Search results for: impedance band-width

Authors: M. Salvador, J. C. Martinez-Garcia, A. Moyano, M. C. Blanco-Lopez, M. Rivas

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Biosensors play a crucial role in the detection of molecules nowadays due to their advantages of user-friendliness, high selectivity, the analysis in real time and in-situ applications. Among them, Lateral Flow Immunoassays (LFIAs) are presented among technologies for point-of-care bioassays with outstanding characteristics such as affordability, portability and low-cost. They have been widely used for the detection of a vast range of biomarkers, which do not only include proteins but also nucleic acids and even whole cells. Although the LFIA has traditionally been a positive/negative test, tremendous efforts are being done to add to the method the quantifying capability based on the combination of suitable labels and a proper sensor. One of the most successful approaches involves the use of magnetic sensors for detection of magnetic labels. Bringing together the required characteristics mentioned before, our research group has developed a biosensor to detect biomolecules. Superparamagnetic nanoparticles (SPNPs) together with LFIAs play the fundamental roles. SPMNPs are detected by their interaction with a high-frequency current flowing on a printed micro track. By means of the instant and proportional variation of the impedance of this track provoked by the presence of the SPNPs, quantitative and rapid measurement of the number of particles can be obtained. This way of detection requires no external magnetic field application, which reduces the device complexity. On the other hand, the major limitations of LFIAs are that they are only qualitative or semiquantitative when traditional gold or latex nanoparticles are used as color labels. Moreover, the necessity of always-constant ambient conditions to get reproducible results, the exclusive detection of the nanoparticles on the surface of the membrane, and the short durability of the signal are drawbacks that can be advantageously overcome with the design of magnetically labeled LFIAs. The approach followed was to coat the SPIONs with a specific monoclonal antibody which targets the protein under consideration by chemical bonds. Then, a sandwich-type immunoassay was prepared by printing onto the nitrocellulose membrane strip a second antibody against a different epitope of the protein (test line) and an IgG antibody (control line). When the sample flows along the strip, the SPION-labeled proteins are immobilized at the test line, which provides magnetic signal as described before. Preliminary results using this practical combination for the detection and quantification of the Prostatic-Specific Antigen (PSA) shows the validity and consistency of the technique in the clinical range, where a PSA level of 4.0 ng/mL is the established upper normal limit. Moreover, a LOD of 0.25 ng/mL was calculated with a confident level of 3 according to the IUPAC Gold Book definition. Its versatility has also been proved with the detection of other biomolecules such as troponin I (cardiac injury biomarker) or histamine.

Keywords: biosensor, lateral flow immunoassays, point-of-care devices, superparamagnetic nanoparticles

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Authors: Cyril O. Ehi-Eromosele, Ajayi Kayode

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The Li-rich layered metal oxides (LLO) are the most promising candidates for promising electrodes of high energy Li-ion battery (LIB). In literature, these electrode system has either been designed as a hetero-structure of the primary components (composite) or as a core-shell structure with improved electrochemistry reported for both configurations when compared with its primary components. With the on-going efforts to improve on the electrochemical performance of the LIB, it is important to investigate comparatively the structural and electrochemical characteristics of the core-shell like and ‘composite’ forms of these materials with the same compositions and synthesis conditions which could influence future engineering of these materials. Therefore, this study concerns the structural and electrochemical properties of the ‘composite’ and core-shell like LLO cathode materials with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₂O₂ (LiNi₀.₅Mn₀.₃Co₀.₂O₂ as core and Li₂MnO₃ as the shell). The results show that the core-shell sample (–CS) gave better electrochemical performance than the ‘composite’ sample (–C). Both samples gave the same initial charge capacity of ~300 mAh/g when cycled at 10 mA/g and comparable charge capacity (246 mAh/g for the –CS sample and 240 mAh/g for the –C sample) when cycled at 200 mA/g. However, the –CS sample gave a higher initial discharge capacity at both current densities. The discharge capacity of the –CS sample was 232 mAh/g and 164 mAh/g while the –C sample is 208 mAh/g and 143 mAh/g at the current densities of 10 mA/g and 200 mA/g, respectively. Electrochemical impedance spectroscopy (EIS) results show that the –CS sample generally exhibited a smaller resistance than the –C sample both for the uncycled and after 50th cycle. Detailed structural analysis is on-going, but preliminary results show that the –CS sample had bigger unit cell volume and a higher degree of cation mixing. The thermal stability of the –CS sample was higher than the –C sample. XPS investigation also showed that the pristine –C sample gave a more reactive surface (showing formation of carbonate species to a greater degree) which could result in the greater resistance seen in the EIS result. To reinforce the results obtained for the 0.5Li₂MnO₃-0.5LiNi₀.₅Mn₀.₃Co₀.₃O₂ composition, the same investigations were extended to another ‘composite’ and core-shell like LLO cathode materials also with the same nominal composition of 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂. In this case, the aim was to determine the electrochemical performance of the material using a low Ni content (LiNi₀.₃Mn₀.₃Co₀.₃O₂) as the core to clarify the contributions of the core-shell configuration to the electrochemical performance of these materials. Ni-rich layered oxides show active catalytic surface leading to electrolyte oxidation resulting in poor thermal stability and cycle life. Here, the core-shell sample also gave better electrochemical performance than the ‘composite’ sample with 0.5Li₂MnO₃-0.5LiNi₀.₃Mn₀.₃Co₀.₃O₂ composition. Furthermore, superior electrochemical performance was also recorded for the core-shell like spinel modified LLO (0.5Li₂MnO₃-0.45LiNi₀.₅Mn₀.₃Co₀.₂O₂-0.05LiNi₀.₅Mn₁.₅O₄) when compared to the composite system. These results show that the core-shell configuration can generally be used to improve the structural and electrochemical properties of the LLO and spinel modified LLO materials.

