Search results for: Grimme dispersion correction

Authors: Dorottya Guban, Irina Borbath, Istvan Bakos, Peter Nemeth, Andras Tompos

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One of the greatest challenges of the implementation of polymer electrolyte membrane fuel cells (PEMFCs) is to find active and durable electrocatalysts. The cell performance is always limited by the oxygen reduction reaction (ORR) on the cathode since it is at least 6 orders of magnitude slower than the hydrogen oxidation on the anode. Therefore high loading of Pt is required. Catalyst corrosion is also more significant on the cathode, especially in case of mobile applications, where rapid changes of loading have to be tolerated. Pt-Sn bulk alloys and SnO2-decorated Pt3Sn nanostructures are among the most studied bimetallic systems for fuel cell applications. Exclusive formation of supported Sn-Pt alloy phases with different Pt/Sn ratios can be achieved by using controlled surface reactions (CSRs) between hydrogen adsorbed on Pt sites and tetraethyl tin. In this contribution our results for commercial and a home-made 20 wt.% Pt/C catalysts modified by tin anchoring via CSRs are presented. The parent Pt/C catalysts were synthesized by modified NaBH4-assisted ethylene-glycol reduction method using ethanol as a solvent, which resulted either in dispersed and highly stable Pt nanoparticles or evenly distributed raspberry-like agglomerates according to the chosen synthesis parameters. The 20 wt.% Pt/C catalysts prepared that way showed improved electrocatalytic performance in the ORR and stability in comparison to the commercial 20 wt.% Pt/C catalysts. Then, in order to obtain Sn-Pt/C catalysts with Pt/Sn= 3 ratio, the Pt/C catalysts were modified with tetraethyl tin (SnEt4) using three and five consecutive tin anchoring periods. According to in situ XPS studies in case of catalysts with highly dispersed Pt nanoparticles, pre-treatment in hydrogen even at 170°C resulted in complete reduction of the ionic tin to Sn0. No evidence of the presence of SnO2 phase was found by means of the XRD and EDS analysis. These results demonstrate that the method of CSRs is a powerful tool to create Pt-Sn bimetallic nanoparticles exclusively, without tin deposition onto the carbon support. On the contrary, the XPS results revealed that the tin-modified catalysts with raspberry-like Pt agglomerates always contained a fraction of non-reducible tin oxide. At the same time, they showed increased activity and long-term stability in the ORR than Pt/C, which was assigned to the presence of SnO2 in close proximity/contact with Pt-Sn alloy phase. It has been demonstrated that the content and dispersion of the fcc Pt3Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. The bimetallic catalysts displayed an outstanding performance in the ORR. The preparation of a highly dispersed 20Pt/C catalyst permits to decrease the Pt content without relevant decline in the electrocatalytic performance of the catalysts.

Keywords: anode catalyst, cathode catalyst, controlled surface reactions, oxygen reduction reaction, PtSn/C electrocatalyst

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Authors: Charlotte Dreger, Erik Bollaert

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This paper presents two environmentally-friendly coastal structures realized on the Lake of Neuchâtel. Both structures reflect current environmental issues of concern on the lake and have been strongly affected by extreme meteorological conditions between their period of design and their actual operational period. The Lake of Neuchatel is one of the biggest Swiss lakes and measures around 38 km in length and 8.2 km in width, for a maximum water depth of 152 m. Its particular topographical alignment, situated in between the Swiss Plateau and the Jura mountains, combines strong winds and large fetch values, resulting in significant wave heights during storm events at both north-east and south-west lake extremities. In addition, due to flooding concerns, historically, lake levels have been lowered by several meters during the Jura correction works in the 19th and 20th century. Hence, during storm events, continuous erosion of the vulnerable molasse shorelines and sand banks generate frequent and abundant littoral transport from the center of the lake to its extremities. This phenomenon does not only cause disturbances of the ecosystem, but also generates numerous problems at natural or man-made infrastructures located along the shorelines, such as reed plants, harbor entrances, canals, etc. A first example is provided at the southwestern extremity, near the city of Yverdon, where an ensemble of 11 small islands, the Iles des Vernes, have been artificially created in view of enhancing biological conditions and food availability for bird species during their migration process, replacing at the same time two larger islands that were affected by lack of morphodynamics and general vegetalization of their surfaces. The article will present the concept and dimensioning of these islands based on 2D numerical modelling, as well as the realization and follow-up campaigns. In particular, the influence of several major storm events that occurred immediately after the works will be pointed out. Second, a sediment retention dike is discussed at the northeastern extremity, at the entrance of the Canal de la Broye into the lake. This canal is heavily used for navigation and suffers from frequent and significant sedimentation at its outlet. The new coastal structure has been designed to minimize sediment deposits around the exutory of the canal into the lake, by retaining the littoral transport during storm events. The article will describe the basic assumptions used to design the dike, as well as the construction works and follow-up campaigns. Especially the huge influence of changing meteorological conditions on the littoral transport of the Lake of Neuchatel since project design ten years ago will be pointed out. Not only the intensity and frequency of storm events are increasing, but also the main wind directions alter, affecting in this way the efficiency of the coastal structure in retaining the sediments.

Keywords: meteorological evolution, sediment transport, lake of Neuchatel, numerical modelling, environmental measures

Procedia PDF Downloads 69

Authors: Loganathan Kumaresan, Velusamy Chidambaram, Arumugam Velayutham Karthikeyani, Alex Cheru Pulikottil, Madhusudan Sau, Gurpreet Singh Kapur, Sankara Sri Venkata Ramakumar

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Environmentally driven regulations throughout the world stipulate dramatic improvements in the quality of transportation fuels and refining operations. The exhaust gases like CO, NOx, and SOx from stationary sources (e.g., refinery) and motor vehicles contribute to a large extent for air pollution. The refining industry is under constant environmental pressure to achieve more rigorous standards on sulphur content in the fuel used in the transportation sector and other off-gas emissions. Fluid catalytic cracking unit (FCCU) is a major secondary process in refinery for gasoline and diesel production. CO-combustion promoter additive and gasoline sulphur reduction (GSR) additive are catalytic systems used in FCCU to assist the combustion of CO to CO₂ in the regenerator and regulate sulphur in gasoline faction respectively along with main FCC catalyst. Effectiveness of these catalysts is governed by the active metal used, its dispersion, the type of base material employed, and retention characteristics of additive in FCCU such as attrition resistance and density. The challenge is to have a high-density microsphere catalyst support for its retention and high activity of the active metals as these catalyst additives are used in low concentration compare to the main FCC catalyst. The present paper discusses in the first part development of high dense microsphere of nanocrystalline alumina by hydro-thermal method for CO combustion promoter application. Performance evaluation of additive was conducted under simulated regenerator conditions and shows CO combustion efficiency above 90%. The second part discusses the efficacy of a co-precipitation method for the generation of the active crystalline spinels of Zn, Mg, and Cu with aluminium oxides as an additive. The characterization and micro activity test using heavy combined hydrocarbon feedstock at FCC unit conditions for evaluating gasoline sulphur reduction activity are studied. These additives were characterized by X-Ray Diffraction, NH₃-TPD & N₂ sorption analysis, TPR analysis to establish structure-activity relationship. The reaction of sulphur removal mechanisms involving hydrogen transfer reaction, aromatization and alkylation functionalities are established to rank GSR additives for their activity, selectivity, and gasoline sulphur removal efficiency. The sulphur shifting in other liquid products such as heavy naphtha, light cycle oil, and clarified oil were also studied. PIONA analysis of liquid product reveals 20-40% reduction of sulphur in gasoline without compromising research octane number (RON) of gasoline and olefins content.

Keywords: hydrothermal, nanocrystalline, spinel, sulphur reduction

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Authors: A. C. Blaga, A. Cârlescu, M. Turnea, A. I. Galaction, D. Caşcaval

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The performance of an aerobic stirred bioreactor for fungal fermentation was analyzed on the basis of mixing time and oxygen mass transfer coefficient, by quantifying the influence of some specific geometrical and operational parameters of the bioreactor, as well as the rheological behavior of Penicillium chrysogenum broth (free mycelia and mycelia aggregates). The rheological properties of the fungus broth, controlled by the biomass concentration, its growth rate, and morphology strongly affect the performance of the bioreactor. Experimental data showed that for both morphological structures the accumulation of fungus biomass induces a significant increase of broths viscosity and modifies the rheological behavior. For lower P. chrysogenum concentrations (both morphological conformations), the mixing time initially increases with aeration rate, reaches a maximum value and decreases. This variation can be explained by the formation of small bubbles, due to the presence of solid phase which hinders the bubbles coalescence, the rising velocity of bubbles being reduced by the high apparent viscosity of fungus broths. By biomass accumulation, the variation of mixing time with aeration rate is gradually changed, the continuous reduction of mixing time with air input flow increase being obtained for 33.5 g/l d.w. P. chrysogenum. Owing to the superior apparent viscosity, which reduces considerably the relative contribution of mechanical agitation to the broths mixing, these phenomena are more pronounced for P. chrysogenum free mycelia. Due to the increase of broth apparent viscosity, the biomass accumulation induces two significant effects on oxygen transfer rate: the diminution of turbulence and perturbation of bubbles dispersion - coalescence equilibrium. The increase of P. chrysogenum free mycelia concentration leads to the decrease of kla values. Thus, for the considered variation domain of the main parameters taken into account, namely air superficial velocity from 8.36 10-4 to 5.02 10-3 m/s and specific power input from 100 to 500 W/m3, kla was reduced for 3.7 times for biomass concentration increase from 4 to 36.5 g/l d.w. The broth containing P. crysogenum mycelia aggregates exhibits a particular behavior from the point of view of oxygen transfer. Regardless of bioreactor operating conditions, the increase of biomass concentration leads initially to the increase of oxygen mass transfer rate, the phenomenon that can be explained by the interaction of pellets with bubbles. The results are in relation with the increase of apparent viscosity of broths corresponding to the variation of biomass concentration between the mentioned limits. Thus, the apparent viscosity of the suspension of fungus mycelia aggregates increased for 44.2 times and fungus free mycelia for 63.9 times for CX increase from 4 to 36.5 g/l d.w. By means of the experimental data, some mathematical correlations describing the influences of the considered factors on mixing time and kla have been proposed. The proposed correlations can be used in bioreactor performance evaluation, optimization, and scaling-up.

