Search

Cocaine (COC) is one of the most widely consumed illegal drugs around the world. Street COC is commonly adulterated with pharmaceutical compounds that mimic or intensify the COC's sensory effect. Adulteration is performed to increase the profit of criminal organizations and each one has their own way of doing it. Therefore, determining the composition of seized COC samples (chemical profile) provides evidence for the police to track criminal organization networks and their activity patterns. Using filter paper as a substrate, we developed a multiple detection paper-based analytical device (PAD) that combines colorimetric and electrochemical measurements to discriminate COC samples according to adulterant's content. A regular graphite lead modified with a gold film made from Au leaf (graphite/Au) to improve electron transfer was used as a working electrode. Silver and Ag/AgCl were used as auxiliary and reference electrodes, respectively. The colorimetric device was patterned using a laser cutter and coupled to the electrochemical device using a double-sided tape, allowing simultaneous analysis to gather more analytical information about COC samples. Graphite/Au was characterized by scanning and transmission electron microscopies and electrochemical assays. The simultaneous colorimetric and electrochemical analyses combined to principal component analysis improved the analytical characterization of COC trial samples and provided a fast discrimination based on the assembled database.

Aims Exhaled breath acetone (EBA) has been described as a new biomarker of heart failure (HF) diagnosis. EBA concentration increases according to severity of HF and is associated with poor prognosis, especially in acute decompensated HF. However, there are no data on chronic HF patients. The aim is to evaluate the role of EBA for predicting cardiac and overall mortality in chronic HF patients. Methods and results In GENIUS‐HF cohort, chronic patients were enrolled between August 2012 and December 2014. All patients had left ventricular ejection fraction ≤ 50%, and the diagnosis was established according to Framingham criteria. After consent, patients were submitted to clinical evaluation and exhaled breath collection. EBA identification and quantitative determination were done by spectrophotometry. The clinical characteristics associated with acetone were identified. All participants were followed for 18 months to assess cardiac and overall mortality. Around 700 participants were enrolled in the current analysis. Patients were 55.4 ± 12.2 years old, 67.6% male patients, and 81% New York Heart Association I/II with left ventricular ejection fraction of 32 ± 8.6%. EBA median concentration was 0.6 (0.3–1.2) ug/L. Acetone levels increased with the number of symptoms of HF and were associated with right HF signs/symptoms and liver biochemical changes. EBA at highest quartile (EBA > 1.2ug/L) was associated with a significantly worse prognosis (log rank test, P 1.20ug/L was an independent predictor of cardiac (P = 0.011) and overall (P = 0.010) mortality in our population. Conclusions This study shows that EBA levels reflect clinical HF features, especially right HF signs/symptoms. EBA is an independent predictor of cardiac and overall mortality in chronic HF patients.

TiO2 has been used as a white pigment and studied since the first decades of the XX century for the undesirable chalking of outdoor paintings exposed to sunlight. Since the first report of Honda and Fujishima (1972) of the water splitting by the harvesting of sunlight on a n-type single crystal TiO2 electrode, the engagement of researchers with the field has grown steadily. TiO2-photocatalysis has joined the group of advanced oxidation processes for potential new water and wastewater treatments but, despite of its high chemical and photochemical stability and the great oxidizing power of its photogenerated holes, photons in UVA spectral region are needed to accomplish the high band gap, limiting the yield of sun-driven environmental applications. Nevertheless, this shortcoming has not restricted benchtop research and small and medium scale applications also relying on artificial UV sources, especially nowadays that highly-efficient UVA-LEDs are available. Herein, we review the fundamental aspects and the practical attributions of the trapping model in the charge transfer kinetics of photogenerated holes in nanoparticulate TiO2. Regarding to new practical uses, we focus our attention on some ingenious applications of this photocatalyst in the field of analytical chemistry, covering also subjects never reviewed before.

The present work describes an Integrated Teaching Tool (ITT) to facilitate the learning process in analytical chemistry. The first instrument integrated in the platform to demonstrate the concept is a wireless, portable fluorometer, produced by 3D printing. The low-cost instrument features a Teensy 3.1 board as the microcontroller, a high-power UV-LED, a secondary filter, a photodiode, and simple auxiliary electronic circuits. Modules of the ITT app were designed to manage the instrument and perform data acquisition remotely from any Android smartphone via Bluetooth, plot and transmit the results. Supporting the educational purpose of the platform, examples of basic concepts about fluorescence as well as technical information about the instrument are also provided to be considered for the app, which also allows instructors to assist and evaluate students through push notifications.

