Search results for: time series chaos

Authors: Bryce Benson, Sooin Lee, Ashwin Belle

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Unrecognized or delayed identification of patient deterioration is a key cause of in-hospitals adverse events. Clinicians rely on vital signs monitoring to recognize patient deterioration. However, due to ever increasing nursing workloads and the manual effort required, vital signs tend to be measured and recorded intermittently, and inconsistently causing large gaps during patient monitoring. Additionally, during deterioration, the body’s autonomic nervous system activates compensatory mechanisms causing the vital signs to be lagging indicators of underlying hemodynamic decline. This study analyzes the predictive efficacy of the Analytic for Hemodynamic Instability (AHI) system, an automated tool that was designed to help clinicians in early identification of deteriorating patients. The lead time analysis in this retrospective observational study assesses how far in advance AHI predicted deterioration prior to the start of an episode of hemodynamic instability (HI) becoming evident through vital signs? Results indicate that of the 362 episodes of HI in this study, 308 episodes (85%) were correctly predicted by the AHI system with a median lead time of 57 minutes and an average of 4 hours (240.5 minutes). Of the 54 episodes not predicted, AHI detected 45 of them while the episode of HI was ongoing. Of the 9 undetected, 5 were not detected by AHI due to either missing or noisy input ECG data during the episode of HI. In total, AHI was able to either predict or detect 98.9% of all episodes of HI in this study. These results suggest that AHI could provide an additional ‘pair of eyes’ on patients, continuously filling the monitoring gaps and consequently giving the patient care team the ability to be far more proactive in patient monitoring and adverse event management.

Keywords: clinical deterioration prediction, decision support system, early warning system, hemodynamic status, physiologic monitoring

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Authors: Esmael Makarian, Ayub Elyasi, Fatemeh Saberi, Olusegun Stanley Tomomewo

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Rock mechanical investigation is one of the most crucial activities in underground operations, especially in surveys related to hydrocarbon exploration and production, geothermal reservoirs, energy storage, mining, and geotechnics. There is a wide range of traditional methods for driving, collecting, and analyzing rock mechanics data. However, these approaches may not be suitable or work perfectly in some situations, such as fractured zones. Cutting-edge technologies have been provided to solve and optimize the mentioned issues. Internet of Things (IoT), Edge, and Cloud Computing technologies (ECt & CCt, respectively) are among the most widely used and new artificial intelligence methods employed for geomechanical studies. IoT devices act as sensors and cameras for real-time monitoring and mechanical-geological data collection of rocks, such as temperature, movement, pressure, or stress levels. Structural integrity, especially for cap rocks within hydrocarbon systems, and rock mass behavior assessment, to further activities such as enhanced oil recovery (EOR) and underground gas storage (UGS), or to improve safety risk management (SRM) and potential hazards identification (P.H.I), are other benefits from IoT technologies. EC techniques can process, aggregate, and analyze data immediately collected by IoT on a real-time scale, providing detailed insights into the behavior of rocks in various situations (e.g., stress, temperature, and pressure), establishing patterns quickly, and detecting trends. Therefore, this state-of-the-art and useful technology can adopt autonomous systems in rock mechanical surveys, such as drilling and production (in hydrocarbon wells) or excavation (in mining and geotechnics industries). Besides, ECt allows all rock-related operations to be controlled remotely and enables operators to apply changes or make adjustments. It must be mentioned that this feature is very important in environmental goals. More often than not, rock mechanical studies consist of different data, such as laboratory tests, field operations, and indirect information like seismic or well-logging data. CCt provides a useful platform for storing and managing a great deal of volume and different information, which can be very useful in fractured zones. Additionally, CCt supplies powerful tools for predicting, modeling, and simulating rock mechanical information, especially in fractured zones within vast areas. Also, it is a suitable source for sharing extensive information on rock mechanics, such as the direction and size of fractures in a large oil field or mine. The comprehensive review findings demonstrate that digital transformation through integrated IoT, Edge, and Cloud solutions is revolutionizing traditional rock mechanical investigation. These advanced technologies have empowered real-time monitoring, predictive analysis, and data-driven decision-making, culminating in noteworthy enhancements in safety, efficiency, and sustainability. Therefore, by employing IoT, CCt, and ECt, underground operations have experienced a significant boost, allowing for timely and informed actions using real-time data insights. The successful implementation of IoT, CCt, and ECt has led to optimized and safer operations, optimized processes, and environmentally conscious approaches in underground geological endeavors.

Keywords: rock mechanical studies, internet of things, edge computing, cloud computing, underground surveys, geological operations

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Authors: Munenari Inoguchi, Keiko Tamura

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In Japan, we were suffered by earthquake, typhoon, and flood disaster in 2019. Especially, 38 of 47 prefectures were affected by typhoon #1919 occurred in October 2019. By this disaster, 99 people were dead, three people were missing, and 484 people were injured as human damage. Furthermore, 3,081 buildings were totally collapsed, 24,998 buildings were half-collapsed. Once disaster occurs, local responders have to inspect damage level of each building by themselves in order to certificate building damage for survivors for starting their life reconstruction process. At that disaster, the total number to be inspected was so high. Based on this situation, Cabinet Office of Japan approved the way to detect building damage level efficiently, that is collectively detection. However, they proposed a just guideline, and local responders had to establish the concrete and infallible method by themselves. Against this issue, we decided to establish the effective and efficient methodology to detect building damage level collectively with flood depth. Besides, we thought that the flood depth was relied on the land height, and we decided to utilize GIS (Geographic Information System) for analyzing the elevation spatially. We focused on the analyzing tool of spatial interpolation, which is utilized to survey the ground water level usually. In establishing the methodology, we considered 4 key-points: 1) how to satisfy the condition defined in the guideline approved by Cabinet Office for detecting building damage level, 2) how to satisfy survivors for the result of building damage level, 3) how to keep equitability and fairness because the detection of building damage level was executed by public institution, 4) how to reduce cost of time and human-resource because they do not have enough time and human-resource for disaster response. Then, we proposed a methodology for detecting building damage level collectively with flood depth utilizing GIS with five steps. First is to obtain the boundary of flooded area. Second is to collect the actual flood depth as sampling over flooded area. Third is to execute spatial analysis of interpolation with sampled flood depth to detect two-dimensional flood depth extent. Fourth is to divide to blocks by four categories of flood depth (non-flooded, over the floor to 100 cm, 100 cm to 180 cm and over 180 cm) following lines of roads for getting satisfaction from survivors. Fifth is to put flood depth level to each building. In Koriyama city of Fukushima prefecture, we proposed the methodology of collectively detection for building damage level as described above, and local responders decided to adopt our methodology at typhoon #1919 in 2019. Then, we and local responders detect building damage level collectively to over 1,000 buildings. We have received good feedback that the methodology was so simple, and it reduced cost of time and human-resources.

