Search results for: relative rates
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 5085

Search results for: relative rates

4455 Oncoplastic Augmentation Mastopexy: Aesthetic Revisional Surgery in Breast Conserving Therapy

Authors: Bar Y. Ainuz, Harry M. Salinas, Aleeza Ali, Eli B. Levitt, Austin J. Pourmoussa, Antoun Bouz, Miguel A. Medina

Abstract:

Introduction: Breast conservation therapy remains the mainstay surgical treatment for early breast cancer. Oncoplastic techniques, in conjunction with lumpectomy and adjuvant radiotherapy, have been demonstrated to achieve good aesthetic results without adversely affecting cancer outcomes in the treatment of patients with macromastia or significant ptosis. In our patient population, many women present for breast conservation with pre-existing cosmetic implants or with breast volumes too small for soft tissue, only oncoplastic techniques. Our study evaluated a consecutive series of patients presenting for breast conservation undergoing concomitant oncoplastic-augmentation-mastopexy (OAM) with a contralateral augmentation-mastopexy for symmetry. Methods: OAM surgical technique involves simultaneous lumpectomy with exchange or placement of implants, oncoplastic mastopexy, and concomitant contralateral augmentation mastopexy for symmetry. Patients undergoing lumpectomy for breast conservation as outpatients were identified via retrospective chart review at a high volume private academic affiliated community-based cancer center. Patients with ptosis and either pre-existing breast implants or insufficient breast volume undergoing oncoplastic implant placement (or exchange) and mastopexy were included in the study. Operative details, aesthetic outcomes, and complications were assessed. Results: Over a continuous three-year period, with a two-surgeon cohort, 30 consecutive patients (56 breasts, 4 unilateral procedures) were identified. Patients had an average age of 52.5 years and an average BMI of 27.5, with 40% smokers or former smokers. The average operative time was 2.5 hours, the average implant size removed was 352 cc, and the average implant size placed was 300 cc. All new implants were smooth silicone, with the majority (92%) placed in a retropectoral fashion. 40% of patients received chemotherapy, and 80% of patients received whole breast adjuvant photon radiotherapy with a total radiation dose of either 42.56 or 52.56 Gy. The average and median length of follow-up were both 8.2 months. Of the 24 patients that received radiotherapy, 21% had asymmetry due to capsular contracture. A total of 7 patients (29.2%) underwent revisions for either positive margins (12.5%), capsular contracture (8.3%), implant loss (4.2%), or cosmetic concerns (4.2%). One patient developed a pulmonary embolism in the acute postoperative period and was treated with anticoagulant therapy. Conclusion: Oncoplastic augmentation mastopexy is a safe technique with good aesthetic outcomes and acceptable complication rates for ptotic patients with breast cancer and a paucity of breast volume or pre-existing implants who wish to pursue breast-conserving therapy. The revision rates compare favorably with single-stage cosmetic augmentation procedures as well as other oncoplastic techniques described in the literature. The short-term capsular contracture rates seem lower than the rates in patients undergoing radiation after mastectomy and implant-based reconstruction. Long term capsular contractures and revision rates are too early to know in this cohort.

Keywords: breast conserving therapy, oncoplastic augmentation mastopexy, capsular contracture, breast reconstruction

Procedia PDF Downloads 137
4454 Sensorless Machine Parameter-Free Control of Doubly Fed Reluctance Wind Turbine Generator

Authors: Mohammad R. Aghakashkooli, Milutin G. Jovanovic

Abstract:

The brushless doubly-fed reluctance generator (BDFRG) is an emerging, medium-speed alternative to a conventional wound rotor slip-ring doubly-fed induction generator (DFIG) in wind energy conversion systems (WECS). It can provide competitive overall performance and similar low failure rates of a typically 30% rated back-to-back power electronics converter in 2:1 speed ranges but with the following important reliability and cost advantages over DFIG: the maintenance-free operation afforded by its brushless structure, 50% synchronous speed with the same number of rotor poles (allowing the use of a more compact, and more efficient two-stage gearbox instead of a vulnerable three-stage one), and superior grid integration properties including simpler protection for the low voltage ride through compliance of the fractional converter due to the comparatively higher leakage inductances and lower fault currents. Vector controlled pulse-width-modulated converters generally feature a much lower total harmonic distortion relative to hysteresis counterparts with variable switching rates and as such have been a predominant choice for BDFRG (and DFIG) wind turbines. Eliminating a shaft position sensor, which is often required for control implementation in this case, would be desirable to address the associated reliability issues. This fact has largely motivated the recent growing research of sensorless methods and developments of various rotor position and/or speed estimation techniques for this purpose. The main limitation of all the observer-based control approaches for grid-connected wind power applications of the BDFRG reported in the open literature is the requirement for pre-commissioning procedures and prior knowledge of the machine inductances, which are usually difficult to accurately identify by off-line testing. A model reference adaptive system (MRAS) based sensor-less vector control scheme to be presented will overcome this shortcoming. The true machine parameter independence of the proposed field-oriented algorithm, offering robust, inherently decoupled real and reactive power control of the grid-connected winding, is achieved by on-line estimation of the inductance ratio, the underlying rotor angular velocity and position MRAS observer being reliant upon. Such an observer configuration will be more practical to implement and clearly preferable to the existing machine parameter dependent solutions, and especially bearing in mind that with very little modifications it can be adapted for commercial DFIGs with immediately obvious further industrial benefits and prospects of this work. The excellent encoder-less controller performance with maximum power point tracking in the base speed region will be demonstrated by realistic simulation studies using large-scale BDFRG design data and verified by experimental results on a small laboratory prototype of the WECS emulation facility.

Keywords: brushless doubly fed reluctance generator, model reference adaptive system, sensorless vector control, wind energy conversion

Procedia PDF Downloads 62
4453 Investigation of the Inhibition Effect of 2,3-Diaminopyridine on Mild Steel Corrosion in Solution Simulating Water of Pores Concrete in Absence and Presence of Chloride Ions

Authors: Fatiha Benghanem, Mokhtar Berarma, Saida Keraghel, Ali Ourari

Abstract:

Corrosion is the result of the reaction between a material and its environment. Steel in concrete is protected from corrosion by a passive film promoted by concrete alkalinity. For the initiation of corrosion, this protective film must be destroyed and this can be mainly done in two ways: by the attack of chlorides on the steel or by carbonation of the cover concrete due the reaction with carbon dioxide, which causes reduction in the alkalinity of concrete. The literature reports several ways to decrease or to prevent reinforcement corrosion. Among them, the use of corrosion inhibitors has been an envisaged solution. Two approaches are generally used to evaluate the efficiency of inhibitors for concrete application; one uses simulated pore solution testing , and the other uses actual concrete or mortar specimens. Both methods are some times used in conjunction. The aim of this study is to investigate the use of 2,3-diaminopyridine as a corrosion inhibitors of steel in alkaline media which simulate the electrolyte in the concrete pores. The effectiveness of this compound as corrosion inhibitor was investigated by measuring the corrosion potentials, the polarization curves and the corrosion current densities of steel with and without chlorides. The study of corrosion inhibition by this compound led to the conclusion that he has low rates of inhibition in the absence of aggressive ions and high rates in their presence. This type of organic compounds are promoting for the protection of armatures in concrete.

