Search results for: anomalous couplings

Authors: P. Suchismita Behera, V. G. Sathe, A. K. Nigam, P. A. Bhobe

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Co-existence of long-range ferromagnetism and semi-conductivity with correlated behavior of structural, magnetic, optical and electrical properties in various sites doping at CdCr2Se4 makes it a most promising candidate for spin-based electronic applications and magnetic devices. It orders ferromagnetically below TC = 130 K with a direct band gap of ~ 1.5 eV. The magnetic ordering is believed to result from strong competition between the direct antiferromagnetic Cr-Cr spin couplings and the ferromagnetic Cr-Se-Cr exchange interactions. With an aim of understanding the influence of crystal structure on its magnetic properties without disturbing the magnetic site, we investigated four compositions with 3%, 5%, 7% and 10% of Sn-substitution at Cd-site. Partial substitution of Cd2+ (0.78Å) by small sized nonmagnetic ion, Sn4+ (0.55Å), is expected to bring about local lattice distortion as well as a change in electronic charge distribution. The structural disorder would affect the Cd/Sn – Se bonds thus affecting the Cr-Cr and Cr-Se-Cr bonds. Whereas, the charge imbalance created due to Sn4+ substitution at Cd2+ leads to the possibility of Cr mixed valence state. Our investigation of the local crystal structure using the EXAFS, Raman spectroscopy and magnetic properties using SQUID magnetometry of the Cd1-xSnxCr2Se4 series reflects this premise. All compositions maintain the Fd3m cubic symmetry with tetrahedral distribution of Sn at Cd-site, as confirmed by XRD analysis. Lattice parameters were determined from the Rietveld refinement technique of the XRD data and further confirmed from the EXAFS spectra recorded at Cr K-edge. Presence of five Raman-active phonon vibrational modes viz. (T2g (1), T2g (2), T2g (3), Eg, A1g) in the Raman spectra further confirms the crystal symmetry. Temperature dependence of the Raman data provides interesting insight to the spin– phonon coupling, known to dominate the magneto-capacitive properties in the parent compound. Below the magnetic ordering temperature, the longitudinal damping of Eg mode associated with Se-Cd/Sn-Se bending and T2g (2) mode associated to Cr-Se-Cr interaction, show interesting deviations with respect to increase in Sn substitution. Besides providing the estimate of TC, the magnetic measurements recorded as a function of field provide the values of total magnetic moment for all the studied compositions indicative of formation of multiple Cr valences.

Keywords: exchange interactions, EXAFS, ferromagnetism, Raman spectroscopy, spinel chalcogenides

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Authors: Gabriele Ciasca, Tanya E. Sassun, Eleonora Minelli, Manila Antonelli, Massimiliano Papi, Antonio Santoro, Felice Giangaspero, Roberto Delfini, Marco De Spirito

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Glioblastoma multiforme (GBM) is an extremely aggressive brain tumor, characterized by a diffuse infiltration of neoplastic cells into the brain parenchyma. Although rarely considered, mechanical cues play a key role in the infiltration process that is extensively mediated by the tumor microenvironment stiffness and, more in general, by the occurrence of aberrant interactions between neoplastic cells and the extracellular matrix (ECM). Here we provide a nano-mechanical characterization of the viscoelastic response of human GBM tissues by indentation-type atomic force microscopy. High-resolution elasticity maps show a large difference between the biomechanics of GBM tissues and the healthy peritumoral regions, opening possibilities to optimize the tumor resection area. Moreover, we unveil the nanomechanical signature of necrotic regions and anomalous vasculature, that are two major hallmarks useful for glioma staging. Actually, the morphological grading of GBM relies mainly on histopathological findings that make extensive use of qualitative parameters. Our findings have the potential to positively impact on the development of novel quantitative methods to assess the tumor grade, which can be used in combination with conventional histopathological examinations. In order to provide a more in-depth description of the role of mechanical cues in tumor progression, we compared the nano-mechanical fingerprint of GBM tissues with that of grade-I (WHO) meningioma, a benign lesion characterized by a completely different growth pathway with the respect to GBM, that, in turn hints at a completely different role of the biomechanical interactions.

Keywords: AFM, nano-mechanics, nanomedicine, brain tumors, glioblastoma

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Authors: Craig Wight

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Tourism visits to sites associated to varying degrees with death and dying have for some time inspired academic debate and research into what has come to be popularly described as ‘dark tourism’. Research to date has been based on the mobilisation of various social scientific methodologies to understand issues such as the motivations of visitors to consume dark tourism experiences and visitor interpretations of the various narratives that are part of the consumption experience. This thesis offers an alternative conceptual perspective for carrying out research into dark tourism by presenting a discourse analysis of Lithuanian occupation-themed museums using Foucault’s concept of ‘discursive formation’ from ‘Archaeology of Knowledge’. A constructivist methodology is therefore applied to locate the rhetorical representations of Lithuanian and Jewish subject positions and to identify the objects of discourse that are produced in five museums that interpret a historical era defined by occupation, the persecution of people and genocide. The discourses and consequent cultural function of these museums are examined, and the key finding of the research proposes that they authorise a particular Lithuanian individualism which marginalises the Jewish subject position and its related objects of discourse into abstraction. The thesis suggests that these museums create the possibility to undermine the ontological stability of Holocaust and the Jewish-Lithuanian subject which is produced as an anomalous, ‘non-Lithuanian’ cultural reference point. As with any Foucauldian archaeological research, it cannot be offered as something that is ‘complete’ since it captures only a partial field, or snapshot of knowledge, bound to a specific temporal and spatial context. The discourses that have been identified are perhaps part of a more elusive ‘positivity’ which is salient across a number of cultural and political surfaces which are ripe for a similar analytical approach in future. It is hoped that the study will motivate others to follow a discourse-analytical approach to research in order to further understand the critical role of museums in public culture when it comes to shaping knowledge about ‘inconvenient’ pasts.

Keywords: genocide heritage, foucault, Lithuanian tourism, discursive formatoin

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Authors: Van Trieu, Shouhuai Xu, Yusheng Feng

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Tracking attack trajectories can be difficult, with limited information about the nature of the attack. Even more difficult as attack information is collected by Intrusion Detection Systems (IDSs) due to the current IDSs having some limitations in identifying malicious and anomalous traffic. Moreover, IDSs only point out the suspicious events but do not show how the events relate to each other or which event possibly cause the other event to happen. Because of this, it is important to investigate new methods capable of performing the tracking of attack trajectories task quickly with less attack information and dependency on IDSs, in order to prioritize actions during incident responses. This paper proposes a two-level graph causality framework for tracking attack trajectories in internet networks by leveraging observable malicious behaviors to detect what is the most probable attack events that can cause another event to occur in the system. Technically, given the time series of malicious events, the framework extracts events with useful features, such as attack time and port number, to apply to the conditional independent tests to detect the relationship between attack events. Using the academic datasets collected by IDSs, experimental results show that the framework can quickly detect the causal pairs that offer meaningful insights into the nature of the internet network, given only reasonable restrictions on network size and structure. Without the framework’s guidance, these insights would not be able to discover by the existing tools, such as IDSs. It would cost expert human analysts a significant time if possible. The computational results from the proposed two-level graph network model reveal the obvious pattern and trends. In fact, more than 85% of causal pairs have the average time difference between the causal and effect events in both computed and observed data within 5 minutes. This result can be used as a preventive measure against future attacks. Although the forecast may be short, from 0.24 seconds to 5 minutes, it is long enough to be used to design a prevention protocol to block those attacks.

