Search results for: electron transport chain
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 6037

Search results for: electron transport chain

4717 Human Centred Design Approach for Public Transportation

Authors: Jo Kuys, Kirsten Day

Abstract:

Improving urban transportation systems requires an emphasis on users’ end-to-end journey experience, from the moment the user steps out of their home to when they arrive at their destination. In considering such end-to-end experiences, human centred design (HCD) must be integrated from the very beginning to generate viable outcomes for the public. An HCD approach will encourage innovative outcomes while acknowledging all factors that need to be understood along the journey. We provide evidence to show that when designing for public transportation, it is not just about the physical manifestation of a particular outcome; moreover, it’s about the context and human behaviours that need to be considered throughout the design process. Humans and their behavioural factors are vitally important to successful implementation of sustainable public transport systems. Through an in-depth literature review of HCD approaches for urban transportation systems, we provide a base to exploit the benefits and highlight the importance of including HCD in public transportation projects for greater patronage, resulting in more sustainable cities. An HCD approach is critical to all public transportation projects to understand different levels of transportation design, from the setting of transport policy to implementation to infrastructure, vehicle, and interface design.

Keywords: human centred design, public transportation, urban planning, user experience

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4716 Industrial Hemp Agronomy and Fibre Value Chain in Pakistan: Current Progress, Challenges, and Prospects

Authors: Saddam Hussain, Ghadeer Mohsen Albadrani

Abstract:

Pakistan is one of the most vulnerable countries to climate change. Being a country where 23% of the country’s GDP relies on agriculture, this is a serious cause of concern. Introducing industrial hemp in Pakistan can help build climate resilience in the agricultural sector of the country, as hemp has recently emerged as a sustainable, eco-friendly, resource-efficient, and climate-resilient crop globally. Hemp has the potential to absorb huge amounts of CO₂, nourish the soil, and be used to create various biodegradable and eco-friendly products. Hemp is twice as effective as trees at absorbing and locking up carbon, with 1 hectare (2.5 acres) of hemp reckoned to absorb 8 to 22 tonnes of CO₂ a year, more than any woodland. Along with its high carbon-sequestration ability, it produces higher biomass and can be successfully grown as a cover crop. Hemp can grow in almost all soil conditions and does not require pesticides. It has fast-growing qualities and needs only 120 days to be ready for harvest. Compared with cotton, hemp requires 50% less water to grow and can produce three times higher fiber yield with a lower ecological footprint. Recently, the Government of Pakistan has allowed the cultivation of industrial hemp for industrial and medicinal purposes, making it possible for hemp to be reinserted into the country’s economy. Pakistan’s agro-climatic and edaphic conditions are well-suitable to produce industrial hemp, and its cultivation can bring economic benefits to the country. Pakistan can enter global markets as a new exporter of hemp products. The production of hemp in Pakistan can be most exciting to the workforce, especially for farmers participating in hemp markets. The minimum production cost of hemp makes it affordable to small holding farmers, especially those who need their cropping system to be as highly sustainable as possible. Dr. Saddam Hussain is leading the first pilot project of Industrial Hemp in Pakistan. In the past three years, he has been able to recruit high-impact research grants on industrial hemp as Principal Investigator. He has already screened the non-toxic hemp genotypes, tested the adaptability of exotic material in various agroecological conditions, formulated the production agronomy, and successfully developed the complete value chain. He has developed prototypes (fabric, denim, knitwear) using hemp fibre in collaboration with industrial partners and has optimized the indigenous fibre processing techniques. In this lecture, Dr. Hussain will talk on hemp agronomy and its complete fibre value chain. He will discuss the current progress, and will highlight the major challenges and future research direction on hemp research.

Keywords: industrial hemp, agricultural sustainability, agronomic evaluation, hemp value chain

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4715 Study of Electrical Properties of An-Fl Based Organic Semiconducting Thin Film

Authors: A.G. S. Aldajani, N. Smida, M. G. Althobaiti, B. Zaidi

Abstract:

In order to exploit the good electrical properties of anthracene and the excellent properties of fluorescein, new hybrid material has been synthesized (An-Fl). Current-voltage measurements were done on a new single-layer ITO/An-FL/Al device of typically 100 nm thickness. Atypical diode behavior is observed with a turn-on voltage of 4.4 V, a dynamic resistance of 74.07 KΩ and a rectification ratio of 2.02 due to unbalanced transport. Results show also that the current-voltage characteristics present three different regimes of the power-law (J~Vᵐ) for which the conduction mechanism is well described with space-charge-limited current conduction mechanism (SCLC) with a charge carrier mobility of 2.38.10⁻⁵cm2V⁻¹S⁻¹. Moreover, the electrical transport properties of this device have been carried out using a dependent frequency study in the range (50 Hz–1.4 MHz) for different applied biases (from 0 to 6 V). At lower frequency, the σdc values increase with bias voltage rising, supporting that the mobile ion can hop successfully to its nearest vacant site. From σac and impedance measurements, the equivalent electrical circuit is evidenced, where the conductivity process is coherent with an exponential trap distribution caused by structural defects and/or chemical impurities.

Keywords: semiconducting polymer, conductivity, SCLC, impedance spectroscopy

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4714 Green Synthesis (Using Environment Friendly Bacteria) of Silver-Nanoparticles and Their Application as Drug Delivery Agents