Keywords: corrosion, inhibitors, mild steel, conjunction

Procedia PDF Downloads 441
4452 Comparison of the Isolation Rates and Characteristics of Salmonella Isolated from Antibiotic-Free and Conventional Chicken Meat Samples

Authors: Jin-Hyeong Park, Hong-Seok Kim, Jin-Hyeok Yim, Young-Ji Kim, Dong-Hyeon Kim, Jung-Whan Chon, Kun-Ho Seo

Abstract:

Salmonella contamination in chicken samples can cause major health problems in humans. However, not only the effects of antibiotic treatment during growth but also the impacts of poultry slaughter line on the prevalence of Salmonella in final chicken meat sold to consumers are unknown. In this study, we compared the isolation rates and antimicrobial resistance of Salmonella between antibiotic-free, conventional, conventional Korean native retail chicken meat samples and clonal divergence of Salmonella isolates by multilocus sequence typing. In addition, the distribution of extended-spectrum β-lactamase (ESBL) genes in ESBL-producing Salmonella isolates was analyzed. A total of 72 retail chicken meat samples (n = 24 antibiotic-free broiler [AFB] chickens, n = 24 conventional broiler [CB] chickens, and n = 24 conventional Korean native [CK] chickens) were collected from local retail markets in Seoul, South Korea. The isolation rates of Salmonella were 66.6% in AFB chickens, 45.8% in CB chickens, and 25% in CK chickens. By analyzing the minimum inhibitory concentrations of β -lactam antibiotics with the disc-diffusion test, we found that 81.2% of Salmonella isolates from AFB chickens, 63.6% of isolates from CB chickens, and 50% of isolates from CK chickens were ESBL producers; all ESBL-positive isolates had the CTX-M-15 genotype. Interestingly, all ESBL-producing Salmonella were revealed as ST16 by multilocus sequence typing. In addition, all CTX-M-15-positive isolates had the genetic platform of blaCTX-M gene (IS26-ISEcp1-blaCTX-M-15-IS903), to the best of our knowledge, this is the first report in Salmonella around the world. The Salmonella ST33 strain (S. Hadar) isolated in this study has never been reported in South Korea. In conclusion, our findings showed that antibiotic-free retail chicken meat products were also largely contaminated with ESBL-producing Salmonella and that their ESBL genes and genetic platforms were the same as those isolated from conventional retail chicken meat products.

Keywords: antibiotic-free poultry, conventional poultry, multilocus sequence typing, extended-spectrum β-lactamase, antimicrobial resistance

Procedia PDF Downloads 277
4451 Aural Skills Pedagogy for Students with Absolute Pitch

Authors: Rika Uchida

Abstract:

In teaching sophomore level aural skills, I have dealt with students with absolute pitch do poorly in my courses, particularly in harmonic dictation. They can identify triads; however, identifying quality of seventh chords or chromatic chords poses serious challenges. Most often, they need to spell all the pitches before identifying the chord qualities and Roman Numerals. Growing up in a country where acquiring absolute pitch is considered essential, I started my early music training with fixed do system at age three and learned all my music with solfege. When I was assigned as a TA in aural skills courses at graduate school in US, I had to learn relative pitch quickly. My survival method was listening to music with absolute pitch first, then quickly "translate" to relative pitch. In teaching my courses, I have been using chord progressions (5-8 chords total), in which students are asked to sing chord arpeggiation with movable do solfege. I use same progressions for harmonic dictation; I hoped that students learn to incorporate singing and listening skills by overlapping same materials. This method has proven to be successful for most students; in particular, it has helped students with absolute pitch to hear chord quality and function. Although original progressions are written in C as a tonic, they can identify chords in harmonic dictation in other keys as well. In short, I believe singing chord progression with movable do arpeggiation helps students with absolute pitch to improve hearing function and quality of chords in harmonic dictation.

Keywords: aural skills pedagogy, music theory, absolute pitch, harmonic dictation

Procedia PDF Downloads 144
4450 Tailoring Piezoelectricity of PVDF Fibers with Voltage Polarity and Humidity in Electrospinning

Authors: Piotr K. Szewczyk, Arkadiusz Gradys, Sungkyun Kim, Luana Persano, Mateusz M. Marzec, Oleksander Kryshtal, Andrzej Bernasik, Sohini Kar-Narayan, Pawel Sajkiewicz, Urszula Stachewicz

Abstract:

Piezoelectric polymers have received great attention in smart textiles, wearables, and flexible electronics. Their potential applications range from devices that could operate without traditional power sources, through self-powering sensors, up to implantable biosensors. Semi-crystalline PVDF is often proposed as the main candidate for industrial-scale applications as it exhibits exceptional energy harvesting efficiency compared to other polymers combined with high mechanical strength and thermal stability. Plenty of approaches have been proposed for obtaining PVDF rich in the desired β-phase with electric polling, thermal annealing, and mechanical stretching being the most prevalent. Electrospinning is a highly tunable technique that provides a one-step process of obtaining highly piezoelectric PVDF fibers without the need for post-treatment. In this study, voltage polarity and relative humidity influence on electrospun PVDF, fibers were investigated with the main focus on piezoelectric β-phase contents and piezoelectric performance. Morphology and internal structure of fibers were investigated using scanning (SEM) and transmission electron microscopy techniques (TEM). Fourier Transform Infrared Spectroscopy (FITR), wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) were used to characterize the phase composition of electrospun PVDF. Additionally, surface chemistry was verified with X-ray photoelectron spectroscopy (XPS). Piezoelectric performance of individual electrospun PVDF fibers was measured using piezoresponse force microscopy (PFM), and the power output from meshes was analyzed via custom-built equipment. To prepare the solution for electrospinning, PVDF pellets were dissolved in dimethylacetamide and acetone solution in a 1:1 ratio to achieve a 24% solution. Fibers were electrospun with a constant voltage of +/-15kV applied to the stainless steel nozzle with the inner diameter of 0.8mm. The flow rate was kept constant at 6mlh⁻¹. The electrospinning of PVDF was performed at T = 25°C and relative humidity of 30 and 60% for PVDF30+/- and PVDF60+/- samples respectively in the environmental chamber. The SEM and TEM analysis of fibers produced at a lower relative humidity of 30% (PVDF30+/-) showed a smooth surface in opposition to fibers obtained at 60% relative humidity (PVDF60+/-), which had wrinkled surface and additionally internal voids. XPS results confirmed lower fluorine content at the surface of PVDF- fibers obtained by electrospinning with negative voltage polarity comparing to the PVDF+ obtained with positive voltage polarity. Changes in surface composition measured with XPS were found to influence the piezoelectric performance of obtained fibers what was further confirmed by PFM as well as by custom-built fiber-based piezoelectric generator. For PVDF60+/- samples humidity led to an increase of β-phase contents in PVDF fibers as confirmed by FTIR, WAXS, and DSC measurements, which showed almost two times higher concentrations of β-phase. A combination of negative voltage polarity with high relative humidity led to fibers with the highest β-phase contents and the best piezoelectric performance of all investigated samples. This study outlines the possibility to produce electrospun PVDF fibers with tunable piezoelectric performance in a one-step electrospinning process by controlling relative humidity and voltage polarity conditions. Acknowledgment: This research was conducted within the funding from m the Sonata Bis 5 project granted by National Science Centre, No 2015/18/E/ST5/00230, and supported by the infrastructure at International Centre of Electron Microscopy for Materials Science (IC-EM) at AGH University of Science and Technology. The PFM measurements were supported by an STSM Grant from COST Action CA17107.