Keywords: building damage inspection, flood, geographic information system, spatial interpolation

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Authors: Amamra Ryma, Djebar Mohamed Reda, Moumeni Ouissem, Otmani Hadjer, Berrebbah Houria

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The problem of environmental contamination by the excessive use of organics cannot be neglected. Extensive application is usually companied with serious problems and health risk. It is established that many chemicals, in common use, can produce some toxic effects on biological systems through their mode of action or by production of free radicals that damage all cell compounds. Deltamethrin, a widely used type II pyrethroid pesticide, is one of the most common contaminants in freshwater aquatic system. In this study, we investigate the effects of deltamethrin exposure on the induction of oxidative stress to the freshwater ciliate Paramecium tetraurelia. After the treatment of paramecium cells with increasing concentrations of insecticide, we followed up the growth kinetics, generation time and the percentage response. Also, we studied the variation in biomarkers of stress such as: GSH content, GST, GPX and CAT activities. Our results showed a significant decrease in the proliferation of cells correlated by the decrease in generation number and the increase in generation time. Also, we noted an inhibition in the percentage response. The monitoring of biomarkers revealed depletion in GSH content in a proportional and dose dependent manner accompanied by an increase in the GST activity. In parallel, a strong induction in the CAT and GPX activities was noted specially for the highest dose. In summary, under the current experimental conditions, deltamethrin is highly toxic to the freshwater ciliate Paramecium tetraurelia. Exposure to low concentrations showed significant adverse on growth accompanied with the induction of oxidative damage supported by the decrease in GSH content and the intensification of the antioxidant enzymes.

Keywords: deltamethrin, Paramecium tetraurelia, growth, oxidative stress, biomarkers, antioxidant

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Authors: Bara' Al-Mistarehi

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Documentation and assessment of conservation state of an archaeological structure is a significant procedure in any management plan. However, it has always been a challenge to apply this with a low coast and safe methodology. It is also a time-demanding procedure. Therefore, a low cost, efficient methodology for documenting the state of a structure is needed. In the scope of this research, this paper will employ digital photogrammetry and laser scanner to one of highly significant structures in Germany, The Old Castle (German: Altes Schloss). The site is well known for its unique features. However, the castle suffers from serious deterioration threats because of the environmental conditions and the absence of continuous monitoring, maintenance and repair plans. Digital photogrammetry is a generally accepted technique for the collection of 3D representations of the environment. For this reason, this image-based technique has been extensively used to produce high quality 3D models of heritage sites and historical buildings for documentation and presentation purposes. Additionally, terrestrial laser scanners are used, which directly measure 3D surface coordinates based on the run-time of reflected light pulses. These systems feature high data acquisition rates, good accuracy and high spatial data density. Despite the potential of each single approach, in this research work maximum benefit is to be expected by a combination of data from both digital cameras and terrestrial laser scanners. Within the paper, the usage, application and advantages of the technique will be investigated in terms of building high realistic 3D textured model for some parts of the old castle. The model will be used as diagnosing tool of the conservation state of the castle and monitoring mean for future changes.

Keywords: Digital photogrammetry, Terrestrial laser scanners, 3D textured model, archaeological structure

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Authors: S. Rozhkova, O. Rozhkova, A. Harlova, V. Lasukov

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For optimal unbiased filter as mean-square and in the case of functioning anomalous noises in the observation memory channel, we have proved insensitivity of filter to inaccurate knowledge of the anomalous noise intensity matrix and its equivalence to truncated filter plotted only by non anomalous components of an observation vector.

Keywords: mathematical expectation, filtration, anomalous noise, memory

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Authors: A. K. M. Zakir Hossain, Faruk-Ul Islam, Muhammad Alamgir Chowdhury, Kazi Morshed Alam, Md. Rashidul Islam, Muhammad Humayun Kabir, Noshin Ara Tunazzina, Taufiqur Rahman, Md. Ashik Mia, Ashaduzzaman Sagar

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The jute retting process is one of the key factors for the excellent jute fibre production as well as maintaining water quality. The traditional method of jute retting is time-consuming and hampers the fish cultivation by polluting the water body. Therefore, a low cost, time-saving, environment-friendly, and improved technique is essential for jute retting to overcome this problem. Thus the study was focused to compare the extent of water pollution and fibre quality of two retting systems, i.e., traditional retting practices over-improved retting method (macha retting) by assessing different physico-chemical and microbiological properties of water and fibre quality parameters. Water samples were collected from the top and bottom of the retting place at the early, mid, and final stages of retting from four districts of Bangladesh viz., Gaibandha, Kurigram, Lalmonirhat, and Rangpur. Different physico-chemical parameters of water samples viz., pH, dissolved oxygen (DO), conductivity (CD), total dissolved solids (TDS), hardness, calcium, magnesium, carbonate, bicarbonate, chloride, phosphorus and sulphur content were measured. Irrespective of locations, the DO of the final stage retting water samples was very low as compared to the mid and early stage, and the DO of traditional jute retting method was significantly lower than the improved macha method. The pH of the water samples was slightly more acidic in the traditional retting method than that of the improved macha method. Other physico-chemical parameters of the water sample were found higher in the traditional method over-improved macha retting in all the stages of retting. Bacterial species were isolated from the collected water samples following the dilution plate technique. Microbiological results revealed that water samples of improved macha method contained more bacterial species that are supposed to involve in jute retting as compared to water samples of the traditional retting method. The bacterial species were then identified by the sequencing of 16SrDNA. Most of the bacterial species identified belong to the genera Pseudomonas, Bacillus, Pectobacterium, and Stenotrophomonas. In addition, the tensile strength of the jute fibre was tested, and the results revealed that the improved macha method showed higher mechanical strength than the traditional method in most of the locations. The overall results indicate that the water and fibre quality were found better in the improved macha retting method than the traditional method. Therefore, a time-saving and cost-friendly improved macha retting method can be widely adopted for the jute retting process to get the quality jute fiber and to keep the environment clean and safe.

