Search results for: structural graph
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 4549

Search results for: structural graph

289 The Role of Macroeconomic Condition and Volatility in Credit Risk: An Empirical Analysis of Credit Default Swap Index Spread on Structural Models in U.S. Market during Post-Crisis Period

Authors: Xu Wang

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This research builds linear regressions of U.S. macroeconomic condition and volatility measures in the investment grade and high yield Credit Default Swap index spreads using monthly data from March 2009 to July 2016, to study the relationship between different dimensions of macroeconomy and overall credit risk quality. The most significant contribution of this research is systematically examining individual and joint effects of macroeconomic condition and volatility on CDX spreads by including macroeconomic time series that captures different dimensions of the U.S. economy. The industrial production index growth, non-farm payroll growth, consumer price index growth, 3-month treasury rate and consumer sentiment are introduced to capture the condition of real economic activity, employment, inflation, monetary policy and risk aversion respectively. The conditional variance of the macroeconomic series is constructed using ARMA-GARCH model and is used to measure macroeconomic volatility. The linear regression model is conducted to capture relationships between monthly average CDX spreads and macroeconomic variables. The Newey–West estimator is used to control for autocorrelation and heteroskedasticity in error terms. Furthermore, the sensitivity factor analysis and standardized coefficients analysis are conducted to compare the sensitivity of CDX spreads to different macroeconomic variables and to compare relative effects of macroeconomic condition versus macroeconomic uncertainty respectively. This research shows that macroeconomic condition can have a negative effect on CDX spread while macroeconomic volatility has a positive effect on determining CDX spread. Macroeconomic condition and volatility variables can jointly explain more than 70% of the whole variation of the CDX spread. In addition, sensitivity factor analysis shows that the CDX spread is the most sensitive to Consumer Sentiment index. Finally, the standardized coefficients analysis shows that both macroeconomic condition and volatility variables are important in determining CDX spread but macroeconomic condition category of variables have more relative importance in determining CDX spread than macroeconomic volatility category of variables. This research shows that the CDX spread can reflect the individual and joint effects of macroeconomic condition and volatility, which suggests that individual investors or government should carefully regard CDX spread as a measure of overall credit risk because the CDX spread is influenced by macroeconomy. In addition, the significance of macroeconomic condition and volatility variables, such as Non-farm Payroll growth rate and Industrial Production Index growth volatility suggests that the government, should pay more attention to the overall credit quality in the market when macroecnomy is low or volatile.

Keywords: autoregressive moving average model, credit spread puzzle, credit default swap spread, generalized autoregressive conditional heteroskedasticity model, macroeconomic conditions, macroeconomic uncertainty

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288 Fructose-Aided Cross-Linked Enzyme Aggregates of Laccase: An Insight on Its Chemical and Physical Properties

Authors: Bipasa Dey, Varsha Panwar, Tanmay Dutta

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Laccase, a multicopper oxidase (EC 1.10.3.2) have been at the forefront as a superior industrial biocatalyst. They are versatile in terms of bestowing sustainable and ecological catalytic reactions such as polymerisation, xenobiotic degradation and bioremediation of phenolic and non-phenolic compounds. Regardless of the wide biotechnological applications, the critical limiting factors viz. reusability, retrieval, and storage stability still prevail. This can cause an impediment in their applicability. Crosslinked enzyme aggregates (CLEAs) have emerged as a promising technique that rehabilitates these essential facets, albeit at the expense of their enzymatic activity. The carrier free crosslinking method prevails over the carrier-bound immobilisation in conferring high productivity, low production cost owing to the absence of additional carrier and circumvent any non-catalytic ballast which could dilute the volumetric activity. To the best of our knowledge, the ε-amino group of lysyl residue is speculated as the best choice for forming Schiff’s base with glutaraldehyde. Despite being most preferrable, excess glutaraldehyde can bring about disproportionate and undesirable crosslinking within the catalytic site and hence could deliver undesirable catalytic losses. Moreover, the surface distribution of lysine residues in Trametes versicolor laccase is significantly less. Thus, to mitigate the adverse effect of glutaraldehyde in conjunction with scaling down the degradation or catalytic loss of the enzyme, crosslinking with inert substances like gelatine, collagen, Bovine serum albumin (BSA) or excess lysine is practiced. Analogous to these molecules, sugars have been well known as a protein stabiliser. It helps to retain the structural integrity, specifically secondary structure of the protein during aggregation by changing the solvent properties. They are comprehended to avert protein denaturation or enzyme deactivation during precipitation. We prepared crosslinked enzyme aggregates (CLEAs) of laccase from T. versicolor with the aid of sugars. The sugar CLEAs were compared with the classic BSA and glutaraldehyde laccase CLEAs concerning physico-chemical properties. The activity recovery for the fructose CLEAs were found to be ~20% higher than the non-sugar CLEA. Moreover, the 𝐾𝑐𝑎𝑡𝐾𝑚⁄ values of the CLEAs were two and three-fold higher than BSA-CLEA and GACLEA, respectively. The half-life (t1/2) deciphered by sugar-CLEA was higher than the t1/2 of GA-CLEAs and free enzyme, portraying more thermal stability. Besides, it demonstrated extraordinarily high pH stability, which was analogous to BSA-CLEA. The promising attributes of increased storage stability and recyclability (>80%) gives more edge to the sugar-CLEAs over conventional CLEAs of their corresponding free enzyme. Thus, sugar-CLEA prevails in furnishing the rudimentary properties required for a biocatalyst and holds many prospects.

Keywords: cross-linked enzyme aggregates, laccase immobilization, enzyme reusability, enzyme stability

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287 The Effect of Nanocomposite on the Release of Imipenem on Bacteria Causing Infections with Implants

Authors: Mohammad Hossein Pazandeh, Monir Doudi, Sona Rostampour Yasouri

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—Results The prudent administration of antibiotics aims to avoid the side effects and the microbes' resistance to antibiotics. An approach developing methods of local administration of antibiotics is especially required for localized infections caused by bacterial colonization of medical devices or implant materials. Among the wide variety of materials used as drug delivery systems, bioactive glasses (BG) have large utilization in regenerative medicine . firstly, the production of bioactive glass/nickel oxide/tin dioxide nanocomposite using sol-gel method, and then, the controlled release of imipenem from the double metal oxide/bioactive glass nanocomposite, and finally, the investigation of the antibacterial property of the nanocomposite. against a number of implant-related infectious agents. In this study, BG/SnO2 and BG/NiO single systema with different metal oxide present and BG/NiO/SnO2 nanocomposites were synthesized by sol-gel as drug carriers for tetracycline and imepinem. These two antibiotics were widely used for osteomyelitis because of its favorable penetration and bactericidal effect on all the probable osteomyelitis pathogens. The antibacterial activity of synthesized samples were evaluated against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa as bacteria model using disk diffusion method. The BG modification using metal oxides results to antibacterial property of samples containing metal oxide with highest efficiency for nancomposite. bioactivity of all samples was assessed by determining the surface morphology, structural and composition changes using scanning electron microscopy (SEM), FTIR and X-ray diffraction (XRD) spectroscopy, respectively, after soaking in simulated body fluid (SBF) for 28 days. The hydroxyapatite formation was clearly observed as a bioactivity measurement. Then, BG nanocomposite sample was loaded using two antibiotics, separately and their release profiles were studied. The BG nancomposite sample was shown the slow and continuous drug releasing for a period of 72 hours which is desirable for a drug delivery system. The loaded antibiotic nanocomposite sample retaining antibacterial property and showing inactivation effect against bacteria under test. The modified bioactive glass forming hydroxyapatite with controlled release drug and effective against bacterial infections can be introduced as scaffolds for bone implants after clinical trials for biomedical applications . Considering the formation of biofilm by infectious bacteria after sticking on the surfaces of implants, medical devices, etc. Also, considering the complications of traditional methods, solving the problems caused by the above-mentioned microorganisms in technical and biomedical industries was one of the necessities of this research.

Keywords: antibacterial, bioglass, drug delivery system, sol- gel

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286 Electrohydrodynamic Patterning for Surface Enhanced Raman Scattering for Point-of-Care Diagnostics

Authors: J. J. Rickard, A. Belli, P. Goldberg Oppenheimer

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Medical diagnostics, environmental monitoring, homeland security and forensics increasingly demand specific and field-deployable analytical technologies for quick point-of-care diagnostics. Although technological advancements have made optical methods well-suited for miniaturization, a highly-sensitive detection technique for minute sample volumes is required. Raman spectroscopy is a well-known analytical tool, but has very weak signals and hence is unsuitable for trace level analysis. Enhancement via localized optical fields (surface plasmons resonances) on nanoscale metallic materials generates huge signals in surface-enhanced Raman scattering (SERS), enabling single molecule detection. This enhancement can be tuned by manipulation of the surface roughness and architecture at the sub-micron level. Nevertheless, the development and application of SERS has been inhibited by the irreproducibility and complexity of fabrication routes. The ability to generate straightforward, cost-effective, multiplex-able and addressable SERS substrates with high enhancements is of profound interest for SERS-based sensing devices. While most SERS substrates are manufactured by conventional lithographic methods, the development of a cost-effective approach to create nanostructured surfaces is a much sought-after goal in the SERS community. Here, a method is established to create controlled, self-organized, hierarchical nanostructures using electrohydrodynamic (HEHD) instabilities. The created structures are readily fine-tuned, which is an important requirement for optimizing SERS to obtain the highest enhancements. HEHD pattern formation enables the fabrication of multiscale 3D structured arrays as SERS-active platforms. Importantly, each of the HEHD-patterned individual structural units yield a considerable SERS enhancement. This enables each single unit to function as an isolated sensor. Each of the formed structures can be effectively tuned and tailored to provide high SERS enhancement, while arising from different HEHD morphologies. The HEHD fabrication of sub-micrometer architectures is straightforward and robust, providing an elegant route for high-throughput biological and chemical sensing. The superior detection properties and the ability to fabricate SERS substrates on the miniaturized scale, will facilitate the development of advanced and novel opto-fluidic devices, such as portable detection systems, and will offer numerous applications in biomedical diagnostics, forensics, ecological warfare and homeland security.