Keywords: lithium-ion battery, lithium rich oxide cathode, core-shell structure, composite structure

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Authors: Orkide Donma, Mustafa M. Donma, Muhammet Demirkol, Murat Aydin, Tuba Gokkus, Burcin Nalbantoglu, Aysin Nalbantoglu, Birol Topcu

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Obesity in childhood establishes a ground for adulthood obesity. Especially morbid obesity is an important problem for the children because of the associated diseases such as diabetes mellitus, cancer and cardiovascular diseases. In this study, body mass index (BMI), body fat ratios, anthropometric measurements and ratios were evaluated together with different laboratory indices upon evaluation of obesity in morbidly obese (MO) children. Children with nutritional problems participated in the study. Written informed consent was obtained from the parents. Study protocol was approved by the Ethics Committee. Sixty-two MO girls aged 129.5±35.8 months and 75 MO boys aged 120.1±26.6 months were included into the scope of the study. WHO-BMI percentiles for age-and-sex were used to assess the children with those higher than 99^th as morbid obesity. Anthropometric measurements of the children were recorded after their physical examination. Bio-electrical impedance analysis was performed to measure fat distribution. Anthropometric ratios, body fat ratios, Index-I and Index-II as well as insulin sensitivity indices (ISIs) were calculated. Girls as well as boys were binary grouped according to homeostasis model assessment-insulin resistance (HOMA-IR) index of <2.5 and >2.5, fasting glucose to insulin ratio (FGIR) of <6 and >6 and quantitative insulin sensitivity check index (QUICKI) of <0.33 and >0.33 as the frequently used cut-off points. They were evaluated based upon their BMIs, arms, legs, trunk, whole body fat percentages, body fat ratios such as fat mass index (FMI), trunk-to-appendicular fat ratio (TAFR), whole body fat ratio (WBFR), anthropometric measures and ratios [waist-to-hip, head-to-neck, thigh-to-arm, thigh-to-ankle, height/2-to-waist, height/2-to-hip circumference (C)]. SPSS/PASW 18 program was used for statistical analyses. p≤0.05 was accepted as statistically significance level. All of the fat percentages showed differences between below and above the specified cut-off points in girls when evaluated with HOMA-IR and QUICKI. Differences were observed only in arms fat percent for HOMA-IR and legs fat percent for QUICKI in boys (p≤ 0.05). FGIR was unable to detect any differences for the fat percentages of boys. Head-to-neck C was the only anthropometric ratio recommended to be used for all ISIs (p≤0.001 for both girls and boys in HOMA-IR, p≤0.001 for girls and p≤0.05 for boys in FGIR and QUICKI). Indices which are recommended for use in both genders were Index-I, Index-II, HOMA/BMI and log HOMA (p≤0.001). FMI was also a valuable index when evaluated with HOMA-IR and QUICKI (p≤0.001). The important point was the detection of the severe significance for HOMA/BMI and log HOMA while they were evaluated also with the other indices, FGIR and QUICKI (p≤0.001). These parameters along with Index-I were unique at this level of significance for all children. In conclusion, well-accepted ratios or indices may not be valid for the evaluation of both genders. This study has emphasized the limiting properties for boys. This is particularly important for the selection process of some ratios and/or indices during the clinical studies. Gender difference should be taken into consideration for the evaluation of the ratios or indices, which will be recommended to be used particularly within the scope of obesity studies.

Keywords: anthropometry, childhood obesity, gender, insulin sensitivity index

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Authors: Gaurav Kumar Sinha

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In an era defined by the proliferation of data and the utilization of cloud computing environments, the efficient transfer and processing of big data workloads across multi-cloud platforms have emerged as critical challenges. This research paper embarks on a comprehensive exploration of the complexities associated with managing and optimizing big data in a multi-cloud ecosystem.The foundation of this study is rooted in the recognition that modern enterprises increasingly rely on multiple cloud providers to meet diverse business needs, enhance redundancy, and reduce vendor lock-in. As a consequence, managing data across these heterogeneous cloud environments has become intricate, necessitating innovative approaches to ensure data integrity, security, and performance.The primary objective of this research is to investigate strategies and techniques for enhancing the efficiency of data transfer and processing in multi-cloud scenarios. It recognizes that big data workloads are characterized by their sheer volume, variety, velocity, and complexity, making traditional data management solutions insufficient for harnessing the full potential of multi-cloud architectures.The study commences by elucidating the challenges posed by multi-cloud environments in the context of big data. These challenges encompass data fragmentation, latency, security concerns, and cost optimization. To address these challenges, the research explores a range of methodologies and solutions. One of the key areas of focus is data transfer optimization. The paper delves into techniques for minimizing data movement latency, optimizing bandwidth utilization, and ensuring secure data transmission between different cloud providers. It evaluates the applicability of dedicated data transfer protocols, intelligent data routing algorithms, and edge computing approaches in reducing transfer times.Furthermore, the study examines strategies for efficient data processing across multi-cloud environments. It acknowledges that big data processing requires distributed and parallel computing capabilities that span across cloud boundaries. The research investigates containerization and orchestration technologies, serverless computing models, and interoperability standards that facilitate seamless data processing workflows.Security and data governance are paramount concerns in multi-cloud environments. The paper explores methods for ensuring data security, access control, and compliance with regulatory frameworks. It considers encryption techniques, identity and access management, and auditing mechanisms as essential components of a robust multi-cloud data security strategy.The research also evaluates cost optimization strategies, recognizing that the dynamic nature of multi-cloud pricing models can impact the overall cost of data transfer and processing. It examines approaches for workload placement, resource allocation, and predictive cost modeling to minimize operational expenses while maximizing performance.Moreover, this study provides insights into real-world case studies and best practices adopted by organizations that have successfully navigated the challenges of multi-cloud big data management. It presents a comparative analysis of various multi-cloud management platforms and tools available in the market.

