Search results for: IR-UV double resonance spectroscopy

Authors: T. Ul Rehman, S. Agnello, F. M. Gelardi, M. M. Calvino, G. Lazzara, G. Buscarino, M. Cannas

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Metal-Organic Frameworks (MOFs) have emerged as promising candidates for detecting metal ions owing to their large surface area, customizable porosity, and diverse functionalities. In recent years, there has been a surge in research focused on MOFs with luminescent properties. These frameworks are constructed through coordinated bonding between metal ions and multi-dentate ligands, resulting in inherent fluorescent structures. Their luminescent behavior is influenced by factors like structural composition, surface morphology, pore volume, and interactions with target analytes, particularly metal ions. MOFs exhibit various sensing mechanisms, including photo-induced electron transfer (PET) and charge transfer processes such as ligand-to-metal (LMCT) and metal-to-ligand (MLCT) transitions. Among these, MIL-53(Al) stands out due to its flexibility, stability, and specific affinity towards certain metal ions, making it a promising platform for selective metal ion sensing. This study investigates the structural, thermal, and luminescent properties of MIL-53(Al) metal-organic framework (MOF) upon Fe3+ cation exchange. Two separate sets of samples were prepared to activate the MOF powder at different temperatures. The first set of samples, referred to as MIL-53(Al), activated (120°C), was prepared by activating the raw powder in a glass tube at 120°C for 12 hours and then sealing it. The second set of samples, referred to as MIL-53(Al), activated (300°C), was prepared by activating the MIL-53(Al) powder in a glass tube at 300°C for 70 hours. Additionally, 25 mg of MIL-53(Al) powder was dispersed in 5 mL of Fe3+ solution at various concentrations (0.1-100 mM) for the cation exchange experiment. The suspension was centrifuged for five minutes at 10,000 rpm to extract MIL-53(Al) powder. After three rounds of washing with ultrapure water, MIL-53(Al) powder was heated at 120°C for 12 hours. For PXRD and TGA analyses, a sample of the obtained MIL-53(Al) was used. We also activated the cation-exchanged samples for time-resolved photoluminescence (TRPL) measurements at two distinct temperatures (120 and 300°C) for comparative analysis. Powder X-ray diffraction patterns reveal amorphization in samples with higher Fe3+ concentrations, attributed to alterations in coordination environments and ion exchange dynamics. Thermal decomposition analysis shows reduced weight loss in Fe3+-exchanged MOFs, indicating enhanced stability due to stronger metal-ligand bonds and altered decomposition pathways. Raman spectroscopy demonstrates intensity decrease, shape disruption, and frequency shifts, indicative of structural perturbations induced by cation exchange. Photoluminescence spectra exhibit ligand-based emission (π-π* or n-π*) and ligand-to-metal charge transfer (LMCT), influenced by activation temperature and Fe3+ incorporation. Quenching of luminescence intensity and shorter lifetimes upon Fe3+ exchange result from structural distortions and Fe3+ binding to organic linkers. In a nutshell, this research underscores the complex interplay between composition, structure, and properties in MOFs, offering insights into their potential for diverse applications in catalysis, gas storage, and luminescent devices.

Keywords: Fe³⁺ cation exchange, luminescent metal-organic frameworks (LMOFs), MIL-53(Al), solid-state analysis

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Authors: Hilal T. Sasmazel, Seda Surucu

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Skin tissue engineering is a promising field for the treatment of skin defects using scaffolds. This approach involves the use of living cells and biomaterials to restore, maintain, or regenerate tissues and organs in the body by providing; (i) larger surface area for cell attachment, (ii) proper porosity for cell colonization and cell to cell interaction, and (iii) 3-dimensionality at macroscopic scale. Recent studies on this area mainly focus on fabrication of scaffolds that can closely mimic the natural extracellular matrix (ECM) for creation of tissue specific niche-like environment at the subcellular scale. Scaffolds designed as ECM-like architectures incorporating into the host with minimal scarring/pain and facilitate angiogenesis. This study is related to combining of synthetic PCL and natural chitosan polymers to form 3D PCL/Chitosan core-shell structures for skin tissue engineering applications. Amongst the polymers used in tissue engineering, natural polymer chitosan and synthetic polymer poly(ε-caprolactone) (PCL) are widely preferred in the literature. Chitosan has been among researchers for a very long time because of its superior biocompatibility and structural resemblance to the glycosaminoglycan of bone tissue. However, the low mechanical flexibility and limited biodegradability properties reveals the necessity of using this polymer in a composite structure. On the other hand, PCL is a versatile polymer due to its low melting point (60°C), ease of processability, degradability with non-enzymatic processes (hydrolysis) and good mechanical properties. Nevertheless, there are also several disadvantages of PCL such as its hydrophobic structure, limited bio-interaction and susceptibility to bacterial biodegradation. Therefore, it became crucial to use both of these polymers together as a hybrid material in order to overcome the disadvantages of both polymers and combine advantages of those. The scaffolds here were fabricated by using electrospinning technique and the characterizations of the samples were done by contact angle (CA) measurements, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-Ray Photoelectron spectroscopy (XPS). Additionally, gas permeability test, mechanical test, thickness measurement and PBS absorption and shrinkage tests were performed for all type of scaffolds (PCL, chitosan and PCL/chitosan core-shell). By using ImageJ launcher software program (USA) from SEM photographs the average inter-fiber diameter values were calculated as 0.717±0.198 µm for PCL, 0.660±0.070 µm for chitosan and 0.412±0.339 µm for PCL/chitosan core-shell structures. Additionally, the average inter-fiber pore size values exhibited decrease of 66.91% and 61.90% for the PCL and chitosan structures respectively, compare to PCL/chitosan core-shell structures. TEM images proved that homogenous and continuous bead free core-shell fibers were obtained. XPS analysis of the PCL/chitosan core-shell structures exhibited the characteristic peaks of PCL and chitosan polymers. Measured average gas permeability value of produced PCL/chitosan core-shell structure was determined 2315±3.4 g.m-2.day-1. In the future, cell-material interactions of those developed PCL/chitosan core-shell structures will be carried out with L929 ATCC CCL-1 mouse fibroblast cell line. Standard MTT assay and microscopic imaging methods will be used for the investigation of the cell attachment, proliferation and growth capacities of the developed materials.

