Search results for: green chemistry

Authors: Y. Mateyshina, A.Ulihin, N.Uvarov

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Electrolytes with different type of charge carrier can find widely application in different using, e.g. sensors, electrochemical equipments, batteries and others. One of important components ensuring stable functioning of the equipment is electrolyte. Electrolyte has to be characterized by high conductivity, thermal stability, and wide electrochemical window. In addition to many advantageous characteristic for liquid electrolytes, the solid state electrolytes have good mechanical stability, wide working range of temperature range. Thus search of new system of solid electrolytes with high conductivity is an actual task of solid state chemistry. Families of alkali perchlorates and nitrates have been investigated by us earlier. In literature data about transport properties of alkali nitrites are absent. Nevertheless, alkali nitrites MeNO2 (Me= Li+, Na+, K+, Rb+ and Cs+), except for the lithium salt, have high-temperature phases with crystal structure of the NaCl-type. High-temperature phases of nitrites are orientationally disordered, i.e. non-spherical anions are reoriented over several equivalents directions in the crystal lattice. Pure lithium nitrite LiNO2 is characterized by ionic conductivity near 10-4 S/cm at 180°C and more stable as compared with lithium nitrate and can be used as a component for synthesis of composite electrolytes. In this work composite solid electrolytes in the binary system LiNO2 - A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) were synthesized and their structural, thermodynamic and electrical properties investigated. Alkali nitrite was obtained by exchange reaction from water solutions of barium nitrite and alkali sulfate. The synthesized salt was characterized by X-ray powder diffraction technique using D8 Advance X-Ray Diffractometer with Cu K radiation. Using thermal analysis, the temperatures of dehydration and thermal decomposition of salt were determined.. The conductivity was measured using a two electrode scheme in a forevacuum (6.7 Pa) with an HP 4284A (Precision LCR meter) in a frequency range 20 Hz < ν < 1 MHz. Solid composite electrolytes LiNO2 - A A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) have been synthesized by mixing of preliminary dehydrated components followed by sintering at 250°C. In the series of nitrite of alkaline metals Li+-Cs+, the conductivity varies not monotonically with increasing radius of cation. The minimum conductivity is observed for KNO2; however, with further increase in the radius of cation in the series, the conductivity tends to increase. The work was supported by the Russian Foundation for Basic research, grant #14-03-31442.

Keywords: conductivity, alkali nitrites, composite electrolytes, transport properties

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Authors: Yiqi Sun, Zhiyuan Zhang, Chenkun Ma

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Regeneration of outmoded urban forms and restorative environments are now recognized as major assets towards achieving sustainable development. Shanghai, like many Chinese cities, is now shifting from an agitated industrial past to more livable development schemes. Therefore, a sustainable approach to Shanghai development consists in turning industrial heritage into places with high potential for improving citizen’s daily life as regard to the three pillars of sustainability, namely: environment, economy, and society. As such, this study focuses on the Corniche in Xuhui West Bund district; a former industrial area converted into recreational public spaces in Xuhui West Bund. This area was the birthplace of the aviation industry of China, and many of the industrial features were preserved. Unused areas have been transformed into exhibition halls and green spaces, integrating some of the original industrial, architectural forms. Our case study investigates the effects of this approach associating urban regeneration with restorative design, as well as its impact on the surrounding neighborhood. Information extracted from visitors’ answers to a questionnaire survey; on-site systematic observation, counts, and measurements allowed us to assess the sustainability of this intervention in terms of accessibility, functionality, cultural and restorative qualities. In general, we found that cycling is not highly encouraged by the current design and level of connectivity, while visitors widely acknowledge the enhancement of cultural heritage resulting from the intervention. Moreover, recreational and restorative areas were found to have a very positive effect on local communities. Indeed, such an approach can provide valuable insights on how future interventions in Chinese major cities could take full advantage of existing assets in creating a more environmental, more livable, and culturally richer city.

Keywords: architectural heritage conservation, cultural urban identity, sustainability assessment, restorative environment, urban regeneration

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Authors: Georgios Koronis, Arlindo Silva

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This study seeks to understand the mechanical behavior of a natural fiber reinforced composite (epoxy/flax) in more depth, utilizing both experimental and numerical methods. It is attempted to identify relationships between the design parameters and the product performance, understand the effect of noise factors and reduce process variations. Optimization of the mechanical performance of manufactured goods has recently been implemented by numerous studies for green composites. However, these studies are limited and have explored in principal mass production processes. It is expected here to discover knowledge about composite’s manufacturing that can be used to design artifacts that are of low batch and tailored to niche markets. The goal is to reach greater consistency in the performance and further understand which factors play significant roles in obtaining the best mechanical performance. A prediction of response function (in various operating conditions) of the process is modeled by the DoE. Normally, a full factorial designed experiment is required and consists of all possible combinations of levels for all factors. An analytical assessment is possible though with just a fraction of the full factorial experiment. The outline of the research approach will comprise of evaluating the influence that these variables have and how they affect the composite mechanical behavior. The coupons will be fabricated by the vacuum infusion process defined by three process parameters: flow rate, injection point position and fiber treatment. Each process parameter is studied at 2-levels along with their interactions. Moreover, the tensile and flexural properties will be obtained through mechanical testing to discover the key process parameters. In this setting, an experimental phase will be followed in which a number of fabricated coupons will be tested to allow for a validation of the design of the experiment’s setup. Finally, the results are validated by performing the optimum set of in a final set of experiments as indicated by the DoE. It is expected that after a good agreement between the predicted and the verification experimental values, the optimal processing parameter of the biocomposite lamina will be effectively determined.

Keywords: design of experiments, flax fabrics, mechanical performance, natural fiber reinforced composites

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Authors: Julia R. Beulig, Stefan Ohla, Detlev Belder

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In contrast to off-line analytical methods, lab-on-a-chip technology delivers direct information about the observed reaction. Therefore, microfluidic devices make an important scientific contribution, e.g. in the field of synthetic chemistry. Herein, the rapid generation of analytical data can be applied for the optimization of chemical reactions. These microfluidic devices enable a fast change of reaction conditions as well as a resource saving method of operation. In the presented work, we focus on the investigation of multiphase regimes, more specifically on a biphasic microfluidic droplet systems. Here, every single droplet is a reaction container with customized conditions. The biggest challenge is the rapid qualitative and quantitative readout of information as most detection techniques for droplet systems are non-specific, time-consuming or too slow. An exception is the electrospray mass spectrometry (ESI-MS). The combination of a reaction screening platform with a rapid and specific detection method is an important step in droplet-based microfluidics. In this work, we present a novel approach for synthesis optimization on the nanoliter scale with direct ESI-MS detection. The development of a droplet-based microfluidic device, which enables the modification of different parameters while simultaneously monitoring the effect on the reaction within a single run, is shown. By common soft- and photolithographic techniques a polydimethylsiloxane (PDMS) microfluidic chip with different functionalities is developed. As an interface for the MS detection, we use a steel capillary for ESI and improve the spray stability with a Teflon siphon tubing, which is inserted underneath the steel capillary. By optimizing the flow rates, it is possible to screen parameters of various reactions, this is exemplarity shown by a Domino Knoevenagel Hetero-Diels-Alder reaction. Different starting materials, catalyst concentrations and solvent compositions are investigated. Due to the high repetition rate of the droplet production, each set of reaction condition is examined hundreds of times. As a result, of the investigation, we receive possible reagents, the ideal water-methanol ratio of the solvent and the most effective catalyst concentration. The developed system can help to determine important information about the optimal parameters of a reaction within a short time. With this novel tool, we make an important step on the field of combining droplet-based microfluidics with organic reaction screening.