Keywords: causality, multilevel graph, cyber-attacks, prediction

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Authors: Marcin Stasiulewicz, Sebastian Filipkowski, Aneta Panuszko

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Background: The hallmark of neurodegenerative diseases, including Alzheimer's and Parkinson's diseases, is an aggregation of the abnormal forms of peptides and proteins. Water is essential to functioning biomolecules, and it is one of the key factors influencing protein folding and misfolding. However, the hydration studies of proteins are complicated due to the complexity of protein systems. The use of model compounds can facilitate the interpretation of results involving larger systems. Objectives: The goal of the research was to characterize the properties of the hydration water surrounding the two three-residue K peptide fragments INS (Isoleucine - Asparagine - Serine) and NSR (Asparagine - Serine - Arginine). Methods: Fourier-transform infrared spectra of aqueous solutions of the tripeptides were recorded on Nicolet 8700 spectrometer (Thermo Electron Co.) Measurements were carried out at 25°C for varying molality of solute. To remove oscillation couplings from water spectra and, consequently, obtain narrow O-D semi-heavy water bands (HDO), the isotopic dilution method of HDO in H₂O was used. The difference spectra method allowed us to isolate the tripeptide-affected HDO spectrum. Results: The structural and energetic properties of water affected by the tripeptides were compared to the properties of pure water. The shift of the values of the gravity center of bands (related to the mean energy of water hydrogen bonds) towards lower values with respect to the ones corresponding to pure water suggests that the energy of hydrogen bonds between water molecules surrounding tripeptides is higher than in pure water. A comparison of the values of the mean oxygen-oxygen distances in water affected by tripeptides and pure water indicates that water-water hydrogen bonds are shorter in the presence of these tripeptides. The analysis of differences in oxygen-oxygen distance distributions between the tripeptide-affected water and pure water indicates that around the tripeptides, the contribution of water molecules with the mean energy of hydrogen bonds decreases, and simultaneously the contribution of strong hydrogen bonds increases. Conclusions: It was found that hydrogen bonds between water molecules in the hydration sphere of tripeptides are shorter and stronger than in pure water. It means that in the presence of the tested tripeptides, the structure of water is strengthened compared to pure water. Moreover, it has been shown that in the vicinity of the Asparagine - Serine - Arginine, water forms stronger and shorter hydrogen bonds. Acknowledgments: This work was funded by the National Science Centre, Poland (grant 2017/26/D/NZ1/00497).

Keywords: amyloids, K-peptide, hydration, FTIR spectroscopy

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Authors: Sarocha Vivatvakin, Thanaporn Ratchataswan, Thiratest Leesutipornchai, Komkrit Ruangritchankul, Somboon Keelawat, Virachai Kerekhanjanarong, Patnarin Mahattanasakul, Saknan Bongsebandhu-Phubhakdi

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In this globalization era, much attention has been drawn to various molecular biomarkers, which may have the potential to predict the progression of cancer. Epidermal growth factor receptor (EGFR) is the classic member of the ErbB family of membrane-associated intrinsic tyrosine kinase receptors. EGFR expression was found in several organs throughout the body as its roles involve in the regulation of cell proliferation, survival, and differentiation in normal physiologic conditions. However, anomalous expression, whether over- or under-expression is believed to be the underlying mechanism of pathologic conditions, including carcinogenesis. Even though numerous discussions regarding the EGFR as a prognostic tool in head and neck cancer have been established, the consensus has not yet been met. The aims of the present study are to assess the correlation between the level of EGFR expression and demographic data as well as clinicopathological features and to evaluate the ability of EGFR as a reliable prognostic marker. Furthermore, another aim of this study is to investigate the probable pathophysiology that explains the finding results. This retrospective study included 30 squamous cell laryngeal carcinoma patients treated at King Chulalongkorn Memorial Hospital from January 1, 2000, to December 31, 2004. EGFR expression level was observed to be significantly downregulated with the progression of the laryngeal cancer stage. (one way ANOVA, p = 0.001) A statistically significant lower EGFR expression in the late stage of the disease compared to the early stage was recorded. (unpaired t-test, p = 0.041) EGFR overexpression also showed the tendency to increase recurrence of cancer (unpaired t-test, p = 0.128). A significant downregulation of EGFR expression was documented in advanced stage laryngeal cancer. The results indicated that EGFR level correlates to prognosis in term of stage progression. Thus, EGFR expression might be used as a prevailing biomarker for laryngeal squamous cell carcinoma prognostic prediction.

Keywords: downregulation, epidermal growth factor receptor, immunohistochemistry, laryngeal squamous cell carcinoma

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Authors: Valerii Levshakov, Olga Fedorova

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Specific features of ship structures, made from composites, i.e. simultaneous shaping of material and structure, large sizes, complicated outlines and tapered thickness have defined leading role of technology, integrating test results from material science, designing and structural analysis. Main procedures of composite shipbuilding are contact molding, vacuum molding and winding. Now, the most demanded composite shipbuilding technology is the manufacture of structures from fiberglass and multilayer hybrid composites by means of vacuum molding. This technology enables the manufacture of products with improved strength properties (in comparison with contact molding), reduction of production duration, weight and secures better environmental conditions in production area. Mechanized winding is applied for the manufacture of parts, shaped as rotary bodies – i.e. parts of ship, oil and other pipelines, deep-submergence vehicles hulls, bottles, reservoirs and other structures. This procedure involves processing of reinforcing fiberglass, carbon and polyaramide fibers. Polyaramide fibers have tensile strength of 5000 MPa, elastic modulus value of 130 MPa and rigidity of the same can be compared with rigidity of fiberglass, however, the weight of polyaramide fiber is 30% less than weight of fiberglass. The same enables to the manufacture different structures, including that, using both – fiberglass and organic composites. Organic composites are widely used for the manufacture of parts with size and weight limitations. High price of polyaramide fiber restricts the use of organic composites. Perspective area of winding technology development is the manufacture of carbon fiber shafts and couplings for ships. JSC ‘Shipbuilding & Shiprepair Technology Center’ (JSC SSTC) developed technology of dielectric uncouplers for cryogenic lines, cooled by gaseous or liquid cryogenic agents (helium, nitrogen, etc.) for temperature range 4.2-300 K and pressure up to 30 MPa – the same is used for separating components of electro physical equipment with different electrical potentials. Dielectric uncouplers were developed, the manufactured and tested in accordance with International Thermonuclear Experimental Reactor (ITER) Technical specification. Spiral uncouplers withstand operating voltage of 30 kV, direct-flow uncoupler – 4 kV. Application of spiral channel instead of rectilinear enables increasing of breakdown potential and reduction of uncouplers sizes. 95 uncouplers were successfully the manufactured and tested. At the present time, Russian the manufacturers of ship composite structures have started absorption of technology of manufacturing the same using automated prepreg laminating; this technology enables the manufacture of structures with improved operational specifications.

