Search results for: inductively coupled plasma-mass spectroscopy

Authors: Natia Jalagonia, Tinatin Kuchukhidze

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Polymer electrolytes (PE) play an important part in electrochemical devices such as batteries and fuel cells. To achieve optimal performance, the PE must maintain a high ionic conductivity and mechanical stability at both high and low relative humidity. The polymer electrolyte also needs to have excellent chemical stability for long and robustness. According to the prevailing theory, ionic conduction in polymer electrolytes is facilitated by the large-scale segmental motion of the polymer backbone, and primarily occurs in the amorphous regions of the polymer electrolyte. Crystallinity restricts polymer backbone segmental motion and significantly reduces conductivity. Consequently, polymer electrolytes with high conductivity at room temperature have been sought through polymers which have highly flexible backbones and have largely amorphous morphology. The interest in polymer electrolytes was increased also by potential applications of solid polymer electrolytes in high energy density solid state batteries, gas sensors and electrochromic windows. Conductivity of 10-3 S/cm is commonly regarded as a necessary minimum value for practical applications in batteries. At present, polyethylene oxide (PEO)-based systems are most thoroughly investigated, reaching room temperature conductivities of 10-7 S/cm in some cross-linked salt in polymer systems based on amorphous PEO-polypropylene oxide copolymers.. It is widely accepted that amorphous polymers with low glass transition temperatures Tg and a high segmental mobility are important prerequisites for high ionic conductivities. Another necessary condition for high ionic conductivity is a high salt solubility in the polymer, which is most often achieved by donors such as ether oxygen or imide groups on the main chain or on the side groups of the PE. It is well established also that lithium ion coordination takes place predominantly in the amorphous domain, and that the segmental mobility of the polymer is an important factor in determining the ionic mobility. Great attention was pointed to PEO-based amorphous electrolyte obtained by synthesis of comb-like polymers, by attaching short ethylene oxide unit sequences to an existing amorphous polymer backbone. The aim of presented work is to obtain of solid polymer electrolyte membranes using PMHS as a matrix. For this purpose the hydrosilylation reactions of α,ω-bis(trimethylsiloxy)methyl¬hydrosiloxane with allyl triethylene-glycol mo¬nomethyl ether and vinyltriethoxysilane at 1:28:7 ratio of initial com¬pounds in the presence of Karstedt’s catalyst, platinum hydrochloric acid (0.1 M solution in THF) and platinum on the carbon catalyst in 50% solution of anhydrous toluene have been studied. The synthesized olygomers are vitreous liquid products, which are well soluble in organic solvents with specific viscosity ηsp ≈ 0.05 - 0.06. The synthesized olygomers were analysed with FTIR, 1H, 13C, 29Si NMR spectroscopy. Synthesized polysiloxanes were investigated with wide-angle X-ray, gel-permeation chromatography, and DSC analyses. Via sol-gel processes of doped with lithium trifluoromethylsulfonate (triflate) or lithium bis¬(trifluoromethylsulfonyl)¬imide polymer systems solid polymer electrolyte membranes have been obtained. The dependence of ionic conductivity as a function of temperature and salt concentration was investigated and the activation energies of conductivity for all obtained compounds are calculated

Keywords: synthesis, PMHS, membrane, electrolyte

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Authors: Sergio Celaschi, Henrique Canavarro de Alencar, Claaudecir Biazoli

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Effluent quality is of the highest priority for compliance with the permit limits of environmental protection agencies and ensures the protection of their local water system. Of the pollutants monitored, the biochemical oxygen demand (BOD) posed one of the greatest challenges. This work presents a solution for wastewater treatment plants - WWTP’s ability to react to different situations and meet treatment goals. Delayed BOD5 results from the lab take 7 to 8 analysis days, hindered the WWTP’s ability to react to different situations and meet treatment goals. Reducing BOD turnaround time from days to hours is our quest. Such a solution is based on a system of two BOD bioreactors associated with Digital Twin (DT) and Machine Learning (ML) methodologies via an Internet of Things (IoT) platform to monitor and control a WWTP to support decision making. DT is a virtual and dynamic replica of a production process. DT requires the ability to collect and store real-time sensor data related to the operating environment. Furthermore, it integrates and organizes the data on a digital platform and applies analytical models allowing a deeper understanding of the real process to catch sooner anomalies. In our system of continuous time monitoring of the BOD suppressed by the effluent treatment process, the DT algorithm for analyzing the data uses ML on a chemical kinetic parameterized model. The continuous BOD monitoring system, capable of providing results in a fraction of the time required by BOD5 analysis, is composed of two thermally isolated batch bioreactors. Each bioreactor contains input/output access to wastewater sample (influent and effluent), hydraulic conduction tubes, pumps, and valves for batch sample and dilution water, air supply for dissolved oxygen (DO) saturation, cooler/heater for sample thermal stability, optical ODO sensor based on fluorescence quenching, pH, ORP, temperature, and atmospheric pressure sensors, local PLC/CPU for TCP/IP data transmission interface. The dynamic BOD system monitoring range covers 2 mg/L < BOD < 2,000 mg/L. In addition to the BOD monitoring system, there are many other operational WWTP sensors. The CPU data is transmitted/received to/from the digital platform, which in turn performs analyses at periodic intervals, aiming to feed the learning process. BOD bulletins and their credibility intervals are made available in 12-hour intervals to web users. The chemical kinetics ML algorithm is composed of a coupled system of four first-order ordinary differential equations for the molar masses of DO, organic material present in the sample, biomass, and products (CO₂ and H₂O) of the reaction. This system is solved numerically linked to its initial conditions: DO (saturated) and initial products of the kinetic oxidation process; CO₂ = H₂0 = 0. The initial values for organic matter and biomass are estimated by the method of minimization of the mean square deviations. A real case of continuous monitoring of BOD wastewater effluent quality is being conducted by deploying an IoT application on a large wastewater purification system located in S. Paulo, Brazil.

Keywords: effluent treatment, biochemical oxygen demand, continuous monitoring, IoT, machine learning

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Authors: Mohamed Sifan, Brabha Nagaratnam, Julian Thamboo, Keerthan Poologanathan

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Ultra high performance concrete (UHPC) is a type of cementitious material known for its exceptional strength, ductility, and durability. However, its production is often associated with high costs due to the significant amount of cementitious materials required and the use of fine powders to achieve the desired strength. The aim of this research is to explore the feasibility of developing cost-effective UHPC mixes using locally available materials. Specifically, the study aims to investigate the use of coarse limestone sand along with other sand types, namely, basalt sand, dolomite sand, and river sand for developing UHPC mixes and evaluating its performances. The study utilises the particle packing model to develop various UHPC mixes. The particle packing model involves optimising the combination of coarse limestone sand, basalt sand, dolomite sand, and river sand to achieve the desired properties of UHPC. The developed UHPC mixes are then evaluated based on their workability (measured through slump flow and mini slump value), compressive strength (at 7, 28, and 90 days), splitting tensile strength, and microstructural characteristics analysed through scanning electron microscope (SEM) analysis. The results of this study demonstrate that cost-effective UHPC mixes can be developed using locally available materials without the need for silica fume or fly ash. The UHPC mixes achieved impressive compressive strengths of up to 149 MPa at 28 days with a cement content of approximately 750 kg/m³. The mixes also exhibited varying levels of workability, with slump flow values ranging from 550 to 850 mm. Additionally, the inclusion of coarse limestone sand in the mixes effectively reduced the demand for superplasticizer and served as a filler material. By exploring the use of coarse limestone sand and other sand types, this study provides valuable insights into optimising the particle packing model for UHPC production. The findings highlight the potential to reduce costs associated with UHPC production without compromising its strength and durability. The study collected data on the workability, compressive strength, splitting tensile strength, and microstructural characteristics of the developed UHPC mixes. Workability was measured using slump flow and mini slump tests, while compressive strength and splitting tensile strength were assessed at different curing periods. Microstructural characteristics were analysed through SEM and energy dispersive X-ray spectroscopy (EDS) analysis. The collected data were then analysed and interpreted to evaluate the performance and properties of the UHPC mixes. The research successfully demonstrates the feasibility of developing cost-effective UHPC mixes using locally available materials. The inclusion of coarse limestone sand, in combination with other sand types, shows promising results in achieving high compressive strengths and satisfactory workability. The findings suggest that the use of the particle packing model can optimise the combination of materials and reduce the reliance on expensive additives such as silica fume and fly ash. This research provides valuable insights for researchers and construction practitioners aiming to develop cost-effective UHPC mixes using readily available materials and an optimised particle packing approach.

Keywords: cost-effective, limestone powder, particle packing model, ultra high performance concrete

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Authors: Thiago E. Goto, Carla C. Lopes, Helena B. Nader, Anielle C. A. Silva, Noelio O. Dantas, José R. Siqueira Jr., Luciano Caseli

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Quantum dots (QD) are semiconductor nanocrystals that can be employed in biological research as a tool for fluorescence imagings, having the potential to expand in vivo and in vitro analysis as cancerous cell biomarkers. Particularly, cadmium selenide (CdSe) magic-sized quantum dots (MSQDs) exhibit stable luminescence that is feasible for biological applications, especially for imaging of tumor cells. For these facts, it is interesting to know the mechanisms of action of how such QDs mark biological cells. For that, simplified models are a suitable strategy. Among these models, Langmuir films of lipids formed at the air-water interface seem to be adequate since they can mimic half a membrane. They are monomolecular films formed at liquid-gas interfaces that can spontaneously form when organic solutions of amphiphilic compounds are spread on the liquid-gas interface. After solvent evaporation, the monomolecular film is formed, and a variety of techniques, including tensiometric, spectroscopic and optic can be applied. When the monolayer is formed by membrane lipids at the air-water interface, a model for half a membrane can be inferred where the aqueous subphase serve as a model for external or internal compartment of the cell. These films can be transferred to solid supports forming the so-called Langmuir-Blodgett (LB) films, and an ampler variety of techniques can be additionally used to characterize the film, allowing for the formation of devices and sensors. With these ideas in mind, the objective of this work was to investigate the specific interactions of CdSe MSQDs with tumorigenic and non-tumorigenic cells using Langmuir monolayers and LB films of lipids and specific cell extracts as membrane models for diagnosis of cancerous cells. Surface pressure-area isotherms and polarization modulation reflection-absorption spectroscopy (PM-IRRAS) showed an intrinsic interaction between the quantum dots, inserted in the aqueous subphase, and Langmuir monolayers, constructed either of selected lipids or of non-tumorigenic and tumorigenic cells extracts. The quantum dots expanded the monolayers and changed the PM-IRRAS spectra for the lipid monolayers. The mixed films were then compressed to high surface pressures and transferred from the floating monolayer to solid supports by using the LB technique. Images of the films were then obtained with atomic force microscopy (AFM) and confocal microscopy, which provided information about the morphology of the films. Similarities and differences between films with different composition representing cell membranes, with or without CdSe MSQDs, was analyzed. The results indicated that the interaction of quantum dots with the bioinspired films is modulated by the lipid composition. The properties of the normal cell monolayer were not significantly altered, whereas for the tumorigenic cell monolayer models, the films presented significant alteration. The images therefore exhibited a stronger effect of CdSe MSQDs on the models representing cancerous cells. As important implication of these findings, one may envisage for new bioinspired surfaces based on molecular recognition for biomedical applications.