Keywords: droplet, mass spectrometry, microfluidics, organic reaction, screening

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Authors: Gina Longo

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Social media, internet technology, and affordable travel have created avenues like tourism and internet chatrooms for Western women to meet foreign partners without paid, third-party intermediaries in regions like the Middle East/North Africa (MENA) and Sub-Saharan Africa (SSA), where men from mid-level developing countries meet and marry Western women and try to relocate. Foreign nationals who marry U.S. citizens have an expedited track to naturalization. U.S. immigration officials require that “green card” petitioning couples demonstrate that their relationships are “valid and subsisting” (i.e., for love) and not fraudulent (i.e., for immigration papers). These requirements are ostensibly gender- and racially-neutral, but migration itself is not; black and white women petitioners who seek partners from these regions and solicit advice from similar others about the potential obstacles to their petitions’ success online. Using an online ethnography and textual analysis of conversation threads on a large on-line immigration forum where U.S. petitioners exchange such information, this study examines how gendered and racialized standards of legitimacy are applied to family and sexuality and used discursively online among women petitioners differently to achieve “genuineness” and define “red flags” indicating potential marriage fraud. This paper argues that forum-women members police immigration requests even before cases reach an immigration officer, and use this social media platform to reconstruct gendered and racialized hierarchies of U.S. citizenship. Women petitioners use the formal criteria of U.S. immigration in ways that reveal gender and racial ideologies, expectations for conformity to a gendered hegemonic family ideal, and policing of women’s sexual agency, fertility, and desirability. These intersectional norms shape their online discussions about the suitability of marriages and of the migration of non-citizen male partners of color to the United States.

Keywords: marriage fraud, migration, online forums, women

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Authors: Zou Xuan, Liu Hongchen

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The ideal dentin desensitizing agent should not only have good biological safety, simple clinical operation mode, the superior treatment effect, but also should have a durable effect to resist the oral environmental temperature change and oral mechanical abrasion, so as to achieve a persistent desensitization effect. Also, when using desensitizing agent to prevent the post-operative hypersensitivity, we should not only prevent it from affecting crowns’ retention, but must understand its effects on bond strength of dentin adhesives. There are various of desensitizers and dentin adhesives in clinical treatment. They have different chemical or physical properties. Whether the use of desensitizing agent would affect the bond strength of dentin adhesives still need further research. In this in vitro study, we built the hypersensitive dentin model and post-operative dentin model, to evaluate the sealing effects and durability on exposed tubule by three different dentin desensitizers and to evaluate the sealing effects and the bond strength of dentin adhesives after using three different dentin desensitizers on post-operative dentin. The result of this study could provide some important references for clinical use of dentin desensitizing agent. 1. As to the three desensitizers, the hypersensitive dentin model was built to evaluate their sealing effects on exposed tubule by SEM observation and dentin permeability analysis. All of them could significantly reduce the dentin permeability. 2. Test specimens of three groups treated by desensitizers were subjected to aging treatment with 5000 times thermal cycling and toothbrush abrasion, and then dentin permeability was measured to evaluate the sealing durability of these three desensitizers on exposed tubule. The sealing durability of three groups were different. 3. The post-operative dentin model was built to evaluate the sealing effects of the three desensitizers on post-operative dentin by SEM and methylene blue. All of three desensitizers could reduce the dentin permeability significantly. 4. The influences of three desensitizers on the bonding efficiency of total-etch and self-etch adhesives were evaluated with the micro-tensile bond strength study and bond interface morphology observation. The dentin bond strength for Green or group was significantly lower than the other two groups (P<0.05).

Keywords: dentin, desensitizer, dentin permeability, thermal cycling, micro-tensile bond strength

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Authors: Khodzhaberdi Allaberdiev

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Aromaticity, one of the most important concepts in organic chemistry, has attracted considerable interest from both experimentalists and theoreticians. The geometry optimization of p-substituted o-(N-dialkyl)aminomethylphenols, o-DEAMPH XC₆ H₅CH ₂Y (X=p-OCH₃, CH₃, H, F, Cl, Br, COCH₃, COOCH₃, CHO, CN and NO₂, Y=o-N (C₂H₅)₂, o-DEAMPHs have been performed in the gas phase using the B3LYP/6-311+G(d,p) level. Aromaticities of the considered molecules were investigated using different indices included geometrical (HOMA and Bird), electronic (FLU, PDI and SA) magnetic (NICS(0), NICS(1) and NICS(1)zz indices. The linear dependencies were obtained between some aromaticity indices. The best correlation is observed between the Bird and PDI indices (R² =0.9240). However, not all types of indices or even different indices within the same type correlate well among each other. Surprisingly, for studied molecules in which geometrical and electronic cannot correctly give the aromaticity of ring, the magnetism based index successfully predicts the aromaticity of systems. 1H NMR spectra of compounds were obtained at B3LYP/6–311+G(d,p) level using the GIAO method. Excellent linear correlation (R²= 0.9996) between values the chemical shift of hydrogen atom obtained experimentally of 1H NMR and calculated using B3LYP/6–311+G(d,p) demonstrates a good assignment of the experimental values chemical shift to the calculated structures of o-DEAMPH. It is found that the best linear correlation with the Hammett substituent constants is observed for the NICS(1)zz index in comparison with the other indices: NICS(1)zz =-21.5552+1,1070 σp- (R²=0.9394). The presence intramolecular hydrogen bond in the studied molecules also revealed changes the aromatic character of substituted o-DEAMPHs. The HOMA index predicted for R=NO2 the reduction in the π-electron delocalization of 3.4% was about double that observed for p-nitrophenol. The influence intramolecular H-bonding on aromaticity of benzene ring in the ground state (S0) are described by equations between NICS(1)zz and H-bond energies: experimental, Eₑₓₚ, predicted IR spectroscopical, Eν and topological, EQTAIM with correlation coefficients R² =0.9666, R² =0.9028 and R² =0.8864, respectively. The NICS(1)zz index also correlates with usual descriptors of the hydrogen bond, while the other indices do not give any meaningful results. The influence of the intramolecular H-bonding formation on the aromaticity of some substituted o-DEAMPHs is criteria to consider the multidimensional character of aromaticity. The linear relationships as well as revealed between NICS(1)zz and both pyramidality nitrogen atom, ΣN(C₂H₅)₂ and dihedral angle, φ CAr – CAr -CCH₂ –N, to characterizing out-of-plane properties.These results demonstrated the nonplanar structure of o-DEAMPHs. Finally, when considering dependencies of NICS(1)zz, were excluded data for R=H, because the NICS(1) and NICS(1)zz values are the most negative for unsubstituted DEAMPH, indicating its highest aromaticity; that was not the case for NICS(0) index.