Keywords: crystallinity, electrospinning, PVDF, voltage polarity

Procedia PDF Downloads 134
4449 Experimental Study of Moisture Effect on the Mechanical Behavior of Flax Fiber Reinforcement

Authors: Marwa Abida, Florian Gehring, Jamel Mars, Alexandre Vivet, Fakhreddine Dammak, Mohamed Haddar

Abstract:

The demand for bio-based materials in semi-structural and structural applications is constantly growing to conform to new environmental policies. Among them, Plant Fiber Reinforced Composites (PFRC) are attractive for the scientific community as well as the industrial world. Due to their relatively low densities and low environmental impact, vegetal fibers appear to be suitable as reinforcing materials for polymers. However, the major issue of plant fibers and PFRC in general is their hydrophilic behavior (high affinity to water molecules). Indeed, when absorbed, water causes fiber swelling and a loss of mechanical properties. Thus, the environmental loadings (moisture, temperature, UV) can strongly affect their mechanical properties and therefore play a critical role in the service life of PFRC. In order to analyze the influence of conditioning at relative humidity on the behavior of flax fiber reinforced composites, a preliminary study on flax fabrics has been conducted. The conditioning of the fabrics in different humid atmospheres made it possible to study the influence of the water content on the hygro-mechanical behavior of flax reinforcement through mechanical tensile tests. This work shows that increasing the relative humidity of the atmosphere induces an increase of the water content in the samples. It also brings up the significant influence of water content on the stiffness and elongation at break of the fabric, while no significant change of the breaking load is detected. Non-linear decrease of flax fabric rigidity and increase of its elongation at maximal force with the increase of water content are observed. It is concluded that water molecules act as a softening agent on flax fabrics. Two kinds of typical tensile curves are identified. Most of the tensile curves of samples show one unique linear region where the behavior appears to be linear prior to the first yarn failure. For some samples in which water content is between 2.7 % and 3.7 % (regardless the conditioning atmosphere), the emergence of a two-linear region behavior is pointed out. This phenomenon could be explained by local heterogeneities of water content which could induce premature local plasticity in some regions of the flax fabric sample behavior.

Keywords: hygro-mechanical behavior, hygroscopy, flax fabric, relative humidity, mechanical properties

Procedia PDF Downloads 188
4448 High Accuracy Analytic Approximations for Modified Bessel Functions I₀(x)

Authors: Pablo Martin, Jorge Olivares, Fernando Maass

Abstract:

A method to obtain analytic approximations for special function of interest in engineering and physics is described here. Each approximate function will be valid for every positive value of the variable and accuracy will be high and increasing with the number of parameters to determine. The general technique will be shown through an application to the modified Bessel function of order zero, I₀(x). The form and the calculation of the parameters are performed with the simultaneous use of the power series and asymptotic expansion. As in Padé method rational functions are used, but now they are combined with other elementary functions as; fractional powers, hyperbolic, trigonometric and exponential functions, and others. The elementary function is determined, considering that the approximate function should be a bridge between the power series and the asymptotic expansion. In the case of the I₀(x) function two analytic approximations have been already determined. The simplest one is (1+x²/4)⁻¹/⁴(1+0.24273x²) cosh(x)/(1+0.43023x²). The parameters of I₀(x) were determined using the leading term of the asymptotic expansion and two coefficients of the power series, and the maximum relative error is 0.05. In a second case, two terms of the asymptotic expansion were used and 4 of the power series and the maximum relative error is 0.001 at x≈9.5. Approximations with much higher accuracy will be also shown. In conclusion a new technique is described to obtain analytic approximations to some functions of interest in sciences, such that they have a high accuracy, they are valid for every positive value of the variable, they can be integrated and differentiated as the usual, functions, and furthermore they can be calculated easily even with a regular pocket calculator.

Keywords: analytic approximations, mathematical-physics applications, quasi-rational functions, special functions

Procedia PDF Downloads 250
4447 Exploring the Impact of Tillage and Manure on Soil Water Retention and Van Genuchten

Authors: Azadeh Safadoust, Ali Akbar Mahboubi

Abstract:

A study was conducted to evaluate hydraulic properties of a sandy loam soil and corn (Zea mays L.) crop production under a short-term tillage and manure combinations field experiment carried out in west of Iran. Treatments included composted cattle manure application rates [0, 30, and 60 Mg (dry weight) ha-1] and tillage systems [no-tillage (NT), chisel plowing (CP), and moldboard plowing (MP)] arranged in a split-plot design. Soil water characteristic curve (SWCC) and saturated hydraulic conductivity (Ks) were significantly affected by manure and tillage treatments. At any matric suction, the soil water content was in the order of MP>CP>NT. At all matric suctions, the amount of water retained by the soil increased as manure application rate increased (i.e. 60>30>0 Mg ha-1). Similar to the tillage effects, at high suctions the differences of water retained due to manure addition were less than that at low suctions. The change of SWCC from tillage methods and manure applications may attribute to the change of pore size and aggregate size distributions. Soil Ks was in the order of CP>MP>NT for the first two layers and in the order of MP>CP and NT for the deeper soil layer. The Ks also increased with increasing rates of manure application (i.e. 60>30>0 Mg ha-1). This was due to the increase in the total pore size and continuity.

Keywords: corn, manure, saturated hydraulic conductivity, soil water characteristic curve, tillage

Procedia PDF Downloads 75
4446 Modeling and Optimization of a Microfluidic Electrochemical Cell for the Electro-Reduction of CO₂ to CH₃OH

Authors: Barzin Rajabloo, Martin Desilets

Abstract:

First, an electrochemical model for the reduction of CO₂ into CH₃OH is developed in which mass and charge transfer, reactions at the surface of the electrodes and fluid flow of the electrolyte are considered. This mathematical model is developed in COMSOL Multiphysics® where both secondary and tertiary current distribution interfaces are coupled to consider concentrations and potentials inside different parts of the cell. Constant reaction rates are assumed as the fitted parameters to minimize the error between experimental data and modeling results. The model is validated through a comparison with experimental data in terms of faradaic efficiency for production of CH₃OH, the current density in different applied cathode potentials as well as current density in different electrolyte flow rates. The comparison between model outputs and experimental measurements shows a good agreement. The model indicates the higher hydrogen evolution in comparison with CH₃OH production as well as mass transfer limitation caused by CO₂ concentration, which are consistent with findings in the literature. After validating the model, in the second part of the study, some design parameters of the cell, such as cathode geometry and catholyte/anolyte channel widths, are modified to reach better performance and higher faradaic efficiency of methanol production.