Keywords: chitosan, coaxial electrospinning, core-shell, PCL, tissue scaffold

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Authors: T. N. Tran Thi, J. Morse, C. Detlefs, P. K. Cook, C. Yıldırım, A. C. Jakobsen, T. Zhou, J. Hartwig, V. Zurbig, D. Caliste, B. Fernandez, D. Eon, O. Loto, M. L. Hicks, A. Pakpour-Tabrizi, J. Baruchel

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The ability to grow boron-doped diamond epilayers of high crystalline quality is a prerequisite for the fabrication of diamond power electronic devices, in particular high voltage diodes and metal-oxide-semiconductor (MOS) transistors. Boron and intrinsic diamond layers are homoepitaxially overgrown by microwave assisted chemical vapour deposition (MWCVD) on single crystal high pressure, high temperature (HPHT) grown bulk diamond substrates. Various epilayer thicknesses were grown, with dopant concentrations ranging from 1021 atom/cm³ at nanometer thickness in the case of 'delta doping', up 1016 atom/cm³ and 50µm thickness or high electric field drift regions. The crystalline quality of these overgrown layers as regards defects, strain, distortion… is critical for the device performance through its relation to the final electrical properties (Hall mobility, breakdown voltage...). In addition to the optimization of the epilayer growth conditions in the MWCVD reactor, other important questions related to the crystalline quality of the overgrown layer(s) are: 1) what is the dependence on the bulk quality and surface preparation methods of the HPHT diamond substrate? 2) how do defects already present in the substrate crystal propagate into the overgrown layer; 3) what types of new defects are created during overgrowth, what are their growth mechanisms, and how can these defects be avoided? 4) how can we relate in a quantitative manner parameters related to the measured crystalline quality of the boron doped layer to the electronic properties of final processed devices? We describe synchrotron-based techniques developed to address these questions. These techniques allow the visualization of local defects and crystal distortion which complements the data obtained by other well-established analysis methods such as AFM, SIMS, Hall conductivity…. We have used Grazing Incidence X-ray Diffraction (GIXRD) at the ID01 beamline of the ESRF to study lattice parameters and damage (strain, tilt and mosaic spread) both in diamond substrate near surface layers and in thick (10–50 µm) overgrown boron doped diamond epi-layers. Micro- and nano-section topography have been carried out at both the BM05 and ID06-ESRF) beamlines using rocking curve imaging techniques to study defects which have propagated from the substrate into the overgrown layer(s) and their influence on final electronic device performance. These studies were performed using various commercially sourced HPHT grown diamond substrates, with the MWCVD overgrowth carried out at the Fraunhofer IAF-Germany. The synchrotron results are in good agreement with low-temperature (5°K) cathodoluminescence spectroscopy carried out on the grown samples using an Inspect F5O FESEM fitted with an IHR spectrometer.

Keywords: synchrotron X-ray diffaction, crystalline quality, defects, diamond overgrowth, rocking curve imaging

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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: 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: 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: 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: 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: Todd H. Buxton, Yong G. Lai

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Temperature management in regulated rivers can involve significant expenditures of water to meet the cold-water requirements of species in summer. For this purpose, flows released from Lewiston Dam on the Trinity River in Northern California are 12.7 cms with temperatures around 11oC in July through September to provide adult spring Chinook cold water to hold in deep pools and mature until spawning in fall. The releases are more than double the flow and 10oC colder temperatures than the natural conditions before the dam was built. The high, cold releases provide springers the habitat they require but may suppress the stream food base and limit future populations of salmon by reducing the juvenile fish size and survival to adults via the positive relationship between the two. Field and modeling research was undertaken to explore whether lowering summer releases from Lewiston Dam may promote thermal stratification in river pools so that both the cold-water needs of adult salmon and warmer water requirements of other organisms in the stream biome may be met. For this investigation, a three-dimensional (3D) computational fluid dynamics (CFD) model was developed and validated with field measurements in two deep pools on the Trinity River. Modeling and field observations were then used to identify the flows and temperatures that may form and maintain thermal stratification under different meteorologic conditions. Under low flows, a pool was found to be well mixed and thermally homogenous until temperatures began to stratify shortly after sunrise. Stratification then strengthened through the day until shading from trees and mountains cooled the inlet flow and decayed the thermal gradient, which collapsed shortly before sunset and returned the pool to a well-mixed state. This diurnal process of stratification formation and destruction was closely predicted by the 3D CFD model. Both the model and field observations indicate that thermal stratification maintained the coldest temperatures of the day at ≥2m depth in a pool and provided water that was around 8oC warmer in the upper 2m of the pool. Results further indicate that the stratified pool under low flows provided almost the same daily average temperatures as when flows were an order of magnitude higher and stratification was prevented, indicating significant water savings may be realized in regulated streams while also providing a diversity in water temperatures the ecosystem requires. With confidence in the 3D CFD model, the model is now being applied to a dozen pools in the Trinity River to understand how pool bathymetry influences thermal stratification under variable flows and diurnal temperature variations. This knowledge will be used to expand the results to 52 pools in a 64 km reach below Lewiston Dam that meet the depth criteria (≥2 m) for spring Chinook holding. From this, rating curves will be developed to relate discharge to the volume of pool habitat that provides springers the temperature (<15.6oC daily average), velocity (0.15 to 0.4 m/s) and depths that accommodate the escapement target for spring Chinook (6,000 adults) under maximum fish densities measured in other streams (3.1 m3/fish) during the holding time of year (May through August). Flow releases that meet these goals will be evaluated for water savings relative to the current flow regime and their influence on indicator species, including the Foothill Yellow-Legged Frog, and aspects of the stream biome that support salmon populations, including macroinvertebrate production and juvenile Chinook growth rates.

Keywords: 3D CFD modeling, flow regulation, thermal stratification, chinook salmon, foothill yellow-legged frogs, water managment

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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

