Search results for: vertical displacement dynamic response
2378 MicroRNA Differential Profiling in Hepatitis C Patients Undergoing Major Surgeries: Propofol versus Sevoflurane Anesthesia
Authors: Hala Demerdash, Ola M. Zanaty, Emad Eldin Arida
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Background: This study investigated the micoRNA expression changes induced by Sevoflurane and Propofol and their effects on liver functions. Patients and methods: The study was designed as randomized controlled study, carried out on 200 adult patients, scheduled for major surgeries under general anesthesia (GA). Patients were randomly divided into four groups; groups SC and PC included chronic hepatitis C (CHC) patients where SC group are patients receiving Sevoflurane, and PC group are patients receiving Propofol anesthesia. While S and P groups included non- hepatitis patients; S group are patients receiving Sevoflurane and P group are patients receiving Propofol. Anesthesia in Group S and SC patients was maintained by sevoflurane, while anesthesia in Group P and PC patients was maintained by propofol infusion. Blood samples were analyzed for PT, PTT and liver enzymes. Serum samples were analyzed for microRNA before and after surgery. Results: Results show miRNA-122 and miRNA-21 were absent in serum of S and P groups in pre-operative samples. However, they were expressed in SC and PC groups. In post-operative samples; miRNA-122 revealed an increased expression in all groups; with more exaggerated response in SC group. On the other hand miRNA-21 revealed increased expression in both SC and PC groups; a slight expression in S group with absent expression in P group. There was a post-operative negative correlation between miR-122 and ALT (r=-0.46) in SC group and (r=-0.411) in PC group and positive correlation between ALT and miR-21 (r=0.335) in SC group and (r=0.379) in PC group. The amount of blood loss was positively correlated with miR-122 (r=0.366) in SC group and (r=0.384) in PC group. Conclusion: Propofol anesthesia is safer than Sevoflurane anesthesia in patients with CHC. Sevoflurane and Propofol anesthesia affect miRNA expression in both CHC and non-hepatitis patients.Keywords: anesthesia, chronic hepatitis C, micoRNA, propofol, sevoflurane
Procedia PDF Downloads 3422377 Real-Time Generative Architecture for Mesh and Texture
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In the evolving landscape of physics-based machine learning (PBML), particularly within fluid dynamics and its applications in electromechanical engineering, robot vision, and robot learning, achieving precision and alignment with researchers' specific needs presents a formidable challenge. In response, this work proposes a methodology that integrates neural transformation with a modified smoothed particle hydrodynamics model for generating transformed 3D fluid simulations. This approach is useful for nanoscale science, where the unique and complex behaviors of viscoelastic medium demand accurate neurally-transformed simulations for materials understanding and manipulation. In electromechanical engineering, the method enhances the design and functionality of fluid-operated systems, particularly microfluidic devices, contributing to advancements in nanomaterial design, drug delivery systems, and more. The proposed approach also aligns with the principles of PBML, offering advantages such as multi-fluid stylization and consistent particle attribute transfer. This capability is valuable in various fields where the interaction of multiple fluid components is significant. Moreover, the application of neurally-transformed hydrodynamical models extends to manufacturing processes, such as the production of microelectromechanical systems, enhancing efficiency and cost-effectiveness. The system's ability to perform neural transfer on 3D fluid scenes using a deep learning algorithm alongside physical models further adds a layer of flexibility, allowing researchers to tailor simulations to specific needs across scientific and engineering disciplines.Keywords: physics-based machine learning, robot vision, robot learning, hydrodynamics
Procedia PDF Downloads 662376 Multiscale Cohesive Zone Modeling of Composite Microstructure
Authors: Vincent Iacobellis, Kamran Behdinan
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A finite element cohesive zone model is used to predict the temperature dependent material properties of a polyimide matrix composite with unidirectional carbon fiber arrangement. The cohesive zone parameters have been obtained from previous research involving an atomistic-to-continuum multiscale simulation of the fiber-matrix interface using the bridging cell multiscale method. The goal of the research was to both investigate the effect of temperature change on the composite behavior with respect to transverse loading as well as the validate the use of cohesive parameters obtained from atomistic-to-continuum multiscale modeling to predict fiber-matrix interfacial cracking. From the multiscale model cohesive zone parameters (i.e. maximum traction and energy of separation) were obtained by modeling the interface between the coarse-grained polyimide matrix and graphite based carbon fiber. The cohesive parameters from this simulation were used in a cohesive zone model of the composite microstructure in order to predict the properties of the macroscale composite with respect to changes in temperature ranging from 21 ˚C to 316 ˚C. Good agreement was found between the microscale RUC model and experimental results for stress-strain response, stiffness, and material strength at low and high temperatures. Examination of the deformation of the composite through localized crack initiation at the fiber-matrix interface also agreed with experimental observations of similar phenomena. Overall, the cohesive zone model was shown to be both effective at modeling the composite properties with respect to transverse loading as well as validated the use of cohesive zone parameters obtained from the multiscale simulation.Keywords: cohesive zone model, fiber-matrix interface, microscale damage, multiscale modeling
Procedia PDF Downloads 4872375 Motor Speech Profile of Marathi Speaking Adults and Children
Authors: Anindita Banik, Anjali Kant, Aninda Duti Banik, Arun Banik
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Speech is a complex, dynamic unique motor activity through which we express thoughts and emotions and respond to and control our environment. The aim was based to compare select Motor Speech parameters and their sub parameters across typical Marathi speaking adults and children. The subjects included a total of 300 divided into Group I, II, III including males and females. Subjects included were reported of no significant medical history and had a rating of 0-1 on GRBAS scale. The recordings were obtained utilizing three stimuli for the acoustic analysis of Diadochokinetic rate (DDK), Second Formant Transition, Voice and Tremor and its sub parameters. And these aforementioned parameters were acoustically analyzed in Motor Speech Profile software in VisiPitch IV. The statistical analyses were done by applying descriptive statistics and Two- Way ANOVA.The results obtained showed statistically significant difference across age groups and gender for the aforementioned parameters and its sub parameters.In DDK, for avp (ms) there was a significant difference only across age groups. However, for avr (/s) there was a significant difference across age groups and gender. It was observed that there was an increase in rate with an increase in age groups. The second formant transition sub parameter F2 magn (Hz) also showed a statistically significant difference across both age groups and gender. There was an increase in mean value with an increase in age. Females had a higher mean when compared to males. For F2 rate (/s) a statistically significant difference was observed across age groups. There was an increase in mean value with increase in age. It was observed for Voice and Tremor MFTR (%) that a statistically significant difference was present across age groups and gender. Also for RATR (Hz) there was statistically significant difference across both age groups and gender. In other words, the values of MFTR and RATR increased with an increase in age. Thus, this study highlights the variation of the motor speech parameters amongst the typical population which would be beneficial for comparison with the individuals with motor speech disorders for assessment and management.Keywords: adult, children, diadochokinetic rate, second formant transition, tremor, voice