Keywords: fiberglass, infusion, polymeric composites, winding

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Authors: Shakti S. Acharya, V. R. R. Medicherla, Rajeev Rawat, Komal Bapna, Deepnarayan Biswas, Khadija Ali, K. Maiti

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The discovery of invar effect in 35% Ni concentration Fe1-xNix alloy has stimulated enormous experimental and theoretical research. Elemental Fe and low Ni concentration Fe1-xNix alloys which possess body centred cubic (bcc) crystal structure at ambient temperature and pressure transform to hexagonally close packed (hcp) phase at around 13 GPa. Magnetic order was found to be absent at 11K for Fe92Ni8 alloy when subjected to a high pressure of 26 GPa. The density functional theoretical calculations predicted substantial hyperfine magnetic fields, but were not observed in Mossbaur spectroscopy. The bulk modulus of fcc Fe1-xNix alloys with Ni concentration more than 35%, is found to be independent of pressure. The magnetic moment of Fe is also found be almost same in these alloys from 4 to 10 GPa pressure. Fe1-xNix alloys exhibit a complex microstructure which is formed by a series of complex phase transformations like martensitic transformation, spinodal decomposition, ordering, mono-tectoid reaction, eutectoid reaction at temperatures below 400°C. Despite the existence of several theoretical models the field is still in its infancy lacking full knowledge about the anomalous properties exhibited by these alloys. Fe1-xNix alloys have been prepared by arc melting the high purity constituent metals in argon ambient. These alloys have annealed at around 3000C in vacuum sealed quartz tube for two days to make the samples homogeneous. These alloys have been structurally characterized by x-ray diffraction and were found to exhibit a transition from bcc to fcc for x > 0.3. Ni 2p core levels of the alloys have been measured using high resolution (0.45 eV) x-ray photoelectron spectroscopy. Ni 2p core level shifts to lower binding energy with respect to that of pure Ni metal giving rise to negative core level shifts (CLSs). Measured CLSs exhibit a linear dependence in fcc region (x > 0.3) and were found to deviate slightly in bcc region (x < 0.3). ESCA potential model fails correlate CLSs with site potentials or charges in metallic alloys. CLSs in these alloys occur mainly due to shift in valence bands with composition due to intra atomic charge redistribution.

Keywords: arc melting, core level shift, ESCA potential model, valence band

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Authors: Heerak Banerjee, Sourov Roy

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Supersymmetry, one of the most celebrated fields of study for explaining experimental observations where the standard model (SM) falls short, is reeling from the lack of experimental vindication. At the same time, the idea of additional gauge symmetry, in particular, the gauged Lμ-Lτ symmetric models have also generated significant interest. They have been extensively proposed in order to explain the tantalizing discrepancy in the predicted and measured value of the muon anomalous magnetic moment alongside several other issues plaguing the SM. While very little parameter space within these models remain unconstrained, this work finds that the γ + Missing Energy (ME) signal at the Belle-II detector will be a smoking gun for supersymmetry (SUSY) in the presence of a gauged U(1)Lμ-Lτ symmetry. A remarkable consequence of breaking the enhanced symmetry appearing in the limit of degenerate (s)leptons is the nondecoupling of the radiative contribution of heavy charged sleptons to the γ-Z΄ kinetic mixing. The signal process, e⁺e⁻ →γZ΄→γ+ME, is an outcome of this ubiquitous feature. Taking the severe constraints on gauged Lμ-Lτ models by several low energy observables into account, it is shown that any significant excess in all but the highest photon energy bin would be an undeniable signature of such heavy scalar fields in SUSY coupling to the additional gauge boson Z΄. The number of signal events depends crucially on the logarithm of the ratio of stau to smuon mass in the presence of SUSY. In addition, the number is also inversely proportional to the e⁺e⁻ collision energy, making a low-energy, high-luminosity collider like Belle-II an ideal testing ground for this channel. This process can probe large swathes of the hitherto free slepton mass ratio vs. additional gauge coupling (gₓ) parameter space. More importantly, it can explore the narrow slice of Z΄ mass (MZ΄) vs. gₓ parameter space still allowed in gauged U(1)Lμ-Lτ models for superheavy sparticles. The spectacular finding that the signal significance is independent of individual slepton masses is an exciting prospect indeed. Further, the prospect that signatures of even superheavy SUSY particles that may have escaped detection at the LHC may show up at the Belle-II detector is an invigorating revelation.

Keywords: additional gauge symmetry, electron-positron collider, kinetic mixing, nondecoupling radiative effect, supersymmetry

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Authors: Kouassi Louis Kra

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The nearshore deep-water gravity flow deposits in the Northern steep slope of Dongying depression, Bohai Bay basin, have been acknowledged as important reservoirs in the rift lacustrine basin. These deep strata term as coarse clastic sediment, deposit at the root of the slope have complex depositional processes and involve wide diagenetic events which made high-quality reservoir prediction to be complex. Based on the integrated study of seismic interpretation, sedimentary analysis, petrography, cores samples, wireline logging data, 3D seismic and lithological data, the reservoir formation mechanism deciphered. The Geoframe software was used to analyze 3-D seismic data to interpret the stratigraphy and build a sequence stratigraphic framework. Thin section identification, point counts were performed to assess the reservoir characteristics. The software PetroMod 1D of Schlumberger was utilized for the simulation of burial history. CL and SEM analysis were performed to reveal diagenesis sequences. Backscattered electron (BSE) images were recorded for definition of the textural relationships between diagenetic phases. The result showed that the nearshore steep slope deposits mainly consist of conglomerate, gravel sandstone, pebbly sandstone and fine sandstone interbedded with mudstone. The reservoir is characterized by low-porosity and ultra-low permeability. The diagenesis reactions include compaction, precipitation of calcite, dolomite, kaolinite, quartz cement and dissolution of feldspars and rock fragment. The main types of reservoir space are primary intergranular pores, residual intergranular pores, intergranular dissolved pores, intergranular dissolved pores, and fractures. There are three obvious anomalous high-porosity zones in the reservoir. Overpressure and early hydrocarbon filling are the main reason for abnormal secondary pores development. Sedimentary facies control the formation of high-quality reservoir, oil and gas filling preserves secondary pores from late carbonate cementation.

