Search results for: mountain-plain transition zones

Authors: Anton G. Akulichev, Avinash Tiwari, Ben Alcock, Andreas Echtermeyer

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Low temperatures are known to pose a major threat for polymers; many are prone to excessive stiffness or even brittleness. There is a technology gap between the properties of existing elastomeric sealing materials and the properties needed for service in extremely cold regions. Moreover, some aspects of low temperature behaviour of rubber are not thoroughly studied and understood. The paper presents results of laboratory testing of a conventional oilfield HNBR (hydrogenated nitrile butadiene rubber) elastomer at low climatic temperatures above and below its glass transition point, as well as the performance of some filled HNBR formulations. Particular emphasis in the experiments is put on rubber viscoelastic characteristics studied by Dynamic Mechanical Analysis (DMA) and quasi-static mechanical testing results at low temperatures. As demonstrated by the stress relaxation and DMA experiments the transition region near Tg of the studied compound has the most striking features, like rapid stress relaxation, as compared to the glassy and rubbery plateau. In addition the quasi-static experiments show that molecular movement below Tg is not completely frozen, but rather evident and manifested in a certain stress decay as well. The effect of temperature and filler additions on typical mechanical and other properties of the materials is also discussed.

Keywords: characterization, filled elastomers, HNBR, low temperature

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Authors: Domenico Carmelo Mongelli, Laura Carnieletto, Michele De Carli, Filippo Busato

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Starting from the current context in which the Russian invasion in Ukraine has highlighted Europe's dependence on natural gas imports for heating buildings, this study proposes solutions to resolve this dependency and evaluates related scenarios in the near future. In the first part of this work the methodologies and results of the economic impact are indicated by simulating a massive replacement of boilers powered by fossil fuels with electrically powered hightemperature air-water heat pumps for heating residential buildings in different European climates, without changing the current energy mix. For each individual European region, the costs for the purchase and installation of heat pumps for all residential buildings have been determined. Again for each individual European region, the economic savings during the operation phase that would be obtained in this future scenario of energy transition from fossil fuels to the electrification of domestic heating were calculated. For the European regions for which the economic savings were identified as positive, the payback times of the economic investments were analysed. In the second part of the work, hypothesizing different scenarios for a possible greater use of renewable energy sources and therefore with different possible future scenarios of the energy mix, the methodologies and results of the simulations on the economic analysis and on the environmental analysis are reported which have allowed us to evaluate the future effects of the energy transition from boilers to heat pumps for each European region. In the third part, assuming a rapid short-term diffusion of cooling for European residential buildings, the penetration shares in the cooling market and future projections of energy needs for cooling for each European region have been identified. A database was created where the results of this research relating to 38 European Nations divided into 179 regions were reported. Other previous works on the topics covered were limited to analyzing individual European nations, without ever going into detail about the individual regions within each nation, while the original contribution of the present work lies in the fact that the results achieved allow a specific numerical analysis and punctual for every single European region.

Keywords: buildings, energy, Europe, future

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Authors: A. Bensaid, T. Mostephaoui, R. Nedjai

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A considerable area of Algerian lands is threatened by the phenomenon of wind erosion. For a long time, wind erosion and its associated harmful effects on the natural environment have posed a serious threat, especially in the arid regions of the country. In recent years, as a result of increases in the irrational exploitation of natural resources (fodder) and extensive land clearing, wind erosion has particularly accentuated. The extent of degradation in the arid region of the Algerian Mecheria department generated a new situation characterized by the reduction of vegetation cover, the decrease of land productivity, as well as sand encroachment on urban development zones. In this study, we attempt to investigate the potential of remote sensing and geographic information systems for detecting the spatial dynamics of the ancient dune cords based on the numerical processing of LANDSAT images (5, 7, and 8) of three scenes 197/37, 198/36 and 198/37 for the year 2020. As a second step, we prospect the use of geospatial techniques to monitor the progression of sand dunes on developed (urban) lands as well as on the formation of sandy accumulations (dune, dunes fields, nebkha, barkhane, etc.). For this purpose, this study made use of the semi-automatic processing method for the dynamic segmentation of images with very high spatial resolution (SENTINEL-2 and Google Earth). This study was able to demonstrate that urban lands under current conditions are located in sand transit zones that are mobilized by the winds from the northwest and southwest directions.

Keywords: land development, GIS, segmentation, remote sensing

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Authors: Hosein Hamisheh Bahar, Mohammad Hossein Fazel Zarandi, Akbar Esfahanipour

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In this paper, a hybrid expert system is developed by using fuzzy genetic network programming with reinforcement learning (GNP-RL). In this system, the frame-based structure of the system uses the trading rules extracted by GNP. These rules are extracted by using technical indices of the stock prices in the training time period. For developing this system, we applied fuzzy node transition and decision making in both processing and judgment nodes of GNP-RL. Consequently, using these method not only did increase the accuracy of node transition and decision making in GNP's nodes, but also extended the GNP's binary signals to ternary trading signals. In the other words, in our proposed Fuzzy GNP-RL model, a No Trade signal is added to conventional Buy or Sell signals. Finally, the obtained rules are used in a frame-based system implemented in Kappa-PC software. This developed trading system has been used to generate trading signals for ten companies listed in Tehran Stock Exchange (TSE). The simulation results in the testing time period shows that the developed system has more favorable performance in comparison with the Buy and Hold strategy.