Keywords: hierarchical electrohydrodynamic patterning, medical diagnostics, point-of care devices, SERS

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285 Smart Architecture and Sustainability in the Built Environment for the Hatay Refugee Camp

Authors: Ali Mohammed Ali Lmbash

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The global refugee crisis points to the vital need for sustainable and resistant solutions to different kinds of problems for displaced persons all over the world. Among the myriads of sustainable concerns, however, there are diverse considerations including energy consumption, waste management, water access, and resiliency of structures. Our research aims to develop distinct ideas for sustainable architecture given the exigent problems in disaster-threatened areas starting with the Hatay Refugee camp in Turkey where the majority of the camp dwellers are Syrian refugees. Commencing community-based participatory research which focuses on the socio-environmental issues of displaced populations, this study will apply two approaches with a specific focus on the Hatay region. The initial experiment uses Richter's predictive model and simulations to forecast earthquake outcomes in refugee campers. The result could be useful in implementing architectural design tactics that enhance structural reliability and ensure the security and safety of shelters through earthquakes. In the second experiment a model is generated which helps us in predicting the quality of the existing water sources and since we understand how greatly water is vital for the well-being of humans, we do it. This research aims to enable camp administrators to employ forward-looking practices while managing water resources and thus minimizing health risks as well as building resilience of the refugees in the Hatay area. On the other side, this research assesses other sustainability problems of Hatay Refugee Camp as well. As energy consumption becomes the major issue, housing developers are required to consider energy-efficient designs as well as feasible integration of renewable energy technologies to minimize the environmental impact and improve the long-term sustainability of housing projects. Waste management is given special attention in this case by imposing recycling initiatives and waste reduction measures to reduce the pace of environmental degradation in the camp's land area. As well, study gives an insight into the social and economic reality of the camp, investigating the contribution of initiatives such as urban agriculture or vocational training to the enhancement of livelihood and community empowerment. In a similar fashion, this study combines the latest research with practical experience in order to contribute to the continuing discussion on sustainable architecture during disaster relief, providing recommendations and info that can be adapted on every scale worldwide. Through collaborative efforts and a dedicated sustainability approach, we can jointly get to the root of the cause and work towards a far more robust and equitable society.

Keywords: smart architecture, Hatay Camp, sustainability, machine learning.

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284 Analysis of Aspergillus fumigatus IgG Serologic Cut-Off Values to Increase Diagnostic Specificity of Allergic Bronchopulmonary Aspergillosis

Authors: Sushmita Roy Chowdhury, Steve Holding, Sujoy Khan

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The immunogenic responses of the lung towards the fungus Aspergillus fumigatus may range from invasive aspergillosis in the immunocompromised, fungal ball or infection within a cavity in the lung in those with structural lung lesions, or allergic bronchopulmonary aspergillosis (ABPA). Patients with asthma or cystic fibrosis are particularly predisposed to ABPA. There are consensus guidelines that have established criteria for diagnosis of ABPA, but uncertainty remains on the serologic cut-off values that would increase the diagnostic specificity of ABPA. We retrospectively analyzed 80 patients with severe asthma and evidence of peripheral blood eosinophilia ( > 500) over the last 3 years who underwent all serologic tests to exclude ABPA. Total IgE, specific IgE and specific IgG levels against Aspergillus fumigatus were measured using ImmunoCAP Phadia-100 (Thermo Fisher Scientific, Sweden). The Modified ISHAM working group 2013 criteria (obligate criteria: asthma or cystic fibrosis, total IgE > 1000 IU/ml or > 417 kU/L and positive specific IgE Aspergillus fumigatus or skin test positivity; with ≥ 2 of peripheral eosinophilia, positive specific IgG Aspergillus fumigatus and consistent radiographic opacities) was used in the clinical workup for the final diagnosis of ABPA. Patients were divided into 3 groups - definite, possible, and no evidence of ABPA. Specific IgG Aspergillus fumigatus levels were not used to assign the patients into any of the groups. Of 80 patients (males 48, females 32; mean age 53.9 years ± SD 15.8) selected for the analysis, there were 30 patients who had positive specific IgE against Aspergillus fumigatus (37.5%). 13 patients fulfilled the Modified ISHAM working group 2013 criteria of ABPA (‘definite’), while 15 patients were ‘possible’ ABPA and 52 did not fulfill the criteria (not ABPA). As IgE levels were not normally distributed, median levels were used in the analysis. Median total IgE levels of patients with definite and possible ABPA were 2144 kU/L and 2597 kU/L respectively (non-significant), while median specific IgE Aspergillus fumigatus at 4.35 kUA/L and 1.47 kUA/L respectively were significantly different (comparison of standard deviations F-statistic 3.2267, significance level p=0.040). Mean levels of IgG anti-Aspergillus fumigatus in the three groups (definite, possible and no evidence of ABPA) were compared using ANOVA (Statgraphics Centurion Professional XV, Statpoint Inc). Mean levels of IgG anti-Aspergillus fumigatus (Gm3) in definite ABPA was 125.17 mgA/L ( ± SD 54.84, with 95%CI 92.03-158.32), while mean Gm3 levels in possible and no ABPA were 18.61 mgA/L and 30.05 mgA/L respectively. ANOVA showed a significant difference between the definite group and the other groups (p < 0.001). This was confirmed using multiple range tests (Fisher's least significant difference procedure). There was no significant difference between the possible ABPA and not ABPA groups (p > 0.05). The study showed that a sizeable proportion of patients with asthma are sensitized to Aspergillus fumigatus in this part of India. A higher cut-off value of Gm3 ≥ 80 mgA/L provides a higher serologic specificity towards definite ABPA. Long-term studies would provide us more information if those patients with 'possible' APBA and positive Gm3 later develop clear ABPA, and are different from the Gm3 negative group in this respect. Serologic testing with clear defined cut-offs are a valuable adjunct in the diagnosis of ABPA.

Keywords: allergic bronchopulmonary aspergillosis, Aspergillus fumigatus, asthma, IgE level

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283 Chinese Acupuncture: A Potential Treatment for Autism Rat Model via Improving Synaptic Function

Authors: Sijie Chen, Xiaofang Chen, Juan Wang, Yingying Zhang, Yu Hong, Wanyu Zhuang, Xinxin Huang, Ping Ou, Longsheng Huang

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Purpose: Autistic symptom improvement can be observed in children treated with acupuncture, but the mechanism is still being explored. In the present study, we used scalp acupuncture to treat autism rat model, and then their improvement in the abnormal behaviors and specific mechanisms behind were revealed by detecting animal behaviors, analyzing the RNA sequencing of the prefrontal cortex(PFC), and observing the ultrastructure of PFC neurons under the transmission electron microscope. Methods: On gestational day 12.5, Wistar rats were given valproic acid (VPA) by intraperitoneal injection, and their offspring were considered to be reliable rat models of autism. They were randomized to VPA or VPA-acupuncture group (n=8). Offspring of Wistar pregnant rats that were simultaneously injected with saline were randomly selected as the wild-type group (WT). VPA_acupuncture group rats received acupuncture intervention at 23 days of age for 4 weeks, and the other two groups followed without intervention. After the intervention, all experimental rats underwent behavioral tests. Immediately afterward, they were euthanized by cervical dislocation, and their prefrontal cortex was isolated for RNA sequencing and transmission electron microscopy. Results: The main results are as follows: 1. Animal behavioural tests: VPA group rats showed more anxiety-like behaviour and repetitive, stereotyped behaviour than WT group rats. While VPA group rats showed less spatial exploration ability, activity level, social interaction, and social novelty preference than WT group rats. It was gratifying to observe that acupuncture indeed improved these abnormal behaviors of autism rat model. 2. RNA-sequencing: The three groups of rats differed in the expression and enrichment pathways of multiple genes related to synaptic function, neural signal transduction, and circadian rhythm regulation. Our experiments indicated that acupuncture can alleviate the major symptoms of ASD by improving these neurological abnormalities. 3. Under the transmission electron microscopy, several lysosomes and mitochondrial structural abnormalities were observed in the prefrontal neurons of VPA group rats, which were manifested as atrophy of the mitochondrial membran, blurring or disappearance of the mitochondrial cristae, and even vacuolization. Moreover, the number of synapses and synaptic vesicles was relatively small. Conversely, the mitochondrial structure of rats in the WT group and VPA_acupuncture was normal, and the number of synapses and synaptic vesicles was relatively large. Conclusion: Acupuncture effectively improved the abnormal behaviors of autism rat model and the ultrastructure of the PFC neurons, which might worked by improving their abnormal synaptic function, synaptic plasticity and promoting neuronal signal transduction.