Keywords: multi-cloud environments, big data workloads, data transfer optimization, data processing strategies

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Authors: Prescilla Lambert, Christophe Roos, Mounim Lebrini

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For several years, the Caribbean islands and West Africa have had to deal with the massive arrival of the brown seaweed Sargassum. Overall, this macroalgae, which constitutes a habitat for a great diversity of marine organisms, is also an additional stress factor for the marine environment (e.g., coral reefs). In addition, the accumulation followed by the significant decomposition of the Sargassum spp. biomass on the coast leads to the release of toxic gases (H₂S and NH₃), which calls into question the functioning of the economic, health and tourist life of the island and the other interested territories. Originally, these algae are formed by the eutrophication of the oceans accentuated by global warming. Unfortunately, scientists predict a significant recurrence of these Sargassum strandings for years to come. It is therefore more than necessary to find solutions by putting in place a sustainable management plan for this phenomenon. Martinique, a small island in the Caribbean arc, is one of the many areas impacted by Sargassum seaweed strandings. Since 2011, there has been a constant increase in the degradation of the materials present in this region, largely due to toxic/corrosive gases released by the algae decomposition. In order to protect the structures and the vulnerable building materials while limiting the use of synthetic/petroleum based molecules as much as possible, research is being conducted on molecules of natural origin. Thus, thanks to the chemical composition, which comprise molecules with interesting properties, algae such as Sargassum could potentially help to solve many issues. Therefore, this study focuses on the green extraction and characterization of molecules from the species Sargassum fluitans and Sargassum natans present in Martinique. The secondary metabolites found in these extracts showed variability in yield rates due to local climatic conditions. The tests carried out shed light on the anticorrosive and antibacterial potential of the algae. These extracts can thus be described as natural inhibitors. The effect of variation in inhibitor concentrations was tested in electrochemistry using electrochemical impedance spectroscopy and polarization curves. The analysis of electrochemical results obtained by direct immersion in the extracts and self-assembled molecular layers (SAMs) for Sargassum fluitans III, Sargassum natans I and VIII species was conclusive in acid and alkaline environments. The excellent results obtained reveal an inhibitory efficacy of 88% at 50mg/L for the crude extract of Sargassum fluitans III and efficacies greater than 97% for the chemical families of Sargassum fluitans III. Similarly, microbiological tests also suggest a bactericidal character. Results for Sargassum fluitans III crude extract show a minimum inhibitory concentration (MIC) of 0.005 mg/mL on Gram-negative bacteria and a MIC greater than 0.6 mg/mL on Gram-positive bacteria. These results make it possible to consider the management of local and international issues while valuing a biomass rich in biodegradable molecules. The next step in this study will therefore be the evaluation of the toxicity of Sargassum spp..

Keywords: Sargassum, secondary metabolites, anticorrosive, antibacterial, natural inhibitors

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Authors: Piotr Kacejko, Mariusz Duk, Miroslaw Wendeker

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This paper presents an adaptive controller to track the maximum power point of a photovoltaic modules (PV) under fast irradiation change on the city-bus roof. Photovoltaic systems have been a prominent option as an additional energy source for vehicles. The Municipal Transport Company (MPK) in Lublin has installed photovoltaic panels on its buses roofs. The solar panels turn solar energy into electric energy and are used to load the buses electric equipment. This decreases the buses alternators load, leading to lower fuel consumption and bringing both economic and ecological profits. A DC–DC boost converter is selected as the power conditioning unit to coordinate the operating point of the system. In addition to the conversion efficiency of a photovoltaic panel, the maximum power point tracking (MPPT) method also plays a main role to harvest most energy out of the sun. The MPPT unit on a moving vehicle must keep tracking accuracy high in order to compensate rapid change of irradiation change due to dynamic motion of the vehicle. Maximum power point track controllers should be used to increase efficiency and power output of solar panels under changing environmental factors. There are several different control algorithms in the literature developed for maximum power point tracking. However, energy performances of MPPT algorithms are not clarified for vehicle applications that cause rapid changes of environmental factors. In this study, an adaptive MPPT algorithm is examined at real ambient conditions. PV modules are mounted on a moving city bus designed to test the solar systems on a moving vehicle. Some problems of a PV system associated with a moving vehicle are addressed. The proposed algorithm uses a scanning technique to determine the maximum power delivering capacity of the panel at a given operating condition and controls the PV panel. The aim of control algorithm was matching the impedance of the PV modules by controlling the duty cycle of the internal switch, regardless of changes of the parameters of the object of control and its outer environment. Presented algorithm was capable of reaching the aim of control. The structure of an adaptive controller was simplified on purpose. Since such a simple controller, armed only with an ability to learn, a more complex structure of an algorithm can only improve the result. The presented adaptive control system of the PV system is a general solution and can be used for other types of PV systems of both high and low power. Experimental results obtained from comparison of algorithms by a motion loop are presented and discussed. Experimental results are presented for fast change in irradiation and partial shading conditions. The results obtained clearly show that the proposed method is simple to implement with minimum tracking time and high tracking efficiency proving superior to the proposed method. This work has been financed by the Polish National Centre for Research and Development, PBS, under Grant Agreement No. PBS 2/A6/16/2013.

Keywords: adaptive control, photovoltaic energy, city bus electric load, DC-DC converter

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Authors: Rajashekar Badam, Vedarajan Raman, Noriyoshi Matsumi