Keywords: fuzzy genetic network programming, hybrid expert system, technical trading signal, Tehran stock exchange

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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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Authors: Mostafa Feiz, Hossein Hadizadeh, Mohammad Safari

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The Chalpo copper area is located in northeastern Iran, which is part of the structural zone of central Iran and the back-arc basin of Sabzevar. This sedimentary basin accumulated in destructive-Oligomiocene sediments is named the Nasr-Chalpo-Sangerd (NCS) basin. The sedimentary layers in this basin originated mainly from Upper Cretaceous ophiolitic rocks and intermediate to mafic-post ophiolitic volcanic rocks, deposited as a nonconformity. The mineralized sandstone layers in the Chalpo area include leached zones (with a thickness of 5 to 8 meters) and mineralized lenses with a thickness of 0.5 to 0.7 meters. Ore minerals include primary sulfide minerals, such as chalcocite, chalcopyrite, and pyrite, as well as secondary minerals, such as covellite, digenite, malachite, and azurite, formed in three stages that comprise primary, simultaneously, and supergene stage. The best agents that control the mineralization in this area include the permeability of host rocks, the presence of fault zones as the conduits for copper oxide solutions, and significant amounts of plant fossils, which create a reducing environment for the deposition of mineralized layers. Statistical studies on copper layers indicate that Ag, Cd, Mo, and S have the maximum positive correlation with Cu, whereas TiO₂, Fe₂O₃, Al₂O₃, Sc, Tm, Sn, and the REEs have a negative correlation. The calculations of mass changes on copper-bearing layers and primary sandstone layers indicate that Pb, As, Cd, Te, and Mo are enriched in the mineralized zones, whereas SiO₂, TiO₂, Fe₂O₃, V, Sr, and Ba are depleted. The combination of geological, stratigraphic, and geochemical studies suggests that the origin of copper may have been the underlying red strata that contained hornblende, plagioclase, biotite, alkaline feldspar, and labile minerals. Dehydration and hydrolysis of these minerals during the diagenetic process caused the leaching of copper and associated elements by circling fluids, which formed an oxidant-hydrothermal solution. Copper and silver in this oxidant solution might have moved upwards through the basin-fault zones and deposited in the reducing environments in the sandstone layers that have had abundant organic matters. Copper in these solutions probably was carried by chloride complexes. The collision of oxidant and reduced solutions caused the deposition of Cu and Ag, whereas some stable elements in oxidant environments (e.g., Fe₂O₃, TiO₂, SiO₂, REEs) become unstable in the reduced condition. Therefore, the copper-bearing sandstones in the study area are depleted from these elements resulting from the leaching process. The results indicate that during the mineralization stage, LREEs and MREEs were depleted, but Cu, Ag, and S were enriched. Based on field evidence, it seems that the circulation of connate fluids in the reb-bed strata, produced by diagenetic processes, encountered to reduced facies, which formed earlier by abundant fossil-plant debris in the sandstones, is the best model for precipitating sulfide-copper minerals.

Keywords: Chalpo, oligo-miocene red beds, sandstone-hosted copper mineralization, mass change, LREEs, MREEs

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Authors: Muna Khethier Abbass, Khairia Salman Hussan, Huda Mohummed AbdudAlaziz

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This work aims to study the effect of shot peening on the mechanical properties of welded joints which performed by two different welding processes: Tungsten inert gas (TIG) welding and friction stir welding (FSW) processes of aluminum alloy 6061 T6. Arc welding process (TIG) was carried out on the sheet with dimensions of (100x50x6 mm) to obtain many welded joints with using electrode type ER4043 (AlSi5) as a filler metal and argon as shielding gas. While the friction stir welding process was carried out using CNC milling machine with a tool of rotational speed (1000 rpm) and welding speed of (20 mm/min) to obtain the same butt welded joints. The welded pieces were tested by X-ray radiography to detect the internal defects and faulty welded pieces were excluded. Tensile test specimens were prepared from welded joints and base alloy in the dimensions according to ASTM17500 and then subjected to shot peening process using steel ball of diameter 0.9 mm and for 15 min. All specimens were subjected to Vickers hardness test and micro structure examination to study the effect of welding process (TIG and FSW) on the micro structure of the weld zones. Results showed that a general decay of mechanical properties of TIG and FSW welded joints comparing with base alloy while the FSW welded joint gives better mechanical properties than that of TIG welded joint. This is due to the micro structure changes during the welding process. It has been found that the surface hardening by shot peening improved the mechanical properties of both welded joints, this is due to the compressive residual stress generation in the weld zones which was measured using X-Ray diffraction (XRD) inspection.

Keywords: friction stir welding, TIG welding, mechanical properties, shot peening

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Authors: Chandra Shekhar Maurya, Chiranjit Sarkar

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The transient response of rheological properties of a carbonyl iron (CI)-water-based magnetorheological fluid (MRF) was studied under shear rate, shear stress, and shear strain working mode subjected to step-change in an applied magnetic field. MR fluid is a kind of smart material whose rheological properties change under an applied magnetic field. We prepared an MR fluid comprising of CI 65 weight %, water 35 weight %, and OPTIGEL WX used as an additive by changing the weight %. It was found that the MR effect of the CI/water suspension was enhanced by using an additive. A transient shear stress response was observed by switched on and switched off of the magnetic field to see the stability, relaxation behavior, and resulting change in rheological properties. When the magnetic field is on, a sudden increase in the shear stress was observed due to the fast motion of magnetic structures that describe the transition from the liquidlike state to the solid-like state due to an increase in dipole-dipole interaction of magnetic particles. Simultaneously, the complete reverse transition occurs due to instantaneous breakage of the chain structure once the magnetic field is switched off.

Keywords: magnetorheological fluid, rheological properties, shears stress, shears strain, viscosity

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Authors: A. Cagnacci, D. F. Barattini, E. Casolati, M. Mangrella, E. Piccolo, S. Rosu, L. C. Pătrașcu

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This Triple study aimed to evaluate the efficacy of polycarbophil vaginal gel (PCV) in treating symptoms of vaginal atrophy (VA) in peri- and post-menopausal women. Women in peri- (n=29) and postmenopause (n=54) diagnosed with VA were progressively enrolled and treated once a day for 30 days. Thereafter, those wishing to continue (n=73) received the PCV treatment for an additional 180 days. The vaginal health index (VHI) and vaginal dryness, irritation, and pain at intercourse, along with treatment safety, were evaluated at baseline, 30 days of treatment, and after additional 180 days. At baseline, the VHI (p<0.056) and VAS of vaginal dryness (p=0.0001,) irritation (p=0.002), and pain at intercourse (p=0.0001) were worse in postmenopausal women than in perimenopausal women. VHI and VA symptoms improved in all women, and after 30 days of PCV administration, they were similar between peri-and postmenopausal women. After an additional 180 days of treatment, VHI further increased (p=0.0001), VAS of all symptoms (P=0.0001) and the Global Symptom Score (P=0.0001) further decreased. The treatment was safe. Treatment with PCV improves VA symptoms in both peri- and post-menopausal women. Prolongation of treatment up to 6 months increases the efficacy of treatment with no side effects.

