Search results for: interpretive structural modelling
3713 The Role of Health Beliefs in Predicting and Explaining Risky Health Behaviours within Cystic Fibrosis
Authors: Rebecca Keyte, Helen Egan, Michail Mantzios
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It is well acknowledged that ongoing adherence is a major concern within CF. However recently literature has indicated that non-adherence should not be viewed just in terms of medical regimens. There are other damaging behaviours that some chronically ill patients engage in which can be viewed as a form of non-adherence, such as risky behaviours. Risky behaviours are a major concern within CF, as they can have adverse health effects on patients regardless of patients adherence to medical regimens. The risky behaviours this research is predominantly focusing on are smoking, excessive alcohol consumption, illicit drug use and risky sexual behaviour. This research investigates patient’s beliefs about their CF and the impact their CF has upon their life, exploring rationales for why some patients engage in risky behaviours. This research utilises qualitative semi-structured interviews taking an interpretive perspective. Twenty-four adult participants have been recruited (16 male, age range 19–66 yrs) from two UK regional CF centres, with a median FEV1 61.77% predicted. Participants were recruited via clinician guidance, with 13 participants identified by clinicians as partaking in risky behaviours. However, during the interviews 17 participants were identified as partaking in risky behaviours, illustrating that not all patients offer full disclosure of engagement in such behaviours to their clinicians. Preliminary findings illustrate a variety of reasons as to why some CF patients engage in risky behaviours, with many participants stating that one challenge in terms of living with CF is accepting their illness. Disclosure of illness was also an issue, the desire to be seen as ‘normal’ was important to many. It is often possible for CF patients to hide their illness as they do not always appear to be unwell. However, literature indicates a desire for normalcy can be accompanied with the engagement of normalised risky behaviours, enabling patients to retaliate against their illness identity. There was also evidence of a life-orientated perspective amongst participants, with some reporting that their desire for fun and enjoyment was the reason for why they were engaging in risky behaviours. Some participants did not acknowledge the impact their risky behaviours could have upon their CF, and others rationalised their continuation with the behaviours by suggesting that they were in fact beneficial to their health. There was an apparent lack of knowledge around the implications of risky behaviours, with participants indicating that they had not been informed of such potential consequences by their clinicians. Given the adverse health effects of risky behaviours within CF, more effective health promotion measures are needed to both reduce and more importantly prevent these behaviours. Due to the initiation of risky behaviours within the CF population commonly occurring during adolescence, the researcher now proposes to conduct semi-structured interviews with paediatric patients to investigate their awareness and beliefs towards risky behaviours. Overall, this research will highlight reasons why some CF patients engage in risky behaviours, in order to inform interventions aimed to prevent the initiation in risky behaviours by increasing patient awareness.Keywords: cystic fibrosis, health beliefs, preliminary findings, risky health behaviours
Procedia PDF Downloads 2903712 Long Short-Time Memory Neural Networks for Human Driving Behavior Modelling
Authors: Lu Zhao, Nadir Farhi, Yeltsin Valero, Zoi Christoforou, Nadia Haddadou
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In this paper, a long short-term memory (LSTM) neural network model is proposed to replicate simultaneously car-following and lane-changing behaviors in road networks. By combining two kinds of LSTM layers and three input designs of the neural network, six variants of the LSTM model have been created. These models were trained and tested on the NGSIM 101 dataset, and the results were evaluated in terms of longitudinal speed and lateral position, respectively. Then, we compared the LSTM model with a classical car-following model (the intelligent driving model (IDM)) in the part of speed decision. In addition, the LSTM model is compared with a model using classical neural networks. After the comparison, the LSTM model demonstrates higher accuracy than the physical model IDM in terms of car-following behavior and displays better performance with regard to both car-following and lane-changing behavior compared to the classical neural network model.Keywords: traffic modeling, neural networks, LSTM, car-following, lane-change
Procedia PDF Downloads 2613711 Development of Solid Electrolytes Based on Networked Cellulose
Authors: Boor Singh Lalia, Yarjan Abdul Samad, Raed Hashaikeh
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Three different kinds of solid polymer electrolytes were prepared using polyethylene oxide (PEO) as a base polymer, networked cellulose (NC) as a physical support and LiClO4 as a conductive salt for the electrolytes. Networked cellulose, a modified form of cellulose, is a biodegradable and environmentally friendly additive which provides a strong fibrous networked support for structural stability of the electrolytes. Although the PEO/NC/LiClO4 electrolyte retains its structural integrity and mechanical properties at 100oC as compared to pristine PEO-based polymer electrolytes, it suffers from poor ionic conductivity. To improve the room temperature conductivity of the electrolyte, PEO is replaced by the polyethylene glycol (PEG) which is a liquid phase that provides high mobility for Li+ ions transport in the electrolyte. PEG/NC/LiClO4 shows improvement in ionic conductivity compared to PEO/NC/LiClO4 at room temperature, but it is brittle and tends to form cracks during processing. An advanced solid polymer electrolyte with optimum ionic conductivity and mechanical properties is developed by using a ternary system: TEGDME/PEO/NC+LiClO4. At room temperature, this electrolyte exhibits an ionic conductivity to the order of 10-5 S/cm, which is very high compared to that of the PEO/LiClO4 electrolyte. Pristine PEO electrolytes start melting at 65 °C and completely lose its mechanical strength. Dynamic mechanical analysis of TEGDME: PEO: NC (70:20:10 wt%) showed an improvement of storage modulus as compared to the pristine PEO in the 60–120 °C temperature range. Also, with an addition of NC, the electrolyte retains its mechanical integrity at 100 oC which is beneficial for Li-ion battery operation at high temperatures. Differential scanning calorimetry (DSC) and thermal gravimetry analysis (TGA) studies revealed that the ternary polymer electrolyte is thermally stable in the lithium ion battery operational temperature range. As-prepared polymer electrolyte was used to assemble LiFePO4/ TEGDME/PEO/NC+LiClO4/Li half cells and their electrochemical performance was studied via cyclic voltammetry and charge-discharge cycling.Keywords: solid polymer electrolyte, ionic conductivity, mechanical properties, lithium ion batteries, cyclic voltammetry
Procedia PDF Downloads 4293710 A New Co(II) Metal Complex Template with 4-dimethylaminopyridine Organic Cation: Structural, Hirshfeld Surface, Phase Transition, Electrical Study and Dielectric Behavior
Authors: Mohamed dammak
