Mass spectrometry parameters optimization for the 46 multiclass pesticides determination in strawberries with gas chromatography ion-trap tandem mass spectrometry

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET),maximum excitation energy or “q” value (q), and isolationmass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit.Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

The influence of count's number in myocardium in the determination of reproducible parameters in Gated-SPECT studies simulated with GATE

Myocardial Perfusion Gated Single Photon Emission Tomography (Gated-SPET) imaging is used for the combined evaluation of myocardial perfusion and left ventricular (LV). The purpose of this study is to evaluate the influence of the total number of counts acquired from myocardium, in the calculation of myocardial functional parameters using routine software procedures. Methods: Gated-SPET studies were simulated using Monte Carlo GATE package and NURBS phantom. Simulated data were reconstructed and processed using the commercial software package Quantitative Gated-SPECT. The Bland-Altman and Mann-Whitney-Wilcoxon tests were used to analyze the influence of the number of total counts in the calculation of LV myocardium functional parameters. Results: In studies simulated with 3MBq in the myocardium there were significant differences in the functional parameters: Left ventricular ejection fraction (LVEF), end-systolic volume (ESV), Motility and Thickness; between studies acquired with 15s/projection and 30s/projection. Simulations with 4.2MBq show significant differences in LVEF, end-diastolic volume (EDV) and Thickness. Meanwhile in the simulations with 5.4MBq and 8.4MBq the differences were statistically significant for Motility and Thickness. Conclusion: The total number of counts per simulation doesn't significantly interfere with the determination of Gated-SPET functional parameters using the administered average activity of 450MBq to 5.4MBq in myocardium.

Evaluation of atmospheric deposition and patterns of polycyclic aromatic hydrocarbons in façades of historic monuments of Oporto (Portugal)

Atmospheric pollution by motor vehicles is considered a relevant source of damage to architectural heritage. Thus the aim of this work was to assess the atmospheric depositions and patterns of polycyclic aromatic hydrocarbons (PAHs) in façades of historical monuments. Eighteen PAHs (16 PAHs considered by US EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in thin black layers collected from façades of two historical monuments: Hospital Santo António and Lapa Church (Oporto, Portugal). Scanning electron microscopy (SEM) was used for morphological and elemental characterisation of thin black layers; PAHs were quantified by microwave-assisted extraction combined with liquid chromatography (MAE-LC). The thickness of thin black layers were 80–110 μm and they contained significant levels of iron, sulfur, calcium and phosphorus. Total concentrations of 18 PAHs ranged from 7.74 to 147.92 ng/g (mean of 45.52 ng/g) in thin black layers of Hospital Santo António, giving a range three times lower than at Lapa Church (5.44– 429.26 ng/g; mean of 110.25 ng/g); four to six rings compounds accounted at both monuments approximately for 80–85% of ΣPAHs. The diagnostic ratios showed that traffic emissions were significant source of PAHs in thin black layers. Composition profiles of PAHs in thin black layers of both monuments were similar to those of ambient air, thus showing that air pollution has a significant impact on the conditions and stone decay of historical building façades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere.

Properties of tantalum oxynitride thin films produced by magnetron sputtering: the influence of processing parameters

The main purpose of this work is to present and to interpret the change of structure and physical properties of tantalum oxynitride (TaNxOy) thin films, produced by dc reactive magnetron sputtering, by varying the processing parameters. A set of TaNxOy films was prepared by varying the reactive gases flow rate, using a N2/O2 gas mixture with a concentration ratio of 17:3. The different films, obtained by this process, exhibited significant differences. The obtained composition and the interpretation of X-ray diffraction results, shows that, depending on the partial pressure of the reactive gases, the films are: essentially dark grey metallic, when the atomic ratio (N + O)/Ta < 0.1, evidencing a tetragonal β-Ta structure; grey-brownish, when 0.1 < (N + O)/Ta < 1, exhibiting a face-centred cubic (fcc) TaN-like structure; and transparent oxide-type, when (N + O)/Ta > 1, evidencing the existence of Ta2O5, but with an amorphous structure. These transparent films exhibit refractive indexes, in the visible region, always higher than 2.0. The wear resistance of the films is relatively good. The best behaviour was obtained for the films with (N + O)/Ta ≈ 0.5 and (N + O)/Ta ≈ 1.3.

