Search results for: motion parameter

Authors: Tamar Grdzelishvili, Zaza Sinauridze

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Introduction: Preeclampsia is a complication of the second trimester of pregnancy, which is characterized by high morbidity and multiorgan damage. Many complex pathogenic mechanisms are now implicated to be responsible for this disease (1). Preeclampsia is one of the leading causes of maternal mortality worldwide. Statistics are enough to convince you of the seriousness of this pathology: about 100,000 women die of preeclampsia every year. It occurs in 3-14% (varies significantly depending on racial origin or ethnicity and geographical region) of pregnant women, in 75% of cases - in a mild form, and in 25% - in a severe form. During severe pre-eclampsia-eclampsia, perinatal mortality increases by 5 times and stillbirth by 9.6 times. Considering that the only way to treat the disease is to end the pregnancy, the main thing is timely diagnosis and prevention of the disease. Identification of high-risk pregnant women for PE and giving prophylaxis would reduce the incidence of preterm PE. First-trimester screening model developed by the Fetal Medicine Foundation (FMF), which uses the Bayes-theorem to combine maternal characteristics and medical history together with measurements of mean arterial pressure, uterine artery pulsatility index, and serum placental growth factor, has been proven to be effective and have superior screening performance to that of traditional risk factor-based approach for the prediction of PE (2) Methods: Retrospective single center screening study. The study population consisted of women from the Tbilisi maternity hospital “Pineo medical ecosystem” who met the following criteria: they spoke Georgian, English, or Russian and agreed to participate in the study after discussing informed consent and answering questions. Prior to the study, the informed consent forms approved by the Institutional Review Board were obtained from the study subjects. Early assessment of preeclampsia was performed between 11-13 weeks of pregnancy. The following were evaluated: anamnesis, dopplerography of the uterine artery, mean arterial blood pressure, and biochemical parameter: Pregnancy-associated plasma protein A (PAPP-A). Individual risk assessment was performed with performed by Fast Screen 3.0 software ThermoFisher scientific. Results: A total of 513 women were recruited and through the study, 51 women were diagnosed with preeclampsia (34.5% in the pregnant women with high risk, 6.5% in the pregnant women with low risk; P<0.000 1). Conclusions: First-trimester screening combining maternal factors with uterine artery Doppler, blood pressure, and pregnancy-associated plasma protein-A is useful to predict PE in a routine care setting. More patient studies are needed for final conclusions. The research is still ongoing.

Keywords: first-trimester, preeclampsia, screening, pregnancy-associated plasma protein

Procedia PDF Downloads 51

Authors: Milada Krejci, Martin Hill, Vaclav Hosek, Dobroslava Jandova, Jiri Kajzar, Pavel Blaha

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The paper declares effects of exercise intervention of the research project “Basic research of balance changes in seniors”, granted by the Czech Science Foundation. The objective of the presented study is to define predictors, which influence bio-psycho-social consequences and effects of balance ability in senior 65 years old and above. We focused on the Fall-Efficacy Scale changes evaluation in seniors. Comprehensive hypothesis of the project declares, that motion uncertainty (dyskinesia) can negatively affect the well-being of a senior in bio-psycho-social context. In total, random selection and testing of 100 seniors (30 males, 70 females) from Prague and Central Bohemian region was provided. The sample was divided by stratified random selection into experimental and control groups, who underwent input and output testing. For diagnostics the methods of Medical Anamnesis, Functional anthropological examinations, Tinetti Balance Assessment Tool, SF-36 Health Survey, Anamnestic comparative self-assessment scale were used. Intervention method called "Life in Balance" based on yoga techniques was applied in four-week cycle. Results of multivariate regression were verified by repeated measures ANOVA: subject factor, phase of intervention (between-subject factor), body fluid (within-subject factor) and phase of intervention × body fluid interaction). ANOVA was performed with a repetition involving the factors of subjects, experimental/control group, phase of intervention (independent variable), and x phase interaction followed by Bonferroni multiple comparison assays with a test strength of at least 0.8 on the probability level p < 0.05. In the paper results of the first-year investigation of the three years running project are analysed. Results of balance tests confirmed no significant difference between females and males in pre-test. Significant improvements in balance and walking ability were observed in experimental group in females comparing to males (F = 128.4, p < 0.001). In the females control group, there was no significant change in post- test, while in the female experimental group positive changes in posture and spine flexibility in post-tests were found. It seems that females even in senior age react better to incentives of intervention in balance and spine flexibility. On the base of results analyses, we can declare the significant improvement in social balance markers after intervention in the experimental group (F = 10.5, p < 0.001). In average, seniors are used to take four drugs daily. Number of drugs can contribute to allergy symptoms and balance problems. It can be concluded that static balance and walking ability of seniors according Tinetti Balance scale correlate significantly with psychic and social monitored markers.

Keywords: exercises, balance, seniors 65+, health, mental and social balance

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Authors: Thomas Larm, Anna Wahlsten

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An international literature study has been carried out for comparison of commonly used methods for the dimensioning of transport systems and stormwater facilities for flow detention. The focus of the literature study regarding the calculation of design flow and detention has been the widely used Rational method and its underlying parameters. The impact of chosen design parameters such as return time, rain intensity, runoff coefficient, and climate factor have been studied. The parameters used in the calculations have been analyzed regarding how they can be calculated and within what limits they can be used. Data used within different countries have been specified, e.g., recommended rainfall return times, estimated runoff times, and climate factors used for different cases and time periods. The literature study concluded that the determination of runoff coefficients is the most uncertain parameter that also affects the calculated flow and required detention volume the most. Proposals have been developed for new runoff coefficients, including a new proposed method with equations for calculating runoff coefficients as a function of return time (years) and rain intensity (l/s/ha), respectively. Suggestions have been made that it is recommended not to limit the use of the Rational Method to a specific catchment size, contrary to what many design manuals recommend, with references to this. The proposed relationships between return time or rain intensity and runoff coefficients need further investigation and to include the quantification of uncertainties. Examples of parameters that have not been considered are the influence on the runoff coefficients of different dimensioning rain durations and the degree of water saturation of green areas, which will be investigated further. The influence of climate effects and design rain on the dimensioning of the stormwater facilities grassed ditches and biofilters (bio retention systems) has been studied, focusing on flow detention capacity. We have investigated how the calculated runoff coefficients regarding climate effect and the influence of changed (increased) return time affect the inflow to and dimensioning of the stormwater facilities. We have developed a smart design of ditches and biofilters that results in both high treatment and flow detention effects and compared these with the effect from dry and wet ponds. Studies of biofilters have generally before focused on treatment of pollutants, but their effect on flow volume and how its flow detention capability can improve is only rarely studied. For both the new type of stormwater ditches and biofilters, it is required to be able to simulate their performance in a model under larger design rains and future climate, as these conditions cannot be tested in the field. The stormwater model StormTac Web has been used on case studies. The results showed that the new smart design of ditches and biofilters had similar flow detention capacity as dry and wet ponds for the same facility area.

Keywords: runoff coefficients, flow detention, smart design, biofilter, ditch

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Authors: Michael Kenomore, Mohamed Hassan, Amjad Shah, Hom Dhakal

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Shale gas reservoirs have been of greater importance compared to shale oil reservoirs since 2009 and with the current nature of the oil market, understanding the technical and economic performance of shale gas reservoirs is of importance. Using the Barnett shale as a case study, an economic model was developed to quantify the effect of finding and development costs and gas prices on the basins in the Barnett shale using net present value as an evaluation parameter. A rate of return of 20% and a payback period of 60 months or less was used as the investment hurdle in the model. The Barnett was split into four basins (Strawn Basin, Ouachita Folded Belt, Forth-worth Syncline and Bend-arch Basin) with analysis conducted on each of the basin to provide a holistic outlook. The dataset consisted of only horizontal wells that started production from 2008 to at most 2015 with 1835 wells coming from the strawn basin, 137 wells from the Ouachita folded belt, 55 wells from the bend-arch basin and 724 wells from the forth-worth syncline. The data was analyzed initially on Microsoft Excel to determine the estimated ultimate recoverable (EUR). The range of EUR from each basin were loaded in the Palisade Risk software and a log normal distribution typical of Barnett shale wells was fitted to the dataset. Monte Carlo simulation was then carried out over a 1000 iterations to obtain a cumulative distribution plot showing the probabilistic distribution of EUR for each basin. From the cumulative distribution plot, the P10, P50 and P90 EUR values for each basin were used in the economic model. Gas production from an individual well with a EUR similar to the calculated EUR was chosen and rescaled to fit the calculated EUR values for each basin at the respective percentiles i.e. P10, P50 and P90. The rescaled production was entered into the economic model to determine the effect of the finding and development cost and gas price on the net present value (10% discount rate/year) as well as also determine the scenario that satisfied the proposed investment hurdle. The finding and development costs used in this paper (assumed to consist only of the drilling and completion costs) were £1 million, £2 million and £4 million while the gas price was varied from $2/MCF-$13/MCF based on Henry Hub spot prices from 2008-2015. One of the major findings in this study was that wells in the bend-arch basin were least economic, higher gas prices are needed in basins containing non-core counties and 90% of the Barnet shale wells were not economic at all finding and development costs irrespective of the gas price in all the basins. This study helps to determine the percentage of wells that are economic at different range of costs and gas prices, determine the basins that are most economic and the wells that satisfy the investment hurdle.

