Development of a sequential injection-square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h(-1). Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 mu L s(-1). For a concentration range between 0.010 and 0.25 mg L(-1), the current (i(p), mu A) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L(-1)): ip = (-20.5 +/- 0.3) Cparaquat -(0.02 +/- 0.03). The limits of detection and quantification were 2.0 and 7.0 mu g L(-1), respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.

Fast and reliable analyses of sulphite in fruit juices using a supramolecular amperometric detector encompassing in flow gas diffusion unit

A new compact system encompassing in flow gas diffusion unit and a wall-jet amperometric FIA detector, coated with a supramolecular porphyrin film, was specially designed as an alternative to the time-consuming Monier-Williams method, allowing fast, reproducible and accurate analyses of free sulphite species in fruit juices. In fact, a linear response between 0.64 and 6.4 ppm of sodium sulphite. LOD = 0.043 ppm, relative standard deviation of +/- 1.5% (n = 10) and analytical frequency of 85 analyses/h were obtained utilising optimised conditions. That superior analytical performance allows the precise evaluation of the amount of free sulphite present in foods, providing an important comparison between the standard addition and the standard injection methods. Although the first one is most frequently used, it was strongly influenced by matrix effects because of the unexpected reactivity of sulphite ions with the juice matrixes, leading to its partial consumption soon after addition. In contrast, the last method was not susceptible to matrix effects yielding accurate results, being more reliable for analytical purposes. (C) 2011 Elsevier Ltd. All rights reserved.

A Graphite-Polyurethane Composite Electrode for the Analysis of Furosemide

A graphite-polyurethane composite electrode has been used for the determination of furosemide, a antihypertensive drug, in pharmaceutical samples by anodic oxidation. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the electrooxidation process at +1.0 V vs. SCE over a wide pH range, with the result that no adsorption of analyte or products occurs, unlike at other carbon-based electrode materials. Quantification was carried out using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry. Linear ranges were determined (up to 21 mu mol L-1 with cyclic voltammetry) as well as limits of detection (0.15 mu mol L-1 by differential pulse voltammetry). Four different types of commercial samples were successfully analyzed. Recovery tests were performed which agreed with those obtained by spectrophotometric evaluation. The advantages of this electrode material for repetitive analyzes, due to the fact that no electrode surface renewal is needed owing to the lack of adsorption, are highlighted.

Determination of Minoxidil by Bleaching the Permanganate Carrier Solution in a Flow-Based Spectrophotometric System

The determination of minoxidil (MX) with potassium permanganate as a carrier in a flow injection method is described. The detection at 550nm was linear from 1.0x10-5 to 5.0x10-4mol L-1. The limit of detection (3 sigma/slope) was 8.92x10-6mol L-1, with an analytical frequency of 32h-1. The proposed method was applied to commercial samples, with recoveries from 104.7 to 106.4%. Comparison with the HPLC procedure reveled relative errors from 0.48 to 1.4%, and the results agreed within a 95% confidence level.

Flow cell within an LED: a proposal for an optical absorption detector

Droplets formed at the tip of a tube under the same conditions possess extreme uniformity of form, volume and weight. These properties of liquid drop formation have been known for a long time and consequently many applications for the drop have been found in instrumentation and chemical analysis methods. In the present paper, we report on the analytical use of a dynamic LED-based flow-through optical absorption detector with optical path length controlled by continuous dropping of a solution. This arrangement consists of a flow cell built within a high-intensity red LED (lambda (max)=630 nm). The feasibility of the detector is demonstrated by colorimetric determination of methylene blue, and ammonium by Berthelot's reaction, in a flow-injection system. For ammonium, the reaction forms a blue dye (indophenol) with a maximum absorption at 630-650 nm. The detection limit, considered as 3 times the signal of the blank, is better than 125 mu g l(-1). The small flow cell represents a good combination of optical path length, low volume and fast washout. This detector can be used advantageously in automated methods and can represent a solution to problems of optical detection involving gas bubbles and precipitation of particles in turbidimetric applications.

