IMPROVED SAMPLE INTRODUCTION SYSTEMS FOR INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY AND THEIR APPLICATION TO THE ANALYSIS OF SIMPLE AND COMPLEX MATRICES

The objective of this thesis is to explore new and improved methods for greater sample introduction efficiency and enhanced analytical performance with inductively coupled plasma optical emission spectrometry (ICP-OES). Three projects are discussed in which the capabilities and applications of ICP-OES are expanded: 1. In the first project, a conventional ultrasonic nebuliser was modified to replace the heater/condenser with an infrared heated pre-evaporation tube. In continuation from previous works with pre-evaporation, the current work investigated the effects of heating with infrared block and rope heaters on two different ICP-OES instruments. Comparisons were made between several methods and setups in which temperatures were varied. By monitoring changes to sensitivity, detection limit, precision, and robustness, and analyzing two certified reference materials, a method with improved sample introduction efficiency and comparable analytical performance to a previous method was established. 2. The second project involved improvements to a previous work in which a multimode sample introduction system (MSIS) was modified by inserting a pre-evaporation tube between the MSIS and torch. The new work focused on applying an infrared heated ceramic rope for pre-evaporation. This research was conducted in all three MSIS modes (nebulisation mode, hydride generation mode, and dual mode) and on two different ICP-OES instruments, and comparisons were made between conventional setups in terms of sensitivity, detection limit, precision, and robustness. By tracking both hydride-forming and non-hydride forming elements, the effects of heating in combination with hydride generation were probed. Finally, optimal methods were validated by analysis of two certified reference materials. 3. A final project was completed in collaboration with ZincNyx Energy Solutions. This project sought to develop a method for the overall analysis of a 12 M KOH zincate fuel, which is used in green energy backup systems. By employing various techniques including flow injection analysis and standard additions, a final procedure was formulated for the verification of K concentration, as well as the measurement of additives (Al, Fe, Mg, In, Si), corrosion products (such C from CO₃²¯), and Zn particles both in and filtered from solution. Furthermore, the effects of exposing the potassium zincate electrolyte fuel to air were assessed.

Study of the tracking performance of a liquid Argon detector based on a novel optical imaging concept

The Deep Underground Neutrino Experiment (DUNE) is a long-baseline accelerator experiment designed to make a significant contribution to the study of neutrino oscillations with unprecedented sensitivity. The main goal of DUNE is the determination of the neutrino mass ordering and the leptonic CP violation phase, key parameters of the three-neutrino flavor mixing that have yet to be determined. An important component of the DUNE Near Detector complex is the System for on-Axis Neutrino Detection (SAND) apparatus, which will include GRAIN (GRanular Argon for Interactions of Neutrinos), a novel liquid Argon detector aimed at imaging neutrino interactions using only scintillation light. For this purpose, an innovative optical readout system based on Coded Aperture Masks is investigated. This dissertation aims to demonstrate the feasibility of reconstructing particle tracks and the topology of CCQE (Charged Current Quasi Elastic) neutrino events in GRAIN with such a technique. To this end, the development and implementation of a reconstruction algorithm based on Maximum Likelihood Expectation Maximization was carried out to directly obtain a three-dimensional distribution proportional to the energy deposited by charged particles crossing the LAr volume. This study includes the evaluation of the design of several camera configurations and the simulation of a multi-camera optical system in GRAIN.

Magnesium-deficient High-fat Diet: Effects On Adiposity, Lipid Profile And Insulin Sensitivity In Growing Rats.

To determine if magnesium deficiency aggravates the effects of a high-fat diet in growing rats in terms of obesity, lipid profile and insulin resistance. The study population comprised 48 newly weaned male Wistar Hannover rats distributed into four groups according to diet, namely, control group (CT; n = 8), control diet provided ad libitum; pair-feeding control group (PF; n = 16), control diet but in the same controlled amount as animals that received high-fat diets; high-fat diet group (HF; n = 12), and magnesium-deficient high-fat diet group (HFMg(-); n = 12). The parameters investigated were adiposity index, lipid profile, magnesium status, insulin sensitivity and the phosphorylation of proteins involved in the insulin-signaling pathway, i.e. insulin receptor β-subunit, insulin receptor substrate 1 and protein kinase B. The HF and HFMg(-) groups were similar regarding gain in body mass, adiposity index and lipid profile, but were significantly different from the PF group. The HFMg(-) group exhibited alterations in magnesium homeostasis as revealed by the reduction in urinary and bone concentrations of the mineral. No inter-group differences were observed regarding glucose homeostasis. Protein phosphorylation in the insulin-signaling pathway was significantly reduced in the high-fat groups compared with the control groups, demonstrating that the intake of fat-rich diets increased insulin resistance, a syndrome that was aggravated by magnesium deficiency. Under the experimental conditions tested, the intake of a magnesium-deficient high-fat diet led to alterations in the insulin-signaling pathway and, consequently, increased insulin resistance.