Keywords: shale gas, Barnett shale, unconventional gas, estimated ultimate recoverable

Procedia PDF Downloads 277

Authors: Diane Ghanem, Arjun Gupta, Rohan Vijayan, Ali Uneri, Babar Shafiq

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Introduction: Ankle sprains and fractures often result in syndesmosis injuries. Unstable syndesmotic injuries result from relative motion between the distal ends of the tibia and fibula, anatomic juncture which should otherwise be rigid, and warrant operative management. Clinical and radiological evaluations of intraoperative syndesmosis stability remain a challenging task as traditional 2D fluoroscopy is limited to a uniplanar translational displacement. The purpose of this pilot cadaveric study is to compare the 2D fluoroscopy and 3D cone beam computed tomography (CBCT) stress-induced syndesmosis displacements. Methods: Three fresh-frozen lower legs underwent 2D fluoroscopy and 3D CIOS CBCT to measure syndesmosis position before dissection. Syndesmotic injury was simulated by resecting the (1) anterior inferior tibiofibular ligament (AITFL), the (2) posterior inferior tibiofibular ligament (PITFL) and the inferior transverse ligament (ITL) simultaneously, followed by the (3) interosseous membrane (IOM). Manual external rotation and Cotton stress test were performed after each of the three resections and 2D and 3D images were acquired. Relevant 2D and 3D parameters included the tibiofibular overlap (TFO), tibiofibular clear space (TCS), relative rotation of the fibula, and anterior-posterior (AP) and medial-lateral (ML) translations of the fibula relative to the tibia. Parameters were measured by two independent observers. Inter-rater reliability was assessed by intraclass correlation coefficient (ICC) to determine measurement precision. Results: Significant mismatches were found in the trends between the 2D and 3D measurements when assessing for TFO, TCS and AP translation across the different resection states. Using 3D CBCT, TFO was inversely proportional to the number of resected ligaments while TCS was directly proportional to the latter across all cadavers and ‘resection + stress’ states. Using 2D fluoroscopy, this trend was not respected under the Cotton stress test. 3D AP translation did not show a reliable trend whereas 2D AP translation of the fibula was positive under the Cotton stress test and negative under the external rotation. 3D relative rotation of the fibula, assessed using the Tang et al. ratio method and Beisemann et al. angular method, suggested slight overall internal rotation with complete resection of the ligaments, with a change < 2mm - threshold which corresponds to the commonly used buffer to account for physiologic laxity as per clinical judgment of the surgeon. Excellent agreement (>0.90) was found between the two independent observers for each of the parameters in both 2D and 3D (overall ICC 0.9968, 95% CI 0.995 - 0.999). Conclusions: The 3D CIOS CBCT appears to reliably depict the trend in TFO and TCS. This might be due to the additional detection of relevant rotational malpositions of the fibula in comparison to the standard 2D fluoroscopy which is limited to a single plane translation. A better understanding of 3D imaging may help surgeons identify the precise measurements planes needed to achieve better syndesmosis repair.

Keywords: 2D fluoroscopy, 3D computed tomography, image processing, syndesmosis injury

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Authors: Gamaliel Salazar, Adriana Chazaro, Oscar Madrigal

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The evolution of Unmanned Aerial Systems (UAS) has made it possible to develop new vehicles capable to perform microgravity experiments which due its cost and complexity were beyond the reach for many institutions. In this study, the aerodynamic behavior of an UAS is studied through its deceleration stage after an initial free fall phase (where the microgravity effect is generated) using Computational Fluid Dynamics (CFD). Due to the fact that the payload would be analyzed under a microgravity environment and the nature of the payload itself, the speed of the UAS must be reduced in a smoothly way. Moreover, the terminal speed of the vehicle should be low enough to preserve the integrity of the payload and vehicle during the landing stage. The UAS model is made by a study pod, control surfaces with fixed and mobile sections, landing gear and two semicircular wing sections. The speed of the vehicle is decreased by increasing the angle of attack (AoA) of each wing section from 2° (where the airfoil S1091 has its greatest aerodynamic efficiency) to 80°, creating a circular wing geometry. Drag coefficients (Cd) and forces (Fd) are obtained employing CFD analysis. A simplified 3D model of the vehicle is analyzed using Ansys Workbench 16. The distance between the object of study and the walls of the control volume is eight times the length of the vehicle. The domain is discretized using an unstructured mesh based on tetrahedral elements. The refinement of the mesh is made by defining an element size of 0.004 m in the wing and control surfaces in order to figure out the fluid behavior in the most important zones, as well as accurate approximations of the Cd. The turbulent model k-epsilon is selected to solve the governing equations of the fluids while a couple of monitors are placed in both wing and all-body vehicle to visualize the variation of the coefficients along the simulation process. Employing a statistical approximation response surface methodology the case of study is parametrized considering the AoA of the wing as the input parameter and Cd and Fd as output parameters. Based on a Central Composite Design (CCD), the Design Points (DP) are generated so the Cd and Fd for each DP could be estimated. Applying a 2nd degree polynomial approximation the drag coefficients for every AoA were determined. Using this values, the terminal speed at each position is calculated considering a specific Cd. Additionally, the distance required to reach the terminal velocity at each AoA is calculated, so the minimum distance for the entire deceleration stage without comprising the payload could be determine. The Cd max of the vehicle is 1.18, so its maximum drag will be almost like the drag generated by a parachute. This guarantees that aerodynamically the vehicle can be braked, so it could be utilized for several missions allowing repeatability of microgravity experiments.

Keywords: microgravity effect, response surface, terminal speed, unmanned system

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Authors: Dyah Purwaningsih, Roto Roto, Hari Sutrisno

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Manganese dioxide (MnO₂) and its derivatives are among the most widely used materials for the positive electrode in both primary and rechargeable lithium batteries. The MnO₂ derivative compound of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) is one of the leading candidates for positive electrode materials in lithium batteries as it is abundant, low cost and environmentally friendly. Over the years, synthesis of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) has been carried out using various methods including sol-gel, gas condensation, spray pyrolysis, and ceramics. Problems with these various methods persist including high cost (so commercially inapplicable) and must be done at high temperature (environmentally unfriendly). This research aims to: (1) synthesize LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) by reflux technique; (2) develop microstructure analysis method from XRD Powder LiMₓMn₂₋ₓO₄ data with the two-stage method; (3) study the electrical conductivity of LiMₓMn₂₋ₓO₄. This research developed the synthesis of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) with reflux. The materials consisting of Mn(CH₃COOH)₂. 4H₂O and Na₂S₂O₈ were refluxed for 10 hours at 120°C to form β-MnO₂. The doping of Co, Ni and Cr were carried out using solid-state method with LiOH to form LiMₓMn₂₋ₓO₄. The instruments used included XRD, SEM-EDX, XPS, TEM, SAA, TG/DTA, FTIR, LCR meter and eight-channel battery analyzer. Microstructure analysis of LiMₓMn₂₋ₓO₄ was carried out on XRD powder data by two-stage method using FullProf program integrated into WinPlotR and Oscail Program as well as on binding energy data from XPS. The morphology of LiMₓMn₂₋ₓO₄ was studied with SEM-EDX, TEM, and SAA. The thermal stability test was performed with TG/DTA, the electrical conductivity was studied from the LCR meter data. The specific capacity of LiMₓMn₂₋ₓO₄ as lithium battery cathode was tested using an eight-channel battery analyzer. The results showed that the synthesis of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) was successfully carried out by reflux. The optimal temperature of calcination is 750°C. XRD characterization shows that LiMn₂O₄ has a cubic crystal structure with Fd3m space group. By using the CheckCell in the WinPlotr, the increase of Li/Mn mole ratio does not result in changes in the LiMn₂O₄ crystal structure. The doping of Co, Ni and Cr on LiMₓMn₂₋ₓO₄ (x = 0.02; 0.04; 0; 0.6; 0.08; 0.10) does not change the cubic crystal structure of Fd3m. All the formed crystals are polycrystals with the size of 100-450 nm. Characterization of LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) microstructure by two-stage method shows the shrinkage of lattice parameter and cell volume. Based on its range of capacitance, the conductivity obtained at LiMₓMn₂₋ₓO₄ (M: Co, Ni, Cr) is an ionic conductivity with varying capacitance. The specific battery capacity at a voltage of 4799.7 mV for LiMn₂O₄; Li₁.₀₈Mn₁.₉₂O₄; LiCo₀.₁Mn₁.₉O₄; LiNi₀.₁Mn₁.₉O₄ and LiCr₀.₁Mn₁.₉O₄ are 88.62 mAh/g; 2.73 mAh/g; 89.39 mAh/g; 85.15 mAh/g; and 1.48 mAh/g respectively.