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Efficiency of energy converting and storage systems like fuel cells and Li-Air battery principally depended on oxygen reduction reaction (ORR) which occurs at cathode. As the kinetics of the ORR is very slow, it becomes the rate determining step. Exploring carbon substrates for enhancing the dispersion and activity of the metal catalyst and commercially viable simple preparation method is a very crucial area of research in the field of energy materials. Hence, many researchers made large number of carbon-based ORR materials today. But, there are hardly few studies on the effect of interaction between Pt-carbon and carbon-electrolyte on activity. In this work, we have prepared functionalized carbon-based Pt catalyst (Pt-FAB) with enhanced interfacial properties that lead to efficient ORR catalysis. The present work deals with a single-pot method to exfoliate and functionalized acetylene black with enhanced interaction with Pt as well as electrolyte. Acetylene black was functionalized and exfoliated using a facile single pot acid treatment method. The resulted FAB was further decorated with Pt-nano particles (Pt-np). The TEM images of Pt-FAB with uniformly decorated Pt-np of ~3 nm. Further, XPS studies of Pt 4f peak revealed that Pt0 peak was shifted by 0.4 eV in Pt-FAB compared to binding energy of typical Pt⁰ found in Pt/C. The shift can be ascribed to the modulation of electronic state and strong electronic interaction of Pt with carbon. Modulated electronic structure of Pt and strong electronic interaction of Pt with FAB enhances the catalytic activity and durability respectively. To understand the electrode electrolyte interface, electrochemical impedance spectroscopy was carried out. These measurements revealed that the charge transfer resistance of electrode to electrolyte for Pt-FAB is 10 times smaller than that of conventional Pt/C. The interaction with electrolyte helps reduce the interface boundaries, which in turn affects the overall catalytic performance of the electrode. Cyclic voltammetric measurements in 0.1M HClO₄ aq. at a potential scan rate of 50 mVs-1 was employed to evaluate electrochemical surface area (ECSA) of Pt. ECSA of Pt-FAB was found to be as high as 67.2 m²g⁻¹. The three-electrode system showed very high ORR catalytic activity. Mass activity at 0.9 V vs. RHE showed 460 A/g which is much higher than the DOE target values for the year 2020. Further, it showed enhanced performance by showing 723 mW/cm² of highest power density and 1006 mA/cm² of current density at 0.6 V in fuel cell single cell type configuration and 1030 mAhg⁻¹ of rechargeable capacity in Li air battery application. The higher catalytic activity can be ascribed to the improved interaction of FAB with Pt and electrolyte. The aforementioned results evince that Pt-FAB will be a promising cathode material for efficient ORR with significant cyclability for its application in fuel cells and Li-Air batteries. In conclusion, a disordered material was prepared from AB and was systematically characterized. The extremely high ORR activity and ease of preparation make it competent for replacing commercially available ORR materials.

Keywords: functionalized acetylene black, oxygen reduction reaction, fuel cells, Functionalized battery

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Authors: Carlos M. Parra, Matthew Sutherland, Ranjita Poudel

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Reduced mental-bandwidth related to low socioeconomic status (low-SES) might lead to impulsivity and risk-taking behavior, which poses as a major hurdle towards asset building (savings) behavior. Understanding the relationship between risk-related personality metrics as well as laboratory risk behavior and real-life savings behavior can help facilitate the development of effective asset building programs, which are vital for mitigating financial vulnerability and income inequality. As such, this study explored the relationship between personality metrics, laboratory behavior in a risky decision-making task and real-life asset building (savings) behaviors among individuals with low-SES from Miami, Florida (FL). Study participants (12 male, 15 female) included racially and ethnically diverse adults (mean age 41.22 ± 12.65 years), with incomplete higher education (18% had High School Diploma, 30% Associates, and 52% Some College), and low annual income (mean $13,872 ± $8020.43). Participants completed eight self-report surveys and played a widely used risky decision-making paradigm called the Balloon Analogue Risk Task (BART). Specifically, participants played three runs of BART (20 trials in each run; total 60 trials). In addition, asset building behavior data was collected for 24 participants who opened and used savings accounts and completed a 6-month savings program that involved monthly matches, and a final reward for completing the savings program without any interim withdrawals. Each participant’s total savings at the end of this program was the main asset building indicator considered. In addition, a new effective use of average pump bet (EUAPB) indicator was developed to characterize each participant’s ability to place winning bets. This indicator takes the ratio of each participant’s total BART earnings to average pump bet (APB) in all 60 trials. Our findings indicated that EUAPB explained more than a third of the variation in total savings among participants. Moreover, participants who managed to obtain BART earnings of at least 30 cents out of their APB, also tended to exhibit better asset building (savings) behavior. In particular, using this criterion to separate participants into high and low EUAPB groups, the nine participants with high EUAPB (mean BART earnings of 35.64 cents per APB) ended up with higher mean total savings ($255.11), while the 15 participants with low EUAPB (mean BART earnings of 22.50 cents per APB) obtained lower mean total savings ($40.01). All mean differences are statistically significant (2-tailed p  .0001) indicating that the relation between higher EUAPB and higher total savings is robust. Overall, these findings can help refine asset building interventions implemented by policy makers and practitioners interested in reducing financial vulnerability among low-SES population. Specifically, by helping identify individuals who are likely to readily take advantage of savings opportunities (such as matched savings programs) and avoiding the stipulation of unnecessary and expensive financial coaching programs to these individuals. This study was funded by J.P. Morgan Chase (JPMC) and carried out by scientists from Florida International University (FIU) in partnership with Catalyst Miami.

Keywords: balloon analogue risk task (BART), matched savings programs, asset building capability, low-SES participants

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Authors: Rohit T. P., Sahil Athrij, Sasi Gopalan

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Currently, the content entertainment industry is dominated by mobile devices. As the trends slowly shift towards Augmented/Virtual Reality applications the computational demands on these devices are increasing exponentially and we are already reaching the limits of hardware optimizations. This paper proposes a software solution to this problem. By leveraging the capabilities of cloud computing we can offload the work from mobile devices to dedicated rendering servers that are way more powerful. But this introduces the problem of latency. This paper introduces a protocol that can achieve high-performance low latency Augmented/Virtual Reality experience. There are two parts to the protocol, 1) In-flight compression The main cause of latency in the system is the time required to transmit the camera frame from client to server. The round trip time is directly proportional to the amount of data transmitted. This can therefore be reduced by compressing the frames before sending. Using some standard compression algorithms like JPEG can result in minor size reduction only. Since the images to be compressed are consecutive camera frames there won't be a lot of changes between two consecutive images. So inter-frame compression is preferred. Inter-frame compression can be implemented efficiently using WebGL but the implementation of WebGL limits the precision of floating point numbers to 16bit in most devices. This can introduce noise to the image due to rounding errors, which will add up eventually. This can be solved using an improved interframe compression algorithm. The algorithm detects changes between frames and reuses unchanged pixels from the previous frame. This eliminates the need for floating point subtraction thereby cutting down on noise. The change detection is also improved drastically by taking the weighted average difference of pixels instead of the absolute difference. The kernel weights for this comparison can be fine-tuned to match the type of image to be compressed. 2) Dynamic Load distribution Conventional cloud computing architectures work by offloading as much work as possible to the servers, but this approach can cause a hit on bandwidth and server costs. The most optimal solution is obtained when the device utilizes 100% of its resources and the rest is done by the server. The protocol balances the load between the server and the client by doing a fraction of the computing on the device depending on the power of the device and network conditions. The protocol will be responsible for dynamically partitioning the tasks. Special flags will be used to communicate the workload fraction between the client and the server and will be updated in a constant interval of time ( or frames ). The whole of the protocol is designed so that it can be client agnostic. Flags are available to the client for resetting the frame, indicating latency, switching mode, etc. The server can react to client-side changes on the fly and adapt accordingly by switching to different pipelines. The server is designed to effectively spread the load and thereby scale horizontally. This is achieved by isolating client connections into different processes.