Authors: Sutapa Mondal Roy, Suban K. Sahoo

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The primary aim of this work is to synthesis silver nanoparticles (AgNPs) through environmentally benign routes to avoid any chemical toxicity related undesired side effects. The nanoparticles were stabilized with drug ciprofloxacin (Cp) and were studied for their effectiveness as drug delivery agent. Targeted drug delivery improves the therapeutic potential of drugs at the diseased site as well as lowers the overall dose and undesired side effects. The small size of nanoparticles greatly facilitates the transport of active agents (drugs) across biological membranes and allows them to pass through the smallest capillaries in the body that are 5-6 μm in diameter, and can minimize possible undesired side effects. AgNPs are non-toxic, inert, stable, and has a high binding capacity and thus can be considered as biomaterials. AgNPs were synthesized from the nutrient broth supernatant after the culture of environment-friendly bacteria Bacillus subtilis. The AgNPs were found to show the surface plasmon resonance (SPR) band at 425 nm. The Cp capped Ag nanoparticles formation was complete within 30 minutes, which was confirmed from absorbance spectroscopy. Physico-chemical nature of the AgNPs-Cp system was confirmed by Dynamic Light Scattering (DLS), Transmission Electron Microscopy (TEM) etc. The AgNPs-Cp system size was found to be in the range of 30-40 nm. To monitor the kinetics of drug release from the surface of nanoparticles, the release of Cp was carried out by careful dialysis keeping AgNPs-Cp system inside the dialysis bag at pH 7.4 over time. The drug release was almost complete after 30 hrs. During the drug delivery process, to understand the AgNPs-Cp system in a better way, the sincere theoretical investigation is been performed employing Density Functional Theory. Electronic charge transfer, electron density, binding energy as well as thermodynamic properties like enthalpy, entropy, Gibbs free energy etc. has been predicted. The electronic and thermodynamic properties, governed by the AgNPs-Cp interactions, indicate that the formation of AgNPs-Cp system is exothermic i.e. thermodynamically favorable process. The binding energy and charge transfer analysis implies the optimum stability of the AgNPs-Cp system. Thus, the synthesized Cp-Ag nanoparticles can be effectively used for biological purposes due to its environmentally benign routes of synthesis procedures, which is clean, biocompatible, non-toxic, safe, cost-effective, sustainable and eco-friendly. The Cp-AgNPs as biomaterials can be successfully used for drug delivery procedures due to slow release of drug from nanoparticles over a considerable period of time. The kinetics of the drug release show that this drug-nanoparticle assembly can be effectively used as potential tools for therapeutic applications. The ease of synthetic procedure, lack of possible chemical toxicity and their biological activity along with excellent application as drug delivery agent will open up vista of using nanoparticles as effective and successful drug delivery agent to be used in modern days.

Keywords: silver nanoparticles, ciprofloxacin, density functional theory, drug delivery

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4713 Joule Self-Heating Effects and Controlling Oxygen Vacancy in La₀.₈Ba₀.₂MnO₃ Ultrathin Films with Nano-Sized Labyrinth Morphology

Authors: Guankai Lin, Wei Tong, Hong Zhu

Abstract:

The electric current induced Joule heating effects have been investigated in La₀.₈Ba₀.₂MnO₃ ultrathin films deposited on LaAlO₃(001) single crystal substrate with smaller lattice constant by using the sol-gel method. By applying moderate bias currents (~ 10 mA), it is found that Joule self-heating simply gives rise to a temperature deviation between the thermostat and the test sample, but the intrinsic ρ(T) relationship measured at a low current (0.1 mA) changes little. However, it is noteworthy that the low-temperature transport behavior degrades from metallic to insulating state after applying higher bias currents ( > 31 mA) in a vacuum. Furthermore, metallic transport can be recovered by placing the degraded film in air. The results clearly suggest that the oxygen vacancy in the La₀.₈Ba₀.₂MnO₃ films is controllable in different atmospheres, particularly with the aid of the Joule self-heating. According to the SEM images, we attribute the controlled oxygen vacancy to the nano-sized labyrinth pattern of the films, where the large surface-to-volume ratio plays a curial role.

Keywords: controlling oxygen vacancy, joule self-heating, manganite, sol-gel method

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4712 Structural and Electrical Properties of VO₂/ZnO Nanostructures

Authors: Sang-Wook Han, Zhenlan Jin, In-Hui Hwang, Chang-In Park

Abstract:

We examined structural and electrical properties of uniformly-oriented VO₂/ZnO nanostructures. VO₂ was deposited on ZnO templates by using a direct current-sputtering deposition. Scanning electron microscope and transmission electron microscope measurements indicated that b-oriented VO₂ were uniformly crystallized on ZnO templates with different lengths. VO₂/ZnO formed nanorods on ZnO nanorods with length longer than 250 nm. X-ray absorption fine structure at V K edge of VO₂/ZnO showed M1 and R phases of VO₂ at 30 and 100 ℃, respectively, suggesting structural phase transition between temperatures. Temperature-dependent resistance measurements of VO₂/ZnO nanostructures revealed metal-to-insulator transition at 65 ℃ and 55 ℃ during heating and cooling, respectively, regardless of ZnO length. The bond lengths of V-O and V-V pairs in VO₂/ZnO nanorods were somewhat distorted, and a substantial amount of structural disorder existed in the atomic pairs, compared to those of VO₂ films without ZnO. Resistance from VO₂/ZnO nanorods revealed a sharp MIT near 65 ℃ during heating and a hysteresis behavior. The resistance results suggest that microchannel for charge carriers exist nearly room temperature during cooling. VO₂/ZnO nanorods are quite stable and reproducible so that they can be widely used for practical applications to electronic devices, gas sensors, and ultra-fast switches, as examples.

Keywords: metal-to-insulator transition, VO₂, ZnO, XAFS, structural-phase transition

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4711 The Mechanical Properties of In-Situ Consolidated Nanocrystalline Aluminum Alloys

Authors: Khaled M. Youssef, Sara I. Ahmed

Abstract:

In this study, artifacts-free bulk nanocrystalline pure aluminum alloy samples were prepared through mechanical milling under ultra-high purity argon and at both liquid nitrogen and room temperatures. The nanostructure evolution during milling was examined using X-ray diffraction and transmission electron microscope techniques. The in-situ consolidated samples after milling exhibited an average grain size of 18 nm. The tensile properties of this novel material are reported in comparison with coarse-grained aluminum alloys. The 0.2% offset yield strength of the nanocrystalline aluminum was found to be 340 MPa. This value is at least one order of magnitude higher than that of the coarse-grained aluminum alloy. In addition to this extraordinarily high strength, the nanocrystalline aluminum showed a significant tensile ductility, with 6% uniform elongation and 11% elongation-to-failure. The transmission electron microscope observations in this study provide evidence of deformation twinning in the plastically deformed nanocrystalline aluminum. These results highlight a change of the deformation mechanism from a typical dislocation slip to twinning deformation induced by partial dislocation activities.

Keywords: nanocrystalline, aluminum, strength, ductility

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4710 Synthesis of Flower-Like Silver Nanoarchitectures in Special Shapes and Their Applications in Surface-Enhanced Raman Scattering

Authors: Radka Králová, Libor Kvítek, Václav Ranc, Aleš Panáček, Radek Zbořil

Abstract:

Surface–Enhanced Raman Scattering (SERS) is an optical spectroscopic technique with very good potential for sensitive detection of substances. In this research, active substrates with high enhancement were provided. Novel silver particles (nanostructures) with high roughened, flower–like morphology were prepared by reduction of cation complex [Ag(NH3)2]+ in presence of sodium borohydride as reducing agent and stabilized polyacrylic acid. The products were characterized by UV/VIS absorption spectrophotometry. Special shapes of silver particles were determined by scanning electron microscopy (SEM) and transmission electron spectroscopy (TEM). Dispersions of this particle were put on fixed substrate to producing suitable layer for SERS. Adenine was applied as basic substance whose effect of enhancement on the layer of silver nanostructures was studied. By comparison with our work, the important influence of stabilizers, polyacrylic acid with various molecular weight and concentration, on the transfer of particles and formation of new structure was confirmed.