Keywords: aminomethylphenols, DFT, aromaticity, correlations

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Authors: Md. Fazlul Karim, Ashik Sharfaraz, Aysha Ferdoushi

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Background: Computational medicinal chemistry approaches are used for designing and identifying new drug-like molecules, predicting properties and pharmacological activities, and optimizing lead compounds in drug development. SIRT7, a nicotinamide adenine dinucleotide (NAD+)-dependent deacylase which regulates aging, is an emerging target for cancer therapy with mounting evidence that SIRT7 downregulation plays important roles in reversing cancer phenotypes and suppressing tumor growth. Activation or altered expression of SIRT7 is associated with the progression and invasion of various cancers, including liver, breast, gastric, prostate, and non-small cell lung cancer. Objectives: The goal of this work was to identify potent and selective bioactive candidate inhibitors of SIRT7 by in silico screening of small molecule compounds obtained from Nigella sativa (N. sativa). Methods: SIRT7 structure was retrieved from The Research Collaboratory for Structural Bioinformatics Protein Data Bank (RCSB PDB), and its active site was identified using CASTp and metaPocket. Molecular docking simulation was performed with PyRx 0.8 virtual screening software. Drug-likeness properties were tested using SwissADME and pkCSM. In silico toxicity was evaluated by Osiris Property Explorer. Bioactivity was predicted by Molinspiration software. Antitumor activity was screened for Prediction of Activity Spectra for Substances (PASS) using Way2Drug web server. Molecular dynamics (MD) simulation was carried out by Desmond v3.6 package. Results: A total of 159 bioactive compounds from the N. Sativa were screened against the SIRT7 enzyme. Five bioactive compounds: chrysin (CID:5281607), pinocembrin (CID:68071), nigellidine (CID:136828302), nigellicine (CID:11402337), and epicatechin (CID:72276) were identified as potent SIRT7 anti-cancer candidates after docking score evaluation and applying Lipinski's Rule of Five. Finally, MD simulation identified Chrysin as the top SIRT7 anti-cancer candidate molecule. Conclusion: Chrysin, which shows a potential inhibitory effect against SIRT7, can act as a possible anti-cancer drug candidate. This inhibitor warrants further evaluation to check its pharmacokinetics and pharmacodynamics properties both in vitro and in vivo.

Keywords: SIRT7, antitumor, molecular docking, molecular dynamics simulation

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Authors: Jae-Hyuk Hyun, Dong-Sung Bae, Jea-Sun Lee

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The COVID-19 pandemic emphasized the benefits of natural green space on mental health in pandemic situations. The effects of greenspace on reducing mental health disorder are detected, but limitations impede highlighting the overall effectiveness of greenspace on mental health to be valid and significant. Therefore, this study aims to comprehensively and quantitatively analyze the effectiveness and significance of greenspace in reducing mental disorders after the COVID-19 outbreak. This study adopted a systematic review to select adequate, necessary studies with significant associations between greenspace and mental health after COVID-19. Meta-analysis is performed using the selected studies for calculating and analyzing the combined effect size of greenspace on reducing mental disorder, difference of effect size in various factors of greenspace or mental health, and variables’ effects on greenspace or mental health. Also, a correlation test using MQRS and effect size is performed to determine significant correlations of factors in greenspace and mental health. The analysis confirmed the combined effect size of the association between greenspace and mental health to be interpreted as large enough (medium effect size, 0.565). Various factors consisting of greenspace or mental health had considerable effect sizes, with heterogeneity existing between studies of different greenspace and mental health aspects (subgroups). A significant correlation between factors in greenspace and mental health was identified, with correlations satisfying both reliability and effectiveness used for suggesting necessary greenspace policies with mental health benefits during the pandemic situation. Different variables of the study period, female proportion, and mean age significantly affected certain factors of greenspace or mental health, while the increase in effects of greenspace on mental health was detected as the COVID-19 period continued. Also, the regional heterogeneity of effects on the association between greenspace and mental health is recognized in all factors consisting of greenspace and mental health except for the visitation of greenspace. In conclusion, valid and significant effects were detected in various associations between greenspace and mental health. Based on the results of this study, conducting elaborate research and establishing adequate and necessary greenspace policies and strategies are recommended to effectively benefit the mental health of citizens in future pandemic situations.

Keywords: greenspace, natural environment, mental health, mental disorder, COVID-19, pandemic, systematic review, meta-analysis

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Authors: Olivia R. Rendon

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More than half of the world population lives in cities, in the UK, for example, 82% of the population was urban by 2013. Cities concentrate valuable and numerous infrastructure and sectors of the national economies. Cities are particularly vulnerable to climate change which will lead to higher damage costs in the future. There is thus a need to develop and invest in adaptation measures for cities to reduce the impact of flooding and other extreme weather events. Recent flood episodes present a significant and growing challenge to the UK and the estimated cost of urban flood damage is 270 million a year for England and Wales. This study aims to carry out cost-benefit analysis (CBA) of a nature-based approach for flood risk management in cities, focusing on the city of Leeds and the wider Aire catchment as a case study. Leeds was chosen as a case study due to its being one of the most flood vulnerable cities in the UK. In Leeds, over 4,500 properties are currently vulnerable to flooding and approximately £450 million of direct damage is estimated for a potential major flood from the River Aire. Leeds is also the second largest Metropolitan District in England with a projected population of 770,000 for 2014. So far the city council has mainly focused its flood risk management efforts on hard infrastructure solutions for the city centre. However, the wider Leeds district is at significant flood risk which could benefit from greener adaptation measures. This study presents estimates of a nature-based adaptation approach for flood risk management in Leeds. This land use management estimate is based on generating costings utilising primary and secondary data. This research contributes findings on the costs of different adaptation measures to flood risk management in a UK city, including the trade-offs and challenges of utilising nature-based solutions. Results also explore the potential implementation of the adaptation measures in the case study and the challenges of data collection and analysis for adaptation in flood risk management.

Keywords: green infrastructure, ecosystem services, woodland, adaptation, flood risk

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Authors: Andrej Pilipović, Branislav Kovačević, Marina Milović, Lazar Kesić, Saša Pekeč, Leopold Poljaković-Pajnik, Saša Orlović

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The effect of landfills on the environment reflects in the dispersion of the contaminants on surrounding soils by the groundwater plume. Such negative effect can be mitigated with the establishment of vegetative buffers surrounding landfills. The “TreeRemEnergy” project funded by the Science Fund of Republic of Serbia – Green program focuses on development of phytobuffers for landfill phytoremediation with the use of Short Rotation Woody Crops (SRWC) plantations that can be further used for the biomass for energy. One of the goals of the project is to select most appropriate poplar (Populus sp.) and willow (Salix sp.) clones through phytorecurrent selection that involves testing of various breeding traits. Physiological parameters serve as a significant contribution to the breeding process aimed to early detection of potential candidates. This study involved testing of the effect of the landfill soils on the photosynthetic processes of the selected poplar and willow candidates. For this purpose, measurements of the gas exchange, chlorophyll content and chlorophyll fluorescence were measured on the tested plants. Obtained results showed that there were differences in the influence of the controlled sources of variation on examined physiological parameters. The effect of clone was significant in all parameters, while the effect of the substrate was not statistically significant in any of measured parameters. However, the effect of interaction Clone×Substrate was significant in intercellular CO2 concentration(ci), stomatal conductance (gs) and transpiration rate (E), suggesting that water regime of the tested clones showed different response to the tested soils. Some clones showed more “generalist” behavior (380, 107/65/9, and PE19/66), while “specialist” behavior was recorded in clones PE4/68, S1-8, and 79/64/2. On the other hand, there was no significant effect of the tested substrate on the pigments content measured with SPAD meter. Results of this study allowed us to narrow the group of clones for further trails in field conditions.

