Search results for: spectral residual

Authors: Matthias Leitner, Gernot Pottlacher

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Experimental determination of critical point data like critical temperature, critical pressure, critical volume and critical compressibility of high-melting metals such as niobium is very rare due to the outstanding experimental difficulties in reaching the necessary extreme temperature and pressure regimes. Experimental techniques to achieve such extreme conditions could be diamond anvil devices, two stage gas guns or metal samples hit by explosively accelerated flyers. Electrical pulse-heating under increased pressures would be another choice. This technique heats thin wire samples of 0.5 mm diameter and 40 mm length from room temperature to melting and then further to the end of the stable phase, the spinodal line, within several microseconds. When crossing the spinodal line, the sample explodes and reaches the gaseous phase. In our laboratory, pulse-heating experiments can be performed under variation of the ambient pressure from 1 to 5000 bar and allow a direct determination of critical point data for low-melting, but not for high-melting metals. However, the critical point also can be estimated by extrapolating the liquid phase density according to theoretical models. A reasonable prerequisite for the extrapolation is the existence of data that cover as much as possible of the liquid phase and at the same time exhibit small uncertainties. Ohmic pulse-heating was therefore applied to determine thermal volume expansion, and from that density of niobium over the entire liquid phase. As a first step, experiments under ambient pressure were performed. The second step will be to perform experiments under high-pressure conditions. During the heating process, shadow images of the expanding sample wire were captured at a frame rate of 4 × 105 fps to monitor the radial expansion as a function of time. Simultaneously, the sample radiance was measured with a pyrometer operating at a mean effective wavelength of 652 nm. To increase the accuracy of temperature deduction, spectral emittance in the liquid phase is also taken into account. Due to the high heating rates of about 2 × 108 K/s, longitudinal expansion of the wire is inhibited which implies an increased radial expansion. As a consequence, measuring the temperature dependent radial expansion is sufficient to deduce density as a function of temperature. This is accomplished by evaluating the full widths at half maximum of the cup-shaped intensity profiles that are calculated from each shadow image of the expanding wire. Relating these diameters to the diameter obtained before the pulse-heating start, the temperature dependent volume expansion is calculated. With the help of the known room-temperature density, volume expansion is then converted into density data. The so-obtained liquid density behavior is compared to existing literature data and provides another independent source of experimental data. In this work, the newly determined off-critical liquid phase density was in a second step utilized as input data for the estimation of niobium’s critical point. The approach used, heuristically takes into account the crossover from mean field to Ising behavior, as well as the non-linearity of the phase diagram’s diameter.

Keywords: critical point data, density, liquid metals, niobium, ohmic pulse-heating, volume expansion

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Authors: Ching-Yu Liao, Ju-Joan Wong

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Recent years have shown a trend of younger stroke patients and an increase in ischemic strokes with the rise in stroke incidence. This has led to a growing demand for telemedicine, particularly during the COVID-19 pandemic, which has made the need for telemedicine even more urgent. This shift in healthcare is also closely related to advancements in Internet of Things (IoT) technology. Stroke-induced hemiparesis is a significant issue for patients. The medical community believes that if intervention occurs within three to six months of stroke onset, 80% of the residual effects can be restored to normal, a period known as the stroke golden period. During this time, patients undergo treatment and rehabilitation, and neural plasticity is at its best. Lower limb rehabilitation for stroke generally includes exercises such as support standing and walking posture, typically involving the healthy limb to guide the affected limb to achieve rehabilitation goals. Existing gait training aids in hospitals usually involve balance gait, sitting posture training, and precise muscle control, effectively addressing issues of poor gait, insufficient muscle activity, and inability to train independently during recovery. However, home training aids, such as braced and wheeled devices, often rely on the healthy limb to pull the affected limb, leading to lower usage of the affected limb, worsening circular walking, and compensatory movement issues. IoT technology connects devices via the internet to record, receive data, provide feedback, and adjust equipment for intelligent effects. Therefore, this study aims to explore how IoT can be integrated into existing gait training aids to monitor and sensor home rehabilitation movements, improve gait training compensatory issues through real-time feedback, and enable healthcare professionals to quickly understand patient conditions and enhance medical communication. To understand the needs of hemiparetic patients, a review of relevant literature from the past decade will be conducted. From the perspective of user experience, participant observation will be used to explore the use of home training aids by stroke patients and therapists, and interviews with physical therapists will be conducted to obtain professional opinions and practical experiences. Design specifications for home training aids for hemiparetic patients will be summarized. Applying IoT technology to lower limb training aids for stroke hemiparesis can help promote walking function recovery in hemiparetic patients, reduce muscle atrophy, and allow healthcare professionals to immediately grasp patient conditions and adjust gait training plans based on collected and analyzed information. Exploring these potential development directions provides a valuable reference for the further application of IoT technology in the field of medical rehabilitation.

Keywords: stroke, hemiplegia, rehabilitation, gait training, internet of things technology

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Authors: Deb Kumar Shah, M. Shaheer Akhtar, Ha Ryeon Lee, O-Bong Yang, Chong Yeal Kim

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The crystalline silicon (Si) solar cells are highly renowned photovoltaic technology and well-established as the commercial solar technology. Most of the solar panels are globally installed with the crystalline Si solar modules. At the present scenario, the major photovoltaic (PV) market is shared by c-Si solar cells, but the cost of c-Si panels are still very high as compared with the other PV technology. In order to reduce the cost of Si solar panels, few necessary steps such as low-cost Si manufacturing, cheap antireflection coating materials, inexpensive solar panel manufacturing are to be considered. It is known that the antireflection (AR) layer in c-Si solar cell is an important component to reduce Fresnel reflection for improving the overall conversion efficiency. Generally, Si wafer exhibits the 30% reflection because it normally poses the two major intrinsic drawbacks such as; the spectral mismatch loss and the high Fresnel reflection loss due to the high contrast of refractive indices between air and silicon wafer. In recent years, researchers and scientists are highly devoted to a lot of researches in the field of searching effective and low-cost AR materials. Silicon nitride (SiNx) is well-known AR materials in commercial c-Si solar cells due to its good deposition and interaction with passivated Si surfaces. However, the deposition of SiNx AR is usually performed by expensive plasma enhanced chemical vapor deposition (PECVD) process which could have several demerits like difficult handling and damaging the Si substrate by plasma when secondary electrons collide with the wafer surface for AR coating. It is very important to explore new, low cost and effective AR deposition process to cut the manufacturing cost of c-Si solar cells. One can also be realized that a nano-texturing process like the growth of nanowires, nanorods, nanopyramids, nanopillars, etc. on Si wafer can provide a low reflection on the surface of Si wafer based solar cells. The above nanostructures might be enhanced the antireflection property which provides the larger surface area and effective light trapping. In this work, we report on the development of crystalline Si solar cells without using the AR layer. The Silicon wafer was modified by growing nanowires like Si nanostructures using the wet controlled etching method and directly used for the fabrication of Si solar cell without AR. The nanostructures over Si wafer were optimized in terms of sizes, lengths, and densities by changing the etching conditions. Well-defined and aligned wires like structures were achieved when the etching time is 20 to 30 min. The prepared Si nanostructured displayed the minimum reflectance ~1.64% at 850 nm with the average reflectance of ~2.25% in the wavelength range from 400-1000 nm. The nanostructured Si wafer based solar cells achieved the comparable power conversion efficiency in comparison with c-Si solar cells with SiNx AR layer. From this study, it is confirmed that the reported method (controlled wet etching) is an easy, facile method for preparation of nanostructured like wires on Si wafer with low reflectance in the whole visible region, which has greater prospects in developing c-Si solar cells without AR layer at low cost.

Keywords: chemical etching, conversion efficiency, silicon nanostructures, silicon solar cells, surface modification

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Authors: Francisco Pereira, António Augusto Vicente, Filipe Vaz, Joel Borges, Pedro Geada

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Light is a growth-limiting factor in microalgae cultivation, where factors like spectral components, intensity, and duration, often characterized by its wavelength, are well-reported to have a substantial impact on cell growth rates and, consequently, photosynthetic performance and mitigation of CO2, one of the most significant greenhouse gases (GHGs). Photobioreactors (PBRs) are commonly used to grow microalgae under controlled conditions, but they often fail to provide an even light distribution to the cultures. For this reason, there is a pressing need for innovations aiming at enhancing the efficient utilization of light. So, one potential approach to address this issue is by implementing plasmonic films, such as the localized surface plasmon resonance (LSPR). LSPR is an optical phenomenon connected to the interaction of light with metallic nanostructures. LSPR excitation is characterized by the oscillation of unbound conduction electrons of the nanoparticles coupled with the electromagnetic field from incident light. As a result of this excitation, highly energetic electrons and a strong electromagnetic field are generated. These effects lead to an amplification of light scattering, absorption, and extinction of specific wavelengths, contingent on the nature of the employed nanoparticle. Thus, microalgae might benefit from this biotechnology as it enables the selective filtration of inhibitory wavelengths and harnesses the electromagnetic fields produced, which could lead to enhancements in both biomass and metabolite productivity. This study aimed at implementing and evaluating a “plasmon-enhanced PBR”. The goal was to utilize LSPR thin films to enhance the growth and CO2 bio-fixation rate of Chlorella vulgaris. The internal/external walls of the PBRs were coated with a TiO2 matrix containing different nanoparticles (Au, Ag, and Au-Ag) in order to evaluate the impact of this approach on microalgae’s performance. Plasmonic films with distinct compositions resulted in different Chlorella vulgaris growth, ranging from 4.85 to 6.13 g.L-1. The highest cell concentrations were obtained with the metallic Ag films, demonstrating a 14% increase compared to the control condition. Moreover, it appeared to be no differences in growth between PBRs with inner and outer wall coatings. In terms of CO2 bio-fixation, distinct rates were obtained depending on the coating applied, ranging from 0.42 to 0.53 gCO2L-1d-1. Ag coating was demonstrated to be the most effective condition for carbon fixation by C. vulgaris. The impact of LSPR films on the biochemical characteristics of biomass (e.g., proteins, lipids, pigments) was analysed as well. Interestingly, Au coating yielded the most significant enhancements in protein content and total pigments, with increments of 15 % and 173 %, respectively, when compared to the PBR without any coating (control condition). Overall, the incorporation of plasmonic films in PBRs seems to have the potential to improve the performance and efficiency of microalgae cultivation, thereby representing an interesting approach to increase both biomass production and GHGs bio-mitigation.