Keywords: jute retting methods, physico-chemical parameters, retting microbes, tensile strength, water quality

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Authors: Peter Boyes, Sarah Sharples, Paul Tennent, Gary Priestnall, Jeremy Morley

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Significant long-term investment projects can involve complex decisions. These are often described as capital projects, and the factors that contribute to their complexity include budgets, motivating reasons for investment, stakeholder involvement, interdependent projects, and the delivery phases required. The complexity of these projects often requires management groups to be established involving stakeholder representatives; these teams are inherently multidisciplinary. This study uses two university campus capital projects as case studies for this type of management group. Due to the interaction of projects with wider campus infrastructure and users, decisions are made at varying spatial granularity throughout the project lifespan. This spatial-related context brings complexity to the group decisions. Sensemaking is the process used to achieve group situational awareness of a complex situation, enabling the team to arrive at a consensus and make a decision. The purpose of this study is to understand the role of people and data in the complex spatial related long-term decision and sensemaking processes. The paper aims to identify and present issues experienced in practical settings of these types of decision. A series of exploratory semi-structured interviews with members of the two projects elicit an understanding of their operation. From two stages of thematic analysis, inductive and deductive, emergent themes are identified around the group structure, the data usage, and the decision making within these groups. When data were made available to the group, there were commonly issues with the perception of veracity and validity of the data presented; this impacted the ability of group to reach consensus and, therefore, for decisions to be made. Similarly, there were different responses to forecasted or modelled data, shaped by the experience and occupation of the individuals within the multidisciplinary management group. This paper provides an understanding of further support required for team sensemaking and decision making in complex capital projects. The paper also discusses the barriers found to effective decision making in this setting and suggests opportunities to develop decision support systems in this team strategic decision-making process. Recommendations are made for further research into the sensemaking and decision-making process of this complex spatial-related setting.

Keywords: decision making, decisions under uncertainty, real decisions, sensemaking, spatial, team decision making

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Authors: Sundaresan Soundararajan, Chor Ngee Tan

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Introduction: Pyogenic spondylitis, otherwise treated conservatively with long term antibiotics, would require surgical debridement and reconstruction in about 10% to 20% of cases. The classical approach adopted many surgeons have always been anterior approach in ensuring thorough and complete debridement. This, however, comes with high rates of morbidity due to the nature of its access. Direct lateral retroperitoneal approach, which has been growing in usage in degenerative lumbar diseases, has the potential in treating pyogenic spondylitis with its ease of approach and relatively low risk of complications. Aims/Objectives: The objective of this study was to evaluate the effectiveness and clinical outcome of using lateral approach surgery in the surgical management of pyogenic spondylitis of the lumbar spine. Methods: Retrospective chart analysis was done on all patients who presented with pyogenic spondylitis (lumbar discitis/vertebral osteomyelitis) and had undergone direct lateral retroperitoneal lumbar vertebral debridement and posterior instrumentation between 2014 and 2016. Data on blood loss, surgical operating time, surgical complications, clinical outcomes and fusion rates were recorded. Results: A total of 6 patients (3 male and 3 female) underwent this procedure at a single institution by a single surgeon during the defined period. One patient presented with infected implant (PLIF) and vertebral osteomyelitis while the other five presented with single level spondylodiscitis. All patients underwent lumbar debridement, iliac strut grafting and posterior instrumentation (revision of screws for infected PLIF case). The mean operating time was 308.3 mins for all 6 cases. Mean blood loss was reported at 341cc (range from 200cc to 600cc). Presenting symptom of back pain resolved in all 6 cases while 2 cases that presented with lower limb weakness had improvement of neurological deficits. One patient had dislodged strut graft while performing posterior instrumentation and needed graft revision intraoperatively. Infective markers normalized for all patients subsequently. All subjects also showed radiological evidence of fusion on 6 months follow up. Conclusions: Lateral approach in treating pyogenic spondylitis is a viable option as it allows debridement and reconstruction without the risk that comes with other anterior approaches. It allows efficient debridement, short surgical time, moderate blood loss and low risk of vascular injuries. Clinical outcomes and fusion rates by this approach also support its use as practical MIS option surgery for such infection cases.

Keywords: lateral approach, minimally invasive, pyogenic spondylitis, XLIF

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Authors: Younis R. Elhaddad, Mohamed A. Alshaari

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Since 2700 B.C the problem of constructing magic squares attracts many researchers. Magic squares one of most difficult challenges for mathematicians. In this work, we describe how to construct and enumerate Pan- magic squares using genetic algorithm, using new chromosome encoding technique. The results were promising within reasonable time.

Keywords: genetic algorithm, magic square, pan-magic square, computational intelligence

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Authors: Fatemeh Rezaei, Mohammad H. Yarmohammadian, Masoud Ferdosi, Abbas Haghshnas

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Background: Failure Modes and Effect Analysis is now having known as the main methods of risk assessment and the accreditation requirements for many organizations. The Risk Priority Number (RPN) approach is generally preferred, especially for its easiness of use. Indeed it does not require statistical data, but it is based on subjective evaluations given by the experts about the Occurrence (O i), the Severity (Si) and the Detectability (D i) of each cause of failure. Methods: This study is a quantitative – qualitative research. In terms of qualitative dimension, method of focus groups with inductive approach is used. To evaluate the results of the qualitative study, quantitative assessment was conducted to calculate RPN score. Results; We have studied patient’s journey process in surgery ward and the most important phase of the process determined Transport of the patient from the holding area to the operating room. Failures of the phase with the highest priority determined by defining inclusion criteria included severity (clinical effect, claim consequence, waste of time and financial loss), occurrence (time- unit occurrence and degree of exposure to risk) and preventability (degree of preventability and defensive barriers) and quantifying risks priority criteria in the context of RPN index. Ability of improved RPN reassess by root cause (RCA) analysis showed some variations. Conclusions: Finally, It could be concluded that understandable criteria should have been developed according to personnel specialized language and communication field. Therefore, participation of both technical and clinical groups is necessary to modify and apply these models.

Keywords: failure mode, effects analysis, risk priority number(RPN), health system, risk assessment

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Authors: Yuekun Chen, Yousef Sardahi, Salam Hajjar, Christopher Greer

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This paper presents a multi-objective optimal design of a cascade control system for an underactuated mechanical system. Cascade control structures usually include two control algorithms (inner and outer). To design such a control system properly, the following conflicting objectives should be considered at the same time: 1) the inner closed-loop control must be faster than the outer one, 2) the inner loop should fast reject any disturbance and prevent it from propagating to the outer loop, 3) the controlled system should be insensitive to measurement noise, and 4) the controlled system should be driven by optimal energy. Such a control problem can be formulated as a multi-objective optimization problem such that the optimal trade-offs among these design goals are found. To authors best knowledge, such a problem has not been studied in multi-objective settings so far. In this work, an underactuated mechanical system consisting of a rotary servo motor and a ball and beam is used for the computer simulations, the setup parameters of the inner and outer control systems are tuned by NSGA-II (Non-dominated Sorting Genetic Algorithm), and the dominancy concept is used to find the optimal design points. The solution of this problem is not a single optimal cascade control, but rather a set of optimal cascade controllers (called Pareto set) which represent the optimal trade-offs among the selected design criteria. The function evaluation of the Pareto set is called the Pareto front. The solution set is introduced to the decision-maker who can choose any point to implement. The simulation results in terms of Pareto front and time responses to external signals show the competing nature among the design objectives. The presented study may become the basis for multi-objective optimal design of multi-loop control systems.

