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Authors: Mohamad Saab, Florent Real, Francois Virot, Laurent Cantrel, Valerie Vallet

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All spent nuclear fuel reprocessing plants use the PUREX process (Plutonium Uranium Refining by Extraction), which is a liquid-liquid extraction method. The organic extracting solvent is a mixture of tri-n-butyl phosphate (TBP) and hydrocarbon solvent such as hydrogenated tetra-propylene (TPH). By chemical complexation, uranium and plutonium (from spent fuel dissolved in nitric acid solution), are separated from fission products and minor actinides. During a normal extraction operation, uranium is extracted in the organic phase as the UO₂(NO₃)₂(TBP)₂ complex. The TBP solvent can form an explosive mixture called red oil when it comes in contact with nitric acid. The formation of this unstable organic phase originates from the reaction between TBP and its degradation products on the one hand, and nitric acid, its derivatives and heavy metal nitrate complexes on the other hand. The decomposition of the red oil can lead to violent explosive thermal runaway. These hazards are at the origin of several accidents such as the two in the United States in 1953 and 1975 (Savannah River) and, more recently, the one in Russia in 1993 (Tomsk). This raises the question of the exothermicity of reactions that involve TBP and all other degradation products, and calls for a better knowledge of the underlying chemical phenomena. A simulation tool (Alambic) is currently being developed at IRSN that integrates thermal and kinetic functions related to the deterioration of uranyl nitrates in organic and aqueous phases, but not of the n-butyl phosphate. To include them in the modeling scheme, there is an urgent need to obtain the thermodynamic and kinetic functions governing the deterioration processes in liquid phase. However, little is known about the thermodynamic properties, like standard enthalpies of formation, of the n-butyl phosphate molecules and of the UO₂(NO₃)₂(TBP)₂ UO₂(NO₃)₂(HDBP)(TBP) and UO₂(NO₃)₂(HDBP)₂ complexes. In this work, we propose to estimate the thermodynamic properties with Quantum Methods (QM). Thus, in the first part of our project, we focused on the mono, di, and tri-butyl complexes. Quantum chemical calculations have been performed to study several reactions leading to the formation of mono-(H₂MBP), di-(HDBP), and TBP in gas and liquid phases. In the gas phase, the optimal structures of all species were optimized using the B3LYP density functional. Triple-ζ def2-TZVP basis sets were used for all atoms. All geometries were optimized in the gas-phase, and the corresponding harmonic frequencies were used without scaling to compute the vibrational partition functions at 298.15 K and 0.1 Mpa. Accurate single point energies were calculated using the efficient localized LCCSD(T) method to the complete basis set limit. Whenever species in the liquid phase are considered, solvent effects are included with the COSMO-RS continuum model. The standard enthalpies of formation of TBP, HDBP, and H2MBP are finally predicted with an uncertainty of about 15 kJ mol⁻¹. In the second part of this project, we have investigated the fundamental properties of three organic species that mostly contribute to the thermal runaway: UO₂(NO₃)₂(TBP)₂, UO₂(NO₃)₂(HDBP)(TBP), and UO₂(NO₃)₂(HDBP)₂ using the same quantum chemical methods that were used for TBP and its derivatives in both the gas and the liquid phase. We will discuss the structures and thermodynamic properties of all these species.

Keywords: PUREX process, red oils, quantum chemical methods, hydrolysis

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Authors: Joanna Gerszon, Aleksandra Rodacka

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In the pathogenesis of neurodegenerative diseases such as Alzheimer's disease and Parkinson's disease, protein and peptide aggregation processes play a vital role in contributing to the formation of intracellular and extracellular protein deposits. One of the major components of these deposits is the oxidatively modified glyceraldehyde-3-phosphate dehydrogenase (GAPDH). Therefore, the purpose of this research was to answer the question whether piceatannol, a stilbene derivative, counteracts and/or slows down oxidative stress-induced GAPDH aggregation. The study also aimed to determine if this natural occurring compound prevents unfavorable nuclear translocation of GAPDH in hippocampal cells. The isothermal titration calorimetry (ITC) analysis indicated that one molecule of GAPDH can bind up to 8 molecules of piceatannol (7.3 ± 0.9). As a consequence of piceatannol binding to the enzyme, the loss of activity was observed. Parallel with GAPDH inactivation the changes in zeta potential, and loss of free thiol groups were noted. Nevertheless, the ligand-protein binding does not influence the secondary structure of the GAPDH. Precise molecular docking analysis of the interactions inside the active center allowed to presume that these effects are due to piceatannol ability to assemble a covalent binding with nucleophilic cysteine residue (Cys149) which is directly involved in the catalytic reaction. Molecular docking also showed that simultaneously 11 molecules of ligand can be bound to dehydrogenase. Taking into consideration obtained data, the influence of piceatannol on level of GAPDH aggregation induced by excessive oxidative stress was examined. The applied methods (thioflavin-T binding-dependent fluorescence as well as microscopy methods - transmission electron microscopy, Congo Red staining) revealed that piceatannol significantly diminishes level of GAPDH aggregation. Finally, studies involving cellular model (Western blot analyses of nuclear and cytosolic fractions and confocal microscopy) indicated that piceatannol-GAPDH binding prevents GAPDH from nuclear translocation induced by excessive oxidative stress in hippocampal cells. In consequence, it counteracts cell apoptosis. These studies demonstrate that by binding with GAPDH, piceatannol blocks cysteine residue and counteracts its oxidative modifications, that induce oligomerization and GAPDH aggregation as well as it prevents hippocampal cells from apoptosis by retaining GAPDH in the cytoplasm. All these findings provide a new insight into the role of piceatannol interaction with GAPDH and present a potential therapeutic strategy for some neurological disorders related to GAPDH aggregation. This work was supported by the by National Science Centre, Poland (grant number 2017/25/N/NZ1/02849).

Keywords: glyceraldehyde-3-phosphate dehydrogenase, neurodegenerative disease, neuroprotection, piceatannol, protein aggregation

Procedia PDF Downloads 157

Authors: Ching Shya Lee, Mohamed Kheireddine Aroua, Wan Mohd Ashri Wan Daud, Patrick Cognet, Yolande Peres, Mohammed Ajeel

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In recent years, with the decreasing supply of fossil fuel, renewable energy has received a significant demand. Biodiesel which is well known as vegetable oil based fatty acid methyl ester is an alternative fuel for diesel. It can be produced from transesterification of vegetable oils, such as palm oil, sunflower oil, rapeseed oil, etc., with methanol. During the transesterification process, crude glycerol is formed as a by-product, resulting in 10% wt of the total biodiesel production. To date, due to the fast growing of biodiesel production in worldwide, the crude glycerol supply has also increased rapidly and resulted in a significant price drop for glycerol. Therefore, extensive research has been developed to use glycerol as feedstock to produce various added-value chemicals, such as tartronic acid, mesoxalic acid, glycolic acid, glyceric acid, propanediol, acrolein etc. The industrial processes that usually involved are selective oxidation, biofermentation, esterification, and hydrolysis. However, the conversion of glycerol into added-value compounds by electrochemical approach is rarely discussed. Currently, the approach is mainly focused on the electro-oxidation study of glycerol under potentiostatic mode for cogenerating energy with other chemicals. The electro-organic synthesis study from glycerol under galvanostatic mode is seldom reviewed. In this study, the glycerol was converted into various added-value compounds by electrochemical method under galvanostatic mode. This work aimed to study the possible compounds produced from glycerol by electrochemical technique in a one-pot electrolysis cell. The electro-organic synthesis study from glycerol was carried out in a single compartment reactor for 8 hours, over the platinum cathode and anode electrodes under acidic condition. Various parameters such as electric current (1.0 A to 3.0 A) and reaction temperature (27 °C to 80 °C) were evaluated. The products obtained were characterized by using gas chromatography-mass spectroscopy equipped with an aqueous-stable polyethylene glycol stationary phase column. Under the optimized reaction condition, the glycerol conversion achieved as high as 95%. The glycerol was successfully converted into various added-value chemicals such as ethylene glycol, glycolic acid, glyceric acid, acetaldehyde, formic acid, and glyceraldehyde; given the yield of 1%, 45%, 27%, 4%, 0.7% and 5%, respectively. Based on the products obtained from this study, the reaction mechanism of this process is proposed. In conclusion, this study has successfully converted glycerol into a wide variety of added-value compounds. These chemicals are found to have high market value; they can be used in the pharmaceutical, food and cosmetic industries. This study effectively opens a new approach for the electrochemical conversion of glycerol. For further enhancement on the product selectivity, electrode material is an important parameter to be considered.

Keywords: biodiesel, glycerol, electrochemical conversion, galvanostatic mode

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Authors: Ayten Ekin Meşe, Selahattin Şentürk, Melike Duvanoğlu

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Petroleum refineries are a highly complex process industry with continuous production and high operating costs. Physical separation of crude oil starts with the crude oil distillation unit, continues with various conversion and purification units, and passes through many stages until obtaining the final product. To meet the desired product specification, process parameters are strictly followed. To be able to ensure the quality of distillates, routine analyses are performed in quality control laboratories based on appropriate international standards such as American Society for Testing and Materials (ASTM) standard methods and European Standard (EN) methods. The cut point of distillates in the crude distillation unit is very crucial for the efficiency of the upcoming processes. In order to maximize the process efficiency, the determination of the quality of distillates should be as fast as possible, reliable, and cost-effective. In this sense, an alternative study was carried out on the crude oil distillation unit that serves the entire refinery process. In this work, studies were conducted with three different crude oil distillates which are Light Straight Run Naphtha (LSRN), Heavy Straight Run Naphtha (HSRN), and Kerosene. These products are named after separation by the number of carbons it contains. LSRN consists of five to six carbon-containing hydrocarbons, HSRN consist of six to ten, and kerosene consists of sixteen to twenty-two carbon-containing hydrocarbons. Physical properties of three different crude distillation unit products (LSRN, HSRN, and Kerosene) were determined using Near-Infrared Spectroscopy with multivariate calibration. The absorbance spectra of the petroleum samples were obtained in the range from 10000 cm⁻¹ to 4000 cm⁻¹, employing a quartz transmittance flow through cell with a 2 mm light path and a resolution of 2 cm⁻¹. A total of 400 samples were collected for each petroleum sample for almost four years. Several different crude oil grades were processed during sample collection times. Extended Multiplicative Signal Correction (EMSC) and Savitzky-Golay (SG) preprocessing techniques were applied to FT-NIR spectra of samples to eliminate baseline shifts and suppress unwanted variation. Two different multivariate calibration approaches (Partial Least Squares Regression, PLS and Genetic Inverse Least Squares, GILS) and an ensemble model were applied to preprocessed FT-NIR spectra. Predictive performance of each multivariate calibration technique and preprocessing techniques were compared, and the best models were chosen according to the reproducibility of ASTM reference methods. This work demonstrates the developed models can be used for routine analysis instead of conventional analytical methods with over 90% accuracy.

