Search results for: peak shaving
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 1350

Search results for: peak shaving

120 Study the Effect of Liquefaction on Buried Pipelines during Earthquakes

Authors: Mohsen Hababalahi, Morteza Bastami

Abstract:

Buried pipeline damage correlations are critical part of loss estimation procedures applied to lifelines for future earthquakes. The vulnerability of buried pipelines against earthquake and liquefaction has been observed during some of previous earthquakes and there are a lot of comprehensive reports about this event. One of the main reasons for impairment of buried pipelines during earthquake is liquefaction. Necessary conditions for this phenomenon are loose sandy soil, saturation of soil layer and earthquake intensity. Because of this fact that pipelines structure are very different from other structures (being long and having light mass) by paying attention to the results of previous earthquakes and compare them with other structures, it is obvious that the danger of liquefaction for buried pipelines is not high risked, unless effective parameters like earthquake intensity and non-dense soil and other factors be high. Recent liquefaction researches for buried pipeline include experimental and theoretical ones as well as damage investigations during actual earthquakes. The damage investigations have revealed that a damage ratio of pipelines (Number/km ) has much larger values in liquefied grounds compared with one in shaking grounds without liquefaction according to damage statistics during past severe earthquakes, and that damages of joints and pipelines connected with manholes were remarkable. The purpose of this research is numerical study of buried pipelines under the effect of liquefaction by case study of the 2013 Dashti (Iran) earthquake. Water supply and electrical distribution systems of this township interrupted during earthquake and water transmission pipelines were damaged severely due to occurrence of liquefaction. The model consists of a polyethylene pipeline with 100 meters length and 0.8 meter diameter which is covered by light sandy soil and the depth of burial is 2.5 meters from surface. Since finite element method is used relatively successfully in order to solve geotechnical problems, we used this method for numerical analysis. For evaluating this case, some information like geotechnical information, classification of earthquakes levels, determining the effective parameters in probability of liquefaction, three dimensional numerical finite element modeling of interaction between soil and pipelines are necessary. The results of this study on buried pipelines indicate that the effect of liquefaction is function of pipe diameter, type of soil, and peak ground acceleration. There is a clear increase in percentage of damage with increasing the liquefaction severity. The results indicate that although in this form of the analysis, the damage is always associated to a certain pipe material, but the nominally defined “failures” include by failures of particular components (joints, connections, fire hydrant details, crossovers, laterals) rather than material failures. At the end, there are some retrofit suggestions in order to decrease the risk of liquefaction on buried pipelines.

Keywords: liquefaction, buried pipelines, lifelines, earthquake, finite element method

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119 Use of Locomotor Activity of Rainbow Trout Juveniles in Identifying Sublethal Concentrations of Landfill Leachate

Authors: Tomas Makaras, Gintaras Svecevičius

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Landfill waste is a common problem as it has an economic and environmental impact even if it is closed. Landfill waste contains a high density of various persistent compounds such as heavy metals, organic and inorganic materials. As persistent compounds are slowly-degradable or even non-degradable in the environment, they often produce sublethal or even lethal effects on aquatic organisms. The aims of the present study were to estimate sublethal effects of the Kairiai landfill (WGS: 55°55‘46.74“, 23°23‘28.4“) leachate on the locomotor activity of rainbow trout Oncorhynchus mykiss juveniles using the original system package developed in our laboratory for automated monitoring, recording and analysis of aquatic organisms’ activity, and to determine patterns of fish behavioral response to sublethal effects of leachate. Four different concentrations of leachate were chosen: 0.125; 0.25; 0.5 and 1.0 mL/L (0.0025; 0.005; 0.01 and 0.002 as part of 96-hour LC50, respectively). Locomotor activity was measured after 5, 10 and 30 minutes of exposure during 1-minute test-periods of each fish (7 fish per treatment). The threshold-effect-concentration amounted to 0.18 mL/L (0.0036 parts of 96-hour LC50). This concentration was found to be even 2.8-fold lower than the concentration generally assumed to be “safe” for fish. At higher concentrations, the landfill leachate solution elicited behavioral response of test fish to sublethal levels of pollutants. The ability of the rainbow trout to detect and avoid contaminants occurred after 5 minutes of exposure. The intensity of locomotor activity reached a peak within 10 minutes, evidently decreasing after 30 minutes. This could be explained by the physiological and biochemical adaptation of fish to altered environmental conditions. It has been established that the locomotor activity of juvenile trout depends on leachate concentration and exposure duration. Modeling of these parameters showed that the activity of juveniles increased at higher leachate concentrations, but slightly decreased with the increasing exposure duration. Experiment results confirm that the behavior of rainbow trout juveniles is a sensitive and rapid biomarker that can be used in combination with the system for fish behavior monitoring, registration and analysis to determine sublethal concentrations of pollutants in ambient water. Further research should be focused on software improvement aimed to include more parameters of aquatic organisms’ behavior and to investigate the most rapid and appropriate behavioral responses in different species. In practice, this study could be the basis for the development and creation of biological early-warning systems (BEWS).

Keywords: fish behavior biomarker, landfill leachate, locomotor activity, rainbow trout juveniles, sublethal effects

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118 Accuracy of Computed Tomography Dose Monitor Values: A Multicentric Study in India

Authors: Adhimoolam Saravana Kumar, K. N. Govindarajan, B. Devanand, R. Rajakumar

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The quality of Computed Tomography (CT) procedures has improved in recent years due to technological developments and increased diagnostic ability of CT scanners. Due to the fact that CT doses are the peak among diagnostic radiology practices, it is of great significance to be aware of patient’s CT radiation dose whenever a CT examination is preferred. CT radiation dose delivered to patients in the form of volume CT dose index (CTDIvol) values, is displayed on scanner monitors at the end of each examination and it is an important fact to assure that this information is accurate. The objective of this study was to estimate the CTDIvol values for great number of patients during the most frequent CT examinations, to study the comparison between CT dose monitor values and measured ones, as well as to highlight the fluctuation of CTDIvol values for the same CT examination at different centres and scanner models. The output CT dose indices measurements were carried out on single and multislice scanners for available kV, 5 mm slice thickness, 100 mA and FOV combination used. The 100 CT scanners were involved in this study. Data with regard to 15,000 examinations in patients, who underwent routine head, chest and abdomen CT were collected using a questionnaire sent to a large number of hospitals. Out of the 15,000 examinations, 5000 were head CT examinations, 5000 were chest CT examinations and 5000 were abdominal CT examinations. Comprehensive quality assurance (QA) was performed for all the machines involved in this work. Followed by QA, CT phantom dose measurements were carried out in South India using actual scanning parameters used clinically by the hospitals. From this study, we have measured the mean divergence between the measured and displayed CTDIvol values were 5.2, 8.4, and -5.7 for selected head, chest and abdomen procedures for protocols as mentioned above, respectively. Thus, this investigation revealed an observable change in CT practices, with a much wider range of studies being performed currently in South India. This reflects the improved capacity of CT scanners to scan longer scan lengths and at finer resolutions as permitted by helical and multislice technology. Also, some of the CT scanners have used smaller slice thickness for routine CT procedures to achieve better resolution and image quality. It leads to an increase in the patient radiation dose as well as the measured CTDIv, so it is suggested that such CT scanners should select appropriate slice thickness and scanning parameters in order to reduce the patient dose. If these routine scan parameters for head, chest and abdomen procedures are optimized than the dose indices would be optimal and lead to the lowering of the CT doses. In South Indian region all the CT machines were routinely tested for QA once in a year as per AERB requirements.

Keywords: CT dose index, weighted CTDI, volumetric CTDI, radiation dose

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117 The Impact of Tourism on the Intangible Cultural Heritage of Pilgrim Routes: The Case of El Camino de Santiago

Authors: Miguel Angel Calvo Salve

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This qualitative and quantitative study will identify the impact of tourism pressure on the intangible cultural heritage of the pilgrim route of El Camino de Santiago (Saint James Way) and propose an approach to a sustainable touristic model for these Cultural Routes. Since 1993, the Spanish Section of the Pilgrim Route of El Camino de Santiago has been on the World Heritage List. In 1994, the International Committee on Cultural Routes (CIIC-ICOMOS) initiated its work with the goal of studying, preserving, and promoting the cultural routes and their significance as a whole. Another ICOMOS group, the Charter on Cultural Routes, pointed out in 2008 the importance of both tangible and intangible heritage and the need for a holistic vision in preserving these important cultural assets. Tangible elements provide a physical confirmation of the existence of these cultural routes, while the intangible elements serve to give sense and meaning to it as a whole. Intangible assets of a Cultural Route are key to understanding the route's significance and its associated heritage values. Like many pilgrim routes, the Route to Santiago, as the result of a long evolutionary process, exhibits and is supported by intangible assets, including hospitality, cultural and religious expressions, music, literature, and artisanal trade, among others. A large increase in pilgrims walking the route, with very different aims and tourism pressure, has shown how the dynamic links between the intangible cultural heritage and the local inhabitants along El Camino are fragile and vulnerable. Economic benefits for the communities and population along the cultural routes are commonly fundamental for the micro-economies of the people living there, substituting traditional productive activities, which, in fact, modifies and has an impact on the surrounding environment and the route itself. Consumption of heritage is one of the major issues of sustainable preservation promoted with the intention of revitalizing those sites and places. The adaptation of local communities to new conditions aimed at preserving and protecting existing heritage has had a significant impact on immaterial inheritance. Based on questionnaires to pilgrims, tourists and local communities along El Camino during the peak season of the year, and using official statistics from the Galician Pilgrim’s Office, this study will identify the risk and threats to El Camino de Santiago as a Cultural Route. The threats visible nowadays due to the impact of mass tourism include transformations of tangible heritage, consumerism of the intangible, changes of local activities, loss in the authenticity of symbols and spiritual significance, and pilgrimage transformed into a tourism ‘product’, among others. The study will also approach some measures and solutions to mitigate those impacts and better preserve this type of cultural heritage. Therefore, this study will help the Route services providers and policymakers to better preserve the Cultural Route as a whole to ultimately improve the satisfying experience of pilgrims.

