Experimental and analytical investigation of refrigerant and lubricant migration

The off-cycle refrigerant mass migration has a direct influence on the on-cycle performance since compressor energy is necessary to redistribute the refrigerant mass. No studies, as of today, are available in the open literature which experimentally measured the lubricant migration within a refrigeration system during cycling or stop/start transients. Therefore, experimental procedures measuring the refrigerant and lubricant migration through the major components of a refrigeration system during stop/start transients were developed and implemented. Results identifying the underlying physics are presented. The refrigerant and lubricant migration of an R134a automotive A/C system-utilizing a fixed orifice tube, minichannel condenser, plate and fin evaporator, U-tube type accumulator and fixed displacement compressor-was measured across five sections divided by ball valves. Using the Quick-Closing Valve Technique (QCVT) combined with the Remove and Weigh Technique (RWT) using liquid nitrogen as the condensing agent resulted in a measurement uncertainty of 0.4 percent regarding the total refrigerant mass in the system. The determination of the lubricant mass distribution was achieved by employing three different techniques-Remove and Weigh, Mix and Sample, and Flushing. To employ the Mix and Sample Technique a device-called the Mix and Sample Device-was built. A method to separate the refrigerant and lubricant was developed with an accuracy-after separation-of 0.04 grams of refrigerant left in the lubricant. When applying the three techniques, the total amount of lubricant mass in the system was determined to within two percent. The combination of measurement results-infrared photography and high speed and real time videography-provide unprecedented insight into the mechanisms of refrigerant and lubricant migration during stop-start operation. During the compressor stop period, the primary refrigerant mass migration is caused by, and follows, the diminishing pressure difference across the expansion device. The secondary refrigerant migration is caused by a pressure gradient as a result of thermal nonequilibrium within the system and causes only vapor phase refrigerant migration. Lubricant migration is proportional to the refrigerant mass during the primary refrigerant mass migration. During the secondary refrigerant mass migration lubricant is not migrating. The start-up refrigerant mass migration is caused by an imbalance of the refrigerant mass flow rates across the compressor and expansion device. The higher compressor refrigerant mass flow rate was a result of the entrainment of foam into the U-tube of the accumulator. The lubricant mass migration during the start-up was not proportional to the refrigerant mass migration. The presence of water condensate on the evaporator affected the refrigerant mass migration during the compressor stop period. Caused by an evaporative cooling effect the evaporator held 56 percent of the total refrigerant mass in the system after three minutes of compressor stop time-compared to 25 percent when no water condensate was present on the evaporator coil. Foam entrainment led to a faster lubricant and refrigerant mass migration out of the accumulator than liquid entrainment through the hole at the bottom of the U-tube. The latter was observed for when water condensate was present on the evaporator coil because-as a result of the higher amount of refrigerant mass in the evaporator before start-up-the entrainment of foam into the U-tube of the accumulator ceased before the steady state refrigerant mass distribution was reached.

Biomarkers of Nitrosative Stress: Development and validation of a new analytical method for 3-Nitrotyrosine quantification

Background: The nitration of tyrosine residues in proteins is associated with nitrosative stress, resulting in the formation of 3-nitrotyrosine (3-NT). 3-NT levels in biological samples have been associated with numerous physiological and pathological conditions. For this reason, several attempts have been made in order to develop methods that accurately quantify 3-NT in biological samples. Regarding chromatographic methods, they seem to be very accurate, showing very good sensibility and specificity. However, accurate quantification of this molecule, which is present at very low concentrations both at physiological and pathological states, is always a complex task and a target of intense research. Objectives: We aimed to develop a simple, rapid, low-cost and sensitive 3-NT quantification method for use in medical laboratories as an additional tool for diagnosis and/or treatment monitoring of a wide range of pathologies. We also aimed to evaluate the performance of the HPLC-based method developed here in a wide range of biological matrices. Material and methods: All experiments were performed on a Hitachi LaChrom Elite® HPLC system and separation was carried out using a Lichrocart® 250-4 Lichrospher 100 RP-18 (5μm) column. The method was further validated according to ICH guidelines. The biological matrices tested were serum, whole blood, urine, B16 F-10 melanoma cell line, growth medium conditioned with the same cell line, bacterial and yeast suspensions. Results: From all the protocols tested, the best results were obtained using 0.5% CH3COOH:MeOH:H2O (15:15:70) as the mobile phase, with detection at wavelengths 215, 276 and 356 nm, at 25ºC, and using a flow rate of 1 mL/min. By using this protocol, it was possible to obtain a linear calibration curve (correlation coefficient = 1), limits of detection and quantification in the order of ng/mL, and a short analysis time (<15 minutes per sample). Additionally, the developed protocol allowed the successful detection and quantification of 3-NT in all biological matrices tested, with detection at 356 nm. Conclusion: The method described in this study, which was successfully developed and validated for 3-NT quantification, is simple, cheap and fast, rendering it suitable for analysis in a wide range of biological matrices.