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Great attention has been paid to the design and synthesis of novel organic-inorganic compounds in recent decades because of their structural variety and the large diversity of atomic arrangements. In this work, the structure for the novel dimethyl aminopyridine tetrachlorocobaltate (C₇H₁₁N₂)₂CoCl₄ prepared by the slow evaporation method at room temperature has been successfully discussed. The X-ray diffraction results indicate that the hybrid material has a triclinic structure with a P space group and features a 0D structure containing isolated distorted [CoCl₄]2- tetrahedra interposed between [C7H11N²⁻]+ cations forming planes perpendicular to the c axis at z = 0 and z = ½. The effect of the synthesis conditions and the reactants used, the interactions between the cationic planes, and the isolated [CoCl4]2- tetrahedra are employing N-H...Cl and C-H…Cl hydrogen bonding contacts. The inspection of the Hirshfeld surface analysis helps to discuss the strength of hydrogen bonds and to quantify the inter-contacts. A phase transition was discovered by thermal analysis at 390 K, and comprehensive dielectric research was reported, showing a good agreement with thermal data. Impedance spectroscopy measurements were used to study the electrical and dielectric characteristics over a wide range of frequencies and temperatures, 40 Hz–10 MHz and 313–483 K, respectively. The Nyquist plot (Z" versus Z') from the complex impedance spectrum revealed semicircular arcs described by a Cole-Cole model. An electrical circuit consisting of a link of grain and grain boundary elements is employed. The real and imaginary parts of dielectric permittivity, as well as tg(δ) of (C₇H₁₁N₂)₂CoCl₄ at different frequencies, reveal a distribution of relaxation times. The presence of grain and grain boundaries is confirmed by the modulus investigations. Electric and dielectric analyses highlight the good protonic conduction of this material.Keywords: organic-inorganic, phase transitions, complex impedance, protonic conduction, dielectric analysis
Procedia PDF Downloads 853709 Dynamic Analysis of Turbo Machinery Foundation for Different Rotating Speed
Authors: Sungyani Tripathy, Atul Desai
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Turbo machinery Frame Foundation is very important for power generation, gas, steam, hydro, geothermal and nuclear power plants. The Turbo machinery Foundation system was simulated in SAP: 2000 software and dynamic response of foundation was analysed. In this paper, the detailed study of turbo machinery foundation with different running speed has considered. The different revolution per minute considered in this study is 4000 rpm, 6000 rpm, 8000 rpm, 1000 rpm and 12000 rpm. The above analysis has been carried out considering Winkler spring soil model, solid finite element modelling and dynamic analysis of Turbo machinery foundations. The comparison of frequency and time periods at various mode shapes are addressed in this study. Current work investigates the effect of damping on the response spectra curve at the foundation top deck, considering the dynamic machine load. It has been found that turbo generator foundation with haunches remains more elastic during seismic action for different running speeds.Keywords: turbo machinery, SAP: 2000, response spectra, running speeds
Procedia PDF Downloads 2553708 PSS®E Based Modelling, Simulation and Synchronous Interconnection of Eastern Grid and North-Eastern Regional Grid of India
Authors: Toushik Maiti, Saibal Chatterjee, Kamaljyoti Gogoi, Arijit Basuray
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Eastern Regional(ER) Grid and North Eastern Regional (NER) Grid are two major grids of Eastern Part of India. Both of the grid consists of voltage level 765kV, 400 kV, 220 kV and numerous buses at lower voltage range. Eastern Regional Grid and North Eastern Regional Grid are not only connected among themselves but are also connected to various other grids of India. ER and NER Grid having various HVDC lines or back to back systems which form the total network. The studied system comprises of 340 buses of different voltage levels and transmission lines running over a length of 32089 km. The validation of load flow has been done using IEEE STANDARD 30 bus system. The power flow simulation analysis has been performed after synchronizing both the Eastern Grid and North-Eastern Regional Grid of India using Power System Simulators for Engineering (PSS®E) Important inferences has been drawn from the study.Keywords: HVDC, load flow, PSS®E, unsymmetrical and symmetrical faults
Procedia PDF Downloads 3833707 Micro-Oscillator: Passive Production and Manipulation of Microdrops
Authors: Khelfaoui Rachid, Chekifi Tawfiq, Dennai Brahim, Maazouzi A. Hak
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A numerical and experimental studies of passive micro drops production have been presented. This paper focuses on the modeling of micro-oscillators systems which are composed by passive amplifier without moving part. The micro-system modeling is based on geometrical oscillators form. An asymmetric micro-oscillator design that is based on a bistable fluidic amplifier is proposed. The characteristic size of the channels is generally about 35 microns of depth. The numerical results indicate that the production and manipulation of microdrops are possible with passive device within a typical oscillators chamber of 2.25 mm diameter and 0.20 mm length when the Reynolds number is Re = 490. The novel micro drops method that is presented in this study provides a simple solution about the production of microdrops problems in micro system. We undertake an experimental step. The first part is based on the realisation of sample oscillator; the second part is consisted of visualization, production and manipulation of microdrops.Keywords: modelling, miscible, micro drops, production, oscillator sample, capillary
Procedia PDF Downloads 3783706 Methylglyoxal Induced Glycoxidation of Human Low Density Lipoprotein: A Biophysical Perspective and Its Role in Diabetes and Periodontitis
Authors: Minhal Abidi, Moinuddin
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Diabetes mellitus (DM) induced metabolic abnormalities causes oxidative stress which leads to the pathogenesis of complications associated with diabetes like retinopathy, nephropathy periodontitis etc. Combination of glycation and oxidation 'glycoxidation' occurs when oxidative reactions affect the early state of glycation products. Low density lipoprotein (LDL) is prone to glycoxidative attack by sugars and methylglyoxal (MGO) being a strong glycating agent may have severe impact on its structure and consequent role in diabetes. Pro-inflammatory cytokines like IL1β and TNFα produced by the action of gram negative bacteria in periodontits (PD) can in turn lead to insulin resistance. This work discusses modifications to LDL as a result of glycoxidation. The changes in the protein molecule have been characterized by various physicochemical techniques and the immunogenicity of the modified molecules was also evaluated as they presented neo-epitopes. Binding of antibodies present in diabetes patients to the native and glycated LDL has been evaluated. Role of modified epitopes in the generation of antibodies in diabetes and periodontitis has been discussed. The structural perturbations induced in LDL were analyzed by UV–Vis, fluorescence, circular dichroism and FTIR spectroscopy, molecular docking studies, thermal denaturation studies, Thioflavin T assay, isothermal titration calorimetry, comet assay. MALDI-TOF, ketoamine moieties, carbonyl content and HMF content were also quantitated in native and glycated LDL. IL1β and TNFα levels were also measured in the type 2 DM and PD patients. We report increased carbonyl content, ketoamine moieties and HMF content in glycated LDL as compared to native analogue. The results substantiate that in hyperglycemic state MGO modification of LDL causes structural perturbations making the protein antigenic which could obstruct normal physiological functions and might contribute in the development of secondary complications in diabetic patients like periodontitis.Keywords: advanced glycation end products, diabetes mellitus, glycation, glycoxidation, low density lipoprotein, periodontitis