Keywords: biomass concentration, mixing time, oxygen mass transfer, P. chrysogenum broth, stirred bioreactor

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Authors: Victoria Esteves

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Online memes have not only impacted different aspects of culture, but they have also left their mark on particular subcultures, where memes have reflected issues and debates surrounding specific spheres of interest. This is the first study that outlines how memes can address cultural intersections within the Lolita fashion community, which are much more specific and which fall outside of the broad focus of politics and/or social commentary. This is done by looking at the way online memes are used in this particular subculture as a form of meaning-making and group identity reinforcement, demonstrating not only the adaptability of online memes to specific cultural groups but also how subcultures tailor these digital objects to discuss both community-centered topics and more broad societal aspects. As part of an online ethnography, this study focuses on qualitative content analysis by taking a look at some of the meme communication that has permeated Lolita fashion communities. Examples of memes used in this context are picked apart in order to understand this specific layered phenomenon of communication, as well as to gain insights into how memes can operate as visual shorthand for the remix of meaning-making. There are existing parallels between internet culture and cultural behaviors surrounding Lolita fashion: not only is the latter strongly influenced by the former (due to its highly globalized dispersion and lack of physical shops, Lolita fashion is almost entirely reliant on the internet for its existence), both also emphasize curatorial roles through a careful collaborative process of documenting significant aspects of their culture (e.g., Know Your Meme and Lolibrary). Further similarities appear when looking at ideas of inclusion and exclusion that permeate both cultures, where memes and language are used in order to both solidify group identity and to police those who do not ascribe to these cultural tropes correctly, creating a feedback loop that reinforces subcultural ideals. Memes function as excellent forms of communication within the Lolita community because they reinforce its coded ideas and allows a kind of participation that echoes other cultural groups that are online-heavy such as fandoms. Furthermore, whilst the international Lolita community was mostly self-contained within its LiveJournal birthplace, it has become increasingly dispersed through an array of different social media groups that have fragmented this subculture significantly. The use of memes is key in maintaining a sense of connection throughout this now fragmentary experience of fashion. Memes are also used in the Lolita fashion community to bridge the gap between Lolita fashion related community issues and wider global topics; these reflect not only an ability to make use of a broader online language to address specific issues of the community (which in turn provide a very community-specific engagement with remix practices) but also memes’ ability to be tailored to accommodate overlapping cultural and political concerns and discussions between subcultures and broader societal groups. Ultimately, online memes provide the necessary elasticity to allow their adaption and adoption by subcultural groups, who in turn use memes to extend their meaning-making processes.

Keywords: internet culture, Lolita fashion, memes, online community, remix

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Authors: S. Jimenez, R.Duarte, J.Sanchez-Choliz, I. Villanua

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There is a certain consensus in economic literature about the factors that have influenced in historical differences in growth rates observed between developed and developing countries. However, it is less clear what elements have marked different paths of growth in developed economies in recent decades. R&D has always been seen as one of the major sources of technological progress, and productivity growth, which is directly influenced by technological developments. Following recent literature, we can say that ‘innovation pushes the technological frontier forward’ as well as encourage future innovation through the creation of externalities. In other words, productivity benefits from innovation are not fully appropriated by innovators, but it also spread through the rest of the economies encouraging absorptive capacities, what have become especially important in a context of increasing fragmentation of production This paper aims to contribute to this literature in two ways, first, exploring alternative indexes of R&D flows embodied in inter-country, inter-sectorial flows of good and services (as approximation to technology spillovers) capturing structural and technological characteristic of countries and, second, analyzing the impact of direct and embodied R&D on the evolution of labor productivity at the country/sector level in recent decades. The traditional way of calculation through a multiregional input-output framework assumes that all countries have the same capabilities to absorb technology, but it is not, each one has different structural features and, this implies, different capabilities as part of literature, claim. In order to capture these differences, we propose to use a weight based on specialization structure indexes; one related with the specialization of countries in high-tech sectors and the other one based on a dispersion index. We propose these two measures because, as far as we understood, country capabilities can be captured through different ways; countries specialization in knowledge-intensive sectors, such as Chemicals or Electrical Equipment, or an intermediate technology effort across different sectors. Results suggest the increasing importance of country capabilities while increasing the trade openness. Besides, if we focus in the country rankings, we can observe that with high-tech weighted R&D embodied countries as China, Taiwan and Germany arose the top five despite not having the highest intensities of R&D expenditure, showing the importance of country capabilities. Additionally, through a fixed effects panel data model we show that, in fact, R&D embodied is important to explain labor productivity increases, in fact, even more that direct R&D investments. This is reflecting that globalization is more important than has been said until now. However, it is true that almost all analysis done in relation with that consider the effect of t-1 direct R&D intensity over economic growth. Nevertheless, from our point of view R&D evolve as a delayed flow and it is necessary some time to be able to see its effects on the economy, as some authors have already claimed. Our estimations tend to corroborate this hypothesis obtaining a gap between 4-5 years.

Keywords: economic growth, embodied, input-output, technology

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Authors: Anna Krukowska, Tomasz Klimczuk, Adriana Zaleska-Medynska

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Photoactive materials have attracted attention due to their potential application in the degradation of environmental pollutants to non-hazardous compounds in an eco-friendly route. Among semiconductor photocatalysts, tantalates such as potassium tantalate (KTaO3) is one of the excellent functional photomaterial. However, tantalates-based materials are less active under visible-light irradiation, the enhancement in photoactivity could be improved with the modification of opto-eletronic properties of KTaO3 by doping rare earth metal (Er) and further photodeposition of noble metal nanoparticles (Pt). Inclusion of rare earth element in orthorhombic structure of tantalate can generate one high-energy photon by absorbing two or more incident low-energy photons, which convert visible-light and infrared-light into the ultraviolet-light to satisfy the requirement of KTaO3 photocatalysts. On the other hand, depositions of noble metal nanoparticles on the surface of semiconductor strongly absorb visible-light due to their surface plasmon resonance, in which their conducting electrons undergo a collective oscillation induced by electric field of visible-light. Furthermore, the high dispersion of Pt nanoparticles, which will be obtained by photodeposition process is additional important factor to improve the photocatalytic activity. The present work is aimed to study the effect of photocatalytic process of the prepared Er-doped KTaO3 and further incorporation of Pt nanoparticles by photodeposition. Moreover, the research is also studied correlations between photocatalytic activity and physico-chemical properties of obtained Pt/Er-KTaO3 samples. The Er-doped KTaO3 microcomposites were synthesized by a hydrothermal method. Then photodeposition method was used for Pt loading over Er-KTaO3. The structural and optical properties of Pt/Er-KTaO3 photocatalytic were characterized using scanning electron microscope (SEM), X-ray diffraction (XRD), volumetric adsorption method (BET), UV-Vis absorption measurement, Raman spectroscopy and luminescence spectroscopy. The photocatalytic properties of Pt/Er-KTaO3 microcomposites were investigated by degradation of phenol in aqueous phase as model pollutant under visible and ultraviolet-light irradiation. Results of this work show that all the prepared photocatalysis exhibit low BET surface area, although doping of the bare KTaO3 with rare earth element (Er) presents a slight increase in this value. The crystalline structure of Pt/Er-KTaO3 powders exhibited nearly identical positions for the main peak at about 22,8o and the XRD pattern could be assigned to an orthorhombic distorted perovskite structure. The Raman spectra of obtained semiconductors confirmed demonstrating perovskite-like structure. The optical absorption spectra of Pt nanoparticles exhibited plasmon absorption band for main peaks at about 216 and 264 nm. The addition of Pt nanoparticles increased photoactivity compared to Er-KTaO3 and pure KTaO3. Summary optical properties of KTaO3 change with its doping Er-element and further photodeposition of Pt nanoparticles.

Keywords: heterogeneous photocatalytic, KTaO3 photocatalysts, Er3+ ion doping, Pt photodeposition

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Authors: Guilherme M. Pereira, Kimmo Teinïla, Danilo Custódio, Risto Hillamo, Célia Alves, Pérola de C. Vasconcellos

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South American large cities often present serious air pollution problems and their atmosphere composition is influenced by a variety of emissions sources. The South American Emissions Megacities, and Climate project (SAEMC) has focused on the study of emissions and its influence on climate in the South American largest cities and it also included Lima (Peru) and Medellin (Colombia), sites where few studies of the genre were done. Lima is a coastal city with more than 8 million inhabitants and the second largest city in South America. Medellin is a 2.5 million inhabitants city and second largest city in Colombia; it is situated in a valley. The samples were collected in quartz fiber filters in high volume samplers (Hi-Vol), in 24 hours of sampling. The samples were collected in intensive campaigns in both sites, in July, 2010. Several species were determined in the aerosol samples of Lima and Medellin. Organic and elemental carbon (OC and EC) in thermal-optical analysis; biomass burning tracers (levoglucosan - Lev, mannosan - Man and galactosan - Gal) in high-performance anion exchange ion chromatography with mass spectrometer detection; water soluble ions in ion chromatography. The average particulate matter was similar for both campaigns, the PM10 concentrations were above the recommended by World Health Organization (50 µg m⁻³ – daily limit) in 40% of the samples in Medellin, while in Lima it was above that value in 15% of the samples. The average total ions concentration was higher in Lima (17450 ng m⁻³ in Lima and 3816 ng m⁻³ in Medellin) and the average concentrations of sodium and chloride were higher in this site, these species also had better correlations (Pearson’s coefficient = 0,63); suggesting a higher influence of marine aerosol in the site due its location in the coast. Sulphate concentrations were also much higher at Lima site; which may be explained by a higher influence of marine originated sulphate. However, the OC, EC and monosaccharides average concentrations were higher at Medellin site; this may be due to the lower dispersion of pollutants due to the site’s location and a larger influence of biomass burning sources. The levoglucosan average concentration was 95 ng m⁻³ for Medellin and 16 ng m⁻³ and OC was well correlated with levoglucosan (Pearson’s coefficient = 0,86) in Medellin; suggesting a higher influence of biomass burning over the organic aerosol in this site. The Lev/Man ratio is often related to the type of biomass burned and was close to 18, similar to the observed in previous studies done at biomass burning impacted sites in the Amazon region; backward trajectories also suggested the transport of aerosol from that region. Biomass burning appears to have a larger influence on the air quality in Medellin, in addition the vehicular emissions; while Lima showed a larger influence of marine aerosol during the study period.

