Search results for: series compensation
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 2915

Search results for: series compensation

2255 Impacts of Climate Elements on the Annual Periodic Behavior of the Shallow Groundwater Level: Case Study from Central-Eastern Europe

Authors: Tamas Garamhegyi, Jozsef Kovacs, Rita Pongracz, Peter Tanos, Balazs Trasy, Norbert Magyar, Istvan G. Hatvani

Abstract:

Like most environmental processes, shallow groundwater fluctuation under natural circumstances also behaves periodically. With the statistical tools at hand, it can easily be determined if a period exists in the data or not. Thus, the question may be raised: Does the estimated average period time characterize the whole time period, or not? This is especially important in the case of such complex phenomena as shallow groundwater fluctuation, driven by numerous factors. Because of the continuous changes in the oscillating components of shallow groundwater time series, the most appropriate method should be used to investigate its periodicity, this is wavelet spectrum analysis. The aims of the research were to investigate the periodic behavior of the shallow groundwater time series of an agriculturally important and drought sensitive region in Central-Eastern Europe and its relationship to the European pressure action centers. During the research ~216 shallow groundwater observation wells located in the eastern part of the Great Hungarian Plain with a temporal coverage of 50 years were scanned for periodicity. By taking the full-time interval as 100%, the presence of any period could be determined in percentages. With the complex hydrogeological/meteorological model developed in this study, non-periodic time intervals were found in the shallow groundwater levels. On the local scale, this phenomenon linked to drought conditions, and on a regional scale linked to the maxima of the regional air pressures in the Gulf of Genoa. The study documented an important link between shallow groundwater levels and climate variables/indices facilitating the necessary adaptation strategies on national and/or regional scales, which have to take into account the predictions of drought-related climatic conditions.

Keywords: climate change, drought, groundwater periodicity, wavelet spectrum and coherence analyses

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2254 Investing the Employees Higher Quitting Intention at the Call Centers of Pakistan: A Reality or a Myth: A Case Study of Pakistan Telecommunication Sector

Authors: Naheed Malik, Marisa Smith

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This study has been undertaken as an attempt to explore the underlying reasons that cause higher employee turnover rates at the call centers of Pakistan. This research also aimed to examine the relationship among the job related variables such as job satisfaction, organizational commitment, supervisor support, self-esteem, organizational stressors (work overload, role ambiguity and work family conflict) and quitting inclination. A total of 340 call centers respondents filled the survey questionnaire. The data was analyzed through SPSS 19.0. Results reveal the significant relationship among the study variables and stress level contributing more towards employee penchant to leave the job. A significant amount of call centers employee have proclivity to quit from their jobs as soon as they would be able to find some other jobs with attractive compensation. The majority of the respondents were found to be unhappy and dissatisfied due to hectic schedule and imbalance between family and work. This research also highlighted the specific areas in which call centre management needs to emphasize deliberately that affect more sharply on employee leaving aptitude. This study also suggests some useful strategies for the well being of employees that can minimize their tendency of quitting and retention in the long run.

Keywords: call centers, stress, job satisfaction, organizational commitment, supervisor’s support, self esteem, employee turnover, employees’ intention to quit, customer service representative (CSRs)

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2253 Spatiotemporal Variability in Rainfall Trends over Sinai Peninsula Using Nonparametric Methods and Discrete Wavelet Transforms

Authors: Mosaad Khadr

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Knowledge of the temporal and spatial variability of rainfall trends has been of great concern for efficient water resource planning, management. In this study annual, seasonal and monthly rainfall trends over the Sinai Peninsula were analyzed by using absolute homogeneity tests, nonparametric Mann–Kendall (MK) test and Sen’s slope estimator methods. The homogeneity of rainfall time-series was examined using four absolute homogeneity tests namely, the Pettitt test, standard normal homogeneity test, Buishand range test, and von Neumann ratio test. Further, the sequential change in the trend of annual and seasonal rainfalls is conducted using sequential MK (SQMK) method. Then the trend analysis based on discrete wavelet transform technique (DWT) in conjunction with SQMK method is performed. The spatial patterns of the detected rainfall trends were investigated using a geostatistical and deterministic spatial interpolation technique. The results achieved from the Mann–Kendall test to the data series (using the 5% significance level) highlighted that rainfall was generally decreasing in January, February, March, November, December, wet season, and annual rainfall. A significant decreasing trend in the winter and annual rainfall with significant levels were inferred based on the Mann-Kendall rank statistics and linear trend. Further, the discrete wavelet transform (DWT) analysis reveal that in general, intra- and inter-annual events (up to 4 years) are more influential in affecting the observed trends. The nature of the trend captured by both methods is similar for all of the cases. On the basis of spatial trend analysis, significant rainfall decreases were also noted in the investigated stations. Overall, significant downward trends in winter and annual rainfall over the Sinai Peninsula was observed during the study period.

Keywords: trend analysis, rainfall, Mann–Kendall test, discrete wavelet transform, Sinai Peninsula

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2252 Triplex Detection of Pistacia vera, Arachis hypogaea and Pisum sativum in Processed Food Products Using Probe Based PCR

Authors: Ergün Şakalar, Şeyma Özçirak Ergün, Emrah Yalazi̇, Emine Altinkaya, Cengiz Ataşoğlu

Abstract:

In recent years, food allergies which cause serious health problems affect to public health around the world. Foodstuffs which contain allergens are either intentionally used as ingredients or are encased as contaminant in food products. The prevalence of clinical allergy to peanuts and nuts is estimated at about 0.4%-1.1% of the adult population, representing the allergy to pistachio the 7% of the cases of tree nut causing allergic reactions. In order to protect public health and enforce the legislation, methods for sensitive analysis of pistachio and peanut contents in food are required. Pea, pistachio and peanut are used together, to reduce the cost in food production such as baklava, snack foods.DNA technology-based methods in food analysis are well-established and well-roundedtools for species differentiation, allergen detection. Especially, the probe-based TaqMan real-time PCR assay can amplify target DNA with efficiency, specificity, and sensitivity.In this study, pistachio, peanut and pea were finely ground and three separate series of triplet mixtures containing 0.1, 1, 10, 100, 1000, 10,000 and 100,000 mg kg-1 of each sample were prepared for each series, to a final weight of 100 g. DNA from reference samples and industrial products was successfully extracted with the GIDAGEN® Multi-Fast DNA Isolation Kit. TaqMan probes were designed for triplex determination of ITS, Ara h 3 and pea lectin genes which are specific regions for identification pistachio, peanut and pea, respectively.The real-time PCR as quantitative detected pistachio, peanut and pea in these mixtures down to the lowest investigated level of 0.1, 0.1 and 1 mg kg-1, respectively. Also, the methods reported here are capable of detecting of as little as 0.001% level of peanut DNA, 0,000001% level of pistachio DNA and 0.000001% level of pea DNA. We accomplish that the quantitative triplex real-time PCR method developed in this study canbe applied to detect pistachio, peanut and peatraces for three allergens at once in commercial food products.