Air pollution is a major environmental risk for human health. Acetaldehyde is present in tobacco smoke and vehicle exhaust. In this study, we show that [13C2]-acetaldehyde induces DNA modification with the formation of isotopically labeled 1, N2-propano-2'-deoxyguanosine adducts in the brain and lungs of rats exposed to concentrations of acetaldehyde found in the atmosphere of megacities. The adduct, with the addition of two molecules of isotopically labeled acetaldehyde [13C4]-1, N2-propano-dGuo, was detected in the lung and brain tissues of exposed rats by micro-HPLC/MS/MS. Structural confirmation of the products was unequivocally performed by nano-LC/ESI+-HRMS3 analyses. DNA modifications induced by acetaldehyde have been regarded as a key factor in the mechanism of mutagenesis and may be involved in the cancer risks associated with air pollution.

Methods for determination of glycerol and its electrooxidation products (neutral diols and carboxylates) by capillary electrophoresis (CE) with dual capacitively coupled contactless conductivity detectors (C4D) are presented. Glycerol, dihydroxyacetone and glyceraldehyde were detected as anionic borate complexes in less than 3 min under counter Electroosmotic Flow (EOF) mode (resolution of the critical pair of 1.8). Limits of detection (LODs) of 15, 15 and 10 µmol L−1 were obtained for glycerol, dihydroxyacetone and glyceraldehyde, respectively. Two methods of separation were used for the separation of carboxylates. The first one used the same Back Ground Electrolyte (BGE) containing borate, and the second used a BGE (pH 6.1) composed by 2-(N-morpholino)ethanesulfonic acid (MES), L -Histidine and a flow modifier. Better separation and LODs for carboxylates were obtained using Mes/Histidine as BGE. However, along with the non-applicability of this BGE to the determination of neutral diols, observation of the C4D signals at two different points of the capillary (10 and 50 cm apart from the injection tip) revealed interaction of the flow modifier with some species (mesoxalate and glyoxylate). The electrooxidation of a glycerol sample in alkaline media on an 8 cm2 gold working electrode was evaluated by the developed methods. After 16 h of electrolysis, 87% of the glycerol had been oxidized and formate, glycolate, hydroxypyruvate and glycerate were detected as the main products.

Crucial steps of a chemical analysis, such as sampling, determination, and statistical analysis of data, are addressed in a well-tested and stimulating laboratory activity that convincingly unveils the stratification of ingredients in a heterogeneous household product for laundry: a powdered oxygen bleach. Three different samples of bleach were taken from a single jar: one from the top, one from the bottom, and a more representative mixture collected by driving a core sampler (a graduated cylinder was found to be appropriate) throughout the full depth of the jar content. The resulting frequency distribution curves (histograms) of the H2O2 titrations with MnO4– presented widely separated maxima for the three samples, while no statistically significant difference was found for the titration of CO32– with HCl. These results intrigue the students, leading them to reflect until they understand that this is due to the presence of a single compound acting as a source of H2O2 (sodium percarbonate), while two ingr...

1-propanol is a primary alcohol extensively used in the pharmaceutical, chemical, and food industries. It has been also found as a contaminant in the atmosphere and is considered a model compound to mimic the behavior and fate of aliphatic alcohols exposed to environmental conditions. In order to understand that role of relevant variables, this paper presents results obtained with a simple experimental set-up to investigate the reactivity of 1-propanol under mild oxidizing conditions. Coupling this system with CE-C4 D allowed the quantification of the carboxylic acids formed. For the described experiments, aqueous solutions of 1-propanol were placed inside a photoreactor and oxidized upon the addition of TiO2 and/or H2 O2 . According to the described results, the addition of H2 O2 (0.1% w/w) was the most significant variable, roughly tripled the amount of carboxylic acids generated and led to the conversion of up to 70% of the initially available 1-propanol (1 mmol/L). More importantly, the reaction yielded the formation (within 10 min) of propionate (50 µmol/L), acetate (400 µmol/L), formate (50 µmol/L), and malonate (200 µmol/L). The latter is critically important because it represents the first example of the photochemical oxidation of both terminal carbons of the C3 -chain of 1-propanol under mild conditions, and opens new avenues for the production of this important chemical building block.