Keywords: clones, net photosynthesis, WUE, transpiration, stomatal conductance, SPAD

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Authors: Tugbanur Ozen Balaban, Gultekin Tarcan, Unsal Gemici, Mumtaz Colak, I. Hakki Karamanderesi

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Buyuk Menderes Graben is located in the Western Anatolia (Turkey). The graben has become the largest industrial and agricultural area with a total population exceeding 3.000.000. There are two big cities within the study areas from west to east as Aydın and Denizli. The study area is very rich with regard to cold ground waters and thermal waters. Electrical production using geothermal potential has become very popular in the last decades in this area. Buyuk Menderes Graben is a tectonically active extensional region and is undergoing a north–south extensional tectonic regime which commenced at the latest during Early Middle Miocene period. The basement of the study area consists of Menderes massif rocks that are made up of high-to low-grade metamorphics and they are aquifer for both cold ground waters and thermal waters depending on the location. Neogene terrestrial sediments, which are mainly composed by alluvium fan deposits unconformably cover the basement rocks in different facies have very low permeability and locally may act as cap rocks for the geothermal systems. The youngest unit is Quaternary alluvium which is the shallow regional aquifer consists of Holocene alluvial deposits in the study area. All the waters are of meteoric origin and reflect shallow or deep circulation according to the 8O, 2H and 3H contents. Meteoric waters move to deep zones by fractured system and rise to the surface along the faults. Water samples (drilling well, spring and surface waters) and local seawater were collected between 2010 and 2012 years. Geochemical modeling was calculated distribution of the aqueous species and exchange processes by using PHREEQCi speciation code. Geochemical analyses show that cold ground water types are evolving from Ca–Mg–HCO3 to Na–Cl–SO4 and geothermal aquifer waters reflect the water types of Na-Cl-HCO3 in Aydın. Water types of Denizli are Ca-Mg-HCO3 and Ca-Mg-HCO3-SO4. Thermal water types reflect generally Na-HCO3-SO4. The B versus Cl rates increase from east to west with the proportion of seawater introduced into the fresh water aquifers and geothermal reservoirs. Concentrations of some elements (As, B, Fe and Ni) are higher than the tolerance limit of the drinking water standard of Turkey (TS 266) and international drinking water standards (WHO, FAO etc).

Keywords: Buyuk Menderes, isotope chemistry, geochemical modelling, water quality

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Authors: Jianuo Sun, Jinghan Wang, Sirui Zhang, Chenhan Xu, Hongxia Hao, Hong Zhou

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In recent years, the diversification and industrialization of drug-related crimes have posed significant threats to public health and safety globally. The widespread and increasingly younger demographics of drug users and the persistence of drug-impaired driving incidents underscore the urgency of this issue. Drug detection, a specialized forensic activity, is pivotal in identifying and analyzing substances involved in drug crimes. It relies on pharmacological and chemical knowledge and employs analytical chemistry and modern detection techniques. However, current drug detection methods are limited by their inability to perform semi-quantitative, real-time field analyses. They require extensive, complex laboratory-based preprocessing, expensive equipment, and specialized personnel and are hindered by long processing times. This study introduces an alternative approach using nucleic acid aptamers and Aggregation-Induced Emission (AIE) technology. Nucleic acid aptamers, selected artificially for their specific binding to target molecules and stable spatial structures, represent a new generation of biosensors following antibodies. Rapid advancements in AIE technology, particularly in tetraphenyl ethene-based luminous, offer simplicity in synthesis and versatility in modifications, making them ideal for fluorescence analysis. This work successfully synthesized, isolated, and purified an AIE molecule and constructed a probe comprising the AIE molecule, nucleic acid aptamers, and exonuclease for cocaine detection. The probe demonstrated significant relative fluorescence intensity changes and selectivity towards cocaine over other drugs. Using 4-Butoxytriethylammonium Bromide Tetraphenylethene (TPE-TTA) as the fluorescent probe, the aptamer as the recognition unit, and Exo I as an auxiliary, the system achieved rapid detection of cocaine within 5 mins in aqueous and urine, with detection limits of 1.0 and 5.0 µmol/L respectively. The probe-maintained stability and interference resistance in urine, enabling quantitative cocaine detection within a certain concentration range. This fluorescent sensor significantly reduces sample preprocessing time, offers a basis for rapid onsite cocaine detection, and promises potential for miniaturized testing setups.

Keywords: drug detection, aggregation-induced emission (AIE), nucleic acid aptamer, exonuclease, cocaine

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Authors: Muhammad Abdul Qyyum, Kinza Qadeer, Moonyong Lee

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Globally, liquefied natural gas (LNG) has drawn interest as a green energy source in comparison with other fossil fuels, mainly because of its ease of transport and low carbon dioxide emissions. It is expected that demand for LNG will grow steadily over the next few decades. In addition, because the demand for clean energy is increasing, LNG production facilities are expanding into new natural gas reserves across the globe. However, LNG production is an energy and cost intensive process because of the huge power requirements for compression and refrigeration. Therefore, one of the major challenges in the LNG industry is to improve the energy efficiency of existing LNG processes through economic and ecological strategies. The advancement in expansion devices such as two-phase cryogenic expander (TPE) and cryogenic hydraulic turbine (HT) were exploited for energy and cost benefits in natural gas liquefaction. Retrofitting the conventional Joule–Thompson (JT) valve with TPE and HT have the potential to improve the energy efficiency of LNG processes. This research investigated the potential feasibility of the retrofitting of a dual mixed refrigerant (DMR) process by replacing the isenthalpic expansion with isentropic expansion corresponding to energy efficient LNG production. To fully take the potential benefit of the proposed process retrofitting, the proposed DMR schemes were optimized by using a Coggins optimization approach, which was implemented in Microsoft Visual Studio (MVS) environment and linked to the rigorous HYSYS® model. The results showed that the required energy of the proposed isentropic expansion based DMR process could be saved up to 26.5% in comparison with the conventional isenthalpic based DMR process using the JT valves. Utilization of the recovered energy into boosting the natural gas feed pressure could further improve the energy efficiency of the LNG process up to 34% as compared to the base case. This work will help the process engineers to overcome the challenges relating to energy efficiency and safety concerns of LNG processes. Furthermore, the proposed retrofitting scheme can also be implemented to improve the energy efficiency of other isenthalpic expansion based energy intensive cryogenic processes.

Keywords: cryogenic liquid turbine, Coggins optimization, dual mixed refrigerant, energy efficient LNG process, two-phase expander

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Authors: Yihenew Simegniew Birhan, Hsieh Chih Tsai

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The recent advancements in synthetic chemistry and nanotechnology fostered the development of different nanocarriers for enhanced intracellular delivery of pharmaceutical agents to tumor cells. Polymeric micelles (PMs), characterized by small size, appreciable drug loading capacity (DLC), better accumulation in tumor tissue via enhanced permeability and retention (EPR) effect, and the ability to avoid detection and subsequent clearance by the mononuclear phagocyte (MNP) system, are convenient to improve the poor solubility, slow absorption and non-selective biodistribution of payloads embedded in their hydrophobic cores and hence, enhance the therapeutic efficacy of chemotherapeutic agents. Recently, redox-responsive polymeric micelles have gained significant attention for the delivery and controlled release of anticancer drugs in tumor cells. In this study, we synthesized redox-responsive diselenide bond containing amphiphilic polymer, Bi(mPEG-PLGA)-Se₂ from mPEG-PLGA, and 3,3'-diselanediyldipropanoic acid (DSeDPA) using DCC/DMAP as coupling agents. The successful synthesis of the copolymers was verified by different spectroscopic techniques. Above the critical micelle concentration, the amphiphilic copolymer, Bi(mPEG-PLGA)-Se₂, self-assembled into stable micelles. The DLS data indicated that the hydrodynamic diameter of the micelles (123.9 ± 0.85 nm) was suitable for extravasation into the tumor cells through the EPR effect. The drug loading content (DLC) and encapsulation efficiency (EE) of DOX-loaded micelles were found to be 6.61 wt% and 54.9%, respectively. The DOX-loaded micelles showed initial burst release accompanied by sustained release trend where 73.94% and 69.54% of encapsulated DOX was released upon treatment with 6mM GSH and 0.1% H₂O₂, respectively. The biocompatible nature of Bi(mPEG-PLGA)-Se₂ copolymer was confirmed by the cell viability study. In addition, the DOX-loaded micelles exhibited significant inhibition against HeLa cells (44.46%), at a maximum dose of 7.5 µg/mL. The fluorescent microscope images of HeLa cells treated with 3 µg/mL (equivalent DOX concentration) revealed efficient internalization and accumulation of DOX-loaded Bi(mPEG-PLGA)-Se₂ micelles in the cytosol of cancer cells. In conclusion, the intelligent, biocompatible, and the redox stimuli-responsive behavior of Bi(mPEG-PLGA)-Se₂ copolymer marked the potential applications of diselenide-linked mPEG-PLGA micelles for the delivery and on-demand release of chemotherapeutic agents in cancer cells.