Keywords: cascade control, multi-Loop control systems, multiobjective optimization, optimal control

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Authors: Lise P. Labéjof, Ivna Mororó, Raquel G. Bastos, Maria Isabel G. Severo, Arno H. de Oliveira

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This work presents an alternative mode of intestine mucosa renewal that may allow to better understand the total loss of villi after irradiation. It was tested a morphological method of 3d reconstruction using micrographs of serial sections of rat duodenum. We used hundreds of sections of each specimen of duodenum placed on glass slides and examined under a light microscope. Those containing the detachment, approximately a dozen, were chosen for observation under a transmission electron microscope (TEM). Each of these sections was glued on a block of epon resin and recut into a hundred of 60 nm-thick sections. Ribbons of these ultrathin sections were distributed on a series of copper grids in the same order of appearance than during the process of microstomia. They were then stained by solutions of uranyl and lead salts and observed under a TEM. The sections were pictured and the electron micrographs showing signs of cells detachment were transferred into two softwares, ImageJ to align the cellular structures and Reconstruct to realize the 3d reconstruction. It has been detected epithelial cells that exhibited all signs of programmed cell death and localized at the villus-crypt junction. Their nucleus was irregular in shape with a condensed chromatin in clumps. Their cytoplasm was darker than that of neighboring cells, containing many swollen mitochondria. In some places of the sections, we could see intercellular spaces enlarged by the presence of shrunk cells which displayed a plasma membrane with an irregular shape in thermowell as if the cell interdigitations would distant from each other. The three-dimensional reconstruction of the crypts has allowed observe gradual loss of intercellular contacts of crypt cells in the longitudinal plan of the duodenal mucosa. In the transverse direction, there was a gradual increase of the intercellular space as if these cells moved away from one another. This observation allows assume that the gradual remoteness of the cells at the villus-crypt junction is the beginning of the mucosa detachment. Thus, the shrinking of cells due to apoptosis is the way that they detach from the mucosa and progressively the villi also. These results are in agreement with our initial hypothesis and thus have demonstrated that the villi become detached from the mucosa at the villus-crypt junction by the programmed cell death process. This type of loss of entire villus helps explain the rapid denudation of the intestinal mucosa in case of irradiation.

Keywords: 3dr, transmission electron microscopy, ionizing radiations, rat small intestine, apoptosis

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Authors: Hsin-Yi Lo, Chia-Yu Hsu

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This article is the nursing experience of a multiple trauma case using Swanson's theory of caring, the nursing period is from May 31 to June 4, 2021, collect data through observation, written talks, interviews, listening, direct care and physical assessment, established cases with health problems such as acute pain, impaired tissue integrity, and anxiety. Nursing process including, evaluate the pain index with the pain assessment scale, assist in acupoint massage, use a corset to fix the wound, and give the patient listening to favorite radio programs to divert attention and relieve pain problems; promote wound healing and avoid infection by assessing wound condition and exudation, changing dressings with aseptic technique, and providing appropriate dressings; encourage patients to express their feelings, provide companionship, and assist in self-care and participation in treatment plans, to enable the case to overcome the anxiety caused by being admitted to the intensive care unit for the first time and not knowing about the disease, and assist the case to overcome the injury caused by the accident and return to normal life. There is no video equipment in the intensive care unit during the nursing period. In response to the problem that family visits cannot be opened during the epidemic, it is a limitation this time. It is recommended that the hospital take this into consideration in the future. In the post-epidemic era, it can reduce the risk of various infections for patients and family members. Traveling between home and hospital, improving the quality of high-quality and technological care.

Keywords: swanson's theory of caring, multiple trauma, anxiety, nursing experience

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Authors: M. S. Matlala, I. Ignatious

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Environmental sustainability has taken the center stage in human life all over the world. Energy is the most essential component of our life. The conventional sources of energy are non-renewable and have a detrimental environmental impact. Therefore, there is a need to move from conventional to non-conventional renewable energy sources to satisfy the world’s energy demands. The study aimed at screening for microbial cellulolytic enzymes using a proteomic approach. The objectives were to screen for microbial cellulases with high specific activity and separate the cellulolytic enzymes using a combination of zymography and two-dimensional (2-D) gel electrophoresis followed by tryptic digestion, Matrix-assisted Laser Desorption Ionisation-Time of Flight (MALDI-TOF) and bioinformatics analysis. Fungal and bacterial isolates were cultured in M9 minimal and Mandel media for a period of 168 hours at 60°C and 30°C with cellobiose and Avicel as carbon sources. Microbial cells were separated from supernatants through centrifugation, and the crude enzyme from the cultures was used for the determination of cellulase activity, zymography, SDS-PAGE, and two-dimensional gel electrophoresis. Five isolates, with lytic action on carbon sources studied, were a bacterial strain (BARK) and fungal strains (VCFF1, VCFF14, VCFF17, and VCFF18). Peak cellulase production by the selected isolates was found to be 3.8U/ml, 2.09U/ml, 3.38U/ml, 3.18U/ml, and 1.95U/ml, respectively. Two-dimensional gel protein maps resulted in the separation and quantitative expression of different proteins by the microbial isolates. MALDI-TOF analysis and database search showed that the expressed proteins in this study closely relate to different glycoside hydrolases produced by other microbial species with an acceptable confidence level of 100%.