Optical And Nonoptical Aids For Reading And Writing In Individuals With Acquired Low Vision.

To evaluate the use of optical and nonoptical aids during reading and writing activities in individuals with acquired low vision. This study was performed using descriptive and cross-sectional surveys. The data collection instrument was created with structured questions that were developed from an exploratory study and a previous test based on interviews, and it evaluated the following variables: personal characteristics, use of optical and nonoptical aids, and activities that required the use of optical and nonoptical aids. The study population included 30 subjects with acquired low vision and visual acuities of 20/200-20/400. Most subjects reported the use of some optical aids (60.0%). Of these 60.0%, the majority (83.3%) cited spectacles as the most widely used optical aid. The majority (63.3%) of subjects also reported the use of nonoptical aids, the most frequent ones being letter magnification (68.4%), followed by bringing the objects closer to the eyes (57.8%). Subjects often used more than one nonoptical aid. The majority of participants reported the use of optical and nonoptical aids during reading activities, highlighting the use of spectacles, magnifying glasses, and letter magnification; however, even after the use of these aids, we found that the subjects often needed to read the text more than once to understand it. During writing activities, all subjects reported the use of optical aids, while most stated that they did not use nonoptical aids for such activities.

Applications Of Visual Evoked Potentials And Fourier-domain Optical Coherence Tomography In Parkinson's Disease: A Controlled Study.

The goal of this cross-sectional observational study was to quantify the pattern-shift visual evoked potentials (VEP) and the thickness as well as the volume of retinal layers using optical coherence tomography (OCT) across a cohort of Parkinson's disease (PD) patients and age-matched controls. Forty-three PD patients and 38 controls were enrolled. All participants underwent a detailed neurological and ophthalmologic evaluation. Idiopathic PD cases were included. Cases with glaucoma or increased intra-ocular pressure were excluded. Patients were assessed by VEP and high-resolution Fourier-domain OCT, which quantified the inner and outer thicknesses of the retinal layers. VEP latencies and the thicknesses of the retinal layers were the main outcome measures. The mean age, with standard deviation (SD), of the PD patients and controls were 63.1 (7.5) and 62.4 (7.2) years, respectively. The patients were predominantly in the initial Hoehn-Yahr (HY) disease stages (34.8% in stage 1 or 1.5, and 55.8 % in stage 2). The VEP latencies and the thicknesses as well as the volumes of the retinal inner and outer layers of the groups were similar. A negative correlation between the retinal thickness and the age was noted in both groups. The thickness of the retinal nerve fibre layer (RNFL) was 102.7 μm in PD patients vs. 104.2 μm in controls. The thicknesses of retinal layers, VEP, and RNFL of PD patients were similar to those of the controls. Despite the use of a representative cohort of PD patients and high-resolution OCT in this study, further studies are required to establish the validity of using OCT and VEP measurements as the anatomic and functional biomarkers for the evaluation of retinal and visual pathways in PD patients.

Effects Of Misalignments In The Retinal Nerve Fiber Layer Thickness Measurements With Spectral Domain Optical Coherence Tomography.

Purpose. To investigate misalignments (MAs) on retinal nerve fiber layer thickness (RNFLT) measurements obtained with Cirrus(©) SD-OCT. Methods. This was a retrospective, observational, cross-sectional study. Twenty-seven healthy and 29 glaucomatous eyes of 56 individuals with one normal exam and another showing MA were included. MAs were defined as an improper alignment of vertical vessels in the en face image. MAs were classified in complete MA (CMA) and partial MA (PMA), according to their site: 1 (superior, outside the measurement ring (MR)), 2 (superior, within MR), 3 (inferior, within MR), and 4 (inferior, outside MR). We compared RNFLT measurements of aligned versus misaligned exams in all 4 sectors, in the superior area (sectors 1 + 2), inferior area (sectors 3 + 4), and within the measurement ring (sectors 2 + 3). Results. RNFLT measurements at 12 clock-hour of eyes with MAs in the superior area (sectors 1 + 2) were significantly lower than those obtained in the same eyes without MAs (P = 0.043). No significant difference was found in other areas (sectors 1 + 2 + 3 + 4, sectors 3 + 4, and sectors 2 + 3). Conclusion. SD-OCT scans with superior MAs may present lower superior RNFLT measurements compared to aligned exams.