Keywords: allergens, DNA, real-time PCR, TaqMan probe

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2251 Redefining Surgical Innovation in Urology: A Historical Perspective of the Original Publications on Pioneering Techniques in Urology

Authors: Samuel Sii, David Homewood, Brendan Dittmer, Tony Nzembela, Jonathan O’Brien, Niall Corcoran, Dinesh Agarwal

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Introduction: Innovation is key to the advancement of medicine and improvement in patient care. This is particularly true in surgery, where pioneering techniques have transformed operative management from a historically highly risky peri-morbid and disfiguring to the contemporary low-risk, sterile and minimally invasive treatment modality. There is a delicate balance between enabling innovation and minimizing patient harm. Publication and discussion of novel surgical techniques allow for independent expert review. Recent journals have increasingly stringent requirements for publications and often require larger case volumes for novel techniques to be published. This potentially impairs the initial publication of novel techniques and slows innovation. The historical perspective provides a better understanding of how requirements for the publication of new techniques have evolved over time. This is essential in overcoming challenges in developing novel techniques. Aims and Objectives: We explore how novel techniques in Urology have been published over the past 200 years. Our objective is to describe the trend and publication requirements of novel urological techniques, both historical and present. Methods: We assessed all major urological operations using multipronged historical analysis. An initial literature search was carried out through PubMed and Google Scholar for original literature descriptions, followed by reference tracing. The first publication of each pioneering urological procedure was recorded. Data collected includes the year of publication, description of the procedure, number of cases and outcomes. Results: 65 papers describing pioneering techniques in Urology were identified. These comprised of 2 experimental studies, 17 case reports and 46 case series. These papers described various pioneering urological techniques in urological oncology, reconstructive urology and endourology. We found that, historically, techniques were published with smaller case numbers. Often, the surgical technique itself was a greater focus of the publication than patient outcome data. These techniques were often adopted prior to larger publications. In contrast, the risks and benefits of recent novel techniques are often well-defined prior to adoption. This historical perspective is important as recent journals have requirements for larger case series and data outcomes. This potentially impairs the initial publication of novel techniques and slows innovation. Conclusion: A better understanding of historical publications and their effect on the adoption of urological techniques into common practice could assist the current generation of Urologists in formulating a safe, efficacious process in promoting surgical innovation and the development of novel surgical techniques. We propose the reassessment of requirements for the publication of novel operative techniques by splitting technical perspectives and data-orientated case series. Existing frameworks such as IDEAL and ASERNIP-S should be integrated into current processes when investigating and developing new surgical techniques to ensure efficacious and safe innovation within surgery is encouraged.

Keywords: urology, surgical innovation, novel surgical techniques, publications

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2250 Bacterial Causes of Cerebral Abscess and Impact on Long Term Patient Outcomes

Authors: Umar Rehman, Holly Roy, K. T. Tsang, D. S. Jeyaretna, W Singleton, B. Fisher, P. A. Glew, J. Greig, Peter C. Whitfield

Abstract:

Introduction: A brain abscess is a life-threatening condition, carrying significant mortality. It requires rapid identification and treatment. Management involves a combination of antibiotics and surgery. The aim of the current study was to identify common bacteria responsible for cerebral abscesses as well as the long term functional and neurological outcomes of patients following treatment in a retrospective series at a single UK neurosurgical centre. Methodology: We analysed patients that had received a diagnosis of 'cerebral abscess' or 'subdural empyema' between June 2002 and June 2018. This was done in the form of a retrospective review. The search resulted in a total of 180 patients; with 37 patients being excluded (spinal abscess, below 18 or non-abscess related admissions). Data were collected from medical case notes including information about demographics, comorbidities, immunosuppression, presentation, size/location of lesions, pathogens, treatment, and outcomes. Results: In total, we analysed 143 patients between the ages of 18-90. Focal neurological deficit and headaches were seen in 84% and 68% of patients respectively. 108 positive brain cultures were seen; with the largest proportion, 59.2% being gram-positive cocci, with strep intermedius being the most common pathogen identified in 13.9% of patients. Of the patients with positive blood cultures (n=11), 72.7% showed the same organism both in the blood and on the brain cultures. Long term outcomes (n=72) revealed that 48% of patients seizure-free without requiring anti-epileptics, 51.3% of patients had full recovery of their neurological symptoms. There was a mortality rate of 13.9% in the series. Conclusion: In conclusion, the largest bacterial cause of abscess within our population was due to gram-positive cocci. The majority of the patient demonstrated full neurological recovery with close to half of patients not requiring anti-epileptics following discharge.

Keywords: bacteria, cerebral abscess, long term outcome, neurological deficit

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2249 Analysis of Kinetin Supramolecular Complex with Glytsirrizinic Acid and Based by Mass-Spectrometry Method

Authors: Bakhtishod Matmuratov, Sakhiba Madraximova, Rakhmat Esanov, Alimjan Matchanov

Abstract:

Studies have been performed to obtain complexes of glycyrrhizic acid and kinetins in a 2:1 ratio. The complex of glycyrrhizic acid and kinetins in a 2:1 ratio was considered evidence of the formation of a molecular complex by determining the molecular masses using chromato-mass spectroscopy and analyzing the IR spectra.

Keywords: monoammonium salt of glycyrrhizic acid, glycyrrhizic acid, supramolecular complex, isomolar series, IR spectroscopy

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2248 Enhanced Magnetoelastic Response near Morphotropic Phase Boundary in Ferromagnetic Materials: Experimental and Theoretical Analysis

Authors: Murtaza Adil, Sen Yang, Zhou Chao, Song Xiaoping

Abstract:

The morphotropic phase boundary (MPB) recently has attracted constant interest in ferromagnetic systems for obtaining enhanced large magnetoelastic response. In the present study, structural and magnetoelastic properties of MPB involved ferromagnetic Tb1-xGdxFe2 (0≤x≤1) system has been investigated. The change of easy magnetic direction from <111> to <100> with increasing x up MPB composition of x=0.9 is detected by step-scanned [440] synchrotron X-ray diffraction reflections. The Gd substitution for Tb changes the composition for the anisotropy compensation near MPB composition of x=0.9, which was confirmed by the analysis of detailed scanned XRD, magnetization curves and the calculation of the first anisotropy constant K1. The spin configuration diagram accompanied with different crystal structures for Tb1-xGdxFe2 was designed. The calculated first anisotropy constant K1 shows a minimum value at MPB composition of x=0.9. In addition, the large ratio between magnetostriction, and the absolute values of the first anisotropy constant │λS∕K1│ appears at MPB composition, which makes it a potential material for magnetostrictive application. Based on experimental results, a theoretically approach was also proposed to signify that the facilitated magnetization rotation and enhanced magnetoelastic effect near MPB composition are a consequence of the anisotropic flattening of free energy of ferromagnetic crystal. Our work specifies the universal existence of MPB in ferromagnetic materials which is important for substantial improvement of magnetic and magnetostrictive properties and may provide a new route to develop advanced functional materials.