Tissue composition and density impact on the clinical parameters for 125I prostate implants dosimetry

The MCNPX code was used to calculate the TG-43U1 recommended parameters in water and prostate tissue in order to quantify the dosimetric impact in 30 patients treated with (125)I prostate implants when replacing the TG-43U1 formalism parameters calculated in water by a prostate-like medium in the planning system (PS) and to evaluate the uncertainties associated with Monte Carlo (MC) calculations. The prostate density was obtained from the CT of 100 patients with prostate cancer. The deviations between our results for water and the TG-43U1 consensus dataset values were -2.6% for prostate V100, -13.0% for V150, and -5.8% for D90; -2.0% for rectum V100, and -5.1% for D0.1; -5.0% for urethra D10, and -5.1% for D30. The same differences between our water and prostate results were all under 0.3%. Uncertainties estimations were up to 2.9% for the gL(r) function, 13.4% for the F(r,θ) function and 7.0% for Λ, mainly due to seed geometry uncertainties. Uncertainties in extracting the TG-43U1 parameters in the MC simulations as well as in the literature comparison are of the same order of magnitude as the differences between dose distributions computed for water and prostate-like medium. The selection of the parameters for the PS should be done carefully, as it may considerably affect the dose distributions. The seeds internal geometry uncertainties are a major limiting factor in the MC parameters deduction.

PV system modeling by five parameters and in situ test

This paper focuses on a novel formalization for assessing the five parameter modeling of a photovoltaic cell. An optimization procedure is used as a feasibility problem to find the parameters tuned at the open circuit, maximum power, and short circuit points in order to assess the data needed for plotting the I-V curve. A comparison with experimental results is presented for two monocrystalline PV modules.

Effect of technical parameters on dose and image quality in a computed radiography system

The discovery of X-rays was undoubtedly one of the greatest stimulus for improving the efficiency in the provision of healthcare services. The ability to view, non-invasively, inside the human body has greatly facilitated the work of professionals in diagnosis of diseases. The exclusive focus on image quality (IQ), without understanding how they are obtained, affect negatively the efficiency in diagnostic radiology. The equilibrium between the benefits and the risks are often forgotten. It is necessary to adopt optimization strategies to maximize the benefits (image quality) and minimize risk (dose to the patient) in radiological facilities. In radiology, the implementation of optimization strategies involves an understanding of images acquisition process. When a radiographer adopts a certain value of a parameter (tube potential [kVp], tube current-exposure time product [mAs] or additional filtration), it is essential to know its meaning and impact of their variation in dose and image quality. Without this, any optimization strategy will be a failure. Worldwide, data show that use of x-rays has been increasingly frequent. In Cabo Verde, we note an effort by healthcare institutions (e.g. Ministry of Health) in equipping radiological facilities and the recent installation of a telemedicine system requires purchase of new radiological equipment. In addition, the transition from screen-films to digital systems is characterized by a raise in patient exposure. Given that this transition is slower in less developed countries, as is the case of Cabo Verde, the need to adopt optimization strategies becomes increasingly necessary. This study was conducted as an attempt to answer that need. Although this work is about objective evaluation of image quality, and in medical practice the evaluation is usually subjective (visual evaluation of images by radiographer / radiologist), studies reported a correlation between these two types of evaluation (objective and subjective) [5-7] which accredits for conducting such studies. The purpose of this study is to evaluate the effect of exposure parameters (kVp and mAs) when using additional Cooper (Cu) filtration in dose and image quality in a Computed Radiography system.

In-situ X-ray diffraction studies during growth of Ni-Ti shape memory alloy films and their complementary ex-situ characterization