Advanced Analytical Microscopy at the Nanoscale: Applications in Wide Bandgap and Solid Oxide Fuel Cell Materials

The atomic-level structure and chemistry of materials ultimately dictate their observed macroscopic properties and behavior. As such, an intimate understanding of these characteristics allows for better materials engineering and improvements in the resulting devices. In our work, two material systems were investigated using advanced electron and ion microscopy techniques, relating the measured nanoscale traits to overall device performance. First, transmission electron microscopy and electron energy loss spectroscopy (TEM-EELS) were used to analyze interfacial states at the semiconductor/oxide interface in wide bandgap SiC microelectronics. This interface contains defects that significantly diminish SiC device performance, and their fundamental nature remains generally unresolved. The impacts of various microfabrication techniques were explored, examining both current commercial and next-generation processing strategies. In further investigations, machine learning techniques were applied to the EELS data, revealing previously hidden Si, C, and O bonding states at the interface, which help explain the origins of mobility enhancement in SiC devices. Finally, the impacts of SiC bias temperature stressing on the interfacial region were explored. In the second system, focused ion beam/scanning electron microscopy (FIB/SEM) was used to reconstruct 3D models of solid oxide fuel cell (SOFC) cathodes. Since the specific degradation mechanisms of SOFC cathodes are poorly understood, FIB/SEM and TEM were used to analyze and quantify changes in the microstructure during performance degradation. Novel strategies for microstructure calculation from FIB-nanotomography data were developed and applied to LSM-YSZ and LSCF-GDC composite cathodes, aged with environmental contaminants to promote degradation. In LSM-YSZ, migration of both La and Mn cations to the grain boundaries of YSZ was observed using TEM-EELS. Few substantial changes however, were observed in the overall microstructure of the cells, correlating with a lack of performance degradation induced by the H2O. Using similar strategies, a series of LSCF-GDC cathodes were analyzed, aged in H2O, CO2, and Cr-vapor environments. FIB/SEM observation revealed considerable formation of secondary phases within these cathodes, and quantifiable modifications of the microstructure. In particular, Cr-poisoning was observed to cause substantial byproduct formation, which was correlated with drastic reductions in cell performance.

Le dopage entre performance et perception du corps en Espagne

The need to address such a complex issue as doping is given by a concern, not only in the sport context, but also in the public arena. Numerous examples illustrate the growing scientific interest and greater media coverage. However, there are few studies with deep and rigorous treatment of historical perspective. Even fewer examples can be found in the Spanish context. The purpose of this text is to offer an analytical approach to the history of doping in Spain. The example of doping cases of Spanish athletes published in the sports newspapers will be used to define the evidences for establishing the analysis with historical and objective rigor and to question the vision of a ?pure? and ?good? sport.

