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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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Authors: Hanna Mamo Ergando

Abstract:

Climate change is already having a severe influence on agriculture, affecting crop yields, the nutritional content of main grains, and livestock productivity. Significant adaptation investments will be necessary to sustain existing yields and enhance production and food quality to fulfill demand. Climate-smart agriculture (CSA) provides numerous potentials in this regard, combining a focus on enhancing agricultural output and incomes while also strengthening resilience and responding to climate change. To improve agriculture production and productivity, the Ethiopian government has adopted and implemented a series of strategies, including the recent agricultural cluster farming that is practiced as an effort to change, improve, and transform subsistence farming to modern, productive, market-oriented, and climate-smart approach through farmers production cluster. Besides, greater attention and focus have been given to wheat production and productivity by the government, and wheat is the major crop grown in cluster farming. Therefore, the objective of this assessment was to examine various opportunities and challenges farmers face in a cluster farming system. A qualitative research approach was used to generate primary and secondary data. Respondents were chosen using the purposeful sampling technique. Accordingly, experts from the Federal Ministry of Agriculture, the Ethiopian Agricultural Transformation Institute, the Ethiopian Agricultural Research Institute, and the Ethiopian Environment Protection Authority were interviewed. The assessment result revealed that farming in clusters is an economically viable technique for sustaining small, resource-limited, and socially disadvantaged farmers' agricultural businesses. The method assists farmers in consolidating their products and delivering them in bulk to save on transportation costs while increasing income. Smallholders' negotiating power has improved as a result of cluster membership, as has knowledge and information spillover. The key challenges, on the other hand, were identified as a lack of timely provision of modern inputs, insufficient access to credit services, conflict of interest in crop selection, and a lack of output market for agro-processing firms. Furthermore, farmers in the cluster farming approach grow wheat year after year without crop rotation or diversification techniques. Mono-cropping has disadvantages because it raises the likelihood of disease and insect outbreaks. This practice may result in long-term consequences, including soil degradation, reduced biodiversity, and economic risk for farmers. Therefore, the government must devote more resources to addressing the issue of environmental sustainability. Farmers' access to complementary services that promote production and marketing efficiencies through infrastructure and institutional services has to be improved. In general, the assessment begins with some hint that leads to a deeper study into the efficiency of the strategy implementation, upholding existing policy, and scaling up good practices in a sustainable and environmentally viable manner.

Keywords: cluster farming, smallholder farmers, wheat, challenges, opportunities

Procedia PDF Downloads 217

Authors: Rajwanlop Kumpoopong, Sukit Yindeesuk, Pornchai Silarom

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Modeling cracks in concrete is complicated by its strain-softening behavior which requires the use of sophisticated energy criteria of fracture mechanics to assure stable and convergent solutions in the finite-element (FE) analysis particularly for relatively large structures. However, for small-scale structures such as beams and slabs, a simpler approach relies on retaining some shear stiffness in the cracking plane has been adopted in literature to model the strain-softening behavior of concrete under monotonically increased loading. According to the shear retaining approach, each element is assumed to be an isotropic material prior to cracking of concrete. Once an element is cracked, the isotropic element is replaced with an orthotropic element in which the new orthotropic stiffness matrix is formulated with respect to the crack orientation. The shear transfer factor of 0.5 is used in parallel to the crack plane. The shear retaining approach is adopted in this research to model cracks in RC bridge deck with some modifications to take into account the effect of repetitive moving truck wheel loads as they cause fatigue cracking of concrete. First modification is the introduction of fatigue tests of concrete and reinforcing steel and the Palmgren-Miner linear criterion of cumulative damage in the conventional FE analysis. For a certain loading, the number of cycles to failure of each concrete or RC element can be calculated from the fatigue or S-N curves of concrete and reinforcing steel. The elements with the minimum number of cycles to failure are the failed elements. For the elements that do not fail, the damage is accumulated according to Palmgren-Miner linear criterion of cumulative damage. The stiffness of the failed element is modified and the procedure is repeated until the deck slab fails. The total number of load cycles to failure of the deck slab can then be obtained from which the S-N curve of the deck slab can be simulated. Second modification is the modification in shear transfer factor. Moving loading causes continuous rubbing of crack interfaces which greatly reduces shear transfer mechanism. It is therefore conservatively assumed in this study that the analysis is conducted with shear transfer factor of zero for the case of moving loading. A customized FE program has been developed using the MATLAB software to accomodate such modifications. The developed procedure has been validated with the fatigue test of the 1/6.6-scale AASHTO bridge deck under the applications of both fixed-point repetitive loading and moving loading presented in the literature. Results are in good agreement both experimental vs. simulated S-N curves and observed vs. simulated crack patterns. Significant contribution of the developed procedure is a series of S-N relations which can now be simulated at any desired levels of cracking in addition to the experimentally derived S-N relation at the failure of the deck slab. This permits the systematic investigation of crack propagation or deterioration of RC bridge deck which is appeared to be useful information for highway agencies to prolong the life of their bridge decks.

Keywords: bridge deck, cracking, deterioration, fatigue, finite-element, moving truck, reinforced concrete

Procedia PDF Downloads 256

Authors: Lizeth Fuentes-Mera, Vanessa Perez-Silos, Nidia K. Moncada-Saucedo, Alejandro Garcia-Ruiz, Alberto Camacho, Jorge Lara-Arias, Ivan Marino-Martinez, Victor Romero-Diaz, Adolfo Soto-Dominguez, Humberto Rodriguez-Rocha, Hang Lin, Victor Pena-Martinez

Abstract:

Biphasic scaffolds in cartilage tissue engineering have been designed to influence not only the recapitulation of the osteochondral architecture but also to take advantage of the healing ability of bone to promote the implant integration with the surrounding tissue and then bone restoration and cartilage regeneration. This study reports the development and characterization of a biphasic scaffold based on the assembly of a cartilage phase constituted by fibroin biofunctionalized with bovine cartilage matrix; cellularized with differentiated pre-chondrocytes from adipose tissue stem cells (autologous) and well attached to a bone phase (bone bovine decellularized) to mimic the structure of the nature of native tissue and to promote the cartilage regeneration in a model of joint damage in pigs. Biphasic scaffolds were assembled by fibroin crystallization with methanol. The histological and ultrastructural architectures were evaluated by optical and scanning electron microscopy respectively. Mechanical tests were conducted to evaluate Young's modulus of the implant. For the biological evaluation, pre-chondrocytes were loaded onto the scaffolds and cellular adhesion, proliferation, and gene expression analysis of cartilage extracellular matrix components was performed. The scaffolds that were cellularized and matured for 10 days were implanted into critical 3 mm in diameter and 9-mm in depth osteochondral defects in a porcine model (n=4). Three treatments were applied per knee: Group 1: monophasic cellular scaffold (MS) (single chondral phase), group 2: biphasic scaffold, cellularized only in the chondral phase (BS1), group 3: BS cellularized in both bone and chondral phases (BS2). Simultaneously, a control without treatment was evaluated. After 4 weeks of surgery, integration and regeneration tissues were analyzed by x-rays, histology and immunohistochemistry evaluation. The mechanical assessment showed that the acellular biphasic composites exhibited Young's modulus of 805.01 kPa similar to native cartilage (400-800 kPa). In vitro biological studies revealed the chondroinductive ability of the biphasic implant, evidenced by an increase in sulfated glycosaminoglycan (GAGs) and type II collagen, both secreted by the chondrocytes cultured on the scaffold during 28 days. No evidence of adverse or inflammatory reactions was observed in the in vivo trial; however, In group 1, the defects were not reconstructed. In group 2 and 3 a good integration of the implant with the surrounding tissue was observed. Defects in group 2 were fulfilled by hyaline cartilage and normal bone. Group 3 defects showed fibrous repair tissue. In conclusion; our findings demonstrated the efficacy of biphasic and bioactive scaffold based on silk fibroin, which entwined chondroinductive features and biomechanical capability with appropriate integration with the surrounding tissue, representing a promising alternative for osteochondral tissue-engineering applications.