Keywords: autism spectrum disorder, acupuncture, animal behavior, RNA sequencing, transmission electron microscope

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282 Leuco Dye-Based Thermochromic Systems for Application in Temperature Sensing

Authors: Magdalena Wilk-Kozubek, Magdalena Rowińska, Krzysztof Rola, Joanna Cybińska

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Leuco dye-based thermochromic systems are classified as intelligent materials because they exhibit thermally induced color changes. Thanks to this feature, they are mainly used as temperature sensors in many industrial sectors. For example, placing a thermochromic material on a chemical reactor may warn about exceeding the maximum permitted temperature for a chemical process. Usually two components, a color former and a developer are needed to produce a system with irreversible color change. The color former is an electron donating (proton accepting) compound such as fluoran leuco dye. The developer is an electron accepting (proton donating) compound such as organic carboxylic acid. When the developer melts, the color former - developer complex is created and the termochromic system becomes colored. Typically, the melting point of the applied developer determines the temperature at which the color change occurs. When the lactone ring of the color former is closed, then the dye is in its colorless state. The ring opening, induced by the addition of a proton, causes the dye to turn into its colored state. Since the color former and the developer are often solid, they can be incorporated into polymer films to facilitate their practical use in industry. The objective of this research was to fabricate a leuco dye-based termochromic system that will irreversibly change color after reaching the temperature of 100°C. For this purpose, benzofluoran leuco dye (as color former) and phenoxyacetic acid (as developer with a melting point of 100°C) were introduced into the polymer films during the drop casting process. The film preparation process was optimized in order to obtain thin films with appropriate properties such as transparency, flexibility and homogeneity. Among the optimized factors were the concentration of benzofluoran leuco dye and phenoxyacetic acid, the type, average molecular weight and concentration of the polymer, and the type and concentration of the surfactant. The selected films, containing benzofluoran leuco dye and phenoxyacetic acid, were combined by mild heat treatment. Structural characterization of single and combined films was carried out by FTIR spectroscopy, morphological analysis was performed by optical microscopy and SEM, phase transitions were examined by DSC, color changes were investigated by digital photography and UV-Vis spectroscopy, while emission changes were studied by photoluminescence spectroscopy. The resulting thermochromic system is colorless at room temperature, but after reaching 100°C the developer melts and it turns irreversibly pink. Therefore, it could be used as an additional sensor to warn against boiling of water in power plants using water cooling. Currently used electronic temperature indicators are prone to faults and unwanted third-party actions. The sensor constructed in this work is transparent, thanks to which it can be unnoticed by an outsider and constitute a reliable reference for the person responsible for the apparatus.

Keywords: color developer, leuco dye, thin film, thermochromism

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281 Age-Related Health Problems and Needs of Elderly People Living in Rural Areas in Poland

Authors: Anna Mirczak

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Introduction: In connection with the aging of the population and the increase in the number of people with chronic illnesses, the priority objective for public health has become not only lengthening life, but also improving quality of life in older persons, as well as maintenance of their relative independence and active participation in social life. The most important determinant of a person’s quality of life is health. According to the literature, older people with chronic illness who live in rural settings are at greater risk for poor outcomes than their urban counterparts. Furthermore research characterizes the rural elderly as having a higher incidence of sickness, dysfunction, disability, restricted mobility, and acute and chronic conditions than their urban citizens. It is dictated by the overlapping certain specific socio-economic factors typical for rural areas which include: social and geography exclusion, limited access to health care centers, and low socioeconomic status. Aim of the study: The objective of this study was to recognize health status and needs of older people living in selected rural areas in Poland and evaluate the impacts of working in the farm on their health status. Material and methods: The study was performed personally, using interviews based on the structural questionnaires, during the period from March 2011 to October 2012. The group of respondents consisted 203 people aged 65 years and over living in selected rural areas in Poland. The analysis of collected research material was performed using the statistical package SPSS 19 for Windows. The level of significance for the tested the hypotheses assumed value of 0.05. Results: The mean age of participants was 75,5 years (SD=5,7) range from 65 to 94 years. Most of the interviewees had children (89.2%) and grandchildren (83.7) and lived mainly with family members (75.9%) mostly in double (46.8%) and triple (20.8%) household. The majority of respondents (71,9%) were physical working on the farm. At the time of interview, each of the respondents reported that they had been diagnosed with at least one chronic diseases by their GP. The most common were: hypertension (67,5%), osteoarthritis (44,8%), atherosclerosis (43,3%), cataract (40,4%), arrhythmia (28,6%), diabetes mellitus (19,7%) and stomach or duodenum ulcer diseases (17,2%).The number of diseases occurring of the sample was dependent on gender and age. Significant associations were observed between working on the farm and frequency of occurrence cardiovascular diseases, the gastrointestinal tract dysfunction and sensory disorders. Conclusions: The most common causes of disability among older citizens were: chronic diseases, malnutrition and complaints about access to health services (especially to cardiologist and an ophthalmologist). Health care access and health status are a particular concern in rural areas where the population is older, has lower education and income levels, and is more likely to be living in medically underserved areas than is the case in urban areas.

Keywords: ageing, health status, older people, rural

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280 Synthesis and Characterisations of Cordierite Bonded Porous SiC Ceramics by Sol Infiltration Technique

Authors: Sanchita Baitalik, Nijhuma Kayal, Omprakash Chakrabarti

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Recently SiC ceramics have been a focus of interest in the field of porous materials due to their unique combination of properties and hence they are considered as an ideal candidate for catalyst supports, thermal insulators, high-temperature structural materials, hot gas particulate separation systems etc. in different industrial processes. Several processing methods are followed for fabrication of porous SiC at low temperatures but all these methods are associated with several disadvantages. Therefore processing of porous SiC ceramics at low temperatures is still challenging. Concerning that of incorporation of secondary bond phase additives by an infiltration technique should result in a homogenous distribution of bond phase in the final ceramics. Present work is aimed to synthesis cordierite (2MgO.2Al2O3.5SiO2) bonded porous SiC ceramics following incorporation of sol-gel bond phase precursor into powder compacts of SiC and heat treating the infiltrated body at 1400 °C. In this paper the primary aim was to study the effect of infiltration of a precursor sol of cordierite into a porous SiC powder compact prepared with pore former of different particle sizes on the porosity, pore size, microstructure and the mechanical properties of the porous SiC ceramics. Cordierite sol was prepared by mixing a solution of magnesium nitrate hexahydrate and aluminium nitrate nonahydrate in 2:4 molar ratio in ethanol another solution containing tetra-ethyl orthosilicate and ethanol in 1:3 molar ratio followed by stirring for several hours. Powders of SiC (α-SiC; d50 =22.5 μm) and 10 wt. % polymer microbead of two sizes 8 and 50µm as the pore former were mixed in a suitable liquid medium, dried and pressed in the form of bars (50×20×16 mm3) at 23 MPa pressure. The well-dried bars were heat treated at 1100° C for 4 h with a hold at 750 °C for 2 h to remove the pore former. Bars were evacuated for 2 hr upto 0.3 mm Hg pressure into a vacuum chamber and infiltrated with cordierite precursor sol. The infiltrated samples were dried and the infiltration process was repeated until the weight gain became constant. Finally the infiltrated samples were sintered at 1400 °C to prepare cordierite bonded porous SiC ceramics. Porous ceramics prepared with 8 and 50 µm sized microbead exhibited lower oxidation degrees of respectively 7.8 and 4.8 % than the sample (23 %) prepared with no microbead. Depending on the size of pore former, the porosity of the final ceramic varied in the range of 36 to 40 vol. % with a variation of flexural strength from 33.7 to 24.6 MPa. XRD analysis showed major crystalline phases of the ceramics as SiC, SiO2 and cordierite. Two forms of cordierite, α-(hexagonal) and µ-(cubic), were detected by the XRD analysis. The SiC particles were observed to be bonded both by cristobalite with fish scale morphology and cordierite with rod shape morphology and thereby formed a porous network. The material and mechanical properties of cordierite bonded porous SiC ceramics are good in agreement to carry out further studies like thermal shock, corrosion resistance etc.

Keywords: cordierite, infiltration technique, porous ceramics, sol-gel

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279 Development of 3D Printed Natural Fiber Reinforced Composite Scaffolds for Maxillofacial Reconstruction

Authors: Sri Sai Ramya Bojedla, Falguni Pati

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Nature provides the best of solutions to humans. One such incredible gift to regenerative medicine is silk. The literature has publicized a long appreciation for silk owing to its incredible physical and biological assets. Its bioactive nature, unique mechanical strength, and processing flexibility make us curious to explore further to apply it in the clinics for the welfare of mankind. In this study, Antheraea mylitta and Bombyx mori silk fibroin microfibers are developed by two economical and straightforward steps via degumming and hydrolysis for the first time, and a bioactive composite is manufactured by mixing silk fibroin microfibers at various concentrations with polycaprolactone (PCL), a biocompatible, aliphatic semi-crystalline synthetic polymer. Reconstructive surgery in any part of the body except for the maxillofacial region deals with replacing its function. But answering both the aesthetics and function is of utmost importance when it comes to facial reconstruction as it plays a critical role in the psychological and social well-being of the patient. The main concern in developing adequate bone graft substitutes or a scaffold is the noteworthy variation in each patient's bone anatomy. Additionally, the anatomical shape and size will vary based on the type of defect. The advent of additive manufacturing (AM) or 3D printing techniques to bone tissue engineering has facilitated overcoming many of the restraints of conventional fabrication techniques. The acquired patient's CT data is converted into a stereolithographic (STL)-file which is further utilized by the 3D printer to create a 3D scaffold structure in an interconnected layer-by-layer fashion. This study aims to address the limitations of currently available materials and fabrication technologies and develop a customized biomaterial implant via 3D printing technology to reconstruct complex form, function, and aesthetics of the facial anatomy. These composite scaffolds underwent structural and mechanical characterization. Atomic force microscopic (AFM) and field emission scanning electron microscopic (FESEM) images showed the uniform dispersion of the silk fibroin microfibers in the PCL matrix. With the addition of silk, there is improvement in the compressive strength of the hybrid scaffolds. The scaffolds with Antheraea mylitta silk revealed higher compressive modulus than that of Bombyx mori silk. The above results of PCL-silk scaffolds strongly recommend their utilization in bone regenerative applications. Successful completion of this research will provide a great weapon in the maxillofacial reconstructive armamentarium.