Removal of BrO3 − from drinking water samples using newly developed agricultural waste-based activated carbon and its determination by ultra-performance liquid chromatography-mass spectrometry

Activated carbon was prepared from date pits via chemical activation with H3PO4. The effects of activating agent concentration and activation temperature on the yield and surface area were studied. The optimal activated carbon was prepared at 450 °C using 55 % H3PO4. The prepared activated carbon was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric-differential thermal analysis, and Brunauer, Emmett, and Teller (BET) surface area. The prepared date pit-based activated carbon (DAC) was used for the removal of bromate (BrO3 −). The concentration of BrO3 − was determined by ultra-performance liquid chromatography-mass tandem spectrometry (UPLC-MS/MS). The experimental equilibrium data for BrO3 − adsorption onto DAC was well fitted to the Langmuir isotherm model and showed maximum monolayer adsorption capacity of 25.64 mg g−1. The adsorption kinetics of BrO3 − adsorption was very well represented by the pseudo-first-order equation. The analytical application of DAC for the analysis of real water samples was studied with very promising results.

Experimental and analytical methodologies for predicting peak loads on building envelopes and roofing systems

The performance of building envelopes and roofing systems significantly depends on accurate knowledge of wind loads and the response of envelope components under realistic wind conditions. Wind tunnel testing is a well-established practice to determine wind loads on structures. For small structures much larger model scales are needed than for large structures, to maintain modeling accuracy and minimize Reynolds number effects. In these circumstances the ability to obtain a large enough turbulence integral scale is usually compromised by the limited dimensions of the wind tunnel meaning that it is not possible to simulate the low frequency end of the turbulence spectrum. Such flows are called flows with Partial Turbulence Simulation.^ In this dissertation, the test procedure and scaling requirements for tests in partial turbulence simulation are discussed. A theoretical method is proposed for including the effects of low-frequency turbulences in the post-test analysis. In this theory the turbulence spectrum is divided into two distinct statistical processes, one at high frequencies which can be simulated in the wind tunnel, and one at low frequencies which can be treated in a quasi-steady manner. The joint probability of load resulting from the two processes is derived from which full-scale equivalent peak pressure coefficients can be obtained. The efficacy of the method is proved by comparing predicted data derived from tests on large-scale models of the Silsoe Cube and Texas-Tech University buildings in Wall of Wind facility at Florida International University with the available full-scale data.^ For multi-layer building envelopes such as rain-screen walls, roof pavers, and vented energy efficient walls not only peak wind loads but also their spatial gradients are important. Wind permeable roof claddings like roof pavers are not well dealt with in many existing building codes and standards. Large-scale experiments were carried out to investigate the wind loading on concrete pavers including wind blow-off tests and pressure measurements. Simplified guidelines were developed for design of loose-laid roof pavers against wind uplift. The guidelines are formatted so that use can be made of the existing information in codes and standards such as ASCE 7-10 on pressure coefficients on components and cladding.^

A graduate piano recital : an analytical study

The purpose of this thesis is to provide a historical and musical analysis that illustrates characteristic features of musical compositions from the Baroque, Classical, Romantic, and Twentieth century styles. The structural analysis of the pieces reveal the evolution in the musical expression regarding line, texture, form, and the technical skills employed by the composers through polyphonic, homophonic, and twelve-tone procedures. The works of this recital represent four different styles: The prelude and fugue among the important forms of the Baroque style; the sonata embodying the principles of balance and unity of the Classical style; the etude and waltz as representative of the Romantic style; and the nocturne as an illustration of the transformation of the melody, harmony, and rhythm in the music of the 20thcentury.

Sleep and academic performance of Portuguese teenagers

Abstract: Sleep has numerous important functions in the body, such as consolidation of memory, concentration and learning. Changes in sleep cycles in adolescents lead to sleep deprivation with consequences to academic performance. Our research question was What are the sleep habits that influence school performance (study environment, study planning, study method, reading skills, motivation to study, overall school performance) in adolescents? We aimed to identify sleep habits predictors of the quality of school performance in adolescents. Research Methods: Crosssectional analytical study. Data were collected through a self-administered questionnaire with socio-demographic questions, sleep habits and school performance scale. The sample consisted of 380 students between 7th and 9th grade, with an average age of 13.56 ± 1.23 years in the school year 2011/2012, from a 2nd and 3rd Cycle Basic School of the municipality of Viseu, Portugal. Findings: School performance in adolescents was associated with better subjective quality of sleep (p=0.000), with longer sleep duration (p=0.000), with watching tv/video before sleep (p=0.000), with the habit of studying before bedtime (p=0.012), with no computer use (p=0.013) and with reading habits before bed (p=0.000). School performance was also associated with adolescents who reported not feeling sleepy during class. The teenagers who sleep more and better, and who watch tv/video, study, do not use computers, and who read before going to bed, have a better school performance.