Procedia PDF Downloads 1913705 Sugarcane Bagasse Ash Geopolymer Mixtures: A Step Towards Sustainable Materials
Authors: Mohammad J. Khattak, Atif Khan, Thomas C. Pesacreta
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Millions of tons of sugarcane bagasse ash (SBA) are produced as a byproduct by burning sugarcane bagasse in powerplants to run the steam engines for sugar production. This bagasse ash is disposed into landfills effecting their overall capacity. SBA contains very fine particles that can easily become airborne, causing serious respiratory health risks when inhaled. This research study evaluated the utilization of high dosage of SBA for developing geopolymer based “Green” construction materials. An experimental design matrix was developed with varying dosages of SBA (0, 20%, 60%, and 80%) and Na₂SiO3/NaOH ratio (0, 0.5, 1, 1.5, 2) based on the response surface methodology. Precursor (consisting of SBA and fly ash) to aggregate ration was kept constant at 30:70 and the alkali to binder ratio was maintained at 0.45 for all the mixtures. Geopolymer samples of size 50.8 x 50.8 mm (2” X 2”) were casted and cured at 65oC for 48 hours in a water bath followed by curing at room temperature for 24 hours. The samples were then tested for compressive strength as per ASTM C39. The results revealed that based on varying SBA dosage the compressive strengths ranged from 6.78 MPa to 22.63 MPa. Moreover, the effect of SiO2, Na₂O and Fe₂O₃ on the compressive strength of these mixtures was also evaluated. The results depicted that the compressive strength increased with increasing Na₂O and Fe₂O₃ concentration in the binder. It was also observed that the compressive strength of SBA based geopolymer mixtures improved as the SiO₂ content increased, reaching an optimum at 42%. However, further increase in SiO₂ reduced the strength of the mixtures. The resulting geopolymer mixtures possess compressive strengths according to the requirements set by ASTM standard. Such mixtures can be used as a structural and non-structural element as strong road bases, sidewalks, curbs, bricks for buildings and highway infrastructure. Using industrial SBA in geopolymer based construction materials can address the carbon emissions related to cement production, reduce landfill burden from SBA storage, and mitigate health risks associated with high content of silica in SBA.Keywords: compressive strength, geopolymer concrete, green materials, sugarcane bagasse ash
Procedia PDF Downloads 103704 Assessment of Pollution of the Rustavi City’s Atmosphere with Microaerosols
Authors: Natia Gigauri, Aleksandre Surmava
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According to observational data, experimental measurements, and numerical modeling, is assessed pollution of one of the industrial centers of Georgia, Rustavi city’s atmosphere with microaerosols. Monthly, daily and hourly changes of the concentrations of PM2.5 and PM10 in the city atmosphere are analyzed. It is accepted that PM2.5 concentrations are always lower than PM10 concentrations, but their change curve is the same. In addition, it has been noted that the maximum concentrations of particles in the atmosphere of Rustavi city will be reached at any part of the day, which is determined by the total impact of the traffic flow and industrial facilities. By numerical modeling has calculated the influence of background western light air and gentle and fresh breeze on the distribution of PM particles in the atmosphere. Calculations showed that background light air and gentle breeze lead to an increase the concentrations of microaerosols in the city's atmosphere, while fresh breeze contribute to the dispersion of dusty clouds. As a result, the level of dust in the city is decreasing, but the distribution area is expanding.Keywords: pollution, modelling, PM2.5, PM10, experimental measurement
Procedia PDF Downloads 893703 A Review of Methods for Handling Missing Data in the Formof Dropouts in Longitudinal Clinical Trials
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Much clinical trials data-based research are characterized by the unavoidable problem of dropout as a result of missing or erroneous values. This paper aims to review some of the various techniques to address the dropout problems in longitudinal clinical trials. The fundamental concepts of the patterns and mechanisms of dropout are discussed. This study presents five general techniques for handling dropout: (1) Deletion methods; (2) Imputation-based methods; (3) Data augmentation methods; (4) Likelihood-based methods; and (5) MNAR-based methods. Under each technique, several methods that are commonly used to deal with dropout are presented, including a review of the existing literature in which we examine the effectiveness of these methods in the analysis of incomplete data. Two application examples are presented to study the potential strengths or weaknesses of some of the methods under certain dropout mechanisms as well as to assess the sensitivity of the modelling assumptions.Keywords: incomplete longitudinal clinical trials, missing at random (MAR), imputation, weighting methods, sensitivity analysis
Procedia PDF Downloads 4153702 Towards Incorporating Context Awareness into Business Process Management
Authors: Xiaohui Zhao, Shahan Mafuz
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Context-aware technologies provide system applications with the awareness of environmental conditions, customer behaviour, object movements, etc. Further, with such capability system applications can be smart to adapt intelligently their responses to the changing conditions. Concerning business operations, this promises businesses that their business processes can run more intelligently, adaptively and flexibly, and thereby either improve customer experience, enhance reliability of service delivery, or lower operational cost, to make the business more competitive and sustainable. Aiming at realizing such context-aware business process management, this paper firstly explores its potential benefit and then identifies some gaps between the current business process management support and the expected. In addition, some preliminary solutions are also discussed with context definition, rule-based process execution, run-time process evolution, etc. A framework is also presented to give a conceptual architecture of context-aware business process management system to guide system implementation.Keywords: business process adaptation, business process evolution, business process modelling, and context awareness
Procedia PDF Downloads 4143701 Protective Efficacy of Moringa oleifera against Oxidative Ovarian Damage and Reproductive Failure in Female Rats Caused by Cyclophosphamide
Authors: Seham Samir Soliman, Ahmed A.Suliman, Khaled Fathy, Ahmed A. Sedik