Keywords: cellulases, energy, two-dimensional gel electrophoresis, matrix-assisted laser desorption ionisation-time of flight, MALDI-TOF MS

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

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

Keywords: carbon dioxide emissions, energy efficiency, sustainable transportation, system dynamics

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Authors: Sonia Mannan

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A qualitative study was conducted in a rural area of the southwestern region of Bangladesh to identify perceptions, practices, and the role of first-time mothers surrounding acute respiratory infections (ARI) in infants and children aged under four years. The study reveals that all mothers had knowledge of ARI and were able to identify a number of signs and symptoms. They also recognized pneumonia and thought it to be caused by exposure to cold or weather change, supernatural causes, evil influences, mothers’ negligence, and failure to observe ‘purdah’. They were able to identify chest retractions, difficult breathing, and inability to feed as signs of severe disease needing treatment outside the home. In these cases, spiritual healers were sought, and allopathic treatment was delayed or avoided. Home care practices involved massaging the child with oil and avoiding 'cooling' foods, including water. With the presence of fever and breathing difficulty, mothers tended to increase the number and diversity of medicines, although more concern was expressed about fever than about breathing difficulty. Effective medical care was more likely to be delayed for infants than for older children (they often waited 2-5 days after signs of illness appeared); infants were also more likely to be taken to a spiritual healer as the first-choice provider. The reasons for these perceptions and practices and their implications on the ARI of infants and young children are discussed. Community intervention is identified as viable, effective, and practical to address the body of local socio-cultural knowledge about family practices and the role of the mother regarding the mitigation of ARI in infants and young children.

Keywords: acute respiratory infections , public health, pneumonia, Bangladesh

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Authors: Silvia D. Vaca, Benjamin J. Kuo, Joao Ricardo Nickenig Vissoci, Catherine A. Staton, Linda W. Xu, Michael Muhumuza, Hussein Ssenyonjo, John Mukasa, Joel Kiryabwire, Henry E. Rice, Gerald A. Grant, Michael M. Haglund

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Background: Patients with traumatic brain injury (TBI) can develop rapid neurological deterioration from swelling and intracranial hematomas, which can result in focal tissue ischemia, brain compression, and herniation. Moreover, delays in management increase the risk of secondary brain injury from hypoxemia and hypotension. Therefore, in TBI patients with subdural hematomas (SDHs) and epidural hematomas (EDHs), surgical intervention is both necessary and time sensitive. Significant delays are seen along the care continuum in low- and middle-income countries (LMICs) largely due to limited healthcare capacity to address the disproportional rates of TBI in Sub Saharan Africa (SSA). While many LMICs have subsidized systems to offset surgical costs, the burden of securing funds by the patients for medications, supplies, and CT diagnostics poses a significant challenge to timely surgical interventions. In Kampala Uganda, the challenge of obtaining timely CT scans is twofold: logistical and financial barriers. These bottlenecks contribute significantly to the care continuum delays and are associated with poor TBI outcomes. Objective: The objectives of this study are to 1) describe the temporal delays through a modified three delays model that fits the context of neurosurgical interventions for TBI patients in Kampala and 2) investigate the association between delays and mortality. Methods: Prospective data were collected for 563 TBI patients presenting to a tertiary hospital in Kampala from 1 June – 30 November 2016. Four time intervals were constructed along five time points: injury, hospital arrival, neurosurgical evaluation, CT results, and definitive surgery. Time interval differences among mild, moderate and severe TBI and their association with mortality were analyzed. Results: The mortality rate of all TBI patients presenting to MNRH was 9.6%, which ranged from 4.7% for mild and moderate TBI patients receiving surgery to 81.8% for severe TBI patients who failed to receive surgery. The duration from injury to surgery varied considerably across TBI severity with the largest gap seen between mild TBI (174 hours) and severe TBI (69 hours) patients. Further analysis revealed care continuum differences for interval 3 (neurosurgical evaluation to CT result) and 4 (CT result to surgery) between severe TBI patients (7 hours for interval 3 and 24 hours for interval 4) and mild TBI patients (19 hours for interval 3, and 96 hours for interval 4). These post-arrival delays were associated with mortality for mild (p=0.05) and moderate TBI (p=0.03) patients. Conclusions: To our knowledge, this is the first analysis using a modified 'three delays' framework to analyze the care continuum of TBI patients in Uganda from injury to surgery. We found significant associations between delays and mortality for mild and moderate TBI patients. As it currently stands, poorer outcomes were observed for these mild and moderate TBI patients who were managed non-operatively or failed to receive surgery while surgical services were shunted to more severely ill patients. While well intentioned, high mortality rates were still observed for the severe TBI patients managed surgically. These results suggest the need for future research to optimize triage practices, understand delay contributors, and improve pre-hospital logistical referral systems.

Keywords: care continuum, global neurosurgery, Kampala Uganda, LMIC, Mulago, traumatic brain injury

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Authors: Yuxiang Pan, Yong Qiu, Chenlei Gu, Ping Wang

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In the past decade, three-dimensional (3D) tumor cell models have attracted increasing interest in the field of drug screening due to their great advantages in simulating more accurately the heterogeneous tumor behavior in vivo. Drug sensitivity testing based on 3D tumor cell models can provide more reliable in vivo efficacy prediction. The gold standard fluorescence staining is hard to achieve the real-time and label-free monitoring of the viability of 3D tumor cell models. In this study, micro-groove impedance sensor (MGIS) was specially developed for dynamic and non-invasive monitoring of 3D cell viability. 3D tumor cells were trapped in the micro-grooves with opposite gold electrodes for the in-situ impedance measurement. The change of live cell number would cause inversely proportional change to the impedance magnitude of the entire cell/matrigel to construct and reflect the proliferation and apoptosis of 3D cells. It was confirmed that 3D cell viability detected by the MGIS platform is highly consistent with the standard live/dead staining. Furthermore, the accuracy of MGIS platform was demonstrated quantitatively using 3D lung cancer model and sophisticated drug sensitivity testing. In addition, the parameters of micro-groove impedance chip processing and measurement experiments were optimized in details. The results demonstrated that the MGIS and 3D cell-based biosensor and would be a promising platform to improve the efficiency and accuracy of cell-based anti-cancer drug screening in vitro.

Keywords: micro-groove impedance sensor, 3D cell-based biosensors, 3D cell viability, micro-electromechanical systems

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Authors: Sabah Yasin, Anum Obaid

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Abstract—Working women in Pakistan should not be neglected, as women make up to half of the population, and are highly educated and diversified in their skills and capabilities. With a shift in global economic and social demands the obligations of a women have altered significantly, impacted by the dual pressures of career and personal life. Despite global efforts to improve economic empowerment and health of women, through Sustainable Development Goals, they suffer from social, economic, psychological and physiological challenges. A sound understanding of working women’s nutrition and health-related stress is a prompt necessity, in areas like Faisalabad, thus leading to a public health issue. The current qualitative study is grounded under the paradigm of in-depth interviews with working women, currently working full time in Faisalabad. Participants collected through snowball sampling were women ages 30-40. This study explores the perceptions and experiences as well as barriers and factors effecting the overall wellbeing of working women, regarding nutrition and health-related stress. Findings of the current study disclosed that the nutritional and health well-being of working women in Faisalabad suffers from the impact of various stressors, like long working hours, excessive workload, low income, poor work place culture, unavailability of healthy food choices at work, lack of time, lack of self-care, unattended nutritional deficiencies and overburdened share of responsibilities. Hence, these findings highlight the need for effective strategies and support systems that will address the unique stressors faced by working women and also by educating them in changing their attitudes and understanding psychosocial barriers that impede their ability to maintain nutrition and overall well-being.

