Search results for: porphyrins synthesis and modification
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 3096

Search results for: porphyrins synthesis and modification

876 Rewilding the River: Assessing the Environmental Effects and Regulatory Influences of the Condit Dam Removal Process

Authors: Neda Safari, Jacob Petersen-Perlman

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There are more than two million dams in the United States, and a considerable portion of them are either non-operational or approaching the end of their designed lifespan. However, this emerging trend is new, and the majority of dam sites have not undergone thorough research and assessments after their removal to determine the overall effectiveness of restoration initiatives, particularly in the case of large-scale dams that may significantly impact their surrounding areas. A crucial factor to consider is the lack of specific regulations pertaining to dam removal at the federal level. Consequently, other environmental regulations that were not originally designed with dam removal considerations are used to execute these projects. This can result in delays or challenges for dam removal initiatives. The process of removing dams is usually the most important first step to restore the ecological and biological health of the river, but often there is a lack of measurable indicators to assess if it has achieved its intended objectives. In addition, the majority of studies on dam removal are only short-term and focus on a particular measure of response. Therefore, it is essential to conduct extensive and continuous monitoring to analyze the river's response throughout every aspect. Our study is divided into two sections. The first section of my research will analyze the establishment and utilization of dam removal laws and regulations in the Condit Dam removal process. We will highlight the areas where the frameworks for policy and dam removal projects remain in need of improvement in order to facilitate successful dam removals in the future. In this part, We will review the policies and plans that affected the decision-making process to remove the Condit dam while also looking at how they impacted the physical changes to the river after the dam was removed. In the second section, we will look at the effects of the dam removal over a decade later and attempt to determine how the river's physical response has been impacted by this modification. Our study aims to investigate the Condit dam removal process and its impact on the ecological response of the river. We anticipate identifying areas for improvement in policies pertaining to dam removal projects and exploring ways to enhance them to ensure improved project outcomes in the future.

Keywords: dam removal, ecolocgical change, water related regulation, water resources

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875 Preparation and Properties of Polylactic Acid/MDI Modified Thermoplastic Starch Blends

Authors: Sukhila Krishnan, Smita Mohanty, Sanjay K. Nayak

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Polylactide (PLA) and thermoplastic starch (TPS) are the most promising bio-based materials presently available on the market. Polylactic acid is one of the versatile biodegradable polyester showing wide range of applications in various fields and starch is a biopolymer which is renewable, cheap as well as extensively available. The usual increase in the cost of petroleum-based commodities in the next decades opens bright future for these materials. Their biodegradability and compostability was an added advantage in applications that are difficult to recycle. Currently, thermoplastic starch (TPS) has been used as a substitute for synthetic plastic in several commercial products. But, TPS shows some limitations mainly due to its brittle and hydrophilic nature, which has to be resolved to widen its application.The objective of the work we report here was to initiate chemical modifications on TPS and to build up a process to control its chemical structure using a solution process which can reduce its water sensitive properties and then blended it with PLA to improve compatibility between PLA and TPS. The method involves in cleavage of starch amylose and amylopectin chain backbone to plasticize with glycerol and water in batch mixer and then the prepared TPS was reacted in solution with diisocyanates i.e, 4,4'-Methylenediphenyl Diisocyanate (MDI).This diisocyanate was used before with great success for the chemical modification of TPS surface. The method utilized here will form an urethane-linkages between reactive isocyanate groups (–NCO) and hydroxyl groups (-OH) of starch as well as of glycerol. New polymer synthesised shows a reduced crystallinity, less hydrophilic and enhanced compatibility with other polymers. The TPS was prepared by Haake Rheomix 600 batch mixer with roller rotors operating at 50 rpm. The produced material is then refluxed for 5hrs with MDI in toluene with constant stirring. Finally, the modified TPS was melt blended with PLA in different compositions. Blends obtained shows an improved mechanical properties. These materials produced are characterized by Fourier Transform Infrared Spectra (FTIR), DSC, X-Ray diffraction and mechanical tests.

Keywords: polylactic acid, thermoplastic starch, Methylenediphenyl Diisocyanate, Polylactide (PLA)

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874 Thomas Kuhn, the Accidental Theologian: An Argument for the Similarity of Science and Religion

Authors: Dominic McGann

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Applying Kuhn’s model of paradigm shifts in science to cases of doctrinal change in religion has been a common area of study in recent years. Few authors, however, have sought an explanation for the ease with which this model of theory change in science can be applied to cases of religious change. In order to provide such an explanation of this analytic phenomenon, this paper aims to answer one central question: Why is it that a theory that was intended to be used in an analysis of the history of science can be applied to something as disparate as the doctrinal history of religion with little to no modification? By way of answering this question, this paper begins with an explanation of Kuhn’s model and its applications in the field of religious studies. Following this, Massa’s recently proposed explanation for this phenomenon, and its notable flaws will be explained by way of framing the central proposal of this article, that the operative parts of scientific and religious changes function on the same fundamental concept of changes in understanding. Focusing its argument on this key concept, this paper seeks to illustrate its operation in cases of religious conversion and in Kuhn’s notion of the incommensurability of different scientific paradigms. The conjecture of this paper is that just as a Pagan-turned-Christian ceases to hear Thor’s hammer when they hear a clap of thunder, so too does a Ptolemaic-turned-Copernican-astronomer cease to see the Sun orbiting the Earth when they view a sunrise. In both cases, the agent in question has undergone a similar change in universal understanding, which provides us with a fundamental connection between changes in religion and changes in science. Following an exploration of this connection, this paper will consider the implications that such a connection has for the concept of the division between religion and science. This will, in turn, lead to the conclusion that religion and science are more alike than they are opposed with regards to the fundamental notion of understanding, thereby providing an answer to our central question. The major finding of this paper is that Kuhn’s model can be applied to religious cases so easily because changes in science and changes in religion operate on the same type of change in understanding. Therefore, in summary, science and religion share a crucial similarity and are not as disparate as they first appear.