Keywords: biomembrane, langmuir monolayers, quantum dots, surfaces

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Authors: Norma Binti Alias, Che Rahim Che The, Norfarizan Mohd Said, Sakinah Abdul Hanan, Akhtar Ali

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This paper discusses on the transportation of magnetic drug targeting through blood within vessels, tissues and cells. There are three integrated mathematical models to be discussed and analyze the concentration of drug and blood flow through magnetic nanoparticles. The cell therapy brought advancement in the field of nanotechnology to fight against the tumors. The systematic therapeutic effect of Single Cells can reduce the growth of cancer tissue. The process of this nanoscale phenomena system is able to measure and to model, by identifying some parameters and applying fundamental principles of mathematical modeling and simulation. The mathematical modeling of single cell growth depends on three types of cell densities such as proliferative, quiescent and necrotic cells. The aim of this paper is to enhance the simulation of three types of models. The first model represents the transport of drugs by coupled partial differential equations (PDEs) with 3D parabolic type in a cylindrical coordinate system. This model is integrated by Non-Newtonian flow equations, leading to blood liquid flow as the medium for transportation system and the magnetic force on the magnetic nanoparticles. The interaction between the magnetic force on drug with magnetic properties produces induced currents and the applied magnetic field yields forces with tend to move slowly the movement of blood and bring the drug to the cancer cells. The devices of nanoscale allow the drug to discharge the blood vessels and even spread out through the tissue and access to the cancer cells. The second model is the transport of drug nanoparticles from the vascular system to a single cell. The treatment of the vascular system encounters some parameter identification such as magnetic nanoparticle targeted delivery, blood flow, momentum transport, density and viscosity for drug and blood medium, intensity of magnetic fields and the radius of the capillary. Based on two discretization techniques, finite difference method (FDM) and finite element method (FEM), the set of integrated models are transformed into a series of grid points to get a large system of equations. The third model is a single cell density model involving the three sets of first order PDEs equations for proliferating, quiescent and necrotic cells change over time and space in Cartesian coordinate which regulates under different rates of nutrients consumptions. The model presents the proliferative and quiescent cell growth depends on some parameter changes and the necrotic cells emerged as the tumor core. Some numerical schemes for solving the system of equations are compared and analyzed. Simulation and computation of the discretized model are supported by Matlab and C programming languages on a single processing unit. Some numerical results and analysis of the algorithms are presented in terms of informative presentation of tables, multiple graph and multidimensional visualization. As a conclusion, the integrated of three types mathematical modeling and the comparison of numerical performance indicates that the superior tool and analysis for solving the complete set of magnetic drug delivery system which give significant effects on the growth of the targeted cancer cell.

Keywords: mathematical modeling, visualization, PDE models, magnetic nanoparticle drug delivery model, drug release model, single cell effects, avascular tumor growth, numerical analysis

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Authors: Anas Hallak, Latifa Seblini, Juergen Wilde

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In mechatronics or sensor technology, plastic housings are used to protect sensitive components from harmful environmental influences, such as moisture, media, or reactive substances. Connections, preferably in the form of metallic lead-frame structures, through the housing wall are required for their electrical supply or control. In this system, an insufficient connection between the plastic component, e.g., Polyamide66, and the metal surface, e.g., copper, due to the incompatibility is dominating. As a result, leakage paths can occur along with the plastic-metal interface. Since adhesive bonding has been established as one of the most important joining processes and its use has expanded significantly, driven by the development of improved high-performance adhesives and bonding techniques, this technology has been involved in metal-plastic hybrid structures. In this study, an epoxy bonding agent from DELO (DUALBOND LT2266) has been used to improve the mechanical and chemical binding between the metal and the polymer. It is an adhesion promoter with two reaction stages. In these, the first stage provides fixation to the lead frame directly after the coating step, which can be done by UV-Exposure for a few seconds. In the second stage, the material will be thermally hardened during injection molding. To analyze the two reaction stages of the primer, dynamic DSC experiments were carried out and correlated with Fourier-transform infrared spectroscopy measurements. Furthermore, the number of crosslinking bonds formed in the system in each reaction stage has also been estimated by a rheological characterization. Those investigations have been performed with different times of UV exposure: 12, 96 s and in an industrial preferred temperature range from -20 to 175°C. The shear viscosity values of primer have been measured as a function of temperature and exposure times. For further interpretation, the storage modulus values have been calculated, and the so-called Booij–Palmen plot has been sketched. The next approach in this study is the self-healing mechanisms in the hydride system in which the primer should flow into micro-damage such as interface, cracks, inhibit them from growing, and close them. The ability of the primer to flow in and penetrate defined capillaries made in Ultramid was investigated. Holes with a diameter of 0.3 mm were produced in injection-molded A3EG7 plates with 4 mm thickness. A copper substrate coated with the DUALBOND was placed on the A3EG7 plate and pressed with a certain force. Metallographic analyses were carried out to verify the filling grade, which showed an almost 95% filling ratio of the capillaries. Finally, to estimate the self-healing mechanism in metal-plastic hybrid systems, characterizations have been done on a simple geometry with a metal inlay developed by the Institute of Polymer Technology in Friedrich-Alexander-University. The specimens have been modified with tungsten wire which was to be pulled out after the injection molding to create a micro-hole in the specimen at the interface between the primer and the polymer. The capability of the primer to heal those micro-cracks upon heating, pressing, and thermal aging has been characterized through metallographic analyses.

Keywords: hybrid structures, self-healing, thermoplastic housing, adhesive

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Authors: Victor Mantilla, Romeu Vicente, António Figueiredo, Victor Ferreira, Sandra Sorte

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Integrating dynamic facades into contemporary building design is shaping a new era of energy efficiency and user comfort. These innovative facades, often constructed using lightweight construction systems and materials, offer an opportunity to have a responsive and adaptive nature to the dynamic behavior of the outdoor climate. Therefore, in regions characterized by high fluctuations in daily temperatures, the ability to adapt to environmental changes is of paramount importance and a challenge. This paper presents a thorough review of the state of the art on double-skin facades (DSF), focusing on lightweight solutions for the external envelope. Dynamic facades featuring elements like movable shading devices, phase change materials, and advanced control systems have revolutionized the built environment. They offer a promising path for reducing energy consumption while enhancing occupant well-being. Lightweight construction systems are increasingly becoming the choice for the constitution of these facade solutions, offering benefits such as reduced structural loads and reduced construction waste, improving overall sustainability. However, the performance of dynamic facades based on low thermal inertia solutions in climatic contexts with high thermal amplitude is still in need of research since their ability to adapt is traduced in variability/manipulation of the thermal transmittance coefficient (U-value). Emerging technologies can enable such a dynamic thermal behavior through innovative materials, changes in geometry and control to optimize the facade performance. These innovations will allow a facade system to respond to shifting outdoor temperature, relative humidity, wind, and solar radiation conditions, ensuring that energy efficiency and occupant comfort are both met/coupled. This review addresses the potential configuration of double-skin facades, particularly concerning their responsiveness to seasonal variations in temperature, with a specific focus on addressing the challenges posed by winter and summer conditions. Notably, the design of a dynamic facade is significantly shaped by several pivotal factors, including the choice of materials, geometric considerations, and the implementation of effective monitoring systems. Within the realm of double skin facades, various configurations are explored, encompassing exhaust air, supply air, and thermal buffering mechanisms. According to the review places a specific emphasis on the thermal dynamics at play, closely examining the impact of factors such as the color of the facade, the slat angle's dimensions, and the positioning and type of shading devices employed in these innovative architectural structures.This paper will synthesize the current research trends in this field, with the presentation of case studies and technological innovations with a comprehensive understanding of the cutting-edge solutions propelling the evolution of building envelopes in the face of climate change, namely focusing on double-skin lightweight solutions to create sustainable, adaptable, and responsive building envelopes. As indicated in the review, flexible and lightweight systems have broad applicability across all building sectors, and there is a growing recognition that retrofitting existing buildings may emerge as the predominant approach.

Keywords: adaptive, control systems, dynamic facades, energy efficiency, responsive, thermal comfort, thermal transmittance

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Authors: Mikaela Kutrolli, Noah S. Pereira, Vanessa Scanlon, Mohamadmahdi Samandari, Ali Tamayol

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Bone tissue engineering has drawn significant attention and various biomaterials have been tested. Polymers such as polycaprolactone (PCL) offer excellent biocompatibility, reasonable mechanical properties, and biodegradability. However, PCL scaffolds suffer a critical drawback: a lack of micro/mesoporosity, affecting cell attachment, tissue integration, and mineralization. It also results in a slow degradation rate. While 3D-printing has addressed the issue of macroporosity through CAD-guided fabrication, PCL scaffolds still exhibit poor smaller-scale porosity. To overcome this, we generated composites of PCL, hydroxyapatite (HA), and powdered sucrose (PS). The latter serves as a sacrificial material to generate porous particles after sucrose dissolution. Additionally, we have incorporated dexamethasone (DEX) to boost the PCL osteogenic properties. The resulting scaffolds maintain controlled macroporosity from the lattice print structure but also develop micro/mesoporosity within PCL fibers when exposed to aqueous environments. The study involved mixing PS into solvent-dissolved PCL in different weight ratios of PS to PCL (70:30, 50:50, and 30:70 wt%). The resulting composite was used for 3D printing of scaffolds at room temperature. Printability was optimized by adjusting pressure, speed, and layer height through filament collapse and fusion test. Enzymatic degradation, porogen leaching, and DEX release profiles were characterized. Physical properties were assessed using wettability, SEM, and micro-CT to quantify the porosity (percentage, pore size, and interconnectivity). Raman spectroscopy was used to verify the absence of sugar after leaching. Mechanical characteristics were evaluated via compression testing before and after porogen leaching. Bone marrow stromal cells (BMSCs) behavior in the printed scaffolds was studied by assessing viability, metabolic activity, osteo-differentiation, and mineralization. The scaffolds with a 70% sugar concentration exhibited superior printability and reached the highest porosity of 80%, but performed poorly during mechanical testing. A 50% PS concentration demonstrated a 70% porosity, with an average pore size of 25 µm, favoring cell attachment. No trace of sucrose was found in Raman after leaching the sugar for 8 hours. Water contact angle results show improved hydrophilicity as the sugar concentration increased, making the scaffolds more conductive to cell adhesion. The behavior of bone marrow stromal cells (BMSCs) showed positive viability and proliferation results with an increasing trend of mineralization and osteo-differentiation as the sucrose concentration increased. The addition of HA and DEX also promoted mineralization and osteo-differentiation in the cultures. The integration of PS as porogen at a concentration of 50%wt within PCL scaffolds presents a promising approach to address the poor cell attachment and tissue integration issues of PCL in bone tissue engineering. The method allows for the fabrication of scaffolds with tunable porosity and mechanical properties, suitable for various applications. The addition of HA and DEX further enhanced the scaffolds. Future studies will apply the scaffolds in an in-vivo model to thoroughly investigate their performance.