Keywords: aerosol transport, atmospheric particulate matter, biomass burning, SAEMC project

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Authors: Bryan Low

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In the coming decades, the global maritime industry will face a most formidable environmental challenge -achieving net zero carbon emissions by 2050. To meet this target, the Maritime Port Authority of Singapore (MPA) has worked to establish green shipping and digital corridors with ports of several other countries around the world where ships will use low-carbon alternative fuels such as ammonia for power generation. While this paradigm shift to the bunkering of greener fuels is encouraging, fuels like ammonia will also introduce a new and unique type of environmental risk in the unlikely scenario of a spill. While numerous modelling studies have been conducted for oil spills and their associated environmental impact on coastal and marine ecosystems, ammonia spills are comparatively less well understood. For example, there is a knowledge gap regarding how the complex hydrodynamic conditions of the Singapore Straits may influence the dispersion of a hypothetical ammonia plume, which has different physical and chemical properties compared to an oil slick. Chemically, ammonia can be absorbed by phytoplankton, thus altering the balance of the marine nitrogen cycle. Biologically, ammonia generally serves the role of a nutrient in coastal ecosystems at lower concentrations. However, at higher concentrations, it has been found to be toxic to many local species. It may also have the potential to trigger eutrophication and harmful algal blooms (HABs) in coastal waters, depending on local hydrodynamic conditions. Thus, the key objective of this research paper is to support the development of a model-based forecasting system that can predict ammonia plume behaviour in coastal waters, given prevailing hydrodynamic conditions and their environmental impact. This will be essential as ammonia bunkering becomes more commonplace in Singapore’s ports and around the world. Specifically, this system must be able to assess the HAB-triggering potential of an ammonia plume, as well as its lethal and sub-lethal toxic effects on local species. This will allow the relevant authorities to better plan risk mitigation measures or choose a time window with the ideal hydrodynamic conditions to conduct ammonia bunkering operations with minimal risk. In this paper, we present the first part of such a forecasting system: a jointly coupled hydrodynamic-water quality model that can capture how advection-diffusion processes driven by ocean currents influence plume behaviour and how the plume interacts with the marine nitrogen cycle. The model is then applied to various ammonia spill scenarios where the results are discussed in the context of current ammonia toxicity guidelines, impact on local ecosystems, and mitigation measures for future bunkering operations conducted in the Singapore Straits.

Keywords: ammonia bunkering, forecasting, harmful algal blooms, hydrodynamics, marine nitrogen cycle, oceanography, water quality modeling

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Authors: Xiaoyong He

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The manipulation of THz waves is still a challenging task due to lack of natural materials interacted with it strongly. Designed by tailoring the characters of unit cells (meta-molecules), the advance of metamaterials (MMs) may solve this problem. However, because of Ohmic and radiation losses, the performance of MMs devices is subjected to the dissipation and low quality factor (Q-factor). This dilemma may be circumvented by Fano resonance, which arises from the destructive interference between a bright continuum mode and dark discrete mode (or a narrow resonance). Different from symmetric Lorentz spectral curve, Fano resonance indicates a distinct asymmetric line-shape, ultrahigh quality factor, steep variations in spectrum curves. Fano resonance is usually realized through symmetry breaking. However, if concentric double rings (DR) are placed closely to each other, the near-field coupling between them gives rise to two hybridized modes (bright and narrowband dark modes) because of the local asymmetry, resulting into the characteristic Fano line shape. Furthermore, from the practical viewpoint, it is highly desirable requirement that to achieve the modulation of Fano spectral curves conveniently, which is an important and interesting research topics. For current Fano systems, the tunable spectral curves can be realized by adjusting the geometrical structural parameters or magnetic fields biased the ferrite-based structure. But due to limited dispersion properties of active materials, it is still a tough work to tailor Fano resonance conveniently with the fixed structural parameters. With the favorable properties of extreme confinement and high tunability, graphene is a strong candidate to achieve this goal. The DR-structure possesses the excitation of so-called “trapped modes,” with the merits of simple structure and high quality of resonances in thin structures. By depositing graphene circular DR on the SiO2/Si/ polymer substrate, the tunable Fano resonance has been theoretically investigated in the terahertz regime, including the effects of graphene Fermi level, structural parameters and operation frequency. The results manifest that the obvious Fano peak can be efficiently modulated because of the strong coupling between incident waves and graphene ribbons. As Fermi level increases, the peak amplitude of Fano curve increases, and the resonant peak position shifts to high frequency. The amplitude modulation depth of Fano curves is about 30% if Fermi level changes in the scope of 0.1-1.0 eV. The optimum gap distance between DR is about 8-12 μm, where the value of figure of merit shows a peak. As the graphene ribbon width increases, the Fano spectral curves become broad, and the resonant peak denotes blue shift. The results are very helpful to develop novel graphene plasmonic devices, e.g. sensors and modulators.

Keywords: graphene, metamaterials, terahertz, tunable

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Authors: Satam Alotibi, Muhammad J. Al-Zahrani, Fahd K. Al-Naqidan, Turki S. Hussein, Moteb Alotaibi, Mohammed Alyami, Mahdy M. Elmahdy, Abdellah Kaiba, Fatehia S. Alhakami, Talal F. Qahtan

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Water pollution is a critical global challenge that demands scalable and effective solutions for water decontamination. In this captivating research, we unveil a groundbreaking strategy for harnessing solar energy to synthesize silver (Ag) clusters on stable titanium dioxide (TiO₂) nanoparticles dispersed in water, without the need for traditional stabilization agents. These Ag-loaded TiO₂ nanoparticles exhibit exceptional photocatalytic activity, surpassing that of pristine TiO₂ nanoparticles, offering a promising solution for highly efficient water decontamination under sunlight irradiation. To the best knowledge, we have developed a unique method to stabilize TiO₂ P25 nanoparticles in water without the use of stabilization agents. This breakthrough allows us to create an ideal platform for the solar-driven synthesis of Ag clusters. Under sunlight irradiation, the stable dispersion of TiO₂ P25 nanoparticles acts as a highly efficient photocatalyst, generating electron-hole pairs. The photogenerated electrons effectively reduce silver ions derived from a silver precursor, resulting in the formation of Ag clusters. The Ag clusters loaded on TiO₂ P25 nanoparticles exhibit remarkable photocatalytic activity for water decontamination under sunlight irradiation. Acting as active sites, these Ag clusters facilitate the generation of reactive oxygen species (ROS) upon exposure to sunlight. These ROS play a pivotal role in rapidly degrading organic pollutants, enabling efficient water decontamination. To confirm the success of our approach, we characterized the synthesized Ag-loaded TiO₂ P25 nanoparticles using cutting-edge analytical techniques, such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and spectroscopic methods. These characterizations unequivocally confirm the successful synthesis of Ag clusters on stable TiO₂ P25 nanoparticles without traditional stabilization agents. Comparative studies were conducted to evaluate the superior photocatalytic performance of Ag-loaded TiO₂ P25 nanoparticles compared to pristine TiO₂ P25 nanoparticles. The Ag clusters loaded on TiO₂ P25 nanoparticles exhibit significantly enhanced photocatalytic activity, benefiting from the synergistic effect between the Ag clusters and TiO₂ nanoparticles, which promotes ROS generation for efficient water decontamination. Our scalable strategy for synthesizing Ag clusters on stable TiO₂ P25 nanoparticles without stabilization agents presents a game-changing solution for highly efficient water decontamination under sunlight irradiation. The use of commercially available TiO₂ P25 nanoparticles streamlines the synthesis process and enables practical scalability. The outstanding photocatalytic performance of Ag-loaded TiO₂ P25 nanoparticles opens up new avenues for their application in large-scale water treatment and remediation processes, addressing the urgent need for sustainable water decontamination solutions.