Keywords: Thomas Kuhn, science and religion, paradigm shifts, incommensurability, insight and understanding, philosophy of science, philosophy of religion

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873 Design of a Thrust Vectoring System for an Underwater ROV

Authors: Isaac Laryea

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Underwater remote-operated vehicles (ROVs) are highly useful in aquatic research and underwater operations. Unfortunately, unsteady and unpredictable conditions underwater make it difficult for underwater vehicles to maintain a steady attitude during motion. Existing underwater vehicles make use of multiple thrusters positioned at specific positions on their frame to maintain a certain pose. This study proposes an alternate way of maintaining a steady attitude during horizontal motion at low speeds by making use of a thrust vector-controlled propulsion system. The study began by carrying out some preliminary calculations to get an idea of a suitable shape and form factor. Flow simulations were carried out to ensure that enough thrust could be generated to move the system. Using the Lagrangian approach, a mathematical system was developed for the ROV, and this model was used to design a control system. A PID controller was selected for the control system. However, after tuning, it was realized that a PD controller satisfied the design specifications. The designed control system produced an overshoot of 6.72%, with a settling time of 0.192s. To achieve the effect of thrust vectoring, an inverse kinematics synthesis was carried out to determine what angle the actuators need to move to. After building the system, intermittent angular displacements of 10°, 15°, and 20° were given during bench testing, and the response of the control system as well as the servo motor angle was plotted. The final design was able to move in water but was not able to handle large angular displacements as a result of the small angle approximation used in the mathematical model.

Keywords: PID control, thrust vectoring, parallel manipulators, ROV, underwater, attitude control

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872 Anti-crisis Public Relations and Aspects of Effective Management in Georgian Companies

Authors: Marine Kobalava

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Introduction. The paper substantiates the crucial role of anti-crisis PR in managing the image and reputation of companies. The critical situation caused by the Covid-19 virus in various countries of the world and the actions taken have had a significant negative impact on the image of companies and public groups. The mentioned circumstance has caused some problems for companies’ products in terms of customer demand. Accordingly, the main goal of PR has become to achieve the optimal relationship between companies and society with effective management. It should also be taken into account that the range of action of PR in crisis situations is much wider than that of advertising. In the paper, Public Relations is evaluated as a determining factor of the companies' prestige, its reliability, which has a decisive effect on the goodwill, trust, and general reputation of the public towards the company. The purpose of the study is to reveal the challenges of anti-crisis PR in Georgian companies and to develop recommendations on effective management mechanisms. Methodologies. Analysis, induction, synthesis, and other methods are used in the paper; Matrix and SWOT analysis are constructed. Ways of establishing and implementing an anti-crisis PR system in companies are proposed. The main aspects of anti-crisis management are identified by using the matrix of the choice of diversification strategy of the companies' activities, the possibilities of making adequate decisions using PR are studied according to the characteristics of the companies' activities and priority directions. Conclusion. The paper draws conclusions on modern problems of anti-crisis PR, offers recommendations on ways to solve it through PR strategies.

Keywords: anti-crisis PR, effective management, company, PR strategy

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871 Bioinformatic Screening of Metagenomic Fosmid Libraries for Identification of Biosynthetic Pathways Derived from the Colombian Soils

Authors: María Fernanda Quiceno Vallejo, Patricia del Portillo, María Mercedes Zambrano, Jeisson Alejandro Triana, Dayana Calderon, Juan Manuel Anzola

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Microorganisms from tropical ecosystems can be novel in terms of adaptations and conservation. Given the macrodiversity of Colombian ecosystems, it is possible that this diversity is also present in Colombian soils. Tropical soil bacteria could offer a potentially novel source of bioactive compounds. In this study we analyzed a metagenomic fosmid library constructed with tropical bacterial DNAs with the aim of understanding its underlying diversity and functional potential. 8640 clones from the fosmid library were sequenced by NANOPORE MiniOn technology, then analyzed with bioinformatic tools such as Prokka, AntiSMASH and Bagel4 in order to identify functional biosynthetic pathways in the sequences. The strains showed ample difference when it comes to biosynthetic pathways. In total we identified 4 pathways related to aryl polyene synthesis, 12 related to terpenes, 22 related to NRPs (Non ribosomal peptides), 11 related PKs (Polyketide synthases) and 7 related to RiPPs (bacteriocins). We designed primers for the metagenomic clones with the most BGCs (sample 6 and sample 2). Results show the biotechnological / pharmacological potential of tropical ecosystems. Overall, this work provides an overview of the genomic and functional potential of Colombian soil and sets the groundwork for additional exploration of tropical metagenomic sequencing.

Keywords: bioactives, biosyntethic pathways, bioinformatic, bacterial gene clusters, secondary metabolites

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870 Peripheral Nerves Cross-Sectional Area for the Diagnosis of Diabetic Polyneuropathy: A Meta-Analysis of Ultrasonographic Measurements

Authors: Saeed Pourhassan, Nastaran Maghbouli

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1) Background It has been hypothesized that, in individuals with diabetes mellitus, the peripheral nerve is swollen due to sorbitol over-accumulation. Additionally growing evidence supported electro diagnostic study of diabetes induced neuropathy as a method having some challenges. 2) Objective To examine the performance of sonographic cross-sectional area (CSA) measurements in the diagnosis of diabetic polyneuropathy (DPN). 3) Data Sources Electronic databases, comprising PubMed and EMBASE and Google scholar, were searched for the appropriate studies before Jan 1, 2020. 4) Study Selection Eleven trials comparing different peripheral nerve CSA measurements between participants with and without DPN were included. 5) Data Extraction Study design, participants' demographic characteristics, diagnostic reference of DPN, and evaluated peripheral nerves and methods of CSA measurement. 6) Data Synthesis Among different peripheral nerves, Tibial nerve diagnostic odds ratios pooled from five studies (713 participants) were 4.46 (95% CI, 0.35–8.57) and the largest one with P<0.0001, I²:64%. Median nerve CSA at wrist and mid-arm took second and third place with ORs= 2.82 (1.50-4.15), 2.02(0.26-3.77) respectively. The sensitivities and specificities pooled from two studies for Sural nerve were 0.78 (95% CI, 0.68–0.89), and 0.68 (95% CI, 0.53–0.74). Included studies for other nerves were limited to one study. The largest sensitivity was for Sural nerve and the largest specificity was for Tibial nerve. 7) Conclusions The peripheral nerves CSA measured by ultrasound imaging is useful for the diagnosis of DPN and is most significantly different between patients and participants without DPN at the Tibial nerve. Because the Tibial nerve CSA in healthy participants, at various locations, rarely exceeds 24 mm2, this value can be considered as a cutoff point for diagnosing DPN.

