Search results for: high damping rubber bearings

Authors: H. Shamoradifar, B. Teimuri, P. Parvaresh, S. Mohammadi

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One of the main characteristics of Heavy Water Moderated Reactors is their high production of plutonium. This article demonstrates the possibility of reduction of plutonium and other actinides in Heavy Water Research Reactor. Among the many ways for reducing plutonium production in a heavy water reactor, in this research, changing the fuel from natural Uranium fuel to Thorium-Uranium mixed fuel was focused. The main fissile nucleus in Thorium-Uranium fuels is U-233 which would be produced after neutron absorption by Th-232, so the Thorium-Uranium fuels have some known advantages compared to the Uranium fuels. Due to this fact, four Thorium-Uranium fuels with different compositions ratios were chosen in our simulations; a) 10% UO₂-90% THO₂ (enriched= 20%); b) 15% UO₂-85% THO₂ (enriched= 10%); c) 30% UO₂-70% THO₂ (enriched= 5%); d) 35% UO₂-65% THO₂ (enriched= 3.7%). The natural Uranium Oxide (UO₂) is considered as the reference fuel, in other words all of the calculated data are compared with the related data from Uranium fuel. Neutronic parameters were calculated and used as the comparison parameters. All calculations were performed by Monte Carol (MCNPX2.6) steady state reaction rate calculation linked to a deterministic depletion calculation (CINDER90). The obtained computational data showed that Thorium-Uranium fuels with four different fissile compositions ratios can satisfy the safety and operating requirements for Heavy Water Research Reactor. Furthermore, Thorium-Uranium fuels have a very good proliferation resistance and consume less fissile material than uranium fuels at the same reactor operation time. Using mixed Thorium-Uranium fuels reduced the long-lived α emitter, high radiotoxic wastes and the radio toxicity level of spent fuel.

Keywords: Heavy Water Reactor, Burn up, Minor Actinides, Neutronic Calculation

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Authors: Glebert C. Dadol, Pamela Mae L. Ucab, Camila Flor Y. Lobarbio, Noel Peter B. Tan

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Water scarcity is a global problem and membrane-based desalination technologies are one of the promising solutions to this problem. In this study, a passive solar-driven membrane distiller was fabricated and tested for its desalination performance. The distiller was composed of a TiNOX plate solar absorber, cellulose-based upper and lower hydrophilic layers, a hydrophobic middle layer, and aluminum heatsinks. The effect of the middle layer material and thickness on the desalination performance was investigated in terms of distillate productivity and salinity. The materials used for the middle layer were a screen mesh (2 mm, 4 mm, 6 mm thickness) to generate an air gap, a PTFE membrane (0.3 mm thickness)), and a combination of the screen mesh and the PTFE membrane (2.3 mm total thickness). Salt water (35 g/L NaCl) was desalinated using the distiller at a rooftop setting at the University of San Carlos, Cebu City, Philippines. The highest distillate productivity of 1.08 L/m2-h was achieved using a 2-mm screen mesh (air gap) but it also resulted in a high distillate salinity of 25.20 g/L. Increasing the thickness of the air gap lowered the distillate salinity but also decreased the distillate productivity. The lowest salinity of 1.07 g/L was achieved using a 6-mm air gap but the productivity was reduced to 0.08 L/m2-h. The use of the hydrophobic PTFE membrane increased the productivity (0.44 L/m2-h) compared to a 6-mm air gap but produced a distillate with high salinity (16.68 g/L). When using a combination of the screen mesh and the PTFE membrane, the productivity was 0.13 L/m2-h and a distillate salinity of 1.61 g/L. The distiller with a thick air gap as the middle layer can deliver a distillate with low salinity and is preferred over a thin hydrophobic PTFE membrane. The use of a combination of the air gap and PTFE membrane slightly increased the productivity with comparable distillate salinity. Modifications and optimizations to the distiller can be done to improve further its performance.

Keywords: desalination, membrane distillation, passive solar-driven membrane distiller, solar distillation

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Authors: Karolina Ordon, Sandrine Coste, Malgorzata Makowska-Janusik, Abdelhadi Kassiba

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Photocatalytic processes play key role in the production of a new source of energy (as hydrogen), design of self-cleaning surfaces or for the environment preservation. The most challenging task deals with the purification of water distinguished by high efficiency. In the mentioned process, organic pollutants in solutions are decomposed to the simple, non-toxic compounds as H2O and CO2. The most known photocatalytic materials are ZnO, CdS and TiO2 semiconductors with a particular involvement of TiO2 as an efficient photocatalysts even with a high band gap equal to 3.2 eV which exploit only UV radiation from solar emitted spectrum. However, promising material with visible light induced photoactivity was searched through the monoclinic polytype of BiVO4 which has energy gap about 2.4 eV. As required in heterogeneous photocatalysis, the high contact surface is required. Also, BiVO4 as photocatalyst can be optimized by increasing its surface area by achieving the mesoporous structure synthesize. The main goal of the present work consists in the synthesis and characterization of BiVO4 mesoporous thin film. The synthesis method based on sol-gel was carried out using a standard surfactants such as P123 and F127. The thin film was deposited by spin and dip coating method. Then, the structural analysis of the obtained material was performed thanks to X-ray diffraction (XRD) and Raman spectroscopy. The surface of resulting structure was investigated using a scanning electron microscopy (SEM). The computer simulations based on modeling the optical and electronic properties of bulk BiVO4 by using DFT (density functional theory) methodology were carried out. The semiempirical parameterized method PM6 was used to compute the physical properties of BiVO4 nanostructures. The Raman and IR absorption spectra were also measured for synthesized mesoporous material, and the results were compared with the theoretical predictions. The simulations of nanostructured BiVO4 have pointed out the occurrence of quantum confinement for nanosized clusters leading to widening of the band gap. This result overcame the relevance of nanosized objects to harvest wide part of the solar spectrum. Also, a balance was searched experimentally through the mesoporous nature of the films devoted to enhancing the contact surface as required for heterogeneous catalysis without to lower the nanocrystallite size under some critical sizes inducing an increased band gap. The present contribution will discuss the relevant features of the mesoporous films with respect to their photocatalytic responses.