Procedia PDF Downloads 3082374 Linear Stability Analysis of a Regularized Two-Fluid Model for Unstable Gas-Liquid Flows in Long Hilly Terrain Pipelines
Authors: David Alejandro Lazo-Vasquez, Jorge Luis Balino
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In the petroleum industry, multiphase flow occurs when oil, gas, and water are transported in the same pipe through large pipeline systems. The flow can take different patterns depending on parameters like fluid velocities, pipe diameter, pipe inclination, and fluid properties. Mainly, intermittent flow is produced by the natural propagation of short and long waves, according to the Kelvin-Helmholtz Stability Theory. To model stratified flow and the onset of intermittent flow, it is crucial to have knowledge of short and long waves behavior. The two-fluid model, frequently employed for characterizing multiphase systems, becomes ill-posed for high liquid and gas velocities and large inclination angles, for short waves can develop infinite growth rates. We are interested in focusing attention on long-wave instability, which leads to the production of roll waves that may grow and result in the transition from stratified flow to intermittent flow. In this study, global and local linear stability analyses for dynamic and kinematic stability criteria predict the regions of stability of the flow for different pipe inclinations and fluid velocities in regularized and non-regularized systems, concurrently. It was possible to distinguish when: wave growth rates are absolutely bounded (stable stratified smooth flow), waves have finite growth rates (unstable stratified wavy flow), and when the equation system becomes elliptic and hyperbolization is needed. In order to bound short wave growth rates and regularize the equation system, we incorporated some lower and higher-order terms like interfacial drag and surface tension, respectively.Keywords: linear stability analysis, multiphase flow, onset of slugging, two-fluid model regularization
Procedia PDF Downloads 1352373 Exploring the Link between Intangible Capital and Urban Economic Development: The Case of Three UK Core Cities
Authors: Melissa Dickinson
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In the context of intense global competitiveness and urban transformations, today’s cities are faced with enormous challenges. There is increasing pressure among cities and regions to respond promptly and efficiently to fierce market progressions, to offer a competitive advantage, higher flexibility, and to be pro-active in creating future markets. Consequently, competition among cities and regions within the dynamics of a worldwide spatial economic system is growing fiercer, amplifying the importance of intangible capital in shaping the competitive and dynamic economic performance of organisations and firms. Accordingly, this study addresses how intangible capital influences urban economic development within an urban environment. Despite substantial research on the economic, and strategic determinants of urban economic development this multidimensional phenomenon remains to be one of the greatest challenges for economic geographers. The research provides a unique contribution, exploring intangible capital through the lenses of entrepreneurial capital and social-network capital. Drawing on business surveys and in-depth interviews with key stakeholders in the case of the three UK Core Cities Birmingham, Bristol and Cardiff. This paper critically considers how entrepreneurial capital and social-network capital is a crucial source of competitiveness and urban economic development. This paper deals with questions concerning the complexity of operationalizing ‘network capital’ in different urban settings and the challenges that reside in characterising its effects. The paper will highlight the role of institutions in facilitating urban economic development. Particular emphasis will be placed on exploring the roles formal and informal institutions have in delivering, supporting and nurturing entrepreneurial capital and social-network capital, to facilitate urban economic development. Discussions will then consider how institutions moderate and contribute to the economic development of urban areas, to provide implications in terms of future policy formulation in the context of large and medium sized cities.Keywords: urban economic development, network capital, entrepreneurialism, institutions
Procedia PDF Downloads 2762372 Climate Change Effects on Agriculture
Authors: Abdellatif Chebboub
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Agricultural production is sensitive to weather and thus directly affected by climate change. Plausible estimates of these climate change impacts require combined use of climate, crop, and economic models. Results from previous studies vary substantially due to differences in models, scenarios, and data. This paper is part of a collective effort to systematically integrate these three types of models. We focus on the economic component of the assessment, investigating how nine global economic models of agriculture represent endogenous responses to seven standardized climate change scenarios produced by two climate and five crop models. These responses include adjustments in yields, area, consumption, and international trade. We apply biophysical shocks derived from the Intergovernmental Panel on Climate Change’s representative concentration pathway with end-of-century radiative forcing of 8.5 W/m2. The mean biophysical yield effect with no incremental CO2 fertilization is a 17% reduction globally by 2050 relative to a scenario with unchanging climate. Endogenous economic responses reduce yield loss to 11%, increase area of major crops by 11%, and reduce consumption by 3%. Agricultural production, cropland area, trade, and prices show the greatest degree of variability in response to climate change, and consumption the lowest. The sources of these differences include model structure and specification; in particular, model assumptions about ease of land use conversion, intensification, and trade. This study identifies where models disagree on the relative responses to climate shocks and highlights research activities needed to improve the representation of agricultural adaptation responses to climate change.Keywords: climate change, agriculture, weather change, danger of climate change
Procedia PDF Downloads 3162371 Improving Fault Tolerance and Load Balancing in Heterogeneous Grid Computing Using Fractal Transform
Authors: Saad M. Darwish, Adel A. El-Zoghabi, Moustafa F. Ashry
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The popularity of the Internet and the availability of powerful computers and high-speed networks as low-cost commodity components are changing the way we use computers today. These technical opportunities have led to the possibility of using geographically distributed and multi-owner resources to solve large-scale problems in science, engineering, and commerce. Recent research on these topics has led to the emergence of a new paradigm known as Grid computing. To achieve the promising potentials of tremendous distributed resources, effective and efficient load balancing algorithms are fundamentally important. Unfortunately, load balancing algorithms in traditional parallel and distributed systems, which usually run on homogeneous and dedicated resources, cannot work well in the new circumstances. In this paper, the concept of a fast fractal transform in heterogeneous grid computing based on R-tree and the domain-range entropy is proposed to improve fault tolerance and load balancing algorithm by improve connectivity, communication delay, network bandwidth, resource availability, and resource unpredictability. A novel two-dimension figure of merit is suggested to describe the network effects on load balance and fault tolerance estimation. Fault tolerance is enhanced by adaptively decrease replication time and message cost while load balance is enhanced by adaptively decrease mean job response time. Experimental results show that the proposed method yields superior performance over other methods.Keywords: Grid computing, load balancing, fault tolerance, R-tree, heterogeneous systems