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Cyclophosphamide (CP), an antineoplastic drug, has been found to induce reproductive damage. It is essential to develop approaches aimed at safeguarding ovarian tissue integrity in women experiencing reproductive toxicity as a result of chemotherapy. The current study was conducted to assess the impact of an extract derived from Moringa oleifera (M. oleifera) leaves on ovarian damage produced by CP. A total of 32 female Wistar Albino rats, which were in a healthy cycling state, were randomly separated into 4 groups, with every group contains 8 rats. The first group was administered intraperitoneal (i.p.) saline. The second group was administered a solitary intraperitoneal dosage of cyclophosphamide (200 mg/kg). The third one received M. oleifera extract (150 mg/kg orally) for 20 days, followed by i.p. of CP on the last day of the experiment. The fourth group received M. oleifera extract (250 mg/kg orally) for 20 days, followed by i.p. of CP on the last day of the experiment. Hormonal assessments, including luteinizing hormone (LH), estrogen (ES), and follicle-stimulating hormone (FSH), were performed 24 hours after CP administration. In addition, evaluating the antioxidant status and inflammatory response against CP. Moreover, conducting detailed histopathological and ultra-structural pictures of the ovary. Our findings reported that rats intoxicated with CP exhibited elevated levels of FSH, LH, malondialdehyde (MDA), tumor necrosis factor-alpha (TNF-α), and a decrease in E₂, and glutathione (GSH) levels. Pre-treatment with M. oleifera extract (250 mg/kg orally) ameliorated the disturbance in hormonal changes, oxidative stress indices, and the levels of pro-inflammatory mediators. Also, the histopathological and ultra-structural pictures of the ovaries were improved significantly in rats. In conclusion, M. oleifera extract possesses a significant protective role against CP-induced acute reproductive toxicity via modulating the values of FSH, LH, E₂ and quenching the release of reactive oxygen species and inflammatory mediators in female rats.Keywords: cyclophosphamide, Moringa oleifera, ovarian function, oxidative stress, pro-inflammatory mediators
Procedia PDF Downloads 803700 Hominin Niche in the Times of Climate Change
Authors: Emilia Hunt, Sally C. Reynolds, Fiona Coward, Fabio Parracho Silva, Philip Hopley
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Ecological niche modeling is widely used in conservation studies, but application to the extinct hominin species is a relatively new approach. Being able to understand what ecological niches were occupied by respective hominin species provides a new perspective into influences on evolutionary processes. Niche separation or overlap can tell us more about specific requirements of the species within the given timeframe. Many of the ancestral species lived through enormous climate changes: glacial and interglacial periods, changes in rainfall, leading to desertification or flooding of regions and displayed impressive levels of adaptation necessary for their survival. This paper reviews niche modeling methodologies and their application to hominin studies. Traditional conservation methods might not be directly applicable to extinct species and are not comparable to hominins. Hominin niche also includes aspects of technologies, use of fire and extended communication, which are not traditionally used in building conservation models. Future perspectives on how to improve niche modeling for extinct hominin species will be discussed.Keywords: hominin niche, climate change, evolution, adaptation, ecological niche modelling
Procedia PDF Downloads 1893699 Sprinting Beyond Sexism and Gender Stereotypes: Indian Women Fans' Experiences in the Sports Fandom
Authors: Siddhi Deshpande, Jo Jo Chacko Eapen
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Despite almost half of India’s female population engages in watching sports, their experiences in the sports fandom are concealed by ‘traditional masculinity,’ leading to potential exclusion and harassment. To explore these experiences in-depth, this qualitative study aims to understand what coping strategies Indian women fans employ, to sustain their team identification. Employing criterion sampling, participants were screened using The Sports Spectators Identification Scale (SSIS) to assess team identification and a Brief Sexism Questionnaire to confirm participants’ experience with sexism as it aligns with the purpose of the study. The participants were Indian women who had been following any sport for more than eight years, were fluent in English, and were not professionals in Sports. Ten highly identified fans with gendered experiences were recruited for one-on-one semi-structured, in-depth interviews. The data was analyzed using Interpretive Phenomenological Analysis (IPA) to understand the lived-in experiences of women fans experiencing sexism and gender stereotypes, revealing superordinate themes of (1) Ontogenesis and Emotional Investment; (2) Gendered Expectations and Sexism; (3) Coping Strategies and Resilience; (4) Identity, Femininity, Empowerment; (5) Advocacy for Equality and Inclusivity. The findings reflect that Indian women fans experience social exclusion, harassment, sexualization, and commodification, in both online and offline fandoms, where they are disproportionately targeted with threats, misogynistic comments, and attraction-based assumptions, questioning their ‘authenticity’ as fans due to their gender. Women fans interchange between proactive strategies of assertiveness, humor, and knowledge demonstration with defensive strategies of selective engagement, self-regulatory censorship, and desensitization to deal with sexism. In this interplay, the integration of women’s ‘fan identity’ with their self-concept showcases how being a sports fan adds meaning to their lives, despite the constant scrutiny in a male-dominated space, reflecting that femininity and sports should coexist. As a result, they find refuge in female fan communities due to their similar experiences in the fandom and advocate for an equal and inclusive environment where sports are above gender, and not the other way around. A key practical implication of this research is enabling sports organizations to develop inclusive fan engagement policies that actively encourage female fan participation. This includes sensitizing stadium staff and security personnel, promoting gender-neutral language, and, most importantly, establishing safety protocols to protect female fans from adverse experiences in the fandom.Keywords: coping strategies, female sports fans, femininity, gendered experiences, team identification
Procedia PDF Downloads 483698 Sensor Network Structural Integration for Shape Reconstruction of Morphing Trailing Edge
Authors: M. Ciminello, I. Dimino, S. Ameduri, A. Concilio
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Improving aircraft's efficiency is one of the key elements of Aeronautics. Modern aircraft possess many advanced functions, such as good transportation capability, high Mach number, high flight altitude, and increasing rate of climb. However, no aircraft has a possibility to reach all of this optimized performance in a single airframe configuration. The aircraft aerodynamic efficiency varies considerably depending on the specific mission and on environmental conditions within which the aircraft must operate. Structures that morph their shape in response to their surroundings may at first seem like the stuff of science fiction, but take a look at nature and lots of examples of plants and animals that adapt to their environment would arise. In order to ensure both the controllable and the static robustness of such complex structural systems, a monitoring network is aimed at verifying the effectiveness of the given control commands together with the elastic response. In order to achieve this kind of information, the use of FBG sensors network is, in this project, proposed. The sensor network is able to measure morphing structures shape which may show large, global displacements due to non-standard architectures and materials adopted. Chord -wise variations may allow setting and chasing the best layout as a function of the particular and transforming reference state, always targeting best aerodynamic performance. The reason why an optical sensor solution has been selected is that while keeping a few of the contraindication of the classical systems (like cabling, continuous deployment, and so on), fibre optic sensors may lead to a dramatic reduction of the wires mass and weight thanks to an extreme multiplexing capability. Furthermore, the use of the ‘light’ as ‘information carrier’, permits dealing with nimbler, non-shielded wires, and avoids any kind of interference with the on-board instrumentation. The FBG-based transducers, herein presented, aim at monitoring the actual shape of adaptive trailing edge. Compared to conventional systems, these transducers allow more fail-safe measurements, by taking advantage of a supporting structure, hosting FBG, whose properties may be tailored depending on the architectural requirements and structural constraints, acting as strain modulator. The direct strain may, in fact, be difficult because of the large deformations occurring in morphing elements. A modulation transducer is then necessary to keep the measured strain inside the allowed range. In this application, chord-wise transducer device is a cantilevered beam sliding trough the spars and copying the camber line of the ATE ribs. FBG sensors array position are dimensioned and integrated along the path. A theoretical model describing the system behavior is implemented. To validate the design, experiments are then carried out with the purpose of estimating the functions between rib rotation and measured strain.Keywords: fiber optic sensor, morphing structures, strain sensor, shape reconstruction
