Search results for: redox cycling

Authors: Angelo Lanzilotto, Martin Kuss-Petermann, Catherine E. Housecroft, Edwin C. Constable, Oliver S. Wenger

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We recently described the synthesis of a new tetraphenylporphyrinatozinc(II)-conjugated 2,2':6',6"-terpyridine (1) in which the tpy domain enables the molecule to act as a metalloligand. The synthetic route to 1 has been optimized, the importance of selecting a particular sequence of synthetic steps will be discussed. Three homoleptic complexes have been prepared, [Zn(1)₂]²⁺, [Fe(1)₂]²⁺ and [Ru(1)₂]²⁺, and have been isolated as the hexafluoridophosphate salts. Spectroelectrochemical measurements have been performed and the spectral changes ascribed to redox processes are partitioned on either the porphyrin or the terpyridine units. Compound 1 undergoes a reversible one-electron oxidation/reduction. The removal/gain of a second electron leads to a further irreversible chemical transformation. For the homoleptic [M(1)₂]²⁺ complexes, a suitable potential can be chosen at which both the oxidation and the reduction of the {ZnTPP} core are reversible. When the homoleptic complex contains a redox active metal such as Fe or Ru, spectroelectrochemistry has been used to investigate the metal to ligand charge transfer (MLCT) transition. The latter is sensitive to the oxidation state of the metal, and electrochemical oxidation of the metal center suppresses it. Detailed spectroelectrochemical studies will be presented.

Keywords: homoleptic complexes, spectroelectrochemistry, tetraphenylporphyrinatozinc(II), 2, 2':6', 6"-terpyridine

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Authors: Ahmed M. Debela, Mayreli Ortiz , Ciara K. O´Sullivan

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The completion of the human genome Project (HGP) has paved the way for mapping the diversity in the overall genome sequence which helps to understand the genetic causes of inherited diseases and susceptibility to drugs or environmental toxins. Arrayed primer extension (APEX) is a microarray based minisequencing strategy for screening disease causing mutations. It is derived from Sanger DNA sequencing and uses fluorescently dideoxynucleotides (ddNTPs) for termination of a growing DNA strand from a primer with its 3´- end designed immediately upstream of a site where single nucleotide polymorphism (SNP) occurs. The use of DNA polymerase offers a very high accuracy and specificity to APEX which in turn happens to be a method of choice for multiplex SNP detection. Coupling the high specificity of this method with the high sensitivity, low cost and compatibility for miniaturization of electrochemical techniques would offer an excellent platform for detection of mutation as well as sequencing of DNA templates. We are developing an electrochemical APEX for the analysis of SNPs found in the MYH7 gene for group of cardiomyopathy patients. ddNTPs were labeled with four different redox active compounds with four distinct potentials. Thiolated oligonucleotide probes were immobilised on gold and glassy carbon substrates which are followed by hybridisation with complementary target DNA just adjacent to the base to be extended by polymerase. Electrochemical interrogation was performed after the incorporation of the redox labelled dedioxynucleotide. The work involved the synthesis and characterisation of the redox labelled ddNTPs, optimisation and characterisation of surface functionalisation strategies and the nucleotide incorporation assays.

Keywords: array based primer extension, labelled ddNTPs, electrochemical, mutations

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Authors: Amer Ali, Jessica Cecchinelli, Antonis Charalambous

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Cycling is one of the most environmentally friendly, economic and healthy modes of transport but it needs more efficient cycle infrastructure and more effective safety measures. This paper represents an investigation into the performance and operation of the London Cycle Hire Scheme which started to operate in July 2010 using 5,000 cycles and 315 docking stations and currently has more than 10,000 cycles and over 700 docking stations across London which are available 24/7, 365 days a year. The study, which was conducted during the second half of 2014, consists of two parts; namely, the longitudinal review of the hire scheme between its introduction in 2010 and November 2014, and a field survey in November 2014 in the form of face-face interviews of the users of the cycle scheme to ascertain the existing limitations and difficulties experienced by those users and how it could be improved in terms of capability and safety. The study also includes a correlation between the usage of the cycle scheme and the corresponding weather conditions. The main findings are that on average the number of users (hiring frequency) had increased from just over two millions hires in 2010 to just less than ten millions in 2014. The field survey showed that 80% of the users are satisfied with the performance of the scheme whilst 50% of the users raised concern about the safety level of using the available cycle routes and infrastructure. The study also revealed that a high percentage of the cycle trips were relatively short (less than 30 minutes). Although the weather condition had some effect on cycling, the cost of using the cycle scheme and the main events in London had more effect on the number of cycle hires. The key conclusions are that despite the safety concern and the lack of infrastructure for continuous routes there was an encouraging number of people who opted for cycling as a clean, affordable, and healthy mode of transport. There is a need to expand the scheme by providing more cycles and docking stations and to support that by more well-designed and maintained cycle routes. More details about the development of London Cycle Hire Scheme during the last five years, its performance and the key issues revealed by the surveyed users will be reported in the full version of the paper.

Keywords: cycling mode of transport, london cycle hire scheme, safety, environmental and health benefits, user satisfaction

Procedia PDF Downloads 364

Authors: Jiří F. Urbánek, David Král

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Small and Middle Enterprises (SME) have a specific mission, characteristics, and behavior in global business competitive environments. They must respect policy, rules, requirements and standards in all their inherent and outer processes of supply - customer chains and networks. Paper aims and purposes are to introduce computational assistance, which enables us the using of prevailing operation system MS Office (SmartArt...) for mathematical models, using DYVELOP (Dynamic Vector Logistics of Processes) method. It is providing for SMS´s global environment the capability and profit to achieve its commitment regarding the effectiveness of the quality management system in customer requirements meeting and also the continual improvement of the organization’s and SME´s processes overall performance and efficiency, as well as its societal security via continual planning improvement. DYVELOP model´s maps - the Blazons are able mathematically - graphically express the relationships among entities, actors, and processes, including the discovering and modeling of the cycling cases and their phases. The blazons need live PowerPoint presentation for better comprehension of this paper mission – added value analysis. The crisis management of SMEs is obliged to use the cycles for successful coping of crisis situations.  Several times cycling of these cases is a necessary condition for the encompassment of the both the emergency event and the mitigation of organization´s damages. Uninterrupted and continuous cycling process is a good indicator and controlling actor of SME continuity and its sustainable development advanced possibilities.