Procedia PDF Downloads 4902370 Electrochemical Detection of the Chemotherapy Agent Methotrexate in vitro from Physiological Fluids Using Functionalized Carbon Nanotube past Electrodes
Authors: Shekher Kummari, V. Sunil Kumar, K. Vengatajalabathy Gobi
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A simple, cost-effective, reusable and reagent-free electrochemical biosensor is developed with functionalized multiwall carbon nanotube paste electrode (f-CNTPE) for the sensitive and selective determination of the important chemotherapeutic drug methotrexate (MTX), which is widely used for the treatment of various cancer and autoimmune diseases. The electrochemical response of the fabricated electrode towards the detection of MTX is examined by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV). CV studies have shown that f-CNTPE electrode system exhibited an excellent electrocatalytic activity towards the oxidation of MTX in phosphate buffer (0.2 M) compared with a conventional carbon paste electrode (CPE). The oxidation peak current is enhanced by nearly two times in magnitude. Applying the DPV method under optimized conditions, a linear calibration plot is achieved over a wide range of concentration from 4.0×10⁻⁷ M to 5.5×10⁻⁶ M with the detection limit 1.6×10⁻⁷ M. further, by applying the SWV method a parabolic calibration plot was achieved starting from a very low concentration of 1.0×10⁻⁸ M, and the sensor could detect as low as 2.9×10⁻⁹ M MTX in 10 s and 10 nM were detected in steady state current-time analysis. The f-CNTPE shows very good selectivity towards the specific recognition of MTX in the presence of important biological interference. The electrochemical biosensor detects MTX in-vitro directly from pharmaceutical sample, undiluted urine and human blood serum samples at a concentration range 5.0×10⁻⁷ M with good recovery limits.Keywords: amperometry, electrochemical detection, human blood serum, methotrexate, MWCNT, SWV
Procedia PDF Downloads 3092369 Enriched Education: The Classroom as a Learning Network through Video Game Narrative Development
Authors: Wayne DeFehr
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This study is rooted in a pedagogical approach that emphasizes student engagement as fundamental to meaningful learning in the classroom. This approach creates a paradigmatic shift, from a teaching practice that reinforces the teacher’s central authority to a practice that disperses that authority among the students in the classroom through networks that they themselves develop. The methodology of this study about creating optimal conditions for learning in the classroom includes providing a conceptual framework within which the students work, as well as providing clearly stated expectations for work standards, content quality, group methodology, and learning outcomes. These learning conditions are nurtured in a variety of ways. First, nearly every class includes a lecture from the professor with key concepts that students need in order to complete their work successfully. Secondly, students build on this scholarly material by forming their own networks, where students face each other and engage with each other in order to collaborate their way to solving a particular problem relating to the course content. Thirdly, students are given short, medium, and long-term goals. Short term goals relate to the week’s topic and involve workshopping particular issues relating to that stage of the course. The medium-term goals involve students submitting term assignments that are evaluated according to a well-defined rubric. And finally, long-term goals are achieved by creating a capstone project, which is celebrated and shared with classmates and interested friends on the final day of the course. The essential conclusions of the study are drawn from courses that focus on video game narrative. Enthusiastic student engagement is created not only with the dynamic energy and expertise of the instructor, but also with the inter-dependence of the students on each other to build knowledge, acquire skills, and achieve successful results.Keywords: collaboration, education, learning networks, video games
Procedia PDF Downloads 1152368 Conception of Increasing the Efficiency of Excavation Shoring by Prestressing Diaphragm Walls
Authors: Mateusz Frydrych
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The construction of diaphragm walls as excavation shoring as well as part of deep foundations is widely used in geotechnical engineering. Today's design challenges lie in the optimal dimensioning of the cross-section, which is demanded by technological considerations. Also in force is the issue of optimization and sustainable use of construction materials, including reduction of carbon footprint, which is currently a relevant challenge for the construction industry. The author presents the concept of an approach to achieving increased efficiency of diaphragm wall excavation shoring by using structural compression technology. The author proposes to implement prestressed tendons in a non-linear manner in the reinforcement cage. As a result bending moment is reduced, which translates into a reduction in the amount of steel needed in the section, a reduction in displacements, and a reduction in the scratching of the casing, including the achievement of better tightness. This task is rarely seen and has not yet been described in a scientific way in the literature. The author has developed a dynamic numerical model that allows the dimensioning of the cross-section of a prestressed shear wall, as well as the study of casing displacements and cross-sectional forces in any defined computational situation. Numerical software from the Sofistik - open source development environment - was used for the study, and models were validated in Plaxis software . This is an interesting idea that allows for optimizing the execution of construction works and reducing the required resources by using fewer materials and saving time. The author presents the possibilities of a prestressed diaphragm wall, among others, using. The example of a diaphragm wall working as a cantilever at the height of two underground floors without additional strutting or stability protection by using ground anchors. This makes the execution of the work more criminal for the contractor and, as a result, cheaper for the investor.Keywords: prestressed diaphragm wall, Plaxis, Sofistik, innovation, FEM, optimisation
Procedia PDF Downloads 772367 Factors Affecting of Musculoskeletal Disorders in Nurses from a Taiwan Hospital
Authors: Hsien Hua Kuo, Wen Chun Lin, Chia Chi Hsu, Hsien Wen Kuo
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Objective: Despite the high prevalence of musculoskeletal disorders (MSDs) among nurses, which has been consistently observed in the studies of Western countries, very little information regarding intensity of workload and work-related quality of life (WRQOL) related to MSDs among nurses is available in Taiwan. The objective of this study is to investigate the factors affecting musculoskeletal disorders in nurses from a hospital. Methods: 550 nurses from a hospital in Taoyuan were interviewed using a modified standardized Nordic Musculoskeletal (NMQ) questionnaire which contained the demographic information, workplace condition and musculoskeletal disorders. Results: Response rate of nurses were 92.5% from a teaching hospital. Based on medical diagnosis by physician, neck of musculoskeletal disorders had the highest percentage in nine body portions. The higher percentage of musculoskeletal disorders in nurses found from wards of internal and surgery. Severity and symptoms of musculoskeletal disorders diagnosed by self-reported questionnaire significantly correlated with WRQOL, job satisfaction and intensity of workload among nurses based on the logistic regression model. Conclusion: The severity and symptoms of musculoskeletal disorders among nurses showed a dose-dependent with WRQOL and workload. When work characteristics in hospital were modified, the severity of musculoskeletal disorders among nurses will be decreased and alleviated. Comment: Multifaceted ergonomic intervention programme to reduce the prevalence of MSDs among nurses was by encouraging nurses to do more physical activity which will make them more flexible and increase their strength. Therefore, the head nurse should encourage nurses to regularly physical activity and to modify unfitting ergonomic environment in order to reduce the prevalence of MSDs.Keywords: musculoskeletal disorders, nurse, WRQOL, job satisfaction
