Square wave adsorptive cathodic stripping voltarnmetry automated by sequential injection analysis - Potentialities and limitations exemplified by the determination of methyl parathion in water samples

This paper describes the development and evaluation of a sequential injection method to automate the determination of methyl parathion by square wave adsorptive cathodic stripping voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. Accumulation and stripping steps are made in the sample medium conditioned with 40 mmol L-1 Britton-Robinson buffer (pH 10) in 0.25 mol L-1 NaNO3. The homogenized mixture is injected at a flow rate of 10 mu Ls(-1) toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode. After a suitable deposition time, the flow is stopped and the potential is scanned from -0.3 to -1.0 V versus Ag/AgCl at frequency of 250 Hz and pulse height of 25 mV The linear dynamic range is observed for methyl parathion concentrations between 0.010 and 0.50 mgL(-1), with detection and quantification limits of 2 and 7 mu gL(-1), respectively. The sampling throughput is 25 h(-1) if the in line standard addition and sample conditioning protocols are followed, but this frequency can be increased up to 61 h(-1) if the sample is conditioned off-line and quantified using an external calibration curve. The method was applied for determination of methyl parathion in spiked water samples and the accuracy was evaluated either by comparison to high performance liquid chromatography with UV detection, or by the recovery percentages. Although no evidences of statistically significant differences were observed between the expected and obtained concentrations, because of the susceptibility of the method to interference by other pesticides (e.g., parathion, dichlorvos) and natural organic matter (e.g., fulvic and humic acids), isolation of the analyte may be required when more complex sample matrices are encountered. (C) 2007 Elsevier B.V. All rights reserved.

Application of solid sampling device for direct determination of chromium and nickel in lubricating oils by graphite furnace atomic absorption spectrometry

One method using a solid sampling device for the direct determination of Cr and Ni in fresh and used lubricating oils by graphite furnace atomic absorption spectrometry are proposed. The high organic content in the samples was minimized using a digestion step at 400 degrees C in combination with an oxidant mixture 1.0% (v v(-1)) HNO3+15% (v v(-1)) H2O2+0.1% (m v(-1)) Triton X-100 for the in situ digestion. The 3-field mode Zeeman-effect allowed the spectrometer calibration up to 5 ng of Cr and Ni. The quantification limits were 0.86 mu g g(-1) for Cr and 0.82 mg g(-1) for Ni, respectively. The analysis of reference materials showed no statistically significant difference between the recommended values and those obtained by the proposed methods.

Determination of ciclopirox olamine in pharmaceutical products by capillary electrophoresis with capacitively coupled contactless conductivity detection

This paper describes the determination of ciclopirox olamine in pharmaceutical formulations using capillary electrophoresis with capacitively coupled contactless conductivity detection. In an alkaline medium, ciclopirox olamine is converted into an anionic species and its detection is possible in capillary electrophoresis with capacitively coupled contactless conductivity detection without an electroosmotic flow modifier, because it is a low-mobility species. A linear working range from 2.64 to 264 mu g/mL in sodium hydroxide electrolyte as well as low detection limit (0.39 mu g/mL) and a good repeatability (RSD = 3.4% for 264 mu g/mL ciclopirox solution (n = 10)) were achieved. It was also possible to determine olamine in its cationic form when acetic acid was used as the electrolyte solution. The results obtained include a linear range from 26.4 to 184.8 mu g/mL and a detection limit of 2.6 mu g/mL olamine. The proposed methods were applied to the analysis of commercial pharmaceutical products and the results were compared with the values indicated by the manufacturer as well as those obtained using a titrimetric method recommended by American Pharmacopoeia.

Rapid method for the determination. of organic acids in wine by capillary electrophoresis with indirect UV detection

A capillary electrophoresis method for organic acids in wine was developed and validated. The optimal electrolyte consisted of 10 mmol/L 3,5-dinitrobenzoic acid (DNB) at pH 3.6 containing 0.2 mmol/L cetyltrimethylammonium bromide as flow reverser. DNB was chosen because it has an effective mobility similar to the organic acids under investigation, good buffering capacity at pH 3.6, and good chromophoric characteristics for indirect UV-absorbance detection at 254 nm. Sample preparation involved dilution and filtration. The method showed good performance characteristics: Linearity at 6 to 285 mg/L (r > 0.99); detection and quantification limits of 0.64 to 1.55 and 2.12 to 5.15 mg/L, respectively; separation time of less than 5.5 min. Coefficients of variation for ten injections were less than 5% and recoveries varied from 95% to 102%. Application to 23 samples of Brazilian wine confirmed good repeatability and demonstrated wide variation in the organic acid concentrations. (C) 2008 Elsevier Ltd. All rights reserved.