Keywords: bismuth vanadate, photocatalysis, thin film, quantum-chemical calculations

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Authors: Kuniyoshi Abe

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Bi-conjugate gradient (Bi-CG) is a well-known method for solving linear equations Ax = b, for x, where A is a given n-by-n matrix, and b is a given n-vector. Typically, the dimension of the linear equation is high and the matrix is sparse. A number of hybrid Bi-CG methods such as conjugate gradient squared (CGS), Bi-CG stabilized (Bi-CGSTAB), BiCGStab2, and BiCGstab(l) have been developed to improve the convergence of Bi-CG. Bi-CGSTAB has been most often used for efficiently solving the linear equation, but we have seen the convergence behavior with a long stagnation phase. In such cases, it is important to have Bi-CG coefficients that are as accurate as possible, and the stabilization strategy, which stabilizes the computation of the Bi-CG coefficients, has been proposed. It may avoid stagnation and lead to faster computation. Motivated by a large number of processors in present petascale high-performance computing hardware, the scalability of Krylov subspace methods on parallel computers has recently become increasingly prominent. The main bottleneck for efficient parallelization is the inner products which require a global reduction. The resulting global synchronization phases cause communication overhead on parallel computers. The parallel variants of Krylov subspace methods reducing the number of global communication phases and hiding the communication latency have been proposed. However, the numerical stability, specifically, the convergence speed of the parallel variants of Bi-CGSTAB may become worse than that of the standard Bi-CGSTAB. In this paper, therefore, we compare the convergence speed between the standard Bi-CGSTAB and the parallel variants by numerical experiments and show that the convergence speed of the standard Bi-CGSTAB is faster than the parallel variants. Moreover, we propose the stabilization strategy for the parallel variants.

Keywords: bi-conjugate gradient stabilized method, convergence speed, Krylov subspace methods, linear equations, parallel variant

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Authors: A. Taoufyq, B. Bakiz, A. Benlhachemi, L. Patout, D. V. Chokouadeua, F. Guinneton, G. Nolibe, A. Lyoussi, J-R. Gavarri

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Currently, the photo catalytic reactions occurring under solar illumination have attracted worldwide attentions due to a tremendous set of environmental problems. Taking the sunlight into account, it is indispensable to develop highly effective visible-light-driver photo catalysts. Nano structured materials such as MxM’1-xWO6 system are widely studied due to its interesting piezoelectric, dielectric and catalytic properties. These materials can be used in photo catalysis technique for environmental applications, such as waste water treatments. The aim of this study was to investigate the photo catalytic activity of polycrystalline phases of bismuth tungstate of formula Bi2WO6. Polycrystalline samples were elaborated using a coprecipitation technique followed by a calcination process at different temperatures (300, 400, 600 and 900°C). The obtained polycrystalline phases have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Crystal cell parameters and cell volume depend on elaboration temperature. High-resolution electron microscopy images and image simulations, associated with X-ray diffraction data, allowed confirming the lattices and space groups Pca21. The photo catalytic activity of the as-prepared samples was studied by irradiating aqueous solutions of Rhodamine B, associated with Bi2WO6 additives having variable crystallite sizes. The photo catalytic activity of such bismuth tungstates increased as the crystallite sizes decreased. The high specific area of the photo catalytic particles obtained at 300°C seems to condition the degradation kinetics of RhB.

Keywords: Bismuth tungstate, crystallite sizes, electron microscopy, photocatalytic activity, X-ray diffraction.

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Authors: Caitlin Bailey, Marian Frattarola Saulino, Beth Steinberg

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Today, virtually all programs offered to people with intellectual and developmental disabilities tout themselves as person-centered, community-based and inclusive, yet there is a vast range in type and quality of services that use these similar descriptors. The issue is exacerbated by the fields’ measurement practices around quality, inclusion, independent living, choice and person-centered outcomes. For instance, community inclusion for people with disabilities is often measured by the number of times person steps into his or her community. These measurement approaches set standards for quality too low so that agencies supporting group home residents to go bowling every week can report the same outcomes as an agency that supports one person to join a book club that includes people based on their literary interests rather than disability labels. Ultimately, lack of delineation in measurement contributes to the confusion between face value “quality” and true quality services and supports for many people with disabilities and their families. This exploratory study adopts alternative approaches to quality measurement including co-production methods and systems theoretical framework in order to identify the factors that 1) lead to high-quality supports and, 2) differentiate high-quality services. Project researchers have partnered with community practitioners who are all committed to providing quality services and supports but vary in the degree to which they are actually able to provide them. The study includes two parts; first, an online survey distributed to more than 500 agencies that have demonstrated commitment to providing high-quality services; and second, four in-depth case studies with agencies in three United States and Israel providing a variety of supports to children and adults with disabilities. Results from both the survey and in-depth case studies were thematically analyzed and coded. Results show that there are specific factors that differentiate service quality; however meaningful quality measurement practices also require that researchers explore the contextual factors that contribute to quality. These not only include direct services and interactions, but also characteristics of service users, their environments as well as organizations providing services, such as management and funding structures, culture and leadership. Findings from this study challenge researchers, policy makers and practitioners to examine existing quality service standards and measurements and to adopt alternate methodologies and solutions to differentiate and scale up evidence-based quality practices so that all people with disabilities have access to services that support them to live, work, and enjoy where and with whom they choose.

Keywords: co-production, inclusion, independent living, quality measurement, quality supports

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Authors: P. S. Dhananjaya Swamy, B. Chinnappa, G. B. Ramesh, Naveen P. Kumar

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Kodagu district is one of the most densely forested districts in the India as around sixty five per cent of geographical areas under tree cover. Nearly 53 per cent of the flora of Kodagu is endemic. The district is also a hotspot of endemic orchids found mainly in the Thadiandamol. Shade grown, eco-friendly coffee farms are perhaps a selected few places on this planet where nature runs wild. The Kodagu accounts for more than 8.8 per cent of floral diversity of Karnataka state. Estimation of unit cost of cultivation plays a vital role in determining the governmental program their market intervention policies. On an average, planters incurred around Rs. 17041 per acre. The extent of production risk was highest among small category of planters (66 %) compared to other two exhibiting production instability. The result shows that, the coffee productivity in medium plantations was 1051.2 kg per acre as against 758.5 and 789.2 kg in the case of small and large plantations. An annual net return per acre was highest in the case of medium planters (Rs. 26109.3) as against Rs. 20566.7 and Rs. 18572.7 in the case of small and large planters. Cost of production was lowest in the case of small planters (Rs. 18.9 per kg of output) followed by medium planters (Rs. 21.2 per kg of output) and large planters (Rs. 22.5 per kg of output). The productivity of coffee is less whenever it is grown under high shade and native tree cover; it is around 6 quintals per acre when compared with low shade conditions, which is around 8.9 quintals per acre, without a significant difference in the amount invested for growing coffee. Net gain was lower by Rs. 15.5 per kg for the planters growing under high shade and native trees cover when compared with low shade and exotic trees cover.