Procedia PDF Downloads 100

Authors: Heather E. Ewart, Keith Jensen, Rebecca N. Cliffe

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Fragmentation and changes in the structural composition of tropical forests – as a result of intensifying anthropogenic disturbance – are increasing pressures on local biodiversity. Species with low dispersal abilities have some of the highest extinction risks in response to environmental change, as even small-scale environmental variation can substantially impact their space use and energetic balance. Understanding the implications of forest disturbance is therefore essential, ultimately allowing for more effective and targeted conservation initiatives. Here, the impact of different levels of forest disturbance on the space use, energetics, movement and behavior of 18 brown-throated sloths (Bradypus variegatus) were assessed in the South Caribbean of Costa Rica. A multi-scale framework was used to measure forest disturbance, including large-scale (landscape-level classifications) and fine-scale (within and surrounding individual home ranges) forest composition. Three landscape-level classifications were identified: primary forests (undisturbed), secondary forests (some disturbance, regenerating) and urban forests (high levels of disturbance and fragmentation). Finer-scale forest composition was determined using measurements of habitat structure and quality within and surrounding individual home ranges for each sloth (home range estimates were calculated using autocorrelated kernel density estimation [AKDE]). Measurements of forest quality included tree connectivity, density, diameter and height, species richness, and percentage of canopy cover. To determine space use, energetics, movement and behavior, six sloths in urban forests, seven sloths in secondary forests and five sloths in primary forests were tracked using a combination of Very High Frequency (VHF) radio transmitters and Global Positioning System (GPS) technology over an average period of 120 days. All sloths were also fitted with micro data-loggers (containing tri-axial accelerometers and pressure loggers) for an average of 30 days to allow for behavior-specific movement analyses (data analysis ongoing for data-loggers and primary forest sloths). Data-loggers included determination of activity budgets, circadian rhythms of activity and energy expenditure (using the vector of the dynamic body acceleration [VeDBA] as a proxy). Analyses to date indicate that home range size significantly increased with the level of forest disturbance. Female sloths inhabiting secondary forests averaged 0.67-hectare home ranges, while female sloths inhabiting urban forests averaged 1.93-hectare home ranges (estimates are represented by median values to account for the individual variation in home range size in sloths). Likewise, home range estimates for male sloths were 2.35 hectares in secondary forests and 4.83 in urban forests. Sloths in urban forests also used nearly double (median = 22.5) the number of trees as sloths in the secondary forest (median = 12). These preliminary data indicate that forest disturbance likely heightens the energetic requirements of sloths, a species already critically limited by low dispersal ability and rates of energy acquisition. Energetic and behavioral analyses from the data-loggers will be considered in the context of fine-scale forest composition measurements (i.e., habitat quality and structure) and are expected to reflect the observed home range and movement constraints. The implications of these results are far-reaching, presenting an opportunity to define a critical index of habitat connectivity for low dispersal species such as sloths.

Keywords: biodiversity conservation, forest disturbance, movement ecology, sloths

Procedia PDF Downloads 76

Authors: Marcos Perez, Christian Dumont, Olivier Nodin, Sebastien Nouveau

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Nickel superalloys are used to manufacture high-temperature rotary engine parts such as high-pressure disks in gas turbine engines. High strength at high operating temperatures is required due to the levels of stress and heat the disk must withstand. Therefore it is necessary parts made from materials that can maintain mechanical strength at high temperatures whilst remain comparatively low in cost. A manufacturing process referred to as the triple melt process has made the production of cast and wrought (C&W) nickel superalloys possible. This means that the balance of cost and performance at high temperature may be optimized. AD730TM is a newly developed Ni-based superalloy for turbine disk applications, with reported superior service properties around 700°C when compared to Inconel 718 and several other alloys. The cast ingot is converted into billet during either cogging process or open die forging. The semi-finished billet is then further processed into its final geometry by forging, heat treating, and machining. Conventional ingot-to-billet conversion is an expensive and complex operation, requiring a significant amount of steps to break up the coarse as-cast structure and interdendritic regions. Due to the size of conventional ingots, it is difficult to achieve a uniformly high level of strain for recrystallization, resulting in non-recrystallized regions that retain large unrecrystallized grains. Non-uniform grain distributions will also affect the ultrasonic inspectability response, which is used to find defects in the final component. The main aim is to analyze the recrystallization behavior and microstructural evolution of AD730 at subsolvus temperatures from a semi-finished product (billet) under conditions representative of both cogging and hot forging operations. Special attention to the presence of large unrecrystallized grains was paid. Double truncated cones (DTCs) were hot forged at subsolvus temperatures in hydraulic press, followed by air cooling. SEM and EBSD analysis were conducted in the as-received (billet) and the as-forged conditions. AD730 from billet alloy presents a complex microstructure characterized by a mixture of several constituents. Large unrecrystallized grains present a substructure characterized by large misorientation gradients with the formation of medium to high angle boundaries in their interior, especially close to the grain boundaries, denoting inhomogeneous strain distribution. A fine distribution of intragranular precipitates was found in their interior, playing a key role on strain distribution and subsequent recrystallization behaviour during hot forging. Continuous dynamic recrystallization (CDRX) mechanism was found to be operating in the large unrecrystallized grains, promoting the formation intragranular DRX grains and the gradual recrystallization of these grains. Evidences that hetero-epitaxial recrystallization mechanism is operating in AD730 billet material were found. Coherent γ-shells around primary γ’ precipitates were found. However, no significant contribution to the overall recrystallization during hot forging was found. By contrast, strain presents the strongest effect on the microstructural evolution of AD730, increasing the recrystallization fraction and refining the structure. Regions with low level of deformation (ε ≤ 0.6) were translated into large fractions of unrecrystallized structures (strain accumulation). The presence of undissolved secondary γ’ precipitates (pinning effect), prior to hot forging operations, could explain these results.

Keywords: AD730 alloy, continuous dynamic recrystallization, hot forging, γ’ precipitates

Procedia PDF Downloads 176

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

Procedia PDF Downloads 99

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

Procedia PDF Downloads 201

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

Procedia PDF Downloads 101

Authors: Kalaumari Mayoral-Peña, Ana I. Montejano-Montelongo, Josué Reyes-Muñoz, Gonzalo A. Ortiz-Mancilla, Mayrin Rodríguez-Cruz, Víctor Hernández-Villalobos, Jesús A. Guzmán-López, Santiago García-Jacobo, Iván Licona-Vázquez, Grisel Fierros-Romero, Rosario Flores-Vallejo