Keywords: water pollution, solar energy, silver clusters, TiO₂ nanoparticles, photocatalytic activity

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Authors: Xuechun Kan, Dongdong Li, Fan Li, Peidang Liu

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Triple-negative breast cancer (TNBC) is the most malignant subtype of breast cancer with a poor prognosis, and radiotherapy is one of the main treatment methods. However, due to the obvious resistance of tumor cells to radiotherapy, high dose of ionizing radiation is required during radiotherapy, which causes serious damage to normal tissues near the tumor. Therefore, how to improve radiotherapy resistance and enhance the specific killing of tumor cells by radiation is a hot issue that needs to be solved in clinic. Recent studies have shown that silver-based nanoparticles have strong radiosensitization, and silver nanoclusters (AgNCs) also provide a broad prospect for tumor targeted radiosensitization therapy due to their ultra-small size, low toxicity or non-toxicity, self-fluorescence and strong photostability. Aptamer 5TR1 is a 25-base oligonucleotide aptamer that can specifically bind to mucin-1 highly expressed on the membrane surface of TNBC 4T1 cells, and can be used as a highly efficient tumor targeting molecule. In this study, AgNCs were synthesized by DNA template based on 5TR1 aptamer (NC-T5-5TR1), and its role as a targeted radiosensitizer in TNBC radiotherapy was investigated. The optimal DNA template was first screened by fluorescence emission spectroscopy, and NC-T5-5TR1 was prepared. NC-T5-5TR1 was characterized by transmission electron microscopy, ultraviolet-visible spectroscopy and dynamic light scattering. The inhibitory effect of NC-T5-5TR1 on cell activity was evaluated using the MTT method. Laser confocal microscopy was employed to observe NC-T5-5TR1 targeting 4T1 cells and verify its self-fluorescence characteristics. The uptake of NC-T5-5TR1 by 4T1 cells was observed by dark-field imaging, and the uptake peak was evaluated by inductively coupled plasma mass spectrometry. The radiation sensitization effect of NC-T5-5TR1 was evaluated through cell cloning and in vivo anti-tumor experiments. Annexin V-FITC/PI double staining flow cytometry was utilized to detect the impact of nanomaterials combined with radiotherapy on apoptosis. The results demonstrated that the particle size of NC-T5-5TR1 is about 2 nm, and the UV-visible absorption spectrum detection verifies the successful construction of NC-T5-5TR1, and it shows good dispersion. NC-T5-5TR1 significantly inhibited the activity of 4T1 cells and effectively targeted and fluoresced within 4T1 cells. The uptake of NC-T5-5TR1 reached its peak at 3 h in the tumor area. Compared with AgNCs without aptamer modification, NC-T5-5TR1 exhibited superior radiation sensitization, and combined radiotherapy significantly inhibited the activity of 4T1 cells and tumor growth in 4T1-bearing mice. The apoptosis level of NC-T5-5TR1 combined with radiation was significantly increased. These findings provide important theoretical and experimental support for NC-T5-5TR1 as a radiation sensitizer for TNBC.

Keywords: 5TR1 aptamer, silver nanoclusters, radio sensitization, triple-negative breast cancer

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Authors: Men An Pan, Hong Ren Chen, Chih Heng Shih, Hsing Yuan Yen

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Pingtung County is located in the southernmost region of Taiwan. During the winter season, pollutants due to insufficient dispersion caused by the downwash of the northeast monsoon lead to the poor air quality of the County. Through the implementation of various control methods, including the application of permits of air pollution, fee collection of air pollution, control oil fume of catering sectors, smoke detection of diesel vehicles, regular inspection of locomotives, and subsidies for low-polluting vehicles. Moreover, to further mitigate the air pollution, additional alternative controlling strategies are also carried out, such as construction site control, prohibition of open-air agricultural waste burning, improvement of river dust, and strengthening of road cleaning operations. The combined efforts have significantly reduced air pollutants in the County. However, in order to effectively and promptly monitor the ambient air quality, the County has subsequently deployed micro-sensors, with a total of 400 IoTs (Internet of Things) micro-sensors for PM2.5 and VOC detection and 3 air quality monitoring stations of the Environmental Protection Agency (EPA), covering 33 townships of the County. The covered area has more than 1,300 listed factories and 5 major industrial parks; thus forming an Internet of Things (IoTs) based multi-level air quality monitoring system. The results demonstrate that the IoTs multi-level air quality sensors combined with other strategies such as “sand and gravel dredging area technology monitoring”, “banning open burning”, “intelligent management of construction sites”, “real-time notification of activation response”, “nighthawk early bird plan with micro-sensors”, “unmanned aircraft (UAV) combined with land and air to monitor abnormal emissions”, and “animal husbandry odour detection service” etc. The satisfaction improvement rate of air control, through a 2021 public survey, reached a high percentage of 81%, an increase of 46% as compared to 2018. For the air pollution complaints for the whole year of 2021, the total number was 4213 in contrast to 7088 in 2020, a reduction rate reached almost 41%. Because of the spatial-temporal features of the air quality monitoring IoTs system by the application of microsensors, the system does assist and strengthen the effectiveness of the existing air quality monitoring network of the EPA and can provide real-time control of the air quality. Therefore, the hot spots and potential pollution locations can be timely determined for law enforcement. Hence, remarkable results were obtained for the two years. That is, both reduction of public complaints and better air quality are successfully achieved through the implementation of the present IoTs system for real-time air quality monitoring throughout Pingtung County.

Keywords: IoT, PM, air quality sensor, air pollution, environmental monitoring

Procedia PDF Downloads 52

Authors: Ines Raies, Eric Kohler, Marc Fleury, Béatrice Ledésert

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In this work, the impact of clay minerals on the formation damage of sandstone reservoirs is studied to provide a better understanding of the problem of deep geothermal reservoir permeability reduction due to fine particle dispersion and migration. In some situations, despite the presence of filters in the geothermal loop at the surface, particles smaller than the filter size (<1 µm) may surprisingly generate significant permeability reduction affecting in the long term the overall performance of the geothermal system. Our study is carried out on cores from a Triassic reservoir in the Paris Basin (Feigneux, 60 km Northeast of Paris). Our goal is to first identify the clays responsible for clogging, a mineralogical characterization of these natural samples was carried out by coupling X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The results show that the studied stratigraphic interval contains mostly illite and chlorite particles. Moreover, the spatial arrangement of the clays in the rocks as well as the morphology and size of the particles, suggest that illite is more easily mobilized than chlorite by the flow in the pore network. Thus, based on these results, illite particles were prepared and used in core flooding in order to better understand the factors leading to the aggregation and deposition of this type of clay particles in geothermal reservoirs under various physicochemical and hydrodynamic conditions. First, the stability of illite suspensions under geothermal conditions has been investigated using different characterization techniques, including Dynamic Light Scattering (DLS) and Scanning Transmission Electron Microscopy (STEM). Various parameters such as the hydrodynamic radius (around 100 nm), the morphology and surface area of aggregates were measured. Then, core-flooding experiments were carried out using sand columns to mimic the permeability decline due to the injection of illite-containing fluids in sandstone reservoirs. In particular, the effects of ionic strength, temperature, particle concentration and flow rate of the injected fluid were investigated. When the ionic strength increases, a permeability decline of more than a factor of 2 could be observed for pore velocities representative of in-situ conditions. Further details of the retention of particles in the columns were obtained from Magnetic Resonance Imaging and X-ray Tomography techniques, showing that the particle deposition is nonuniform along the column. It is clearly shown that very fine particles as small as 100 nm can generate significant permeability reduction under specific conditions in high permeability porous media representative of the Triassic reservoirs of the Paris basin. These retention mechanisms are explained in the general framework of the DLVO theory

Keywords: geothermal energy, reinjection, clays, colloids, retention, porosity, permeability decline, clogging, characterization, XRD, SEM-EDS, STEM, DLS, NMR, core flooding experiments

Procedia PDF Downloads 152

Authors: Tanya Kaur Bedi, Shankha Pratim Bhattacharya

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The US Environmental Protection Agency defines indoor air quality as “The air quality within and around buildings, especially as it relates to the health and comfort of building occupants”. According to the 2021 report by the Energy Policy Institute at Chicago, Indian residents, a country which is home to the highest levels of air pollution in the world, lose about 5.9 years from life expectancy due to poor air quality and yet has numerous dwellings dependent on natural ventilation. Currently the urban population spends 90% of the time indoors, this scenario raises a concern for occupant health and well-being. The built environment can affect health directly and indirectly through immediate or long-term exposure to indoor air pollutants. Health effects associated with indoor air pollutants include eye/nose/throat irritation, respiratory diseases, heart disease, and even cancer. This study attempts to demonstrate the causal relationship between the indoor air quality and its determining aspects. Detailed indoor air quality audits were conducted in residential buildings located in Kolkata, India in the months of December and January 2021. According to the air pollution knowledge assessment city program in India, Kolkata is also the second most polluted mega-city after Delhi. Although the air pollution levels are alarming year-long, the winter months are most crucial due to the unfavorable environmental conditions. While emissions remain typically constant throughout the year, cold air is denser and moves slower than warm air, trapping the pollution in place for much longer and consequently is breathed in at a higher rate than the summers. The air pollution monitoring period was selected considering environmental factors and major pollution contributors like traffic and road dust. This study focuses on the relationship between the built environment and the spatial-temporal distribution of air pollutants in and around it. The measured parameters include, temperature, relative humidity, air velocity, particulate matter, volatile organic compounds, formaldehyde, and benzene. A total of 56 rooms were audited, selectively targeting the most dominant middle-income group. The data-collection was conducted using a set of instruments positioned in the human breathing-zone. The study assesses indoor air quality based on factors determining natural ventilation and air pollution dispersion such as surrounding environment, dominant wind, openable window to floor area ratio, windward or leeward side openings, and natural ventilation type in the room: single side or cross-ventilation, floor height, residents cleaning habits, etc.