Keywords: coffee, cultivation, economics, Kodagu

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Authors: Sarah K. Amer, Walaa Alaa

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Epilepsy is an important cause of mortality and morbidity, according to WHO statistics. It is characterized by the presence of frequent seizures occurring more than 24 hours apart. Carbamazepine (CBZ) is considered first-line treatment for epilepsy. However, reports have shown that CBZ oral formulations failed to achieve optimum systemic delivery, minimize side effects, and enhance patient compliance. Besides, the literature has signified the lack of therapeutically efficient CBZ transdermal formulation and the urge for its existence owing to its ease and convenient method of application and highlighted capability to attain higher bioavailability and more extended-release profiles compared to conventional oral CBZ tablets. This work aims to prepare CBZ microspheres (MS) that are embedded in a transdermal gel containing Vitamin B to be co-delivered. MS were prepared by emulsion-solvent diffusion method using Eudragit S as core forming polymer and hydroxypropyl methylcellulose (HPMC) polymer. The MS appeared to be spherical and porous in nature, offering a large surface area and high entrapment efficiency of CBZ. The transdermal gel was prepared by solvent-evaporation technique using HPMC that, offered high entrapment efficiency and Eudragit S that provided an extended-release profile. Polyethylene glycol, Span 80 and Pyridoxine were also added. Data indicated that combinations of CBZ with pyridoxine can reduce epileptic seizures without affecting motor coordination. Extended-release profiles were evident for this system. The patches were furthermore tested for thickness, moisture content, folding endurance, spreadability and viscosity measurements. This novel pharmaceutical formulation would be of great influence on seizure control, offering better therapeutic effects.

Keywords: epilepsy, carbamazepine, pyridoxine, transdermal

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Authors: Lorenzo Casagrande, Antonio Bonati, Ferdinando Auricchio, Antonio Occhiuzzi

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This paper summarizes the results of a survey on smart non-structural element dynamic dissipation when installed in modern high-rise mega-frame prototypes. An innovative glazed curtain wall was designed using Shape Memory Alloy (SMA) joints in order to increase the energy dissipation and enhance the seismic/wind response of the structures. The studied buildings consisted of thirty- and sixty-storey planar frames, extracted from reference three-dimensional steel Moment Resisting Frame (MRF) with outriggers and belt trusses. The internal core was composed of a CBF system, whilst outriggers were placed every fifteen stories to limit second order effects and inter-storey drifts. These structural systems were designed in accordance with European rules and numerical FE models were developed with an open-source code, able to account for geometric and material nonlinearities. With regard to the characterization of non-structural building components, full-scale crescendo tests were performed on aluminium/glass curtain wall units at the laboratory of the Construction Technologies Institute (ITC) of the Italian National Research Council (CNR), deriving force-displacement curves. Three-dimensional brick-based inelastic FE models were calibrated according to experimental results, simulating the fac¸ade response. Since recent seismic events and extreme dynamic wind loads have generated the large occurrence of non-structural components failure, which causes sensitive economic losses and represents a hazard for pedestrians safety, a more dissipative glazed curtain wall was studied. Taking advantage of the mechanical properties of SMA, advanced smart joints were designed with the aim to enhance both the dynamic performance of the single non-structural unit and the global behavior. Thus, three-dimensional brick-based plastic FE models were produced, based on the innovated non-structural system, simulating the evolution of mechanical degradation in aluminium-to-glass and SMA-to-glass connections when high deformations occurred. Consequently, equivalent nonlinear links were calibrated to reproduce the behavior of both tested and smart designed units, and implemented on the thirty- and sixty-storey structural planar frame FE models. Nonlinear time history analyses (NLTHAs) were performed to quantify the potential of the new system, when considered in the lateral resisting frame system (LRFS) of modern high-rise MRFs. Sensitivity to the structure height was explored comparing the responses of the two prototypes. Trends in global and local performance were discussed to show that, if accurately designed, advanced materials in non-structural elements provide new sources of energy dissipation.

Keywords: advanced technologies, glazed curtain walls, non-structural elements, seismic-action reduction, shape memory alloy

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Authors: Haithem Elderrat, Huw Davies, Emmanuel Brousseau

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Elastomeric polymer foam has been used widely in the automotive industry, especially for isolating unwanted vibrations. Such material is able to absorb unwanted vibration due to its combination of elastic and viscous properties. However, the ‘creep effect’, poor stress distribution and susceptibility to high temperatures are the main disadvantages of such a system. In this study, improvements in the performance of elastomeric foam as a vibration isolator were investigated using the concept of Foam Filled Fluid (FFFluid). In FFFluid devices, the foam takes the form of capsule shapes, and is mixed with viscous fluid, while the mixture is contained in a closed vessel. When the FFFluid isolator is affected by vibrations, energy is absorbed, due to the elastic strain of the foam. As the foam is compressed, there is also movement of the fluid, which contributes to further energy absorption as the fluid shears. Also, and dependent on the design adopted, the packaging could also attenuate vibration through energy absorption via friction and/or elastic strain. The present study focuses on the advantages of the FFFluid concept over the dry polymeric foam in the role of vibration isolation. This comparative study between the performance of dry foam and the FFFluid was made according to experimental procedures. The paper concludes by evaluating the performance of the FFFluid isolator in the suspension system of a light vehicle. One outcome of this research is that the FFFluid may preferable over elastomer isolators in certain applications, as it enables a reduction in the effects of high temperatures and of ‘creep effects’, thereby increasing the reliability and load distribution. The stiffness coefficient of the system has increased about 60% by using an FFFluid sample. The technology represented by the FFFluid is therefore considered by this research suitable for application in the suspension system of a light vehicle.

Keywords: FFFluid, dry foam, anti-vibration devices, elastomeric polymer foam

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Authors: Anjuri Srivastava, Akhouri Nishant Bhanu

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Soil is a natural material with a distinctive form. It is regarded to be a natural source of nutrients and minerals for plants. It meets many of our needs through the crops, trees, and inhabited places that have grown on or underneath it. Productive and rich soil plays a crucial role in both its wealth and well-being. If any external substance changes the soil's composition, it directly impacts the plant that was grown in that soil. If the soil is deficient in one or more essential components, fly ash can be utilized as fertilizer by incorporating it into the soil. This can also increase the porosity of the soil. Fly ash has a sufficient concentration of essential components to promote the growth of plants. The high concentration of elements in fly ash, including C, Na, K, Fe, and Zn, increases crop yields. Hazardous compounds harm plant life as soon as they get into the soil. The US Environmental Protection Agency and other regulatory agencies have found it as non-hazardous. By employing fly ash as a potential fertilizer supplement for degraded soils, the problem of disposing of solid waste can be partially handled. Fly ash's rapid growth can slow down mineralization because it contains a higher proportion of harmful heavy metals. The chemical characteristics, inclusion ratio, and composting process of fly ash have a significant impact on the fly ash compost’s potential to improve soil nutrition. Research institutions and regulatory agencies have been thoroughly investigating fly ash for a long time. Guard cells on plant leaves that accumulate fly ash trigger the regulatory system. Fly ash increases both chemical and physical damage at certain humidity levels. The lengthy sowing period is caused by the high levels of fly ash in the soil, which also slows down seedling germination and growth. For the sake of human health, it is crucial to consider the bioaccumulation of dangerous heavy metals and their necessary concentrations in plant tissues and soil.