Keywords: compressive modulus, 3d printing, maxillofacial reconstruction, natural fiber reinforced composites, silk fibroin microfibers

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278 High Strain Rate Behavior of Harmonic Structure Designed Pure Nickel: Mechanical Characterization Microstructure Analysis and 3D Modelisation

Authors: D. Varadaradjou, H. Kebir, J. Mespoulet, D. Tingaud, S. Bouvier, P. Deconick, K. Ameyama, G. Dirras

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The development of new architecture metallic alloys with controlled microstructures is one of the strategic ways for designing materials with high innovation potential and, particularly, with improved mechanical properties as required for structural materials. Indeed, unlike conventional counterparts, metallic materials having so-called harmonic structure displays strength and ductility synergy. The latter occurs due to a unique microstructure design: a coarse grain structure surrounded by a 3D continuous network of ultra-fine grain known as “core” and “shell,” respectively. In the present study, pure harmonic-structured (HS) Nickel samples were processed via controlled mechanical milling and followed by spark plasma sintering (SPS). The present work aims at characterizing the mechanical properties of HS pure Nickel under room temperature dynamic loading through a Split Hopkinson Pressure Bar (SHPB) test and the underlying microstructure evolution. A stopper ring was used to maintain the strain at a fixed value of about 20%. Five samples (named B1 to B5) were impacted using different striker bar velocities from 14 m/s to 28 m/s, yielding strain rate in the range 4000-7000 s-1. Results were considered until a 10% deformation value, which is the deformation threshold for the constant strain rate assumption. The non-deformed (INIT – post-SPS process) and post-SHPB microstructure (B1 to B5) were investigated by EBSD. It was observed that while the strain rate is increased, the average grain size within the core decreases. An in-depth analysis of grains and grain boundaries was made to highlight the thermal (such as dynamic recrystallization) or mechanical (such as grains fragmentation by dislocation) contribution within the “core” and “shell.” One of the most widely used methods for determining the dynamic behavior of materials is the SHPB technique developed by Kolsky. A 3D simulation of the SHPB test was created through ABAQUS in dynamic explicit. This 3D simulation allows taking into account all modes of vibration. An inverse approach was used to identify the material parameters from the equation of Johnson-Cook (JC) by minimizing the difference between the numerical and experimental data. The JC’s parameters were identified using B1 and B5 samples configurations. Predictively, identified parameters of JC’s equation shows good result for the other sample configuration. Furthermore, mean rise of temperature within the harmonic Nickel sample can be obtained through ABAQUS and show an elevation of about 35°C for all fives samples. At this temperature, a thermal mechanism cannot be activated. Therefore, grains fragmentation within the core is mainly due to mechanical phenomena for a fixed final strain of 20%.

Keywords: 3D simulation, fragmentation, harmonic structure, high strain rate, Johnson-cook model, microstructure

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277 A Protocol of Procedures and Interventions to Accelerate Post-Earthquake Reconstruction

Authors: Maria Angela Bedini, Fabio Bronzini

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The Italian experiences, positive and negative, of the post-earthquake are conditioned by long times and structural bureaucratic constraints, also motivated by the attempt to contain mafia infiltration and corruption. The transition from the operational phase of the emergency to the planning phase of the reconstruction project is thus hampered by a series of inefficiencies and delays, incompatible with the need for rapid recovery of the territories in crisis. In fact, intervening in areas affected by seismic events means at the same time associating the reconstruction plan with an urban and territorial rehabilitation project based on strategies and tools in which prevention and safety play a leading role in the regeneration of territories in crisis and the return of the population. On the contrary, the earthquakes that took place in Italy have instead further deprived the territories affected of the minimum requirements for habitability, in terms of accessibility and services, accentuating the depopulation process, already underway before the earthquake. The objective of this work is to address with implementing and programmatic tools the procedures and strategies to be put in place, today and in the future, in Italy and abroad, to face the challenge of the reconstruction of activities, sociality, services, risk mitigation: a protocol of operational intentions and firm points, open to a continuous updating and implementation. The methodology followed is that of the comparison in a synthetic form between the different Italian experiences of the post-earthquake, based on facts and not on intentions, to highlight elements of excellence or, on the contrary, damage. The main results obtained can be summarized in technical comparison cards on good and bad practices. With this comparison, we intend to make a concrete contribution to the reconstruction process, certainly not only related to the reconstruction of buildings but privileging the primary social and economic needs. In this context, the recent instrument applied in Italy of the strategic urban and territorial SUM (Minimal Urban Structure) and the strategic monitoring process become dynamic tools for supporting reconstruction. The conclusions establish, by points, a protocol of interventions, the priorities for integrated socio-economic strategies, multisectoral and multicultural, and highlight the innovative aspects of 'inversion' of priorities in the reconstruction process, favoring the take-off of 'accelerator' interventions social and economic and a more updated system of coexistence with risks. In this perspective, reconstruction as a necessary response to the calamitous event can and must become a unique opportunity to raise the level of protection from risks and rehabilitation and development of the most fragile places in Italy and abroad.

Keywords: an operational protocol for reconstruction, operational priorities for coexistence with seismic risk, social and economic interventions accelerators of building reconstruction, the difficult post-earthquake reconstruction in Italy

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276 Characteristics of Bio-hybrid Hydrogel Materials with Prolonged Release of the Model Active Substance as Potential Wound Dressings

Authors: Katarzyna Bialik-Wąs, Klaudia Pluta, Dagmara Malina, Małgorzata Miastkowska

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In recent years, biocompatible hydrogels have been used more and more in medical applications, especially as modern dressings and drug delivery systems. The main goal of this research was the characteristics of bio-hybrid hydrogel materials incorporated with the nanocarrier-drug system, which enable the release in a gradual and prolonged manner, up to 7 days. Therefore, the use of such a combination will provide protection against mechanical damage and adequate hydration. The proposed bio-hybrid hydrogels are characterized by: transparency, biocompatibility, good mechanical strength, and the dual release system, which allows for gradual delivery of the active substance, even up to 7 days. Bio-hybrid hydrogels based on sodium alginate (SA), poly(vinyl alcohol) (PVA), glycerine, and Aloe vera solution (AV) were obtained through the chemical crosslinking method using poly(ethylene glycol) diacrylate as a crosslinking agent. Additionally, a nanocarrier-drug system was incorporated into SA/PVA/AV hydrogel matrix. Here, studies were focused on the release profiles of active substances from bio-hybrid hydrogels using the USP4 method (DZF II Flow-Through System, Erweka GmbH, Langen, Germany). The equipment incorporated seven in-line flow-through diffusion cells. The membrane was placed over support with an orifice of 1,5 cm in diameter (diffusional area, 1.766 cm²). All the cells were placed in a cell warmer connected with the Erweka heater DH 2000i and the Erweka piston pump HKP 720. The piston pump transports the receptor fluid via seven channels to the flow-through cells and automatically adapts the setting of the flow rate. All volumes were measured by gravimetric methods by filling the chambers with Milli-Q water and assuming a density of 1 g/ml. All the determinations were made in triplicate for each cell. The release study of the model active substance was carried out using a regenerated cellulose membrane Spectra/Por®Dialysis Membrane MWCO 6-8,000 Carl Roth® Company. These tests were conducted in buffer solutions – PBS at pH 7.4. A flow rate of receptor fluid of about 4 ml /1 min was selected. The experiments were carried out for 7 days at a temperature of 37°C. The released concentration of the model drug in the receptor solution was analyzed using UV-Vis spectroscopy (Perkin Elmer Company). Additionally, the following properties of the modified materials were studied: physicochemical, structural (FT-IR analysis), morphological (SEM analysis). Finally, the cytotoxicity tests using in vitro method were conducted. The obtained results exhibited that the dual release system allows for the gradual and prolonged delivery of the active substances, even up to 7 days.

Keywords: wound dressings, SA/PVA hydrogels, nanocarrier-drug system, USP4 method

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275 Implications of Social Rights Adjudication on the Separation of Powers Doctrine: Colombian Case

Authors: Mariam Begadze

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Separation of Powers (SOP) has often been the most frequently posed objection against the judicial enforcement of socio-economic rights. Although a lot has been written to refute those, very rarely has it been assessed what effect the current practice of social rights adjudication has had on the construction of SOP doctrine in specific jurisdictions. Colombia is an appropriate case-study on this question. The notion of collaborative SOP in the 1991 Constitution has affected the court’s conception of its role. On the other hand, the trends in the jurisprudence have further shaped the collaborative notion of SOP. Other institutional characteristics of the Colombian constitutional law have played its share role as well. Tutela action, particularly flexible and fast judicial action for individuals has placed the judiciary in a more confrontational relation vis-à-vis the political branches. Later interventions through abstract review of austerity measures further contributed to that development. Logically, the court’s activism in this sphere has attracted attacks from political branches, which have turned out to be unsuccessful precisely due to court’s outreach to the middle-class, whose direct reliance on the court has turned into its direct democratic legitimacy. Only later have the structural judgments attempted to revive the collaborative notion behind SOP doctrine. However, the court-supervised monitoring process of implementation has itself manifested fluctuations in the mode of collaboration, moving into more managerial supervision recently. This is not surprising considering the highly dysfunctional political system in Colombia, where distrust seems to be the default starting point in the interaction of the branches. The paper aims to answer the question, what the appropriate judicial tools are to realize the collaborative notion of SOP in a context where the court has to strike a balance between the strong executive and the weak and largely dysfunctional legislative branch. If the recurrent abuse lies in the indifference and inaction of legislative branches to engage with political issues seriously, what are the tools in the court’s hands to activate the political process? The answer to this question partly lies in the court’s other strand of jurisprudence, in which it combines substantive objections with procedural ones concerning the operation of the legislative branch. The primary example is the decision on value-added tax on basic goods, in which the court invalidated the law based on the absence of sufficient deliberation in Congress on the question of the bills’ implications on the equity and progressiveness of the entire taxing system. The decision led to Congressional rejection of an identical bill based on the arguments put forward by the court. The case perhaps is the best illustration of the collaborative notion of SOP, in which the court refrains from categorical pronouncements, while does its bit for activating political process. This also legitimizes the court’s activism based on its role to counter the most perilous abuse in the Colombian context – failure of the political system to seriously engage with serious political questions.