Keywords: LiMₓMn₂₋ₓO₄, solid-state, reflux, two-stage method, ionic conductivity, specific capacity

Procedia PDF Downloads 161

Authors: Rajinder Kumar Gupta, Rajni Kant Agrawal, Jaganniwas

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One of the most frightening phenomena of nature is the occurrence of earthquake as it has terrible and disastrous effects. Many earthquakes occur every day worldwide. There is need to have knowledge regarding the trends in earthquake occurrence worldwide. The recoding and interpretation of data obtained from the establishment of the worldwide system of seismological stations made this possible. From the analysis of recorded earthquake data, the earthquake parameters and source parameters can be computed and the earthquake catalogues can be prepared. These catalogues provide information on origin, time, epicenter locations (in term of latitude and longitudes) focal depths, magnitude and other related details of the recorded earthquakes. Theses catalogues are used for seismic hazard estimation. Manual interpretation and analysis of these data is tedious and time consuming. A geographical information system is a computer based system designed to store, analyzes and display geographic information. The implementation of integrated GIS technology provides an approach which permits rapid evaluation of complex inventor database under a variety of earthquake scenario and allows the user to interactively view results almost immediately. GIS technology provides a powerful tool for displaying outputs and permit to users to see graphical distribution of impacts of different earthquake scenarios and assumptions. An endeavor has been made in present study to compile the earthquake data for the whole world in visual Basic on ARC GIS Plate form so that it can be used easily for further analysis to be carried out by earthquake engineers. The basic data on time of occurrence, location and size of earthquake has been compiled for further querying based on various parameters. A preliminary analysis tool is also provided in the user interface to interpret the earthquake recurrence in region. The user interface also includes the seismic hazard information already worked out under GHSAP program. The seismic hazard in terms of probability of exceedance in definite return periods is provided for the world. The seismic zones of the Indian region are included in the user interface from IS 1893-2002 code on earthquake resistant design of buildings. The City wise satellite images has been inserted in Map and based on actual data the following information could be extracted in real time: • Analysis of soil parameters and its effect • Microzonation information • Seismic hazard and strong ground motion • Soil liquefaction and its effect in surrounding area • Impacts of liquefaction on buildings and infrastructure • Occurrence of earthquake in future and effect on existing soil • Propagation of earth vibration due of occurrence of Earthquake GIS based earthquake information system has been prepared for whole world in Visual Basic on ARC GIS Plate form and further extended micro level based on actual soil parameters. Individual tools has been developed for liquefaction, earthquake frequency etc. All information could be used for development of infrastructure i.e. multi story structure, Irrigation Dam & Its components, Hydro-power etc in real time for present and future.

Keywords: GIS based earthquake information system, microzonation, analysis and real time information about liquefaction, infrastructure development

Procedia PDF Downloads 294

Authors: Edgar Santoyo, Daniel Perez-Zarate, Agustin Acevedo, Lorena Diaz-Gonzalez, Mirna Guevara

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Four new gas geothermometers have been derived from a multivariate geo chemometric analysis of a geothermal fluid chemistry database, two of which use the natural logarithm of CO₂ and H2S concentrations (mmol/mol), respectively, and the other two use the natural logarithm of the H₂S/H₂ and CO₂/H₂ ratios. As a strict compilation criterion, the database was created with gas-phase composition of fluids and bottomhole temperatures (BHTM) measured in producing wells. The calibration of the geothermometers was based on the geochemical relationship existing between the gas-phase composition of well discharges and the equilibrium temperatures measured at bottomhole conditions. Multivariate statistical analysis together with the use of artificial neural networks (ANN) was successfully applied for correlating the gas-phase compositions and the BHTM. The predicted or simulated bottomhole temperatures (BHTANN), defined as output neurons or simulation targets, were statistically compared with measured temperatures (BHTM). The coefficients of the new geothermometers were obtained from an optimized self-adjusting training algorithm applied to approximately 2,080 ANN architectures with 15,000 simulation iterations each one. The self-adjusting training algorithm used the well-known Levenberg-Marquardt model, which was used to calculate: (i) the number of neurons of the hidden layer; (ii) the training factor and the training patterns of the ANN; (iii) the linear correlation coefficient, R; (iv) the synaptic weighting coefficients; and (v) the statistical parameter, Root Mean Squared Error (RMSE) to evaluate the prediction performance between the BHTM and the simulated BHTANN. The prediction performance of the new gas geothermometers together with those predictions inferred from sixteen well-known gas geothermometers (previously developed) was statistically evaluated by using an external database for avoiding a bias problem. Statistical evaluation was performed through the analysis of the lowest RMSE values computed among the predictions of all the gas geothermometers. The new gas geothermometers developed in this work have been successfully used for predicting subsurface temperatures in high-temperature geothermal systems of Mexico (e.g., Los Azufres, Mich., Los Humeros, Pue., and Cerro Prieto, B.C.) as well as in a blind geothermal system (known as Acoculco, Puebla). The last results of the gas geothermometers (inferred from gas-phase compositions of soil-gas bubble emissions) compare well with the temperature measured in two wells of the blind geothermal system of Acoculco, Puebla (México). Details of this new development are outlined in the present research work. Acknowledgements: The authors acknowledge the funding received from CeMIE-Geo P09 project (SENER-CONACyT).

Keywords: artificial intelligence, gas geochemistry, geochemometrics, geothermal energy

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Authors: Debabrata Adhikari, Mikhail Matveev, Louise Brown, Andy Long, Jan Kočí

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A good understanding of mesoscale permeability of complex architectures in fibrous porous preforms is of particular interest in order to achieve efficient and cost-effective resin impregnation of liquid composite molding (LCM). Fabrics used in structural reinforcements are typically woven or stitched. However, 3D fabric reinforcement is of particular interest because of the versatility in the weaving pattern with the binder yarn and in-plain yarn arrangements to manufacture thick composite parts, overcome the limitation in delamination, improve toughness etc. To predict the permeability based on the available pore spaces between the inter yarn spaces, unit cell-based computational fluid dynamics models have been using the Stokes Darcy model. Typically, the preform consists of an arrangement of yarns with spacing in the order of mm, wherein each yarn consists of thousands of filaments with spacing in the order of μm. The fluid flow during infusion exchanges the mass between the intra and inter yarn channels, meaning there is no dead-end of flow between the mesopore in the inter yarn space and the micropore in the yarn. Several studies have employed the Brinkman equation to take into account the flow through dual-scale porosity reinforcement to estimate their permeability. Furthermore, to reduce the computational effort of dual scale flow, scale separation criteria based on the ratio between yarn permeability to the yarn spacing was also proposed to quantify the dual scale and negligible micro-scale flow regime for the prediction of mesoscale permeability. In the present work, the key parameter to identify the influence of intra yarn permeability on the mesoscale permeability has been investigated with the systematic study of weft and warp yarn spacing on the plane weave as well as the position of binder yarn and number of in-plane yarn layers on 3D weave fabric. The permeability tensor has been estimated using an OpenFOAM-based model for the various weave pattern with idealized geometry of yarn implemented using open-source software TexGen. Additionally, scale separation criterion has been established based on the various configuration of yarn permeability for the 3D fabric with both the isotropic and anisotropic yarn from Gebart’s model. It was observed that the variation of mesoscale permeability Kxx within 30% when the isotropic porous yarn is considered for a 3D fabric with binder yarn. Furthermore, the permeability model developed in this study will be used for multi-objective optimizations of the preform mesoscale geometry in terms of yarn spacing, binder pattern, and a number of layers with an aim to obtain improved permeability and reduced void content during the LCM process.

Keywords: permeability, 3D fabric, dual-scale flow, liquid composite molding

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Authors: Dino Carpentras, Paul J. Maher, Caoimhe O'Reilly, Michael Quayle

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Opinion dynamics is a sub-field of agent-based modeling that focuses on people’s opinions and their evolutions over time. Despite the rapid increase in the number of publications in this field, it is still not clear how to apply these models to real-world scenarios. Indeed, there is no agreement on how people update their opinion while interacting. Furthermore, it is not clear if different topics will show the same dynamics (e.g., more polarized topics may behave differently). These problems are mostly due to the lack of experimental validation of the models. Some previous studies started bridging this gap in the literature by directly measuring people’s opinions before and after the interaction. However, these experiments force people to express their opinion as a number instead of using natural language (and then, eventually, encoding it as numbers). This is not the way people normally interact, and it may strongly alter the measured dynamics. Another limitation of these studies is that they usually average all the topics together, without checking if different topics may show different dynamics. In our work, we collected data from 200 participants on 5 unpolarized topics. Participants expressed their opinions in natural language (“agree” or “disagree”). We also measured the certainty of their answer, expressed as a number between 1 and 10. However, this value was not shown to other participants to keep the interaction based on natural language. We then showed the opinion (and not the certainty) of another participant and, after a distraction task, we repeated the measurement. To make the data compatible with opinion dynamics models, we multiplied opinion and certainty to obtain a new parameter (here called “continuous opinion”) ranging from -10 to +10 (using agree=1 and disagree=-1). We firstly checked the 5 topics individually, finding that all of them behaved in a similar way despite having different initial opinions distributions. This suggested that the same model could be applied for different unpolarized topics. We also observed that people tend to maintain similar levels of certainty, even when they changed their opinion. This is a strong violation of what is suggested from common models, where people starting at, for example, +8, will first move towards 0 instead of directly jumping to -8. We also observed social influence, meaning that people exposed with “agree” were more likely to move to higher levels of continuous opinion, while people exposed with “disagree” were more likely to move to lower levels. However, we also observed that the effect of influence was smaller than the effect of random fluctuations. Also, this configuration is different from standard models, where noise, when present, is usually much smaller than the effect of social influence. Starting from this, we built an opinion dynamics model that explains more than 80% of data variance. This model was also able to show the natural conversion of polarization from unpolarized states. This experimental approach offers a new way to build models grounded on experimental data. Furthermore, the model offers new insight into the fundamental terms of opinion dynamics models.