Keywords: diabetes, diagnosis, polyneuropathy, ultrasound

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869 A Glycerol-Free Process of Biodiesel Production through Chemical Interesterification of Jatropha Oil

Authors: Ratna Dewi Kusumaningtyas, Riris Pristiyani, Heny Dewajani

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Biodiesel is commonly produced via the two main routes, i.e. the transesterification of triglycerides and the esterification of free fatty acid (FFA) using short-chain alcohols. Both the two routes have drawback in term of the side product yielded during the reaction. Transesterification reaction of triglyceride results in glycerol as side product. On the other hand, FFA esterification brings in water as side product. Both glycerol and water in the biodiesel production are managed as waste. Hence, a separation process is necessary to obtain a high purity biodiesel. Meanwhile, separation processes is generally the most capital and energy intensive part in industrial process. Therefore, to reduce the separation process, it is essential to produce biodiesel via an alternative route eliminating glycerol or water side-products. In this work, biodiesel synthesis was performed using a glycerol-free process through chemical interesterification of jatropha oil with ethyl acetate in the presence on sodium acetate catalyst. By using this method, triacetine, which is known as fuel bio-additive, is yielded instead of glycerol. This research studied the effects of catalyst concentration on the jatropha oil interesterification process in the range of 0.5 – 1.25% w/w oil. The reaction temperature and molar ratio of oil to ethyl acetate were varied at 50, 60, and 70°C, and 1:6, 1:9, 1:15, 1:30, and 1:60, respectively. The reaction time was evaluated from 0 to 8 hours. It was revealed that the best yield was obtained with the catalyst concentration of 0.5%, reaction temperature of 70 °C, molar ratio of oil to ethyl acetate at 1:60, at 6 hours reaction time.

Keywords: biodiesel, interesterification, glycerol-free, triacetine, jatropha oil

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868 Advancements in Dielectric Materials: A Comprehensive Study on Properties, Synthesis, and Applications

Authors: M. Mesrar, T. Lamcharfi, Nor-S. Echatoui, F. Abdi

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The solid-state reaction method was used to synthesize ferroelectric systems with lead-free properties, specifically (1-x-y)(Na₀.₅Bi₀.₅)TiO₃-xBaTiO₃-y(K₀.₅ Bi₀.₅)TiO₃. To achieve a pure perovskite phase, the optimal calcination temperature was determined to be 1000°C for 4 hours. X-ray diffraction (XRD) analysis identified the presence of the morphotropic phase boundary (MPB) in the (1-x-y)NBT xBT-yKBT ceramics for specific molar compositions, namely (0.95NBT-0.05BT, 0.84NBT-0.16KBT, and 0.79NBT-0.05BT-0.16KBT). To enhance densification, the sintering temperature was set at 1100°C for 4 hours. Scanning electron microscopy (SEM) images exhibited homogeneous distribution and dense packing of the grains in the ceramics, indicating a uniform microstructure. These materials exhibited favorable characteristics, including high dielectric permittivity, low dielectric loss, and diffused phase transition behavior. The ceramics composed of 0.79NBT-0.05BT-0.16KBT exhibited the highest piezoelectric constant (d33=148 pC/N) and electromechanical coupling factor (kp = 0.292) among all compositions studied. This enhancement in piezoelectric properties can be attributed to the presence of the morphotropic phase boundary (MPB) in the material. This study presents a comprehensive approach to improving the performance of lead-free ferroelectric systems of composition 0.79(Na₀.₅Bi₀.₅)Ti O₃-0.05BaTiO₃-0.16(K₀.₅Bi₀.₅)TiO₃.

Keywords: solid-state method, (1-x-y)NBT-xBT-yKBT, morphotropic phase boundary, Raman spectroscopy, dielectric properties

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867 Thermoluminescent Response of Nanocrystalline BaSO4:Eu to 85 MeV Carbon Beams

Authors: Shaila Bahl, S. P. Lochab, Pratik Kumar

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Nanotechnology and nanomaterials have attracted researchers from different fields, especially from the field of luminescence. Recent studies on various luminescent nanomaterials have shown their relevance in dosimetry of ionizing radiations for the measurements of high doses using the Thermoluminescence (TL) technique, where the conventional microcrystalline phosphors saturate. Ion beams have been used for diagnostic and therapeutic purposes due to their favorable profile of dose deposition at the end of the range known as the Bragg peak. While dealing with human beings, doses from these beams need to be measured with great precision and accuracy. Henceforth detailed investigations of suitable thermoluminescent dosimeters (TLD) for dose verification in ion beam irradiation are required. This paper investigates the TL response of nanocrystalline BaSO4 doped with Eu to 85 MeV carbon beam. The synthesis was done using Co-precipitation technique by mixing Barium chloride and ammonium sulphate solutions. To investigate the crystallinity and particle size, analytical techniques such as X-ray diffraction (XRD) and Transmission electron microscopy (TEM) were used which revealed the average particle sizes to 45 nm with orthorhombic structure. Samples in pellet form were irradiated by 85 MeV carbon beam in the fluence range of 1X1010-5X1013. TL glow curves of the irradiated samples show two prominent glow peaks at around 460 K and 495 K. The TL response is linear up to 1X1013 fluence after which saturation was observed. The wider linear TL response of nanocrystalline BaSO4: Eu and low fading make it a superior candidate as a dosimeter to be used for detecting the doses of carbon beam.

Keywords: radiation, dosimetry, carbon ions, thermoluminescence

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866 Microwave Assisted Solvent-free Catalytic Transesterification of Glycerol to Glycerol Carbonate

Authors: Wai Keng Teng, Gek Cheng Ngoh, Rozita Yusoff, Mohamed Kheireddine Aroua

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As a by-product of the biodiesel industries, glycerol has been vastly generated which surpasses the market demand. It is imperative to develop an efficient glycerol valorization processes in minimizing the net energy requirement and intensifying the biodiesel production. In this study, base-catalyzed transesterification of glycerol with dimethyl carbonate using microwave irradiation as heating method to produce glycerol carbonate was conducted by varing grades of glycerol i.e. 70%, 86% and 99% purity that obtained from biodiesel plant. Metal oxide catalysts were used with varying operating parameters including reaction time, DMC/glycerol molar ratio, catalyst weight %, temperature and stirring speed. From the study on the effect of different operating parameters; it was found that the type of catalyst used has the most significant effect on the transesterification reaction. Admist the metal oxide catalysts examined, CaO gave the best performance. This study indicates the feasibility of producing glycerol carbonate using different grade of glycerol in both conventional thermal activation and microwave irradiation with CaO as catalyst. Microwave assisted transesterification (MAT) of glycerol into glycerol carbonate has demostrated itself as an energy efficient route by achieving 94.3% yield of GC at 65°C, 5 minutes reaction time, 1 wt% CaO and DMC/glycerol molar ratio of 2. The advantages of MAT transesterification route has made the direct utilization of bioglycerol from biodiesel production without the need of purification. This has marked a more economical and less-energy intensive glycerol carbonate synthesis route.