Keywords: Colombian constitutional court, judicial review, separation of powers, social rights

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274 Dynamic-cognition of Strategic Mineral Commodities; An Empirical Assessment

Authors: Carlos Tapia Cortez, Serkan Saydam, Jeff Coulton, Claude Sammut

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Strategic mineral commodities (SMC) both energetic and metals have long been fundamental for human beings. There is a strong and long-run relation between the mineral resources industry and society's evolution, with the provision of primary raw materials, becoming one of the most significant drivers of economic growth. Due to mineral resources’ relevance for the entire economy and society, an understanding of the SMC market behaviour to simulate price fluctuations has become crucial for governments and firms. For any human activity, SMC price fluctuations are affected by economic, geopolitical, environmental, technological and psychological issues, where cognition has a major role. Cognition is defined as the capacity to store information in memory, processing and decision making for problem-solving or human adaptation. Thus, it has a significant role in those systems that exhibit dynamic equilibrium through time, such as economic growth. Cognition allows not only understanding past behaviours and trends in SCM markets but also supports future expectations of demand/supply levels and prices, although speculations are unavoidable. Technological developments may also be defined as a cognitive system. Since the Industrial Revolution, technological developments have had a significant influence on SMC production costs and prices, likewise allowing co-integration between commodities and market locations. It suggests a close relation between structural breaks, technology and prices evolution. SCM prices forecasting have been commonly addressed by econometrics and Gaussian-probabilistic models. Econometrics models may incorporate the relationship between variables; however, they are statics that leads to an incomplete approach of prices evolution through time. Gaussian-probabilistic models may evolve through time; however, price fluctuations are addressed by the assumption of random behaviour and normal distribution which seems to be far from the real behaviour of both market and prices. Random fluctuation ignores the evolution of market events and the technical and temporal relation between variables, giving the illusion of controlled future events. Normal distribution underestimates price fluctuations by using restricted ranges, curtailing decisions making into a pre-established space. A proper understanding of SMC's price dynamics taking into account the historical-cognitive relation between economic, technological and psychological factors over time is fundamental in attempting to simulate prices. The aim of this paper is to discuss the SMC market cognition hypothesis and empirically demonstrate its dynamic-cognitive capacity. Three of the largest and traded SMC's: oil, copper and gold, will be assessed to examine the economic, technological and psychological cognition respectively.

Keywords: commodity price simulation, commodity price uncertainties, dynamic-cognition, dynamic systems

Procedia PDF Downloads 433
273 Linking Information Systems Capabilities for Service Quality: The Role of Customer Connection and Environmental Dynamism

Authors: Teng Teng, Christos Tsinopoulos

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The purpose of this research is to explore the link between IS capabilities, customer connection, and quality performance in the service context, with investigation of the impact of firm’s stable and dynamic environments. The application of Information Systems (IS) has become a significant effect on contemporary service operations. Firms invest in IS with the presumption that they will facilitate operations processes so that their performance will improve. Yet, IS resources by themselves are not sufficiently 'unique' and thus, it would be more useful and theoretically relevant to focus on the processes they affect. One such organisational process, which has attracted a lot of research attention by supply chain management scholars, is the integration of customer connection, where IS-enabled customer connection enhances communication and contact processes, and with such customer resources integration comes greater success for the firm in its abilities to develop a good understanding of customer needs and set accurate customer. Nevertheless, prior studies on IS capabilities have focused on either one specific type of technology or operationalised it as a highly aggregated concept. Moreover, although conceptual frameworks have been identified to show customer integration is valuable in service provision, there is much to learn about the practices of integrating customer resources. In this research, IS capabilities have been broken down into three dimensions based on the framework of Wade and Hulland: IT for supply chain activities (ITSCA), flexible IT infrastructure (ITINF), and IT operations shared knowledge (ITOSK); and focus on their impact on operational performance of firms in services. With this background, this paper addresses the following questions: -How do IS capabilities affect the integration of customer connection and service quality? -What is the relationship between environmental dynamism and the relationship of customer connection and service quality? A survey of 156 service establishments was conducted, and the data analysed to determine the role of customer connection in mediating the effects of IS capabilities on firms’ service quality. Confirmatory factor analysis was used to check convergent validity. There is a good model fit for the structural model. Moderating effect of environmental dynamism on the relationship of customer connection and service quality is analysed. Results show that ITSCA, ITINF, and ITOSK have a positive influence on the degree of the integration of customer connection. In addition, customer connection positively related to service quality; this relationship is further emphasised when firms work in a dynamic environment. This research takes a step towards quelling concerns about the business value of IS, contributing to the development and validation of the measurement of IS capabilities in the service operations context. Additionally, it adds to the emerging body of literature linking customer connection to the operational performance of service firms. Managers of service firms should consider the strength of the mediating role of customer connection when investing in IT-related technologies and policies. Particularly, service firms developing IS capabilities should simultaneously implement processes that encourage supply chain integration.

Keywords: customer connection, environmental dynamism, information systems capabilities, service quality, service supply chain

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272 Gradient Length Anomaly Analysis for Landslide Vulnerability Analysis of Upper Alaknanda River Basin, Uttarakhand Himalayas, India

Authors: Hasmithaa Neha, Atul Kumar Patidar, Girish Ch Kothyari

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The northward convergence of the Indian plate has a dominating influence over the structural and geomorphic development of the Himalayan region. The highly deformed and complex stratigraphy in the area arises from a confluence of exogenic and endogenetic geological processes. This region frequently experiences natural hazards such as debris flows, flash floods, avalanches, landslides, and earthquakes due to its harsh and steep topography and fragile rock formations. Therefore, remote sensing technique-based examination and real-time monitoring of tectonically sensitive regions may provide crucial early warnings and invaluable data for effective hazard mitigation strategies. In order to identify unusual changes in the river gradients, the current study demonstrates a spatial quantitative geomorphic analysis of the upper Alaknanda River basin, Uttarakhand Himalaya, India, using gradient length anomaly analysis (GLAA). This basin is highly vulnerable to ground creeping and landslides due to the presence of active faults/thrusts, toe-cutting of slopes for road widening, development of heavy engineering projects on the highly sheared bedrock, and periodic earthquakes. The intersecting joint sets developed in the bedrocks have formed wedges that have facilitated the recurrence of several landslides. The main objective of current research is to identify abnormal gradient lengths, indicating potential landslide-prone zones. High-resolution digital elevation data and geospatial techniques are used to perform this analysis. The results of GLAA are corroborated with the historical landslide events and ultimately used for the generation of landslide susceptibility maps of the current study area. The preliminary results indicate that approximately 3.97% of the basin is stable, while about 8.54% is classified as moderately stable and suitable for human habitation. However, roughly 19.89% fall within the zone of moderate vulnerability, 38.06% are classified as vulnerable, and 29% fall within the highly vulnerable zones, posing risks for geohazards, including landslides, glacial avalanches, and earthquakes. This research provides valuable insights into the spatial distribution of landslide-prone areas. It offers a basis for implementing proactive measures for landslide risk reduction, including land-use planning, early warning systems, and infrastructure development techniques.

Keywords: landslide vulnerability, geohazard, GLA, upper Alaknanda Basin, Uttarakhand Himalaya

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271 Catalytic Ammonia Decomposition: Cobalt-Molybdenum Molar Ratio Effect on Hydrogen Production

Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

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Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.

Keywords: CEDI, hydrogen carrier, LHHW, RDS

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270 A Biophysical Study of the Dynamic Properties of Glucagon Granules in α Cells by Imaging-Derived Mean Square Displacement and Single Particle Tracking Approaches

Authors: Samuele Ghignoli, Valentina de Lorenzi, Gianmarco Ferri, Stefano Luin, Francesco Cardarelli

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Insulin and glucagon are the two essential hormones for maintaining proper blood glucose homeostasis, which is disrupted in Diabetes. A constantly growing research interest has been focused on the study of the subcellular structures involved in hormone secretion, namely insulin- and glucagon-containing granules, and on the mechanisms regulating their behaviour. Yet, while several successful attempts were reported describing the dynamic properties of insulin granules, little is known about their counterparts in α cells, the glucagon-containing granules. To fill this gap, we used αTC1 clone 9 cells as a model of α cells and ZIGIR as a fluorescent Zinc chelator for granule labelling. We started by using spatiotemporal fluorescence correlation spectroscopy in the form of imaging-derived mean square displacement (iMSD) analysis. This afforded quantitative information on the average dynamical and structural properties of glucagon granules having insulin granules as a benchmark. Interestingly, the iMSD sensitivity to average granule size allowed us to confirm that glucagon granules are smaller than insulin ones (~1.4 folds, further validated by STORM imaging). To investigate possible heterogeneities in granule dynamic properties, we moved from correlation spectroscopy to single particle tracking (SPT). We developed a MATLAB script to localize and track single granules with high spatial resolution. This enabled us to classify the glucagon granules, based on their dynamic properties, as ‘blocked’ (i.e., trajectories corresponding to immobile granules), ‘confined/diffusive’ (i.e., trajectories corresponding to slowly moving granules in a defined region of the cell), or ‘drifted’ (i.e., trajectories corresponding to fast-moving granules). In cell-culturing control conditions, results show this average distribution: 32.9 ± 9.3% blocked, 59.6 ± 9.3% conf/diff, and 7.4 ± 3.2% drifted. This benchmarking provided us with a foundation for investigating selected experimental conditions of interest, such as the glucagon-granule relationship with the cytoskeleton. For instance, if Nocodazole (10 μM) is used for microtubule depolymerization, the percentage of drifted motion collapses to 3.5 ± 1.7% while immobile granules increase to 56.0 ± 10.7% (remaining 40.4 ± 10.2% of conf/diff). This result confirms the clear link between glucagon-granule motion and cytoskeleton structures, a first step towards understanding the intracellular behaviour of this subcellular compartment. The information collected might now serve to support future investigations on glucagon granules in physiology and disease. Acknowledgment: This work has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 866127, project CAPTUR3D).