Keywords: bone, PCL, 3D printing, tissue engineering

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Authors: Andrew D. Henshaw, James M. Austin

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Introduction: Human trafficking is an increasingly serious transnational criminal enterprise and social security issue. Despite ongoing efforts to mitigate the phenomenon and a significant expansion of security scrutiny over past decades, it is not receding. This is true for many nations in Southeast Asia, widely recognized as the global hub for trafficked persons, including men, women, and children. Clearly, human trafficking is difficult to address because there are numerous drivers, causes, and motivators for it to persist, such as non-military and non-traditional security challenges, i.e., climate change, global warming displacement, and natural disasters. These make displaced persons and refugees particularly vulnerable. The issue is so large conservative estimates put a dollar value at around $150 billion-plus per year (Niethammer, 2020) spanning sexual slavery and exploitation, forced labor, construction, mining and in conflict roles, and forced marriages of girls and women. Coupled with corruption throughout military, police, and civil authorities around the world, and the active hands of powerful transnational criminal organizations, it is likely that such figures are grossly underestimated as human trafficking is misreported, under-detected, and deliberately obfuscated to protect those profiting from it. For example, the 2022 UN report on human trafficking shows a 56% reduction in convictions in that year alone (UNODC, 2022). Our Approach: To better understand this, our research utilizes a bespoke methodology. Applying a JAM (Juxtaposition Assessment Matrix), which we previously developed to detect flows of dark money around the globe (Henshaw, A & Austin, J, 2021), we now focus on the human trafficking paradigm. Indeed, utilizing a JAM methodology has identified key indicators of human trafficking not previously explored in depth. Being a set of structured analytical techniques that provide panoramic interpretations of the subject matter, this iteration of the JAM further incorporates behavioral and driver indicators, including the employment of Open-Source Artificial Intelligence (OS-AI) across multiple collection points. The extracted behavioral data was then applied to identify non-traditional indicators as they contribute to human trafficking. Furthermore, as the JAM OS-AI analyses data from the inverted position, i.e., the viewpoint of the traffickers, it examines the behavioral and physical traits required to succeed. This transposed examination of the requirements of success delivers potential leverage points for exploitation in the fight against human trafficking in a new and novel way. Findings: Our approach identified new innovative datasets that have previously been overlooked or, at best, undervalued. For example, the JAM OS-AI approach identified critical 'dark agent' lynchpins within human trafficking that are difficult to detect and harder to connect to actors and agents within a network. Our preliminary data suggests this is in part due to the fact that ‘dark agents’ in extant research have been difficult to detect and potentially much harder to directly connect to the actors and organizations in human trafficking networks. Our research demonstrates that using new investigative techniques such as OS-AI-aided JAM introduces a powerful toolset to increase understanding of human trafficking and transnational crime and illuminate networks that, to date, avoid global law enforcement scrutiny.

Keywords: human trafficking, open-source intelligence, transnational crime, human security, international human rights, intelligence analysis, JAM OS-AI, Dark Money

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Authors: Sara Mosteller, Larissa K. Samuelson, Sobanawartiny Wijeakumar, John P. Spencer

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This study was designed to examine how humans are able to teach and learn semantic information as well as cooperate in order to jointly achieve sophisticated goals. Specifically, we are measuring individual differences in how these abilities develop from foundational building blocks in early childhood. The current study adopts a paradigm for novel noun learning developed by Samuelson, Smith, Perry, and Spencer (2011) to a hyperscanning paradigm [Cui, Bryant and Reiss, 2012]. This project measures coordinated brain activity between a parent and child using simultaneous functional near infrared spectroscopy (fNIRS) in pairs of 2.5, 3.5 and 4.5-year-old children and their parents. We are also separately testing pairs of adult friends. Children and parents, or adult friends, are seated across from one another at a table. The parent (in the developmental study) then teaches their child the names of novel toys. An experimenter then tests the child by presenting the objects in pairs and asking the child to retrieve one object by name. Children are asked to choose from both pairs of familiar objects and pairs of novel objects. In order to explore individual differences in cooperation with the same participants, each dyad plays a cooperative game of Jenga, in which their joint score is based on how many blocks they can remove from the tower as a team. A preliminary analysis of the noun-learning task showed that, when presented with 6 word-object mappings, children learned an average of 3 new words (50%) and that the number of objects learned by each child ranged from 2-4. Adults initially learned all of the new words but were variable in their later retention of the mappings, which ranged from 50-100%. We are currently examining differences in cooperative behavior during the Jenga playing game, including time spent discussing each move before it is made. Ongoing analyses are examining the social dynamics that might underlie the differences between words that were successfully learned and unlearned words for each dyad, as well as the developmental differences observed in the study. Additionally, the Jenga game is being used to better understand individual and developmental differences in social coordination during a cooperative task. At a behavioral level, the analysis maps periods of joint visual attention between participants during the word learning and the Jenga game, using head-mounted eye trackers to assess each participant’s first-person viewpoint during the session. We are also analyzing the coherence in brain activity between participants during novel word-learning and Jenga playing. The first hypothesis is that visual joint attention during the session will be positively correlated with both the number of words learned and with the number of blocks moved during Jenga before the tower falls. The next hypothesis is that successful communication of new words and success in the game will each be positively correlated with synchronized brain activity between the parent and child/the adult friends in cortical regions underlying social cognition, semantic processing, and visual processing. This study probes both the neural and behavioral mechanisms of learning and cooperation in a naturalistic, interactive and developmental context.

Keywords: communication, cooperation, development, interaction, neuroscience

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Authors: P. J. Sweeney, T. Ahtoniemi, J. Puoliväli, T. Laitinen, K. Lehtimäki, A. Nurmi, D. Wells

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Duchenne muscular dystrophy (DMD) is caused by an X linked mutation in the dystrophin gene; lack of dystrophin causes a progressive muscle necrosis which leads to a progressive decrease in mobility in those suffering from the disease. The MDX mouse, a mutant mouse model which displays a frank dystrophinopathy, is currently widely employed in pre clinical efficacy models for treatments and therapies aimed at DMD. In general the end-points examined within this model have been based on invasive histopathology of muscles and serum biochemical measures like measurement of serum creatine kinase (sCK). It is established that a “critical period” between 4 and 6 weeks exists in the MDX mouse when there is extensive muscle damage that is largely sub clinical but evident with sCK measurements and histopathological staining. However, a full characterization of the MDX model remains largely incomplete especially with respect to the ability to aggravate of the muscle damage beyond the critical period. The purpose of this study was to attempt to aggravate the muscle damage in the MDX mouse and to create a wider, more readily translatable and discernible, therapeutic window for the testing of potential therapies for DMD. The study consisted of subjecting 15 male mutant MDX mice and 15 male wild-type mice to an intense chronic exercise regime that consisted of bi-weekly (two times per week) treadmill sessions over a 12 month period. Each session was 30 minutes in duration and the treadmill speed was gradually built up to 14m/min for the entire session. Baseline plasma creatine kinase (pCK), treadmill training performance and locomotor activity were measured after the “critical period” at around 10 weeks of age and again at 14 weeks of age, 6 months, 9 months and 12 months of age. In addition, kinematic gait analysis was employed using a novel analysis algorithm in order to compare changes in gait and fine motor skills in diseased exercised MDX mice compared to exercised wild type mice and non exercised MDX mice. In addition, a morphological and metabolic profile (including lipid profile), from the muscles most severely affected, the gastrocnemius muscle and the tibialis anterior muscle, was also measured at the same time intervals. Results indicate that by aggravating or exacerbating the underlying muscle damage in the MDX mouse by exercise a more pronounced and severe phenotype in comes to light and this can be picked up earlier by kinematic gait analysis. A reduction in mobility as measured by open field is not apparent at younger ages nor during the critical period, but changes in gait are apparent in the mutant MDX mice. These gait changes coincide with pronounced morphological and metabolic changes by non-invasive anatomical MRI and proton spectroscopy (1H-MRS) we have reported elsewhere. Evidence of a progressive asymmetric pathology in imaging parameters as well as in the kinematic gait analysis was found. Taken together, the data show that chronic exercise regime exacerbates the muscle damage beyond the critical period and the ability to measure through non-invasive means are important factors to consider when performing preclinical efficacy studies in the MDX mouse.

Keywords: Gait, muscular dystrophy, Kinematic analysis, neuromuscular disease

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Authors: M. Naveed Yasin, Robert Brooke, Andrew Chan, Geoffrey I. N. Waterhouse, Drew Evans, Darren Svirskis, Ilva D. Rupenthal

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Poly(3,4-ethylenedioxythiophene) (PEDOT) is a robust conducting polymer (CP) exhibiting high conductivity and environmental stability. It can be synthesized by either chemical, electrochemical or vapour phase polymerization (VPP). Dexamethasone sodium phosphate (dexP) is an anionic drug molecule which has previously been loaded onto PEDOT as a dopant via electrochemical polymerisation; however this technique requires conductive surfaces from which polymerization is initiated. On the other hand, VPP produces highly organized biocompatible CP structures while polymerization can be achieved onto a range of surfaces with a relatively straight forward scale-up process. Following VPP of PEDOT, dexP can be loaded and subsequently released via ion-exchange. This study aimed at preparing and characterising both non-porous and porous VPP PEDOT structures including examining drug loading and release via ion-exchange. Porous PEDOT structures were prepared by first depositing a sacrificial polystyrene (PS) colloidal template on a substrate, heat curing this deposition and then spin coating it with the oxidant solution (iron tosylate) at 1500 rpm for 20 sec. VPP of both porous and non-porous PEDOT was achieved by exposing to monomer vapours in a vacuum oven at 40 mbar and 40 °C for 3 hrs. Non-porous structures were prepared similarly on the same substrate but without any sacrificial template. Surface morphology, compositions and behaviour were then characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) respectively. Drug loading was achieved by 50 CV cycles in a 0.1 M dexP aqueous solution. For drug release, each sample was exposed to 20 mL of phosphate buffer saline (PBS) placed in a water bath operating at 37 °C and 100 rpm. Film was stimulated (continuous pulse of ± 1 V at 0.5 Hz for 17 mins) while immersed into PBS. Samples were collected at 1, 2, 6, 23, 24, 26 and 27 hrs and were analysed for dexP by high performance liquid chromatography (HPLC Agilent 1200 series). AFM and SEM revealed the honey comb nature of prepared porous structures. XPS data showed the elemental composition of the dexP loaded film surface, which related well with that of PEDOT and also showed that one dexP molecule was present per almost three EDOT monomer units. The reproducible electroactive nature was shown by several cycles of reduction and oxidation via CV. Drug release revealed success in drug loading via ion-exchange, with stimulated porous and non-porous structures exhibiting a proof of concept burst release upon application of an electrical stimulus. A similar drug release pattern was observed for porous and non-porous structures without any significant statistical difference, possibly due to the thin nature of these structures. To our knowledge, this is the first report to explore the potential of VPP prepared PEDOT for stimuli-responsive drug delivery via ion-exchange. The produced porous structures were ordered and highly porous as indicated by AFM and SEM. These porous structures exhibited good electroactivity as shown by CV. Future work will investigate porous structures as nano-reservoirs to increase drug loading while sealing these structures to minimize spontaneous drug leakage.