Procedia PDF Downloads 3293697 A Data-Driven Compartmental Model for Dengue Forecasting and Covariate Inference
Authors: Yichao Liu, Peter Fransson, Julian Heidecke, Jonas Wallin, Joacim Rockloev
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Dengue, a mosquito-borne viral disease, poses a significant public health challenge in endemic tropical or subtropical countries, including Sri Lanka. To reveal insights into the complexity of the dynamics of this disease and study the drivers, a comprehensive model capable of both robust forecasting and insightful inference of drivers while capturing the co-circulating of several virus strains is essential. However, existing studies mostly focus on only one aspect at a time and do not integrate and carry insights across the siloed approach. While mechanistic models are developed to capture immunity dynamics, they are often oversimplified and lack integration of all the diverse drivers of disease transmission. On the other hand, purely data-driven methods lack constraints imposed by immuno-epidemiological processes, making them prone to overfitting and inference bias. This research presents a hybrid model that combines machine learning techniques with mechanistic modelling to overcome the limitations of existing approaches. Leveraging eight years of newly reported dengue case data, along with socioeconomic factors, such as human mobility, weekly climate data from 2011 to 2018, genetic data detecting the introduction and presence of new strains, and estimates of seropositivity for different districts in Sri Lanka, we derive a data-driven vector (SEI) to human (SEIR) model across 16 regions in Sri Lanka at the weekly time scale. By conducting ablation studies, the lag effects allowing delays up to 12 weeks of time-varying climate factors were determined. The model demonstrates superior predictive performance over a pure machine learning approach when considering lead times of 5 and 10 weeks on data withheld from model fitting. It further reveals several interesting interpretable findings of drivers while adjusting for the dynamics and influences of immunity and introduction of a new strain. The study uncovers strong influences of socioeconomic variables: population density, mobility, household income and rural vs. urban population. The study reveals substantial sensitivity to the diurnal temperature range and precipitation, while mean temperature and humidity appear less important in the study location. Additionally, the model indicated sensitivity to vegetation index, both max and average. Predictions on testing data reveal high model accuracy. Overall, this study advances the knowledge of dengue transmission in Sri Lanka and demonstrates the importance of incorporating hybrid modelling techniques to use biologically informed model structures with flexible data-driven estimates of model parameters. The findings show the potential to both inference of drivers in situations of complex disease dynamics and robust forecasting models.Keywords: compartmental model, climate, dengue, machine learning, social-economic
Procedia PDF Downloads 843696 Seismic Retrofit of Existing Bridge Foundations with Micropiles: 3D Finite Element Analysis
Authors: Mohanad Talal Alfach
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This paper concerns the seismic behaviour of soil-piles-bridge reinforced by additional micropiles. The analysis carried out by three-dimensional finite element modelling using the FE software ABAQUS. The soil behaviour is assumed to be elastic with Rayleigh damping, while the micropiles are modeled as 3D elastic beam elements. The bridge deck slab was represented by a concentrated mass at the top of the pier column. The interaction between the added micropiles and the existing piles as well as the performance of the retrofitted soil-pile-superstructure system were investigated for different configurations of additional micropiles (number, position, inclination). Numerical simulation results show that additional micropiles constitute an efficient retrofitting solution. Analysis of results also shows that spacing between existing piles and retrofitting micropiles has little effect; while it is observed a substantial improvement (in case of weak piles/micropiles - soil interface) with reducing the inclination angle of retrofitting micropiles.Keywords: retrofitting, seismic, finite element, micropiles, elastic
Procedia PDF Downloads 1463695 Thin-Layer Drying Characteristics and Modelling of Instant Coffee Solution
Authors: Apolinar Picado, Ronald Solís, Rafael Gamero
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The thin-layer drying characteristics of instant coffee solution were investigated in a laboratory tunnel dryer. Drying experiments were carried out at three temperatures (80, 100 and 120 °C) and an air velocity of 1.2 m/s. Drying experimental data obtained are fitted to six (6) thin-layer drying models using the non-linear least squares regression analysis. The acceptability of the thin-layer drying model has been based on a value of the correlation coefficient that should be close to one, and low values for root mean square error (RMSE) and chi-square (x²). According to this evaluation, the most suitable model for describing drying process of thin-layer instant coffee solution is the Page model. Further, the effective moisture diffusivity and the activation energy were computed employing the drying experimental data. The effective moisture diffusivity values varied from 1.6133 × 10⁻⁹ to 1.6224 × 10⁻⁹ m²/s over the temperature range studied and the activation energy was estimated to be 162.62 J/mol.Keywords: activation energy, diffusivity, instant coffee, thin-layer models
Procedia PDF Downloads 2623694 An Approach on Robust Multi Inversion of a Nonlinear Model for an Omni-Directional Mobile
Authors: Fernando P. Silva, Valter J. S. Leite, Erivelton G. Nepomuceno
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In this paper, a nonlinear controller design for an omnidirectional mobile is presented. The robot controller consists of an inner-loop controller and an outer-loop controller, the first is designed using state feedback (robust allocation) and the second controller is designed based on Robust Multi Inversion (RMI) approach. The objective of RMI controller is rendering the robust inversion of the dynamic, when the model is affected by uncertainties. A model nonlinear MIMO of an omni-directional robot (small-league of Robocup) is used to simulate the RMI approach. The parameters of linear and nonlinear model are varied to cause modelling uncertainties among the model and the real model (real system) generating an error in inner-loop controller signal that must be compensated by RMI controller. The simulation test results show that the RMI is capable of compensating the uncertainties and keep the system stable and controlled under uncertainties.Keywords: robust multi inversion, omni-directional robot, robocup, nonlinear control