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The group B-lactamic antibiotics include some of the most frequently used small drug molecules against bacterial infections. Nevertheless, an alarming decrease in their efficacy has been reported due to the emergence of antibiotic-resistant bacteria. Infections caused by bacteria expressing extended Spectrum B-lactamases (ESBLs) are difficult to treat and account for higher morbidity and mortality rates, delayed recovery, and high economic burden. According to the Global Report on Antimicrobial Resistance Surveillance, it is estimated that mortality due to resistant bacteria will ascend to 10 million cases per year worldwide. These facts highlight the importance of developing low-cost and readily accessible detection methods of drug-resistant ESBLs bacteria to prevent their spread and promote accurate and fast diagnosis. Bacterial detection is commonly done using molecular diagnostic techniques, where PCR stands out for its high performance. However, this technique requires specialized equipment not available everywhere, is time-consuming, and has a high cost. Loop-Mediated Isothermal Amplification (LAMP) is an alternative technique that works at a constant temperature, significantly decreasing the equipment cost. It yields double-stranded DNA of several lengths with repetitions of the target DNA sequence as a product. Although positive and negative results from LAMP can be discriminated by colorimetry, fluorescence, and turbidity, there is still a large room for improvement in the point-of-care implementation. DNA origami is a technique that allows the formation of 3D nanometric structures by folding a large single-stranded DNA (scaffold) into a determined shape with the help of short DNA sequences (staples), which hybridize with the scaffold. This research aimed to generate DNA origami structures using LAMP products as scaffolds to improve the sensitivity to detect ESBLs in point-of-care diagnosis. For this study, the coding sequence of the CTM-X-15 ESBL of E. coli was used to generate the LAMP products. The set of LAMP primers were designed using PrimerExplorerV5. As a result, a target sequence of 200 nucleotides from CTM-X-15 ESBL was obtained. Afterward, eight different DNA origami structures were designed using the target sequence in the SDCadnano and analyzed with CanDo to evaluate the stability of the 3D structures. The designs were constructed minimizing the total number of staples to reduce costs and complexity for point-of-care applications. After analyzing the DNA origami designs, two structures were selected. The first one was a zig-zag flat structure, while the second one was a wall-like shape. Given the sequence repetitions in the scaffold sequence, both were able to be assembled with only 6 different staples each one, ranging between 18 to 80 nucleotides. Simulations of both structures were performed using scaffolds of different sizes yielding stable structures in all the cases. The generation of the LAMP products were tested by colorimetry and electrophoresis. The formation of the DNA structures was analyzed using electrophoresis and colorimetry. The modeling of novel detection methods through bioinformatics tools allows reliable control and prediction of results. To our knowledge, this is the first study that uses LAMP products and DNA-origami in combination to delect ESBL-producing bacterial strains, which represent a promising methodology for diagnosis in the point-of-care.

Keywords: beta-lactamases, antibiotic resistance, DNA origami, isothermal amplification, LAMP technique, molecular diagnosis

Procedia PDF Downloads 188

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

Procedia PDF Downloads 130

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

Procedia PDF Downloads 147

Authors: Sanaz Alizadeh, Yves Comeau, Arshath Abdul Rahim, Sunhasis Ghoshal

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The application of silver nanoparticles (AgNPs) in personal care products, various household and industrial products has resulted in an inevitable environmental exposure of such engineered nanoparticles (ENPs). Ag ENPs, released via household and industrial wastes, reach water resource recovery facilities (WRRFs), yet the fate and transport of ENPs in WRRFs and their potential risk in the biological wastewater processes are poorly understood. Accordingly, our main objective was to elucidate the impact of long-term continuous exposure to AgNPs on biological activity of aerobic wastewater biofilm. The fate, transport and toxicity of 10 μg.L-1and 100 μg.L-1 PVP-stabilized AgNPs (50 nm) were evaluated in an attached growth biological treatment process, using lab-scale moving bed bioreactors (MBBRs). Two MBBR systems for organic matter removal were fed with a synthetic influent and operated at a hydraulic retention time (HRT) of 180 min and 60% volumetric filling ratio of Anox-K5 carriers with specific surface area of 800 m2/m3. Both reactors were operated for 85 days after reaching steady state conditions to develop a mature biofilm. The impact of AgNPs on the biological performance of the MBBRs was characterized over a period of 64 days in terms of the filtered biodegradable COD (SCOD) removal efficiency, the biofilm viability and key enzymatic activities (α-glucosidase and protease). The AgNPs were quantitatively characterized using single-particle inductively coupled plasma mass spectroscopy (spICP-MS), determining simultaneously the particle size distribution, particle concentration and dissolved silver content in influent, bioreactor and effluent samples. The generation of reactive oxygen species and the oxidative stress were assessed as the proposed toxicity mechanism of AgNPs. Results indicated that a low concentration of AgNPs (10 μg.L-1) did not significantly affect the SCOD removal efficiency whereas a significant reduction in treatment efficiency (37%) was observed at 100 μg.L-1AgNPs. Neither the viability nor the enzymatic activities of biofilm were affected at 10 μg.L-1AgNPs but a higher concentration of AgNPs induced cell membrane integrity damage resulting in 31% loss of viability and reduced α-glucosidase and protease enzymatic activities by 31% and 29%, respectively, over the 64-day exposure period. The elevated intercellular ROS in biofilm at a higher AgNPs concentration over time was consistent with a reduced biological biofilm performance, confirming the occurrence of a nanoparticle-induced oxidative stress in the heterotrophic biofilm. The spICP-MS analysis demonstrated a decrease in the nanoparticles concentration over the first 25 days, indicating a significant partitioning of AgNPs into the biofilm matrix in both reactors. The concentration of nanoparticles increased in effluent of both reactors after 25 days, however, indicating a decreased retention capacity of AgNPs in biofilm. The observed significant detachment of biofilm also contributed to a higher release of nanoparticles due to cell-wall destabilizing properties of AgNPs as an antimicrobial agent. The removal efficiency of PVP-AgNPs and the biofilm biological responses were a function of nanoparticle concentration and exposure time. This study contributes to a better understanding of the fate and behavior of AgNPs in biological wastewater processes, providing key information that can be used to predict the environmental risks of ENPs in aquatic ecosystems.

Keywords: biofilm, silver nanoparticle, single particle ICP-MS, toxicity, wastewater

Procedia PDF Downloads 247

Authors: Guilherme Giacomini, Ana Luiza Menegatti Pavan, Allan Felipe Fattori Alves, Marcela de Oliveira, Fernando Antonio Bacchim Neto, José Ricardo de Arruda Miranda, Seizo Yamashita, Diana Rodrigues de Pina

Abstract:

The maxillary sinus (MS), part of the paranasal sinus complex, is one of the most enigmatic structures in modern humans. The literature has suggested that MSs function as olfaction accessories, to heat or humidify inspired air, for thermoregulation, to impart resonance to the voice and others. Thus, the real function of the MS is still uncertain. Furthermore, the MS anatomy is complex and varies from person to person. Many diseases may affect the development process of sinuses. The incidence of rhinosinusitis and other pathoses in the MS is comparatively high, so, volume analysis has clinical value. Providing volume values for MS could be helpful in evaluating the presence of any abnormality and could be used for treatment planning and evaluation of the outcome. The computed tomography (CT) has allowed a more exact assessment of this structure, which enables a quantitative analysis. However, this is not always possible in the clinical routine, and if possible, it involves much effort and/or time. Therefore, it is necessary to have a convenient, robust, and practical tool correlated with the MS volume, allowing clinical applicability. Nowadays, the available methods for MS segmentation are manual or semi-automatic. Additionally, manual methods present inter and intraindividual variability. Thus, the aim of this study was to develop an automatic tool to quantity the MS volume in CT scans of paranasal sinuses. This study was developed with ethical approval from the authors’ institutions and national review panels. The research involved 30 retrospective exams of University Hospital, Botucatu Medical School, São Paulo State University, Brazil. The tool for automatic MS quantification, developed in Matlab®, uses a hybrid method, combining different image processing techniques. For MS detection, the algorithm uses a Support Vector Machine (SVM), by features such as pixel value, spatial distribution, shape and others. The detected pixels are used as seed point for a region growing (RG) segmentation. Then, morphological operators are applied to reduce false-positive pixels, improving the segmentation accuracy. These steps are applied in all slices of CT exam, obtaining the MS volume. To evaluate the accuracy of the developed tool, the automatic method was compared with manual segmentation realized by an experienced radiologist. For comparison, we used Bland-Altman statistics, linear regression, and Jaccard similarity coefficient. From the statistical analyses for the comparison between both methods, the linear regression showed a strong association and low dispersion between variables. The Bland–Altman analyses showed no significant differences between the analyzed methods. The Jaccard similarity coefficient was > 0.90 in all exams. In conclusion, the developed tool to quantify MS volume proved to be robust, fast, and efficient, when compared with manual segmentation. Furthermore, it avoids the intra and inter-observer variations caused by manual and semi-automatic methods. As future work, the tool will be applied in clinical practice. Thus, it may be useful in the diagnosis and treatment determination of MS diseases. Providing volume values for MS could be helpful in evaluating the presence of any abnormality and could be used for treatment planning and evaluation of the outcome. The computed tomography (CT) has allowed a more exact assessment of this structure which enables a quantitative analysis. However, this is not always possible in the clinical routine, and if possible, it involves much effort and/or time. Therefore, it is necessary to have a convenient, robust and practical tool correlated with the MS volume, allowing clinical applicability. Nowadays, the available methods for MS segmentation are manual or semi-automatic. Additionally, manual methods present inter and intraindividual variability. Thus, the aim of this study was to develop an automatic tool to quantity the MS volume in CT scans of paranasal sinuses. This study was developed with ethical approval from the authors’ institutions and national review panels. The research involved 30 retrospective exams of University Hospital, Botucatu Medical School, São Paulo State University, Brazil. The tool for automatic MS quantification, developed in Matlab®, uses a hybrid method, combining different image processing techniques. For MS detection, the algorithm uses a Support Vector Machine (SVM), by features such as pixel value, spatial distribution, shape and others. The detected pixels are used as seed point for a region growing (RG) segmentation. Then, morphological operators are applied to reduce false-positive pixels, improving the segmentation accuracy. These steps are applied in all slices of CT exam, obtaining the MS volume. To evaluate the accuracy of the developed tool, the automatic method was compared with manual segmentation realized by an experienced radiologist. For comparison, we used Bland-Altman statistics, linear regression and Jaccard similarity coefficient. From the statistical analyses for the comparison between both methods, the linear regression showed a strong association and low dispersion between variables. The Bland–Altman analyses showed no significant differences between the analyzed methods. The Jaccard similarity coefficient was > 0.90 in all exams. In conclusion, the developed tool to automatically quantify MS volume proved to be robust, fast and efficient, when compared with manual segmentation. Furthermore, it avoids the intra and inter-observer variations caused by manual and semi-automatic methods. As future work, the tool will be applied in clinical practice. Thus, it may be useful in the diagnosis and treatment determination of MS diseases.

Keywords: maxillary sinus, support vector machine, region growing, volume quantification

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Authors: Julie Anne Braun, Leonardo D. da Fonseca, Gerson C. Parreira, Ricardo J. E. Andrade

Abstract:

Polyurethanes (PU) are multifunctional polymers used across various industries. In construction, thermosetting polyurethanes are applied as coatings for flooring, paints, and waterproofing. They are widely specified in Brazil for waterproofing concrete structures like roof slabs and parking decks. Applied to concrete, they form a fully adhered membrane, providing a protective barrier with low water absorption, high chemical resistance, impermeability to liquids, and low vapor permeability. Their mechanical properties, including tensile strength (1 to 35 MPa) and Shore A hardness (83 to 88), depend on resin molecular weight and functionality, often using Methylene diphenyl diisocyanate. PU production, reliant on fossil-derived isocyanates and polyols, contributes significantly to carbon emissions. Sustainable alternatives, such as biopolyurethanes from renewable sources, are needed. Castor oil is a viable option for synthesizing sustainable polyurethanes. As a bio-based feedstock, castor oil is extensively cultivated in Brazil, making it a feasible option for the national market and ranking third internationally. This study aims to develop and characterize castor oil-based biopolyurethane for high-performance waterproofing and coating applications. A comparative analysis between castor oil-based PU and polyether polyol-based PU was conducted. Mechanical tests (tensile strength, Shore A hardness, abrasion resistance) and surface properties (contact angle, water absorption) were evaluated. Thermal, chemical, and morphological properties were assessed using thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The results demonstrated that both polyurethanes exhibited high mechanical strength. Specifically, the tensile strength for castor oil-based PU was 19.18 MPa, compared to 12.94 MPa for polyether polyol-based PU. Similarly, the elongation values were 146.90% for castor oil-based PU and 135.50% for polyether polyol-based PU. Both materials exhibited satisfactory performance in terms of abrasion resistance, with mass loss of 0.067% for castor oil PU and 0.043% for polyether polyol PU and Shore A hardness values of 89 and 86, respectively, indicating high surface hardness. The results of the water absorption and contact angle tests confirmed the hydrophilic nature of polyether polyol PU, with a contact angle of 58.73° and water absorption of 2.53%. Conversely, the castor oil-based PU exhibited hydrophobic properties, with a contact angle of 81.05° and water absorption of 0.45%. The results of the FTIR analysis indicated the absence of a peak around 2275 cm-1, which suggests that all of the NCO groups were consumed in the stoichiometric reaction. This conclusion is supported by the high mechanical test results. The TGA results indicated that polyether polyol PU demonstrated superior thermal stability, exhibiting a mass loss of 13% at the initial transition (around 310°C), in comparison to castor oil-based PU, which experienced a higher initial mass loss of 25% at 335°C. In summary, castor oil-based PU demonstrated mechanical properties comparable to polyether polyol PU, making it suitable for applications such as trafficable coatings. However, its higher hydrophobicity makes it more promising for watertightness. Increasing environmental concerns necessitate reducing reliance on non-renewable resources and mitigating the environmental impacts of polyurethane production. Castor oil is a viable option for sustainable polyurethanes, aligning with emission reduction goals and responsible use of natural resources.

