Search results for: symmetric cryptography
5 Solution Thermodynamics, Photophysical and Computational Studies of TACH2OX, a C-3 Symmetric 8-Hydroxyquinoline: Abiotic Siderophore Analogue of Enterobactin
Authors: B. K. Kanungo, Monika Thakur, Minati Baral
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8-hydroxyquinoline, (8HQ), experiences a renaissance due to its utility as a building block in metallosupramolecular chemistry and its versatile use of its derivatives in various fields of analytical chemistry, materials science, and pharmaceutics. It forms stable complexes with a variety of metal ions. Assembly of more than one such unit to form a polydentate chelator enhances its coordinating ability and the related properties due to the chelate effect resulting in high stability constant. Keeping in view the above, a nonadentate chelator N-[3,5-bis(8-hydroxyquinoline-2-amido)cyclohexyl]-8-hydroxyquinoline-2-carboxamide, (TACH2OX), containing a central cis,cis-1,3,5-triaminocyclohexane appended to three 8-hydroxyquinoline at 2-position through amide linkage is developed, and its solution thermodynamics, photophysical and Density Functional Theory (DFT) studies were undertaken. The synthesis of TACH2OX was carried out by condensation of cis,cis-1,3,5-triaminocyclohexane, (TACH) with 8‐hydroxyquinoline‐2‐carboxylic acid. The brown colored solid has been fully characterized through melting point, infrared, nuclear magnetic resonance, electrospray ionization mass and electronic spectroscopy. In solution, TACH2OX forms protonated complexes below pH 3.4, which consecutively deprotonates to generate trinegative ion with the rise of pH. Nine protonation constants for the ligand were obtained that ranges between 2.26 to 7.28. The interaction of the chelator with two trivalent metal ion Fe3+ and Al3+ were studied in aqueous solution at 298 K. The metal-ligand formation constants (ML) obtained by potentiometric and spectrophotometric method agree with each other. The protonated and hydrolyzed species were also detected in the system. The in-silico studies of the ligand, as well as the complexes including their protonated and deprotonated species assessed by density functional theory technique, gave an accurate correlation with each observed properties such as the protonation constants, stability constants, infra-red, nmr, electronic absorption and emission spectral bands. The nature of electronic and emission spectral bands in terms of number and type were ascertained from time-dependent density functional theory study and the natural transition orbitals (NTO). The global reactivity indices parameters were used for comparison of the reactivity of the ligand and the complex molecules. The natural bonding orbital (NBO) analysis could successfully describe the structure and bonding of the metal-ligand complexes specifying the percentage of contribution in atomic orbitals in the creation of molecular orbitals. The obtained high value of metal-ligand formation constants indicates that the newly synthesized chelator is a very powerful synthetic chelator. The minimum energy molecular modeling structure of the ligand suggests that the ligand, TACH2OX, in a tripodal fashion firmly coordinates to the metal ion as hexa-coordinated chelate displaying distorted octahedral geometry by binding through three sets of N, O- donor atoms, present in each pendant arm of the central tris-cyclohexaneamine tripod.Keywords: complexes, DFT, formation constant, TACH2OX
Procedia PDF Downloads 1504 Innovative Technologies of Distant Spectral Temperature Control
Authors: Leonid Zhukov, Dmytro Petrenko
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Optical thermometry has no alternative in many cases of industrial most effective continuous temperature control. Classical optical thermometry technologies can be used on available for pyrometers controlled objects with stable radiation characteristics and transmissivity of the intermediate medium. Without using temperature corrections, it is possible in the case of a “black” body for energy pyrometry and the cases of “black” and “grey” bodies for spectral ratio pyrometry or with using corrections – for any colored bodies. Consequently, with increasing the number of operating waves, optical thermometry possibilities to reduce methodical errors significantly expand. That is why, in recent 25-30 years, research works have been reoriented on more perfect spectral (multicolor) thermometry technologies. There are two physical material substances, i.e., substance (controlled object) and electromagnetic field (thermal radiation), to be operated in optical thermometry. Heat is transferred by