Keywords: crude distillation unit, multivariate calibration, near infrared spectroscopy, data preprocessing, refinery

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Authors: Seyed Mehdi Seyed Alizadeh, Christoph Arns, Shane Latham

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Geomechanical characterization of rocks in detail and its possible implications on flow properties is an important aspect of reservoir characterization workflow. In order to gain more understanding of the microstructure evolution of reservoir rocks under stress a series of axisymmetric triaxial tests were performed on two different analogue rock samples. In-situ compression tests were coupled with high resolution micro-Computed Tomography to elucidate the changes in the pore/grain network of the rocks under pressurized conditions. Two outcrop sandstones were chosen in the current study representing a various cementation status of well-consolidated and weakly-consolidated granular system respectively. High resolution images were acquired while the rocks deformed in a purpose-built compression cell. A detailed analysis of the 3D images in each series of step-wise compression tests (up to the failure point) was conducted which includes the registration of the deformed specimen images with the reference pristine dry rock image. Digital Image Correlation (DIC) technique based on the intensity of the registered 3D subsets and particle tracking are utilized to map the displacement fields in each sample. The results suggest the complex architecture of the localized shear zone in well-cemented Bentheimer sandstone whereas for the weakly-consolidated Castlegate sandstone no discernible shear band could be observed even after macroscopic failure. Post-mortem imaging a sister plug from the friable rock upon undergoing continuous compression reveals signs of a shear band pattern. This suggests that for friable sandstones at small scales loading mode may affect the pattern of deformation. Prior to mechanical failure, the continuum digital image correlation approach can reasonably capture the kinematics of deformation. As failure occurs, however, discrete image correlation (i.e. particle tracking) reveals superiority in both tracking the grains as well as quantifying their kinematics (in terms of translations/rotations) with respect to any stage of compaction. An attempt was made to quantify the displacement field in compression using continuum Digital Image Correlation which is based on the reference and secondary image intensity correlation. Such approach has only been previously applied to unconsolidated granular systems under pressure. We are applying this technique to sandstones with various degrees of consolidation. Such element of novelty will set the results of this study apart from previous attempts to characterize the deformation pattern in consolidated sands.

Keywords: deformation mechanism, displacement field, shear behavior, triaxial compression, X-ray micro-CT

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Authors: komal verma, V. S. Moholkar

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In this current study, the challenge of effectively treating and mineralizing industrial wastewater prior to its discharge into natural water bodies, such as rivers and lakes, is being addressed. Particularly, the focus is on the wastewater produced by chemical process industries, including refineries, petrochemicals, fertilizer, pharmaceuticals, pesticides, and dyestuff industries. These wastewaters often contain stubborn organic pollutants that conventional techniques, such as microbial processes cannot efficiently degrade. To tackle this issue, a ternary hybrid technique comprising of adsorption, heterogeneous Fenton process, and sonication has been employed. The study aims to evaluate the effectiveness of this approach for treating and mineralizing wastewater from a fertilizer industry located in Northeast India. The study comprises several key components, starting with the synthesis of the Fe3O4@AC nanocomposite using the co-precipitation method. The nanocomposite is then subjected to comprehensive characterization through various standard techniques, including FTIR, FE-SEM, EDX, TEM, BET surface area analysis, XRD, and magnetic property determination using VSM. Next, the process parameters of wastewater treatment are statistically optimized, focusing on achieving a high level of COD (Chemical Oxygen Demand) removal as the response variable. The Fe3O4@AC nanocomposite's adsorption characteristics and kinetics are also assessed in detail. The remarkable outcome of this study is the successful application of the ternary hybrid technique, combining adsorption, Fenton process, and sonication. This approach proves highly effective, leading to nearly complete mineralization (or TOC removal) of the fertilizer industry wastewater. The results highlight the potential of the Fe3O4@AC nanocomposite and the ternary hybrid technique as a promising solution for tackling challenging wastewater pollutants from various chemical process industries. This paper reports investigations in the mineralization of industrial wastewater (COD = 3246 mg/L, TOC = 2500 mg/L) using a ternary (ultrasound + Fenton + adsorption) hybrid advanced oxidation process. Fe3O4 decorated activated charcoal (Fe3O4@AC) nanocomposites (surface area = 538.88 m2/g; adsorption capacity = 294.31 mg/g) were synthesized using co-precipitation. The wastewater treatment process was optimized using central composite statistical design. At optimum conditions, viz. pH = 4.2, H2O2 loading = 0.71 M, adsorbent dose = 0.34 g/L, reduction in COD and TOC of wastewater were 94.75% and 89%, respectively. This result results from synergistic interactions among the adsorption of pollutants onto activated charcoal and surface Fenton reactions induced due to the leaching of Fe2+/Fe3+ ions from the Fe3O4 nanoparticles. Micro-convection generated due to sonication assisted faster mass transport (adsorption/desorption) of pollutants between Fe3O4@AC nanocomposite and the solution. The net result of this synergism was high interactions and reactions among and radicals and pollutants that resulted in the effective mineralization of wastewater. The Fe3O4@AC showed excellent recovery (> 90 wt%) and reusability (> 90% COD removal) in 5 successive cycles of treatment. LC-MS analysis revealed effective (> 50%) degradation of more than 25 significant contaminants (in the form of herbicides and pesticides) after the treatment with ternary hybrid AOP. Similarly, the toxicity analysis test using the seed germination technique revealed ~ 60% reduction in the toxicity of the wastewater after treatment.

Keywords: chemical oxygen demand (cod), fe3o4@ac nanocomposite, kinetics, lc-ms, rsm, toxicity

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Authors: Paula I. Buonfiglio, Carlos David Bruque, Lucia Salatino, Vanesa Lotersztein, Sebastián Menazzi, Paola Plazas, Ana Belén Elgoyhen, Viviana Dalamón

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Hearing loss (HL) is the most prevalent sensorineural disorder affecting about 10% of the global population, with more than half due to genetic causes. About 1 in 500-1000 newborns present congenital HL. Most of the patients are non-syndromic with an autosomal recessive mode of inheritance. To date, more than 100 genes are related to HL. Therefore, the Whole-exome sequencing (WES) technique has become a cost-effective alternative approach for molecular diagnosis. Nevertheless, new challenges arise from the detection of novel variants, in particular missense changes, which can lead to a spectrum of genotype-to-phenotype correlations, which is not always straightforward. In this work, we aimed to identify the genetic causes of HL in isolated and familial cases by designing a multistep approach to analyze target genes related to hearing impairment. Moreover, we performed in silico and in vivo analyses in order to further study the effect of some of the novel variants identified in the hair cell function using the zebrafish model. A total of 650 patients were studied by Sanger Sequencing and Gap-PCR in GJB2 and GJB6 genes, respectively, diagnosing 15.5% of sporadic cases and 36% of familial ones. Overall, 50 different sequence variants were detected. Fifty of the undiagnosed patients with moderate HL were tested for deletions in STRC gene by Multiplex ligation-dependent probe amplification technique (MLPA), leading to 6% of diagnosis. After this initial screening, 50 families were selected to be analyzed by WES, achieving diagnosis in 44% of them. Half of the identified variants were novel. A missense variant in MYO6 gene detected in a family with postlingual HL was selected to be further analyzed. A protein modeling with AlphaFold2 software was performed, proving its pathogenic effect. In order to functionally validate this novel variant, a knockdown phenotype rescue assay in zebrafish was carried out. Injection of wild-type MYO6 mRNA in embryos rescued the phenotype, whereas using the mutant MYO6 mRNA (carrying c.2782C>A variant) had no effect. These results strongly suggest the deleterious effect of this variant on the mobility of stereocilia in zebrafish neuromasts, and hence on the auditory system. In the present work, we demonstrated that our algorithm is suitable for the sequential multigenic approach to HL in our cohort. These results highlight the importance of a combined strategy in order to identify candidate variants as well as the in silico and in vivo studies to analyze and prove their pathogenicity and accomplish a better understanding of the mechanisms underlying the physiopathology of the hearing impairment.

Keywords: diagnosis, genetics, hearing loss, in silico analysis, in vivo analysis, WES, zebrafish

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Authors: Ann P. Daunic, Nancy Corbett

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Background and Significance: Researchers emphasize the role that motivation, self-esteem, and self-regulation play in children’s early adjustment to the school culture, including skills such as identifying their own feelings and understanding the feelings of others. As social-emotional growth, academic learning, and successful integration within culture and society are inextricably connected, the Social-Emotional Learning Foundations (SELF) curriculum was designed to integrate social-emotional learning (SEL) instruction within early literacy instruction (specifically, reading) for Kindergarten and first-grade students at risk for emotional and behavioral difficulties. Storybook reading is a typically occurring activity in the primary grades; thus SELF provides an intervention that is both theoretically and practically sound. Methodology: The researchers will report on findings from the first two years of a three-year study funded by the US Department of Education’s Institute of Education Sciences to evaluate the effects of the SELF curriculum versus “business as usual” (BAU). SELF promotes the development of self-regulation by incorporating instructional strategies that support children’s use of SEL related vocabulary, self-talk, and critical thinking. The curriculum consists of a carefully coordinated set of materials and pedagogy designed specifically for primary grade children at early risk for emotional and behavioral difficulties. SELF lessons (approximately 50 at each grade level) are organized around 17 SEL topics within five critical competencies. SELF combines whole-group (the first in each topic) and small-group lessons (the 2nd and 3rd in each topic) to maximize opportunities for teacher modeling and language interactions. The researchers hypothesize that SELF offers a feasible and substantial opportunity within the classroom setting to provide a small-group social-emotional learning intervention integrated with K-1 literacy-related instruction. Participating target students (N = 876) were identified by their teachers as potentially at risk for emotional or behavioral issues. These students were selected from 122 Kindergarten and 100 first grade classrooms across diverse school districts in a southern state in the US. To measure the effectiveness of the SELF intervention, the researchers asked teachers to complete assessments related to social-emotional learning and adjustment to the school culture. A social-emotional learning related vocabulary assessment was administered directly to target students receiving small-group instruction. Data were analyzed using a 3-level MANOVA model with full information maximum likelihood to estimate coefficients and test hypotheses. Major Findings: SELF had significant positive effects on vocabulary, knowledge, and skills associated with social-emotional competencies, as evidenced by results from the measures administered. Effect sizes ranged from 0.41 for group (SELF vs. BAU) differences in vocabulary development to 0.68 for group differences in SEL related knowledge. Conclusion: Findings from two years of data collection indicate that SELF improved outcomes related to social-emotional learning and adjustment to the school culture. This study thus supports the integration of SEL with literacy instruction as a feasible and effective strategy to improve outcomes for K-1 students at risk for emotional and behavioral difficulties.

