Exploring Liquid Sequential Injection Chromatography To Teach Fundamentals of Separation Methods: A Very Fast Analytical Chemistry Experiment

Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP)

Improving the Detectability of Sequential Injection Chromatography (SIC): Determination of Triazines by Exploiting Liquid Core Waveguide (LCW) Detection

Coupling a liquid core waveguide cell to a sequential injection chromatograph improved the detection limits for determination of triazine herbicides without compromising peak resolution. Separation of simazine, atrazine, and propazine was achieved in water samples by a 25mm long C18 monolithic column. Detection was made at 238nm using a type II LCW (silica capillary coated with Teflon (R) AF2400) cell with 100cm of optical path length. Detection limits for simazine, atrazine, and propazine were 2.3, 1.9, and 4.5 mu g L-1, respectively. Reduced analysis time and low solvent consumption are other remarkable features of the proposed method.

Electrical and optical properties of poly(2-dodecanoylsulfanyl-p-phenylenevnylene) and its application in electroluminescent devices

We describe the optical and electrical characterization of a poly(p-phenylenevinylene) derivative: poly(2-dodecanoylsulfanyl-p-phenylenevinylene) (12COS-PPV). The electrical characterization was carried out on devices with the FTO\PEDOT:PSS\12COS-PPV/Al structure. Positive charge carrier mobility mu(h) of similar to 1.0 x 10(-6) cm(2) V(-1) s(-1) and barrier height phi of similar to 0.1 eV for positive charge carrier injection at the PEDOT:PSS/12COS-PPV interface were obtained using a thermionic injection model. FTO\PEDOT:P55\12COS-PPV/Ca devices exhibited green-yellow electroluminescence with maximum emission at lambda = 540 nm.

Development of a spectrophotometric Sequential Injection Analysis (SIA) procedure for determination of ammonium: A Response Surface Methodology (RSM) approach

This paper describes the optimization and use of a Sequential Injection Analysis (SIA) procedure for ammonium determination in waters. Response Surface Methodology (RSM) was used as a tool for optimization of a procedure based on the modified Berthelot reaction. The SIA system was designed to (i) prepare the reaction media by injecting an air-segmented zone containing the reagents in a mixing chamber, (ii) to aspirate the mixture back to the holding coil after homogenization, (iii) drive it to a thermostated reaction coil, where the flow is stopped for a previously established time, and (iv) to pump the mixture toward the detector flow cell for the spectrophotometric measurements. Using a 100 mu mol L(-1) ammonium solution, the following factors were considered for optimization: reaction temperature (25 - 45 degrees C), reaction time (30 - 90 s), hypochlorite concentration (20 - 40 mmol L(-1)) nitroprusside concentration (10 - 40 mmol L(-1)) and salicylate concentration (0.1 - 0.3 mol L(-1)). The proposed system fed the statistical program with absorbance data for fast construction of response surface plots. After optimization of the method, figures of merit were evaluated, as well as the ammonium concentration in some water samples. No evidence of statistical difference was observed in the results obtained by the proposed method in comparison to those obtained by a reference method based on the phenol reaction. (C) 2010 Elsevier B.V. All rights reserved.

Automated two-dimensional separation flow system with electrochemical preconcentration, stripping, capillary electrophoresis and contactless conductivity detection for trace metal ion analysis

This paper describes the automation of a fully electrochemical system for preconcentration, cleanup, separation and detection, comprising the hyphenation of a thin layer electrochemical flow cell with CE coupled with contactless conductivity detection (CE-C(4)D). Traces of heavy metal ions were extracted from the pulsed-flowing sample and accumulated on a glassy carbon working electrode by electroreduction for some minutes. Anodic stripping of the accumulated metals was synchronized with hydrodynamic injection into the capillary. The effect of the angle of the slant polished tip of the CE capillary and its orientation against the working electrode in the electrochemical preconcentration (EPC) flow cell and of the accumulation time were studied, aiming at maximum CE-C(4)D signal enhancement. After 6 min of EPC, enhancement factors close to 50 times were obtained for thallium, lead, cadmium and copper ions, and about 16 for zinc ions. Limits of detection below 25 nmol/L were estimated for all target analytes but zinc. A second separation dimension was added to the CE separation capabilities by staircase scanning of the potentiostatic deposition and/or stripping potentials of metal ions, as implemented with the EPC-CE-C(4)D flow system. A matrix exchange between the deposition and stripping steps, highly valuable for sample cleanup, can be straightforwardly programmed with the multi-pumping flow management system. The automated simultaneous determination of the traces of five accumulable heavy metals together with four non-accumulated alkaline and alkaline earth metals in a single run was demonstrated, to highlight the potentiality of the system.