Optimization and validation of an analytical method for determination of glyphosate and AMPA in apples using SPE-HPLC with post-column derivatization.

2008

Exploring New Material and Analytical Method for Characterization and Conservation of Artifacts

In this dissertation, we focus on developing new green bio-based gel systems and evaluating both the cleaning efficiency and the release of residues on the treated surface, different micro or no destructive techniques, such as optical microscopy, TGA, FTIR spectroscopy, HS-SPME and micro-Spatially Offset Raman spectroscopy (micro-SORS) were tested, proposing advanced analytical protocols. In the first part, a ternary PHB-DMC/BD gel system composed by biodiesel, dimethyl carbonate and poly-3 hydroxybutyrate was developed for cleaning of wax-based coatings applied on indoor bronze. The evaluation of the cleaning efficacy of the gel was carried out on a standard bronze sample which covered a layer of beeswax by restores of Opificio delle Pietre Dure in Florence, and a real case precious indoor bronze sculpture Pulpito della Passione attributed to Donatello. Results obtained by FTIR analysis showed an efficient removal of the wax coating. In the second part, two new kinds of combined gels based on electrospun tissues (PVA and nylon) and PHB-GVL gel were developed for removal of dammar varnish from painting. The electrospun tissue combined gels exhibited good mechanical property, and showed good efficient in cleaning over normal gel. In the third part, green deep eutectic solvent which consists urea and choline chloride was proposed to produce the rigid gel with agar for the removal of proteinaceous coating from oil painting. Rabbit glue and whole egg decorated oil painting mock-ups were selected for evaluating its cleaning efficiency, results obtained by ATR analysis showed the DES-agar gel has good cleaning performance. Furthermore, we proposed micro-SORS as a valuable alternative non-destructive method to explore the DES diffusion on painting mock-up. As a result, the micro-SORS was successful applied for monitoring the liquid diffusion behavior in painting sub-layer, providing a great and useful instrument for noninvasive residues detection in the conservation field.

Development of new immunochemical and spectroscopic analytical methods for the characterization and conservation of works of art

Cultural heritage is constituted by complex and heterogenous materials, such as paintings but also ancient remains. However, all ancient materials are exposed to external environment and their interaction produces different changes due to chemical, physical and biological phenomena. The organic fraction, especially the proteinaceous one, has a crucial role in all these materials: in archaeology proteins reveal human habits, in artworks they disclose technics and help for a correct restoration. For these reasons the development of methods that allow the preservation of the sample as much as possible and a deeper knowledge of the deterioration processes is fundamental. The research activities presented in this PhD thesis have been focused on the development of new immunochemical and spectroscopic approaches in order to detect and identify organic substances in artistic and archaeological samples. Organic components could be present in different cultural heritage materials as constituent element (e.g., binders in paintings, collagen in bones) and their knowledge is fundamental for a complete understanding of past life, degradation processes and appropriate restauration approaches. The combination of immunological approach with a chemiluminescence detection and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry allowed a sensitive and selective localization of collagen and elements in ancient bones and teeth. Near-infrared spectrometer and hyper spectral imaging have been applied in combination with chemometric data analysis as non-destructive methods for bones prescreening for the localization of collagen. Moreover, an investigation of amino acids in enamel has been proposed, in order to clarify teeth biomolecules survival overtime through the optimization and application of High-Performance Liquid Chromatography on modern and ancient enamel powder. New portable biosensors were developed for ovalbumin identification in paintings, thanks to the combination between biocompatible Gellan gel and electro-immunochemical sensors, to extract and identify painting binders with the contact only between gel and painting and between gel and electrodes.