Keywords: base-catalyzed transesterification, glycerol, glycerol carbonate, microwave irradiation

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865 Modelling the Tensile Behavior of Plasma Sprayed Freestanding Yttria Stabilized Zirconia Coatings

Authors: Supriya Patibanda, Xiaopeng Gong, Krishna N. Jonnalagadda, Ralph Abrahams

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Yttria stabilized zirconia (YSZ) is used as a top coat in thermal barrier coatings in high-temperature turbine/jet engine applications. The mechanical behaviour of YSZ depends on the microstructural features like crack density and porosity, which are a result of coating method. However, experimentally ascertaining their individual effect is difficult due to the inherent challenges involved like material synthesis and handling. The current work deals with the development of a phenomenological model to replicate the tensile behavior of air plasma sprayed YSZ obtained from experiments. Initially, uniaxial tensile experiments were performed on freestanding YSZ coatings of ~300 µm thick for different crack densities and porosities. The coatings exhibited a nonlinear behavior and also a huge variation in strength values. With the obtained experimental tensile curve as a base and crack density and porosity as prime variables, a phenomenological model was developed using ABAQUS interface with new user material defined employing VUMAT sub routine. The relation between the tensile stress and the crack density was empirically established. Further, a parametric study was carried out to investigate the effect of the individual features on the non-linearity in these coatings. This work enables to generate new coating designs by varying the key parameters and predicting the mechanical properties with the help of a simulation, thereby minimizing experiments.

Keywords: crack density, finite element method, plasma sprayed coatings, VUMAT

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864 Features of Technological Innovation Management in Georgia

Authors: Ketevan Goletiani, Parmen Khvedelidze

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discusses the importance of the topic, which is reflected in the advanced and developed countries in the formation of a new innovative stage of the distinctive mark of the modern world development. This phase includes the construction of the economy, which generates stockpiling and use is based. Intensifying the production and use of the results of new scientific and technical innovation has led to a sharp reduction in the cycle and accelerate the pace of product and technology updates. The world's leading countries in the development of innovative management systems for the formation of long-term and stable development of the socio-economic order conditions. The last years of the 20th century, the social and economic relations, modification, accelerating economic reforms, and profound changes in the system of the time. At the same time, the country should own place in the world geopolitical and economic space. Accelerated economic development tasks, the World Trade Organization, the European Union deep and comprehensive trade agreement, the new system of economic management, technical and technological renewal of production potential, and scientific fields in the share of the total volume of GDP growth requires new approaches. XX - XXI centuries Georgia's socio-economic changes is one of the urgent tasks in the form of a rise to the need for change, involving the use of natural resource-based economy to the latest scientific and technical achievements of an innovative and dynamic economy based on an accelerated pace. But Georgia still remains unresolved in many methodological, theoretical, and practical nature of the problem relating to the management of the economy in various fields for the development of innovative systems for optimal implementation. Therefore, the development of an innovative system for the formation of a complex and multi-problem, which is reflected in the following: countries should have higher growth rates than the geopolitical space of the neighboring countries that its competitors are. Formation of such a system is possible only in a deep theoretical research and innovative processes in the multi-level (micro, meso- and macro-levels) management on the basis of creation.

Keywords: georgia, innovative, socio-economic, innovative manage

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863 Anti-Melanogenesis and Anti-Inflammatory Effects of Opuntia humifusa

Authors: Yonghwa Lee, Yoon Suk Kim, Yongsub Yi

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This study was to confirm the effects of anti-melanogenesis and anti-inflammatory effects from Opuntia humifusa fruit and stem extracts. A potent anti-oxidant activity was shown from the leaf extract at IC50 value of 38.33±1.07 μg/mL and fruit extract at IC50 value of 40.23±2.21 μg/mL by 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay. Also, phenolic contents were confirmed total phenolic assay by high performance liquid chromatography (HPLC). Fraction of taxifolin from leaf extract was identified using HPLC and gas chromatography/mass spectrometry. The extracts of Opuntia humifusa fruit and stem were confirmed about toxicity effect in B16 F1 by cell viability. Melanin contents were decreased. Opuntia humifusa fruit and stem extracts had a positive effect of melanin synthesis inhibition for skin whitening. In investigating the anti-inflammatory activities of Opuntia humifusa, the results of cell viability indicated that taxifolin did not show cytotoxicity on RAW264.7 cells at 500 μM of concentration. The results show that taxifolin inhibited lipopolysaccharide (LPS)-induced production of Nitrite oxide (NO). In addition, taxifolin indicated the inhibition of lipopolysaccharide (LPS)-induced tumor necrosis factor (TNF) -α and interleukin (IL) -6 productions by cytokine assay and cyclooxygenase (COX)-2 expression by western blot analysis, meaning that taxifolin had a significant anti-inflammatory effect. Our results suggested that taxifolin from Opuntia humifusa has anti-melanogenesis and anti-inflammatory activities.

Keywords: anti-melanogenesis, anti-inflammatory, Opuntia humifusa, taxifolin

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862 Prediction of Ionic Liquid Densities Using a Corresponding State Correlation

Authors: Khashayar Nasrifar

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Ionic liquids (ILs) exhibit particular properties exemplified by extremely low vapor pressure and high thermal stability. The properties of ILs can be tailored by proper selection of cations and anions. As such, ILs are appealing as potential solvents to substitute traditional solvents with high vapor pressure. One of the IL properties required in chemical and process design is density. In developing corresponding state liquid density correlations, scaling hypothesis is often used. The hypothesis expresses the temperature dependence of saturated liquid densities near the vapor-liquid critical point as a function of reduced temperature. Extending the temperature dependence, several successful correlations were developed to accurately correlate the densities of normal liquids from the triple point to a critical point. Applying mixing rules, the liquid density correlations are extended to liquid mixtures as well. ILs are not molecular liquids, and they are not classified among normal liquids either. Also, ILs are often used where the condition is far from equilibrium. Nevertheless, in calculating the properties of ILs, the use of corresponding state correlations would be useful if no experimental data were available. With well-known generalized saturated liquid density correlations, the accuracy in predicting the density of ILs is not that good. An average error of 4-5% should be expected. In this work, a data bank was compiled. A simplified and concise corresponding state saturated liquid density correlation is proposed by phenomena-logically modifying reduced temperature using the temperature-dependence for an interacting parameter of the Soave-Redlich-Kwong equation of state. This modification improves the temperature dependence of the developed correlation. Parametrization was next performed to optimize the three global parameters of the correlation. The correlation was then applied to the ILs in our data bank with satisfactory predictions. The correlation of IL density applied at 0.1 MPa and was tested with an average uncertainty of around 2%. No adjustable parameter was used. The critical temperature, critical volume, and acentric factor were all required. Methods to extend the predictions to higher pressures (200 MPa) were also devised. Compared to other methods, this correlation was found more accurate. This work also presents the chronological order of developing such correlations dealing with ILs. The pros and cons are also expressed.