Keywords: biphasic scaffold, extracellular cartilage matrix, silk fibroin, osteochondral tissue engineering

Procedia PDF Downloads 151

Authors: Siddharudha B. Patil

Abstract:

Cotton is a premier commercial fibre crop of India subjected to ravages of insect pests. Sucking pests viz thrips, Thrips tabaci,(lind) leaf hopper Amrsca devastance,(dist) miridbug, Poppiocapsidea beseratense (Dist) and bollworms continue to inflict damage Bt Cotton right from seeding stage. Their infestation impact cotton yield to an extent of 30-40 percent. Chemical control is still adoptable as one of the techniques for combating these pests. Presently, growers have many challenges in selecting effective chemicals which fit in with an integrated pest management. Spinetoram has broad spectrum with excellent insecticidal activity against both sucking pests and bollworms. Hence, it is expected to make a great contribution to stable production and quality improvement of agricultural products. Spinetoram is a derivative of biologically active substances (Spinosyns) produced by soil actinomycetes, Saccharopolypara spinosa which is semi synthetic active ingredient representing Spinosyn chemical class of insecticide and has demonstrated higher level of efficacy with reduced risk on beneficial arthropods. The efforts were made in the present study to test the efficacy of Spinetoram against sucking pests and bollworms in comparison with other insecticides in Bt Cotton under field condition. Field experiment was laid out during 2013-14 and 2014-15 at Agricultural Research station Dharwad (Karnataka-India) in a randomized block design comprising eight treatments and three replications. Bt cotton genotype, Bunny BG-II was sown in a plot size of 5.4 m x5.4 m. Recommend agronomical practices were followed. The Spinetoram 12% SC alone and incombination with sulfaxaflore with varied dosages against pest complex was tested. Performance was compared with Spinosad 45% SC and thiamethoxam 25% WG. The results of consecutive seasons revealed that nonsignificant difference in thrips and leafhopper population and varied significantly after 3 days of imposition. Among the treatments, combiproduct, Spinetoram 10%WG + Sulfoxaflor 30% WG@ 140 gai/ha registered lowest population of thrips (3.91/3 leaves) and leaf hoppers (1.08/3 leaves) followed by its lower dosages viz 120 gai/ha (4.86/3 leaves and 1.14/3 leaves of thrips and leaf hoppers, respectively) and 100 gai/ha (6.02 and 1.23./3 leaves of thrips and leaf hoppers respectively) being at par, significantly superior to rest of the treatments. On the contrary, the population of thrips, leaf hopper and miridbugs in untreated control was on higher side. Similarly the higher dosage of Spinetoram 10% WG+ Sulfoxaflor 30% WG (140 gai/ha) proved its bioefficacy by registering lowest miridbug incidence of 1.70/25 squares, followed by its lower dosage (1.78 and 1.83/25 squares respectively) Further observation made on bollworms incidence revealed that the higher dosage of Spinetoram 10% WG+Sulfoxaflor 30% WG (140 gai/ha) registered lowest percentage of boll damage (7.22%), more number of good opened bolls (36.89/plant) and higher seed cotton yield (19.45q/ha) followed by rest of its lower dosages, Spinetoram 12% SC alone and Spinosad 45% SC being at par significantly superior to rest of the treatments. However, significantly higher boll damage (15.13%) and lower seed cotton yield (14.45 q/ha) was registered in untreated control. Thus Spinetoram10% WG+Sulfoxaflor 30% WG can be a promising option for pest management in Bt Cotton.

Keywords: Spinetoram10% WG+Sulfoxaflor 30% WG, sucking pests, bollworms, Bt cotton, management

Procedia PDF Downloads 250

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

Abstract:

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

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

Procedia PDF Downloads 146

Authors: Nalika S. Rajapaksha, James Airton, Amina Aboobakar, Nick Chappell, Andy Dyer

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Nutrient pollution and their impact on water quality is a key concern in England. Many water quality issues originate from multiple sources of pollution spread across the catchment. The river water quality in England has improved since 1990s and wastewater effluent discharges into rivers now contain less phosphorus than in the past. However, excess phosphorus is still recognised as the prevailing issue for rivers failing Water Framework Directive (WFD) good ecological status. To achieve WFD Phosphorus objectives, Wastewater Treatment Works (WwTW) permit limits are becoming increasingly stringent. Nevertheless, in some rural catchments, the apportionment of Phosphorus pollution can be greater from agricultural runoff and other sources such as septic tanks. Therefore, the challenge of meeting the requirements of watercourses to deliver WFD objectives often goes beyond water company activities, providing significant opportunities to co-deliver activities in wider catchments to reduce nutrient load at source. The aim of this study was to apply the United Utilities' Catchment Systems Thinking (CaST) strategy and pilot an innovative permitting approach - Catchment Nutrient Balancing (CNB) in a rural catchment in Cumbria (the River Petteril) in collaboration with the regulator and others to achieve WFD objectives and multiple benefits. The study area is mainly agricultural land, predominantly livestock farms. The local ecology is impacted by significant nutrient inputs which require intervention to meet WFD obligations. There are a range of Phosphorus inputs into the river, including discharges from wastewater assets but also significantly from agricultural contributions. Solely focusing on the WwTW discharges would not have resolved the problem hence in order to address this issue effectively, a CNB trial was initiated at a small WwTW, targeting the removal of a total of 150kg of Phosphorus load, of which 13kg were to be reduced through the use of catchment interventions. Various catchment interventions were implemented across selected farms in the upstream of the catchment and also an innovative polonite reactive filter media was implemented at the WwTW as an alternative to traditional Phosphorus treatment methods. During the 3 years of this trial, the impact of the interventions in the catchment and the treatment works were monitored. In 2020 and 2022, it respectively achieved a 69% and 63% reduction in the phosphorus level in the catchment against the initial reduction target of 9%. Phosphorus treatment at the WwTW had a significant impact on overall load reduction. The wider catchment impact, however, was seven times greater than the initial target when wider catchment interventions were also established. While it is unlikely that all the Phosphorus load reduction was delivered exclusively from the interventions implemented though this project, this trial evidenced the enhanced benefits that can be achieved with an integrated approach, that engages all sources of pollution within the catchment - rather than focusing on a one-size-fits-all solution. Primarily, the CNB approach and the act of collaboratively engaging others, particularly the agriculture sector is likely to yield improved farm and land management performance and better compliance, which can lead to improved river quality as well as wider benefits.

Keywords: agriculture, catchment nutrient balancing, phosphorus pollution, water quality, wastewater

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Authors: Chen Jiang, Eric Jordan, Maurice Gell, Balakrishnan Nair

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Nuclear fusion, one of the most promising options for reliably generating large amounts of carbon-free energy in the future, has seen a plethora of ground-breaking technological advances in recent years. An efficient and durable “breeding blanket”, needed to ensure a reactor’s self-sufficiency by maintaining the optimal coolant temperature as well as by minimizing radiation dosage behind the blanket, still remains a technological challenge for the various reactor designs for commercial fusion power plants. A relatively new dual-coolant lead-lithium (DCLL) breeder design has exhibited great potential for high-temperature (>700oC), high-thermal-efficiency (>40%) fusion reactor operation. However, the structural material, namely reduced activation ferritic-martensitic (RAFM) steel, is not chemically stable in contact with molten Pb-17%Li coolant. Thus, to utilize this new promising reactor design, the demand for effective corrosion-resistant coatings on RAFM steels represents a pressing need. Solution Spray Technologies LLC (SST) is developing a double-layer ceramic coating design to address the corrosion protection of RAFM steels, using a novel solution and solution/suspension plasma spray technology through a US Department of Energy-funded project. Plasma spray is a coating deposition method widely used in many energy applications. Novel derivatives of the conventional powder plasma spray process, known as the solution-precursor and solution/suspension-hybrid plasma spray process, are powerful methods to fabricate thin, dense ceramic coatings with complex compositions necessary for the corrosion protection in DCLL breeders. These processes can be used to produce ultra-fine molten splats and to allow fine adjustment of coating chemistry. Thin, dense ceramic coatings with chosen chemistry for superior chemical stability in molten Pb-Li, low activation properties, and good radiation tolerance, is ideal for corrosion-protection of RAFM steels. A key challenge is to accommodate its CTE mismatch with the RAFM substrate through the selection and incorporation of appropriate bond layers, thus allowing for enhanced coating durability and robustness. Systematic process optimization is being used to define the optimal plasma spray conditions for both the topcoat and bond-layer, and X-ray diffraction and SEM-EDS are applied to successfully validate the chemistry and phase composition of the coatings. The plasma-sprayed double-layer corrosion resistant coatings were also deposited onto simulated RAFM steel substrates, which are being tested separately under thermal cycling, high-temperature moist air oxidation as well as molten Pb-Li capsule corrosion conditions. Results from this testing on coated samples, and comparisons with bare RAFM reference samples will be presented and conclusions will be presented assessing the viability of the new ceramic coatings to be viable corrosion prevention systems for DCLL breeders in commercial nuclear fusion reactors.