Keywords: CO₂ bio-fixation, plasmonic effect, photobioreactor, photosynthetic microalgae

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Authors: K. S. Rao, Ankesh Kumar

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The search for alternative energy sources to petroleum has increased these days because of increase in need and depletion of petroleum reserves. Therefore the importance of oil shales as an economically viable substitute has increased many folds in last 20 years. The technologies like hydro-fracturing have opened the field of oil extraction from these unconventional rocks. Oil shale is a compact laminated rock of sedimentary origin containing organic matter known as kerogen which yields oil when distilled. Oil shales are formed from the contemporaneous deposition of fine grained mineral debris and organic degradation products derived from the breakdown of biota. Conditions required for the formation of oil shales include abundant organic productivity, early development of anaerobic conditions, and a lack of destructive organisms. These rocks are not gown through the high temperature and high pressure conditions in Mother Nature. The most common approach for oil extraction is drastically breaking the bond of the organics which involves retorting process. The two approaches for retorting are surface retorting and in-situ processing. The most environmental friendly approach for extraction is In-situ processing. The three steps involved in this process are fracturing, injection to achieve communication, and fluid migration at the underground location. Upon heating (retorting) oil shale at temperatures in the range of 300 to 400°C, the kerogen decomposes into oil, gas and residual carbon in a process referred to as pyrolysis. Therefore it is very important to understand the physico-mechenical behavior of such rocks, to improve the technology for in-situ extraction. It is clear from the past research and the physical observations that these rocks will behave as an anisotropic rock so it is very important to understand the mechanical behavior under high pressure at different orientation angles for the economical use of these resources. By knowing the engineering behavior under above conditions will allow us to simulate the deep ground retorting conditions numerically and experimentally. Many researchers have investigate the effect of organic content on the engineering behavior of oil shale but the coupled effect of organic and inorganic matrix is yet to be analyzed. The favourable characteristics of Assam coal for conversion to liquid fuels have been known for a long time. Studies have indicated that these coals and carbonaceous shale constitute the principal source rocks that have generated the hydrocarbons produced from the region. Rock cores of the representative samples are collected by performing on site drilling, as coring in laboratory is very difficult due to its highly anisotropic nature. Different tests are performed to understand the petrology of these samples, further the chemical analyses are also done to exactly quantify the organic content in these rocks. The mechanical properties of these rocks are investigated by considering different anisotropic angles. Now the results obtained from petrology and chemical analysis are correlated with the mechanical properties. These properties and correlations will further help in increasing the producibility of these rocks. It is well established that the organic content is negatively correlated to tensile strength, compressive strength and modulus of elasticity.

Keywords: oil shale, producibility, hydro-fracturing, kerogen, petrology, mechanical behavior

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Authors: Artur Cichowicz

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The last active mine in the Central Rand Goldfields area (50 km x 15 km) ceased operations in 2008. This resulted in the closure of the pumping stations, which previously maintained the underground water level in the mining voids. As a direct consequence of the water being allowed to flood the mine voids, seismic activity has increased directly beneath the populated area of Johannesburg. Monitoring of seismicity in the area has been on-going for over five years using the network of 17 strong ground motion sensors. The objective of the project is to improve strategies for mine closure. The evolution of the seismicity pattern was investigated in detail. Special attention was given to seismic source parameters such as magnitude, scalar seismic moment and static stress drop. Most events are located within historical mine boundaries. The seismicity pattern shows a strong relationship between the presence of the mining void and high levels of seismicity; no seismicity migration patterns were observed outside the areas of old mining. Seven years after the pumping stopped, the evolution of the seismicity has indicated that the area is not yet in equilibrium. The level of seismicity in the area appears to not be decreasing over time since the number of strong events, with Mw magnitudes above 2, is still as high as it was when monitoring began over five years ago. The average rate of seismic deformation is 1.6x1013 Nm/year. Constant seismic deformation was not observed over the last 5 years. The deviation from the average is in the order of 6x10^13 Nm/year, which is a significant deviation. The variation of cumulative seismic moment indicates that a constant deformation rate model is not suitable. Over the most recent five year period, the total cumulative seismic moment released in the Central Rand Basin was 9.0x10^14 Nm. This is equivalent to one earthquake of magnitude 3.9. This is significantly less than what was experienced during the mining operation. Characterization of seismicity triggered by a rising water level in the area can be achieved through the estimation of source parameters. Static stress drop heavily influences ground motion amplitude, which plays an important role in risk assessments of potential seismic hazards in inhabited areas. The observed static stress drop in this study varied from 0.05 MPa to 10 MPa. It was found that large static stress drops could be associated with both small and large events. The temporal evolution of the inter-event time provides an understanding of the physical mechanisms of earthquake interaction. Changes in the characteristics of the inter-event time are produced when a stress change is applied to a group of faults in the region. Results from this study indicate that the fluid-induced source has a shorter inter-event time in comparison to a random distribution. This behaviour corresponds to a clustering of events, in which short recurrence times tend to be close to each other, forming clusters of events.

Keywords: inter-event time, fluid induced seismicity, mine closure, spectral parameters of seismic source

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Authors: Jiri Cecrdle

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This paper describes the concept of the W-WING whirl flutter aeroelastic demonstrator. Whirl flutter is the specific case of flutter that accounts for the additional dynamic and aerodynamic influences of the engine rotating parts. The instability is driven by motion-induced unsteady aerodynamic propeller forces and moments acting in the propeller plane. Whirl flutter instability is a serious problem that may cause the unstable vibration of a propeller mounting, leading to the failure of an engine installation or an entire wing. The complicated physical principle of whirl flutter required the experimental validation of the analytically gained results. W-WING aeroelastic demonstrator has been designed and developed at Czech Aerospace Research Centre (VZLU) Prague, Czechia. The demonstrator represents the wing and engine of the twin turboprop commuter aircraft. Contrary to the most of past demonstrators, it includes a powered motor and thrusting propeller. It allows the changes of the main structural parameters influencing the whirl flutter stability characteristics. Propeller blades are adjustable at standstill. The demonstrator is instrumented by strain gauges, accelerometers, revolution-counting impulse sensor, sensor of airflow velocity, and the thrust measurement unit. Measurement is supported by the in house program providing the data storage and real-time depiction in the time domain as well as pre-processing into the form of the power spectral densities. The engine is linked with a servo-drive unit, which enables maintaining of the propeller revolutions (constant or controlled rate ramp) and monitoring of immediate revolutions and power. Furthermore, the program manages the aerodynamic excitation of the demonstrator by the aileron flapping (constant, sweep, impulse). Finally, it provides the safety guard to prevent any structural failure of the demonstrator hardware. In addition, LMS TestLab system is used for the measurement of the structure response and for the data assessment by means of the FFT- and OMA-based methods. The demonstrator is intended for the experimental investigations in the VZLU 3m-diameter low-speed wind tunnel. The measurement variant of the model is defined by the structural parameters: pitch and yaw attachment stiffness, pitch and yaw hinge stations, balance weight station, propeller type (duralumin or steel blades), and finally, angle of attack of the propeller blade 75% section (). The excitation is provided either by the airflow turbulence or by means of the aerodynamic excitation by the aileron flapping using a frequency harmonic sweep. The experimental results are planned to be utilized for validation of analytical methods and software tools in the frame of development of the new complex multi-blade twin-rotor propulsion system for the new generation regional aircraft. Experimental campaigns will include measurements of aerodynamic derivatives and measurements of stability boundaries for various configurations of the demonstrator.

Keywords: aeroelasticity, flutter, whirl flutter, W WING demonstrator

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Authors: Md. Afroz Ansari

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The Bengal basin is a spectacular example of a peripheral foreland basin formed by the convergence of the Indian plate beneath the Eurasian and Burmese plates. The basin is embraced on three sides; north, west and east by different fault-controlled tectonic features whereas released in the south where the rivers are drained into the Bay of Bengal. The Bengal basin in the eastern part of the Indian subcontinent constitutes the largest fluvio-deltaic to shallow marine sedimentary basin in the world today. This continental basin coupled with the offshore Bengal Fan under the Bay of Bengal forms the biggest sediment dispersal system. The continental basin is continuously receiving the sediments by the two major rivers Ganga and Brahmaputra (known as Jamuna in Bengal), and Meghna (emerging from the point of conflux of the Ganga and Brahmaputra) and large number of rain-fed, small tributaries originating from the eastern Indian Shield. The drained sediments are ultimately delivered into the Bengal fan. The significance of the present study is to delineate the variations in thicknesses of the sediments, different crustal structures, and the mantle lithosphere throughout the onshore-offshore Bengal basin. In the present study, the different crustal/geological units and the shallower mantle lithosphere were delineated by analyzing the Bouguer Gravity Anomaly (BGA) data along two long traverses South-North (running from Bengal fan cutting across the transition offshore-onshore of the Bengal basin and intersecting the Main Frontal Thrust of India-Himalaya collision zone in Sikkim-Bhutan Himalaya) and West-East (running from the Peninsular Indian Shield across the Bengal basin to the Chittagong–Tripura Fold Belt). The BGA map was derived from the analysis of topex data after incorporating Bouguer correction and all terrain corrections. The anomaly map was compared with the available ground gravity data in the western Bengal basin and the sub-continents of India for consistency of the data used. Initially, the anisotropy associated with the thicknesses of the different crustal units, crustal interfaces and moho boundary was estimated through spectral analysis of the gravity data with varying window size over the study area. The 2D density sections along the traverses were finalized after a number of iterations with the acceptable root mean square (RMS) errors. The estimated thicknesses of the different crustal units and dips of the Moho boundary along both the profiles are consistent with the earlier results. Further the results were encouraged by examining the earthquake database and focal mechanism solutions for better understanding the geodynamics. The earthquake data were taken from the catalogue of US Geological Survey, and the focal mechanism solutions were compiled from the Harvard Centroid Moment Tensor Catalogue. The concentrations of seismic events at different depth levels are not uncommon. The occurrences of earthquakes may be due to stress accumulation as a result of resistance from three sides.