Procedia PDF Downloads 5893693 Contribution to the Analytical Study of Barrier Surface Waves: Decomposition of the Solution
Authors: T. Zitoun, M. Bouhadef
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When a partially or completely immersed solid moves in a liquid such as water, it undergoes a force called hydrodynamic drag. Reducing this force has always been the objective of hydrodynamic engineers to make water slide better on submerged bodies. This paper deals with the examination of the different terms composing the analytical solution of the flow over an obstacle embedded at the bottom of a hydraulic channel. We have chosen to use a linear method to study a two-dimensional flow over an obstacle, in order to understand the evolution of the drag. We set the following assumptions: incompressible inviscid fluid, irrotational flow, low obstacle height compared to the water height. Those assumptions allow overcoming the difficulties associated with modelling these waves. We will mathematically formulate the equations that allow the determination of the stream function, and then the free surface equation. A similar method is used to determine the exact analytical solution for an obstacle in the shape of a sinusoidal arch.Keywords: analytical solution, free-surface wave, hydraulic channel, inviscid fluid
Procedia PDF Downloads 1973692 A Damage-Plasticity Concrete Model for Damage Modeling of Reinforced Concrete Structures
Authors: Thanh N. Do
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This paper addresses the modeling of two critical behaviors of concrete material in reinforced concrete components: (1) the increase in strength and ductility due to confining stresses from surrounding transverse steel reinforcements, and (2) the progressive deterioration in strength and stiffness due to high strain and/or cyclic loading. To improve the state-of-the-art, the author presents a new 3D constitutive model of concrete material based on plasticity and continuum damage mechanics theory to simulate both the confinement effect and the strength deterioration in reinforced concrete components. The model defines a yield function of the stress invariants and a compressive damage threshold based on the level of confining stresses to automatically capture the increase in strength and ductility when subjected to high compressive stresses. The model introduces two damage variables to describe the strength and stiffness deterioration under tensile and compressive stress states. The damage formulation characterizes well the degrading behavior of concrete material, including the nonsymmetric strength softening in tension and compression, as well as the progressive strength and stiffness degradation under primary and follower load cycles. The proposed damage model is implemented in a general purpose finite element analysis program allowing an extensive set of numerical simulations to assess its ability to capture the confinement effect and the degradation of the load-carrying capacity and stiffness of structural elements. It is validated against a collection of experimental data of the hysteretic behavior of reinforced concrete columns and shear walls under different load histories. These correlation studies demonstrate the ability of the model to describe vastly different hysteretic behaviors with a relatively consistent set of parameters. The model shows excellent consistency in response determination with very good accuracy. Its numerical robustness and computational efficiency are also very good and will be further assessed with large-scale simulations of structural systems.Keywords: concrete, damage-plasticity, shear wall, confinement
Procedia PDF Downloads 1693691 Health and Greenhouse Gas Emission Implications of Reducing Meat Intakes in Hong Kong
Authors: Cynthia Sau Chun Yip, Richard Fielding
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High meat and especially red meat intakes are significantly and positively associated with a multiple burden of diseases and also high greenhouse gas (GHG) emissions. This study investigated population meat intake patterns in Hong Kong. It quantified the burden of disease and GHG emission outcomes by modeling to adjust Hong Kong population meat intakes to recommended healthy levels. It compared age- and sex-specific population meat, fruit and vegetable intakes obtained from a population survey among adults aged 20 years and over in Hong Kong in 2005-2007, against intake recommendations suggested in the Modelling System to Inform the Revision of the Australian Guide to Healthy Eating (AGHE-2011-MS) technical document. This study found that meat and meat alternatives, especially red meat intakes among Hong Kong males aged 20+ years and over are significantly higher than recommended. Red meat intakes among females aged 50-69 years and other meat and alternatives intakes among aged 20-59 years are also higher than recommended. Taking the 2005-07 age- and sex-specific population meat intake as baselines, three counterfactual scenarios of adjusting Hong Kong adult population meat intakes to AGHE-2011-MS and Pre-2011 AGHE recommendations by the year 2030 were established. Consequent energy intake gaps were substituted with additional legume, fruit and vegetable intakes. To quantify the consequent GHG emission outcomes associated with Hong Kong meat intakes, Cradle-to-ready-to-eat lifecycle assessment emission outcome modelling was used. Comparative risk assessment of burden of disease model was used to quantify the health outcomes. This study found adjusting meat intakes to recommended levels could reduce Hong Kong GHG emission by 17%-44% when compared against baseline meat intake emissions, and prevent 2,519 to 7,012 premature deaths in males and 53 to 1,342 in females, as well as multiple burden of diseases when compared to the baseline meat intake scenario. Comparing lump sum meat intake reduction and outcome measures across the entire population, and using emission factors, and relative risks from individual studies in previous co-benefit studies, this study used age- and sex-specific input and output measures, emission factors and relative risks obtained from high quality meta-analysis and meta-review respectively, and has taken government dietary recommendations into account. Hence evaluations in this study are of better quality and more reflective of real life practices. Further to previous co-benefit studies, this study pinpointed age- and sex-specific population and meat-type-specific intervention points and leverages. When compared with similar studies in Australia, this study also showed that intervention points and leverages among populations in different geographic and cultural background could be different, and that globalization also globalizes meat consumption emission effects. More regional and cultural specific evaluations are recommended to promote more sustainable meat consumption and enhance global food security.Keywords: burden of diseases, greenhouse gas emissions, Hong Kong diet, sustainable meat consumption
Procedia PDF Downloads 3113690 Rail Degradation Modelling Using ARMAX: A Case Study Applied to Melbourne Tram System
Authors: M. Karimpour, N. Elkhoury, L. Hitihamillage, S. Moridpour, R. Hesami
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There is a necessity among rail transportation authorities for a superior understanding of the rail track degradation overtime and the factors influencing rail degradation. They need an accurate technique to identify the time when rail tracks fail or need maintenance. In turn, this will help to increase the level of safety and comfort of the passengers and the vehicles as well as improve the cost effectiveness of maintenance activities. An accurate model can play a key role in prediction of the long-term behaviour of railroad tracks. An accurate model can decrease the cost of maintenance. In this research, the rail track degradation is predicted using an autoregressive moving average with exogenous input (ARMAX). An ARMAX has been implemented on Melbourne tram data to estimate the values for the tram track degradation. Gauge values and rail usage in Million Gross Tone (MGT) are the main parameters used in the model. The developed model can accurately predict the future status of the tram tracks.Keywords: ARMAX, dynamic systems, MGT, prediction, rail degradation