Keywords: metals, nanostructures, chemical reduction, Raman spectroscopy, optical properties

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4709 Leveraging Information for Building Supply Chain Competitiveness

Authors: Deepika Joshi

Abstract:

Operations in automotive industry rely greatly on information shared between Supply Chain (SC) partners. This leads to efficient and effective management of SC activity. Automotive sector in India is growing at 14.2 percent per annum and has huge economic importance. We find that no study has been carried out on the role of information sharing in SC management of Indian automotive manufacturers. Considering this research gap, the present study is planned to establish the significance of information sharing in Indian auto-component supply chain activity. An empirical research was conducted for large scale auto component manufacturers from India. Twenty four Supply Chain Performance Indicators (SCPIs) were collected from existing literature. These elements belong to eight diverse but internally related areas of SC management viz., demand management, cost, technology, delivery, quality, flexibility, buyer-supplier relationship, and operational factors. A pair-wise comparison and an open ended questionnaire were designed using these twenty four SCPIs. The questionnaire was then administered among managerial level employees of twenty-five auto-component manufacturing firms. Analytic Network Process (ANP) technique was used to analyze the response of pair-wise questionnaire. Finally, twenty-five priority indexes are developed, one for each respondent. These were averaged to generate an industry specific priority index. The open-ended questions depicted strategies related to information sharing between buyers and suppliers and their influence on supply chain performance. Results show that the impact of information sharing on certain performance indicators is relatively greater than their corresponding variables. For example, flexibility, delivery, demand and cost related elements have massive impact on information sharing. Technology is relatively less influenced by information sharing but it immensely influence the quality of information shared. Responses obtained from managers reveal that timely and accurate information sharing lowers the cost, increases flexibility and on-time delivery of auto parts, therefore, enhancing the competitiveness of Indian automotive industry. Any flaw in dissemination of information can disturb the cycle time of both the parties and thus increases the opportunity cost. Due to supplier’s involvement in decisions related to design of auto parts, quality conformance is found to improve, leading to reduction in rejection rate. Similarly, mutual commitment to share right information at right time between all levels of SC enhances trust level. SC partners share information to perform comprehensive quality planning to ingrain total quality management. This study contributes to operations management literature which faces scarcity of empirical examination on this subject. It views information sharing as a building block which firms can promote and evolve to leverage the operational capability of all SC members. It will provide insights for Indian managers and researchers as every market is unique and suppliers and buyers are driven by local laws, industry status and future vision. While major emphasis in this paper is given to SC operations happening between domestic partners, placing more focus on international SC can bring in distinguished results.

Keywords: Indian auto component industry, information sharing, operations management, supply chain performance indicators

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4708 A System Dynamics Approach for Assessing Policy Impacts on Closed-Loop Supply Chain Efficiency: A Case Study on Electric Vehicle Batteries

Authors: Guannan Ren, Thomas Mazzuchi, Shahram Sarkani

Abstract:

Electric vehicle battery recycling has emerged as a critical process in the transition toward sustainable transportation. As the demand for electric vehicles continues to rise, so does the need to address the end-of-life management of their batteries. Electric vehicle battery recycling benefits resource recovery and supply chain stability by reclaiming valuable metals like lithium, cobalt, nickel, and graphite. The reclaimed materials can then be reintroduced into the battery manufacturing process, reducing the reliance on raw material extraction and the environmental impacts of waste. Current battery recycling rates are insufficient to meet the growing demands for raw materials. While significant progress has been made in electric vehicle battery recycling, many areas can still improve. Standardization of battery designs, increased collection and recycling infrastructures, and improved efficiency in recycling processes are essential for scaling up recycling efforts and maximizing material recovery. This work delves into key factors, such as regulatory frameworks, economic incentives, and technological processes, that influence the cost-effectiveness and efficiency of battery recycling systems. A system dynamics model that considers variables such as battery production rates, demand and price fluctuations, recycling infrastructure capacity, and the effectiveness of recycling processes is created to study how these variables are interconnected, forming feedback loops that affect the overall supply chain efficiency. Such a model can also help simulate the effects of stricter regulations on battery disposal, incentives for recycling, or investments in research and development for battery designs and advanced recycling technologies. By using the developed model, policymakers, industry stakeholders, and researchers may gain insights into the effects of applying different policies or process updates on electric vehicle battery recycling rates.

Keywords: environmental engineering, modeling and simulation, circular economy, sustainability, transportation science, policy

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4707 Investigation of the Dielectric Response of Ppy/V₂c Mxene-Zns from First Principle Calculation

Authors: Anthony Chidi Ezika, Gbolahan Joseph Adekoya, Emmanuel Rotimi Sadiku, Yskandar Hamam, Suprakas Sinha Ray

Abstract:

High-energy-density polymer/ceramic composites require a high breakdown strength and dielectric constant. Interface polarization and electric percolation are responsible for the high dielectric constant. In order to create composite dielectrics, high conductivity ceramic particles are combined with polymers to increase the dielectric constant. In this study, bonding and the non-uniform distribution of charges in the ceramic/ceramic interface zone are investigated using density functional theory (DFT) modeling. This non-uniform distribution of charges is intended to improve the ceramic/ceramic interface's dipole polarization (dielectric response). The interfacial chemical bond formation can also improve the structural stability of the hybrid filler and, consequently, of the composite films. To comprehend the electron-transfer process, the density of state and electron localization function of the PPy with hybrid fillers are also studied. The polymer nanocomposite is anticipated to provide a suitable dielectric response for energy storage applications.