Keywords: blazons, computational assistance, DYVELOP method, small and middle enterprises

Procedia PDF Downloads 318

Authors: Joo-Hack Lee, Jin-Seung Choi, Dong-Won Kang, Jeong-Woo Seo, Ju-Young Kim, Dae-Hyeok Kim, Seung-Tae Yang, Gye-Rae Tack

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For cycling, the analysis of the pedal force is one of the important factors in the study of exercise ability assessment and overuse injuries. In past studies, a two-axis measurement sensor was used at the sagittal plane to measure the force only in the anterior, posterior, and vertical directions and to analyze the loss of force and the injury on the frontal plane due to the forces in the right and left directions. In this study, which is a basic study on diverse analyses of the pedal force that consider the forces on the sagittal plane and the frontal plane, a three-axis pedal force measurement sensor was developed to measure the anterior-posterior (Fx), medio-lateral (Fz), and vertical (Fy) forces. The sensor was fabricated with a size and shape similar to those of the general flat pedal, and had a 550g weight that allowed smooth pedaling. Its measurement range was ±1000 N for Fx and Fz and ±2000 N for Fy, and its non-linearity, hysteresis, and repeatability were approximately 0.5%. The data were sampled at 1000 Hz using a signal collector. To use the developed sensor, the pedaling efficiency (index of efficiency, IE) and the range of left and right (medio-lateral, ML) forces were measured with two seat heights (low and high). The results of the measurement showed that the IE was higher and the force range in the ML direction was lower with the high position than with the low position. The developed measurement sensor and its application results will be useful in understanding and explaining the complicated pedaling technique, and will enable diverse kinematic analyses of the pedal force on the sagittal plane and the frontal plane.

Keywords: cycling, pedal force, index of effectiveness, measuring

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Authors: Živa Ravnikar, Alfonso Bahillo Martinez, Barbara Goličnik Marušić

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Climate change mitigation has been formally adopted and announced by countries over the globe, where cities are targeting carbon neutrality through various more or less successful, systematic, and fragmentary actions. The article is based on the fact that environmental conditions affect human comfort and the usage of space. Urban planning can, with its sustainable solutions, not only support climate mitigation in terms of a planet reduction of global warming but as well enabling natural processes that in the immediate vicinity produce environmental conditions that encourage people to walk or cycle. However, the article draws attention to the importance of integrating climate consideration into urban planning, where detailed environmental data play a key role, enabling urban planners to improve or monitor environmental conditions on cycle paths. In a practical aspect, this paper tests a particular ICT tool, a prototype used for environmental data. Data gathering was performed along the cycling lanes in Ljubljana (Slovenia), where the main objective was to assess the tool's data applicable value within the planning of comfortable cycling lanes. The results suggest that such transportable devices for in-situ measurements can help a researcher interpret detailed environmental information, characterized by fine granularity and precise data spatial and temporal resolution. Data can be interpreted within human comfort zones, where graphical representation is in the form of a map, enabling the link of the environmental conditions with a spatial context. The paper also provides preliminary results in terms of the potential of such tools for identifying the correlations between environmental conditions and different spatial settings, which can help urban planners to prioritize interventions in places. The paper contributes to multidisciplinary approaches as it demonstrates the usefulness of such fine-grained data for better consideration of microclimatology in urban planning, which is a prerequisite for creating climate-comfortable cycling lanes promoting active mobility.

Keywords: information and communication technology tools, urban planning, human comfort, microclimate, cycling lanes

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Authors: Wiqar Hussain Shah

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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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Authors: Tze-Sian Pui, Aung Than, Song-Wei Loo, Yuan-Li Hoe

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A paper-based electrode devised from an array of carboxylated multi-walled carbon nanotubes (MWNTs) and poly (diallyldimethylammonium chloride) (PDDA) has been successfully developed for the simultaneous detection of dopamine (DA) and ascorbic acid (AA) in 0.1 M phosphate buffer solution (PBS). The PDDA/MWNTs electrodes were fabricated by allowing PDDA to absorb onto the surface of carboxylated MWNTs, followed by drop-casting the resulting mixture onto a paper. Cyclic voltammetry performed using 5 mM [Fe(CN)₆]³⁻/⁴⁻ as the redox marker showed that the PDDA/MWNTs electrode has higher redox activity compared to non-functionalized carboxylated MWNT electrode. Differential pulse voltammetry was conducted with DA concentration ranging from 2 µM to 500 µM in the presence of 1 mM AA. The distinctive potential of 0.156 and -0.068 V (vs. Ag/AgCl) measured on the surface of the PDDA/MWNTs electrode revealed that both DA and AA were oxidized. The detection limit of DA was estimated to be 0.8 µM. This nanocomposite paper-based electrode has great potential for future applications in bioanalysis and biomedicine.

Keywords: dopamine, differential pulse voltammetry, paper sensor, carbon nanotube

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Authors: Fang Li, Jiazhao Wang, Jianmin Ma

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The practical application of Li-S batteries is hampered due to poor cycling stability caused by electrolyte-dissolved lithium polysulfides. Dual functionalities such as strong chemical adsorption stability and high conductivity are highly desired for an ideal host material for a sulfur-based cathode. Polypyrrole (PPy), as a conductive polymer, was widely studied as matrixes for sulfur cathode due to its high conductivity and strong chemical interaction with soluble polysulfides. Thus, a novel cathode structure consisting of a free-standing sulfur-polypyrrole cathode and a polypyrrole coated separator was designed for flexible Li-S batteries. The PPy materials show strong interaction with dissoluble polysulfides, which could suppress the shuttle effect and improve the cycling stability. In addition, the synthesized PPy film with a rough surface acts as a current collector, which improves the adhesion of sulfur materials and restrain the volume expansion, enhancing the structural stability during the cycling process. For further enhancing the cycling stability, a PPy coated separator was also applied, which could make polysulfides into the cathode side to alleviate the shuttle effect. Moreover, the PPy layer coated on commercial separator is much lighter than other reported interlayers. A soft-packaged flexible Li-S battery has been designed and fabricated for testing the practical application of the designed cathode and separator, which could power a device consisting of 24 light-emitting diode (LED) lights. Moreover, the soft-packaged flexible battery can still show relatively stable cycling performance after repeated bending, indicating the potential application in flexible batteries. A novel vapor phase deposition method was also applied to prepare uniform polypyrrole layer coated sulfur/graphene aerogel composite. The polypyrrole layer simultaneously acts as host and adsorbent for efficient suppression of polysulfides dissolution through strong chemical interaction. The density functional theory (DFT) calculations reveal that the polypyrrole could trap lithium polysulfides through stronger bonding energy. In addition, the deflation of sulfur/graphene hydrogel during the vapor phase deposition process enhances the contact of sulfur with matrixes, resulting in high sulfur utilization and good rate capability. As a result, the synthesized polypyrrole coated sulfur/graphene aerogel composite delivers a specific discharge capacity of 1167 mAh g⁻¹ and 409.1 mAh g⁻¹ at 0.2 C and 5 C respectively. The capacity can maintain at 698 mAh g⁻¹ at 0.5 C after 500 cycles, showing an ultra-slow decay rate of 0.03% per cycle.