Keywords: correlation, corresponding state principle, ionic liquid, density

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861 The Romero-System Clarinet: A Milestone in the 19th Century Clarinet Manufacture

Authors: Pedro Rubio

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Antonio Romero y Andía, was one of the most active and interesting figures in 19th century Spanish music. He was not only an exceptional clarinetist, he was also a publisher, a brilliant oboist, a music critic, and he revitalized Madrid’s musical scene by promoting orchestras and a national opera. In 1849, Romero was appointed Professor of Clarinet at the Conservatory of Madrid. Shortly after, Romero introduced to Spain the Boehm-System clarinet recently appeared in France. However, when initial interest in that system waned, he conceived his own system in 1853. The clarinet was manufactured in Paris by Lefêvre, who registered its first patent in 1862. In 1867 a second version was patented, and a year earlier, in 1866, the Romero clarinet was adopted as an official instrument for teaching the clarinet at the Conservatory of Madrid. The Romero-System clarinet mechanism has incorporated numerous additional devices and several extra keys, its skillful combination in a single instrument represents not only one of the pinnacles in the manufacture of musical instruments of the 19th century, but also an authentic synthesis of knowledge and practice in an era in which woodwind instruments were shaped as we know them today. Through the description and analysis of the data related to the aforementioned historical period, this lecture will try to show a crucial time in the history of all woodwind instruments, a period of technological effervescence in which the Romero-System clarinet emerged. The different stages of conception of the clarinet will be described, as well as its manufacturing and marketing process. Romero played with his clarinet system over twenty-five years. The research has identified the repertoire associated with this instrument whose conclusions will be presented in its case in the Congress.

Keywords: Antonio Romero, clarinet, keywork, 19th century

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860 In-Situ Fabrication of ZnO PES Membranes for Treatment of Pharmaceuticals

Authors: Oranso T. Mahlangi, Bhekie B. Mamba

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The occurrence of trace organic compounds (TOrCs) in water has raised health concerns for living organisms. The majority of TorCs, including pharmaceuticals and volatile organic compounds, are poorly monitored, partly due to the high cost of analysis and less strict water quality guidelines in South Africa. Therefore, the removal of TorCs is important to guarantee safe potable water. In this study, ZnO nanoparticles were fabricated in situ in polyethersulfone (PES) polymer solutions. This was followed by membrane synthesis using the phase inversion technique. Techniques such as FTIR, Raman, SEM, AFM, EDS, and contact angle measurements were used to characterize the membranes for several physicochemical properties. The membranes were then evaluated for their efficiency in treating pharmaceutical wastewater and resistance to organic (sodium alginate) and protein (bovine serum albumin) fouling. EDS micrographs revealed uniform distribution of ZnO nanoparticles within the polymer matrix, while SEM images showed uniform fingerlike structures. The addition of ZnO increased membrane roughness as well as hydrophilicity (which in turn improved water fluxes). The membranes poorly rejected monovalent and divalent salts (< 10%), making them resistant to flux decline due to concentration polarization effects. However, the membranes effectively removed carbamazepine, caffeine, sulfamethoxazole, ibuprofen, and naproxen by over 50%. ZnO PES membranes were resistant to organic and protein fouling compared to the neat membrane. ZnO PES ultrafiltration membranes may provide a solution in the reclamation of wastewater.

Keywords: trace organic compounds, pharmaceuticals, membrane fouling, wastewater reclamation

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859 Conceptual Synthesis as a Platform for Psychotherapy Integration: The Case of Transference and Overgeneralization

Authors: Merav Rabinovich

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Background: Psychoanalytic and cognitive therapy attend problems from a different point of view. At the recent decade the integrating movement gaining momentum. However only little has been studied regarding the theoretical interrelationship among these therapy approaches. Method: 33 transference case-studies that were published in peer-reviewed academic journals were coded by Luborsky's Core Conflictual Relationship Theme (CCRT) method (components of wish, response from other – real or imaginal - and the response of self). CCRT analysis was conducted through tailor-made method, a valid tool to identify transference patterns. Rabinovich and Kacen's (2010, 2013) Relationship Between Categories (RBC) method was used to analyze the relationship among these transference patterns with cognitive and behavior components appearing at those psychoanalytic case-studies. Result: 30 of 33 cases (90%) were found to connect the transference themes with cognitive overgeneralization. In these cases, overgeneralizations were organized around Luborsky's transference themes of response from other and response of self. Additionally, overgeneralization was found to be an antithesis of the wish component, and the tension between them found to be linked with powerful behavioral and emotional reactions. Conclusion: The findings indicate that thinking distortions of overgeneralization (cognitive therapy) are the actual expressions of transference patterns. These findings point to a theoretical junction, a platform for clinical integration. Awareness to this junction can help therapists to promote well psychotherapy outcomes relying on the accumulative wisdom of the different therapies.

Keywords: transference, overgeneralization, theoretical integration, case-study metasynthesis, CCRT method, RBC method

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858 Tattooing: Personal Markings with Meaning: Themes Uncovered While Making a Video Documentary

Authors: Byrad Yyelland, Robert Bianchi

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No longer the secret mark of outlaw bikers, criminals, and sailors, tattooing has become mainstream in much of the world. The current study showcases data gathered for a video documentary on the triangulated relationship connecting tattoos as a form of body modification, cultural norms, and personal meanings. This research has revealed that some religious belief systems, Buddhism in Thailand, is one example, connect tattooing with spirituality in an intimate manner. Buddhist monks provide tattoos using traditional bamboo implements and processes, and they pray over the tattoo, infusing magic into the tattoo and consequently, into the body of the receiver. In contrast, although there is no direct mention of tattooing in the Qur’an, many Islamic scholars argue that permanent tattooing is considered haram—forbidden for Muslims. Only the temporary henna is acceptable. In fact, tattooing is illegal in Qatar. Some Indigenous belief systems in Canada adopt a similar stance on the basis that we were all created by the Creator and as such, we do not have the right to alter what the Creator has made. Still other belief systems such as Spiritism in Brazil and mainstream Christianity in the West are more inclined to regard tattooing as a matter of personal choice. It is practically impossible for any culture to resist the dual impacts of time and globalization. Long term cultural change has resulted in mainstream acceptance of tattooing in the west and increased acceptance in Japan. Short-term cultural change is seen in Qatar where tattoos are on on public display amongst expats and migrant laborers. This tolerance of tattooed individuals was clearly evident with the choice of David Beckham as ambassador for the FIFA World Cup and during the corresponding tourist celebrations. Themes uncovered in this multicultural research also include individual meanings attributed to tattoo imagery and processes, experiences of personal empowerment, devotion to family, personal philosophy, gender identity, and aesthetics.