Keywords: anisotropy, interfaces, seismicity, spectrum analysis

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Authors: Robert Pečenko, Karin Tomažič, Igor Planinc, Sabina Huč, Tomaž Hozjan

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Timber is favourable structural material due to high strength to weight ratio, recycling possibilities, and green credentials. Despite being flammable material, it has relatively high fire resistance. Everyday engineering practice around the word is based on an outdated design of timber structures considering standard fire exposure, while modern principles of performance-based design enable use of advanced non-standard fire curves. In Europe, standard for fire design of timber structures EN 1995-1-2 (Eurocode 5) gives two methods, reduced material properties method and reduced cross-section method. In the latter, fire resistance of structural elements depends on the effective cross-section that is a residual cross-section of uncharred timber reduced additionally by so called zero strength layer. In case of standard fire exposure, Eurocode 5 gives a fixed value of zero strength layer, i.e. 7 mm, while for non-standard parametric fires no additional comments or recommendations for zero strength layer are given. Thus designers often implement adopted 7 mm rule also for parametric fire exposure. Since the latest scientific evidence suggests that proposed value of zero strength layer can be on unsafe side for standard fire exposure, its use in the case of a parametric fire is also highly questionable and more numerical and experimental research in this field is needed. Therefore, the purpose of the presented study is to use advanced calculation methods to investigate the thickness of zero strength layer and parametric charring rates used in effective cross-section method in case of parametric fire. Parametric studies are carried out on a simple solid timber beam that is exposed to a larger number of parametric fire curves Zero strength layer and charring rates are determined based on the numerical simulations which are performed by the recently developed advanced two step computational model. The first step comprises of hygro-thermal model which predicts the temperature, moisture and char depth development and takes into account different initial moisture states of timber. In the second step, the response of timber beam simultaneously exposed to mechanical and fire load is determined. The mechanical model is based on the Reissner’s kinematically exact beam model and accounts for the membrane, shear and flexural deformations of the beam. Further on, material non-linear and temperature dependent behaviour is considered. In the two step model, the char front temperature is, according to Eurocode 5, assumed to have a fixed temperature of around 300°C. Based on performed study and observations, improved levels of charring rates and new thickness of zero strength layer in case of parametric fires are determined. Thus, the reduced cross section method is substantially improved to offer practical recommendations for designing fire resistance of timber structures. Furthermore, correlations between zero strength layer thickness and key input parameters of the parametric fire curve (for instance, opening factor, fire load, etc.) are given, representing a guideline for a more detailed numerical and also experimental research in the future.

Keywords: advanced numerical modelling, parametric fire exposure, timber structures, zero strength layer

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Authors: Lesly Y Carmona-Sarabia, Luisa Barraza-Vergara, Vilmalí López-Mejías, Wandaliz Torres-García, Maribella Domenech-Garcia, Madeline Torres-Lugo

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Biosensors are used in many applications providing real-time monitoring to treat long-term conditions. Thus, understanding the physicochemical properties and biological side effects on the skin of polymers (e. g., poly(methyl methacrylate), PMMA) employed in the fabrication of wearable biosensors is crucial for the selection of manufacturing materials within this field. The PMMA (hydrophobic and thermoplastic polymer) is commonly employed as a coating material or substrate in the fabrication of wearable devices. The cytotoxicityof PMMA (including residual monomers or degradation products) on the skin, in terms of cells and tissue, is required to prevent possible adverse effects (cell death, skin reactions, sensitization) on human health. Within this work, accelerated aging of PMMA (Mw ~ 15000) through thermal and photochemical degradation was under-taken. The accelerated aging of PMMA was carried out by thermal (200°C, 1h) and photochemical degradation (UV-Vis, 8-15d) adapted employing ISO protocols (ISO-10993-12, ISO-4892-1:2016, ISO-877-1:2009, ISO-188: 2011). In addition, in vitro cytotoxicity evaluation of PMMA degradation products was performed using NIH3T3 fibroblast cells to assess the response of skin tissues (in terms of cell viability) exposed with polymers utilized to manufacture wearable biosensors, such as PMMA. The PMMA (Mw ~ 15000) before and after accelerated aging experiments was characterized by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), powder X-ray diffractogram (PXRD), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) to determine and verify the successful degradation of this polymer under the specific conditions previously mention. The degradation products were characterized through nuclear magnetic resonance (NMR) to identify possible byproducts generated after the accelerated aging. Results demonstrated a percentage (%) weight loss between 1.5-2.2% (TGA thermographs) for PMMA after accelerated aging. The EDS elemental analysis reveals a 1.32 wt.% loss of carbon for PMMA after thermal degradation. These results might be associated with the amount (%) of PMMA degrade after the accelerated aging experiments. Furthermore, from the thermal degradation products was detected the presence of the monomer and methyl formate (low concentrations) and a low molecular weight radical (·COOCH3) in higher concentrations by NMR. In the photodegradation products, methyl formate was detected in higher concentrations. These results agree with the proposed thermal or photochemical degradation mechanisms found in the literature.1,2 Finally, significant cytotoxicity on the NIH3T3 cells was obtained for the thermal and photochemical degradation products. A decrease in cell viability by > 90% (stock solutions) was observed. It is proposed that the presence of byproducts (e.g. methyl formate or radicals such as ·COOCH₃) from the PMMA degradation might be responsible for the cytotoxicity observed in the NIH3T3 fibroblast cells. Additionally, experiments using skin models will be employed to compare with the NIH3T3 fibroblast cells model.

Keywords: biosensors, polymer, skin irritation, degradation products, cell viability

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Authors: Chris J. Boreham, Dianne S. Edwards, Amber Jarrett, Justin Davies, Robert Poreda, Alex Sessions, John Eiler

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The origins of natural gases in the Amadeus Basin have been assessed using molecular and stable isotope (C, H, N, He) systematics. A dominant end-member thermogenic, oil-associated gas is considered for the Ordovician Pacoota−Stairway sandstones of the Mereenie gas and oil field. In addition, an abiogenic end-member is identified in the latest Proterozoic lower Arumbera Sandstone of the Dingo gasfield, being most likely associated with radiolysis of methane with polymerisation to wet gases. The latter source assignment is based on a similar geochemical fingerprint derived from the laboratory gamma irradiation experiments on methane. A mixed gas source is considered for the Palm Valley gasfield in the Ordovician Pacoota Sandstone. Gas wetness (%∑C₂−C₅/∑C₁−C₅) decreases in the order Mereenie (19.1%) > Palm Valley (9.4%) > Dingo (4.1%). Non-produced gases at Magee-1 (23.5%; Late Proterozoic Heavitree Quartzite) and Mount Kitty-1 (18.9%; Paleo-Mesoproterozoic fractured granitoid basement) are very wet. Methane thermometry based on clumped isotopes of methane (¹³CDH₃) is consistent with the abiogenic origin for the Dingo gas field with methane formation temperature of 254ᵒC. However, the low methane formation temperature of 57°C for the Mereenie gas suggests either a mixed thermogenic-biogenic methane source or there is no thermodynamic equilibrium between the methane isotopomers. The shallow reservoir depth and present-day formation temperature below 80ᵒC would support microbial methanogenesis, but there is no accompanying alteration of the C- and H-isotopes of the wet gases and CO₂ that is typically associated with biodegradation. The Amadeus Basin gases show low to extremely high inorganic gas contents. Carbon dioxide is low in abundance (< 1% CO₂) and becomes increasing depleted in ¹³C from the Palm Valley (av. δ¹³C 0‰) to the Mereenie (av. δ¹³C -6.6‰) and Dingo (av. δ¹³C -14.3‰) gas fields. Although the wide range in carbon isotopes for CO₂ is consistent with multiple origins from inorganic to organic inputs, the most likely process is fluid-rock alteration with enrichment in ¹²C in the residual gaseous CO₂ accompanying progressive carbonate precipitation within the reservoir. Nitrogen ranges from low−moderate (1.7−9.9% N₂) abundance (Palm Valley av. 1.8%; Mereenie av. 9.1%; Dingo av. 9.4%) to extremely high abundance in Magee-1 (43.6%) and Mount Kitty-1 (61.0%). The nitrogen isotopes for the production gases have δ¹⁵N = -3.0‰ for Mereenie, -3.0‰ for Palm Valley and -7.1‰ for Dingo, suggest all being mixed inorganic and thermogenic nitrogen sources. Helium (He) abundance varies over a wide range from a low of 0.17% to one of the world’s highest at 9% (Mereenie av. 0.23%; Palm Valley av. 0.48%, Dingo av. 0.18%, Magee-1 6.2%; Mount Kitty-1 9.0%). Complementary helium isotopes (R/Ra = ³He/⁴Hesample / ³He/⁴Heair) range from 0.013 to 0.031 R/Ra, indicating a dominant crustal origin for helium with a sustained input of radiogenic 4He from the decomposition of U- and Th-bearing minerals, effectively diluting any original mantle helium input. The high helium content in the non-produced gases compared to the shallower producing wells most likely reflects their stratigraphic position relative to the Tonian Bitter Springs Group with the former below and the latter above an effective carbonate-salt seal.

Keywords: amadeus gas, thermogenic, abiogenic, C, H, N, He isotopes

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Authors: Prajakta Patil, Yash Huzurbazar, Abhijeet Shinde

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Aim: To develop a treatment protocol for the management of tinnitus through multi-modality brain stimulation. Methodology: Present study included 33 adults with unilateral (31 subjects) and bilateral (2 subjects) chronic tinnitus with and/or without hearing loss independent of their etiology. The Treatment protocol included 5 consecutive sessions with follow-up of 6 months. Each session was divided into 3 parts: • Pre-treatment: a) Informed consent b) Pitch and loudness matching. • Treatment: Bimanual paper pen task with tinnitus masking for 30 minutes. • Post-treatment: a) Pitch and loudness matching b) Directive counseling and obtaining feedback. Paper-pen task is to be performed bimanually that included carrying out two different writing activities in different context. The level of difficulty of the activities was increased in successive sessions. Narrowband noise of a frequency same as that of tinnitus was presented at 10 dBSL of tinnitus for 30 minutes simultaneously in the ear with tinnitus. Result: The perception of tinnitus was no longer present in 4 subjects while in remaining subjects it reduced to an intensity that its perception no longer troubled them without causing residual facilitation. In all subjects, the intensity of tinnitus decreased by an extent of 45 dB at an average. However, in few subjects, the intensity of tinnitus also decreased by more than 45 dB. The approach resulted in statistically significant reductions in Tinnitus Functional Index and Tinnitus Handicap Inventory scores. The results correlate with pre and post treatment score of Tinnitus Handicap Inventory that dropped from 90% to 0%. Discussion: Brain mapping(qEEG) Studies report that there is multiple parallel overlapping of neural subnetworks in the non-auditory areas of the brain which exhibits abnormal, constant and spontaneous neural activity involved in the perception of tinnitus with each subnetwork and area reflecting a specific aspect of tinnitus percept. The paper pen task and directive counseling are designed and delivered respectively in a way that is assumed to induce normal, rhythmically constant and premeditated neural activity and mask the abnormal, constant and spontaneous neural activity in the above-mentioned subnetworks and the specific non-auditory area. Counseling was focused on breaking the vicious cycle causing and maintaining the presence of tinnitus. Diverting auditory attention alone is insufficient to reduce the perception of tinnitus. Conscious awareness of tinnitus can be suppressed when individuals engage in cognitively demanding tasks of non-auditory nature as the paper pen task used in the present study. To carry out this task selective, divided, sustained, simultaneous and split attention act cumulatively. Bimanual paper pen task represents a top-down activity which underlies brain’s ability to selectively attend to the bimanual written activity as a relevant stimulus and to ignore tinnitus that is the irrelevant stimuli in the present study. Conclusion: The study suggests that this novel treatment approach is cost effective, time saving and efficient to vanish the tinnitus or to reduce the intensity of tinnitus to a negligible level and thereby eliminating the negative reactions towards tinnitus.