Measurement Of The Hydrodynamic Radius Of Quantum Dots By Fluorescence Correlation Spectroscopy Excluding Blinking.

One of the most important properties of quantum dots (QDs) is their size. Their size will determine optical properties and in a colloidal medium their range of interaction. The most common techniques used to measure QD size are transmission electron microscopy (TEM) and X-ray diffraction. However, these techniques demand the sample to be dried and under a vacuum. This way any hydrodynamic information is excluded and the preparation process may alter even the size of the QDs. Fluorescence correlation spectroscopy (FCS) is an optical technique with single molecule sensitivity capable of extracting the hydrodynamic radius (HR) of the QDs. The main drawback of FCS is the blinking phenomenon that alters the correlation function implicating in a QD apparent size smaller than it really is. In this work, we developed a method to exclude blinking of the FCS and measured the HR of colloidal QDs. We compared our results with TEM images, and the HR obtained by FCS is higher than the radius measured by TEM. We attribute this difference to the cap layer of the QD that cannot be seen in the TEM images.

Comparison between the 1% and 2% ibopamine provocative test in primary open-angle glaucoma patients: sensitivity, specificity and tolerability

PURPOSE: To compare intraocular pressure (IOP) rise in normal individuals and primary open-angle glaucoma patients and the safety and efficacy of ibopamine eye drops in different concentrations as a provocative test for glaucoma. METHODS: Glaucoma patients underwent (same eye) the ibopamine provocative test with two concentrations, 1% and 2%, in a random sequence at least 3 weeks apart, but not more than 3 months. The normal individuals were randomly submitted to one of the concentrations of ibopamine (1% and 2%). The test was considered positive if there was an IOP rise greater than 3 or 4 mmHg at 30 or 45 minutes to test which subset of the test has the best sensitivity (Se)/specificity (Sp). RESULTS: There was no statistically significant difference in any of the IOP measurements, comparing 1% with 2% ibopamine. The IOP was significantly higher at 30 and 45 minutes with both concentrations (p<0.001). The best sensitivity/specificity ratio was achieved with the cutoff point set as greater than 3 mmHg at 45 minutes with 2% ibopamine (area under the ROC curve: 0.864, Se: 84.6%; Sp:73.3%). All patients described a slight burning after ibopamine's instillation. CONCLUSION: 2% ibopamine is recommended as a provocative test for glaucoma. Because both concentrations have similar ability to rise IOP, 1% ibopamine may be used to treat ocular hypotony.

Sensitivity to halothane and its relationship to the development of PSE (Pale, Soft, Exudative) meat in female lineage broilers

This work aimed to evaluate female lineage broilers for halothane sensitivity and for their susceptibility to the subsequent development of PSE meat. The halothane test was carried out in an anesthetic chamber with 3.0% halothane. The unconscious birds were examined for leg muscle rigidity. If one or both legs became extended and rigid, the birds were classified as halothane sensitive (HAL+), while unresponsive birds were classified as halothane negative (HAL-). The results showed that of 298 birds aged 42 days old, 95.6% were HAL- and 4.4% were HAL+. A sample of pectoralis major muscle was collected from HAL- (n=105) and HAL+ (n=13) birds. The pH and breast fillet color were determined at 4ºC, 24 hours post-mortem. Interestingly, only 2.5% of HAL+ birds displayed PSE meat characteristics compared to 12.7% of HAL- individuals. The halothane test demonstrated that female lineage broilers displayed very little sensitivity towards halothane, indicating that the development of PSE meat is related to other environmental factors.