Keywords: Socio-cultural context for learning, social-emotional learning, social skills, vocabulary development

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Authors: Brajendra S. Sengar, Vivek Garg, Gaurav Siddharth, Nisheka Anadkat, Amitesh Kumar, Shaibal Mukherjee

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The optimal band gap (~ 1 to 1.5 eV) and high absorption coefficient ~104 cm⁻¹ has made Cu₂ZnSn(S,Se)₄ (CZTSSe) films as one of the most promising absorber materials in thin-film photovoltaics. Additionally, CZTSSe consists of elements that are abundant and non-toxic, makes it even more favourable. The CZTSSe thin films are grown at 100 to 500ᵒC substrate temperature (Tsub) on Soda lime glass (SLG) substrate by Elettrorava dual ion beam sputtering (DIBS) system by utilizing a target at 2.43x10⁻⁴ mbar working pressure with RF power of 45 W in argon ambient. The chemical composition, depth profiling, structural properties and optical properties of these CZTSSe thin films prepared on SLG were examined by energy dispersive X-ray spectroscopy (EDX, Oxford Instruments), Hiden secondary ion mass spectroscopy (SIMS) workstation with oxygen ion gun of energy up to 5 keV, X-ray diffraction (XRD) (Rigaku Cu Kα radiation, λ=.154nm) and Spectroscopic Ellipsometry (SE, M-2000D from J. A. Woollam Co., Inc). It is observed that from that, the thin films deposited at Tsub=200 and 300°C show Cu-poor and Zn-rich states (i.e., Cu/(Zn + Sn) < 1 and Zn/Sn > 1), which is not the case for films grown at other Tsub. It has been reported that the CZTSSe thin films with the highest efficiency are typically at Cu-poor and Zn-rich states. The values of band gap in the fundamental absorption region of CZTSSe are found to be in the range of 1.23-1.70 eV depending upon the Cu/(Zn+Sn) ratio. It is also observed that there is a decline in optical band gap with the increase in Cu/(Zn+Sn) ratio (evaluated from EDX measurement). Cu-poor films are found to have higher optical band gap than Cu-rich films. The decrease in the band gap with the increase in Cu content in case of CZTSSe films may be attributed to changes in the extent of p-d hybridization between Cu d-levels and (S, Se) p-levels. CZTSSe thin films with Cu/(Zn+Sn) ratio in the range 0.86–1.5 have been successfully deposited using DIBS. Optical band gap of the films is found to vary from 1.23 to 1.70 eV based on Cu/(Zn+Sn) ratio. CZTSe films with Cu/ (Zn+Sn) ratio of .86 are found to have optical band gap close to the ideal band gap (1.49 eV) for highest theoretical conversion efficiency. Thus by tailoring the value of Cu/(Zn+Sn), CZTSSe thin films with the desired band gap could be obtained. Acknowledgment: We are thankful to DIBS, EDX, and XRD facility equipped at Sophisticated Instrument Centre (SIC) at IIT Indore. The authors B. S. S and A. K. acknowledge CSIR, and V. G. acknowledges UGC, India for their fellowships. B. S. S is thankful to DST and IUSSTF for BASE Internship Award. Prof. Shaibal Mukherjee is thankful to DST and IUSSTF for BASE Fellowship and MEITY YFRF award. This work is partially supported by DAE BRNS, DST CERI, and DST-RFBR Project under India-Russia Programme of Cooperation in Science and Technology. We are thankful to Mukul Gupta for SIMS facility equipped at UGC-DAE Indore.

Keywords: CZTSSe, DIBS, EDX, solar cell

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Authors: Sugam Kale, Arif Uzair Bin Mohammed Roslan, Cindy Lee, Syed Beevee Mohammed Ismail

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Preemptive analgesia is an established concept in the modern practice of anaesthesia. To be most effective, it is best instituted earlier than the surgical stimulus and should last beyond the offset of surgically induced pain till healing is complete. Whereas the start of afferent pain blockade with regional anaesthesia is common, its effect often falls short to cover the entire period of pain impulses making their way to CNS in the post-operative period. We tried to use a combination of two regional anaesthetic techniques used sequentially to overcome this handicap. Madam S., a 56 year old lady, was scheduled for elective surgery for pancreatic cancer. She underwent laparotomy and distal pancreatectomy, splenectomy, bilateral salpingo oophorectomy, and sigmoid colectomy. Surgery was expected to be extensive, and it was presumed that the standard pain relief with PCA with opiates and oral analgesics would not be adequate. After counselling the patient pre-operative about the technique of regional anaesthesia techniques, including epidural catheterization and rectus sheath catheter placement, their benefits, and potential complications, informed consent was obtained. Epidural catheter was placed awake, and general anaesthesia was then induced. Epidural infusion of local anaesthetics was started prior to surgical incision and was continued till 60 hours into the postoperative period. Before skin closure, the surgeons inserted commercially available rectus sheath catheters bilaterally along the midline incision used for laparotomy. After 46 hours post-op, local anaesthetic infusion via these was started as bridging while the epidural infusion rate was tapered off. The epidural catheter was removed at 75 hours. Elastomeric pumps were used to provide local anaesthetic infusion with the ability to vary infusion rates. Acute pain service followed up the patient’s vital signs and effectiveness of pain relief twice daily or more frequently as required. Rectus sheath catheters were removed 137 hours post-op. The patient had good post-op analgesia with the minimal additional analgesic requirement. For the most part, the visual analog score (VAS) for pain remained at 1-3 on a scale of 1 to 10. Haemodynamics remained stable, and surgical recovery was as expected. Minimal opiate requirement after an extensive laparotomy also translates to the early return of intestinal motility. Our experience was encouraging, and we are hoping to extend this combination of two regional anaesthetic techniques to patients undergoing similar surgeries. Epidural analgesia is denser and offers excellent pain relief for both visceral and somatic pain in the first few days after surgery. As the pain intensity grows weaker, rectus sheath block and oral analgesics provide almost the same degree of pain relief after the epidural catheter is removed. We discovered that the background infusion of local anaesthetic down the rectus sheath catherter largely reduced the requirement for other classes of analgesics. We aim to study this further with a larger patient cohort and hope that it may become an established clinical practice that benefits patients everywhere.

Keywords: rectus sheath, epidural infusion, post operative analgesia, elastomeric

Procedia PDF Downloads 127

Authors: Malkhaz Jokhadze, Vakhtang Mshvildadze, Levan Makaradze, Ekaterine Mosidze, Salome Barbaqadze, Mariam Murtazashvili, Dali Berashvili, Koba sivsivadze, Lasha Bakuridze, Aliosha Bakuridze

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Essential oils are one of the most important groups of biologically active substances present in plants. Due to the chemical diversity of components, essential oils and their preparations have a wide spectrum of pharmacological action. They have bactericidal, antiviral, fungicidal, antiprotozoal, anti-inflammatory, spasmolytic, sedative and other activities. They are expectorant, spasmolytic, sedative, hypotensive, secretion enhancing, antioxidant remedies. Based on preliminary pharmacological studies, we have developed a formulation called “Phytobiotic” containing essential oils, a feed additive for poultry as an alternative to antibiotics. Phytobiotic is a water-soluble powder containing a composition of essential oils of thyme, clary, monarda and auxiliary substances: dry extract of liquorice and inhalation lactose. On this stage of research, the goal was to study the chemical composition of provided phytobiotic, identify the main substances and determine their quantity, investigate the biological activity of phytobiotic through in vitro and in vivo studies. Using gas chromatography-mass spectrometry, 38 components were identified in phytobiotic, representing acyclic-, monocyclic-, bicyclic-, and sesquiterpenes. Together with identification of main active substances, their quantitative content was determined, including acyclic terpene alcohol β-linalool, acyclic terpene ketone linalyl acetate, monocyclic terpenes: D-limonene and γ-terpinene, monocyclic aromatic terpene thymol. Provided phytobiotic has pronounced and at the same time broad spectrum of antibacterial activity. In the cell model, phytobiotic showed weak antioxidant activity, and it was stronger in the ORAC (chemical model) tests. Meanwhile anti-inflammatory activity was also observed. When fowls were supplied feed enriched with phytobiotic, it was observed that gained weight of the chickens in the experimental group exceeded the same data for the control group during the entire period of the experiment. The survival rate of broilers in the experimental group during the growth period was 98% compared to -94% in the control group. As a result of conducted researches probable four different mechanisms which are important for the action of phytobiotics were identified: sensory, metabolic, antioxidant and antibacterial action. General toxic, possible local irritant and allergenic effects of phytobiotic were also investigated. Performed assays proved that formulation is safe.

Keywords: clary, essential oils, monarda, poultry, phytobiotics, thyme

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Authors: Pedro A. Marques, Francisco Monteiro, Alessandra Zumbo, Alessia Simonini, Miguel A. Mendez

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Cryogenic fuels such as Liquid Hydrogen (LH₂) must be transported and stored at extremely low temperatures. Without expensive active cooling solutions, preventing fuel boil-off over time is impossible. Hence, one must resort to venting systems at the cost of significant energy and fuel mass loss. These losses increase significantly in propellant tanks installed on vehicles, as the presence of external accelerations induces sloshing. Sloshing increases heat and mass transfer rates and leads to significant pressure oscillations, which might further trigger propellant venting. To make LH₂ economically viable, it is essential to minimize these factors by using advanced control techniques. However, these require accurate modelling and a full understanding of the tank's thermodynamics. The present research aims to implement a simple thermodynamic model capable of predicting the state of a cryogenic fuel tank under different operating conditions (i.e., filling, pressurization, fuel extraction, long-term storage, and sloshing). Since this model relies on a set of closure parameters to drive the system's transient response, it must be calibrated using experimental or numerical data. This work focuses on the former approach, wherein the model is calibrated through an experimental campaign carried out on a reduced-scale model of a cryogenic tank. The thermodynamic model of the system is composed of three control volumes: the ullage, the liquid, and the insulating walls. Under this lumped formulation, the governing equations are derived from energy and mass balances in each region, with mass-averaged properties assigned to each of them. The gas-liquid interface is treated as an infinitesimally thin region across which both phases can exchange mass and heat. This results in a coupled system of ordinary differential equations, which must be closed with heat and mass transfer coefficients between each control volume. These parameters are linked to the system evolution via empirical relations derived from different operating regimes of the tank. The derivation of these relations is carried out using an inverse method to find the optimal relations that allow the model to reproduce the available data. This approach extends classic system identification methods beyond linear dynamical systems via a nonlinear optimization step. Thanks to the data-driven assimilation of the closure problem, the resulting model accurately predicts the evolution of the tank's thermodynamics at a negligible computational cost. The lumped model can thus be easily integrated with other submodels to perform complete system simulations in real time. Moreover, by setting the model in a dimensionless form, a scaling analysis allowed us to relate the tested configurations to a representative full-size tank for naval applications. It was thus possible to compare the relative importance of different transport phenomena between the laboratory model and the full-size prototype among the different operating regimes.