Keywords: health triangle, lifestyle behaviors, nutrition-related, professional life, stress, working women

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Authors: Bassem Nassar, Wessam Hussein, Medhat Mokhtar

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The crucial concern of satellite operations is to ensure the health and safety of satellites. The worst case in this perspective is probably the loss of a mission but the more common interruption of satellite functionality can result in compromised mission objectives. All the data acquiring from the spacecraft are known as Telemetry (TM), which contains the wealth information related to the health of all its subsystems. Each single item of information is contained in a telemetry parameter, which represents a time-variant property (i.e. a status or a measurement) to be checked. As a consequence, there is a continuous improvement of TM monitoring systems in order to reduce the time required to respond to changes in a satellite's state of health. A fast conception of the current state of the satellite is thus very important in order to respond to occurring failures. Statistical multivariate latent techniques are one of the vital learning tools that are used to tackle the aforementioned problem coherently. Information extraction from such rich data sources using advanced statistical methodologies is a challenging task due to the massive volume of data. To solve this problem, in this paper, we present a proposed unsupervised learning algorithm based on Principle Component Analysis (PCA) technique. The algorithm is particularly applied on an actual remote sensing spacecraft. Data from the Attitude Determination and Control System (ADCS) was acquired under two operation conditions: normal and faulty states. The models were built and tested under these conditions and the results shows that the algorithm could successfully differentiate between these operations conditions. Furthermore, the algorithm provides competent information in prediction as well as adding more insight and physical interpretation to the ADCS operation.

Keywords: space telemetry monitoring, multivariate analysis, PCA algorithm, space operations

Procedia PDF Downloads 417

Authors: Bruno R. A. Oliveira, Italo V. V. Braga, Jonas P. Reges, Luiz P. O. Santos, Sidney C. Duarte, Emilson R. R. Melo, Auzuir R. Alexandria

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This project aims to building a controlled greenhouse, or for better understanding, a structure where one can maintain a given range of temperature values (°C) coming from radiation emitted by an incandescent light, as previously defined, characterizing as a kind of on-off control and a differential, which is the plotting of temperature versus time graphs assisted by MATLAB software via serial communication. That way it is possible to connect the stove with a computer and monitor parameters. In the control, it was performed using a PIC 16F877A microprocessor which enabled convert analog signals to digital, perform serial communication with the IC MAX232 and enable signal transistors. The language used in the PIC's management is Basic. There are also a cooling system realized by two coolers 12V distributed in lateral structure, being used for venting and the other for exhaust air. To find out existing temperature inside is used LM35DZ sensor. Other mechanism used in the greenhouse construction was comprised of a reed switch and a magnet; their function is in recognition of the door position where a signal is sent to a buzzer when the door is open. Beyond it exist LEDs that help to identify the operation which the stove is located. To facilitate human-machine communication is employed an LCD display that tells real-time temperature and other information. The average range of design operating without any major problems, taking into account the limitations of the construction material and structure of electrical current conduction, is approximately 65 to 70 ° C. The project is efficient in these conditions, that is, when you wish to get information from a given material to be tested at temperatures not as high. With the implementation of the greenhouse automation, facilitating the temperature control and the development of a structure that encourages correct environment for the most diverse applications.

Keywords: greenhouse, microcontroller, temperature, control, MATLAB

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Authors: O. Adjoul, A. Feugier, K. Benfriha, A. Aoussat

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In general, issues related to design and maintenance are considered in an independent manner. However, the decisions made in these two sets influence each other. The design for maintenance is considered an opportunity to optimize the life cycle cost of a product, particularly in the nuclear or aeronautical field, where maintenance expenses represent more than 60% of life cycle costs. The design of large-scale systems starts with product architecture, a choice of components in terms of cost, reliability, weight and other attributes, corresponding to the specifications. On the other hand, the design must take into account maintenance by improving, in particular, real-time monitoring of equipment through the integration of new technologies such as connected sensors and intelligent actuators. We noticed that different approaches used in the Design For Maintenance (DFM) methods are limited to the simultaneous characterization of the reliability and maintainability of a multi-component system. This article proposes a method of DFM that assists designers to propose dynamic maintenance for multi-component industrial systems. The term "dynamic" refers to the ability to integrate available monitoring data to adapt the maintenance decision in real time. The goal is to maximize the availability of the system at a given life cycle cost. This paper presents an approach for simultaneous optimization of the design and maintenance of multi-component systems. Here the design is characterized by four decision variables for each component (reliability level, maintainability level, redundancy level, and level of monitoring data). The maintenance is characterized by two decision variables (the dates of the maintenance stops and the maintenance operations to be performed on the system during these stops). The DFM model helps the designers choose technical solutions for the large-scale industrial products. Large-scale refers to the complex multi-component industrial systems and long life-cycle, such as trains, aircraft, etc. The method is based on a two-level hybrid algorithm for simultaneous optimization of design and maintenance, using genetic algorithms. The first level is to select a design solution for a given system that considers the life cycle cost and the reliability. The second level consists of determining a dynamic and optimal maintenance plan to be deployed for a design solution. This level is based on the Maintenance Free Operating Period (MFOP) concept, which takes into account the decision criteria such as, total reliability, maintenance cost and maintenance time. Depending on the life cycle duration, the desired availability, and the desired business model (sales or rental), this tool provides visibility of overall costs and optimal product architecture.