Keywords: cultural routes, El Camino de Santiago, impact of tourism, intangible heritage

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116 Modelling of Air-Cooled Adiabatic Membrane-Based Absorber for Absorption Chillers Using Low Temperature Solar Heat

Authors: M. Venegas, M. De Vega, N. García-Hernando

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Absorption cooling chillers have received growing attention over the past few decades as they allow the use of low-grade heat to produce the cooling effect. The combination of this technology with solar thermal energy in the summer period can reduce the electricity consumption peak due to air-conditioning. One of the main components, the absorber, is designed for simultaneous heat and mass transfer. Usually, shell and tubes heat exchangers are used, which are large and heavy. Cooling water from a cooling tower is conventionally used to extract the heat released during the absorption and condensation processes. These are clear inconvenient for the generalization of the absorption technology use, limiting its benefits in the contribution to the reduction in CO2 emissions, particularly for the H2O-LiBr solution which can work with low heat temperature sources as provided by solar panels. In the present work a promising new technology is under study, consisting in the use of membrane contactors in adiabatic microchannel mass exchangers. The configuration here proposed consists in one or several modules (depending on the cooling capacity of the chiller) that contain two vapour channels, separated from the solution by adjacent microporous membranes. The solution is confined in rectangular microchannels. A plastic or synthetic wall separates the solution channels between them. The solution entering the absorber is previously subcooled using ambient air. In this way, the need for a cooling tower is avoided. A model of the configuration proposed is developed based on mass and energy balances and some correlations were selected to predict the heat and mass transfer coefficients. The concentration and temperatures along the channels cannot be explicitly determined from the set of equations obtained. For this reason, the equations were implemented in a computer code using Engineering Equation Solver software, EES™. With the aim of minimizing the absorber volume to reduce the size of absorption cooling chillers, the ratio between the cooling power of the chiller and the absorber volume (R) is calculated. Its variation is shown along the solution channels, allowing its optimization for selected operating conditions. For the case considered the solution channel length is recommended to be lower than 3 cm. Maximum values of R obtained in this work are higher than the ones found in optimized horizontal falling film absorbers using the same solution. Results obtained also show the variation of R and the chiller efficiency (COP) for different ambient temperatures and desorption temperatures typically obtained using flat plate solar collectors. The configuration proposed of adiabatic membrane-based absorber using ambient air to subcool the solution is a good technology to reduce the size of the absorption chillers, allowing the use of low temperature solar heat and avoiding the need for cooling towers.

Keywords: adiabatic absorption, air-cooled, membrane, solar thermal energy

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115 Influence of Footing Offset over Stability of Geosynthetic Reinforced Soil Abutments with Variable Facing under Lateral Excitation

Authors: Ashutosh Verma, Satyendra MIttal

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The loss of strength at the facing-reinforcement interface brought on by the seasonal thermal expansion/contraction of the bridge deck has been responsible for several geosynthetic reinforced soil abutment failures over the years. This results in excessive settlement below the bridge seat, which results in bridge bumps along the approach road and shortens abutment's design life. There are surely a wide variety of facing configurations available to designers when choosing the sort of facade. These layouts can generally be categorised into three groups: continuous, full height rigid (FHR) and modular (panels/block). The current work aims to experimentally explore the behavior of these three facing categories using 1g physical model testing under serviceable cyclic lateral displacements. With configurable facing arrangements to represent these three facing categories, a field instrumented GRS abutment prototype was modelled into a N scaled down 1g physical model (N = 5) to reproduce field behavior. Peak earth pressure coefficient (K) on the facing and vertical settlement of the footing (s/B) for footing offset (x/H) as 0.1, 0.2, 0.3, 0.4 and 0.5 at 100 cycles have been measured for cyclic lateral displacement of top of facing at loading rate of 1mm/min. Three types of cyclic displacements have been carried out to replicate active condition (CA), passive condition (CP), and active-passive condition (CAP) for each footing offset. The results demonstrated that a significant decrease in the earth pressure over the facing occurs when footing offset increases. It is worth noticing that the highest rate of increment in earth pressure and footing settlement were observed for each facing configuration at the nearest footing offset. Interestingly, for the farthest footing offset, similar responses of each facing type were observed, which indicates that the upon reaching a critical offset point presumably beyond the active region in the backfill, the lateral responses become independent of the stresses from the external footing load. Evidently, the footing load complements the stresses developed due to lateral excitation resulting in significant footing settlements for nearer footing offsets. The modular facing proved inefficient in resisting footing settlement due to significant buckling along the depth of facing. Instead of relative displacement along the depth of facing, continuous facing rotates around the base when it fails, especially for nearer footing offset causing significant depressions in the backfill area surrounding the footing. FHR facing, on the other hand, have been successful in confining the stresses in the soil domain itself reducing the footing settlement. It may be suitably concluded that increasing the footing offset may render stability to the GRS abutment with any facing configuration even for higher cycles of excitation.

Keywords: GRS abutments, 1g physical model, footing offset, cyclic lateral displacement

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114 Polymer Nanocomposite Containing Silver Nanoparticles for Wound Healing

Authors: Patrícia Severino, Luciana Nalone, Daniele Martins, Marco Chaud, Classius Ferreira, Cristiane Bani, Ricardo Albuquerque

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Hydrogels produced with polymers have been used in the development of dressings for wound treatment and tissue revitalization. Our study on polymer nanocomposites containing silver nanoparticles shows antimicrobial activity and applications in wound healing. The effects are linked with the slow oxidation and Ag⁺ liberation to the biological environment. Furthermore, bacterial cell membrane penetration and metabolic disruption through cell cycle disarrangement also contribute to microbial cell death. The silver antimicrobial activity has been known for many years, and previous reports show that low silver concentrations are safe for human use. This work aims to develop a hydrogel using natural polymers (sodium alginate and gelatin) combined with silver nanoparticles for wound healing and with antimicrobial properties in cutaneous lesions. The hydrogel development utilized different sodium alginate and gelatin proportions (20:80, 50:50 and 80:20). The silver nanoparticles incorporation was evaluated at the concentrations of 1.0, 2.0 and 4.0 mM. The physico-chemical properties of the formulation were evaluated using ultraviolet-visible (UV-Vis) absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric (TG) analysis. The morphological characterization was made using transmission electron microscopy (TEM). Human fibroblast (L2929) viability assay was performed with a minimum inhibitory concentration (MIC) assessment as well as an in vivo cicatrizant test. The results suggested that sodium alginate and gelatin in the (80:20) proportion with 4 mM of AgNO₃ in the (UV-Vis) exhibited a better hydrogel formulation. The nanoparticle absorption spectra of this analysis showed a maximum band around 430 - 450 nm, which suggests a spheroidal form. The TG curve exhibited two weight loss events. DSC indicated one endothermic peak at 230-250 °C, due to sample fusion. The polymers acted as stabilizers of a nanoparticle, defining their size and shape. Human fibroblast viability assay L929 gave 105 % cell viability with a negative control, while gelatin presented 96% viability, alginate: gelatin (80:20) 96.66 %, and alginate 100.33 % viability. The sodium alginate:gelatin (80:20) exhibited significant antimicrobial activity, with minimal bacterial growth at a ratio of 1.06 mg.mL⁻¹ in Pseudomonas aeruginosa and 0.53 mg.mL⁻¹ in Staphylococcus aureus. The in vivo results showed a significant reduction in wound surface area. On the seventh day, the hydrogel-nanoparticle formulation reduced the total area of injury by 81.14 %, while control reached a 45.66 % reduction. The results suggest that silver-hydrogel nanoformulation exhibits potential for wound dressing therapeutics.

Keywords: nanocomposite, wound healing, hydrogel, silver nanoparticle

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113 Techno Economic Analysis for Solar PV and Hydro Power for Kafue Gorge Power Station

Authors: Elvis Nyirenda

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This research study work was done to evaluate and propose an optimum measure to enhance the uptake of clean energy technologies such as solar photovoltaics, the study also aims at enhancing the country’s energy mix from the overdependence on hydro power which is susceptible to droughts and climate change challenges The country in the years 2015 - 2016 and 2018 - 2019 had received rainfall below average due to climate change and a shift in the weather pattern; this resulted in prolonged power outages and load shedding for more than 10 hours per day. ZESCO Limited, the utility company that owns infrastructure in the generation, transmission, and distribution of electricity (state-owned), is seeking alternative sources of energy in order to reduce the over-dependence on hydropower stations. One of the alternative sources of energy is Solar Energy from the sun. However, solar power is intermittent in nature and to smoothen the load curve, investment in robust energy storage facilities is of great importance to enhance security and reliability of electricity supply in the country. The methodology of the study looked at the historical performance of the Kafue gorge upper power station and utilised the hourly generation figures as input data for generation modelling in Homer software. The average yearly demand was derived from the available data on the system SCADA. The two dams were modelled as natural battery with the absolute state of charging and discharging determined by the available water resource and the peak electricity demand. The software Homer Energy System is used to simulate the scheme incorporating a pumped storage facility and Solar photovoltaic systems. The pumped hydro scheme works like a natural battery for the conservation of water, with the only losses being evaporation and water leakages from the dams and the turbines. To address the problem of intermittency on the solar resource and the non-availability of water for hydropower generation, the study concluded that utilising the existing Hydro power stations, Kafue Gorge upper and Kafue Gorge Lower to work conjunctively with Solar energy will reduce power deficits and increase the security of supply for the country. An optimum capacity of 350MW of solar PV can be integrated while operating Kafue Gorge power station in both generating and pumping mode to enable efficient utilisation of water at Kafue Gorge upper Dam and Kafue Gorge Lower dam.