Keywords: destratification, hydrogen, modeling, pressure-drop, pressurization, sloshing, thermodynamics

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Authors: Sinead Impey, Gaye Stephens, Declan O’Sullivan

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Mitigating organisational knowledge loss presents challenges for knowledge managers. Expert knowledge is embodied in people and captured in ‘routines, processes, practices and norms’ as well as in the paper system. These knowledge stores have limitations in so far as they make knowledge diffusion beyond geography or over time difficult. However, technology could present a potential solution by facilitating the capture and management of expert knowledge in a codified and sharable format. Before it can be digitised, however, the knowledge of healthcare experts must be captured. Methods: As a first step in a larger project on this topic, a scoping review was conducted to identify how expert healthcare knowledge is captured digitally. The aim of the review was to identify current healthcare knowledge capture practices, identify gaps in the literature, and justify future research. The review followed a scoping review framework. From an initial 3,430 papers retrieved, 22 were deemed relevant and included in the review. Findings: Two broad approaches –direct and indirect- with themes and subthemes emerged. ‘Direct’ describes a process whereby knowledge is taken directly from subject experts. The themes identified were: ‘Researcher mediated capture’ and ‘Digital mediated capture’. The latter was further distilled into two sub-themes: ‘Captured in specified purpose platforms (SPP)’ and ‘Captured in a virtual community of practice (vCoP)’. ‘Indirect’ processes rely on extracting new knowledge using artificial intelligence techniques from previously captured data. Using this approach, the theme ‘Generated using artificial intelligence methods’ was identified. Although presented as distinct themes, some papers retrieved discuss combining more than one approach to capture knowledge. While no approach emerged as superior, two points arose from the literature. Firstly, human input was evident across themes, even with indirect approaches. Secondly, a range of challenges common among approaches was highlighted. These were (i) ‘Capturing an expert’s knowledge’- Difficulties surrounding capturing an expert’s knowledge related to identifying the ‘expert’ say from the very experienced and how to capture their tacit or difficult to articulate knowledge. (ii) ‘Confirming quality of knowledge’- Once captured, challenges noted surrounded how to validate knowledge captured and, therefore, quality. (iii) ‘Continual knowledge capture’- Once knowledge is captured, validated, and used in a system; however, the process is not complete. Healthcare is a knowledge-rich environment with new evidence emerging frequently. As such, knowledge needs to be reviewed, updated, or removed (redundancy) as appropriate. Although some methods were proposed to address this, such as plausible reasoning or case-based reasoning, conclusions could not be drawn from the papers retrieved. It was, therefore, highlighted as an area for future research. Conclusion: The results described two broad approaches – direct and indirect. Three themes were identified: ‘Researcher mediated capture (Direct)’; ‘Digital mediated capture (Direct)’ and ‘Generated using artificial intelligence methods (Indirect)’. While no single approach was deemed superior, common challenges noted among approaches were: ‘capturing an expert’s knowledge’, ‘confirming quality of knowledge’, and ‘continual knowledge capture’. However, continual knowledge capture was not fully explored in the papers retrieved and was highlighted as an important area for future research. Acknowledgments: This research is partially funded by the ADAPT Centre under the SFI Research Centres Programme (Grant 13/RC/2106) and is co-funded under the European Regional Development Fund.

Keywords: expert knowledge, healthcare, knowledge capture and knowledge management

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Authors: Dario Milani, Guido Morgenthal

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Fluid dynamic computation of wind caused forces on bluff bodies e.g light flexible civil structures or high incidence of ground approaching airplane wings, is one of the major criteria governing their design. For such structures a significant dynamic response may result, requiring the usage of small scale devices as guide-vanes in bridge design to control these effects. The focus of this paper is on the numerical simulation of the bluff body problem involving multiscale phenomena induced by small scale devices. One of the solution methods for the CFD simulation that is relatively successful in this class of applications is the Vortex Particle Method (VPM). The method is based on a grid free Lagrangian formulation of the Navier-Stokes equations, where the velocity field is modeled by particles representing local vorticity. These vortices are being convected due to the free stream velocity as well as diffused. This representation yields the main advantages of low numerical diffusion, compact discretization as the vorticity is strongly localized, implicitly accounting for the free-space boundary conditions typical for this class of FSI problems, and a natural representation of the vortex creation process inherent in bluff body flows. When the particle resolution reaches the Kolmogorov dissipation length, the method becomes a Direct Numerical Simulation (DNS). However, it is crucial to note that any solution method aims at balancing the computational cost against the accuracy achievable. In the classical VPM method, if the fluid domain is discretized by Np particles, the computational cost is O(Np2). For the coupled FSI problem of interest, for example large structures such as long-span bridges, the aerodynamic behavior may be influenced or even dominated by small structural details such as barriers, handrails or fairings. For such geometrically complex and dimensionally large structures, resolving the complete domain with the conventional VPM particle discretization might become prohibitively expensive to compute even for moderate numbers of particles. It is possible to reduce this cost either by reducing the number of particles or by controlling its local distribution. It is also possible to increase the accuracy of the solution without increasing substantially the global computational cost by computing a correction of the particle-particle interaction in some regions of interest. In this paper different strategies are presented in order to extend the conventional VPM method to reduce the computational cost whilst resolving the required details of the flow. The methods include temporal sub stepping to increase the accuracy of the particles convection in certain regions as well as dynamically re-discretizing the particle map to locally control the global and the local amount of particles. Finally, these methods will be applied on a test case and the improvements in the efficiency as well as the accuracy of the proposed extension to the method are presented. The important benefits in terms of accuracy and computational cost of the combination of these methods will be thus presented as long as their relevant applications.

Keywords: adaptation, fluid dynamic, remeshing, substepping, vortex particle method

Procedia PDF Downloads 257

Authors: Akane Uda, Ami Tabata, Mi An, Misa Komaki, Ryotaro Ito, Mayumi Inoue, Takehiro Sasai, Yusuke Kusano, Toshihiro Kato

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Early intervention is recommended for children with autism spectrum disorder (ASD), and an increasing number of children have received support and intervention before school age in recent years. In this study, we systematically reviewed preschool interventions focused on repetitive behaviors observed in children with ASD, which are often observed at younger ages. Inclusion criteria were as follows : (1) Child of preschool status (age ≤ 7 years) with a diagnosis of ASD (including autism, Asperger's, and pervasive developmental disorder) or a parent (caregiver) with a preschool child with ASD, (2) Physician-confirmed diagnosis of ASD (autism, Asperger's, and pervasive developmental disorder), (3) Interventional studies for repetitive behaviors, (4) Original articles published within the past 10 years (2012 or later), (5) Written in English and Japanese. Exclusion criteria were as follows: (1) Systematic reviews or meta-analyses, (2) Conference reports or books. We carefully scrutinized databases to remove duplicate references and used a two-step screening process to select papers. The primary screening included close scrutiny of titles and abstracts to exclude articles that did not meet the eligibility criteria. During the secondary screening, we carefully read the complete text to assess eligibility, which was double-checked by six members at the laboratory. Disagreements were resolved through consensus-based discussion. Our search yielded 304 papers, of which nine were included in the study. The level of evidence was as follows: three randomized controlled trials (level 2), four pre-post studies (level 4b), and two case reports (level 5). Seven articles selected for this study described the effectiveness of interventions. Interventions for repetitive behaviors in preschool children with ASD were categorized as five interventions that directly involved the child and four educational programs for caregivers and parents. Studies that directly intervened with children used early intensive intervention based on applied behavior analysis (Early Start Denver Model, Early Intensive Behavioral Intervention, and the Picture Exchange Communication System) and individualized education based on sensory integration. Educational interventions for caregivers included two methods; (a) education regarding combined methods and practices of applied behavior analysis in addition to classification and coping methods for repetitive behaviors, and (b) education regarding evaluation methods and practices based on children’s developmental milestones in play. With regard to the neurophysiological basis of repetitive behaviors, environmental factors are implicated as possible contributors. We assumed that applied behavior analysis was shown to be effective in reducing repetitive behaviors because analysis focused on the interaction between the individual and the environment. Additionally, with regard to educational interventions for caregivers, the intervention was shown to promote behavioral change in children based on the caregivers' understanding of the classification of repetitive behaviors and the children’s developmental milestones in play and adjustment of the person-environment context led to a reduction in repetitive behaviors.

