design

Keywords: Power Plant, hydrogen gas, lightning energy, resistive element

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2144 Underivatized Amino Acids Analyses Using Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) in Scalp Hair of Children with Autism Spectrum Disorder

Authors: Mazin Alqhazo, AyatBani Rashaid, Zain Khasawneh, Shreen Nusair, Mohammad El-Khateeb, Mahmoud Bashtawi

Abstract:

Autism Spectrum disorder (ASD) is a psychiatric disorder with unknown etiology that mainly affects children in the first three years of life. Alterations of amino acid levels are believed to contribute to ASD. The levels of 6 essential amino acids (methionine, histidine, valine, leucine, threonine, and phenylalanine), 5 conditional amino acids (proline, tyrosine, glutamine, cysteine, and cystine), and 5 non-essential amino acids (asparagine, aspartic acid, alanine, serine, and glutamic acid) in hair samples of children with ASD (n = 25) were analyzed and compared to corresponding levels in healthy age-matched controls (n = 25). The results showed that the levels of methionine, alanine, and asparagine were significantly lower in the hair samples of ASD group compared to those of the control group (p ≤ 0.05). However, the levels of glutamic acid were significantly higher in the ASD group than the control group (p ≤ 0.05). The current findings could contribute towards further understanding of ASD etiology and provide specialists with a hair amino acid profile utilized as a biomarker for early diagnosis of ASD. Such biomarkers could participate in future developments of therapies that reduce ASD related symptoms.

Keywords: Amino Acids, Autism spectrum disorder, human hair, liquid chromatography-tandem mass spectrometry

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2143 A Paper Based Sensor for Mercury Ion Detection

Authors: Emine G. Cansu Ergun

Abstract:

Conjugated system based sensors for selective detection of metal ions have been taking attention during last two decades. Fluorescent sensors are the promising candidates for ion detection due to their high selectivity towards metal ions, and rapid response times. Detection of mercury in an environmenet is important since mercury is a toxic element for human. Beyond the maximum allowable limit, mercury may cause serious problems in human health by spreading into the atmosphere, water and the food chain. In this study, a quinoxaline and 3,4-ethylenedioxy thiophene based donor-acceptor-donor type conjugated molecule used as a fluorescent sensor for detecting the mercury ion in aqueous medium. Among other various cations, existence of mercury resulted in a full quenching of the fluorescence signal. Then, a paper based sensor is constructed and used for mercury detection. As a result it is concluded that the offering sensor is a good candidate for selective mercury detection in aqueous media both in solution and paper based forms.

Keywords: Sensors, fluorescence quenching, Conjugated molecules, metal ion detection

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2142 Effect of Sodium Chloride Concentration and Degree of Neutralization on the Structure and Dynamics of Poly(Methacrylic Acid) (PMA) in Dilute Aqueous Solutions – a Molecular Dynamics Simulations Study

Authors: Abhishek Kumar Gupta

Abstract:

Atomistic Molecular Dynamics (MD) Simulations have been performed to study the effect of monovalent salt i.e. NaCl concentration (Cs) and chain degree of neutralization (f) on the structure and dynamics of anionic poly(methacrylic acid) (PMA) in dilute aqueous solutions. In the present study, the attention is to unveil the conformational structure, hydrogen-bonding, local polyion-counterion structure, h-bond dynamics, chain dynamics and thermodynamic enthalpy of solvation of a-PMA in dilute aqueous solutions as a function of salt concentration, Cs and f. The results have revealed that at low salt concentration, the conformational radius of gyration (Rg) increases and then decreases reaching a maximum in agreement with the reported light scattering experimental results. The Rg at f = 1 shows a continual decrease and acquire a plateau value at higher salt concentration in agreement with results obtained by light scattering experiments. The radial distribution functions between PMA, salt and water atoms has been computed with respect to atom and centre-of-mass to understand the intermolecular structure in detail. The results pertaining to PMA chain conformations and hydrogen bond autocorrelation function showcasing the h-bond dynamics will be presented. The results pertaining to chain dynamics will be presented. The results pertaining to counterion condensation on the PMA chain shows greater condensation of Na+ ions on to the carboxylate ions with increase in salt concentration. Moreover, the solvation enthalpy of the system as a function of salt concentration will be presented.

Keywords: Molecular Dynamics Simulations, conformations, NaCl concentration, radial distribution functions

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2141 Screening of Metal Chloride Anion-based Ionic Liquids for Direct Conversion of Hydrogen Sulfide by COSMO-RS

Authors: Zakaria Man, Muhammad Syahir Aminuddin, Mohamad Azmi Bustam Khalil

Abstract:

In order to identify the best possible reaction media for performing H₂S conversion, a total number of 300 different ILs from a combination of 20 cations and 15 anions were screened via COSMO-RS model simulations. By COSMO-RS method, thermodynamic and physicochemical properties of 300 ILs, such as Henry's law constants, activity coefficient, selectivity, capacity, and performance index, are obtained and analyzed. Thus, by comparing the performance of ILs via COSMO-RS, a series of TSILs containing cation of [P66614] with metal chloride anions such as Fe, Ga, and Al were chosen and selected for synthesis based on their performance predicted by COSMO-RS and their economic values. Consequently, the physiochemical properties such as density, viscosity, thermal properties, as well as H₂S absorptive oxidation performances in those TSILs will be systematically investigated.

