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>

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T12:34:18Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T12:34:18Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T12:34:18Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T12:34:18Z (GMT). No. of bitstreams: 0 / O entendimento dos mecanismos de degradação que agem sob os nanocompósitos poliméricos frente ao intemperismo (luz UV, calor, oxigênio, chuva ácida, entre outros), é o ponto chave para o desenvolvimento de novos aditivos e novas aplicações. Para este trabalho a síntese do nanocompósito foi realizada no estado fundido, utilizando-se uma extrusora de dupla rosca. A matriz polimérica utilizada foi o HMS-PP (polipropileno com alta resistência do fundido) sintetizado por irradiação gama e a argila Montmorilonita. Para melhor compatibilização entre a matriz e a nanocarga, foi utilizada o agente compatibilizante andrido maléico. Para os ensaios de envelhecimento ambiental e acelerado em estufa, os corpos de prova foram confeccionados por meio de termoprensagem. A caracterização dos efeitos da adição de argila e do envelhecimento nos nanocompósitos, presupôs o emprego das técnicas de ensaios mecânicos, Calorimetria Diferencial Exploratória (DSC), Termogravimetria (TGA), Espectroscopia no Infravermelho por Transformada de Fourier (FT-IR), Espectrometria de Fluorescêcia de Raios X por Dispersão de Comprimento de Onda (WDXRF), Microscopia Eletrônica de Varredura (MEV), Índice de Fluidez (IF), Difração de Raios-X (DRX) e Espectroscopia de Energia Dispersiva (EDS). Foram ensaiadas amostras com 0,1; 1; 3; 5 e 10% de argila. A amostra com porcentagem de 5% de argila demonstrou uma melhor estabilidade frente ao ensaio de envelhecimento ambiental e no envelhecimento acelerado em estufa. Por outro lado na amostra com maior porcentagem de argila (10%) ocorreu o inverso, sob ensaio ambiental houve maior degradação e sob envelhecimento acelerado em estufa, manteve-se resistente até 56 dias de envelhecimento. Nas porcentagens estudas (menor que &le; 3%) de argila, pode-se constatar um equilíbrio entre o efeito barreira da argila e a ação dos íons metálicos que aceleram o processo degradativo. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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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.

Photonic crystals (PCs), consisting of a periodic pattern of variations in the material properties, are one of the platforms proposed as synthetic optical materials to meet the need for optical materials with desired properties. Recently, applications based on dispersive properties of the PCs have been proposed in which PCs are envisioned as optical materials with controllable dispersive properties. Unlike the conventional use of PCs to achieve localization, in these new applications propagation inside the photonic crystal is studied, and their dispersive properties are utilized. Among these applications, the possibility of demultiplexing light using the superprism effect is of particular interest. Possibility of integration and compactness are two main advantages of PC-based wavelength demultiplexers compared to other demultiplexing techniques, for applications including compact spectrometers (for sensing applications), demultiplexers (for communications), and spectral analysis (for information processing systems). I develop the necessary simulation tools to study the dispersive properties of photonic crystals. In particular, I will focus on superprism-based demultiplexing in PCs, and define a phenomenological model to describe different effects in these structures and to study important parameters and trends. A systematic method for the optimization and design of these structures is presented. Implementation of these structures is experimentally demonstrated using the devices fabricated in a planar SOI platform based on designed parameters. In the next step, different approaches to improve the performance of these devices (for better resolution and lower insertion loss) are studied, and extension of the concepts to other material platforms is discussed.

No description available.