Keywords: autism spectrum disorder, early intervention, repetitive behaviors, systematic review

Procedia PDF Downloads 137

Authors: Sarah Nauwelaerts, Koen De Cremer, Alfred Bernard, Meredith Verlooy, Kristel Heremans, Natalia Bustos Sierra, Katrien Tersago, Tim Nawrot, Jordy Vercauteren, Christophe Stroobants, Sigrid C. J. De Keersmaecker, Nancy Roosens

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Projected climate changes could lead to exacerbation of respiratory disorders associated with reduced air quality. Air pollution and climate changes influence each other through complex interactions. The poor air quality in urban and rural areas includes high levels of particulate matter (PM), ozone (O3) and nitrogen oxides (NOx), representing a major threat to public health and especially for the most vulnerable population strata, and especially young children. In this study, we aim to develop generic standardized policy supporting tools and methods that allow evaluating in future follow-up larger scale epidemiological studies the risks of the combined short-term effects of O3 and PM on the cardiorespiratory system of children. We will use non-invasive indicators of airway damage/inflammation and of genetic or epigenetic variations by using urine or saliva as alternative to blood samples. Therefore, a multi-phase field study will be organized in order to assess the sensitivity and applicability of these tests in large cohorts of children during episodes of air pollution. A first test phase was planned in March 2018, not yet taking into account ‘critical’ pollution periods. Working with non-invasive samples, choosing the right set-up for the field work and the volunteer selection were parameters to consider, as they significantly influence the feasibility of this type of study. During this test phase, the selection of the volunteers was done in collaboration with medical doctors from the Centre for Student Assistance (CLB), by choosing a class of pre-pubertal children of 9-11 years old in a primary school in Flemish Brabant, Belgium. A questionnaire, collecting information on the health and background of children and an informed consent document were drawn up for the parents as well as a simplified cartoon-version of this document for the children. A detailed study protocol was established, giving clear information on the study objectives, the recruitment, the sample types, the medical examinations to be performed, the strategy to ensure anonymity, and finally on the sample processing. Furthermore, the protocol describes how this field study will be conducted in relation with the prevision and monitoring of air pollutants for the future phases. Potential protein, genetic and epigenetic biomarkers reflecting the respiratory function and the levels of air pollution will be measured in the collected samples using unconventional technologies. The test phase results will be used to address the most important bottlenecks before proceeding to the following phases of the study where the combined effect of O3 and PM during pollution peaks will be examined. This feasibility study will allow identifying possible bottlenecks and providing missing scientific knowledge, necessary for the preparation, implementation and evaluation of federal policies/strategies, based on the most appropriate epidemiological studies on the health effects of air pollution. The research leading to these results has been funded by the Belgian Science Policy Office through contract No.: BR/165/PI/PMOLLUGENIX-V2.

Keywords: air pollution, biomarkers, children, field study, feasibility study, non-invasive

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Authors: Celine Bonnaud, Isabelle Billard, Nicolas Papaiconomou, Eric Chainet

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Thanks to their high magnetization and low mass, permanent magnets (NdFeB and SmCo) have quickly became essential for new energies (wind turbines, electrical vehicles…). They contain large quantities of neodymium, samarium and dysprosium, that have been recently classified as critical elements and that therefore need to be recycled. Electrochemical processes including electrodissolution followed by electrodeposition are an elegant and environmentally friendly solution for the recycling of such lanthanides contained in permanent magnets. However, electrochemistry of the lanthanides is a real challenge as their standard potentials are highly negative (around -2.5V vs ENH). Consequently, non-aqueous solvents are required. Ionic liquids (IL) are novel electrolytes exhibiting physico-chemical properties that fulfill many requirements of the sustainable chemistry principles, such as extremely low volatility and non-flammability. Furthermore, their chemical and electrochemical properties (solvation of metallic ions, large electrochemical windows, etc.) render them very attractive media to implement alternative and sustainable processes in view of integrated processes. All experiments that will be presented were carried out using butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide. Linear sweep, cyclic voltammetry and potentiostatic electrochemical techniques were used. The reliability of electrochemical experiments, performed without glove box, for the classic three electrodes cell used in this study has been assessed. Deposits were obtained by chronoamperometry and were characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The IL cathodic behavior under different constraints (argon, nitrogen, oxygen atmosphere or water content) and using several electrode materials (Pt, Au, GC) shows that with argon gas flow and gold as a working electrode, the cathodic potential can reach the maximum value of -3V vs Fc+/Fc; thus allowing a possible reduction of lanthanides. On a gold working electrode, the reduction potential of samarium and neodymium was found to be -1.8V vs Fc+/Fc while that of dysprosium was -2.1V vs Fc+/Fc. The individual deposits obtained were found to be porous and presented some significant amounts of C, N, F, S and O atoms. Selective deposition of neodymium in presence of dysprosium was also studied and will be discussed. Next, metallic Sm, Nd and Dy electrodes were used in replacement of Au, which induced changes in the reduction potential values and the deposit structures of lanthanides. The individual corrosion potentials were also measured in order to determine the parameters influencing the electrodissolution of these metals. Finally, a full recycling process was investigated. Electrodissolution of a real permanent magnet sample was monitored kinetically. Then, the sequential electrodeposition of all lanthanides contained in the IL was investigated. Yields, quality of the deposits and consumption of chemicals will be discussed in depth, in view of the industrial feasibility of this process for real permanent magnets recycling.

Keywords: electrodeposition, electrodissolution, ionic liquids, lanthanides, rcycling

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Authors: Hossein Aghababaei, Sergio Vitale, Giampaolo Ferraioli

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In the context of Synthetic Aperture Radar (SAR) data, polarization is an important source of information for Earth's surface monitoring. SAR Systems are often considered to transmit only one polarization. This constraint leads to either single or dual polarimetric SAR imaging modalities. Single polarimetric systems operate with a fixed single polarization of both transmitted and received electromagnetic (EM) waves, resulting in a single acquisition channel. Dual polarimetric systems, on the other hand, transmit in one fixed polarization and receive in two orthogonal polarizations, resulting in two acquisition channels. Dual polarimetric systems are obviously more informative than single polarimetric systems and are increasingly being used for a variety of remote sensing applications. In dual polarimetric systems, the choice of polarizations for the transmitter and the receiver is open. The choice of circular transmit polarization and coherent dual linear receive polarizations forms a special dual polarimetric system called hybrid polarimetry, which brings the properties of rotational invariance to geometrical orientations of features in the scene and optimizes the design of the radar in terms of reliability, mass, and power constraints. The complete characterization of target scattering, however, requires fully polarimetric data, which can be acquired with systems that transmit two orthogonal polarizations. This adds further complexity to data acquisition and shortens the coverage area or swath of fully polarimetric images compared to the swath of dual or hybrid polarimetric images. The search for solutions to augment dual polarimetric data to full polarimetric data will therefore take advantage of full characterization and exploitation of the backscattered field over a wider coverage with less system complexity. Several methods for reconstructing fully polarimetric images using hybrid polarimetric data can be found in the literature. Although the improvements achieved by the newly investigated and experimented reconstruction techniques are undeniable, the existing methods are, however, mostly based upon model assumptions (especially the assumption of reflectance symmetry), which may limit their reliability and applicability to vegetation and forest scenarios. To overcome the problems of these techniques, this paper proposes a new framework for reconstructing fully polarimetric information from hybrid polarimetric data. The framework uses Deep Learning solutions to augment hybrid polarimetric data without relying on model assumptions. A convolutional neural network (CNN) with a specific architecture and loss function is defined for this augmentation problem by focusing on different scattering properties of the polarimetric data. In particular, the method controls the CNN training process with respect to several characteristic features of polarimetric images defined by the combination of different terms in the cost or loss function. The proposed method is experimentally validated with real data sets and compared with a well-known and standard approach from the literature. From the experiments, the reconstruction performance of the proposed framework is superior to conventional reconstruction methods. The pseudo fully polarimetric data reconstructed by the proposed method also agree well with the actual fully polarimetric images acquired by radar systems, confirming the reliability and efficiency of the proposed method.

Keywords: SAR image, polarimetric SAR image, convolutional neural network, deep learnig, deep neural network

Procedia PDF Downloads 66

Authors: Karen L. Lindsay, Sonja Entringer, Claudia Buss, Pathik D. Wadhwa

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Maternal nutrition and stress are independently recognized as among the most important factors that influence prenatal biology, with implications for fetal development and poor pregnancy outcomes. While there is substantial evidence from non-pregnancy human and animal studies that a complex, bi-directional relationship exists between nutrition and stress, to the author’s best knowledge, their interaction in the context of pregnancy has been significantly understudied. The aim of this study is to assess the interaction between maternal psychological stress and diet quality across pregnancy and its effects on biomarkers of prenatal insulin resistance and inflammation. This is a prospective longitudinal study of N=235 women carrying a healthy, singleton pregnancy, recruited from prenatal clinics of the University of California, Irvine Medical Center. Participants completed a 4-day ambulatory assessment in early, middle and late pregnancy, which included multiple daily electronic diary entries using Ecological Momentary Assessment (EMA) technology on a dedicated study smartphone. The EMA diaries gathered moment-level data on maternal perceived stress, negative mood, positive mood and quality of social interactions. The numerical scores for these variables were averaged across each study time-point and converted to Z-scores. A single composite variable for 'STRESS' was computed as follows: (Negative mood+Perceived stress)–(Positive mood+Social interaction quality). Dietary intakes were assessed by three 24-hour dietary recalls conducted within two weeks of each 4-day assessment. Daily nutrient and food group intakes were averaged across each study time-point. The Alternative Healthy Eating Index adapted for pregnancy (AHEI-P) was computed for early, middle and late pregnancy as a validated summary measure of diet quality. At the end of each 4-day ambulatory assessment, women provided a fasting blood sample, which was assayed for levels of glucose, insulin, Interleukin (IL)-6 and Tumor Necrosis Factor (TNF)-α. Homeostasis Model Assessment of Insulin Resistance (HOMA-IR) was computed. Pearson’s correlation was used to explore the relationship between maternal STRESS and AHEI-P within and between each study time-point. Linear regression was employed to test the association of the stress-diet interaction (STRESS*AHEI-P) with the biological markers HOMA-IR, IL-6 and TNF-α at each study time-point, adjusting for key covariates (pre-pregnancy body mass index, maternal education level, race/ethnicity). Maternal STRESS and AHEI-P were significantly inversely correlated in early (r=-0.164, p=0.018) and mid-pregnancy (-0.160, p=0.019), and AHEI-P from earlier gestational time-points correlated with later STRESS (early AHEI-P x mid STRESS: r=-0.168, p=0.017; mid AHEI-P x late STRESS: r=-0.142, p=0.041). In regression models, the interaction term was not associated with HOMA-IR or IL-6 at any gestational time-point. The stress-diet interaction term was significantly associated with TNF-α according to the following patterns: early AHEI-P*early STRESS vs early TNF-α (p=0.005); early AHEI-P*early STRESS vs mid TNF-α (p=0.002); early AHEI-P*mid STRESS vs mid TNF-α (p=0.005); mid AHEI-P*mid STRESS vs mid TNF-α (p=0.070); mid AHEI-P*late STRESS vs late TNF-α (p=0.011). Poor diet quality is significantly related to higher psychosocial stress levels in pregnant women across gestation, which may promote inflammation via TNF-α. Future prenatal studies should consider the combined effects of maternal stress and diet when evaluating either one of these factors on pregnancy or infant outcomes.