Keywords: PEDOT for ion-exchange drug delivery, stimuli-responsive drug delivery, template based porous PEDOT structures, vapour phase polymerization of PEDOT

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Authors: Ece A. Irmak, Amdulla O. Mekhrabov, M. Vedat Akdeniz

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There is a growing interest on the synthesis and characterization of nanoalloys since the unique chemical, and physical properties of nanoalloys can be tuned and, consequently, new structural motifs can be created by varying the type of constituent elements, atomic and magnetic ordering, as well as size and shape of the nanoparticles. Due to the fine size effects, magnetic nanoalloys have considerable attention with their enhanced mechanical, electrical, optical and magnetic behavior. As an important magnetic nanoalloy, the novel application area of Fe-Ni based nanoalloys is expected to be widened in the chemical, aerospace industry and magnetic biomedical applications. Noble metals have been using in biomedical applications for several years because of their surface plasmon properties. In this respect, iron-nickel nanoalloys are promising materials for magnetic biomedical applications because they show novel properties such as superparamagnetism and surface plasmon resonance property. Also, there is great attention for the usage Fe-Ni based nanoalloys as radar absorbing materials in aerospace and stealth industry due to having high Curie temperature, high permeability and high saturation magnetization with good thermal stability. In this study, FeNi₃ bimetallic nanoalloys were synthesized by mechanical alloying in a planetary high energy ball mill. In mechanical alloying, micron size powders are placed into the mill with milling media. The powders are repeatedly deformed, fractured and alloyed by high energy collision under the impact of balls until the desired composition and particle size is achieved. The experimental studies were carried out in two parts. Firstly, dry mechanical alloying with high energy dry planetary ball milling was applied to obtain FeNi₃ nanoparticles. Secondly, dry milling was followed by surfactant-assisted ball milling to observe the surfactant and solvent effect on the structure, size, and properties of the FeNi₃ nanoalloys. In the first part, the powder sample of iron-nickel was prepared according to the 1:3 iron to nickel ratio to produce FeNi₃ nanoparticles and the 1:10 powder to ball weight ratio. To avoid oxidation during milling, the vials had been filled with Ar inert gas before milling started. The powders were milled for 80 hours in total and the synthesis of the FeNi₃ intermetallic nanoparticles was succeeded by mechanical alloying in 40 hours. Also, regarding the particle size, it was found that the amount of nano-sized particles raised with increasing milling time. In the second part of the study, dry milling of the Fe and Ni powders with the same stoichiometric ratio was repeated. Then, to prevent agglomeration and to obtain smaller sized nanoparticles with superparamagnetic behavior, surfactants and solvent are added to the system, after 40-hour milling time, with the completion of the mechanical alloying. During surfactant-assisted ball milling, heptane was used as milling medium, and as surfactants, oleic acid and oleylamine were used in the high energy ball milling processes. The characterization of the alloyed particles in terms of microstructure, morphology, particle size, thermal and magnetic properties with respect to milling time was done by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, vibrating-sample magnetometer, and differential scanning calorimetry.

Keywords: iron-nickel systems, magnetic nanoalloys, mechanical alloying, nanoalloy characterization, surfactant-assisted ball milling

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Authors: Saleh Gorji, Sahil Gulati, Ana Pakzad

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Continuous electron diffraction tomography, also known as microcrystal electron diffraction (MicroED) or three-dimensional electron diffraction (3DED), is a powerful technique, which in combination with cryo-electron microscopy (cryo-ED), can provide atomic-scale 3D information about the crystal structure and composition of different classes of crystalline materials such as proteins, peptides, and small molecules. Unlike the well-established X-ray crystallography method, 3DED does not require large single crystals and can collect accurate electron diffraction data from crystals as small as 50 – 100 nm. This is a critical advantage as growing larger crystals, as required by X-ray crystallography methods, is often very difficult, time-consuming, and expensive. In most cases, specimens studied via 3DED method are electron beam sensitive, which means there is a limitation on the maximum amount of electron dose one can use to collect the required data for a high-resolution structure determination. Therefore, collecting data using a conventional scintillator-based fiber coupled camera brings additional challenges. This is because of the inherent noise introduced during the electron-to-photon conversion in the scintillator and transfer of light via the fibers to the sensor, which results in a poor signal-to-noise ratio and requires a relatively higher and commonly specimen-damaging electron dose rates, especially for protein crystals. As in other cryo-EM techniques, damage to the specimen can be mitigated if a direct detection camera is used which provides a high signal-to-noise ratio at low electron doses. In this work, we have used two classes of such detectors from Gatan, namely the K3® camera (a monolithic active pixel sensor) and Stela™ (that utilizes DECTRIS hybrid-pixel technology), to address this problem. The K3 is an electron counting detector optimized for low-dose applications (like structural biology cryo-EM), and Stela is also a counting electron detector but optimized for diffraction applications with high speed and high dynamic range. Lastly, data collection workflows, including crystal screening, microscope optics setup (for imaging and diffraction), stage height adjustment at each crystal position, and tomogram acquisition, can be one of the other challenges of the 3DED technique. Traditionally this has been all done manually or in a partly automated fashion using open-source software and scripting, requiring long hours on the microscope (extra cost) and extensive user interaction with the system. We have recently introduced Latitude® D in DigitalMicrograph® software, which is compatible with all pre- and post-energy-filter Gatan cameras and enables 3DED data acquisition in an automated and optimized fashion. Higher quality 3DED data enables structure determination with higher confidence, while automated workflows allow these to be completed considerably faster than before. Using multiple examples, this work will demonstrate how to direct detection electron counting cameras enhance 3DED results (3 to better than 1 Angstrom) for protein and small molecule structure determination. We will also show how Latitude D software facilitates collecting such data in an integrated and fully automated user interface.

Keywords: continuous electron diffraction tomography, direct detection, diffraction, Latitude D, Digitalmicrograph, proteins, small molecules

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Authors: Helena Pera, Arcadi Sanmartin, Albert Falques, Rafael Rebolo, Xavier Ametller, Heiko Zillgen, Cecile Prum, Boris Even, Eric Kapornyai

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Sheet piles system can be an interesting solution when dealing with harbors or quays designs. However, current design methods lead to conservative approaches due to the lack of specific basis of design. For instance, some design features still deal with pseudo-static approaches, although being a dynamic problem. Under this concern, the study particularly focuses on hydrodynamic water pressure definition and stability analysis of sheet pile system under seismic loads. During a seismic event, seawater produces hydrodynamic pressures on structures. Currently, design methods introduce hydrodynamic forces by means of Westergaard formulation and Eurocodes recommendations. They apply constant hydrodynamic pressure on the front sheet pile during the entire earthquake. As a result, the hydrodynamic load may represent 20% of the total forces produced on the sheet pile. Nonetheless, some studies question that approach. Hence, this study assesses the soil-structure-fluid interaction of sheet piles under seismic action in order to evaluate if current design strategies overestimate hydrodynamic pressures. For that purpose, this study performs various simulations by Plaxis 2D, a well-known geotechnical software, and CFD models, which treat fluid dynamic behaviours. Knowing that neither Plaxis nor CFD can resolve a soil-fluid coupled problem, the investigation imposes sheet pile displacements from Plaxis as input data for the CFD model. Then, it provides hydrodynamic pressures under seismic action, which fit theoretical Westergaard pressures if calculated using the acceleration at each moment of the earthquake. Thus, hydrodynamic pressures fluctuate during seismic action instead of remaining constant, as design recommendations propose. Additionally, these findings detect that hydrodynamic pressure contributes a 5% to the total load applied on sheet pile due to its instantaneous nature. These results are in line with other studies that use added masses methods for hydrodynamic pressures. Another important feature in sheet pile design is the assessment of the geotechnical overall stability. It uses pseudo-static analysis since the dynamic analysis cannot provide a safety calculation. Consequently, it estimates the seismic action. One of its relevant factors is the selection of the seismic reduction factor. A huge amount of studies discusses the importance of it but also about all its uncertainties. Moreover, current European standards do not propose a clear statement on that, and they recommend using a reduction factor equal to 1. This leads to conservative requirements when compared with more advanced methods. Under this situation, the study calibrates seismic reduction factor by fitting results from pseudo-static to dynamic analysis. The investigation concludes that pseudo-static analyses could reduce seismic action by 40-50%. These results are in line with some studies from Japanese and European working groups. In addition, it seems suitable to account for the flexibility of the sheet pile-soil system. Nevertheless, the calibrated reduction factor is subjected to particular conditions of each design case. Further research would contribute to specifying recommendations for selecting reduction factor values in the early stages of the design. In conclusion, sheet pile design still has chances for improving its design methodologies and approaches. Consequently, design could propose better seismic solutions thanks to advanced methods such as findings of this study.