Keywords: energy storage, V₂C/ ZnS hybrid, polypyrrole, MXene, nanocomposite, dielectric

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4706 Regional Rates of Sand Supply to the New South Wales Coast: Southeastern Australia

Authors: Marta Ribo, Ian D. Goodwin, Thomas Mortlock, Phil O’Brien

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Coastal behavior is best investigated using a sediment budget approach, based on the identification of sediment sources and sinks. Grain size distribution over the New South Wales (NSW) continental shelf has been widely characterized since the 1970’s. Coarser sediment has generally accumulated on the outer shelf, and/or nearshore zones, with the latter related to the presence of nearshore reef and bedrocks. The central part of the NSW shelf is characterized by the presence of fine sediments distributed parallel to the coastline. This study presents new grain size distribution maps along the NSW continental shelf, built using all available NSW and Commonwealth Government holdings. All available seabed bathymetric data form prior projects, single and multibeam sonar, and aerial LiDAR surveys were integrated into a single bathymetric surface for the NSW continental shelf. Grain size information was extracted from the sediment sample data collected in more than 30 studies. The information extracted from the sediment collections varied between reports. Thus, given the inconsistency of the grain size data, a common grain size classification was her defined using the phi scale. The new sediment distribution maps produced, together with new detailed seabed bathymetric data enabled us to revise the delineation of sediment compartments to more accurately reflect the true nature of sediment movement on the inner shelf and nearshore. Accordingly, nine primary mega coastal compartments were delineated along the NSW coast and shelf. The sediment compartments are bounded by prominent nearshore headlands and reefs, and major river and estuarine inlets that act as sediment sources and/or sinks. The new sediment grain size distribution was used as an input in the morphological modelling to quantify the sediment transport patterns (and indicative rates of transport), used to investigate sand supply rates and processes from the lower shoreface to the NSW coast. The rate of sand supply to the NSW coast from deep water is a major uncertainty in projecting future coastal response to sea-level rise. Offshore transport of sand is generally expected as beaches respond to rising sea levels but an onshore supply from the lower shoreface has the potential to offset some of the impacts of sea-level rise, such as coastline recession. Sediment exchange between the lower shoreface and sub-aerial beach has been modelled across the south, central, mid-north and far-north coast of NSW. Our model approach is that high-energy storm events are the primary agents of sand transport in deep water, while non-storm conditions are responsible for re-distributing sand within the beach and surf zone.

Keywords: New South Wales coast, off-shore transport, sand supply, sediment distribution maps

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4705 Electrode Performance of Carbon Coated Nanograined LiFePO4 in Lithium Batteries

Authors: Princess Stephanie P. Llanos, Rinlee Butch M. Cervera

Abstract:

Lithium iron phosphate (LiFePO4) is a potential cathode material for lithium-ion batteries due to its promising characteristics. In this study, carbon-coated nanograined LiFePO4 is synthesized via wet chemistry method at a low temperature of 400 °C and investigated its performance as a cathode in Lithium battery. The X-ray diffraction pattern of the synthesized samples can be indexed to an orthorhombic LiFePO4 structure. Agglomerated particles that range from 200 nm to 300 nm are observed from scanning electron microscopy images. Transmission electron microscopy images confirm the crystalline structure of LiFePO4 and coating of amorphous carbon layer. Elemental mapping using Energy dispersive spectroscopy analysis revealed the homogeneous dispersion of Fe, P, O, and C elements. On the other hand, the electrochemical performances of the synthesized cathodes were investigated using cyclic voltammetry, galvanostatic charge/discharge tests with different C-rates, and cycling performances. Galvanostatic charge and discharge measurements revealed that the sample sintered at 400 °C for 3 hours with carbon coating demonstrated the highest capacity among the samples which reaches up to 160 mAhg⁻¹ at 0.1C rate.

Keywords: cathode, charge-discharge, electrochemical, lithium batteries

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4704 Analysis of Cannabinol and Cannabidiol affinity with GBRA1

Authors: Hamid Hossein Khezri, Afsaneh Javdani-Mallak

Abstract:

Fast inhibitory neurotransmission in the mammalian nervous system is largely mediated by GABAA receptors, chloride-selective members of the superfamily of pentameric Cys-loop receptors. Cannabidiol (CBD) is one of the members of cannabinoid compounds found in cannabis. CBD and Cannabinol (CBN), as the other extract of plant Cannabis were able to reduce myofascial pain in rats with immunosuppressive and anti-inflammatory activities. In this study, we accomplished protein-protein BLAST, and the sequence was found to be for Gamma-aminobutyric acid receptor subunit alpha-1 (GBRA1) chain A and its 3D structure was subsequently downloaded from Protein Data Bank. The structures of the ligands, cannabinol, and cannabidiol, were obtained from PubChem. After the necessary process of the obtained files, AutoDock Vina was used to perform molecular docking. Docking between the ligands and GBRA1 chain A revealed that cannabinol has a higher affinity to GBRA1 (binding energy = -7.5 kcal/mol) compared to cannabidiol (binding energy = -6.5 kcal/mol). Furthermore, cannabinol seems to be able to interact with 10 residues of the protein, out of which 3 are in the neurotransmitter-gated ion-channel transmembrane domain of GBRA1, whereas cannabidiol interacts with two other residues. Although the results of this project do not indicate the activating /or inhibitory capability of the studied compounds, it suggests that cannabinol can act as a relatively strong ligand for GBRA1.

Keywords: protein-ligand docking, cannabinol, cannabidiol, GBRA1

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4703 Excited State Structural Dynamics of Retinal Isomerization Revealed by a Femtosecond X-Ray Laser

Authors: Przemyslaw Nogly, Tobias Weinert, Daniel James, Sergio Carbajo, Dmitry Ozerov, Antonia Furrer, Dardan Gashi, Veniamin Borin, Petr Skopintsev, Kathrin Jaeger, Karol Nass, Petra Bath, Robert Bosman, Jason Koglin, Matthew Seaberg, Thomas Lane, Demet Kekilli, Steffen Brünle, Tomoyuki Tanaka, Wenting Wu, Christopher Milne, Thomas A. White, Anton Barty, Uwe Weierstall, Valerie Panneels, Eriko Nango, So Iwata, Mark Hunter, Igor Schapiro, Gebhard Schertler, Richard Neutze, Jörg Standfuss

Abstract:

Ultrafast isomerization of retinal is the primary step in a range of photoresponsive biological functions including vision in humans and ion-transport across bacterial membranes. We studied the sub-picosecond structural dynamics of retinal isomerization in the light-driven proton pump bacteriorhodopsin using an X-ray laser. Twenty snapshots with near-atomic spatial and temporal resolution in the femtosecond regime show how the excited all-trans retinal samples conformational states within the protein binding pocket prior to passing through a highly-twisted geometry and emerging in the 13-cis conformation. The aspartic acid residues and functional water molecules in proximity of the retinal Schiff base respond collectively to formation and decay of the initial excited state and retinal isomerization. These observations reveal how the protein scaffold guides this remarkably efficient photochemical reaction.