Keywords: hydropower, solar power systems, energy storage, photovoltaics, solar irradiation, pumped hydro storage system, supervisory control and data acquisition, Homer energy

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112 Evolution of Microstructure through Phase Separation via Spinodal Decomposition in Spinel Ferrite Thin Films

Authors: Nipa Debnath, Harinarayan Das, Takahiko Kawaguchi, Naonori Sakamoto, Kazuo Shinozaki, Hisao Suzuki, Naoki Wakiya

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Nowadays spinel ferrite magnetic thin films have drawn considerable attention due to their interesting magnetic and electrical properties with enhanced chemical and thermal stability. Spinel ferrite magnetic films can be implemented in magnetic data storage, sensors, and spin filters or microwave devices. It is well established that the structural, magnetic and transport properties of the magnetic thin films are dependent on microstructure. Spinodal decomposition (SD) is a phase separation process, whereby a material system is spontaneously separated into two phases with distinct compositions. The periodic microstructure is the characteristic feature of SD. Thus, SD can be exploited to control the microstructure at the nanoscale level. In bulk spinel ferrites having general formula, MₓFe₃₋ₓ O₄ (M= Co, Mn, Ni, Zn), phase separation via SD has been reported only for cobalt ferrite (CFO); however, long time post-annealing is required to occur the spinodal decomposition. We have found that SD occurs in CoF thin film without using any post-deposition annealing process if we apply magnetic field during thin film growth. Dynamic Aurora pulsed laser deposition (PLD) is a specially designed PLD system through which in-situ magnetic field (up to 2000 G) can be applied during thin film growth. The in-situ magnetic field suppresses the recombination of ions in the plume. In addition, the peak’s intensity of the ions in the spectra of the plume also increases when magnetic field is applied to the plume. As a result, ions with high kinetic energy strike into the substrate. Thus, ion-impingement occurred under magnetic field during thin film growth. The driving force of SD is the ion-impingement towards the substrates that is induced by in-situ magnetic field. In this study, we report about the occurrence of phase separation through SD and evolution of microstructure after phase separation in spinel ferrite thin films. The surface morphology of the phase separated films show checkerboard like domain structure. The cross-sectional microstructure of the phase separated films reveal columnar type phase separation. Herein, the decomposition wave propagates in lateral direction which has been confirmed from the lateral composition modulations in spinodally decomposed films. Large magnetic anisotropy has been found in spinodally decomposed nickel ferrite (NFO) thin films. This approach approves that magnetic field is also an important thermodynamic parameter to induce phase separation by the enhancement of up-hill diffusion in thin films. This thin film deposition technique could be a more efficient alternative for the fabrication of self-organized phase separated thin films and employed in controlling of the microstructure at nanoscale level.

Keywords: Dynamic Aurora PLD, magnetic anisotropy, spinodal decomposition, spinel ferrite thin film

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111 Detection of Some Drugs of Abuse from Fingerprints Using Liquid Chromatography-Mass Spectrometry

Authors: Ragaa T. Darwish, Maha A. Demellawy, Haidy M. Megahed, Doreen N. Younan, Wael S. Kholeif

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The testing of drug abuse is authentic in order to affirm the misuse of drugs. Several analytical approaches have been developed for the detection of drugs of abuse in pharmaceutical and common biological samples, but few methodologies have been created to identify them from fingerprints. Liquid Chromatography-Mass Spectrometry (LC-MS) plays a major role in this field. The current study aimed at assessing the possibility of detection of some drugs of abuse (tramadol, clonazepam, and phenobarbital) from fingerprints using LC-MS in drug abusers. The aim was extended in order to assess the possibility of detection of the above-mentioned drugs in fingerprints of drug handlers till three days of handling the drugs. The study was conducted on randomly selected adult individuals who were either drug abusers seeking treatment at centers of drug dependence in Alexandria, Egypt or normal volunteers who were asked to handle the different studied drugs (drug handlers). An informed consent was obtained from all individuals. Participants were classified into 3 groups; control group that consisted of 50 normal individuals (neither abusing nor handling drugs), drug abuser group that consisted of 30 individuals who abused tramadol, clonazepam or phenobarbital (10 individuals for each drug) and drug handler group that consisted of 50 individuals who were touching either the powder of drugs of abuse: tramadol, clonazepam or phenobarbital (10 individuals for each drug) or the powder of the control substances which were of similar appearance (white powder) and that might be used in the adulteration of drugs of abuse: acetyl salicylic acid and acetaminophen (10 individuals for each drug). Samples were taken from the handler individuals for three consecutive days for the same individual. The diagnosis of drug abusers was based on the current Diagnostic and Statistical Manual of Mental disorders (DSM-V) and urine screening tests using immunoassay technique. Preliminary drug screening tests of urine samples were also done for drug handlers and the control groups to indicate the presence or absence of the studied drugs of abuse. Fingerprints of all participants were then taken on a filter paper previously soaked with methanol to be analyzed by LC-MS using SCIEX Triple Quad or QTRAP 5500 System. The concentration of drugs in each sample was calculated using the regression equations between concentration in ng/ml and peak area of each reference standard. All fingerprint samples from drug abusers showed positive results with LC-MS for the tested drugs, while all samples from the control individuals showed negative results. A significant difference was noted between the concentration of the drugs and the duration of abuse. Tramadol, clonazepam, and phenobarbital were also successfully detected from fingerprints of drug handlers till 3 days of handling the drugs. The mean concentration of the chosen drugs of abuse among the handlers group decreased when the days of samples intake increased.

Keywords: drugs of abuse, fingerprints, liquid chromatography–mass spectrometry, tramadol

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110 Effect of Maturation on the Characteristics and Physicochemical Properties of Banana and Its Starch

Authors: Chien-Chun Huang, P. W. Yuan

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Banana is one of the important fruits which constitute a valuable source of energy, vitamins and minerals and an important food component throughout the world. The fruit ripening and maturity standards vary from country to country depending on the expected shelf life of market. During ripening there are changes in appearance, texture and chemical composition of banana. The changes of component of banana during ethylene-induced ripening are categorized as nutritive values and commercial utilization. The objectives of this study were to investigate the changes of chemical composition and physicochemical properties of banana during ethylene-induced ripening. Green bananas were harvested and ripened by ethylene gas at low temperature (15℃) for seven stages. At each stage, banana was sliced and freeze-dried for banana flour preparation. The changes of total starch, resistant starch, chemical compositions, physicochemical properties, activity of amylase, polyphenolic oxidase (PPO) and phenylalanine ammonia lyase (PAL) of banana were analyzed each stage during ripening. The banana starch was isolated and analyzed for gelatinization properties, pasting properties and microscopic appearance each stage of ripening. The results indicated that the highest total starch and resistant starch content of green banana were 76.2% and 34.6%, respectively at the harvest stage. Both total starch and resistant starch content were significantly declined to 25.3% and 8.8%, respectively at the seventh stage. Soluble sugars content of banana increased from 1.21% at harvest stage to 37.72% at seventh stage during ethylene-induced ripening. Swelling power of banana flour decreased with the progress of ripening stage, but solubility increased. These results strongly related with the decreases of starch content of banana flour during ethylene-induced ripening. Both water insoluble and alcohol insoluble solids of banana flour decreased with the progress of ripening stage. Both activity of PPO and PAL increased, but the total free phenolics content decreased, with the increases of ripening stages. As ripening stage extended, the gelatinization enthalpy of banana starch significantly decreased from 15.31 J/g at the harvest stage to 10.55 J/g at the seventh stage. The peak viscosity and setback increased with the progress of ripening stages in the pasting properties of banana starch. The highest final viscosity, 5701 RVU, of banana starch slurry was found at the seventh stage. The scanning electron micrograph of banana starch showed the shapes of banana starch appeared to be round and elongated forms, ranging in 10-50 μm at the harvest stage. As the banana closed to ripe status, some parallel striations were observed on the surface of banana starch granular which could be caused by enzyme reaction during ripening. These results inferred that the highest resistant starch was found in the green banana could be considered as a potential application of healthy foods. The changes of chemical composition and physicochemical properties of banana could be caused by the hydrolysis of enzymes during the ethylene-induced ripening treatment.

Keywords: maturation of banana, appearance, texture, soluble sugars, resistant starch, enzyme activities, physicochemical properties of banana starch

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109 Development and Total Error Concept Validation of Common Analytical Method for Quantification of All Residual Solvents Present in Amino Acids by Gas Chromatography-Head Space

Authors: A. Ramachandra Reddy, V. Murugan, Prema Kumari

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Residual solvents in Pharmaceutical samples are monitored using gas chromatography with headspace (GC-HS). Based on current regulatory and compendial requirements, measuring the residual solvents are mandatory for all release testing of active pharmaceutical ingredients (API). Generally, isopropyl alcohol is used as the residual solvent in proline and tryptophan; methanol in cysteine monohydrate hydrochloride, glycine, methionine and serine; ethanol in glycine and lysine monohydrate; acetic acid in methionine. In order to have a single method for determining these residual solvents (isopropyl alcohol, ethanol, methanol and acetic acid) in all these 7 amino acids a sensitive and simple method was developed by using gas chromatography headspace technique with flame ionization detection. During development, no reproducibility, retention time variation and bad peak shape of acetic acid peaks were identified due to the reaction of acetic acid with the stationary phase (cyanopropyl dimethyl polysiloxane phase) of column and dissociation of acetic acid with water (if diluent) while applying temperature gradient. Therefore, dimethyl sulfoxide was used as diluent to avoid these issues. But most the methods published for acetic acid quantification by GC-HS uses derivatisation technique to protect acetic acid. As per compendia, risk-based approach was selected as appropriate to determine the degree and extent of the validation process to assure the fitness of the procedure. Therefore, Total error concept was selected to validate the analytical procedure. An accuracy profile of ±40% was selected for lower level (quantitation limit level) and for other levels ±30% with 95% confidence interval (risk profile 5%). The method was developed using DB-Waxetr column manufactured by Agilent contains 530 µm internal diameter, thickness: 2.0 µm, and length: 30 m. A constant flow of 6.0 mL/min. with constant make up mode of Helium gas was selected as a carrier gas. The present method is simple, rapid, and accurate, which is suitable for rapid analysis of isopropyl alcohol, ethanol, methanol and acetic acid in amino acids. The range of the method for isopropyl alcohol is 50ppm to 200ppm, ethanol is 50ppm to 3000ppm, methanol is 50ppm to 400ppm and acetic acid 100ppm to 400ppm, which covers the specification limits provided in European pharmacopeia. The accuracy profile and risk profile generated as part of validation were found to be satisfactory. Therefore, this method can be used for testing of residual solvents in amino acids drug substances.