Keywords: culture, norms, tattooing, spirituality, personal motivations and personal meanings

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857 Synthesis, Characterization, Theoretical Crystal Structures and Antitubercular Activity Study of (E)-N'-(2,4-Dihydroxybenzylidene) Nicotinohydrazide and Some of Its Metal Complexes

Authors: Ogunniran Kehinde Olurotimi, Adekoya Joseph, Ehi-Eromosele Cyril, Mehdi Shihab, Mesubi Adediran, Tadigoppula Narender

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Nicotinic acid hydrazide and 2,4-dihydoxylbenzaldehyde were condensed at 20°C to form an acylhydrazone (H3L) with ONO coordination pattern. The structure of the acylhydrazone was elucidated by using CHN analyzer, ESI mass spectrometry, IR, 1H NMR, 13C NMR and 2D NMR such as COSY and HSQC. Thereafter, five novel metal complexes [Mn(II), Fe(II), Pt(II) Zn(II) and Pd(II)] of the hydrazone ligand were synthesized and their structural characterization were achieved by several physicochemical methods, namely elemental analysis, electronic spectra, infrared, EPR, molar conductivity and powder X-ray diffraction studies. Structural geometries of some of the compounds were supported by using Hyper Chem-8 program for the molecular mechanics and semi-empirical calculations. The stability energy (E) and electron potentials (eV) for the frontier molecules were calculated by using PM3 method. An octahedral geometry was suggested for both Pd(II) and Zn(II) complexes while both Mn(II) and Fe(II) complexes conformed with tetrahedral pyramidal. However, Pt(II) complex agreed with tetrahedral geometry. In vitro antitubercular activity study of the ligand and the metal complexes were evaluated against Mycobacterium tuberculosis, H37Rv, by using micro-diluted method. The results obtained revealed that (PtL1) (MIC = 0.56 µg/mL), (ZnL1) (MIC = 0.61 µg/mL), (MnL1) (MIC = 0.71 µg/mL) and (FeL1) (MIC = 0.82 µg/mL), exhibited a significant activity when compared with first line drugs such as isoniazid (INH) (MIC = 0.9 µg/mL). H3L1 exhibited lesser antitubercular activity with MIC value of 1.02 µg/mL. However, the metal complexes displayed higher cytoxicity but were found to be non-significant different (P ˂ 0.05) to isoniazid drug.

Keywords: hydrazones, electron spin resonance, thermogravimetric, powder X-ray diffraction, antitubercular agents

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856 Stimulation of Stevioside Accumulation on Stevia rebaudiana (Bertoni) Shoot Culture Induced with Red LED Light in TIS RITA® Bioreactor System

Authors: Vincent Alexander, Rizkita Esyanti

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Leaves of Stevia rebaudiana contain steviol glycoside which mainly comprise of stevioside, a natural sweetener compound that is 100-300 times sweeter than sucrose. Current cultivation method of Stevia rebaudiana in Indonesia has yet to reach its optimum efficiency and productivity to produce stevioside as a safe sugar substitute sweetener for people with diabetes. An alternative method that is not limited by environmental factor is in vitro temporary immersion system (TIS) culture method using recipient for automated immersion (RITA®) bioreactor. The aim of this research was to evaluate the effect of red LED light induction towards shoot growth and stevioside accumulation in TIS RITA® bioreactor system, as an endeavour to increase the secondary metabolite synthesis. The result showed that the stevioside accumulation in TIS RITA® bioreactor system induced with red LED light for one hour during night was higher than that in TIS RITA® bioreactor system without red LED light induction, i.e. 71.04 ± 5.36 μg/g and 42.92 ± 5.40 μg/g respectively. Biomass growth rate reached as high as 0.072 ± 0.015/day for red LED light induced TIS RITA® bioreactor system, whereas TIS RITA® bioreactor system without induction was only 0.046 ± 0.003/day. Productivity of Stevia rebaudiana shoots induced with red LED light was 0.065 g/L medium/day, whilst shoots without any induction was 0.041 g/L medium/day. Sucrose, salt, and inorganic consumption in both bioreactor media increased as biomass increased. It can be concluded that Stevia rebaudiana shoot in TIS RITA® bioreactor induced with red LED light produces biomass and accumulates higher stevioside concentration, in comparison to bioreactor without any light induction.

Keywords: LED, Stevia rebaudiana, Stevioside, TIS RITA

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855 Alleviation of Endoplasmic Reticulum Stress in Mosquito Cells to Survive Dengue 2 Virus Infection

Authors: Jiun-Nan Hou, Tien-Huang Chen, Wei-June Chen

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Dengue viruses (DENVs) are naturally transmitted between humans by mosquito vectors. Mosquito cells usually survive DENV infection, allowing infected mosquitoes to retain an active status for virus transmission. In this study, we found that DENV2 virus infection in mosquito cells causes the unfolded protein response (UPR) that activates the protein kinase RNA-like endoplasmic reticulum kinase (PERK) signal pathway, leading to shutdown of global protein translation in infected cells which was apparently regulated by the PERK signal pathway. According to observation in this study, the PERK signal pathway in DENV2-infected C6/36 cells alleviates ER stress, and reduces initiator and effector caspases, as well as the apoptosis rate via shutdown of cellular proteins. In fact, phosphorylation of eukaryotic initiation factor 2ɑ (eIF2ɑ) by the PERK signal pathway may impair recruitment of ribosomes that bind to the mRNA 5’-cap structure, resulting in an inhibitory effect on canonical cap-dependent cellular protein translation. The resultant pro-survival “byproduct” of infected mosquito cells is undoubtedly advantageous for viral replication. This finding provides insights into elucidating the PERK-mediated modulating web that is actively involved in dynamic protein synthesis, cell survival, and viral replication in mosquito cells.

