Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-08-07T14:21:56Z No. of bitstreams: 0 / Made available in DSpace on 2015-08-07T14:21:56Z (GMT). No. of bitstreams: 0 / Profenofós é um organofosforado empregado como inseticida e acaricida amplamente utilizado no Brasil para o controle de pragas de cebolas, milho, soja, café, tomate, algodão, feijão, batata e outros. A irradiação é um processo empregado em todo o mundo e recomendada por diversos órgãos de saúde para a conservação de alimentos. A radiação ionizante utiliza raios gama, raios X ou aceleradores de elétrons e tem sido aplicada para eliminar ou reduzir a ação de agentes patogênicos e contribuir para aumentar o tempo de estocagem de vários alimentos. Os objetivos desse trabalho foram: (a) avaliar a degradação de soluções aquosas de profenofós submetidas à radiação ionizante, identificar e quantificar a formação de novos produtos por GC-MS; (b) analisar o efeito de feixe de elétrons em ervilhas inoculadas com soluções aquosas de profenofós; (c) sintetizar Polímeros Molecularmente Impressos (MIP) e Sílica Impressa Molecularmente (MIS), posteriormente, caracterizar os adsorventes em fase sólida e verificar sua seletividade para profenofós. O tratamento com aceleradores de elétrons com dose 31,6 kGy promoveu a formação de um novo produto de degradação e redução de 93,40 % de profenofós em soluções aquosas. Em ervilhas inoculadas com 1 μg de profenofós submetidas à radiação ionizante de 30,4 kGy promoveu uma redução na concentração de profenofós em 57,46 %. Além disso, foram realizadas sínteses de MIP e MIS para a extração em fase sólida de profenofós. Os MIS sintetizados por sol-gel mostraram-se eficazes para o reconhecimento molecular e extração seletiva de profenofós. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

No description available.

This thesis presents a solid state approach to the ion detection system used in the back-end of modern mass spectrometers. Although various techniques already exist to detect ions – even with the sensitivity of a single particle, the existing techniques require high voltage or lower operation temperature to counteract the noise inherent in the system. The suggested design presents an alternative to the more popular detection system whereby the requirement of high operation voltage or low operation temperature can be precluded. This is made possible through the gate capacitance of a Metal Oxide Semiconductor Field Effect Transistor (MOSFET). This thesis presents the design that utilizes the MOSFET as an ion signal amplifier; including the simulation and silicon testbench results.

An analytical method was developed for detection and quantitation of diazinon and chlorpyrifos, two widely used pesticides in local water pathway. Solid phase extraction combined with GC/MS detection with selected ion monitoring was employed. In establishing calibration curves for GC/MS analysis, it may be impractical to use isotope-labeled analogs as internal standards for all analytes in a complicated matrix. Compounds may have to be used as internal standards which could cause non-linear effects because of different response of analytes and internal standards. A novel sample introduction method, which could eliminate this negative effect of non-linearity, was proposed. Calibration data were acquired using the traditional constant volume injection method, and a new method: constant mass injection of analytes. Calibration curves by the constant mass injection method show a better linearity and y-intercept. The nonlinear effect observed with data obtained in low concentration ranges using the constant volume injection method was eliminated. The effectiveness of these curves by two methods was also tested. Better accuracy was obtained with the constant mass injection method. This constant mass injection of analytes method could be very useful in quantitative studies of a complicated sample matrix, such as those encountered in the environmental analysis of pesticides, or in the quality control analysis of medical and industrial product. In solid phase extraction, Varian Bondelute SPE C8 cartridge was selected for extraction. With the standard water sample spiked at 500 ng/L for the two analytes, the recovery for diazinon was about 50% and for chlorpyrifos about 60%. With the standard water sample at 1000 ng/L, the recovery for diazinon was about 60% and for chlorpyrifos about 70%. Among three samples from three different sampling sites, diazinon was detected and confirmed. The quantitation of diazinon was done to water sample from the Calaveras River near the Sanguetti Street crossing Stockton, California, with observed concentration 143.2 ng/L.

<p> In the last thirty years, ion/ion reactions have been developed and applied to answer increasingly difficult analytical problems across a variety of industries. This requires the constant development of instrumentation that can enable work with the analyte modalities of highest impact. Such analytes have become increasingly high in molecular weight precluding many analysis techniques, such as mass spectrometry. In this work, a commercial quadrupole time-of-flight mass spectrometer was modified and adapted to support the analysis of high-mass bio-ions using ion/ion reactions. Using a highly modified instrument, novel capabilities and theory were developed around the analysis and detection of ions with <em>m/z</em> ratios as high as 400,000 <em>m/z</em> and 2.2 mDa. These capabilities enabled and benefitted the analysis of polymers, peptides, and proteins and in this work was demonstrated as an effective instrument a variety of applications. By using data generated on this apparatus, the rapid characterization of PS 80 samples using MATLAB programs to aide in peak identification, native ion parking, and novel ETD reagents were completed. Given the expanding role of biological systems in all areas of science, the development, characterization, and utilization of a highly versatile mass spectrometer is described herein.</p>

No description available.

The cylindrical ion trap (CIT) is made up of two planar endcap electrodes and a cylindrical ring electrode. The investigation of simpler geometries like CIT has been started off in recent years with a view towards miniaturization. As a step towards this, numerical studies on CITs were carried out in our laboratory. Here in this study, our motive is to characterize a CIT through experiments. We have designed a mass spectrometer where a CIT is used as the mass analyzer. The trap performance was observed by varying six parameters associated with our experiment. The parameters are (1) the ionization voltage, (2) the ramp time, (3) the ionization time, (4) the cooling time, (5) the dead time and (6) the bias voltage applied across the filaments. All the experiments have been performed in the mass selective boundary ejection mode.