Keywords: amino acid, head space, gas chromatography, total error

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108 Machine Learning Techniques in Seismic Risk Assessment of Structures

Authors: Farid Khosravikia, Patricia Clayton

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The main objective of this work is to evaluate the advantages and disadvantages of various machine learning techniques in two key steps of seismic hazard and risk assessment of different types of structures. The first step is the development of ground-motion models, which are used for forecasting ground-motion intensity measures (IM) given source characteristics, source-to-site distance, and local site condition for future events. IMs such as peak ground acceleration and velocity (PGA and PGV, respectively) as well as 5% damped elastic pseudospectral accelerations at different periods (PSA), are indicators of the strength of shaking at the ground surface. Typically, linear regression-based models, with pre-defined equations and coefficients, are used in ground motion prediction. However, due to the restrictions of the linear regression methods, such models may not capture more complex nonlinear behaviors that exist in the data. Thus, this study comparatively investigates potential benefits from employing other machine learning techniques as statistical method in ground motion prediction such as Artificial Neural Network, Random Forest, and Support Vector Machine. The results indicate the algorithms satisfy some physically sound characteristics such as magnitude scaling distance dependency without requiring pre-defined equations or coefficients. Moreover, it is shown that, when sufficient data is available, all the alternative algorithms tend to provide more accurate estimates compared to the conventional linear regression-based method, and particularly, Random Forest outperforms the other algorithms. However, the conventional method is a better tool when limited data is available. Second, it is investigated how machine learning techniques could be beneficial for developing probabilistic seismic demand models (PSDMs), which provide the relationship between the structural demand responses (e.g., component deformations, accelerations, internal forces, etc.) and the ground motion IMs. In the risk framework, such models are used to develop fragility curves estimating exceeding probability of damage for pre-defined limit states, and therefore, control the reliability of the predictions in the risk assessment. In this study, machine learning algorithms like artificial neural network, random forest, and support vector machine are adopted and trained on the demand parameters to derive PSDMs for them. It is observed that such models can provide more accurate estimates of prediction in relatively shorter about of time compared to conventional methods. Moreover, they can be used for sensitivity analysis of fragility curves with respect to many modeling parameters without necessarily requiring more intense numerical response-history analysis.

Keywords: artificial neural network, machine learning, random forest, seismic risk analysis, seismic hazard analysis, support vector machine

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107 Comparative Vector Susceptibility for Dengue Virus and Their Co-Infection in A. aegypti and A. albopictus

Authors: Monika Soni, Chandra Bhattacharya, Siraj Ahmed Ahmed, Prafulla Dutta

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Dengue is now a globally important arboviral disease. Extensive vector surveillance has already established A.aegypti as a primary vector, but A.albopictus is now accelerating the situation through gradual adaptation to human surroundings. Global destabilization and gradual climatic shift with rising in temperature have significantly expanded the geographic range of these species These versatile vectors also host Chikungunya, Zika, and yellow fever virus. Biggest challenge faced by endemic countries now is upsurge in co-infection reported with multiple serotypes and virus co-circulation. To foster vector control interventions and mitigate disease burden, there is surge for knowledge on vector susceptibility and viral tolerance in response to multiple infections. To address our understanding on transmission dynamics and reproductive fitness, both the vectors were exposed to single and dual combinations of all four dengue serotypes by artificial feeding and followed up to third generation. Artificial feeding observed significant difference in feeding rate for both the species where A.albopictus was poor artificial feeder (35-50%) compared to A.aegypti (95-97%) Robust sequential screening of viral antigen in mosquitoes was followed by Dengue NS1 ELISA, RT-PCR and Quantitative PCR. To observe viral dissemination in different mosquito tissues Indirect immunofluorescence assay was performed. Result showed that both the vectors were infected initially with all dengue(1-4)serotypes and its co-infection (D1 and D2, D1 and D3, D1 and D4, D2 and D4) combinations. In case of DENV-2 there was significant difference in the peak titer observed at 16th day post infection. But when exposed to dual infections A.aegypti supported all combinations of virus where A.albopictus only continued single infections in successive days. There was a significant negative effect on the fecundity and fertility of both the vectors compared to control (PANOVA < 0.001). In case of dengue 2 infected mosquito, fecundity in parent generation was significantly higher (PBonferroni < 0.001) for A.albopicus compare to A.aegypti but there was a complete loss of fecundity from second to third generation for A.albopictus. It was observed that A.aegypti becomes infected with multiple serotypes frequently even at low viral titres compared to A.albopictus. Possible reason for this could be the presence of wolbachia infection in A.albopictus or mosquito innate immune response, small RNA interference etc. Based on the observations it could be anticipated that transovarial transmission may not be an important phenomenon for clinical disease outcome, due to the absence of viral positivity by third generation. Also, Dengue NS1 ELISA can be used for preliminary viral detection in mosquitoes as more than 90% of the samples were found positive compared to RT-PCR and viral load estimation.

Keywords: co-infection, dengue, reproductive fitness, viral quantification

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106 A New Perspective in Cervical Dystonia: Neurocognitive Impairment

Authors: Yesim Sucullu Karadag, Pinar Kurt, Sule Bilen, Nese Subutay Oztekin, Fikri Ak

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Background: Primary cervical dystonia is thought to be a purely motor disorder. But recent studies revealed that patients with dystonia had additional non-motor features. Sensory and psychiatric disturbances could be included into the non-motor spectrum of dystonia. The Basal Ganglia receive inputs from all cortical areas and throughout the thalamus project to several cortical areas, thus participating to circuits that have been linked to motor as well as sensory, emotional and cognitive functions. However, there are limited studies indicating cognitive impairment in patients with cervical dystonia. More evidence is required regarding neurocognitive functioning in these patients. Objective: This study is aimed to investigate neurocognitive profile of cervical dystonia patients in comparison to healthy controls (HC) by employing a detailed set of neuropsychological tests in addition to self-reported instruments. Methods: Totally 29 (M/F: 7/22) cervical dystonia patients and 30 HC (M/F: 10/20) were included into the study. Exclusion criteria were depression and not given informed consent. Standard demographic, educational data and clinical reports (disease duration, disability index) were recorded for all patients. After a careful neurological evaluation, all subjects were given a comprehensive battery of neuropsychological tests: Self report of neuropsychological condition (by visual analogue scale-VAS, 0-100), RAVLT, STROOP, PASAT, TMT, SDMT, JLOT, DST, COWAT, ACTT, and FST. Patients and HC were compared regarding demographic, clinical features and neurocognitive tests. Also correlation between disease duration, disability index and self report -VAS were assessed. Results: There was no difference between patients and HCs regarding socio-demographic variables such as age, gender and years of education (p levels were 0.36, 0.436, 0.869; respectively). All of the patients were assessed at the peak of botulinum toxine effect and they were not taking an anticholinergic agent or benzodiazepine. Dystonia patients had significantly impaired verbal learning and memory (RAVLT, p<0.001), divided attention and working memory (ACTT, p<0.001), attention speed (TMT-A and B, p=0.008, 0.050), executive functions (PASAT, p<0.001; SDMT, p= 0.001; FST, p<0.001), verbal attention (DST, p=0.001), verbal fluency (COWAT, p<0.001), visio-spatial processing (JLOT, p<0.001) in comparison to healthy controls. But focused attention (STROOP-spontaneous correction) was not different between two groups (p>0.05). No relationship was found regarding disease duration and disability index with any neurocognitive tests. Conclusions: Our study showed that neurocognitive functions of dystonia patients were worse than control group with the similar age, sex, and education independently clinical expression like disease duration and disability index. This situation may be the result of possible cortical and subcortical changes in dystonia patients. Advanced neuroimaging techniques might be helpful to explain these changes in cervical dystonia patients.

Keywords: cervical dystonia, neurocognitive impairment, neuropsychological test, dystonia disability index

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105 Contentious Politics during a Period of Transition to Democracy from an Authoritarian Regime: The Spanish Cycle of Protest of November 1975-December 1978

Authors: Juan Sanmartín Bastida

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When a country experiences a period of transition from authoritarianism to democracy, involving an earlier process of political liberalization and a later process of democratization, a cycle of protest usually outbreaks, as there is a reciprocal influence between that kind of political change and the frequency and scale of social protest events. That is what happened in Spain during the first years of its transition to democracy from the Francoist authoritarian regime, roughly between November 1975 and December 1978. Thus, the object of this study is to show and explain how that cycle of protest started, developed, and finished in relation to such a political change, and offer specific information about the main features of all protest cycles: the social movements that arose during that period, the number of protest events by month, the forms of collective action that were utilized, the groups of challengers that engaged in contentious politics, the reaction of the authorities to the action and claims of those groups, etc. The study of this cycle of protest, using the primary sources and analytical tools that characterize the model of research of protest cycles, will make a contribution to the field of contentious politics and its phenomenon of cycles of contention, and more broadly to the political and social history of contemporary Spain. The cycle of protest and the process of political liberalization of the authoritarian regime began around the same time, but the first concluded long before the process of democratization was completed in 1982. The ascending phase of the cycle and therefore the process of liberalization started with the death of Francisco Franco and the proclamation of Juan Carlos I as King of Spain in November 1975; the peak of the cycle was around the first months of 1977; the descending phase started after the first general election of June 1977; and the level of protest stabilized in the last months of 1978, a year that finished with a referendum in which the Spanish people approved the current democratic constitution. It was then when we can consider that the cycle of protest came to an end. The primary sources are the news of protest events and social movements in the three main Spanish newspapers at the time, other written or audiovisual documents, and in-depth interviews; and the analytical tools are the political opportunities that encourage social protest, the available repertoire of contention, the organizations and networks that brought together people with the same claims and allowed them to engage in contentious politics, and the interpretative frames that justify, dignify and motivates their collective action. These are the main four factors that explain the beginning, development and ending of the cycle of protest, and therefore the accompanying social movements and events of collective action. Among those four factors, the political opportunities -their opening, exploitation, and closure-proved to be most decisive.