Keywords: carbon dioxide, electrochemical reduction, methanol, modeling

Procedia PDF Downloads 109
4445 Modeling of Age Hardening Process Using Adaptive Neuro-Fuzzy Inference System: Results from Aluminum Alloy A356/Cow Horn Particulate Composite

Authors: Chidozie C. Nwobi-Okoye, Basil Q. Ochieze, Stanley Okiy

Abstract:

This research reports on the modeling of age hardening process using adaptive neuro-fuzzy inference system (ANFIS). The age hardening output (Hardness) was predicted using ANFIS. The input parameters were ageing time, temperature and percentage composition of cow horn particles (CHp%). The results show the correlation coefficient (R) of the predicted hardness values versus the measured values was of 0.9985. Subsequently, values outside the experimental data points were predicted. When the temperature was kept constant, and other input parameters were varied, the average relative error of the predicted values was 0.0931%. When the temperature was varied, and other input parameters kept constant, the average relative error of the hardness values predictions was 80%. The results show that ANFIS with coarse experimental data points for learning is not very effective in predicting process outputs in the age hardening operation of A356 alloy/CHp particulate composite. The fine experimental data requirements by ANFIS make it more expensive in modeling and optimization of age hardening operations of A356 alloy/CHp particulate composite.

Keywords: adaptive neuro-fuzzy inference system (ANFIS), age hardening, aluminum alloy, metal matrix composite

Procedia PDF Downloads 153
4444 Determination of Direct Solar Radiation Using Atmospheric Physics Models

Authors: Pattra Pukdeekiat, Siriluk Ruangrungrote

Abstract:

This work was originated to precisely determine direct solar radiation by using atmospheric physics models since the accurate prediction of solar radiation is necessary and useful for solar energy applications including atmospheric research. The possible models and techniques for a calculation of regional direct solar radiation were challenging and compulsory for the case of unavailable instrumental measurement. The investigation was mathematically governed by six astronomical parameters i.e. declination (δ), hour angle (ω), solar time, solar zenith angle (θz), extraterrestrial radiation (Iso) and eccentricity (E0) along with two atmospheric parameters i.e. air mass (mr) and dew point temperature at Bangna meteorological station (13.67° N, 100.61° E) in Bangkok, Thailand. Analyses of five models of solar radiation determination with the assumption of clear sky were applied accompanied by three statistical tests: Mean Bias Difference (MBD), Root Mean Square Difference (RMSD) and Coefficient of determination (R2) in order to validate the accuracy of obtainable results. The calculated direct solar radiation was in a range of 491-505 Watt/m2 with relative percentage error 8.41% for winter and 532-540 Watt/m2 with relative percentage error 4.89% for summer 2014. Additionally, dataset of seven continuous days, representing both seasons were considered with the MBD, RMSD and R2 of -0.08, 0.25, 0.86 and -0.14, 0.35, 3.29, respectively, which belong to Kumar model for winter and CSR model for summer. In summary, the determination of direct solar radiation based on atmospheric models and empirical equations could advantageously provide immediate and reliable values of the solar components for any site in the region without a constraint of actual measurement.

Keywords: atmospheric physics models, astronomical parameters, atmospheric parameters, clear sky condition

Procedia PDF Downloads 409
4443 Analysis and Study of Growth Rates of Indigenous Phytoplankton in Enriched Spent Oil Impacted Ecosystems in South Western Nigeria Coastal Waters

Authors: Lauretta Ighedo, Bukola Okunade, Monisade Okunade

Abstract:

In order to determine the effect of spent oil on the growth rates of indigenous phytoplankton in an aquaculture pond, a study was carried out on varying concentrations of samples using the bioassay procedure for a period of 14 days. Four divisions Cyanophyta, Chlorophyta, Euglenophyta and Bacillariophyta were observed in the water samples collected from the Aquaculture pond. The growth response was measured using a microprocessor photocolorimeter at optical density of 680nm. A general assessment of spent oil contaminated samples showed either a sharp rise or fall in growth rate from day 0 to day 2 followed by increased growth response for most higher concentration of pollutants up to Day 8, then fluctuations in the growth response pattern for the other days. There was no marked significant difference in the growth response of phytoplankton in the spent oil impacted water samples. The lowest and highest phytoplankton abundance was recorded in 10/90ml and 2.5/97.5ml spent oil impacted water sample respectively. Oscillatoria limosa, Chlorella sp., Microcystis aeruginosa, Nitzschia sp. and Navicula sp. showed high tolerance to oil pollution and these species used as bioindicators of an organic polluted environment increased abundantly and can therefore be employed in the cleanup and bioremediation process of an oil polluted freshwater body.

Keywords: phytoplankton, pollution, species abundance, environmental characteristics

Procedia PDF Downloads 372
4442 An Analysis of Pick Travel Distances for Non-Traditional Unit Load Warehouses with Multiple P/D Points

Authors: Subir S. Rao

Abstract:

Existing warehouse configurations use non-traditional aisle designs with a central P/D point in their models, which is mathematically simple but less practical. Many warehouses use multiple P/D points to avoid congestion for pickers, and different warehouses have different flow policies and infrastructure for using the P/D points. Many warehouses use multiple P/D points with non-traditional aisle designs in their analytical models. Standard warehouse models introduce one-sided multiple P/D points in a flying-V warehouse and minimize pick distance for a one-way travel between an active P/D point and a pick location with P/D points, assuming uniform flow rates. A simulation of the mathematical model generally uses four fixed configurations of P/D points which are on two different sides of the warehouse. It can be easily proved that if the source and destination P/D points are both chosen randomly, in a uniform way, then minimizing the one-way travel is the same as minimizing the two-way travel. Another warehouse configuration analytically models the warehouse for multiple one-sided P/D points while keeping the angle of the cross-aisles and picking aisles as a decision variable. The minimization of the one-way pick travel distance from the P/D point to the pick location by finding the optimal position/angle of the cross-aisle and picking aisle for warehouses having different numbers of multiple P/D points with variable flow rates is also one of the objectives. Most models of warehouses with multiple P/D points are one-way travel models and we extend these analytical models to minimize the two-way pick travel distance wherein the destination P/D is chosen optimally for the return route, which is not similar to minimizing the one-way travel. In most warehouse models, the return P/D is chosen randomly, but in our research, the return route P/D point is chosen optimally. Such warehouses are common in practice, where the flow rates at the P/D points are flexible and depend totally on the position of the picks. A good warehouse management system is efficient in consolidating orders over multiple P/D points in warehouses where the P/D is flexible in function. In the latter arrangement, pickers and shrink-wrap processes are not assigned to particular P/D points, which ultimately makes the P/D points more flexible and easy to use interchangeably for picking and deposits. The number of P/D points considered in this research uniformly increases from a single-central one to a maximum of each aisle symmetrically having a P/D point below it.