Keywords: anticancer drug delivery, diselenide bond, polymeric micelles, redox-responsive

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Authors: Richa Soni, Vibha Bhatnagar, N. K. Jain

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This study was conducted to develop a computer mediated programme for weight management and physical fitness and examining its efficacy in reducing weight and improving physical fitness in obese adults. A user friendly, computer based programme was developed to provide a simple, quick, easy and user-friendly method of assessing energy balance at individual level. The programme had four main sections viz. personal Profile, know about your weight, fitness and food exchange list. The computer programme was developed to provide facilities of creating individual profile, tracking meal and physical activities, suggesting nutritional and exercise requirements, planning calorie specific menus, keeping food diaries and revising the diet and exercise plans if needed. The programme was also providing information on obesity, underweight, physical fitness. An exhaustive food exchange list was also given in the programme to assist user to make right food choice decisions. The developed programme was evaluated by a panel of 15 experts comprising endocrinologists, nutritionists and diet counselors. Suggestions given by the experts were paned down and the entire programme was modified in light of suggestions given by the panel members and was reevaluated by the same panel of experts. For assessing the impact of the programme 22 obese subjects were selected purposively and randomly assigned to intervention group (n=12) and no information control group. (n=10). The programme group was asked to strictly follow the programme for one month. Significant reduction in the intake of energy, fat and carbohydrates was observed while intake of fruits, green leafy vegetables was increased. The programme was also found to be effective in reducing body weight, body fat percent and body fat mass whereas total body water and physical fitness scores improved significantly. There was no significant alteration observed in any parameters in the control group.

Keywords: body composition, body weight, computer programme, physical fitness

Procedia PDF Downloads 262

Authors: Prasanna Belur, P. R. Ashwini, Sampath Charanyaa, I. Regupathi

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Indian oil sardine (Sardinella longiceps) are one of the richest and cheapest sources of n-3 polyunsaturated fatty acids (n-3 PUFA) such as Eicosapentaenoic acid (EPA) and Docosahexaenoic acid (DHA). The health benefits conferred by n-3 PUFA upon consumption, in the prevention and treatment of coronary, neuromuscular, immunological disorders and allergic conditions are well documented. Natural refined Indian Sardine oil generally contain about 25% (w/w) n-3 PUFA along with various unsaturated and saturated fatty acids in the form of mono, di, and triglycerides. Having high concentration of n-3 PUFA content in the glyceride form is most desirable for human consumption to avail maximum health benefits. Thus, enhancing the n-3 PUFA content while retaining it in the glyceride form with green technology is the need of the hour. In this study, refined Indian Sardine oil was subjected to selective hydrolysis by Candida antartica lipase to enhance n-3 PUFA content. The degree of hydrolysis and enhancement of n-3 PUFA content was estimated by determining acid value, Iodine value, EPA and DHA content (by Gas Chromatographic methods after derivitization) before and after hydrolysis. Various reaction parameters such as pH, temperature, enzyme load, lipid to aqueous phase volume ratio and incubation time were optimized by conducting trials with one parameter at a time approach. Incubating enzyme solution with refined sardine oil with a volume ratio of 1:1, at pH 7.0, for 60 minutes at 50 °C, with an enzyme load of 60 mg/ml was found to be optimum. After enzymatic treatment, the oil was subjected to refining to remove free fatty acids and moisture content using previously optimized refining technology. Enzymatic treatment at the optimal conditions resulted in 12.11 % enhancement in Degree of hydrolysis. Iodine number had increased by 9.7 % and n-3 PUFA content was enhanced by 112 % (w/w). Selective enhancement of n-3 PUFA glycerides, eliminating saturated and unsaturated fatty acids from the oil using enzyme is an interesting preposition as this technique is environment-friendly, cost effective and provide natural source of n-3 PUFA rich oil.

Keywords: Candida antartica, lipase, n-3 polyunsaturated fatty acids, sardine oil

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Authors: Nicole Virgili, Marco Utili

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The design of the Breeding Blanket in Tokamak fusion energy systems has to guarantee sufficient availability in addition to its functions, that are, tritium breeding self-sufficiency, power extraction and shielding (the magnets and the VV). All these function in the presence of extremely harsh operating conditions in terms of heat flux and neutron dose as well as chemical environment of the coolant and breeder that challenge structural materials (structural resistance and corrosion resistance). The movement and activation of fluids from the BB to the Ex-vessel components in a fusion power plant have an important radiological consideration because flowing material can carry radioactivity to safety-critical areas. This includes gamma-ray emission from activated fluid and activated corrosion products, and secondary activation resulting from neutron emission, with implication for the safety of maintenance personnel and damage to electrical and electronic equipment. In addition to the PbLi breeder activation, it is important to evaluate the contribution due to the activated corrosion products (ACPs) dissolved in the lead-lithium eutectic alloy, at different concentration levels. Therefore, the purpose of the study project is to evaluate the PbLi activity utilizing the FISPACT II inventory code. Emphasis is given on how the design of the EU-DEMO WCLL, and potential recycling of the breeder material will be impacted by the activation of PbLi and the associated active corrosion products (ACPs). For this scope the following Computational Tools, Data and Geometry have been considered: • Neutron source: EU-DEMO neutron flux < 1014/cm2/s • Neutron flux distribution in equatorial breeding blanket module (BBM) #13 in the WCLL BB outboard central zone, which is the most activated zone, with the aim to introduce a conservative component utilizing MNCP6. • The recommended geometry model: 2017 EU DEMO CAD model. • Blanket Module Material Specifications (Composition) • Activation calculations for different ACP concentration levels in the PbLi breeder, with a given chemistry in stationary equilibrium conditions, using FISPACT II code. Results suggest that there should be a waiting time of about 10 years from the shut-down (SD) to be able to safely manipulate the PbLi for recycling operations with simple shielding requirements. The dose rate is mainly given by the PbLi and the ACP concentration (x1 or x 100) does not shift the result. In conclusion, the results show that there is no impact on PbLi activation due to ACPs levels.

Keywords: activation, corrosion products, recycling, WCLL BB., PbLi

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Authors: Ourvashi Bissoon

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Sub-Saharan Africa in addition to being resource rich is increasingly being seen as having a huge growth potential and as a result, is increasingly attracting MNEs on its soil. To empirically assess the effectiveness of GDP in tracking sustainable resource use and the role played by MNEs in Sub-Saharan Africa, a panel data analysis has been undertaken for 32 countries over thirty-five years. The time horizon spans the period 1980-2014 to reflect the evolution from before the publication of the pioneering Brundtland report on sustainable development to date. Multinationals’ presence is proxied by the level of FDI stocks. The empirical investigation first focuses on the impact of trade openness and MNE presence on the traditional measure of economic growth namely the GDP growth rate, and then on the genuine savings (GS) rate, a measure of weak sustainability developed by the World Bank, which assumes the substitutability between different forms of capital and finally, the impact on the adjusted Net National Income (aNNI), a measure of green growth which caters for the depletion of natural resources is examined. For countries with significant exhaustible natural resources and important foreign investor presence, the adjusted net national income (aNNI) can be a better indicator of economic performance than GDP growth (World Bank, 2010). The issue of potential endogeneity and reverse causality is also addressed in addition to robustness tests. The findings indicate that FDI and openness contribute significantly and positively to the GDP growth of the countries in the sample; however there is a threshold level of institutional quality below which FDI has a negative impact on growth. When the GDP growth rate is substituted for the GS rate, a natural resource curse becomes evident. The rents being generated from the exploitation of natural resources are not being re-invested into other forms of capital namely human and physical capital. FDI and trade patterns may be setting the economies in the sample on a unsustainable path of resource depletion. The resource curse is confirmed when utilising the aNNI as well, thus implying that GDP growth measure may not be a reliable to capture sustainable development.