Keywords: multi-modality brain stimulation, neural subnetworks, non-auditory areas, paper-pen task, top-down activity

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Authors: Carlos E. Rodríguez-Rodríguez, Karla Ruiz-Hidalgo, Kattia Madrigal-Zúñiga, Juan Salvador Chin-Pampillo, Mario Masís-Mora, Elizabeth Carazo-Rojas

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One of the main causes of contamination linked to agricultural activities is the spillage and disposal of pesticides, especially during the loading, mixing or cleaning of agricultural spraying equipment. One improvement in the handling of pesticides is the use of biopurification systems (BPS), simple and cheap degradation devices where the pesticides are biologically degraded at accelerated rates. The biologically active core of BPS is the biomixture, which is constituted by soil pre-exposed to the target pesticide, a lignocellulosic substrate to promote the activity of ligninolitic fungi and a humic component (peat or compost), mixed at a volumetric proportion of 50:25:25. Considering the known ability of lignocellulosic fungi to degrade a wide range of organic pollutants, and the high amount of lignocellulosic waste used in biomixture preparation, the bioaugmentation of biomixtures with these fungi represents an interesting approach for improving biomixtures. The present work aimed at evaluating the effect of the bioaugmentation of rice husk based biomixtures with the fungus Trametes versicolor in the removal of the insectice/nematicide carbofuran (CFN) and to optimize the composition of the biomixture to obtain the best performance in terms of CFN removal and mineralization, reduction in formation of transformation products and decrease in residual toxicity of the matrix. The evaluation of several lignocellulosic residues (rice husk, wood chips, coconut fiber, sugarcane bagasse or newspaper print) revealed the best colonization by T. versicolor in rice husk. Pre-colonized rice husk was then used in the bioaugmentation of biomixtures also containing soil pre-exposed to CFN and either peat (GTS biomixture) or compost (GCS biomixture). After spiking with 10 mg/kg CBF, the efficiency of the biomixture was evaluated through a multi-component approach that included: monitoring of CBF removal and production of CBF transformation products, mineralization of radioisotopically labeled carbofuran (14C-CBF) and changes in the toxicity of the matrix after the treatment (Daphnia magna acute immobilization test). Estimated half-lives of CBF in the biomixtures were 3.4 d and 8.1 d in GTS and GCS, respectively. The transformation products 3-hydroxycarbofuran and 3-ketocarbofuran were detected at the moment of CFN application, however their concentration continuously disappeared. Mineralization of 14C-CFN was also faster in GTS than GCS. The toxicological evaluation showed a complete toxicity removal in the biomixtures after 48 d of treatment. The composition of the GCS biomixture was optimized using a central composite design and response surface methodology. The design variables were the volumetric content of fungally pre-colonized rice husk and the volumetric ratio compost/soil. According to the response models, maximization of CFN removal and mineralization rate, and minimization in the accumulation of transformation products were obtained with an optimized biomixture of composition 30:43:27 (pre-colonized rice husk:compost:soil), which differs from the 50:25:25 composition commonly employed in BPS. Results suggest that fungal bioaugmentation may enhance the performance of biomixtures in CFN removal. Optimization reveals the importance of assessing new biomixture formulations in order to maximize their performance.

Keywords: bioaugmentation, biopurification systems, degradation, fungi, pesticides, toxicity

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Authors: V. Mantey, N. Findlay, I. Maddox

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The quality and quantity of global satellite data have been increasing exponentially in recent years as spaceborne systems become more affordable and the sensors themselves become more sophisticated. This is a valuable resource for many applications, including disaster management and relief. However, while more information can be valuable, the volume of data available is impossible to manually examine. Therefore, the question becomes how to extract as much information as possible from the data with limited manpower. Buildings are a key feature of interest in satellite imagery with applications including telecommunications, population models, and disaster relief. Machine learning tools are fast becoming one of the key resources to solve this problem, and models have been developed to detect buildings in optical satellite imagery. However, by and large, most models focus on affluent regions where buildings are generally larger and constructed further apart. This work is focused on the more difficult problem of detection in populated regions. The primary challenge with detecting small buildings in densely populated regions is both the spatial and spectral resolution of the optical sensor. Densely packed buildings with similar construction materials will be difficult to separate due to a similarity in color and because the physical separation between structures is either non-existent or smaller than the spatial resolution. This study finds that training models until they are overfitting the input sample can perform better in these areas than a more robust, generalized model. An overfitted model takes less time to fine-tune from a generalized pre-trained model and requires fewer input data. The model developed for this study has also been fine-tuned using existing, open-source, building vector datasets. This is particularly valuable in the context of disaster relief, where information is required in a very short time span. Leveraging existing datasets means that little to no manpower or time is required to collect data in the region of interest. The training period itself is also shorter for smaller datasets. Requiring less data means that only a few quality areas are necessary, and so any weaknesses or underpopulated regions in the data can be skipped over in favor of areas with higher quality vectors. In this study, a landcover classification model was developed in conjunction with the building detection tool to provide a secondary source to quality check the detected buildings. This has greatly reduced the false positive rate. The proposed methodologies have been implemented and integrated into a configurable production environment and have been employed for a number of large-scale commercial projects, including continent-wide DEM production, where the extracted building footprints are being used to enhance digital elevation models. Overfitted machine learning models are often considered too specific to have any predictive capacity. However, this study demonstrates that, in cases where input data is scarce, overfitted models can be judiciously applied to solve time-sensitive problems.

Keywords: building detection, disaster relief, mask-RCNN, satellite mapping

Procedia PDF Downloads 166

Authors: Davide Gotti, Milan Prodanovic, Sergio Pinilla, David Muñoz-Torrero

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Since its proposal, the Doyle-Fuller-Newman (DFN) lithium-ion battery model has gained popularity in the electrochemical field. In fact, this model provides the user with theoretical support for designing the lithium-ion battery parameters, such as the material particle or the diffusion coefficient adjustment direction. However, the model is mathematically complex as it is composed of several partial differential equations (PDEs) such as Fick’s law of diffusion, the MacInnes and Ohm’s equations, among other phenomena. Thus, to efficiently use the model in a time-domain simulation environment, the selection of the discretization technique is of a pivotal importance. There are several numerical methods available in the literature that can be used to carry out this task. In this study, a comparison between the explicit Euler, Crank-Nicolson, and Chebyshev discretization methods is proposed. These three methods are compared in terms of accuracy, stability, and computational times. Firstly, the explicit Euler discretization technique is analyzed. This method is straightforward to implement and is computationally fast. In this work, the accuracy of the method and its stability properties are shown for the electrolyte diffusion partial differential equation. Subsequently, the Crank-Nicolson method is considered. It represents a combination of the implicit and explicit Euler methods that has the advantage of being of the second order in time and is intrinsically stable, thus overcoming the disadvantages of the simpler Euler explicit method. As shown in the full paper, the Crank-Nicolson method provides accurate results when applied to the DFN model. Its stability does not depend on the integration time step, thus it is feasible for both short- and long-term tests. This last remark is particularly important as this discretization technique would allow the user to implement parameter estimation and optimization techniques such as system or genetic parameter identification methods using this model. Finally, the Chebyshev discretization technique is implemented in the DFN model. This discretization method features swift convergence properties and, as other spectral methods used to solve differential equations, achieves the same accuracy with a smaller number of discretization nodes. However, as shown in the literature, these methods are not suitable for handling sharp gradients, which are common during the first instants of the charge and discharge phases of the battery. The numerical results obtained and presented in this study aim to provide the guidelines on how to select the adequate discretization technique for the DFN model according to the type of application to be performed, highlighting the pros and cons of the three methods. Specifically, the non-eligibility of the simple Euler method for longterm tests will be presented. Afterwards, the Crank-Nicolson and the Chebyshev discretization methods will be compared in terms of accuracy and computational times under a wide range of battery operating scenarios. These include both long-term simulations for aging tests, and short- and mid-term battery charge/discharge cycles, typically relevant in battery applications like grid primary frequency and inertia control and electrical vehicle breaking and acceleration.