Keywords: non-traditional warehouse, V cross-aisle, multiple P/D point, pick travel distance

Procedia PDF Downloads 39
4441 Gene Expression Profiling of Iron-Related Genes of Pasteurella multocida Serotype A Strain PMTB2.1

Authors: Shagufta Jabeen, Faez Jesse Firdaus Abdullah, Zunita Zakaria, Nurulfiza Mat Isa, Yung Chie Tan, Wai Yan Yee, Abdul Rahman Omar

Abstract:

Pasteurella multocida is associated with acute, as well as, chronic infections in avian and bovine such as pasteurellosis and hemorrhagic septicemia (HS) in cattle and buffaloes. Iron is one of the most important nutrients for pathogenic bacteria including Pasteurella and acts as a cofactor or prosthetic group in several essential enzymes and is needed for amino acid, pyrimidine, and DNA biosynthesis. In our recent study, we showed that 2% of Pasteurella multocida serotype A strain PMTB2.1 encode for iron regulating genes (Accession number CP007205.1). Genome sequencing of other Pasteurella multocida serotypes namely PM70 and HB01 also indicated up to 2.5% of the respective genome encode for iron regulating genes, suggesting that Pasteurella multocida genome comprises of multiple systems for iron uptake. Since P. multocida PMTB2.1 has more than 40 CDs out of 2097 CDs (approximately 2%), encode for iron-regulated. The gene expression profiling of four iron-regulating genes namely fbpb, yfea, fece and fur were characterized under iron-restricted environment. The P. multocida strain PMTB2.1 was grown in broth with and without iron chelating agent and samples were collected at different time points. Relative mRNA expression profile of these genes was determined using Taqman probe based real-time PCR assay. The data analysis, normalization with two house-keeping genes and the quantification of fold changes were carried out using Bio-Rad CFX manager software version 3.1. Results of this study reflect that iron reduced environment has significant effect on expression profile of iron regulating genes (p < 0.05) when compared to control (normal broth) and all evaluated genes act differently with response to iron reduction in media. The highest relative fold change of fece gene was observed at early stage of treatment indicating that PMTB2.1 may utilize its periplasmic protein at early stage to acquire iron. Furthermore, down-regulation expression of fece with the elevated expression of other genes at later time points suggests that PMTB2.1 control their iron requirements in response to iron availability by down-regulating the expression of iron proteins. Moreover, significantly high relative fold change (p ≤ 0.05) of fbpb gene is probably associated with the ability of P. multocida to directly use host iron complex such as hem, hemoglobin. In addition, the significant increase (p ≤ 0.05) in fbpb and yfea expressions also reflects the utilization of multiple iron systems in P. multocida strain PMTB2.1. The findings of this study are very much important as relative scarcity of free iron within hosts creates a major barrier to microbial growth inside host and utilization of outer-membrane proteins system in iron acquisition probably occurred at early stage of infection with P. multocida. In conclusion, the presence and utilization of multiple iron system in P. multocida strain PMTB2.1 revealed the importance of iron in the survival of P. multocida.

Keywords: iron-related genes, real-time PCR, gene expression profiling, fold changes

Procedia PDF Downloads 460
4440 Incentive Policies to Promote Green Infrastructure in Urban Jordan

Authors: Zayed Freah Zeadat

Abstract:

The wellbeing of urban dwellers is strongly associated with the quality and quantity of green infrastructure. Nevertheless, urban green infrastructure is still lagging in many Arab cities, and Jordan is no exception. The capital city of Jordan, Amman, is becoming more urban dense with limited green spaces. The unplanned urban growth in Amman has caused several environmental problems such as urban heat islands, air pollution, and lack of green spaces. This study aims to investigate the most suitable drivers to leverage the implementation of urban green infrastructure in Jordan through qualitative and quantitative analysis. The qualitative research includes an extensive literature review to discuss the most common drivers used internationally to promote urban green infrastructure implementation in the literature. The quantitative study employs a questionnaire survey to rank the suitability of each driver. Consultants, contractors, and policymakers were invited to fill the research questionnaire according to their judgments and opinions. Relative Importance Index has been used to calculate the weighted average of all drivers and the Kruskal-Wallis test to check the degree of agreement among groups. This study finds that research participants agreed that indirect financial incentives (i.e., tax reductions, reduction in stormwater utility fee, reduction of interest rate, density bonus, etc.) are the most effective incentive policy whilst granting sustainability certificate policy is the least effective driver to ensure widespread of UGI is elements in Jordan.

Keywords: urban green infrastructure, relative importance index, sustainable urban development, urban Jordan

Procedia PDF Downloads 154
4439 Temporal Effects on Chemical Composition of Treated Wastewater and Borehole Water Used for Irrigation in Limpopo Province, South Africa

Authors: Pholosho M. Kgopa, Phatu W. Mashela, Alen Manyevere

Abstract:

Increasing incidents of drought spells in most Sub-Saharan Africa call for using alternative sources of water for irrigation in arid and semi-arid regions. A study was conducted to investigate chemical composition of borehole and treated wastewater from different sampling disposal sites at University of Limpopo Experimental Farm (ULEF). A 4 × 5 factorial experiment, with the borehole as a reference sampling site and three other sampling sites along the wastewater disposal system was conducted over five months. Water samples were collected at four sites namely, (a) exit from Pond 16 into the furrow, (b) entry into night-dam, (c) exit from night dam to irrigated fields and (d) exit from borehole to irrigated fields. Water samples were collected in the middle of each month, starting from July to November 2016. Samples were analysed for pH, EC, Ca, Mg, Na, K, Al, B, Zn, Cu, Cr, Pb, Cd and As. The site × time interactions were highly significant for Ca, Mg, Zn, Cu, Cr, Pb, Cd, and As variables, but not for Na and K. Sampling site was highly significant on all variables, with sampling period not significant for K and Na. Relative to water from the borehole, Na concentration in wastewater samples from the night-dam exit, night-dam entry and Pond16 exit were lower by 69, 34 and 55%, respectively. Relative to borehole water, Al was higher in wastewater sampling sites. In conclusion, both sampling site and period affected the chemical composition of treated wastewater.