Keywords: experimental validation, micro-dynamics rule, opinion dynamics, update rule

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Authors: Shimeles Terefe Mengistue, Ascensión Del Olmo, Paola Marziani, Mirjana Pović, María Angeles Martínez-Carballo, Jaime Perea, Isabel M. Árquez

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Quasars have historically been classified into two distinct classes, radio-loud (RL) and radio-quiet (RQ), taking into account the presence and absence of relativistic radio jets, respectively. The absence of spectra with a high S/N ratio led to the impression that all quasars (QSOs) are spectroscopically similar. Although different attempts were made to unify these two classes, there is a long-standing open debate involving the possibility of a real physical dichotomy between RL and RQ quasars. In this work, we present new high S/N spectra of 11 extremely powerful jetted quasars with radio-to-optical flux density ratio > 1000 that concomitantly cover the low-ionization emission of Mgii𝜆2800 and Hbeta𝛽 as well as the Feii blends in the redshift range 0.35 < z < 1, observed at Calar Alto Observatory (Spain). This work aims to quantify broad emission line differences between RL and RQ quasars by using the four-dimensional eigenvector 1 (4DE1) parameter space and its main sequence (MS) and to check the effect of powerful radio ejection on the low ionization broad emission lines. Emission lines are analysed by making two complementary approaches, a multicomponent non-linear fitting to account for the individual components of the broad emission lines and by analysing the full profile of the lines through parameters such as total widths, centroid velocities at different fractional intensities, asymmetry, and kurtosis indices. It is found that broad emission lines show large reward asymmetry both in Hbeta𝛽 and Mgii2800A. The location of our RL sources in a UV plane looks similar to the optical one, with weak Feii UV emission and broad Mgii2800A. We supplement the 11 sources with large samples from previous work to gain some general inferences. The result shows, compared to RQ, our extreme RL quasars show larger median Hbeta full width at half maximum (FWHM), weaker Feii emission, larger 𝑀BH, lower 𝐿bol/𝐿Edd, and a restricted space occupation in the optical and UV MS planes. The differences are more elusive when the comparison is carried out by restricting the RQ population to the region of the MS occupied by RL quasars, albeit an unbiased comparison matching 𝑀BH and 𝐿bol/𝐿Edd suggests that the most powerful RL quasars show the highest redward asymmetries in Hbeta.

Keywords: galaxies, active, line, profiles, quasars, emission lines, supermassive black holes

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Authors: T. Thein, S. Kalyar Myo

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Human uses visual information for understanding the speech contents in noisy conditions or in situations where the audio signal is not available. The primary advantage of visual information is that it is not affected by the acoustic noise and cross talk among speakers. Using visual information from the lip movements can improve the accuracy and robustness of automatic speech recognition. However, a major challenge with most automatic lip reading system is to find a robust and efficient method for extracting the linguistically relevant speech information from a lip image sequence. This is a difficult task due to variation caused by different speakers, illumination, camera setting and the inherent low luminance and chrominance contrast between lip and non-lip region. Several researchers have been developing methods to overcome these problems; the one is lip reading. Moreover, it is well known that visual information about speech through lip reading is very useful for human speech recognition system. Lip reading is the technique of a comprehensive understanding of underlying speech by processing on the movement of lips. Therefore, lip reading system is one of the different supportive technologies for hearing impaired or elderly people, and it is an active research area. The need for lip reading system is ever increasing for every language. This research aims to develop a visual teaching method system for the hearing impaired persons in Myanmar, how to pronounce words precisely by identifying the features of lip movement. The proposed research will work a lip reading system for Myanmar Consonants, one syllable consonants (င (Nga)၊ ည (Nya)၊ မ (Ma)၊ လ (La)၊ ၀ (Wa)၊ သ (Tha)၊ ဟ (Ha)၊ အ (Ah) ) and two syllable consonants ( က(Ka Gyi)၊ ခ (Kha Gway)၊ ဂ (Ga Nge)၊ ဃ (Ga Gyi)၊ စ (Sa Lone)၊ ဆ (Sa Lain)၊ ဇ (Za Gwe) ၊ ဒ (Da Dway)၊ ဏ (Na Gyi)၊ န (Na Nge)၊ ပ (Pa Saug)၊ ဘ (Ba Gone)၊ ရ (Ya Gaug)၊ ဠ (La Gyi) ). In the proposed system, there are three subsystems, the first one is the lip localization system, which localizes the lips in the digital inputs. The next one is the feature extraction system, which extracts features of lip movement suitable for visual speech recognition. And the final one is the classification system. In the proposed research, Two Dimensional Discrete Cosine Transform (2D-DCT) and Linear Discriminant Analysis (LDA) with Active Contour Model (ACM) will be used for lip movement features extraction. Support Vector Machine (SVM) classifier is used for finding class parameter and class number in training set and testing set. Then, experiments will be carried out for the recognition accuracy of Myanmar consonants using the only visual information on lip movements which are useful for visual speech of Myanmar languages. The result will show the effectiveness of the lip movement recognition for Myanmar Consonants. This system will help the hearing impaired persons to use as the language learning application. This system can also be useful for normal hearing persons in noisy environments or conditions where they can find out what was said by other people without hearing voice.

Keywords: feature extraction, lip reading, lip localization, Active Contour Model (ACM), Linear Discriminant Analysis (LDA), Support Vector Machine (SVM), Two Dimensional Discrete Cosine Transform (2D-DCT)

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Authors: Virany Diana, Martono Tri Utomo, Risa Etika

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Background: Shock is one severe condition that can be a major cause of morbidity and mortality in the Neonatal Intensive Care Unit. Preterm infants are very susceptible to shock caused by many complications such as asphyxia, patent ductus arteriosus, intra ventricle haemorrhage, necrotizing enterocolitis, persistent pulmonal hypertension of the newborn, and septicaemia. Limited hemodynamic monitoring for early detection of shock causes delayed intervention and comprises the outcomes. Clinical parameters still used in neonatal shock detection, such as Capillary Refill Time, heart rate, cold extremity, and urine production. Blood pressure is most frequently used to evaluate preterm's circulation, but hypotension indicates uncompensated shock. Near-infrared spectroscopy (NIRS) is known as a noninvasive tool for monitoring and detecting the state of inadequate tissue perfusion. Muscle oxygen saturation shows decreased cardiac output earlier than systemic parameters of tissue oxygenation when cerebral regional oxygen saturation is still stabilized by autoregulation. However, to our best knowledge, until now, no study has analyzed the decrease of muscle oxygen regional saturation (mRSO₂) and the ratio of muscle and cerebral oxygen regional saturation (mRSO₂/cRSO₂) by NIRS in preterm with shock. Purpose: The purpose of this study is to analyze the decrease of mRSO₂ and ratio of muscle to cerebral oxygen regional saturation (mRSO₂/cRSO₂) by NIRS in preterm with shock. Patients and Methods: This cross-sectional study was conducted on preterm infants with 28-34 weeks gestational age, admitted to the NICU of Dr. Soetomo Hospital from November to January 2022. Patients were classified into two groups: shock and non-shock. The diagnosis of shock is based on clinical criteria (tachycardia, prolonged CRT, cold extremity, decreased urine production, and MAP Blood Pressure less than GA in weeks). Measurement of mRSO₂ and cRSO₂ by NIRS was performed by the doctor in charge when the patient came to NICU. Results: We enrolled 40 preterm infants. The initial conventional hemodynamic parameter as the basic diagnosis of shock showed significant differences in all variables. Preterm with shock had higher mean HR (186.45±1.5), lower MAP (29.8±2.1), and lower SBP (45.1±4.28) than non-shock children, and most had a prolonged CRT. The patients’ outcome was not a significant difference between shock and non-shock patients. The mean mRSO₂ in the shock and non-shock groups were 33,65 ± 11,32 vs. 69,15 ± 3,96 (p=0.001), and the mean ratio mRSO₂/cRSO₂ 0,45 ± 0,12 vs. 0,84 ± 0,43 (p=0,001), were significantly different. The mean cRSO₂ in the shock and non-shock groups were 71,60 ± 4,90 vs. 81,85 ± 7,85 (p 0.082), not significantly different. Conclusion: The decrease of mRSO₂ and ratio of mRSO₂/cRSO₂ can differentiate between shock and non-shock in the preterm infant when cRSO₂ is still normal.

Keywords: preterm infant, regional muscle oxygen saturation, regional cerebral oxygen saturation, NIRS, shock

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Authors: Mariam Tsitsagi, Ana Berdzenishvili

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Rainfall intensity change is one of the main indicators of climate change. It has a great influence on agriculture as one of the main factors causing soil erosion. Splash and sheet erosion are one of the most prevalence and harmful for agriculture. It is invisible for an eye at first stage, but the process will gradually move to stream cutting erosion. Our study provides the assessment of rainfall erosivity potential with the use of modern research methods in Kakheti region. The region is the major provider of wheat and wine in the country. Kakheti is located in the eastern part of Georgia and characterized quite a variety of natural conditions. The climate is dry subtropical. For assessment of the exact rate of rainfall erosion potential several year data of rainfall with short intervals are needed. Unfortunately, from 250 active metro stations running during the Soviet period only 55 of them are active now and 5 stations in Kakheti region respectively. Since 1936 we had data on rainfall intensity in this region, and rainfall erosive potential is assessed, in some old papers, but since 1990 we have no data about this factor, which in turn is a necessary parameter for determining the rainfall erosivity potential. On the other hand, researchers and local communities suppose that rainfall intensity has been changing and the number of haily days has also been increasing. However, finding a method that will allow us to determine rainfall erosivity potential as accurate as possible in Kakheti region is very important. The study period was divided into three sections: 1936-1963; 1963-1990 and 1990-2015. Rainfall erosivity potential was determined by the scientific literature and old meteorological stations’ data for the first two periods. And it is known that in eastern Georgia, at the boundary between steppe and forest zones, rainfall erosivity in 1963-1990 was 20-75% higher than that in 1936-1963. As for the third period (1990-2015), for which we do not have data of rainfall intensity. There are a variety of studies, where alternative ways of calculating the rainfall erosivity potential based on lack of data are discussed e.g.based on daily rainfall data, average annual rainfall data and the elevation of the area, etc. It should be noted that these methods give us a totally different results in case of different climatic conditions and sometimes huge errors in some cases. Three of the most common methods were selected for our research. Each of them was tested for the first two sections of the study period. According to the outcomes more suitable method for regional climatic conditions was selected, and after that, we determined rainfall erosivity potential for the third section of our study period with use of the most successful method. Outcome data like attribute tables and graphs was specially linked to the database of Kakheti, and appropriate thematic maps were created. The results allowed us to analyze the rainfall erosivity potential changes from 1936 to the present and make the future prospect. We have successfully implemented a method which can also be use for some another region of Georgia.