Procedia PDF Downloads 3332366 Metal-Based Deep Eutectic Solvents for Extractive Desulfurization of Fuels: Analysis from Molecular Dynamics Simulations
Authors: Aibek Kukpayev, Dhawal Shah
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Combustion of sour fuels containing high amount of sulfur leads to the formation of sulfur oxides, which adversely harm the environment and has a negative impact on human health. Considering this, several legislations have been imposed to bring down the sulfur content in fuel to less than 10 ppm. In recent years, novel deep eutectic solvents (DESs) have been developed to achieve deep desulfurization, particularly to extract thiophenic compounds from liquid fuels. These novel DESs, considered as analogous to ionic liquids are green, eco-friendly, inexpensive, and sustainable. We herein, using molecular dynamic simulation, analyze the interactions of metal-based DESs with model oil consisting of thiophenic compounds. The DES used consists of polyethylene glycol (PEG-200) as a hydrogen bond donor, choline chloride (ChCl) or tetrabutyl ammonium chloride (TBAC) as a hydrogen bond acceptor, and cobalt chloride (CoCl₂) as metal salt. In particular, the combination of ChCl: PEG-200:CoCl₂ at a ratio 1:2:1 and the combination of TBAC:PEG-200:CoCl₂ at a ratio 1:2:0.25 were simulated, separately, with model oil consisting of octane and thiophenes at 25ᵒC and 1 bar. The results of molecular dynamics simulations were analyzed in terms of interaction energies between different components. The simulations revealed a stronger interaction between DESs/thiophenes as compared with octane/thiophenes, suggestive of an efficient desulfurization process. In addition, our analysis suggests that the choice of hydrogen bond acceptor strongly influences the efficiency of the desulfurization process. Taken together, the results also show the importance of the metal ion, although present in small amount, in the process, and the role of the polymer in desulfurization of the model fuel.Keywords: deep eutectic solvents, desulfurization, molecular dynamics simulations, thiophenes
Procedia PDF Downloads 1462365 Early Childhood Care and Education in the North-West of Nigeria: Trends and Challenges
Authors: Muhammad Adamu Kwankwaso
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Early childhood is a critical period of rapid physical, cognitive and psycho-social development of a child. The quality of care and Education which a child receives at this crucial age will determine to a great extent the level of his/her physical and cognitive development in the future. In Nigeria, Early Childhood Care and Education (ECCE) is a fundamental aspect or form of Education for children between the age of 3-6. It was started after independence as pre-primary Education or early child development as contained in the 1977 National Policy on Education. The trends towards ECCE in Nigeria and the northwestern part of the country in particular keep up changing as in the case of other part of the world. The current trends are now towards expansions, inclusiveness, redefinition, early literacy, increased government participation and the unprecedented societal response and awareness towards the Education of the younger children. While all hands are on deck to ensure successful implementation of the ECCE programme, it is unfortunate that, ECCE is facing some challenges. This paper therefore, examines the trends in Early Childhood Care and Education and the major challenges in the north west of Nigeria. Some of the major challenges include, inadequate trained ECCE teachers, lack of unified curriculum, teacher pupil’s ratio, and the medium of instructions and inadequate infrastructural and teaching facilities respectively. To improve the situation the paper offered the following recommendations; establishment of more ECCE classes, enforcement for the use of mothers’ tongue or the languages of the immediate community as a medium of instructions, and adequate provision of infrastructural facilities and the unified curriculum across the northwestern States of Nigeria.Keywords: early childhood care, education, trends, challenges
Procedia PDF Downloads 4742364 Bimetallic Cu/Au Nanostructures and Bio-Application
Authors: Si Yin Tee
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Bimetallic nanostructures have received tremendous interests as a new class of nanomaterials which may have better technological usefulness with distinct properties from those of individual atoms and molecules or bulk matter. They excelled over the monometallic counterparts because of their improved electronic, optical and catalytic performances. The properties and the applicability of these bimetallic nanostructures not only depend on their size and shape, but also on the composition and their fine structure. These bimetallic nanostructures are potential candidates for bio-applications such as biosensing, bioimaging, biodiagnostics, drug delivery, targeted therapeutics, and tissue engineering. Herein, gold-incorporated copper (Cu/Au) nanostructures were synthesized through the controlled disproportionation of Cu⁺-oleylamine complex at 220 ºC to form copper nanowires and the subsequent reaction with Au³⁺ at different temperatures of 140, 220 and 300 ºC. This is to achieve their synergistic effect through the combined use of the merits of low-cost transition and high-stability noble metals. Of these Cu/Au nanostructures, Cu/Au nanotubes display the best performance towards electrochemical non-enzymatic glucose sensing, originating from the high conductivity of gold and the high aspect ratio copper nanotubes with high surface area so as to optimise the electroactive sites and facilitate mass transport. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose.Keywords: bimetallic, electrochemical sensing, glucose oxidation, gold-incorporated copper nanostructures
Procedia PDF Downloads 5212363 Development of Personal Protection Equipment for Dental Surgeon
Authors: Thi. A. D. Tran, Matthieu Arnold, Dominique Adolphe, Laurence Schcher, Guillaume Reys
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During daily oral health cares, dental surgeons are in contact with numerous potentially infectious germs from patients' saliva and blood. In order to take into account these risks, a product development process has been unrolled to propose to the dental surgeon a personal protection equipment that is suitable with their expectations in terms of images, protection and comfort. After a consumer study, to evaluate how the users wear the garment and their expectations, specifications have been carried out and technical solutions have been developed in order to answer to the maximum of the desiderata. Thermal studies and comfort studies have been performed. The obtained results lead to define the technical solutions concerning the design of the new scrub. Three main functions have been investigated, the ergonomic aspect, the protection and the thermal comfort. In terms of ergonomic aspect, instrumented garments have been worn and pressure measurements have been done. The results highlight that a raglan shape for the sleeves has to be selected for a better dynamic comfort. Moreover, spray tests helped us to localize the potential contamination area and therefore protection devices have been placed on the garment. Concerning the thermal comfort, an I-R study was conducted in consulting room under the real working conditions; the heating zones have been detected. Based on these results, solutions have been proposed and implemented in a new gown. This new gown is currently composed of three different parts; a protective layer placed in the chest area to avoid contamination; a breathable layer placed in the back and in the armpits and a normal PET/Cotton fabric for the rest of the gown. Through the fitting tests conducted in hospital, it was obtained that the new design was highly appreciated. Some points can nevertheless be further improved. A final product will be produced based on necessary improvements.Keywords: comfort, dentists, garment, thermal