Keywords: late menopausal transition, postmenopause, polycarbophil, sexuality, vaginal dryness

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Authors: Rajkumar Ghosh

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The study examines the structural analysis of Chaura Thrust in Himachal Pradesh, India, focusing on the activation timing of Main Central Thrust (MCT) and South Tibetan Detachment System (STDS), mylonitised zones, and the characterization of box fold and its signature in the regional geology of Himachal Himalaya. The research aims to document the Higher Himalayan Out-of-Sequence Thrust (OOST) in Himachal Pradesh, which activated the MCTL and in between a zone south of MCTU. The study also documents the GBM-associated temperature range and the activation of Higher Himalayan Out-of-Sequence Thrust (OOST) in Himachal Pradesh. The findings contribute to understanding the structural analysis of Chaura Thrust and its signature in the regional geology of Himachal Himalaya. The study highlights the significance of microscopic studies in documenting mylonitized zones and identifying various types of crenulated schistosity. The study concludes that Chaura Thrust is not a blind thrust and details the field evidence for the OOST. The study characterizes the box fold and its signature in the regional geology of Himachal Himalaya. The study also documents the activation timing and ages of MCT, STDS, MBT, and MFT and identifies various types of crenulated schistosity under the microscope. The study also highlights the significance of microscopic studies in the structural analysis of Chaura Thrust. Finally, the study documents the activation of Higher Himalayan Out-of-Sequence Thrust (OOST) in Himachal Pradesh and the expectations for strain variation near the OOST.

Keywords: Chaura Thrust, Higher Himalaya, Jhakri Thrust, Main Central Thrust, Out-of-Sequence Thrust, Sarahan Thrust

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Authors: Sohil I. Alqazlan

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Introduction and Objectives: There is limited research focusing on young adults with intellectual disabilities (ID) and their experiences after finishing compulsory education, especially in the Middle Eastern/Arab countries. This paper aims to further understand the lives of young adults with ID in Riyadh [the capital city of Saudi Arabia], particularly as they go on to access Post-Secondary Education [PSE]. As part of this study, it is important to understand the roles of high schools in Riyadh in terms of preparing their students for post-school life. To achieve this, the researcher has asked Saudi Arabia’s Ministry of Education to provide student transition plans (TPs) for post-school opportunities. However, and unfortunately, high schools in Riyadh do not use transition plans for their students. Therefore, the researcher has requested individual education plans (IEPs) for students with ID in their final year at high school to find the type of support the students had regarding both their long- and short-term goals that might help them access PSE or the labour market. Methods: The researcher analysed 10 IEPs of students in their final year at high school. To achieve the aim of the study, the researcher compared these IEPs with expectations set out in the official IEP framework of the MoE in Saudi Arabia, such as collaboration on the IEP sample and the focus on adult life. By analysing the students’ IEPs in terms of various goals, this study attempts to highlight skills that might offer students more independence after finishing compulsory education and going on to PSE. Results: Unfortunately, communication between IEP team members proved persistently absent in the sample. This was clear from the fact that none of the team members, apart from the SEN teachers, had signed any of the IEPs. Thus, none of the daily or weekly goals outlined were sent to parents to review at home. As a result of this, there were no goals in the IEPs that clearly referred to PSE. However, some long-term goals were set which might help those with ID become more independent in their adult life. For example, in the IEPs, which dealt with computer skills, the student had goals related to using Microsoft Word. Finally, just one goal of these IEPs set an important independent skill for the young adults with ID: “the student will learn how to use public transportation”. Conclusions: From analysing the ten IEPs, it was clear that SEN teachers in Riyadh schools were working without any help from other professionals. The students with ID, as well as their families, were not consulted on their views on important goals. Therefore, more work needs to be done with the students regarding their transition to PSE, perhaps by building partnerships between high schools and potential PSE institutions. Finally, more PSE programmes and a higher level of employer awareness could help create a bridge for students transferring from high school to PSE. Schools could also focus their IEP goals towards specific PSE programmes the student might attend, which could increase their chances of success.

Keywords: high school, post-secondary education, PSE, students with intellectual disabilities

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Authors: Amine.Harbia, Hicham. Moutaabbidb, Yann. Le Godecb, Said. Benmokhtara, Mouhammed. Moutaabbida

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This study explores the structural and magnetic characteristics of newly synthesized double perovskite oxides, La₂NiₓCo1-xMnO₆, with x ranging from 0.2 to 0.8. Utilizing X-ray powder diffraction and SQUID magnetometry, we analyzed the compounds that consistently exhibit a monoclinic structure with the P21/n space group at ambient temperature. it findings reveal that as Ni2+ is progressively substituted by Co2+, there is a corresponding decrease in cell parameters, attributable to the smaller ionic radius of Ni2+ (0.69 Å) compared to Co2+ (0.74 Å). The crystal structure features octahedrally coordinated (Co/Ni)2+ and Mn4+ cations with oxygen, forming (Co/Ni)O6 and MnO6 octahedra linked via oxygen atoms along different crystallographic axes. Magnetic characterization conducted over a temperature range of 2 to 300 K in both DC and AC magnetic fields, showed a predominant paramagnetic to ferromagnetic transition between 232 K and 260 K, with the Curie temperature notably increasing with higher x values. Samples with x=0.2, 0.25, and 0.5 exhibited a secondary PM-FM transition between 200 K and 208 K. Cation ordering was quantitatively assessed, indicating a higher ordering in Ni2+-rich samples (x=0.75 and 0.8) at over 96%, whereas the sample with x=0.25 showed minimal ordering. Furthermore, the out-of-phase component of the AC susceptibility displayed frequency-dependent transitions between 65 K and 110 K, suggesting the presence of superparamagnetic domains across all samples.

