Search results for: reaction diffusion equation
Commenced in January 2007
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Edition: International
Paper Count: 5254

Search results for: reaction diffusion equation

3844 Surface Modified Nano-Diamond/Polyimide Hybrid Composites

Authors: Hati̇ce Bi̇rtane, Asli Beyler Çi̇ği̇l, Memet Vezi̇r Kahraman

Abstract:

Polyimide (PI) is one of the most important super-engineering materials because of its mechanical properties and its thermal stability. Electronic industry is the typical extensive applications of polyimides including interlayer insulation films, buffer coating, films, alpha-ray shielding films, and alignment films for liquid crystal displays. The mechanical and thermal properties of polymers are generally improved by the addition of inorganic additives. The challenges in this area of high-performance organic/inorganic hybrid materials are to obtain significant improvements in the interfacial adhesion between the polymer matrix and the reinforcing material since the organic matrix is relatively incompatible with the inorganic phase. In this study, modified nanodiamond was prepared from the reaction of nanodiamond and (3-Mercaptopropyl)trimethoxysilane. Poly(amic acid) was prepared from the reaction of 3,3',4,4'-Benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-Oxydianiline (ODA). Polyimide/modified nanodiamond hybrids were prepared by blending of poly(amic acid) and organically modified nanodiamond. The morphology of the Polyimide/ modified nanodiamond hybrids was characterized by scanning electron microscopy (SEM). Chemical structure of polyimide and Polyimide/modified nanodiamond hybrids was characterized by FTIR. FTIR results showed that the Polyimide/modified nanodiamond hybrids were successfully prepared. A thermal property of the Polyimide/modified nanodiamond hybrids was characterized by thermogravimetric analysis (TGA).

Keywords: hybrid materials, nanodiamond, polyimide, polymer

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3843 Surge in U. S. Citizens Expatriation: Testing Structual Equation Modeling to Explain the Underlying Policy Rational

Authors: Marco Sewald

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Comparing present to past the numbers of Americans expatriating U. S. citizenship have risen. Even though these numbers are small compared to the immigrants, U. S. citizens expatriations have historically been much lower, making the uptick worrisome. In addition, the published lists and numbers from the U.S. government seems incomplete, with many not counted. Different branches of the U. S. government report different numbers and no one seems to know exactly how big the real number is, even though the IRS and the FBI both track and/or publish numbers of Americans who renounce. Since there is no single explanation, anecdotal evidence suggests this uptick is caused by global tax law and increased compliance burdens imposed by the U.S. lawmakers on U.S. citizens abroad. Within a research project the question arose about the reasons why a constant growing number of U.S. citizens are expatriating – the answers are believed helping to explain the underlying governmental policy rational, leading to such activities. While it is impossible to locate former U.S. citizens to conduct a survey on the reasons and the U.S. government is not commenting on the reasons given within the process of expatriation, the chosen methodology is Structural Equation Modeling (SEM), in the first step by re-using current surveys conducted by different researchers within the population of U. S. citizens residing abroad during the last years. Surveys questioning the personal situation in the context of tax, compliance, citizenship and likelihood to repatriate to the U. S. In general SEM allows: (1) Representing, estimating and validating a theoretical model with linear (unidirectional or not) relationships. (2) Modeling causal relationships between multiple predictors (exogenous) and multiple dependent variables (endogenous). (3) Including unobservable latent variables. (4) Modeling measurement error: the degree to which observable variables describe latent variables. Moreover SEM seems very appealing since the results can be represented either by matrix equations or graphically. Results: the observed variables (items) of the construct are caused by various latent variables. The given surveys delivered a high correlation and it is therefore impossible to identify the distinct effect of each indicator on the latent variable – which was one desired result. Since every SEM comprises two parts: (1) measurement model (outer model) and (2) structural model (inner model), it seems necessary to extend the given data by conducting additional research and surveys to validate the outer model to gain the desired results.

Keywords: expatriation of U. S. citizens, SEM, structural equation modeling, validating

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3842 Novel Adomet Analogs as Tools for Nucleic Acids Labeling

Authors: Milda Nainyte, Viktoras Masevicius

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Biological methylation is a methyl group transfer from S-adenosyl-L-methionine (AdoMet) onto N-, C-, O- or S-nucleophiles in DNA, RNA, proteins or small biomolecules. The reaction is catalyzed by enzymes called AdoMet-dependent methyltransferases (MTases), which represent more than 3 % of the proteins in the cell. As a general mechanism, the methyl group from AdoMet replaces a hydrogen atom of nucleophilic center producing methylated DNA and S-adenosyl-L-homocysteine (AdoHcy). Recently, DNA methyltransferases have been used for the sequence-specific, covalent labeling of biopolymers. Two types of MTase catalyzed labeling of biopolymers are known, referred as two-step and one-step. During two-step labeling, an alkylating fragment is transferred onto DNA in a sequence-specific manner and then the reporter group, such as biotin, is attached for selective visualization using suitable chemistries of coupling. This approach of labeling is quite difficult and the chemical hitching does not always proceed at 100 %, but in the second step the variety of reporter groups can be selected and that gives the flexibility for this labeling method. In the one-step labeling, AdoMet analog is designed with the reporter group already attached to the functional group. Thus, the one-step labeling method would be more comfortable tool for labeling of biopolymers in order to prevent additional chemical reactions and selection of reaction conditions. Also, time costs would be reduced. However, effective AdoMet analog appropriate for one-step labeling of biopolymers and containing cleavable bond, required for reduction of PCR interferation, is still not known. To expand the practical utility of this important enzymatic reaction, cofactors with activated sulfonium-bound side-chains have been produced and can serve as surrogate cofactors for a variety of wild-type and mutant DNA and RNA MTases enabling covalent attachment of these chains to their target sites in DNA, RNA or proteins (the approach named methyltransferase-directed Transfer of Activated Groups, mTAG). Compounds containing hex-2-yn-1-yl moiety has proved to be efficient alkylating agents for labeling of DNA. Herein we describe synthetic procedures for the preparation of N-biotinoyl-N’-(pent-4-ynoyl)cystamine starting from the coupling of cystamine with pentynoic acid and finally attaching the biotin as a reporter group. The synthesis of the first AdoMet based cofactor containing a cleavable reporter group and appropriate for one-step labeling was developed.