Procedia PDF Downloads 3102362 BiFeO3-CoFe2O4-PbTiO3 Composites: Structural, Multiferroic and Optical Characteristics
Authors: Nidhi Adhlakha, K. L. Yadav
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Three phase magnetoelectric (ME) composites (1-x)(0.7BiFeO3-0.3CoFe2O4)-xPbTiO3 (or equivalently written as (1-x)(0.7BFO-0.3CFO)-xPT) with x variations 0, 0.30, 0.35, 0.40, 0.45 and 1.0 were synthesized using hybrid processing route. The effects of PT addition on structural, multiferroic and optical properties have been subsequently investigated. A detailed Rietveld refinement analysis of X-ray diffraction patterns has been performed, which confirms the presence of structural phases of individual constituents in the composites. Field emission scanning electron microscopy (FESEM) images are taken for microstructural analysis and grain size determination. Transmission electron microscopy (TEM) analysis of 0.3CFO-0.7BFO reveals the average particle size to be lying in the window of 8-10 nm. The temperature dependent dielectric constant at various frequencies (1 kHz, 10 kHz, 50 kHz, 100 kHz and 500 kHz) has been studied and the dielectric study reveals that the increase of dielectric constant and decrease of average dielectric loss of composites with incorporation of PT content. The room temperature ferromagnetic behavior of composites is confirmed through the observation of Magnetization vs. Magnetic field (M-H) hysteresis loops. The variation of magnetization with temperature indicates the presence of spin glass behavior in composites. Magnetoelectric coupling is evidenced in the composites through the observation of the dependence of the dielectric constant on the magnetic field, and magnetodielectric response of 2.05 % is observed for 45 mol% addition of PT content. The fractional change of magnetic field induced dielectric constant can also be expressed as ∆ε_r~γM^2 and the value of γ is found to be ~1.08×10-2 (emu/g)-2 for composite with x=0.40. Fourier transformed infrared (FTIR) spectroscopy of samples is carried out to analyze various bonds formation in the composites.Keywords: composite, X-ray diffraction, dielectric properties, optical properties
Procedia PDF Downloads 3082361 A Case Study on the Seismic Performance Assessment of the High-Rise Setback Tower Under Multiple Support Excitations on the Basis of TBI Guidelines
Authors: Kamyar Kildashti, Rasoul Mirghaderi
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This paper describes the three-dimensional seismic performance assessment of a high-rise steel moment-frame setback tower, designed and detailed per the 2010 ASCE7, under multiple support excitations. The vulnerability analyses are conducted based on nonlinear history analyses under a set of multi-directional strong ground motion records which are scaled to design-based site-specific spectrum in accordance with ASCE41-13. Spatial variation of input motions between far distant supports of each part of the tower is considered by defining time lag. Plastic hinge monotonic and cyclic behavior for prequalified steel connections, panel zones, as well as steel columns is obtained from predefined values presented in TBI Guidelines, PEER/ATC72 and FEMA P440A to include stiffness and strength degradation. Inter-story drift ratios, residual drift ratios, as well as plastic hinge rotation demands under multiple support excitations, are compared to those obtained from uniform support excitations. Performance objectives based on acceptance criteria declared by TBI Guidelines are compared between uniform and multiple support excitations. The results demonstrate that input motion discrepancy results in detrimental effects on the local and global response of the tower.Keywords: high-rise building, nonlinear time history analysis, multiple support excitation, performance-based design
Procedia PDF Downloads 2852360 Enhancement of 2, 4-Dichlorophenoxyacetic Acid Solubility via Solid Dispersion Technique
Authors: Tamer M. Shehata, Heba S. Elsewedy, Mashel Al Dosary, Alaa Elshehry, Mohamed A. Khedr, Maged E. Mohamed
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Objective: 2,4-Dichlorophenoxy acetic acid (2,4-D) is a well-known herbicide widely used as a weed killer. Recently, 2,4-D was rediscovered as a new anti-inflammatory agent through in silico as well as in-vivo experiments. However, poor solubility of 2,4-D could represent a problems during pharmaceutical development in addition to lower bioavailability. Solid dispersion (SD) refers to a group of solid products consisting of at least two different components, usually a hydrophobic drug and hydrophilic matrix. It is well known technique for enhancing drug solubility. Therefore, selecting SD as a tool for enhancing 2,4-D could be of great interest to the formulator. Method: In our project, several polymers were investigated (such as PEG, HPMC, citric acid and others) in addition to drug polymer ratios and its effect on solubility. Evaluation of drug polymer interaction was investigated through both Fourier Transform Infrared (FTIR) and Differential Scanning Calorimetry (DSC). Finally, in-vivo evaluation was performed for the best selected preparation through inflammatory response of rat induce hind paw. Results: Results indicated that, citric acid 2,4-D and in ratio of 0.75 : 1 showed modified the dissolution profile of the drug. The FTIR resltes indicated no significant chemical interaction, however DSC showed shifting of the drug melting point. Finally, Carragenan induced rat hind paw edema showed significant reduction of the drug solid dispersion in comparison to the pure drug, indicating rapid and complete absorption of the drug in solid dispersion form. Conclusion: Solid dispersion technology can be utilized efficiently to enhance the solubility of 2,4-D.Keywords: solid dispersion, 2, 4-D solubility, carragenan induced edema
Procedia PDF Downloads 4532359 Synthesis of a Hybrid of PEG-b-PCL and G1-PEA Dendrimer Based Six-Armed Star Polymer for Nano Delivery of Vancomycin
Authors: Calvin A. Omolo, Rahul S. Kalhapure, Mahantesh Jadhav, Sanjeev Rambharose, Chunderika Mocktar, Thirumala Govender
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Treatment of infections is compromised by limitations of conventional dosage forms and drug resistance. Nanocarrier system is a strategy to overcome these challenges and improve therapy. Thus, the development of novel materials for drug delivery via nanocarriers is essential. The aim of the study was to synthesize a multi-arm polymer (6-mPEPEA) for enhanced activity of vancomycin (VM) against susceptible and resistant Staphylococcus aureus (MRSA). The synthesis steps of the star polymer followed reported procedures. The synthesized 6-mPEPEA was characterized by FTIR, ¹H and ¹³CNMR and MTT assays. VM loaded micelles were prepared from 6-mPEPEA and characterized for size, polydispersity index (PI) and surface charge (ZP) (Dynamic Light Scattering), morphology by TEM, drug loading (UV Spectrophotometry), drug release (dialysis bag), in vitro and in vivo efficacy against sensitive and resistant S. aureus. 6-mPEPEA was synthesized, and its structure was confirmed. MTT assays confirmed its nontoxic nature with a high cell viability (77%-85%). Unimolecular spherical micelles were prepared. Size, PI, and ZP was 52.48 ± 2.6 nm, 0.103 ± 0.047, -7.3 ± 1.3 mV, respectively and drug loading was 62.24 ± 3.8%. There was a 91% drug release from VCM-6-mPEPEA after 72 hours. In vitro antibacterial test revealed that VM-6-mPEPEA had 8 and 16-fold greater activity against S. aureus and MRSA when compared to bare VM. Further investigations using flow cytometry showed that VM-6-mPEPEA had 99.5% killing rate of MRSA at the MIC concentration. In vivo antibacterial activity revealed that treatment with VM-6-mPEPEA had a 190 and a 15-fold reduction in the MRSA load in untreated and VM treated respectively. These findings confirmed the potential of 6-mPEPEA as a promising bio-degradable nanocarrier for antibiotic delivery to improve treatment of bacterial infections.Keywords: biosafe, MRSA, nanocarrier, resistance, unimolecular-micelles