Keywords: irrigation water quality, spatial effects, temporal effects, water reuse, water scarcity

Procedia PDF Downloads 238
4438 Hydrochemistry and Stable Isotopes (ẟ18O and ẟ2H) Tools Applied to the Study of Karst Aquifers in Wonderfonteinspruit Valley: North West, South Africa

Authors: Naziha Mokadem, Rainier Dennis, Ingrid Dennis

Abstract:

In South Africa, Karst aquifers are receiving greater attention since they provide large supplies of water which is used for domestic and agricultural purposes as well as for industry. Accordingly, a better insight into the origin of water mineralization and the geochemical processes controlling the recharge of the aquifer is crucial. Analyses of geochemical and environmental isotopes could lead to relevant information regarding karstification and infiltration processes, groundwater chemistry and isotopy. A study was conducted in a typical karst landscape of Wonderfonteinspruit catchment, also known as Wonderfonteinspruit Valley in North-western -South Africa. Furthermore, fifty-two samples were collected from (35 boreholes, 5 surface waters, 4 Dams, 4 springs, 1 canal, 2 pipelines, 1 cave) within the study area for hydrochemistry and 2H and 18O analysis. The determination of the anions (Cl-, SO42-, NO2, NO3-) were performed using Metrohm ion chromatography, model: 761 compact IC, with a precision of ± 0.001 mg/l. While, the cations (Na+, Mg2+, K+, Ca2+) were determined using Metrohm ion chromatography, Model: ICP-MS 7500 series. The alkalinity (Alk) was determined by pH meter with volumetric titration using HCL to pH 4.5; 4.2; and 8.2. In addition, 18O and 2H relative to the Vienna-Standard Mean Ocean Water (RVSMOW), were determined by picarro L2130-I Isotopic H2O (Cavity Ringdown laser spectrometer, Picarro Ltd). The hydrochemical analysis of Wonderfonteinspruit groundwater showed a dominance of the cations Ca-Mg and the anion HCO3. Piper diagram shows that the groundwater sample of study area is characterized by four hydrochemical facies: Two main groups: (1) Ca–Mg–Cl–SO4; (2) Ca–Mg–HCO3 and two minor groups: (3) Ca–Mg–Cl; (4) Na–K–HCO3. The majority of boreholes of Malmani (Transvaal Supergroup) aquifer are plotted in Ca–Mg–HCO3.Oxygen-18 (18O‰SMOW) and deuterium (D‰SMOW) isotopic data indicate that the aquifer’s recharge is influenced by two phenomena; precipitation rates for most of the samples and river flow (Wonderfonteinspruit, Middelvieinspruit, Renfonteinspruit) for some samples.

Keywords: South Africa, Wonderfonteinspruit Valley, isotopic, hydrochemical, carbonate aquifers

Procedia PDF Downloads 154
4437 In and Out-Of-Sample Performance of Non Simmetric Models in International Price Differential Forecasting in a Commodity Country Framework

Authors: Nicola Rubino

Abstract:

This paper presents an analysis of a group of commodity exporting countries' nominal exchange rate movements in relationship to the US dollar. Using a series of Unrestricted Self-exciting Threshold Autoregressive models (SETAR), we model and evaluate sixteen national CPI price differentials relative to the US dollar CPI. Out-of-sample forecast accuracy is evaluated through calculation of mean absolute error measures on the basis of two-hundred and fifty-three months rolling window forecasts and extended to three additional models, namely a logistic smooth transition regression (LSTAR), an additive non linear autoregressive model (AAR) and a simple linear Neural Network model (NNET). Our preliminary results confirm presence of some form of TAR non linearity in the majority of the countries analyzed, with a relatively higher goodness of fit, with respect to the linear AR(1) benchmark, in five countries out of sixteen considered. Although no model appears to statistically prevail over the other, our final out-of-sample forecast exercise shows that SETAR models tend to have quite poor relative forecasting performance, especially when compared to alternative non-linear specifications. Finally, by analyzing the implied half-lives of the > coefficients, our results confirms the presence, in the spirit of arbitrage band adjustment, of band convergence with an inner unit root behaviour in five of the sixteen countries analyzed.

Keywords: transition regression model, real exchange rate, nonlinearities, price differentials, PPP, commodity points

Procedia PDF Downloads 278
4436 Differentiating Morphological Patterns of the Common Benthic Anglerfishes from the Indian Waters

Authors: M. P. Rajeeshkumar, K. V. Aneesh Kumar, J. L. Otero-Ferrer, A. Lombarte, M. Hashim, N. Saravanane, V. N.Sanjeevan, V. M. Tuset

Abstract:

The anglerfishes are widely distributed from shallow to deep-water habitats and are highly diverse in morphology, behaviour, and niche occupancy patterns. To understand this interspecific variability and degree of niche overlap, we performed a functional analysis of five species inhabiting Indian waters where diversity of deep-sea anglerfishes is very high. The sensory capacities (otolith shape and eye size) were also studied to improve the understanding of coexistence of species. The analyses of fish body and otolith shape clustered species in two morphotypes related to phylogenetic lineages: i) Malthopsis lutea, Lophiodes lugubri and Halieutea coccinea were characterized by a dorso-ventrally flattened body with high swimming ability and relative small otoliths, and ii) Chaunax spp. were distinguished by their higher body depth, lower swimming efficiency, and relative big otoliths. The sensory organs did not show a pattern linked to depth distribution of species. However, the larger eye size in M. lutea suggested a nocturnal feeding activity, whereas Chaunax spp. had a large mouth and deeper body in response to different ecological niches. Therefore, the present study supports the hypothesis of spatial and temporal segregation of anglerfishes in the Indian waters, which can be explained from a functional approach and understanding from sensory capabilities.

Keywords: functional traits, otoliths, niche overlap, fishes, Indian waters

Procedia PDF Downloads 133
4435 Pharmacodynamic Enhancement of Repetitive rTMS Treatment Outcomes for Major Depressive Disorder

Authors: A. Mech

Abstract:

Repetitive transcranial magnetic stimulation has proven to be a valuable treatment option for patients who have failed to respond to multiple courses of antidepressant medication. In fact, the American Psychiatric Association recommends TMS after one failed treatment course of antidepressant medication. Genetic testing has proven valuable for pharmacokinetic variables, which, if understood, could lead to more efficient dosing of psychotropic medications to improve outcomes. Pharmacodynamic testing can identify biomarkers, which, if addressed, can improve patients' outcomes in antidepressant therapy. Monotherapy treatment of major depressive disorder with methylated B vitamin treatment has been shown to be safe and effective in patients with MTHFR polymorphisms without waiting for multiple trials of failed medication treatment for depression. Such treatment has demonstrated remission rates similar to antidepressant clinical trials. Combining pharmacodynamics testing with repetitive TMS treatment with NeuroStar has shown promising potential for enhancing remission rates and durability of treatment. In this study, a retrospective chart review (ongoing) of patients who obtained repetitive TMS treatment enhanced by dietary supplementation guided by Pharmacodynamic testing, displayed a greater remission rate (90%) than patients treated with only NeuroStar TMS (62%).

Keywords: improved remission rate, major depressive disorder, pharmacodynamic testing, rTMS outcomes

Procedia PDF Downloads 57
4434 Predictors of Academic Dishonesty among Serially Frustrated Students in Ogun State, Southwest, Nigeria

Authors: Oyesoji Aremu, Taiwo Williams

Abstract:

This study examined some factors (academic self-efficacy, locus of control, motivation and gender) that could predict academic dishonesty among serially frustrated students in Ogun State, South West, Nigeria. Serial academically frustrated students are students who are unable to attain and meet academic expectations set by themselves or significant others. A sample of 250 undergraduate students selected from two faculties from a University in Ogun State,South West Nigeria took part in the study. Multiple regression analysis was employed to determine the joint and relative contributions of the independent variables to the prediction of the dependent variable. T-test was used to test the hypothesis determining the gender difference between the independent variables (academic self-efficacy, locus of control and motivation) and academic dishonesty of serial academically frustrated male and female students. The results of the study showed all the independent variables jointly contributed to predicting academic dishonesty, while only academic self-efficacy and motivation had relative contributions to the dependent measure. There was no significant difference in the academic self-efficacy and motivation among males and females on academic dishonesty of the serial academically frustrated students but locus of control showed a significant difference between male and female students on academic dishonesty. Implications for counseling of the findings are discussed in the study.