Keywords: double perovskite oxides, magnetic transitions, cation ordering, squid magnetometry

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Authors: Barbara Covarrubias Venegas, Sabine Groblschegg, Bernhard Klaus, Julia Domnanovich

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Research Objectives: The roles and activities of human resource management (HRM) have changed a lot in the past years. Driven by a changing environment and therefore, new business requirements, the scope of human resource (HR) activities has widened. The extent to which these activities should focus on strategic issues to support the long-term success of a company has been discussed in science for many years. As many economies of Central and Eastern Europe (CEE) experienced a phase of transition after the socialist era and are now recovering from the 2008 global crisis it is needed to examine the current state of HR positioning. Furthermore, a trend in HR work developing from rather administrative units to being strategic partners of management can be noticed. This leads to the question of better understanding the underlying competencies which are necessary to support organisations. This topic was addressed by the international study “HR Competencies in international comparison”. The quantitative survey was conducted by the Institute for Human Resources & Organisation of FHWien University of Applied Science of WKW (A) in cooperation with partner universities in the countries Bosnia-Herzegovina, Croatia, Serbia and Slovenia. Methodology: Using the questionnaire developed by Dave Ulrich we tested whether the HR Competency model can be used for Austria, Bosnia and Herzegovina, Croatia, Serbia and Slovenia. After performing confirmatory and exploratory factor analysis for the whole data set containing all five countries we could clearly distinguish between four competencies. In a further step, our analysis focused on median and average comparisons between the HR competency dimensions. Conclusion: Our literature review, in alignment with other studies, shows a relatively rapid pace of development of HR Roles and HR Competencies in BCSS in the past decades. Comparing data from BCSS and Austria we still can notice that regards strategic orientation there is a lack in BCSS countries, thus competencies are not as developed as in Austria. This leads us to the tentative conclusion that HR has undergone a rapid change but is still in a State of Transition from being a rather administrative unit to performing the role of a strategic partner.

Keywords: comparative study, HR competencies, HRM, HR roles

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Authors: Sudhakara Naidu Neppalli, Tejas S. Bhosale

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It is well known that the block copolymer (BCP) can form a complex molecule, through non-covalent bonds such as hydrogen bond, ionic bond and co-ordination bond, with low molecular weight compound as well as with macromolecules, which provide vast applications, includes the alteration of morphology and properties of polymers. Hence we covered the research that, the importance of non-covalent bonds in increasing the non-favourable segmental interactions of the blocks was well examined by attaching and detaching the bonds between the BCP and additive. We also monitored the phase transition of block copolymer and effective interaction parameter (χeff) for Li-doped polymers using small angle x-ray scattering and transmission electron microscopy. The effective interaction parameter (χeff) between two block components was evaluated using Leibler theory based on the incompressible random phase approximation (RPA) for ionized BCP in a disordered state. Furthermore, conductivity experiments demonstrate that the ionic conductivity in the samples quenched from the different structures is morphology-independent, while it increases with increasing ion salt concentration. Morphological transitions, interaction parameter, and thermal stability also examined in quarternized block copolymer. D-spacing was used to estimate effective interaction parameter (χeff) of block components in weak and strong segregation regimes of ordered phase. Metal-containing polymer has been the topic of great attention in recent years due to their wide range of potential application. Similarly, metal- ligand complex is used as a supramolecular linker between the polymers giving rise to a ‘Metallo-Supramolecule assembly. More precisely, functionalized polymer end capped with 2, 2’:6’, 2”- terpyridine ligand can be selectively complexed with wide range of transition metal ions and then subsequently attached to other terpyridine terminated polymer block. In compare to other supramolecular assembly, BCP involved metallo-supramolecule assembly offers vast applications such as optical activity, electrical conductivity, luminescence and photo refractivity.

Keywords: band gap, block copolymer, conductivity, interaction parameter, phase transition

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Authors: Joao Gouveia

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This is a study about Hegelian political and moral philosophy. Our aim is to understand the relevance that Hegel attributes to ethics in the concrete political configuration of society. But our analysis isn’t limited to Hegel’s most known political work (the Grundlinien der Philosophie des Rechts). Instead, we also analyze the Phänomenologie des Geistes and establish a comparison between them. In the Moralität of the Grundlinien der Philosophie des Rechts, consciousness acquires the disposition that allows it to see any determination as its own (the certainty about itself or Gewissen). This certainty is the essential disposition that makes itself felt throughout all Sittlichkeit –the dispositions of family member and citizen (Bürger) are only configurations of it. Although consciousness is alienated in these dispositions, it doesn’t lose the certainty about itself that it reached in the Moralität. As our major finding, we point out that it is the moral learning that allows consciousness to resist the temptation of focusing so intensely on specific content that it excludes all the others (a temptation that is stimulated by the very intensity with which each content presents itself to consciousness). As the world of Bildung of the Phänomenologie des Geistes isn’t preceded by a sphere of Moralität, consciousness is thrown into a frenzy of destruction of all the powers of objectivity, and it ends up having to withdraw from the concrete contents and to focus in an abstract whole, where it doesn’t find opposite determinacies. The evidence supporting our thesis is the fact that the transition from abstraction into particularity, that we see in the Grundlinien der Philosophie des Rechts, allows the preservation of abstraction (it isn’t lost as we penetrate in particularity). On the other hand, the transition we find in the Phänomenologie des Geistes is a transition from particularity to abstraction, which takes every particularity to be eliminated in the war with others. While in the Phänomenologie des Geistes, the state may only be seen as a moment or facet of the object (it is only Staatsmacht); in the Grundlinien der Philosophie des Rechts, it is seen as a whole that contains various moments in itself (Staat). Therefore, the element of the Phänomenologie des Geistes that is closer to the State of the Grundlinien der Philosophie des Rechts is language (or the language of perversion) –something that can’t be defined as an individuality. This way, we want to show that, between the Phänomenologie des Geistes and the Grundlinien der Philosophie des Rechts, there is truly no remarkable evolution to report in Hegel’s ethical thought. What the difference in the structure of the two works show is a specific thesis respecting the influence of ethics in the configuration of society, and this thesis has implications at various levels, including in the philosophy of history.