Keywords: glucagon granules, single particle tracking, correlation spectroscopy, ZIGIR

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269 Compositional Influence in the Photovoltaic Properties of Dual Ion Beam Sputtered Cu₂ZnSn(S,Se)₄ Thin Films

Authors: Brajendra S. Sengar, Vivek Garg, Gaurav Siddharth, Nisheka Anadkat, Amitesh Kumar, Shaibal Mukherjee

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The optimal band gap (~ 1 to 1.5 eV) and high absorption coefficient ~104 cm⁻¹ has made Cu₂ZnSn(S,Se)₄ (CZTSSe) films as one of the most promising absorber materials in thin-film photovoltaics. Additionally, CZTSSe consists of elements that are abundant and non-toxic, makes it even more favourable. The CZTSSe thin films are grown at 100 to 500ᵒC substrate temperature (Tsub) on Soda lime glass (SLG) substrate by Elettrorava dual ion beam sputtering (DIBS) system by utilizing a target at 2.43x10⁻⁴ mbar working pressure with RF power of 45 W in argon ambient. The chemical composition, depth profiling, structural properties and optical properties of these CZTSSe thin films prepared on SLG were examined by energy dispersive X-ray spectroscopy (EDX, Oxford Instruments), Hiden secondary ion mass spectroscopy (SIMS) workstation with oxygen ion gun of energy up to 5 keV, X-ray diffraction (XRD) (Rigaku Cu Kα radiation, λ=.154nm) and Spectroscopic Ellipsometry (SE, M-2000D from J. A. Woollam Co., Inc). It is observed that from that, the thin films deposited at Tsub=200 and 300°C show Cu-poor and Zn-rich states (i.e., Cu/(Zn + Sn) < 1 and Zn/Sn > 1), which is not the case for films grown at other Tsub. It has been reported that the CZTSSe thin films with the highest efficiency are typically at Cu-poor and Zn-rich states. The values of band gap in the fundamental absorption region of CZTSSe are found to be in the range of 1.23-1.70 eV depending upon the Cu/(Zn+Sn) ratio. It is also observed that there is a decline in optical band gap with the increase in Cu/(Zn+Sn) ratio (evaluated from EDX measurement). Cu-poor films are found to have higher optical band gap than Cu-rich films. The decrease in the band gap with the increase in Cu content in case of CZTSSe films may be attributed to changes in the extent of p-d hybridization between Cu d-levels and (S, Se) p-levels. CZTSSe thin films with Cu/(Zn+Sn) ratio in the range 0.86–1.5 have been successfully deposited using DIBS. Optical band gap of the films is found to vary from 1.23 to 1.70 eV based on Cu/(Zn+Sn) ratio. CZTSe films with Cu/ (Zn+Sn) ratio of .86 are found to have optical band gap close to the ideal band gap (1.49 eV) for highest theoretical conversion efficiency. Thus by tailoring the value of Cu/(Zn+Sn), CZTSSe thin films with the desired band gap could be obtained. Acknowledgment: We are thankful to DIBS, EDX, and XRD facility equipped at Sophisticated Instrument Centre (SIC) at IIT Indore. The authors B. S. S and A. K. acknowledge CSIR, and V. G. acknowledges UGC, India for their fellowships. B. S. S is thankful to DST and IUSSTF for BASE Internship Award. Prof. Shaibal Mukherjee is thankful to DST and IUSSTF for BASE Fellowship and MEITY YFRF award. This work is partially supported by DAE BRNS, DST CERI, and DST-RFBR Project under India-Russia Programme of Cooperation in Science and Technology. We are thankful to Mukul Gupta for SIMS facility equipped at UGC-DAE Indore.

Keywords: CZTSSe, DIBS, EDX, solar cell

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268 Electroactive Fluorene-Based Polymer Films Obtained by Electropolymerization

Authors: Mariana-Dana Damaceanu

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Electrochemical oxidation is one of the most convenient ways to obtain conjugated polymer films as polypyrrole, polyaniline, polythiophene or polycarbazole. The research in the field has been mainly directed to the study of electrical conduction properties of the materials obtained by electropolymerization, often the main reason being their use as electroconducting electrodes, and very little attention has been paid to the morphological and optical quality of the films electrodeposited on flat surfaces. Electropolymerization of the monomer solution was scarcely used in the past to manufacture polymer-based light-emitting diodes (PLED), most probably due to the difficulty of obtaining defectless polymer films with good mechanical and optical properties, or conductive polymers with well controlled molecular weights. Here we report our attempts in using electrochemical deposition as appropriate method for preparing ultrathin films of fluorene-based polymers for PLED applications. The properties of these films were evaluated in terms of structural morphology, optical properties, and electrochemical conduction. Thus, electropolymerization of 4,4'-(9-fluorenylidene)-dianiline was performed in dichloromethane solution, at a concentration of 10-2 M, using 0.1 M tetrabutylammonium tetrafluoroborate as electrolyte salt. The potential was scanned between 0 and 1.3 V on the one hand, and 0 - 2 V on the other hand, when polymer films with different structures and properties were obtained. Indium tin oxide-coated glass substrate of different size was used as working electrode, platinum wire as counter electrode and calomel electrode as reference. For each potential range 100 cycles were recorded at a scan rate of 100 mV/s. The film obtained in the potential range from 0 to 1.3 V, namely poly(FDA-NH), is visible to the naked eye, being light brown, transparent and fluorescent, and displays an amorphous morphology. Instead, the electrogrowth poly(FDA) film in the potential range of 0 - 2 V is yellowish-brown and opaque, presenting a self-assembled structure in aggregates of irregular shape and size. The polymers structure was identified by FTIR spectroscopy, which shows the presence of broad bands specific to a polymer, the band centered at approx. 3443 cm-1 being ascribed to the secondary amine. The two polymer films display two absorption maxima, at 434-436 nm assigned to π-π* transitions of polymers, and another at 832 and 880 nm assigned to polaron transitions. The fluorescence spectra indicated the presence of emission bands in the blue domain, with two peaks at 422 and 488 nm for poly (FDA-NH), and four narrow peaks at 422, 447, 460 and 484 nm for poly(FDA), peaks originating from fluorene-containing segments of varying degrees of conjugation. Poly(FDA-NH) exhibited two oxidation peaks in the anodic region and the HOMO energy value of 5.41 eV, whereas poly(FDA) showed only one oxidation peak and the HOMO level localized at 5.29 eV. The electrochemical data are discussed in close correlation with the proposed chemical structure of the electrogrowth films. Further research will be carried out to study their use and performance in light-emitting devices.

Keywords: electrogrowth polymer films, fluorene, morphology, optical properties

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267 Enhancing Efficiency of Building through Translucent Concrete

Authors: Humaira Athar, Brajeshwar Singh

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Generally, the brightness of the indoor environment of buildings is entirely maintained by the artificial lighting which has consumed a large amount of resources. It is reported that lighting consumes about 19% of the total generated electricity which accounts for about 30-40% of total energy consumption. One possible way is to reduce the lighting energy by exploiting sunlight either through the use of suitable devices or energy efficient materials like translucent concrete. Translucent concrete is one such architectural concrete which allows the passage of natural light as well as artificial light through it. Several attempts have been made on different aspects of translucent concrete such as light guiding materials (glass fibers, plastic fibers, cylinder etc.), concrete mix design and manufacturing methods for use as building elements. Concerns are, however, raised on various related issues such as poor compatibility between the optical fibers and cement paste, unaesthetic appearance due to disturbance occurred in the arrangement of fibers during vibration and high shrinkage in flowable concrete due to its high water/cement ratio. Need is felt to develop translucent concrete to meet the requirement of structural safety as OPC concrete with the maximized saving in energy towards the power of illumination and thermal load in buildings. Translucent concrete was produced using pre-treated plastic optical fibers (POF, 2mm dia.) and high slump white concrete. The concrete mix was proportioned in the ratio of 1:1.9:2.1 with a w/c ratio of 0.40. The POF was varied from 0.8-9 vol.%. The mechanical properties and light transmission of this concrete were determined. Thermal conductivity of samples was measured by a transient plate source technique. Daylight illumination was measured by a lux grid method as per BIS:SP-41. It was found that the compressive strength of translucent concrete increased with decreasing optical fiber content. An increase of ~28% in the compressive strength of concrete was noticed when fiber was pre-treated. FE-SEM images showed little-debonded zone between the fibers and cement paste which was well supported with pull-out bond strength test results (~187% improvement over untreated). The light transmission of concrete was in the range of 3-7% depending on fiber spacing (5-20 mm). The average daylight illuminance (~75 lux) was nearly equivalent to the criteria specified for illumination for circulation (80 lux). The thermal conductivity of translucent concrete was reduced by 28-40% with respect to plain concrete. The thermal load calculated by heat conduction equation was ~16% more than the plain concrete. Based on Design-Builder software, the total annual illumination energy load of a room using one side translucent concrete was 162.36 kW compared with the energy load of 249.75 kW for a room without concrete. The calculated energy saving on an account of the power of illumination was ~25%. A marginal improvement towards thermal comfort was also noticed. It is concluded that the translucent concrete has the advantages of the existing concrete (load bearing) with translucency and insulation characteristics. It saves a significant amount of energy by providing natural daylight instead of artificial power consumption of illumination.