Analytical approaches for the measurement of sulfide in biological and pharmaceutical fields

Hydrogen sulfide (H2S) is a widely recognized gasotransmitter, with key roles in physiological and pathological processes. The accurate quantification of H2S and reactive sulfur species (RSS) may hold important implications for the diagnosis and prognosis of various diseases. However, H2S species quantification in biological matrices is still a challenge. Among the sulfide detection methods, monobromobimane (MBB) derivatization coupled with reversed phase high-performance liquid chromatography (RP-HPLC) is one of the most reported. However, it is characterized by a complex preparation and time-consuming process, which may alter the actual H2S level. Moreover, quantitative validation has still not been described based on a survey of previously published works. In this study, we developed and validated an improved analytical protocol for the MBB RP-HPLC method. Main parameters like MBB concentration, temperature, reaction time, and sample handling were optimized, and the calibration method was further validated using leave-one-out cross-validation (CV) and tested in a clinical setting. The method shows high sensitivity and allows the quantification of H2S species, with a limit of detection (LOD) of 0.5 µM and a limit of quantification (LOQ) of 0.9 µM. Additionally, this model was successfully applied in measurements of H2S levels in the serum of patients subjected to inhalation with vapors rich in H2S. In addition, a properly procedure was established for H2S release with the modified MBB HPLC-FLD method. The proposed analytical approach demonstrated the slow-release kinetics of H2S from the multilayer Silk-Fibroin scaffolds with the combination of different H2S donor’s concentration with respect to the weight of PLGA nanofiber. In the end, some efforts were made on sulfide measurements by using size exclusion chromatography fluorescence/ultraviolet detection and inductively coupled plasma-mass spectrometry (SEC-FLD/UV-ICP/MS). It’s intended as a preliminary study in order to define the feasibility of a separation-detection-quantification platform to analyze biological samples and quantify sulfur species.

Novel methods of state estimation and parameter identification for high-performance motorcycles

This research activity aims at providing a reliable estimation of particular state variables or parameters concerning the dynamics and performance optimization of a MotoGP-class motorcycle, integrating the classical model-based approach with new methodologies involving artificial intelligence. The first topic of the research focuses on the estimation of the thermal behavior of the MotoGP carbon braking system. Numerical tools are developed to assess the instantaneous surface temperature distribution in the motorcycle's front brake discs. Within this application other important brake parameters are identified using Kalman filters, such as the disc convection coefficient and the power distribution in the disc-pads contact region. Subsequently, a physical model of the brake is built to estimate the instantaneous braking torque. However, the results obtained with this approach are highly limited by the knowledge of the friction coefficient (μ) between the disc rotor and the pads. Since the value of μ is a highly nonlinear function of many variables (namely temperature, pressure and angular velocity of the disc), an analytical model for the friction coefficient estimation appears impractical to establish. To overcome this challenge, an innovative hybrid solution is implemented, combining the benefit of artificial intelligence (AI) with classical model-based approach. Indeed, the disc temperature estimated through the thermal model previously implemented is processed by a machine learning algorithm that outputs the actual value of the friction coefficient thus improving the braking torque computation performed by the physical model of the brake. Finally, the last topic of this research activity regards the development of an AI algorithm to estimate the current sideslip angle of the motorcycle's front tire. While a single-track motorcycle kinematic model and IMU accelerometer signals theoretically enable sideslip calculation, the presence of accelerometer noise leads to a significant drift over time. To address this issue, a long short-term memory (LSTM) network is implemented.

Genetic Aspects Of Athletic Performance: The African Runners Phenomenon.

The current dominance of African runners in long-distance running is an intriguing phenomenon that highlights the close relationship between genetics and physical performance. Many factors in the interesting interaction between genotype and phenotype (eg, high cardiorespiratory fitness, higher hemoglobin concentration, good metabolic efficiency, muscle fiber composition, enzyme profile, diet, altitude training, and psychological aspects) have been proposed in the attempt to explain the extraordinary success of these runners. Increasing evidence shows that genetics may be a determining factor in physical and athletic performance. But, could this also be true for African long-distance runners? Based on this question, this brief review proposed the role of genetic factors (mitochondrial deoxyribonucleic acid, the Y chromosome, and the angiotensin-converting enzyme and the alpha-actinin-3 genes) in the amazing athletic performance observed in African runners, especially the Kenyans and Ethiopians, despite their environmental constraints.