Keywords: adoMet analogs, DNA alkylation, cofactor, methyltransferases

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3841 Effect of Quenching Medium on the Hardness of Dual Phase Steel Heat Treated at a High Temperature

Authors: Tebogo Mabotsa, Tamba Jamiru, David Ibrahim

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Dual phase(DP) steel consists essentially of fine grained equiaxial ferrite and a dispersion of martensite. Martensite is the primary precipitate in DP steels, it is the main resistance to dislocation motion within the material. The objective of this paper is to present a relation between the intercritical annealing holding time and the hardness of a dual phase steel. The initial heat treatment involved heating the specimens to 1000oC and holding the sample at that temperature for 30 minutes. After the initial heat treatment, the samples were heated to 770oC and held for a varying amount of time at constant temperature. The samples were held at 30, 60, and 90 minutes respectively. After heating and holding the samples at the austenite-ferrite phase field, the samples were quenched in water, brine, and oil for each holding time. The experimental results proved that an equation for predicting the hardness of a dual phase steel as a function of the intercritical holding time is possible. The relation between intercritical annealing holding time and hardness of a dual phase steel heat treated at high temperatures is parabolic in nature. Theoretically, the model isdependent on the cooling rate because the model differs for each quenching medium; therefore, a universal hardness equation can be derived where the cooling rate is a variable factor.

Keywords: quenching medium, annealing temperature, dual phase steel, martensite

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3840 Laboratory Investigation of Fly Ash Based Geopolymer Stabilized Recycled Asphalt Pavement as a Base Material

Authors: Menglim Hoy, Suksun Horpibulsuk, Arul Arulrajah

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The results of laboratory investigation of recycled asphalt pavement (RAP) – fly ash (FA) based geopolymer as a base material is presented in this paper. An alkaline activator, the mixture of NaOH and Na₂SiO₃, is used to synthesis RAP-FA based geopolymer. RAP-FA with water (RAP-FA blend) prepared as a control material. The strength develops and the strength against wet-dry was determined by the unconfined compression strength (UCS) test, then the microstructural properties were examined by scanning electron microscopy (SEM) and X-ray Diffraction (XRD) analysis. The toxicity characteristic leaching procedure (TCLP) test is conducted to measure its leachability of heavy metal. The results show both the RAP-FA blend and geopolymer can be used as a base course as its UCS values meet the minimum strength requirement specified by the Department of Highway, Thailand. The durability test results show the UCS of these materials increases with increasing the number of wet-dry cycles, reaching its peak at six wet-dry cycles. The XRD and SEM analyses indicate strength development of the RAP-FA blend occurs due to chemical reaction between a high Calcium in RAP with a high Silica and Alumina in FA led to producing calcium aluminate hydrate formation. The strength development of the RAP-FA geopolymer occurred resulted from the polymerization reaction. The TCLP results demonstrate there is no environmental risk of these stabilized materials. Furthermore, FA based geopolymer can reduce the leachability of heavy metal in the RAP-FA blend.

Keywords: recycled asphalt pavement, geopolymer, heavy metal, microstructure

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3839 Computational Fluid Dynamic Modeling of Mixing Enhancement by Stimulation of Ferrofluid under Magnetic Field

Authors: Neda Azimi, Masoud Rahimi, Faezeh Mohammadi

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Computational fluid dynamics (CFD) simulation was performed to investigate the effect of ferrofluid stimulation on hydrodynamic and mass transfer characteristics of two immiscible liquid phases in a Y-micromixer. The main purpose of this work was to develop a numerical model that is able to simulate hydrodynamic of the ferrofluid flow under magnetic field and determine its effect on mass transfer characteristics. A uniform external magnetic field was applied perpendicular to the flow direction. The volume of fluid (VOF) approach was used for simulating the multiphase flow of ferrofluid and two-immiscible liquid flows. The geometric reconstruction scheme (Geo-Reconstruct) based on piecewise linear interpolation (PLIC) was used for reconstruction of the interface in the VOF approach. The mass transfer rate was defined via an equation as a function of mass concentration gradient of the transported species and added into the phase interaction panel using the user-defined function (UDF). The magnetic field was solved numerically by Fluent MHD module based on solving the magnetic induction equation method. CFD results were validated by experimental data and good agreements have been achieved, which maximum relative error for extraction efficiency was about 7.52 %. It was showed that ferrofluid actuation by a magnetic field can be considered as an efficient mixing agent for liquid-liquid two-phase mass transfer in microdevices.

Keywords: CFD modeling, hydrodynamic, micromixer, ferrofluid, mixing

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3838 Capillary Wave Motion and Atomization Induced by Surface Acoustic Waves under the Navier-Slip Condition at the Wall

Authors: Jaime E. Munoz, Jose C. Arcos, Oscar E. Bautista, Ivan E. Campos

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The influence of slippage phenomenon over the destabilization and atomization mechanisms induced via surface acoustic waves on a Newtonian, millimeter-sized, drop deposited on a hydrophilic substrate is studied theoretically. By implementing the Navier-slip model and a lubrication-type approach into the equations which govern the dynamic response of a drop exposed to acoustic stress, a highly nonlinear evolution equation for the air-liquid interface is derived in terms of the acoustic capillary number and the slip coefficient. By numerically solving such an evolution equation, the Spatio-temporal deformation of the drop's free surface is obtained; in this context, atomization of the initial drop into micron-sized droplets is predicted at our numerical model once the acoustically-driven capillary waves reach a critical value: the instability length. Our results show slippage phenomenon at systems with partial and complete wetting favors the formation of capillary waves at the free surface, which traduces in a major volume of liquid being atomized in comparison to the no-slip case for a given time interval. In consequence, slippage at the wall possesses the capability to affect and improve the atomization rate for a drop exposed to a high-frequency acoustic field.

Keywords: capillary instability, lubrication theory, navier-slip condition, SAW atomization

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3837 Fintech Credit and Bank Efficiency Two-way Relationship: A Comparison Study Across Country Groupings

Authors: Tan Swee Liang

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This paper studies the two-way relationship between fintech credit and banking efficiency using the Generalized panel Method of Moment (GMM) estimation in structural equation modeling (SEM). Banking system efficiency, defined as its ability to produce the existing level of outputs with minimal inputs, is measured using input-oriented data envelopment analysis (DEA), where the whole banking system of an economy is treated as a single DMU. Banks are considered an intermediary between depositors and borrowers, utilizing inputs (deposits and overhead costs) to provide outputs (increase credits to the private sector and its earnings). Analysis of the interrelationship between fintech credit and bank efficiency is conducted to determine the impact in different country groupings (ASEAN, Asia and OECD), in particular the banking system response to fintech credit platforms. Our preliminary results show that banks do respond to the greater pressure caused by fintech platforms to enhance their efficiency, but differently across the different groups. The author’s earlier research on ASEAN-5 high bank overhead costs (as a share of total assets) as the determinant of economic growth suggests that expenses may not have been channeled efficiently to income-generating activities. One practical implication of the findings is that policymakers should enable alternative financing, such as fintech credit, as a warning or encouragement for banks to improve their efficiency.