Keywords: diet quality, inflammation, insulin resistance, nutrition, pregnancy, stress, tumor necrosis factor-alpha

Procedia PDF Downloads 198

Authors: Keita Nishio, Takashi Kaburagi, Yosuke Kurihara

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Recent advances in medical technology have served to enhance average life expectancy. However, the total time for which the patients are prescribed complete bedrest has also increased. With patients being required to maintain a constant lying posture- also called bedsore- development of a system to detect patient roll-over becomes imperative. For this purpose, extant studies have proposed the use of cameras, and favorable results have been reported. Continuous on-camera monitoring, however, tends to violate patient privacy. We have proposed unconstrained bio-signal measurement system that could detect body-motion during sleep and does not violate patient’s privacy. Therefore, in this study, we propose a roll-over detection method by the date obtained from the bi-signal measurement system. Signals recorded by the sensor were assumed to comprise respiration, pulse, body motion, and noise components. Compared the body-motion and respiration, pulse component, the body-motion, during roll-over, generate large vibration. Thus, analysis of the body-motion component facilitates detection of the roll-over tendency. The large vibration associated with the roll-over motion has a great effect on the Root Mean Square (RMS) value of time series of the body motion component calculated during short 10 s segments. After calculation, the RMS value during each segment was compared to a threshold value set in advance. If RMS value in any segment exceeded the threshold, corresponding data were considered to indicate occurrence of a roll-over. In order to validate the proposed method, we conducted experiment. A bi-directional microphone was adopted as a high-sensitivity pressure sensor and was placed between the mattress and bedframe. Recorded signals passed through an analog Band-pass Filter (BPF) operating over the 0.16-16 Hz bandwidth. BPF allowed the respiration, pulse, and body-motion to pass whilst removing the noise component. Output from BPF was A/D converted with the sampling frequency 100Hz, and the measurement time was 480 seconds. The number of subjects and data corresponded to 5 and 10, respectively. Subjects laid on a mattress in the supine position. During data measurement, subjects—upon the investigator's instruction—were asked to roll over into four different positions—supine to left lateral, left lateral to prone, prone to right lateral, and right lateral to supine. Recorded data was divided into 48 segments with 10 s intervals, and the corresponding RMS value for each segment was calculated. The system was evaluated by the accuracy between the investigator’s instruction and the detected segment. As the result, an accuracy of 100% was achieved. While reviewing the time series of recorded data, segments indicating roll-over tendencies were observed to demonstrate a large amplitude. However, clear differences between decubitus and the roll-over motion could not be confirmed. Extant researches possessed a disadvantage in terms of patient privacy. The proposed study, however, demonstrates more precise detection of patient roll-over tendencies without violating their privacy. As a future prospect, decubitus estimation before and after roll-over could be attempted. Since in this paper, we could not confirm the clear differences between decubitus and the roll-over motion, future studies could be based on utilization of the respiration and pulse components.

Keywords: bedsore, high-sensitivity pressure sensor, roll-over, unconstrained bio-signal measurement

Procedia PDF Downloads 119

Authors: Federico Herrera, Valle Gomez García de Soria, Itxaso Portero Sainz, Carlos Fernández Arandojo, Mercedes Royg, Ana Marcos Jimenez, Anna Kreutzman, Cecilia MuñozCalleja

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Introduction: Graft-versus-host disease (GVHD) still remains the major complication associated with allogeneic stem cell transplantation (SCT). The pathogenesis involves migration of donor naïve T-cells into recipient secondary lymphoid organs. Two molecules are important in this process: CD62L and CCR7, which are characteristically expressed in naïve/central memory T-cells. With this background, we aimed to study the influence of CCR7 and CD62L on donor lymphocytes in the development and severity of GVHD. Material and methods: This single center study included 98 donor-recipient pairs. Samples were collected prospectively from the apheresis product and phenotyped by flow cytometry. CCR7 and CD62L expression in CD4+ and CD8+ T-cells were compared between patients who developed acute (n=40) or chronic GVHD (n=33) and those who did not (n=38). Results: The patients who developed acute GVHD were transplanted with a higher percentage of CCR7+CD4+ T-cells (p = 0.05) compared to the no GVHD group. These results were confirmed when these patients were divided in degrees according to the severity of the disease; the more severe disease, the higher percentage of CCR7+CD4+ T-cells. Conversely, chronic GVHD patients received a higher percentage of CCR7+CD8+ T-cells (p=0.02) in comparison to those who did not develop the complication. These data were also confirmed when patients were subdivided in degrees of the disease severity. A multivariable analysis confirmed that percentage of CCR7+CD4+ T-cells is a predictive factor of acute GVHD whereas the percentage of CCR7+CD8+ T-cells is a predictive factor of chronic GVHD. In vitro functional assays (migration and activation assays) supported the idea of CCR7+ T-cells were involved in the development of GVHD. As low levels of CD62L expression were detected in all apheresis products, we tested the hypothesis that CD62L was shed during apheresis procedure. Comparing CD62L surface levels in T-cells from the same donor immediately before collecting the apheresis product, and the final apheresis product we found that this process down-regulated CD62L in both CD4+ and CD8+ T cells (p=0.008). Interestingly, when CD62L levels were analysed in days 30 or 60 after engraftment, they recovered to baseline (p=0.008). However, to investigate the relation between CD62L expression and the development of GVHD in the recipient samples after the engraftment, no differences were observed comparing patients with GVHD to those who did not develop the disease. Discussion: Our prospective study indicates that the CCR7+ T-cells from the donor, which include naïve and central memory T-cells, contain the alloreactive cells with a high ability to mediate GVHD (in the case of both migration and activation). Therefore we suggest that the proportion and functional properties of CCR7+CD4+ and CCR7+CD8+ T-cells in the apheresis could act as a predictive biomarker to both acute and chronic GVHD respectively. Importantly, our study precludes that CD62L is lost in the apheresis and therefore it is not a reliable biomarker for the development of GVHD.

Keywords: CCR7, CD62L, GVHD, SCT

Procedia PDF Downloads 285

Authors: Ambali Alade Odebowale, Andargachew Mekonnen Berhe, Haroldo T. Hattori, Andrey E. Miroshnichenko

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Solar thermophotovoltaic systems (STPV) have emerged as a promising solution to overcome the Shockley-Queisser limit, a significant impediment in the direct conversion of solar radiation into electricity using conventional solar cells. The STPV system comprises essential components such as an optical concentrator, selective emitter, and a thermophotovoltaic (TPV) cell. The pivotal element in achieving high efficiency in an STPV system lies in the design of a spectrally selective emitter or absorber. Traditional methods for designing and optimizing selective emitters are often time-consuming and may not yield highly selective emitters, posing a challenge to the overall system performance. In recent years, the application of machine learning techniques in various scientific disciplines has demonstrated significant advantages. This paper proposes a novel nanostructure composed of four-layered materials (SiC/W/SiO2/W) to function as a selective emitter in the energy conversion process of an STPV system. Unlike conventional approaches widely adopted by researchers, this study employs a machine learning-based approach for the design and optimization of the selective emitter. Specifically, a random forest algorithm (RFA) is employed for the design of the selective emitter, while the optimization process is executed using genetic algorithms. This innovative methodology holds promise in addressing the challenges posed by traditional methods, offering a more efficient and streamlined approach to selective emitter design. The utilization of a machine learning approach brings several advantages to the design and optimization of a selective emitter within the STPV system. Machine learning algorithms, such as the random forest algorithm, have the capability to analyze complex datasets and identify intricate patterns that may not be apparent through traditional methods. This allows for a more comprehensive exploration of the design space, potentially leading to highly efficient emitter configurations. Moreover, the application of genetic algorithms in the optimization process enhances the adaptability and efficiency of the overall system. Genetic algorithms mimic the principles of natural selection, enabling the exploration of a diverse range of emitter configurations and facilitating the identification of optimal solutions. This not only accelerates the design and optimization process but also increases the likelihood of discovering configurations that exhibit superior performance compared to traditional methods. In conclusion, the integration of machine learning techniques in the design and optimization of a selective emitter for solar thermophotovoltaic systems represents a groundbreaking approach. This innovative methodology not only addresses the limitations of traditional methods but also holds the potential to significantly improve the overall performance of STPV systems, paving the way for enhanced solar energy conversion efficiency.

Keywords: emitter, genetic algorithm, radiation, random forest, thermophotovoltaic

Procedia PDF Downloads 59

Authors: Veenu Bala, Yashpal S. Chhonker, Bhavana Kushwaha, Rabi S. Bhatta, Gopal Gupta, Vishnu L. Sharma

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According to UNAIDS 2013 estimate nearly 52% of all individuals living with HIV are now women of reproductive age (15–44 years). Seventy-five percent cases of HIV acquisition are through heterosexual contacts and sexually transmitted infections (STIs), attributable to unsafe sexual behaviour. Each year, an estimated 500 million people acquire atleast one of four STIs: chlamydia, gonorrhoea, syphilis and trichomoniasis. Trichomonas vaginalis (TV) is exclusively sexually transmitted in adults, accounting for 30% of STI cases and associated with pelvic inflammatory disease (PID), vaginitis and pregnancy complications in women. TV infection resulted in impaired vaginal milieu, eventually favoring HIV transmission. In the absence of an effective prophylactic HIV vaccine, prevention of new infections has become a priority. It was thought worthwhile to integrate HIV prevention and reproductive health services including unintended pregnancy protection for women as both are related with unprotected sex. Initially, nonoxynol-9 (N-9) had been proposed as a spermicidal agent with microbicidal activity but on the contrary it increased HIV susceptibility due to surfactant action. Thus, to accomplish an urgent need of novel woman controlled non-detergent microbicidal spermicides benzenepropanamine analogues have been synthesized. At first, five benzenepropanamine-dithiocarbamate hybrids have been synthesized and evaluated for their spermicidal, anti-Trichomonas and anti-fungal activities along with safety profiling to cervicovaginal cells. In order to further enhance the scope of above study benzenepropanamine was hybridized with thiourea as to introduce anti-HIV potential. The synthesized hybrid molecules were evaluated for their reverse transcriptase (RT) inhibition, spermicidal, anti-Trichomonas and antimicrobial activities as well as their safety against vaginal flora and cervical cells. simulated vaginal fluid (SVF) stability and pharmacokinetics of most potent compound versus N-9 was examined in female Newzealand (NZ) rabbits to observe its absorption into systemic circulation and subsequent exposure in blood plasma through vaginal wall. The study resulted in the most promising compound N-butyl-4-(3-oxo-3-phenylpropyl) piperazin-1-carbothioamide (29) exhibiting better activity profile than N-9 as it showed RT inhibition (72.30 %), anti-Trichomonas (MIC, 46.72 µM against MTZ susceptible and MIC, 187.68 µM against resistant strain), spermicidal (MEC, 0.01%) and antifungal activity (MIC, 3.12–50 µg/mL) against four fungal strains. The high safety against vaginal epithelium (HeLa cells) and compatibility with vaginal flora (lactobacillus), SVF stability and least vaginal absorption supported its suitability for topical vaginal application. Docking study was performed to gain an insight into the binding mode and interactions of the most promising compound, N-butyl-4-(3-oxo-3-phenylpropyl) piperazin-1-carbothioamide (29) with HIV-1 Reverse Transcriptase. The docking study has revealed that compound (29) interacted with HIV-1 RT similar to standard drug Nevirapine. It may be concluded that hybridization of benzenepropanamine and thiourea moiety resulted into novel lead with multiple activities including RT inhibition. A further lead optimization may result into effective vaginal microbicides having spermicidal, anti-Trichomonas, antifungal and anti-HIV potential altogether with enhanced safety to cervico-vaginal cells in comparison to Nonoxynol-9.