On-line preconcentration and speciation analysis of Cr(III) and Cr(VI) using baker's yeast cells immobilised on controlled pore glass

A study was undertaken to evaluate Saccharonzyces cerevisiae as a substrate for the biosorption of Cr(III) and Cr(VI) aiming to the selective determination of these species in aqueous solutions. The yeast cells were covalently immobilised on controlled pore glass (CPG), packed in a minicolumn and incorporated in an on-line flow injection system. The effect of chemical and physical variables affecting the biosorption process was tested in order to select the optimal analytical conditions for the Cr retention by S. cerevisiae. Cr(III) was retained by the immobilised cells and Cr(VI) were retained by CPG. The speciation was possible by selective and sequential elution of Cr(III) with 0.05 mol L-1 HCl and 2.0 mol L-1 HNO3 for Cr(VI). The influence of some concomitant ions up to 20 mg L-1 was also tested. Quantitative determinations of Cr were carried out by means of inductively coupled plasma optical emission spectrometry (ICP OES). Preconcentration factors of 12 were achieved for Cr(III) and 5 for Cr(VI) when 1.7 mL of sample were processed reaching detection limits of 0.45 for Cr(III) and 1.5 mu g L-1 for Cr(VI). The speciation of inorganic Cr in different kinds of natural waters was performed following the proposed method. Spiked water samples were also analysed and the recoveries were in all cases between 81 and 103%. (c) 2005 Elsevier B.V. All rights reserved.

On-line redox speciation analysis of antimony using L-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Analysis of Nucleocytoplasmic Protein Shuttling by Imaging Flow Cytometry

Many intracellular signal transduction events involve the reversible shuttling of proteins between the cytoplasm and the nucleus. Study of these processes requires imaging information on the protein localization in a given cell and a large number of measurements to obtain sufficient statistics on the protein localization in the whole population. The protocol describes method for quantitative imaging flow cytometry analysis of intracellular distribution of NF-kappaB in ARPE-19 cells stained with specific fluorochrome-conjugated antibodies. The described technique alone or in combination with standard flow cytometry methods can be applied to study any protein undergoing translocation from cytoplasm into the nucleus in a variety of cell lines as well as in heterogeneous primary cell populations

An analysis of nonequilibrium inviscid flow,

"Air Force contract no. AF40(600)-928."

User interface design for social web theme and opinion analysis

The Social Web is a torrent of real-time information and an emerging discipline is now focussed on harnessing this information flow for analysis of themes, opinions and sentiment. This short paper reports on early work on designing better user interfaces for end users in manipulating the outcomes from these analysis engines.

Delivery of nitric oxide for analysis of the function of cytochrome c'

On delivery of nitric oxide (NO) to protein samples (e.g., cytochrome c'), for spectroscopic experiments it is important to avoid exposure to oxygen and to remove contaminants from the NO gas. We describe a number of techniques for steady-state UV/Vis spectrophotometry and pre-steady-state stopped-flow spectrophotometry analysis of cytochrome c'.

Integrated lean six sigma approach for patient flow improvement in hospital emergency department

This research aims to develop an Integrated Lean Six Sigma approach to investigate and resolve the patient flow problems in hospital emergency departments. It was proposed that the voice of the customer and the voice of the process should be considered simultaneously to investigate the current process of patient flow. Statistical analysis, visual process mapping with A3 problem solving sheet, and cause and effect diagrams have been used to identify the major patient flow issues. This research found that engaged frontline workers, long-term leadership obligation, an understanding of patients' requirements and the implementation of a systematic integration of lean strategies could continuously improve patient flow, health care service and growth in the emergency departments.

Improving Flow-Insensitive Solutions for Non-Separable Dataflow Problems

Flow-insensitive solutions to dataflow problems have been known to be highly scalable; however also hugely imprecise. For non-separable dataflow problems this solution is further degraded due to spurious facts generated as a result of dependence among the dataflow facts. We propose an improvement to the standard flow-insensitive analysis by creating a generalized version of the dominator relation that reduces the number of spurious facts generated. In addition, the solution obtained contains extra information to facilitate the extraction of a better solution at any program point, very close to the flow-sensitive solution. To improve the solution further, we propose the use of an intra-block variable renaming scheme. We illustrate these concepts using two classic non-separable dataflow problems --- points-to analysis and constant propagation.