Procedia PDF Downloads 2483689 Modelling of Cavity Growth in Underground Coal Gasification
Authors: Preeti Aghalayam, Jay Shah
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Underground coal gasification (UCG) is the in-situ gasification of unmineable coals to produce syngas. In UCG, gasifying agents are injected into the coal seam, and a reactive cavity is formed due to coal consumption. The cavity formed is typically hemispherical, and this report consists of the MATLAB model of the UCG cavity to predict the composition of the output gases. There are seven radial and two time-variant ODEs. A MATLAB solver (ode15s) is used to solve the radial ODEs from the above equations. Two for-loops are implemented in the model, i.e., one for time variations and another for radial variation. In the time loop, the radial odes are solved using the MATLAB solver. The radial loop is nested inside the time loop, and the density odes are numerically solved using the Euler method. The model is validated by comparing it with the literature results of laboratory-scale experiments. The model predicts the radial and time variation of the product gases inside the cavity.Keywords: gasification agent, MATLAB model, syngas, underground coal gasification (UCG)
Procedia PDF Downloads 2063688 Text Mining of Twitter Data Using a Latent Dirichlet Allocation Topic Model and Sentiment Analysis
Authors: Sidi Yang, Haiyi Zhang
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Twitter is a microblogging platform, where millions of users daily share their attitudes, views, and opinions. Using a probabilistic Latent Dirichlet Allocation (LDA) topic model to discern the most popular topics in the Twitter data is an effective way to analyze a large set of tweets to find a set of topics in a computationally efficient manner. Sentiment analysis provides an effective method to show the emotions and sentiments found in each tweet and an efficient way to summarize the results in a manner that is clearly understood. The primary goal of this paper is to explore text mining, extract and analyze useful information from unstructured text using two approaches: LDA topic modelling and sentiment analysis by examining Twitter plain text data in English. These two methods allow people to dig data more effectively and efficiently. LDA topic model and sentiment analysis can also be applied to provide insight views in business and scientific fields.Keywords: text mining, Twitter, topic model, sentiment analysis
Procedia PDF Downloads 1793687 Fire Resistance of High Alumina Cement and Slag Based Ultra High Performance Fibre-Reinforced Cementitious Composites
Authors: A. Q. Sobia, M. S. Hamidah, I. Azmi, S. F. A. Rafeeqi
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Fibre-reinforced polymer (FRP) strengthened reinforced concrete (RC) structures are susceptible to intense deterioration when exposed to elevated temperatures, particularly in the incident of fire. FRP has the tendency to lose bond with the substrate due to the low glass transition temperature of epoxy; the key component of FRP matrix. In the past few decades, various types of high performance cementitious composites (HPCC) were explored for the protection of RC structural members against elevated temperature. However, there is an inadequate information on the influence of elevated temperature on the ultra high performance fibre-reinforced cementitious composites (UHPFRCC) containing ground granulated blast furnace slag (GGBS) as a replacement of high alumina cement (HAC) in conjunction with hybrid fibres (basalt and polypropylene fibres), which could be a prospective fire resisting material for the structural components. The influence of elevated temperatures on the compressive as well as flexural strength of UHPFRCC, made of HAC-GGBS and hybrid fibres, were examined in this study. Besides control sample (without fibres), three other samples, containing 0.5%, 1% and 1.5% of basalt fibres by total weight of mix and 1 kg/m3 of polypropylene fibres, were prepared and tested. Another mix was also prepared with only 1 kg/m3 of polypropylene fibres. Each of the samples were retained at ambient temperature as well as exposed to 400, 700 and 1000 °C followed by testing after 28 and 56 days of conventional curing. Investigation of results disclosed that the use of hybrid fibres significantly helped to improve the ambient temperature compressive and flexural strength of UHPFRCC, which was found to be 80 and 14.3 MPa respectively. However, the optimum residual compressive strength was marked by UHPFRCC-CP (with polypropylene fibres only), equally after both curing days (28 and 56 days), i.e. 41%. In addition, the utmost residual flexural strength, after 28 and 56 days of curing, was marked by UHPFRCC– CP and UHPFRCC– CB2 (1 kg/m3 of PP fibres + 1% of basalt fibres) i.e. 39% and 48.5% respectively.Keywords: fibre reinforced polymer materials (FRP), ground granulated blast furnace slag (GGBS), high-alumina cement, hybrid, fibres
Procedia PDF Downloads 2873686 The Impact of Universal Design for Learning Implementation on Teaching Practices for Students with Intellectual Disabilities in the Kingdom of Saudi Arabia
Authors: Adnan Alhazmi
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Background: UDL can be understood as a framework that holds the potential to elaborate the alternatives and platforms for the students with intellectual disabilities within general education settings and aims at offering flexible pathways that can support all the students in gaining a mastering over the goals of learning. This system of learning addresses the problem of the variability of the learner by delineating the diverse ways in which the individuals can understand, conceive, express and deal with the information. Goal: The aim of the proposed research is to examine the impact of the implementation of UDL in teaching practices for the students with intellectual disabilities in Saudi Arabian schools. Method: This research has used a combination of quantitative and qualitative designs. Survey questionnaires were used to gather the data for under this analytical descriptive method. The application of the qualitative interpretive approach was applied with the help of the interview to gather a detailed understanding on the aim of the research. For this purpose, the semi-structured interviews were conducted. Thus, the primary data will be gathered with the help of survey and interview to examine the impact of universal design learning implementation on teaching practices for intellectually disabled students in Saudi Arabian schools. The survey was conducted to examine the prevailing teaching practices for the students with intellectual disabilities in Saudi Arabia and evaluate if the teaching experience influences the current practices or not. The surveys were distributed to 50 teachers who teach the students with intellectual disabilities. However, the interviews were conducted to explore barriers of implementing UDL in Saudi Arabia and provide suggested guideline for the implementation of UDL in Saudi Arabia. The interviews, therefore, were with 10 teachers teaching the same subject. Findings: A key findings highlighted in this study revealed that the UDL framework serves as a crucial guide for teachers within inclusive settings to undertake meaningful planning for the individuals with intellectual disabilities so that they are able to access, participate, and grow within the general education curriculum. Other findings of the study highlighted the need to prepare the educators and all faculty members to understand the purpose and need for inclusion, the UDL framework so that better information about academic and social expectations for individuals with intellectual disabilities can be delivered. Conclusion: On the basis of the preliminary study undertaken on the subject of research, it could be suggested that UDL can serve to be an effective support for undertaking a meaningful inclusion of students with intellectual disability (ID) in general educational settings. It holds the potential role of working as an institutional design framework that could be used for designing curriculum for students with intellectual disabilities.Keywords: intellectual disability, inclusion, universal design for learning, teaching practice