Keywords: bacteriorhodopsin, free-electron laser, retinal isomerization mechanism, time-resolved crystallography

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4702 The Developing Method of Supply Chain Economy in Eurasia and North America

Authors: Tae Ho Kim

Abstract:

Using the center of gravity method, we intend to find the center of gravity of Eurasia and North America, focusing on the local population, and study economic development plans in Eurasia and North America. By analyzing the strengths and opportunities of an industrial location for each region, we find ways for the country to grow and develop. Through economic cooperation and support between countries, we want to reduce the cause of conflict and dispute through economic growth in countries or regions. Furthermore, we want to create conditions for peaceful and happy regions or countries. Eurasia and North America are rich in resources, have great growth potential in terms of global supply chains, and have a good position to develop further. By analyzing intimacy between countries using REM, a CRM method, we intend to transform it into a region where a hopeful future of peace and prosperity begins. The future can be transformed through positive thinking or love for humanity. Indicators of intimacy between countries or regions can also be created anew if they change how they view each other. The Earth we live on is facing great risks, such as climate change and war. In order to reduce this crisis and maintain peace and prosperity, we must cooperate with each other in new directions.

Keywords: supply chain economy, REM, Indicators of intimacy, peace and prosperity

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4701 Enhanced Iron Accumulation in Chickpea Though Expression of Iron-Regulated Transport and Ferritin Genes

Authors: T. M. L. Hoang, G. Tan, S. D. Bhowmik, B. Williams, A. Johnson, M. R. Karbaschi, Y. Cheng, H. Long, S. G. Mundree

Abstract:

Iron deficiency is a worldwide problem affecting both developed and developing countries. Currently, two major approaches namely iron supplementation and food fortification have been used to combat this issue. These measures, however, are limited by the economic status of the targeted demographics. Iron biofortification through genetic modification to enhance the inherent iron content and bioavailability of crops has been employed recently. Several important crops such as rice, wheat, and banana were reported successfully improved iron content via this method, but there is no known study in legumes. Chickpea (Cicer arietinum) is an important leguminous crop that is widely consumed, particularly in India where iron deficiency anaemia is prevalent. Chickpea is also an ideal pulse in the formulation of complementary food between pulses and cereals to improve micronutrient contents. This project aims at generating enhanced ion accumulation and bioavailability chickpea through the exogenous expression of genes related to iron transport and iron homeostasis in chickpea plants. Iron-Regulated Transport (IRT) and Ferritin genes in combination were transformed into chickpea half-embryonic axis by agrobacterium–mediated transformation. Transgenic independent event was confirmed by Southern Blot analysis. T3 leaves and seeds of transgenic chickpea were assessed for iron contents using LA-ICP-MS (Laser Ablation – Inductively Coupled Plasma Mass Spectrometry) and ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry). The correlation between transgene expression levels and iron content in T3 plants and seeds was assessed using qPCR. Results show that iron content in transgenic chickpea expressing the above genes significantly increased compared to that in non-transgenic controls.

Keywords: iron biofortification, chickpea, IRT, ferritin, Agrobacterium-mediated transformation, LA-ICP-MS, ICP-OES

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4700 European Drug Serialization: Securing the Pharmaceutical Drug Supply Chain from Counterfeiters

Authors: Vikram Chowdhary, Marek Vins

Abstract:

The profitability of the pharmaceutical drug business has attracted considerable interest, but it also faces significant challenges. Counterfeiters take advantage of the industry's vulnerabilities, which are further exacerbated by the globalization of the market, online trading, and complex supply chains. Governments and organizations worldwide are dedicated to creating a secure environment that ensures a consistent and genuine supply of pharmaceutical products. In 2019, the European authorities implemented regulation EU 2016/161 to strengthen traceability and transparency throughout the entire drug supply chain. This regulation requires the addition of enhanced security features, such as serializing items to the saleable unit level or individual packs. Despite these efforts, the incidents of pharmaceutical counterfeiting continue to rise globally, with regulated territories being particularly affected. This paper examines the effectiveness of the drug serialization system implemented by European authorities. By conducting a systematic literature review, we assess the implementation of drug serialization and explore the potential benefits of integrating emerging digital technologies, such as RFID and Blockchain, to improve traceability and management. The objective is to fortify pharmaceutical supply chains against counterfeiters and manipulators and ensure their security.

Keywords: blockchain, counterfeit drugs, EU drug serialization, pharmaceutical industry, RFID

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4699 A Mathematical Model for Reliability Redundancy Optimization Problem of K-Out-Of-N: G System

Authors: Gak-Gyu Kim, Won Il Jung

Abstract:

According to a remarkable development of science and technology, function and role of the system of engineering fields has recently been diversified. The system has become increasingly more complex and precise, and thus, system designers intended to maximize reliability concentrate more effort at the design stage. This study deals with the reliability redundancy optimization problem (RROP) for k-out-of-n: G system configuration with cold standby and warm standby components. This paper further intends to present the optimal mathematical model through which the following three elements of (i) multiple components choices, (ii) redundant components quantity and (iii) the choice of redundancy strategies may be combined in order to maximize the reliability of the system. Therefore, we focus on the following three issues. First, we consider RROP that there exists warm standby state as well as cold standby state of the component. Second, as eliminating an approximation approach of the previous RROP studies, we construct a precise model for system reliability. Third, given transition time when the state of components changes, we present not simply a workable solution but the advanced method. For the wide applicability of RROPs, moreover, we use absorbing continuous time Markov chain and matrix analytic methods in the suggested mathematical model.

Keywords: RROP, matrix analytic methods, k-out-of-n: G system, MTTF, absorbing continuous time Markov Chain

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4698 Second Harmonic Generation of Higher-Order Gaussian Laser Beam in Density Rippled Plasma

Authors: Jyoti Wadhwa, Arvinder Singh

Abstract:

This work presents the theoretical investigation of an enhanced second-harmonic generation of higher-order Gaussian laser beam in plasma having a density ramp. The mechanism responsible for the self-focusing of a laser beam in plasma is considered to be the relativistic mass variation of plasma electrons under the effect of a highly intense laser beam. Using the moment theory approach and considering the Wentzel-Kramers-Brillouin approximation for the non-linear Schrodinger wave equation, the differential equation is derived, which governs the spot size of the higher-order Gaussian laser beam in plasma. The nonlinearity induced by the laser beam creates the density gradient in the background plasma electrons, which is responsible for the excitation of the electron plasma wave. The large amplitude electron plasma wave interacts with the fundamental beam, which further produces the coherent radiations with double the frequency of the incident beam. The analysis shows the important role of the different modes of higher-order Gaussian laser beam and density ramp on the efficiency of generated harmonics.