Keywords: erosivity potential, Georgia, GIS, Kakheti, rainfall

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Authors: Velvizhi Dharmalingam, Rajalaksmi Ramalingam, Rekha Prabhu, Ilavarasan Raju

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Background: The use of herbal products for various therapeutic regimens has increased tremendously in the developing countries. Elaeocarpus ganitrus(Rudraksha) is a broad-leaved tree, belonging to the family Elaeocarpaceae found in tropical and subtropical areas. It is popular in an indigenous system of medicine like Ayurveda, Siddha, and Unani. According to Ayurvedic medicine, Rudraksha is used in the managing of blood pressure, asthma, mental disorders, diabetes, gynaecological disorders, neurological disorders such as epilepsy and liver diseases. Objectives: The present study aimed to study the physicochemical parameters of Elaeocarpus ganitrus(fruits) and identify the phenolic compounds (gallic acid, ellagic acid, and chebulinic acid). To estimate the microbial load and the antibacterial activity of extract of Elaeocarpus ganitrus for selective pathogens. Methodology: The dried powdered fruit of Elaeocarpus ganitrus was performed the physicochemical parameters (such as Loss on drying, Alcohol soluble extractive, Water soluble extractive, Total ash and Acid insoluble ash) and pH was measured. The dried coarse powdered fruit of Elaeocarpus ganitrus was extracted successively with hexane, chloroform, ethylacetate and aqueous alcohol by cold percolation method. Identification of phenolic compounds (gallic acid, ellagic acid, chebulinic acid) was done by HPTLC method and confirmed by co-TLC using different solvent system.The successive extracts of Elaeocarpus ganitrus and standards (like gallic acid, ellagic acid, and chebulinic acid) was approximately weighed and made up with alcohol. HPTLC (CAMAG) analysis was performed on a TLC over silica gel 60F254 precoated aluminium plate, layer thickness 0.2 mm (E.Merck, Germany) by using ATS4, Visualizer and Scanner with wavelength at 254 nm, 366 nm and derivatized with different reagents. The microbial load such as total bacterial count, total fungal count, Enterobacteria, Escherichia coli, Salmonella species, Staphylococcus aureus and Pseudomonas aeruginosa by serial dilution method and antibacterial activity of was measured by Kirby bauer method for selective pathogens. Results: The physicochemical parameter of Elaeocarpus ganitrus was studied for standardization of crude drug. Among all the successive extracts were identified with phenolic compounds and Elaeocarpus ganitrus extract having potent antibacterial activity against gram-positive and gram-negative bacteria.

Keywords: antimicrobial activity, Elaeocarpus ganitrus, HPTLC, phenolic compounds

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Authors: Swati Tomar, Sunil Kumar Gupta

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Anammox is a novel and promising technology that has changed the traditional concept of biological nitrogen removal. The process facilitates direct oxidation of ammonical nitrogen under anaerobic conditions with nitrite as an electron acceptor without the addition of external carbon sources. The present study investigated the feasibility of anammox hybrid reactor (AHR) combining the dual advantages of suspended and attached growth media for biodegradation of ammonical nitrogen in wastewater. The experimental unit consisted of 4 nos. of 5L capacity AHR inoculated with mixed seed culture containing anoxic and activated sludge (1:1). The process was established by feeding the reactors with synthetic wastewater containing NH4-H and NO2-N in the ratio 1:1 at HRT (hydraulic retention time) of 1 day. The reactors were gradually acclimated to higher ammonium concentration till it attained pseudo steady state removal at a total nitrogen concentration of 1200 mg/l. During this period, the performance of the AHR was monitored at twelve different HRTs varying from 0.25-3.0 d with increasing NLR from 0.4 to 4.8 kg N/m3d. AHR demonstrated significantly higher nitrogen removal (95.1%) at optimal HRT of 1 day. Filter media in AHR contributed an additional 27.2% ammonium removal in addition to 72% reduction in the sludge washout rate. This may be attributed to the functional mechanism of filter media which acts as a mechanical sieve and reduces the sludge washout rate many folds. This enhances the biomass retention capacity of the reactor by 25%, which is the key parameter for successful operation of high rate bioreactors. The effluent nitrate concentration, which is one of the bottlenecks of anammox process was also minimised significantly (42.3-52.3 mg/L). Process kinetics was evaluated using first order and Grau-second order models. The first-order substrate removal rate constant was found as 13.0 d-1. Model validation revealed that Grau second order model was more precise and predicted effluent nitrogen concentration with least error (1.84±10%). A new mathematical model based on mass balance was developed to predict N2 gas in AHR. The mass balance model derived from total nitrogen dictated significantly higher correlation (R2=0.986) and predicted N2 gas with least error of precision (0.12±8.49%). SEM study of biomass indicated the presence of the heterogeneous population of cocci and rod shaped bacteria of average diameter varying from 1.2-1.5 mm. Owing to enhanced NRE coupled with meagre production of effluent nitrate and its ability to retain high biomass, AHR proved to be the most competitive reactor configuration for dealing with nitrogen laden wastewater.

Keywords: anammox, filter media, kinetics, nitrogen removal

Procedia PDF Downloads 357

Authors: Mojtaba Eshraghi Arani

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The freight forwarders, who are known as the Architect of Transportation, play a vital role in the supply chain management. The package of various services which they provide has made the legal nature of freight forwarders very controversial, so that they might be qualified once as principal or carrier and, on other occasions, as agent of the shipper as the case may be. They could even be involved in the transportation process as the agent of shipping line, which makes the situation much more complicated. The courts in all countries have long had trouble in distinguishing the “forwarder as agent” from “forwarder as principal” (as it is outstanding in the prominent case of “Vastfame Camera Ltd v Birkart Globistics Ltd And Others” 2005, Hong Kong). It is not fully known that in the case of a claim against the forwarder, what particular parameter would be used by the judge among multiple, and sometimes contradictory, tests for determining the scope of the forwarder liability. In particular, every country has its own legal parameters for qualifying the freight forwarders that is completely different from others, as it is the case in France in comparison with Germany and England. The unpredictability of the courts’ decisions in this regard has provided the freight forwarders with the opportunity to impose any limitation or exception of liability while pretending to play the role of a principal, consequently making the cargo interests incur ever-increasing damage. The transportation industry needs to remove such uncertainty by unifying national laws governing freight forwarders liability. A long time ago, in 1967, The International Institute for Unification of Private Law (UNIDROIT) prepared a draft convention called “Draft Convention on Contract of Agency for Forwarding Agents Relating to International Carriage of Goods” (hereinafter called “UNIDROIT draft convention”). The UNIDROIT draft convention provided a clear and certain framework for the liability of freight forwarder in each capacity as agent or carrier, but it failed to transform to a convention, and eventually, it was consigned to oblivion. Today, after nearly 6 decades from that era, the necessity of such convention can be felt apparently. However, one might reason that the same grounds, in particular, the resistance by forwarders’ association, FIATA, exist yet, and thus it is not logical to revive a forgotten draft convention after such long period of time. It is argued in this article that the main reason for resisting the UNIDROIT draft convention in the past was pending efforts for developing the “1980 United Nation Convention on International Multimodal Transport of Goods”. However, the latter convention failed to become in force on due time in a way that there was no new accession since 1996, as a result of which the UNIDROIT draft convention must be revived strongly and immediately submitted to the relevant diplomatic conference. A qualitative method with the concept of interpretation of data collection has been used in this manuscript. The source of the data is the analysis of international conventions and cases.