Keywords: indoor air quality, occupant health, urban housing, air pollution, natural ventilation, architecture, urban issues

Procedia PDF Downloads 101

Authors: Yollande Sènan Djivoh, Dominique de Jaeger

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Background: Abdominal exercises are commonly practised nowadays. Specific techniques of abdominal muscles strengthening like hypopressive exercises have recently emerged and their practice is encouraged against the practice of Curl-up especially in postpartum. The acute and the training effects of these exercises did not allow to advise one exercise to the detriment of another. However, physiotherapists remain reluctant to perform Curl-up with postpartum women because of its potential harmful effect on the pelvic floor. Design: This study was a randomized control trial registered under the number PACTR202110679363984. Objective: to observe the training effect of two experimental protocols (Curl-up versus Drawing-in+Diaphragmatic aspiration) on the abdominal wall (interrecti distance, rectus and transversus abdominis thickness, abdominal strength) in Beninese postpartum women. Pelvic floor function (tone, endurance, urinary incontinence) will be assessed to evaluate potential side effects of exercises on the pelvic floor. Method: Postpartum women diagnosed with diastasis recti were randomly assigned to one of three groups (Curl-up, Drawingin+Diaphragmatic aspiration and control). Abdominal and pelvic floor parameters were assessed before and at the end of the 6-week protocol. The interrecti distance and the abdominal muscles thickness were assessed by ultrasound and abdominal strength by dynamometer. Pelvic floor tone and strength were assessed with Biofeedback and urinary incontinence was quantified by pad test. To compare the results between the three groups and the two measurements, a two-way Anova test with repeated measures was used (p<0.05). When interaction was significant, a posthoc using Student t test, with Bonferroni correction, was used to compare the three groups regarding the difference (end value minus initial value). To complete these results, a paired Student t test was used to compare in each group the initial and end values. Results: Fifty-eight women participated in this study, divided in three groups with similar characteristics regarding their age (29±5 years), parity (2±1 children), BMI (26±4 kg/m2 ), time since the last birth (10±2 weeks), weight of their baby at birth (330±50 grams). Time effect and interaction were significant (p<0.001) for all abdominal parameters. Experimental groups improved more than control group. Curl-up group improved more (p=0.001) than Drawing-in+Diaphragmatic aspiration group regarding the interrecti distance (9.3±4.2 mm versus 6.6±4.6 mm) and abdominal strength (20.4±16.4 Newton versus 11.4±12.8 Newton). Drawingin+Diaphragmatic aspiration group improved (0.8±0.7 mm) more than Curl-up group (0.5±0.7 mm) regarding the transversus abdominis thickness (p=0.001). Only Curl-up group improved (p<0.001) the rectus abdominis thickness (1.5±1.2 mm). For pelvic floor parameters, both experimental groups improved (p=0.01) except for tone which improved (p=0.03) only in Drawing-in+Diaphragmatic aspiration group from 19.9±4.1 cmH2O to 22.2±4.5 cmH2O. Conclusion: Curl-up was more efficient to improve abdominal function than Drawingin+Diaphragmatic aspiration. However, these exercises are complementary. None of them degraded the pelvic floor, but Drawing-in+Diaphragmatic aspiration improved further the pelvic floor function. Clinical implications: Curl-up, Drawing-in and Diaphragmatic aspiration can be used for the management of abdominal function in postpartum women. Exercises must be chosen considering the specific needs of each woman’s abdominal and pelvic floor function.

Keywords: curl-up, drawing-in, diaphragmatic aspiration, hypopressive exercise, postpartum women

Procedia PDF Downloads 63

Authors: Ewelina Grabowska, Martyna Marchelek

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Among the various semiconductors, nanosized TiO2 has been widely studied due to its high photosensitivity, low cost, low toxicity, and good chemical and thermal stability. However, there are two main drawbacks to the practical application of pure TiO2 films. One is that TiO2 can be induced only by ultraviolet (UV) light due to its intrinsic wide bandgap (3.2 eV for anatase and 3.0 eV for rutile), which limits its practical efficiency for solar energy utilization since UV light makes up only 4-5% of the solar spectrum. The other is that a high electron-hole recombination rate will reduce the photoelectric conversion efficiency of TiO2. In order to overcome the above drawbacks and modify the electronic structure of TiO2, some semiconductors (eg. CdS, ZnO, PbS, Cu2O, Bi2S3, and CdSe) have been used to prepare coupled TiO2 composites, for improving their charge separation efficiency and extending the photoresponse into the visible region. It has been proved that the fabrication of p-n heterostructures by combining n-type TiO2 with p-type semiconductors is an effective way to improve the photoelectric conversion efficiency of TiO2. SrTiO3 is a good candidate for coupling TiO2 and improving the photocatalytic performance of the photocatalyst because its conduction band edge is more negative than TiO2. Due to the potential differences between the band edges of these two semiconductors, the photogenerated electrons transfer from the conduction band of SrTiO3 to that of TiO2. Conversely, the photogenerated electrons transfer from the conduction band of SrTiO3 to that of TiO2. Then the photogenerated charge carriers can be efficiently separated by these processes, resulting in the enhancement of the photocatalytic property in the photocatalyst. Additionally, one of the methods for improving photocatalyst performance is addition of nanoparticles containing one or two noble metals (Pt, Au, Ag and Pd) deposited on semiconductor surface. The mechanisms were proposed as (1) the surface plasmon resonance of noble metal particles is excited by visible light, facilitating the excitation of the surface electron and interfacial electron transfer (2) some energy levels can be produced in the band gap of TiO2 by the dispersion of noble metal nanoparticles in the TiO2 matrix; (3) noble metal nanoparticles deposited on TiO2 act as electron traps, enhancing the electron–hole separation. In view of this, we recently obtained series of TiO2@SrTiO3 and SrTiO3 photocatalysts loaded with noble metal NPs. using photodeposition method. The M- TiO2@SrTiO3 and M-SrTiO3 photocatalysts (M= Rh, Rt, Pt) were studied for photodegradation of phenol in aqueous phase under UV-Vis and visible irradiation. Moreover, in the second part of our research hydroxyl radical formations were investigated. Fluorescence of irradiated coumarin solution was used as a method of ˙OH radical detection. Coumarin readily reacts with generated hydroxyl radicals forming hydroxycoumarins. Although the major hydroxylation product is 5-hydroxycoumarin, only 7-hydroxyproduct of coumarin hydroxylation emits fluorescent light. Thus, this method was used only for hydroxyl radical detection, but not for determining concentration of hydroxyl radicals.

Keywords: composites TiO2, SrTiO3, photocatalysis, phenol degradation

Procedia PDF Downloads 202

Authors: Sahar El Shair, Laura Greco, William Reay, Murray Cairns

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Background: Rheumatoid arthritis (RA) is a chronic, systematic, inflammatory, autoimmune disease that involves damages to joints and erosions to the associated bones and cartilage, resulting in reduced physical function and disability. RA is a multifactorial disorder influenced by heterogenous genetic and environmental factors. Whilst different medications have proven successful in reducing inflammation associated with RA, they often come with significant side effects and limited efficacy. To address this, the novel pharmagenic enrichment score (PES) algorithm was tested in self-reported RA patients from the UK Biobank (UKBB), which is a cohort of predominantly European ancestry, and identified individuals with a high genetic risk in clinically actionable biological pathways to identify novel opportunities for precision interventions and drug repurposing to treat RA. Methods and materials: Genetic association data for rheumatoid arthritis was derived from publicly available genome-wide association studies (GWAS) summary statistics (N=97173). The PES framework exploits competitive gene set enrichment to identify pathways that are associated with RA to explore novel treatment opportunities. This data is then integrated into WebGestalt, Drug Interaction database (DGIdb) and DrugBank databases to identify existing compounds with existing use or potential for repurposed use. The PES for each of these candidates was then profiled in individuals with RA in the UKBB (Ncases = 3,719, Ncontrols = 333,160). Results A total of 209 pathways with known drug targets after multiple testing correction were identified. Several pathways, including interferon gamma signaling and TID pathway (which relates to a chaperone that modulates interferon signaling), were significantly associated with self-reported RA in the UKBB when adjusting for age, sex, assessment centre month and location, RA polygenic risk and 10 principal components. These pathways have a major role in RA pathogenesis, including autoimmune attacks against certain citrullinated proteins, synovial inflammation, and bone loss. Encouragingly, many also relate to the mechanism of action of existing RA medications. The analyses also revealed statistically significant association between RA polygenic scores and self-reported RA with individual PES scorings, highlighting the potential utility of the PES algorithm in uncovering additional genetic insights that could aid in the identification of individuals at risk for RA and provide opportunities for more targeted interventions. Conclusions In this study, pharmacologically annotated genetic risk was explored through the PES framework to overcome inter-individual heterogeneity and enable precision drug repurposing in RA. The results showed a statistically significant association between RA polygenic scores and self-reported RA and individual PES scorings for 3,719 RA patients. Interestingly, several enriched PES pathways were targeted by already approved RA drugs. In addition, the analysis revealed genetically supported drug repurposing opportunities for future treatment of RA with a relatively safe profile.