Keywords: breeding blanket, corrosion protection, coating, plasma spray

Procedia PDF Downloads 306

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

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

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

Procedia PDF Downloads 131

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

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

Keywords: ferulic acid, ginger, synthesis, zingerone

Procedia PDF Downloads 174

Authors: Ahmad Ali, Muhammad Imran Ghani, Haiyan Ding, Zhihui Cheng, Muhammad Iqbal

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Background and Aims: In recent years, protected cultivation trend, especially in the northern parts of China, spread dynamically where production area, structure, and crops diversity have expanded gradually under plastic greenhouse vegetable cropping (PGVC) system. Under this growing system, continuous monoculture with excessive synthetic fertilizers inputs are common cultivation practices frequently adopted by commercial producers. Such long-term cumulative wild exercise year after year sponsor the continuous cropping obstacles in PGVC soil, which have greatly threatened the regional soil eco-sustainability and further impose the continuous assault on soil ecological diversity leading to the exhaustion of agriculture productivity. The aim of this study was to develop new allelopathic insights by exploiting available biological resources in the favor of sustainable PGVC to illuminate the continuous obstacle factors in plastic greenhouse. Method: A greenhouse study was executed under plastic tunnel located at the Horticulture Experimental Station of the College of Horticulture, Northwest A&F University, Yangling, Shaanxi Province, one of the prominent regions for intensive commercial PGVC in China. Post-harvest garlic residues (stalk, leaves) mechanically smashed, homogenized into powder size and incorporated at the ratio of 1:100; 3:100; 5:100 as a soil amendment in a replanted soil that have been used for continuous cucumber monoculture for 7 years (annually double cropping system in a greenhouse). Results: Incorporated C-rich garlic stalk significantly influenced the soil condition through various ways; organic matter decomposition and mineralization, moderately adjusted the soil pH, enhanced the soil nutrient availability, increased enzymatic activities, and promoted 20% more cucumber yield in short-time. Using Illumina MiSeq sequencing analysis of bacterial 16S rRNA and fungal 18S rDNA genes, the current study revealed that addition of garlic stalk/residue could also improve the microbial abundance and community composition in extensively exploited soil, and contributed in soil functionality, caused prosper changes in soil characteristics, reinforced to good crop yield. Conclusion: Our study provided evidence that addition of garlic stalk as soil fertility amendment is a feasible, cost-effective and efficient resource utilization way for renovation of degraded soil health, ameliorate soil quality components and improve ecological environment in short duration. Our study may provide a better scientific understanding for efficient crop residue management typically from allelopathic source.

Keywords: garlic stalk, microbial community dynamics, plant growth, soil amendment, soil-plant system

Procedia PDF Downloads 134

Authors: Nuno Biga

Abstract:

Artificial Intelligence (AI) has the potential to transform management into several impactful ways. It allows machines to interpret information to find patterns in big data and learn from context analysis, optimize operations, make predictions sensitive to each specific situation and support data-driven decision making. The introduction of an 'artificial brain' in organization also enables learning through complex information and data provided by those who train it, namely its users. The "Assisted-BIGAMES" version of the Accident & Emergency (A&E) simulator introduces the concept of a "Virtual Assistant" (VA) sensitive to context, that provides users useful suggestions to pursue the following operations such as: a) to relocate workstations in order to shorten travelled distances and minimize the stress of those involved; b) to identify in real time existing bottleneck(s) in the operations system so that it is possible to quickly act upon them; c) to identify resources that should be polyvalent so that the system can be more efficient; d) to identify in which specific processes it may be advantageous to establish partnership with other teams; and e) to assess possible solutions based on the suggested KPIs allowing action monitoring to guide the (re)definition of future strategies. This paper is built on the BIGAMES© simulator and presents the conceptual AI model developed and demonstrated through a pilot project (BIG-AI). Each Virtual Assisted BIGAME is a management simulator developed by the author that guides operational and strategic decision making, providing users with useful information in the form of management recommendations that make it possible to predict the actual outcome of different alternative management strategic actions. The pilot project developed incorporates results from 12 editions of the BIGAME A&E that took place between 2017 and 2022 at AESE Business School, based on the compilation of data that allows establishing causal relationships between decisions taken and results obtained. The systemic analysis and interpretation of data is powered in the Assisted-BIGAMES through a computer application called "BIGAMES Virtual Assistant" (VA) that players can use during the Game. Each participant in the VA permanently asks himself about the decisions he should make during the game to win the competition. To this end, the role of the VA of each team consists in guiding the players to be more effective in their decision making, through presenting recommendations based on AI methods. It is important to note that the VA's suggestions for action can be accepted or rejected by the managers of each team, as they gain a better understanding of the issues along time, reflect on good practice and rely on their own experience, capability and knowledge to support their own decisions. Preliminary results show that the introduction of the VA provides a faster learning of the decision-making process. The facilitator designated as “Serious Game Controller” (SGC) is responsible for supporting the players with further analysis. The recommended actions by the SGC may differ or be similar to the ones previously provided by the VA, ensuring a higher degree of robustness in decision-making. Additionally, all the information should be jointly analyzed and assessed by each player, who are expected to add “Emotional Intelligence”, an essential component absent from the machine learning process.

Keywords: artificial intelligence, gamification, key performance indicators, machine learning, management simulators, serious games, virtual assistant

Procedia PDF Downloads 102

Authors: Solanki Ravirajsinh, Kudo Kuniaki, Sharma Ankit, Devi Sherine, Kuboshima Misaki, Tachi Shuntaro

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In software development life cycles, the absence of scalable CI/CD significantly impacts organizations, leading to increased overall maintenance costs, prolonged release delivery times, heightened manual efforts, and difficulties in meeting tight deadlines. Implementing CI/CD with standard serverless technologies using cloud services overcomes all the above-mentioned issues and helps organizations improve efficiency and faster delivery without the need to manage server maintenance and capacity. By integrating scalable CI/CD with scalable automation testing, productivity, quality, and agility are enhanced while reducing the need for repetitive work and manual efforts. Implementing scalable CI/CD for development using cloud services like ECS (Container Management Service), AWS Fargate, ECR (to store Docker images with all dependencies), Serverless Computing (serverless virtual machines), Cloud Log (for monitoring errors and logs), Security Groups (for inside/outside access to the application), Docker Containerization (Docker-based images and container techniques), Jenkins (CI/CD build management tool), and code management tools (GitHub, Bitbucket, AWS CodeCommit) can efficiently handle the demands of diverse development environments and are capable of accommodating dynamic workloads, increasing efficiency for faster delivery with good quality. CI/CD pipelines encourage collaboration among development, operations, and quality assurance teams by providing a centralized platform for automated testing, deployment, and monitoring. Scalable CI/CD streamlines the development process by automatically fetching the latest code from the repository every time the process starts, building the application based on the branches, testing the application using a scalable automation testing framework, and deploying the builds. Developers can focus more on writing code and less on managing infrastructure as it scales based on the need. Serverless CI/CD eliminates the need to manage and maintain traditional CI/CD infrastructure, such as servers and build agents, reducing operational overhead and allowing teams to allocate resources more efficiently. Scalable CI/CD adjusts the application's scale according to usage, thereby alleviating concerns about scalability, maintenance costs, and resource needs. Creating scalable automation testing using cloud services (ECR, ECS Fargate, Docker, EFS, Serverless Computing) helps organizations run more than 500 test cases in parallel, aiding in the detection of race conditions, performance issues, and reducing execution time. Scalable CI/CD offers flexibility, dynamically adjusting to varying workloads and demands, allowing teams to scale resources up or down as needed. It optimizes costs by only paying for the resources as they are used and increases reliability. Scalable CI/CD pipelines employ automated testing and validation processes to detect and prevent errors early in the development cycle.