Keywords: energy saving, light transmission, microstructure, plastic optical fibers, translucent concrete

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266 Boredom in the Classroom: Sentiment Analysis on Teaching Practices and Related Outcomes

Authors: Elisa Santana-Monagas, Juan L. Núñez, Jaime León, Samuel Falcón, Celia Fernández, Rocío P. Solís

Abstract:

Students’ emotional experiences have been a widely discussed theme among researchers, proving a central role on students’ outcomes. Yet, up to now, far too little attention has been paid to teaching practices that negatively relate with students’ negative emotions in the higher education. The present work aims to examine the relationship between teachers’ teaching practices (i.e., students’ evaluations of teaching and autonomy support), the students’ feelings of boredom and agentic engagement and motivation in the higher education context. To do so, the present study incorporates one of the most popular tools in natural processing language to address students’ evaluations of teaching: sentiment analysis. Whereas most research has focused on the creation of SA models and assessing students’ satisfaction regarding teachers and courses to the author’s best knowledge, no research before has included results from SA into an explanatory model. A total of 225 university students (Mean age = 26.16, SD = 7.4, 78.7 % women) participated in the study. Students were enrolled in degree and masters’ studies at the faculty of Education of a public university of Spain. Data was collected using an online questionnaire students could access through a QR code they completed during a teaching period where the assessed teacher was not present. To assess students’ sentiments towards their teachers’ teaching, we asked them the following open-ended question: “If you had to explain a peer who doesn't know your teacher how he or she communicates in class, what would you tell them?”. Sentiment analysis was performed with Microsoft's pre-trained model. For this study, we relied on the probability of the students answer belonging to the negative category. To assess the reliability of the measure, inter-rater agreement between this NLP tool and one of the researchers, who independently coded all answers, was examined. The average pairwise percent agreement and the Cohen’s kappa were calculated with ReCal2. The agreement reached was of 90.8% and Cohen’s kappa .68, both considered satisfactory. To test the hypothesis relations a structural equation model (SEM) was estimated. Results showed that the model fit indices displayed a good fit to the data; χ² (134) = 351.129, p < .001, RMSEA = .07, SRMR = .09, TLI = .91, CFI = .92. Specifically, results show that boredom was negatively predicted by autonomy support practices (β = -.47[-.61, -.33]), whereas for the negative sentiment extracted from SET, this relation was positive (β = .23[.16, .30]). In other words, when students’ opinion towards their instructors’ teaching practices was negative, it was more likely for them to feel bored. Regarding the relations among boredom and student outcomes, results showed a negative predictive value of boredom on students’ motivation to study (β = -.46[-.63, -.29]) and agentic engagement (β = -.24[-.33, -.15]). Altogether, results show a promising future for sentiment analysis techniques in the field of education as they proved the usefulness of this tool when evaluating relations among teaching practices and student outcomes.

Keywords: sentiment analysis, boredom, motivation, agentic engagement

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265 Crosslinked Porous 3-Dimensional Cellulose Nanofibers/Gelatin Based Biocomposite Aerogels for Tissue Engineering Application

Authors: Ali Mirtaghavi, Andy Baldwin, Rajendarn Muthuraj, Jack Luo

Abstract:

Recent advances in biomaterials have led to utilizing biopolymers to develop 3D scaffolds in tissue regeneration. One of the major challenges of designing biomaterials for 3D scaffolds is to mimic the building blocks similar to the extracellular matrix (ECM) of the native tissues. Biopolymer based aerogels obtained by freeze-drying have shown to provide structural similarities to the ECM owing to their 3D format and a highly porous structure with interconnected pores, similar to the ECM. Gelatin (GEL) is known to be a promising biomaterial with inherent regenerative characteristics owing to its chemical similarities to the ECM in native tissue, biocompatibility abundance, cost-effectiveness and accessible functional groups, which makes it facile for chemical modifications with other biomaterials to form biocomposites. Despite such advantages, gelatin offers poor mechanical properties, sensitive enzymatic degradation and high viscosity at room temperature which limits its application and encourages its use to develop biocomposites. Hydrophilic biomass-based cellulose nanofibrous (CNF) has been explored to use as suspension for biocomposite aerogels for the development of 3D porous structures with excellent mechanical properties, biocompatibility and slow enzymatic degradation. In this work, CNF biocomposite aerogels with various ratios of CNF:GEL) (90:10, 70:30 and 50:50) were prepared by freeze-drying technique, and their properties were investigated in terms of physicochemical, mechanical and biological characteristics. Epichlorohydrin (EPH) was used to investigate the effect of chemical crosslinking on the molecular interaction of CNF: GEL, and its effects on physicochemical, mechanical and biological properties of the biocomposite aerogels. Ultimately, chemical crosslinking helped to improve the mechanical resilience of the resulting aerogels. Amongst all the CNF-GEL composites, the crosslinked CNF: GEL (70:30) biocomposite was found to be favourable for cell attachment and viability. It possessed highly porous structure (porosity of ~93%) with pore sizes ranging from 16-110 µm, adequate mechanical properties (compression modulus of ~47 kPa) and optimal biocompatibility both in-vitro and in-vivo, as well as controlled enzymatic biodegradation, high water penetration, which could be considered a suitable option for wound healing application. In-vivo experiments showed improvement on inflammation and foreign giant body cell reaction for the crosslinked CNF: GEL (70:30) compared to the other samples. This could be due to the superior interaction of CNF with gelatin through chemical crosslinking, resulting in more optimal in-vivo improvement. In-vitro cell culture investigation on human dermal fibroblasts showed satisfactory 3D cell attachment over time. Overall, it has been observed that the developed CNF: GEL aerogel can be considered as a potential scaffold for soft tissue regeneration application.

Keywords: 3D scaffolds, aerogels, Biocomposites , tissue engineering

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264 A Density Function Theory Based Comparative Study of Trans and Cis - Resveratrol

Authors: Subhojyoti Chatterjee, Peter J. Mahon, Feng Wang

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Resveratrol (RvL), a phenolic compound, is a key ingredient in wine and tomatoes that has been studied over the years because of its important bioactivities such as anti-oxidant, anti-aging and antimicrobial properties. Out of the two isomeric forms of resveratrol i.e. trans and cis, the health benefit is primarily associated with the trans form. Thus, studying the structural properties of the isomers will not only provide an insight into understanding the RvL isomers, but will also help in designing parameters for differentiation in order to achieve 99.9% purity of trans-RvL. In the present study, density function theory (DFT) study is conducted, using the B3LYP/6-311++G** model to explore the through bond and through space intramolecular interactions. Properties such as vibrational spectroscopy (IR and Raman), nuclear magnetic resonance (NMR) spectra, excess orbital energy spectrum (EOES), energy based decomposition analyses (EDA) and Fukui function are calculated. It is discovered that the structure of trans-RvL, although it is C1 non-planar, the backbone non-H atoms are nearly in the same plane; whereas the cis-RvL consists of two major planes of R1 and R2 that are not in the same plane. The absence of planarity gives rise to a H-bond of 2.67Å in cis-RvL. Rotation of the C(5)-C(8) single bond in trans-RvL produces higher energy barriers since it may break the (planar) entire conjugated structure; while such rotation in cis-RvL produces multiple minima and maxima depending on the positions of the rings. The calculated FT-IR spectrum shows very different spectral features for trans and cis-RvL in the region 900 – 1500 cm-1, where the spectral peaks at 1138-1158 cm-1 are split in cis-RvL compared to a single peak at 1165 cm-1 in trans-RvL. In the Raman spectra, there is significant enhancement of cis-RvL in the region above 3000cm-1. Further, the carbon chemical environment (13C NMR) of the RvL molecule exhibit a larger chemical shift for cis-RvL compared to trans-RvL (Δδ = 8.18 ppm) for the carbon atom C(11), indicating that the chemical environment of the C group in cis-RvL is more diverse than its other isomer. The energy gap between highest occupied molecular orbital (HOMO) and the lowest occupied molecular orbital (LUMO) is 3.95 eV for trans and 4.35 eV for cis-RvL. A more detailed inspection using the recently developed EOES revealed that most of the large energy differences i.e. Δεcis-trans > ±0.30 eV, in their orbitals are contributed from the outer valence shell. They are MO60 (HOMO), MO52-55 and MO46. The active sites that has been captured by Fukui function (f + > 0.08) are associated with the stilbene C=C bond of RvL and cis-RvL is more active at these sites than in trans-RvL, as cis orientation breaks the large conjugation of trans-RvL so that the hydroxyl oxygen’s are more active in cis-RvL. Finally, EDA highlights the interaction energy (ΔEInt) of the phenolic compound, where trans is preferred over the cis-RvL (ΔΔEi = -4.35 kcal.mol-1) isomer. Thus, these quantum mechanics results could help in unwinding the diversified beneficial activities associated with resveratrol.

Keywords: resveratrol, FT-IR, Raman, NMR, excess orbital energy spectrum, energy decomposition analysis, Fukui function

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263 Seismotectonics and Seismology the North of Algeria

Authors: Djeddi Mabrouk

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The slow coming together between the Afro-Eurasia plates seems to be the main cause of the active deformation in the whole of North Africa which in consequence come true in Algeria with a large zone of deformation in an enough large limited band, southern through Saharan atlas and northern through tell atlas. Maghrebin and Atlassian Chain along North Africa are the consequence of this convergence. In junction zone, we have noticed a compressive regime NW-SE with a creases-faults structure and structured overthrust. From a geological point of view the north part of Algeria is younger then Saharan platform, it’s changing so unstable and constantly in movement, it’s characterized by creases openly reversed, overthrusts and reversed faults, and undergo perpetually complex movement vertically and horizontally. On structural level the north of Algeria it's a part of erogenous alpine peri-Mediterranean and essentially the tertiary age It’s spread from east to the west of Algeria over 1200 km.This oogenesis is extended from east to west on broadband of 100 km.The alpine chain is shaped by 3 domains: tell atlas in north, high plateaus in mid and Saharan atlas in the south In extreme south we find the Saharan platform which is made of Precambrian bedrock recovered by Paleozoic practically not deformed. The Algerian north and the Saharan platform are separated by an important accident along of 2000km from Agadir (Morocco) to Gabes (Tunisian). The seismic activity is localized essentially in a coastal band in the north of Algeria shaped by tell atlas, high plateaus, Saharan atlas. Earthquakes are limited in the first 20km of the earth's crust; they are caused by movements along faults of inverted orientation NE-SW or sliding tectonic plates. The center region characterizes Strong Earthquake Activity who locates mainly in the basin of Mitidja (age Neogene).The southern periphery (Atlas Blidéen) constitutes the June, more Important seism genic sources in the city of Algiers and east (Boumerdes region). The North East Region is also part of the tellian area, but it is characterized by a different strain in other parts of northern Algeria. The deformation is slow and low to moderate seismic activity. Seismic activity is related to the tectonic-slip earthquake. The most pronounced is that of 27 October 1985 (Constantine) of seismic moment magnitude Mw = 5.9. North-West region is quite active and also artificial seismic hypocenters which do not exceed 20km. The deep seismicity is concentrated mainly a narrow strip along the edge of Quaternary and Neogene basins Intra Mountains along the coast. The most violent earthquakes in this region are the earthquake of Oran in 1790 and earthquakes Orléansville (El Asnam in 1954 and 1980).