Keywords: Doyle-Fuller-Newman battery model, partial differential equations, discretization, numerical methods

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Authors: Patrick Cormier, Cesar Meylan, Matt Jensen, Dana Agar-Newman, Chloe Werle, Ming-Chang Tsai, Marc Klimstra

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Sprint-derived horizontal force-velocity-power (FVP) profiles can be developed with adequate validity and reliability with satellite (GPS/GNSS) systems. However, FVP metrics are sensitive to small nuances in data processing procedures such that minor differences in defining the onset and end of the sprint could result in different FVP metric outcomes. Furthermore, in team-sports, there is a requirement for rapid analysis and feedback of results from multiple athletes, therefore developing standardized and automated methods to improve the speed, efficiency and reliability of this process are warranted. Thus, the purpose of this study was to compare different methods of sprint end detection on the development of FVP profiles from 10Hz GPS/GNSS data through goodness-of-fit and intertrial reliability statistics. Seventeen national team female soccer players participated in the FVP protocol which consisted of 2x40m maximal sprints performed towards the end of a soccer specific warm-up in a training session (1020 hPa, wind = 0, temperature = 30°C) on an open grass field. Each player wore a 10Hz Catapult system unit (Vector S7, Catapult Innovations) inserted in a vest in a pouch between the scapulae. All data were analyzed following common procedures. Variables computed and assessed were the model parameters, estimated maximal sprint speed (MSS) and the acceleration constant τ, in addition to horizontal relative force (F₀), velocity at zero (V₀), and relative mechanical power (Pmax). The onset of the sprints was standardized with an acceleration threshold of 0.1 m/s². The sprint end detection methods were: 1. Time when peak velocity (MSS) was achieved (zero acceleration), 2. Time after peak velocity drops by -0.4 m/s, 3. Time after peak velocity drops by -0.6 m/s, and 4. When the integrated distance from the GPS/GNSS signal achieves 40-m. Goodness-of-fit of each sprint end detection method was determined using the residual sum of squares (RSS) to demonstrate the error of the FVP modeling with the sprint data from the GPS/GNSS system. Inter-trial reliability (from 2 trials) was assessed utilizing intraclass correlation coefficients (ICC). For goodness-of-fit results, the end detection technique that used the time when peak velocity was achieved (zero acceleration) had the lowest RSS values, followed by -0.4 and -0.6 velocity decay, and 40-m end had the highest RSS values. For intertrial reliability, the end of sprint detection techniques that were defined as the time at (method 1) or shortly after (method 2 and 3) when MSS was achieved had very large to near perfect ICC and the time at the 40 m integrated distance (method 4) had large to very large ICCs. Peak velocity was reached at 29.52 ± 4.02-m. Therefore, sport scientists should implement end of sprint detection either when peak velocity is determined or shortly after to improve goodness of fit to achieve reliable between trial FVP profile metrics. Although, more robust processing and modeling procedures should be developed in future research to improve sprint model fitting. This protocol was seamlessly integrated into the usual training which shows promise for sprint monitoring in the field with this technology.

Keywords: automated, biomechanics, team-sports, sprint

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Authors: G. M. Vlasceanu, H. Iovu, E. Vasile, M. Ionita

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Herein, the synthesis and characterization of chitosan-gelatin highly porous scaffold reinforced with graphene oxide, and hydroxyapatite (HAp), crosslinked with genipin was targeted. In tissue engineering, chitosan and gelatin are two of the most robust biopolymers with wide applicability due to intrinsic biocompatibility, biodegradability, low antigenicity properties, affordability, and ease of processing. HAp, per its exceptional activity in tuning cell-matrix interactions, is acknowledged for its capability of sustaining cellular proliferation by promoting bone-like native micro-media for cell adjustment. Genipin is regarded as a top class cross-linker, while graphene oxide (GO) is viewed as one of the most performant and versatile fillers. The composites with natural bone HAp/biopolymer ratio were obtained by cascading sonochemical treatments, followed by uncomplicated casting methods and by freeze-drying. Their structure was characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction, while overall morphology was investigated by Scanning Electron Microscopy (SEM) and micro-Computer Tomography (µ-CT). Ensuing that, in vitro enzyme degradation was performed to detect the most promising compositions for the development of in vivo assays. Suitable GO dispersion was ascertained within the biopolymer mix as nanolayers specific signals lack in both FTIR and XRD spectra, and the specific spectral features of the polymers persisted with GO load enhancement. Overall, correlations between the GO induced material structuration, crystallinity variations, and chemical interaction of the compounds can be correlated with the physical features and bioactivity of each composite formulation. Moreover, the HAp distribution within follows an auspicious density gradient tuned for hybrid osseous/cartilage matter architectures, which were mirrored in the mice model tests. Hence, the synthesis route of a natural polymer blend/hydroxyapatite-graphene oxide composite material is anticipated to emerge as influential formulation in bone tissue engineering. Acknowledgement: This work was supported by the project 'Work-based learning systems using entrepreneurship grants for doctoral and post-doctoral students' (Sisteme de invatare bazate pe munca prin burse antreprenor pentru doctoranzi si postdoctoranzi) - SIMBA, SMIS code 124705 and by a grant of the National Authority for Scientific Research and Innovation, Operational Program Competitiveness Axis 1 - Section E, Program co-financed from European Regional Development Fund 'Investments for your future' under the project number 154/25.11.2016, P_37_221/2015. The nano-CT experiments were possible due to European Regional Development Fund through Competitiveness Operational Program 2014-2020, Priority axis 1, ID P_36_611, MySMIS code 107066, INOVABIOMED.

Keywords: biopolymer blend, ectopic osteoinduction, graphene oxide composite, hydroxyapatite

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Authors: Trevor C. Brown, David J. Miron

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Gas-solid physical adsorption methods are central to the characterization and optimization of the effective surface area, pore size and porosity for applications such as heterogeneous catalysis, and gas separation and storage. Properties such as adsorption uptake, capacity, equilibrium constants and Gibbs free energy are dependent on the composition and structure of both the gas and the adsorbent. However, challenges remain, in accurately calculating these properties from experimental data. Gas adsorption experiments involve measuring the amounts of gas adsorbed over a range of pressures under isothermal conditions. Various constant-parameter models, such as Langmuir and Brunauer-Emmett-Teller (BET) theories are used to provide information on adsorbate and adsorbent properties from the isotherm data. These models typically do not provide accurate interpretations across the full range of pressures and temperatures. The Langmuir adsorption isotherm is a simple approximation for modelling equilibrium adsorption data and has been effective in estimating surface areas and catalytic rate laws, particularly for high surface area solids. The Langmuir isotherm assumes the systematic filling of identical adsorption sites to a monolayer coverage. The BET model is based on the Langmuir isotherm and allows for the formation of multiple layers. These additional layers do not interact with the first layer and the energetics are equal to the adsorbate as a bulk liquid. This BET method is widely used to measure the specific surface area of materials. Both Langmuir and BET models assume that the affinity of the gas for all adsorption sites are identical and so the calculated adsorbent uptake at the monolayer and equilibrium constant are independent of coverage and pressure. Accurate representations of adsorption data have been achieved by extending the Langmuir and BET models to include pressure-varying uptake capacities and equilibrium constants. These parameters are determined using a novel regression technique called flexible least squares for time-varying linear regression. For isothermal adsorption the adsorption parameters are assumed to vary slowly and smoothly with increasing pressure. The flexible least squares for pressure-varying linear regression (FLS-PVLR) approach assumes two distinct types of discrepancy terms, dynamic and measurement for all parameters in the linear equation used to simulate the data. Dynamic terms account for pressure variation in successive parameter vectors, and measurement terms account for differences between observed and theoretically predicted outcomes via linear regression. The resultant pressure-varying parameters are optimized by minimizing both dynamic and measurement residual squared errors. Validation of this methodology has been achieved by simulating adsorption data for n-butane and isobutane on activated carbon at 298 K, 323 K and 348 K and for nitrogen on mesoporous alumina at 77 K with pressure-varying Langmuir and BET adsorption parameters (equilibrium constants and uptake capacities). This modeling provides information on the adsorbent (accessible surface area and micropore volume), adsorbate (molecular areas and volumes) and thermodynamic (Gibbs free energies) variations of the adsorption sites.

Keywords: Langmuir adsorption isotherm, BET adsorption isotherm, pressure-varying adsorption parameters, adsorbate and adsorbent properties and energetics

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Authors: Elena Ionescu, Elena Iacob, Marie-Louise Ionescu, Carmen Elena Tebrencu, Oana Teodora Ciuperca

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Echinacea species (Asteraceae) has received a global attention because it is widely used for treatment of cold, flu and upper respiratory tract infections. Echinacea species contain a great variety of chemical components that contribute to their activity. The most important components responsible for the biological activity are those with high molecular-weight such as polysaccharides, polyacetylenes, highly unsaturated alkamides and caffeic acid derivatives. The principal factors that may influence the chemical composition of Echinacea include the species and the part of plant used (aerial parts or roots ). In recent years the market for Echinacea has grown rapidly and also the cases of adultery/replacement especially for Echinacea root. The identification of presence or absence of same biomarkers provide information for safe use of Echinacea species in food supplements industry. The aim of the study was the preliminary evaluation and fingerprinting by UV-VISIBLE spectroscopy of biomarkers in terms of content in phenolic derivatives of some Echinacea species (E. purpurea, E. angustifolia and E. pallida) for identification and authentication of the species. The steps of the study were: (1) samples (extracts) preparation from Echinacea species (non-hydrolyzed and hydrolyzed ethanol extracts); (2) samples preparation of reference substances (polyphenol acids: caftaric acid, caffeic acid, chlorogenic acid, ferulic acid; flavonoids: rutoside, hyperoside, isoquercitrin and their aglycones: quercitri, quercetol, luteolin, kaempferol and apigenin); (3) identification of specific absorption at wavelengths between 700-200 nm; (4) identify the phenolic compounds from Echinacea species based on spectral characteristics and the specific absorption; each class of compounds corresponds to a maximum absorption in the UV spectrum. The phytochemical compounds were identified at specific wavelengths between 700-200 nm. The absorption intensities were measured. The obtained results proved that ethanolic extract showed absorption peaks attributed to: phenolic compounds (free phenolic acids and phenolic acids derivatives) registrated between 220-280 nm, unsymmetrical chemical structure compounds (caffeic acid, chlorogenic acid, ferulic acid) with maximum absorption peak and absorption "shoulder" that may be due to substitution of hydroxyl or methoxy group, flavonoid compounds (in free form or glycosides) between 330-360 nm, due to the double bond in position 2,3 and carbonyl group in position 4 flavonols. UV spectra showed two major peaks of absorption (quercetin glycoside, rutin, etc.). The results obtained by UV-VIS spectroscopy has revealed the presence of phenolic derivatives such as cicoric acid (240 nm), caftaric acid (329 nm), caffeic acid (240 nm), rutoside (205 nm), quercetin (255 nm), luteolin (235 nm) in all three species of Echinacea. The echinacoside is absent. This profile mentioned above and the absence of phenolic compound echinacoside leads to the conclusion that species harvested as Echinacea angustifolia and Echinacea pallida are Echinacea purpurea also; It can be said that preliminary fingerprinting of Echinacea species through correspondence with the phenolic derivatives profile can be achieved by UV-VIS spectroscopic investigation, which is an adequate technique for preliminary identification and authentication of Echinacea in medicinal herbs.