Keywords: achieve parallel execution, cloud services, scalable automation testing, scalable continuous integration and deployment

Procedia PDF Downloads 42

Authors: Bin Shi, Mouhab Meshreki, Grégoire Bazin, Helmi Attia

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Large monolithic components are widely used in the aerospace industry in order to reduce airplane weight. Milling is an important operation in manufacturing of the monolithic parts. More than 90% of the material could be removed in the milling operation to obtain the final shape. This results in low rigidity and post-machining distortion. The post-machining distortion is the deviation of the final shape from the original design after releasing the clamps. It is a major challenge in machining of the monolithic parts, which costs billions of economic losses every year. Three sources are directly related to the part distortion, including initial residual stresses (RS) generated from previous manufacturing processes, machining-induced RS and thermal load generated during machining. A finite element model was developed to simulate a milling process and predicate the post-machining distortion. In this study, a rolled-aluminum plate AA7175 with a thickness of 60 mm was used for the raw block. The initial residual stress distribution in the block was measured using a layer-removal method. A stress-mapping technique was developed to implement the initial stress distribution into the part. It is demonstrated that this technique significantly accelerates the simulation time. Machining-induced residual stresses on the machined surface were measured using MTS3000 hole-drilling strain-gauge system. The measured RS was applied on the machined surface of a plate to predict the distortion. The predicted distortion was compared with experimental results. It is found that the effect of the machining-induced residual stress on the distortion of a thick plate is very limited. The distortion can be ignored if the wall thickness is larger than a certain value. The RS generated from the thermal load during machining is another important factor causing part distortion. Very limited number of research on this topic was reported in literature. A coupled thermo-mechanical FE model was developed to evaluate the thermal effect on the plastic deformation of a plate. A moving heat source with a feed rate was used to simulate the dynamic cutting heat in a milling process. When the heat source passed the part surface, a small layer was removed to simulate the cutting operation. The results show that for different feed rates and plate thicknesses, the plastic deformation/distortion occurs only if the temperature exceeds a critical level. It was found that the initial residual stress has a major contribution to the part distortion. The machining-induced stress has limited influence on the distortion for thin-wall structure when the wall thickness is larger than a certain value. The thermal load can also generate part distortion when the cutting temperature is above a critical level. The developed numerical model was employed to predict the distortion of a frame part with complex structures. The predictions were compared with the experimental measurements, showing both are in good agreement. Through optimization of the position of the part inside the raw plate using the developed numerical models, the part distortion can be significantly reduced by 50%.

Keywords: modelling, monolithic parts, optimization, post-machining distortion, residual stresses

Procedia PDF Downloads 51

Authors: Teresa Wanjiru Mbatia

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On 7th June 2011, the government Minister of Roads in Kenya announced the proposed construction of a major highway known as a southern bypass to run on the northern border of the Nairobi National Park. The following day on 8th June 2011, the chairperson of the Friends of Nairobi National Park (FONNAP) posted a protest statement on their website, with the heading, ‘Nairobi Park is Not a cake’ alerting its members and conservation groups, with the aim of getting support to the campaign against the government’s intention to hive off a section of the park for road construction. This was the first and earliest statement that led to a series of other events that culminated in conservationists and some other members of the public campaign against the government’s plan to hive off sections of the park to build road and railway infrastructure in or around the park. Together with other non-state actors, mostly non-governmental organisations in conservation/environment and tourism businesses, FoNNAP issued a series of other statements on social, print and electronic media to battle against road and railway construction. This paper examined the strategies, outcomes and interests of actors involved in opposing/proposing the development of transport infrastructure in and around the Nairobi National Park. Specifically, the objectives were to analyse the: (1) Arguments put forward by the eco-warriors to protest infrastructure development; (2) Background and interests of the eco-warriors; (3) Needs/interests and opinions of ordinary common citizens on transport infrastructural development, particularly in and around the urban nature reserve and (4) Final outcomes of the eco-politics surrounding infrastructure development in and around Nairobi National Park. The methodological approach used was environmental history and the social construction of nature. The study collected combined qualitative data using four main approaches, the grounded theory approach, narratives, case studies and a phenomenological approach. The information collected was analysed using critical discourse analysis. The major findings of the study were that under the guise of “public participation,” influential non-state actors have the capacity to perpetuate social-spatial inequalities in the form of curtailing the majority from accessing common public goods. A case in point in this study is how the efforts of powerful conservationists, environmentalists, and tourism businesspersons managed to stall the construction of much-needed road and railway infrastructure severally through litigations in lengthy environmental court processes involving injunctions and stop orders to the government bodies in charge. Moreover, powerful non-state actors were found to have formed informal and sometimes formal coalitions with politicians with selfish interests, which serves to deepen the exclusionary practices and the common good. The study concludes that mostly composed of certain types of elites (NGOs, business communities, politicians and privileged social-cultural groups), non-state actors have used participatory policies to advance their own interests at the expense of the majority whom they claim to represent. These practices are traced to the historically unjust social, political, and economic forces involved in the production of space in Nairobi.

Keywords: eco-politics, exclusion, infrastructure, Nairobi national park, non-state actors, protests

Procedia PDF Downloads 179

Authors: Evans Oteng, Clement Yeboah, Alexander Otechere-Fianko

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In today’s economy, despite achievements and advances in the banking and financial institutions, there are challenges that will require intensive attempts on the portion of the banks in Ghana. The perceived decline in profitability of banks seems to have emanated from ineffective branding. Hence, the purpose of this quantitative descriptive-correlational study was to examine the effects of branding on the profitability of banks in Ghana. The researchers purposively sampled some 116 banks in Ghana. Self-developed Likert scale questionnaires were administered to the finance officers of the financial institutions. The results were found to be statistically significant, F (1, 114) = 4. 50, p = .036. This indicates that those banks in Ghana with good branding practices have strong marketing tools to identify and sell their products and services and, as such, have a big market share. The correlation coefficients indicate that branding has a positive correlation with profitability and are statistically significant (r=.207, p<0.05), which signifies that as branding increases, the return on equity’s profitability indicator improves and vice versa. Future researchers can consider other factors beyond branding, such as online banking. The study has significant implications for the success and competitive advantage of those banks that effective branding allows them to differentiate themselves from their competitors. A strong and unique brand identity can help a bank stand out in a crowded market, attract customers, and build customer loyalty. This can lead to increased market share and profitability. Branding influences customer perception and trust. A well-established and reputable brand can create a positive image in the minds of customers, enhancing their confidence in the bank's products and services. This can result in increased customer acquisition, customer retention and a positive impact on profitability. Banks with strong brands can leverage their reputation and customer trust to cross-sell additional products and services. When customers have confidence in the brand, they are more likely to explore and purchase other offerings from the same institution. Cross-selling can boost revenue streams and profitability. Successful branding can open up opportunities for brand extensions and diversification into new products or markets. Banks can leverage their trusted brand to introduce new financial products or expand their presence into related areas, such as insurance or investment services. This can lead to additional revenue streams and improved profitability. This study can have implications for education. Thus, increased profitability of banks due to effective branding can result in higher financial resources available for corporate social responsibility (CSR) activities. Banks may invest in educational initiatives, such as scholarships, grants, research projects, and sponsorships, to support the education sector in Ghana. Also, this study can have implications for logistics and supply chain management. Thus, strong branding can create trust and credibility among customers, leading to increased customer loyalty. This loyalty can positively impact the bank's relationships with its suppliers and logistics partners. It can result in better negotiation power, improved supplier relationships, and enhanced supply chain coordination, ultimately leading to more efficient and cost-effective logistics operations.