Keywords: 2D kernelling, augmented reality, cloud computing, dynamic load distribution, immersive experience, mobile computing, motion tracking, protocols, real-time systems, web-based augmented reality application

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Authors: Keita Nishio, Takashi Kaburagi, Yosuke Kurihara

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Recent advances in medical technology have served to enhance average life expectancy. However, the total time for which the patients are prescribed complete bedrest has also increased. With patients being required to maintain a constant lying posture- also called bedsore- development of a system to detect patient roll-over becomes imperative. For this purpose, extant studies have proposed the use of cameras, and favorable results have been reported. Continuous on-camera monitoring, however, tends to violate patient privacy. We have proposed unconstrained bio-signal measurement system that could detect body-motion during sleep and does not violate patient’s privacy. Therefore, in this study, we propose a roll-over detection method by the date obtained from the bi-signal measurement system. Signals recorded by the sensor were assumed to comprise respiration, pulse, body motion, and noise components. Compared the body-motion and respiration, pulse component, the body-motion, during roll-over, generate large vibration. Thus, analysis of the body-motion component facilitates detection of the roll-over tendency. The large vibration associated with the roll-over motion has a great effect on the Root Mean Square (RMS) value of time series of the body motion component calculated during short 10 s segments. After calculation, the RMS value during each segment was compared to a threshold value set in advance. If RMS value in any segment exceeded the threshold, corresponding data were considered to indicate occurrence of a roll-over. In order to validate the proposed method, we conducted experiment. A bi-directional microphone was adopted as a high-sensitivity pressure sensor and was placed between the mattress and bedframe. Recorded signals passed through an analog Band-pass Filter (BPF) operating over the 0.16-16 Hz bandwidth. BPF allowed the respiration, pulse, and body-motion to pass whilst removing the noise component. Output from BPF was A/D converted with the sampling frequency 100Hz, and the measurement time was 480 seconds. The number of subjects and data corresponded to 5 and 10, respectively. Subjects laid on a mattress in the supine position. During data measurement, subjects—upon the investigator's instruction—were asked to roll over into four different positions—supine to left lateral, left lateral to prone, prone to right lateral, and right lateral to supine. Recorded data was divided into 48 segments with 10 s intervals, and the corresponding RMS value for each segment was calculated. The system was evaluated by the accuracy between the investigator’s instruction and the detected segment. As the result, an accuracy of 100% was achieved. While reviewing the time series of recorded data, segments indicating roll-over tendencies were observed to demonstrate a large amplitude. However, clear differences between decubitus and the roll-over motion could not be confirmed. Extant researches possessed a disadvantage in terms of patient privacy. The proposed study, however, demonstrates more precise detection of patient roll-over tendencies without violating their privacy. As a future prospect, decubitus estimation before and after roll-over could be attempted. Since in this paper, we could not confirm the clear differences between decubitus and the roll-over motion, future studies could be based on utilization of the respiration and pulse components.

Keywords: bedsore, high-sensitivity pressure sensor, roll-over, unconstrained bio-signal measurement

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Authors: Utpal Das, Sona Das

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InAs/GaSb type-II superlattice (T2SL) Mid-wave infrared (MWIR) focal plane arrays (FPAs) have recently seen rapid development. However, in small pixel size large format FPAs, the occurrence of high mesa sidewall surface leakage current is a major constraint necessitating proper surface passivation. A simple pixel isolation technique in InAs/GaSb T2SL detector arrays without the conventional mesa etching has been proposed to isolate the pixels by forming a more resistive higher band gap material from the SL, in the inter-pixel region. Here, a single step femtosecond (fs) laser anneal of the T2SL structure of the inter-pixel T2SL regions, have been used to increase the band gap between the pixels by QW-intermixing and hence increase isolation between the pixels. The p-i-n photodiode structure used here consists of a 506nm, (10 monolayer {ML}) InAs:Si (1x10¹⁸cm⁻³)/(10ML) GaSb SL as the bottom n-contact layer grown on an n-type GaSb substrate. The undoped absorber layer consists of 1.3µm, (10ML)InAs/(10ML)GaSb SL. The top p-contact layer is a 63nm, (10ML)InAs:Be(1x10¹⁸cm⁻³)/(10ML)GaSb T2SL. In order to improve the carrier transport, a 126nm of graded doped (10ML)InAs/(10ML)GaSb SL layer was added between the absorber and each contact layers. A 775nm 150fs-laser at a fluence of ~6mJ/cm² is used to expose the array where the pixel regions are masked by a Ti(200nm)-Au(300nm) cap. Here, in the inter-pixel regions, the p+ layer have been reactive ion etched (RIE) using CH₄+H₂ chemistry and removed before fs-laser exposure. The fs-laser anneal isolation improvement in 200-400μm pixels due to spatially selective quantum well intermixing for a blue shift of ~70meV in the inter-pixel regions is confirmed by FTIR measurements. Dark currents are measured between two adjacent pixels with the Ti(200nm)-Au(300nm) caps used as contacts. The T2SL quality in the active photodiode regions masked by the Ti-Au cap is hardly affected and retains the original quality of the detector. Although, fs-laser anneal of p+ only etched p-i-n T2SL diodes show a reduction in the reverse dark current, no significant improvement in the full RIE-etched mesa structures is noticeable. Hence for a 128x128 array fabrication of 8μm square pixels and 10µm pitch, SU8 polymer isolation after RIE pixel delineation has been used. X-n+ row contacts and Y-p+ column contacts have been used to measure the optical response of the individual pixels. The photo-response of these 8μm and other 200μm pixels under a 2ns optical pulse excitation from an Optical-Parametric-Oscillator (OPO), shows a peak responsivity of ~0.03A/W and 0.2mA/W, respectively, at λ~3.7μm. Temporal response of this detector array is seen to have a fast response ~10ns followed typical slow decay with ringing, attributed to impedance mismatch of the connecting co-axial cables. In conclusion, response times of a few ns have been measured in 8µm pixels of a 128x128 array. Although fs-laser anneal has been found to be useful in increasing the inter-pixel isolation in InAs/GaSb T2SL arrays by QW inter-mixing, it has not been found to be suitable for passivation of full RIE etched mesa structures with vertical walls on InAs/GaSb T2SL.