Keywords: free energy, magnetic anisotropy, magnetostriction, morphotropic phase boundary (MPB)

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2247 Endoscopic Pituitary Surgery: Learning Curve and Nasal Quality of Life

Authors: Martin Dupuy, Solange Grunenwald, Pierre-Louis Colombo, Laurence Mahieu, Pomone Richard, Philippe Bartoli

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Endonasal endoscopic trans-sphenoidal surgery for pituitary tumours has become a mainstay of treatment over the last two decades. Although it is generally accepted that there is no significant difference between endoscopic versus microscopic approach for surgical outcomes (endocrine and ophthalmologic status), nasal morbidity seems to the benefit of endoscopic procedures. Minimally invasive endoscopic surgery needs an operative learning curve to achieve surgeon’s efficiency. This learning curve is now well known for surgical outcomes and complications rate, however, few data are available for nasal morbidity. The aim of our series is to document operative experience and nasal quality of life after (NQOL) endoscopic trans-sphenoidal surgery. The prospective pituitary surgical cohort consisted of 525 consecutives patients referred to our Skull Base Diseases Department. Endoscopic procedures were performed by a single neurosurgeon using an uninostril approach. NQOL was evaluated using the Sino-Nasal Test (SNOT-22), the Anterior Base Nasal Inventory (ASBNI) and the Skull Base Inventory Score (SBIS). Data were collected before surgery during hospital stay and 3 months after the surgery. The seventy first patients were compared to the latest 70 patients. There was no significant difference between comparison score before versus after surgery for SNOT-22, ASBNI and SBIS during the single surgeon’s learning curve. Our series demonstrates that in our institution there is no statistically significant learning curve for NQOL after uninostril endoscopic pituitary surgery. A careful progression through sinonasal structures with very limited mucosal incision is associated with minimal morbidity and preserves nasal function. Conservative and minimal invasive approach could be achieved early during learning curve.

Keywords: pituitary surgery, quality of life, minimal invasive surgery, learning curve, pituitary tumours, skull base surgery, endoscopic surgery

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2246 Nonstationary Modeling of Extreme Precipitation in the Wei River Basin, China

Authors: Yiyuan Tao

Abstract:

Under the impact of global warming together with the intensification of human activities, the hydrological regimes may be altered, and the traditional stationary assumption was no longer satisfied. However, most of the current design standards of water infrastructures were still based on the hypothesis of stationarity, which may inevitably result in severe biases. Many critical impacts of climate on ecosystems, society, and the economy are controlled by extreme events rather than mean values. Therefore, it is of great significance to identify the non-stationarity of precipitation extremes and model the precipitation extremes in a nonstationary framework. The Wei River Basin (WRB), located in a continental monsoon climate zone in China, is selected as a case study in this study. Six extreme precipitation indices were employed to investigate the changing patterns and stationarity of precipitation extremes in the WRB. To identify if precipitation extremes are stationary, the Mann-Kendall trend test and the Pettitt test, which is used to examine the occurrence of abrupt changes are adopted in this study. Extreme precipitation indices series are fitted with non-stationary distributions that selected from six widely used distribution functions: Gumbel, lognormal, Weibull, gamma, generalized gamma and exponential distributions by means of the time-varying moments model generalized additive models for location, scale and shape (GAMLSS), where the distribution parameters are defined as a function of time. The results indicate that: (1) the trends were not significant for the whole WRB, but significant positive/negative trends were still observed in some stations, abrupt changes for consecutive wet days (CWD) mainly occurred in 1985, and the assumption of stationarity is invalid for some stations; (2) for these nonstationary extreme precipitation indices series with significant positive/negative trends, the GAMLSS models are able to capture well the temporal variations of the indices, and perform better than the stationary model. Finally, the differences between the quantiles of nonstationary and stationary models are analyzed, which highlight the importance of nonstationary modeling of precipitation extremes in the WRB.

Keywords: extreme precipitation, GAMLSSS, non-stationary, Wei River Basin

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2245 Development and Adaptation of a LGBM Machine Learning Model, with a Suitable Concept Drift Detection and Adaptation Technique, for Barcelona Household Electric Load Forecasting During Covid-19 Pandemic Periods (Pre-Pandemic and Strict Lockdown)

Authors: Eric Pla Erra, Mariana Jimenez Martinez

Abstract:

While aggregated loads at a community level tend to be easier to predict, individual household load forecasting present more challenges with higher volatility and uncertainty. Furthermore, the drastic changes that our behavior patterns have suffered due to the COVID-19 pandemic have modified our daily electrical consumption curves and, therefore, further complicated the forecasting methods used to predict short-term electric load. Load forecasting is vital for the smooth and optimized planning and operation of our electric grids, but it also plays a crucial role for individual domestic consumers that rely on a HEMS (Home Energy Management Systems) to optimize their energy usage through self-generation, storage, or smart appliances management. An accurate forecasting leads to higher energy savings and overall energy efficiency of the household when paired with a proper HEMS. In order to study how COVID-19 has affected the accuracy of forecasting methods, an evaluation of the performance of a state-of-the-art LGBM (Light Gradient Boosting Model) will be conducted during the transition between pre-pandemic and lockdowns periods, considering day-ahead electric load forecasting. LGBM improves the capabilities of standard Decision Tree models in both speed and reduction of memory consumption, but it still offers a high accuracy. Even though LGBM has complex non-linear modelling capabilities, it has proven to be a competitive method under challenging forecasting scenarios such as short series, heterogeneous series, or data patterns with minimal prior knowledge. An adaptation of the LGBM model – called “resilient LGBM” – will be also tested, incorporating a concept drift detection technique for time series analysis, with the purpose to evaluate its capabilities to improve the model’s accuracy during extreme events such as COVID-19 lockdowns. The results for the LGBM and resilient LGBM will be compared using standard RMSE (Root Mean Squared Error) as the main performance metric. The models’ performance will be evaluated over a set of real households’ hourly electricity consumption data measured before and during the COVID-19 pandemic. All households are located in the city of Barcelona, Spain, and present different consumption profiles. This study is carried out under the ComMit-20 project, financed by AGAUR (Agència de Gestiód’AjutsUniversitaris), which aims to determine the short and long-term impacts of the COVID-19 pandemic on building energy consumption, incrementing the resilience of electrical systems through the use of tools such as HEMS and artificial intelligence.