Keywords: soil, fly ash, plant, fertilizer, composts

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Authors: Ram Sharan Mehta, Dina Khanal, Pushpa Parajuli, Gayanand Mandal, Bijaya Bartuala

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Background: Cardiovascular disease (CVD) is the leading cause of death worldwide. Adequate awareness of risk factors of CVD is the first step towards effective preventive strategies to combat the CVD burden in diabetes patients.This study aims to assess the awareness on risk factors of CVD among patients with diabetes mellitus attending diabetic clinic of BPKIHS and to find the association between awareness with their selected socio demographic variables. Methods and Material: A descriptive cross sectional study was conducted among 112 patients with diabetes in diabetic clinic of BPKIHS. Convenient sampling technique was used for data collection over duration of one month using interview schedule by HDFQ II tool. Data were analyzed by using descriptive and inferential statistics. (Chi square). Results: The mean age of respondents was 55.4±12.13 years. That mean HDFQ score was 14.31± 5.08. Only 33% of the respondents had adequate level of awareness whereas majority of the respondents (67%) had inadequate level of awareness. Majority of the respondent (83.9%) were aware about smoking, (78.6%) physical activity, (75%) increasing age, (75.9%) high blood pressure, (71.4%) overweight respectively. Whereas most of the respondents were not aware of high cholesterol, fatty diet, preventive strategies and association of diabetes with CVD. Awareness was statistically significant with (p=0.043) educational status, (p=0.025) monthly income, (p=0.05) residence, (p=0.006) CVD information received and (p=0.022) co morbid condition as a heart disease. Conclusion: The findings of this study concluded most of the respondents had an inadequate level of awareness on risk factors of CVD. So Effective education and appropriate preventive strategies of CVD are indeed important to reduce CVD burden in diabetes patients.

Keywords: cardiovascular disease, awareness, diabetes patients, risk

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Authors: Selin Top, Raul Marcos, M. Sinan Bilgili

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Although there have been several studies related to collection, temporary storage, handling and disposal of solid wastes generated by hospitals, there are only a few studies related to liquid wastes generated by hospitals or hospital wastewaters. There is an important amount of water consumptions in hospitals. While minimum domestic water consumption per person is 100 L/day, water consumption per bed in hospitals is generally ranged between 400-1200 L. This high amount of consumption causes high amount of wastewater. The quantity of wastewater produced in a hospital depends on different factors: bed numbers, hospital age, accessibility to water, general services present inside the structure (kitchen, laundry, laboratory, diagnosis, radiology, and air conditioning), number and type of wards and units, institution management policies and awareness in managing the structure in safeguarding the environment, climate and cultural and geographic factors. In our country, characterization of hospital wastewaters conducted by classical parameters in a very few studies. However, as mentioned above, this type of wastewaters may contain different compounds than domestic wastewaters. Hospital Wastewater (HWW) is wastewater generated from all activities of the hospital, medical and non medical. Nowadays, hospitals are considered as one of the biggest sources of wastewater along with urban sources, agricultural effluents and industrial sources. As a health-care waste, hospital wastewater has the same quality as municipal wastewater, but may also potentially contain various hazardous components due to using disinfectants, pharmaceuticals, radionuclides and solvents making not suitable the connection of hospital wastewater to the municipal sewage network. These characteristics may represent a serious health hazard and children, adults and animals all have the potential to come into contact with this water. Therefore, the treatment of hospital wastewater is an important current interest point to focus on. This paper aims to approach on the investigation of hospital wastewater treatment by membrane systems. This study aim is to determined hospital wastewater’s characterization and also evaluates the efficiency of hospital wastewater treatment by high pressure filtration systems such as ultrafiltration (UF). Hospital wastewater samples were taken directly from sewage system from Şişli Etfal Training and Research Hospital, located in the district of Şişli, in the European part of Istanbul. The hospital is a 784 bed tertiary care center with a daily outpatient department of 3850 patients. Ultrafiltration membrane is used as an experimental treatment and the influence of the pressure exerted on the membranes was examined, ranging from 1 to 3 bar. The permeate flux across the membrane was observed to define the flooding membrane points. The global COD and BOD5 removal efficiencies were 54% and 75% respectively for ultrafiltration, all the SST removal efficiencies were above 90% and a successful removal of the pathological bacteria measured was achieved.

Keywords: hospital wastewater, membrane, ultrafiltration, treatment

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Authors: Mahmoud Almasri, Xavier Marjou, Fanny Parzysz

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The demand for services provided by Unmanned Aerial Vehicles (UAVs) is increasing pervasively across several sectors including potential public safety, economic, and delivery services. As the number of applications using UAVs grows rapidly, more and more powerful, quality of service, and power efficient computing units are necessary. Recently, cellular technology draws more attention to connectivity that can ensure reliable and flexible communications services for UAVs. In cellular technology, flying with a high speed and altitude is subject to several key challenges, such as frequent handovers (HOs), high interference levels, connectivity coverage holes, etc. Additional HOs may lead to “ping-pong” between the UAVs and the serving cells resulting in a decrease of the quality of service and energy consumption. In order to optimize the number of HOs, we develop in this paper a Q-learning-based algorithm. While existing works focus on adjusting the number of HOs in a static network topology, we take into account the impact of cells deployment for three different simulation scenarios (Rural, Semi-rural and Urban areas). We also consider the impact of the decision distance, where the drone has the choice to make a switching decision on the number of HOs. Our results show that a Q-learning-based algorithm allows to significantly reduce the average number of HOs compared to a baseline case where the drone always selects the cell with the highest received signal. Moreover, we also propose which hyper-parameters have the largest impact on the number of HOs in the three tested environments, i.e. Rural, Semi-rural, or Urban.