Keywords: fintech lending, banking efficiency, data envelopment analysis, structural equation modeling

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3836 Latent Factors of Severity in Truck-Involved and Non-Truck-Involved Crashes on Freeways

Authors: Shin-Hyung Cho, Dong-Kyu Kim, Seung-Young Kho

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Truck-involved crashes have higher crash severity than non-truck-involved crashes. There have been many studies about the frequency of crashes and the development of severity models, but those studies only analyzed the relationship between observed variables. To identify why more people are injured or killed when trucks are involved in the crash, we must examine to quantify the complex causal relationship between severity of the crash and risk factors by adopting the latent factors of crashes. The aim of this study was to develop a structural equation or model based on truck-involved and non-truck-involved crashes, including five latent variables, i.e. a crash factor, environmental factor, road factor, driver’s factor, and severity factor. To clarify the unique characteristics of truck-involved crashes compared to non-truck-involved crashes, a confirmatory analysis method was used. To develop the model, we extracted crash data from 10,083 crashes on Korean freeways from 2008 through 2014. The results showed that the most significant variable affecting the severity of a crash is the crash factor, which can be expressed by the location, cause, and type of the crash. For non-truck-involved crashes, the crash and environment factors increase severity of the crash; conversely, the road and driver factors tend to reduce severity of the crash. For truck-involved crashes, the driver factor has a significant effect on severity of the crash although its effect is slightly less than the crash factor. The multiple group analysis employed to analyze the differences between the heterogeneous groups of drivers.

Keywords: crash severity, structural structural equation modeling (SEM), truck-involved crashes, multiple group analysis, crash on freeway

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3835 Nanostructure of Gamma-Alumina Prepared by a Modified Sol-Gel Technique

Authors: Débora N. Zambrano, Marina O. Gosatti, Leandro M. Dufou, Daniel A. Serrano, M. Mónica Guraya, Soledad Perez-Catán

Abstract:

Nanoporous g-Al2O3 samples were synthesized via a sol-gel technique, introducing changes in the Yoldas´ method. The aim of the work was to achieve an effective control of the nanostructure properties and morphology of the final g-Al2O3. The influence of the reagent temperature during the hydrolysis was evaluated in case of water at 5 ºC and 98 ºC, and alkoxide at -18 ºC and room temperature. Sol-gel transitions were performed at 120 ºC and room temperature. All g-Al2O3 samples were characterized by X-ray diffraction, nitrogen adsorption and thermal analysis. Our results showed that temperature of both water and alkoxide has not much influence on the nanostructure of the final g-Al2O3, thus giving a structure very similar to that of samples obtained by the reference method as long as the reaction temperature above 75 ºC is reached soon enough. XRD characterization showed diffraction patterns corresponding to g-Al2O3 for all samples. Also BET specific area values (253-280 m2/g) were similar to those obtained by Yoldas’s original method. The temperature of the sol-gel transition does not affect the resulting sample structure, and crystalline boehmite particles were identified in all dried gels. We analyzed the reproducibility of the samples’ structure by preparing different samples under identical conditions; we found that performing the sol-gel transition at 120 ºC favors the production of more reproducible samples and also reduces significantly the time of the sol-gel reaction.

Keywords: nanostructure alumina, boehmite, sol-gel technique, N2 adsorption/desorption isotherm, pore size distribution, BET area.

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3834 Bandgap Engineering of CsMAPbI3-xBrx Quantum Dots for Intermediate Band Solar Cell

Authors: Deborah Eric, Abbas Ahmad Khan

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Lead halide perovskites quantum dots have attracted immense scientific and technological interest for successful photovoltaic applications because of their remarkable optoelectronic properties. In this paper, we have simulated CsMAPbI3-xBrx based quantum dots to implement their use in intermediate band solar cells (IBSC). These types of materials exhibit optical and electrical properties distinct from their bulk counterparts due to quantum confinement. The conceptual framework provides a route to analyze the electronic properties of quantum dots. This layer of quantum dots optimizes the position and bandwidth of IB that lies in the forbidden region of the conventional bandgap. A three-dimensional MAPbI3 quantum dot (QD) with geometries including spherical, cubic, and conical has been embedded in the CsPbBr3 matrix. Bound energy wavefunction gives rise to miniband, which results in the formation of IB. If there is more than one miniband, then there is a possibility of having more than one IB. The optimization of QD size results in more IBs in the forbidden region. One band time-independent Schrödinger equation using the effective mass approximation with step potential barrier is solved to compute the electronic states. Envelope function approximation with BenDaniel-Duke boundary condition is used in combination with the Schrödinger equation for the calculation of eigen energies and Eigen energies are solved for the quasi-bound states using an eigenvalue study. The transfer matrix method is used to study the quantum tunneling of MAPbI3 QD through neighbor barriers of CsPbI3. Electronic states are computed using Schrödinger equation with effective mass approximation by considering quantum dot and wetting layer assembly. Results have shown the varying the quantum dot size affects the energy pinning of QD. Changes in the ground, first, second state energies have been observed. The QD is non-zero at the center and decays exponentially to zero at boundaries. Quasi-bound states are characterized by envelope functions. It has been observed that conical quantum dots have maximum ground state energy at a small radius. Increasing the wetting layer thickness exhibits energy signatures similar to bulk material for each QD size.

Keywords: perovskite, intermediate bandgap, quantum dots, miniband formation

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3833 Effect of Catalyst Preparation Method on Dry Reforming of Methane with Supported and Promoted Catalysts

Authors: Sanjay P. Gandhi, Sanjay S. Patel

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Dry (CO2) reforming of methane (DRM) is both scientific and industrial importance. In recent decades, CO2 utilization has become increasingly important in view of the escalating global warming phenomenon. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer–Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800–1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The catalysts used are often composed of transition Methods like Nickel, supported on metallic and non-metallic oxides such as alumina and silica. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. CO2 reforming methane over promoted catalyst was studied. The influence of ZrO2, CeO2 and the behavior of Ni-Al2O3 Catalyst, prepare by wet-impregnation and Co-precipitated method was studied. XRD, BET Analysis for different promoted and unprompted Catalyst was studied.