Keywords: alpine chain, seismicity north Algeria, earthquakes in Algeria, geophysics, Earth

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262 Exploratory Study on Mediating Role of Commitment-to-Change in Relations between Employee Voice, Employee Involvement and Organizational Change Readiness

Authors: Rohini Sharma, Chandan Kumar Sahoo, Rama Krishna Gupta Potnuru

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Strong competitive forces and requirements to achieve efficiency are forcing the organizations to realize the necessity and inevitability of change. What's more, the trend does not appear to be abating. Researchers have estimated that about two thirds of change project fails. Empirical evidences further shows that organizations invest significantly in the planned change but people side is accounted for in a token or instrumental way, which is identified as one of the important reason, why change endeavours fail. However, whatever be the reason for change, organizational change readiness must be gauged prior to the institutionalization of organizational change. Hence, in this study the influence of employee voice and employee involvement on organizational change readiness via commitment-to-change is examined, as it is an area yet to be extensively studied. Also, though a recent study has investigated the interrelationship between leadership, organizational change readiness and commitment to change, our study further examined these constructs in relation with employee voice and employee involvement that plays a consequential role for organizational change readiness. Further, integrated conceptual model weaving varied concepts relating to organizational readiness with focus on commitment to change as mediator was found to be an area, which required more theorizing and empirical validation, and this study rooted in an Indian public sector organization is a step in this direction. Data for the study were collected through a survey among employees of Rourkela Steel Plant (RSP), a unit of Steel Authority of India Limited (SAIL); the first integrated Steel Plant in the public sector in India, for which stratified random sampling method was adopted. The schedule was distributed to around 700 employees, out of which 516 complete responses were obtained. The pre-validated scales were used for the study. All the variables in the study were measured on a five-point Likert scale ranging from “strongly disagree (1)” to “strongly agree (5)”. Structural equation modeling (SEM) using AMOS 22 was used to examine the hypothesized model, which offers a simultaneous test of an entire system of variables in a model. The study results shows that inter-relationship between employee voice and commitment-to-change, employee involvement and commitment-to-change and commitment-to-change and organizational change readiness were significant. To test the mediation hypotheses, Baron and Kenny’s technique was used. Examination of direct and mediated effect of mediators confirmed that commitment-to-change partially mediated the relation between employee involvement and organizational change readiness. Furthermore, study results also affirmed that commitment-to-change does not mediate the relation between employee involvement and organizational change readiness. The empirical exploration therefore establishes that it is important to harness employee’s valuable suggestions regarding change for building organizational change readiness. Regarding employee involvement, it was found that sharing information and involving people in decision-making, leads to a creation of participative climate, which educes employee commitment during change and commitment-to-change further, fosters organizational change readiness.

Keywords: commitment-to-change, change management, employee voice, employee involvement, organizational change readiness

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261 Optimization of Cobalt Oxide Conversion to Co-Based Metal-Organic Frameworks

Authors: Aleksander Ejsmont, Stefan Wuttke, Joanna Goscianska

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Gaining control over particle shape, size and crystallinity is an ongoing challenge for many materials. Especially metalorganic frameworks (MOFs) are recently widely studied. Besides their remarkable porosity and interesting topologies, morphology has proven to be a significant feature. It can affect the further material application. Thus seeking new approaches that enable MOF morphology modulation is important. MOFs are reticular structures, where building blocks are made up of organic linkers and metallic nodes. The most common strategy of ensuring metal source is using salts, which usually exhibit high solubility and hinder morphology control. However, there has been a growing interest in using metal oxides as structure-directing agents towards MOFs due to their very low solubility and shape preservation. Metal oxides can be treated as a metal reservoir during MOF synthesis. Up to now, reports in which receiving MOFs from metal oxides mostly present ZnO conversion to ZIF-8. However, there are other oxides, for instance, Co₃O₄, which often is overlooked due to their structural stability and insolubility in aqueous solutions. Cobalt-based materials are famed for catalytic activity. Therefore the development of their efficient synthesis is worth attention. In the presented work, an optimized Co₃O₄transition to Co-MOFviaa solvothermal approach was proposed. The starting point of the research was the synthesis of Co₃O₄ flower petals and needles under hydrothermal conditions using different cobalt salts (e.g., cobalt(II) chloride and cobalt(II) nitrate), in the presence of urea, and hexadecyltrimethylammonium bromide (CTAB) surfactant as a capping agent. After receiving cobalt hydroxide, the calcination process was performed at various temperatures (300–500 °C). Then cobalt oxides as a source of cobalt cations were subjected to reaction with trimesic acid in solvothermal environment and temperature of 120 °C leading to Co-MOF fabrication. The solution maintained in the system was a mixture of water, dimethylformamide, and ethanol, with the addition of strong acids (HF and HNO₃). To establish how solvents affect metal oxide conversion, several different solvent ratios were also applied. The materials received were characterized with analytical techniques, including X-ray powder diffraction, energy dispersive spectroscopy,low-temperature nitrogen adsorption/desorption, scanning, and transmission electron microscopy. It was confirmed that the synthetic routes have led to the formation of Co₃O₄ and Co-based MOF varied in shape and size of particles. The diffractograms showed receiving crystalline phase for Co₃O₄, and also for Co-MOF. The Co₃O₄ obtained from nitrates and with using low-temperature calcination resulted in smaller particles. The study indicated that cobalt oxide particles of different size influence the efficiency of conversion and morphology of Co-MOF. The highest conversion was achieved using metal oxides with small crystallites.

Keywords: Co-MOF, solvothermal synthesis, morphology control, core-shell

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260 Improving the Biocontrol of the Argentine Stem Weevil; Using the Parasitic Wasp Microctonus hyperodae

Authors: John G. Skelly, Peter K. Dearden, Thomas W. R. Harrop, Sarah N. Inwood, Joseph Guhlin

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The Argentine stem weevil (ASW; L. bonariensis) is an economically important pasture pest in New Zealand, which causes about $200 million of damage per annum. Microctonus hyperodae (Mh), a parasite of the ASW in its natural range in South America, was introduced into New Zealand to curb the pasture damage caused by the ASW. Mh is an endoparasitic wasp that lays its eggs in the ASW halting its reproduction. Mh was initially successful at preventing ASW proliferation and reducing pasture damage. The effectiveness of Mh has since declined due to decreased parasitism rates and has resulted in increased pasture damage. Although the mechanism through which ASW has developed resistance to Mh has not been discovered, it has been proposed to be due to the different reproductive modes used by Mh and the ASW in New Zealand. The ASW reproduces sexually, whereas Mh reproduces asexually, which has been hypothesised to have allowed the ASW to ‘out evolve’ Mh. Other species within the Microctonus genus reproduce both sexually and asexually. Strains of Microctonus aethiopoides (Ma), a species closely related to Mh, reproduce either by sexual or asexual reproduction. Comparing the genomes of sexual and asexual Microctonus may allow for the identification of the mechanism of asexual reproduction and other characteristics that may improve Mh as a biocontrol agent. The genomes of Mh and three strains of Ma, two of which reproduce sexually and one reproduces asexually, have been sequenced and annotated. The French (MaFR) and Moroccan (MaMO) reproduce sexually, whereas the Irish strain (MaIR) reproduces asexually. Like Mh, The Ma strains are also used as biocontrol agents, but for different weevil species. The genomes of Mh and MaIR were subsequently upgraded using Hi-C, resulting in a set of high quality, highly contiguous genomes. A subset of the genes involved in mitosis and meiosis, which have been identified though the use of Hidden Markov Models generated from genes involved in these processes in other Hymenoptera, have been catalogued in Mh and the strains of Ma. Meiosis and mitosis genes were broadly conserved in both sexual and asexual Microctonus species. This implies that either the asexual species have retained a subset of the molecular components required for sexual reproduction or that the molecular mechanisms of mitosis and meiosis are different or differently regulated in Microctonus to other insect species in which these mechanisms are more broadly characterised. Bioinformatic analysis of the chemoreceptor compliment in Microctonus has revealed some variation in the number of olfactory receptors, which may be related to host preference. Phylogenetic analysis of olfactory receptors highlights variation, which may be able to explain different host range preferences in the Microctonus. Hi-C clustering implies that Mh has 12 chromosomes, and MaIR has 8. Hence there may be variation in gene regulation between species. Genome alignment of Mh and MaIR implies that there may be large scale genome structural variation. Greater insight into the genetics of these agriculturally important group of parasitic wasps may be beneficial in restoring or maintaining their biocontrol efficacy.

Keywords: argentine stem weevil, asexual, genomics, Microctonus hyperodae

Procedia PDF Downloads 127