Keywords: concept drift, forecasting, home energy management system (HEMS), light gradient boosting model (LGBM)

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2244 A Composite Indicator to Monitoring European Water Policies Using a Flexible Sustainability Approach

Authors: De Castro-Pardo M., Cabello J. M., Martin J. M., Ruiz F.

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In this paper, we propose a new Water Sustainability Indicator based on a Multi-Reference methodology that permits modeling compensation between the analysed criteria and provides a participative approach. The proposed indicator provides results based on 19 variables grouped into 5 dimensions: availability, access, resilience, good governance and economic capacity. The indicator was applied to assess water sustainability in 27 European countries. The results showed that Finland, the Netherlands, Sweden and the United Kingdom obtained the best global results in terms of weak water (compensatory) sustainability. In terms of strong water (non-compensatory) sustainability, no country gained acceptable results in terms of strong sustainability. Climate change and the state of freshwater resources were detected as especially vulnerable in all the analysed countries. The results identified some eastern European countries with low GDP and good performance of availability and cost of water, with bad results in terms of governance and water productivity. These results could jeopardize water sustainability in the event of a potential economic development if these limitations are not addressed. In a context of economic and political instability due to the current armed conflict in nearby countries such as Ukraine, it is especially important to pay attention to these countries, whose good governance indicators could worsen even more. The proposed indicator allowed to the identification of warning signs and could contribute to the improvement in decision-making processes. Moreover, it could improve the monitoring of international water policies.

Keywords: water sustainability, composite indicators, compensatory approach, sustainability European policies

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2243 Implementation of Unclos 1982 on Capture Fisheries in the Case of Illegal Fishing in the Waters of Indonesia’s Exclusive Economic Zone

Authors: Habson Batubara, Patawari, Lisa Mery, Mohammad Syaichuddin, Sitti Faridah, Hamzah, Akmal, Abdul Gafur, Iman Sudrajad, Lideman, Yuani Mundaya, Kamaruddin, Muslimin, Herlina Jompa, Joula Sondack, Nani Undap, Suciati, Elisa Winanda, Arfandi Amin, Suciati

Abstract:

This study aims to determine the status of the law, legislation, and its implementation against Foreign Nationals (WNA) Illegal Fishing Business Actors in the waters of the Indonesian Exclusive Economic Zone (EEZ), based on the Indonesian Positive Law and UNCLOS 1982. The research method used is normative juridical with a qualitative approach to study the Fisheries Criminal Verdict (Tipikan) and the Bitung District Court / Fisheries SIPP from 2019 to 2020. The results showed that cases of Illegal Fishing by Foreign Nationals (WNA) in the Indonesian Exclusive Economic Zone (EEZ) were examined, tried, and decided in accordance with the fisheries law, criminal sanctions were not in accordance with and contrary to Indonesian positive law, both criminal law and fisheries law, but followed and were in line with UNCLOS Year 1982. Legal status and responsibility are only imposed on the master as the leader on board the ship as the representative of the ship owner/company. Meanwhile, the application of Indonesia's positive law to Unclos in 1982 was only in the form of fines and confiscation of evidence as an effort to seek compensation for illegal fishing activities in the waters of the Indonesian Exclusive Zone (EEZ).

Keywords: EEZ, illegal fishing, WNA, positive law, Unclos 1982

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2242 Research and Development of Net-Centric Information Sharing Platform

Authors: Wang Xiaoqing, Fang Youyuan, Zheng Yanxing, Gu Tianyang, Zong Jianjian, Tong Jinrong

Abstract:

Compared with traditional distributed environment, the net-centric environment brings on more demanding challenges for information sharing with the characteristics of ultra-large scale and strong distribution, dynamic, autonomy, heterogeneity, redundancy. This paper realizes an information sharing model and a series of core services, through which provides an open, flexible and scalable information sharing platform.

Keywords: net-centric environment, information sharing, metadata registry and catalog, cross-domain data access control

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2241 Ultradrawing and Ultimate Pensile Properties of Ultra-High Molecular Weight Polyethylene Nanocomposite Fibers Filled with Cellulose Nanofibers

Authors: Zhong-Dan Tu, Wang-Xi Fan, Yi-Chen Huang, Jen-Taut Yeh

Abstract:

Novel ultrahigh molecular weight polyethylene (UHMWPE)/cellulose nanofiber (CNF) (F100CNFy) and UHMWPE/modified cellulose nanofiber (MCNF) (F100MCNFxy) as-prepared nanocomposite fibers were prepared by spinning F100CNFy and F100MCNFxy gel solutions, respectively. Cellulose nanofibers were successfully prepared by proper acid treatment of cotton fibers using sulfuric acid solutions. The best prepared CNF is with specific surface areas around 120 m2/g and a nanofiber diameter of 20 nm. Modified cellulose nanofiber was prepared by grafting maleic anhydride grafted polyethylene (PE-g-MAH) onto cellulose nanofibers. The achievable draw ratio (Dra) values of each F100MCNFxy as-prepared fiber series specimens approached a maximal value as their MCNF contents reached the optimal value at 0.05 phr. In which, the maximum Dra value obtained for F100MCNFx0.05 as-prepared fiber specimen prepared at the optimal MCNF content reached another maximum value as the weight ratio of PE-g-MAH to CNF approach an optimal value at 6. Similar to those found for the achievable drawing properties of the as-prepared fibers, the orientation factor, tensile strength (σ f) and initial modulus (E) values of drawn F100MCNF6y fiber series specimens with a fixed draw ratio reach a maximal value as their MCNF contents approach the optimal value, wherein the σ f and E values of the drawn F100MCNFxy fiber specimens are significantly higher than those of the drawn F100 fiber specimens and corresponding drawn F100CNFy fiber specimens prepared at the same draw ratios and CNF contents but without modification. To understand the interesting ultradrawing, thermal, orientation and tensile properties of F100CNFy and F100MCNFxy fiber specimens, Fourier transform infra-red, specific surface areas, and transmission electron microcopic analyses of the original and modified CNF nanofillers were performed in this study.