Keywords: computational fluid dynamics, hydrodynamic pressures, pseudo-static analysis, quays, seismic design, steel sheet pile

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Authors: Anitha Kandasamy, Thirumurugan Ramaiah

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Interestingly, organic materials exhibit large optical nonlinearity with quick responses and having the flexibility of molecular tailoring using computational modelling and favourable synthetic methodologies. Pyridine based organic compounds and carboxylic acid contained aromatic compounds play a crucial role in crystal engineering of NCS complexes that displays admirable optical nonlinearity with fast response and favourable physicochemical properties such as low dielectric constant, wide optical transparency and large laser damage threshold value requires for optoelectronics device applications. Based on these facts, it was projected to form an acentric molecule of π-conjugated system interaction with appropriately replaced electron donor and acceptor groups for achieving higher SHG activity in which quinoline-2-carboyxlic acid is chosen as an electron acceptor and capable of acting as an acid as well as a base molecule, while 2-amino-4-methylpyridine is used as an electron donor and previously employed in numerous proton transfer complexes for synthesis of NLO materials for optoelectronic applications. 2-amino-4-mehtylpyridinium quinoline-2-carboxylate molecular complex (2AQ) is having π-donor-acceptor groups in which 2-amino-4-methylpyridine donates one of its electron to quinoline -2-carboxylic acid thereby forming a protonated 2-amino-4-methyl pyridinium moiety and mono ionized quinoline-2-carboxylate moiety which are connected via N-H…O intermolecular interactions with non-centrosymmetric crystal packing arrangement at microscopic scale is accountable to the enhancement of macroscopic second order NLO activity. The 2AQ crystal was successfully grown by a slow evaporation solution growth technique and its structure was determined in orthorhombic crystal system with acentric, P212121, space group. Hirshfeld surface analysis reveals that O…H intermolecular interactions primarily contributed with 31.0 % to the structural stabilization of 2AQ. The molecular structure of title compound has been confirmed by 1H and 13C NMR spectral studies. The vibrational modes of functional groups present in 2AQ have been assigned by using FTIR and FT-Raman spectroscopy. The grown 2AQ crystal exhibits high optical transparency with lower cut-off wavelength (275 nm) within the region of 275-1500 nm. The laser study confirmed that 2AQ exhibits high SHG efficiency of 12.6 times greater than that of KDP. TGA-DTA analysis revealed that 2AQ crystal had a thermal stability of 223 °C. The low dielectric constant and low dielectric loss at higher frequencies confirmed good crystalline nature with fewer defects of grown 2AQ crystal. The grown crystal exhibits soft material and positive photoconduction behaviour. Mulliken atomic distribution and FMOs analysis suggested that the strong intermolecular hydrogen bonding which lead to the enhancement of NLO activity. These properties suggest that 2AQ crystal is a suitable material for optoelectronic and laser frequency conversion applications.

Keywords: crystal growth, NLO activity, proton transfer complex, quantum chemical investigation

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Authors: Ajit Rai, Hamza Deroui, Blandine Vacher, Khwansiri Ninpan, Arthur Aumont, Francesco Vitillo, Robert Plana

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Large-scale critical industrial scheduling problems are based on Resource-Constrained Project Scheduling Problems (RCPSP), that necessitate integration with other optimization problems (e.g., vehicle routing, supply chain, or unique industrial ones), thus requiring practical solutions (i.e., modular, computationally efficient with feasible solutions). To the best of our knowledge, the current industrial state of the art is not addressing this holistic problem. We propose an original modular solution that answers the issues exhibited by the delivery of complex projects. With three interlinked entities (project, task, resources) having their constraints, it uses a greedy heuristic with a dynamic cost function for each task with a situational assessment at each time step. It handles large-scale data and can be easily integrated with other optimization problems, already existing industrial tools and unique constraints as required by the use case. The solution has been tested and validated by domain experts on three use cases: outage management in Nuclear Power Plants (NPPs), planning of future NPP maintenance operation, and application in the defense industry on supply chain and factory relocation. In the first use case, the solution, in addition to the resources’ availability and tasks’ logical relationships, also integrates several project-specific constraints for outage management, like, handling of resource incompatibility, updating of tasks priorities, pausing tasks in a specific circumstance, and adjusting dynamic unit of resources. With more than 20,000 tasks and multiple constraints, the solution provides a feasible schedule within 10-15 minutes on a standard computer device. This time-effective simulation corresponds with the nature of the problem and requirements of several scenarios (30-40 simulations) before finalizing the schedules. The second use case is a factory relocation project where production lines must be moved to a new site while ensuring the continuity of their production. This generates the challenge of merging job shop scheduling and the RCPSP with location constraints. Our solution allows the automation of the production tasks while considering the rate expectation. The simulation algorithm manages the use and movement of resources and products to respect a given relocation scenario. The last use case establishes a future maintenance operation in an NPP. The project contains complex and hard constraints, like on Finish-Start precedence relationship (i.e., successor tasks have to start immediately after predecessors while respecting all constraints), shareable coactivity for managing workspaces, and requirements of a specific state of "cyclic" resources (they can have multiple states possible with only one at a time) to perform tasks (can require unique combinations of several cyclic resources). Our solution satisfies the requirement of minimization of the state changes of cyclic resources coupled with the makespan minimization. It offers a solution of 80 cyclic resources with 50 incompatibilities between levels in less than a minute. Conclusively, we propose a fast and feasible modular approach to various industrial scheduling problems that were validated by domain experts and compatible with existing industrial tools. This approach can be further enhanced by the use of machine learning techniques on historically repeated tasks to gain further insights for delay risk mitigation measures.

Keywords: deterministic scheduling, optimization coupling, modular scheduling, RCPSP

Procedia PDF Downloads 161

Authors: Joshua Doe, George Amoako

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Purpose: In an increasingly digital world, the realm of sports fandom has extended its borders, creating a vibrant ecosystem of online communities centered around football clubs. This study ventures into the intricate interplay of motivations that drive football fans to respond to brand activism and its profound implications for brand antagonism and engagement among two of Ghana's most revered premier football clubs. Methods: A sample of 459 fervent fans from these two rival clubs were engaged through self-administered questionnaires expertly distributed via social media and online platforms. Data was analysed, using PLS-SEM. Findings: The tapestry of motivations that weave through these online football communities is as diverse as the fans themselves. It becomes apparent that fans are propelled by a spectrum of incentives. They seek education, yearn for information, revel in entertainment, embrace socialization, and fortify their self-esteem through their interactions within these digital spaces. Yet, it is the nuanced distinction in these motivations that shapes the trajectory of brand antagonism and engagement. Surprisingly, the study reveals a remarkable pattern. Football fans, despite their fierce rivalries, do not engage in brand antagonism based on educational pursuits, information-seeking endeavors, or socialization. Instead, it is motivations rooted in entertainment and self-esteem that serve as the fertile grounds for brand antagonism. Paradoxically, it is these very motivations coupled with the desire for socialization that nurture brand engagement, manifesting as active support and advocacy for their chosen club brand. Originality: Our research charters new waters by extending the boundaries of existing theories in the field. The Technology Acceptance Uses and Gratifications Theory, and Social Identity Theory all find new dimensions within the context of online brand community engagement. This not only deepens our understanding of the multifaceted world of online football fandom but also invites us to explore the implications these insights carry within the digital realm. Contribution to Practice: For marketers, our findings offer a treasure trove of actionable insights. They beckon the development of targeted content strategies that resonate with fan motivations. The implementation of brand advocacy programs, fostering opportunities for socialization, and the effective management of brand antagonism emerge as pivotal strategies. Furthermore, the utilization of data-driven insights is poised to refine consumer engagement strategies and strengthen brand affinity. Future Studies: For future studies, we advocate for longitudinal, cross-cultural, and qualitative studies that could shed further light on this topic. Comparative analyses across different types of online brand communities, an exploration of the role of brand community leaders, and inquiries into the factors that contribute to brand community dissolution all beckon the research community. Furthermore, understanding motivation-specific antagonistic behaviors and the intricate relationship between information-seeking and engagement present exciting avenues for further exploration. This study unfurls a vibrant tapestry of fan motivations, brand activism, and rivalry within online football communities. It extends a hand to scholars and marketers alike, inviting them to embark on a journey through this captivating digital realm, where passion, rivalry, and engagement harmonize to shape the world of sports fandom as we know it.

Keywords: online brand engagement, football fans, brand antagonism, motivations

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Authors: Vanita Singh

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In developing countries, there are conflicting political agendas; policy makers have to prioritize issues from a list of issues competing for the limited resources. Thus, it is imperative to understand how some issues gain attention, and others lose in the policy circles. Multiple-Streams Theory of Kingdon (1984) is among the influential theories that help to understand the public policy process and is utilitarian for health policy makers to understand how certain health issues emerge on the policy agendas. The issue of maternal mortality was long standing in India and was linked with high birth rate thus the focus of maternal health policy was on family planning since India’s independence. However, a paradigm shift was noted in the maternal health policy in the year 1992 with the launch of Safe Motherhood Programme and then in the year 2005, when the agenda of maternal health policy became universalizing institutional deliveries and phasing-out of Traditional Birth Attendants (TBAs) from the health system. There were many solutions proposed by policy communities other than universalizing of institutional deliveries, including training of TBAs and improving socio-economic conditions of pregnant women. However, Government of India favored medical community, which was advocating for the policy of universalizing institutional delivery, and neglected the solutions proposed by other policy communities. It took almost 15 years for the advocates of institutional delivery to transform their proposed solution into a program - the Janani Suraksha Yojana (JSY), a safe-motherhood program promoting institutional delivery through cash incentives to pregnant women. Thus, the case of safe motherhood policy in India is worth studying to understand how certain issues/problems gain political attention and how advocacy work in policy circles. This paper attempts to understand the factors that favored the agenda of safe-motherhood in the policy circle in India, using John Kingdon’s Multiple-Stream model of agenda-setting. Through document analysis and literature review, the paper traces the evolution of safe motherhood program and maternal health policy. The study has used open source documents available on the website of Ministry of Health and Family Welfare, media reports (Times of India Archive) and related research papers. The documents analyzed include National health policy-1983, National Health Policy-2002, written reports of Ministry of Health and Family Welfare Department, National Rural Health Mission (NRHM) document, documents related to Janani Suraksha Yojana and research articles related to maternal health programme in India. The study finds that focusing events and credible indicators coupled with media attention has the potential to recognize a problem. The political elites favor clearly defined and well-accepted solutions. The trans-national organizations affect the agenda-setting process in a country through conditional resource provision. The closely-knit policy communities and political entrepreneurship are required for advocating solutions high on agendas. The study has implications for health policy makers in identifying factors that have the potential to affect the agenda-setting process for a desired policy agenda and identify the challenges in generating political priorities.