Keywords: CO2 reforming of methane, Ni catalyst, promoted and unprompted catalyst, effect of catalyst preparation

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3832 Experimental Investigation on the Role of Thermoacoustics on Soot Formation

Authors: Sambit Supriya Dash, Rahul Ravi R, Vikram Ramanan, Vinayak Malhotra

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Combustion in itself is a complex phenomenon that involves the interaction and interplay of multiple phenomena, the combined effect of which gives rise to the common flame that we see and use in our daily life applications from cooking to propelling our vehicles to space. The most important thing that goes unnoticed about these flames is the effect of the various phenomena from its surrounding environment that affects its behavior and properties. These phenomena cause a variety of energy interactions that lead to various types of energy transformations which in turn affect the flame behavior. This paper focuses on experimentally investigating the effect of one such phenomenon, which is the acoustics or sound energy on diffusion flames. The subject in itself is extensively studied upon as thermo-acoustics globally, whereas the current work focuses on studying its effect on soot formation on diffusion flames. The said effect is studied in this research work by the use of a butane as fuel, fitted with a nozzle that houses 3 arrays consisting of 4 holes each that are placed equidistant to each other and the resulting flame impinged with sound from two independent and similar sound sources that are placed equidistant from the centre of the flame. The entire process is systematically video graphed using a 60 fps regular CCD and analysed for variation in flame heights and flickering frequencies where the fuel mass flow rate is maintained constant and the configuration of entrainment holes and frequency of sound are varied, whilst maintaining constant ambient atmospheric conditions. The current work establishes significant outcomes on the effect of acoustics on soot formation; it is noteworthy that soot formation is the main cause of pollution and a major cause of inefficiency of current propulsion systems. This work is one of its kinds, and its outcomes are widely applicable to commercial and domestic appliances that utilize combustion for energy generation or propulsion and help us understand them better, so that we can increase their efficiency and decrease pollution.

Keywords: thermoacoustics, entrainment, propulsion system, efficiency, pollution

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3831 Detection of Arcobacter and Helicobacter pylori Contamination in Organic Vegetables by Cultural and Polymerase Chain Reaction (PCR) Methods

Authors: Miguel García-Ferrús, Ana González, María A. Ferrús

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The most demanded organic foods worldwide are those that are consumed fresh, such as fruits and vegetables. However, there is a knowledge gap about some aspects of organic food microbiological quality and safety. Organic fruits and vegetables are more exposed to pathogenic microorganisms due to surface contact with natural fertilizers such as animal manure, wastes and vermicompost used during farming. It has been suggested that some emergent pathogens, such as Helicobacter pylori or Arcobacter spp., could reach humans through the consumption of raw or minimally processed vegetables. Therefore, the objective of this work was to study the contamination of organic fresh green leafy vegetables by Arcobacter spp. and Helicobacter pylori. For this purpose, a total of 24 vegetable samples, 13 lettuce and 11 spinach were acquired from 10 different ecological supermarkets and greengroceries and analyzed by culture and PCR. Arcobacter spp. was detected in 5 samples (20%) by PCR, 4 spinach and one lettuce. One spinach sample was found to be also positive by culture. For H. pylori, the H. pylori VacA gene-specific band was detected in 12 vegetable samples (50%), 10 lettuces and 2 spinach. Isolation in the selective medium did not yield any positive result, possibly because of low contamination levels together with the presence of the organism in its viable but non-culturable form. Results showed significant levels of H. pylori and Arcobacter contamination in organic vegetables that are generally consumed raw, which seems to confirm that these foods can act as transmission vehicles to humans.

Keywords: Arcobacter sp., Helicobacter pylori, Organic Vegetables, Polymerase Chain Reaction (PCR)

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3830 Flow Characteristics around Rectangular Obstacles with the Varying Direction of Obstacles

Authors: Hee-Chang Lim

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The study aims to understand the surface pressure distribution around the bodies such as the suction pressure in the leading edge on the top and side-face when the aspect ratio of bodies and the wind direction are changed, respectively. We carried out the wind tunnel measurement and numerical simulation around a series of rectangular bodies (40d×80w×80h, 80d×80w×80h, 160d×80w×80h, 80d×40w×80h and 80d×160w×80h in mm3) placed in a deep turbulent boundary layer. Based on a modern numerical platform, the Navier-Stokes equation with the typical 2-equation (k-ε model) and the DES (Detached Eddy Simulation) turbulence model has been calculated, and they are both compared with the measurement data. Regarding the turbulence model, the DES model makes a better prediction comparing with the k-ε model, especially when calculating the separated turbulent flow around a bluff body with sharp edged corner. In order to observe the effect of wind direction on the pressure variation around the cube (e.g., 80d×80w×80h in mm), it rotates at 0º, 10º, 20º, 30º, and 45º, which stands for the salient wind directions in the tunnel. The result shows that the surface pressure variation is highly dependent upon the approaching wind direction, especially on the top and the side-face of the cube. In addition, the transverse width has a substantial effect on the variation of surface pressure around the bodies, while the longitudinal length has little or no influence.

Keywords: rectangular bodies, wind direction, aspect ratio, surface pressure distribution, wind-tunnel measurement, k-ε model, DES model, CFD

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3829 Competitive Coordination Strategy Towards Reversible Hybrid Hetero-Homogeneous Oxygen-Evolving Catalyst

Authors: Peikun Zhang, Chunhua Cui

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Photoelectrochemical (PEC) water splitting provides a promising pathway to convert solar energy into renewable fuels. However, the main and seemingly insurmountable obstacle is that the sluggish kinetics of oxygen evolution reaction (OER) severely jeopardizes the overall efficiency, thus exploring highly active, stable, and appreciable catalysts is urgently requested. Herein a competitive coordination strategy was demonstrated to form a reversible hybrid homo-heterogeneous catalyst for efficient OER in alkaline media. The dynamic process involves an in-situ anchoring of soluble nickel–bipyridine pre-catalyst to a conductive substrate under OER and a re-dissolution course under open circuit potential, induced by the competitive coordination between nickel–bipyridine and nickel-hydroxyls. This catalyst allows to elaborately self-modulate a charge-transfer layer thickness upon the catalytic on-off operation, which affords substantially increased active sites, yet remains light transparency, and sustains the stability of over 200 hours of continuous operation. The integration of this catalyst with exemplified state-of-the-art Ni-sputtered Si photoanode can facilitate a ~250 mV cathodic shift at a current density of 20 mA cm-2. This finding helps the understanding of catalyst from a “dynamic” perspective, which represents a viable alternative to address remaining hurdles toward solar-driven water oxidation.