Keywords: Hydrogen Sulfide, H2S, sour natural gas, conversion of hydrogen sulfide, task specific ionic liquids

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2140 Screening of Ionic Liquids for Hydrogen Sulfide Removal Using COSMO-RS

Authors: Zulaika Mohd Khasiran

Abstract:

The capability of ionic liquids in various applications makes them attracted by many researchers. They have potential to be developed as “green” solvents for gas separation, especially H2S gas. In this work, it is attempted to predict the solubility of hydrogen sulfide (H2S) in ILs by COSMO-RS method. Since H2S is a toxic pollutant, it is difficult to work on it in the laboratory, therefore an appropriate model will be necessary in prior work. The COSMO-RS method is implemented to predict the Henry’s law constants and activity coefficient of H2S in 140 ILs with various combinations of cations and anions. It is found by the screening that more H2S can be absorbed in ILs with [Cl] and [Ac] anion. The solubility of H2S in ILs with different alkyl chain at the cations not much affected and with different type of cations are slightly influence H2S capture capacities. Even though the cations do not affect much in solubility of H2S, we still need to consider the effectiveness of cation in different way. The prediction results only show their physical absorption ability, but the absorption of H2S need to be consider chemically to get high capacity of absorption of H2S.

Keywords: Ionic Liquids, Hydrogen Sulfide, H2S, COSMO-RS

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2139 Tuning the Surface Roughness of Patterned Nanocellulose Films: An Alternative to Plastic Based Substrates for Circuit Priniting in High-Performance Electronics

Authors: Kunal Bhardwaj, Christine Browne

Abstract:

With the increase in global awareness of the environmental impacts of plastic-based products, there has been a massive drive to reduce our use of these products. Use of plastic-based substrates in electronic circuits has been a matter of concern recently. Plastics provide a very smooth and cheap surface for printing high-performance electronics due to their non-permeability to ink and easy mouldability. In this research, we explore the use of nano cellulose (NC) films in electronics as they provide an advantage of being 100% recyclable and eco-friendly. The main hindrance in the mass adoption of NC film as a substitute for plastic is its higher surface roughness which leads to ink penetration, and dispersion in the channels on the film. This research was conducted to tune the RMS roughness of NC films to a range where they can replace plastics in electronics(310-470nm). We studied the dependence of the surface roughness of the NC film on the following tunable aspects: 1) composition by weight of the NC suspension that is sprayed on a silicon wafer 2) the width and the depth of the channels on the silicon wafer used as a base. Various silicon wafers with channel depths ranging from 6 to 18 um and channel widths ranging from 5 to 500um were used as a base. Spray coating method for NC film production was used and two solutions namely, 1.5wt% NC and a 50-50 NC-CNC (cellulose nanocrystal) mixture in distilled water, were sprayed through a Wagner sprayer system model 117 at an angle of 90 degrees. The silicon wafer was kept on a conveyor moving at a velocity of 1.3+-0.1 cm/sec. Once the suspension was uniformly sprayed, the mould was left to dry in an oven at 50°C overnight. The images of the films were taken with the help of an optical profilometer, Olympus OLS 5000. These images were converted into a ‘.lext’ format and analyzed using Gwyddion, a data and image analysis software. Lowest measured RMS roughness of 291nm was with a 50-50 CNC-NC mixture, sprayed on a silicon wafer with a channel width of 5 µm and a channel depth of 12 µm. Surface roughness values of 320+-17nm were achieved at lower (5 to 10 µm) channel widths on a silicon wafer. This research opened the possibility of the usage of 100% recyclable NC films with an additive (50% CNC) in high-performance electronics. Possibility of using additives like Carboxymethyl Cellulose (CMC) is also being explored due to the hypothesis that CMC would reduce friction amongst fibers, which in turn would lead to better conformations amongst the NC fibers. CMC addition would thus be able to help tune the surface roughness of the NC film to an even greater extent in future.

Keywords: Electronic Circuits, nano cellulose films, nanocrystals and surface roughness

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2138 Infrared Lightbox and iPhone App for Improving Detection Limit of Phosphate Detecting Dip Strips

Authors: H. Heidari-Bafroui, B. Ribeiro, A. Charbaji, C. Anagnostopoulos, M. Faghri

Abstract:

In this paper, we report the development of a portable and inexpensive infrared lightbox for improving the detection limits of paper-based phosphate devices. Commercial paper-based devices utilize the molybdenum blue protocol to detect phosphate in the environment. Although these devices are easy to use and have a long shelf life, their main deficiency is their low sensitivity based on the qualitative results obtained via a color chart. To improve the results, we constructed a compact infrared lightbox that communicates wirelessly with a smartphone. The system measures the absorbance of radiation for the molybdenum blue reaction in the infrared region of the spectrum. It consists of a lightbox illuminated by four infrared light-emitting diodes, an infrared digital camera, a Raspberry Pi microcontroller, a mini-router, and an iPhone to control the microcontroller. An iPhone application was also developed to analyze images captured by the infrared camera in order to quantify phosphate concentrations. Additionally, the app connects to an online data center to present a highly scalable worldwide system for tracking and analyzing field measurements. In this study, the detection limits for two popular commercial devices were improved by a factor of 4 for the Quantofix devices (from 1.3 ppm using visible light to 300 ppb using infrared illumination) and a factor of 6 for the Indigo units (from 9.2 ppm to 1.4 ppm) with repeatability of less than or equal to 1.2% relative standard deviation (RSD). The system also provides more granular concentration information compared to the discrete color chart used by commercial devices and it can be easily adapted for use in other applications.

Keywords: infrared lightbox, paper-based device, phosphate detection, smartphone colorimetric analyzer

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2137 Opportunities and Challenges for Decarbonizing Steel Production by Creating Markets for ‘Green Steel’ Products

Authors: Hasan Muslemani, Xi Liang, Kathi Kaesehage, Francisco Ascui, Jeffrey Wilson

Abstract:

The creation of a market for lower-carbon steel products, here called ‘green steel’, has been identified as an important means to support the introduction of breakthrough emission reduction technologies into the steel sector. However, the definition of what ‘green’ entails in the context of steel production, the implications on the competitiveness of green steel products in local and international markets, and the necessary market mechanisms to support their successful market penetration remain poorly explored. This paper addresses this gap by holding semi-structured interviews with international sustainability experts and commercial managers from leading steel trade associations, research institutes and steelmakers. Our findings show that there is an urgent need to establish a set of standards to define what ‘greenness’ means in the steelmaking context; standards that avoid market disruptions, unintended consequences, and opportunities for greenwashing. We also highlight that the introduction of green steel products will have implications on product competitiveness on three different levels: 1) between primary and secondary steelmaking routes, 2) with traditional, lesser green steel, and 3) with other substitutable materials (e.g. cement and plastics). This paper emphasises the need for steelmakers to adopt a transitional approach in deploying different low-carbon technologies, based on their stage of technological maturity, applicability in certain country contexts, capacity to reduce emissions over time, and the ability of the investment community to support their deployment. We further identify market mechanisms to support green steel production, including carbon border adjustments and public procurement, highlighting a need for implementing a combination of complementary policies to ensure the products’ roll-out. The study further shows that the auto industry is a likely candidate for green steel consumption, where a market would be supported by price premiums paid by willing consumers, such as those of high-end luxury vehicles.

Keywords: Decarbonisation, Business Model Innovation, Market analysis, green steel

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2136 Assessment of Carbon Dioxide Separation by Amine Solutions Using Electrolyte Non-Random Two-Liquid and Peng-Robinson Models: Carbon Dioxide Absorption Efficiency

Authors: Arash Esmaeili, Zhibang Liu, Yang Xiang, Jimmy Yun, Lei Shao

Abstract:

A high pressure carbon dioxide (CO₂) absorption from a specific gas in a conventional column has been evaluated by the Aspen HYSYS simulator using a wide range of single absorbents and blended solutions to estimate the outlet CO₂ concentration, absorption efficiency and CO₂ loading to choose the most proper solution in terms of CO₂ capture for environmental concerns. The property package (Acid Gas-Chemical Solvent), which is compatible with all applied solutions for the simulation in this study, estimates the properties based on electrolyte non-random two-liquid (E-NRTL) model for electrolyte thermodynamics and Peng-Robinson equation of state for vapor and liquid hydrocarbon phase. Among all the investigated single amines as well as blended solutions, piperazine (PZ) and the mixture of piperazine and monoethanolamine (MEA) have been found as the most effective absorbents respectively for CO₂ absorption with high reactivity based on the simulated operational conditions.

Keywords: Simulation, Absorption, Carbon Dioxide, aspen HYSYS, amine solutions

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2135 Sustainability and Clustering: A Bibliometric Assessment

Authors: Fernanda M. Assef, Maria Teresinha A. Steiner, David Gabriel F. Barros

Abstract:

Review researches are useful in terms of analysis of research problems. Between the types of review documents, we commonly find bibliometric studies. This type of application often helps the global visualization of a research problem and helps academics worldwide to understand the context of a research area better. In this document, a bibliometric view surrounding clustering techniques and sustainability problems is presented. The authors aimed at which issues mostly use clustering techniques, and, even which sustainability issue would be more impactful on today’s moment of research. During the bibliometric analysis, we found ten different groups of research in clustering applications for sustainability issues: Energy; Environmental; Non-urban planning; Sustainable Development; Sustainable Supply Chain; Transport; Urban Planning; Water; Waste Disposal; and, Others. And, by analyzing the citations of each group, we discovered that the Environmental group could be classified as the most impactful research cluster in the area mentioned. Now, after the content analysis of each paper classified in the environmental group, we found that the k-means technique is preferred for solving sustainability problems with clustering methods since it appeared the most amongst the documents. The authors finally conclude that a bibliometric assessment could help indicate a gap of researches on waste disposal – which was the group with the least amount of publications – and the most impactful research on environmental problems.