Keywords: Echinacea species, Fingerprinting, Phenolic compounds, UV-VIS spectroscopy

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Authors: Álvaro Ramírez Vidal, Martín Muñoz Morales, Francisco Jesús Fernández Morales, Luis Rodríguez Romero, José Villaseñor Camacho, Javier Llanos López

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In recent times, environmental problems have led to the extensive use of biological systems to solve them. Among the different types of biological systems, the use of plants such as aquatic macrophytes in constructed wetlands and terrestrial plant species for treating polluted soils and sludge has gained importance. Though the use of constructed wetlands for wastewater treatment is a well-researched domain, the slowness of pollutant degradation and high biomass production pose some challenges. Plants used in CW participate in different mechanisms for the capture and degradation of pollutants that also can retain some pharmaceutical and personal care products (PPCPs) that are very persistent in the environment. Thus, these systems present advantages in line with the guidelines published for the transition towards friendly and ecological procedures as they are environmentally friendly systems, consume low energy, or capture atmospheric CO₂. However, the use of CW presents some drawbacks, as the slowness of pollutant degradation or the production of important amounts of plant biomass, which need to be harvested and managed periodically. Taking this opportunity in mind, it is important to highlight that this residual biomass (of lignocellulosic nature) could be used as the feedstock for the generation of carbonaceous materials using thermochemical transformations such as slow pyrolysis or hydrothermal carbonization to produce high-value biomass-derived carbons through sustainable processes as adsorbents, catalysts…, thereby improving the circular carbon economy. Thus, this work carried out the analysis of some PPCPs commonly found in urban wastewater, as salicylic acid or ibuprofen, to evaluate the remediation carried out for the Phragmites Australis. Then, after the harvesting, this biomass can be used to synthesize electrodes through hydrothermal carbonization (HTC) and produce high-value biomass-derived carbons with electrocatalytic activity to remove heavy metals and persistent pollutants, promoting circular economy concepts. To do this, it was chosen biomass derived from the natural environment in high environmental risk as the Daimiel Wetlands National Park in the center of Spain, and the rest of the biomass developed in a CW specifically designed to remove pollutants. The research emphasizes the impact of the composition of the biomass waste and the synthetic parameters applied during HTC on the electrocatalytic activity. Additionally, this parameter can be related to the physicochemical properties, as porosity, surface functionalization, conductivity, and mass transfer of the electrodes lytic inks. Data revealed that carbon materials synthesized have good surface properties (good conductivities and high specific surface area) that enhance the electro-oxidants generated and promote the removal of PPCPs and the chemical oxygen demand of polluted waters.

Keywords: constructed wetlands, carbon materials, heavy metals, pharmaceutical and personal care products, hydrothermal carbonization

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Authors: A. Matiushkina, A. Bazhenova, I. Litvinov, E. Kornilova, A. Dubavik, A. Orlova

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Magnetic-luminescent complexes based on superparamagnetic iron oxide nanoparticles (SPIONs) and semiconductor quantum dots (QDs) have been recognized as a new class of materials that have high potential in modern medicine. These materials can serve for theranostics of oncological diseases, and also as a target agent for drug delivery. They combine the qualities characteristic of magnetic nanoparticles, that is, magneto-controllability and the ability to local heating under the influence of an external magnetic field, as well as phosphors, due to luminescence of which, for example, early tumor imaging is possible. The complexity of creating complexes is the energy transfer between particles, which quenches the luminescence of QDs in complexes with SPIONs. In this regard, a relatively new type of alloyed (CdₓZn₁₋ₓSeᵧS₁₋ᵧ)-ZnS QDs is used in our work. The presence of a sufficiently thick gradient semiconductor shell in alloyed QDs makes it possible to reduce the probability of energy transfer from QDs to SPIONs in complexes. At the same time, Forster Resonance Energy Transfer (FRET) is a perfect instrument to confirm the formation of complexes based on QDs and different-type energy acceptors. The formation of complexes in the aprotic bipolar solvent dimethyl sulfoxide is ensured by the coordination of the carboxyl group of the stabilizing QD molecule (L-cysteine) on the surface iron atoms of the SPIONs. An analysis of the photoluminescence (PL) spectra has shown that a sequential increase in the SPIONs concentration in the samples is accompanied by effective quenching of the luminescence of QDs. However, it has not confirmed the formation of complexes yet, because of a decrease in the PL intensity of QDs due to reabsorption of light by SPIONs. Therefore, a study of the PL kinetics of QDs at different SPIONs concentrations was made, which demonstrates that an increase in the SPIONs concentration is accompanied by a symbatic reduction in all characteristic PL decay times. It confirms the FRET from QDs to SPIONs, which indicates the QDs/SPIONs complex formation, rather than a spontaneous aggregation of QDs, which is usually accompanied by a sharp increase in the percentage of the QD fraction with the shortest characteristic PL decay time. The complexes have been studied by the magnetic circular dichroism (MCD) spectroscopy that allows one to estimate the response of magnetic material to the applied magnetic field and also can be useful to check SPIONs aggregation. An analysis of the MCD spectra has shown that the complexes have zero residual magnetization, which is an important factor for using in biomedical applications, and don't contain SPIONs aggregates. Cell penetration, biocompatibility, and stability of QDs/SPIONs complexes in cancer cells have been studied using HeLa cell line. We have found that the complexes penetrate in HeLa cell and don't demonstrate cytotoxic effect up to 25 nM concentration. Our results clearly demonstrate that alloyed (CdₓZn₁₋ₓSeᵧS₁₋ᵧ)-ZnS QDs can be successfully used in complexes with SPIONs reached new hybrid nanostructures, which combine bright luminescence for tumor imaging and magnetic properties for targeted drug delivery and magnetic hyperthermia of tumors. Acknowledgements: This work was supported by the Ministry of Science and Higher Education of Russian Federation, goszadanie no. 2019-1080 and was financially supported by Government of Russian Federation, Grant 08-08.

Keywords: alloyed quantum dots, magnetic circular dichroism, magneto-luminescent complexes, superparamagnetic iron oxide nanoparticles

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Authors: Inna Kornienko, Svetlana Guryeva, Anatoly Shekhter, Elena Petersen

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Transplantation is an effective treatment option for patients suffering from different end-stage diseases. However, it is plagued by a constant shortage of donor organs and the subsequent need of a lifelong immunosuppressive therapy for the patient. Currently some researchers look towards using of pig organs to replace human organs for transplantation since the matrix derived from porcine organs is a convenient substitute for the human matrix. As an initial step to create a new ex vivo tissue engineered model, optimized protocols have been created to obtain organ-specific acellular matrices and evaluated their potential as tissue engineered scaffolds for culture of normal cells and tumor cell lines. These protocols include decellularization by perfusion in a bioreactor system and immersion-agitation on an orbital shaker with use of various detergents (SDS, Triton X-100) and freezing. Complete decellularization – in terms of residual DNA amount – is an important predictor of probability of immune rejection of materials of natural origin. However, the signs of cellular material may still remain within the matrix even after harsh decellularization protocols. In this regard, the matrices obtained from tissues of low-immunogenic pigs with α3Galactosyl-tranferase gene knock out (GalT-KO) may be a promising alternative to native animal sources. The research included a study of induced effect of frozen and fresh fragments of GalT-KO skin on healing of full-thickness plane wounds in 80 rats. Commercially available wound dressings (Ksenoderm, Hyamatrix and Alloderm) as well as allogenic skin were used as a positive control and untreated wounds were analyzed as a negative control. The results were evaluated on the 4th day after grafting, which corresponds to the time of start of normal wound epithelization. It has been shown that a non-specific immune response in models treated with GalT-Ko pig skin was milder than in all the control groups. Research has been performed to measure technical skin characteristics: stiffness and elasticity properties, corneometry, tevametry, and cutometry. These metrics enabled the evaluation of hydratation level, corneous layer husking level, as well as skin elasticity and micro- and macro-landscape. These preliminary data may contribute to development of personalized transplantable organs from GalT-Ko pigs with significantly limited potential of immune rejection. By applying growth factors to a decellularized skin sample it is possible to achieve various regenerative effects based on the particular situation. In this particular research BMP2 and Heparin-binding EGF-like growth factor have been used. Ideally, a bioengineered organ must be biocompatible, non-immunogenic and support cell growth. Porcine organs are attractive for xenotransplantation if severe immunologic concerns can be bypassed. The results indicate that genetically modified pig tissues with knock-outed α3Galactosyl-tranferase gene may be used for production of low-immunogenic matrix suitable for transplantation.

Keywords: decellularization, low-immunogenic, matrix, scaffolds, transplants

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Authors: Nodar Kekelidze, David Kekelidze, Elza Khutsishvili, Bela Kvirkvelia

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The semiconductor devices are irreplaceable elements for investigations in Space (artificial Earth satellite, interplanetary space craft, probes, rockets) and for investigation of elementary particles on accelerators, for atomic power stations, nuclear reactors, robots operating on heavily radiation contaminated territories (Chernobyl, Fukushima). Unfortunately, the most important parameters of semiconductors dramatically worsen under irradiation. So creation of radiation-resistant semiconductor materials for opto and microelectronic devices is actual problem, as well as investigation of complicated processes developed in irradiated solid states. Homogeneous single crystals of InP-InAs solid solutions were grown with zone melting method. There has been studied the dependence of the optical absorption coefficient vs photon energy near fundamental absorption edge. This dependence changes dramatically with irradiation. The experiments were performed on InP, InAs and InP-InAs solid solutions before and after irradiation with electrons and fast neutrons. The investigations of optical properties were carried out on infrared spectrophotometer in temperature range of 10K-300K and 1mkm-50mkm spectral area. Radiation fluencies of fast neutrons was equal to 2·1018neutron/cm2 and electrons with 3MeV, 50MeV up to fluxes of 6·1017electron/cm2. Under irradiation, there has been revealed the exponential type of the dependence of the optical absorption coefficient vs photon energy with energy deficiency. The indicated phenomenon takes place at high and low temperatures as well at impurity different concentration and practically in all cases of irradiation by various energy electrons and fast neutrons. We have developed the common mechanism of this phenomenon for unirradiated materials and implemented the quantitative calculations of distinctive parameter; this is in a satisfactory agreement with experimental data. For the irradiated crystals picture get complicated. In the work, the corresponding analysis is carried out. It has been shown, that in the case of InP, irradiated with electrons (Ф=1·1017el/cm2), the curve of optical absorption is shifted to lower energies. This is caused by appearance of the tails of density of states in forbidden band due to local fluctuations of ionized impurity (defect) concentration. Situation is more complicated in the case of InAs and for solid solutions with composition near to InAs when besides noticeable phenomenon there takes place Burstein effect caused by increase of electrons concentration as a result of irradiation. We have shown, that in certain conditions it is possible the prevalence of Burstein effect. This causes the opposite effect: the shift of the optical absorption edge to higher energies. So in given solid solutions there take place two different opposite directed processes. By selection of solid solutions composition and doping impurity we obtained such InP-InAs, solid solution in which under radiation mutual compensation of optical absorption curves displacement occurs. Obtained result let create on the base of InP-InAs, solid solution radiation-resistant optical materials. Conclusion: It was established the nature of optical absorption near fundamental edge in semiconductor materials and it was created radiation-resistant optical material.