Keywords: microbicidal, nonoxynol-9, reverse transcriptase, spermicide

Procedia PDF Downloads 343

Authors: Zofija Tupikovskaja-Omovie, David Tyler, Sam Dhanapala, Steve Hayes

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The UK is leading in online retail and mobile adoption. However, there is a dearth of information relating to mobile apparel retail, and developing an understanding about consumer browsing and purchase behavior in m-retail channel would provide apparel marketers, mobile website and app developers with the necessary understanding of consumers’ needs. Despite the rapid growth of mobile retail businesses, no published study has examined shopping behaviour on fashion mobile websites and apps. A mixed method approach helped to understand why fashion consumers prefer websites on mobile devices, when mobile apps are also available. The following research methods were employed: survey, eye-tracking experiments, observation, and interview with retrospective think aloud. The mobile gaze tracking device by SensoMotoric Instruments was used to understand frustrations in navigation and other issues facing consumers in mobile channel. This method helped to validate and compliment other traditional user-testing approaches in order to optimize user experience and enhance the development of mobile retail channel. The study involved eight participants - females aged 18 to 35 years old, who are existing mobile shoppers. The participants used the Topshop mobile app and website on a smart phone to complete a task according to a specified scenario leading to a purchase. The comparative study was based on: duration and time spent at different stages of the shopping journey, number of steps involved and product pages visited, search approaches used, layout and visual clues, as well as consumer perceptions and expectations. The results from the data analysis show significant differences in consumer behaviour when using a mobile app or website on a smart phone. Moreover, two types of problems were identified, namely technical issues and human errors. Having a mobile app does not guarantee success in satisfying mobile fashion consumers. The differences in the layout and visual clues seem to influence the overall shopping experience on a smart phone. The layout of search results on the website was different from the mobile app. Therefore, participants, in most cases, behaved differently on different platforms. The number of product pages visited on the mobile app was triple the number visited on the website due to a limited visibility of products in the search results. Although, the data on traffic trends held by retailers to date, including retail sector breakdowns for visits and views, data on device splits and duration, might seem a valuable source of information, it cannot explain why consumers visit many product pages, stay longer on the website or mobile app, or abandon the basket. A comprehensive list of pros and cons was developed by highlighting issues for website and mobile app, and recommendations provided. The findings suggest that fashion retailers need to be aware of actual consumers’ behaviour on the mobile channel and their expectations in order to offer a seamless shopping experience. Added to which is the challenge of retaining existing and acquiring new customers. There seem to be differences in the way fashion consumers search and shop on mobile, which need to be explored in further studies.

Keywords: consumer behavior, eye-tracking technology, fashion retail, mobile app, m-retail, smart phones, topshop, user experience, website

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Authors: Antònio Inês, Davide Silva, Filipa Carvalho, Luís Filipe-Riberiro, Fernando M. Nunes, Luís Abrunhosa, Fernanda Cosme

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The presence of mycotoxins in foodstuff is a matter of concern for food safety. Mycotoxins are toxic secondary metabolites produced by certain molds, being ochratoxin A (OTA) one of the most relevant. Wines can also be contaminated with these toxicants. Several authors have demonstrated the presence of mycotoxins in wine, especially ochratoxin A. Its chemical structure is a dihydro-isocoumarin connected at the 7-carboxy group to a molecule of L-β-phenylalanine via an amide bond. As these toxicants can never be completely removed from the food chain, many countries have defined levels in food in order to attend health concerns. OTA contamination of wines might be a risk to consumer health, thus requiring treatments to achieve acceptable standards for human consumption. The maximum acceptable level of OTA in wines is 2.0 μg/kg according to the Commission regulation No. 1881/2006. Therefore, the aim of this work was to reduce OTA to safer levels using different fining agents, as well as their impact on white wine physicochemical characteristics. To evaluate their efficiency, 11 commercial fining agents (mineral, synthetic, animal and vegetable proteins) were used to get new approaches on OTA removal from white wine. Trials (including a control without addition of a fining agent) were performed in white wine artificially supplemented with OTA (10 µg/L). OTA analyses were performed after wine fining. Wine was centrifuged at 4000 rpm for 10 min and 1 mL of the supernatant was collected and added of an equal volume of acetonitrile/methanol/acetic acid (78:20:2 v/v/v). Also, the solid fractions obtained after fining, were centrifuged (4000 rpm, 15 min), the resulting supernatant discarded, and the pellet extracted with 1 mL of the above solution and 1 mL of H2O. OTA analysis was performed by HPLC with fluorescence detection. The most effective fining agent in removing OTA (80%) from white wine was a commercial formulation that contains gelatin, bentonite and activated carbon. Removals between 10-30% were obtained with potassium caseinate, yeast cell walls and pea protein. With bentonites, carboxymethylcellulose, polyvinylpolypyrrolidone and chitosan no considerable OTA removal was verified. Following, the effectiveness of seven commercial activated carbons was also evaluated and compared with the commercial formulation that contains gelatin, bentonite and activated carbon. The different activated carbons were applied at the concentration recommended by the manufacturer in order to evaluate their efficiency in reducing OTA levels. Trial and OTA analysis were performed as explained previously. The results showed that in white wine all activated carbons except one reduced 100% of OTA. The commercial formulation that contains gelatin, bentonite and activated carbon reduced only 73% of OTA concentration. These results may provide useful information for winemakers, namely for the selection of the most appropriate oenological product for OTA removal, reducing wine toxicity and simultaneously enhancing food safety and wine quality.

Keywords: wine, ota removal, food safety, fining

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Authors: M. Nerantzaki, I. Koliakou, D. Bikiaris

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This study evaluates the hypothesis that the incorporation of fibrous hydroxyapatite nanoparticles (nHA) with high crystallinity and high aspect ratio, synthesized by hydrothermal method, into Poly(butylene succinate) (PBSu), improves the bioactivity of the aliphatic polyester and affects new bone growth inhibiting resorption and enhancing bone formation. Hydroxyapatite nanorods were synthesized using a simple hydrothermal procedure. First, the HPO42- -containing solution was added drop-wise into the Ca2+-containing solution, while the molar ratio of Ca/P was adjusted at 1.67. The HA precursor was then treated hydrothermally at 200°C for 72 h. The resulting powder was characterized using XRD, FT-IR, TEM, and EDXA. Afterwards, PBSu nanocomposites containing 2.5wt% (nHA) were prepared by in situ polymerization technique for the first time and were examined as potential scaffolds for bone engineering applications. For comparison purposes composites containing either 2.5wt% micro-Bioglass (mBG) or 2.5wt% mBG-nHA were prepared and studied, too. The composite scaffolds were characterized using SEM, FTIR, and XRD. Mechanical testing (Instron 3344) and Contact Angle measurements were also carried out. Enzymatic degradation was studied in an aqueous solution containing a mixture of R. Oryzae and P. Cepacia lipases at 37°C and pH=7.2. In vitro biomineralization test was performed by immersing all samples in simulated body fluid (SBF) for 21 days. Biocompatibility was assessed using rat Adipose Stem Cells (rASCs), genetically modified by nucleofection with DNA encoding SB100x transposase and pT2-Venus-neo transposon expression plasmids in order to attain fluorescence images. Cell proliferation and viability of cells on the scaffolds were evaluated using fluoresce microscopy and MTT (3-(4,5-dimethylthiazol-2-yl)-2,5 diphenyltetrazolium bromide) assay. Finally, osteogenic differentiation was assessed by staining rASCs with alizarine red using cetylpyridinium chloride (CPC) method. TEM image of the fibrous HAp nanoparticles, synthesized in the present study clearly showed the fibrous morphology of the synthesized powder. The addition of nHA decreased significantly the contact angle of the samples, indicating that the materials become more hydrophilic and hence they absorb more water and subsequently degrade more rapidly. In vitro biomineralization test confirmed that all samples were bioactive as mineral deposits were detected by X-ray diffractometry after incubation in SBF. Metabolic activity of rASCs on all PBSu composites was high and increased from day 1 of culture to day 14. On day 28 metabolic activity of rASCs cultured on samples enriched with bioceramics was significantly decreased due to possible differentiation of rASCs to osteoblasts. Staining rASCs with alizarin red after 28 days in culture confirmed our initial hypothesis as the presence of calcium was detected, suggesting osteogenic differentiation of rACS on PBSu/nHAp/mBG 2.5% and PBSu/mBG 2.5% composite scaffolds.