Procedia PDF Downloads 1882358 Effect of Microstructure and Texture of Magnesium Alloy Due to Addition of Pb
Authors: Yebeen Ji, Jimin Yun, Kwonhoo Kim
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Magnesium alloys were limited for industrial applications due to having a limited slip system and high plastic anisotropy. It has been known that specific textures were formed during processing (rolling, etc.), and These textures cause poor formability. To solve these problems, many researchers have studied controlling texture by adding rare-earth elements. However, the high cost limits their use; therefore, alternatives are needed to replace them. Although Pb addition doesn’t directly improve magnesium properties, it has been known to suppress the diffusion of other alloying elements and reduce grain boundary energy. These characteristics are similar to the additions of rare-earth elements, and a similar texture behavior is expected as well. However, there is insufficient research on this. Therefore, this study investigates the behavior of texture and microstructure development after adding Pb to magnesium. This study compared and analyzed AZ61 alloy and Mg-15wt%Pb alloy to determine the effect of adding solute elements. The alloy was hot rolled and annealed to form a single phase and initial texture. Afterward, the specimen was set to contraction and elongate parallel to the rolling surface and the rolling direction and then subjected to high-temperature plane strain compression under the conditions of 723K and 0.05/s. Microstructural analysis and texture measurements were performed by SEM-EBSD. The peak stress in the true strain-stress curve after compression was higher in AZ61, but the shape of the flow curve was similar for both alloys. For both alloys, continuous dynamic recrystallization was confirmed to occur during the compression process. The basal texture developed parallel to the compressed surface, and the pole density was lower in the Mg-15wt%Pb alloy. It is confirmed that this change in behavior is because the orientation distribution of recrystallized grains has a more random orientation compared to the parent grains when Pb is added.Keywords: Mg, texture, Pb, DRX
Procedia PDF Downloads 492357 Rheological Evaluation of Wall Materials and β-Carotene Loaded Microencapsules
Authors: Gargi Ghoshal, Ashay Jain, Deepika Thakur, U. S. Shivhare, O. P. Katare
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The main objectives of this work were the rheological characterization of dispersions, emulsions at different pH used in the microcapsules preparation and the microcapsules obtain from gum arabic (A), guar gum (G), casein (C) and whey protein isolate (W) to keep β-carotene protected from degradation using the complex coacervation microencapsulation technique (CCM). The evaluation of rheological properties of dispersions, emulsions of different pH and so obtained microencapsules manifest the changes occur in the molecular structure of wall materials during the encapsulation process of β-carotene. These dispersions, emulsions of different pH and formulated microencapsules were subjected to go through various conducted experiments (flow curve test, amplitude sweep, and frequency sweep test) using controlled stress dynamic rheometer. Flow properties were evaluated as a function of apparent viscosity under steady shear rate ranging from 0.1 to 100 s-1. The frequency sweep test was conducted to determine the extent of viscosity and elasticity present in the samples at constant strain under changing angular frequency range from 0.1 to 100 rad/s at 25ºC. The dispersions and emulsion exhibited a shear thinning non-Newtonian behavior whereas microencapsules are considered as shear-thickening respectively. The apparent viscosity for dispersion, emulsions were decreased at low shear rates 20 s-1 and for microencapsules, it decreases up to ~50 s-1 besides these value, it has shown constant pattern. Oscillatory shear experiments showed a predominant viscous liquid behavior up to crossover frequencies of dispersions of C, W, A at 49.47 rad/s, 57.60 rad/s and 21.45 rad/s emulsion sample of AW at pH 5.0 it was 17.85 rad/s and GW microencapsules 61.40 rad/s respectively whereas no such crossover was found in G dispersion, emulsion with C and microencapsules still it showed more viscous behavior. Storage and loss modulus decreases with time also a shift of the crossover towards lower frequencies for A, W and C was observed respectively. However, their microencapsules showed more viscous behavior as compared to samples prior to blending.Keywords: viscosity, gums, proteins, frequency sweep test, apparent viscosity
Procedia PDF Downloads 2472356 Computational Aided Approach for Strut and Tie Model for Non-Flexural Elements
Authors: Mihaja Razafimbelo, Guillaume Herve-Secourgeon, Fabrice Gatuingt, Marina Bottoni, Tulio Honorio-De-Faria
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The challenge of the research is to provide engineering with a robust, semi-automatic method for calculating optimal reinforcement for massive structural elements. In the absence of such a digital post-processing tool, design office engineers make intensive use of plate modelling, for which automatic post-processing is available. Plate models in massive areas, on the other hand, produce conservative results. In addition, the theoretical foundations of automatic post-processing tools for reinforcement are those of reinforced concrete beam sections. As long as there is no suitable alternative for automatic post-processing of plates, optimal modelling and a significant improvement of the constructability of massive areas cannot be expected. A method called strut-and-tie is commonly used in civil engineering, but the result itself remains very subjective to the calculation engineer. The tool developed will facilitate the work of supporting the engineers in their choice of structure. The method implemented consists of defining a ground-structure built on the basis of the main constraints resulting from an elastic analysis of the structure and then to start an optimization of this structure according to the fully stressed design method. The first results allow to obtain a coherent return in the first network of connecting struts and ties, compared to the cases encountered in the literature. The evolution of the tool will then make it possible to adapt the obtained latticework in relation to the cracking states resulting from the loads applied during the life of the structure, cyclic or dynamic loads. In addition, with the constructability constraint, a final result of reinforcement with an orthogonal arrangement with a regulated spacing will be implemented in the tool.Keywords: strut and tie, optimization, reinforcement, massive structure
Procedia PDF Downloads 1412355 Early-Onset Asthma and Early Smoking Increase Risk of Bipolar Disorder in Adolescents and Young Adults
Authors: Meng-Huan Wu, Wei-Er Wang, Tsu-Nai Wang, Wei-Jian Hsu, Vincent Chin-Hung Chen