A New Indirect Electrochemical Method for Determination of Ozone in Water Using Multiwalled Carbon Nanotubes

A new electrochemical methodology has been developed for the detection of ozone using multiwalled carbon nanotubes (MWCNT). The method presented here is based on the reaction of ozone with indigo blue dye producing anthranilic acid (ATN). The electrochemical profile of ATN on an electrode of glassy carbon (GC) modified with MWCNT showed an oxidation peak potential at 750 mV vs. Ag/AgCl. An analytical method was developed using differential pulse voltammetry (DPV) to determine ATN in a range of 50-400 nmol L(-1), with a detection limit of 9.7 nmol L(-1). Ozonated water samples were successfully analyzed by GC/MWCNT electrode and the recovery procedure yielded values between of 96.5 and 102.3%.

Rapid and direct determination of glyphosate and aminomethylphosphonic acid in water using anion-exchange chromatography with coulometric detection

A simple, rapid, and low-cost coulometric method for direct detection of glyphosate and aminomethylphosphonic acid (AMPA) in water samples using anion-exchange chromatography and coulometric detection with copper electrode is presented. Under optimized conditions, the limits of detection (LODs) (S/N = 3) were 0.038 mu g ml(-1) for glyphosate and 0.24 mu g ml(-1) for AMPA, without any preconcentration method. The calibration curves were linear and presented an excellent correlation coefficient. The method was successfully applied to the determination of glyphosate and AMPA in water samples without any kind of extraction, clean-up, or preconcentration step. No interferent was found in the water, like this, the recovery was, practically, 100%. (c) 2008 Elsevier B.V. All rights reserved.

Electroanalytical determination of promethazine hydrochloride in pharmaceutical formulations on highly boron-doped diamond electrodes using square-wave adsorptive voltammetry

The electrochemical oxidation of promethazine hydrochloride was made on highly boron-doped diamond electrodes. Cyclic voltammetry experiments showed that the oxidation mechanisms involved the formation of an adsorbed product that is more readily oxidized, producing a new peak with lower potential values whose intensity can be increased by applying the accumulation potential for given times. The parameters were optimized and the highest current intensities were obtained by applying +0.78 V for 30 seconds. The square-wave adsorptive voltammetry results obtained in BR buffer showed two well-defined peaks, dependent on the pH and on the voltammetric parameters. The best responses were obtained at pH 4.0, frequency of 50 s(-1), step of 2 mV, and amplitude of 50 mV. Under these conditions, linear responses were obtained for concentrations from 5.96 x 10(-7) to 4.76 x 10(-6) mol L-1, and calculated detection limits of 2.66 x 10(-8) mol L-1 (8.51 mu g L-1) for peak 1 and of 4.61 x 10(-8) mol L-1 (14.77 mu g L-1) for peak 2. The precision and accuracy were evaluated by repeatability and reproducibility experiments, which yielded values of less than 5.00% for both voltammetric peaks. ne applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples. All results obtained were compared to recommended procedure by British Pharmacopeia. The voltammetric results indicate that the proposed procedure is stable and sensitive, with good reproducibility even when the accumulation steps involve short times. It is therefore very suitable for the development of the electroanalytical procedure, providing adequate sensitivity and a reliable method.

Determination of amino acids by capillary electrophoresis-electrospray ionization-mass spectrometry: An evaluation of different protein hydrolysis procedures

In this work, a CE equipment, online hyphenated to an IT MS analyzer by a linear sheath liquid interface promoting ESI, was used to develop a method for quantitative determination of amino acids. Under appropriate conditions (BGE composition, 0.8% HCOOH, 20% CH(3)OH; sheath liquid composition, 0.8% HCOOH, 60% methanol; V(ESI), +4.50 W), analytical curves of all amino acids from 3 to 80 mg/L were recorded presenting acceptable linearity (r > 0.99). LODs in the range of 16-172 mu mol/L were obtained. BSA, a model protein, was submitted to different hydrolysis procedures (classical acid and basic, and catalyzed by the H(+) form of a cation exchanger resin) and its amino acid profiles determined. In general, the resin-mediated hydrolysis yields were overall similar or better than those obtained by classical acid or basic hydrolysis. The resulting experimental-to-theoretical BSA concentration ratios served as correction factors for the quantitation of amino acids in Brazil nut resin generated hydrolysates.