Keywords: density rippled plasma, higher order Gaussian laser beam, moment theory approach, second harmonic generation.

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4697 Preparation, Characterization and Photocatalytic Activity of a New Noble Metal Modified TiO2@SrTiO3 and SrTiO3 Photocatalysts

Authors: Ewelina Grabowska, Martyna Marchelek

Abstract:

Among the various semiconductors, nanosized TiO2 has been widely studied due to its high photosensitivity, low cost, low toxicity, and good chemical and thermal stability. However, there are two main drawbacks to the practical application of pure TiO2 films. One is that TiO2 can be induced only by ultraviolet (UV) light due to its intrinsic wide bandgap (3.2 eV for anatase and 3.0 eV for rutile), which limits its practical efficiency for solar energy utilization since UV light makes up only 4-5% of the solar spectrum. The other is that a high electron-hole recombination rate will reduce the photoelectric conversion efficiency of TiO2. In order to overcome the above drawbacks and modify the electronic structure of TiO2, some semiconductors (eg. CdS, ZnO, PbS, Cu2O, Bi2S3, and CdSe) have been used to prepare coupled TiO2 composites, for improving their charge separation efficiency and extending the photoresponse into the visible region. It has been proved that the fabrication of p-n heterostructures by combining n-type TiO2 with p-type semiconductors is an effective way to improve the photoelectric conversion efficiency of TiO2. SrTiO3 is a good candidate for coupling TiO2 and improving the photocatalytic performance of the photocatalyst because its conduction band edge is more negative than TiO2. Due to the potential differences between the band edges of these two semiconductors, the photogenerated electrons transfer from the conduction band of SrTiO3 to that of TiO2. Conversely, the photogenerated electrons transfer from the conduction band of SrTiO3 to that of TiO2. Then the photogenerated charge carriers can be efficiently separated by these processes, resulting in the enhancement of the photocatalytic property in the photocatalyst. Additionally, one of the methods for improving photocatalyst performance is addition of nanoparticles containing one or two noble metals (Pt, Au, Ag and Pd) deposited on semiconductor surface. The mechanisms were proposed as (1) the surface plasmon resonance of noble metal particles is excited by visible light, facilitating the excitation of the surface electron and interfacial electron transfer (2) some energy levels can be produced in the band gap of TiO2 by the dispersion of noble metal nanoparticles in the TiO2 matrix; (3) noble metal nanoparticles deposited on TiO2 act as electron traps, enhancing the electron–hole separation. In view of this, we recently obtained series of TiO2@SrTiO3 and SrTiO3 photocatalysts loaded with noble metal NPs. using photodeposition method. The M- TiO2@SrTiO3 and M-SrTiO3 photocatalysts (M= Rh, Rt, Pt) were studied for photodegradation of phenol in aqueous phase under UV-Vis and visible irradiation. Moreover, in the second part of our research hydroxyl radical formations were investigated. Fluorescence of irradiated coumarin solution was used as a method of ˙OH radical detection. Coumarin readily reacts with generated hydroxyl radicals forming hydroxycoumarins. Although the major hydroxylation product is 5-hydroxycoumarin, only 7-hydroxyproduct of coumarin hydroxylation emits fluorescent light. Thus, this method was used only for hydroxyl radical detection, but not for determining concentration of hydroxyl radicals.

Keywords: composites TiO2, SrTiO3, photocatalysis, phenol degradation

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4696 Chitosan Magnetic Nanoparticles and Its Analytical Applications

Authors: Eman Alzahrani

Abstract:

Efficient extraction of proteins by removing interfering materials is necessary in proteomics, since most instruments cannot handle such contaminated sample matrices directly. In this study, chitosan-coated magnetic nanoparticles (CS-MNPs) for purification of myoglobin were successfully fabricated. First, chitosan (CS) was prepared by a deacetylation reaction during its extraction from shrimp-shell waste. Second, magnetic nanoparticles (MNPs) were synthesised, using the coprecipitation method, from aqueous Fe2+ and Fe3+ salt solutions by the addition of a base under an inert atmosphere, followed by modification of the surface of MNPs with chitosan. The morphology of the formed nanoparticles, which were about 23 nm in average diameter, was observed by transmission electron microscopy (TEM). In addition, nanoparticles were characterised using X-ray diffraction patterns (XRD), which showed the naked magnetic nanoparticles have a spinel structure and the surface modification did not result in phase change of the Fe3O4. The coating of MNPs was also demonstrated by scanning electron microscopy (SEM) analysis, energy dispersive analysis of X-ray spectroscopy (EDAX), and Fourier transform infrared (FT-IR) spectroscopy. The adsorption behaviour of MNPs and CS-MNPs towards myoglobin was investigated. It was found that the difference in adsorption capacity between MNPs and CS-MNPs was larger for CS-MNPs. This result makes CS-MNPs good adsorbents and attractive for using in protein extraction from biological samples.

Keywords: chitosan, magnetic nanoparticles, coprecipitation, adsorption

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4695 Catalytic Deoxygenation of Non-Edible Oil to Renewable Fuel by Using Calcium-Based Nanocatalyst

Authors: Hwei Voon Lee, N. Asikin-Mijana, Y. H. Taufiq-Yap, J. C. Juan, N. A. Rahman

Abstract:

Cracking–Deoxygenation process is one of the important reaction pathways for the production of bio-fuel with desirable n-C17 hydrocarbon chain via removal of oxygen compounds. Calcium-based catalyst has attracted much attention in deoxygenation process due to its relatively high capacity in removing oxygenated compounds in the form of CO₂ and CO under decarboxylation and decarbonylation reaction, respectively. In the present study, deoxygenation of triolein was investigated using Ca(OH)₂ nanocatalyst derived from low cost natural waste shells. The Ca(OH)₂ nanocatalyst was prepared via integration techniques between surfactant treatment (anionic and non-ionic) and wet sonochemical effect. Results showed that sonochemically assisted surfactant treatment has successfully enhanced the physicochemical properties of Ca(OH)₂ nanocatalyst in terms of nanoparticle sizes (∼50 nm), high surface area(∼130 m²g⁻¹), large porosity (∼18.6 nm) and strong basic strength. The presence of superior properties from surfactant treated Ca(OH)₂ nanocatalysts rendered high deoxygenation degree, which is capable of producing high alkane and alkene selectivity in chain length of n-C17(high value of C17/(n-C17+ n-C18)ratio = 0.88). Furthermore, both Ca(OH)₂–EG and Ca(OH)₂–CTAB nanocatalysts showed high reactivity with 47.37% and 44.50%, respectively in total liquid hydrocarbon content of triolein conversion with high H/C and low O/C ratio.