Keywords: academic dishonesty, serially frustrated students, academic self-efficacy, locus of control

Procedia PDF Downloads 253
4433 Effects of Storage Methods on Proximate Compositions of African Yam Bean (Sphenostylis stenocarpa) Seeds

Authors: Iyabode A. Kehinde, Temitope A. Oyedele, Clement G. Afolabi

Abstract:

One of the limitations of African yam bean (AYB) (Sphenostylis sternocarpa) is poor storage ability due to the adverse effect of seed-borne fungi. This study was conducted to examine the effects of storage methods on the nutritive composition of AYB seeds stored in three types of storage materials viz; Jute bags, Polypropylene bags, and Plastic Bowls. Freshly harvested seeds of AYB seeds were stored in all the storage materials for 6 months using 2 × 3 factorial (2 AYB cultivars and 3 storage methods) in 3 replicates. The proximate analysis of the stored AYB seeds was carried out at 3 and 6 months after storage using standard methods. The temperature and relative humidity of the storeroom was recorded monthly with Kestrel pocket weather tracker 4000. Seeds stored in jute bags gave the best values for crude protein (24.87%), ash (5.69%) and fat content (6.64%) but recorded least values for crude fibre (2.55%), carbohydrate (50.86%) and moisture content (12.68%) at the 6th month of storage. The temperature of the storeroom decreased from 32.9ºC - 28.3ºC, while the relative humidity increased from 78% - 86%. Decreased incidence of field fungi namely: Rhizopus oryzae, Aspergillus flavus, Geotricum candidum, Aspergillus fumigatus and Mucor meihei was accompanied by the increase in storage fungi viz: Apergillus niger, Mucor hiemalis, Penicillium espansum and Penicillium atrovenetum with prolonged storage. The study showed that of the three storage materials jute bag was more effective at preserving AYB seeds.

Keywords: storage methods, proximate composition, African Yam Bean, fungi

Procedia PDF Downloads 134
4432 Control of Base Isolated Benchmark using Combined Control Strategy with Fuzzy Algorithm Subjected to Near-Field Earthquakes

Authors: Hashem Shariatmadar, Mozhgansadat Momtazdargahi

Abstract:

The purpose of control structure against earthquake is to dissipate earthquake input energy to the structure and reduce the plastic deformation of structural members. There are different methods for control structure against earthquake to reduce the structure response that they are active, semi-active, inactive and hybrid. In this paper two different combined control systems are used first system comprises base isolator and multi tuned mass dampers (BI & MTMD) and another combination is hybrid base isolator and multi tuned mass dampers (HBI & MTMD) for controlling an eight story isolated benchmark steel structure. Active control force of hybrid isolator is estimated by fuzzy logic algorithms. The influences of the combined systems on the responses of the benchmark structure under the two near-field earthquake (Newhall & Elcentro) are evaluated by nonlinear dynamic time history analysis. Applications of combined control systems consisting of passive or active systems installed in parallel to base-isolation bearings have the capability of reducing response quantities of base-isolated (relative and absolute displacement) structures significantly. Therefore in design and control of irregular isolated structures using the proposed control systems, structural demands (relative and absolute displacement and etc.) in each direction must be considered separately.

Keywords: base-isolated benchmark structure, multi-tuned mass dampers, hybrid isolators, near-field earthquake, fuzzy algorithm

Procedia PDF Downloads 304
4431 Mobility-Aware Relay Selection in Two Hop Unmanned Aerial Vehicles Network

Authors: Tayyaba Hussain, Sobia Jangsher, Saqib Ali, Saqib Ejaz

Abstract:

Unmanned Aerial vehicles (UAV’s) have gained great popularity due to their remoteness, ease of deployment and high maneuverability in different applications like real-time surveillance, image capturing, weather atmospheric studies, disaster site monitoring and mapping. These applications can involve a real-time communication with the ground station. However, altitude and mobility possess a few challenges for the communication. UAV’s at high altitude usually require more transmit power. One possible solution can be with the use of multi hops (UAV’s acting as relays) and exploiting the mobility pattern of the UAV’s. In this paper, we studied a relay (UAV’s acting as relays) selection for a reliable transmission to a destination UAV. We exploit the mobility information of the UAV’s to propose a Mobility-Aware Relay Selection (MARS) algorithm with the objective of giving improved data rates. The results are compared with Non Mobility-Aware relay selection scheme and optimal values. Numerical results show that our proposed MARS algorithm gives 6% better achievable data rates for the mobile UAV’s as compared with Non MobilityAware relay selection scheme. On average a decrease of 20.2% in data rate is achieved with MARS as compared with SDP solver in Yalmip.

Keywords: mobility aware, relay selection, time division multiple acess, unmanned aerial vehicle

Procedia PDF Downloads 238
4430 Proposal of Optimality Evaluation for Quantum Secure Communication Protocols by Taking the Average of the Main Protocol Parameters: Efficiency, Security and Practicality

Authors: Georgi Bebrov, Rozalina Dimova

Abstract:

In the field of quantum secure communication, there is no evaluation that characterizes quantum secure communication (QSC) protocols in a complete, general manner. The current paper addresses the problem concerning the lack of such an evaluation for QSC protocols by introducing an optimality evaluation, which is expressed as the average over the three main parameters of QSC protocols: efficiency, security, and practicality. For the efficiency evaluation, the common expression of this parameter is used, which incorporates all the classical and quantum resources (bits and qubits) utilized for transferring a certain amount of information (bits) in a secure manner. By using criteria approach whether or not certain criteria are met, an expression for the practicality evaluation is presented, which accounts for the complexity of the QSC practical realization. Based on the error rates that the common quantum attacks (Measurement and resend, Intercept and resend, probe attack, and entanglement swapping attack) induce, the security evaluation for a QSC protocol is proposed as the minimum function taken over the error rates of the mentioned quantum attacks. For the sake of clarity, an example is presented in order to show how the optimality is calculated.