Keywords: Sustainability, Clustering, bibliometric assessment, territorial partitioning

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2134 Multi-Objective Optimization for the Green Vehicle Routing Problem: Approach to Case Study of the Newspaper Distribution Problem

Authors: Julio C. Ferreira, Maria T. A. Steiner

Abstract:

The aim of this work is to present a solution procedure referred to here as the Multi-objective Optimization for Green Vehicle Routing Problem (MOOGVRP) to provide solutions for a case study. The proposed methodology consists of three stages to resolve Scenario A. Stage 1 consists of the “treatment” of data; Stage 2 consists of applying mathematical models of the p-Median Capacitated Problem (with the objectives of minimization of distances and homogenization of demands between groups) and the Asymmetric Traveling Salesman Problem (with the objectives of minimizing distances and minimizing time). The weighted method was used as the multi-objective procedure. In Stage 3, an analysis of the results is conducted, taking into consideration the environmental aspects related to the case study, more specifically with regard to fuel consumption and air pollutant emission. This methodology was applied to a (partial) database that addresses newspaper distribution in the municipality of Curitiba, Paraná State, Brazil. The preliminary findings for Scenario A showed that it was possible to improve the distribution of the load, reduce the mileage and the greenhouse gas by 17.32% and the journey time by 22.58% in comparison with the current scenario. The intention for future works is to use other multi-objective techniques and an expanded version of the database and explore the triple bottom line of sustainability.

Keywords: Multi-objective optimization, Asymmetric Traveling Salesman Problem, Green Vehicle Routing Problem, p-Median Capacitated Problem

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2133 Optimizing Hydrogen Production from Biomass Pyro-Gasification in a Multi-Staged Fluidized Bed Reactor

Authors: Chetna Mohabeer, Luis Reyes, Lokmane Abdelouahed, Bechara Taouk

Abstract:

In the transition to sustainability and the increasing use of renewable energy, hydrogen will play a key role as an energy carrier. Biomass has the potential to accelerate the realization of hydrogen as a major fuel of the future. Pyro-gasification allows the conversion of organic matter mainly into synthesis gas, or “syngas”, majorly constituted by CO, H2, CH4, and CO2. A second, condensable fraction of biomass pyro-gasification products are “tars”. Under certain conditions, tars may decompose into hydrogen and other light hydrocarbons. These conditions include two types of cracking: homogeneous cracking, where tars decompose under the effect of temperature ( > 1000 °C), and heterogeneous cracking, where catalysts such as olivine, dolomite or biochar are used. The latter process favors cracking of tars at temperatures close to pyro-gasification temperatures (~ 850 °C). Pyro-gasification of biomass coupled with water-gas shift is the most widely practiced process route for biomass to hydrogen today. In this work, an innovating solution will be proposed for this conversion route, in that all the pyro-gasification products, not only methane, will undergo processes that aim to optimize hydrogen production. First, a heterogeneous cracking step was included in the reaction scheme, using biochar (remaining solid from the pyro-gasification reaction) as catalyst and CO2 and H2O as gasifying agents. This process was followed by a catalytic steam methane reforming (SMR) step. For this, a Ni-based catalyst was tested under different reaction conditions to optimize H2 yield. Finally, a water-gas shift (WGS) reaction step with a Fe-based catalyst was added to optimize the H2 yield from CO. The reactor used for cracking was a fluidized bed reactor, and the one used for SMR and WGS was a fixed bed reactor. The gaseous products were analyzed continuously using a µ-GC (Fusion PN 074-594-P1F). With biochar as bed material, it was seen that more H2 was obtained with steam as a gasifying agent (32 mol. % vs. 15 mol. % with CO2 at 900 °C). CO and CH4 productions were also higher with steam than with CO2. Steam as gasifying agent and biochar as bed material were hence deemed efficient parameters for the first step. Among all parameters tested, CH4 conversions approaching 100 % were obtained from SMR reactions using Ni/γ-Al2O3 as a catalyst, 800 °C, and a steam/methane ratio of 5. This gave rise to about 45 mol % H2. Experiments about WGS reaction are currently being conducted. At the end of this phase, the four reactions are performed consecutively, and the results analyzed. The final aim is the development of a global kinetic model of the whole system in a multi-stage fluidized bed reactor that can be transferred on ASPEN PlusTM.