Keywords: contentious politics, cycles of protest, political opportunities, social movements, Spanish transition to democracy

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104 Iron Doping Enhanced Photocatalytic Nitrogen Fixation Performance of WO₃ with Three-Dimensionally Orderd Macroporous Structure

Authors: Xiaoling Ren, Guidong Yang

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Ammonia, as one of the largest-volume industrial chemicals, is mostly produced by century-old Haber-Bosch process with extreme conditionsand high-cost. Under the circumstance, researchersarededicated in finding new ways to replace the Haber-Bosch process. Photocatalytic nitrogen fixation is a promising sustainable, clear and green strategy for ammonia synthesis, butit is still a big challenge due to the high activation energy for nitrogen. It is essential to develop an efficient photocatalyst for making this approach industrial application. Constructing chemisorption active sites through defect engineering can be defined as an effective and reliable means to improve nitrogen activation by forming the extraordinary coordination environment and electronic structure. Besides, the construction of three-dimensionally orderdmacroporous (3DOM) structured photocatalyst is considered to be one of effectivestrategiesto improve the activity due to it canincrease the diffusion rate of reactants in the interior, which isbeneficial to the mass transfer process of nitrogen molecules in photocatalytic nitrogen reduction. Herein, Fe doped 3DOM WO₃(Fe-3DOM WO₃) without noble metal cocatalysts is synthesized by a polystyrene-template strategy, which is firstly used for photocatalytic nitrogen fixation. To elucidate the chemical nature of the dopant, the X-ray diffraction (XRD) analysiswas conducted. The pure 3DOM WO₃ has a monoclinic type crystal structure. And no additional peak is observed in Fe doped 3DOM WO₃, indicating that the incorporation of Fe atoms did not result in a secondary phase formation. In order to confirm the morphologies of Fe-3DOM WO₃and 3DOM WO₃, scanning electron microscopy (SEM) was employed. The synthesized Fe-3DOM WO₃and 3DOM WO₃ both exhibit a highly ordered three dimensional inverse opal structure with interconnected pores. From high-resolution TEM image of Fe-3DOM WO₃, the ordered lattice fringes with a spacing of 3.84 Å can be assigned to the (001) plane of WO₃, which is consistent with the XRD results. Finally, the photocatalytic nitrogen reduction performance of 3DOM WO₃ and Fe doped 3DOM WO₃with various Fe contents were examined. As a result, both Fe-3DOM WO₃ samples achieve higher ammonia production rate than that of pure 3DOM WO₃, indicating that the doped Fe plays a critical role in the photocatalytic nitrogen fixation performance. To verify the reaction process upon N2 reduction on the Fe-3DOM WO₃, in-situ diffuse reflectance infrared Fourier-transform spectroscopy was employed to monitor the intermediates. The in-situ DRIFTS spectra of Fe-3DOM WO₃ exhibit the increased signals with the irradiation time from 0–60min in the N2 atmosphere. The above results prove that nitrogen is gradually hydrogenated to produce ammonia over Fe-3DOM WO₃. Thiswork would enrich our knowledge in designing efficient photocatalystsfor photocatalytic nitrogen reduction.

Keywords: ammonia, photocatalytic, nitrogen fixation, Fe doped 3DOM WO₃

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103 Approach-Avoidance Conflict in the T-Maze: Behavioral Validation for Frontal EEG Activity Asymmetries

Authors: Eva Masson, Andrea Kübler

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Anxiety disorders (AD) are the most prevalent psychological disorders. However, far from most affected individuals are diagnosed and receive treatment. This gap is probably due to the diagnosis criteria, relying on symptoms (according to the DSM-5 definition) with no objective biomarker. Approach-avoidance conflict tasks are one common approach to simulate such disorders in a lab setting, with most of the paradigms focusing on the relationships between behavior and neurophysiology. Approach-avoidance conflict tasks typically place participants in a situation where they have to make a decision that leads to both positive and negative outcomes, thereby sending conflicting signals that trigger the Behavioral Inhibition System (BIS). Furthermore, behavioral validation of such paradigms adds credibility to the tasks – with overt conflict behavior, it is safer to assume that the task actually induced a conflict. Some of those tasks have linked asymmetrical frontal brain activity to induced conflicts and the BIS. However, there is currently no consensus for the direction of the frontal activation. The authors present here a modified version of the T-Maze paradigm, a motivational conflict desktop task, in which behavior is recorded simultaneously to the recording of high-density EEG (HD-EEG). Methods: In this within-subject design, HD-EEG and behavior of 35 healthy participants was recorded. EEG data was collected with a 128 channels sponge-based system. The motivational conflict desktop task consisted of three blocks of repeated trials. Each block was designed to record a slightly different behavioral pattern, to increase the chances of eliciting conflict. This variety of behavioral patterns was however similar enough to allow comparison of the number of trials categorized as ‘overt conflict’ between the blocks. Results: Overt conflict behavior was exhibited in all blocks, but always for under 10% of the trials, in average, in each block. However, changing the order of the paradigms successfully introduced a ‘reset’ of the conflict process, therefore providing more trials for analysis. As for the EEG correlates, the authors expect a different pattern for trials categorized as conflict, compared to the other ones. More specifically, we expect an elevated alpha frequency power in the left frontal electrodes at around 200ms post-cueing, compared to the right one (relative higher right frontal activity), followed by an inversion around 600ms later. Conclusion: With this comprehensive approach of a psychological mechanism, new evidence would be brought to the frontal asymmetry discussion, and its relationship with the BIS. Furthermore, with the present task focusing on a very particular type of motivational approach-avoidance conflict, it would open the door to further variations of the paradigm to introduce different kinds of conflicts involved in AD. Even though its application as a potential biomarker sounds difficult, because of the individual reliability of both the task and peak frequency in the alpha range, we hope to open the discussion for task robustness for neuromodulation and neurofeedback future applications.

Keywords: anxiety, approach-avoidance conflict, behavioral inhibition system, EEG

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102 The Functionality of Ovarian Follicle on Steroid Hormone Secretion under Heat Stress

Authors: Petnamnueng Dettipponpong, Shuen E. Chen

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Heat stress is known to have negative effects on reproductive functions, such as follicular development and ovulation. This study aimed to investigate the specific effects of heat stress on steroid hormone secretion of ovarian follicle cells, particularly in relation to the expression of Apolipoprotein B (ApoB) and microsomal triglyceride transfer protein (MTP). The aim of the study was to understand the impact of heat stress on steroid hormone secretion in ovarian follicle cells and to explore the role of ApoB and MTP in this process. Primary granulosa and theca cells were collected from follicles and cultured under heat stress conditions (42 °C) for various time periods. Controls were maintained under normal conditions (37.5 °C ). The culture medium was collected at different time points to measure levels of progesterone and estradiol using ELISA kits. ApoB and MTP expression levels were analyzed using homemade antibodies and western blot. Data were assessed by a one-way ANOVA comparison test with Duncan’s new multiple-range test. Results were expressed as mean±S.E. Difference was considered significant at P<0.05. The results showed that heat stress significantly increased progesterone secretion in granulosa cells, with the peak observed after 13 hours of recovery under thermoneutral conditions. Estradiol secretion by theca cells was not affected. Heat stress also had a significant negative effect on granulosa cell viability. Additionally, the expression of ApoB and MTP was found to be differentially regulated by heat stress. ApoB expression in theca cells was transiently promoted, while ApoB expression in granulosa cells was consistently suppressed. MTP expression increased after 5 hours of recovery in both cell types. These findings suggest a mechanism by which chicken follicle cells export cellular lipids as very low-density lipoprotein (VLDL) in response to thermal stress. These contribute to our understanding of the role of ApoB and MTP steroidogenesis and lipid metabolism under heat stress conditions. The study involved the collection of primary granulosa and theca cells, culture under different temperature conditions, and analysis of the culture medium for hormone levels using ELISA kits. ApoB and MTP expression levels were assessed using homemade antibodies and western blot. This study aimed to address the effects of heat stress on steroid hormone secretion in ovarian follicle cells, as well as the role of ApoB and MTP in this process. The study demonstrates that heat stress stimulates steroidogenesis in granulosa cells, affecting progesterone secretion. ApoB and MTP expression were found to be differentially regulated by heat stress, indicating a potential mechanism for the export of cellular lipids in response to thermal stress.