Electroanalytical determination of N-nitrosamines in aqueous solution using a boron-doped diamond electrode

The electrochemical methods cyclic and square-wave voltammetry were applied to develop an electroanalytical procedure for the determination of N-nitrosamines (N-nitrosopyrrolidine, N-nitrosopiperidine and N-nitrosodiethylamine) in aqueous solutions. Cyclic voltammetry was used to evaluate the electrochemical behaviors of N-nitrosamines on boron-doped diamond electrodes. It was observed an irreversible electrooxidation peak located in approximately 1.8 V (vs. Ag/AgCl) for both N-nitrosamines. The optimal electrochemical response was obtained using the following square-wave voltammetry parameters: f = 250 Hz, E(sw) = 50 mV and E(s) = 2 mV using a Britton-Robinson buffer solution as electrolyte (pH 2). The detection and quantification limits determined for total N-nitrosamines were 6.0 x 10(-8) and 2.0 x 10(-7) mol L(-1), respectively.

THE POTENTIALITIES OF USING A GRAPHITE-SILICONE RUBBER COMPOSITE ELECTRODE IN THE DETERMINATION OF PROPRANOLOL

A graphite silicone-rubber composite electrode (GSR) was used for the determination of propranolol in drug formulation. Cyclic voltammetry (CV) at the GSR presented an irreversible oxidation peak at + 0.8V vs. SCE, in Britton Robinson (B-R) buffer pH 7.4. The quantitative determination was carried out using differential pulse voltammetry (DPV). Under optimized parameters a linear dynamic range from 5.0 to 80.6 mu mol L(-1) with a detection limit of 1.1 mu mol L(-1) was observed. A repeatability of 4.5 +/- 0.1 mu A (n = 10) peak current was found after 10 successive DPV voltammograms of propranolol in the same solution after surface renovations. Using the proposed electrode, propranolol was quantified in a pharmaceutical formulation with results that agreed within 95% confidence level (t-test) with those from an official method.

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.

Simultaneous voltammetric determination of paracetamol and caffeine in pharmaceutical formulations using a boron-doped diamond electrode

A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-doped diamond (BDD) electrode using square wave voltammetry (SWV) or differential Pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials Of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 x 10(-7) mol L(-1) to 8.3 x 10(-7) mol L(-1) for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 x 10(-7) mol L-1 and 3.5 x 10(-8) mol L(-1), respectively. The proposed method Was Successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level). (C) 2008 Elsevier BY. All rights reserved.

Integrating open innovation in the social innovation process: an exploratory study

Inovação tem se tornado um fenômeno cada vez mais complexo e dinâmico, com a mudança de um paradigma focado na inovação industrial, onde a inovação acontecia no produto ou no processo de fabricação, para outro baseado no conhecimento, muito mais amplo. Além disso, o conhecimento e a competência técnica não são mais considerados como um monopólio do departamento de pesquisa e desenvolvimento. Isto trouxe mudanças nas práticas de inovação, que se tornaram mais abertas e levaram as empresas a interagir cada vez mais com o seu ambiente. Por outro lado, a inovação tecnológica, cujo primeiro objetivo é de criar valor para a empresa, tem experimentado alguns limites para resolver problemas sociais, como o aquecimento global. As novas tecnologias têm a capacidade de melhorar a qualidade de vida de muita gente, mas não é suficiente. É nesse contexto que surge outro tipo de inovação, cujo objetivo é de maximizar o impacto positivo na sociedade: a inovação social. Estes dois paradigmas de inovação, mais adequados aos desafios atuais, têm alguns pontos em comum na sua integração com o ambiente externo: a sociedade e outros atores da inovação. No entanto, praticamente não existem estudos integrando inovação aberta e inovação social. Este trabalho estuda a integração destes dois modelos a partir de uma pesquisa exploratória, realizando entrevistas em profundidade com 11 dirigentes de organizações sociais. As iniciativas sociais parecem atrair mais organizações externas para colaborar do que empresas com fins lucrativos, já que são mais altruístas. Parecem integrar essas pessoas e procurar por mais ajuda, especialmente no momento de escalar o negócio. Ainda que algumas organizações têm como prioridade institucionalizar a inovação aberta, outras veem isto como secundário ou simplesmente não sabem como fazer. Isto resulta em uma colaboração mais informal, que não é focada em atividades de pesquisa e desenvolvimento, prática ausente nas empresas da nossa amostra.