Reserve carbohydrates and lipids from the seeds of four tropical tree species with different sensitivity to desiccation

Considering the importance of water content for the conservation and storage of seeds, and the involvement of soluble carbohydrates and lipids for embryo development, a comparative study was carried out among the seeds of Inga vera (ingá), Eugenia uniflora (pitanga), both classified as recalcitrant, and Caesalpinia echinata (brazilwood) and Erythrina speciosa (mulungu), considered as orthodox seeds. Low concentrations of cyclitols (0.3-0.5%), raffinose family oligosaccharides (ca. 0.05%) and unsaturated fatty acids (0-19%) were found in the seeds of ingá and pitanga, while larger amounts of cyclitols (2-3%) and raffinose (4.6-13%) were found in brazilwood and mulungu, respectively. These results, in addition to higher proportions of unsaturated fatty acids (53-71%) in orthodox seeds, suggested that sugars and lipids played important role in water movement, protecting the embryo cell membranes against injuries during dehydration.

Variations in the sensitivity of different primers for detecting Wolbachia in Anastrepha (diptera: tephritidae)

Wolbachia are endosymbiont bacteria of the family Rickettsiacea that are widespread in invertebrates and occur between 20% and 60% of Neotropical insects. These bacteria are responsible for reproductive phenomena such as cytoplasmic incompatibility, male killing, feminization and parthenogenesis. Supergroups A and B of Wolbachia are common in insects and can be identified using primers for 16S rDNA, ftsZ and wsp; these primers vary in their ability to detect Wolbachia. The ftsZ primer was the first primer used to detect Wolbachia in Anastrepha fruit flies. The primers for 16S rDNA, ftsZ and wsp and the corresponding PCR conditions have been optimized to study the distribution of Wolbachia and their effect on the biology of Anastrepha in Brazil. In this work, we examined the ability of these primers to detect Wolbachia in Anastrepha populations from three regions in the State of São Paulo, southeastern Brazil. All of the samples were positive for Wolbachia supergroup A when screened with primers for 16S A rDNA and wsp A; the wsp B primer also gave a positive result, indicating cross-reactivity. The ftsZ primer showed a poor ability to detect Wolbachia in Anastrepha and generated false negatives in 44.9% of the samples. These findings indicate that reliable PCR detection of Wolbachia requires the use of primers for 16S rDNA and wsp to avoid cross-reactions and false negatives, and that the ftsZ primer needs to be redesigned to improve its selectivity.

The optical analysis of the abdominal wall using the biospeckle after implants of polypropylene mesh in rats

PURPOSE: To evaluate an experimental animal model to study the abdominal tissue activity considering its interaction with a polypropylene mesh, through the use of one of the optical phenomena of light Laser, the biospeckle. METHODS: Fifty Wistar male rats were divided into four groups: Group 1: ten animals not submitted to surgery; Group 2: ten animals submitted to surgery without polypropylene mesh; Group 3: 20 animals submitted to surgery followed by the mesh placement; Group 4: (sham) with ten animals. None of the animals presented post surgical complications being submitted to the optical tests at the 20th postoperative day. RESULTS: The analysis from the biospeckle tests, comparing the medians and standard deviations with T Student test, indicated that no significative difference was observed on the abdominal wall tissue activity in the four groups considered, with and without polypropylene mesh prosthesis implantation. CONCLUSION: The animal model is viable and the biospeckle open ways for a great number of experiments to be developed in evaluating tissue activity.

Psychophysical measurements of luminance and chromatic spatial and temporal contrast sensitivity in Duchenne muscular dystrophy

In children with Duchenne muscular dystrophy, color vision losses have been related to dystrophin deletions downstream of exon 30, which affect a dystrophin isoform, Dp260, present in the retina. To further evaluate visual function in DMD children, we measured spatial, temporal, and chromatic red-green and blue-yellow contrast sensitivity in two groups of DMD children with gene deletion downstream and upstream of exon 30. Psychophysical spatial contrast sensitivity was measured for low, middle, and high spatial frequencies with achromatic gratings and for low and middle frequencies with red-green and blue-yellow chromatic gratings. Temporal contrast sensitivity was also measured with achromatic stimuli. A reduction in sensitivity at all spatial luminance contrasts was found for the DMD patients with deletion downstream of exon 30. Similar results were found for temporal luminance contrast sensitivity. Red-green chromatic contrast sensitivity was reduced in DMD children with deletion downstream of exon 30, whereas blue-yellow chromatic contrast sensitivity showed no significant differences. We conclude that visual function is impaired in DMD children. Furthermore, we report a genotype-phenotype relationship because the visual impairment occurred in children with deletion downstream but not upstream of exon 30, affecting the retinal isoform of dystrophin Dp260.