Keywords: InAs-InP, electrons concentration, irradiation, solid solutions

Procedia PDF Downloads 191

Authors: Miroslava Cuperlovic-Culf, Lipu Wang, Ketty Boyle, Nadine Makley, Ian Burton, Anissa Belkaid, Mohamed Touaibia, Marc E. Surrette

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Metabolic changes are one of the major factors in the development of a variety of diseases in various species. Metabolism of agricultural plants is altered the following infection with pathogens sometimes contributing to resistance. At the same time, pathogens use metabolites for infection and progression. In humans, metabolism is a hallmark of cancer development for example. Quantified metabolomics data combined with other omics or clinical data and analyzed using various unsupervised and supervised methods can lead to better diagnosis and prognosis. It can also provide information about resistance as well as contribute knowledge of compounds significant for disease progression or prevention. In this work, different methods for metabolomics quantification and analysis from Nuclear Magnetic Resonance (NMR) measurements that are used for investigation of disease development in wheat and human cells will be presented. One-dimensional 1H NMR spectra are used extensively for metabolic profiling due to their high reliability, wide range of applicability, speed, trivial sample preparation and low cost. This presentation will describe a new method for metabolite quantification from NMR data that combines alignment of spectra of standards to sample spectra followed by multivariate linear regression optimization of spectra of assigned metabolites to samples’ spectra. Several different alignment methods were tested and multivariate linear regression result has been compared with other quantification methods. Quantified metabolomics data can be analyzed in the variety of ways and we will present different clustering methods used for phenotype determination, network analysis providing knowledge about the relationships between metabolites through metabolic network as well as biomarker selection providing novel markers. These analysis methods have been utilized for the investigation of fusarium head blight resistance in wheat cultivars as well as analysis of the effect of estrogen receptor and carbonic anhydrase activation and inhibition on breast cancer cell metabolism. Metabolic changes in spikelet’s of wheat cultivars FL62R1, Stettler, MuchMore and Sumai3 following fusarium graminearum infection were explored. Extensive 1D 1H and 2D NMR measurements provided information for detailed metabolite assignment and quantification leading to possible metabolic markers discriminating resistance level in wheat subtypes. Quantification data is compared to results obtained using other published methods. Fusarium infection induced metabolic changes in different wheat varieties are discussed in the context of metabolic network and resistance. Quantitative metabolomics has been used for the investigation of the effect of targeted enzyme inhibition in cancer. In this work, the effect of 17 β -estradiol and ferulic acid on metabolism of ER+ breast cancer cells has been compared to their effect on ER- control cells. The effect of the inhibitors of carbonic anhydrase on the observed metabolic changes resulting from ER activation has also been determined. Metabolic profiles were studied using 1D and 2D metabolomic NMR experiments, combined with the identification and quantification of metabolites, and the annotation of the results is provided in the context of biochemical pathways.

Keywords: metabolic biomarkers, metabolic network, metabolomics, multivariate linear regression, NMR quantification, quantified metabolomics, spectral alignment

Procedia PDF Downloads 333

Authors: Nikolaus Wilke, Boaz Paz

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Museum staff, conservators, restorers, curators, registrars, art handlers but potentially also museum visitors are often exposed to the harmful effects of biocides, which have been applied to collections in the past for the protection and preservation of cultural heritage. Due to stable light, moisture, and temperature conditions, the biocidal active ingredients were preserved for much longer than originally assumed by chemists, pest controllers, and museum scientists. Given the requirements to minimize the use and handling of toxic substances and the obligations of employers regarding safe working environments for their employees, but also for visitors, the museum sector worldwide needs adequate decontamination solutions. Today there are millions of contaminated objects in museums. This paper introduces the results of a systematic investigation into the reduction rate of biocide contamination in various organic materials that were treated with the humidity and temperature controlled ICM (Integrated Contamination Management) method. In the past, collections were treated with a wide range, at times even with a combination of toxins, either preventively or to eliminate active insect or fungi infestations. It was only later that most of those toxins were recognized as CMR (cancerogenic mutagen reprotoxic) substances. Among them were numerous chemical substances that are banned today because of their toxicity. While the biocidal effect of inorganic salts such as arsenic (arsenic(III) oxide), sublimate (mercury(II) chloride), copper oxychloride (basic copper chloride) and zinc chloride was known very early on, organic tar distillates such as paradichlorobenzene, carbolineum, creosote and naphthalene were increasingly used from the 19th century onwards, especially as wood preservatives. With the rapid development of organic synthesis chemistry in the 20th century and the development of highly effective warfare agents, pesticides and fungicides, these substances were replaced by chlorogenic compounds (e.g. γ-hexachlorocyclohexane (lindane), dichlorodiphenyltrichloroethane (DDT), pentachlorophenol (PCP), hormone-like derivatives such as synthetic pyrethroids (e.g., permethrin, deltamethrin, cyfluthrin) and phosphoric acid esters (e.g., dichlorvos, chlorpyrifos). Today we know that textile artifacts (costumes, uniforms, carpets, tapestries), wooden objects, herbaria, libraries, archives and historical wall decorations made of fabric, paper and leather were also widely treated with toxic inorganic and organic substances. The migration (emission) of pollutants from the contaminated objects leads to continuous (secondary) contamination and accumulation in the indoor air and dust. It is important to note that many of mentioned toxic substances are also material-damaging; they cause discoloration and corrosion. Some, such as DDT, form crystals, which in turn can cause micro tectonic, destructive shifting, for example, in paint layers. Museums must integrate sustainable solutions to address the residual biocide problems already in the planning phase. Gas and dust phase measurements and analysis must become standard as well as methods of decontamination.

Keywords: biocides, decontamination, museum collections, toxic substances in museums

Procedia PDF Downloads 106

Authors: Maria Amelia V. C. Araujo, Billy J. Araujo, Brian Greenwood

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The flow over a backward-facing step is characterized by the presence of flow separation, recirculation and reattachment, for a simple geometry. This type of fluid behaviour takes place in many practical engineering applications, hence the reason for being investigated. Historically, fluid flows over a backward-facing step have been examined in many experiments using a variety of measuring techniques such as laser Doppler velocimetry (LDV), hot-wire anemometry, particle image velocimetry or hot-film sensors. However, some of these techniques cannot conveniently be used in separated flows or are too complicated and expensive. In this work, the applicability of the acoustic Doppler velocimetry (ADV) technique is investigated to such type of flows, at various Reynolds numbers corresponding to different flow regimes. The use of this measuring technique in separated flows is very difficult to find in literature. Besides, most of the situations where the Reynolds number effect is evaluated in separated flows are in numerical modelling. The ADV technique has the advantage in providing nearly non-invasive measurements, which is important in resolving turbulence. The ADV Nortek Vectrino+ was used to characterize the flow, in a recirculating laboratory flume, at various Reynolds Numbers (Reh = 3738, 5452, 7908 and 17388) based on the step height (h), in order to capture different flow regimes, and the results compared to those obtained using other measuring techniques. To compare results with other researchers, the step height, expansion ratio and the positions upstream and downstream the step were reproduced. The post-processing of the AVD records was performed using a customized numerical code, which implements several filtering techniques. Subsequently, the Vectrino noise level was evaluated by computing the power spectral density for the stream-wise horizontal velocity component. The normalized mean stream-wise velocity profiles, skin-friction coefficients and reattachment lengths were obtained for each Reh. Turbulent kinetic energy, Reynolds shear stresses and normal Reynolds stresses were determined for Reh = 7908. An uncertainty analysis was carried out, for the measured variables, using the moving block bootstrap technique. Low noise levels were obtained after implementing the post-processing techniques, showing their effectiveness. Besides, the errors obtained in the uncertainty analysis were relatively low, in general. For Reh = 7908, the normalized mean stream-wise velocity and turbulence profiles were compared directly with those acquired by other researchers using the LDV technique and a good agreement was found. The ADV technique proved to be able to characterize the flow properly over a backward-facing step, although additional caution should be taken for measurements very close to the bottom. The ADV measurements showed reliable results regarding: a) the stream-wise velocity profiles; b) the turbulent shear stress; c) the reattachment length; d) the identification of the transition from transitional to turbulent flows. Despite being a relatively inexpensive technique, acoustic Doppler velocimetry can be used with confidence in separated flows and thus very useful for numerical model validation. However, it is very important to perform adequate post-processing of the acquired data, to obtain low noise levels, thus decreasing the uncertainty.