Keywords: Bohai Bay, Dongying Sag, deep strata, formation mechanism, high-quality reservoir

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Authors: Emma Castiglioni, Nigel Scrutton, Derren Heyes, Alistair Fielding

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By using light as trigger, it is possible to study many biological processes, such as the activity of genes, proteins, and other molecules, with precise spatiotemporal control. Caged compounds, where biologically active molecules are generated from an inert precursor upon laser photolysis, offer the potential to initiate such biological reactions with high temporal resolution. As light acts as the trigger for cleaving the protecting group, the ‘caging’ technique provides a number of advantages as it can be intracellular, rapid and controlled in a quantitative manner. We are developing caging strategies to study the catalytic cycle of a number of enzyme systems, such as nitric oxide synthase and ethanolamine ammonia lyase. These include the use of caged substrates, caged electrons and the possibility of caging the enzyme itself. In addition, we are developing a novel freeze-quench instrument to study these reactions, which combines rapid mixing and flashing capabilities. Reaction intermediates will be trapped at low temperatures and will be analysed by using electron paramagnetic resonance (EPR) spectroscopy to identify the involvement of any radical species during catalysis. EPR techniques typically require relatively long measurement times and very often, low temperatures to fully characterise these short-lived species. Therefore, common rapid mixing techniques, such as stopped-flow or quench-flow are not directly suitable. However, the combination of rapid freeze-quench (RFQ) followed by EPR analysis provides the ideal approach to kinetically trap and spectroscopically characterise these transient radical species. In a typical RFQ experiment, two reagent solutions are delivered to the mixer via two syringes driven by a pneumatic actuator or stepper motor. The new mixed solution is then sprayed into a cryogenic liquid or surface, and the frozen sample is then collected and packed into an EPR tube for analysis. The earliest RFQ instrument consisted of a hydraulic ram unit as a drive unit with direct spraying of the sample into a cryogenic liquid (nitrogen, isopentane or petroleum). Improvements to the RFQ technique have arisen from the design of new mixers in order to reduce both the volume and the mixing time. In addition, the cryogenic isopentane bath has been coupled to a filtering system or replaced by spraying the solution onto a surface that is frozen via thermal conductivity with a cryogenic liquid. In our work, we are developing a novel RFQ instrument which combines the freeze-quench technology with flashing capabilities to enable the studies of both thermally-activated and light-activated biological reactions. This instrument also uses a new rotating plate design based on magnetic couplings and removes the need for mechanical motorised rotation, which can otherwise be problematic at cryogenic temperatures.

Keywords: caged compounds, freeze-quench apparatus, photolysis, radicals

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Authors: Tshipeng Mwenze, Charles Okujeni, Abdi Siad, Russel Bailie, Dirk Frei, Marcelene Voigt, Petrus Le Roux

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The Platreef is a platinum group element (PGE) deposit in the northern limb of the Bushveld Igneous Complex (BIC) which was emplaced as a series of mafic and ultramafic sills between the Main Zone (MZ) and the country rocks. The PGE mineralisation in the Platreef is hosted in different rock types, and its distribution and style vary with depth and along strike. This study contributes towards understanding the processes involved in the genesis of the Platreef. Twenty-four Platreef (2 harzburgites, 4 olivine pyroxenites, 17 feldspathic pyroxenites and 1 gabbronorite) and few MZ (1 gabbronorite and 1 leucogabbronorite) quarter core samples were collected from four drill cores (e.g., TN754, TN200, SS339, and OY482) and analysed for whole-rock Sr-Nd isotope data. The results show positive ɛNd values (+3.53 to +7.51) for harzburgites suggesting their parental magmas derived from the depleted Mantle. The remaining Platreef rocks have negative ɛNd values (-2.91 to -22.88) and show significant variations in Sr-Nd isotopic compositions. The first group of Platreef samples has relatively high isotopic compositions (ɛNd= -2.91 to -5.68; ⁸⁷Sr/⁸⁶Sri= 0.709177 - 0.711998). The second group of Platreef samples has Sr ratios (⁸⁷Sr/⁸⁶Sri= 0.709816-0.712106) overlapping with samples of the first group but slightly lower ɛNd values (-7.44 to -8.39). Lastly, the third group of Platreef samples has low ɛNd values (-10.82 to -14.32) and low Sr ratios (⁸⁷Sr/⁸⁶Sri= 0.707545-0.710042) than those from samples of the two Platreef groups mentioned above. There is, however, a Platreef sample with ɛNd value (-5.26) in range with the Platreef samples of the first group, but its Sr ratio (0.707281) is the lowest even when compared to samples of the third Platreef group. There are also five other Platreef samples which have either anomalous ɛNd or Sr ratios which make it difficult to assess their isotopic compositions relative to other samples. These isotopic variations for the Platreef samples indicate both multiple sources and multiple magma chambers where varying crustal contamination styles have operated during the evolution of these magmas prior their emplacements into the Platreef setting as sills. Furthermore, the MZ rocks have different Sr-Nd isotopic compositions (For OY482 gabbronorite [ɛNd= +0.65; ⁸⁷Sr/⁸⁶Sri= 0.711746]; for TN754 leucogabbronorite [ɛNd= -7.44; ⁸⁷Sr/⁸⁶Sri= 0.709322]) which do not only indicate different MZ magma chambers, but also different magmas from those of the Platreef. Although the Platreef is still considered a single stratigraphic unit in the northern limb of the BIC, its genesis involved multiple magmatic processes which evolved independently from each other.

Keywords: crustal contamination styles, magma chambers, magma sources, multiple sills emplacement

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Authors: Michel Pons, Anthony Delahaye, Laurence Fournaison

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Secondary refrigeration consists of splitting large-size direct-cooling units into volume-limited primary cooling units complemented by secondary loops for transporting and distributing cold. Such a design reduces the refrigerant leaks, which represents a source of greenhouse gases emitted into the atmosphere. However, inserting the secondary circuit between the primary unit and the ‘users’ heat exchangers (UHX) increases the energy consumption of the whole process, which induces an indirect emission of greenhouse gases. It is thus important to check whether that efficiency loss is sufficiently limited for the change to be globally beneficial to the environment. Among the likely secondary fluids, phase change slurries offer several advantages: they transport latent heat, they stabilize the heat exchange temperature, and the formerly evaporators still can be used as UHX. The temperature level can also be adapted to the desired cooling application. Herein, the slurry {ice in mono-propylene-glycol solution} (melting temperature Tₘ of 6°C) is considered for food preservation, and the slurry {mixed hydrate of CO₂ + tetra-n-butyl-phosphonium-bromide in aqueous solution of this salt + CO₂} (melting temperature Tₘ of 13°C) is considered for air conditioning. For the sake of thermodynamic consistency, the analysis encompasses the whole process, primary cooling unit plus secondary slurry loop, and the various properties of the slurries, including their non-Newtonian viscosity. The design of the whole process is optimized according to the properties of the chosen slurry and under explicit constraints. As a first constraint, all the units must deliver the same cooling power to the user. The other constraints concern the heat exchanges areas, which are prescribed, and the flow conditions, which prevent deposition of the solid particles transported in the slurry, and their agglomeration. Minimization of the total energy consumption leads to the optimal design. In addition, the results are analyzed in terms of exergy losses, which allows highlighting the couplings between the primary unit and the secondary loop. One important difference between the ice-slurry and the mixed-hydrate one is the presence of gaseous carbon dioxide in the latter case. When the mixed-hydrate crystals melt in the UHX, CO₂ vapor is generated at a rate that depends on the phase change kinetics. The flow in the UHX, and its heat and mass transfer properties are significantly modified. This effect has never been investigated before. Lastly, inserting the secondary loop between the primary unit and the users increases the temperature difference between the refrigerated space and the evaporator. This results in a loss of global energy efficiency, and therefore in an increased energy consumption. The analysis shows that this loss of efficiency is not critical in the first case (Tₘ = 6°C), while the second case leads to more ambiguous results, partially because of the higher melting temperature.The consequences in terms of greenhouse gases emissions are also analyzed.