Keywords: agenda-setting, focusing events, Kingdon’s model, safe motherhood program India

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Authors: Vladimir A. Basiuk, Laura J. Flores-Sanchez, Victor Meza-Laguna, Jose O. Flores-Flores, Lauro Bucio-Galindo, Elena V. Basiuk

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Noncovalent nanohybrid materials combining carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of increasing research effort, with a particular emphasis on the design of new heterogeneous catalysts, efficient organic photovoltaic cells, lithium batteries, gas sensors, field effect transistors, among other possible applications. The possibility of using unsubstituted Pcs for CNT functionalization is very attractive due to their very moderate cost and easy commercial availability. However, unfortunately, the deposition of unsubstituted Pcs onto nanotube sidewalls through the traditional liquid-phase protocols turns to be very problematic due to extremely poor solubility of Pcs. On the other hand, unsubstituted free-base H₂Pc phthalocyanine ligand, as well as many of its transition metal complexes, exhibit very high thermal stability and considerable volatility under reduced pressure, which opens the possibility for their physical vapor deposition onto solid surfaces, including nanotube sidewalls. In the present work, we show the possibility of simple, fast and efficient noncovalent functionalization of single-walled carbon nanotubes (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me= Co, Ni, Cu, and Zn. The functionalization can be performed in a temperature range of 400-500 °C under moderate vacuum and requires about 2-3 h only. The functionalized materials obtained were characterized by means of Fourier-transform infrared (FTIR), Raman, UV-visible and energy-dispersive X-ray spectroscopy (EDS), scanning and transmission electron microscopy (SEM and TEM, respectively) and thermogravimetric analysis (TGA). TGA suggested that Me(II)Pc weight content is 30%, 17% and 35% for NiPc, CuPc, and ZnPc, respectively (CoPc exhibited anomalous thermal decomposition behavior). The above values are consistent with those estimated from EDS spectra, namely, of 24-39%, 27-36% and 27-44% for CoPc, CuPc, and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Me(II)Pc hybrids, as compared to that of pristine nanotubes, implies very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO, respectively) distribution patterns, calculated with density functional theory by using Perdew-Burke-Ernzerhof general gradient approximation correlation functional in combination with the Grimme’s empirical dispersion correction (PBE-D) and the double numerical basis set (DNP), also suggested that the interactions between Me(II) phthalocyanines and nanotube sidewalls are very strong. The authors thank the National Autonomous University of Mexico (grant DGAPA-IN200516) and the National Council of Science and Technology of Mexico (CONACYT, grant 250655) for financial support. The authors are also grateful to Dr. Natalia Alzate-Carvajal (CCADET of UNAM), Eréndira Martínez (IF of UNAM) and Iván Puente-Lee (Faculty of Chemistry of UNAM) for technical assistance with FTIR, TGA measurements, and TEM imaging, respectively.

Keywords: carbon nanotubes, functionalization, gas-phase, metal(II) phthalocyanines

Procedia PDF Downloads 101

Authors: Pierre-Andre Mudry, Jean Decaix, Jeremy Schmid, Cesar Papilloud, Cecile Munch-Alligne

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In most of the Swiss Alpine regions, the availability of water resources is usually adequate even in times of drought, as evidenced by the 2003 and 2018 summers. Indeed, important natural stocks are for the moment available in the form of snow and ice, but the situation is likely to change in the future due to global and regional climate change. In addition, alpine mountain regions are areas where climate change will be felt very rapidly and with high intensity. For instance, the ice regime of these regions has already been affected in recent years with a modification of the monthly availability and extreme events of precipitations. The current research, focusing on the municipality of Val de Bagnes, located in the canton of Valais, Switzerland, is part of a project led by the Altis company and achieved in collaboration with WSL, BlueArk Entremont, and HES-SO Valais-Wallis. In this region, water occupies a key position notably for winter and summer tourism. Thus, multiple actors want to apprehend the future needs and availabilities of water, on both the 2050 and 2100 horizons, in order to plan the modifications to the water supply and distribution networks. For those changes to be salient and efficient, a good knowledge of the current water distribution networks is of most importance. In the current case, the water drinking network is well documented, but this is not the case for the irrigation one. Since the water consumption for irrigation is ten times higher than for drinking water, data acquisition on the irrigation network is a major point to determine future scenarios. This paper first presents the instrumentation and simulation of the irrigation network using custom-designed IoT devices, which are coupled with a digital clone simulated to reduce the number of measuring locations. The developed IoT ad-hoc devices are energy-autonomous and can measure flows and pressures using industrial sensors such as calorimetric water flow meters. Measurements are periodically transmitted using the LoRaWAN protocol over a dedicated infrastructure deployed in the municipality. The gathered values can then be visualized in real-time on a dashboard, which also provides historical data for analysis. In a second phase, a digital clone of the irrigation network was modeled using EPANET, a software for water distribution systems that performs extended-period simulations of flows and pressures in pressurized networks composed of reservoirs, pipes, junctions, and sinks. As a preliminary work, only a part of the irrigation network was modelled and validated by comparisons with the measurements. The simulations are carried out by imposing the consumption of water at several locations. The validation is performed by comparing the simulated pressures are different nodes with the measured ones. An accuracy of +/- 15% is observed on most of the nodes, which is acceptable for the operator of the network and demonstrates the validity of the approach. Future steps will focus on the deployment of the measurement devices on the whole network and the complete modelling of the network. Then, scenarios of future consumption will be investigated. Acknowledgment— The authors would like to thank the Swiss Federal Office for Environment (FOEN), the Swiss Federal Office for Agriculture (OFAG) for their financial supports, and ALTIS for the technical support, this project being part of the Swiss Pilot program 'Adaptation aux changements climatiques'.

Keywords: hydraulic digital clone, IoT water monitoring, LoRaWAN water measurements, EPANET, irrigation network

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Authors: Simone Dell'Agnello

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There are laser retroreflectors on the Moon and no laser retroreflectors on Mars. Here we describe the design, construction, qualification and imminent deployment of next-generation, optimized laser retroreflectors on the Moon and on Mars (where they will be the first ones). These instruments are positioned by time-of-flight measurements of short laser pulses, the so-called 'laser ranging' technique. Data analysis is carried out with PEP, the Planetary Ephemeris Program of CfA (Center for Astrophysics). Since 1969 Lunar Laser Ranging (LLR) to Apollo/Lunokhod laser retro-reflector (CCR) arrays supplied accurate tests of General Relativity (GR) and new gravitational physics: possible changes of the gravitational constant Gdot/G, weak and strong equivalence principle, gravitational self-energy (Parametrized Post Newtonian parameter beta), geodetic precession, inverse-square force-law; it can also constraint gravitomagnetism. Some of these measurements also allowed for testing extensions of GR, including spacetime torsion, non-minimally coupled gravity. LLR has also provides significant information on the composition of the deep interior of the Moon. In fact, LLR first provided evidence of the existence of a fluid component of the deep lunar interior. In 1969 CCR arrays contributed a negligible fraction of the LLR error budget. Since laser station range accuracy improved by more than a factor 100, now, because of lunar librations, current array dominate the error due to their multi-CCR geometry. We developed a next-generation, single, large CCR, MoonLIGHT (Moon Laser Instrumentation for General relativity high-accuracy test) unaffected by librations that supports an improvement of the space segment of the LLR accuracy up to a factor 100. INFN also developed INRRI (INstrument for landing-Roving laser Retro-reflector Investigations), a microreflector to be laser-ranged by orbiters. Their performance is characterized at the SCF_Lab (Satellite/lunar laser ranging Characterization Facilities Lab, INFN-LNF, Frascati, Italy) for their deployment on the lunar surface or the cislunar space. They will be used to accurately position landers, rovers, hoppers, orbiters of Google Lunar X Prize and space agency missions, thanks to LLR observations from station of the International Laser Ranging Service in the USA, in France and in Italy. INRRI was launched in 2016 with the ESA mission ExoMars (Exobiology on Mars) EDM (Entry, descent and landing Demonstration Module), deployed on the Schiaparelli lander and is proposed for the ExoMars 2020 Rover. Based on an agreement between NASA and ASI (Agenzia Spaziale Italiana), another microreflector, LaRRI (Laser Retro-Reflector for InSight), was delivered to JPL (Jet Propulsion Laboratory) and integrated on NASA’s InSight Mars Lander in August 2017 (launch scheduled in May 2018). Another microreflector, LaRA (Laser Retro-reflector Array) will be delivered to JPL for deployment on the NASA Mars 2020 Rover. The first lunar landing opportunities will be from early 2018 (with TeamIndus) to late 2018 with commercial missions, followed by opportunities with space agency missions, including the proposed deployment of MoonLIGHT and INRRI on NASA’s Resource Prospectors and its evolutions. In conclusion, we will extend significantly the CCR Lunar Geophysical Network and populate the Mars Geophysical Network. These networks will enable very significantly improved tests of GR.

Keywords: general relativity, laser retroreflectors, lunar laser ranging, Mars geodesy

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Authors: Dimitra Das, Anuradha Mitra, Kalyan Kumar Chattopadhyay

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Organic polymers, constructed from light elements like carbon, hydrogen, nitrogen, oxygen, sulphur, and boron atoms, are the emergent class of non-toxic, metal-free, environmental benign advanced materials. Covalent triazine-based polymers with a functional triazine group are significant class of organic materials due to their remarkable stability arising out of strong covalent bonds. They can conventionally form hydrogen bonds, favour π–π contacts, and they were recently revealed to be involved in interesting anion–π interactions. The present work mainly focuses upon the development of a single-crystalline, highly cross-linked triazine-based nitrogen-rich organic polymer with nanodendritic morphology and significant thermal stability. The polymer has been synthesized through hydrothermal treatment of melamine and ethylene glycol resulting in cross-polymerization via condensation-polymerization reaction. The crystal structure of the polymer has been evaluated by employing Rietveld whole profile fitting method. The polymer has been found to be composed of monoclinic melamine having space group P21/a. A detailed insight into the chemical structure of the as synthesized polymer has been elucidated by Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopic analysis. X-Ray Photoelectron Spectroscopic (XPS) analysis has also been carried out for further understanding of the different types of linkages required to create the backbone of the polymer. The unique rod-like morphology of the triazine based polymer has been revealed from the images obtained from Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Interestingly, this polymer has been found to selectively detect mercury (Hg²⁺) ions at an extremely low concentration through fluorescent quenching with detection limit as low as 0.03 ppb. The high toxicity of mercury ions (Hg²⁺) arise from its strong affinity towards the sulphur atoms of biological building blocks. Even a trace quantity of this metal is dangerous for human health. Furthermore, owing to its small ionic radius and high solvation energy, Hg²⁺ ions remain encapsulated by water molecules making its detection a challenging task. There are some existing reports on fluorescent-based heavy metal ion sensors using covalent organic frameworks (COFs) but reports on mercury sensing using triazine based polymers are rather undeveloped. Thus, the importance of ultra-trace detection of Hg²⁺ ions with high level of selectivity and sensitivity has contemporary significance. A plausible sensing phenomenon by the polymer has been proposed to understand the applicability of the material as a potential sensor. The impressive sensitivity of the polymer sample towards Hg²⁺ is the very first report in the field of highly crystalline triazine based polymers (without the introduction of any sulphur groups or functionalization) towards mercury ion detection through photoluminescence quenching technique. This crystalline metal-free organic polymer being cheap, non-toxic and scalable has current relevance and could be a promising candidate for Hg²⁺ ion sensing at commercial level.