Shape Memory Alloy (SMA) Ni-Ti films have attracted much interest as functional and smart materials due to their unique properties. However, there are still important issues unresolved like formation of film texture and its control as well as substrate effects. Thus, the main challenge is not only the control of the microstructure, including stoichiometry and precipitates, but also the identification and control of the preferential orientation since it is a crucial factor in determining the shape memory behaviour. The aim of this PhD thesis is to study the optimisation of the deposition conditions of films of Ni-Ti in order to obtain the material fully crystallized at the end of the deposition, and to establish a clear relationship between the substrates and texture development. In order to achieve this objective, a two-magnetron sputter deposition chamber has been used allowing to heat and to apply a bias voltage to the substrate. It can be mounted into the six-circle diffractometer of the Rossendorf Beamline (ROBL) at the European Synchrotron Radiation Facility (ESRF), Grenoble, France, enabling an in-situ characterization by X-ray diffraction(XRD) of the films during their growth and annealing. The in-situ studies enable us to identify the different steps of the structural evolution during deposition with a set of parameters as well as to evaluate the effect of changing parameters on the structural characteristics of the deposited film. Besides the in-situ studies, other complementary ex-situ characterization techniques such as XRD at a laboratory source, Rutherford backscattering spectroscopy(RBS), Auger electron spectroscopy (AES), cross-sectional transmission electron microscopy (X-TEM), scanning electron microscopy (SEM), and electrical resistivity (ER) measurements during temperature cycling have been used for a fine structural characterization. In this study, mainly naturally and thermally oxidized Si(100) substrates, TiN buffer layers with different thicknesses (i.e. the TiN topmost layer crystallographic orientation is thickness dependent) and MgO(100) single crystals were used as substrates. The chosen experimental procedure led to a controlled composition and preferential orientation of the films. The type of substrate plays an important role for the texture of the sputtered Ni-Ti films and according to the ER results, the distinct crystallographic orientations of the Ni-Ti films influence their phase transformation characteristics.

The influence of number of counts in the myocardium in the determination of reproducible functional parameters in gated-SPECT studies simulated with GATE

Myocardial perfusion gated-single photon emission computed tomography (gated-SPECT) imaging is used for the combined evaluation of myocardial perfusion and left ventricular (LV) function. The aim of this study is to analyze the influence of counts/pixel and concomitantly the total counts in the myocardium for the calculation of myocardial functional parameters. Material and methods: Gated-SPECT studies were performed using a Monte Carlo GATE simulation package and the NCAT phantom. The simulations of these studies use the radiopharmaceutical 99mTc-labeled tracers (250, 350, 450 and 680MBq) for standard patient types, effectively corresponding to the following activities of myocardium: 3, 4.2, 5.4-8.2MBq. All studies were simulated using 15 and 30s/projection. The simulated data were reconstructed and processed by quantitative-gated-SPECT software, and the analysis of functional parameters in gated-SPECT images was done by using Bland-Altman test and Mann-Whitney-Wilcoxon test. Results: In studies simulated using different times (15 and 30s/projection), it was noted that for the activities for full body: 250 and 350MBq, there were statistically significant differences in parameters Motility and Thickness. For the left ventricular ejection fraction (LVEF), end-systolic volume (ESV) it was only for 250MBq, and 350MBq in the end-diastolic volume (EDV), while the simulated studies with 450 and 680MBq showed no statistically significant differences for global functional parameters: LVEF, EDV and ESV. Conclusion: The number of counts/pixel and, concomitantly, the total counts per simulation do not significantly interfere with the determination of gated-SPECT functional parameters, when using the administered average activity of 450MBq, corresponding to the 5.4MBq of the myocardium, for standard patient types.

Influence of the cohesive law parameters on the strength prediction of adhesively-bonded joints

Adhesive joints are largely employed nowadays as a fast and effective joining process. The respective techniques for strength prediction have also improved over the years. Cohesive Zone Models (CZM’s) coupled to Finite Element Method (FEM) analyses surpass the limitations of stress and fracture criteria and allow modelling damage. CZM’s require the energy release rates in tension (Gn) and shear (Gs) and respective fracture energies in tension (Gnc) and shear (Gsc). Additionally, the cohesive strengths (tn0 for tension and ts0 for shear) must also be defined. In this work, the influence of the CZM parameters of a triangular CZM used to model a thin adhesive layer is studied, to estimate their effect on the predictions. Some conclusions were drawn for the accuracy of the simulation results by variations of each one of these parameters.

PV system modeling by five parameters and in Situ test

This paper focuses on a novel formalization for assessing the five parameter modeling of a photovoltaic cell. An optimization procedure is used as a feasibility problem to find the parameters tuned at the open circuit, maximum power, and short circuit points in order to assess the data needed for plotting the I-V curve. A comparison with experimental results is presented for two monocrystalline PV modules.