Keywords: freight forwarder, revival, agent, principal, uidroit, draft convention

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Authors: O. Squillace, R. L. Thompson

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Migration of small molecules to, and across the surface of polymer matrices is a little-studied problem with important industrial applications. Tackifiers in adhesives, flavors in foods and binding agents in paints all present situations where the function of a product depends on the ability of small molecules to migrate through a polymer matrix to achieve the desired properties such as softness, dispersion of fillers, and to deliver an effect that is felt (or tasted) on a surface. It’s been shown that the chemical and molecular structure, surface free energies, phase behavior, close environment and compatibility of the system, influence the migrants’ motion. When differences in behavior, such as occurrence of segregation to the surface or not, are observed it is then of crucial importance to identify and get a better understanding of the driving forces involved in the process of molecular migration. In this aim, experience is meant to be allied with theory in order to deliver a validated theoretical and computational toolkit to describe and predict these phenomena. The systems that have been chosen for this study aim to address the effect of polarity mismatch between the migrants and the polymer matrix and that of a second migrant over the first one. As a non-polar resin polymer, polyvinyl acetate is used as the material to which more or less polar migrants (sorbitol, carvone, octanoic acid (OA), triacetin) are to be added. Through contact angle measurement a surface excess is seen for sorbitol (polar) mixed with PVAc as the surface energy is lowered compare to the one of pure PVAc. This effect is increased upon the addition of carvon or triacetin (non-polars). Surface micro-structures are also evidenced by atomic force microscopy (AFM). Ion beam analysis (Nuclear Reaction Analysis), supplemented by neutron reflectometry can accurately characterize the self-organization of surfactants, oligomers, aromatic molecules in polymer films in order to relate the macroscopic behavior to the length scales that are amenable to simulation. The nuclear reaction analysis (NRA) data for deuterated OA 20% shows the evidence of a surface excess which is enhanced after annealing. The addition of 10% triacetin, as a second migrant, results in the formation of an underlying layer enriched in triacetin below the surface excess of OA. The results show that molecules in polarity mismatch with the matrix tend to segregate to the surface, and this is favored by the addition of a second migrant of the same polarity than the matrix. As studies have been restricted to materials that are model supported films under static conditions in a first step, it is also wished to address the more challenging conditions of materials under controlled stress or strain. To achieve this, a simple rig and PDMS cell have been designed to stretch the material to a defined strain and to probe these mechanical effects by ion beam analysis and atomic force microscopy. This will make a significant step towards exploring the influence of extensional strain on surface segregation, flavor release in cross-linked rubbers.

Keywords: polymers, surface segregation, thin films, molecular migration

Procedia PDF Downloads 102

Authors: Demet Devrimsel Dogan, Ecem Deniz Kirkpantur, Muharrem Dogan, Ahmet Aykut, Ebru Unal Akoglu, Ozge Ecmel Onur

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Introduction: Median Arcuate Ligament Syndrome (MALS) is a rare cause of chronic abdominal pain due to external compression of the celiac trunk by a fibrous arch that unites diaphragmatic crura on each side of the aortic hiatus. While 10-24% of the population may suffer from compression of celiac trunk, it rarely causes patients to develop symptoms. The typical clinical triad of symptoms includes postprandial epigastric pain, weight loss and vomiting. The diagnosis can be made using thin section multi-detector computed tomography (CT) scans which delineate the ligament and the compressed vessel. The treatment of MALS is aimed at relieving the compression of the celiac artery to restore adequate blood flow through the vessel and neurolysis to address chronic pain. Case: A 68-year-old male presented to our clinic with acute postprandial epigastric pain. This was patients’ first attack, and the pain was the worst pain of his life. The patient did not have any other symptoms like nausea, vomiting, chest pain or dyspnea. In his medical history, the patient has had an ischemic cerebrovascular stroke 5 years ago which he recovered with no sequel, and he was using 75 mg clopidogrel and 100 mg acetylsalicylic acid. He was not using any other medication and did not have a story of cardiovascular disease. His vital signs were stable (BP:113/72 mmHg, Spo2:97, temperature:36.3°C, HR:90/bpm). In his electrocardiogram, there was ST depression in leads II, III and AVF. In his physical examination, there was only epigastric tenderness, other system examinations were normal. Physical examination through his upper gastrointestinal system showed no bleeding. His laboratory results were as follows: creatinine:1.26 mg/dL, AST:42 U/L, ALT:17 U/L, amylase:78 U/L, lipase:26 U/L, troponin:10.3 pg/ml, WBC:28.9 K/uL, Hgb:12.7 gr/dL, Plt:335 K/uL. His serial high-sensitive troponin levels were also within normal limits, his echocardiography showed no segmental wall motion abnormalities, an acute myocardial infarction was excluded. In his abdominal ultrasound, no pathology was founded. Contrast-enhanced abdominal CT and CT angiography reported ‘thickened diaphragmatic cruras are compressing and stenosing truncus celiacus superior, this is likely compatible with MALS’. The patient was consulted to general surgery, and they admitted the patient for laparoscopic ligament release. Results: MALS is a syndrome that causes postprandial pain, nausea and vomiting as its most common symptoms. Affected patients are normally young, slim women between the ages of 30 and 50 who have undergone extensive examinations to find the source of their symptoms. To diagnose MALS, other underlying pathologies should initially be excluded. The gold standard is aortic angiography. Although diagnosis and treatment of MALS are unclear, symptom resolution has been achieved with multiple surgical modalities, including open, laparoscopic or robotic ligament release as well as celiac ganglionectomy, which often requires celiac artery revascularisation.

Keywords: differential diagnosis, epigastric pain, median arcuate ligament syndrome, celiac trunk

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Authors: Mustafa M. Donma, Orkide Donma

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The impact of metabolic syndrome (MetS) on cognition and functions of the brain is being investigated. Iron deficiency and deficiencies of B9 (folate) as well as B12 (cobalamin) vitamins are best-known nutritional anemias. They are associated with cognitive disorders and learning difficulties. The antidepressant effects of vitamin D are known and the deficiency state affects mental functions negatively. The aim of this study is to investigate possible correlations of MetS with serum brain-derived neurotrophic factor (BDNF), iron, folate, cobalamin and vitamin D in pediatric patients. 30 children, whose age- and sex-dependent body mass index (BMI) percentiles vary between 85 and 15, 60 morbid obese children with above 99^th percentiles constituted the study population. Anthropometric measurements were taken. BMI values were calculated. Age- and sex-dependent BMI percentile values were obtained using the appropriate tables prepared by the World Health Organization (WHO). Obesity classification was performed according to WHO criteria. Those with MetS were evaluated according to MetS criteria. Serum BDNF was determined by enzyme-linked immunosorbent assay. Serum folate was analyzed by an immunoassay analyzer. Serum cobalamin concentrations were measured using electrochemiluminescence immunoassay. Vitamin D status was determined by the measurement of 25-hydroxycholecalciferol [25-hydroxy vitamin D3, 25(OH)D] using high performance liquid chromatography. Statistical evaluations were performed using SPSS for Windows, version 16. The p values less than 0.05 were accepted as statistically significant. Although statistically insignificant, lower folate and cobalamin values were found in MO children compared to those observed for children with normal BMI. For iron and BDNF values, no alterations were detected among the groups. Significantly decreased vitamin D concentrations were noted in MO children with MetS in comparison with those in children with normal BMI (p ≤ 0.05). The positive correlation observed between iron and BDNF in normal-BMI group was not found in two MO groups. In THE MetS group, the partial correlation among iron, BDNF, folate, cobalamin, vitamin D controlling for waist circumference and BMI was r = -0.501; p ≤ 0.05. None was calculated in MO and normal BMI groups. In conclusion, vitamin D should also be considered during the assessment of pediatric MetS. Waist circumference and BMI should collectively be evaluated during the evaluation of MetS in children. Within this context, BDNF appears to be a key biochemical parameter during the examination of obesity degree in terms of mental functions, cognition and learning capacity. The association observed between iron and BDNF in children with normal BMI was not detected in MO groups possibly due to development of inflammation and other obesity-related pathologies. It was suggested that this finding may contribute to mental function impairments commonly observed among obese children.

Keywords: brain-derived neurotrophic factor, iron, vitamin B9, vitamin B12, vitamin D

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Authors: Jason Blair, Adeboye Adebayo, Mohamed Saad, Jeannette M. Byrne, Fabien A. Basset

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Running economy is a key physiological parameter of an individual’s running efficacy and a valid tool for predicting performance outcomes. Of the many factors known to influence running economy (RE), footwear certainly plays a role owing to its characteristics that vary substantially from model to model. Although minimalist footwear is believed to enhance RE and thereby endurance performance, conclusive research reports are scarce. Indeed, debates remain as to which footwear characteristics most alter RE. The purposes of this study were, therefore, two-fold: (a) to determine whether wearing minimalist shoes results in better RE compared to shod and to identify relationships with kinematic and muscle activation patterns; (b) to determine whether changes in RE with minimalist shoes are still evident following a fatiguing bout of exercise. Well-trained male distance runners (n=10; 29.0 ± 7.5 yrs; 71.0 ± 4.8 kg; 176.3 ± 6.5 cm) partook first in a maximal O₂ uptake determination test (VO₂ₘₐₓ = 61.6 ± 7.3 ml min⁻¹ kg⁻¹) 7 days prior to the experimental sessions. Second, in a fully randomized fashion, an RE test consisting of three 8-min treadmill runs in shod and minimalist footwear were performed prior to and following exercise induced fatigue (EIF). The minimalist and shod conditions were tested with a minimum of 7-day wash-out period between conditions. The RE bouts, interspaced by 2-min rest periods, were run at 2.79, 3.33, and 3.89 m s⁻¹ with a 1% grade. EIF consisted of 7 times 1000 m at 94-97% VO₂ₘₐₓ interspaced with 3-min recovery. Cardiorespiratory, electromyography (EMG), kinematics, rate of perceived exertion (RPE) and blood lactate were measured throughout the experimental sessions. A significant main speed effect on RE (p=0.001) and stride frequency (SF) (p=0.001) was observed. The pairwise comparisons showed that running at 2.79 m s⁻¹ was less economic compared to 3.33, and 3.89 m s⁻¹ (3.56 ± 0.38, 3.41 ± 0.45, 3.40 ± 0.45 ml O₂ kg⁻¹ km⁻¹; respectively) and that SF increased as a function of speed (79 ± 5, 82 ± 5, 84 ± 5 strides min⁻¹). Further, EMG analyses revealed that root mean square EMG significantly increased as a function of speed for all muscles (Biceps femoris, Gluteus maximus, Gastrocnemius, Tibialis anterior, Vastus lateralis). During EIF, the statistical analysis revealed a significant main effect of time on lactate production (from 2.7 ± 5.7 to 11.2 ± 6.2 mmol L⁻¹), RPE scores (from 7.6 ± 4.0 to 18.4 ± 2.7) and peak HR (from 171 ± 30 to 181 ± 20 bpm), expect for the recovery period. Surprisingly, a significant main footwear effect was observed on running speed during intervals (p=0.041). Participants ran faster with minimalist shoes compared to shod (3:24 ± 0:44 min [95%CI: 3:14-3:34] vs. 3:30 ± 0:47 min [95%CI: 3:19-3:41]). Although EIF altered lactate production and RPE scores, no other effect was noticeable on RE, EMG, and SF pre- and post-EIF, except for the expected speed effect. The significant footwear effect on running speed during EIF was unforeseen but could be due to shoe mass and/or heel-toe-drop differences. We also cannot discard the effect of speed on foot-strike pattern and therefore, running performance.