Keywords: band-gap blue-shift, fs-laser-anneal, InAs/GaSb T2SL, Inter-pixel isolation, ns-Response, photodiode array

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Authors: Ksenia Volkova, Artur Petrosyan, Ignatii Dubyshkin, Alexei Ossadtchi

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Brain-computer interfaces are a growing research field producing many implementations that find use in different fields and are used for research and practical purposes. Despite the popularity of the implementations using non-invasive neuroimaging methods, radical improvement of the state channel bandwidth and, thus, decoding accuracy is only possible by using invasive techniques. Electrocorticography (ECoG) is a minimally invasive neuroimaging method that provides highly informative brain activity signals, effective analysis of which requires the use of machine learning methods that are able to learn representations of complex patterns. Deep learning is a family of machine learning algorithms that allow learning representations of data with multiple levels of abstraction. This study explores the potential of deep learning approaches for ECoG processing, decoding movement intentions and the perception of proprioceptive information. To obtain synchronous recording of kinematic movement characteristics and corresponding electrical brain activity, a series of experiments were carried out, during which subjects performed finger movements at their own pace. Finger movements were recorded with a three-axis accelerometer, while ECoG was synchronously registered from the electrode strips that were implanted over the contralateral sensorimotor cortex. Then, multichannel ECoG signals were used to track finger movement trajectory characterized by accelerometer signal. This process was carried out both causally and non-causally, using different position of the ECoG data segment with respect to the accelerometer data stream. The recorded data was split into training and testing sets, containing continuous non-overlapping fragments of the multichannel ECoG. A deep convolutional neural network was implemented and trained, using 1-second segments of ECoG data from the training dataset as input. To assess the decoding accuracy, correlation coefficient r between the output of the model and the accelerometer readings was computed. After optimization of hyperparameters and training, the deep learning model allowed reasonably accurate causal decoding of finger movement with correlation coefficient r = 0.8. In contrast, the classical Wiener-filter like approach was able to achieve only 0.56 in the causal decoding mode. In the noncausal case, the traditional approach reached the accuracy of r = 0.69, which may be due to the presence of additional proprioceptive information. This result demonstrates that the deep neural network was able to effectively find a representation of the complex top-down information related to the actual movement rather than proprioception. The sensitivity analysis shows physiologically plausible pictures of the extent to which individual features (channel, wavelet subband) are utilized during the decoding procedure. In conclusion, the results of this study have demonstrated that a combination of a minimally invasive neuroimaging technique such as ECoG and advanced machine learning approaches allows decoding motion with high accuracy. Such setup provides means for control of devices with a large number of degrees of freedom as well as exploratory studies of the complex neural processes underlying movement execution.

Keywords: brain-computer interface, deep learning, ECoG, movement decoding, sensorimotor cortex

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Authors: Philipp Wenger, Michael Beltle, Stefan Tenbohlen, Uwe Riechert

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The integration of renewable energy introduces new challenges to the transmission grid, as the power generation is located far from load centers. The associated necessary long-range power transmission increases the demand for high voltage direct current (HVDC) transmission lines and DC distribution grids. HVDC gas-insulated switchgears (GIS) are considered being a key technology, due to the combination of the DC technology and the long operation experiences of AC-GIS. To ensure long-term reliability of such systems, insulation defects must be detected in an early stage. Operational experience with AC systems has proven evidence, that most failures, which can be attributed to breakdowns of the insulation system, can be detected and identified via partial discharge (PD) measurements beforehand. In AC systems the identification of defects relies on the phase resolved partial discharge pattern (PRPD). Since there is no phase information within DC systems this method cannot be transferred to DC PD diagnostic. Furthermore, the behaviour of e.g. free-moving particles differs significantly at DC: Under the influence of a constant direct electric field, charge carriers can accumulate on particles’ surfaces. As a result, a particle can lift-off, oscillate between the inner conductor and the enclosure or rapidly bounces at just one electrode, which is known as firefly motion. Depending on the motion and the relative position of the particle to the electrodes, broadband electromagnetic PD pulses are emitted, which can be recorded by ultra-high frequency (UHF) measuring methods. PDs are often accompanied by light emissions at the particle’s tip which enables optical detection. This contribution investigates PD characteristics of free moving metallic particles in a commercially available 300 kV SF6-insulated HVDC-GIS. The influences of various defect parameters on the particle motion and the PD characteristic are evaluated experimentally. Several particle geometries, such as cylinder, lamella, spiral and sphere with different length, diameter and weight are determined. The applied DC voltage is increased stepwise from inception voltage up to UDC = ± 400 kV. Different physical detection methods are used simultaneously in a time-synchronized setup. Firstly, the electromagnetic waves emitted by the particle are recorded by an UHF measuring system. Secondly, a photomultiplier tube (PMT) detects light emission with a wavelength in the range of λ = 185…870 nm. Thirdly, a high-speed camera (HSC) tracks the particle’s motion trajectory with high accuracy. Furthermore, an electrically insulated electrode is attached to the grounded enclosure and connected to a current shunt in order to detect low frequency ion currents: The shunt measuring system’s sensitivity is in the range of 10 nA at a measuring bandwidth of bw = DC…1 MHz. Currents of charge carriers, which are generated at the particle’s tip migrate through the gas gap to the electrode and can be recorded by the current shunt. All recorded PD signals are analyzed in order to identify characteristic properties of different particles. This includes e.g. repetition rates and amplitudes of successive pulses, characteristic frequency ranges and detected signal energy of single PD pulses. Concluding, an advanced understanding of underlying physical phenomena particle motion in direct electric field can be derived.