Keywords: drones connectivity, reinforcement learning, handovers optimization, decision distance

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Authors: Ayesha Akbar

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Pakistan is moving from a security state to a welfare state despite several security challenges both internal and external. Human security signifies a varied approach in different regions depending upon the leadership and policy priorities. The link between human development and economic growth is not automatic. It has to be created consciously by forward-looking policies and strategies by national governments. There are seven components or categories of human security these include: Economic Security, Personal Security, Health Security, Environmental Security, Food Security, Community Security and Political Security. The increasing interest of the international community to clearly understand the dimensions of human security provided the grounds to Pakistani scholars as well to ponder on the issue and delineate lines of human security. A great deal of work has been either done or in process to evaluate human security indicators in Pakistan. Notwithstanding, after having been done a great deal of work the human security in Pakistan is not satisfactory. A range of deteriorating indicators of human development that lies under the domain of human security leaves certain inquiries to be answered. What are the dimensions of human security in Pakistan? And how are they being dealt from the perspective of policy and institution in terms of its operationalization in Pakistan? Is the human security discourse reflects evidence-based policy changes. The methodology is broadly based on qualitative methods that include interviews, content analysis of policy documents. Pakistan is among the most populous countries in the world and faces high vulnerability to climate change. Literacy rate has gone down with the surge of youth bulge to accommodate in the job market. Increasing population is creating food problems as the resources have not been able to compete with the raising demands of food and other social amenities of life. Majority of the people are facing acute poverty. Health outcomes are also not satisfactory with the high infant and maternal mortality rate. Pakistan is on the verge of facing water crisis as the water resources are depleting so fast with the high demand in agriculture and energy sector. Pakistan is striving hard to deal with the declining state of human security but the dilemma is lack of resources that hinders in meeting up with the emerging demands. The government requires to bring about more change with scaling-up economic growth avenues with enhancing the capacity of human resources. A modern performance drive culture with the integration of technology is required to deliver efficient and effective service delivery. On an already fast track process of reforms; e-governance and evidence based policy mechanism is being instilled in the government process for better governance and evidence based decisions.

Keywords: governance, human development index, human security, Pakistan, policy

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Authors: Abdelrahman Elsehsah

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The main objective of this study is to assess changes in the water capacity of Aswan High Dam Lake (AHDL) caused by evaporation and seepage losses. To achieve this objective, a comprehensive methodology was employed. The methodology involves acquiring Sentinel-3 imagery and extracting the surface area of the lake using remote sensing techniques. Using water areas calculated from sentinel images, collected field data, and the lake’s water balance equation, monthly evaporation and seepage losses were estimated for the years 2021 and 2022. Based on the water balance method results, the average monthly evaporation losses for the year 2021 were estimated to be around 1.41 billion cubic meters (Bm3), which closely matches the estimates provided by the Ministry of Water Resources and Irrigation (MWRI) annual reports (approximately 1.37 Bm3 in the same year). This means that the water balance method slightly overestimated the monthly evaporation losses by about 2.92%. Similarly, the average monthly seepage losses for the year 2022 were estimated to be around 0.005 Bm3, while the MWRI reports indicated approximately 0.0046 Bm3. By another means, the water balance method overestimated the monthly seepage losses by about 8.70%. Furthermore, the study found that the average monthly evaporation rate within AHDL was 210.88 mm/month, which closely aligns with the computed value of approximately 204.9 mm/month by AHDA. These findings indicated that the applied water balance method, utilizing remote sensing and field data, is a reliable tool for estimating monthly evaporation and seepage losses as well as monthly evaporation rates in AHDL.

Keywords: Aswan high dam lake, remote sensing, water balance equation, seepage loss, evaporation loss

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Authors: Hande Yesil, Seda Aycan Altan, M. Vehbi Bal, Alper Uyar, O. Cumhur Sipahi

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Purpose: Fixed partial dentures (FPDs) must fulfill functional requirements such as phonetics, chewing efficiency and esthetics especially in the anterior region. A convex type tissue surface is usually recommended for pontics of FPDs. That pontic design also provides suitable oral hygiene and ease of cleaning. However, high esthetic requirements and correct emergence profile are not always achievable because of the convex shape of adjacent soft tissues. Therefore, the ovate type pontic which fulfills the high esthetic demands of the patients may be a good alternative to the modified ridge lap pontic design. Clinical Report: A female patient referred with the complaint of anterior upper edentulousness. In the oral examination it was determined that teeth 11, 12, 21, 22 were deficient. A thick and convex gingival tissue that may cause aesthetic problems was also observed.. Periodontal augmentation surgery was performed to ensure proper papillary configuration and gingival contour. An interim removable partial denture (IRPD) which applied pressure to operated gingival tissues was fabricated postoperatively. The IRPD was used for 4 weeks and after completion of tissue sculpting, the permanent FPD with an ovate pontic was fabricated and cemented. After a follow-up period of 6 months, not any esthetical and hygienic problem was detected and the patient was satisfied with her prosthesis. Conclusion: It was concluded that shaping of gingival contours with IRPD and use of a FPD with ovate pontic fulfills all esthetic and hygienic requirements.

Keywords: interim appliance, ovate pontic, tissue sculpturing, fixed partial denture

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Authors: Tri Harianto, Lawalenna Samang, St. Hijraini Nur, Arwin

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Recently, a port development is constructed in Makassar city, South Sulawesi Province, Indonesia. Makassar city is located in lowland area that dominated by soft marine clay deposit. A two kilometers causeway construction was built which is situated on the soft clay layer. In order to investigate the behavior of causeway embankment, a full-scale test was conducted of high embankment built on a soft clay deposit. The embankment with 3,5 m high was supported by two types of reinforcement such as raft and raft-aggregate column foundation. Since the ground was undergoing consolidation due to the preload, the raft and raft-aggregate column foundations were monitored in order to analyze the vertical ground movement by inducing the settlement of the foundation. In this study, two types of foundation (raft and raft-aggregate column) were tested to observe the effectiveness of raft-aggregate column compare to raft foundation in reducing the settlement. The settlement monitored during the construction stage by using the settlement plates, which is located in the center and toe of the embankment. Measurements were taken every day for each embankment construction stage (4 months). In addition, an analytical calculation was conducted in this study to compare the full-scale test result. The result shows that the raft-aggregate column foundation significantly reduces the settlement by 30% compared to the raft foundation. A raft-aggregate column foundation also reduced the time period of each loading stage. The Good agreement of analytical calculation compared to the full-scale test result also found in this study.