Cutting forces and wear analysis of Si3N4 diamond coated tools in high speed machining

Si3N4 tools were coated with a thin diamond film using a Hot-Filament Chemical Vapour Deposition (HFCVD) reactor, in order to machining a grey cast iron. Wear behaviour of these tools in high speed machining was the main subject of this work. Turning tests were performed with a combination of cutting speeds of 500, 700 and 900 m min−1, and feed rates of 0.1, 0.25 and 0.4 mm rot−1, remaining constant the depth of cut of 1 mm. In order to evaluate the tool behaviour during the turning tests, cutting forces were analyzed being verified a significant increase with feed rate. Diamond film removal occurred for the most severe set of cutting parameters. It was also observed the adhesion of iron and manganese from the workpiece to the tool. Tests were performed on a CNC lathe provided with a 3-axis dynamometer. Results were collected and registered by homemade software. Tool wear analysis was achieved by a Scanning Electron Microscope (SEM) provided with an X-ray Energy Dispersive Spectroscopy (EDS) system. Surface analysis was performed by a profilometer.

Weather parameters and nosocomial bloodstream infection: a case-referent study

OBJECTIVE To evaluate if temperature and humidity influenced the etiology of bloodstream infections in a hospital from 2005 to 2010.METHODS The study had a case-referent design. Individual cases of bloodstream infections caused by specific groups or pathogens were compared with several references. In the first analysis, average temperature and humidity values for the seven days preceding collection of blood cultures were compared with an overall “seven-days moving average” for the study period. The second analysis included only patients with bloodstream infections. Several logistic regression models were used to compare different pathogens and groups with respect to the immediate weather parameters, adjusting for demographics, time, and unit of admission.RESULTS Higher temperatures and humidity were related to the recovery of bacteria as a whole (versus fungi) and of gram-negative bacilli. In the multivariable models, temperature was positively associated with the recovery of gram-negative bacilli (OR = 1.14; 95%CI 1.10;1.19) or Acinetobacter baumannii (OR = 1.26; 95%CI 1.16;1.37), even after adjustment for demographic and admission data. An inverse association was identified for humidity.CONCLUSIONS The study documented the impact of temperature and humidity on the incidence and etiology of bloodstream infections. The results correspond with those from ecological studies, indicating a higher incidence of gram-negative bacilli during warm seasons. These findings should guide policies directed at preventing and controlling healthcare-associated infections.

Optimisation of exposure parameters for spinal curvature measurements in paediatric radiography

This review aims to identify strategies to optimise radiography practice using digital technologies, for full spine studies on paediatrics focusing particularly on methods used to diagnose and measure severity of spinal curvatures. The literature search was performed on different databases (PubMed, Google Scholar and ScienceDirect) and relevant websites (e.g., American College of Radiology and International Commission on Radiological Protection) to identify guidelines and recent studies focused on dose optimisation in paediatrics using digital technologies. Plain radiography was identified as the most accurate method. The American College of Radiology (ACR) and European Commission (EC) provided two guidelines that were identified as the most relevant to the subject. The ACR guidelines were updated in 2014; however these guidelines do not provide detailed guidance on technical exposure parameters. The EC guidelines are more complete but are dedicated to screen film systems. Other studies provided reviews on the several exposure parameters that should be included for optimisation, such as tube current, tube voltage and source-to-image distance; however, only explored few of these parameters and not all of them together. One publication explored all parameters together but this was for adults only. Due to lack of literature on exposure parameters for paediatrics, more research is required to guide and harmonise practice.

Evaluation of the influence of testing parameters on the melt flow index of thermoplastics

The main goals of the present work are the evaluation of the influence of several variables and test parameters on the melt flow index (MFI) of thermoplastics, and the determination of the uncertainty associated with the measurements. To evaluate the influence of test parameters on the measurement of MFI the design of experiments (DOE) approach has been used. The uncertainty has been calculated using a "bottom-up" approach given in the "Guide to the Expression of the Uncertainty of Measurement" (GUM). Since an analytical expression relating the output response (MFI) with input parameters does not exist, it has been necessary to build mathematical models by adjusting the experimental observations of the response variable in accordance with each input parameter. Subsequently, the determination of the uncertainty associated with the measurement of MFI has been performed by applying the law of propagation of uncertainty to the values of uncertainty of the input parameters. Finally, the activation energy (Ea) of the melt flow at around 200 degrees C and the respective uncertainty have also been determined.