Keywords: FDI, sustainable development, genuine savings, sub-Saharan Africa

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Authors: Zelalem B. Gurmessa, Ignatius W. Ferreira, Henry F. Wissink

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The aim of this paper is to critically examine the factors contributing to academic brain drain in the Sub-Saharan Africa with specific reference to the higher education sector. Africa in general and Sub-Saharan African (SSA) countries, in particular, are experiencing an exodus of highly trained, qualified and competent human resources to other developing and developed countries thereby threatening the overall development of the relevant regions and impeding both public and private service delivery systems in the nation states. The region is currently in a dire situation in terms of health care services, education, science, and technology. The contribution of SSA countries to Science, Technology and Innovation is relatively minimal owing to the migration of skilled professionals due to both push and pull factors. The phenomenon calls for both international and trans-boundary, regional, national and institutional interventions to curb the exodus. Based on secondary data and the review of the literature, the article conceptualizes the antecedents and impacts of human capital flight or brain drain in the SSA countries from a higher education perspective. To this end, the article explores the magnitude, causes, and impacts of brain drain in the region. Despite the lack of consistent data on the magnitude of academic brain drain in the region, a critical analysis of the existing sources shows that pay disparity between developing and developed countries, the lack of enabling working conditions at source countries, fear of security due to political turmoil or unrest, the availability of green pastures and opportunity for development in the receiving countries were identified as major factors contributing to academic brain drain in the region. This hampers the socio-economic, technological and political development of the region. The paper also recommends that further research can be undertaken on the magnitude, causes, characteristics and impact of brain drain on the sustainability and competitiveness of SSA higher education institutions in the region.

Keywords: brain drain, higher education, sub-Saharan Africa, sustainable development

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Authors: Thummalapalli CSM Gupta, Banti Sidhiwala

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Mineral oils of naphthenic and paraffinic type have been traditionally been used as insulating liquids in the transformer applications to protect the solid insulation from moisture and ensures effective heat transfer/cooling. The performance of these type of oils have been proven in the field over many decades and the condition monitoring and diagnosis of transformer performance have been successfully monitored through oil properties and dissolved gas analysis methods successfully. Different type of gases representing various types of faults due to components or operating conditions effectively. While large amount of data base has been generated in the industry on dissolved gas analysis for mineral oil based transformer oils and various models for predicting the fault and analysis, oil specifications and standards have also been modified to include stray gassing limits which cover the low temperature faults and becomes an effective preventative maintenance tool that can benefit greatly to know the reasons for the breakdown of electrical insulating materials and related components. Natural esters have seen a rise in popularity in recent years due to their "green" credentials. Some of its benefits include biodegradability, a higher fire point, improvement in load capability of transformer and improved solid insulation life than mineral oils. However, the Stray gases evolution like hydrogen and hydrocarbons like methane (CH4) and ethane (C2H6) show very high values which are much higher than the limits of mineral oil standards. Though the standards for these type esters are yet to be evolved, the higher values of hydrocarbon gases that are available in the market is of concern which might be interpreted as a fault in transformer operation. The current paper focuses on developing a natural ester based transformer oil which shows very levels of stray gassing by standard test methods show much lower values compared to the products available currently and experimental results on various test conditions and the underlying mechanism explained.

Keywords: biodegadability, fire point, dissolved gassing analysis, stray gassing

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Authors: V. Mani Rathnam, Giridhar Madras

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Fossil fuels are depleting rapidly as the demand for energy, and its allied chemicals are continuously increasing in the modern world. Therefore, sustainable renewable energy sources based on non-edible oils are being explored as a viable option as they do not compete with the food commodities. Oils such as castor oil are rich in fatty acids and thus can be used for the synthesis of biodiesel, bio-lubricants, and many other fine industrial chemicals. There are several processes available for the synthesis of different chemicals obtained from the castor oil. One such process is the transesterification of castor oil, which results in a mixture of fatty acid methyl esters. The main products in the above reaction are methyl ricinoleate and methyl 10-undecenoate. To separate these compounds, supercritical carbon dioxide (SCCO₂) was used as a green solvent. SCCO₂ was chosen as a solvent due to its easy availability, non-toxic, non-flammable, and low cost. In order to design any separation process, the preliminary requirement is the solubility or phase equilibrium data. Therefore, the solubility of a mixture of methyl ricinoleate with methyl 10-undecenoate in SCCO₂ was determined in the present study. The temperature and pressure range selected for the investigation were T = 313 K to 333 K and P = 10 MPa to 18 MPa. It was observed that the solubility (mol·mol⁻¹) of methyl 10-undecenoate varied from 2.44 x 10⁻³ to 8.42 x 10⁻³ whereas it varied from 0.203 x 10⁻³ to 6.28 x 10⁻³ for methyl ricinoleate within the chosen operating conditions. These solubilities followed a retrograde behavior (characterized by the decrease in the solubility values with the increase in temperature) throughout the range of investigated operating conditions. An association theory model, coupled with regular solution theory for activity coefficients, was developed in the present study. The deviation from the experimental data using this model can be quantified using the average absolute relative deviation (AARD). The AARD% for the present compounds is 4.69 and 8.08 for methyl 10-undecenoate and methyl ricinoleate, respectively in a mixture of methyl ricinoleate and methyl 10-undecenoate. The maximum solubility enhancement of 32% was observed for the methyl ricinoleate in a mixture of methyl ricinoleate and methyl 10-undecenoate. The highest selectivity of SCCO₂ was observed to be 12 for methyl 10-undecenoate in a mixture of methyl ricinoleate and methyl 10-undecenoate.

Keywords: association theory, liquid mixtures, solubilities, supercritical carbon dioxide

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Authors: A. H. Nanher, N. P. Singh, Shashidhar Yadav, Sachin Tyagi

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Agricultural production system is an outcome of a complex interaction of seed, soil, water and agro-chemicals (including fertilizers). Therefore, judicious management of all the inputs is essential for the sustainability of such a complex system. Precision agriculture gives farmers the ability to use crop inputs more effectively including fertilizers, pesticides, tillage and irrigation water. More effective use of inputs means greater crop yield and/or quality, without polluting the environment the focus on enhancing the productivity during the Green Revolution coupled with total disregard of proper management of inputs and without considering the ecological impacts, has resulted into environmental degradation. To evaluate a new approach for site-specific nutrient management (SSNM). Large variation in initial soil fertility characteristics and indigenous supply of N, P, and K was observed among Field- and season-specific NPK applications were calculated by accounting for the indigenous nutrient supply, yield targets, and nutrient demand as a function of the interactions between N, P, and K. Nitrogen applications were fine-tuned based on season-specific rules and field-specific monitoring of crop N status. The performance of SSNM did not differ significantly between high-yielding and low-yielding climatic seasons, but improved over time with larger benefits observed in the second year Future, strategies for nutrient management in intensive rice systems must become more site-specific and dynamic to manage spatially and temporally variable resources based on a quantitative understanding of the congruence between nutrient supply and crop demand. The SSNM concept has demonstrated promising agronomic and economic potential. It can be used for managing plant nutrients at any scale, i.e., ranging from a general recommendation for homogenous management of a larger domain to true management of between-field variability. Assessment of pest profiles in FFP and SSNM plots suggests that SSNM may also reduce pest incidence, particularly diseases that are often associated with excessive N use or unbalanced plant nutrition.