Keywords: rheumatoid arthritis, precision medicine, drug repurposing, system biology, bioinformatics

Procedia PDF Downloads 55

Authors: Maja Benkovic, Dubravka Novotni, Bojana Voucko, Duska Curic, Damir Jezek, Nikolina Cukelj

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Cryo-grinding is an ultra-fine grinding method used in the pharmaceutical industry, production of herbs and spices and in the production and handling of cereals, due to its ability to produce powders with small particle sizes which maintain their favorable bioactive profile. The aim of this study was to determine the particle size distributions of the proso millet (Panicum miliaceum) bran fraction grinded at cryogenic temperature (using liquid nitrogen (LN₂) cooling, T = - 196 °C), in comparison to non-cooled grinding. Proso millet bran is primarily used as an animal feed, but has a potential in food applications, either as a substrate for extraction of bioactive compounds or raw material in the bakery industry. For both applications finer particle sizes of the bran could be beneficial. Thus, millet bran was ground for 2, 4, 8 and 12 minutes using the ball mill (CryoMill, Retsch GmbH, Haan, Germany) at three grinding modes: (I) without cooling, (II) at cryo-temperature, and (III) at cryo-temperature with included 1 minute of intermediate cryo-cooling step after every 2 minutes of grinding, which is usually applied when samples require longer grinding times. The sample was placed in a 50 mL stainless steel jar containing one grinding ball (Ø 25 mm). The oscillation frequency in all three modes was 30 Hz. Particle size distributions of the bran were determined by a laser diffraction particle sizing method (Mastersizer 2000) using the Scirocco 2000 dry dispersion unit (Malvern Instruments, Malvern, UK). Three main effects of the grinding set-up were visible from the results. Firstly, grinding time at all three modes had a significant effect on all particle size parameters: d(0.1), d(0.5), d(0.9), D[3,2], D[4,3], span and specific surface area. Longer grinding times resulted in lower values of the above-listed parameters, e.g. the averaged d(0.5) of the sample (229.57±1.46 µm) dropped to 51.29±1.28 µm after 2 minutes grinding without LN₂, and additionally to 43.00±1.33 µm after 4 minutes of grinding without LN₂. The only exception was the sample ground for 12 minutes without cooling, where an increase in particle diameters occurred (d(0.5)=62.85±2.20 µm), probably due to particles adhering to one another and forming larger particle clusters. Secondly, samples with LN₂ cooling exhibited lower diameters in comparison to non-cooled. For example, after 8 minutes of non-cooled grinding d(0.5)=46.97±1.05 µm was achieved, while the LN₂ cooling enabled collection of particles with average sizes of d(0.5)=18.57±0.18 µm. Thirdly, the application of intermediate cryo-cooling step resulted in similar particle diameters (d(0.5)=15.83±0.36 µm, 12 min of grinding) as cryo-milling without this step (d(0.5)=16.33±2.09 µm, 12 min of grinding). This indicates that intermediate cooling is not necessary for the current application, which consequently reduces the consumption of LN₂. These results point out the potential beneficial effects of millet bran grinding at cryo-temperatures. Further research will show if the lower particle size achieved in comparison to non-cooled grinding could result in increased bioavailability of bioactive compounds, as well as protein digestibility and solubility of dietary fibers of the proso millet bran fraction.

Keywords: ball mill, cryo-milling, particle size distribution, proso millet (Panicum miliaceum) bran

Procedia PDF Downloads 131

Authors: Bashar Mahmoud, Lee Mortimer, Michael Fairweather

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New methods have recently been introduced to improve the thermal property values of molten nitrate salts (a binary mixture of NaNO3:KNO3in 60:40 wt. %), by doping them with minute concentration of nanoparticles in the range of 0.5 to 1.5 wt. % to form the so-called: Nano-heat-transfer-fluid, apt for thermal energy transfer and storage applications. The present study aims to assess the stability of these nanofluids using the advanced computational modelling technique, Lagrangian particle tracking. A multi-phase solid-liquid model is used, where the motion of embedded nanoparticles in the suspended fluid is treated by an Euler-Lagrange hybrid scheme with fixed time stepping. This technique enables measurements of various multi-scale forces whose characteristic (length and timescales) are quite different. Two systems are considered, both consisting of 50 nm Al2O3 ceramic nanoparticles suspended in fluids of different density ratios. This includes both water (5 to 95 °C) and molten nitrate salt (220 to 500 °C) at various volume fractions ranging between 1% to 5%. Dynamic properties of both phases are coupled to the ambient temperature of the fluid suspension. The three-dimensional computational region consists of a 1μm cube and particles are homogeneously distributed across the domain. Periodic boundary conditions are enforced. The particle equations of motion are integrated using the fourth order Runge-Kutta algorithm with a very small time-step, Δts, set at 10-11 s. The implemented technique demonstrates the key dynamics of aggregated nanoparticles and this involves: Brownian motion, soft-sphere particle-particle collisions, and Derjaguin, Landau, Vervey, and Overbeek (DLVO) forces. These mechanisms are responsible for the predictive model of aggregation of nano-suspensions. An energy transport-based method of predicting the thermal conductivity of the nanofluids is also used to determine thermal properties of the suspension. The simulation results confirms the effectiveness of the technique. The values are in excellent agreement with the theoretical and experimental data obtained from similar studies. The predictions indicates the role of Brownian motion and DLVO force (represented by both the repulsive electric double layer and an attractive Van der Waals) and its influence in the level of nanoparticles agglomeration. As to the nano-aggregates formed that was found to play a key role in governing the thermal behavior of nanofluids at various particle concentration. The presentation will include a quantitative assessment of these forces and mechanisms, which would lead to conclusions about nanofluids, heat transfer performance and thermal characteristics and its potential application in solar thermal energy plants.

Keywords: thermal energy storage, molten salt, nano-fluids, multi-scale computational modelling

Procedia PDF Downloads 170

Authors: C. Silveira, A. Ascenso, J. Ferreira, A. I. Miranda, P. Tuccella, G. Curci

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Poor air quality is one of the main environmental causes of premature deaths worldwide, and mainly in cities, where the majority of the population lives. It is a consequence of successive land cover (LC) and use changes, as a result of the intensification of human activities. Knowing these landscape modifications in a comprehensive spatiotemporal dimension is, therefore, essential for understanding variations in air pollutant concentrations. In this sense, the use of air quality models is very useful to simulate the physical and chemical processes that affect the dispersion and reaction of chemical species into the atmosphere. However, the modelling performance should always be evaluated since the resolution of the input datasets largely dictates the reliability of the air quality outcomes. Among these data, the updated LC is an important parameter to be considered in atmospheric models, since it takes into account the Earth’s surface changes due to natural and anthropic actions, and regulates the exchanges of fluxes (emissions, heat, moisture, etc.) between the soil and the air. This work aims to evaluate the performance of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem), when different LC classifications are used as an input. The influence of two LC classifications was tested: i) the 24-classes USGS (United States Geological Survey) LC database included by default in the model, and the ii) CLC (Corine Land Cover) and specific high-resolution LC data for Portugal, reclassified according to the new USGS nomenclature (33-classes). Two distinct WRF-Chem simulations were carried out to assess the influence of the LC on air quality over Europe and Portugal, as a case study, for the year 2015, using the nesting technique over three simulation domains (25 km², 5 km² and 1 km² horizontal resolution). Based on the 33-classes LC approach, particular emphasis was attributed to Portugal, given the detail and higher LC spatial resolution (100 m x 100 m) than the CLC data (5000 m x 5000 m). As regards to the air quality, only the LC impacts on tropospheric ozone concentrations were evaluated, because ozone pollution episodes typically occur in Portugal, in particular during the spring/summer, and there are few research works relating to this pollutant with LC changes. The WRF-Chem results were validated by season and station typology using background measurements from the Portuguese air quality monitoring network. As expected, a better model performance was achieved in rural stations: moderate correlation (0.4 – 0.7), BIAS (10 – 21µg.m^-3) and RMSE (20 – 30 µg.m^-3), and where higher average ozone concentrations were estimated. Comparing both simulations, small differences grounded on the Leaf Area Index and air temperature values were found, although the high-resolution LC approach shows a slight enhancement in the model evaluation. This highlights the role of the LC on the exchange of atmospheric fluxes, and stresses the need to consider a high-resolution LC characterization combined with other detailed model inputs, such as the emission inventory, to improve air quality assessment.

Keywords: land use, spatial resolution, WRF-Chem, air quality assessment

Procedia PDF Downloads 136

Authors: Tomaz Oliveira, Rui Medeiros, André Lacerda

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Introduction: Cleft lip and/or palate are the most frequent forms of congenital craniofacial anomalies, affecting mainly the middle third of the face and manifesting by functional and aesthetic changes. Bilateral cleft lip represents a reconstructive surgical challenge, not only for the labial component but also for the associated nasal deformation. Recently, the paradigm of the approach to this pathology has changed, placing the focus on muscle reconstruction and anatomical repositioning of the nasal cartilages in order to obtain the best aesthetic and functional results. The aim of this study is to carry out a systematic review of the surgical approach to bilateral cleft lip, retrospectively analyzing the case series of Plastic Surgery Service at Hospital Santa Maria (Lisbon, Portugal) regarding this pathology, the global assessment of the characteristics of the operated patients and the study of the different surgical approaches and their complications in the last 20 years. Methods: The present work demonstrates a retrospective and descriptive study of patients who underwent at least one reconstructive surgery for cleft lip and/or palate, in the CPRE service of the HSM, in the period between January 1 of 1997 and December 31 of 2017, in which the data relating to 361 individuals were analyzed who, after applying the exclusion criteria, constituted a sample of 212 participants. The variables analyzed were the year of the first surgery, gender, age, type of orofacial cleft, surgical approach, and its complications. Results: There was a higher overall prevalence in males, with cleft lip and cleft palate occurring in greater proportion in males, with the cleft palate being more common in females. The most frequently recorded malformation was cleft lip and palate, which is complete in most cases. Regarding laterality, alterations with a unilateral labial component were the most commonly observed, with the left lip being described as the most affected. It was found that the vast majority of patients underwent primary intervention up to 12 months of age. The surgical techniques used in the approach to this pathology showed an important chronological variation over the years. Discussion: Cleft lip and/or palate is a medical condition associated with high aesthetic and functional morbidity, which requires early treatment in order to optimize the long-term outcome. The existence of a nasolabial component and its respective surgical correction plays a central role in the treatment of this pathology. The high rates of post-surgical complications and unconvincing aesthetic results have motivated an evolution of the surgical technique, increasingly evident in recent years, allowing today to achieve satisfactory aesthetic results, even in bilateral cleft lip with high deformation complexity. The introduction of techniques that favor nasolabial reconstruction based on anatomical principles has been producing increasingly convincing results. The analyzed sample shows that most of the results obtained in this study are, in general, compatible with the results published in the literature. Conclusion: This work showed that the existence of small variations in the surgical technique can bring significant improvements in the functional and aesthetic results in the treatment of bilateral cleft lip.