Keywords: full-scale, preloading, raft-aggregate column, soft clay

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Authors: R. R. Dewi Rahmawaty Aktyani Putri, Earmporn Thongkrajai, Dedy Purwito

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There were many instruments have been developed to assess social support which has the different dimension in breast cancer patients. The Issue of measurement is a challenge to determining the component of dimensional concept, defining the unit of measurement, and establishing the validity and reliability of the measurement. However, the instruments where need to know how much support which obtained and perceived among women with breast cancer who undergone chemotherapy which it can help nurses to prevent of non-adherence in chemotherapy. This study aimed to measure the reliability of BC-SSAS instrument among 30 Indonesian women with breast cancer aged 18 years and above who undergone chemotherapy for six cycles in the oncological unit of Outpatient Department (OPD), Margono Soekardjo Hospital, Central Java, Indonesia. Data were collected during October to December 2015 by using modified the Breast Cancer Social Support Assessment (BC-SSAS). The Cronbach’s alpha analysis was carried out to measure internal consistency for reliability test of BC-SSAS instrument. This study used five experts for content validity index. The results showed that for content validity, I-CVI was 0.98 and S-CVI was 0.98; Cronbach’s alpha value was 0.971 and the Cronbach’s alpha coefficients for the subscales were high, with 0.903 for emotional support, 0.865 for informational support, 0.901 for tangible support, 0.897 for appraisal support and 0.884 for positive interaction support. The results confirmed that the BC-SSAS instrument has high reliability. BC-SSAS instruments were reliable and can be used in health care services to measure the social support received and perceived among women with breast cancer who undergone chemotherapy so that preventive interventions can be developed and the quality of health services can be improved.

Keywords: BC-SSAS, women with breast cancer, chemotherapy, Indonesia

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Authors: Dina L. DiSantis

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Strengthening a sense of responsibility while relating global sustainability concepts such as water quality and pollution to a local water system can be achieved by teaching students to conduct and interpret water quality monitoring tests. When students conduct their own research, they become better stewards of the environment. Providing outdoor learning and place-based opportunities for students helps connect them to the natural world. By conducting stream studies and collecting data, students are able to better understand how the natural environment is a place where everything is connected. Students have been collecting physical, chemical and biological data along the West and East Branches of the Brandywine River, in Pennsylvania for over ten years. The stream studies are part of the advanced placement environmental science and aquatic science courses that are offered as electives to juniors and seniors at the Downingtown High School West Campus in Downingtown, Pennsylvania. Physical data collected includes: temperature, turbidity, width, depth, velocity, and volume of flow or discharge. The chemical tests conducted are: dissolved oxygen, carbon dioxide, pH, nitrates, alkalinity and phosphates. Macroinvertebrates are collected with a kick net, identified and then released. Students collect the data from several locations while traveling by canoe. In the classroom, students prepare a water quality data analysis and interpretation report based on their collected data. The summary of the results from longitudinal water quality data collection by students, as well as the strengths and weaknesses of student data collection will be presented.

Keywords: place-based, student data collection, sustainability, water quality monitoring

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Authors: Miguel Mellado, Cecilia Zapata

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Goats can be exploited in harsh environments due to their capacity to adjust to limited quantity and quality forage sources. In these environments, leguminous trees can be used as supplementary feeds as foliage and fruits of these trees can contribute to maintain or improve production efficiency in ruminants. The objective of this study was to determine the nutritional value of three leguminous trees heavily selected by goats in a xerophyllous shrubland. Chemical composition and in vitro dry matter disappearance (IVDMD) of leaves and pods from leucaena (Leucaena leucocephala), mesquite (Prosopis laevigata) and huisache (Acacia farnesiana) is presented. Crude protein (CP) ranged from 17.3% for leaves of huisache to 21.9% for leucaena. The neutral detergent fiber (NDF) content ranged from 39.0 to 40.3 with no difference among fodder threes. Across tree species, mean IVDMD was 61.6% for pods and 52.2% for leaves. IVDMD for leaves was highest (P < 0.01) for leucaena (54.9%) and lowest for huisache (47.3%). Condensed tannins in an acetonic extract were highest for leaves of huisache (45.3 mg CE/g DM) and lowest for mesquite (25.9 mg CE/g DM). Pods and leaves of huisache presented the highest number of secondary metabolites, mainly related to hydrobenzoic acid and flavonols; leucaena and mesquite presented mainly flavonols and anthocyanins. It was concluded that leaves and pods of leucaena, mesquite and huisache constitute valuable forages for ruminant livestock due to its low fiber, high CP levels, moderate in vitro fermentation characteristics and high mineral content. Keywords: Fodder tree; ruminants; secondary metabolites; minerals; tannins

Keywords: fodder tree, ruminants, secondary metabolites, minerals, tannins

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Authors: Girts Bumanis, Diana Bajare

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With demand for primary energy continuously growing, search for renewable and efficient energy sources has been high on agenda of our society. One of the most promising energy sources is biogas technology. Residues coming from dairy industry and milk processing could be used in biogas production; however, low efficiency and high cost impede wide application of such technology. One of the main problems is management and conversion of organic residues through the anaerobic digestion process which is characterized by acidic environment due to the low whey pH (<6) whereas additional pH control system is required. Low buffering capacity of whey is responsible for the rapid acidification in biological treatments; therefore alkali activated material is a promising solution of this problem. Alkali activated material is formed using SiO2 and Al2O3 rich materials under highly alkaline solution. After material structure forming process is completed, free alkalis remain in the structure of materials which are available for leaching and could provide buffer capacity potential. In this research porous alkali activated material was investigated. Highly porous material structure ensures gradual leaching of alkalis during time which is important in biogas digestion process. Research of mixture composition and SiO2/Na2O and SiO2/Al2O ratio was studied to test the buffer capacity potential of alkali activated material. This research has proved that by changing molar ratio of components it is possible to obtain a material with different buffer capacity, and this novel material was seen to have considerable potential for using it in processes where buffer capacity and pH control is vitally important.

Keywords: alkaline material, buffer capacity, biogas production, bioreactors

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Authors: Charles Amoo, Joshua New, Bill Eckman

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Buildings in the United States account for a significant proportion of energy consumption and greenhouse gas (GHG) emissions, and this trend is expected to continue as well as rise in the near future. Low-income households, in particular, bear a disproportionate burden of high building energy consumption and spending due to high energy costs. Energy efficiency improvements need to reach an average of 4% per year in this decade in order to meet global net zero emissions target by 2050, but less than 1 % of U.S. buildings are improved each year. The government has recognized the importance of technology in addressing this issue, and energy efficiency programs have been developed to tackle the problem. The Weatherization Assistance Program (WAP), the largest residential whole-house energy efficiency program in the U.S., is specifically designed to reduce energy costs for low-income households. Under the WAP, energy auditors must follow specific audit procedures and use Department of Energy (DOE) approved energy audit tools or software. This article proposes an expanded framework of factors that should be considered in energy audit software that is approved for use in energy efficiency programs, particularly for low-income households. The framework includes more than 50 factors organized under 14 assessment criteria and can be used to qualitatively and quantitatively score different energy audit software to determine their suitability for specific energy efficiency programs. While the tool can be useful for developers to build new tools and improve existing software, as well as for energy efficiency program administrators to approve or certify tools for use, there are limitations to the model, such as the lack of flexibility that allows continuous scoring to accommodate variability and subjectivity. These limitations can be addressed by using aggregate scores of each criterion as weights that could be combined with value function and direct rating scores in a multicriteria decision analysis for a more flexible scoring.