Keywords: ultradrawing, cellulose nanofibers, ultrahigh molecular weight polyethylene, nanocomposite fibers

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2240 Psychological Factors Predicting Social Distance during the COVID-19 Pandemic: An Empirical Investigation

Authors: Calogero Lo Destro

Abstract:

Numerous nations around the world are facing exceptional challenges in employing measures to stop the spread of COVID-19. Following the recommendations of the World Health Organization, a series of preventive measures have been adopted. However, individuals must comply with these rules and recommendations in order to make these measures effective. While COVID-19 was climaxing, it seemed of crucial importance to analyze which psychosocial factors contribute to the acceptance of such preventive behavior, thus favoring the management of COVID-19 worldwide health crisis. In particular, the identification of aspects related to obstacles and facilitation of adherence to social distancing has been considered crucial in the containment of the virus spread. Since the virus was firstly detected in China, Asian people could be considered a relevant outgroup targeted for exclusion. We also hypothesized social distance could be influenced by characteristics of the target, such as smiling or coughing. 260 participants participated in this research on a voluntary basis. They filled a survey designed to explore a series of COVID-19 measures (such as exposure to virus and fear of infection). We also assessed participants state and trait anxiety. The dependent variable was social distance, based on a measure of seating distance designed ad hoc for the present work. Our hypothesis that participants could report greater distance in response to Asian people was not confirmed. On the other hand, significantly lower distance in response to smiling compared to coughing targets was reported. Adopting a regression analysis model, we found that participants' social distance, in response to both coughing and smiling targets, was predicted by fear of infection and by the perception COVID-19 could become a pandemic. Social distance in response to the coughing target was also significantly and positively predicted by age and state anxiety. In summary, the present work has sought to identify a set of psychological variables, which may still be predictive of social distancing.

Keywords: COVID-19, social distancing, health, preventive behaviors, risk of infection

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2239 Design, Synthesis and in-vitro Antitumor Evaluation of Some Novel Substituted Quinazoline Derivatives

Authors: Adel S. El-Azab, Alaa A. M. Abdel-Aziz, Ibrahim A. Al-Suwaidan, Amer M. Alanazi

Abstract:

A novel series of 2,3,6-trisubstitute quinazolinone were designed, synthesized, and evaluated for their in-vitro antitumor activity. 3 (Benzylideneamino)-6-chloro-2-p-tolylquinazolin-4(3H)-One, 2-[(4-oxo-3-phenethyl-3,4-dihydroquinazolin-2-yl)thio]-N-(3,4;5-trimethoxyphenyl) acetamide and 3-(3-benzyl-6-methyl-4-oxo-3, 4-dihydroquinazolin-2-ylthio)-N-(3,4,5-trimethoxyphenyl) propanamide have shown amazing broad spectrum antitumor activity with mean GI50; 15.8, 3.16, and 7.4 μM respectively compared to known Quinazoline Derivatives antitumor drug 5-FU mean GI50=22.6 μM.

Keywords: quinazoline derivatives, in vitro antitumor, synthesis, 5-FU, NCI

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2238 The Influence of Training on the Special Aerial Gymnastics Instruments on Selected C-Reactive Proteins in Cadets’ Serum

Authors: Z. Wochyński, K. A. Sobiech, Z. Kobos

Abstract:

To C-Reactive Proteins include ferritin, transferrin, and ceruloplasmin- metalloproteins. The study aimed at assessing an effect of training on the Special Aerial Gymnastics Instruments (SAGI) on changes of serum ferritin, transferrin, and ceruloplasmin and cadets’ physical fitness in comparison with a control group. Fifty-five cadets in the mean age 20 years were included into this study. They were divided into two groups: Group A (N=41) trained on SAGI and Group B (N=14) trained according the standard program of physical education (control group). In both groups, blood was a material for assays. Samples were collected twice before and after training at the start of the program (training I), during (training II), and after education program completion (training III). Commercially available kits were used to assay blood serum ferritin, transferrin, and ceruloplasmin. Cadets’ physical fitness was evaluated with exercise tests before and after education program completion. In Group A, serum post-exercise ferritin decreased statistically insignificantly in training I and II and increased in training III in comparison with pre-exercise values. In Group B, post-exercise serum ferritin decreased statistically insignificantly in training I and III and significantly increased in training II in comparison with the pre-exercise values. In Group A, serum transferrin decreased statistically insignificantly in training I, and significantly increased in training II, whereas in training III it increased insignificantly in comparison with pre-exercise values. In Group B, post-exercise serum transferrin increased statistically significantly in training I, II, and III in comparison with pre-exercise values. I n Group A, serum ceruloplasmin decreased in all three series in comparison with pre-exercise values. In Group B, serum ceruloplasmin increased significantly in training II. It was showed that the training on SAGI significantly decreased serum ceruloplasmin in Group A in all three series of assays and did not produce significant changes in serum ferritin also was showed significant increase in serum transferrin.

Keywords: special aerial gymnastics instruments, ferritin, ceruloplasmin, transferrin

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2237 Lineup Optimization Model of Basketball Players Based on the Prediction of Recursive Neural Networks

Authors: Wang Yichen, Haruka Yamashita

Abstract:

In recent years, in the field of sports, decision making such as member in the game and strategy of the game based on then analysis of the accumulated sports data are widely attempted. In fact, in the NBA basketball league where the world's highest level players gather, to win the games, teams analyze the data using various statistical techniques. However, it is difficult to analyze the game data for each play such as the ball tracking or motion of the players in the game, because the situation of the game changes rapidly, and the structure of the data should be complicated. Therefore, it is considered that the analysis method for real time game play data is proposed. In this research, we propose an analytical model for "determining the optimal lineup composition" using the real time play data, which is considered to be difficult for all coaches. In this study, because replacing the entire lineup is too complicated, and the actual question for the replacement of players is "whether or not the lineup should be changed", and “whether or not Small Ball lineup is adopted”. Therefore, we propose an analytical model for the optimal player selection problem based on Small Ball lineups. In basketball, we can accumulate scoring data for each play, which indicates a player's contribution to the game, and the scoring data can be considered as a time series data. In order to compare the importance of players in different situations and lineups, we combine RNN (Recurrent Neural Network) model, which can analyze time series data, and NN (Neural Network) model, which can analyze the situation on the field, to build the prediction model of score. This model is capable to identify the current optimal lineup for different situations. In this research, we collected all the data of accumulated data of NBA from 2019-2020. Then we apply the method to the actual basketball play data to verify the reliability of the proposed model.