Simultaneous analysis of five antidepressant drugs using direct injection of biofluids in a capillary restricted-access media-liquid chromatography-tandem mass spectrometry system

Direct analysis, with minimal sample pretreatment, of antidepressant drugs, fluoxetine, imipramine, desipramine, amitriptyline, and nortriptyline in biofluids was developed with a total run time of 8 min. The setup consists of two HPLC pumps, injection valve, capillary RAM-ADS-C18 pre-column and a capillary analytical C 18 column connected by means of a six-port valve in backflush mode. Detection was performed with ESI-MS/MS and only 1 mu m of sample was injected. Validation was adequately carried out using FLU-d(5) as internal standard. Calibration curves were constructed under a linear range of 1-250 ng mL(-1) in plasma, being the limit of quantification (LOQ), determined as 1 ng mL(-1), for all the analytes. With the described approach it was possible to reach a quantified mass sensitivity of 0.3 pg for each analyte (equivalent to 1.1-1.3 fmol), translating to a lower sample consumption (in the order of 103 less sample than using conventional methods). (C) 2008 Elsevier B.V. All rights reserved.

Fluoxetine and norfluoxetine analysis by direct injection of human plasma in a column switching liquid chromatographic system

A column switching LC method is presented for the analysis of fluoxetine (FLU) and norfluoxetine (NFLU) by direct injection of human plasma using a lab-made restricted access media (RAM) column. A RAM-BSA-octadecyl silica (C-18) column (40 min x 4.6 mm, 10 mu m) is evaluated in both backflush and foreflush elution modes and coupled with a C-18 lab-made (50 mm x 4.6 mm, 3 pm) analytical column in order to perform online sample preparation. Direct injection of 100 mu L, of plasma samples is possible with the developed approach. In addition, reduction of sample handling is obtained when compared with traditional liquid-liquid extraction (LLE) and SPE. The total analysis time is around 20 min. A LOQ of 15 ng/mL is achieved in a concentration range of 15-500 ng/mL, allowing the therapeutic drug monitoring of clinical samples. The precision values achieved are lower than 15% for all the evaluated points with adequate recovery and accuracy. Furthermore, no matrix interferences are found in the analysis and the proposed method shows to be an adequate alternative for analysis of FLU in plasma.

Energy Storage for a Grid-Connected PV-System: A Feasibility Study

The work presented in this thesis concerns the dimensioning of an Energy Storage System (ESS) which will be used as an energy buffer for a grid-connected PV plant. This ESS should help managing the PV plant to inject electricity into the grid according to the requirements of the grid System Operator. It is desired to obtain a final production not below 1300kWh/kWp with a maximum ESS budget of 0.9€/Wp. The PV plant will be sited in Martinique Island and connected to the main grid. This grid is a small one where the perturbations due clouds in the PV generation are not negligible anymore. A software simulation tool, incorporating a model for the PV-plant production, the ESS and the required injection pattern of electricity into the grid has been developed in MS Excel. This tool has been used to optimize the relevant parameters defining the ESS so that the feed-in of electricity into the grid can be controlled to fulfill the conditions given by the System Operator. The inputs used for this simulation tool are, besides the conditions given by the System Operator on the allowed injection pattern, the production data from a similar PV-plant in a close-by location, and variables for defining the ESS. The PV production data used is from a site with similar climate and weather conditions as for the site on the Martinique Island and hence gives information on the short term insolation variations as well as expected annual electricity production. The ESS capacity and the injected electric energy will be the main figures to compare while doing an economic study of the whole plant. Hence, the Net Present Value, Benefit to Cost method and Pay-back period studies are carried on as dependent of the ESS capacity. The conclusion of this work is that it is possible to obtain the requested injection pattern by using an ESS. The design of the ESS can be made within an acceptable budget. The capacity of ESS to link with the PV system depends on the priorities of the final output characteristics, and it also depends on which economic parameter that is chosen as a priority.