Keywords: exercise-induced fatigue, interval training, minimalist footwear, running economy

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Authors: Richard Vuijk, Arnoud Arntz

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Rationale: To our knowledge treatment of personality disorder comorbidity in adults with autism spectrum disorder (ASD) is understudied and is still in its infancy: We do not know if treatment of personality disorders may be applicable to adults with ASD. In particular, it is unknown whether patients with ASD benefit from experiential techniques that are part of schema therapy developed for the treatment of personality disorders. Objective: The aim of the study is to investigate the efficacy of a schema mode focused treatment with adult clients with ASD and comorbid personality pathology (i.e. at least one personality disorder). Specifically, we investigate if they can benefit from both cognitive-behavioral, and experiential interventions. Study design: A multiple baseline case series study. Study population: Adult individuals (age > 21 years) with ASD and at least one personality disorder. Participants will be recruited from Sarr expertise center for autism in Rotterdam. The study requires 12 participants. Intervention: The treatment protocol consists of 35 weekly offered sessions, followed by 10 monthly booster sessions. A multiple baseline design will be used with baseline varying from 5 to 10 weeks, with weekly supportive sessions. After baseline, a 5-week exploration phase follows with weekly sessions during which current and past functioning, psychological symptoms, schema modes are explored, and information about the treatment will be given. Then 15 weekly sessions with cognitive-behavioral interventions and 15 weekly sessions with experiential interventions will be given. Finally, there will be a 10-month follow-up phase with monthly booster sessions. Participants are randomly assigned to baseline length, and respond weekly during treatment and monthly at follow-up on Belief Strength of negative core beliefs (by VAS), and fill out SMI, SCL-90 and SRS-A 7 times during screening procedure (i.e. before baseline), after baseline, after exploration, after cognitive and behavioral interventions, after experiential interventions, and after 5- and 10- month follow-up. The SCID-II will be administered during screening procedure (i.e. before baseline), at 5- and at 10-month follow-up. Main study parameters: The primary study parameter is negative core beliefs. Secondary study parameters include schema modes, personality disorder manifestations, psychological symptoms, and social interaction and communication. Discussion: To the best of author’s knowledge so far no study has been published on the application of schema mode focused interventions in adult patients with ASD and comorbid PD(s). This study offers the first systematic test of application of schema therapy for adults with ASD. The results of this study will provide initial evidence for the effectiveness of schema therapy in treating adults with both ASD and PD(s). The study intends to provide valuable information for future development and implementation of therapeutic interventions for adults with both ASD and PD(s).

Keywords: adults, autism spectrum disorder, personality disorder, schema therapy

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Authors: Sarah Crawford, Gerry Lesley

Abstract:

This research is a pre-clinical assessment of anti-cancer effects of novel non-steroidal diethyl stilbestrol-like estrogen analogs in estrogen-receptor positive/ progesterone-receptor positive human breast cancer microtumors of MCF 7 cell line. Tamoxifen analog formulation (Tam A1) was used as a single agent or in combination with therapeutic concentrations of 4-hydroxytamoxifen, currently used as a long-term treatment for the prevention of breast cancer recurrence in women with estrogen receptor positive/ progesterone receptor positive malignancies. At concentrations ranging from 30-50 microM, Tam A1 induced microtumor disaggregation and cell death. Incremental cytotoxic effects correlated with increasing concentrations of Tam A1. Live tumor microscopy showed that microtumos displayed diffuse borders and substrate-attached cells were rounded-up and poorly adherent. A complete cytotoxic effect was observed using 40-50 microM Tam A1 with time course kinetics similar to 4-hydroxytamoxifen. Combined treatment with TamA1 (30-50 microM) and 4-hydroxytamoxifen (10-15 microM) induced a highly cytotoxic, synergistic combined treatment response that was more rapid and complete than using 4-hydroxytamoxifen as a single agent therapeutic. Microtumors completely dispersed or formed necrotic foci indicating a highly cytotoxic combined treatment response. Moreover, breast cancer microtumors treated with both 4-hydroxytamoxifen and Tam A1 displayed lower levels of long-term post-treatment regrowth, a critical parameter of primary drug resistance, than observed for 4-hydroxytamoxifen when used as a single agent therapeutic. Tumor regrowth at 6 weeks post-treatment with either single agent 4-hydroxy tamoxifen, Tam A1 or a combined treatment was assessed for the development of drug resistance. Breast cancer cells treated with both 4-hydroxytamoxifen and Tam A1 displayed significantly lower levels of post-treatment regrowth, indicative of decreased drug resistance, than observed for either single treatment modality. The preclinical data suggest that combined treatment involving the use of tamoxifen analogs may be a novel clinical approach for long-term maintenance therapy in patients with estrogen-receptor positive/progesterone-receptor positive breast cancer receiving hormonal therapy to prevent disease recurrence. Detailed data on time-course, IC50 and tumor regrowth assays post- treatment as well as a proposed mechanism of action to account for observed synergistic drug effects will be presented.

Keywords: 4-hydroxytamoxifen, tamoxifen analog, drug-resistance, microtumors

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Authors: Tony R. Walker, N. Devin MacAskill, Andrew Thalhiemer

Abstract:

Sydney Harbour, Nova Scotia has long been subject to effluent and atmospheric inputs of metals, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) from a large coking operation and steel plant that operated in Sydney for nearly a century until closure in 1988. Contaminated effluents from the industrial site resulted in the creation of the Sydney Tar Ponds, one of Canada’s largest contaminated sites. Since its closure, there have been several attempts to remediate this former industrial site and finally, in 2004, the governments of Canada and Nova Scotia committed to remediate the site to reduce potential ecological and human health risks to the environment. The Sydney Tar Ponds and Coke Ovens cleanup project has become the most prominent remediation project in Canada today. As an integral part of remediation of the site (i.e., which consisted of solidification/stabilization and associated capping of the Tar Ponds), an extensive multiple media environmental effects program was implemented to assess what effects remediation had on the surrounding environment, and, in particular, harbour sediments. Additionally, longer-term natural sediment recovery rates of select contaminants predicted for the harbour sediments were compared to current conditions. During remediation, potential contributions to sediment quality, in addition to remedial efforts, were evaluated which included a significant harbour dredging project, propeller wash from harbour traffic, storm events, adjacent loading/unloading of coal and municipal wastewater treatment discharges. Two sediment sampling methodologies, sediment grab and gravity corer, were also compared to evaluate the detection of subtle changes in sediment quality. Results indicated that overall spatial distribution pattern of historical contaminants remains unchanged, although at much lower concentrations than previously reported, due to natural recovery. Measurements of sediment indicator parameter concentrations confirmed that natural recovery rates of Sydney Harbour sediments were in broad agreement with predicted concentrations, in spite of ongoing remediation activities. Overall, most measured parameters in sediments showed little temporal variability even when using different sampling methodologies, during three years of remediation compared to baseline, except for the detection of significant increases in total PAH concentrations noted during one year of remediation monitoring. The data confirmed the effectiveness of mitigation measures implemented during construction relative to harbour sediment quality, despite other anthropogenic activities and the dynamic nature of the harbour.

Keywords: contaminated sediment, monitoring, recovery, remediation

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Authors: Marina Bubalo, Davor Romić, Stjepan Husnjak, Helena Bakić

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Even though European Council Directive 91/676/EEC known as Nitrates Directive was adopted in 1991, the issue of water quality preservation in areas of intensive agricultural production still persist all over Europe. High nitrate nitrogen concentrations in surface and groundwater originating from diffuse sources are one of the most important environmental problems in modern intensive agriculture. The fate of nitrogen in soil, surface and groundwater in agricultural area is mostly affected by anthropogenic activity (i.e. agricultural practice) and hydrological and climatological conditions. The aim of this study was to identify impact of land use, soil type, soil vulnerability to pollutant percolation, and natural aquifer vulnerability to nitrate occurrence in surface and groundwater within an intensive agricultural area. The study was set in Varaždin County (northern Croatia), which is under significant influence of the large rivers Drava and Mura and due to that entire area is dominated by alluvial soil with shallow active profile mainly on gravel base. Negative agricultural impact on water quality in this area is evident therefore the half of selected county is a part of delineated nitrate vulnerable zones (NVZ). Data on water quality were collected from 7 surface and 8 groundwater monitoring stations in the County. Also, recent study of the area implied detailed inventory of agricultural production and fertilizers use with the aim to produce new agricultural land use database as one of dominant parameters. The analysis of this database done using ArcGIS 10.1 showed that 52,7% of total County area is agricultural land and 59,2% of agricultural land is used for intensive agricultural production. On the other hand, 56% of soil within the county is classified as soil vulnerable to pollutant percolation. The situation is similar with natural aquifer vulnerability; northern part of the county ranges from high to very high aquifer vulnerability. Statistical analysis of water quality data is done using SPSS 13.0. Cluster analysis group both surface and groundwater stations in two groups according to nitrate nitrogen concentrations. Mean nitrate nitrogen concentration in surface water – group 1 ranges from 4,2 to 5,5 mg/l and in surface water – group 2 from 24 to 42 mg/l. The results are similar, but evidently higher, in groundwater samples; mean nitrate nitrogen concentration in group 1 ranges from 3,9 to 17 mg/l and in group 2 from 36 to 96 mg/l. ANOVA analysis confirmed statistical significance between stations that are classified in the same group. The previously listed parameters (land use, soil type, etc.) were used in factorial correspondence analysis (FCA) to detect importance of each stated parameter in local water quality. Since stated parameters mostly cannot be altered, there is obvious necessity for more precise and more adapted land management in such conditions.