Keywords: molecular catalyst, oxygen evolution reaction, solar energy, transition metal complex, water splitting

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3828 The Analysis of the Effect of Brand Image on Creating Brand Loyalty with the Structural Equation Model: A Research Study on the Sports Equipment Brand Users

Authors: Murat Erdoğdu, Murat Koçyiğit

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Brand image and brand loyalty are among the most important relational marketing elements for brand owners to be able to set up long – term relationships with their customers and to maintain these relationships. Brand owners improve their brand images with the positive perceptions remaining in the consumers’ minds. In addition, they try to find the customers that are both emotionally and behaviourally faithful to themselves in order to set up long – term relationships. Therefore, the aim of this study is to analyse the effects of the brand image that has a very important role among relational marketing elements on the brand loyalty in terms of the variables such as the perceived value, the trust in brand and the brand satisfaction. In this context, a conceptual model was created to determine the effect of the brand image on the brand loyalty thanks to the Structural Equation Model (SEM). According to this aim and this model, the study was carried out in the scope of the data collected through the questionnaires in Konya with the method of convenience sampling. The results of the research showed that the brand image has positive significant effects on the perceived value and the trust in brand and that the trust in brand has positive significant effects on the brand satisfaction, and that the brand satisfaction has positive significant effects on the brand loyalty. Thus, the hypotheses that the brand image has direct effects on the perceived value and the trust in brand and that the trust in brand has direct effects on the brand satisfaction and that the brand satisfaction has direct effects on the brand loyalty were supported. In addition, the findings about whether the perceived value has a significant effect on the brand satisfaction were also acquired.

Keywords: brand image, brand loyalty, perceived value, satisfaction, trust

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3827 A Study of Heavy Hydrocarbons Upgrading by Microwave Pyrolysis

Authors: Thanida Sritangthong, Suksun Amornraksa

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By-product upgrading is crucial in hydrocarbon industries as it can increase overall profit margin of the business. Microwave-assisted pyrolysis is relatively new technique which induces heat directly to raw materials. This results in a more energy saving and more energy-efficient process. It is also a promising method to enhance and accelerate chemical reactions, thus reducing the pyrolysis reaction time and increasing the quality of value-added products from different kinds of feedstocks. In this study, upgrading opportunity of fuel oil by-product from an olefins plant is investigated by means of microwave pyrolysis. The experiment was conducted in a lab-scale quartz reactor placed inside a 1,100 watts household microwave oven. Operating temperature was varied from 500 to 900C to observe the consequence on the quality of pyrolysis products. Several microwave receptors i.e. activated carbon, silicon carbide (SiC) and copper oxide (CuO) were used as a material to enhance the heating and reaction in the reactor. The effect of residence time was determined by adjusting flow rate of N2 carrier gas. The chemical composition and product yield were analyzed by using gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). The results showed that hydrogen, methane, ethylene, and ethane were obtained as the main gaseous products from all operating temperatures while the main liquid products were alkane, cycloalkane and polycyclic aromatic groups. The results indicated that microwave pyrolysis has a potential to upgrade low value hydrocarbons to high value products.

Keywords: fuel oil, heavy hydrocarbons, microwave pyrolysis, pyrolysis

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3826 Digitalize or Die-Responsible Innovations in Healthcare and Welfare Sectors

Authors: T. Iakovleva

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Present paper suggests a theoretical model that describes the process of the development of responsible innovations on the firm level in health and welfare sectors. There is a need to develop new firm strategies in these sectors. This paper suggests to look on the concept of responsible innovation that was originally developed on the social level and to apply this new concept to the new area of firm strategy. The rapid global diffusion of information and communication technologies has greatly improved access to knowledge. At the same time, communication is cheap, information is a commodity, and global trade increases technological diffusion. As a result, firms and users, including those outside of industrialized nations, get early exposure to the latest technologies and information. General-purpose technologies such as mobile phones and 3D printers enable individuals to solve local needs and customize products. The combined effect of these changes is having a profound impact on the innovation landscape. Meanwhile, the healthcare sector is facing unprecedented challenges, which are magnified by budgetary constraints, an aging population and the desire to provide care for all. On the other hand, patients themselves are changing. They are savvier about their diseases, they expect their relation with the healthcare professionals to be open and interactive, but above all they want to be part of the decision process. All of this is a reflection of what is already happening in other industries where customers have access to large amount of information and became educated buyers. This article addresses the question of how ICT research and innovation may contribute to developing solutions to grand societal challenges in a responsible way. A broad definition of the concept of responsibility in the context of innovation is adopted in this paper. Responsibility is thus seen as a collective, uncertain and future-oriented activity. This opens the questions of how responsibilities are perceived and distributed and how innovation and science can be governed and stewarded towards socially desirable and acceptable ends. This article addresses a central question confronting politicians, business leaders, and regional planners.

Keywords: responsible innovation, ICT, healthcare, welfare sector

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3825 Medical Student's Responses to Emotional Content in Doctor-Patient Communication: To Explore Differences in Communication Training of Medical Students and Its Impact on Doctor-Patient Communication

Authors: Stephanie Yun Yu Law

Abstract:

Background: This study aims to investigate into communication between trainee doctors and patients, especially how doctor’s reaction to patient’s emotional issues expressed in the consultation affect patient’s satisfaction. Objectives: Thus, there are three aims in this study, 1.) how do trainee doctors react to patients emotional cues in OSCE station? 2.) Any differences in the respond type to emotional cues between first year students and third year students? 3.) Is response type (reducing space) related to OSCE outcome (patient satisfaction and expert rating)? Methods: Fifteen OSCE stations was videotaped, in which 9 were stations with first-year students and 6 were with third-year students. OSCE outcomes were measured by Communication Assessment Tool and Examiners Checklist. Analyses: All patient’s cues/concerns and student’s reaction were coded by Verona Coding Definitions of Emotional Sequence. Descriptive data was gathered from Observer XT and logistic regression (two-level) was carried out to see if occurrence of reducing space response can be predicted by OSCE outcomes. Results: Reducing space responses from all students were slightly less than a half in total responses to patient’s cues. The mean percentage of reducing space behaviours was lower among first year students when compared to third year students. Patient’s satisfaction significantly (p<0.05) and negatively predicted reducing space behaviours. Conclusions: Most of the medical students, to some extent, did not provide adequate responses for patient’s emotional cues. But first year students did provide more space for patients to talk about their emotional issues when compared to third year students. Lastly, patients would feel less satisfied if trainee doctors use more reducing space responses in reaction to patient’s expressed emotional cues/concerns. Practical implications: Firstly, medical training programme can be tailored on teaching students how to detect and respond appropriately to emotional cues in order to improve underperformed student’s communication skills in healthcare setting. Furthermore, trainee doctor’s relationship with patients in clinical practice can also be improved by reacting appropriately to patient’s emotive cues in consultations (such as limit the use of reducing space behaviours).