Keywords: exergy, hydrates, optimization, phase change material, thermodynamics

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Authors: John Christian Lequiron, Gerry Bagtasa, Olivia Cabrera, Leoncio Amadore, Tolentino Moya

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Changes in air surface temperature play an important role in the Philippine’s economy, industry, health, and food production. While increasing global mean temperature in the recent several decades has prompted a number of climate change and variability studies in the Philippines, most studies still focus on rainfall and tropical cyclones. This study aims to investigate the trend and variability of observed air surface temperature and determine its major influencing factor/s in the Philippines. A non-parametric Mann-Kendall trend test was applied to monthly mean temperature of 17 synoptic stations covering 56 years from 1960 to 2015 and a mean change of 0.58 °C or a positive trend of 0.0105 °C/year (p < 0.05) was found. In addition, wavelet decomposition was used to determine the frequency of temperature variability show a 12-month, 30-80-month and more than 120-month cycles. This indicates strong annual variations, interannual variations that coincide with ENSO events, and interdecadal variations that are attributed to PDO and CO2 concentrations. Air surface temperature was also correlated with smoothed sunspot number and galactic cosmic rays, the results show a low to no effect. The influence of ENSO teleconnection on temperature, wind pattern, cloud cover, and outgoing longwave radiation on different ENSO phases had significant effects on regional temperature variability. Particularly, an anomalous anticyclonic (cyclonic) flow east of the Philippines during the peak and decay phase of El Niño (La Niña) events leads to the advection of warm southeasterly (cold northeasterly) air mass over the country. Furthermore, an apparent increasing cloud cover trend is observed over the West Philippine Sea including portions of the Philippines, and this is believed to lessen the effect of the increasing air surface temperature. However, relative humidity was also found to be increasing especially on the central part of the country, which results in a high positive trend of heat index, exacerbating the effects on human discomfort. Finally, an assessment of gridded temperature datasets was done to look at the viability of using three high-resolution datasets in future climate analysis and model calibration and verification. Several error statistics (i.e. Pearson correlation, Bias, MAE, and RMSE) were used for this validation. Results show that gridded temperature datasets generally follows the observed surface temperature change and anomalies. In addition, it is more representative of regional temperature rather than a substitute to station-observed air temperature.

Keywords: air surface temperature, carbon dioxide, ENSO, galactic cosmic rays, smoothed sunspot number

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Authors: Raptis Sotirios

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Health and social care (HSc) services planning and scheduling are facing unprecedented challenges due to the pandemic pressure and also suffer from unplanned spending that is negatively impacted by the global financial crisis. Data-driven can help to improve policies, plan and design services provision schedules using algorithms assist healthcare managers’ to face unexpected demands using fewer resources. The paper discusses services packing using statistical significance tests and machine learning (ML) to evaluate demands similarity and coupling. This is achieved by predicting the range of the demand (class) using ML methods such as CART, random forests (RF), and logistic regression (LGR). The significance tests Chi-Squared test and Student test are used on data over a 39 years span for which HSc services data exist for services delivered in Scotland. The demands are probabilistically associated through statistical hypotheses that assume that the target service’s demands are statistically dependent on other demands as a NULL hypothesis. This linkage can be confirmed or not by the data. Complementarily, ML methods are used to linearly predict the above target demands from the statistically found associations and extend the linear dependence of the target’s demand to independent demands forming, thus groups of services. Statistical tests confirm ML couplings making the prediction also statistically meaningful and prove that a target service can be matched reliably to other services, and ML shows these indicated relationships can also be linear ones. Zero paddings were used for missing years records and illustrated better such relationships both for limited years and in the entire span offering long term data visualizations while limited years groups explained how well patients numbers can be related in short periods or can change over time as opposed to behaviors across more years. The prediction performance of the associations is measured using Receiver Operating Characteristic(ROC) AUC and ACC metrics as well as the statistical tests, Chi-Squared and Student. Co-plots and comparison tables for RF, CART, and LGR as well as p-values and Information Exchange(IE), are provided showing the specific behavior of the ML and of the statistical tests and the behavior using different learning ratios. The impact of k-NN and cross-correlation and C-Means first groupings is also studied over limited years and the entire span. It was found that CART was generally behind RF and LGR, but in some interesting cases, LGR reached an AUC=0 falling below CART, while the ACC was as high as 0.912, showing that ML methods can be confused padding or by data irregularities or outliers. On average, 3 linear predictors were sufficient, LGR was found competing RF well, and CART followed with the same performance at higher learning ratios. Services were packed only if when significance level(p-value) of their association coefficient was more than 0.05. Social factors relationships were observed between home care services and treatment of old people, birth weights, alcoholism, drug abuse, and emergency admissions. The work found that different HSc services can be well packed as plans of limited years, across various services sectors, learning configurations, as confirmed using statistical hypotheses.