An Injection-locked Diode Laser for Cold Rydberg Atom Experiments

A free-running, temperature stabilized diode laser has been injection-locked to an external cavity diode laser for use in cold Rydberg atom experiments. Cold rubidium atoms in a magneto-optical trap (MOT) are excited to Rydberg states using a 10 ns laser pulse. The Rydberg atoms spontaneously ionize due to dipole forces, and the collisional ionization dynamics are observed as a function of atom density and principal quantum number of the Rydberg state, n. The injection-locked diode laser will be used as a repumper in conjunction with a dark spontaneous-force optical trap (SPOT) to increase the Rydberg state density. We report on the design of the injection-locked laser system.

Solução da equação de condução de calor bidimensional, em meios multicompostos, pelos métodos nodal, com parâmetros concentrados, e a técnica da transformada de Laplace

Neste trabalho, desenvolvemos uma metodologia semi-analítica para solução de problemas de condução de calor bidimensional, não-estacionária em meios multicompostos. Esta metodologia combina os métodos nodal, com parâmetros concentrados, e a técnica da transformada de Laplace. Inicialmente, aplicamos o método nodal. Nele, a equação diferencial parcial que descreve o problema é integrada, transversalmente, em relação a uma das variáveis espaciais. Em seguida, é utilizado o método de parâmetros concentrados, onde a distribuição de temperatura nos contornos superior e inferior é substituída pelo seu valor médio. Os problemas diferenciais unidimensionais resultantes são então resolvidos com o uso da técnica da transformada de Laplace, cuja inversão é avaliada numericamente. O método proposto é usado na solução do problema de condução de calor, em paredes de edificações. A implementação computacional é feita, utilizando-se a linguagem FORTRAN e os resultados numéricos obtidos são comparados com os disponíveis na literatura.

Desempenho animal em sistema silvipastoril com acácia-negra (Acacia mearnsii De Wild.) e rendimento de matéria seca de cultivares de Panicum maximum Jacq. sob dois regimes de luz solar

Esse estudo foi compreendido por dois experimentos de campo, no período de outubro/2003 a abril/2004, na Fundação Estadual de Pesquisa Agropecuária (FEPAGRO), localizado em Tupanciretã, no Planalto Médio, região ecoclimática do RS. O principal objetivo do primeiro experimento foi avaliar o desempenho de novilhas de corte e a dinâmica de três pastos constituídos por Panicum maximum cvs. Gatton e Aruana e por Digitaria diversinervis em um sistema silvipastoril (SSP), associadas com acácia-negra (Acacia mearnsii De Wild.) sob duas densidades arbóreas (833 e 500 árvores/ha). Os resultados mostraram que não houve efeito da densidade arbórea com relação à dinâmica dos pastos e no desempenho animal. As cvs. de P. maximum apresentaram maiores resultados de massa de forragem residual do que a D. diversinervis. A taxa de acúmulo diário de MS, forragem total, oferta de forragem real e relação folha/colmo não diferiram entre as espécies. A cv. Gatton obteve maior resultado de forragem disponível quando comparado com a D. diversinervis. O ganho médio diário, ganho por área, animais.dia/ha, lotação animal e carga animal média também não diferiram com relação as forrageiras. O objetivo do segundo experimento foi avaliar o rendimento de matéria seca total de cinco cultivares de Panicum maximum, crescendo dentro e fora de um bosque de Eucalyptus sp. de 17 anos de idade, estabelecido na densidade de 1111 árvores/ha. A produção media de MS e a taxa de crescimento diário foram significativamente menores (P≤0.05) na condição de sombra (5.529 kg/ha) do que em pleno sol (22.346 kg/ha). Na condição de sombra, os resultados das cvs. não diferiram, enquanto que os resultados em pleno sol apresentaram diferenças significativas (P≤0,01), onde a cv. Tanzânia apresentou menores resultados no rendimento de matéria seca e taxa de crescimento e a cv. Mombaça os maiores resultados Pode-se concluir que as cvs. Mombaça, Tobiatã, Gatton e Vencedor são boas promissoras para o uso em SSP. Esse estudo indicou claramente altos níveis de desempenho animal sob pastejo em SSP com algumas cvs. de P. maximum selecionadas ou D. diversinervis usando Acacia-Negra no Sul do Brasil.