Keywords: polypyrrole, strong chemical interaction, long-term stability, Li-S batteries

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Authors: S. Ghosh, L. Ramos, A. N. Kouamé, A.-L. Teillout, H. Remita

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Catalytic materials have attracted continuous attention due to their promising applications in a variety of energy and environmental applications including clean energy, energy conversion and storage, purification and separation, degradation of pollutants and electrochemical reactions etc. With the advanced synthetic technologies, polymer nanostructures and nanocomposites can be directly synthesized through soft template mediated approach using swollen hexagonal mesophases and modulate the size, morphology, and structure of polymer nanostructures. As an alternative to conventional catalytic materials, one-dimensional PDPB polymer nanostructures shows high photocatalytic activity under visible light for the degradation of pollutants. These photocatalysts are very stable with cycling. Transmission electron microscopy (TEM), and AFM-IR characterizations reveal that the morphology and structure of the polymer nanostructures do not change after photocatalysis. These stable and cheap polymer nanofibers and metal polymer nanocomposites are easy to process and can be reused without appreciable loss of activity. The polymer nanocomposites formed via one pot chemical redox reaction with 3.4 nm Pd nanoparticles on poly(diphenylbutadiyne) (PDPB) nanofibers (30 nm). The reduction of Pd (II) ions is accompanied by oxidative polymerization leading to composites materials. Hybrid Pd/PDPB nanocomposites used as electrode materials for the electrocatalytic oxidation of ethanol without using support of proton exchange Nafion membrane. Hence, these conducting polymer nanofibers and nanocomposites offer the perspective of developing a new generation of efficient photocatalysts for environmental protection and in electrocatalysis for fuel cell applications.

Keywords: conducting polymer, swollen hexagonal mesophases, solar photocatalysis, electrocatalysis, water depollution

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Authors: Görkem Ülkü, Nesrin Köken, Esin A. Güvel, Nilgün Kızılcan

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Ethoxylated nonyl phenols (ENP) and ceric ammonium nitrate redox systems have been used for the polymerization of vinyl and acrylic monomers. In that case, ENP acted as an organic reducing agent in the presence of Ce (IV) salt and a radical was formed. The polymers obtained with that redox system contained ENP chain ends because the radicals are formed on the reducing molecules. Similar copolymer synthesis has been reported using poly(ethylene oxide) instead of its nonyl phenol terminated derivative, ENP. However, copolymers of poly(ethylene oxide) and conducting polymers synthesized by ferric ions were produced in two steps. Firstly, heteroatoms (pyrrole, thiophene etc.) were attached to the poly(ethylene oxide) chains then copolymerization with heterocyclic monomers was carried out. In this work, ethoxylated nonylphenol (ENP) was reacted with 2-thiophenecarbonyl chloride in order to synthesize a macromonomer containing thienyl end-group (ENP-ThC). Then, copolymers of ENP-ThC and pyrrole were synthesized by chemical oxidative polymerization using iron (III) chloride as an oxidant.

Keywords: end capped polymer, ethoxylated nonylphenol, heterophase polymerization, polypyrrole

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Authors: Suneet Jagdev, Hrishabh Amrodia, Siddharth Menon, Abhishek Singh, Mansi Shivhare

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Delhi, the National Capital, has undergone a surge in development rate, consequently engendering an unprecedented increase in population. Over the years the city has transformed into a car-centric infrastructure with high-speed corridors, flyovers and fast lanes. A considerable section of the population is hankering to rehabilitate to the good old cycling days, in order to contribute towards a green environment as well as to maintain their physical well-being. Furthermore, an extant section of Delhi’s population relies on cycles as their primary means of commuting in the city. Delhi has the highest number of cyclists and second highest number of pedestrians in the country. However, the tumultuous problems of unregulated traffic, inadequate space on roads, adverse weather conditions stifle them to opt for cycling. Lately, the city has been facing a conglomeration of problems such as haphazard traffic movement, clogged roads, congestion, pollution, accidents, safety issues, etc. In 1957, Delhi’s cyclists accounted for 36 per cent of trips which dropped down to a mere 4 per cent in 2008. The declining rate is due to unsafe roads and lack of proper cycle lanes. Now as the 10 percent of the city has cycle tracks. There is also a lack of public recreational activities in the city. These conundrums incite the need of a covered elevated cycling bridge track to facilitate the safe and smooth cycle commutation in the city which would also serve the purpose of an alternate urban public space over the cycle bridge reducing the cost as well as the space requirement for the same, developing a user–friendly transportation and public interaction system for urban areas in the city. Based on the archival research methodologies, the following research draws information and extracts records from the data accounts of the Delhi Metro Rail Corporation Ltd. as well as the Centre for Science and Environment, India. This research will predominantly focus on developing a prototype design for high speed elevated bicycle lanes based on different road typologies, which can be replicated with minor variations in similar situations, all across the major cities of our country including the proposed smart cities. Furthermore, how these cycling lanes could be utilized for the place making process accommodating cycle parking and renting spaces, public recreational spaces, food courts as well as convenient shopping facilities with appropriate optimization. How to preserve and increase the share of smooth and safe cycling commute cycling for the routine transportation of the urban community of the polluted capital which has been on a steady decline over the past few decades.