1-propanol is a primary alcohol extensively used in the pharmaceutical, chemical, and food industries. It has been also found as a contaminant in the atmosphere and is considered a model compound to mimic the behavior and fate of aliphatic alcohols exposed to environmental conditions. In order to understand that role of relevant variables, this paper presents results obtained with a simple experimental set-up to investigate the reactivity of 1-propanol under mild oxidizing conditions. Coupling this system with CE-C

A new composite electrode (G-PSE) was developed from graphite powder and expanded polystyrene (EPS, Styrofoam) by simply dissolving the foam in chloroform, incorporating the graphite particles under mixing and volatilizing the solvent at 80 °C. The resulting rigid black composite can be softened with acetone and so it can easily be molded to any shape, e.g., into a PTFE tube with an electric contact, to build the electrode. A 75% graphite content (w/w) was found appropriate for preparing the G-PSE with a working potential similar to that of carbon paste electrodes, superior mechanical stability and a much faster response to ferrocyanide, close to reversible and similar to that of the much more expensive glassy carbon electrode. Applications of the G-PSE to dipyrone and paracetamol quantification in pharmaceutical formulations were demonstrated. The results accomplished by flow injection analysis with amperometric detection at the G-PSE were successfully validated against standards methods.

Time consuming thermal treatments are a common place in the preparation of photocatalysts and their immobilization on substrates. In this work nanolayers of TiO 2 were applied at room temperature on gold surfaces by simply exposing the metal during a minute to an acidic aqueous suspension of P25 TiO 2 (10 g L −1 in 0.1 mol L −1 HCl). Repulverization of the commercial semiconductor by dry grinding in a mortar increased the stability of the suspension and more than doubled the photoelectrocatalytic activity of the TiO 2 nanolayer. While the average TiO 2 particle size in the suspension was of 103 ± 3 nm (obtained by DLS), the less than 100 nm thick TiO 2 nanolayer on the gold surface was dominated by particles with diameters ranging from 20 nm (anatase) to 30 nm (rutile) (observed by SEM, TEM and EDS). Photooxidation experiments with EDTA −an emerging organic pollutant– revealed a linear relationship between the photocurrent and the potential applied to the TiO 2 modified electrode until the saturation photocurrent was attained. For a 1.0 mmol L −1 EDTA solution the integrated saturation photocurrent resulted in a net charge, repeatable from one electrode modification to another, of 38 ± 3C L mol −1 cm −2 (conditions: 100 s irradiation with an UV-LED at 365 nm, 91 mW cm −2 ; 0.5 V vs. Ag/AgCl applied potential). A micrometric TiO 2 layer applied on gold by drop casting enhances this net charge by just 50%. Cyclic voltammograms of the ferrocyanide/ferricyanide redox probe on gold remained undisturbed (in the dark) after the application of the TiO 2 nanolayer, but they became distorted with the drop-cast micrometric layer. The photoactivity of the TiO 2 nanolayer lasts with little decay for many days of photoelectrocatalytic treatment of EDTA. The simple and quick modification process at room temperature can be easily scaled-up to large areas.

Glass is one of the most convenient materials for the development of microfluidic devices. However, most fabrication protocols require long processing times and expensive facilities. As a convenient alternative, polymeric materials have been extensively used due their lower cost and versatility. Although CO2 laser ablation has been used for fast prototyping on polymeric materials, it cannot be applied to glass devices because the local heating causes thermal stress and results in extensive cracking. A few papers have shown the ablation of channels or thin holes (used as reservoirs) on glass but the process is still far away from yielding functional glass microfluidic devices. To address these shortcomings, this communication describes a simple method to engrave glass-based capillary electrophoresis devices using standard (1 mm-thick) microscope glass slides. The process uses a sacrificial layer of wax as heat sink and enables the development of both channels (with semicircular shape) and pass-through reservoirs. Although microscope images showed some small cracks around the channels (that became irrelevant after sealing the engraved glass layer to PDMS) the proposed strategy is a leap forward in the application of the technology to glass. In order to demonstrate the capabilities of the approach, the separation of dopamine, catechol and uric acid was accomplished in less than 100 s.

The science of semiconductors, essential in electronics, is pivotal also for the most active research fields of environmental science and engineering today - the development of solar energy conversions and advanced oxidation processes, exemplified by the harvesting of sun daylight to produce electric energy, environmentally friendly fuels and to clean up water from harmful pollutants. The advancement of such fields relies on the fundamentals of the photocatalysis at semiconductors, summarized in this review in language familiar to chemists. The theory and experimental onrush emerged mainly during the first half of the 20th century but the rising interest in the science of nanostructured materials in recent decades, besides many insights about the potential of this scale-down of sizes, also forced a revision of the theoretical models. Essentially, the interfacial model of the space-charge layer cannot explain the behavior of nanoparticulate films, even at doped conditions comparable to monocrystalline materials. The present work encompasses the conformation of classical photocatalytic models to the nanoscale size, critically reviewing their features and role for modern electrochemical applications.