An exploratory study on how to improve the economy of American Samoa

Deep in the South Pacific region about 2,300 miles southwest of the Hawaiian islands1 lies a United States territory that many Americans have never heard of nor known anything about. However, some famous Americans such as Troy Polamalu of the Pittsburgh Steelers, semi retired professional wrestler Dwayne “The Rock” Johnson, and Hawaii Congresswoman Tulsi Gabbard have genealogical roots there. More importantly, many of the Territory’s sons and daughters have served and lost their lives for the United States flag and the cause of freedom around the world. This place is called American Samoa, a collection of seven islands that if glued together would have a total landmass of approximately 76 square miles, just a tad bigger than the capital city of the United States. According to the United States Census Bureau, there were 55,519 residents of American Samoa in 2010.1 The majority of them are ethnic Samoans, a Polynesian sect that traces its history back to early migrants from Southeast Asia who settled the islands around 1500 B.C.2 3 The climate is warm all year long and the forests along the mountains are ripe with vegetation. The main island is Tutuila with its beautiful and coveted landlocked harbor that was used as a coaling station by the United States naval ships during World War II. In fact, it was the Pago Pago Harbor that diminished the impact of the 2009 Tsunami that devastated the Samoan islands by channeling the waters of the Pacific Ocean towards the end of the harbor instead of flooding many other villages surrounding the Pago Pago Bay area. Lives and property were destroyed near the end of the Harbor but it could have been worse for the entire Bay area. Locally grown foods include coconut, taro, banana, guava, sugar cane, papaya, yam, pineapple, and breadfruit. It is completely surrounded by the Pacific Ocean from which the locals obtain a variety of seafood. There is a popular saying in Samoa that goes, “In Samoa, it is impossible to starve 1 American Samoa Department of Commerce, 2012 Statistical Yearbook, http://www.doc.as/wpcontent/uploads/2011/06/2012-Statistical-Yearbook-1.pdf 2 U.S. Census Bureau News, U.S. Census Bureau Releases 2010 Census Population Counts for American Samoa, http://www.census.gov/2010census/news/releases/operations/cb11-cn177.html (Aug. 24, 2011). 3 3 J. Robert Shaffer, American Samoa: 100 Years Under the United States Flag (Honolulu, Hawaii: Island Heritage Publishing, 2000), 34. 4 because people live off of the land’s and the ocean’s abundant resources.” To the west of American Samoa lies a larger group of four islands that make up the Sovereign State of Samoa, which became independent from New Zealand in 1962. Samoa and American Samoa share the same language, culture, and religion but are divided by government and political systems. The focus of this study will be on American Samoa, which became a United States territory in 1900 when the principal chiefs of Tutuila (the largest island in American Samoa) ceded the islands to the United States.

Motivation of german entrepreneurs to seek equity via crowdfunding: an exploratory study

Equity crowdfunding, ou financiamento de um projeto ou empreendimento através de diversos pequenos investimentos ou um grande grupo de investidores, tem recebido uma crescente atenção da mídia e acadêmicos. A discussão questiona se crowdfunding pode de uma forma geral transformar a maneira como as pessoas captam capital para os seus negócios. Enquanto que pesquisas tem até então focado em explorar porque crowdinvestors têm motivação em financiar empreitadas, este estudo foca em revelar o que motiva empreendedores a procurar soluções de crowdfund. Para isso, o estudo investigou a motivação de 11 empreendedores que usaram plataformas alemãs de crowdfunding. Como estudos existentes sobre a motivação de empreendedores são na sua grande maioria superficiais, este estudo utiliza uma nova abordagem de pesquisa na área de financiamento de projetos, a abordagem de means-end. Sob essa abordagem a forma de pensar dos empreendedores em relação ao uso de equity crowdfunding foi estudada de forma holística, revelando todo o processo de raciocínio até a decisão final de optar por uma estratégia de crowdfunding. Uma das descobertas é que empreendedores usam equity crowdfunding para arrecadar fundos de crowdinvestors consideravelmente não-racionais (emocionais) para financiar o crescimento futuro de seus negócios e também sinalizar viabilidade de investimento para futuros investidores. Além disso, empreendedores esperam que crowdinvestors sejam engajados e ajudem tanto a promover o negócio como a dar feedback. Crowdfunding também possibilita que empreendedores mantenham o poder de decisão sobre a empresa mais facilmente se comparado a outras fontes tradicionais de financiamento. As descobertas indicam que crowdfunding atrai empreendedores que não conseguiriam arrecadar investimentos a partir de outras fontes de capital assim como empreendedores que entendem os benefícios adicionais que esta oferece em relação à outras fontes.