Keywords: cap-dependent protein translation, dengue virus, endoplasmic reticulum stress, mosquito cells, PERK signal pathway

Procedia PDF Downloads 255
854 A Picture is worth a Billion Bits: Real-Time Image Reconstruction from Dense Binary Pixels

Authors: Tal Remez, Or Litany, Alex Bronstein

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The pursuit of smaller pixel sizes at ever increasing resolution in digital image sensors is mainly driven by the stringent price and form-factor requirements of sensors and optics in the cellular phone market. Recently, Eric Fossum proposed a novel concept of an image sensor with dense sub-diffraction limit one-bit pixels (jots), which can be considered a digital emulation of silver halide photographic film. This idea has been recently embodied as the EPFL Gigavision camera. A major bottleneck in the design of such sensors is the image reconstruction process, producing a continuous high dynamic range image from oversampled binary measurements. The extreme quantization of the Poisson statistics is incompatible with the assumptions of most standard image processing and enhancement frameworks. The recently proposed maximum-likelihood (ML) approach addresses this difficulty, but suffers from image artifacts and has impractically high computational complexity. In this work, we study a variant of a sensor with binary threshold pixels and propose a reconstruction algorithm combining an ML data fitting term with a sparse synthesis prior. We also show an efficient hardware-friendly real-time approximation of this inverse operator. Promising results are shown on synthetic data as well as on HDR data emulated using multiple exposures of a regular CMOS sensor.

Keywords: binary pixels, maximum likelihood, neural networks, sparse coding

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853 Malate Dehydrogenase Enabled ZnO Nanowires as an Optical Tool for Malic Acid Detection in Horticultural Products

Authors: Rana Tabassum, Ravi Kant, Banshi D. Gupta

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Malic acid is an extensively distributed organic acid in numerous horticultural products in minute amounts which significantly contributes towards taste determination by balancing sugar and acid fractions. An enhanced concentration of malic acid is utilized as an indicator of fruit maturity. In addition, malic acid is also a crucial constituent of several cosmetics and pharmaceutical products. An efficient detection and quantification protocol for malic acid is thus highly demanded. In this study, we report a novel detection scheme for malic acid by synergistically collaborating fiber optic surface plasmon resonance (FOSPR) and distinctive features of nanomaterials favorable for sensing applications. The design blueprint involves the deposition of an assembly of malate dehydrogenase enzyme entrapped in ZnO nanowires forming the sensing route over silver coated central unclad core region of an optical fiber. The formation and subsequent decomposition of the enzyme-analyte complex on exposure of the sensing layer to malic acid solutions of diverse concentration results in modification of the dielectric function of the sensing layer which is manifested in terms of shift in resonance wavelength. Optimization of experimental variables such as enzyme concentration entrapped in ZnO nanowires, dip time of probe for deposition of sensing layer and working pH range of the sensing probe have been accomplished through SPR measurements. The optimized sensing probe displays high sensitivity, broad working range and a minimum limit of detection value and has been successfully tested for malic acid determination in real samples of fruit juices. The current work presents a novel perspective towards malic acid determination as the unique and cooperative combination of FOSPR and nanomaterials provides myriad advantages such as enhanced sensitivity, specificity, compactness together with the possibility of online monitoring and remote sensing.

Keywords: surface plasmon resonance, optical fiber, sensor, malic acid

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852 Migrantional Entrepreneurship: Ethnography of a Journey That Changes Lives and the Territory

Authors: Francesca Alemanno

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As a complex socio-spatial phenomenon, migration is a practice that also contains a strong imaginative component with respect to the place that, through displacement, one person wants to reach. Every migrant has undertaken his journey having in his mind an image of the displacement he was about to make, of its implications and finally, of the place or city in which he was or would have liked to land. Often, however, the imaginary that has come to build before departure does not fully correspond to the reality of landing; this discrepancy, which can be more or less wide, plays an important role in the relationship that is established with the territory and in the evolution, therefore, of the city itself. In this sense, therefore, the clash that occurs between the imagined and the real is one of the factors that can contribute to making the entry of a migrant into new territory as critical as it can be. Starting from this perspective, the experiences of people who derive from a migratory context and who, over time, manage to create a bond with the land of reception, are taken into account as stories of resistance as they are necessarily charged with a force that is capable of driving difficult and articulated processes of change. The phenomenon of migrant entrepreneurship that is taken into consideration by this abstract plays a very important role because it highlights the story of many people who have managed to build such a close bond with the new territory of arrival that they can imagine and then realize the construction of their own personal business. The margin of contrast between the imagined city and the one that will be inhabited will be observed through the narratives of those who, through the realization of his business project has acted directly on the reality in which he landed. The margin of contrast that exists between the imagined city and the one actually inhabited, together with the implications that this may have on real life, has been observed and analyzed through a period of fieldwork, practicing ethnography, through the narratives of people who find themselves living in a new city as a result of a migration path, and has been contextualized with the support of semi-structured interviews and field notes. At the theoretical level, the research is inserted into a constructionist framework, particularly suited to detect and analyze processes of change, construction of the imaginary and its own modification, being able to capture the consequent repercussions of this process on the conceptual, emotional and practical level.

Keywords: entrepreneurship, imagination, migration, resistance

Procedia PDF Downloads 142
851 Rural-Urban Partnership for Balanced Spatial Development in Latvia

Authors: Zane Bulderberga

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Spatial dimension in development planning is becoming more topical in 21st century as a result of changes in population structure. Sustainable spatial development focuses on identifying and using territorial advantages to foster the harmonized development of the entire country, reducing negative effects of population concentration, increasing availability and mobility. EU and national development planning documents state polycentrism as main tool for balance spatial development, including investment concentration in growth centres. If mutual cooperation of growth centres as well as urban-rural cooperation is not fostered, then territorial differences can deepen and create unbalanced development. The aim of research: to evaluate the urban-rural interaction, elaborating spatial development scenarios in framework of Latvian regional policy. To perform the research monographic, comparison, abstract-logical method, synthesis and analysis will be used when studying the theoretical aspects of research aiming at collecting the ideas of scientists from different countries, concepts, regulations as well as to create meaningful scientific discussion. Hierarchy analysis process (AHP) will be used to state further scenarios of spatial development in Latvia. Experts from various institutions recognized urban-rural interaction and co-operation as an essential tool for the development. The most important factors for balanced spatial development in Latvia are availability of public transportation and improvement of service availability. Evaluating the three alternative scenarios, it was concluded that the urban-rural partnership will ensure a balanced development in Latvian regions.