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Objective: Studies have reported a strong link between asthma and bipolar disorder. We conducted a 17-year community-based large cohort study to examine the relationship between asthma, early smoking initiation, and bipolar disorder during adolescence and early adulthood. Methods: A total of 162,766 participants aged 11–16 years were categorized into asthma and non-asthma groups at baseline and compared within the observation period. Covariates during late childhood or adolescence included parental education, cigarette smoking by family members of participants, and participant’s gender, age, alcohol consumption, smoking, and exercise habits. Data for urbanicity, prednisone use, allergic comorbidity, and Charlson comorbidity index were acquired from the National Health Insurance Research Database. The Cox proportional-hazards model was used to evaluate the association between asthma and bipolar disorder. Results: Our findings revealed that asthma increased the risk of bipolar disorder after adjustment for key confounders in the Cox proportional hazard regression model (adjusted HR: 1.31, 95% CI: 1.12-1.53). Hospitalizations or visits to the emergency department for asthma exhibited a dose–response effect on bipolar disorder (adjusted HR: 1.59, 95% CI: 1.22-2.06). Patients with asthma with onset before 20 years of age who smoked during late childhood or adolescence had the greatest risk for bipolar disorder (adjusted HR: 3.10, 95% CI: 1.29-7.44). Conclusions: Patients newly diagnosed with asthma had a 1.3 times higher risk of developing bipolar disorder. Smoking during late childhood or adolescence increases the risk of developing bipolar disorder in patients with asthma.Keywords: adolescence, asthma, smoking, bipolar disorder, early adulthood
Procedia PDF Downloads 3372354 The Impact of Artificial Intelligence on Digital Crime
Authors: Á. L. Bendes
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By the end of the second decade of the 21st century, artificial intelligence (AI) has become an unavoidable part of everyday life and has necessarily aroused the interest of researchers in almost every field of science. This is no different in the case of jurisprudence, whose main task is not only to create its own theoretical paradigm related to AI. Perhaps the biggest impact on digital crime is artificial intelligence. In addition, the need to create legal frameworks suitable for the future application of the law has a similar importance. The prognosis according to which AI can reshape the practical application of law and, ultimately, the entire legal life is also of considerable importance. In the past, criminal law was basically created to sanction the criminal acts of a person, so the application of its concepts with original content to AI-related violations is not expected to be sufficient in the future. Taking this into account, it is necessary to rethink the basic elements of criminal law, such as the act and factuality, but also, in connection with criminality barriers and criminal sanctions, several new aspects have appeared that challenge both the criminal law researcher and the legislator. It is recommended to continuously monitor technological changes in the field of criminal law as well since it will be timely to re-create both the legal and scientific frameworks to correctly assess the events related to them, which may require a criminal law response. Artificial intelligence has completely reformed the world of digital crime. New crimes have appeared, which the legal systems of many countries do not or do not adequately regulate. It is considered important to investigate and sanction these digital crimes. The primary goal is prevention, for which we need a comprehensive picture of the intertwining of artificial intelligence and digital crimes. The goal is to explore these problems, present them, and create comprehensive proposals that support legal certainty.Keywords: artificial intelligence, chat forums, defamation, international criminal cooperation, social networking, virtual sites
Procedia PDF Downloads 892353 Study on the Effects of Geometrical Parameters of Helical Fins on Heat Transfer Enhancement of Finned Tube Heat Exchangers
Authors: H. Asadi, H. Naderan Tahan
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The aim of this paper is to investigate the effect of geometrical properties of helical fins in double pipe heat exchangers. On the other hand, the purpose of this project is to derive the hydraulic and thermal design tables and equations of double heat exchangers with helical fins. The numerical modeling is implemented to calculate the considered parameters. Design tables and correlated equations are generated by repeating the parametric numerical procedure for different fin geometries. Friction factor coefficient and Nusselt number are calculated for different amounts of Reynolds, fluid Prantle and fin twist angles for the range of laminar fluid flow in annular tube with helical fins. Results showed that friction factor coefficient and Nusselt number will be increased for higher Reynolds numbers and fins’ twist angles in general. These two parameters follow different patterns in response to Reynolds number increment. Thermal performance factor is defined to analyze these different patterns. Temperature and velocity contours are plotted against twist angle and number of fins to describe the changes in flow patterns in different geometries of twisted finned annulus. Finally twisted finned annulus friction factor coefficient, Nusselt Number and thermal performance factor are correlated by simulating the model in different design points.Keywords: double pipe heat exchangers, heat exchanger performance, twisted fins, computational fluid dynamics
Procedia PDF Downloads 2892352 Use Cloud-Based Watson Deep Learning Platform to Train Models Faster and More Accurate
Authors: Susan Diamond
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Machine Learning workloads have traditionally been run in high-performance computing (HPC) environments, where users log in to dedicated machines and utilize the attached GPUs to run training jobs on huge datasets. Training of large neural network models is very resource intensive, and even after exploiting parallelism and accelerators such as GPUs, a single training job can still take days. Consequently, the cost of hardware is a barrier to entry. Even when upfront cost is not a concern, the lead time to set up such an HPC environment takes months from acquiring hardware to set up the hardware with the right set of firmware, software installed and configured. Furthermore, scalability is hard to achieve in a rigid traditional lab environment. Therefore, it is slow to react to the dynamic change in the artificial intelligent industry. Watson Deep Learning as a service, a cloud-based deep learning platform that mitigates the long lead time and high upfront investment in hardware. It enables robust and scalable sharing of resources among the teams in an organization. It is designed for on-demand cloud environments. Providing a similar user experience in a multi-tenant cloud environment comes with its own unique challenges regarding fault tolerance, performance, and security. Watson Deep Learning as a service tackles these challenges and present a deep learning stack for the cloud environments in a secure, scalable and fault-tolerant manner. It supports a wide range of deep-learning frameworks such as Tensorflow, PyTorch, Caffe, Torch, Theano, and MXNet etc. These frameworks reduce the effort and skillset required to design, train, and use deep learning models. Deep Learning as a service is used at IBM by AI researchers in areas including machine translation, computer vision, and healthcare.Keywords: deep learning, machine learning, cognitive computing, model training
Procedia PDF Downloads 2092351 Urban Heat Islands Analysis of Matera, Italy Based on the Change of Land Cover Using Satellite Landsat Images from 2000 to 2017
Authors: Giuseppina Anna Giorgio, Angela Lorusso, Maria Ragosta, Vito Telesca