Keywords: branding, profitability, competitors, customer loyalty, customer retention, corporate social responsibility, cost-effective, logistics operations

Procedia PDF Downloads 77

Authors: Mohamed Emran, Giovanni Pardini, Maria Gispert, Mohamed Rashad

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Land use and abandonment in semi-arid degraded ecosystems may cause regressive dynamics in vegetation cover affecting organic matter contents, soil nutrients and structural stability, thus reducing soil resistance to erosion. Mediterranean areas are generally subjected to climatic fluctuations, which modify soil conditions and hydrological processes, such as runoff and water infiltration within the upper soil horizons. Low erosion rates occur in very fragile and shallow soils with minor clay content progressively decrease organic carbon C and nitrogen N pools in the upper soil horizons. Seven soils were selected representing variant context of land use and abandonment at the Cap de Creus Peninsula, Catalonia, NE Spain, from recent cultivated vines and olive groves, mid abandoned forests standing under cork and pine trees, pasture to late abandoned Cistus and Erica scrubs. The aim of this work was to study the effect of changes in land use and abandonment on the depletion of soil organic carbon and nitrogen transported by runoff water in shallow soils after natural rainfall events during two years with different rainfall patterns (1st year with low rainfall and 2nd year with high rainfall) by i) monitoring the most significant soil erosion parameters at recorded rainfall events, ii) studying the most relevant soil physical and chemical characteristics on seasonal basis and iii) analysing the seasonal trends of depleted carbon and nitrogen and their interaction with soil surface compaction parameters. Significant seasonal variability was observed in the relevant soil physical and chemical parameters and soil erosion parameters in all soils to establish their evolution under land use and abandonment during two years of different rainfall patterns (214 and 487 mm per year), giving important indications on soil response to rainfall impacts. Erosion rates decreased significantly with the increasing of soil C and N under low and high rainfall. In cultivated soils, C and N depletion increased by 144% and 115%, respectively by 13% increase in erosion rates during the 1st year with respect to the 2nd year. Depleted C and N were proportionally higher in soils under vines and olive with vulnerable soil structure and low soil resilience leading to degradation, altering nutrients cycles and causing adverse impact on environmental quality. Statistical analysis underlined that, during the 1st year, soil surface was less effective in preserving stocks of organic resources leading to higher susceptibility to erosion with consequent C and N depletion. During the 2nd year, higher organic reserve and water storage occurred despite the increasing of C and N loss with an effective contribution from soil surface compaction parameters. The overall estimation during the two years indicated clear differences among soils under vines, olive, cork and pines, suggesting on the one hand, that current cultivation practices are inappropriate and that reforestation with pines may delay the achievement of better soil conditions. On the other hand, the natural succession of vegetation under Cistus, pasture and Erica suggests the recovery of good soil conditions.

Keywords: land abandonment, land use, nutrient's depletion, soil erosion

Procedia PDF Downloads 344

Authors: Andrew Laming, John Hattie, Mark Wilson

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Nine Queensland Independent high schools provided deidentified student-matched ATAR and NAPLAN data for all 1217 ATAR graduates since 2020 who also sat NAPLAN at the school. Graduating cohorts from the nine schools contained a mean 100 ATAR graduates with previous NAPLAN data from their school. Excluded were vocational students (mean=27) and any ATAR graduates without NAPLAN data (mean=20). Based on Index of Community Socio-Educational Access (ICSEA) prediction, all schools had larger that predicted proportions of their students graduating with ATARs. There were an additional 173 students not releasing their ATARs to their school (14%), requiring this data to be inferred by schools. Gain was established by first converting each student’s strongest NAPLAN domain to a statewide percentile, then subtracting this result from final ATAR. The resulting ‘percentile shift’ was corrected for plausible ATAR participation at each NAPLAN level. Strongest NAPLAN domain had the highest correlation with ATAR (R2=0.58). RESULTS School mean NAPLAN scores fitted ICSEA closely (R2=0.97). Schools achieved a mean cohort gain of two ATAR rankings, but only 66% of students gained. This ranged from 46% of top-NAPLAN decile students gaining, rising to 75% achieving gains outside the top decile. The 54% of top-decile students whose ATAR fell short of prediction lost a mean 4.0 percentiles (or 6.2 percentiles prior to correction for regression to the mean). 71% of students in smaller schools gained, compared to 63% in larger schools. NAPLAN variability in each of the 13 ICSEA1100 cohorts was 17%, with both intra-school and inter-school variation of these values extremely low (0.3% to 1.8%). Mean ATAR change between years in each school was just 1.1 ATAR ranks. This suggests consecutive school cohorts and ICSEA-similar schools share very similar distributions and outcomes over time. Quantile analysis of the NAPLAN/ATAR revealed heteroscedasticity, but splines offered little additional benefit over simple linear regression. The NAPLAN/ATAR R2 was 0.33. DISCUSSION Standardised data like NAPLAN and ATAR offer educators a simple no-cost progression metric to analyse performance in conjunction with their internal test results. Change is expressed in percentiles, or ATAR shift per student, which is layperson intuitive. Findings may also reduce ATAR/vocational stream mismatch, reveal proportions of cohorts meeting or falling short of expectation and demonstrate by how much. Finally, ‘crashed’ ATARs well below expectation are revealed, which schools can reasonably work to minimise. The percentile shift method is neither value-add nor a growth percentile. In the absence of exit NAPLAN testing, this metric is unable to discriminate academic gain from legitimate ATAR-maximizing strategies. But by controlling for ICSEA, ATAR proportion variation and student mobility, it uncovers progression to ATAR metrics which are not currently publicly available. However achieved, ATAR maximisation is a sought-after private good. So long as standardised nationwide data is available, this analysis offers useful analytics for educators and reasonable predictivity when counselling subsequent cohorts about their ATAR prospects.  

Keywords: NAPLAN, ATAR, analytics, measurement, gain, performance, data, percentile, value-added, high school, numeracy, reading comprehension, variability, regression to the mean

Procedia PDF Downloads 67

Authors: Alena Nesterenko, Svetlana Petrikova

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Research evaluation is one of the most important elements of self-regulation and development of researchers as it is impartial and independent process of assessment. The method of expert evaluations as a scientific instrument solving complicated non-formalized problems is firstly a scientifically sound way to conduct the assessment which maximum effectiveness of work at every step and secondly the usage of quantitative methods for evaluation, assessment of expert opinion and collective processing of the results. These two features distinguish the method of expert evaluations from long-known expertise widespread in many areas of knowledge. Different typical problems require different types of expert evaluations methods. Several issues which arise with these methods are experts’ selection, management of assessment procedure, proceeding of the results and remuneration for the experts. To address these issues an on-line system was created with the primary purpose of development of a versatile application for many workgroups with matching approaches to scientific work management. Online documentation assessment and statistics system allows: - To realize within one platform independent activities of different workgroups (e.g. expert officers, managers). - To establish different workspaces for corresponding workgroups where custom users database can be created according to particular needs. - To form for each workgroup required output documents. - To configure information gathering for each workgroup (forms of assessment, tests, inventories). - To create and operate personal databases of remote users. - To set up automatic notification through e-mail. The next stage is development of quantitative and qualitative criteria to form a database of experts. The inventory was made so that the experts may not only submit their personal data, place of work and scientific degree but also keywords according to their expertise, academic interests, ORCID, Researcher ID, SPIN-code RSCI, Scopus AuthorID, knowledge of languages, primary scientific publications. For each project, competition assessments are processed in accordance to ordering party demands in forms of apprised inventories, commentaries (50-250 characters) and overall review (1500 characters) in which expert states the absence of conflict of interest. Evaluation is conducted as follows: as applications are added to database expert officer selects experts, generally, two persons per application. Experts are selected according to the keywords; this method proved to be good unlike the OECD classifier. The last stage: the choice of the experts is approved by the supervisor, the e-mails are sent to the experts with invitation to assess the project. An expert supervisor is controlling experts writing reports for all formalities to be in place (time-frame, propriety, correspondence). If the difference in assessment exceeds four points, the third evaluation is appointed. As the expert finishes work on his expert opinion, system shows contract marked ‘new’, managers commence with the contract and the expert gets e-mail that the contract is formed and ready to be signed. All formalities are concluded and the expert gets remuneration for his work. The specificity of interaction of the examination officer with other experts will be presented in the report.