Keywords: steam methane reforming, multi-staged fluidized bed reactor, pyro-gasification, water-gas shift

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2132 Antioxidant and Acute Toxicity of Stem Extracts of the Ficus Iteophylla

Authors: Muhammad Mukhtar

Abstract:

The aim of this study is to evaluate the antioxidant activity and acute toxicity of the extracts of Ficus iteophylla by reactions with 1, 1-diphenyl-2-picryhydrazyl radical (DPPH) and method developed by Lork 1983, respectively. Stem bark of Ficus iteophylla was collected, air dried, pulverized to fine powdered and sequentially extracted using acetone, methanol and water in order of increasing polarity. The result shows strong radical scavenging activity against DPPH for all the extracts when compared with ascorbic acid. The LD50 of 316 mg/kg was calculated for all the three extras, and the values were found to be within the practically toxic range, and therefore, care should be taken when using the plants in traditional medicine.

Keywords: acute toxicity, antioxidant, Ficus iteophylla

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2131 Dual-Layer Microporous Layer of Gas Diffusion Layer for Proton Exchange Membrane Fuel Cells under Various RH Conditions

Authors: Grigoria Athanasaki, Veerarajan Vimala, A. M. Kannan, Louis Cindrella

Abstract:

Energy usage has been increased throughout the years, leading to severe environmental impacts. Since the majority of the energy is currently produced from fossil fuels, there is a global need for clean energy solutions. Proton Exchange Membrane Fuel Cells (PEMFCs) offer a very promising solution for transportation applications because of their solid configuration and low temperature operations, which allows them to start quickly. One of the main components of PEMFCs is the Gas Diffusion Layer (GDL), which manages water and gas transport and shows direct influence on the fuel cell performance. In this work, a novel dual-layer GDL with gradient porosity was prepared, using polyethylene glycol (PEG) as pore former, to improve the gas diffusion and water management in the system. The microporous layer (MPL) of the fabricated GDL consists of carbon powder PUREBLACK, sodium dodecyl sulfate as a surfactant, 34% wt. PTFE and the gradient porosity was created by applying one layer using 30% wt. PEG on the carbon substrate, followed by a second layer without using any pore former. The total carbon loading of the microporous layer is ~ 3 mg.cm-2. For the assembly of the catalyst layer, Nafion membrane (Ion Power, Nafion Membrane NR211) and Pt/C electrocatalyst (46.1% wt.) were used. The catalyst ink was deposited on the membrane via microspraying technique. The Pt loading is ~ 0.4 mg.cm-2, and the active area is 5 cm2. The sample was ex-situ characterized via wetting angle measurement, Scanning Electron Microscopy (SEM), and Pore Size Distribution (PSD) to evaluate its characteristics. Furthermore, for the performance evaluation in-situ characterization via Fuel Cell Testing using H2/O2 and H2/air as reactants, under 50, 60, 80, and 100% relative humidity (RH), took place. The results were compared to a single layer GDL, fabricated with the same carbon powder and loading as the dual layer GDL, and a commercially available GDL with MPL (AvCarb2120). The findings reveal high hydrophobic properties of the microporous layer of the GDL for both PUREBLACK based samples, while the commercial GDL demonstrates hydrophilic behavior. The dual layer GDL shows high and stable fuel cell performance under all the RH conditions, whereas the single layer manifests a drop in performance at high RH in both oxygen and air, caused by catalyst flooding. The commercial GDL shows very low and unstable performance, possibly because of its hydrophilic character and thinner microporous layer. In conclusion, the dual layer GDL with PEG appears to have improved gas diffusion and water management in the fuel cell system. Due to its increasing porosity from the catalyst layer to the carbon substrate, it allows easier access of the reactant gases from the flow channels to the catalyst layer, and more efficient water removal from the catalyst layer, leading to higher performance and stability.

Keywords: Proton Exchange Membrane Fuel Cells, gas diffusion layer, relative humidity, microporous layer

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2130 N Doped Multiwall Carbon Nanotubes Growth over a Ni Catalyst Substrate

Authors: Angie Quevedo, Juan Bussi, Nestor Tancredi, Juan Fajardo-Díaz, Florentino López-Urías, Emilio Muñóz-Sandoval

Abstract:

In this work, we study the carbon nanotubes (CNTs) formation by catalytic chemical vapor deposition (CCVD) over a catalyst with 20 % of Ni supported over La₂Zr₂O₇ (Ni20LZO). The high C solubility of Ni made it one of the most used in CNTs synthesis. Nevertheless, Ni presents also sintering and coalescence at high temperature. These troubles can be reduced by choosing a suitable support. We propose La₂Zr₂O₇ as for this matter since the incorporation of Ni by co-precipitation and calcination at 900 °C allows a good dispersion and interaction of the active metal (in the oxidized form, NiO) with this support. The CCVD was performed using 1 g of Ni20LZO at 950 °C during 30 min in Ar:H₂ atmosphere (2.5 L/min). The precursor, benzylamine, was added by a nebulizer-sprayer. X ray diffraction study shows the phase separation of NiO and La₂Zr₂O₇ after the calcination and the reduction to Ni after the synthesis. Raman spectra show D and G bands with a ID/IG ratio of 0.75. Elemental study verifies the incorporation of 1% of N. Thermogravimetric analysis shows the oxidation process start at around 450 °C. Future studies will determine the application potential of the samples.