Keywords: fluorescence quenching , mercury ion sensing, single-crystalline, triazine-based polymer

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Authors: Piotr Jablonski, Krzysztof Mars, Wiktor Niemiec, Agnieszka Kyziol, Marek Hebda, Halina Krawiec, Karol Kyziol

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NiTi alloys, possessing unique mechanical properties such as pseudoelasticity and shape memory effect (SME), are suitable for many applications, including implanthology and biomedical devices. Additionally, these alloys have similar values of elastic modulus to those of human bones, what is very important in orthopedics. Unfortunately, the environment of physiological fluids in vivo causes unfavorable release of Ni ions, which in turn may lead to metalosis as well as allergic reactions and toxic effects in the body. For these reasons, the surface properties of NiTi alloys should be improved to increase corrosion resistance, taking into account biological properties, i.e. excellent biocompatibility. The prospective in this respect are layers based on DLC (Diamond-Like Carbon) structures, which are an attractive solution for many applications in implanthology. These coatings (DLC), usually obtained by PVD (Physical Vapour Deposition) and PA CVD (Plasma Activated Chemical Vapour Deposition) methods, can be also modified by doping with other elements like silicon, nitrogen, oxygen, fluorine, titanium and silver. These methods, in combination with a suitably designed structure of the layers, allow the possibility co-decide about physicochemical and biological properties of modified surfaces. Mentioned techniques provide specific physicochemical properties of substrates surface in a single technological process. In this work, the following types of layers based on DLC structures (incl. Si-DLC or Si/N-DLC) were proposed as prospective and attractive approach in surface functionalization of shape memory alloy. Nitinol substrates were modified in plasma conditions, using RF CVD (Radio Frequency Chemical Vapour Deposition). The influence of plasma treatment on the useful properties of modified substrates after deposition DLC layers doped with silica and/or nitrogen atoms, as well as only pre-treated in O2 NH3 plasma atmosphere in a RF reactor was determined. The microstructure and topography of the modified surfaces were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Furthermore, the atomic structure of coatings was characterized by IR and Raman spectroscopy. The research also included the evaluation of surface wettability, surface energy as well as the characteristics of selected mechanical and biological properties of the layers. In addition, the corrosion properties of alloys after and before modification in the physiological saline were also investigated. In order to determine the corrosion resistance of NiTi in the Ringer solution, the potentiodynamic polarization curves (LSV – Linear Sweep Voltamperometry) were plotted. Furthermore, the evolution of corrosion potential versus immersion time of TiNi alloy in Ringer solution was performed. Based on all carried out research, the usefullness of proposed modifications of nitinol for medical applications was assessed. It was shown, inter alia, that the obtained Si-DLC layers on the surface of NiTi alloy exhibit a characteristic complex microstructure, increased surface development, which is an important aspect in improving the osteointegration of an implant. Furthermore, the modified alloy exhibits biocompatibility, the transfer of the metal (Ni, Ti) to Ringer’s solution is clearly limited.

Keywords: bioactive coatings, corrosion resistance, doped DLC structure, NiTi alloy, RF CVD

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Authors: Borokini Funmilayo Boede

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B. alba L., commonly called ‘Amunututu’ and Solanecio biafrae called ‘Worowo’ among the Yoruba tribe in the southwest part of Nigeria are reported to be of great ethnomedicinal importance but are among many underutilized green leafy vegetables in the country. Many studies have established the nutritional values of these vegetables, utilization are very poor and indepth information on their chemical profiles is scarce. The aqueous, methanolic and ethanolic extracts of these vegetables were subjected to phytochemical screening and phenolic profiles of the alcoholic extracts were characterized by using high-performance liquid chromatography coupled with diode array detector (HPLC-DAD). Total phenol and flavonoid contents were determined, antioxidant activities were evaluated using five in vitro assays to assess DPPH, nitric oxide and hydroxyl radical-scavenging abilities, as well as reducing power with ferric reducing antioxidant assay and phosphomolybdate method. The antibacterial activities of the extracts against Staphylococcus aureus, Pseudomonas aeruginosa, and Salmonella typhi were evaluated by using agar well diffusion method and the antifungal activity evaluated against food-associated filamentous fungi by using poisoned food technique with the aim of assessing their nutraceutical potentials to encourage their production and utilization. The results revealed the presence of saponnin, steroids, tannin, terpenoid and flavonoid as well as phenolic compounds: gallic acid, chlorogenic acid, caffeic acid, coumarin, rutin, quercitrin, quercetin and kaemferol. The vegetables showed varying concentration dependent reducing and radical scavenging abilities from weak to strong compared with gallic acid, rutin, trolox and ascorbic acid used as positive controls; the aqueous extracts which gave higher concentrations of total phenol displayed higher ability to reduce Fe (lll) to Fe (ll) and stronger inhibiting power against hydroxyl radical than the alcoholic extracts and in most cases exhibited more potency than the ascorbic acids used as positive controls, at the same concentrations, whereas, methanol and / or ethanol extracts were found to be more effective in scavenging 2, 2-diphenyl-1-picryl hydrazyl radical and showed higher ability to reduce Mo (VI) to Mo (V) in total antioxidant assay than the aqueous extracts. However, the inhibition abilities of all the extracts against nitric oxide were comparable with the ascorbic acid control at the same concentrations. There were strong positive correlations with total phenol (mg GAE/g) and total flavonoid (mg RE/g) contents in the range TFC (r=0.857- 0999 and r= 0.904-1.000) and TPC (r= 0.844- 0.992 and r= 0.900 -0.999) for Basella alba and Senecio biafrae respectively. Inhibition concentration at 50 % (IC50) for each extract to scavenge DPPH, OH and NO radicals ranged from 32.73 to 1.52 compared with control (0.846 - -6.42) mg/ml. At 0.05g/ml, the vegetables were found to exhibit mild antibacterial activities against Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi compared with streptomycin sulphate used as control but appreciable antifungi activities against (Trichoderma rubrum and Aspergillus fumigates) compared with bonlate antibiotic positive control. The vegetables possess appreciable antioxidant and antimicrobial properties for promoting good health, their cultivation and utilization should be encouraged especially in the face of increasing health and economic challenges and food insecurity in many parts of the world.

Keywords: antimicrobial, antioxidants, extracts, phytochemicals

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Authors: Dina Ibrahim Abouelamaiem, Ana Jorge Sobrido, Magdalena Titirici, Paul R. Shearing, Daniel J. L. Brett

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Global warming and scarcity of fossil fuels have had a radical impact on the world economy and ecosystem. The urgent need for alternative energy sources has hence elicited an extensive research for exploiting efficient and sustainable means of energy conversion and storage. Among various electrochemical systems, supercapacitors attracted significant attention in the last decade due to their high power supply, long cycle life compared to batteries and simple mechanism. Recently, the performance of these devices has drastically improved, as tuning of nanomaterials provided efficient charge and storage mechanisms. Carbon materials, in various forms, are believed to pioneer the next generation of supercapacitors due to their attractive properties that include high electronic conductivities, high surface areas and easy processing and functionalization. Cellulose has eco-friendly attributes that are feasible to replace man-made fibers. The carbonization of cellulose yields carbons, including activated carbon and graphite fibers. Activated carbons successively are the most exploited candidates for supercapacitor electrode materials that can be complemented with pseudocapacitive materials to achieve high energy and power densities. In this work, the optimum functionalization conditions of cellulose have been investigated for supercapacitor electrode materials. The precursor was treated with potassium hydroxide (KOH) at different KOH/cellulose ratios prior to the carbonization process in an inert nitrogen atmosphere at 850 °C. The chalky products were washed, dried and characterized with different techniques including transmission electron microscopy (TEM), x-ray tomography and nitrogen adsorption-desorption isotherms. The morphological characteristics and their effect on the electrochemical performances were investigated in two and three-electrode systems. The KOH/cellulose ratios of 0.5:1 and 1:1 exhibited the highest performances with their unique hierarchal porous network structure, high surface areas and low cell resistances. Both samples acquired the best results in three-electrode systems and coin cells with specific gravimetric capacitances as high as 187 F g-1 and 20 F g-1 at a current density of 1 A g-1 and retention rates of 72% and 70%, respectively. This is attributed to the morphology of the samples that constituted of a well-balanced micro-, meso- and macro-porosity network structure. This study reveals that the electrochemical performance doesn’t solely depend on high surface areas but also an optimum pore size distribution, specifically at low current densities. The micro- and meso-pore contribution to the final pore structure was found to dominate at low KOH loadings, reaching ‘equilibrium’ with macropores at the optimum KOH loading, after which macropores dictate the porous network. The wide range of pore sizes is detrimental for the mobility and penetration of electrolyte ions in the porous structures. These findings highlight the influence of various morphological factors on the double-layer capacitances and high performance rates. In addition, they open a platform for the investigation of the optimized conditions for double-layer capacitance that can be coupled with pseudocapacitive materials to yield higher energy densities and capacities.

Keywords: carbon, electrochemical performance, electrodes, KOH/cellulose optimized ratio, morphology, supercapacitor

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Authors: Elvin P. Chizenga, Heidi Abrahamse

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Cancer cell resistance to therapy is the main cause of treatment failures and the poor prognosis of cancer convalescence. The progression of cervical cancer to other parts of the genitourinary system and the reported recurrence rates are overwhelming. Current treatments, including surgery, chemo and radiation have been inefficient in eradicating the tumor cells. These treatments are also associated with poor prognosis and reduced quality of life, including fertility loss. This has inspired the need for the development of new treatment modalities to eradicate cervical cancer successfully. Photodynamic Therapy (PDT) is a modern treatment modality that induces cell death by photochemical interactions of light and a photosensitizer, which in the presence of molecular oxygen, yields a set of chemical reactions that generate Reactive Oxygen Species (ROS) and other free radical species causing cell damage. Enhancing PDT using modified drug delivery can increase the concentration of the photosensitizer in the tumor cells, and this has the potential to maximize its therapeutic efficacy. In cervical cancer, all infected cells constitutively express genes of the E6 and E7 HPV viral oncoproteins, resulting in high concentrations of E6 and E7 in the cytoplasm. This provides an opportunity for active targeting of cervical cancer cells using immune-mediated drug delivery to maximize therapeutic efficacy. The use of nanoparticles in PDT has also proven effective in enhancing therapeutic efficacy. Gold nanoparticles (AuNps) in particular, are explored for their use in biomedicine due to their biocompatibility, low toxicity, and enhancement of drug uptake by tumor cells. In this present study, a biomolecule comprising of AuNPs, anti-E6 monoclonal antibodies, and Aluminium Phthalocyanine photosensitizer was synthesized for use in targeted PDT of cervical cancer. The AuNp-Anti-E6-Sulfonated Aluminium Phthalocyanine mix (AlPcSmix) photosensitizing biomolecule was synthesized by coupling AuNps and anti-E6 monoclonal antibodies to the AlPcSmix via Polyethylene Glycol (PEG) chemical links. The final product was characterized using Transmission Electron Microscope (TEM), Zeta Potential, Uv-Vis Spectrophotometry, Fourier Transform Infrared Spectroscopy (FTIR), and X-ray diffraction (XRD), to confirm its chemical structure and functionality. To observe its therapeutic role in treating cervical cancer, cervical cancer cells, HeLa cells were seeded in 3.4 cm² diameter culture dishes at a concentration of 5x10⁵ cells/ml, in vitro. The cells were treated with varying concentrations of the photosensitizing biomolecule and irradiated using a 673.2 nm wavelength of laser light. Post irradiation cellular responses were performed to observe changes in morphology, viability, proliferation, cytotoxicity, and cell death pathways induced. Dose-Dependent response of the cells to treatment was demonstrated as significant morphologic changes, increased cytotoxicity, and decreased cell viability and proliferation This study presented a synthetic biomolecule for targeted PDT of cervical cancer. The study suggested that PDT using this AuNp- Anti-E6- AlPcSmix photosensitizing biomolecule is a very effective treatment method for the eradication of cervical cancer cells, in vitro. Further studies in vivo need to be conducted to support the use of this biomolecule in treating cervical cancer in clinical settings.