Keywords: expertise, management of research evaluation, method of expert evaluations, research evaluation

Procedia PDF Downloads 204

Authors: M. Naveed Yasin, Robert Brooke, Andrew Chan, Geoffrey I. N. Waterhouse, Drew Evans, Darren Svirskis, Ilva D. Rupenthal

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Poly(3,4-ethylenedioxythiophene) (PEDOT) is a robust conducting polymer (CP) exhibiting high conductivity and environmental stability. It can be synthesized by either chemical, electrochemical or vapour phase polymerization (VPP). Dexamethasone sodium phosphate (dexP) is an anionic drug molecule which has previously been loaded onto PEDOT as a dopant via electrochemical polymerisation; however this technique requires conductive surfaces from which polymerization is initiated. On the other hand, VPP produces highly organized biocompatible CP structures while polymerization can be achieved onto a range of surfaces with a relatively straight forward scale-up process. Following VPP of PEDOT, dexP can be loaded and subsequently released via ion-exchange. This study aimed at preparing and characterising both non-porous and porous VPP PEDOT structures including examining drug loading and release via ion-exchange. Porous PEDOT structures were prepared by first depositing a sacrificial polystyrene (PS) colloidal template on a substrate, heat curing this deposition and then spin coating it with the oxidant solution (iron tosylate) at 1500 rpm for 20 sec. VPP of both porous and non-porous PEDOT was achieved by exposing to monomer vapours in a vacuum oven at 40 mbar and 40 °C for 3 hrs. Non-porous structures were prepared similarly on the same substrate but without any sacrificial template. Surface morphology, compositions and behaviour were then characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) respectively. Drug loading was achieved by 50 CV cycles in a 0.1 M dexP aqueous solution. For drug release, each sample was exposed to 20 mL of phosphate buffer saline (PBS) placed in a water bath operating at 37 °C and 100 rpm. Film was stimulated (continuous pulse of ± 1 V at 0.5 Hz for 17 mins) while immersed into PBS. Samples were collected at 1, 2, 6, 23, 24, 26 and 27 hrs and were analysed for dexP by high performance liquid chromatography (HPLC Agilent 1200 series). AFM and SEM revealed the honey comb nature of prepared porous structures. XPS data showed the elemental composition of the dexP loaded film surface, which related well with that of PEDOT and also showed that one dexP molecule was present per almost three EDOT monomer units. The reproducible electroactive nature was shown by several cycles of reduction and oxidation via CV. Drug release revealed success in drug loading via ion-exchange, with stimulated porous and non-porous structures exhibiting a proof of concept burst release upon application of an electrical stimulus. A similar drug release pattern was observed for porous and non-porous structures without any significant statistical difference, possibly due to the thin nature of these structures. To our knowledge, this is the first report to explore the potential of VPP prepared PEDOT for stimuli-responsive drug delivery via ion-exchange. The produced porous structures were ordered and highly porous as indicated by AFM and SEM. These porous structures exhibited good electroactivity as shown by CV. Future work will investigate porous structures as nano-reservoirs to increase drug loading while sealing these structures to minimize spontaneous drug leakage.

Keywords: PEDOT for ion-exchange drug delivery, stimuli-responsive drug delivery, template based porous PEDOT structures, vapour phase polymerization of PEDOT

Procedia PDF Downloads 230

Authors: Ece A. Irmak, Amdulla O. Mekhrabov, M. Vedat Akdeniz

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There is a growing interest on the synthesis and characterization of nanoalloys since the unique chemical, and physical properties of nanoalloys can be tuned and, consequently, new structural motifs can be created by varying the type of constituent elements, atomic and magnetic ordering, as well as size and shape of the nanoparticles. Due to the fine size effects, magnetic nanoalloys have considerable attention with their enhanced mechanical, electrical, optical and magnetic behavior. As an important magnetic nanoalloy, the novel application area of Fe-Ni based nanoalloys is expected to be widened in the chemical, aerospace industry and magnetic biomedical applications. Noble metals have been using in biomedical applications for several years because of their surface plasmon properties. In this respect, iron-nickel nanoalloys are promising materials for magnetic biomedical applications because they show novel properties such as superparamagnetism and surface plasmon resonance property. Also, there is great attention for the usage Fe-Ni based nanoalloys as radar absorbing materials in aerospace and stealth industry due to having high Curie temperature, high permeability and high saturation magnetization with good thermal stability. In this study, FeNi₃ bimetallic nanoalloys were synthesized by mechanical alloying in a planetary high energy ball mill. In mechanical alloying, micron size powders are placed into the mill with milling media. The powders are repeatedly deformed, fractured and alloyed by high energy collision under the impact of balls until the desired composition and particle size is achieved. The experimental studies were carried out in two parts. Firstly, dry mechanical alloying with high energy dry planetary ball milling was applied to obtain FeNi₃ nanoparticles. Secondly, dry milling was followed by surfactant-assisted ball milling to observe the surfactant and solvent effect on the structure, size, and properties of the FeNi₃ nanoalloys. In the first part, the powder sample of iron-nickel was prepared according to the 1:3 iron to nickel ratio to produce FeNi₃ nanoparticles and the 1:10 powder to ball weight ratio. To avoid oxidation during milling, the vials had been filled with Ar inert gas before milling started. The powders were milled for 80 hours in total and the synthesis of the FeNi₃ intermetallic nanoparticles was succeeded by mechanical alloying in 40 hours. Also, regarding the particle size, it was found that the amount of nano-sized particles raised with increasing milling time. In the second part of the study, dry milling of the Fe and Ni powders with the same stoichiometric ratio was repeated. Then, to prevent agglomeration and to obtain smaller sized nanoparticles with superparamagnetic behavior, surfactants and solvent are added to the system, after 40-hour milling time, with the completion of the mechanical alloying. During surfactant-assisted ball milling, heptane was used as milling medium, and as surfactants, oleic acid and oleylamine were used in the high energy ball milling processes. The characterization of the alloyed particles in terms of microstructure, morphology, particle size, thermal and magnetic properties with respect to milling time was done by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, vibrating-sample magnetometer, and differential scanning calorimetry.

Keywords: iron-nickel systems, magnetic nanoalloys, mechanical alloying, nanoalloy characterization, surfactant-assisted ball milling

Procedia PDF Downloads 179

Authors: D. Heinemann, S. Schramm, S. Knabner, D. Baumgarten

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Purpose: Applying solder paste to printed circuit boards (PCB) with stencils has been the method of choice over the past years. A new method uses a jet printer to deposit tiny droplets of solder paste through an ejector mechanism onto the board. This allows for more flexible PCB layouts with smaller components. Due to the viscosity of the solder paste, air blisters can be trapped in the cartridge. This can lead to missing solder joints or deviations in the applied solder volume. Therefore, a built-in and real-time inspection of the printing process is needed to minimize uncertainties and increase the efficiency of the process by immediate correction. The objective of the current study is the design of an optimal imaging system and the development of an automatic algorithm for the detection of applied solder joints from optical from the captured images. Methods: In a first approach, a camera module connected to a microcomputer and LED strips are employed to capture images of the printed circuit board under four different illuminations (white, red, green and blue). Subsequently, an improved system including a ring light, an objective lens, and a monochromatic camera was set up to acquire higher quality images. The obtained images can be divided into three main components: the PCB itself (i.e., the background), the reflections induced by unsoldered positions or screw holes and the solder joints. Non-uniform illumination is corrected by estimating the background using a morphological opening and subtraction from the input image. Image sharpening is applied in order to prevent error pixels in the subsequent segmentation. The intensity thresholds which divide the main components are obtained from the multimodal histogram using three probability density functions. Determining the intersections delivers proper thresholds for the segmentation. Remaining edge gradients produces small error areas which are removed by another morphological opening. For quantitative analysis of the segmentation results, the dice coefficient is used. Results: The obtained PCB images show a significant gradient in all RGB channels, resulting from ambient light. Using different lightings and color channels 12 images of a single PCB are available. A visual inspection and the investigation of 27 specific points show the best differentiation between those points using a red lighting and a green color channel. Estimating two thresholds from analyzing the multimodal histogram of the corrected images and using them for segmentation precisely extracts the solder joints. The comparison of the results to manually segmented images yield high sensitivity and specificity values. Analyzing the overall result delivers a Dice coefficient of 0.89 which varies for single object segmentations between 0.96 for a good segmented solder joints and 0.25 for single negative outliers. Conclusion: Our results demonstrate that the presented optical imaging system and the developed algorithm can robustly detect solder joints on printed circuit boards. Future work will comprise a modified lighting system which allows for more precise segmentation results using structure analysis.