Keywords: buildings, energy efficiency, energy audit, software

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Authors: P. M. Sreekanth

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Teak (Tectona grandis L. f.) is a tree species indigenous to India and other Southeastern countries. It produces high-value timber and is easily established in plantations. Reforestation requires a constant supply of high quality seeds. Seed Production Areas (SPA) of teak are improved stands used for collection of open-pollinated quality seeds in large quantities. Information on the genetic diversity of major teak SPAs in India is scanty. The genetic structure of four important seed production areas of Kerala State in Southern India was analyzed employing amplified fragment length polymorphism markers using ten selective primer combinations on 80 samples (4 populations X 20 trees). The study revealed that the gene diversity of the SPAs varied from 0.169 (Konni SPA) to 0.203 (Wayanad SPA). The percentage of polymorphic loci ranged from 74.42 (Parambikulam SPA) to 84.06 (Konni SPA). The mean total gene diversity index (HT) of all the four SPAs was 0.2296 ±0.02. A high proportion of genetic diversity was observed within the populations (83%) while diversity between populations was lower (17%) (GST = 0.17). Principal coordinate analysis and STRUCTURE analysis of the genotypes indicated that the pattern of clustering was in accordance with the origin and geographic location of SPAs, indicating specific identity of each population. A UPGMA dendrogram was prepared and showed that all the twenty samples from each of Konni and Parambikulam SPAs clustered into two separate groups, respectively. However, five Nilambur genotypes and one Wayanad genotype intruded into the Konni cluster. The higher gene flow estimated (Nm = 2.4) reflected the inclusion of Konni origin planting stock in the Nilambur and Wayanad plantations. Evidence for population structure investigated using 3D Principal Coordinate Analysis of FAMD software 1.30 indicated that the pattern of clustering was in accordance with the origin of SPAs. The present study showed that assessment of genetic diversity in seed production plantations can be achieved using AFLP markers. The AFLP fingerprinting was also capable of identifying the geographical origin of planting stock and there by revealing the occurrence of the errors in genotype labeling. Molecular marker-based selective culling of genetically similar trees from a stand so as to increase the genetic base of seed production areas could be a new proposition to improve quality of seeds required for raising commercial plantations of teak. The technique can also be used to assess the genetic diversity status of plus trees within provenances during their selection for raising clonal seed orchards for assuring the quality of seeds available for raising future plantations.

Keywords: AFLP, genetic structure, spa, teak

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Authors: Debabrata Bhadra, B. K. Chaudhuri

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The operation of organic thin film transistors (OFETs) with low voltage is currently a prevailing issue. We have fabricated anthracene thin-film transistor (TFT) with an ultrathin layer (~450nm) of Poly-vinylidene fluoride (PVDF)/CuO nanocomposites as a gate insulator. We obtained a device with excellent electrical characteristics at low operating voltages (<1V). Different layers of the film were also prepared to achieve the best optimization of ideal gate insulator with various static dielectric constant (εr ). Capacitance density, leakage current at 1V gate voltage and electrical characteristics of OFETs with a single and multi layer films were investigated. This device was found to have highest field effect mobility of 2.27 cm2/Vs, a threshold voltage of 0.34V, an exceptionally low sub threshold slope of 380 mV/decade and an on/off ratio of 106. Such favorable combination of properties means that these OFETs can be utilized successfully as voltages below 1V. A very simple fabrication process has been used along with step wise poling process for enhancing the pyroelectric effects on the device performance. The output characteristic of OFET after poling were changed and exhibited linear current-voltage relationship showing the evidence of large polarization. The temperature dependent response of the device was also investigated. The stable performance of the OFET after poling operation makes it reliable in temperature sensor applications. Such High-ε CuO/PVDF gate dielectric appears to be highly promising candidates for organic non-volatile memory and sensor field-effect transistors (FETs).

Keywords: organic field effect transistors, thin film transistor, gate dielectric, organic semiconductor

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Authors: Malika Souada, Juanita Rausch, Benjamin Guinot, Christine Bugajny

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The increase of global commerce and tourism makes the shipping sector an important contributor of atmospheric pollution. Both, airborne particles and gaseous pollutants have negative impact on health and climate. This is especially the case in port cities, due to the proximity of the exposed population to the shipping emissions in addition to other multiple sources of pollution linked to the surrounding urban activity. The objective of this study is to determine the concentrations of fine particles (immission), specifically PM2.5, PM1, PM0.3, BC and sulphates, in a context where maritime passenger traffic plays an important role (port area of Bordeaux centre). The methodology is based on high temporal resolution measurements of pollutants, correlated with meteorological and ship movements data. Particles and gaseous pollutants from seven maritime passenger ships were sampled and analysed during the docking, manoeuvring and berthing phases. The particle mass measurements were supplemented by measurements of the number concentration of ultrafine particles (<300 nm diameter). The different measurement points were chosen by taking into account the local meteorological conditions and by pre-modelling the dispersion of the smoke plumes. The results of the measurement campaign carried out during the summer of 2021 in the port of Bordeaux show that the detection of concentrations of particles emitted by ships proved to be punctual and stealthy. Punctual peaks of ultrafine particle concentration in number (P#/m3) and BC (ng/m3) were measured during the docking phases of the ships, but the concentrations returned to their background level within minutes. However, it appears that the influence of the docking phases does not significantly affect the air quality of Bordeaux centre in terms of mass concentration. Additionally, no clear differences in PM2.5 concentrations between the periods with and without ships at berth were observed. The urban background pollution seems to be mainly dominated by exhaust and non-exhaust road traffic emissions. However, temporal high-resolution measurements suggest a probable emission of gaseous precursors responsible for the formation of secondary aerosols related to the ship activities. This was evidenced by the high values of the PM1/BC and PN/BC ratios, tracers of non-primary particle formation, during periods of ship berthing vs. periods without ships at berth. The research findings from this study provide robust support for port area air quality assessment and source apportionment.