Keywords: Grundlinien der Philosophie des Rechts, Hegelian ethics, Hegelian politics, Phänomenologie des Geistes

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Authors: Mrinal Mukherjee, Gargi Seal, Bitopan Mazumdar, Prakhar Agarwal

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The central sector of Palghat-Cauvery Shear zone Tamil Nadu, India, had been studied with reference to development, mode of occurrence, interrelationship and variation of structural elements. The litho assemblages of the study area include gneisses migmatites granites and bear signature of multistage deformation patterns. The early deformation D1 is characterized in migmatites and gneisses by the development of tight to isoclinal, recumbent to reclined folds within the compositional bands that are refolded subsequently to produce D2 deformation structures ranging from type-II to type-III superposed geometry. The granite, in general, is undeformed, save a few places where strong mylonitic foliation developed with stretching lineation on it. The D1-D2 structures of gneisses and migmatites were affected by a D3 stage- E-W trending shear zone (Palghat-Cauvery Shear zone) that dips steeply towards north. The shear zone is characterized by the development of mylonite zone with stretching lineation on foliation, shear band structures, modification of geometry and orientation of earlier folds and foliations within the shear zone and development of shear induced folds and foliations. Several anastomosing lenses of shear zones define the larger Palghat-Cauvery Shear zone. The orientation of the shear induced folds and foliations and deflections of earlier foliation and folds within the Palghat-Cauvery shear zone indicate an oblique-slip thrust-shear with north-towards-east sense of displacement. The E-W trending shear zone is further openly folded along N-S in the D4 stage of deformation.

Keywords: deformation, migmatites, mylonites, shear zones

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Authors: Bilal Ahmad Ashwar, Inam u nisa, Asima Shah, Adil Gani, Farooq Ahmad Masoodi

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The effects of 5% BHT and green tea extracts (GTE) on the physical, barrier, mechanical, thermal and antioxidant properties of potato starch films were investigated. Results showed both BHT and GTE significantly lowered solubility of films. Addition of BHT significantly decreased water vapour transmission rate. Both BHT and GTE promoted significant increase in the elastic modulus but a decrease in % EAB, however BHT was more effective in increasing elastic modulus. Increase in glass transition temperature (Tg) and enthalpy of transition (ΔH) of films was observed with the incorporation of GTE and BHT. Scanning electron microscopy (SEM) revealed smooth surface of the films. The DPPH radical scavenging ability of both BHT and GTE films were stronger in fatty food stimulant (95% ethanol. The GTE and BHT films were individually applied to fresh beef samples and were stored at 4 0C and room temperature for 10 days. Metmyoglobin formation and lipid oxidation (TBARS) were monitored periodically. The addition of GTE extracts and BHT resulted in decreases in metmyoglobin and TBARS values. We conclude that extracts of GTE and BHT have potential as preservatives for fresh beef.

Keywords: starch film, WVTR, tensile properties, SEM, thermal analysis, DPPH scavenging activity, TBARS, metmyoglobin

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Authors: Ojo F. M., Nwekeocha C. C., Faluyi J. O.

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Morphological studies were carried out on Andropogongayanus-Andropogontectorum complex collected in Southwestern Nigeria to provide full characterizationof the two species of Andropogon; elucidating their population dynamics. Morphological data from selected accessions of A. gayanus and A. tectorum from different parts of Southwestern Nigeria were collected and characterized using an adaptation of the Descriptors for Wild and Cultivated Rice (Oryza spp). Preliminary morphological descriptions were carried out at the points of collection. Garden populations were raised from the vegetative parts of some accessions, and hybrids were maintained in Botanical Garden of the Obafemi Awolowo University, Ile- Ife. The data obtained were subjected to inferential tests and Duncan’s multiple range test. This study has revealed distribution pattern of the two species in the area of study, which suggests a south-ward migration of Andropogongayanus from the northern vegetational zones of Nigeria to the southern ecological zones. The migration of A. gayanus around Igbeti with occasional occurrence of A. tectorum along the roadsides without any distinct phenotypic hybrid and Budo-Ode in Oyo State has been established as the southern limit of the spread of A. gayanus, the migration of A. gayanus to the South is not an invasion but a slow process. A. gayanus was not encountered in Osun, Ondo, Ekiti, and Ogun States. Andropogongayanus and Andropogon tectorum not only emerge from the rootstocks rapidly but can also produce independent propagules by rooting at some nodes. The plants can spread by means of these propagules even if it does not produce sexual or apomictic seeds. This potential for vegetative propagation, in addition to the perennial habit, confer considerable advantage for colonization by the Andropogongayanus-AndropogontectorumComplex.

Keywords: accessions, distribution, migration, propagation

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Authors: Dagem Alemayehu, Samson Gebersilassie, Jan Frank

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Climate change is impacting nutrition through reducing food quantity and access, limiting dietary diversity, and decreased nutritional food content as well as strongly affecting seasonal rainfall in Ethiopia. Nevertheless, only a few data is available on the impacts of seasonality in Infant, and Young Child Feeding (IYCF) practices undernutrition among 6-23 months old children in different agro-ecological zones of poor resource settings of Ethiopia. Methods: Socio-demographic, anthropometry, and IYCF indicators were assessed in the harvest and lean seasons among children aged 6–23 months of age randomly selected from rural villages of lowland and midland agro-ecological zones. Results: Child stunting and underweight increased from prevalence of 32.8 % and 23.9 % (lowland &midland respectively) in the lean season to 36.1% and 33.8 % harvest seasons, respectively. The biggest increase in the prevalence of stunting and underweight between harvest and lean seasons was noted in the lowland zone. Wasting decreased from 11.6% lean to 8.5% harvest, with the biggest decline recorded in the midland zone. Minimum meal frequency, minimum acceptable diet, and poor dietary diversity increased considerably in harvest compared to a lean season in the lowland zone. Feeding practices and maternal age were predictors of wasting, while women's dietary diversity and children's age was a predictor of child dietary diversity in both seasons. Conclusion: There is seasonal variation in undernutrition and IYCF practices among children 6-23 months of age with more pronounced effect lowland agro-ecological zone.