Keywords: agricultural area, nitrate, factorial correspondence analysis, water quality

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Authors: Balwinder Singh, Veerpaul Kaur Mann

Abstract:

A composite material is formed by the combination of two or more phases or materials. Natural minerals-derived Basalt fiber is a kind of fiber being introduced in the polymer composite industry due to its good mechanical properties similar to synthetic fibers and low cost, environment friendly. Also, there is a rising trend towards the use of industrial wastes as fillers in polymer composites with the aim of improving the properties of the composites. The mechanical properties of the fiber-reinforced polymer composites are influenced by various factors like fiber length, fiber weight %, filler weight %, filler size, etc. Thus, a detailed study has been done on the characterization of short-chopped Basalt fiber-reinforced polymer matrix composites using fly ash as filler. Taguchi’s L9 orthogonal array has been used to develop the composites by considering fiber length (6, 9 and 12 mm), fiber weight % (25, 30 and 35 %) and filler weight % (0, 5 and 10%) as input parameters with their respective levels and a thorough analysis on the mechanical characteristics (tensile strength and impact strength) has been done using ANOVA analysis with the help of MINITAB14 software. The investigation revealed that fiber weight is the most significant parameter affecting tensile strength, followed by fiber length and fiber weight %, respectively, while impact characterization showed that fiber length is the most significant factor, followed by fly ash weight, respectively. Introduction of fly ash proved to be beneficial in both the characterization with enhanced values upto 5% fly ash weight. The present study on the natural fibres reinforced epoxy composites using fly ash as filler material to study the effect of input parameters on the tensile strength in order to maximize tensile strength of the composites. Fabrication of composites based on Taguchi L9 orthogonal array design of experiments by using three factors fibre type, fibre weight % and fly ash % with three levels of each factor. The Optimization of composition of natural fibre reinforces composites using ANOVA for obtaining maximum tensile strength on fabricated composites revealed that the natural fibres along with fly ash can be successfully used with epoxy resin to prepare polymer matrix composites with good mechanical properties. Paddy- Paddy fibre gives high elasticity to the fibre composite due to presence of approximately hexagonal structure of cellulose present in paddy fibre. Coir- Coir fibre gives less tensile strength than paddy fibre as Coir fibre is brittle in nature when it pulls breakage occurs showing less tensile strength. Banana- Banana fibre has the least tensile strength in comparison to the paddy & coir fibre due to less cellulose content. Higher fibre weight leads to reduction in tensile strength due to increased nuclei of air pockets. Increasing fly ash content reduces tensile strength due to nonbonding of fly ash particles with natural fibre. Fly ash is also not very strong as compared to the epoxy resin leading to reduction in tensile strength.

Keywords: tensile strength and epoxy resin. basalt Fiber, taguchi, polymer matrix, natural fiber

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Authors: Nurul Huda Baharuddin, Nik Meriam Nik Sulaiman, Mohammed Kheireddine Aroua

Abstract:

The effects of pH, polymer concentration, and metal ions feed concentration for four selected heavy metals Zn (II), Pb (II), Cr (III) and Cr (VI) were tested by using Polymer Enhanced Ultrafiltration (PEUF). An alternative biopolymer namely unmodified starch is proposed as a binding reagent in consequences, as compared to commonly used water-soluble polymers namely polyethylene glycol (PEG) and polyethyleneimine (PEI) in the removal of selected four heavy metal ions. The speciation species profiles of four selected complexes ions namely Zn (II), Pb (II), Cr (III) and Cr (VI) and the present of hydroxides ions (OH-) in variously charged ions were investigated by available software at certain pH range. In corresponds to identify the potential of complexation behavior between metal ion-polymers, potentiometric titration studies were obtained at first before carried out experimental works. Experimental works were done using ultrafiltration systems obtained by laboratory ultrafiltration bench scale equipped with 10 kDa polysulfone hollow fiber membrane. Throughout the laboratory works, the rejection coefficient and permeate flux were found to be significantly affected by the main operating parameter, namely the effects of pH, polymer composition and metal ions concentrations. The interaction of complexation between two binding polymers namely unmodified starch and PEG were occurred due to physical attraction of metal ions to the polymer on the molecular surface with high possibility of chemical occurrence. However, these selected metal ions are mainly complexes by polymer functional groups whenever there is interaction with PEI polymer. For study of single metal ions solutions, Zn (II) ions' rejections approaching over 90% were obtained at pH 7 for each tested polymer. This behavior was similar to Pb (II), Cr (III) and Cr (VI); where the rejections were obtained at lower acidic pH and increased at neutral pH of 7. Different behavior was found by Cr (VI) ions where a high rejection was only achieved at acidic pH region with PEI. Polymer concentration and metal ions concentration are found to have a significant effect on rejections. For mixed metal ion solutions, the behavior of metal ion rejections was similar to single metal ion solutions for investigation on the effects of pH. Rejection values were high at pH 7 for Zn (II) pH 7 for Zn (II) and Cr (III) ions, corresponding to higher rejections with unmodified starch. Pb (II) ions obtained high rejections when tested with PEG whenever carried out in mixed metal ion solutions. High Cr (VI) ions' rejection was found with PEI in single and mixed metal ions solutions at neutral pH range. The influence of starch’s granule structure towards the rejections of these four selected metal ions is found to be attracted in a non-ionic manner. No significant effects on permeate flux were obtained when tested at different pH ranges, polymer concentrations and metal ions feed either by single or mixtures metal ions solutions. Canizares Model was employed as the theoretical model to predict permeate flux and metal ions retention on the study of heavy metal ions removal.

Keywords: polyethyleneimine, polyethylene glycol, polymer-enhanced ultrafiltration, unmodified starch

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Authors: Ingrid Snustad, Asmund Ervik, Anders Austegard, Amy Brunsvold, Jianying He, Zhiliang Zhang

Abstract:

CO₂ capture, transport and storage (CCS) is essential to mitigate global anthropogenic CO₂ emissions. To make CCS a widely implemented technology in, e.g. the power sector, the reduction of costs is crucial. For a large cost reduction, every part of the CCS chain must contribute. By increasing the heat transfer efficiency during liquefaction of CO₂, which is a necessary step, e.g. ship transportation, the costs associated with the process are reduced. Heat transfer rates during dropwise condensation are up to one order of magnitude higher than during filmwise condensation. Dropwise condensation usually occurs on a non-wetting surface (Superlyophobic surface). The vapour condenses in discrete droplets, and the non-wetting nature of the surface reduces the adhesion forces and results in shedding of condensed droplets. This, again, results in fresh nucleation sites for further droplet condensation, effectively increasing the liquefaction efficiency. In addition, the droplets in themselves have a smaller heat transfer resistance than a liquid film, resulting in increased heat transfer rates from vapour to solid. Surface tension is a crucial parameter for dropwise condensation, due to its impact on the solid-liquid contact angle. A low surface tension usually results in a low contact angle, and again to spreading of the condensed liquid on the surface. CO₂ has very low surface tension compared to water. However, at relevant temperatures and pressures for CO₂ condensation, the surface tension is comparable to organic compounds such as pentane, a dropwise condensation of CO₂ is a completely new field of research. Therefore, knowledge of several important parameters such as contact angle and drop size distribution must be gained in order to understand the nature of the condensation. A new setup has been built to measure these relevant parameters. The main parts of the experimental setup is a pressure chamber in which the condensation occurs, and a high- speed camera. The process of CO₂ condensation is visually monitored, and one can determine the contact angle, contact angle hysteresis and hence, the surface adhesion of the liquid. CO₂ condensation on different surfaces can be analysed, e.g. copper, aluminium and stainless steel. The experimental setup is built for accurate measurements of the temperature difference between the surface and the condensing vapour and accurate pressure measurements in the vapour. The temperature will be measured directly underneath the condensing surface. The next step of the project will be to fabricate nanostructured surfaces for inducing superlyophobicity. Roughness is a key feature to achieve contact angles above 150° (limit for superlyophobicity) and controlled, and periodical roughness on the nanoscale is beneficial. Surfaces that are non- wetting towards organic non-polar liquids are candidates surface structures for dropwise condensation of CO₂.

Keywords: CCS, dropwise condensation, low surface tension liquid, superlyophobic surfaces

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Authors: Igor B. Sivaev

Abstract:

Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

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