Keywords: characterization, fine particulate matter, harbour air quality, shipping impacts

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Authors: Benoit Atge, Alice Dhersin, Oscar Da Silva Cacao, Beatrice Martinez, Dominique Ducint, Catherine Verdun-Esquer, Isabelle Baldi, Mathieu Molimard, Antoine Villa, Mireille Canal-Raffin

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Introduction: Healthcare workers' exposure to antineoplastic drugs (AD) is a burning issue for occupational medicine practitioners. Biological monitoring of occupational exposure (BMOE) is an essential tool for assessing AD contamination of healthcare workers. In addition to BMOE, surface sampling is a useful tool in order to understand how workers get contaminated, to identify sources of environmental contamination, to verify the effectiveness of surface decontamination way and to ensure monitoring of these surfaces. The objective of this work was to develop a complete tool including a kit for surface sampling and a quantification analytical method for AD traces detection. The development was realized with the three following criteria: the kit capacity to sample in every professional environment (healthcare services, veterinaries, etc.), the detection of very low AD traces with a validated analytical method and the easiness of the sampling kit use regardless of the person in charge of sampling. Material and method: AD mostly used in term of quantity and frequency have been identified by an analysis of the literature and consumptions of different hospitals, veterinary services, and home care settings. The kind of adsorbent device, surface moistening solution and mix of solvents for the extraction of AD from the adsorbent device have been tested for a maximal yield. The AD quantification was achieved by an ultra high-performance liquid chromatography method coupled with tandem mass spectrometry (UHPLC-MS/MS). Results: With their high frequencies of use and their good reflect of the diverse activities through healthcare, 15 AD (cyclophosphamide, ifosfamide, doxorubicin, daunorubicin, epirubicin, 5-FU, dacarbazin, etoposide, pemetrexed, vincristine, cytarabine, methothrexate, paclitaxel, gemcitabine, mitomycin C) were selected. The analytical method was optimized and adapted to obtain high sensitivity with very low limits of quantification (25 to 5000ng/mL), equivalent or lowest that those previously published (for 13/15 AD). The sampling kit is easy to use, provided with a didactic support (online video and protocol paper). It showed its effectiveness without inter-individual variation (n=5/person; n= 5 persons; p=0,85; ANOVA) regardless of the person in charge of sampling. Conclusion: This validated tool (sampling kit + analytical method) is very sensitive, easy to use and very didactic in order to control the chemical risk brought by AD. Moreover, BMOE permits a focal prevention. Used in routine, this tool is available for every intervention of occupational health.

Keywords: surface contamination, sampling kit, analytical method, sensitivity

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Authors: Ahmad I. Ayesh

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This work reports on the fabrication of tin nanoclusters by sputtering and inert-gas condensation inside an ultra-high vacuum compatible system. This technique allows to fine tune the size and yield of nanoclusters by controlling the nanocluster source parameters. The produced nanoclusters are deposited on SiO2/Si substrate with pre-formed electrical electrodes to produce a nanocluster device. Those devices can be potentially used for gas sensor applications.

Keywords: tin, nanoclusters, inert-gas condensation, nanotechnology

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Authors: Hiba T. Allah ALtieb Gusm ALsied, Amna Beshir Medani Ahmed, Ikram Mohamed ELtayeb, Saad Mohamed Hussein Ayoub

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This study was carried out to determine the hepatoactivity and the antioxidant activity of Coiradrum sativum L. aerial part and fruit extracts against CCL4 induced acute liver damages in Wistar rats. The aerial parts and fruits part of the plant were extracted 96% ethanol with soxhlet apparatus. Hepatic injury was achieved by subcutaneous injection of 3 ml/kg of CCL4 diluted with olive oil with ratio 1:1. The extracts were mixed together 1:1 ratio and given in different doses 100,200,400 mg/kg/day for 5 days under CCL4 induction at 3rd day. The significance of differences between means by using T-test was compared among the groups. The mixture of the two extracts didn’t show any significant result in protecting liver injury (antagonistic effects), it shows high level of liver enzyme like alkaline phosphatase (ALP), glutamate oxaloacetate transaminase (SGOT) and glutamate pyruvate transaminase (SGPT). Serological studies further confirmed the results. The results obtained were compared with silymarin (70 mg/kg/day) orally, the standard drug for hepatoprotection which show recovery close to normalization almost like that of silymarin; therefore, further studies on this plant with different ratios especially in isolated tissue to spot more light on antagonistic effects of the two extracts. Antioxidant activity of the extracts was determined by the DPPH method. The results obtained show high anti-oxidant activity for fruits extract while slight or moderate antioxidant activity to aerial extracts.

Keywords: antioxidant, aerial part, Coriadrum sativum L., fruity, hepatoprotection, Silymarin, phytochemical screening

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Authors: Kuheli Chakrabarty, Animesh Ghosh, Atanu Roy, Gourab Kanti Das

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Aldol reaction is an important class of carbon-carbon bond forming reactions. One of the popular ways to impose asymmetry in aldol reaction is the introduction of chiral auxiliary that binds the approaching reactants and create dissymmetry in the reaction environment, which finally evolves to enantiomeric excess in the aldol products. The last decade witnesses the usage of natural amino acids as chiral auxiliary to control the stereoselectivity in various carbon-carbon bond forming processes. In this context, L-proline was found to be an effective organocatalyst in asymmetric aldol additions. In last few decades the use of water as solvent or co-solvent in asymmetric organocatalytic reaction is increased sharply. Simple amino acids like L-proline does not catalyze asymmetric aldol reaction in aqueous medium not only that, In organic solvent medium high catalytic loading (~30 mol%) is required to achieve moderate to high asymmetric induction. In this context, huge efforts have been made to modify L-proline and 4-hydroxy-L-proline to prepare organocatalyst for aqueous medium asymmetric aldol reaction. Here, we report the result of our DFT calculations on asymmetric aldol reaction of benzaldehyde, p-NO2 benzaldehyde and t-butyraldehyde with a number of ketones using L-proline hydrazide as organocatalyst in wet solvent free condition. Gaussian 09 program package and Gauss View program were used for the present work. Geometry optimizations were performed using B3LYP hybrid functional and 6-31G(d,p) basis set. Transition structures were confirmed by hessian calculation and IRC calculation. As the reactions were carried out in solvent free condition, No solvent effect were studied theoretically. Present study has revealed for the first time, the direct involvement of two water molecules in the aldol transition structures. In the TS, the enamine and the aldehyde is connected through hydrogen bonding by the assistance of two intervening water molecules forming a supramolecular network. Formation of this type of supramolecular assembly is possible due to the presence of protonated -NH2 group in the L-proline hydrazide moiety, which is responsible for the favorable entropy contribution to the aldol reaction. It is also revealed from the present study that, water assisted TS is energetically more favorable than the TS without involving any water molecule. It can be concluded from this study that, insertion of polar group capable of hydrogen bond formation in the L-proline skeleton can lead to a favorable aldol reaction with significantly high enantiomeric excess in wet solvent free condition by reducing the activation barrier of this reaction.

Keywords: aldol reaction, DFT, organocatalysis, transition structure

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