Keywords: nutrient, pesticide, crop, yield

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Authors: Dadasaheb R. Jawre, Maya G. Unde

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Prioritization of sub-watershed plays important role in watershed management. It shows the requirement of watershed to give a treatment for the green growth of the region and conservation of the sub-watersheds. There is a number of factors like topography of the region, climatic characteristics like rainfall and runoff, land-use land-cover, social factors which are related to the development of watershed for agricultural uses and domestic purposes in the region. The present research is throwing a focus on how morphometric parameters in association with GIS analysis will help in identifying the ranking of the sub-watersheds for further development which help of suggested watershed structures. Shevgaon and Pathardi tahsils are drought prone tahsils of Ahmednagar district in Maharashtra. These tahsils come under the semi-arid region. Sub-watershed prioritization is necessary for proper planning and management of natural resources for sustainable development of the study area. Less rainfall and increasing population pressure on the land as well as water resources lead to scarcity of the water in the region. Hence, researcher has selected Shevgaon and Pathardi tahsils for sub-watershed prioritization. There are seven sub-watersheds which selected for the present research paper. In the morphological analysis linear aspects, aerial aspects and relief aspects are considered for the prioritization. The largest sub-watershed is Erdha which is located at Karanji in Pathardi tahsil having an area of 145.06 km2 and smallest sub-watershed is Erandgaon which is located in Shevgaon tahsil having an area of 40.143 km2. For all seven sub-watersheds, seven morphometric parameters were considered for calculating the compound parameter values. Finally, compound parameter values are grouped into three groups such as, high priority (below 4.0), moderate priority (4.0 to 5.0) and low priority (above 5.0) according to the compound value Erandgaon, Chapadgaon and Tarak sub-watersheds comes under high priority group, Erdha and Domeshwar sub-watersheds come under moderate priority group and Chandani and Kasichi sub-watershed come under low priority group. Both the tahsils falls in drought prone area, after getting the watershed structure overall development of the region will take place.

Keywords: sub-watersheds, GIS and remote sensing, morphometric analysis, compound parameter value, prioritization

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Authors: Vichai Tienthavorn

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Background: Recently, the patients of non-communicable diseases (NCDs) are increasing in Thailand; especially hypertension and diabetes. Hypertension and Diabetes patients were found to be of 3.7 million in 2008. The varieties of human behaviors have been extensively changed in health. Hence, Thai Government has a policy to reduce NCDs. Generally, primary care plays an important role in treatment using medical process. However, NCDs patients have not been decreased. Objectives: This study not only reduce the patient and mortality rate but also increase the quality of life, could apply in different areas and propose to be the national policy, effectively for a long term operation. Methods: Here we report that primary health care (PHC), which is a primary process to screening, rapidly seek the person's risk. The screening tool of the study was Vichai's 7 color balls model, the medical education tool to transfer knowledge from student health team to community through health volunteers, creating community engagement in terms of social participation. It was found that people in community were realized in their health and they can evaluate the level of risk using this model. Results: Projects implementation (2015) in Nong Lom Health Center in Phayao (target group 15-65 years, 2529); screening hypertension coveraged 99.01%, risk group (light green) was decreased to normal group (white) from 1806 to 1893, significant severe patient (red) was decreased to moderate (orange) from 10 to 5. Health Program in behaving change with best practice of 3Es (Eating, Exercise, Emotion) and 3Rs (Reducing tobacco, alcohol, obesity) were applied in risk group; and encourage strictly medication, investigation in severe patient (red). Conclusion: This is the first demonstration of knowledge transfer to community engagement by student, which is the sustainable education in PHC.

Keywords: non-communicable disease, surveillance control and prevention systems, community engagement, primary health care

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Authors: Ana Lambelho

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Nowadays is very common that an activity may be performed independently or dependently. In Portugal, the Labour Law exclusively protects the dependent labour relations. The independent work is regulated by civil law, where the autonomy of the will is the main principle. For companies is more advantageous to hire people under a service agreement since, in that case, the relation is not submitted to the limits established in Labour law and collective bargaining. This practice has nothing wrong, if the performance of work is, in fact, made autonomously. The problem is the increased frequency of the celebration of service agreements to hide a legal relation of subordination. Aware of this and regarding the huge difficulty to demonstrate the existence of subordinated work (that often runs against the employee), the Portuguese legislator devoted some legislative rules in order to facilitate the evidence of legal subordination and, on the other hand, to avoid the misuse of the provision of service agreements. This study focuses precisely on the analysis of this solution, namely the so-called presumption of ‘laboralidade’ and on the lawsuit to recognize the existence of a labour contract. The presumption of the existence of a labour contract is present in the Portuguese legal system since 2003, and received, with the 2009 Labour Code, a new redaction that, according to the doctrine and the jurisprudence, finally approached it to a legal presumption, with the consequent reversal of the burden of proof and, in consequence, made easier to proof the legal subordination, because the employee will just have to plead and prove the existence of two of the elements described in the law to use this presumption. Another change in the Portuguese legal framework is related with the competencies of the Authority for Working Conditions (AWC): now, if during an inspection, the Authority finds a situation that seems to be an undeclared employment situation, it may access the company and, if it does not regularize voluntarily the situation, AWC has a duty to communicate to the public prosecutor, who will begin the lawsuit for the recognition of the existence of an employment contract. To defend the public interest, the action to recognize the existence of an employment contract will follow its terms, even against the employee will. Although the existence of these mechanisms does not solve by itself the problem of evasion of labour law and false ‘green receipts’, it is undeniable that it is an important step in combating fraud in this field.

Keywords: independent work, labour contract, Portugal, service agreement

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Authors: Parikshit Gogo, N. N. Dutta

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The oxidative enzymes specially laccase (benzenediol: oxygen oxidoreductase, E.C.1.10.3.2) from bacteria, fungi and plants have been playing an important role in green technologies due to their specific advantageous properties. Laccase from different sources and in different forms was used as a biocatalyst in many oxidation and conjugation reactions starting from phenol to hydrocarbons. Tea polyphenols and its derivatives attract the scientific community because of their potential use as antioxidants in food, pharmaceutical and cosmetic industries. Conjugate of polyphenols emerged as a novel materials which shows better stability and antioxidant properties in applied fields. The conjugation reaction of catechin with poly (allylamine) has been studied using free, immobilized and cross-linked enzyme crystals (CLEC) of laccase from Trametes versicolor with particular emphasis on the effect of pertinent variables and kinetic aspects of the reaction. The stability and antioxidant property of the conjugated product was improved as compared to the unconjugated tea polyphenols. The reaction was studied in 11 different solvents in order to deduce the solvent effect through an attempt to correlate the initial reaction rate with solvent properties such as hydrophobicity (logP), water solubility (logSw), electron pair acceptance (ETN) and donation abilities (DNN), polarisibility and dielectric constant which exhibit reasonable correlations. The study revealed, in general that polar solvents favour the initial reaction rate. The kinetics of the conjugation reaction conformed to the so-called Ping-Pong-Bi-Bi mechanism with catechin inhibition. The stability as well as activity of the CLEC was better than the free enzymes and immobilized laccase for practical application. In case of immobilized laccase system marginal diffusional limitation could be inferred from the experimental data. The kinetic parameters estimated by non-linear regression analysis were found to be KmPAA(mM) = 0.75, 1.8967 and Kmcat (mM) = 11.769, 15.1816 for free and immobilized laccase respectively. An attempt has been made to assess the activity of the laccase for the conjugation reaction in relation to other reactions such as dimerisation of ferulic acids and develop a protocol to enhance polyphenol antioxidant activity.