Keywords: printed circuit board jet-printing, inspection, segmentation, solder paste detection

Procedia PDF Downloads 334

Authors: Md Shafiqul Bari, Md Shafiqul Islam Sikdar

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This paper summarizes the current knowledge on Agroforestry practices in the Barind tract of Bangladesh. The part of greater Rajshahi, Dinajpur, Rangpur and Bogra district of Bangladesh is geographically identified as the Barind tract. The hard red soil of these areas is very significant in comparison to that of the other parts of the country. A typical dry climate with comparatively high temperature prevails in the Barind area. Scanty rainfall and excessive extraction of groundwater have created an alarming situation among the Barind people and others about irrigation to the rice field. In addition, the situation may cause an adverse impact on the people whose livelihood largely depends on agriculture. The groundwater table has been declined by at least 10 to 15 meters in some areas of the Barind tract during the last 20 years. Due to absent of forestland in the Barind tract, the soil organic carbon content can decrease more rapidly because of the higher rate of decomposition. The Barind soils are largely carbon depleted but can be brought back to carbon-carrying capacity by bringing under suitable Agroforestry systems. Agroforestry has tremendous potential for carbon sequestration not only in above C biomass but also root C biomass in deeper soil depths. Agroforestry systems habitually conserve soil organic carbon and maintain a great natural nutrient pool. Cultivation of trees with arable crops under Agroforestry systems help in improving soil organic carbon content and sequestration carbon, particularly in the highly degraded Barind lands. Agroforestry systems are a way of securing the growth of cash crops that may constitute an alternative source of income in moments of crisis. Besides being a source of fuel wood, a greater presence of trees in cropping system contributes to decreasing temperatures and to increasing rainfall, thus contrasting the negative environmental impact of climate changes. In order to fulfill the objectives of this study, two experiments were conducted. The first experiment was survey on the impact of existing agroforestry system on the livelihood security in the Barind tract of Bangladesh and the second one was the role of agroforestry system on the improvement of soil properties in a multilayered coconut orchard. Agroforestry systems have been generated a lot of employment opportunities in the Barind area. More crops mean involvement of more people in various activities like involvements in dairying, sericulture, apiculture and additional associated agro-based interventions. Successful adoption of Agroforestry practices in the Barind area has shown that the Agroforestry practitioners of this area were very sound positioned economically, and had added social status too. However, from the findings of the present study, it may be concluded that the majority rural farmers of the Barind tract of Bangladesh had a very good knowledge and medium extension contact related to agroforestry production system. It was also observed that 85 per cent farmers followed agroforestry production system and received benefits to a higher extent. Again, from the research study on orchard based mutistoried agroforestry cropping system, it was evident that there was an important effect of agroforestry cropping systems on the improvement of soil chemical properties. As a result, the agroforestry systems may be helpful to attain the development objectives and preserve the biosphere core.

Keywords: agroforestry systems, Barind tract, carbon sequestration, climate changes

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Authors: Maria Zulema Morquecho Vega, Fabiola CarolinaMiranda Castro, Rafael Verdugo Miranda, Ignacio Yocupicio Villegas, Ana lidia Barron Raygoza, Martin enrique MArquez Cordova, Jose Alberto Duarte Moller

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Background: Anemopsis californica, also called (tame grass) belongs to the Saururaceae family small, green plant. The blade is long and wide. Gives a white flower. The plant population is only found in humid, swampy habitats, it grows where there is water, along the banks of streams and water holes. In the winter, it dries up. The leaves, rhizomes, or roots of this plant have been used to treat a range of diseases. Some of its healing properties are used to treat wounds, cold and flu symptoms, spasmodic cough, infection, pain and inflammation, burns, swollen feet, as well as lung ailments, asthma, circulatory problems (varicose veins), rheumatoid arthritis, purifies blood, helps in urinary and digestive tract diseases, sores and healing, for headache, sore throat, diarrhea, kidney pain. The tea made from the leaves and roots is used to treat uterine cancer, womb cancer, relieves menstrual pain and stops excessive bleeding after childbirth. It is also used as a gynecological treatment for infections, hemorrhoids, candidiasis and vaginitis. Objective: To study the cytotoxicity of gels prepared with silver nanoparticles in AC extract combined with chitosan, collagen and hyaluronic acid as an alternative therapy for skin conditions. Methods: The Ag NPs were synthesized according to the following method. A 0.3 mg/mL solution is prepared in 10 ml of deionized water, adjust to pH 12 with NaOH, stirring is maintained constant magnetic and a temperature of 80 °C. Subsequently, 100 ul of a 0.1 M AgNO3 solution and kept stirring constantly for 15 min. Once the reaction is complete, measurements are performed by UV-Vis. A gel was prepared in a 5% solution of acetic acid with the respective nanoparticles and AC extract of silver in the extract of AC. Chitosan is added until the process begins to occur gel. At that time, collagen will be added in a ratio of 3 to 5 drops, and later, hyaluronic acid in 2% of the total compound formed. Finally, after resting for 24 hours, the cytotoxic effect of the gels was studied. in the presence of highly positive bacteria Staphylococcus aureus and highly negative for Escherichia coli. Cultures will be incubated for 24 hours in the presence of the compound and compared with the reference. Results: Silver nanoparticles obtained had a spherical shape and sizes among 20 and 30 nm. UV-Vis spectra confirm the presence of silver nanoparticles showing a surface plasmon around 420 nm. Finally, the test in presence of bacteria yield a good antibacterial property of this nanocompound and tests in people were successful. Conclusion: Gel prepared by biogenic synthesis shown beneficious effects in severe acne, acne vulgaris and wound healing with diabetic patients.

Keywords: anemopsis californica, nanomedicina, biotechnology, biomedicine

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

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

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

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Authors: Stephen Tullis, M. David DiDonato, Hong Sung Park

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Rowing boats (shells) are often steered by a small rudder operated by one of the backward-facing rowers; the attention required of that athlete then slightly decreases the power that that athlete can provide. Reducing the steering distraction would then increase the overall boat speed. Races are straight 2000 m courses with each boat in a 13.5 m wide lane marked by small (~15 cm) widely-spaced (~10 m) buoys, and the boat trajectory is affected by both cross-currents and winds. An optical buoy recognition and tracking system has been developed that provides the boat’s location and orientation with respect to the lane edges. This information is provided to the steering athlete as either: a simple overlay on a video display, or fed to a simplified autopilot system giving steering directions to the athlete or directly controlling the rudder. The system is then effectively a “lane-assist” device but with small, widely-spaced lane markers viewed from a very shallow angle due to constraints on camera height. The image is captured with a lightweight 1080p webcam, and most of the image analysis is done in OpenCV. The colour RGB-image is converted to a grayscale using the difference of the red and blue channels, which provides good contrast between the red/yellow buoys and the water, sky, land background and white reflections and noise. Buoy detection is done with thresholding within a tight mask applied to the image. Robust linear regression using Tukey’s biweight estimator of the previously detected buoy locations is used to develop the mask; this avoids the false detection of noise such as waves (reflections) and, in particular, buoys in other lanes. The robust regression also provides the current lane edges in the camera frame that are used to calculate the displacement of the boat from the lane centre (lane location), and its yaw angle. The interception of the detected lane edges provides a lane vanishing point, and yaw angle can be calculated simply based on the displacement of this vanishing point from the camera axis and the image plane distance. Lane location is simply based on the lateral displacement of the vanishing point from any horizontal cut through the lane edges. The boat lane position and yaw are currently fed what is essentially a stripped down marine auto-pilot system. Currently, only the lane location is used in a PID controller of a rudder actuator with integrator anti-windup to deal with saturation of the rudder angle. Low Kp and Kd values decrease unnecessarily fast return to lane centrelines and response to noise, and limiters can be used to avoid lane departure and disqualification. Yaw is not used as a control input, as cross-winds and currents can cause a straight course with considerable yaw or crab angle. Mapping of the controller with rudder angle “overall effectiveness” has not been finalized - very large rudder angles stall and have decreased turning moments, but at less extreme angles the increased rudder drag slows the boat and upsets boat balance. The full system has many features similar to automotive lane-assist systems, but with the added constraints of the lane markers, camera positioning, control response and noise increasing the challenge.