Keywords: class, cohorts, data frames, grouping, prediction, prob-ability, services

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Authors: Roberta Martino, Viviana Ventre

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Intertemporal choices are choices under conditions of uncertainty in which the consequences are distributed over time. The Discounted Utility Model is the essential reference for describing the individual in the context of intertemporal choice. The model is based on the idea that the individual selects the alternative with the highest utility, which is calculated by multiplying the cardinal utility of the outcome, as if the reception were instantaneous, by the discount function that determines a decrease in the utility value according to how the actual reception of the outcome is far away from the moment the choice is made. Initially, the discount function was assumed to have an exponential trend, whose decrease over time is constant, in line with a profile of a rational investor described by classical economics. Instead, empirical evidence called for the formulation of alternative, hyperbolic models that better represented the actual actions of the investor. Attitudes that do not comply with the principles of classical rationality are termed anomalous, i.e., difficult to rationalize and describe through normative models. The development of behavioral finance, which describes investor behavior through cognitive psychology, has shown that deviations from rationality are due to the limited rationality condition of human beings. What this means is that when a choice is made in a very difficult and information-rich environment, the brain does a compromise job between the cognitive effort required and the selection of an alternative. Moreover, the evaluation and selection phase of the alternative, the collection and processing of information, are dynamics conditioned by systematic distortions of the decision-making process that are the behavioral biases involving the individual's emotional and cognitive system. In this paper we present an original decomposition of the discount function to investigate the psychological principles of hyperbolic discounting. It is possible to decompose the curve into two components: the first component is responsible for the smaller decrease in the outcome as time increases and is related to the individual's impatience; the second component relates to the change in the direction of the tangent vector to the curve and indicates how much the individual perceives the indeterminacy of the future indicating his or her aversion to uncertainty. This decomposition allows interesting conclusions to be drawn with respect to the concept of impatience and the emotional drives involved in decision-making. The contribution that neuroscience can make to decision theory and inter-temporal choice theory is vast as it would allow the description of the decision-making process as the relationship between the individual's emotional and cognitive factors. Neurofinance is a discipline that uses a multidisciplinary approach to investigate how the brain influences decision-making. Indeed, considering that the decision-making process is linked to the activity of the prefrontal cortex and amygdala, neurofinance can help determine the extent to which abnormal attitudes respect the principles of rationality.

Keywords: impatience, intertemporal choice, neurofinance, rationality, uncertainty

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Authors: Debashis Nath

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Drawn from multiple reanalysis datasets, an increasing trend and westward shift in the number of Potential Vorticity (PV) intrusion events over the Pacific are evident. The increased frequency can be linked to a long-term trend in upper tropospheric (UT, 200 hPa) equatorial westerly wind and subtropical jets (STJ) during boreal winter to spring. These may be resulting from anomalous warming and cooling over the western Pacific warm pool and the tropical eastern Pacific, respectively. The intrusions brought dry and ozone rich air of stratospheric origin deep into the tropics. In the tropical UT, interannual ozone variability is mainly related to convection associated with El Niño/Southern Oscillation. Zonal mean stratospheric overturning circulation organizes the transport of ozone rich air poleward and downward to the high and midlatitudes leading there to higher ozone concentration. In addition to these well described mechanisms, we observe a long-term increasing trend in ozone flux over the northern hemispheric outer tropical (10–25°N) central Pacific that results from equatorward transport and downward mixing from the midlatitude UT and lower stratosphere (LS) during PV intrusions. This increase in tropospheric ozone flux over the Pacific Ocean may affect the radiative processes and changes the budget of atmospheric hydroxyl radicals. The results demonstrate a long-term increase in outer tropical Pacific PV intrusions linked with the strengthening of the upper tropospheric equatorial westerlies and weakening of the STJ. Zonal variation in SST, characterized by gradual warming in the western Pacific–warm pool and cooling in the central–eastern Pacific, is associated with the strengthening of the Pacific Walker circulation. In the Western Pacific enhanced convective activity leads to precipitation, and the latent heat released in the process strengthens the Pacific Walker circulation. However, it is linked with the trend in global mean temperature, which is related to the emerging anthropogenic greenhouse signal and negative phase of PDO. On the other hand, the central-eastern Pacific cooling trend is linked to the weakening of the central–eastern Pacific Hadley circulation. It suppresses the convective activity due to sinking air motion and imports less angular momentum to the STJ leading to a weakened STJ. While, more PV intrusions result from this weaker STJ on its equatorward side; significantly increase the stratosphere-troposphere exchange processes on the longer timescale. This plays an important role in determining the atmospheric composition, particularly of tropospheric ozone, in the northern outer tropical central Pacific. It may lead to more ozone of stratospheric origin in the LT and even in the marine boundary, which may act as harmful pollutants and affect the radiative processes by changing the global budgets of atmospheric hydroxyl radicals.

Keywords: PV intrusion, westerly duct, ozone, Central Pacific

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Authors: Ankan Roy, Niharika, Samir Kumar Patra

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Anomalous nexus of complex topological assemblies and spatiotemporal epigenetic choreography at chromosomal territory may forms the most sophisticated regulatory layer of gene expression in cancer. Colon cancer is one of the leading malignant neoplasms of the lower gastrointestinal tract worldwide. There is still a paucity of information about the complex molecular mechanisms of colonic cancerogenesis. Bioinformatics prediction and analysis helps to identify essential genes and significant pathways for monitoring and conquering this deadly disease. The present study investigates and explores potential hub genes as biomarkers and effective therapeutic targets for colon cancer treatment. Colon cancer patient sample containing gene expression profile datasets, such as GSE44076, GSE20916, and GSE37364 were downloaded from Gene Expression Omnibus (GEO) database and thoroughly screened using the GEO2R tool and Funrich software to find out common 2 differentially expressed genes (DEGs). Other approaches, including Gene Ontology (GO) and KEGG pathway analysis, Protein-Protein Interaction (PPI) network construction and hub gene investigation, Overall Survival (OS) analysis, gene correlation analysis, methylation pattern analysis, and hub gene-Transcription factors regulatory network construction, were performed and validated using various bioinformatics tool. Initially, we identified 166 DEGs, including 68 up-regulated and 98 down-regulated genes. Up-regulated genes are mainly associated with the Cytokine-cytokine receptor interaction, IL17 signaling pathway, ECM-receptor interaction, Focal adhesion and PI3K-Akt pathway. Downregulated genes are enriched in metabolic pathways, retinol metabolism, Steroid hormone biosynthesis, and bile secretion. From the protein-protein interaction network, thirty hub genes with high connectivity are selected using the MCODE and cytoHubba plugin. Survival analysis, expression validation, correlation analysis, and methylation pattern analysis were further verified using TCGA data. Finally, we predicted COL1A1, COL1A2, COL4A1, SPP1, SPARC, and THBS2 as potential master regulators in colonic cancerogenesis. Moreover, our experimental data highlights that disruption of lipid raft and RAS/MAPK signaling cascade affects this gene hub at mRNA level. We identified COL1A1, COL1A2, COL4A1, SPP1, SPARC, and THBS2 as determinant hub genes in colon cancer progression. They can be considered as biomarkers for diagnosis and promising therapeutic targets in colon cancer treatment. Additionally, our experimental data advertise that signaling pathway act as connecting link between membrane hub and gene hub.