This thesis describes the final precision mass measurements with SMILETRAP I, where a relative precision of &lt; 1 ppb (10-9) was reached routinely, and the development of SMILETRAP II, aiming for measurements with &lt; 0.1 ppb relative precision. The emphasis of the thesis is on the implementation of new techniques for achieving this precision improvement with SMILETRAP II. The Ramsey multiple-pulse excitation technique was tested at SMILETRAP I, and a reduction of the statistical uncertainty by factor three could by verified. The technique was applied in the last measurement with SMILETRAP I on H2+ and D+ ions. From these measurements the proton mass was deduced with a relative error of 0.18 ppb. It was found that temperature dependent magnetic field oscillations limited us from reducing the uncertainties further. A technical achievement of reducing the peak to peak temperature oscillation in the trapping region of SMILETRAP II by a factor four is presented, which should give an extended observation time and likewise improved precision. The new SMILETRAP II super-conducting magnet, with a slightly stronger field of 5.8 T compared with the previous of 4.7 T, was installed and adjusted.  A careful field alignment and reduction of inhomogeneities was done for minimizing the disturbances of the cyclotron frequency for improved precision. In that attempt, the localization and control of the trapped ion motion is also important. Thus a new cooling trap was set up. In the spring of 2009 coherent axial motion of a confined ion cloud was discovered in the cooling trap. By observation of the axial oscillations we can see the effects of evaporative cooling in the reduction of the axial energy distribution. Storing the ions up to 1 s in the cooling trap reduces the energy distribution by a factor of five. Other remarkable results of the ion oscillations are also reported. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: In progress. Paper 3: Submitted.

Mass spectrometers have proven to be vital to understanding the Solar System and the planets within it. Spacecraft containing mass spectrometers have been sent to numerous remote places and have determined important information about the atmospheric composition of Venus, Earth, Mars, Jupiter, and Saturn, along with other celestial bodies. Such results have shown a variety of small neutral molecules, such as CH4 NH3, H2O, CO2, and CO, neutral radicals such as atomic O, H, and N, and a host of small ions, such as H+, N+, and NH4+. Closed ion source inlets, which allow for the detection of these small neutral molecules, contain a spherical antechamber that allows the neutrals to thermalize with the walls of the chamber through many successive collisions before they are introduced into the ionization region of the spacecraft mass spectrometer. These collisions, however, energetically excite neutral molecules and lead to many chemical changes, such as racemization, ionization, or even dissociation. When these changes occur, smaller neutrals can be produced, even if they were not in the original sample from the atmosphere or surface. As a result, the determination of the true composition of an atmosphere or a surface is cast into doubt. Herein is given a brief description of mass spectrometry in space research and how the closed ion source has greatly assisted this process. Dissociation and other chemical changes caused by the high velocity impacts that occur in closed source antechambers is also addressed. A theoretical approach to understanding such dissociative processes that occur after high energy collisions in closed source antechambers is described and undertaken. Chapter 2 describes a proof-of-concept study using hexane as a representative molecule and determines the velocity at which widespread dissociation of hexane molecules is likely to occur in closed source antechambers. This same theoretical process is then utilized in Chapter 3 with many more members of the n-alkane family to probe what effect molecular weight has on the amount of dissociation. Alkanes of both higher and lower molecular weight than hexane (C6H14) are used to show the effect as a function of molecular weight. In all cases, it was found that the velocity at which half of the incoming neutral n-alkane molecules dissociate is roughly the same for all molecular weights studied. This result is then applied to current and future space research through a proposed hardware solution, which will reduce the amount of dissociation and a discussion of how this effect may be seen in the results obtained from future mission instruments. Lastly, future work with different molecular weights and with successive collisions (the second, third, fourth, etc.) is described. This future work will further expand the present study to show how different functional groups, which may be partly responsible for higher-than-expected levels of NH3 and CO2, are affected after a high velocity, high energy impact.

Spaceborne impact ionization mass spectrometers, such as the Cosmic Dust Analyzer on board the past Cassini spacecraft or the SUrface Dust Analyzer being built for NASA's upcoming Europa Clipper mission, are of crucial importance for the exploration of icy moons in the Solar System, such as Saturn's moon Enceladus or Jupiter's moon Europa. For the interpretation of data produced by these instruments, analogue experiments on Earth are essential. To date, thousands of laboratory mass spectra have been recorded with an analogue experiment for impact ionization mass spectrometers. Simulation of mass spectra of ice grains in space is achieved by a Laser Induced Liquid Beam Ion Desorption (LILBID) approach. The desorbed cations or anions are analyzed in a time-of-flight mass spectrometer. The amount of unstructured raw data is increasingly challenging to sort, process, interpret and compare with data from space. Thus far this has been achieved manually for individual mass spectra because no database containing the recorded reference spectra was available. Here we describe the development of a comprehensive, extendable database containing cation and anion mass spectra from the laboratory LILBID facility. The database is based on a Relational Database Management System with a web server interface and enables filtering of the laboratory data using a wide range of parameters. The mass spectra can be compared not only with data from past and future space missions but also mass spectral data generated by other, terrestrial, techniques. The validated and approved subset of the database is available for general public (https://lilbid-db.planet.fu-berlin.de).