Keywords: rural-urban interaction, rural-urban cooperation, spatial development, AHP

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850 The Utilization of Salicylic Acid of the Extract from Avocado Skin as an Inhibitor of Ethylene Production to Keep the Quality of Banana in Storage

Authors: Adira Nofeadri Ryofi, Alvin Andrianus, Anna Khairunnisa, Anugrah Cahyo Widodo, Arbhyando Tri Putrananda, Arsy Imanda N. Raswati, Gita Rahmaningsih, Ina Agustina

Abstract:

The consumption level of fresh bananas from 2005 until 2010, increased from 8.2 to 10 kg/capita/year. The commercial scale of banana generally harvested when it still green to make the banana avoid physical damage, chemical, and disease after harvest and ripe fruit. That first metabolism activity can be used as a synthesis reaction. Ripening fruit was influenced by ethylene hormone that synthesized in fruit which is experiencing ripe and including hormone in the ripening fruit process in klimaterik phase. This ethylene hormone is affected by the respiration level that would speed up the restructuring of carbohydrates inside the fruit, so the weighting of fruit will be decreased. Compared to other klimaterik fruit, banana is a fruit that has a medium ethylene production rate and the rate of respiration is low. The salicylic acid can regulate the result number of the growth process or the development of fruits and plants. Salicylic acid serves to hinder biosynthesis ethylene and delay senses. The research aims to understand the influence of salicylic acid concentration that derived from the waste of avocado skin in inhibition process to ethylene production that the maturation can be controlled, so it can keep the quality of banana for storage. It is also to increase the potential value of the waste of avocado skin that were still used in industrial cosmetics.

Keywords: ethylene hormone, extract avocado skin, inhibitor, salicylic acid

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849 Biodiesel Production Using Eggshells as a Catalyst

Authors: Ieva Gaide, Violeta Makareviciene

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Increasing environmental pollution is caused by various factors, including the usage of vehicles. Legislation is focused on the increased usage of renewable energy sources for fuel production. Electric car usage is also important; however, it is relatively new and expensive transport. It is necessary to increase the amount of renewable energy in the production of diesel fuel, whereas many agricultural machineries are powered by diesel, as are water vehicles. For this reason, research on biodiesel production is relevant. The majority of studies globally are related to the improvement of conventional biofuel production technologies by applying the transesterification process of oil using alcohol and catalyst. Some of the more recent methods to produce biodiesel are based on heterogeneous catalysis, which has the advantage of easy separation of catalyst from the final product. It is known that a large amount of eggshells is treated as waste; therefore, it is eliminated in landfills without any or with minimal pre-treatment. CaO, which is known as a good catalyst for biodiesel synthesis, is a key component of eggshells. In the present work, we evaluated the catalytic efficiency of eggshells and determined the optimal transesterification conditions to obtain biodiesel that meets the standards. Content CaO in eggshells was investigated. Response surface methodology was used to determine the optimal reaction conditions. Three independent variables were investigated: the molar ratio of alcohol to oil, the amount of the catalyst, and the duration of the reaction. It was obtained that the optimum transesterification conditions when the methanol and eggshells as a heterogeneous catalyst are used and the process temperature is 64°C are the following: the alcohol-to-oil molar ratio 10.93:1, the reaction duration 9.48 h, and the catalyst amount 6.80 wt%. Under these conditions, 97.79 wt% of the ester yield was obtained.

Keywords: heterogeneous catalysis, eggshells, biodiesel, oil

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848 Numerical Study of Natural Convection in Isothermal Open Cavities

Authors: Gaurav Prabhudesai, Gaetan Brill

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The sun's energy source comes from a hydrogen-to-helium thermonuclear reaction, generating a temperature of about 5760 K on its outer layer. On account of this high temperature, energy is radiated by the sun, a part of which reaches the earth. This sunlight, even after losing part of its energy en-route to scattering and absorption, provides a time and space averaged solar flux of 174.7 W/m^2 striking the earth’s surface. According to one study, the solar energy striking earth’s surface in one and a half hour is more than the energy consumption that was recorded in the year 2001 from all sources combined. Thus, technology for extraction of solar energy holds much promise for solving energy crisis. Of the many technologies developed in this regard, Concentrating Solar Power (CSP) plants with central solar tower and receiver system are very impressive because of their capability to provide a renewable energy that can be stored in the form of heat. One design of central receiver towers is an open cavity where sunlight is concentrated into by using mirrors (also called heliostats). This concentrated solar flux produces high temperature inside the cavity which can be utilized in an energy conversion process. The amount of energy captured is reduced by losses occurring at the cavity through all three modes viz., radiation to the atmosphere, conduction to the adjoining structure and convection. This study investigates the natural convection losses to the environment from the receiver. Computational fluid dynamics were used to simulate the fluid flow and heat transfer of the receiver; since no analytical solution can be obtained and no empirical correlations exist for the given geometry. The results provide guide lines for predicting natural convection losses for hexagonal and circular shaped open cavities. Additionally, correlations are given for various inclination angles and aspect ratios. These results provide methods to minimize natural convection through careful design of receiver geometry and modification of the inclination angle, and aspect ratio of the cavity.

Keywords: concentrated solar power (CSP), central receivers, natural convection, CFD, open cavities

Procedia PDF Downloads 280
847 Macrocycles Enable Tuning of Uranyl Electrochemistry by Lewis Acids

Authors: Amit Kumar, Davide Lionetti, Victor Day, James Blakemore

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Capture and activation of the water-soluble uranyl dication (UO22+) remains a challenging problem, as few rational approaches are available for modulating the reactivity of this species. Here, we report the divergent synthesis of heterobimetallic complexes in which UO22+ is held in close proximity to a range of redox-inactive metals by tailored macrocyclic ligands. Crystallographic and spectroscopic studies confirm assembly of homologous UVI(μ-OAr)2Mn+ cores with a range of mono-, di-, and trivalent Lewis acids (Mn+). X-ray diffraction (XRD) and cyclic voltammetry (CV) data suggest preferential binding of K+ in an 18-crown-6-like cavity and Na+ in a 15-crown-5-like cavity, both appended to Schiff-base type sites that selectively bind UO22+. CV data demonstrate that the UVI/UV reduction potential in these complexes shifts positive and the rate of electron transfer decreases with increasing Lewis acidity of the incorporated redox-inactive metals. Moreover, spectroelectrochemical studies confirm the formation of [UV] species in the case of monometallic UO22+ complex, consistent with results from prior studies. However, unique features were observed during spectroelectrochemical studies in the presence of the K+ ion, suggesting new insights into electronic structure may be accessible with the heterobimetallic complexes. Overall, these findings suggest that interactions with Lewis acids could be effectively leveraged for rational tuning of the electronic and thermochemical properties of the 5f elements, reminiscent of strategies more commonly employed with 3d transition metals.

Keywords: electrochemistry, Lewis acid, macrocycle, uranyl

Procedia PDF Downloads 133