Keywords: N doped carbon nanotubes, catalytic chemical vapor deposition, nickel catalyst, bimetallic oxide

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2129 Synthesis of 2-Aminoisocoumarinoselenazoles via Transition Metal-Free Alkylation and Ru(II)-Catalyzed [4+2] Alkyne Annulation

Authors: Sunil Kumar, Sandip Dhole, Deepak Salunke, Chung-ming Sun

Abstract:

Heterocycles bearing nitrogen, oxygen, and selenium are present in innumerable biologically active compounds. For instance, coumarin containing dicoumarol acts as naturally occurring anticoagulant. 2-Acylamido selenazole works as Store-Operated Calcium (SOC) channel regulator. Therefore, due to biologically significance of selenazole and coumarin and our quest to develop efficient methodologies for the synthesis of complex heterocycles, the trisubstituted angular isocoumarinoselenazole synthesis was proposed and achieved by starting from nitrobenzoic acid derivative, available commercially. Synthetic procedure involves three steps: i) the construction of 2-aminobenzoselenazoles, ii) their regioselective N-alkylation at position-2 and iii) alkyne insertion via Ru catalyzed C-H activation. Transition metal free synthesis of benzoselenazoles was successfully brought about by the addition/elimination reaction via intramolecular C-Se bond formation. In the next step, N-alkylation of selenazole furnished two regioisomers. Both the isomers exhibited different reactivity towards [4+2] alkyne annulation reaction. The fusion of α-pyrone ring on the benzo[1,3-d]selenazole skeleton was achieved via Ru(II)-catalyzed C-H activation and alkyne insertion. As evident from mechanism, the selenazole 'N' plays an important role for the experiential selectivity.

Keywords: alkylation, coumarin, alkyne insertion, selenazole

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2128 Digitalized Cargo Coordination to Eliminate Emissions in the Shipping Ecosystem: A System Dynamical Approach

Authors: Henry Schwartz, Bogdan Iancu, Magnus Gustafsson, Johan Lilius

Abstract:

The shipping sector generates significant amounts of carbon emissions on annual basis. The excess amount of carbon dioxide is harmful for both the environment and the society, and partly for that reason, there is acute interest to decrease the volume of anthropogenic carbon dioxide emissions in shipping. The usage of the existing cargo carrying capacity can be maximized, and the share of time used in actual transportation operations could be increased if the whole transportation and logistics chain was optimized with the aid of information sharing done through a centralized marketplace and an information-sharing platform. The outcome of this change would be decreased carbon dioxide emission volumes produced per each metric ton of cargo transported by a vessel. Cargo coordination is a platform under development that matches the need for waterborne transportation services with the ships that operate at a given moment in time. In this research, the transition towards adopting cargo coordination is modelled with system dynamics. The model encompasses the complex supply-demand relationships of ship operators and cargo owners. The built scenarios predict the pace at which different stakeholders start using the digitalized platform and by doing so reduce the amount of annual CO2 emissions generated. To improve the reliability of the results, various sensitivity analyses considering the pace of transition as well as the overall impact on the environment (carbon dioxide emissions per amount of cargo transported) are conducted. The results of the study can be used to support investors and politicians in decision making towards more environmentally sustainable solutions. In addition, the model provides concepts and ideas for a wider discussion considering the paths towards carbon neutral transportation.

Keywords: Energy Efficiency, System Dynamics, Sustainable Transportation, carbon dioxide emissions

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2127 Deconvolution of Anomalous Fast Fourier Transform Patterns for Tin Sulfide

Authors: I. Shuro

Abstract:

The crystal structure of Tin Sulfide prepared by certain chemical methods is investigated using High-Resolution Transmission Electron Microscopy (HRTEM), Scanning Electron Microscopy (SEM), and X-ray diffraction (XRD) methods. An anomalous HRTEM Fast Fourier Transform (FFT) exhibited a central scatter of diffraction spots, which is surrounded by secondary clusters of spots arranged in a hexagonal pattern around the central cluster was observed. FFT analysis has revealed a long lattice parameter and mostly viewed along a hexagonal axis where there many columns of atoms slightly displaced from one another. This FFT analysis has revealed that the metal sulfide has a long-range order interwoven chain of atoms in its crystal structure. The observed crystalline structure is inconsistent with commonly observed FFT patterns of chemically synthesized Tin Sulfide nanocrystals and thin films. SEM analysis showed the morphology of a myriad of multi-shaped crystals ranging from hexagonal, cubic, and spherical micro to nanostructured crystals. This study also investigates the presence of quasi-crystals as reflected by the presence of mixed local symmetries.