Keywords: heat stress, granulosa cells, theca cells, steroidogenesis, chicken, apolipoprotein B, microsomal triglyceride transfer protein

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101 Preparation, Solid State Characterization of Etraverine Co-Crystals with Improved Solubility for the Treatment of Human Immunodeficiency Virus

Authors: B. S. Muddukrishna, Karthik Aithal, Aravind Pai

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Introduction: Preparation of binary cocrystals of Etraverine (ETR) by using Tartaric Acid (TAR) as a conformer was the main focus of this study. Etravirine is a Class IV drug, as per the BCS classification system. Methods: Cocrystals were prepared by slow evaporation technique. A mixture of total 500mg of ETR: TAR was weighed in molar ratios of 1:1 (371.72mg of ETR and 128.27mg of TAR). Saturated solution of Etravirine was prepared in Acetone: Methanol (50:50) mixture in which tartaric acid is dissolved by sonication and then this solution was stirred using a magnetic stirrer until the solvent got evaporated. Shimadzu FTIR – 8300 system was used to acquire the FTIR spectra of the cocrystals prepared. Shimadzu thermal analyzer was used to achieve DSC measurements. X-ray diffractometer was used to obtain the X-ray powder diffraction pattern. Shake flask method was used to determine the equilibrium dynamic solubility of pure, physical mixture and cocrystals of ETR. USP buffer (pH 6.8) containing 1% of Tween 80 was used as the medium. The pure, physical mixture and the optimized cocrystal of ETR were accurately weighed sufficient to maintain the sink condition and were filled in hard gelatine capsules (size 4). Electrolab-Tablet Dissolution tester using basket apparatus at a rotational speed of 50 rpm and USP phosphate buffer (900 mL, pH = 6.8, 37 ˚C) + 1% Tween80 as a media, was used to carry out dissolution. Shimadzu LC-10 series chromatographic system was used to perform the analysis with PDA detector. An Hypersil BDS C18 (150mm ×4.6 mm ×5 µm) column was used for separation with mobile phase comprising of a mixture of ace¬tonitrile and phosphate buffer 20mM, pH 3.2 in the ratio 60:40 v/v. The flow rate was 1.0mL/min and column temperature was set to 30°C. The detection was carried out at 304 nm for ETR. Results and discussions: The cocrystals were subjected to various solid state characterization and the results confirmed the formation of cocrystals. The C=O stretching vibration (1741cm-1) in tartaric acid was disappeared in the cocrystal and the peak broadening of primary amine indicates hydrogen bond formation. The difference in the melting point of cocrystals when compared to pure Etravirine (265 °C) indicates interaction between the drug and the coformer which proves that first ordered transformation i.e. melting endotherm has disappeared. The difference in 2θ values of pure drug and cocrystals indicates the interaction between the drug and the coformer. Dynamic solubility and dissolution studies were also conducted by shake flask method and USP apparatus one respectively and 3.6 fold increase in the dynamic solubility were observed and in-vitro dissolution study shows four fold increase in the solubility for the ETR: TAR (1:1) cocrystals. The ETR: TAR (1:1) cocrystals shows improved solubility and dissolution as compared to the pure drug which was clearly showed by solid state characterization and dissolution studies.

Keywords: dynamic solubility, Etraverine, in vitro dissolution, slurry method

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100 Using Google Distance Matrix Application Programming Interface to Reveal and Handle Urban Road Congestion Hot Spots: A Case Study from Budapest

Authors: Peter Baji

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In recent years, a growing body of literature emphasizes the increasingly negative impacts of urban road congestion in the everyday life of citizens. Although there are different responses from the public sector to decrease traffic congestion in urban regions, the most effective public intervention is using congestion charges. Because travel is an economic asset, its consumption can be controlled by extra taxes or prices effectively, but this demand-side intervention is often unpopular. Measuring traffic flows with the help of different methods has a long history in transport sciences, but until recently, there was not enough sufficient data for evaluating road traffic flow patterns on the scale of an entire road system of a larger urban area. European cities (e.g., London, Stockholm, Milan), in which congestion charges have already been introduced, designated a particular zone in their downtown for paying, but it protects only the users and inhabitants of the CBD (Central Business District) area. Through the use of Google Maps data as a resource for revealing urban road traffic flow patterns, this paper aims to provide a solution for a fairer and smarter congestion pricing method in cities. The case study area of the research contains three bordering districts of Budapest which are linked by one main road. The first district (5th) is the original downtown that is affected by the congestion charge plans of the city. The second district (13th) lies in the transition zone, and it has recently been transformed into a new CBD containing the biggest office zone in Budapest. The third district (4th) is a mainly residential type of area on the outskirts of the city. The raw data of the research was collected with the help of Google’s Distance Matrix API (Application Programming Interface) which provides future estimated traffic data via travel times between freely fixed coordinate pairs. From the difference of free flow and congested travel time data, the daily congestion patterns and hot spots are detectable in all measured roads within the area. The results suggest that the distribution of congestion peak times and hot spots are uneven in the examined area; however, there are frequently congested areas which lie outside the downtown and their inhabitants also need some protection. The conclusion of this case study is that cities can develop a real-time and place-based congestion charge system that forces car users to avoid frequently congested roads by changing their routes or travel modes. This would be a fairer solution for decreasing the negative environmental effects of the urban road transportation instead of protecting a very limited downtown area.

Keywords: Budapest, congestion charge, distance matrix API, application programming interface, pilot study

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99 Traumatic Brain Injury Induced Lipid Profiling of Lipids in Mice Serum Using UHPLC-Q-TOF-MS

Authors: Seema Dhariwal, Kiran Maan, Ruchi Baghel, Apoorva Sharma, Poonam Rana

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Introduction: Traumatic brain injury (TBI) is defined as the temporary or permanent alteration in brain function and pathology caused by an external mechanical force. It represents the leading cause of mortality and morbidity among children and youth individuals. Various models of TBI in rodents have been developed in the laboratory to mimic the scenario of injury. Blast overpressure injury is common among civilians and military personnel, followed by accidents or explosive devices. In addition to this, the lateral Controlled cortical impact (CCI) model mimics the blunt, penetrating injury. Method: In the present study, we have developed two different mild TBI models using blast and CCI injury. In the blast model, helium gas was used to create an overpressure of 130 kPa (±5) via a shock tube, and CCI injury was induced with an impact depth of 1.5mm to create diffusive and focal injury, respectively. C57BL/6J male mice (10-12 weeks) were divided into three groups: (1) control, (2) Blast treated, (3) CCI treated, and were exposed to different injury models. Serum was collected on Day1 and day7, followed by biphasic extraction using MTBE/Methanol/Water. Prepared samples were separated on Charged Surface Hybrid (CSH) C18 column and acquired on UHPLC-Q-TOF-MS using ESI probe with inhouse optimized parameters and method. MS peak list was generated using Markerview TM. Data were normalized, Pareto-scaled, and log-transformed, followed by multivariate and univariate analysis in metaboanalyst. Result and discussion: Untargeted profiling of lipids generated extensive data features, which were annotated through LIPID MAPS® based on their m/z and were further confirmed based on their fragment pattern by LipidBlast. There is the final annotation of 269 features in the positive and 182 features in the negative mode of ionization. PCA and PLS-DA score plots showed clear segregation of injury groups to controls. Among various lipids in mild blast and CCI, five lipids (Glycerophospholipids {PC 30:2, PE O-33:3, PG 28:3;O3 and PS 36:1 } and fatty acyl { FA 21:3;O2}) were significantly altered in both injury groups at Day 1 and Day 7, and also had VIP score >1. Pathway analysis by Biopan has also shown hampered synthesis of Glycerolipids and Glycerophospholipiods, which coincides with earlier reports. It could be a direct result of alteration in the Acetylcholine signaling pathway in response to TBI. Understanding the role of a specific class of lipid metabolism, regulation and transport could be beneficial to TBI research since it could provide new targets and determine the best therapeutic intervention. This study demonstrates the potential lipid biomarkers which can be used for injury severity diagnosis and identification irrespective of injury type (diffusive or focal).

Keywords: LipidBlast, lipidomic biomarker, LIPID MAPS®, TBI

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98 A Galectin from Rock Bream Oplegnathus fasciatus: Molecular Characterization and Immunological Properties

Authors: W. S. Thulasitha, N. Umasuthan, G. I. Godahewa, Jehee Lee

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In fish, innate immune defense is the first immune response against microbial pathogens which consists of several antimicrobial components. Galectins are one of the carbohydrate binding lectins that have the ability to identify pathogen by recognition of pathogen associated molecular patterns. Galectins play a vital role in the regulation of innate and adaptive immune responses. Rock bream Oplegnathus fasciatus is one of the most important cultured species in Korea and Japan. Considering the losses due to microbial pathogens, present study was carried out to understand the molecular and functional characteristics of a galectin in normal and pathogenic conditions, which could help to establish an understanding about immunological components of rock bream. Complete cDNA of rock bream galectin like protein B (rbGal like B) was identified from the cDNA library, and the in silico analysis was carried out using bioinformatic tools. Genomic structure was derived from the BAC library by sequencing a specific clone and using Spidey. Full length of rbGal like B (contig14775) cDNA containing 517 nucleotides was identified from the cDNA library which comprised of 435 bp in the open reading frame encoding a deduced protein composed of 145 amino acids. The molecular mass of putative protein was predicted as 16.14 kDa with an isoelectric point of 8.55. A characteristic conserved galactose binding domain was located from 12 to 145 amino acids. Genomic structure of rbGal like B consisted of 4 exons and 3 introns. Moreover, pairwise alignment showed that rock bream rbGal like B shares highest similarity (95.9 %) and identity (91 %) with Takifugu rubripes galectin related protein B like and lowest similarity (55.5 %) and identity (32.4 %) with Homo sapiens. Multiple sequence alignment demonstrated that the galectin related protein B was conserved among vertebrates. A phylogenetic analysis revealed that rbGal like B protein clustered together with other fish homologs in fish clade. It showed closer evolutionary link with Takifugu rubripes. Tissue distribution and expression patterns of rbGal like B upon immune challenges were performed using qRT-PCR assays. Among all tested tissues, level of rbGal like B expression was significantly high in gill tissue followed by kidney, intestine, heart and spleen. Upon immune challenges, it showed an up-regulated pattern of expression with Edwardsiella tarda, rock bream irido virus and poly I:C up to 6 h post injection and up to 24 h with LPS. However, In the presence of Streptococcus iniae rbGal like B showed an up and down pattern of expression with the peak at 6 - 12 h. Results from the present study revealed the phylogenetic position and role of rbGal like B in response to microbial infection in rock bream.