radiation; therefore, radiation has the energy, entropy, and temperature. Optical thermometry was originating simultaneously with the developing of thermal radiation theory when the concept and the term "radiation temperature" was not used, and therefore concepts and terms "conditional temperatures" or "pseudo temperature" of controlled objects were introduced. They do not correspond to the physical sense and definitions of temperature in thermodynamics, molecular-kinetic theory, and statistical physics. Launched by the scientific thermometric society, discussion about the possibilities of temperature measurements of objects, including colored bodies, using the temperatures of their radiation is not finished. Are the information about controlled objects transferred by their radiation enough for temperature measurements? The positive and negative answers on this fundamental question divided experts into two opposite camps. Recent achievements of spectral thermometry develop events in her favour and don’t leave any hope for skeptics. This article presents the results of investigations and developments in the field of spectral thermometry carried out by the authors in the Department of Thermometry and Physics-Chemical Investigations. The authors have many-year’s of experience in the field of modern optical thermometry technologies. Innovative technologies of optical continuous temperature control have been developed: symmetric-wave, two-color compensative, and based on obtained nonlinearity equation of spectral emissivity distribution linear, two-range, and parabolic. Тhe technologies are based on direct measurements of physically substantiated and proposed by Prof. L. Zhukov, radiation temperatures with the next calculation of the controlled object temperature using this radiation temperatures and corresponding mathematical models. Тhe technologies significantly increase metrological characteristics of continuous contactless and light-guide temperature control in energy, metallurgical, ceramic, glassy, and other productions. For example, under the same conditions, the methodical errors of proposed technologies are less than the errors of known spectral and classical technologies in 2 and 3-13 times, respectively. Innovative technologies provide quality products obtaining at the lowest possible resource-including energy costs. More than 600 publications have been published on the completed developments, including more than 100 domestic patents, as well as 34 patents in Australia, Bulgaria, Germany, France, Canada, the USA, Sweden, and Japan. The developments have been implemented in the enterprises of USA, as well as Western Europe and Asia, including Germany and Japan.Keywords: emissivity, radiation temperature, object temperature, spectral thermometry
Procedia PDF Downloads 983 Design and Implementation of a Hardened Cryptographic Coprocessor with 128-bit RISC-V Core
Authors: Yashas Bedre Raghavendra, Pim Vullers
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This study presents the design and implementation of an abstract cryptographic coprocessor, leveraging AMBA(Advanced Microcontroller Bus Architecture) protocols - APB (Advanced Peripheral Bus) and AHB (Advanced High-performance Bus), to enable seamless integration with the main CPU(Central processing unit) and enhance the coprocessor’s algorithm flexibility. The primary objective is to create a versatile coprocessor that can execute various cryptographic algorithms, including ECC(Elliptic-curve cryptography), RSA(Rivest–Shamir–Adleman), and AES (Advanced Encryption Standard) while providing a robust and secure solution for modern secure embedded systems. To achieve this goal, the coprocessor is equipped with a tightly coupled memory (TCM) for rapid data access during cryptographic operations. The TCM is placed within the coprocessor, ensuring quick retrieval of critical data and optimizing overall performance. Additionally, the program memory is positioned outside the coprocessor, allowing for easy updates and reconfiguration, which enhances adaptability to future algorithm implementations. Direct links are employed instead of DMA(Direct memory access) for data transfer, ensuring faster communication and reducing complexity. The AMBA-based communication architecture facilitates seamless interaction between the coprocessor and the main CPU, streamlining data flow and ensuring efficient utilization of system resources. The abstract nature of the coprocessor allows for easy integration of new cryptographic algorithms in the future. As the security landscape continues to evolve, the coprocessor can adapt and incorporate emerging algorithms, making it a