Keywords: ADV, experimental data, multiple Reynolds number, post-processing

Procedia PDF Downloads 136

Authors: Adrienn Kiss, Karoly Zauer, Gyorgy Keglevich, Rita Molnarne Bernath

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Ginger (Zingiber officinale) is a perennial plant from Southeast Asia, widely used as a spice, herb, and medicine for many illnesses since its beneficial health effects were observed thousands of years ago. Among the compounds found in ginger, zingerone [4-hydroxy-3- methoxyphenyl-2-butanone] deserves special attention: it has an anti-inflammatory and antispasmodic effect, it can be used in case of diarrheal disease, helps to prevent the formation of blood clots, has antimicrobial properties, and can also play a role in preventing the Alzheimer's disease. Ferulic acid [(E)-3-(4-hydroxy-3-methoxyphenyl)-prop-2-enoic acid] is another cinnamic acid derivative in ginger, which has promising properties. Like many phenolic compounds, ferulic acid is also an antioxidant. Based on the results of animal experiments, it is assumed to have a direct antitumoral effect in lung and liver cancer. It also deactivates free radicals that can damage the cell membrane and the DNA and helps to protect the skin against UV radiation. The aim of this work was to synthesize these two compounds by new methods. A few of the reactions were based on the hydrogenation of dehydrozingerone [4-(4-Hydroxy-3-methoxyphenyl)-3-buten-2-one] to zingerone. Dehydrozingerone can be synthesized by a relatively simple method from acetone and vanillin with good yield (80%, melting point: 41 °C). Hydrogenation can be carried out chemically, for example by the reaction of zinc and acetic acid, or Grignard magnesium and ethyl alcohol. Another way to complete the reduction is the electrochemical pathway. The electrolysis of dehydrozingerone without diaphragm in aqueous media was attempted to produce ferulic acid in the presence of sodium carbonate and potassium iodide using platinum electrodes. The electrolysis of dehydrozingerone in the presence of potassium carbonate and acetic acid to prepare zingerone was carried out similarly. Ferulic acid was expected to be converted to dihydroferulic acid [3-(4-Hydroxy-3-methoxyphenyl)propanoic acid] in potassium hydroxide solution using iron electrodes, separating the anode and cathode space with a Soxhlet paper sheath impregnated with saturated magnesium chloride solution. For this reaction, ferulic acid was synthesized from vanillin and malonic acid in the presence of pyridine and piperidine (yield: 88.7%, melting point: 173°C). Unfortunately, in many cases, the expected transformations did not happen or took place in low conversions, although gas evolution occurred. Thus, a deeper understanding of these experiments and optimization are needed. Since both compounds are found in different plants, they can also be obtained by alkaline extraction or steam distillation from distinct plant parts (ferulic acid from ground bamboo shoots, zingerone from grated ginger root). The products of these reactions are rich in several other organic compounds as well; therefore, their separation must be solved to get the desired pure material. The products of the reactions described above were characterized by infrared spectral data and melting points. The use of these two simple methods may be informative for the formation of the products. In the future, we would like to study the ferulic acid and zingerone content of other plants and extract them efficiently. The optimization of electrochemical reactions and the use of other test methods are also among our plans.

Keywords: ferulic acid, ginger, synthesis, zingerone

Procedia PDF Downloads 166

Authors: Mingqian Zhang

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Tip-enhanced Raman spectroscopy (TERS) is a scanning probe technique for individual objects and structured surfaces investigation that provides a wealth of enhanced spectral information with nanoscale spatial resolution and high detection sensitivity. It has become a powerful and promising chemical and physical information detection method in the nanometer scale. The TERS technique uses a sharp metallic tip regulated in the near-field of a sample surface, which is illuminated with a certain incident beam meeting the excitation conditions of the wave-vector matching. The local electric field, and, consequently, the Raman scattering, from the sample in the vicinity of the tip apex are both greatly tip-enhanced owning to the excitation of localized surface plasmons and the lightning-rod effect. Typically, a TERS setup is composed of a scanning probe microscope, excitation and collection optical configurations, and a Raman spectroscope. In the illumination configuration, an objective lens or a parabolic mirror is always used as the most important component, in order to focus the incident beam on the tip apex for excitation. In this research, a novel TERS setup was built up by introducing a plasmonic lens to the excitation optics as a focusing device. A plasmonic lens with symmetry breaking semi-annular slits corrugated on gold film was designed for the purpose of generating concentrated sub-wavelength light spots with strong longitudinal electric field. Compared to conventional far-field optical components, the designed plasmonic lens not only focuses an incident beam to a sub-wavelength light spot, but also realizes a strong z-component that dominants the electric field illumination, which is ideal for the excitation of tip-enhancement. Therefore, using a PL in the illumination configuration of TERS contributes to improve the detection sensitivity by both reducing the far-field background and effectively exciting the localized electric field enhancement. The FDTD method was employed to investigate the optical near-field distribution resulting from the light-nanostructure interaction. And the optical field distribution was characterized using an scattering-type scanning near-field optical microscope to demonstrate the focusing performance of the lens. The experimental result is in agreement with the theoretically calculated one. It verifies the focusing performance of the plasmonic lens. The optical field distribution shows a bright elliptic spot in the lens center and several arc-like side-lobes on both sides. After the focusing performance was experimentally verified, the designed plasmonic lens was used as a focusing component in the excitation configuration of TERS setup to concentrate incident energy and generate a longitudinal optical field. A collimated linearly polarized laser beam, with along x-axis polarization, was incident from the bottom glass side on the plasmonic lens. The incident light focused by the plasmonic lens interacted with the silver-coated tip apex and enhanced the Raman signal of the sample locally. The scattered Raman signal was gathered by a parabolic mirror and detected with a Raman spectroscopy. Then, the plasmonic lens based setup was employed to investigate carbon nanotubes and TERS experiment was performed. Experimental results indicate that the Raman signal is considerably enhanced which proves that the novel TERS configuration is feasible and promising.

Keywords: longitudinal electric field, plasmonics, raman spectroscopy, tip-enhancement

Procedia PDF Downloads 364

Authors: Anitha Kandasamy, Thirumurugan Ramaiah

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Interestingly, organic materials exhibit large optical nonlinearity with quick responses and having the flexibility of molecular tailoring using computational modelling and favourable synthetic methodologies. Pyridine based organic compounds and carboxylic acid contained aromatic compounds play a crucial role in crystal engineering of NCS complexes that displays admirable optical nonlinearity with fast response and favourable physicochemical properties such as low dielectric constant, wide optical transparency and large laser damage threshold value requires for optoelectronics device applications. Based on these facts, it was projected to form an acentric molecule of π-conjugated system interaction with appropriately replaced electron donor and acceptor groups for achieving higher SHG activity in which quinoline-2-carboyxlic acid is chosen as an electron acceptor and capable of acting as an acid as well as a base molecule, while 2-amino-4-methylpyridine is used as an electron donor and previously employed in numerous proton transfer complexes for synthesis of NLO materials for optoelectronic applications. 2-amino-4-mehtylpyridinium quinoline-2-carboxylate molecular complex (2AQ) is having π-donor-acceptor groups in which 2-amino-4-methylpyridine donates one of its electron to quinoline -2-carboxylic acid thereby forming a protonated 2-amino-4-methyl pyridinium moiety and mono ionized quinoline-2-carboxylate moiety which are connected via N-H…O intermolecular interactions with non-centrosymmetric crystal packing arrangement at microscopic scale is accountable to the enhancement of macroscopic second order NLO activity. The 2AQ crystal was successfully grown by a slow evaporation solution growth technique and its structure was determined in orthorhombic crystal system with acentric, P212121, space group. Hirshfeld surface analysis reveals that O…H intermolecular interactions primarily contributed with 31.0 % to the structural stabilization of 2AQ. The molecular structure of title compound has been confirmed by 1H and 13C NMR spectral studies. The vibrational modes of functional groups present in 2AQ have been assigned by using FTIR and FT-Raman spectroscopy. The grown 2AQ crystal exhibits high optical transparency with lower cut-off wavelength (275 nm) within the region of 275-1500 nm. The laser study confirmed that 2AQ exhibits high SHG efficiency of 12.6 times greater than that of KDP. TGA-DTA analysis revealed that 2AQ crystal had a thermal stability of 223 °C. The low dielectric constant and low dielectric loss at higher frequencies confirmed good crystalline nature with fewer defects of grown 2AQ crystal. The grown crystal exhibits soft material and positive photoconduction behaviour. Mulliken atomic distribution and FMOs analysis suggested that the strong intermolecular hydrogen bonding which lead to the enhancement of NLO activity. These properties suggest that 2AQ crystal is a suitable material for optoelectronic and laser frequency conversion applications.

Keywords: crystal growth, NLO activity, proton transfer complex, quantum chemical investigation

Procedia PDF Downloads 119

Authors: Wei Ji

Abstract:

This study was conducted in the Kansas City metropolitan area of the United States, which has experienced significant urban sprawling in recent decades. The remote sensing of land cover changes in this area spanned over four decades from 1972 through 2010. The project was implemented in two stages: the first stage focused on detection of long-term trends of urban land cover change, while the second one examined how to detect the coupled effects of human impact and climate change on urban landscapes. For the first-stage study, six Landsat images were used with a time interval of about five years for the period from 1972 through 2001. Four major land cover types, built-up land, forestland, non-forest vegetation land, and surface water, were mapped using supervised image classification techniques. The study found that over the three decades the built-up lands in the study area were more than doubled, which was mainly at the expense of non-forest vegetation lands. Surprisingly and interestingly, the area also saw a significant gain in surface water coverage. This observation raised questions: How have human activities and precipitation variation jointly impacted surface water cover during recent decades? How can we detect such coupled impacts through remote sensing analysis? These questions led to the second stage of the study, in which we designed and developed approaches to detecting fine-scale surface waters and analyzing coupled effects of human impact and precipitation variation on the waters. To effectively detect urban landscape changes that might be jointly shaped by precipitation variation, our study proposed “urban wetscapes” (loosely-defined urban wetlands) as a new indicator for remote sensing detection. The study examined whether urban wetscape dynamics was a sensitive indicator of the coupled effects of the two driving forces. To better detect this indicator, a rule-based classification algorithm was developed to identify fine-scale, hidden wetlands that could not be appropriately detected based on their spectral differentiability by a traditional image classification. Three SPOT images for years 1992, 2008, and 2010, respectively were classified with this technique to generate the four types of land cover as described above. The spatial analyses of remotely-sensed wetscape changes were implemented at the scales of metropolitan, watershed, and sub-watershed, as well as based on the size of surface water bodies in order to accurately reveal urban wetscape change trends in relation to the driving forces. The study identified that urban wetscape dynamics varied in trend and magnitude from the metropolitan, watersheds, to sub-watersheds in response to human impacts at different scales. The study also found that increased precipitation in the region in the past decades swelled larger wetlands in particular while generally smaller wetlands decreased mainly due to human development activities. These results confirm that wetscape dynamics can effectively reveal the coupled effects of human impact and climate change on urban landscapes. As such, remote sensing of this indicator provides new insights into the relationships between urban land cover changes and driving forces.

Keywords: urban land cover, human impact, climate change, rule-based classification, across-scale analysis

Procedia PDF Downloads 305