Keywords: hub genes, colon cancer, DNA methylation, epigenetic engineering, bioinformatic predictions

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Authors: Safaa M. Hassan; Safwat S. Gabr, Mohamed F. Sadek

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This study is proposed for the lithological and iron oxides detection in the old mine areas of El-Bahariya Depression, Western Desert, using ASTER and Landsat-8 remote sensing data. Four old iron ore occurrences, namely; El-Gedida, El-Haraa, Ghurabi, and Nasir mine areas found in the El-Bahariya area. This study aims to find new high potential areas for iron mineralization around El-Baharyia depression. Image processing methods such as principle component analysis (PCA) and band ratios (b4/b5, b5/b6, b6/b7, and 4/2, 6/7, band 6) images were used for lithological identification/mapping that includes the iron content in the investigated area. ASTER and Landsat-8 visible and short-wave infrared data found to help mapping the ferruginous sandstones, iron oxides as well as the clay minerals in and around the old mines area of El-Bahariya depression. Landsat-8 band ratio and the principle component of this study showed well distribution of the lithological units, especially ferruginous sandstones and iron zones (hematite and limonite) along with detection of probable high potential areas for iron mineralization which can be used in the future and proved the ability of Landsat-8 and ASTER data in mapping these features. Minimum Noise Fraction (MNF), Mixture Tuned Matched Filtering (MTMF), pixel purity index methods as well as Spectral Ange Mapper classifier algorithm have been successfully discriminated the hematite and limonite content within the iron zones in the study area. Various ASTER image spectra and ASD field spectra of hematite and limonite and the surrounding rocks are compared and found to be consistent in terms of the presence of absorption features at range from 1.95 to 2.3 μm for hematite and limonite. Pixel purity index algorithm and two sub-pixel spectral methods, namely Mixture Tuned Matched Filtering (MTMF) and matched filtering (MF) methods, are applied to ASTER bands to delineate iron oxides (hematite and limonite) rich zones within the rock units. The results are validated in the field by comparing image spectra of spectrally anomalous zone with the USGS resampled laboratory spectra of hematite and limonite samples using ASD measurements. A number of iron oxides rich zones in addition to the main surface exposures of the El-Gadidah Mine, are confirmed in the field. The proposed method is a successful application of spectral mapping of iron oxides deposits in the exposed rock units (i.e., ferruginous sandstone) and present approach of both ASTER and ASD hyperspectral data processing can be used to delineate iron-rich zones occurring within similar geological provinces in any parts of the world.

Keywords: Landsat-8, ASTER, lithological mapping, iron exploration, western desert

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Authors: Adil Murtaza, Muhammad Tahir Khan, Awais Ghani, Chao Zhou, Sen Yang, Xiaoping Song

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The morphotropic phase boundary (MPB); a boundary between two different crystallographic symmetries in the composition–temperature phase diagram has been widely studied in ferroelectrics and recently has drawn interest in ferromagnets for obtaining enhanced large field-induced strain. At MPB, the system gets a compressed free energy state, which allows the polarization to freely rotate and hence results in a high magnetoelastic response (e.g., high magnetization, low coercivity, and large magnetostriction). Based on the same mechanism, we designed MPB in a ferromagnetic Tb₁₋ₓNdₓCo₂ system. The temperature-dependent magnetization curves showed spin reorientation (SR); which can be explained by a two-sublattice model. Contrary to previously reported MPB involved ferromagnetic systems, the MPB composition of Tb₀.₃₅Nd₀.₆₅Co₂ exhibits a low saturation magnetization (MS), indicating a compensation of the Tb and Nd magnetic moments at MPB. The coercive field (HC) under a low magnetic field and first anisotropy constant (K₁) shows a minimum value at MPB composition of x=0.65. A detailed spin configuration diagram is provided for the Tb₁₋ₓNdₓCo₂ around the composition for the anisotropy compensation; this can guide the development of novel magnetostrictive materials. The anisotropic magnetostriction (λS) first decreased until x=0.8 and then continuously increased in the negative direction with further increase of Nd concentration. In addition, the large ratio between magnetostriction and the absolute values of the first anisotropy constant (λS/K₁) appears at MPB, indicating that Tb₀.₃₅Nd₀.₆₅Co₂ has good magnetostrictive properties. Present work shows an anomalous type of MPB in ferromagnetic materials, revealing that MPB can also lead to a weakening of magnetoelastic behavior as shown in the ferromagnetic Tb₁₋ₓNdₓCo₂ system. Our work shows the universal presence of MPB in ferromagnetic materials and suggests the differences between different ferromagnetic MPB systems that are important for substantial improvement of magnetic and magnetostrictive properties. Based on the results of this study, similar MPB effects might be achieved in other ferroic systems that can be used for technological applications. The finding of magnetic MPB in the ferromagnetic system leads to some important significances. First, it provides a better understanding of the fundamental concept of spin reorientation transitions (SRT) like ferro-ferro transitions are not only reorientation of magnetization but also crystal symmetry change upon magnetic ordering. Second, the flattened free energy corresponding to a low energy barrier for magnetization rotation and enhanced magnetoelastic response near MPB. Third, to attain large magnetostriction with MPB approach two terminal compounds have different easy magnetization directions below Curie temperature Tc in order to accomplish the weakening of magnetization anisotropy at MPB (as in ferroelectrics), thus easing the magnetic domain switching and the lattice distortion difference between two terminal compounds should be large enough, e.g., lattice distortion of R symmetry ˃˃ lattice distortion of T symmetry). So that the MPB composition agrees to a nearly isotropic state along with large ‘net’ lattice distortion, which is revealed in a higher value of magnetostriction.

Keywords: magnetization, magnetostriction, morphotropic phase boundary (MPB), phase transition

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Authors: Pibool Waijittragum

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This paper has its objectives to reveal contents and personality suitable to women’s newspapers. The research methodology employed in this study is the questionnaire which is derived from a literature review related to newspapers, graphic elements method for print media design and 12 sample sizes of different daily newspapers. In order to acquire an in-depth understanding and comprehensible view of desirable for a women’s newspaper design, graphic elements that related to that personality as well as other preferable elements for a women’s newspaper, including seven editorial Many Thai newspapers were offer a women’s documentary and column space. With its feminine looks, most of them appeared with warm tones and friendly mood through their headlines, contents, illustrations and graphics. The study found that most desirable personalities for a women’s newspaper design in Thailand are: Modern, Chic and Natural. Each personality has significant graphic elements as follows: 1. Modern: significant elements of modern personality comprises of the composition with graduation pattern which creates attractiveness by using an anomalous alignment layout grid and outstanding structure to create focal points and dynamic movement. Dark to black color that has narrowed, limited hue coupled with bright color tones. The round shape of the Thai font style was suitable for this concept. Such Thai fonts have harmonious proportion and consistent stroke with the urban-polite look. 2. Chic: significant elements of chic personality comprises of the proper composition with distinctive scale, using rhythmic repetition and a contrast of scale to draw in reader attention. Vivid and bright color tones with extensive hues coupled with similar color tones and round shape of the Thai font style with a light stroke and consistent line. 3. Natural: significant elements of natural personality comprises of the proper composition using rhythmic repetition that creates a focal point through striking images and harmonious perspective. Warm color tones with restricted hues that appear to look natural. Duo tone color was suitable through the gradually increasing gradient. The Thai style with hand writing font was suitable through the inconsistent stroke. There are 10 types of daily content that were revealed to be the most desirable for Thai women readers, these are: Daily News, Economics News, Education News, Entertainment News, International news, Political News, Public Health News, Scientific News, Social News and Sports News. As well, there are 16 topics identified as very desirable for Thai women readers, such as: Art and Culture, Automobile, Classified, Special Scoop, Editorial, Advertisement, Entertainment, Health and Quality of Life, History, Horoscope, Lifestyle and Fashion, Literature, Nature - Environment and Tourism, Night Life, Stars and Jet Set Gossip, Women’s Issue.