Keywords: clamshell, cracking, decarboxylation-decarbonylation, hydrocarbon

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4694 Isolation of Three Bioactive Phenantroindolizidine Alkaloids from the Fruit Latex of Ficus botryocarpa Miq.

Authors: Jayson Wau, David Timi, Anthony Harakuwe, Bruce Bowden, Cherie Motti, Harry Sakulas, Rag Gubag-Sipou

Abstract:

The latex of F. botryocarpa fruit is applied on sores, wounds and other skin infections in Papua New Guinea ethnotherapeutic practices. Systematic bioassay guided separation and isolation of subsequent fractions of latex extracts resulted in three bioactive fractions active against Staphylococcus aureus and Escherichia coli. This study reports structural elucidation of the three isolates. Structures were determined by physical (M.pt and Rf values) and spectroscopic (1D-1H NMR, 2D-HSQC NMR, 2D-HMBC NMR) and MS ESI-POS. The two methylene protons (2H-1) and (2H-3) resonate as triplets at δ 3.59 and δ 4.99 respectively. Electron dense δ 4.99 (2H-3) on (C-3) depicts the strong electron-withdrawing component, quaternary nitrogen (=N= +). Protons resonating at δ 3.88 and 3.89 are singlets depicting two methoxy groups. Both δ 3.88 and δ 3.89 are para-aryls substituents. The methines δ 9.13 and 8.60 are singlets depicting two lone protons on the indolizidinium aryl component. All isolates, (1), (2) and (3) were identified to be ficuseptine by comparing 1D-NMR assignments. 2D-NMR and MS of (2) found it to be ficuseptine chloride '2, 3-dihydro-6, 8-bis (4-methoxyphenyl)-, 1H-indolizinium chloride'. Their counter ions of the ficuseptines were not established and provide promising lead for the further investigation.

Keywords: Ficus botryocarpa, antimicrobial activity, ficuseptine, sores

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4693 Vitamin B9 Separation by Synergic Pertraction

Authors: Blaga Alexandra Cristina, Kloetzer Lenuta, Bompa Amalia Stela, Galaction Anca Irina, Cascaval Dan

Abstract:

Vitamin B9 is an important member of vitamins B group, being a growth factor, important for making genetic material as DNA and RNA, red blood cells, for building muscle tissues, especially during periods of infancy, adolescence and pregnancy. Its production by biosynthesis is based on the high metabolic potential of mutant Bacillus subtilis, due to a superior biodisponibility compared to that obtained by chemical pathways. Pertraction, defined as the extraction and transport through liquid membranes consists in the transfer of a solute between two aqueous phases of different pH-values, phases that are separated by a solvent layer of various sizes. The pertraction efficiency and selectivity could be significantly enhanced by adding a carrier in the liquid membrane, such as organophosphoric compounds, long chain amines or crown-ethers etc., the separation process being called facilitated pertraction. The aim of the work is to determine the impact of the presence of two extractants/carriers in the bulk liquid membrane, i.e. di(2-ethylhexyl) phosphoric acid (D2EHPA) and lauryltrialkylmetilamine (Amberlite LA2) on the transport kinetics of vitamin B9. The experiments have been carried out using two pertraction equipments for a free liquid membrane or bulk liquid membrane. One pertraction cell consists on a U-shaped glass pipe (used for the dichloromethane membrane) and the second one is an H-shaped glass pipe (used for h-heptane), having 45 mm inner diameter of the total volume of 450 mL, the volume of each compartment being of 150 mL. The aqueous solutions are independently mixed by means of double blade stirrers with 6 mm diameter and 3 mm height, having the rotation speed of 500 rpm. In order to reach high diffusional rates through the solvent layer, the organic phase has been mixed with a similar stirrer, at a similar rotation speed (500 rpm). The area of mass transfer surface, both for extraction and for reextraction, was of 1.59x10-³ m2. The study on facilitated pertraction with the mixture of two carriers, namely D2EHPA and Amberlite LA-2, dissolved in two solvents with different polarities: n-heptane and dichloromethane, indicated the possibility to obtain the synergic effect. The synergism has been analyzed by considering the vitamin initial and final mass flows, as well as the permeability factors through liquid membrane. The synergic effect has been observed at low D2EHPA concentrations and high Amberlite LA-2 concentrations, being more important for the low-polar solvent (n-heptane). The results suggest that the mechanism of synergic pertraction consists on the reaction between the organophosphoric carrier and vitamin B9 at the interface between the feed and membrane phases, while the aminic carrier enhances the hydrophobicity of this compound by solvation. However, the formation of this complex reduced the reextraction rate and, consequently, affects the synergism related to the final mass flows and permeability factor. For describing the influences of carriers concentrations on the synergistic coefficients, some equations have been proposed by taking into account the vitamin mass flows or permeability factors, with an average deviations between 4.85% and 10.73%.

Keywords: pertraction, synergism, vitamin B9, Amberlite LA-2, di(2-ethylhexyl) phosphoric acid

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4692 Competing Interactions, and Magnetization Dynamics in Doped Rare-Earth Manganites Nanostructural System

Authors: Wiqar Hussain Shah

Abstract:

The Structural, magnetic and transport behavior of La1-xCaxMnO3+ (x=0.48, 0.50, 0.52 and 0.55 and =0.015) compositions close to charge ordering, was studied through XRD, resistivity, DC magnetization and AC susceptibility measurements. With time and thermal cycling (T<300 K) there is an irreversible transformation of the low-temperature phase from a partially ferromagnetic and metallic to one that is less ferromagnetic and highly resistive. For instance, an increase of resistivity can be observed by thermal cycling, where no effect is obtained for lower Ca concentration. The time changes in the magnetization are logarithmic in general and activation energies are consistent with those expected for electron transfer between Mn ions. The data suggest that oxygen non-stoichiometry results in mechanical strains in this two-phase system, leading to the development of irreversible metastable states, which relax towards the more stable charge-ordered and antiferromagnetic microdomains at the nano-meter size. This behavior is interpreted in terms of strains induced charge localization at the interface between FM/AFM domains in the antiferromagnetic matrix. Charge, orbital ordering and phase separation play a prominent role in the appearance of such properties, since they can be modified in a spectacular manner by external factor, making the different physical properties metastable. Here we describe two factors that deeply modify those properties, viz. the doping concentration and the thermal cycling. The metastable state is recovered by the high temperature annealing. We also measure the magnetic relaxation in the metastable state and also the revival of the metastable state (in a relaxed sample) due to high temperature (800 ) thermal treatment.