Keywords: doctors-patients communication, applied clinical psychology, health psychology, healthcare professionals

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3824 Copper (II) Complex of New Tetradentate Asymmetrical Schiff Base Ligand: Synthesis, Characterization, and Catecholase-Mimetic Activity

Authors: Cahit Demetgul, Sahin Bayraktar, Neslihan Beyazit

Abstract:

Metalloenzymes are enzyme proteins containing metal ions, which are directly bound to the protein or to enzyme-bound nonprotein components. One of the major metalloenzymes that play a key role in oxidation reactions is catechol oxidase, which shows catecholase activity i.e. oxidation of a broad range of catechols to quinones through the four-electron reduction of molecular oxygen to water. Studies on the model compounds mimicking the catecholase activity are very useful and promising for the development of new, more efficient bioinspired catalysts, for in vitro oxidation reactions. In this study, a new tetradentate asymmetrical Schiff-base and its Cu(II) complex were synthesized by condensation of 4-nitro-1,2-phenylenediamine with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one and by using an appropriate Cu(II) salt, respectively. The prepared compounds were characterized by elemental analysis, FT-IR, NMR, UV-Vis and magnetic susceptibility. The catecholase-mimicking activity of the new Schiff Base Cu(II) complex was performed for the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) in methanol at 25 °C, where the electronic spectra were recorded at different time intervals. The yield of the quinone (3,5-DTBQ) was determined from the measured absorbance at 400 nm of the resulting solution. The compatibility of catalytic reaction with Michaelis-Menten kinetics was also investigated. In conclusion, we have found that our new Schiff Base Cu(II) complex presents a significant capacity to catalyze the oxidation reaction of the catechol to o-quinone.

Keywords: catecholase activity, Michaelis-Menten kinetics, Schiff base, transition metals

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3823 Solvent-Free Synthesis of Sorbents for Removal of Oil Spills

Authors: Mohammad H. Al-Sayah, Khalid Jarrah, Soleiman Hisaindee

Abstract:

Hydrophobic sorbents are usually used to remove oil spills from water surfaces. In this study, the hydrophilic fibers of natural cotton were chemically modified with a solvent-free process to modify them into hydrophobic fibers that can remove oil from water surfaces. The cellulose-based fibers of cotton were reacted with trichlorosilanes through gas-solid reaction in a dry chamber. Cotton fibers were exposed to vapors of four different chloroalkylsilanes at room temperature for 24 hours. The chlorosilanes were namely trichloromethylsilane, dichlorodimethyl silane, butyltrichlorosilane, and trichloro (3,3,3-trifluoropropyl) silane. The modified cotton fibers were characterized by IR-spectroscopy, thermogravimetric analysis (TGA) and Scanning Electron Microscopy/Energy Dispersive X-Ray Spectroscopy (SEM-EDS). The degree of substitution for each of the grafted alkyl groups was in the range between 0.1 and 0.3 per glucose residue. As a result of sialylation, the cotton fibers became hydrophobic; this was reflected by water contact-angle measurements of the fibers which increased from zero for the unmodified cotton to above 100 degrees for the modified fibers. In addition, the adsorption capacity of the fibers for oil from water surfaces increased by about five times that of the unmodified cotton reaching 18 g oil/g of cotton modified by dimethyl substituted silyl ethers. The optimal fiber-oil contact time and temperature for adsorption were 10 mins at 25°C, respectively. Therefore, the efficacy of cotton fibers to remove oil spills from contaminated water surfaces was significantly enhanced by using a simple solvent-free and environment-friendly process.

Keywords: gas-solid silyl reaction, modified cellulose, solvent-free, oil pollution, cotton

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3822 Melatonin Improved Vase Quality by Delaying Oxidation Reaction and Supplying More Energies in Cut Peony (Paeonia Lactiflora cv. Sarah)

Authors: Tai Chen, Caihuan Tian, Xiuxia Ren, Jingqi Xue, Xiuxin Zhang

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The herbaceous peony has become increasingly popular worldwide in recent years, especially as a cut flower with great economic value. However, peony has a very short vase life, only 3-5 d usually, which seriously affects its commodity value. In this study, we used the cut peony (Paeonia lactiflora cv. Sarah) as a material and found that melatonin treatment significantly improved its postharvest performance. In the control group, its vase life was 4.8 d, accompanied by petal dropping at last; melatonin treatment (40 μM) increased this time to 6.9 d without petal dropping at the end. Further study showed that melatonin treatment significantly increased the activity of antioxidant enzymes as well as reduced sugar content in petals, whereas the starch content in petals decreased. These results indicated that melatonin treatment may delay the oxidation reaction caused by aging, which also provides extra energy for maintaining flowering. Through full-length transcriptome sequencing, a total of 2819 differentially expressed genes (DEGs) between control and melatonin treatment groups were identified. KEGG enrichment analysis showed that these DEGs were mainly involved in three pathways, including melatonin synthesis, starch and sucrose conversion, and plant disease resistance. After the RT-qPCR verification, we identified three DEGs, named PlBAM3, PlWRKY22 and PlTIP1, and they should play major roles in melatonin-improved postharvest performance. One possible reason is that PlBAM3 caused maltose production (by starch degradation), maintained the proline biosynthesis, and then alleviated oxidative stress. Another reason is that both PlBAM3 and PlWRKY22 are key drought resistance regulators, which have the ability to alleviate osmotic stress and improve water absorption, which may also help to improve the postharvest quality of cut peony. In addition, PlTIP1 is involved in the sugar signal pathway, indicating sugar may also as a signal substance during this process. Our work may give new ideas for developing new ways to prolong the vase life of cut peony and improve its commodity value eventually.

Keywords: cut peony, melatonin, vase life, oxidation reaction, energy supply, differentially expressed genes

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3821 Characterization of Aerosol Droplet in Absorption Columns to Avoid Amine Emissions

Authors: Hammad Majeed, Hanna Knuutila, Magne Hilestad, Hallvard Svendsen

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Formation of aerosols can cause serious complications in industrial exhaust gas CO2 capture processes. SO3 present in the flue gas can cause aerosol formation in an absorption based capture process. Small mist droplets and fog formed can normally not be removed in conventional demisting equipment because their submicron size allows the particles or droplets to follow the gas flow. As a consequence of this aerosol based emissions in the order of grams per Nm3 have been identified from PCCC plants. In absorption processes aerosols are generated by spontaneous condensation or desublimation processes in supersaturated gas phases. Undesired aerosol development may lead to amine emissions many times larger than what would be encountered in a mist free gas phase in PCCC development. It is thus of crucial importance to understand the formation and build-up of these aerosols in order to mitigate the problem.Rigorous modelling of aerosol dynamics leads to a system of partial differential equations. In order to understand mechanics of a particle entering an absorber an implementation of the model is created in Matlab. The model predicts the droplet size, the droplet internal variable profiles and the mass transfer fluxes as function of position in the absorber. The Matlab model is based on a subclass method of weighted residuals for boundary value problems named, orthogonal collocation method. The model comprises a set of mass transfer equations for transferring components and the essential diffusion reaction equations to describe the droplet internal profiles for all relevant constituents. Also included is heat transfer across the interface and inside the droplet. This paper presents results describing the basic simulation tool for the characterization of aerosols formed in CO2 absorption columns and gives examples as to how various entering droplets grow or shrink through an absorber and how their composition changes with respect to time. Below are given some preliminary simulation results for an aerosol droplet composition and temperature profiles. Results: As an example a droplet of initial size of 3 microns, initially containing a 5M MEA, solution is exposed to an atmosphere free of MEA. Composition of the gas phase and temperature is changing with respect to time throughout the absorber.