Keywords: galectin like protein B, immune response, Oplegnathus fasciatus, molecular characterization

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97 Fast Detection of Local Fiber Shifts by X-Ray Scattering

Authors: Peter Modregger, Özgül Öztürk

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Glass fabric reinforced thermoplastic (GFRT) are composite materials, which combine low weight and resilient mechanical properties rendering them especially suitable for automobile construction. However, defects in the glass fabric as well as in the polymer matrix can occur during manufacturing, which may compromise component lifetime or even safety. One type of these defects is local fiber shifts, which can be difficult to detect. Recently, we have experimentally demonstrated the reliable detection of local fiber shifts by X-ray scattering based on the edge-illumination (EI) principle. EI constitutes a novel X-ray imaging technique that utilizes two slit masks, one in front of the sample and one in front of the detector, in order to simultaneously provide absorption, phase, and scattering contrast. The principle of contrast formation is as follows. The incident X-ray beam is split into smaller beamlets by the sample mask, resulting in small beamlets. These are distorted by the interaction with the sample, and the distortions are scaled up by the detector masks, rendering them visible to a pixelated detector. In the experiment, the sample mask is laterally scanned, resulting in Gaussian-like intensity distributions in each pixel. The area under the curves represents absorption, the peak offset refraction, and the width of the curve represents the scattering occurring in the sample. Here, scattering is caused by the numerous glass fiber/polymer matrix interfaces. In our recent publication, we have shown that the standard deviation of the absorption and scattering values over a selected field of view can be used to distinguish between intact samples and samples with local fiber shift defects. The quantification of defect detection performance was done by using p-values (p=0.002 for absorption and p=0.009 for scattering) and contrast-to-noise ratios (CNR=3.0 for absorption and CNR=2.1 for scattering) between the two groups of samples. This was further improved for the scattering contrast to p=0.0004 and CNR=4.2 by utilizing a harmonic decomposition analysis of the images. Thus, we concluded that local fiber shifts can be reliably detected by the X-ray scattering contrasts provided by EI. However, a potential application in, for example, production monitoring requires fast data acquisition times. For the results above, the scanning of the sample masks was performed over 50 individual steps, which resulted in long total scan times. In this paper, we will demonstrate that reliable detection of local fiber shift defects is also possible by using single images, which implies a speed up of total scan time by a factor of 50. Additional performance improvements will also be discussed, which opens the possibility for real-time acquisition. This contributes a vital step for the translation of EI to industrial applications for a wide variety of materials consisting of numerous interfaces on the micrometer scale.

Keywords: defects in composites, X-ray scattering, local fiber shifts, X-ray edge Illumination

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96 Designing Sustainable and Energy-Efficient Urban Network: A Passive Architectural Approach with Solar Integration and Urban Building Energy Modeling (UBEM) Tools

Authors: A. Maghoul, A. Rostampouryasouri, MR. Maghami

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The development of an urban design and power network planning has been gaining momentum in recent years. The integration of renewable energy with urban design has been widely regarded as an increasingly important solution leading to climate change and energy security. Through the use of passive strategies and solar integration with Urban Building Energy Modeling (UBEM) tools, architects and designers can create high-quality designs that meet the needs of clients and stakeholders. To determine the most effective ways of combining renewable energy with urban development, we analyze the relationship between urban form and renewable energy production. The procedure involved in this practice include passive solar gain (in building design and urban design), solar integration, location strategy, and 3D models with a case study conducted in Tehran, Iran. The study emphasizes the importance of spatial and temporal considerations in the development of sector coupling strategies for solar power establishment in arid and semi-arid regions. The substation considered in the research consists of two parallel transformers, 13 lines, and 38 connection points. Each urban load connection point is equipped with 500 kW of solar PV capacity and 1 kWh of battery Energy Storage (BES) to store excess power generated from solar, injecting it into the urban network during peak periods. The simulations and analyses have occurred in EnergyPlus software. Passive solar gain involves maximizing the amount of sunlight that enters a building to reduce the need for artificial lighting and heating. Solar integration involves integrating solar photovoltaic (PV) power into smart grids to reduce emissions and increase energy efficiency. Location strategy is crucial to maximize the utilization of solar PV in an urban distribution feeder. Additionally, 3D models are made in Revit, and they are keys component of decision-making in areas including climate change mitigation, urban planning, and infrastructure. we applied these strategies in this research, and the results show that it is possible to create sustainable and energy-efficient urban environments. Furthermore, demand response programs can be used in conjunction with solar integration to optimize energy usage and reduce the strain on the power grid. This study highlights the influence of ancient Persian architecture on Iran's urban planning system, as well as the potential for reducing pollutants in building construction. Additionally, the paper explores the advances in eco-city planning and development and the emerging practices and strategies for integrating sustainability goals.

Keywords: energy-efficient urban planning, sustainable architecture, solar energy, sustainable urban design

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95 Primary-Color Emitting Photon Energy Storage Nanophosphors for Developing High Contrast Latent Fingerprints

Authors: G. Swati, D. Haranath

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Commercially available long afterglow /persistent phosphors are proprietary materials and hence the exact composition and phase responsible for their luminescent characteristics such as initial intensity and afterglow luminescence time are not known. Further to generate various emission colors, commercially available persistence phosphors are physically blended with fluorescent organic dyes such as rodhamine, kiton and methylene blue etc. Blending phosphors with organic dyes results into complete color coverage in visible spectra, however with time, such phosphors undergo thermal and photo-bleaching. This results in the loss of their true emission color. Hence, the current work is dedicated studies on inorganic based thermally and chemically stable primary color emitting nanophosphors namely SrAl2O4:Eu2+, Dy3+, (CaZn)TiO3:Pr3+, and Sr2MgSi2O7:Eu2+, Dy3+. SrAl2O4: Eu2+, Dy3+ phosphor exhibits a strong excitation in UV and visible region (280-470 nm) with a broad emission peak centered at 514 nm is the characteristic emission of parity allowed 4f65d1→4f7 transitions of Eu2+ (8S7/2→2D5/2). Sunlight excitable Sr2MgSi2O7:Eu2+,Dy3+ nanophosphors emits blue color (464 nm) with Commercial international de I’Eclairage (CIE) coordinates to be (0.15, 0.13) with a color purity of 74 % with afterglow time of > 5 hours for dark adapted human eyes. (CaZn)TiO3:Pr3+ phosphor system possess high color purity (98%) which emits intense, stable and narrow red emission at 612 nm due intra 4f transitions (1D2 → 3H4) with afterglow time of 0.5 hour. Unusual property of persistence luminescence of these nanophoshphors supersedes background effects without losing sensitive information these nanophosphors offer several advantages of visible light excitation, negligible substrate interference, high contrast bifurcation of ridge pattern, non-toxic nature revealing finger ridge details of the fingerprints. Both level 1 and level 2 features from a fingerprint can be studied which are useful for used classification, indexing, comparison and personal identification. facile methodology to extract high contrast fingerprints on non-porous and porous substrates using a chemically inert, visible light excitable, and nanosized phosphorescent label in the dark has been presented. The chemistry of non-covalent physisorption interaction between the long afterglow phosphor powder and sweat residue in fingerprints has been discussed in detail. Real-time fingerprint development on porous and non-porous substrates has also been performed. To conclude, apart from conventional dark vision applications, as prepared primary color emitting afterglow phosphors are potentional candidate for developing high contrast latent fingerprints.

Keywords: fingerprints, luminescence, persistent phosphors, rare earth

Procedia PDF Downloads 180
94 Design Flood Estimation in Satluj Basin-Challenges for Sunni Dam Hydro Electric Project, Himachal Pradesh-India

Authors: Navneet Kalia, Lalit Mohan Verma, Vinay Guleria

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Introduction: Design Flood studies are essential for effective planning and functioning of water resource projects. Design flood estimation for Sunni Dam Hydro Electric Project located in State of Himachal Pradesh, India, on the river Satluj, was a big challenge in view of the river flowing in the Himalayan region from Tibet to India, having a large catchment area of varying topography, climate, and vegetation. No Discharge data was available for the part of the river in Tibet, whereas, for India, it was available only at Khab, Rampur, and Luhri. The estimation of Design Flood using standard methods was not possible. This challenge was met using two different approaches for upper (snow-fed) and lower (rainfed) catchment using Flood Frequency Approach and Hydro-metrological approach. i) For catchment up to Khab Gauging site (Sub-Catchment, C1), Flood Frequency approach was used. Around 90% of the catchment area (46300 sqkm) up to Khab is snow-fed which lies above 4200m. In view of the predominant area being snow-fed area, 1 in 10000 years return period flood estimated using Flood Frequency analysis at Khab was considered as Probable Maximum Flood (PMF). The flood peaks were taken from daily observed discharges at Khab, which were increased by 10% to make them instantaneous. Design Flood of 4184 cumec thus obtained was considered as PMF at Khab. ii) For catchment between Khab and Sunni Dam (Sub-Catchment, C2), Hydro-metrological approach was used. This method is based upon the catchment response to the rainfall pattern observed (Probable Maximum Precipitation - PMP) in a particular catchment area. The design flood computation mainly involves the estimation of a design storm hyetograph and derivation of the catchment response function. A unit hydrograph is assumed to represent the response of the entire catchment area to a unit rainfall. The main advantage of the hydro-metrological approach is that it gives a complete flood hydrograph which allows us to make a realistic determination of its moderation effect while passing through a reservoir or a river reach. These studies were carried out to derive PMF for the catchment area between Khab and Sunni Dam site using a 1-day and 2-day PMP values of 232 and 416 cm respectively. The PMF so obtained was 12920.60 cumec. Final Result: As the Catchment area up to Sunni Dam has been divided into 2 sub-catchments, the Flood Hydrograph for the Catchment C1 has been routed through the connecting channel reach (River Satluj) using Muskingum method and accordingly, the Design Flood was computed after adding the routed flood ordinates with flood ordinates of catchment C2. The total Design Flood (i.e. 2-Day PMF) with a peak of 15473 cumec was obtained. Conclusion: Even though, several factors are relevant while deciding the method to be used for design flood estimation, data availability and the purpose of study are the most important factors. Since, generally, we cannot wait for the hydrological data of adequate quality and quantity to be available, flood estimation has to be done using whatever data is available. Depending upon the type of data available for a particular catchment, the method to be used is to be selected.