Keywords: cleft lip, palate lip, congenital abnormalities, cranofacial malformations

Procedia PDF Downloads 88

Authors: Elissandro Voigt Beier, Cristiano Poleto

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The main objective of the research is to assess the loss through the quantification of material culture (archaeological fragments) in rural areas, sites explored economically by machining on seasonal crops, and also permanent, in a hydrographic subsystem Camaquã River in the state of Rio Grande do Sul, Brazil. The study area consists of different micro basins and differs in area, ranging between 1,000 m² and 10,000 m², respectively the largest and the smallest, all with a large number of occurrences and outcrop locations of archaeological material and high density in intense farm environment. In the first stage of the research aimed to identify the dispersion of points of archaeological material through field survey through plot points by the Global Positioning System (GPS), within each river basin, was made use of concise bibliography on the topic in the region, helping theoretically in understanding the old landscaping with preferences of occupation for reasons of ancient historical people through the settlements relating to the practice observed in the field. The mapping was followed by the cartographic development in the region through the development of cartographic products of the land elevation, consequently were created cartographic products were to contribute to the understanding of the distribution of the absolute materials; the definition and scope of the material dispersed; and as a result of human activities the development of revolving letter by mechanization of in situ material, it was also necessary for the preparation of materials found density maps, linking natural environments conducive to ancient historical occupation with the current human occupation. The third stage of the project it is for the systematic collection of archaeological material without alteration or interference in the subsurface of the indigenous settlements, thus, the material was prepared and treated in the laboratory to remove soil excesses, cleaning through previous communication methodology, measurement and quantification. Approximately 15,000 were identified archaeological fragments belonging to different periods of ancient history of the region, all collected outside of its environmental and historical context and it also has quite changed and modified. The material was identified and cataloged considering features such as object weight, size, type of material (lithic, ceramic, bone, Historical porcelain and their true association with the ancient history) and it was disregarded its principles as individual lithology of the object and functionality same. As observed preliminary results, we can point out the change of materials by heavy mechanization and consequent soil disturbance processes, and these processes generate loading of archaeological materials. Therefore, as a next step will be sought, an estimate of potential losses through a mathematical model. It is expected by this process, to reach a reliable model of high accuracy which can be applied to an archeological site of lower density without encountering a significant error.

Keywords: degradation of heritage, quantification in archaeology, watershed, use and occupation of land

Procedia PDF Downloads 252

Authors: Seungsik Yu, Minho Kang

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As the threat of terrorism to nuclear facilities is increasing globally after the attacks of September 11, we are striving to recognize the physical protection system and strengthen the emergency response system. Since 2015, Korea has implemented physical protection security exercise for nuclear facilities. The exercise should be carried out with full cooperation between the operator and response forces. Performance testing of the physical protection system should include appropriate exercises, for example, force-on-force exercises, to determine if the response forces can provide an effective and timely response to prevent sabotage. Significant deficiencies and actions taken should be reported as stipulated by the competent authority. The IAEA(International Atomic Energy Agency) is also preparing force-on-force exercise program documents to support exercise of member states. Currently, ROK(Republic of Korea) is implementing exercise on the force-on-force exercise evaluation system which is developed by itself for the nuclear power plant, and it is necessary to establish the exercise procedure considering the use of the force-on-force exercise evaluation system. The purpose of this study is to establish the work procedures of the three major organizations related to the force-on-force exercise of nuclear power plants in ROK, which conduct exercise using force-on-force exercise evaluation system. The three major organizations are composed of licensee, KINAC (Korea Institute of Nuclear Nonproliferation and Control), and the NSSC(Nuclear Safety and Security Commission). Major activities are as follows. First, the licensee establishes and conducts an exercise plan, and when recommendations are derived from the result of the exercise, it prepares and carries out a force-on-force result report including a plan for implementation of the recommendations. Other detailed tasks include consultation with surrounding units for adversary, interviews with exercise participants, support for document evaluation, and self-training to improve the familiarity of the MILES (Multiple Integrated Laser Engagement System). Second, KINAC establishes a force-on-force exercise plan review report and reviews the force-on-force exercise plan report established by licensee. KINAC evaluate force-on-force exercise using exercise evaluation system and prepare training evaluation report. Other detailed tasks include MILES training, adversary consultation, management of exercise evaluation systems, and analysis of exercise evaluation results. Finally, the NSSC decides whether or not to approve the force-on-force exercise and makes a correction request to the nuclear facility based on the exercise results. The most important part of ROK's force-on-force exercise system is the analysis through the exercise evaluation system implemented by KINAC after the exercise. The analytical method proceeds in the order of collecting data from the exercise evaluation system and analyzing the collected data. The exercise application process of the exercise evaluation system introduced in ROK in 2016 will be concretely set up, and a system will be established to provide objective and consistent conclusions between exercise sessions. Based on the conclusions drawn up, the ultimate goal is to complement the physical protection system of licensee so that the system makes licensee respond effectively and timely against sabotage or unauthorized removal of nuclear materials.

Keywords: Force-on-Force exercise, nuclear power plant, physical protection, sabotage, unauthorized removal

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Authors: Alla Ovsyannikova, Oksana Rymar, Elena Shakhtshneider, Mikhail Voevoda

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In Siberia endocrinologists increasingly noted young patients with the course of diabetes mellitus differing from 1 and 2 types. Therefore we did a molecular genetic study for this group of patients to verify the monogenic forms of diabetes mellitus in them and researched the characteristics of this pathology. When confirming the monogenic form of diabetes, we performed a correction therapy for many patients (transfer from insulin to tablets), prevented specific complications, examined relatives and diagnosed their diabetes at the preclinical stage, revealed phenotypic characteristics of the pathology which led to the high significance of this work. Materials and Methods: We observed 5 patients (4 families). We diagnosed MODY (Maturity Onset Diabetes of the Young) during the molecular genetic testing (direct automatic sequencing). All patients had a full clinical examination, blood samples for biochemical research, determination of C-peptide and TSH, antibodies to b-cells, microalbuminuria, abdominal ultrasound, heart and thyroid ultrasound, examination of ophthalmologist. Results: We diagnosed 3 rare types of MODY: two women had MODY8, one man – MODY6 and man and his mother - MODY12. Patients with types 8 and 12 had clinical features. Age of onset hyperglycemia ranged from 26 to 34 years. In a patient with MODY6 fasting hyperglycemia was detected during a routine examination. Clinical symptoms, complications were not diagnosed. The patient observes a diet. In the first patient MODY8 was detected during first pregnancy, she had itchy skin and mostly postprandial hyperglycemia. Upon examination we determined glycated hemoglobin 7.5%, retinopathy, non-proliferative stage, peripheral neuropathy. She uses a basic bolus insulin therapy. The second patient with MODY8 also had clinical manifestations of hyperglycemia (pruritus, thirst), postprandial hyperglycemia and diabetic nephropathy, a stage of microalbuminuria. The patient was diagnosed autoimmune thyroiditis. She used inhibitors of DPP-4. The patient with MODY12 had an aggressive course. In the detection of hyperglycemia he had complaints of visual impairment, intense headaches, leg cramps. The patient had a history of childhood convulsive seizures of non-epileptic genesis, without organic pathology, which themselves were stopped at the age of 12 years. When we diagnosed diabetes a patient was 28 years, he had hypertriglyceridemia, atherosclerotic plaque in the carotid artery, proliferative retinopathy (lacerocoagulation). Diabetes and early myocardial infarction were observed in three cases in family. We prescribe therapy with sulfonylureas and SGLT-2 inhibitors with a positive effect. At the patient's mother diabetes began at a later age (30 years) and a less aggressive course was observed. She also has hypertriglyceridemia and uses oral hypoglycemic drugs. Conclusions: 1) When young patients with hyperglycemia have extrapancreatic pathologies and diabetic complications with a short duration of diabetes we can assume they have one of type of MODY diabetes. 2) In patients with monogenic forms of diabetes mellitus, the clinical manifestations of hyperglycemia in each succeeding generation are revealed at an earlier age. Research had increased our knowledge of the monogenic forms of diabetes. The reported study was supported by RSCF, research project No. 14-15-00496-P.

Keywords: diabetes mellitus, MODY diabetes, monogenic forms, young patients

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Authors: M. Grandcolas, N. Rival, H. Bu, S. Jahren, R. Schmid, H. Johnsen

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The concept of an autonomic self-healing material, where initiation of repair is integrated to the material, is now being considered for engineering applications and is a hot topic in the literature. Among several concepts/techniques, two are most interesting: i) Capsules: Integration of microcapsules in or at the surface of coatings or fibre-like structures has recently gained much attention. Upon damage-induced cracking, the microcapsules are broken by the propagating crack fronts resulting in a release of an active chemical (healing agent) by capillary action, subsequently repairing and avoiding further crack growth. ii) Self-healing polymers: Interestingly, the introduction of dynamic covalent bonds into polymer networks has also recently been used as a powerful approach towards the design of various intrinsically self-healing polymer systems. The idea behind this is to reconnect the chemical crosslinks which are broken when a material fractures, restoring the integrity of the material and thereby prolonging its lifetime. We propose here to integrate both self-healing concepts (capsules, self-healing polymers) in electrospun fibres and coatings. Different capsule preparation approaches have been investigated in SINTEF. The most advanced method to produce capsules is based on emulsification to create a water-in-oil emulsion before polymerisation. The healing agent is a polyurethane-based dispersion that was encapsulated in shell materials consisting of urea-benzaldehyde resins. Results showed the successful preparation of microcapsules and release of the agent when capsules break. Since capsules are produced in water-in-oil systems we mainly investigated organic solvent based coatings while a major challenge resides in the incorporation of capsules into water-based coatings. We also focused on developing more robust microcapsules to prevent premature rupture of the capsules. The capsules have been characterized in terms of size, and encapsulation and release might be visualized by incorporating fluorescent dyes and examine the capsules by microscopy techniques. Alternatively, electrospinning is an innovative technique that has attracted enormous attention due to unique properties of the produced nano-to-micro fibers, ease of fabrication and functionalization, and versatility in controlling parameters. Especially roll-to-roll electrospinning is a unique method which has been used in industry to produce nanofibers continuously. Electrospun nanofibers can usually reach a diameter down to 100 nm, depending on the polymer used, which is of interest for the concept with self-healing polymer systems. In this work, we proved the feasibility of fabrication of POSS-based (POSS: polyhedral oligomeric silsesquioxanes, tradename FunzioNano™) nanofibers via electrospinning. Two different formulations based on aqueous or organic solvents have shown nanofibres with a diameter between 200 – 450nm with low defects. The addition of FunzioNano™ in the polymer blend also showed enhanced properties in term of wettability, promising for e.g. membrane technology. The self-healing polymer systems developed are here POSS-based materials synthesized to develop dynamic soft brushes.