Keywords: amine solvents, emissions, global climate change, simulation and modelling, aerosol generation

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3820 Upward Millennium: Enterprise Resource Planning (ERP) Development and Implementation in Pakistani Organizations

Authors: Sara Aziz, Madiha Arooj, Hira Rizwani, Wasim Irshad

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Enterprise Resource Planning (ER) as component of Information Resource System has turned up as one of the most demanding software in market for the new millennium. ERP system automates the core activities of any organization such as finance, manufacturing and supply chain management, human resource etc. to generate an access to the information in real time environment. Despite this fact many of the organizations globally particularly in developing country Pakistan are unaware and avoid adopting it. The development and implementation of ERP system is a complex and challenging process. This research was aimed to explore the benefits and coping strategies (with reference to end user reaction) of organizations those have implemented ERP. The problems addressed in this study focused the challenges and key success factors regarding implementing ERP Pakistani Organizations. Secondly, it has explored the stumbling blocks and business integration of those organizations that are not implementing ERP. The public and corporate sector organizations in Pakistan were selected to collect the data. The research finding shows that the organizational culture, openness towards adoption and learning, deployment and development, top management commitment and change systems, business processes and compatibility and user acceptance and reaction are contributing factors for successful implementation and development of ERP system. This research is thus an addition to enhance knowledge and understanding of implementation of ERP system in Pakistan.

Keywords: ERP system, user acceptance and involvement, change management, organizational culture

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3819 Evaluation of the Irritation Potential of Three Topical Formulations of Minoxidil 5% Using Patch Test

Authors: Sule Pallavi, Shah Priyank, Thavkar Amit, Mehta Suyog, Rohira Poonam

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Minoxidil is used topically to help hair growth in the treatment of male androgenetic alopecia. The objective of this study is to compare irritation potential of three conventional formulation of minoxidil 5% topical solution of in human patch test. The study was a single centre, double blind, non-randomized controlled study in 56 healthy adult Indian subjects. Occlusive patch test for 24 hours was performed with three formulation of minoxidil 5% topical solution. Products tested included aqueous based minoxidil 5% (AnasureTM 5%, Sun Pharma, India – Brand A), alcohol based minoxidil 5% (Brand B) and aqueous based minoxidil 5% (Brand C). Isotonic saline 0.9% and 1% w/w sodium lauryl sulphate were included as negative control and positive control respectively. Patches were applied and removed after 24hours. The skin reaction was assessed and clinically scored 24 hours after the removal of the patches under constant artificial daylight source using Draize scale (0-4 points scale for erythema/wrinkles/dryness and for oedema). A combined mean score up to 2.0/8.0 indicates a product is “non-irritant” and score between 2.0/8.0 and 4.0/8.0 indicates “mildly irritant” and score above 4.0/8.0 indicates “irritant”. Follow-up was scheduled after one week to confirm recovery for any reaction. The procedure of the patch test followed the principles outlined by Bureau of Indian standards (BIS) (IS 4011:2018; Methods of Test for safety evaluation of Cosmetics-3rd revision). Fifty six subjects with mean age 30.9 years (27 males and 29 females) participated in the study. The combined mean score (± standard deviation) were: 0.13 ± 0.33 (Brand A), 0.39 ± 0.49 (Brand B), 0.22 ± 0.41 (Brand C), 2.91 ± 0.79 (Positive control) and 0.02 ± 0.13 (Negative control). The mean score of Brand A (Sun Pharma product) was significantly lower than Brand B (p=0.001) and was comparable with Brand C (p=0.21). The combined mean erythema score (± standard deviation) were: 0.09 ± 0.29 (Brand A), 0.27 ± 0.5 (Brand B), 0.18 ± 0.39 (Brand C), 2.02 ± 0.49 (Positive control) and 0.0 ± 0.0 (Negative control). The mean erythema score of Brand A was significantly lower than Brand B (p=0.01) and was comparable with Brand C (p=0.16). Any reaction observed at 24hours after patch removal subsided in a week. All the three topical formulation of minoxidil 5% were non-irritant. Brand A of 5% minoxidil (Sun Pharma) was found to be least irritant than Brand B and Brand C based on the combined mean score and mean erythema score in the human patch test as per the BIS, IS 4011;2018.

Keywords: erythema, irritation, minoxidil, patch test

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3818 Investigation of Time Pressure and Instinctive Reaction in Moral Dilemmas While Driving

Authors: Jacqueline Miller, Dongyuan Y. Wang, F. Dan Richard

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Before trying to make an ethical machine that holds a higher ethical standard than humans, a better understanding of human moral standards that could be used as a guide is crucial. How humans make decisions in dangerous driving situations like moral dilemmas can contribute to developing acceptable ethical principles for autonomous vehicles (AVs). This study uses a driving simulator to investigate whether drivers make utilitarian choices (choices that maximize lives saved and minimize harm) in unavoidable automobile accidents (moral dilemmas) with time pressure manipulated. This study also investigates how impulsiveness influences drivers’ behavior in moral dilemmas. Manipulating time pressure results in collisions that occur at varying time intervals (4 s, 5 s, 7s). Manipulating time pressure helps investigate how time pressure may influence drivers’ response behavior. Thirty-one undergraduates participated in this study using a STISM driving simulator to respond to driving moral dilemmas. The results indicated that the percentage of utilitarian choices generally increased when given more time to respond (from 4 s to 7 s). Additionally, participants in vehicle scenarios preferred responding right over responding left. Impulsiveness did not influence utilitarian choices. However, as time pressure decreased, response time increased. Findings have potential implications and applications on the regulation of driver assistance technologies and AVs.