Keywords: availability, design for maintenance (DFM), dynamic maintenance, life cycle cost (LCC), maintenance free operating period (MFOP), simultaneous optimization

Procedia PDF Downloads 119

Authors: Opeyemi Atiba-Oyewo, Maurice S. Onya, Christian Wolkersdorfer

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Nanostructure formation and characterization of eco-friendly banana peels nanosorbent are thoroughly described in this paper. The transformation of material during mechanical milling to enhance certain properties such as changes in microstructure and surface area to solve the current problems involving water pollution and water quality were studied. The mechanical milling was employed using planetary continuous milling machine and ethanol as process control agent, the sample were taken at time interval between 10 h to 30 h to examine the structural changes. The samples were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra-red (FTIR), Transmission electron microscopy (TEM) and Brunauer Emmett and teller (BET). Results revealed that the three typical structures with different grain-size, lattice strain and shapes were observed, and the deformation mechanisms in these structures were found to be different, further particles fracturing results to surface area increment which was confirmed by Brunauer Emmett and teller (BET) analysis. X-ray diffraction (XRD) shows high densities of dislocations in large crystallites, implying that dislocation slip is the dominant deformation mechanism. Scanning electron microscopy revealed the morphological properties of the materials at different milling time, nanostructure of the particles and fibres were confirmed by Transmission electron microscopy and FT-IR identified the functional groups responsible for its capacity to coordinate and remove metal ions, such as the carboxylic and amine groups at absorption bands of 1730 and 889 cm-1, respectively. However, the choice of this sorbent material for the sorption of any contaminants will depend on the composition of the effluent to be treated.

Keywords: banana peels, eco-friendly, mechanical milling, nanosorbent, nanostructure water quality

Procedia PDF Downloads 256

Authors: Nehal Adel Khalil, Amel Foad Ketat, Fairouz Elsayed Mohamed Ali, Nahla Abdelmoneim Hamid, Hazem Farag Manaa

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Background: Chronic myeloid leukemia (CML) represents 15% of adult leukemias. Imatinib Mesylate (IM) is the gold standard treatment for new cases of CML. Treatment with IM results in improvement of the majority of cases. However, about 25% of cases may develop resistance. Sensitive and specific early predictors of IM resistance in CML patients have not been established to date. Aim: To investigate the value of miR-451 in CML as an early predictor for IM resistance in Egyptian CML patients. Methods: The study employed Real time Polymerase Reaction (qPCR) technique to investigate the leucocytic expression of miR-451 in fifteen newly diagnosed CML patients (group I), fifteen IM responder CML patients (group II), fifteen IM resistant CML patients (group III) and fifteen healthy subjects of matched age and sex as a control group (group IV). The response to IM was defined as < 10% BCR-ABL transcript level after 3 months of therapy. The following parameters were assessed in subjects of all the studied groups: 1- Complete blood count (CBC). 2- Measurement of plasma level of miRNA 451 using real-time Polymerase Chain Reaction (qPCR). 3- Detection of BCR-ABL gene mutation in CML using qPCR. Results: The present study revealed that miR-451 was significantly down-regulated in leucocytes of newly diagnosed CML patients as compared to healthy subjects. IM responder CML patients showed an up-regulation of miR- 451 compared with IM resistant CML patients. Conclusion: According to the data from the present study, it can be concluded that leucocytic miR- 451 expression is a useful additional follow-up marker for the response to IM and a promising prognostic biomarker for CML.

Keywords: chronic myeloid leukemia, imatinib resistance, microRNA 451, Polymerase Chain Reaction

Procedia PDF Downloads 296

Authors: M. J. Geca, T. Tulwin, A. Majczak

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On-board electricity consumption in the diesel city bus during operation is an important energy source. Electricity is generated by a combustion engine-driven alternator. Increased fuel consumption to generate on-board electricity in the bus has a negative impact on the emission of toxic components and carbon dioxide. At the same time, the bus roof surface allows placing a set of lightweight photovoltaic panels with power from 1 to 1.5 kW. The article presents an experimental study of electricity consumption of a city bus with diesel engine equipped with photovoltaic installation. The stream of electricity consumed by the bus and generated by a standard alternator and PV system was recorded. Base on the experimental research carried out in central Europe; the article analyses the impact of an additional source of electricity in the form of a photovoltaic installation on fuel consumption and emissions of toxic components of vehicles located in the latitude of Sydney. In Poland, the maximum global value of horizontal irradiation GHI is 1150 kWh/m², while for Sydney 1652 kWh/m². In addition, the profile of temperature and sunshine per year is different for these two different latitudes as presented in the article. Electricity generated directly from the sun powers the bus's electrical receivers. The photovoltaic system is able to replace 23% of annual electricity consumption, which at the same time will reduce 4% of fuel consumption and CO₂ reduction. Approximately 25% of the light is lost during vehicle traffic in Sydney latitude. The temperature losses of photovoltaic panels are comparable due to the cooling during vehicle motion. Acknowledgement: The project/research was financed in the framework of the project Lublin University of Technology - Regional Excellence Initiative, funded by the Polish Ministry of Science and Higher Education (contract no. 030/RID/2018/19).

Keywords: electric energy, photovoltaic system, fuel consumption, CO₂

Procedia PDF Downloads 114

Authors: Nkereke M. Essien

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The intention of this paper is to examine stress in the Educated Nigerian Accent of English (ENAE) with the aim of analyzing stress and rhythmic patterns of Nigerian English. Our aim also is to isolate differences and similarities in the stress patterns studied and also know what forms the accent of these Educated Nigerian English (ENE) which marks them off from other groups or English’s of the world, to ascertain and characterize it and to provide documented evidence for its existence. Nigerian stress and rhythmic patterns are significantly different from the British English stress and rhythmic patterns consequently, the educated Nigerian English (ENE) features more stressed syllables than the native speakers’ varieties. The excessive stressed of syllables causes a contiguous “Ss” in the rhythmic flow of ENE, and this brings about a “jerky rhythm’ which distorts communication. To ascertain this claim, ten (10) Nigerian speakers who are educated in the English Language were selected by a stratified Random Sampling technique from two Federal Universities in Nigeria. This classification belongs to the education to the educated class or standard variety. Their performance was compared to that of a Briton (control). The Metrical system of analysis was used. The respondents were made to read some words and utterance which was recorded and analyzed perceptually, statistically and acoustically using the one-way Analysis of Variance (ANOVA). The Turky-Kramer Post Hoc test, the Wilcoxon Matched Pairs Signed Ranks test, and the Praat analysis software were used in the analysis. It was revealed from our findings that the Educated Nigerian English speakers feature more stressed syllables in their productions by spending more time in pronouncing stressed syllables and sometimes lesser time in pronouncing the unstressed syllables. Their overall tempo was faster. The ENE speakers used tone to mark prominence while the native speaker used stress to mark pronounce, typified by the control. We concluded that the stress pattern of the ENE speakers was significantly different from the native speaker’s variety represented by the control’s performance.