Keywords: recurrent neural network, players lineup, basketball data, decision making model

Procedia PDF Downloads 126
2236 True Detective as a Southern Gothic: A Study of Its Music-Lyrics

Authors: Divya Sharma

Abstract:

Nic Pizzolatto’s True Detective offers profound mythological and philosophical ramblings for audiences with literary sensibilities. An American Sothern Gothic with its bayon landscape of the Gulf Coast of Louisiana, where two detectives Rustin Cohle and Martin Hart begin investigating the isolated murder of Dora Lange, only to discover an entrenched network of perversion and corruption, offers an existential outlook. The proposed research paper shall attempt to investigate the pervasive themes of gothic and existentialism in the music of the first season of the series.

Keywords: gothic, music, existentialism, mythology, philosophy

Procedia PDF Downloads 503
2235 Optimization of Bifurcation Performance on Pneumatic Branched Networks in next Generation Soft Robots

Authors: Van-Thanh Ho, Hyoungsoon Lee, Jaiyoung Ryu

Abstract:

Efficient pressure distribution within soft robotic systems, specifically to the pneumatic artificial muscle (PAM) regions, is essential to minimize energy consumption. This optimization involves adjusting reservoir pressure, pipe diameter, and branching network layout to reduce flow speed and pressure drop while enhancing flow efficiency. The outcome of this optimization is a lightweight power source and reduced mechanical impedance, enabling extended wear and movement. To achieve this, a branching network system was created by combining pipe components and intricate cross-sectional area variations, employing the principle of minimal work based on a complete virtual human exosuit. The results indicate that modifying the cross-sectional area of the branching network, gradually decreasing it, reduces velocity and enhances momentum compensation, preventing flow disturbances at separation regions. These optimized designs achieve uniform velocity distribution (uniformity index > 94%) prior to entering the connection pipe, with a pressure drop of less than 5%. The design must also consider the length-to-diameter ratio for fluid dynamic performance and production cost. This approach can be utilized to create a comprehensive PAM system, integrating well-designed tube networks and complex pneumatic models.

Keywords: pneumatic artificial muscles, pipe networks, pressure drop, compressible turbulent flow, uniformity flow, murray's law

Procedia PDF Downloads 69
2234 Springback Prediction for Sheet Metal Cold Stamping Using Convolutional Neural Networks

Authors: Lei Zhu, Nan Li

Abstract:

Cold stamping has been widely applied in the automotive industry for the mass production of a great range of automotive panels. Predicting the springback to ensure the dimensional accuracy of the cold-stamped components is a critical step. The main approaches for the prediction and compensation of springback in cold stamping include running Finite Element (FE) simulations and conducting experiments, which require forming process expertise and can be time-consuming and expensive for the design of cold stamping tools. Machine learning technologies have been proven and successfully applied in learning complex system behaviours using presentative samples. These technologies exhibit the promising potential to be used as supporting design tools for metal forming technologies. This study, for the first time, presents a novel application of a Convolutional Neural Network (CNN) based surrogate model to predict the springback fields for variable U-shape cold bending geometries. A dataset is created based on the U-shape cold bending geometries and the corresponding FE simulations results. The dataset is then applied to train the CNN surrogate model. The result shows that the surrogate model can achieve near indistinguishable full-field predictions in real-time when compared with the FE simulation results. The application of CNN in efficient springback prediction can be adopted in industrial settings to aid both conceptual and final component designs for designers without having manufacturing knowledge.

Keywords: springback, cold stamping, convolutional neural networks, machine learning

Procedia PDF Downloads 139
2233 Thulium Laser Vaporisation and Enucleation of Prostate in Patients on Anticoagulants and Antiplatelet Agents

Authors: Abdul Fatah, Naveenchandra Acharya, Vamshi Krishna, T. Shivaprasad, Ramesh Ramayya

Abstract:

Background: Significant number of patients with bladder outlet obstruction due to BPH are on anti-platelets and anticoagulants. Prostate surgery in this group of patients either in the form of TURP or Open prostatectomy is associated with increased risk of bleeding complications requiring transfusions, packing of the prostatic fossa or ligation or embolization of internal iliac arteries. Withholding of antiplatelets and anticoagulants may be associated with cardiac and other complications. Efficacy of Thulium Laser in the above group of patients was evaluated in terms of peri-operative, postoperative and delayed bleeding complications as well as cardiac events in peri-operative and immediate postoperative period. Methods: 217 patients with a mean age of 68.8 years were enrolled between March 2009 and March 2013 (36 months), and treated for BPH with ThuLEP. Every patient was evaluated at base line according to: Digital Rectal Examination (DRE), prostate volume, Post-Voided volume (PVR), International Prostate Symptoms Score (I-PSS), PSA values, urine analysis and urine culture, uroflowmetry. The post operative complications in the form of drop in hemoglobin level, transfusion rates, post –operative cardiac events within a period of 30 days, delayed hematuria and events like deep vein thrombosis and pulmonary embolism were noted. Results: Our data showed a better post-operative outcome in terms of, postoperative bleeding requiring intervention 7 (3.2%), transfusion rate 4 (1.8%) and cardiac events within a period of 30 days 4(1.8%), delayed hematuria within 6 months 2(0.9 %) compared other series of prostatectomies. Conclusion: The thulium LASER prostatectomy is a safe and effective option for patients with cardiac comorbidties and those patients who are on antiplatelet agents and anticoagulants. The complication rate is less as compared to larger series reported with open and transurethral prostatectomies.

Keywords: thulium laser, prostatectomy, antiplatelet agents, bleeding

Procedia PDF Downloads 389
2232 Comparison between the Roller-Foam and Neuromuscular Facilitation Stretching on Flexibility of Hamstrings Muscles

Authors: Paolo Ragazzi, Olivier Peillon, Paul Fauris, Mathias Simon, Raul Navarro, Juan Carlos Martin, Oriol Casasayas, Laura Pacheco, Albert Perez-Bellmunt

Abstract:

Introduction: The use of stretching techniques in the sports world is frequent and widely used for its many effects. One of the main benefits is the gain in flexibility, range of motion and facilitation of the sporting performance. Recently the use of Roller-Foam (RF) has spread in sports practice both at elite and recreational level for its benefits being similar to those observed in stretching. The objective of the following study is to compare the results of the Roller-Foam with the proprioceptive neuromuscular facilitation stretching (PNF) (one of the stretchings with more evidence) on the hamstring muscles. Study design: The design of the study is a single-blind, randomized controlled trial and the participants are 40 healthy volunteers. Intervention: The subjects are distributed randomly in one of the following groups; stretching (PNF) intervention group: 4 repetitions of PNF stretching (5seconds of contraction, 5 second of relaxation, 20 second stretch), Roller-Foam intervention group: 2 minutes of Roller-Foam was realized on the hamstring muscles. Main outcome measures: hamstring muscles flexibility was assessed at the beginning, during (30’’ of intervention) and the end of the session by using the Modified Sit and Reach test (MSR). Results: The baseline results data given in both groups are comparable to each other. The PNF group obtained an increase in flexibility of 3,1 cm at 30 seconds (first series) and of 5,1 cm at 2 minutes (the last of all series). The RF group obtained a 0,6 cm difference at 30 seconds and 2,4 cm after 2 minutes of application of roller foam. The results were statistically significant when comparing intragroups but not intergroups. Conclusions: Despite the fact that the use of roller foam is spreading in the sports and rehabilitation field, the results of the present study suggest that the gain of flexibility on the hamstrings is greater if PNF type stretches are used instead of RF. These results may be due to the fact that the use of roller foam intervened more in the fascial tissue, while the stretches intervene more in the myotendinous unit. Future studies are needed, increasing the sample number and diversifying the types of stretching.

Keywords: hamstring muscle, stretching, neuromuscular facilitation stretching, roller foam

Procedia PDF Downloads 183
2231 The Impact of Developing an Educational Unit in the Light of Twenty-First Century Skills in Developing Language Skills for Non-Arabic Speakers: A Proposed Program for Application to Students of Educational Series in Regular Schools

Authors: Erfan Abdeldaim Mohamed Ahmed Abdalla

Abstract:

The era of the knowledge explosion in which we live requires us to develop educational curricula quantitatively and qualitatively to adapt to the twenty-first-century skills of critical thinking, problem-solving, communication, cooperation, creativity, and innovation. The process of developing the curriculum is as significant as building it; in fact, the development of curricula may be more difficult than building them. And curriculum development includes analyzing needs, setting goals, designing the content and educational materials, creating language programs, developing teachers, applying for programmes in schools, monitoring and feedback, and then evaluating the language programme resulting from these processes. When we look back at the history of language teaching during the twentieth century, we find that developing the delivery method is the most crucial aspect of change in language teaching doctrines. The concept of delivery method in teaching is a systematic set of teaching practices based on a specific theory of language acquisition. This is a key consideration, as the process of development must include all the curriculum elements in its comprehensive sense: linguistically and non-linguistically. The various Arabic curricula provide the student with a set of units, each unit consisting of a set of linguistic elements. These elements are often not logically arranged, and more importantly, they neglect essential points and highlight other less important ones. Moreover, the educational curricula entail a great deal of monotony in the presentation of content, which makes it hard for the teacher to select adequate content; so that the teacher often navigates among diverse references to prepare a lesson and hardly finds the suitable one. Similarly, the student often gets bored when learning the Arabic language and fails to fulfill considerable progress in it. Therefore, the problem is not related to the lack of curricula, but the problem is the development of the curriculum with all its linguistic and non-linguistic elements in accordance with contemporary challenges and standards for teaching foreign languages. The Arabic library suffers from a lack of references for curriculum development. In this paper, the researcher investigates the elements of development, such as the teacher, content, methods, objectives, evaluation, and activities. Hence, a set of general guidelines in the field of educational development were reached. The paper highlights the need to identify weaknesses in educational curricula, decide the twenty-first-century skills that must be employed in Arabic education curricula, and the employment of foreign language teaching standards in current Arabic Curricula. The researcher assumes that the series of teaching Arabic to speakers of other languages in regular schools do not address the skills of the twenty-first century, which is what the researcher tries to apply in the proposed unit. The experimental method is the method of this study. It is based on two groups: experimental and control. The development of an educational unit will help build suitable educational series for students of the Arabic language in regular schools, in which twenty-first-century skills and standards for teaching foreign languages will be addressed and be more useful and attractive to students.

Keywords: curriculum, development, Arabic language, non-native, skills

Procedia PDF Downloads 77
2230 Ultracapacitor State-of-Energy Monitoring System with On-Line Parameter Identification

Authors: N. Reichbach, A. Kuperman

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The paper describes a design of a monitoring system for super capacitor packs in propulsion systems, allowing determining the instantaneous energy capacity under power loading. The system contains real-time recursive-least-squares identification mechanism, estimating the values of pack capacitance and equivalent series resistance. These values are required for accurate calculation of the state-of-energy.

Keywords: real-time monitoring, RLS identification algorithm, state-of-energy, super capacitor

Procedia PDF Downloads 526
2229 The Influence of Immunity on the Behavior and Dignity of Judges

Authors: D. Avnieli

Abstract:

Immunity of judges from liability represents a departure from the principle that all are equal under the law, and that victims may be granted compensation from their offenders. The purpose of the study is to determine if judicial immunity coincides with the need to ensure the existence of highly independent and incorruptible judiciary. Judges are immune from civil and criminal liability for their judicial acts. Judicial immunity is justified by the need to maintain complete independence and discretion of the judiciary. Scholars and judges believe that absolute immunity is needed to shield judges from pressures, threats, or outside interference. It is commonly accepted, that judges should be free to perform their judicial role in accordance with their assessment of the fact and their understanding of the law, without any restrictions, influences, inducements or interferences. In most countries, immunity applies when judges act in excess of jurisdiction. In some countries, it applies even when they act maliciously or corruptly. The only exception to absolute immunity applicable in all judicial systems is when judges act without jurisdiction over the subject matter. The Israeli Supreme Court recently decided to embrace absolute immunity and strike off a lawsuit of a refugee, who was unlawfully incarcerated. The Court ruled that the plaintiff cannot sue the State or the judge for damages. The questions of malice, dignity, and public scrutiny were not discussed. This paper, based on comparative analysis of many cases, aims to determine if immunity affects the dignity and behavior of judges. It demonstrates that most judges maintain their dignity and ethical code of behavior, but sometimes do not hesitate to act consciously in excess of jurisdiction, and in rare cases even corruptly. Therefore, in order to maintain independent and incorruptible judiciary, immunity should not be applied where judges act consciously in excess of jurisdiction or with malicious incentives.