Keywords: Rare-earth maganites, nano-structural materials, doping effects on electrical, magnetic properties, competing interactions

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4691 Preparation and Characterization of CuFe2O4/TiO2 Photocatalyst for the Conversion of CO2 into Methanol under Visible Light

Authors: Md. Maksudur Rahman Khan, M. Rahim Uddin, Hamidah Abdullah, Kaykobad Md. Rezaul Karim, Abu Yousuf, Chin Kui Cheng, Huei Ruey Ong

Abstract:

A systematic study was conducted to explore the photocatalytic reduction of carbon dioxide (CO2) into methanol on TiO2 loaded copper ferrite (CuFe2O4) photocatalyst under visible light irradiation. The phases and crystallite size of the photocatalysts were characterized by X-ray diffraction (XRD) and it indicates CuFe2O4 as tetragonal phase incorporation with anatase TiO2 in CuFe2O4/TiO2 hetero-structure. The XRD results confirmed the formation of spinel type tetragonal CuFe2O4 phases along with predominantly anatase phase of TiO2 in the CuFe2O4/TiO2 hetero-structure. UV-Vis absorption spectrum suggested the formation of the hetero-junction with relatively lower band gap than that of TiO2. Photoluminescence (PL) technique was used to study the electron–hole (e/h+) recombination process. PL spectra analysis confirmed the slow-down of the recombination of electron–hole (e/h+) pairs in the CuFe2O4/TiO2 hetero-structure. The photocatalytic performance of CuFe2O4/TiO2 was evaluated based on the methanol yield with varying amount of TiO2 over CuFe2O4 (0.5:1, 1:1, and 2:1) and changing light intensity. The mechanism of the photocatalysis was proposed based on the fact that the predominant species of CO2 in aqueous phase were dissolved CO2 and HCO3- at pH ~5.9. It was evident that the CuFe2O4 could harvest the electrons under visible light irradiation, which could further be injected to the conduction band of TiO2 to increase the life time of the electron and facilitating the reactions of CO2 to methanol. The developed catalyst showed good recycle ability up to four cycles where the loss of activity was ~25%. Methanol was observed as the main product over CuFe2O4, but loading with TiO2 remarkably increased the methanol yield. Methanol yield over CuFe2O4/TiO2 was found to be about three times higher (651 μmol/gcat L) than that of CuFe2O4 photocatalyst. This occurs because the energy of the band excited electrons lies above the redox potentials of the reaction products CO2/CH3OH.

Keywords: photocatalysis, CuFe2O4/TiO2, band-gap energy, methanol

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4690 Investigation of the Growth Kinetics of Phases in Ni–Sn System

Authors: Varun A Baheti, Sanjay Kashyap, Kamanio Chattopadhyay, Praveen Kumar, Aloke Paul

Abstract:

Ni–Sn system finds applications in the microelectronics industry, especially with respect to flip–chip or direct chip, attach technology. Here the region of interest is under bump metallization (UBM), and solder bump (Sn) interface due to the formation of brittle intermetallic phases there. Understanding the growth of these phases at UBM/Sn interface is important, as in many cases it controls the electro–mechanical properties of the product. Cu and Ni are the commonly used UBM materials. Cu is used for good bonding because of fast reaction with solder and Ni often acts as a diffusion barrier layer due to its inherently slower reaction kinetics with Sn–based solders. Investigation on the growth kinetics of phases in Ni–Sn system is reported in this study. Just for simplicity, Sn being major solder constituent is chosen. Ni–Sn electroplated diffusion couples are prepared by electroplating pure Sn on Ni substrate. Bulk diffusion couples prepared by the conventional method are also studied along with Ni–Sn electroplated diffusion couples. Diffusion couples are annealed for 25–1000 h at 50–215°C to study the phase evolutions and growth kinetics of various phases. The interdiffusion zone was analysed using field emission gun equipped scanning electron microscope (FE–SEM) for imaging. Indexing of selected area diffraction (SAD) patterns obtained from transmission electron microscope (TEM) and composition measurements done in electron probe micro−analyser (FE–EPMA) confirms the presence of various product phases grown across the interdiffusion zone. Time-dependent experiments indicate diffusion controlled growth of the product phase. The estimated activation energy in the temperature range 125–215°C for parabolic growth constants (and hence integrated interdiffusion coefficients) of the Ni₃Sn₄ phase shed light on the growth mechanism of the phase; whether its grain boundary controlled or lattice controlled diffusion. The location of the Kirkendall marker plane indicates that the Ni₃Sn₄ phase grows mainly by diffusion of Sn in the binary Ni–Sn system.

Keywords: diffusion, equilibrium phase, metastable phase, the Ni-Sn system

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4689 Biomimetic Dinitrosyl Iron Complexes: A Synthetic, Structural, and Spectroscopic Study

Authors: Lijuan Li

Abstract:

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

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

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4688 Reaction Kinetics for the Pyrolysis of Urea Phosphate

Authors: P. A. Broodryk, A. F. Van Der Merwe, H. W. J. P. Neomagus

Abstract:

The production of the clear liquid fertilizer ammonium polyphosphate (APP) is best achieved by the pyrolysis of urea phosphate, as it produces a product that is free from any of the impurities present in the raw phosphoric acid it was made from. This is a multiphase, multi-step reaction that produces carbon dioxide and ammonia as gasses and ammonium polyphosphate as liquid products. The polyphosphate chain length affects the solubility and thus the applicability of the product as liquid fertiliser, thus proper control of the reaction conditions is thus required for the use of this reaction in the production of fertilisers. This study investigates the reaction kinetics of the aforementioned reaction, describing a mathematical model for the kinetics of the reaction along with the accompanying rate constants. The reaction is initially exothermic, producing only carbon dioxide as a gas product and ammonium diphosphate, at higher temperatures the reaction becomes endothermic, producing ammonia gas as an additional by-product and longer chain polyphosphates, which when condensed too far becomes highly water insoluble. The aim of this study was to (i) characterise the pyrolysis reaction of urea phosphate by determining the mechanisms and the associated kinetic constants, and (ii) to determine the optimum conditions for ammonium diphosphate production. A qualitative investigation was also done to find the rate of hydrolysis of APP as this provides an estimate of the shelf life of an APP clear liquid fertiliser solution.

Keywords: ammonium polyphosphate, kinetics, pyrolysis, urea phosphate

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