Keywords: polyurethane, castor oil, sustainable, waterproofing, construction industry

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Authors: Mara Getachew Zenebe, Luuk Fleskens, Abdu Obieda Ahmed

Abstract:

This paper seeks to advance our scientific understanding of optimizing flood utilization in regions impacted by climate change, with a focus on enhancing agricultural productivity through effective irrigation management. The study was conducted as part of a three-year (2021 to 2023) USAID-supported initiative aimed at promoting Economic Growth and Peace in the Gash Agricultural Scheme (GAS), situated in Sudan's water-stressed Eastern region. GAS is the country's largest flood-irrigated scheme, covering 100,800 hectares of cultivable land, with a potential to provide the food security needs of over a quarter of a million agro-pastoral community members. GAS relies on the Gash River, which sources its water from high-intensity rainfall events in the highlands of Ethiopia and Eritrea. However, climate change and variations in these highlands have led to increased variability in the Gash River's flow. The study conducted water balance analyses based on a ten-year dataset of the annual Gash River flow, irrigated area; as well as the evapotranspiration demand of the major sorghum crop. Data collection methods included field measurements, surveys, remote sensing, and CropWat modelling. The water balance assessment revealed that the existing three-year rotation-based irrigation system management, capping cultivated land at 33,000 hectares annually, is excessively risk-averse. While this system reduced conflicts among the agro-pastoral communities by consistently delivering on the land promised to be annually cultivated, it also increased GAS's vulnerability to flood damage due to several reasons. The irrigation efficiency over the past decade was approximately 30%, leaving significant unharnessed floodwater that caused damage to infrastructure and agricultural land. The three-year rotation resulted in inadequate infrastructural maintenance, given the destructive nature of floods. Additionally, it led to infrequent land tillage, allowing the encroachment of mesquite trees hindering major sorghum crop growth. Remote sensing data confirmed that mesquite trees have overtaken 70,000 hectares in the past two decades, rendering them unavailable for agriculture. The water balance analyses suggest shifting to a two-year rotation, covering approximately 50,000 hectares annually while maintaining risk aversion. This shift could boost GAS's annual sorghum production by two-thirds, exceeding 850,000 tons. The scheme's efficiency can be further enhanced through low-cost on-farm interventions. Currently, large irrigation plots that range from 420 to 756 hectares are irrigated with limited water distribution guidance, leading to uneven irrigation. As demonstrated through field trials, implementing internal longitudinal bunds and horizontal deflector bunds can increase adequately irrigated parts of the irrigation plots from 50% to 80% and thus nearly double the sorghum yield to 2 tons per hectare while reducing the irrigation duration from 30 days to a maximum of 17 days. Flow measurements in 2021 and 2022 confirmed that these changes sufficiently meet the sorghum crop's water requirements, even with a conservative 60% field application efficiency assumption. These insights and lessons from the GAS on enhancing agricultural resilience and sustainability in the face of climate change are relevant to flood-based livelihood systems globally.

Keywords: climate change, irrigation management and productivity, variable flood flows, water balance analysis

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Authors: Kashima Arora, Monika Tomar, Vinay Gupta

Abstract:

Biosensors have found potential applications ranging from environmental testing and biowarfare agent detection to clinical testing, health care, and cell analysis. This is driven in part by the desire to decrease the cost of health care and to obtain precise information more quickly about the health status of patient by the development of various biosensors, which has become increasingly prevalent in clinical testing and point of care testing for a wide range of biological elements. Uric acid is an important byproduct in human body and a number of pathological disorders are related to its high concentration in human body. In past few years, rapid growth in the development of new materials and improvements in sensing techniques have led to the evolution of advanced biosensors. In this context, metal oxide thin film based matrices due to their bio compatible nature, strong adsorption ability, high isoelectric point (IEP) and abundance in nature have become the materials of choice for recent technological advances in biotechnology. In the past few years, wide band-gap metal oxide semiconductors including ZnO, SnO₂ and CeO₂ have gained much attention as a matrix for immobilization of various biomolecules. Tin oxide (SnO₂), wide band gap semiconductor (Eg =3.87 eV), despite having multifunctional properties for broad range of applications including transparent electronics, gas sensors, acoustic devices, UV photodetectors, etc., it has not been explored much for biosensing purpose. To realize a high performance miniaturized biomolecular electronic device, rf sputtering technique is considered to be the most promising for the reproducible growth of good quality thin films, controlled surface morphology and desired film crystallization with improved electron transfer property. Recently, iron oxide and its composites have been widely used as matrix for biosensing application which exploits the electron communication feature of Fe, for the detection of various analytes using urea, hemoglobin, glucose, phenol, L-lactate, H₂O₂, etc. However, to the authors’ knowledge, no work is being reported on modifying the electronic properties of SnO₂ by implanting with suitable metal (Fe) to induce the redox couple in it and utilizing it for reagentless detection of uric acid. In present study, Fe implanted SnO₂ based matrix has been utilized for reagentless uric acid biosensor. Implantation of Fe into SnO₂ matrix is confirmed by energy-dispersive X-Ray spectroscopy (EDX) analysis. Electrochemical techniques have been used to study the response characteristics of Fe modified SnO₂ matrix before and after uricase immobilization. The developed uric acid biosensor exhibits a high sensitivity to about 0.21 mA/mM and a linear variation in current response over concentration range from 0.05 to 1.0 mM of uric acid besides high shelf life (~20 weeks). The Michaelis-Menten kinetic parameter (Km) is found to be relatively very low (0.23 mM), which indicates high affinity of the fabricated bioelectrode towards uric acid (analyte). Also, the presence of other interferents present in human serum has negligible effect on the performance of biosensor. Hence, obtained results highlight the importance of implanted Fe:SnO₂ thin film as an attractive matrix for realization of reagentless biosensors towards uric acid.