Keywords: auto-pilot, lane-assist, marine, optical, rowing

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Authors: Steven W. Carruthers

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The purpose of the present research is to equate two test forms as part of a study to evaluate the educational effectiveness of the ARTé: Mecenas art history learning game. The researcher applied Item Response Theory (IRT) procedures to calculate item, test, and mean-sigma equating parameters. With the sample size n=134, test parameters indicated “good” model fit but low Test Information Functions and more acute than expected equating parameters. Therefore, the researcher applied equipercentile equating and linear equating to raw scores and compared the equated form parameters and effect sizes from each method. Item scaling in IRT enables the researcher to select a subset of well-discriminating items. The mean-sigma step produces a mean-slope adjustment from the anchor items, which was used to scale the score on the new form (Form R) to the reference form (Form Q) scale. In equipercentile equating, scores are adjusted to align the proportion of scores in each quintile segment. Linear equating produces a mean-slope adjustment, which was applied to all core items on the new form. The study followed a quasi-experimental design with purposeful sampling of students enrolled in a college level art history course (n=134) and counterbalancing design to distribute both forms on the pre- and posttests. The Experimental Group (n=82) was asked to play ARTé: Mecenas online and complete Level 4 of the game within a two-week period; 37 participants completed Level 4. Over the same period, the Control Group (n=52) did not play the game. The researcher examined between group differences from post-test scores on test Form Q and Form R by full-factorial Two-Way ANOVA. The raw score analysis indicated a 1.29% direct effect of form, which was statistically non-significant but may be practically significant. The researcher repeated the between group differences analysis with all three equating methods. For the IRT mean-sigma adjusted scores, form had a direct effect of 8.39%. Mean-sigma equating with a small sample may have resulted in inaccurate equating parameters. Equipercentile equating aligned test means and standard deviations, but resultant skewness and kurtosis worsened compared to raw score parameters. Form had a 3.18% direct effect. Linear equating produced the lowest Form effect, approaching 0%. Using linearly equated scores, the researcher conducted an ANCOVA to examine the effect size in terms of prior knowledge. The between group effect size for the Control Group versus Experimental Group participants who completed the game was 14.39% with a 4.77% effect size attributed to pre-test score. Playing and completing the game increased art history knowledge, and individuals with low prior knowledge tended to gain more from pre- to post test. Ultimately, researchers should approach test equating based on their theoretical stance on Classical Test Theory and IRT and the respective  assumptions. Regardless of the approach or method, test equating requires a representative sample of sufficient size. With small sample sizes, the application of a range of equating approaches can expose item and test features for review, inform interpretation, and identify paths for improving instruments for future study.

Keywords: effectiveness, equipercentile equating, IRT, learning games, linear equating, mean-sigma equating

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Authors: Anitha Kandasamy, Thirumurugan Ramaiah

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

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

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Authors: Juliana A. B. Silva, Caio H. T. L. Albuquerque, Leonardo L. dos Santos, Cristiane K. Oliveira, Ivani Malvestiti, Fernando Hallwass, Ricardo L. Longo

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Complexes with lanthanide ions have been extensively studied due to their applications as luminescent, magnetic and catalytic materials as molecular or extended crystals, thin films, glasses, polymeric matrices, ionic liquids, and in solution. NMR chemical shift data in solution have been reported and suggest fluxional structures in a wide range of coordination compounds with rare earth ions. However, the fluxional mechanisms for these compounds are still not established. This structural fluxionality may affect the photophysical, catalytic and magnetic properties in solution. Thus, understanding the structural interconversion mechanisms may aid the design of coordination compounds with, for instance, improved (electro)luminescence, catalytic and magnetic behaviors. The [Eu(btfa)₃bipy] complex, where btfa= 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and bipy= 2,2’-bipiridyl, has a well-defined X-ray crystallographic structure and preliminary 1H NMR data suggested a structural fluxionality. Thus, we have investigated a series of coordination compounds with lanthanide ions [Ln(btfa)₃L], where Ln = La, Eu, Gd or Yb and L= bipy or phen (phen=1,10-phenanthroline) using a combined theoretical-experimental approach. These complexes were synthesized and fully characterized, and detailed NMR measurements were obtained. They were also studied by quantum chemical computational methods (DFT-PBE0). The aim was to determine the relevant factors in the structure of these compounds that favor or not the fluxional behavior. Measurements of the 1H NMR signals at variable temperature in CD₂Cl₂ of the [Eu(btfa)₃L] complexes suggest that these compounds have a fluxional structure, because the crystal structure has non-equivalent btfa ligands that should lead to non-equivalent hydrogen atoms and thus to more signals in the NMR spectra than those obtained at room temperature, where all hydrogen atoms of the btfa ligands are equivalent, and phen ligand has an effective vertical symmetry plane. For the [Eu(btfa)₃bipy] complex, the broadening of the signals at –70°C provides a lower bound for the coalescence temperature, which indicates the energy barriers involved in the structural interconversion mechanisms are quite small. These barriers and, consequently, the coalescence temperature are dependent upon the radii of the lanthanide ion as well as to their paramagnetic effects. The PBE0 calculated structures are in very good agreement with the crystallographic data and, for the [Eu(btfa)₃bipy] complex, this method provided several distinct structures with almost the same energy. However, the energy barrier for structural interconversion via dissociative pathways were found to be quite high and could not explain the experimental observations. Whereas the pseudo-rotation pathways, involving the btfa and bipy ligands, have very small activation barriers, in excellent agreement with the NMR data. The results also showed an increase in the activation barrier along the lanthanide series due to the decrease of the ionic radii and consequent increase of the steric effects. TD-DFT calculations showed a dependence of the ligand donor state energy with different structures of the complex [Eu(btfa)₃phen], which can affect the energy transfer rates and the luminescence. The energy required to promote the structural fluxionality may also enhance the luminescence quenching in solution. These results can aid in the design of more luminescent compounds and more efficient devices.

Keywords: computational chemistry, lanthanide-based compounds, NMR, structural fluxionality

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Authors: Yi-Hao Wong, Li-Li Chan, Chee-Onn Leong, Stephen Ambu, Joon-Wah Mak, Priyasashi Sahu

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Background: Acanthamoeba is a genus of amoebae which lives as a free-living in nature or as a human pathogen that causes severe brain and eye infections. Virulence potential of Acanthamoeba is not constant and can change with growth conditions. DNA methylation, an epigenetic process which adds methyl groups to DNA, is used by eukaryotic cells, including several human parasites to control their gene expression. We used qPCR, siRNA gene silencing, and RNA sequencing (RNA-Seq) to study DNA-methyltransferase gene family (DNMT) in order to indicate the possibility of its involvement in programming Acanthamoeba virulence potential. Methods: A virulence-attenuated Acanthamoeba isolate (designation: ATCC; original isolate: ATCC 50492) was subjected to mouse passages to restore its pathogenicity; a virulence-reactivated isolate (designation: AC/5) was generated. Several established factors associated with Acanthamoeba virulence phenotype were examined to confirm the succession of reactivation process. Differential gene expression of DNMT between ATCC and AC/5 isolates was performed by qPCR. Silencing on DNMT gene expression in AC/5 isolate was achieved by siRNA duplex. Total RNAs extracted from ATCC, AC/5, and siRNA-treated (designation: si-146) were subjected to RNA-Seq for comparative transcriptomic analysis in order to identify the genome-wide effect of DNMT in regulating Acanthamoeba gene expression. qPCR was performed to validate the RNA-Seq results. Results: Physiological and cytophatic assays demonstrated an increased in virulence potential of AC/5 isolate after mouse passages. DNMT gene expression was significantly higher in AC/5 compared to ATCC isolate (p ≤ 0.01) by qPCR. si-146 duplex reduced DNMT gene expression in AC/5 isolate by 30%. Comparative transcriptome analysis identified the differentially expressed genes, with 3768 genes in AC/5 vs ATCC isolate; 2102 genes in si-146 vs AC/5 isolate and 3422 genes in si-146 vs ATCC isolate, respectively (fold-change of ≥ 2 or ≤ 0.5, p-value adjusted (padj) < 0.05). Of these, 840 and 1262 genes were upregulated and downregulated, respectively, in si-146 vs AC/5 isolate. Eukaryotic orthologous group (KOG) assignments revealed a higher percentage of downregulated gene expression in si-146 compared to AC/5 isolate, were related to posttranslational modification, signal transduction and energy production. Gene Ontology (GO) terms for those downregulated genes shown were associated with transport activity, oxidation-reduction process, and metabolic process. Among these downregulated genes were putative genes encoded for heat shock proteins, transporters, ubiquitin-related proteins, proteins for vesicular trafficking (small GTPases), and oxidoreductases. Functional analysis of similar predicted proteins had been described in other parasitic protozoa for their survival and pathogenicity. Decreased expression of these genes in si146-treated isolate may account in part for Acanthamoeba reduced pathogenicity. qPCR on 6 selected genes upregulated in AC/5 compared to ATCC isolate corroborated the RNA sequencing findings, indicating a good concordance between these two analyses. Conclusion: To the best of our knowledge, this study represents the first genome-wide analysis of DNA methylation and its effects on gene expression in Acanthamoeba spp. The present data indicate that DNA methylation has substantial effect on global gene expression, allowing further dissection of the genome-wide effects of DNA-methyltransferase gene in regulating Acanthamoeba pathogenicity.

Keywords: Acanthamoeba, DNA methylation, RNA sequencing, virulence

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