future-proof solution for cryptographic processing. Furthermore, this study explores the addition of custom instructions into RISC-V ISE (Instruction Set Extension) to enhance cryptographic operations. By incorporating custom instructions specifically tailored for cryptographic algorithms, the coprocessor achieves higher efficiency and reduced cycles per instruction (CPI) compared to traditional instruction sets. The adoption of RISC-V 128-bit architecture significantly reduces the total number of instructions required for complex cryptographic tasks, leading to faster execution times and improved overall performance. Comparisons are made with 32-bit and 64-bit architectures, highlighting the advantages of the 128-bit architecture in terms of reduced instruction count and CPI. In conclusion, the abstract cryptographic coprocessor presented in this study offers significant advantages in terms of algorithm flexibility, security, and integration with the main CPU. By leveraging AMBA protocols and employing direct links for data transfer, the coprocessor achieves high-performance cryptographic operations without compromising system efficiency. With its TCM and external program memory, the coprocessor is capable of securely executing a wide range of cryptographic algorithms. This versatility and adaptability, coupled with the benefits of custom instructions and the 128-bit architecture, make it an invaluable asset for secure embedded systems, meeting the demands of modern cryptographic applications.Keywords: abstract cryptographic coprocessor, AMBA protocols, ECC, RSA, AES, tightly coupled memory, secure embedded systems, RISC-V ISE, custom instructions, instruction count, cycles per instruction
Procedia PDF Downloads 702 Evaluating Forecasting Strategies for Day-Ahead Electricity Prices: Insights From the Russia-Ukraine Crisis
Authors: Alexandra Papagianni, George Filis, Panagiotis Papadopoulos
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The liberalization of the energy market and the increasing penetration of fluctuating renewables (e.g., wind and solar power) have heightened the importance of the spot market for ensuring efficient electricity supply. This is further emphasized by the EU’s goal of achieving net-zero emissions by 2050. The day-ahead market (DAM) plays a key role in European energy trading, accounting for 80-90% of spot transactions and providing critical insights for next-day pricing. Therefore, short-term electricity price forecasting (EPF) within the DAM is crucial for market participants to make informed decisions and improve their market positioning. Existing literature highlights out-of-sample performance as a key factor in assessing EPF accuracy, with influencing factors such as predictors, forecast horizon, model selection, and strategy. Several studies indicate that electricity demand is a primary price determinant, while renewable energy sources (RES) like wind and solar significantly impact price dynamics, often lowering prices. Additionally, incorporating data from neighboring countries, due to market coupling, further improves forecast accuracy. Most studies predict up to 24 steps ahead using hourly data, while some extend forecasts using higher-frequency data (e.g., half-hourly or quarter-hourly). Short-term EPF methods fall into two main categories: statistical and computational intelligence (CI) methods, with hybrid models combining both. While many studies use advanced statistical methods, particularly through different versions of traditional AR-type models, others apply computational techniques such as artificial neural networks (ANNs) and support vector machines (SVMs). Recent research combines multiple methods to enhance forecasting performance. Despite extensive research on EPF accuracy, a gap remains in understanding how forecasting strategy affects prediction outcomes. While iterated strategies are commonly used, they are often chosen without justification. This paper contributes by examining whether the choice of forecasting strategy impacts the quality of day-ahead price predictions, especially for multi-step forecasts. We evaluate both iterated and direct methods, exploring alternative ways of conducting iterated forecasts on benchmark and state-of-the-art forecasting frameworks. The goal is to assess whether these factors should be considered by end-users to improve forecast quality. We focus on the Greek DAM using data from July 1, 2021, to March 31, 2022. This period is chosen due to significant price volatility in Greece, driven by its dependence on natural gas and limited interconnection capacity with larger European grids. The analysis covers two phases: pre-conflict (January 1, 2022, to February 23, 2022) and post-conflict (February 24, 2022, to March 31, 2022), following the Russian-Ukraine conflict that initiated an energy crisis. We use the mean absolute percentage error (MAPE) and symmetric mean absolute percentage error (sMAPE) for evaluation, as well as the Direction of Change (DoC) measure to assess the accuracy of price movement predictions. Our findings suggest that forecasters need to apply all strategies across different horizons and models. Different strategies may be required for different horizons to optimize both accuracy and directional predictions, ensuring more reliable forecasts.Keywords: short-term electricity price forecast, forecast strategies, forecast horizons, recursive strategy, direct strategy
Procedia PDF Downloads 71 Drug Reaction with Eosinophilia and Systemic Symptoms (Dress) Syndrome Presenting as Multi-Organ Failure
Authors: Keshari Shrestha, Philip Vatterott
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Introduction: Drug reaction with eosinophilia and systemic symptoms (DRESS) syndrome is a rare and potentially fatal drug-related syndrome. DRESS classically presents with a diffuse maculopapular rash, fevers, and eosinophilia more than three weeks after drug exposure. DRESS can present with multi-organ involvement, with liver damage being the most common and severe. Pulmonary involvement is a less common manifestation and is associated with poor clinical outcomes. Chest imaging is often nonspecific, and symptoms can range from mild cough to acute respiratory distress syndrome (ARDS) . This is a case of a 49-year-old female with a history of recent clostridium difficile colitis status post treatment with oral vancomycin who presented with rash, acute liver and kidney failure, as well as diffuse nodular alveolar lung opacities concerning for DRESS syndrome with multi-organ involvement. Clinical Course: This patient initially presented to an outside hospital with clostridium difficile colitis, acute liver injury, and acute kidney injury. She developed a desquamating maculopapular rash in the setting of recent oral vancomycin, meloxicam, and furosemide initiation. She was hospitalized on two additional occasions with worsening altered mental status, liver injury, and acute kidney injury and was initiated on intermittent hemodialysis. Notably, she was found to have systemic eosinophilia (4100 cells/microliter) several weeks prior. She was transferred to this institution for further management where she was found to have encephalopathy, jaundice, lower extremity edema, and diffuse bilateral rhonchorous breath sounds on pulmonary examination. The patient was started on methylprednisolone for suspected DRESS syndrome. She underwent an evaluation for alternative causes of her organ failure. Her workup included a negative infectious, autoimmune, metabolic, toxic, and malignant work-up. Abdominal computed tomography (CT) and ultrasound were remarkable for evidence of hepatic steatosis and possible cirrhotic morphology. Additionally, a chest CT demonstrated diffuse and symmetric nodular alveolar lung opacities with peripheral sparing not consistent with acute respiratory distress syndrome or edema. Ultimately, her condition continued to decline, and she required intubation on several occasions. On hospital day 25 she succumbed to distributive shock in the setting of probable sepsis and multi-organ failure. Discussion: DRESS syndrome occurs in 1 in 1,000 to 10,000 patients with a mortality rate of around 10%. Anti-convulsant, anti-bacterial, anti-viral, and sulfonamide drugs are the most common drugs implicated in the development of DRESS syndrome; however, the list of offending agents is extensive . The diagnosis of DRESS syndrome is made after excluding other causes of disease such as infectious and autoimmune etiologies. The RegiSCAR scoring system is used to diagnose DRESS syndrome with 2-3 points indicating possible disease, 4-5 probable disease, and >5 definite disease. This patient scored a 7 on the RegiSCAR scale for eosinophilia, rash, organ involvement, and exclusion of other causes (infectious and autoimmune). While the pharmacologic trigger in this case is unknown, it is speculated to be caused by vancomycin, meloxicam, or furosemide due to the favorable timeline of initiation. Despite aggressive treatment, DRESS syndrome can often be fatal. Because of this, early diagnosis and treatment of patients with suspected DRESS syndrome is imperative.Keywords: drug reaction with eosinophilia and systemic symptoms, multi-organ failure, pulmonary involvement, renal failure
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