Keywords: anti-E6 monoclonal antibody, cervical cancer, gold nanoparticles, photodynamic therapy

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Authors: Fani Sakellariadou, Danae Antivachis

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Purpose of this paper is to evaluate the environmental status of a coastal Mediterranean lake, named Koumoundourou, located in the northeastern coast of Elefsis Bay, in the western region of Attiki in Greece, 15 km far from Athens. It is preserved from ancient times having an important archaeological interest. Koumoundourou lake is also considered as a valuable wetland accommodating an abundant flora and fauna, with a variety of bird species including a few world’s threatened ones. Furthermore, it is a heavily modified lake, affected by various anthropogenic pollutant sources which provide industrial, urban and agricultural contaminants. The adjacent oil refineries and the military depot are the major pollution providers furnishing with crude oil spills and leaks. Moreover, the lake accepts a quantity of groundwater leachates from the major landfill of Athens. The environmental status of the lake results from the intensive land uses combined with the permeable lithology of the surrounding area and the existence of karstic springs which discharge calcareous mountains. Sediment samples were collected along the shoreline of the lake using a Van Veen grab stainless steel sampler. They were studied for the determination of the total metal content and the metal fractionation in geochemical phases as well as the characterization of the dissolved organic matter (DOM). These constituents have a significant role in the ecological consideration of the lake. Metals may be responsible for harmful environmental impacts. The metal partitioning offers comprehensive information for the origin, mode of occurrence, biological and physicochemical availability, mobilization and transport of metals. Moreover, DOM has a multifunctional importance interacting with inorganic and organic contaminants leading to biogeochemical and ecological effects. The samples were digested using microwave heating with a suitable laboratory microwave unit. For the total metal content, the samples were treated with a mixture of strong acids. Then, a sequential extraction procedure was applied for the removal of exchangeable, carbonate hosted, reducible, organic/sulphides and residual fractions. Metal content was determined by an ICP-MS (Perkin Elmer, ICP MASS Spectrophotometer NexION 350D). Furthermore, the DOM was removed via a gentle extraction procedure and then it was characterized by fluorescence spectroscopy using a Perkin-Elmer LS 55 luminescence spectrophotometer equipped with the WinLab 4.00.02 software for data processing (Agilent, Cary Eclipse Fluorescence). Mono dimensional emission, excitation, synchronous-scan excitation and total luminescence spectra were recorded for the classification of chromophoric units present in the aqueous extracts. Total metal concentrations were determined and compared with those of the Elefsis gulf sediments. Element partitioning showed the anthropogenic sources and the contaminant bioavailability. All fluorescence spectra, as well as humification indices, were evaluated in detail to find out the nature and origin of DOM. All the results were compared and interpreted to evaluate the environmental quality of Koumoundourou lake and the need for environmental management and protection.

Keywords: anthropogenic contaminant, dissolved organic matter, lake, metal, pollution

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Authors: Suman Chaudhary, Rupinder K. Kanwar, Jagat R. Kanwar

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Azadirachta indica, also known as Neem belonging to the mahogany family is actively gaining interest in the era of modern day medicine due to its extensive applications in homeopathic medicine such as Ayurveda and Unani. More than 140 phytochemicals have been extracted from neem leaves, seed, bark and flowers for agro-medicinal applications. Among the various components, neem leaf protein (NLP) is currently the most investigated active ingredient, due to its immunomodulatory activities against tumor growth. However, these therapeutic ingredients of neem are susceptible to degradation and cannot withstand the drastic pH changes under physiological environment, and therefore, there is an urgent need of an alternative strategy such as a nano-delivery system to exploit its medicinal benefits. This study hypothesizes that guar gum (GG) derived biodegradable nano-carrier based encapsulation of NLP will improve its stability, specificity and sensitivity, thus facilitating targeted anti-cancer therapeutics. GG is a galactomannan derived from the endosperm of the guar beans seeds. Synthesis of guar nanocapsules (NCs) was performed using nanoprecipitation technique where the GG was encapsulated with NLP. Preliminary experiments conducted to characterize the NCs confirmed spherical morphology with a narrow size distribution of 30-40 nm. Differential scanning colorimetric analysis (DSC) validated the stability of these NCs even at a temperature range of 50-60°C which was well within the physiological and storage conditions. Thermogravimetric (TGA) analysis indicated high decomposition temperature of these NCs ranging upto 350°C. Additionally, Fourier Transform Infrared spectroscopy (FTIR) and the SDS-PAGE data acquired confirmed the successful encapsulation of NLP in the NCs. The anti-cancerous therapeutic property of this NC was tested on colon cancer cells (caco-2) as they are one of the most prevalent form of cancer. These NCs (both NLP loaded and void) were also tested on human intestinal epithelial cells (FHs 74) cells to evaluate their effect on normal cells. Cytotoxicity evaluation of the NCs in the cell lines confirmed that the IC50 for NLP in FHs 74 cells was ~2 fold higher than in caco-2 cells, indicating that this nanoformulation system possessed biocompatible anti-cancerous properties Immunoconfocal microscopy analysis confirmed the time dependent internalization of the NCs within 6h. Recent findings performed using Annexin V and PI staining indicated a significant increase (p ≤ 0.001) in the early and late apoptotic cell population when treated with the NCs signifying the role of NLP in inducing apoptosis in caco-2 cells. This was further validated using Western blot, Polymerase chain reaction (PCR) and Fluorescence activated cell sorter (FACS) aided protein expressional analysis which presented a downregulation of survivin, an anti-apoptotic cell marker and upregulation of Bax/Bcl-2 ratio (pro-apoptotic indicator). Further, both the NLP NC and unencapsulated NLP treatment destabilized the mitochondrial membrane potential subsequently facilitating the release of the pro-apoptotic caspase cascade initiator, cytochrome-c. Future studies will be focused towards granting specificity to these NCs towards cancer cells, along with a comprehensive analysis of the anti-cancer potential of this naturally occurring compound in different cancer and in vivo animal models, will validate the clinical application of this unprecedented protein therapeutic.

Keywords: anti-tumor, guar gum, nanocapsules, neem leaf protein

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Authors: Danyi Wang, Andrew Schriefer, Dennis O'Rourke, Brajendra Kumar, Yang Liu, Fei Zhong, Juergen Scheuenpflug, Zheng Feng

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Purpose: It has been recognized that the microbiome plays critical roles in disease pathogenesis, including cancer, autoimmune disease, and multiple sclerosis. To develop a clinical-grade assay for exploring microbiome-derived clinical biomarkers across disease areas, a two-phase approach is implemented. 1) Identification of the optimal sample preparation reagents using pre-mixed bacteria and healthy donor stool samples coupled with proprietary Sigma-Aldrich® bioinformatics solution. 2) Exploratory analysis of patient samples for enabling precision medicine. Study Procedure: In phase 1 study, we first compared the 16S sequencing results of two ATCC® microbiome standards (MSA 2002 and MSA 2003) across five different extraction kits (Kit A, B, C, D & E). Both microbiome standards samples were extracted in triplicate across all extraction kits. Following isolation, DNA quantity was determined by Qubit assay. DNA quality was assessed to determine purity and to confirm extracted DNA is of high molecular weight. Bacterial 16S ribosomal ribonucleic acid (rRNA) amplicons were generated via amplification of the V3/V4 hypervariable region of the 16S rRNA. Sequencing was performed using a 2x300 bp paired-end configuration on the Illumina MiSeq. Fastq files were analyzed using the Sigma-Aldrich® Microbiome Platform. The Microbiome Platform is a cloud-based service that offers best-in-class 16S-seq and WGS analysis pipelines and databases. The Platform and its methods have been extensively benchmarked using microbiome standards generated internally by MilliporeSigma and other external providers. Data Summary: The DNA yield using the extraction kit D and E is below the limit of detection (100 pg/µl) of Qubit assay as both extraction kits are intended for samples with low bacterial counts. The pre-mixed bacterial pellets at high concentrations with an input of 2 x106 cells for MSA-2002 and 1 x106 cells from MSA-2003 were not compatible with the kits. Among the remaining 3 extraction kits, kit A produced the greatest yield whereas kit B provided the least yield (Kit-A/MSA-2002: 174.25 ± 34.98; Kit-A/MSA-2003: 179.89 ± 30.18; Kit-B/MSA-2002: 27.86 ± 9.35; Kit-B/MSA-2003: 23.14 ± 6.39; Kit-C/MSA-2002: 55.19 ± 10.18; Kit-C/MSA-2003: 35.80 ± 11.41 (Mean ± SD)). Also, kit A produced the greatest yield, whereas kit B provided the least yield. The PCoA 3D visualization of the Weighted Unifrac beta diversity shows that kits A and C cluster closely together while kit B appears as an outlier. The kit A sequencing samples cluster more closely together than both the other kits. The taxonomic profiles of kit B have lower recall when compared to the known mixture profiles indicating that kit B was inefficient at detecting some of the bacteria. Conclusion: Our data demonstrated that the DNA extraction method impacts DNA concentration, purity, and microbial communities detected by next-generation sequencing analysis. Further microbiome analysis performance comparison of using healthy stool samples is underway; also, colorectal cancer patients' samples will be acquired for further explore the clinical utilities. Collectively, our comprehensive qualification approach, including the evaluation of optimal DNA extraction conditions, the inclusion of positive controls, and the implementation of a robust qualified bioinformatics pipeline, assures accurate characterization of the microbiota in a complex matrix for deciphering the deep biology and enabling precision medicine.

Keywords: 16S rRNA sequencing, analytical validation, bioinformatics pipeline, metagenomics

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