Keywords: laccase, catechin, conjugation reaction, antioxidant properties

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Authors: Juan Li, Hui Tian, Min Wang

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In China, under the considerable pressure of 'Gaokao' –the highly competitive college entrance examination, high school teachers and parents often worry that doing physical activity would take away the students’ precious study time and may have a negative impact on the academic grades. There was a tendency to achieve high academic scores at the cost of physical exercise. Therefore, the purpose of this study was to examine the relationship between the physical fitness and academic achievement of Chinese high school students. The participants were 968 grade one (N=457) and grade two students (N=511) with an average age of 16 years from three high schools of different levels in Beijing, China. 479 were boys, and 489 were girls. One of the schools is a top high school in China, another is a key high school in Beijing, and the other is an ordinary high school. All analyses were weighted using SAS 9.4 to ensure the representatives of the sample. The weights were based on 12 strata of schools, sex, and grades. Physical fitness data were collected using the scores of the National Physical Fitness Test, which is an annual official test administered by the Ministry of Education in China. It includes 50m run, sits and reach test, standing long jump, 1000m run (for boys), 800m run (for girls), pull-ups for 1 minute (for boys), and bent-knee sit-ups for 1 minute (for girls). The test is an overall evaluation of the students’ physical health on the major indexes of strength, endurance, flexibility, and cardiorespiratory function. Academic scores were obtained from the three schools with the students’ consent. The statistical analysis was conducted with SPSS 24. Independent-Samples T-test was used to examine the gender group differences. Spearman’s Rho bivariate correlation was adopted to test for associations between physical test results and academic performance. Statistical significance was set at p<.05. The study found that girls obtained higher fitness scores than boys (p=.000). The girls’ physical fitness test scores were positively associated with the total academic grades (rs=.103, p=.029), English (rs=.096, p=.042), physics (rs=.202, p=.000) and chemistry scores (rs=.131, p=.009). No significant relationship was observed in boys. Cardiorespiratory fitness had a positive association with physics (rs=.196, p=.000) and biology scores (rs=.168, p=.023) in girls, and with English score in boys (rs=.104, p=.029). A possible explanation for the greater association between physical fitness and academic achievement in girls rather than boys was that girls showed stronger motivation in achieving high scores in whether academic tests or fitness tests. More driven by the test results, girls probably tended to invest more time and energy in training for the fitness test. Higher fitness levels were associated with an academic benefit among girls generally in Chinese high schools. Therefore, physical fitness needs to be given greater emphasis among Chinese adolescents and gender differences need to be taken into consideration.

Keywords: physical fitness; adolescents; academic achievement; high school

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Authors: Rasha Al-Saedi, Anthony Meijer

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The progress of new porous materials has increased rapidly over the past decade for use in applications such as catalysis, gas storage and removal of environmentally unfriendly species due to their high surface area and high thermal stability. In this work, a theoretical study of the zirconium-based metal organic framework (MOFs) were examined in order to determine their potential for gas adsorption of various guest molecules: CO2, N2, CH4 and H2. The zirconium cluster consists of an inner Zr6O4(OH)4 core in which the triangular faces of the Zr6- octahedron are alternatively capped by O and OH groups which bound to nine formate groups and three benzoate groups linkers. General formula is [Zr(μ-O)4(μ-OH)4(HCOO)9((phyO2C)3X))] where X= CH2OH, CH2NH2, CH2CONH2, n(NH2); (n = 1-3). Three types of adsorption sites on the Zr metal center have been studied, named according to capped chemical groups as the ‘−O site’; the H of (μ-OH) site removed and added to (μ-O) site, ‘–OH site’; (μ-OH) site removed, the ‘void site’ where H2O molecule removed; (μ-OH) from one site and H from other (μ-OH) site, in addition to no defect versions. A series of investigations have been performed aiming to address this important issue. First, density functional theory DFT-B3LYP method with 6-311G(d,p) basis set was employed using Gaussian 09 package in order to evaluate the gas adsorption performance of missing-linker defects in zirconium cluster. Next, study the gas adsorption behaviour on different functionalised zirconium clusters. Those functional groups as mentioned above include: amines, alcohol, amide, in comparison with non-substitution clusters. Then, dispersion-corrected density functional theory (DFT-D) calculations were performed to further understand the enhanced gas binding on zirconium clusters. Finally, study the water effect on CO2 and N2 adsorption. The small functionalized Zr clusters were found to result in good CO2 adsorption over N2, CH4, and H2 due to the quadrupole moment of CO2 while N2, CH4 and H2 weakly polar or non-polar. The adsorption efficiency was determined using the dispersion method where the adsorption binding improved as most of the interactions, for example, van der Waals interactions are missing with the conventional DFT method. The calculated gas binding strengths on the no defect site are higher than those on the −O site, −OH site and the void site, this difference is especially notable for CO2. It has been stated that the enhanced affinity of CO2 of no defect versions is most likely due to the electrostatic interactions between the negatively charged O of CO2 and the positively charged H of (μ-OH) metal site. The uptake of the gas molecule does not enhance in presence of water as the latter binds to Zr clusters more strongly than gas species which attributed to the competition on adsorption sites.

Keywords: density functional theory, gas adsorption, metal- organic frameworks, molecular simulation, porous materials, theoretical chemistry

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Authors: Luminita Marin, Dalila Belei, Carmen Dumea

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Aggregation induced emission (AIE) is an intriguing optical phenomenon recently evidenced by Tang and his co-workers, for which aggregation works constructively in the improving of light emission. The AIE challenging phenomenon is quite opposite to the notorious aggregation caused quenching (ACQ) of light emission in the condensed phase, and comes in line with requirements of photonic and optoelectronic devices which need solid state emissive substrates. This paper reports a series of ten new aggregation induced emission (AIE) low molecular weight compounds based on triazole and pyridine-N-oxide heterocyclic units bonded by short flexible chains, obtained by a „click” chemistry reaction. The compounds present extremely weak luminescence in solution but strong light emission in solid state. To distinguish the influence of the crystallinity degree on the emission efficiency, the photophysical properties were explored by UV-vis and photoluminescence spectroscopy in solution, water suspension, amorphous and crystalline films. On the other hand, the compound morphology of the up mentioned states was monitored by dynamic light scattering, scanning electron microscopy, atomic force microscopy and polarized light microscopy methods. To further understand the structural design – photophysical properties relationship, single crystal X-ray diffraction on some understudy compounds was performed too. The UV-vis absorption spectra of the triazole water suspensions indicated a typical behaviour for nanoparticle formation, while the photoluminescence spectra revealed an emission intensity enhancement up to 921-fold higher of the crystalline films compared to solutions, clearly indicating an AIE behaviour. The compounds have the tendency to aggregate forming nano- and micro- crystals in shape of rose-like and fibres. The crystals integrity is kept due to the strong lateral intermolecular forces, while the absence of face-to-face forces explains the enhanced luminescence in crystalline state, in which the intramolecular rotations are restricted. The studied flexible triazoles draw attention to a new structural design in which small biologically friendly luminophore units are linked together by small flexible chains. This design enlarges the variety of the AIE luminogens to the flexible molecules, guiding further efforts in development of new AIE structures for appropriate applications, the biological ones being especially envisaged.

Keywords: aggregation induced emission, pyridine-N-oxide, triazole

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