Keywords: design flood, design storm, flood frequency, PMF, PMP, unit hydrograph

Procedia PDF Downloads 298
93 Initial Resistance Training Status Influences Upper Body Strength and Power Development

Authors: Stacey Herzog, Mitchell McCleary, Istvan Kovacs

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Purpose: Maximal strength and maximal power are key athletic abilities in many sports disciplines. In recent years, velocity-based training (VBT) with a relatively high 75-85% 1RM resistance has been popularized in preparation for powerlifting and various other sports. The purpose of this study was to discover differences between beginner/intermediate and advanced lifters’ push/press performances after a heavy resistance-based BP training program. Methods: A six-week, three-workouts per week program was administered to 52 young, physically active adults (age: 22.4±5.1; 12 female). The majority of the participants (84.6%) had prior experience in bench pressing. Typical workouts began with BP using 75-95% 1RM in the 1-5 repetition range. The sets in the lower part of the range (75-80% 1RM) were performed with velocity-focus as well. The BP sets were followed by seated dumbbell presses and six additional upper-body assistance exercises. Pre- and post-tests were conducted on five test exercises: one-repetition maximum BP (1RM), calculated relative strength index: BP/BW (RSI), four-repetition maximal-effort dynamic BP for peak concentric velocity with 80% 1RM (4RV), 4-repetition ballistic pushups (BPU) for height (4PU), and seated medicine ball toss for distance (MBT). For analytic purposes, the participant group was divided into two subgroups: self-indicated beginner or intermediate initial resistance training status (BITS) [n=21, age: 21.9±3.6; 10 female] and advanced initial resistance training status (ATS) [n=31, age: 22.7±5.9; 2 female]. Pre- and post-test results were compared within subgroups. Results: Paired-sample t-tests indicated significant within-group improvements in all five test exercises in both groups (p < 0.05). BITS improved 18.1 lbs. (13.0%) in 1RM, 0.099 (12.8%) in RSI, 0.133 m/s (23.3%) in 4RV, 1.55 in. (27.1%) in BPU, and 1.00 ft. (5.8%) in MBT, while the ATS group improved 13.2 lbs. (5.7%) in 1RM, 0.071 (5.8%) in RSI, 0.051 m/s (9.1%) in 4RV, 1.20 in. (13.7%) in BPU, and 1.15 ft. (5.5%) in MBT. Conclusion: While the two training groups had different initial resistance training backgrounds, both showed significant improvements in all test exercises. As expected, the beginner/intermediate group displayed better relative improvements in four of the five test exercises. However, the medicine ball toss, which had the lightest resistance among the tests, showed similar relative improvements between the two groups. These findings relate to two important training principles: specificity and transfer. The ATS group had more specific experiences with heavy-resistance BP. Therefore, fewer improvements were detected in their test performances with heavy resistances. On the other hand, while the heavy resistance-based training transferred to increased power outcomes in light-resistance power exercises, the difference in the rate of improvement between the two groups disappeared. Practical applications: Based on initial training status, S&C coaches should expect different performance gains in maximal strength training-specific test exercises. However, the transfer from maximal strength to a non-training-specific performance category along the F-v curve continuum (i.e., light resistance and high velocity) might not depend on initial training status.

Keywords: exercise, power, resistance training, strength

Procedia PDF Downloads 26
92 Electroactive Fluorene-Based Polymer Films Obtained by Electropolymerization

Authors: Mariana-Dana Damaceanu

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Electrochemical oxidation is one of the most convenient ways to obtain conjugated polymer films as polypyrrole, polyaniline, polythiophene or polycarbazole. The research in the field has been mainly directed to the study of electrical conduction properties of the materials obtained by electropolymerization, often the main reason being their use as electroconducting electrodes, and very little attention has been paid to the morphological and optical quality of the films electrodeposited on flat surfaces. Electropolymerization of the monomer solution was scarcely used in the past to manufacture polymer-based light-emitting diodes (PLED), most probably due to the difficulty of obtaining defectless polymer films with good mechanical and optical properties, or conductive polymers with well controlled molecular weights. Here we report our attempts in using electrochemical deposition as appropriate method for preparing ultrathin films of fluorene-based polymers for PLED applications. The properties of these films were evaluated in terms of structural morphology, optical properties, and electrochemical conduction. Thus, electropolymerization of 4,4'-(9-fluorenylidene)-dianiline was performed in dichloromethane solution, at a concentration of 10-2 M, using 0.1 M tetrabutylammonium tetrafluoroborate as electrolyte salt. The potential was scanned between 0 and 1.3 V on the one hand, and 0 - 2 V on the other hand, when polymer films with different structures and properties were obtained. Indium tin oxide-coated glass substrate of different size was used as working electrode, platinum wire as counter electrode and calomel electrode as reference. For each potential range 100 cycles were recorded at a scan rate of 100 mV/s. The film obtained in the potential range from 0 to 1.3 V, namely poly(FDA-NH), is visible to the naked eye, being light brown, transparent and fluorescent, and displays an amorphous morphology. Instead, the electrogrowth poly(FDA) film in the potential range of 0 - 2 V is yellowish-brown and opaque, presenting a self-assembled structure in aggregates of irregular shape and size. The polymers structure was identified by FTIR spectroscopy, which shows the presence of broad bands specific to a polymer, the band centered at approx. 3443 cm-1 being ascribed to the secondary amine. The two polymer films display two absorption maxima, at 434-436 nm assigned to π-π* transitions of polymers, and another at 832 and 880 nm assigned to polaron transitions. The fluorescence spectra indicated the presence of emission bands in the blue domain, with two peaks at 422 and 488 nm for poly (FDA-NH), and four narrow peaks at 422, 447, 460 and 484 nm for poly(FDA), peaks originating from fluorene-containing segments of varying degrees of conjugation. Poly(FDA-NH) exhibited two oxidation peaks in the anodic region and the HOMO energy value of 5.41 eV, whereas poly(FDA) showed only one oxidation peak and the HOMO level localized at 5.29 eV. The electrochemical data are discussed in close correlation with the proposed chemical structure of the electrogrowth films. Further research will be carried out to study their use and performance in light-emitting devices.

Keywords: electrogrowth polymer films, fluorene, morphology, optical properties

Procedia PDF Downloads 322
91 A Density Function Theory Based Comparative Study of Trans and Cis - Resveratrol

Authors: Subhojyoti Chatterjee, Peter J. Mahon, Feng Wang

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Resveratrol (RvL), a phenolic compound, is a key ingredient in wine and tomatoes that has been studied over the years because of its important bioactivities such as anti-oxidant, anti-aging and antimicrobial properties. Out of the two isomeric forms of resveratrol i.e. trans and cis, the health benefit is primarily associated with the trans form. Thus, studying the structural properties of the isomers will not only provide an insight into understanding the RvL isomers, but will also help in designing parameters for differentiation in order to achieve 99.9% purity of trans-RvL. In the present study, density function theory (DFT) study is conducted, using the B3LYP/6-311++G** model to explore the through bond and through space intramolecular interactions. Properties such as vibrational spectroscopy (IR and Raman), nuclear magnetic resonance (NMR) spectra, excess orbital energy spectrum (EOES), energy based decomposition analyses (EDA) and Fukui function are calculated. It is discovered that the structure of trans-RvL, although it is C1 non-planar, the backbone non-H atoms are nearly in the same plane; whereas the cis-RvL consists of two major planes of R1 and R2 that are not in the same plane. The absence of planarity gives rise to a H-bond of 2.67Å in cis-RvL. Rotation of the C(5)-C(8) single bond in trans-RvL produces higher energy barriers since it may break the (planar) entire conjugated structure; while such rotation in cis-RvL produces multiple minima and maxima depending on the positions of the rings. The calculated FT-IR spectrum shows very different spectral features for trans and cis-RvL in the region 900 – 1500 cm-1, where the spectral peaks at 1138-1158 cm-1 are split in cis-RvL compared to a single peak at 1165 cm-1 in trans-RvL. In the Raman spectra, there is significant enhancement of cis-RvL in the region above 3000cm-1. Further, the carbon chemical environment (13C NMR) of the RvL molecule exhibit a larger chemical shift for cis-RvL compared to trans-RvL (Δδ = 8.18 ppm) for the carbon atom C(11), indicating that the chemical environment of the C group in cis-RvL is more diverse than its other isomer. The energy gap between highest occupied molecular orbital (HOMO) and the lowest occupied molecular orbital (LUMO) is 3.95 eV for trans and 4.35 eV for cis-RvL. A more detailed inspection using the recently developed EOES revealed that most of the large energy differences i.e. Δεcis-trans > ±0.30 eV, in their orbitals are contributed from the outer valence shell. They are MO60 (HOMO), MO52-55 and MO46. The active sites that has been captured by Fukui function (f + > 0.08) are associated with the stilbene C=C bond of RvL and cis-RvL is more active at these sites than in trans-RvL, as cis orientation breaks the large conjugation of trans-RvL so that the hydroxyl oxygen’s are more active in cis-RvL. Finally, EDA highlights the interaction energy (ΔEInt) of the phenolic compound, where trans is preferred over the cis-RvL (ΔΔEi = -4.35 kcal.mol-1) isomer. Thus, these quantum mechanics results could help in unwinding the diversified beneficial activities associated with resveratrol.

Keywords: resveratrol, FT-IR, Raman, NMR, excess orbital energy spectrum, energy decomposition analysis, Fukui function

Procedia PDF Downloads 173