Keywords: agroecology, seasonality, stunting, wasting

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Authors: Mohammad Zafar-ul Islam, Shaily Menon, Xingong Li, A. Townsend Peterson

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In addition to the mounting empirical data on direct implications of climate change for natural and human systems, evidence is increasing for other, indirect climate change phenomena such as sea-level rise. Rising sea levels and associated marine intrusion into terrestrial environments are predicted to be among the most serious eventual consequences of climate change. The many complex and interacting factors affecting sea levels create considerable uncertainty in sea-level rise projections: conservative estimates are on the order of 0.5-1.0 m globally, while other estimates are much higher, approaching 6 m. Marine intrusion associated with 1– 6 m sea-level rise will impact species and habitats in coastal ecosystems severely. Examining areas most vulnerable to such impacts may allow design of appropriate adaptation and mitigation strategies. We present an overview of potential effects of 1 and 6 m sea level rise for coastal conservation areas in the Indian Subcontinent. In particular, we examine the projected magnitude of areal losses in relevant biogeographic zones, ecoregions, protected areas (PAs), and Important Bird Areas (IBAs). In addition, we provide a more detailed and quantitative analysis of likely effects of marine intrusion on 22 coastal PAs and IBAs that provide critical habitat for birds in the form of breeding areas, migratory stopover sites, and overwintering habitats. Several coastal PAs and IBAs are predicted to experience higher than 50% losses to marine intrusion. We explore consequences of such inundation levels on species and habitat in these areas.

Keywords: sea-level change, coastal inundation, marine intrusion, biogeographic zones, ecoregions, protected areas, important bird areas, adaptation, mitigation

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Authors: Neha Pranav Kolhe, Harithapriya Vijaye, Arushi Kamle

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The economic growth engines are urban regions. As the economy expands, so does the need for peace and quiet, and noise pollution is one of the important social and environmental issue. Health and wellbeing are at risk from environmental noise pollution. Because of urbanisation, population growth, and the consequent rise in the usage of increasingly potent, diverse, and highly mobile sources of noise, it is now more severe and pervasive than ever before, and it will only become worse. Additionally, it will expand as long as there is an increase in air, train, and highway traffic, which continue to be the main contributors of noise pollution. The current study will be conducted in two zones of class I city of central India (population range: 1 million–4 million). Total 56 measuring points were chosen to assess noise pollution. The first objective evaluates the noise pollution in various urban habitats determined as formal and informal settlement. It identifies the comparison of noise pollution within the settlements using T- Test analysis. The second objective assess the noise pollution in silent zones (as stated in Central Pollution Control Board) in a hierarchical way. It also assesses the noise pollution in the settlements and compares with prescribed permissible limits using class I sound level equipment. As appropriate indices, equivalent noise level on the (A) frequency weighting network, minimum sound pressure level and maximum sound pressure level were computed. The survey is conducted for a period of 1 week. Arc GIS is used to plot and map the temporal and spatial variability in urban settings. It is discovered that noise levels at most stations, particularly at heavily trafficked crossroads and subway stations, were significantly different and higher than acceptable limits and squares. The study highlights the vulnerable areas that should be considered while city planning. The study demands area level planning while preparing a development plan. It also demands attention to noise pollution from the perspective of residential and silent zones. The city planning in urban areas neglects the noise pollution assessment at city level. This contributes to that, irrespective of noise pollution guidelines, the ground reality is far away from its applicability. The result produces incompatible land use on a neighbourhood scale with respect to noise pollution. The study's final results will be useful to policymakers, architects and administrators in developing countries. This will be useful for noise pollution in urban habitat governance by efficient decision making and policy formulation to increase the profitability of these systems.

Keywords: noise pollution, formal settlements, informal settlements, built environment, silent zone, residential area

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Authors: Christopher Meyer, Laima Gerlitz

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European ports are facing high political pressure through the implementation of initiatives such as the European Green Deal or IMO's 2030 targets (Fit for 55). However, small and medium-sized ports face even higher challenges compared to bigger ones due to lower capacities in various fields such as investments, infra-structure, Human Resources, and funding opportunities. Small and Medium-Sized Ports (SMPs) roles in economic systems are various depending on their specific functionality in maritime ecosystems. Depending on their different situations, being an actor in multiport gateways, aligned to core ports, regional nodes in peripheries for the hinterland, specialized cluster members, or logistical nodes, different strategic business models may be applied to increase SMPs' competitiveness among other bigger ports. Additionally, SMPs are facing more challenges for future development in terms of digital and green transition of their operations. Thus, it is necessary to evaluate the own strategical position and apply management strategies alongside the regional growth and innovation strategies for diversification or specialisation of own port businesses. The research uses inductive perspectives to set up a transferable framework based on case studies to be analysed. In line with particular research and document analysis, qualitative approaches were considered. The research is based on a deep literature review on SMPs as well as theories on diversification and specialisation. Existing theories from different fields are evaluated on their application for the port sector and these specific maritime actors, paying respect to enabling innovation incorporation to enhance digital and environmental transition with fu-ture perspectives for SMPs. The paper aims to provide a decision-making matrix for the strategic positioning of SMPs in Europe, including opportunities to get access to particular EU funds for future development alongside the Regional In-novation Strategies on Smart Specialisation.