Keywords: accent, Nigerian English, rhythm, stress

Procedia PDF Downloads 242

Authors: Saif Alomari

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The paper aims at giving physical and mathematical descriptions of how the structural parameters of a resonant tunnelling diode (RTD) affect its output characteristics. Specifically, the value of the peak voltage, peak current, peak to valley current ratio (PVCR), and the difference between peak and valley voltages and currents ΔV and ΔI. A simulation-based approach using the Non-Equilibrium Green Function (NEGF) formalism based on the Silvaco ATLAS simulator is employed to conduct a series of designed experiments. These experiments show how the doping concentration in the emitter and collector layers, their thicknesses, and the width of the barriers and the quantum well influence the above-mentioned output characteristics. Each of these parameters was systematically changed while holding others fixed in each set of experiments. Factorial experiments are outside the scope of this work and will be investigated in future. The physics involved in the operation of the device is thoroughly explained and mathematical models based on curve fitting and underlaying physical principles are deduced. The models can be used to design devices with predictable output characteristics. These models were found absent in the literature that the author acanned. Results show that the doping concentration in each region has an effect on the value of the peak voltage. It is found that increasing the carrier concentration in the collector region shifts the peak to lower values, whereas increasing it in the emitter shifts the peak to higher values. In the collector’s case, the shift is either controlled by the built-in potential resulting from the concentration gradient or the conductivity enhancement in the collector. The shift to higher voltages is found to be also related to the location of the Fermi-level. The thicknesses of these layers play a role in the location of the peak as well. It was found that increasing the thickness of each region shifts the peak to higher values until a specific characteristic length, afterwards the peak becomes independent of the thickness. Finally, it is shown that the thickness of the barriers can be optimized for a particular well width to produce the highest PVCR or the highest ΔV and ΔI. The location of the peak voltage is important in optoelectronic applications of RTDs where the operating point of the device is usually the peak voltage point. Furthermore, the PVCR, ΔV, and ΔI are of great importance for building RTD-based oscillators as they affect the frequency response and output power of the oscillator.

Keywords: peak to valley ratio, peak voltage shift, resonant tunneling diodes, structural parameters

Procedia PDF Downloads 142

Authors: Willian L. G. Silva, Fabio R. M. Batista, Matthieu Tubino

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Microalgae can be considered a potential source of oil for biodiesel synthesis since this microorganism can grow rapidly in either fresh or salty water, not competing with food production. There are several favorable conditions in Brazil for this type of culture due to the country’s great amount of water. Another very positive aspect of this type of culture is its ability to fix atmospheric CO2, contributing to the reduction of greenhouse gases and their effects on global warming. Despite this biodiesel environmental advantages it degrades resulting in changes in its physical and chemical properties. In this work, the methyl and ethyl microalgae biodiesel oxidative stability was studied in the absence and presence of a synthetic antioxidant. The synthetic antioxidants used were propyl gallate (PG) and tert-butylhydroquinone (TBHQ), at a 0,12% (w/w) concentration. The biodiesel mixture was kept in a sealed glass flask, sheltered from light, and at room temperature (about 25 ºC) for 180 days. During this period, aliquots from this biodiesel were subjected to induced degradation by the Rancimat method, which determines an important quality parameter, provided in the current methods, and is used to monitor the degradation processes that occur in the biodiesel over time. The induction period (IP) expresses the biodiesel oxidative stability. It was stablished that the minimum accepted IP value for biodiesel is 8 hours. The results show that ethylic biodiesel increased its IP value from 7,6 hours to 31 hours when using PG, and to 67 hours when using TBHQ, exceeding the minimum accepted IP value. When the antioxidants were added to the methylic biodiesel samples, the IP was raised to 28 hours when using PG, and to 62 hours when using TBHQ. These values were maintained throughout the entire period of study (180 days). On the other hand, the biodiesel samples without additives maintained an IP above the allowed value for only 30 days. Therefore, in order to preserve microalgae biodiesel for longer periods of time, it is necessary to add antioxidants to both derivatives, i.e., the ethylic and methylic.

Keywords: biodiesel, microalgae, oxidative stability, storage, synthetic antioxidants

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Authors: K. V. Ramanaiah, R. Jagan, N. N. Murthy

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Trinuclear oxo-centered carboxylate-bridged iron complexes, [Fe3(µ3-O)(µ2-O2CR)L¬3]+/0 (where R = alkyl or aryl; L = H2O, ROH, Py, solvent) have attracted tremendous attention because of their interesting structural and magnetic properties, exhibit mixed-valent trapped and de-trapped states, and have bioinorganic relevance. The presence of a trinuclear iron binding center has been implicated in the formation of both bacterial and human iron storage protein, Ft. They are used as precursors for the synthesis of models for the active-site structures of non-heme proteins, hemerythrin (Hr), methane monooxygenase (MMO) and polyiron storage protein, ferritin (Ft). Used as important building blocks for the design and synthesis of supramolecules this can exhibit single molecular magnetism (SMM). Such studies have often employed simple and compact carboxylate ligands and the use of bulky carboxylates is scarce. In the present study, we employed two different type of sterically hindered carboxylates and synthesized a series of novel oxo-centered, carboxylate-bridged triiron complexes of general formula [Fe3(O)(O2CCPh3)6L3]X (L = H2O, 1; py, 2; 4-NMe2py, 3; X = ClO4; L = CH3CN, 4; X = FeCl4) and [Fe3(O)(O2C-anth)6L3]X (L = H2O, 5; X = ClO4; L = CH3OH, 6; X = Cl). Along with complex [Fe(OMe)2(O2CCPh3)]10, 7 was prepared by the self-assemble of anhydrous FeCl3, sodium triphenylacetate and sodium methoxide at ratio of 1:1:2 in CH3OH. The Electronic absorption spectra of these complexes 1-6, in CH2Cl2 display weak bands at near FTIR region (970-1135 nm, ε > 15M-1cm-1). For complex 7, one broad band centered at ~670nm and also an additional intense charge transfer (L→M or O→M) bands between 300 to 550nm observed for all the complexes. Paramagnetic 1H NMR is introduced as a good probe for the characterization of trinuclear oxo - cantered iron compounds in solution when the L ligand coordinated to iron varies as: H2O, py, 4-NMe2py, and CH3OH. The solution state magnetic moment values calculated by using Evans method for all the complexes and also solid state magnetic moment value of complex, 7 was calculated by VSM method, which is comparable with solution state value. These all magnetic moment values indicate there is a spin exchange process through oxo and carboxylate bridges in between two irons (d5). The ESI-mass data complement the data obtained from single crystal X-ray structure. Further purity of the compounds was confirmed by elemental analysis. Finally, structural determination of complexes 1, 3, 4, 5, 6 and 7 were unambiguously conformed by single crystal x-ray studies.

Keywords: decanuclear, paramagnetic NMR, trinuclear, uv-visible

Procedia PDF Downloads 348