Keywords: Fe implanted tin oxide, reagentless uric acid biosensor, rf sputtering, thin film

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Authors: Junkal Gutierrez, Hernane S. Barud, Sidney J. L. Ribeiro, Agnieszka Tercjak

Abstract:

Nowadays the interest on green nanocomposites and on the development of more environmental friendly products has been increased. Bacterial cellulose has been recently investigated as an attractive environmentally friendly material for the preparation of low-cost nanocomposites. The formation of cellulose by laboratory bacterial cultures is an interesting and attractive biomimetic access to obtain pure cellulose with excellent properties. Additionally, properties as molar mass, molar mass distribution, and the supramolecular structure could be control using different bacterial strain, culture mediums and conditions, including the incorporation of different additives. This kind of cellulose is a natural nanomaterial, and therefore, it has a high surface-to-volume ratio which is highly advantageous in composites production. Such property combined with good biocompatibility, high tensile strength, and high crystallinity makes bacterial cellulose a potential material for applications in different fields. The aim of this investigation work was the fabrication of novel hybrid inorganic-organic composites based on bacterial cellulose, cultivated in our laboratory, as a template. This kind of biohybrid nanocomposites gathers together excellent properties of bacterial cellulose with the ones displayed by typical inorganic nanoparticles like optical, magnetic and electrical properties, luminescence, ionic conductivity and selectivity, as well as chemical or biochemical activity. In addition, the functionalization of cellulose with inorganic materials opens new pathways for the fabrication of novel multifunctional hybrid materials with promising properties for a wide range of applications namely electronic paper, flexible displays, solar cells, sensors, among others. In this work, different pathways for fabrication of multifunctional biohybrid nanopapers with tunable properties based on BC modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) block copolymer, sol-gel synthesized nanoparticles (titanium, vanadium and a mixture of both oxides) and functionalized iron oxide nanoparticles will be presented. In situ (biosynthesized) and ex situ (at post-production level) approaches were successfully used to modify BC membranes. Bacterial cellulose based biocomposites modified with different EPE block copolymer contents were developed by in situ technique. Thus, BC growth conditions were manipulated to fabricate EPE/BC nanocomposite during the biosynthesis. Additionally, hybrid inorganic/organic nanocomposites based on BC membranes and inorganic nanoparticles were designed via ex-situ method, by immersion of never-dried BC membranes into different nanoparticle solutions. On the one hand, sol-gel synthesized nanoparticles (titanium, vanadium and a mixture of both oxides) and on the other hand superparamagnetic iron oxide nanoparticles (SPION), Fe2O3-PEO solution. The morphology of designed novel bionanocomposites hybrid materials was investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). In order to characterized obtained materials from the point of view of future applications different techniques were employed. On the one hand, optical properties were analyzed by UV-vis spectroscopy and spectrofluorimetry and on the other hand electrical properties were studied at nano and macroscale using electric force microscopy (EFM), tunneling atomic force microscopy (TUNA) and Keithley semiconductor analyzer, respectively. Magnetic properties were measured by means of magnetic force microscopy (MFM). Additionally, mechanical properties were also analyzed.

Keywords: bacterial cellulose, block copolymer, advanced characterization techniques, nanoparticles

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Authors: Adewale Tolulope Irewale, Elias Emeka Elemike, Christian O. Dimkpa, Emeka Emmanuel Oguzie

Abstract:

As the global population steadily approaches the 10billion mark, the world is currently faced with two major challenges among others – accessing sustainable and clean energy, and food security. Accessing cleaner and sustainable energy sources to drive global economy and technological advancement, and feeding the teeming human population require sustainable, innovative, and smart solutions. To solve the food production problem, producers have relied on fertilizers as a way of improving crop productivity. Commercial inorganic fertilizers, which is employed to boost agricultural food production, however, pose significant ecological sustainability and economic problems including soil and water pollution, reduced input efficiency, development of highly resistant weeds, micronutrient deficiency, soil degradation, and increased soil toxicity. These ecological and sustainability concerns have raised uncertainties about the continued effectiveness of conventional fertilizers. With the application of nanotechnology, plant biomass upcycling offers several advantages in greener energy production and sustainable agriculture through reduction of environmental pollution, increasing soil microbial activity, recycling carbon thereby reducing GHG emission, and so forth. This innovative technology has the potential for a circular economy and creating a sustainable agricultural practice. Nanomaterials have the potential to greatly enhance the quality and nutrient composition of organic biomass which in turn, allows for the conversion of biomass into nanofertilizers that are potentially more efficient. Water hyacinth plant harvested from an inland water at Warri, Delta State Nigeria were air-dried and milled into powder form. The dry biomass were used to prepare biochar at a pre-determined temperature in an oxygen deficient atmosphere. Physicochemical analysis of the resulting biochar was carried out to determine its porosity and general morphology using the Scanning Transmission Electron Microscopy (STEM). The functional groups (-COOH, -OH, -NH2, -CN, -C=O) were assessed using the Fourier Transform InfraRed Spectroscopy (FTIR) while the heavy metals (Cr, Cu, Fe, Pb, Mg, Mn) were analyzed using Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES). Impregnation of the biochar with nanonutrients were achieved under varied conditions of pH, temperature, nanonutrient concentrations and resident time to achieve optimum adsorption. Adsorption and desorption studies were carried out on the resulting nanofertilizer to determine kinetics for the potential nutrients’ bio-availability to plants when used as green fertilizers. Water hyacinth (Eichhornia crassipes) which is an aggressively invasive aquatic plant known for its rapid growth and profusion is being examined in this research to harness its biomass as a sustainable feedstock to formulate functionalized nano-biochar fertilizers, offering various benefits including water hyacinth biomass upcycling, improved nutrient delivery to crops and aquatic ecosystem remediation. Altogether, this work aims to create output values in the three dimensions of environmental, economic, and social benefits.