Keywords: current shunt, free moving particles, high-speed imaging, HVDC-GIS, UHF

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Authors: Sylvie Michel, François Cocula

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Digital agriculture is an approach that exploits information and communication technologies. These encompass data acquisition tools like mobile applications, satellites, sensors, connected devices, and smartphones. Additionally, it involves transfer and storage technologies such as 3G/4G coverage, low-bandwidth terrestrial or satellite networks, and cloud-based systems. Furthermore, embedded or remote processing technologies, including drones and robots for process automation, along with high-speed communication networks accessible through supercomputers, are integral components of this approach. While farm-level adoption studies regarding digital agricultural technologies have emerged in recent years, they remain relatively limited in comparison to other agricultural practices. To bridge this gap, this study delves into understanding farmers' intention to adopt digital tools, employing the technology, organization, environment framework. A qualitative research design encompassed semi-structured interviews, totaling fifteen in number, conducted with key stakeholders both prior to and following the 2020-2021 COVID-19 lockdowns in France. Subsequently, the interview transcripts underwent thorough thematic content analysis, and the data and verbatim were triangulated for validation. A coding process aimed to systematically organize the data, ensuring an orderly and structured classification. Our research extends its contribution by delineating sub-dimensions within each primary dimension. A total of nine sub-dimensions were identified, categorized as follows: perceived usefulness for communication, perceived usefulness for productivity, and perceived ease of use constitute the first dimension; technological resources, financial resources, and human capabilities constitute the second dimension, while market pressure, institutional pressure, and the COVID-19 situation constitute the third dimension. Furthermore, this analysis enriches the TOE framework by incorporating entrepreneurial orientation as a moderating variable. Managerial orientation emerges as a pivotal factor influencing adoption intention, with producers acknowledging the significance of utilizing digital sales support tools to combat "greenwashing" and elevate their overall brand image. Specifically, it illustrates that producers recognize the potential of digital tools in time-saving and streamlining sales processes, leading to heightened productivity. Moreover, it highlights that the intent to adopt digital sales support tools is influenced by a market mimicry effect. Additionally, it demonstrates a negative association between the intent to adopt these tools and the pressure exerted by institutional partners. Finally, this research establishes a positive link between the intent to adopt digital sales support tools and economic fluctuations, notably during the COVID-19 pandemic. The adoption of sales support tools in agriculture is a multifaceted challenge encompassing three dimensions and nine sub-dimensions. The research delves into the adoption of digital farming technologies at the farm level through the TOE framework. This analysis provides significant insights beneficial for policymakers, stakeholders, and farmers. These insights are instrumental in making informed decisions to facilitate a successful digital transition in agriculture, effectively addressing sector-specific challenges.

Keywords: adoption, digital agriculture, e-commerce, TOE framework

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Authors: Francesca Crivellari, Nicholas Mavrogiannis, Zachary Gagnon

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Portable diagnostic methods have become increasingly important for a number of different purposes: point-of-care screening in developing nations, environmental contamination studies, bio/chemical warfare agent detection, and end-user use for commercial health monitoring. The cheapest and most portable methods currently available are paper-based – lateral flow and dipstick methods are widely available in drug stores for use in pregnancy detection and blood glucose monitoring. These tests are successful because they are cheap to produce, easy to use, and require minimally invasive sampling. While adequate for their intended uses, in the realm of blood-borne pathogens and numerous cancers, these paper-based methods become unreliable, as they lack the nM/pM sensitivity currently achieved by clinical diagnostic methods. Clinical diagnostics, however, utilize techniques involving surface plasmon resonance (SPR) and enzyme-linked immunosorbent assays (ELISAs), which are expensive and unfeasible in terms of portability. To develop a better, competitive biosensor, we must reduce the cost of one, or increase the sensitivity of the other. Electric fields are commonly utilized in microfluidic devices to manipulate particles, biomolecules, and cells. Applications in this area, however, are primarily limited to interfaces formed between immiscible interfaces. Miscible, liquid-liquid interfaces are common in microfluidic devices, and are easily reproduced with simple geometries. Here, we demonstrate the use of electrical fields at liquid-liquid electrical interfaces, known as fluidic dielectrophoresis, (fDEP) for biodetection in a microfluidic device. In this work, we apply an AC electric field across concurrent laminar streams with differing conductivities and permittivities to polarize the interface and induce a discernible, near-immediate, frequency-dependent interfacial tilt. We design this aqueous electrical interface, which becomes the biosensing “substrate,” to be intelligent – it “moves” only when a target of interest is present. This motion requires neither labels nor expensive electrical equipment, so the biosensor is inexpensive and portable, yet still capable of sensitive detection. Nanoparticles, due to their high surface-area-to-volume ratio, are often incorporated to enhance detection capabilities of schemes like SPR and fluorimetric assays. Most studies currently investigate binding at an immobilized solid-liquid or solid-gas interface, where particles are adsorbed onto a planar surface, functionalized with a receptor to create a reactive substrate, and subsequently flushed with a fluid or gas with the relevant analyte. These typically involve many preparation and rinsing steps, and are susceptible to surface fouling. Our microfluidic device is continuously flowing and renewing the “substrate,” and is thus not subject to fouling. In this work, we demonstrate the ability to electrokinetically detect biomolecules binding to functionalized nanoparticles at liquid-liquid interfaces using fDEP. In biotin-streptavidin experiments, we report binding detection limits on the order of 1-10 pM, without amplifying signals or concentrating samples. We also demonstrate the ability to detect this interfacial motion, and thus the presence of binding, using impedance spectroscopy, allowing this scheme to become non-optical, in addition to being label-free.