Keywords: bicycle track, prototype, road safety, urban spaces

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Authors: Mohsen Adabi, Mahdi Adabi, Reza Saber

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The recent advancements in nanomaterials have provided a platform to develop efficient transduction matrices for sensors. Modified electrodes allow to electrochemists to enhance the property of electrode surface and provide desired properties such as improved sensing capabilities, higher electron transfer rate and prevention of undesirable reactions competing kinetically with desired electrode process. Nanostructured electrodes including arrays of carbon nanotubes have demonstrated great potential for the development of electrochemical sensors and biosensors. The aim of this work is to evaluate the concentration of multi-walled carbon nanotubes (MWCNTs) on the conductivity of gold electrode. For this work, raw MWCNTs was functionalized and shortened. Raw and shorten MWCNTs were characterized using transfer electron microscopy (TEM). Next, 0.5, 2 and 3.5 mg of Shortened and functionalized MWCNTs were dispersed in 2 mL Dimethyl formamide (DMF) and cysteamine modified gold electrodes were incubated in the different concentrations of MWCNTs for 8 hours. Then, the immobilization of MWCNTs on cysteamine modified gold electrode was characterized by scanning electron microscopy (SEM) and the effect of MWCNT concentrations on electron transfer of modified electrodes was investigated by cyclic voltammetry (CV). The results demonstrated that CV response of ferricyanide redox at modified gold electrodes increased as concentration of MWCNTs enhanced from 0.5 to 2 mg in 2 mL DMF. This increase can be attributed to the number of MWCNTs which enhance on the surface of cysteamine modified gold electrode as the MWCNTs concentration increased whereas CV response of ferricyanide redox at modified gold electrodes did not changed significantly as the MWCNTs concentration increased from 2 to 3.5 mg in 2 mL DMF. The reason may be that amine groups of cysteamine modified gold electrodes are limited to a given number which can interact with the given number of carboxylic groups of MWCNTs and CV response of ferricyanide redox at modified gold do not enhance after amine groups of cysteamine are saturated with carboxylic groups of MWCNTs.

Keywords: carbon nanotube, cysteamine, electrochemical sensor, gold electrode

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Authors: Christos Karolemeas, Avgi Vassi, Georgia Christodoulopoulou

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Although the past decades, planning a cycle network became an inseparable part of all transportation plans, there is still a lot of room for improvement in the way planning is made, in order to create safe and direct cycling networks that gather the parameters that positively influence one's decision to cycle. The aim of this article is to study, evaluate and visualize the bikeability of cities. This term is often used as the 'the ability of a person to bike' but this study, however, adopts the term in the sense of bikeability as 'the ability of the urban landscape to be biked'. The methodology used included assessing cities' accessibility by cycling, based on international literature and corresponding walkability methods and the creation of a 'bikeability index'. Initially, a literature review was made to identify the factors that positively affect the use of bicycle infrastructure. Those factors were used in order to create the spatial index and quantitatively compare the city network. Finally, the bikeability index was applied in two case studies: two Greek municipalities that, although, they have similarities in terms of land uses, population density and traffic congestion, they are totally different in terms of geomorphology. The factors suggested by international literature were (a) safety, (b) directness, (c) comfort and (d) the quality of the urban environment. Those factors were quantified through the following parameters: slope, junction density, traffic density, traffic speed, natural environment, built environment, activities coverage, centrality and accessibility to public transport stations. Each road section was graded for the above-mentioned parameters, and the overall grade shows the level of bicycle accessibility (low, medium, high). Each parameter, as well as the overall accessibility levels, were analyzed and visualized through Geographic Information Systems. This paper presents the bikeability index, its' results, the problems that have arisen and the conclusions from its' implementation through Strengths-Weaknesses-Opportunities-Threats analysis. The purpose of this index is to make it easy for researchers, practitioners, politicians, and stakeholders to quantify, visualize and understand which parts of the urban fabric are suitable for cycling.

Keywords: accessibility, cycling, green spaces, spatial data, urban environment

Procedia PDF Downloads 87

Authors: Victoria Yu. Garnova, Vladimir G. Merzlikin, Sergey V. Khudyakov, Valeriy A. Tovstonog, Svyatoslav V. Cheranev

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Long-term scientific forecasts confirm that diesel engines still will be the basis of the transport and stationary power in the near future. This is explained by their high efficiency and profitability compared to other types of heat engines. In the automotive industry carried basic researches are aimed at creating a new generation of diesel engines with reduced exhaust emissions (with stable performance) determining the minimum impact on the environment. The application of thermal barrier coatings (TBCs) and especially their modifications based on semitransparent ceramic materials allows solving this problem. For such researches, the preliminary stage of testing of physical characteristics materials and coatings especially with semitransparent properties the authors proposed experimental operating innovative radiative-and-convective cycling simulator. This setup contains original radiation sources (imitator) with tunable spectrum for modeling integral flux up to several MW/m2.

Keywords: environment saving, radiative and convective cycling simulator, semitransparent ceramic coatings, imitator radiant energy