Keywords: biochar-based nanofertilizers, eichhornia crassipes, greener agriculture, sustainable ecosystem, water hyacinth

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Authors: Ling Ai, Ziyu Zhao, Zeyu Zhou, Xiaochen Yang, Heng Zhai, Stuart Holmes

Abstract:

Optimizing the catalyst layer structure is crucial for enhancing the performance of proton exchange membrane fuel cells (PEMFCs) with low Platinum (Pt) loading. Current works focused on the utilization, durability, and site activity of Pt particles on support, and performance enhancement has been achieved by loading Pt onto porous support with different morphology, such as graphene, carbon fiber, and carbon black. Some schemes have also incorporated cost considerations to achieve lower Pt loading. However, the design of the catalyst layer (CL) structure in the membrane electrode assembly (MEA) must consider the interactions between the layers. Addressing the crucial aspects of water management, low contact resistance, and the establishment of effective three-phase boundary for MEA, multi-walled carbon nanotubes (MWCNTs) are promising CL support due to their intrinsically high hydrophobicity, high axial electrical conductivity, and potential for ordered alignment. However, the drawbacks of MWCNTs, such as strong agglomeration, wall surface chemical inertness, and unopened ends, are unfavorable for Pt nanoparticle loading, which is detrimental to MEA processing and leads to inhomogeneous CL surfaces. This further deteriorates the utilization of Pt and increases the contact resistance. Robust chemical oxidation or nitrogen doping can introduce polar functional groups onto the surface of MWCNTs, facilitating the creation of open tube ends and inducing defects in tube walls. This improves dispersibility and load capacity but reduces length and conductivity. Consequently, a trade-off exists between maintaining the intrinsic properties and the degree of functionalization of MWCNTs. In this work, MWCNTs were modified based on the operational requirements of the MEA from the viewpoint of interlayer interactions, including the search for the optimal degree of oxidation, N-doping, and micro-arrangement. MWCNT were functionalized by oxidizing, N-doping, as well as micro-alignment to achieve lower contact resistance between CL and proton exchange membrane (PEM), better hydrophobicity, and enhanced performance. Furthermore, this work expects to construct a more continuously distributed three-phase boundary by aligning MWCNT to form a locally ordered structure, which is essential for the efficient utilization of Pt active sites. Different from other chemical oxidation schemes that used HNO3:H2SO4 (1:3) mixed acid to strongly oxidize MWCNT, this scheme adopted pure HNO3 to partially oxidize MWCNT at a lower reflux temperature (80 ℃) and a shorter treatment time (0 to 10 h) to preserve the morphology and intrinsic conductivity of MWCNT. The maximum power density of 979.81 mw cm-2 was achieved by Pt loading on 6h MWCNT oxidation time (Pt-MWCNT6h). This represented a 59.53% improvement over the commercial Pt/C catalyst of 614.17 (mw cm-2). In addition, due to the stronger electrical conductivity, the charge transfer resistance of Pt-MWCNT6h in the electrochemical impedance spectroscopy (EIS) test was 0.09 Ohm cm-2, which was 48.86% lower than that of Pt/C. This study will discuss the developed catalysts and their efficacy in a working fuel cell system. This research will validate the impact of low-functionalization modification of MWCNTs on the performance of PEMFC, which simplifies the preparation challenges of CL and contributing for the widespread commercial application of PEMFCs on a larger scale.

Keywords: carbon nanotubes, electrocatalyst, membrane electrode assembly, proton exchange membrane fuel cell

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Authors: Agman Gupta, Rajashekar Badam, Noriyoshi Matsumi

Abstract:

Introduction: Recently, silicon has been recognized as one of the potential alternatives as anode active material in Li-ion batteries (LIBs) to replace the conventionally used graphite anodes. Silicon is abundantly present in the nature, it can alloy with lithium metal, and has a higher theoretical capacity (~4200 mAhg-1) that is approximately 10 times higher than graphite. However, because of a large volume expansion (~400%) upon repeated de-/alloying, the pulverization of Si particles causes the exfoliation of electrode laminate leading to the loss of electrical contact and adversely affecting the formation of solid-electrolyte interface (SEI).1 Functional polymers as binders have emerged as a competitive strategy to mitigate these drawbacks and failure mechanism of silicon anodes.1 A variety of aqueous/non-aqueous polymer binders like sodium carboxy-methyl cellulose (CMC-Na), styrene butadiene rubber (SBR), poly(acrylic acid), and other variants like mussel inspired binders have been investigated to overcome these drawbacks.1 However, there are only a few reports that mention the attempt of addressing all the drawbacks associated with silicon anodes effectively using a single novel functional polymer system as a binder. In this regard, here, we report a novel highly robust n-type bisiminoacenaphthenequinone (BIAN)-paraphenylene-based crosslinked polymer as a binder for Si anodes in lithium-ion batteries (Fig. 1). On its application, crosslinked-BIAN binder was evaluated to provide mechanical robustness to the large volume expansion of Si particles, maintain electrical conductivity within the electrode laminate, and facilitate in the formation of a thin SEI by restricting the extent of electrolyte decomposition on the surface of anode. The fabricated anodic half-cells were evaluated electrochemically for their rate capability, cyclability, and discharge capacity. Experimental: The polymerized BIAN (P-BIAN) copolymer was synthesized as per the procedure reported by our group.2 The synthesis of crosslinked P-BIAN: a solution of P-BIAN copolymer (1.497 g, 10 mmol) in N-methylpyrrolidone (NMP) (150 ml) was set-up to stir under reflux in nitrogen atmosphere. To this, 1,6-dibromohexane (5 mmol, 0.77 ml) was added dropwise. The resultant reaction mixture was stirred and refluxed at 150 °C for 24 hours followed by refrigeration for 3 hours at 5 °C. The product was obtained by evaporating the NMP solvent under reduced pressure and drying under vacuum at 120 °C for 12 hours. The obtained product was a black colored sticky compound. It was characterized by 1H-NMR, XPS, and FT-IR techniques. Results and Discussion: The N 1s XPS spectrum of the crosslinked BIAN polymer showed two characteristic peaks corresponding to the sp2 hybridized nitrogen (-C=N-) at 399.6 eV of the diimine backbone in the BP and quaternary nitrogen at 400.7 eV corresponding to the crosslinking of BP via dibromohexane. The DFT evaluation of the crosslinked BIAN binder showed that it has a low lying lowest unoccupied molecular orbital (LUMO) that enables it to get doped in the reducing environment and influence the formation of a thin (SEI). Therefore, due to the mechanically robust crosslinked matrices as well as its influence on the formation of a thin SEI, the crosslinked BIAN binder stabilized the Si anode-based half-cell for over 1000 cycles with a reversible capacity of ~2500 mAhg-1 and ~99% capacity retention as shown in Fig. 2. The dynamic electrochemical impedance spectroscopy (DEIS) characterization of crosslinked BIAN-based anodic half-cell confirmed that the SEI formed was thin in comparison with the conventional binder-based anodes. Acknowledgement: We are thankful to the financial support provided by JST-Mirai Program, Grant Number: JP18077239

Keywords: self-healing binder, n-type binder, thin solid-electrolyte interphase (SEI), high-capacity silicon anodes, low-LUMO

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