Keywords: biodetection, dielectrophoresis, microfluidics, nanoparticles

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Authors: Wafaa Hasan

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In May of 2022, Palestinian parents in Toronto, Canada, became aware that educators and staff in the Toronto District School Board were attempting to include the International Holocaust and Remembrance Definition of Antisemitism (IHRA) in The Child Abuse and Neglect Policy of the largest school board in Canada, The Toronto District School Board (TDSB). The idea was that if students were to express any form of antisemitism, as defined by the IHRA, then an investigation could follow with Child Protective Services (CPS). That is, the student’s parents could be reported to the state and investigated for custodial rights to their children. The TDSB has set apparent goals for “Decolonizing Pedagogy” (“TDSB Equity Leadership Competencies”), Culturally Responsive and Relevant Practices (CRRP) and inclusive education. These goals promote the centering of colonized, racialized and marginalized voices. CRRP cannot be effective without the application of anti-racist and settler colonial analyses. In order for CRRP to be effective, school boards need a comprehensive understanding of the ways in which the vilification of Palestinians operates through anti-indigenous and white supremacist systems and logic. Otherwise, their inclusion will always be in tension with the inclusion of settler colonial agendas and worldviews. Feminist maternalism frames racial mothering as degenerate (viewing the contributions of racialized students and their parents as products of primitive and violent cultures) and also indirectly inhibits the actualization of the tenets of CRRP and inclusive education through its extensions into the welfare state and public education. The contradiction between the tenets of CRRP and settler colonial systems of erasure and repression is resolved by the continuation of tactics to 1) force assimilation, 2) punish those who push back on that assimilation and 3) literally fragment familial and community structures of racialized students, educators and parents. This paper draws on interdisciplinary (history, philosophy, anthropology) critiques of white feminist “maternalism” from the 19th century onwards in North America and Europe (Jacobs, Weber), as well as “anti-racist education” theory (Dei), and more specifically,” culturally responsive learning,” (Muhammad) and “bandwidth” pedagogy theory (Verschelden) to make its claims. This research contributes to vibrant debates about anti-racist and decolonial pedagogies in public education systems globally. This paper also documents first-hand interviews and experiences of diasporic Palestinian mothers and motherhoods and situates their experiences within longstanding histories of white feminist maternalist (and eugenicist) politics. This informal qualitative data from "participatory conversations" (Swain) is situated within a set of formal interview data collected with Palestinian women in the West Bank (approved by the McMaster University Humanities Research Ethics Board) relating to white feminist maternalism in the peace and dialogue industry.

Keywords: decolonial feminism, maternal feminism, anti-racist pedagogies, settler colonial studies, motherhood studies, pedagogy theory, cultural theory

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

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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

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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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Authors: Leila Safazadeh, Brad Berron

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Self-assembled monolayers have tremendous impact in interfacial science, due to the unique opportunity they offer to tailor surface properties. Low-density self-assembled monolayers are an emerging class of monolayers where the environment-interfacing portion of the adsorbate has a greater level of conformational freedom when compared to traditional monolayer chemistries. This greater range of motion and increased spacing between surface-bound molecules offers new opportunities in tailoring adsorption phenomena in sensing systems. In particular, we expect low-density surfaces to offer a unique opportunity to intercalate surface bound ligands into the secondary structure of protiens and other macromolecules. Additionally, as many conventional sensing surfaces are built upon gold surfaces (SPR or QCM), these surfaces must be compatible with gold substrates. Here, we present the first stable method of generating low-density self assembled monolayer surfaces on gold for the analysis of their interactions with protein targets. Our approach is based on the 2:1 addition of thiol-yne chemistry to develop new classes of y-shaped adsorbates on gold, where the environment-interfacing group is spaced laterally from neighboring chemical groups. This technique involves an initial deposition of a crystalline monolayer of 1,10 decanedithiol on the gold substrate, followed by grafting of a low-packed monolayer on through a photoinitiated thiol-yne reaction in presence of light. Orthogonality of the thiol-yne chemistry (commonly referred to as a click chemistry) allows for preparation of low-density monolayers with variety of functional groups. To date, carboxyl, amine, alcohol, and alkyl terminated monolayers have been prepared using this core technology. Results from surface characterization techniques such as FTIR, contact angle goniometry and electrochemical impedance spectroscopy confirm the proposed low chain-chain interactions of the environment interfacing groups. Reductive desorption measurements suggest a higher stability for the click-LDMs compared to traditional SAMs, along with the equivalent packing density at the substrate interface, which confirms the proposed stability of the monolayer-gold interface. In addition, contact angle measurements change in the presence of an applied potential, supporting our description of a surface structure which allows the alkyl chains to freely orient themselves in response to different environments. We are studying the differences in protein adsorption phenomena between well packed and our loosely packed surfaces, and we expect this data will be ready to present at the GRC meeting. This work aims to contribute biotechnology science in the following manner: Molecularly imprinted polymers are a promising recognition mode with several advantages over natural antibodies in the recognition of small molecules. However, because of their bulk polymer structure, they are poorly suited for the rapid diffusion desired for recognition of proteins and other macromolecules. Molecularly imprinted monolayers are an emerging class of materials where the surface is imprinted, and there is not a bulk material to impede mass transfer. Further, the short distance between the binding site and the signal transduction material improves many modes of detection. My dissertation project is to develop a new chemistry for protein-imprinted self-assembled monolayers on gold, for incorporation into SPR sensors. Our unique contribution is the spatial imprinting of not only physical cues (seen in current imprinted monolayer techniques), but to also incorporate complementary chemical cues. This is accomplished through a photo-click grafting of preassembled ligands around a protein template. This conference is important for my development as a graduate student to broaden my appreciation of the sensor development beyond surface chemistry.

Keywords: low-density self-assembled monolayers, thiol-yne click reaction, molecular imprinting

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