Procedia PDF Downloads 241

Authors: Sudeshna Chandra, Christian Gäbler, Christian Schliebe, Heinrich Lang

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Highly branched dendrimers provide structural homogeneity, controlled composition, comparable size to biomolecules, internal porosity and multiple functional groups for conjugating reactions. Electro-active dendrimers containing multiple redox units have generated great interest in their use as electrode modifiers for development of biosensors. The electron transfer between the redox-active dendrimers and the biomolecules play a key role in developing a biosensor. Ferrocenes have multiple and electrochemically equivalent redox units that can act as electron “pool” in a system. The ferrocenyl-terminated polyamidoamine dendrimer is capable of transferring multiple numbers of electrons under the same applied potential. Therefore, they can be used for dual purposes: one in building a film over the electrode for immunosensors and the other for immobilizing biomolecules for sensing. Electrochemical immunosensor, thus developed, exhibit fast and sensitive analysis, inexpensive and involve no prior sample pre-treatment. Electrochemical amperometric immunosensors are even more promising because they can achieve a very low detection limit with high sensitivity. Detection of the cancer biomarkers at an early stage can provide crucial information for foundational research of life science, clinical diagnosis and prevention of disease. Elevated concentration of biomarkers in body fluid is an early indication of some type of cancerous disease and among all the biomarkers, IgG is the most common and extensively used clinical cancer biomarkers. We present an IgG (=immunoglobulin) electrochemical immunosensor using a newly synthesized redox-active ferrocenyl dendrimer of generation 2 (G2Fc) as glassy carbon electrode material for immobilizing the antibody. The electrochemical performance of the modified electrodes was assessed in both aqueous and non-aqueous media using varying scan rates to elucidate the reaction mechanism. The potential shift was found to be higher in an aqueous electrolyte due to presence of more H-bond which reduced the electrostatic attraction within the amido groups of the dendrimers. The cyclic voltammetric studies of the G2Fc-modified GCE in 0.1 M PBS solution of pH 7.2 showed a pair of well-defined redox peaks. The peak current decreased significantly with the immobilization of the anti-goat IgG. After the immunosensor is blocked with BSA, a further decrease in the peak current was observed due to the attachment of the protein BSA to the immunosensor. A significant decrease in the current signal of the BSA/anti-IgG/G2Fc/GCE was observed upon immobilizing IgG which may be due to the formation of immune-conjugates that blocks the tunneling of mass and electron transfer. The current signal was found to be directly related to the amount of IgG captured on the electrode surface. With increase in the concentration of IgG, there is a formation of an increasing amount of immune-conjugates that decreased the peak current. The incubation time and concentration of the antibody was optimized for better analytical performance of the immunosensor. The developed amperometric immunosensor is sensitive to IgG concentration as low as 2 ng/mL. Tailoring of redox-active dendrimers provides enhanced electroactivity to the system and enlarges the sensor surface for binding the antibodies. It may be assumed that both electron transfer and diffusion contribute to the signal transformation between the dendrimers and the antibody.

Keywords: ferrocenyl dendrimers, electrochemical immunosensors, immunoglobulin, amperometry

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Authors: Daniel Botero, Oscar Rubiano, Pedro P. Barragan, Jaime Baron, Leonardo Rodriguez Perdomo, Jaime Rodriguez

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In the last decade interval training (IT) has gained importance when is compare with strength training (ST). However, there are few studies analyzing the impact of these training over the autonomic nervous system (ANS). This work has aimed to compare the activity of the autonomic nervous system, when is expose to an IT or ST indoor cycling mode. After approval by the ethics committee, a cross-over clinical trial with 22 healthy participants (age 21 ± 3 years) was implemented. The selection of participants for the groups with sequence force-interval (F-I) and interval-force (I-F) was made randomly with assignation of 11 participants for each group. The temporal series of heart rate was obtained before and after each training using the POLAR TEAM® heart monitor. The evaluation of the ANS was performed with spectral analysis of the heart rate variability (HRV) using the fast Fourier transform (Kubios software). A training of 8 weeks in each sequence (4 weeks with each training) with an intermediate period of two weeks of washout was implemented for each group. The power parameter of the HRV in the low frequency band (LF = 0.04-0.15Hz related to the sympathetic nervous system), high frequency (HF = 0.15-0.4Hz, related to the parasympathetic) and LF/HF (with reference to a modulation of parasympathetic over the sympathetic), were calculated. Afterward, the difference between the parameters before and after was realized. Then, to evaluate statistical differences between each training was implemented the method of Wellek (Wellek and Blettner, 2012, Medicine, 109 (15), 276-81). To determine the difference of effect over parasympathetic when FT and IT are used, the T test is implemented obtaining a T value of 0.73 with p-value ≤ 0.1. For the sympathetic was obtained a T of 0.33 with p ≤ 0.1 and for LF/HF the T was 1.44 with a p ≥ 0.1. Then, the carry over effect was evaluated and was not present. Significant changes over autonomic activity with strength or interval training were not observed. However, a modulation of the parasympathetic over the sympathetic can be observed. Probably, these findings should be explained because the sample is little and/or the time of training was insufficient to generate changes.

Keywords: autonomic nervous, force training, indoor cycling, interval training

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Authors: Nazli Eslamirad, Peter C. Junk, Jun Wang, Glen B. Deacon

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Since coordination behavior of pyrazoles and pyrazolate ions are widely versatile towards a great range of metals such as d-block, f-block as well as main group elements; they attract interest as ligands for preparing compounds. A variety of rare-earth pyrazolate complexes have been synthesized by redox transmetalation/protolysis (RTP) previously, therefore, a variety of rare-earth pyrazolate complexes using two pyrazoles, 3,5-dimethylpyrazole (Me₂pzH) and 3,5-di-tert -butylpyrazolate (t-Bu₂pzH), in which the structures span the whole La-Lu array beside Sc and Y has been synthesized by RTP reaction. There have been further developments in this study: Synthesizing structure of [Tb(Me₂pz)₃(thf)]₂ which is isomorphous with those of the previously reported [Dy(Me₂pz)₃(thf)]₂ and [Lu(Me₂pz)₃(thf)]₂ analogous that has two µ-1(N):2(Nʹ)-Me2pz ligands (the most common pyrazolate ligation for non-rare-earth complexes). Previously most of the reported compounds using t-Bu2pzH were monomeric compounds however the lanthanum derivative [La(Me₂pz)₃thf₂] ,which has been reported previously without crystal structure, has now been structurally characterized, along with cerium and lutetium analogue. Also a polymeric structure with samarium has now been synthesized which the neodymium analogue has been reported previously and comparing these polymeric structures can support the idea that the geometry of Sm(tBu₂pz)₃ affect the coordination of the solvent. Also, by using 1,2-dimethoxyethane (DME) instead of tetrahydrofuran (THF) new [Er(tBu₂pz)₃ (dme)₂] has now been reported.