Keywords: fast fourier transform, tin sulfide, crystalline structure, high resolution transmission electron microscopy

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2126 Isolation and Identification of Fungi from Different Types of Medicinal Plants Cultivated in Ecuador

Authors: Ana Paola Echavarria, Mariuxi Medina, Haydelba D'Armas, Carmita Jaramillo, Diana San Martin

Abstract:

The use of medicinal plants is one of the oldest and most extended medical therapies that goes back to prehistoric times, and nowadays, they are also used in the preparation of phytopharmaceuticals with options to cure diseases. The test for the determination of fungi was carried out in the Pharmacy Pilot Plant (treatment of the leaves of the plant species) and the Microbiology Laboratory (determination of fungi of the plant species, using growth medium called Sabouraud agar plus the vegetal sample), of the Academic Unit of Chemical Sciences and Health, of the Universidad Tecnica de Machala. Subsequently, colony counting was performed, both macroscopic, which is determined in the growth medium of the seeding, and microscopic, to identify the germinative forms using blue lactophenol. The procedure was repeated in duplicate to replicate the results data. The determination of the total fungal content of the following plant species was evaluated: Cymbopogon citratus (lemon verbena), Melissa officinalis (lemon balm), Taraxacum officinale (dandelion), Artemisia absinthium (absinthe), Piper carpunya (guaviduca), Moringa oleifera (moringa), Coriandrum sativum (coriander), Momordica charantia (achochilla), Borago officinalis (borage), Aloysia citriodora (cedron), Ambrosia artemisifolia (altamisa) and Ageratum conyzoides (mastrante). The results obtained showed that all the samples of the twelve plant species studied developed filamentous fungi, with great variability of them, within the permissible limits and contemplated by the Ecuadorian Institute of Normalization (INEN), being suitable as raw material for its use in the preparation of nutraceuticals and medicinal products or phytodrugs; with the exception of A. conyzoides (mastranto) which is the only species that exceeds the regulation in the average of dilutions.

Keywords: Medicinal Plants, Fungi, Microbiological Quality, colonies, Sabouraud agar

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2125 Evaluation of Electrophoretic and Electrospray Deposition Methods for Preparing Graphene and Activated Carbon Modified Nano-Fibre Electrodes for Hydrogen/Vanadium Flow Batteries and Supercapacitors

Authors: Barun Chakrabarti, Vladimir Yufit, Nigel Brandon, Xinhua Liu, Evangelos Kalamaras, Billy Wu, C. T. John Low

Abstract:

In this work, we perform electrophoretic deposition of activated carbon on a number of substrates to prepare symmetrical coin cells for supercapacitor applications. From several recipes that involve the evaluation of a few solvents such as isopropyl alcohol, N-Methyl-2-pyrrolidone (NMP), or acetone to binders such as polyvinylidene fluoride (PVDF) and charging agents such as magnesium chloride, we display a working means for achieving supercapacitors that can achieve 100 F/g in a consistent manner. We then adapt this EPD method to deposit reduced graphene oxide on SGL 10AA carbon paper to achieve cathodic materials for testing in a hydrogen/vanadium flow battery. In addition, a self-supported hierarchical carbon nano-fibre is prepared by means of electrospray deposition of an iron phthalocyanine solution onto a temporary substrate followed by carbonisation to remove heteroatoms. This process also induces a degree of nitrogen doping on the carbon nano-fibres (CNFs), which allows its catalytic performance to improve significantly as detailed in other publications. The CNFs are then used as catalysts by attaching them to graphite felt electrodes facing the membrane inside an all-vanadium flow battery (Scribner cell using serpentine flow distribution channels) and efficiencies as high as 60% is noted at high current densities of 150 mA/cm². About 20 charge and discharge cycling show that the CNF catalysts consistently perform better than pristine graphite felt electrodes. Following this, we also test the CNF as an electro-catalyst in the hydrogen/vanadium flow battery (cathodic side as mentioned briefly in the first paragraph) facing the membrane, based upon past studies from our group. Once again, we note consistently good efficiencies of 85% and above for CNF modified graphite felt electrodes in comparison to 60% for pristine felts at low current density of 50 mA/cm² (this reports 20 charge and discharge cycles of the battery). From this preliminary investigation, we conclude that the CNFs may be used as catalysts for other systems such as vanadium/manganese, manganese/manganese and manganese/hydrogen flow batteries in the future. We are generating data for such systems at present, and further publications are expected.

Keywords: Electrocatalysis, Electrospinning, carbon nano-fibres, all-vanadium redox flow battery, hydrogen-vanadium fuel cell

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2124 Synthesis of Fluorescent PET-Type “Turn-Off” Triazolyl Coumarin Based Chemosensors for the Sensitive and Selective Sensing of Fe⁺³ Ions in Aqueous Solutions

Authors: Aidan Battison, Neliswa Mama

Abstract:

Environmental pollution by ionic species has been identified as one of the biggest challenges to the sustainable development of communities. The widespread use of organic and inorganic chemical products and the release of toxic chemical species from industrial waste have resulted in a need for advanced monitoring technologies for environment protection, remediation and restoration. Some of the disadvantages of conventional sensing methods include expensive instrumentation, well-controlled experimental conditions, time-consuming procedures and sometimes complicated sample preparation. On the contrary, the development of fluorescent chemosensors for biological and environmental detection of metal ions has attracted a great deal of attention due to their simplicity, high selectivity, eidetic recognition, rapid response and real-life monitoring. Coumarin derivatives S1 and S2 (Scheme 1) containing 1,2,3-triazole moieties at position -3- have been designed and synthesized from azide and alkyne derivatives by CuAAC “click” reactions for the detection of metal ions. These compounds displayed a strong preference for Fe3+ ions with complexation resulting in fluorescent quenching through photo-induced electron transfer (PET) by the “sphere of action” static quenching model. The tested metal ions included Cd2+, Pb2+, Ag+, Na+, Ca2+, Cr3+, Fe3+, Al3+, Cd2+, Ba2+, Cu2+, Co2+, Hg2+, Zn2+ and Ni2+. The detection limits of S1 and S2 were determined to be 4.1 and 5.1 uM, respectively. Compound S1 displayed the greatest selectivity towards Fe3+ in the presence of competing for metal cations. S1 could also be used for the detection of Fe3+ in a mixture of CH3CN/H¬2¬O. Binding stoichiometry between S1 and Fe3+ was determined by using both Jobs-plot and Benesi-Hildebrand analysis. The binding was shown to occur in a 1:1 ratio between the sensor and a metal cation. Reversibility studies between S1 and Fe3+ were conducted by using EDTA. The binding site of Fe3+ to S1 was determined by using 13 C NMR and Molecular Modelling studies. Complexation was suggested to occur between the lone-pair of electrons from the coumarin-carbonyl and the triazole-carbon double bond.

Keywords: Fluorescence, triazole, coumarin, chemosensor, click" chemistry, static quenching

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2123 Flexible Feedstock Concept in Gasification Process for Carbon-Negative Energy Technology: A Case Study in Malaysia

Authors: Zahrul Faizi M. S., Ali A., Norhuda A. M.

Abstract:

Emission of greenhouse gases (GHG) from solid waste treatment and dependency on fossil fuel to produce electricity are the major concern in Malaysia as well as global. Innovation in downdraft gasification with combined heat and power (CHP) systems has the potential to minimize solid waste and reduce the emission of anthropogenic GHG from conventional fossil fuel power plants. However, the efficiency and capability of downdraft gasification to generate electricity from various alternative fuels, for instance, agriculture residues (i.e., woodchip, coconut shell) and municipal solid waste (MSW), are still controversial, on top of the toxicity level from the produced bottom ash. Thus this study evaluates the adaptability and reliability of the 20 kW downdraft gasification system to generate electricity (while considering environmental sustainability from the bottom ash) using flexible local feedstock at 20, 40, and 60% mixed ratio of MSW: agriculture residues. Feedstock properties such as feed particle size, moisture, and ash contents are also analyzed to identify optimal characteristics for the combination of feedstock (feedstock flexibility) to obtain maximum energy generation. Results show that the gasification system is capable to flexibly accommodate different feedstock compositions subjected to specific particle size (less than 2 inches) at a moisture content between 15 to 20%. These values exhibit enhance gasifier performance and provide a significant effect to the syngas composition utilizes by the internal combustion engine, which reflects energy production. The result obtained in this study is able to provide a new perspective on the transition of the conventional gasification system to a future reliable carbon-negative energy technology. Subsequently, promoting commercial scale-up of the downdraft gasification system.

Keywords: Renewable Energy, gasification, carbon-negative energy, feedstock flexibility

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2122 Photocatalytic Glucose Electrooxidation Applications of Titanium Dioxide Supported CD and CdTe Catalysts

Authors: Nahit Aktas, Hilal Kivrak, Aykut ÇağLar, Ali Osman Solak

Abstract:

At present, Cd/TiO₂ and CdTe/TiO₂ catalysts are prepared via sodium borohydride (NaBH4) reduction method. These catalysts are characterized by fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). These Cd/TiO₂ and CdTe/TiO₂ are employed as catalysts for the photocatalytic oxidation of glucose. Cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) measurements are used to investigate their glucose electrooxidation activities of catalysts at long and under UV illumination (ʎ=354 nm). CdTe/TiO₂ catalyst is showed the best photocatalytic glucose electrooxidation activity compared to Cd/TiO₂ catalyst.

Keywords: TiO2, cadmium, NaBH4 reduction method, photocatalytic glucose electrooxidation, Tellerium

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2121 Determination of Antioxidant Activities of Sumac (Rhus Coriaria) Extracts with Different Solvents

Authors: F. T. Senberber, E. Moroydor Derun, N. Tugrul

Abstract:

As a nutraceutical, sumac (Rhus Coriaria) was extracted by using different solvents of methanol, ethanol, and water. The DPPH (2,2-diphenyl-1-picryl-hydrazyl-hydrate) method of free radical scavenging capacity was used to determine the effects of solvent on antioxidant activities of the plant. The total phenolic content was studied by The Folin Ciocalteu Reagent method. The antioxidant activities of extracts exhibit minor changes in different solvents and varied in the range of 84.3–86.4 %. The total phenolic contents are affected by the selected solvent. The highest total phenolic content was determined at the liquid phase of water and it was estimated as 26.3 mg/g in gallic acid.

Keywords: Solvent, DPPH, total phenolic content, sumac

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