Keywords: incorruptible judiciary, immunity, independent, judicial, judges, jurisdiction

Procedia PDF Downloads 99
2228 Analysis of Standard Tramway Surge Protection Methods Based on Real Cases

Authors: Alain Rousseau, Alfred Aragones, Gilles Rougier

Abstract:

The study is based on lightning and surge standards mainly the EN series 62305 for facility protection, EN series 61643 for Low Voltage Surge Protective Devices, High Voltage surge arrester standard en 60099-4 and the traction arrester standards namely EN 50526-1 and 50526-1 dealing respectively with railway applications fixed installations D.C. surge arresters and voltage limiting devices. The more severe stress for tramways installations is caused by direct lightning on the catenary line. In such case, the surge current propagates towards the various poles and sparkover the insulators leading to a lower stress. If the impact point is near enough, a significant surge current will flow towards the traction surge arrester that is installed on the catenary at the location the substation is connected. Another surge arrester can be installed at the entrance of the substation or even inside the rectifier to avoid insulation damages. In addition, surge arresters can be installed between + and – to avoid damaging sensitive circuits. Based on disturbances encountered in a substation following a lighting event, the engineering department of RATP has decided to investigate the cause of such damage and more generally to question the efficiency of the various possible protection means. Based on the example of a recent tramway line the paper present the result of a lightning study based on direct lightning strikes. As a matter of fact, the induced surges on the catenary are much more frequent but much less damaging. First, a lightning risk assessment is performed for the substations that takes into account direct lightning and induced lightning both on the substation and its connected lines such as the catenary. Then the paper deals with efficiency of the various surge arresters is discussed based on field experience and calculations. The efficiency of the earthing system used at the bottom of the pole is also addressed based on high frequency earthing measurement. As a conclusion, the paper is making recommendations for an enhanced efficiency of existing protection means.

Keywords: surge arrester, traction, lightning, risk, surge protective device

Procedia PDF Downloads 255
2227 FACTS Based Stabilization for Smart Grid Applications

Authors: Adel. M. Sharaf, Foad H. Gandoman

Abstract:

Nowadays, Photovoltaic-PV Farms/ Parks and large PV-Smart Grid Interface Schemes are emerging and commonly utilized in Renewable Energy distributed generation. However, PV-hybrid-Dc-Ac Schemes using interface power electronic converters usually has negative impact on power quality and stabilization of modern electrical network under load excursions and network fault conditions in smart grid. Consequently, robust FACTS based interface schemes are required to ensure efficient energy utilization and stabilization of bus voltages as well as limiting switching/fault onrush current condition. FACTS devices are also used in smart grid-Battery Interface and Storage Schemes with PV-Battery Storage hybrid systems as an elegant alternative to renewable energy utilization with backup battery storage for electric utility energy and demand side management to provide needed energy and power capacity under heavy load conditions. The paper presents a robust interface PV-Li-Ion Battery Storage Interface Scheme for Distribution/Utilization Low Voltage Interface using FACTS stabilization enhancement and dynamic maximum PV power tracking controllers. Digital simulation and validation of the proposed scheme is done using MATLAB/Simulink software environment for Low Voltage- Distribution/Utilization system feeding a hybrid Linear-Motorized inrush and nonlinear type loads from a DC-AC Interface VSC-6-pulse Inverter Fed from the PV Park/Farm with a back-up Li-Ion Storage Battery.

Keywords: AC FACTS, smart grid, stabilization, PV-battery storage, Switched Filter-Compensation (SFC)

Procedia PDF Downloads 406
2226 Biomimetic Dinitrosyl Iron Complexes: A Synthetic, Structural, and Spectroscopic Study

Authors: Lijuan Li

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Nitric oxide (NO) has become a fascinating entity in biological chemistry over the past few years. It is a gaseous lipophilic radical molecule that plays important roles in several physiological and pathophysiological processes in mammals, including activating the immune response, serving as a neurotransmitter, regulating the cardiovascular system, and acting as an endothelium-derived relaxing factor. NO functions in eukaryotes both as a signal molecule at nanomolar concentrations and as a cytotoxic agent at micromolar concentrations. The latter arises from the ability of NO to react readily with a variety of cellular targets leading to thiol S-nitrosation, amino acid N-nitrosation, and nitrosative DNA damage. Nitric oxide can readily bind to metals to give metal-nitrosyl (M-NO) complexes. Some of these species are known to play roles in biological NO storage and transport. These complexes have different biological, photochemical, or spectroscopic properties due to distinctive structural features. These recent discoveries have spawned a great interest in the development of transition metal complexes containing NO, particularly its iron complexes that are central to the role of nitric oxide in the body. Spectroscopic evidence would appear to implicate species of “Fe(NO)2+” type in a variety of processes ranging from polymerization, carcinogenesis, to nitric oxide stores. Our research focuses on isolation and structural studies of non-heme iron nitrosyls that mimic biologically active compounds and can potentially be used for anticancer drug therapy. We have shown that reactions between Fe(NO)2(CO)2 and a series of imidazoles generated new non-heme iron nitrosyls of the form Fe(NO)2(L)2 [L = imidazole, 1-methylimidazole, 4-methylimidazole, benzimidazole, 5,6-dimethylbenzimidazole, and L-histidine] and a tetrameric cluster of [Fe(NO)2(L)]4 (L=Im, 4-MeIm, BzIm, and Me2BzIm), resulted from the interactions of Fe(NO)2 with a series of substituted imidazoles was prepared. Recently, a series of sulfur bridged iron di nitrosyl complexes with the general formula of [Fe(µ-RS)(NO)2]2 (R = n-Pr, t-Bu, 6-methyl-2-pyridyl, and 4,6-dimethyl-2-pyrimidyl), were synthesized by the reaction of Fe(NO)2(CO)2 with thiols or thiolates. Their structures and properties were studied by IR, UV-vis, 1H-NMR, EPR, electrochemistry, X-ray diffraction analysis and DFT calculations. IR spectra of these complexes display one weak and two strong NO stretching frequencies (νNO) in solution, but only two strong νNO in solid. DFT calculations suggest that two spatial isomers of these complexes bear 3 Kcal energy difference in solution. The paramagnetic complexes [Fe2(µ-RS)2(NO)4]-, have also been investigated by EPR spectroscopy. Interestingly, the EPR spectra of complexes exhibit an isotropic signal of g = 1.998 - 2.004 without hyperfine splitting. The observations are consistent with the results of calculations, which reveal that the unpaired electron dominantly delocalize over the two sulfur and two iron atoms. The difference of the g values between the reduced form of iron-sulfur clusters and the typical monomeric di nitrosyl iron complexes is explained, for the first time, by of the difference in unpaired electron distributions between the two types of complexes, which provides the theoretical basis for the use of g value as a spectroscopic tool to differentiate these biologically active complexes.

Keywords: di nitrosyl iron complex, metal nitrosyl, non-heme iron, nitric oxide

Procedia PDF Downloads 300