Keywords: lanthanoid complexes, pyrazolate, redox transmetalation/protolysis, x-ray crystal structures

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Authors: Hu-Cheng Weng, Jhen-Ting Huang, Chia-Chia Chang, An-Ya Lo

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In this study, carbon mesoporous material, CMK-3, was adopted as supporting material for electroactive polymerspolyaniline (PANI), polyaniline, for supercapacitor application, where hydroquinone (HQ) was integrated to enhance the redox reaction of PANI. The results show that the addition of PANI improves the capacitance of electrode from 89 F/g (CMK-3) to 337 F/g (PANI/CMK-3), the addition of HQ furtherly improves the capacitance to 463 F/g (PANI/CMK-3/HQ). The PANI provides higher energy density and also acts as binder of the electrode; the CMK-3 provides higher electron double layer capacitance EDLC and stabilize the polyaniline by its highly porosity. With the addition of HQ, the capacitance of PANI/CMK-3 was further enhanced. In-situ analyses including cyclic voltammetry (CV), chronopotentiometry (CP), electron impedance spectrum (EIS) analyses were applied for electrode performance examination. For materials characterization, the crystal structure, morphology, microstructure, and porosity were examined by X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscopy (TEM), and 77K N2 adsorption/desorption analyses, respectively. The effects of electrolyte pH value, PANI polymerization time, HQ concentration, and PANI/CMK-3 ratio on capacitance were discussed. The durability was also studied by long-term operation test. The results show that PANI/CMK-3/HQ with great potential for supercapacitor application. Finally, the potential of all-solid PANI/CMK-3/HQ based supercapacitor was successfully demonstrated.

Keywords: CMK3, PANI, redox electrolyte, solid supercapacitor

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Authors: Emmanuel A. Oriaifo, Noel Perera, Alan Guy, Pak. S. Leung, Kian T. Tan

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Concerns on corrosion and effective coating protection of double hull tankers and bulk carriers in service have been raised especially in water ballast tanks (WBTs). Test protocols/methodologies specifically that which is incorporated in the International Maritime Organisation (IMO), Performance Standard for Protective Coatings for Dedicated Sea Water ballast tanks (PSPC) are being used to assess and evaluate the performance of the coatings for type approval prior to their application in WBTs. However, some of the type approved coatings may be applied as very thick films to less than ideally prepared steel substrates in the WBT. As such films experience hygrothermal cycling from operating and environmental conditions, they become embrittled which may ultimately result in cracking. This embrittlement of the coatings is identified as an undesirable feature in the PSPC but is not mentioned in the test protocols within it. There is therefore renewed industrial research aimed at understanding this issue in order to eliminate cracking and achieve the intended coating lifespan of 15 years in good condition. This paper will critically review test protocols currently used for assessing and evaluating coating performance, particularly the IMO PSPC.

Keywords: corrosion test, hygrothermal cycling, coating test protocols, water ballast tanks

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Authors: Urbánek Jiří J., Krahulec Josef, Urbánek Jiří F., Johanidesová Jitka

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These Computational assistance for the research and modelling of critical infrastructure subjects continuity deal with this paper. It enables us the using of prevailing operation system MS Office (SmartArt...) for mathematical models, using DYVELOP (Dynamic Vector Logistics of Processes) method. It serves for crisis situations investigation and modelling within the organizations of critical infrastructure. In the first part of the paper, it will be introduced entities, operators and actors of DYVELOP method. It uses just three operators of Boolean algebra and four types of the entities: the Environments, the Process Systems, the Cases and the Controlling. The Process Systems (PrS) have five “brothers”: Management PrS, Transformation PrS, Logistic PrS, Event PrS and Operation PrS. The Cases have three “sisters”: Process Cell Case, Use Case and Activity Case. They all need for the controlling of their functions special Ctrl actors, except ENV – it can do without Ctrl. Model´s maps are named the Blazons and they are able mathematically - graphically express the relationships among entities, actors and processes. In the second part of this paper, the rich blazons of DYVELOP method will be used for the discovering and modelling of the cycling cases and their phases. The blazons need live PowerPoint presentation for better comprehension of this paper mission. The crisis management of energetic crisis infrastructure organization is obliged to use the cycles for successful coping of crisis situations. Several times cycling of these cases is a necessary condition for the encompassment of the both the emergency event and the mitigation of organization´s damages. Uninterrupted and continuous cycling process bring for crisis management fruitfulness and it is a good indicator and controlling actor of organizational continuity and its sustainable development advanced possibilities. The research reliable rules are derived for the safety and reliable continuity of energetic critical infrastructure organization in the crisis situation.

Keywords: blazons, computational assistance, DYVELOP method, critical infrastructure

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Authors: Ludmila A. Gavriliuc, Jerry McLarty, Heather E. Kleiner, J. Michael Mathis

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Abstract -- Background: The citrus coumarine Auraptene (Aur) is an effective chemopreventive agent, as manifested in many models of diseases and cancer. Nuclear factor erythroid 2-related factor (Nrf2) is an important regulator of genes induced by oxidative stress, such as glutathione S-transferases, heme oxygenase-1, and peroxiredoxin 1, by activating the antioxidant response element (ARE). Genetic and biochemical evidence has demonstrated that glutathione (GSH) and glutathione-dependent enzymes, glutathione reductase (GR), glutathione peroxidases (GPs), glutathione S-transferases (GSTs) are responsible for the control of intracellular reduction-oxidation status and participate in cellular adaptation to oxidative stress. The effect of Aur on the activity of GR, GPs (Se-GP and Se-iGP), and content of GSH in the liver, kidney, and spleen is insufficiently explored. Aim: Our goal was the examination of the Aur influence on the redox-system of GSH in Nrf2 wild type and Nrf2 knockout mice via activation of Nrf2 and ARE. Methods: Twenty female mice, 10 Nrf2 wild-type (WT) and 10 Nrf2 (-/-) knockout (KO), were bred and genotyped for our study. The activity of GR, Se-GP, Se-iGP, GST, G6PD, CytP450 reductase, catalase (Cat), and content of GSH were analyzed in the liver, kidney, and spleen using Spectrophotometry methods. The results of the specific activity of enzymes and the amount of GSH were analyzed with ANOVA and Spearman statistical methods. Results: Aur (200 mg/kg) treatment induced hepatic GST, GR, Se-GP activity and inhibited their activity in the spleen of mice, most likely via activation of the ARE through Nrf2. Activation in kidney Se-GP and G6PD by Aur is also controlled, apparently through Nrf2. Results of the non-parametric Spearman correlation analysis indicated the strong positive correlation between GR and G6PD only in the liver in WT control mice (r=+0.972; p < 0.005) and in the kidney KO control mice (r=+0.958; p < 0.005). The observed low content of GSH in the liver of KO mice indicated an increase in its participation in the neutralization of toxic substances with the absence of induction of GSH-dependent enzymes, such as GST, GR, Se-GP, and Se-iGP. Activation of CytP450 in kidney and spleen and Cat in the liver in KO mice probably revealed another regulatory mechanism for these enzymes. Conclusion: Thereby, obtained results testify that Aur can modulate the activity of genes and antioxidant enzymatic redox-system of GSH, responsible for the control of intracellular reduction-oxidation status.