Keywords: biomaterials, hydroxyapatite nanorods, poly(butylene succinate), scaffolds

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Authors: Hossein Aghababaei, Sergio Vitale, Giampaolo ferraioli

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In the context of Synthetic Aperture Radar (SAR) data, polarization is an important source of information for Earth's surface monitoring . SAR Systems are often considered to transmit only one polarization. This constraint leads to either single or dual polarimetric SAR imaging modalities. Single polarimetric systems operate with a fixed single polarization of both transmitted and received electromagnetic (EM) waves, resulting in a single acquisition channel. Dual polarimetric systems, on the other hand, transmit in one fixed polarization and receive in two orthogonal polarizations, resulting in two acquisition channels. Dual polarimetric systems are obviously more informative than single polarimetric systems and are increasingly being used for a variety of remote sensing applications. In dual polarimetric systems, the choice of polarizations for the transmitter and the receiver is open. The choice of circular transmit polarization and coherent dual linear receive polarizations forms a special dual polarimetric system called hybrid polarimetry, which brings the properties of rotational invariance to geometrical orientations of features in the scene and optimizes the design of the radar in terms of reliability, mass, and power constraints. The complete characterization of target scattering, however, requires fully polarimetric data, which can be acquired with systems that transmit two orthogonal polarizations. This adds further complexity to data acquisition and shortens the coverage area or swath of fully polarimetric images compared to the swath of dual or hybrid polarimetric images. The search for solutions to augment dual polarimetric data to full polarimetric data will therefore take advantage of full characterization and exploitation of the backscattered field over a wider coverage with less system complexity. Several methods for reconstructing fully polarimetric images using hybrid polarimetric data can be found in the literature. Although the improvements achieved by the newly investigated and experimented reconstruction techniques are undeniable, the existing methods are, however, mostly based upon model assumptions (especially the assumption of reflectance symmetry), which may limit their reliability and applicability to vegetation and forest scenarios. To overcome the problems of these techniques, this paper proposes a new framework for reconstructing fully polarimetric information from hybrid polarimetric data. The framework uses Deep Learning solutions to augment hybrid polarimetric data without relying on model assumptions. A convolutional neural network (CNN) with a specific architecture and loss function is defined for this augmentation problem by focusing on different scattering properties of the polarimetric data. In particular, the method controls the CNN training process with respect to several characteristic features of polarimetric images defined by the combination of different terms in the cost or loss function. The proposed method is experimentally validated with real data sets and compared with a well-known and standard approach from the literature. From the experiments, the reconstruction performance of the proposed framework is superior to conventional reconstruction methods. The pseudo fully polarimetric data reconstructed by the proposed method also agree well with the actual fully polarimetric images acquired by radar systems, confirming the reliability and efficiency of the proposed method.

Keywords: SAR image, deep learning, convolutional neural network, deep neural network, SAR polarimetry

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Authors: Pedro Felgueiras, Ana Miguel, Nélson Almeida, Raquel Silva

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Objective: Through the study of a clinical case of delusional somatic disorder secondary to phantogeusia, we aim to highlight the importance of considering psychosomatic conditions in differential diagnosis, as well as to emphasize the complexity of its comprehension, treatment, and respective impact on patients’ functioning. Methods: Bearing this in mind, we conducted a critical analysis of a case series based on patient observations, clinical data, and complementary diagnostic methods, as well as a non-systematic review of the literature on the subject. Results: A 61-year-old female patient with no history of psychiatric conditions. Family psychiatric history of mood disorder (depression), with psychotic features found in her mother. Medical history of many comorbidities affecting different organ systems (endocrine, gastrointestinal, genitourinary, ophthalmological). Documented neuroticism traits of personality. The patient’s family described a persistent concern about several physical symptoms across her life, with a continuous effort to obtain explanations about any sensation out of her normal perception. Since being subjected to endoscopy in 2018, she started complaints of persistent phantogeusia (acid taste) and developed excessive thoughts, feelings, and behaviors associated with this somatic symptom. The patient was evaluated by several medical specialties, and an extensive panel of medical exams was carried out, excluding any disease. Besides all the investigation and with no evidence of disease signs, acute anxiety, time, and energy dispended to this symptom culminated in severe psychosocial impairment. The patient was admitted to a psychiatric ward for investigation and treatment of this clinical picture, leading to the diagnosis of the delusional somatic disorder. In order to exclude the acute organic etiology of this psychotic disorder, an analytic panel was carried out with no abnormal results. In the context of a psychotic clinical picture, a CT scan was performed, which revealed a right cortical vascular lesion. Neuropsychological evaluation was made, with the description of cognitive functioning being globally normative. During treatment with an antipsychotic (pimozide), a complete remission of the somatic delusion was associated with the disappearance of gustative perception disturbance. In follow-up, a relapse of gustative sensation was documented, and her thoughts and speech were dominated by concerns about multiple somatic symptoms. Conclusion: In terms of abnormal bodily sensations, the oral cavity is one of the frequent sites of delusional disorder. Patients with these gustatory perception distortions complain about unusual sensations without corresponding abnormal findings in the oral area. Its pathophysiology has not been fully elucidated yet. In terms of its comprehensive psychopathology, this case was hypothesized as a paranoid development of a delusional somatic disorder triggered by a post-invasive procedure phantogeusia (which is described as a possible side effect of an endoscopy) in a patient with an anankastic personality. This case presents interesting psychopathology, reinforcing the complexity of psychosomatic disorders in terms of their etiopathogenesis, clinical treatment, and long-term prognosis.

Keywords: psychosomatics, delusional somatic disorder, phantogeusia, paranoid development

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Authors: Dechao Meng, Yongqi Dong, Qiyuan Feng, Zhangzhang Cui, Xiang Hu, Haoliang Huang, Genhao Liang, Huanhua Wang, Hua Zhou, Hawoong Hong, Jinghua Guo, Qingyou Lu, Xiaofang Zhai, Yalin Lu

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Great efforts have been taken to reveal the intrinsic origins of emerging ferromagnetism (FM) in strained LaCoO₃ (LCO) films. However, some macro magnetic performances of LCO are still not well understood and even controversial, such as magnetic anisotropy. Determining and understanding magnetic anisotropy might help to find the true causes of FM in turn. Perpendicular magnetic anisotropy (PMA) was the first time to be directly observed in high-quality LCO films with different thickness. The in-plane (IP) and out of plane (OOP) remnant magnetic moment ratio of 30 unit cell (u.c.) films is as large as 20. The easy axis lays in the OOP direction with an IP/OOP coercive field ratio of 10. What's more, the PMA could be simply tuned by changing the thickness. With the thickness increases, the IP/OOP magnetic moment ratio remarkably decrease with magnetic easy axis changing from OOP to IP. Such a huge and tunable PMA performance exhibit strong potentials in fundamental researches or applications. What causes PMA is the first concern. More OOP orbitals occupation may be one of the micro reasons of PMA. A cluster-like magnetic domain pattern was found in 30 u.c. with no obvious color contrasts, similar to that of LaAlO₃/SrTiO₃ films. And the nanosize domains could not be totally switched even at a large OOP magnetic field of 23 T. It indicates strong IP characters or none OOP magnetism of some clusters. The IP magnetic domains might influence the magnetic performance and help to form PMA. Meanwhile some possible nonmagnetic clusters might be the reason why the measured moments of LCO films are smaller than the calculated values 2 μB/Co, one of the biggest confusions in LCO films.What tunes PMA seems much more interesting. Totally different magnetic domain patterns were found in 180 u.c. films with cluster magnetic domains surrounded by < 110 > cross-hatch lines. These lines were regarded as structure domain walls (DWs) determined by 3D reciprocal space mapping (RSM). Two groups of in-plane features with fourfold symmetry were observed near the film diffraction peaks in (002) 3D-RSM. One is along < 110 > directions with a larger intensity, which is well match the lines on the surfaces. The other is much weaker and along < 100 > directions, which is from the normal lattice titling of films deposited on cubic substrates. The < 110 > domain features obtained from (103) and (113) 3D-RSMs exhibit similar evolution of the DWs percentages and magnetic behavior. Structure domains and domain walls are believed to tune PMA performances by transform more IP magnetic moments to OOP. Last but not the least, thick films with lots of structure domains exhibit different electrical transport behaviors. A metal-to-insulator transition (MIT) and an angular dependent negative magnetic resistivity were observed near 150 K, higher than FM transition temperature but similar to that of spin-orbital coupling related 1/4 order diffraction peaks.

Keywords: structure domain, magnetic anisotropy, magnetic domain, domain wall, 3D-RSM, strain

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Authors: Guillaume Bélanger, Jean-Philippe Fontaine, Clémence Hauduc

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There is an undeniable thirst from organic chemists and from the pharmaceutical industry to access complex alkaloids with short syntheses. While medicinal chemists are interested in the fascinating wide range of biological properties of alkaloids, synthetic chemists are rather interested in finding new routes to access these challenging natural products of often low availability from nature. To synthesize complex polycyclic cores of natural products, reaction cascades or sequences performed one-pot offer a neat advantage over classical methods for their rapid increase in molecular complexity in a single operation. In counterpart, reaction cascades need to be run on substrates bearing all the required functional groups necessary for the key cyclizations. Chemoselectivity is thus a major issue associated with such a strategy, in addition to diastereocontrol and regiocontrol for the overall transformation. In the pursuit of synthetic efficiency, our research group developed an innovative one-pot transformation of linear substrates into bi- and tricyclic adducts applied to the construction of Aspidospermatan-type alkaloids. The latter is a rich class of indole alkaloids bearing a unique bridged azatricyclic core. Despite many efforts toward the synthesis of members of this family, efficient and versatile synthetic routes are still coveted. Indeed, very short, non-racemic approaches are rather scarce: for example, in the cases of aspidospermidine and aspidospermine, syntheses are all fifteen steps and over. We envisaged a unified approach to access several members of the Aspidospermatan alkaloids family. The key sequence features a highly chemoselective formamide activation that triggers a Vilsmeier-Haack cyclization, followed by an azomethine ylide generation and intramolecular cycloaddition. Despite the high density and variety of functional groups on the substrates (electron-rich and electron-poor alkenes, nitrile, amide, ester, enol ether), the sequence generated three new carbon-carbon bonds and three rings in a single operation with good yield and high chemoselectivity. A detailed study of amide, nucleophile, and dipolarophile variations to finally get to the successful combination required for the key transformation will be presented. To complete the indoline fragment of the natural products, we developed an original approach. Indeed, all reported routes to Aspidospermatan alkaloids introduce the indoline or indole early in the synthesis. In our work, the indoline needs to be installed on the azatricyclic core after the key cyclization sequence. As a result, typical Fischer indolization is not suited since this reaction is known to fail on such substrates. We thus envisaged a unique photocatalyzed decarboxylative radical cyclization. The development of this reaction as well as the scope and limitations of the methodology, will also be presented. The original Vilsmeier-Haack and azomethine ylide cyclization sequence as well as the new photocatalyzed decarboxylative radical cyclization will undoubtedly open access to new routes toward polycyclic indole alkaloids and derivatives of pharmaceutical interest in general.

Keywords: Aspidospermatan alkaloids, azomethine ylide cycloaddition, decarboxylative radical cyclization, indole and indoline synthesis, one-pot sequential cyclizations, photocatalysis, Vilsmeier-Haack Cyclization

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