Procedia PDF Downloads 1393685 Optimal-Based Structural Vibration Attenuation Using Nonlinear Tuned Vibration Absorbers
Authors: Pawel Martynowicz
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Vibrations are a crucial problem for slender structures such as towers, masts, chimneys, wind turbines, bridges, high buildings, etc., that is why most of them are equipped with vibration attenuation or fatigue reduction solutions. In this work, a slender structure (i.e., wind turbine tower-nacelle model) equipped with nonlinear, semiactive tuned vibration absorber(s) is analyzed. For this study purposes, magnetorheological (MR) dampers are used as semiactive actuators. Several optimal-based approaches to structural vibration attenuation are investigated against the standard ‘ground-hook’ law and passive tuned vibration absorber(s) implementations. The common approach to optimal control of nonlinear systems is offline computation of the optimal solution, however, so determined open loop control suffers from lack of robustness to uncertainties (e.g., unmodelled dynamics, perturbations of external forces or initial conditions), and thus perturbation control techniques are often used. However, proper linearization may be an issue for highly nonlinear systems with implicit relations between state, co-state, and control. The main contribution of the author is the development as well as numerical and experimental verification of the Pontriagin maximum-principle-based vibration control concepts that produce directly actuator control input (not the demanded force), thus force tracking algorithm that results in control inaccuracy is entirely omitted. These concepts, including one-step optimal control, quasi-optimal control, and optimal-based modified ‘ground-hook’ law, can be directly implemented in online and real-time feedback control for periodic (or semi-periodic) disturbances with invariant or time-varying parameters, as well as for non-periodic, transient or random disturbances, what is a limitation for some other known solutions. No offline calculation, excitations/disturbances assumption or vibration frequency determination is necessary, moreover, all of the nonlinear actuator (MR damper) force constraints, i.e., no active forces, lower and upper saturation limits, hysteresis-type dynamics, etc., are embedded in the control technique, thus the solution is optimal or suboptimal for the assumed actuator, respecting its limitations. Depending on the selected method variant, a moderate or decisive reduction in the computational load is possible compared to other methods of nonlinear optimal control, while assuring the quality and robustness of the vibration reduction system, as well as considering multi-pronged operational aspects, such as possible minimization of the amplitude of the deflection and acceleration of the vibrating structure, its potential and/or kinetic energy, required actuator force, control input (e.g. electric current in the MR damper coil) and/or stroke amplitude. The developed solutions are characterized by high vibration reduction efficiency – the obtained maximum values of the dynamic amplification factor are close to 2.0, while for the best of the passive systems, these values exceed 3.5.Keywords: magnetorheological damper, nonlinear tuned vibration absorber, optimal control, real-time structural vibration attenuation, wind turbines
Procedia PDF Downloads 1243684 Biomimetic Dinitrosyl Iron Complexes: A Synthetic, Structural, and Spectroscopic Study
Authors: Lijuan Li
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Nitric oxide (NO) has become a fascinating entity in biological chemistry over the past few years. It is a gaseous lipophilic radical molecule that plays important roles in several physiological and pathophysiological processes in mammals, including activating the immune response, serving as a neurotransmitter, regulating the cardiovascular system, and acting as an endothelium-derived relaxing factor. NO functions in eukaryotes both as a signal molecule at nanomolar concentrations and as a cytotoxic agent at micromolar concentrations. The latter arises from the ability of NO to react readily with a variety of cellular targets leading to thiol S-nitrosation, amino acid N-nitrosation, and nitrosative DNA damage. Nitric oxide can readily bind to metals to give metal-nitrosyl (M-NO) complexes. Some of these species are known to play roles in biological NO storage and transport. These complexes have different biological, photochemical, or spectroscopic properties due to distinctive structural features. These recent discoveries have spawned a great interest in the development of transition metal complexes containing NO, particularly its iron complexes that are central to the role of nitric oxide in the body. Spectroscopic evidence would appear to implicate species of “Fe(NO)2+” type in a variety of processes ranging from polymerization, carcinogenesis, to nitric oxide stores. Our research focuses on isolation and structural studies of non-heme iron nitrosyls that mimic biologically active compounds and can potentially be used for anticancer drug therapy. We have shown that reactions between Fe(NO)2(CO)2 and a series of imidazoles generated new non-heme iron nitrosyls of the form Fe(NO)2(L)2 [L = imidazole, 1-methylimidazole, 4-methylimidazole, benzimidazole, 5,6-dimethylbenzimidazole, and L-histidine] and a tetrameric cluster of [Fe(NO)2(L)]4 (L=Im, 4-MeIm, BzIm, and Me2BzIm), resulted from the interactions of Fe(NO)2 with a series of substituted imidazoles was prepared. Recently, a series of sulfur bridged iron di nitrosyl complexes with the general formula of [Fe(µ-RS)(NO)2]2 (R = n-Pr, t-Bu, 6-methyl-2-pyridyl, and 4,6-dimethyl-2-pyrimidyl), were synthesized by the reaction of Fe(NO)2(CO)2 with thiols or thiolates. Their structures and properties were studied by IR, UV-vis, 1H-NMR, EPR, electrochemistry, X-ray diffraction analysis and DFT calculations. IR spectra of these complexes display one weak and two strong NO stretching frequencies (νNO) in solution, but only two strong νNO in solid. DFT calculations suggest that two spatial isomers of these complexes bear 3 Kcal energy difference in solution. The paramagnetic complexes [Fe2(µ-RS)2(NO)4]-, have also been investigated by EPR spectroscopy. Interestingly, the EPR spectra of complexes exhibit an isotropic signal of g = 1.998 - 2.004 without hyperfine splitting. The observations are consistent with the results of calculations, which reveal that the unpaired electron dominantly delocalize over the two sulfur and two iron atoms. The difference of the g values between the reduced form of iron-sulfur clusters and the typical monomeric di nitrosyl iron complexes is explained, for the first time, by of the difference in unpaired electron distributions between the two types of complexes, which provides the theoretical basis for the use of g value as a spectroscopic tool to differentiate these biologically active complexes.Keywords: di nitrosyl iron complex, metal nitrosyl, non-heme iron, nitric oxide
Procedia PDF Downloads 304