Keywords: auraptene, glutathione, GST, Nrf2

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Authors: Avani Chhajlani

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Fashion is considered to be the most destructive industry, second only to the oil rigging industry, which has a greater impact on the environment. While fashion today banks upon fast fashion to generate a higher turnover of designs and patterns in apparel and related accessories, crafts push us towards a more slow and thoughtful approach with culturally identifiably unique work and slow community-centered production. Despite this strong link between indigenous crafts and sustainability, it has not been extensively researched and explored upon. In the forthcoming years, the fashion industry will have to reinvent itself to move towards a more holistic and sustainable circular model to balance the harm already caused. And closed loops of the circular economy will help the integration of indigenous craft knowledge, which is regenerative. Though sustainability and crafts of a region go hand-in-hand, the craft still have to find its standing in the mainstream fashion world; craft practices have a strong local congruence and knowledge that has been passed down generation-to-generation through oration or written materials. This paper aims to explore ways a circular economy can be created by amalgamating fashion and craft while creating a sustainable business model and how this is slowly being created today through brands like – RaasLeela, Pero, and KaSha, to name a few.

Keywords: circular economy, fashion, India, indigenous crafts, slow fashion, sustainability, up-cycling

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Authors: Sarish Rehman, Kishwar Khan, Yanglong Hou

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Among the existed myriad energy-storage technologies, lithium–sulfur batteries (LSBs) show the appealing potential for the ubiquitous growth of next-generation electrical energy storage application, owing to their unparalleled theoretical energy density of 2600 Wh/kg that is over five times larger than that of conventional lithium-ion batteries (LIBs). Despite its significant advances, its large scale implementations are plagued by multitude issues: particularly the intrinsic insulating nature of the sulfur (10-30 S/cm), mechanical degradation of the cathode due to large volume changes of sulfur up to 80 % during cycling and loss of active material (producing polysulfide shuttle effect). We design a unique structure, namely silicon/silica (Si/SiO2) crosslink with hierarchical porous carbon spheres (Si/SiO2@C), and use it as a new and efficient sulfur host to prepare Si/SiO2@C-S hybrid spheres to solve the hurdle of the polysulfides dissolution. As results of intriguing structural advantages developed hybrids spheres, it acts as efficient polysulfides reservoir for enhancing lithium sulfur battery (LSB) in the terms of capacity, rate ability and cycling stability via combined chemical and physical effects.

Keywords: high specific surface area, high power density, high content of sulfur, lithium sulfur battery

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Authors: Shuo Li, Yannick Coffinier, Chann Lagadec, Fabrizio Cleri, Katsuhiko Nishiguchi, Akira Fujiwara, Soo Hyeon Kim, Nicolas Clément

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The need for single cell detection and analysis techniques has increased in the past decades because of the heterogeneity of individual living cells, which increases the complexity of the pathogenesis of malignant tumors. In the search for early cancer detection, high-precision medicine and therapy, the technologies most used today for sensitive detection of target analytes and monitoring the variation of these species are mainly including two types. One is based on the identification of molecular differences at the single-cell level, such as flow cytometry, fluorescence-activated cell sorting, next generation proteomics, lipidomic studies, another is based on capturing or detecting single tumor cells from fresh or fixed primary tumors and metastatic tissues, and rare circulating tumors cells (CTCs) from blood or bone marrow, for example, dielectrophoresis technique, microfluidic based microposts chip, electrochemical (EC) approach. Compared to other methods, EC sensors have the merits of easy operation, high sensitivity, and portability. However, despite various demonstrations of low limits of detection (LOD), including aptamer sensors, arrayed EC sensors for detecting single-cell have not been demonstrated. In this work, a new technique based on 20-nm-thick nanopillars array to support cells and keep them at ideal recognition distance for redox-labeled aptamers grafted on the surface. The key advantages of this technology are not only to suppress the false positive signal arising from the pressure exerted by all (including non-target) cells pushing on the aptamers by downward force but also to stabilize the aptamer at the ideal hairpin configuration thanks to a confinement effect. With the first implementation of this technique, a LOD of 13 cells (with5.4 μL of cell suspension) was estimated. In further, the nanosupported cell technology using redox-labeled aptasensors has been pushed forward and fully integrated into a single-cell electrochemical aptasensor array. To reach this goal, the LOD has been reduced by more than one order of magnitude by suppressing parasitic capacitive electrochemical signals by minimizing the sensor area and localizing the cells. Statistical analysis at the single-cell level is demonstrated for the recognition of cancer cells. The future of this technology is discussed, and the potential for scaling over millions of electrodes, thus pushing further integration at sub-cellular level, is highlighted. Despite several demonstrations of electrochemical devices with LOD of 1 cell/mL, the implementation of single-cell bioelectrochemical sensor arrays has remained elusive due to their challenging implementation at a large scale. Here, the introduced nanopillar array technology combined with redox-labeled aptamers targeting epithelial cell adhesion molecule (EpCAM) is perfectly suited for such implementation. Combining nanopillar arrays with microwells determined for single cell trapping directly on the sensor surface, single target cells are successfully detected and analyzed. This first implementation of a single-cell electrochemical aptasensor array based on Brownian-fluctuating redox species opens new opportunities for large-scale implementation and statistical analysis of early cancer diagnosis and cancer therapy in clinical settings.