Keywords: strategic planning, sustainability transition, competitiveness portfolio, EU green deal

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Authors: Carolin Anna Joy, Rohith K. R, Rehin Sulay, Parvathy Santhoshkumar, G.Anil Kumar, Vibin Ipe Thomas

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Ullmann coupling reactions are gaining great relevance owing to their contribution in the synthesis of biologically and pharmaceutically important compounds. Palladium and many other heavy metals have proven their excellent ability in coupling reaction, but the toxicity matters. The first-row transition metal also possess toxicity, except in the case of iron and manganese. The suitability of manganese as a catalyst is achieving great interest in oxidation, reduction, C-H activation, coupling reaction etc. In this presentation, we discuss the thermo chemistry of ligand free manganese catalyzed C-O coupling reaction between phenol and aryl halide for the synthesis of biaryl ethers using Density functional theory techniques. The mechanism involves an oxidative addition-reductive elimination step. The transition state for both the step had been studied and confirmed using Intrinsic Reaction Coordinate (IRC) calculation. The barrier height for the reaction had also been calculated from the rate determining step. The possibility of other mechanistic way had also been studied. To achieve further insight into the mechanism, substrate having various functional groups is considered in our study to direct their effect on the feasibility of the reaction.

Keywords: Density functional theory, Molecular Modeling, ligand free, biaryl ethers, Ullmann coupling

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Authors: Gaoyuan Wang, Tian Chen

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China’s emission peak and carbon neutrality strategies lead to the transformation of development patterns and call for new green urban design thinking. This paper begins by revealing the evolution of green urban design thinking during the periods of carbon enlightenment, carbon dependency, and carbon decoupling from the perspective of the energy transition. Combined with the current energy situation, national strengths, and technological trends, the emergence of green urban design towards carbon neutrality becomes inevitable. Based on the preliminary analysis of its connotation, the characteristics of the new type of green urban design are generalized as low-carbon orientation, carbon-related objects, carbon-reduction means, and carbon-control patterns. Its theory is briefly clarified in terms of the human-earth synergism, quality-energy interconnection, and form-flow interpromotion. Then, its mechanism is analyzed combined with the core tasks of carbon neutrality, and the scope of design issues is defined, including carbon flow mapping, carbon source regulation, carbon sink construction, and carbon emission management. Finally, a multi-scale spatial response system is proposed across the region, city, cluster, and neighborhood level. The discussion aims to provide support for the innovation of green urban design theories and methods in the context of peak neutrality.

Keywords: carbon neutrality, green urban design, energy transition, theoretical exploration

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Authors: Kristin Prentice, Carri Hand

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As the Canadian population ages and chronic health conditions continue to escalate, older adults will require various types of housing, such as long term care or retirement homes. Moving to a new home may require a change in leisure activities and social networks, which could be challenging to maintain identity and create a sense of home. Leisure has been known to help older adults maintain or increase their quality of life and life satisfaction and may help older adults in moving to new homes. Sense of home and identity within older adults' transitions to new homes are concepts that may also relate to leisure engagement. Literature is scant regarding the role of leisure in older adults moving to new homes and how the sense of home and identity inter-relate. This study aims to explore how leisure may play a role in older adults' transitioning to new homes, including how sense of home and identity inter-relate. An ethnographic approach will be used to understand the culture of older adults transitioning to new homes. This study will involve older adults who have recently relocated to a mid-sized city in Ontario, Canada. The study will focus on the older adult’s interactions with and connections to their home environment through leisure. Data collection will take place via video-conferencing and will include a narrative interview and two other interviews to discuss an activity diary of leisure engagement pre and post move and mental maps to capture spaces where participants engaged in leisure. Participants will be encouraged to share photographs of leisure engagement taken inside and outside their home to help understand the social spaces the participants refer to in their activity diaries and mental maps. Older adults attempt to adjust to their new homes by maintaining their identity, developing a sense of home through creating attachment to place, and maintaining social networks, all of which have been linked to engaging in leisure. This research will provide insight into the role of leisure in this transition process and the extent that the home and community can contribute to aiding their transition to the new home. This research will contribute to existing literature on the inter-relationships of leisure, sense of home, and identity and how they relate to older adults moving to new homes. This research also has potential for influencing policy and practice for meeting the housing needs of older adults.

Keywords: leisure, older adults, transition, identity

Procedia PDF Downloads 103

Authors: Mirna Guevara, Edgar Santoyo, Daniel Perez-Zarate, Erika Almirudis

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The Acoculco caldera located in Puebla (Mexico) has been preliminary identified as a blind hot-dry rock geothermal system. Two drilled wells suggest the existence of high temperatures >300°C and non-conventional tools are been applied to study this system. A comprehensive survey of soil-gas (CO₂) flux measurements (1,500 sites) was carried out during the dry seasons over almost two years (2015 and 2016). Isotopic analyses of δ¹³CCO₂ were performed to discriminate the origin source of the CO2 fluxes. The soil CO2 flux measurements were made in situ by the accumulation chamber method, whereas gas samples for δ13CCO2 were selectively collected from the accumulation chamber with evacuated gas vials via a septum. Two anomalous geothermal zones were identified as a result of these campaigns: Los Azufres (19°55'29.4'' N; 98°08'39.9'' W; 2,839 masl) and Alcaparrosa (19°55'20.6'' N; 98°08'38.3'' W; 2,845 masl). To elucidate the origin of the C in soil CO₂ fluxes, the isotopic signature of δ¹³C was used. Graphical Statistical Analysis (GSA) and a three end-member mixing diagram were used to corroborate the presence of distinctive statistical samples, and trends for the diffuse gas fluxes. Spatial and temporal distributions of the CO₂ fluxes were studied. High CO₂ emission rates up to 38,217 g/m2/d and 33,706 g/m2/d were measured for the Los Azufres and Alcaparrosa respectively; whereas the δ¹³C signatures showed values ranging from -3.4 to -5.5 o/oo for both zones, confirming their magmatic origin. This study has provided a valuable framework to set the direction of further exploration campaigns in the Acoculco caldera. Acknowledgements: The authors acknowledge the funding received from CeMIE-Geo P09 project (SENER-CONACyT).