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Climate change is a major public health threat due to the effects of extreme weather events on human health and on quality of life in general. In this context, mean temperatures are increasing, in particular, extreme temperatures, with heat waves becoming more frequent, more intense, and longer lasting. In many cities, extreme heat waves have drastically increased, giving rise to so-called Urban Heat Island (UHI) phenomenon. In an urban centre, maximum temperatures may be up to 10° C warmer, due to different local atmospheric conditions. UHI occurs in the metropolitan areas as function of the population size and density of a city. It consists of a significant difference in temperature compared to the rural/suburban areas. Increasing industrialization and urbanization have increased this phenomenon and it has recently also been detected in small cities. Weather conditions and land use are one of the key parameters in the formation of UHI. In particular surface urban heat island is directly related to temperatures, to land surface types and surface modifications. The present study concern a UHI analysis of Matera city (Italy) based on the analysis of temperature, change in land use and land cover, using Corine Land Cover maps and satellite Landsat images. Matera, located in Southern Italy, has a typical Mediterranean climate with mild winters and hot and humid summers. Moreover, Matera has been awarded the international title of the 2019 European Capital of Culture. Matera represents a significant example of vernacular architecture. The structure of the city is articulated by a vertical succession of dug layers sometimes excavated or partly excavated and partly built, according to the original shape and height of the calcarenitic slope. In this study, two meteorological stations were selected: MTA (MaTera Alsia, in industrial zone) and MTCP (MaTera Civil Protection, suburban area located in a green zone). In order to evaluate the increase in temperatures (in terms of UHI occurrences) over time, and evaluating the effect of land use on weather conditions, the climate variability of temperatures for both stations was explored. Results show that UHI phenomena is growing in Matera city, with an increase of maximum temperature values at a local scale. Subsequently, spatial analysis was conducted by Landsat satellite images. Four years was selected in the summer period (27/08/2000, 27/07/2006, 11/07/2012, 02/08/2017). In Particular, Landsat 7 ETM+ for 2000, 2006 and 2012 years; Landsat 8 OLI/TIRS for 2017. In order to estimate the LST, Mono Window Algorithm was applied. Therefore, the increase of LST values spatial scale trend has been verified, in according to results obtained at local scale. Finally, the analysis of land use maps over the years by the LST and/or the maximum temperatures measured, show that the development of industrialized area produces a corresponding increase in temperatures and consequently a growth in UHI.Keywords: climate variability, land surface temperature, LANDSAT images, urban heat island
Procedia PDF Downloads 1242350 Competency and Strategy Formulation in Automobile Industry
Authors: Chandan Deep Singh
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In present days, companies are facing the rapid competition in terms of customer requirements to be satisfied, new technologies to be integrated into future products, new safety regulations to be followed, new computer-based tools to be introduced into design activities that becomes more scientific. In today’s highly competitive market, survival focuses on various factors such as quality, innovation, adherence to standards, and rapid response as the basis for competitive advantage. For competitive advantage, companies have to produce various competencies: for improving the capability of suppliers and for strengthening the process of integrating technology. For more competitiveness, organizations should operate in a strategy driven way and have a strategic architecture for developing core competencies. Traditional ways to take such experience and develop competencies tend to take a lot of time and they are expensive. A new learning environment, which is built around a gaming engine, supports the development of competences in specific subject areas. Technology competencies have a significant role in firm innovation and competitiveness; they interact with the competitive environment. Technological competencies vary according to the type of competitive environment, thus enhancing firm innovativeness. Technological competency is gained through extensive experimentation and learning in its research, development and employment in manufacturing. This is a review paper based on competency and strategic success of automobile industry. The aim here is to study strategy formulation and competency tools in the industry. This work is a review of literature related to competency and strategy in automobile industry. This study involves review of 34 papers related to competency and strategy.Keywords: manufacturing competency, strategic success, competitiveness, strategy formulation
Procedia PDF Downloads 3112349 Structural Fluxionality of Luminescent Coordination Compounds with Lanthanide Ions
Authors: Juliana A. B. Silva, Caio H. T. L. Albuquerque, Leonardo L. dos Santos, Cristiane K. Oliveira, Ivani Malvestiti, Fernando Hallwass, Ricardo L. Longo
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Complexes with lanthanide ions have been extensively studied due to their applications as luminescent, magnetic and catalytic materials as molecular or extended crystals, thin films, glasses, polymeric matrices, ionic liquids, and in solution. NMR chemical shift data in solution have been reported and suggest fluxional structures in a wide range of coordination compounds with rare earth ions. However, the fluxional mechanisms for these compounds are still not established. This structural fluxionality may affect the photophysical, catalytic and magnetic properties in solution. Thus, understanding the structural interconversion mechanisms may aid the design of coordination compounds with, for instance, improved (electro)luminescence, catalytic and magnetic behaviors. The [Eu(btfa)₃bipy] complex, where btfa= 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and bipy= 2,2’-bipiridyl, has a well-defined X-ray crystallographic structure and preliminary 1H NMR data suggested a structural fluxionality. Thus, we have investigated a series of coordination compounds with lanthanide ions [Ln(btfa)₃L], where Ln = La, Eu, Gd or Yb and L= bipy or phen (phen=1,10-phenanthroline) using a combined theoretical-experimental approach. These complexes were synthesized and fully characterized, and detailed NMR measurements were obtained. They were also studied by quantum chemical computational methods (DFT-PBE0). The aim was to determine the relevant factors in the structure of these compounds that favor or not the fluxional behavior. Measurements of the 1H NMR signals at variable temperature in CD₂Cl₂ of the [Eu(btfa)₃L] complexes suggest that these compounds have a fluxional structure, because the crystal structure has non-equivalent btfa ligands that should lead to non-equivalent hydrogen atoms and thus to more signals in the NMR spectra than those obtained at room temperature, where all hydrogen atoms of the btfa ligands are equivalent, and phen ligand has an effective vertical symmetry plane. For the [Eu(btfa)₃bipy] complex, the broadening of the signals at –70°C provides a lower bound for the coalescence temperature, which indicates the energy barriers involved in the structural interconversion mechanisms are quite small. These barriers and, consequently, the coalescence temperature are dependent upon the radii of the lanthanide ion as well as to their paramagnetic effects. The PBE0 calculated structures are in very good agreement with the crystallographic data and, for the [Eu(btfa)₃bipy] complex, this method provided several distinct structures with almost the same energy. However, the energy barrier for structural interconversion via dissociative pathways were found to be quite high and could not explain the experimental observations. Whereas the pseudo-rotation pathways, involving the btfa and bipy ligands, have very small activation barriers, in excellent agreement with the NMR data. The results also showed an increase in the activation barrier along the lanthanide series due to the decrease of the ionic radii and consequent increase of the steric effects. TD-DFT calculations showed a dependence of the ligand donor state energy with different structures of the complex [Eu(btfa)₃phen], which can affect the energy transfer rates and the luminescence. The energy required to promote the structural fluxionality may also enhance the luminescence quenching in solution. These results can aid in the design of more luminescent compounds and more efficient devices.Keywords: computational chemistry, lanthanide-based compounds, NMR, structural fluxionality
Procedia PDF Downloads 199