Keywords: women behaviors, feminine looks, newspaper design, news content

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Authors: Giorgi Chichinadze, David Shengelia, Tamara Tsutsunava, Nikoloz Maisuradze, Giorgi Beridze

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The Jalovchat gabbro intrusive is exposed on the northern and southern slopes of Main Range zone of the Greater Caucasus, on an area about 25km2. It is intruded in Precambrian crystalline schists and amphibolites intensively metamorphose them along the contact zone. The intrusive is represented by hornblende-bearing gabbro, gabbro-norites and norites including thin vein bodies of gabbro-pegmatites, anorthosites and micro-gabbros. Especially should be noted the veins of gabbro-pegmatites with the gigantic (up to 0.5m) hornblende crystals. From this point of view, the Jalovchat gabbroid intrusive is particularly interesting and by its unusual composition has no analog in the Caucasus overall. The comprehensive petrologic and geochemical study of the intrusive was carried out by the authors. The results of investigations are following. Amphiboles correspond to magnesiohastingsite and magnesiohornblende. In hastingsite and hornblende as a result of isovalent isomorphism of Fe2+ by Mg, content of the latter has been increased. By AMF and Na20+K diagrams the intrusive rocks correspond to tholeiitic basalts or to basalts close to it by composition. According to ACM-AMF double diagram the samples distributed in the fields of MORB and alkali cumulates. In TiO2/FeO+Fe2O3, Zr/Y-Zr and Ti-Cr/Ni diagrams and Ti-Cr-Y triangular diagram samples are arranged in the fields of island-arc and mid-oceanic basalts or along the trends reflecting mid-oceanic ridges or island arcs. K2O/TiO2 diagram shows that these rocks belong to normal and enriched MORB type. According to Th/Nb/Y ratio, the Jalovchat intrusive composition corresponds to depleted mantle, but by Sm/Y-Ce/Sm - to the MORB area. Th/Y and Nb/Y ratios coincide with the MORB composition, Th/Yb-Ta/Yb and La/Nb-Ti ratios correspond to N MORB, and Rb/Y and N/Y - to the lower crust formations. Exceptional are Ce/Pb-Ce and Nb/Th-Nb diagrams, showing the area of primitive mantle. Spidergrams are characterized by almost horizontal trend, weakly expressed Eu minimums and by a slight depletion of light REE. Similar are characteristic of typical tholeiit basalts. In comparison to MORB spidergrams, they are characterized by depletion of light REE. Their correlation to the spidergrams of Jalovchat intrusive proves that they are more depleted. The above cited points to the gradual depletion of mantle with the light REE in geological time. The RE and REE diagrams reveal unexpected regularity. In particular, petro-geochemical characteristics of Jalovchat gabbroid intrusive predominantly correspond to MORB, that usually is an anomalous phenomenon, since in ‘ophiolitic’ section magmatic formations represented mainly by gigantic prismatic hornblende-bearing gabbro and gabbro-pegmatite are not indicated. On the basis of petro-mineralogical and petro-geochemical data analysis, the authors consider that the Jalovchat intrusive belongs to the subduction geodynamic type. In the depleted mantle rich in water the MORB rock system has subducted, where the favorable conditions for crystallization of hornblende and especially for its gigantic crystals occurred. It is considered that the Jalovchat intrusive was formed in deep horizons of the Earth’s crust as a result of crystallization of water-bearing Bajocian basalt magma.

Keywords: The Greater Caucasus, gabbro-pegmatite, hornblende-bearing gabbro, petrogenesis

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Authors: Vladimir A. Basiuk, Laura J. Flores-Sanchez, Victor Meza-Laguna, Jose O. Flores-Flores, Lauro Bucio-Galindo, Elena V. Basiuk

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Noncovalent nanohybrid materials combining carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of increasing research effort, with a particular emphasis on the design of new heterogeneous catalysts, efficient organic photovoltaic cells, lithium batteries, gas sensors, field effect transistors, among other possible applications. The possibility of using unsubstituted Pcs for CNT functionalization is very attractive due to their very moderate cost and easy commercial availability. However, unfortunately, the deposition of unsubstituted Pcs onto nanotube sidewalls through the traditional liquid-phase protocols turns to be very problematic due to extremely poor solubility of Pcs. On the other hand, unsubstituted free-base H₂Pc phthalocyanine ligand, as well as many of its transition metal complexes, exhibit very high thermal stability and considerable volatility under reduced pressure, which opens the possibility for their physical vapor deposition onto solid surfaces, including nanotube sidewalls. In the present work, we show the possibility of simple, fast and efficient noncovalent functionalization of single-walled carbon nanotubes (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me= Co, Ni, Cu, and Zn. The functionalization can be performed in a temperature range of 400-500 °C under moderate vacuum and requires about 2-3 h only. The functionalized materials obtained were characterized by means of Fourier-transform infrared (FTIR), Raman, UV-visible and energy-dispersive X-ray spectroscopy (EDS), scanning and transmission electron microscopy (SEM and TEM, respectively) and thermogravimetric analysis (TGA). TGA suggested that Me(II)Pc weight content is 30%, 17% and 35% for NiPc, CuPc, and ZnPc, respectively (CoPc exhibited anomalous thermal decomposition behavior). The above values are consistent with those estimated from EDS spectra, namely, of 24-39%, 27-36% and 27-44% for CoPc, CuPc, and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Me(II)Pc hybrids, as compared to that of pristine nanotubes, implies very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO, respectively) distribution patterns, calculated with density functional theory by using Perdew-Burke-Ernzerhof general gradient approximation correlation functional in combination with the Grimme’s empirical dispersion correction (PBE-D) and the double numerical basis set (DNP), also suggested that the interactions between Me(II) phthalocyanines and nanotube sidewalls are very strong. The authors thank the National Autonomous University of Mexico (grant DGAPA-IN200516) and the National Council of Science and Technology of Mexico (CONACYT, grant 250655) for financial support. The authors are also grateful to Dr. Natalia Alzate-Carvajal (CCADET of UNAM), Eréndira Martínez (IF of UNAM) and Iván Puente-Lee (Faculty of Chemistry of UNAM) for technical assistance with FTIR, TGA measurements, and TEM imaging, respectively.

Keywords: carbon nanotubes, functionalization, gas-phase, metal(II) phthalocyanines

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