Analysis of forest soil chemistry and hydrology with a dynamic model ACIDIC.

In this study we analyze how the ion concentrations in forest soil solution are determined by hydrological and biogeochemical processes. A dynamic model ACIDIC was developed, including processes common to dynamic soil acidification models. The model treats up to eight interacting layers and simulates soil hydrology, transpiration, root water and nutrient uptake, cation exchange, dissolution and reactions of Al hydroxides in solution, and the formation of carbonic acid and its dissociation products. It includes also a possibility to a simultaneous use of preferential and matrix flow paths, enabling the throughfall water to enter the deeper soil layers in macropores without first reacting with the upper layers. Three different combinations of routing the throughfall water via macro- and micropores through the soil profile is presented. The large vertical gradient in the observed total charge was simulated succesfully. According to the simulations, gradient is mostly caused by differences in the intensity of water uptake, sulfate adsorption and organic anion retention at the various depths. The temporal variations in Ca and Mg concentrations were simulated fairly well in all soil layers. For H+, Al and K there were much more variation in the observed than in the simulated concentrations. Flow in macropores is a possible explanation for the apparent disequilibrium of the cation exchange for H+ and K, as the solution H+ and K concentrations have great vertical gradients in soil. The amount of exchangeable H+ increased in the O and E horizons and decreased in the Bs1 and Bs2 horizons, the net change in whole soil profile being a decrease. A large part of the decrease of the exchangeable H+ in the illuvial B horizon was caused by sulfate adsorption. The model produces soil water amounts and solution ion concentrations which are comparable to the measured values, and it can be used in both hydrological and chemical studies of soils.

Evidence for follicle-stimulating hormone mediation in the hemiorchidectomy-induced compensatory increase in the function of the remaining testis of the adult male bonnet monkey (Macaca radiata)

Hemiorchidectomy (HO) in the adult male bonnet monkey results in a selective increase in circulating concentrations of FSH and testosterone, and this is accompanied by compensatory increase in sperm production by the remaining testis. We investigated the possible role of increased FSH concentration that occurs after HO in the compensatory increase in the activity of the remaining testis. Of eight adult male bonnet monkeys that underwent HO, four received i.v. injections every other day for 30 days of a well-characterized ovine FSH antiserum (a/s) that cross-reacts with monkey FSH. The remaining four males received normal monkey serum (NMS) as control treatment in a protocol similar to that employed for ais-treated males. Blood samples were collected between 2100 and 2200 h before and 1/2, 1, 3, 5, 7, 14, 22, and 29 days after HO. Testicular weight, number of 3 beta-hydroxy steroid dehydrogenase-positive (3 beta-HSD+) cells, and DNA flow cytometric analysis of germ cell populations were obtained for testes collected before and at the termination of NMS or ais treatment. In NMS-treated males, circulating serum FSH concentrations progressively increased to reach a maximal level by Day 7 after HO (1.95 +/- 0.3 vs. 5.6 +/- 0.7 ng/ml on Days -1 and 7, respectively). Within 30 min of ais injection, FSH antibodies were detected in circulation, and the antibody level was maintained at a constant level between Day 7 and end of treatment (exhibiting 50-60% binding to I-125-hFSH). Although circulating mean nocturnal serum testosterone concentration showed an initial decrease, it rose gradually to pre-HO concentrations by Day 7 in NMS-treated males. In contrast, nocturnal mat serum testosterone concentrations in a/s-treated males remained lower than in NMS-treated controls (p < 0.05) up to Day 22 and thereafter only marginally increased. Testicular weights increased (p < 0.05) over the pre-HO weight in NMS- but not in ais-treated males. After HO, the number of 3 beta-HSD+ cells (Leydig cells) was markedly increased but was significantly (p < 0.05) higher in NMS-treated males compared to a/s-treated males. A significant (p < 0.05) reduction in the primary spermatocyte population of germ cells was observed in ais-treated compared to NMS-treated males. These results suggest that the increased FSH occurring after HO could be intimately involved in increasing the compensatory functional activity of the remaining testis in the male bonnet monkey.