Keywords: time pressure, automobile moral dilemmas, impulsiveness, reaction time

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3817 The Amount of Information Processing and Balance Performance in Children: The Dual-Task Paradigm

Authors: Chin-Chih Chiou, Tai-Yuan Su, Ti-Yu Chen, Wen-Yu Chiu, Chungyu Chen

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The purpose of this study was to investigate the effect of reaction time (RT) or balance performance as the number of stimulus-response choices increases, the amount of information processing of 0-bit and 1-bit conditions based on Hick’s law, using the dual-task design. Eighteen children (age: 9.38 ± 0.27 years old) were recruited as the participants for this study, and asked to assess RT and balance performance separately and simultaneously as following five conditions: simple RT (0-bit decision), choice RT (1-bit decision), single balance control, balance control with simple RT, and balance control with choice RT. Biodex 950-300 balance system and You-Shang response timer were used to record and analyze the postural stability and information processing speed (RT) respectively for the participants. Repeated measures one-way ANOVA with HSD post-hoc test and 2 (balance) × 2 (amount of information processing) repeated measures two-way ANOVA were used to test the parameters of balance performance and RT (α = .05). The results showed the overall stability index in the 1-bit decision was lower than in 0-bit decision, and the mean deflection in the 1-bit decision was lower than in single balance performance. Simple RTs were faster than choice RTs both in single task condition and dual task condition. It indicated that the chronometric approach of RT could use to infer the attention requirement of the secondary task. However, this study did not find that the balance performance is interfered for children by the increasing of the amount of information processing.

Keywords: capacity theory, reaction time, Hick’s law, balance

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3816 Highly Selective Phosgene Free Synthesis of Methylphenylcarbamate from Aniline and Dimethyl Carbonate over Heterogeneous Catalyst

Authors: Nayana T. Nivangune, Vivek V. Ranade, Ashutosh A. Kelkar

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Organic carbamates are versatile compounds widely employed as pesticides, fungicides, herbicides, dyes, pharmaceuticals, cosmetics and in the synthesis of polyurethanes. Carbamates can be easily transformed into isocyanates by thermal cracking. Isocyantes are used as precursors for manufacturing agrochemicals, adhesives and polyurethane elastomers. Manufacture of polyurethane foams is a major application of aromatic ioscyanates and in 2007 the global consumption of polyurethane was about 12 million metric tons/year and the average annual growth rate was about 5%. Presently Isocyanates/carbamates are manufactured by phosgene based process. However, because of high toxicity of phoegene and formation of waste products in large quantity; there is a need to develop alternative and safer process for the synthesis of isocyanates/carbamates. Recently many alternative processes have been investigated and carbamate synthesis by methoxycarbonylation of aromatic amines using dimethyl carbonate (DMC) as a green reagent has emerged as promising alternative route. In this reaction methanol is formed as a by-product, which can be converted to DMC either by oxidative carbonylation of methanol or by reacting with urea. Thus, the route based on DMC has a potential to provide atom efficient and safer route for the synthesis of carbamates from DMC and amines. Lot of work is being carried out on the development of catalysts for this reaction and homogeneous zinc salts were found to be good catalysts for the reaction. However, catalyst/product separation is challenging with these catalysts. There are few reports on the use of supported Zn catalysts; however, deactivation of the catalyst is the major problem with these catalysts. We wish to report here methoxycarbonylation of aniline to methylphenylcarbamate (MPC) using amino acid complexes of Zn as highly active and selective catalysts. The catalysts were characterized by XRD, IR, solid state NMR and XPS analysis. Methoxycarbonylation of aniline was carried out at 170 °C using 2.5 wt% of the catalyst to achieve >98% conversion of aniline with 97-99% selectivity to MPC as the product. Formation of N-methylated products in small quantity (1-2%) was also observed. Optimization of the reaction conditions was carried out using zinc-proline complex as the catalyst. Selectivity was strongly dependent on the temperature and aniline:DMC ratio used. At lower aniline:DMC ratio and at higher temperature, selectivity to MPC decreased (85-89% respectively) with the formation of N-methylaniline (NMA), N-methyl methylphenylcarbamate (MMPC) and N,N-dimethyl aniline (NNDMA) as by-products. Best results (98% aniline conversion with 99% selectivity to MPC in 4 h) were observed at 170oC and aniline:DMC ratio of 1:20. Catalyst stability was verified by carrying out recycle experiment. Methoxycarbonylation preceded smoothly with various amine derivatives indicating versatility of the catalyst. The catalyst is inexpensive and can be easily prepared from zinc salt and naturally occurring amino acids. The results are important and provide environmentally benign route for MPC synthesis with high activity and selectivity.

Keywords: aniline, heterogeneous catalyst, methoxycarbonylation, methylphenyl carbamate

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3815 Peculiar Mineralogical and Chemical Evolution of Contaminated Igneous Rocks at a Gabbro-Carbonate Contact, Wadai Bayhan, Yemen

Authors: Murad Ali, Shoji Arai, Mohamed Khedr, Mukhtar Nasher, Shawki Nasr

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The Wadi Bayhan area of southeastern Yemen is about 60 km NW of Al-Bayda city in the Al-Bayda uplift terrane at the southeast margin of the Arabian-Nubian Shield. Intrusion of alkali gabbro into carbonate rocks apparently produced an 8m to 10 m thick reaction zone at the contact. This had been identified as nepheline pyroxenite. We have observed this to be mineralogically zoned with calc-silicate assemblages (e.g. pyroxene, calcite, spinel, garnet and melilite). The presence of melilite implies a skarn. The sinuous embayed pyroxenite-skarn contact, the presence of skarn minerals in pyroxenite, and textural evidence for growth of calc-silicate skarn by replacement of both carbonate rocks and solid pyroxenite indicate that reaction involved assimilation of carbonate wall rock by magma and loss of Al and Si to the skarn. Textural relationships between minerals provide evidence for a metasomatic development of the skarn at the expense of the pyroxenite. This process, related to the circulation of fluids equilibrated with carbonates, is responsible for those pyroxenite-spinel (± calcite) skarns. The uneven modal distribution of euhedral pyroxenite and enveloping nepheline in pyroxenite, the restricted occurrence of alkali gabbro as dikes in pyroxenite and skarn and the leucocratic matrix of pyroxenite suggest that pyroxenite represents an accumulation of titanaugite cemented by an alkali-rich residual magma and that alkali gabbro represents a part of the residual contaminated magma that was squeezed out of the pyroxene crystal mush. Carbonate assimilation is modeled by reaction of calcite and magmatic plagioclase, which results in resorption of plagioclase, growth of pyroxene enriched in Ca, Fe, Ti, and Al, and solution of nepheline in residual contaminated magma. The composition of nepheline pyroxenite evolved by addition of Ca from dissolved carbonate rocks, loss of Al and Si to skarn, and local segregation of solid pyroxene and alkali gabbro magma. The predominance of pyroxenite among contaminated rocks and their restriction to a large zone along the intrusive contact provide little evidence for the genesis of a significant volume of alkaline magmatic surroundings by carbonate assimilation.

Keywords: Yemen, Wadi Bayhan, skarn, pyroxenite, carbonatite, metasomatic

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