Keywords: quantum cryptography, quantum secure communcation, quantum secure direct communcation security, quantum secure direct communcation efficiency, quantum secure direct communcation practicality

Procedia PDF Downloads 184
4429 Outcome of Anastomosis of Mechanically Prepared vs Mechanically Unprepared Bowel in Laparoscopic Anterior Resection in Surgical Units of Teaching Hospital Karapitiya ,Sri Lanka

Authors: K. P. v. R. de Silva, R. W. Senevirathna, M. M. A. J. Kumara, J. P. M. Kumarasinghe, R. L. Gunawardana, S. M. Uluwitiya, G. C. P. Jayawickrama, W. K. T. I. Madushani

Abstract:

Introduction: The limited literature supporting the utilization of mechanical bowel preparation (MBP) for patients undergoing laparoscopic anterior resection (LAR) remains a notable issue. This study was conducted to examine the clinical consequences of anastomosis in colorectal surgery with MBP compared to cases where MBP was not utilized (no-MBP) in the context of LAR. Methods: This was a retrospective comparative study conducted in the professorial surgical wards of the teaching hospital karapitiya (THK). Colorectal cancer patients(n=306) participated in the study, including 151 MBP patients and 155 no-MBP patients, where the postoperative complications and mortality rates were compared. Results: The anastomotic leakage rate was 2.6%(n=4) in the no-MBP group and 6.0%(n=9) in the MBP group (p=0.143). The postoperative paralytic ileus rate was 18.5%(n=28) and 5.8%(n=9) in the MBP group and no-MBP group, respectively, displaying a statistically significant difference (p=0.001). Wound infection, pneumonia, urinary tract infection, and cardiac complication rates also were higher in the MBP group. The overall mortality rate was 1.3%(n=3) in the no-MBP group and 2.0%(n=2) in the MBP group. Conclusions: The evidence concludes that MBP increases post-operative complications. Therefore, prophylactic MBP in LAR has not been proven to benefit patients. However, further research is necessary to understand the comparative effects of MBP versus no preparation comprehensively.

Keywords: MBP, anastomosis, LAR, paralytic ileus

Procedia PDF Downloads 92
4428 Correlation Analysis of Reactivity in the Oxidation of Para and Meta-Substituted Benzyl Alcohols by Benzimidazolium Dichromate in Non-Aqueous Media: A Kinetic and Mechanistic Aspects

Authors: Seema Kothari, Dinesh Panday

Abstract:

An observed correlation of the reaction rates with the changes in the nature of substituent present on one of the reactants often reveals the nature of transition state. Selective oxidation of organic compounds under non-aqueous media is an important transformation in synthetic organic chemistry. Inorganic chromates and dichromates being drastic oxidant and are generally insoluble in most organic solvents, a number of different chromium (VI) derivatives have been synthesized. Benzimidazolium dichromate (BIDC) is one of the recently reported Cr(VI) reagents which is neither hygroscopic nor light sensitive being, therefore, much stable. Not many reports on the kinetics of the oxidations by BIDC are seemed to be available in the literature. In the present investigation, the kinetics and mechanism of benzyl alcohol (BA) and a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, is reported. The reactions were followed spectrophotometrically at 364 nm by monitoring the decrease in [BIDC] for up to 85-90% reaction, the temperature being constant. The observed oxidation product is the corresponding benzaldehyde. The reactions were of first order with respect to each the alcohol and BIDC. The reactions are catalyzed by proton, and the dependence is of the form: kobs = a + b[H+]. The reactions thus follow both, an acid-dependent and acid-independent paths. The oxidation of [1,1 2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect ( kH/kD = 6.20 at 298 K ). This indicated the cleavage of a α-C-H bond in the rate-determining step. An analysis of the temperature dependence of the deuterium isotope effect showed that the loss of hydrogen proceeds through a concerted cyclic process. The rate of oxidation of BA was determined in 19 organic solvents. An analysis of the solvent effect by Swain’s equation indicated that though both the anion and cation-solvating powers of the solvent contribute to the observed solvent effect, the role of cation-solvation is major. The rates of the para and meta compounds, at 298 K, failed to exhibit a significant correlation in terms of Hammett or Brown's substituent constants. The rates were then subjected to analyses in terms of dual substituent parameter (DSP) equations. The rates of oxidation of the para-substituted benzyl alcohols show an excellent correlation with Taft's σI and σRBA values. However, the rates for the meta-substituted benzyl alcohols show an excellent correlation with σI and σR0. The polar reaction constants are negative indicating an electron-deficient transition state. Hence the overall mechanism is proposed to involve the formation of a chromate ester in a fast pre-equilibrium and then a decomposition of the ester in a subsequent slow step via a cyclic concerted symmetrical transition state, involving hydride-ion transfer, leading to the product. The first order dependence on alcohol may be accounted in terms of the small value of the formation constant of the ester intermediate. An another reaction mechanism accounting the acid-catalysis involve the formation of a protonated BIDC prior to formation of an ester intermediate which subsequently decomposes in a slow step leading to the product.

Keywords: benzimidazolium dichromate, benzyl alcohols, correlation analysis, kinetics, oxidation

Procedia PDF Downloads 344
4427 Hot Corrosion Susceptibility of Uncoated Boiler Tubes during High Vanadium Containing Fuel Oil Operation in Boiler Applications

Authors: Nicole Laws, William L. Roberts, Saumitra Saxena, Krishnamurthy Anand, Sreenivasa Gubba, Ziad Dawood, Aiping Chen

Abstract:

Boiler-fired power plants that operate steam turbines in Saudi Arabia use vanadium-containing fuel oil. In a super- or sub-critical steam cycle, the skin temperature of boiler tube metal can reach close to 600-1000°C depending on the location of the tubes. At high temperatures, corrosion by the sodium-vanadium-oxygen-sulfur eutectic can become a significant risk. The experimental work utilized a state-of-the-art high-temperature, high-pressure burner rig at KAUST, King Abdullah University of Science and Technology. To establish corrosion rates of different boiler tubes and materials, SA 213 T12, SA 213 T22, SA 213 T91, and Inconel 600, were used under various corrosive media, including vanadium to sulfur levels and vanadium to sodium ratios. The results obtained from the experiments establish a corrosion rate map for the materials involved and layout an empirical framework to rank the life of boiler tube materials under different operating conditions. Safe windows of operation are proposed for burning liquid fuels under varying vanadium, sodium, and sulfur levels before corrosion rates become a matter of significance under high-temperature conditions

Keywords: boiler tube life, hot corrosion, steam boilers, vanadium in fuel oil

Procedia PDF Downloads 233
4426 Health Promotion Programs for Fifteen Years Decreased Loneliness and Increased Happiness for Elementary School Children in Yuzawa Town, Japan

Authors: Takeo Shibata, Arihito Endo, Chika Hiraga, Akemi Kunimatsu, Yoko Shimizu

Abstract:

Introduction: A health promotion program, Yuzawa family health plan, was initiated in 2002. It has been held for fifteen years. Yuzawa Town is famous with hot springs and ski resorts. We evaluated the changes in mental status in elementary school children. Methods: questionnaires survey had been held every five years. 196 questionnaires were corrected (94 boys and 102 girls). Changes for their anxieties, loneliness, confiding, problem-solving, risk breaching, communications, happiness, and life satisfaction were evaluated by chi-square test. Results: The rate of loneliness and life dissatisfactions decreased. The rates of happiness, confiding in grandparents, and risk breaching, increased. Especially, happiness rates increased for boys, loneliness rate decreased for girls, confiding in grandparents and risk breaching rate increased for girls. Conclusion: Our health promotion programs could increase mental health status in elementary school children.

Keywords: health promotion, mental status, elementary school, loneliness, happiness

Procedia PDF Downloads 276