Keywords: accumulation chamber method, carbon dioxide, diffusive degassing, geothermal exploration

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Authors: Njoku, Joy

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The re-calibration of the Campanian to Maastritchian of some parts Anambra basin was carried outusing samples from two exploration wells (Amama-1 and Bara-1), Amama-1 (219M–1829M) and Bara-1 (317M-1594M). Palynological and Paleontological analyses werecarried out on 100 ditch cutting samples. The faunal and floral succession were of terrestrialand marine origin as described and logged. The well penetrated four stratigraphic units inAnambra Basin (the Nkporo, Mamu, Ajali and Nsukka) the wells yielded well preservedformanifera and palynormorphs. The well yielded 53 species of foram and 69 species ofpalynomorphs, with 12 genera Bara-1 (25 Species of foram and 101 species of palynormorphs). Amama-1permitted the recognition of 21 genera with 31 formainiferal assemblage zones, 32 pollen and 37 sporesassemblage zones, and dinoflagellate cyst, biozonation, ranging from late Campanian – earlyPaleocene. Bara-1 yielded (60 pollen, 41 spore assemblage zone and 18 dinoflagellate cyst).The zones, in stratigraphically ascending order for the foraminifera and palynomorphs are asfollows. AmamaBiozone A-Globotruncanellahavanensis zone: Late Campanian –Maastrichtian (695 – 1829m) Biozone B-Morozovellavelascoensis zone: Early Paleocene(165–695m) Bara-1 Biozone A-Globotruncanellahavanensis zone: Late Campanian(1512m) Biozone B-Bolivinaafra, B. explicate zone: Maastrichtian (634–1204m) BiozoneC- Indeterminate (305 – 634m) Palynological Amama-1 A.Ctenolophoniditescostatus zone:Early Maastrichtian (1829m) B-Retidiporitesminiporatus Zone: Late Maastrichtian (1274m)Constructipollenitesineffectus Zone: Early Paleocene(695m) Bara-1 Droseriditessenonicus Zone: Late Campanian (994– 1600m) B. Ctenolophoniditescostatus Zone: EarlyMaastrichtian (713–994m) C. Retidiporitesminiporatus Zone: Late Maastrichtian (305 –713m) The paleo – environment of deposition were determined to range from non-marine toouter netritic. A detailed categorization of the palynormorphs into terrestrially derivedpalynormorphs and marine derived palynormorphs based on the distribution of three broadvegetation types; mangrove, fresh water swamps and hinther land communities were used toevaluate sea level fluctuations with respect to sediments deposited in the basins and linkedwith a particular depositional system tract. Amama-1 recorded 4 maximum flooding surface(MFS) at depth 165-1829, dated b/w 61ma-76ma and three sequence boundary(SB) at depth1048m-1533m and 1581 dated b/w 634m-1387m, dated 69.5ma-82ma and four sequenceboundary(SB) at 552m-876m, dated 68ma-77.5ma respectively. The application ofecostratigraphic description is characterised by the prominent expansion of the hinterlandcomponent consisting of the Mangrove to Lowland Rainforest and Afromontane – Savannah vegetation.

Keywords: formanifera, palynomorphs. campanian, maastritchian, ecostratigraphic anambra

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Authors: M. M. S. Prahastomi, M. Muhajir Saputra, Axel Derian

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Lapindo mud (LUSI ) phenomenon which occurred in Sidoarjo 2006 is a national scale of the geological phenomenon. This mudflow forms a mud volcano that spreads by time is in the need of serious treatment. Some further research has been conducted either by the application method of geodesy, geophysics, and subsurface geology, but still remains a mystery to this phenomenon. Sidoarjo Physiographic regions are included in the Kendeng zone flanked by Rembang zones in northern and Solo zones in southern. In this region revealed Kabuh formation, Jombang formation, and alluvium. In general, in the northern part of the area is composed of sedimentary rocks Sidoarjo klastika, epiklastic, pyroclastics, and older alluvium of the Early Pleistocene to Resen. The study was conducted with the literature study of the stratigraphy and regional geology as well as secondary data from observations coupled gravity method (Anomaly Bouger). The aim of the study is to reveal the subsurface geology structure pattern and the changes in mass flow. Gravity anomaly data were obtained from the calculation of the value of gravity and altitude, then processed into gravity anomaly contours which reflect changes in density of each group observed gravity. The gravity data could indicate a bottom surface which deformation occur the stronger or more intense to the south. Deformation in the form of gravity impairment was associated with a decrease in future density which is indicated by the presence of gas, water and gas bursts. Sectional analysis of changes in the measured value of gravity at different times indicates a change in the value of gravity caused by the presence of subsurface subsidence. While the gravity anomaly section describes the fault zone causes the zone to be unstable.

Keywords: mud volcano, Lumpur Sidoarjo, Bouger anomaly, Indonesia

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Authors: Tsedeke Lambore Gemecho, Ayele Taye Goshu

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The main objective of this study is to identify the determinants of the number of international migrants in a household and to compare regression models for count response. This study is done by collecting data from total of 2288 household heads of 16 randomly sampled districts in Hadiya and Kembata-Tembaro zones of Southern Ethiopia. The Poisson mixed models, as special cases of the generalized linear mixed model, is explored to determine effects of the predictors: age of household head, farm land size, and household size. Two ethnicities Hadiya and Kembata are included in the final model as dummy variables. Stepwise variable selection has indentified four predictors: age of head, farm land size, family size and dummy variable ethnic2 (0=other, 1=Kembata). These predictors are significant at 5% significance level with count response number of migrant. The Poisson mixed model consisting of the four predictors with random effects districts. Area specific random effects are significant with the variance of about 0.5105 and standard deviation of 0.7145. The results show that the number of migrant increases with heads age, family size, and farm land size. In conclusion, there is a significantly high number of international migration per household in the area. Age of household head, family size, and farm land size are determinants that increase the number of international migrant in households. Community-based intervention is needed so as to monitor and regulate the international migration for the benefits of the society.

Keywords: Poisson regression, GLM, number of migrant, Hadiya and Kembata Tembaro zones

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Authors: Igor B. Sivaev

Abstract:

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

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

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