Keywords: capsules, coatings, electrospinning, fibers

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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

Procedia PDF Downloads 249

Authors: Valentina V. Goftman, Vladislav A. Pankratov, Alexey V. Markin, Tangi Aubert, Zeger Hens, Sarah De Saeger, Irina Yu. Goryacheva

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The most important requirements for biochemical applicability of quantum dots (QDs) are: 1) the surface cap should render intact or improved optical properties; 2) mono-dispersion and good stability in aqueous phase in a wide range of pH and ionic strength values; 3) presence of functional groups, available for bioconjugation; 4) minimal impact from the environment on the QDs’ properties and, vice versa, minimal influence of the QDs’ components on the environment; and 5) stability against chemical/biochemical/physical influence. The latter is especially important for in vitro and in vivo applications. For example, some physical intracellular delivery strategies (e.g., electroporation) imply a rapid high-voltage electric field impulse in order to temporarily generate hydrophilic pores in the cell plasma membrane, necessary for the passive transportation of QDs into the cell. In this regard, it is interesting to investigate how different capping layers, which can provide high stability and sufficient fluorescent properties of QDs in a water solution, behave under these abnormal conditions. In this contribution, hydrophobic core-shell CdSe/CdS/CdZnS/ZnS QDs (λem=600 nm), produced by means of the Successive Ion Layer Adsorption and Reaction (SILAR) technique, were transferred to a water solution using two of the most commonly used methods: (i) encapsulation in an amphiphilic brush polymer based on poly(maleic anhydride-alt-1-octadecene) (PMAO) modified with polyethylene glycol (PEG) chains and (ii) silica covering. Polymer encapsulation preserves the initial ligands on the QDs’ surface owing to the hydrophobic attraction between the hydrophobic groups of the amphiphilic molecules and the surface hydrophobic groups of the QDs. This covering process allows maintaining the initial fluorescent properties, but it leads to a considerable increase of the QDs’ size. However, covering with a silica shell, by means of the reverse microemulsion method, allows maintaining both size and fluorescent properties of the initial QDs. The obtained water solutions of polymer covered and silica-coated QDs in three different concentrations were exposed to a low-voltage electric field for a short time and the fluorescent properties were investigated. It is shown that the PMAO-PEG polymer acquires some additional charges in the presence of the electric field, which causes repulsion between the polymer and the QDs’ surface. This process destroys the homogeneity of the whole amphiphilic shell and it dramatically decreases the fluorescent properties (dropping to 10% from its initial value) because of the direct contact of the QDs with the strongly oxidative environment (water). In contrast, a silica shell possesses dielectric properties which allow retaining 90% of its initial fluorescence intensity, even after a longer electric impact. Thus, silica shells are clearly a preferable covering for bio-application of QDs, because – besides the high uniform morphology, controlled size and biocompatibility – it allows protecting QDs from oxidation, even under the influence of an electric field.

Keywords: electric field, polymer coating, quantum dots, silica covering, stability

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Authors: Anna Kolanowska, Anna Kuziel, Sławomir Boncel

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Carbon nanotubes (CNTs) represent a combination of lightness and nanoscopic size with high tensile strength, excellent thermal and electrical conductivity. By now, CNTs have been used as a support in heterogeneous catalysis (CuCl anchored to pre-functionalized CNTs) in the Ullmann-type coupling with aryl halides toward formation of C-N and C-O bonds. The results indicated that the stability of the catalyst was much improved and the elaborated catalytic system was efficient and recyclable. However, CNTs have not been considered as the substrate itself in the Ullmann-type reactions. But if successful, this functionalization would open new areas of CNT chemistry leading to enhanced in-solvent/matrix nanotube individualization. The copper-catalyzed Ullmann-type reaction is an attractive method for the formation of carbon-heteroatom and carbon-carbon bonds in organic synthesis. This condensation reaction is usually conducted at temperature as high as 200 oC, often in the presence of stoichiometric amounts of copper reagent and with activated aryl halides. However, a small amount of organic additive (e.g. diamines, amino acids, diols, 1,10-phenanthroline) can be applied in order to increase the solubility and stability of copper catalyst, and at the same time to allow performing the reaction under mild conditions. The copper (pre-)catalyst is prepared by in situ mixing of copper salt and the appropriate chelator. Our research is focused on the application of Ullmann-type reaction for the covalent functionalization of CNTs. Firstly, CNTs were chlorinated by using iodine trichloride (ICl3) in carbon tetrachloride (CCl4). This method involves formation of several chemical species (ICl, Cl2 and I2Cl6), but the most reactive is the dimer. The fact (that the dimer is the main individual in CCl4) is the reason for high reactivity and possibly high functionalization levels of CNTs. This method, indeed, yielded a notable amount of chlorine onto the MWCNT surface. The next step was the reaction of CNT-Cl with three substrates: aniline, iodobenzene and phenol for the formation C-N, C-C and C-O bonds, respectively, in the presence of 1,10-phenanthroline and cesium carbonate (Cs2CO3) as a base. As the CNT substrates, two multi-wall CNT (MWCNT) types were used: commercially available Nanocyl NC7000™ (9.6 nm diameter, 1.5 µm length, 90% purity) and thicker MWCNTs (in-house) synthesized in our laboratory using catalytic chemical vapour deposition (c-CVD). In-house CNTs had diameter ranging between 60-70 nm and length up to 300 µm. Since classical Ullmann reaction was found as suffering from poor yields, we have investigated the effect of various solvents (toluene, acetonitrile, dimethyl sulfoxide and N,N-dimethylformamide) on the coupling of substrates. Owing to the fact that the aryl halides show the reactivity order of I>Br>Cl>F, we have also investigated the effect of iodine presence on CNT surface on reaction yield. In this case, in first step we have used iodine monochloride instead of iodine trichloride. Finally, we have used the optimized reaction conditions with p-bromophenol and 1,2,4-trihydroxybenzene for the control of CNT dispersion.

Keywords: carbon nanotubes, coupling reaction, functionalization, Ullmann reaction

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Authors: Nazila Dehbari, Javad Tavakoli, Yakani Kambu, Youhong Tang

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Superabsorbent hydrogels (SAP), as an enviro-sensitive material have been widely used for industrial and biomedical applications due to their unique structure and capabilities. Poor mechanical properties of SAPs - which is extremely related to their large volume change – count as a great weakness in adopting for high-tech applications. Therefore, improving SAPs’ mechanical properties via toughening methods by mixing different types of cross-linked polymer or introducing energy-dissipating mechanisms is highly focused. In this work, in order to change the intrinsic brittle character of commercialized Poly Acrylic Acid (here as SAP) to be semi-ductile, a commercial available highly branched tree-like dendritic polymers with numerous –OH end groups known as hyper-branched polymer (HB) has been added to PAA-SAP system in a single step, cost effective and environment friendly solvent casting method. Samples were characterized by FTIR, SEM and TEM and their physico-chemical characterization including swelling capabilities, hydraulic permeability, surface tension and thermal properties had been performed. Toughness energy, stiffness, elongation at breaking point, viscoelastic properties and samples extensibility were mechanical properties that had been performed and characterized as a function of samples lateral cracks’ length in different HB concentration. Addition of HB to PAA-SAP significantly improved mechanical and surface properties. Increasing equilibrium swelling ratio by about 25% had been experienced by the SAP-HB samples in comparison with SAPs; however, samples swelling kinetics remained without changes as initial rate of water uptake and equilibrium time haven’t been subjected to any changes. Thermal stability analysis showed that HB is participating in hybrid network formation while improving mechanical properties. Samples characterization by TEM showed that, the aggregated HB polymer binders into nano-spheres with diameter in range of 10–200 nm. So well dispersion in the SAP matrix occurred as it was predictable due to the hydrophilic character of the numerous hydroxyl groups at the end of HB which enhance the compatibility of HB with PAA-SAP. As the profused -OH groups in HB could react with -COOH groups in the PAA-SAP during the curing process, the formation of a 2D structure in the SAP-HB could be attributed to the strong interfacial adhesion between HB and the PAA-SAP matrix which hinders the activity of PAA chains (SEM analysis). FTIR spectra introduced new peaks at 1041 and 1121 cm-1 that attributed to the C–O(–OH) stretching hydroxyl and O–C stretching ester groups of HB polymer binder indicating the incorporation of HB polymer into the SAP structure. SAP-HB polymer has significant effects on the final mechanical properties. The brittleness of PAA hydrogels are decreased by introducing HB as the fracture energies of hydrogels increased from 8.67 to 26.67. PAA-HBs’ stretch ability enhanced about 10 folds while reduced as a function of different notches depth.

Keywords: superabsorbent polymer, toughening, viscoelastic properties, hydrogel network

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