Keywords: bioelectrochemistry, aptasensors, single-cell, nanopillars

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Authors: Malgorzata Rudnicka, Waldemar Karcz

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Introduction: Naphthoquinones are widely occurring organic compounds produced by bacteria, fungi, and plants. They can act as the functional components of biochemical systems (plastoquinone) as well as biologically active substances, which have a negative impact on environmental processes. Naphthoquinones seem to act through two mechanisms: a covalent modification of biological molecules at their nucleophilic sites or by generation of reactive oxygen species (ROS) connected with redox cycling. Investigating the effect of naphthoquinones (1,4-naphthoquinone, lawsone and naphthazarin) on the elongation growth, membrane potential and the level of oxidative stress of maize cells seems to be important due to the possibility of using these substances as herbicides. Methods: All experiments were performed on etiolated maize coleoptile segments. Simultaneous measurements of elongation growth and pH of the incubation medium were carried out using an angular position transducer, allowing a precise record of the growth kinetics. To compare the oxidative stress level induced by all tested naphthoquinones, the changes in malondialdehyde content, as well as superoxide dismutase and catalase activities were measured. In order to measure the membrane potential of parenchymal cells the standard electrophysiology technique was used. Results: Naphthoquinones such as: 1,4-naphthoquinone, lawsone and naphthazarin were studied. It was found that all of the naphthoquinones diminished the growth of the maize coleoptile cells depending on the type of naphthoquinones and their concentration. Interestingly, naphthazarin at the intermediate concentration was less toxic compared to the others. In addition, the effect of naphthoquinones on the oxidative stress was dependent on their concentration as well. Superoxide dismutase and catalase activities were changed in the presence of higher concentrations of naphthoquinones. Similar interrelations were observed for membrane potential changes. Conclusion: It can be concluded that naphthoquinones tested differ in their toxic effect on the growth of maize coleoptile cells. Furthermore, naphthoquinones can be distinguish considering the oxidative stress level and membrane potential changes. The results presented here give new insight into the possible opportunities of practical usage of naphthoquinones for herbicides improvement.

Keywords: growth rate, membrane potential, naphthoquinones, oxidative stress

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Authors: Sadia Rafiq, Md. Ashab Siddique Zaki, Ananya Roy

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Mountain cycling is a type of off-road bicycle racing that typically takes place on rocky, arid, or other challenging terrains on specially-made mountain cycles. Professional cyclists race while attempting to stay on their bikes in a variety of locales across the world. For safety measures in mountain cycling, as there we have a high chance of injury in case of tire puncture, it’s a preferable way to use an airless tire instead of a pneumatic tire. As airless tire does not tend to go flat, it needs to be replaced less frequently. The airless tire replaces the pneumatic tire, wheel, and tire system with a single unit. It consists of a stiff hub connected to a shear band by flexible, pliable spokes, which is made of poly-composite and a tread band, all of which work together as a single unit to replace all of the components of a normal radial tire. In this paper, an analysis of airless tires in the mountain cycle is shown along with structure and material study. We will be taking the Honeycomb and Diamond Structure of spokes to compare the deformation in both cases and choose our preferable structure. As we know, the tread and spokes deform with the surface roughness and impact. So, the tire tread thickness and the design of spokes can control how much the tire can distort. Through the simulation, we can come to the conclusion that the diamond structure deforms less than the honeycomb structure. So, the diamond structure is more preferable.

Keywords: airless tire, diamond structure, honeycomb structure, deformation

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Authors: Fredrick O. Okumu, Mangaka C. Matoetoe

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Silver-platinum (Ag-Pt) bimetallic nanoparticles (NPs) with varying mole fractions (1:1, 1:3 and 3:1) were prepared by co-reduction of hexachloroplatinate and silver nitrate with sodium citrate. Upon successful formation of both monometallic and bimetallic (BM) core shell nanoparticles, cyclic voltammetry (CV) was used to characterize the NPs. The drop coated nanofilms on the GC substrate showed characteristic peaks of monometallic Ag NPs; Ag+/Ag0 redox couple as well as the Pt NPs; hydrogen adsorption and desorption peaks. These characteristic peaks were confirmed in the bimetallic NPs voltammograms. The following varying current trends were observed in the BM NPs ratios; GCE/Ag-Pt 1:3 > GCE/Ag-Pt 3:1 > GCE/Ag-Pt 1:1. Fundamental electrochemical properties which directly or indirectly affects the applicability of films such as; diffusion coefficient (D), electroactive surface coverage, electrochemical band gap, electron transfer coefficient (α) and charge (Q) were assessed using Randles - Sevcik plot and Laviron’s equations . High charge and surface coverage was observed in GCE/Ag-Pt 1:3 which supports its enhanced current. GCE/Ag-Pt 3:1 showed high diffusion coefficient while GCE/Ag-Pt 1:1 possessed high electron transfer coefficient that is facilitated by its high apparent heterogeneous rate constant relative to other BM NPs ratios. Surface redox reaction was determined as adsorption controlled in all modified GCEs. Surface coverage is inversely proportional to size; therefore the surface coverage data suggests that Ag-Pt 1:1 NPs have a small particle size. Generally, GCE/Ag-Pt 1:3 depicts the best electrochemical properties.

Keywords: characterization, core-shell, electrochemical, nanoparticles

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Authors: A. Dėdelė, A. Miškinytė

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The assessment of air pollution exposure in different microenvironments is important for better understanding the relationship between health effects caused by air pollution. The recent researches revealed that the level of air pollution in transport microenvironment contributes considerably to the total exposure of air pollution. The aim of the study was to determine air pollution of nitrogen dioxide and to assess the exposure of NO2 dependence on the chosen commuting mode using a global positioning system (GPS). The same travel destination was chosen and 30 rides in three different commuting modes: cycling, walking, and public transport were made. Every different mean of transport is associated with different route. GPS device and travel diary data were used to track all routes of different commuting modes. Air pollution of nitrogen dioxide was determined using the ADMS-Urban dispersion model. The average annual concentration of nitrogen dioxide was modeled for 2011 year in Kaunas city. The geographical information systems were used to visualize the travel routes, to create maps indicating the route of different commuting modes and to combine modelled nitrogen dioxide data. The results showed that there is a significant difference between the selected commuting mode and the exposure of nitrogen dioxide. The concentrations in the microenvironments were 22.4 μg/m3, 21.4 μg/m3, and 25.9 μg/m3 for cycling, walking and public transport respectively. Of all the modes of commuting, the highest average exposure of nitrogen dioxide was found travelling by public transport, while the lowest average concentration of NO2 was determined by walking.

Keywords: nitrogen dioxide, dispersion model, commuting mode, GPS

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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

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