Recently our group has developed a simple and practical procedure to immobilize glucose oxidase (GOD) on poly(methyl methacrylate) (PMMA) microchannels. In the present study not only was the GOD microreactor preparation optimized but also, more important, it is shown that the functionalization of PMMA microchannels with polyethyleneimine (PEI) is a methodology of wider applicability to anchor enzymes with glutaraldehyde, with a potential for the development of microanalytical devices and systems. As a demonstration, the preparation and evaluation of microreactors with immobilized ascorbate oxidase (AAO), catalase (CAT), glutamate dehydrogenase (GDH) and a dual enzymatic system (GOD and horseradish peroxidase) is reported. Direct (GOD) and indirect (AAO and CAT) chronoamperometric measurements were made in order to evaluate the reactors' activity. GDH immobilization was confirmed photometrically through a thiazolyl blue tetrazolium bromide based reaction while a Trinder's reaction based method was used to evaluate the GOD/HRP microreactor. A small volume flow cell built in the lab was connected to two optical fibers to implement spectrophotometric measurements. After 15 days of use (~ 1000 injections), no change was observed in the efficiency of the CAT reactor (100% destruction of the analyte) while the GOD/HRP reactor that decayed to 25% of the original activity, was still useful despite the decrease in sensitivity.

Um sistema completo foi desenvolvido para o novo acoplamento de uma célula eletroquímica em fluxo com um eletroforese capilar equipado com detector condutométrico sem contato (EC-CE-C4D). Este acoplamento compreendeu o design da interface EC-CE, um potenciostato protegido contra fuga de alta tensão, subsistema de controle de fluxo por bombas solenóide e um equipamento CE-C4D adaptado para a aplicação. Um software dedicado para aquisição de dados, controle e operação do sistema foi desenvolvido na ferramenta gráfica de programação LabView. O sistema foi inicialmente aplicado na eletrodeposição de traços dos metais Cd2+, Pb2+, Cu2+, Zn2+ e Tl+, seguida pela redissolução e separação destes por CE, o que resultou em fator de pré-concentração de até 55 vezes para todos os metais, exceto Zn2+. Os metais acumulados foram redissolvidos na matriz original da amostra para permitir a separação e determinação conjunta com cátions majoritários (p. ex. alcalinos e alcalinos terrosos e amônio, se acima do LD). Para amostras cuja matriz possa causar interferência, pouco antes da injeção no CE, foi realizado processo de cleanup pela redissolução dos metais no eletrólito de separação. Experimentos pra separação bidimensional com o potencial de deposição ou redissolução voltamétrica como primeira dimensão e o tempo de eletromigração como segunda dimensão foram propostos e demonstrados. A oxidação eletroquímica de espécies orgânicas na interface EC-CE surgiu como um segundo campo de aplicação para: a) derivatização de analitos neutros tornando-os carregados ou ionizaveis, p. ex., conversão de álcoois alifáticos de cadeia curta em carboxilatos que possam ser separados e quantificados por CE-C4D; b) investigação/monitoramento de processos de eletrodo pela detecção de produtos carregados ou ionizáveis de reação de eletrodo, p. ex., investigação de condições experimentais para eletrooxidação de glicerol objetivando-se a síntese de produtos com maior valor comercial. A complete instrumental system was developed for the new coupling of an electrochemical flow cell to capillary electrophoresis with contactless conductivity detection (EC-CE-C4D) and comprising an innovative design of the EC-CE interface, a potentiostat circuit protected from high voltage leakages, a solenoid pump based flow management subsystem, and a CE-C4D equipment tailored for this application. Dedicated software for data acquisition, devices control and operation automation was developed in LabVIEW graphical programming tool. The system was first applied to the electrodeposition of traces of Cd2+, Pb2+, Cu2+, Zn2+ and Tl+ , followed by stripping and separation by CE, allowing a 55-fold preconcentration factor in 6 min for all metals but Zn2+. The accumulated metals were stripped into the original sample matrix to allow their separation together with the sample\'s major cations (e.g. alkaline and alkaline earth metals and ammonium, if above LOQ). For samples with a matrix that originates interferences, cleanup was achieved by stripping the metals into background electrolyte shortly before injection in the capillary. Two-dimensional separations with voltammetric deposition or stripping potential as one dimension and electromigration time as the second one were proposed and demonstrated. Electrochemical oxidation of organic species in the EC-CE interface emerged as a second field of application for: a) derivatization of neutral analytes into charged or ionizable species, e.g., conversion of short chain aliphatic alcohols into carboxylates that can been determined by CE-C4D; b) investigation/monitoring of electrode processes by detection of charged or ionizable reaction products of electrode reactions, e.g., investigation of experimental conditions for glycerol electro-oxidation aiming the synthesis of commercially valuable products.

Gold is among the most used materials in electrocatalysis. Despite this, this noble metal is still too expensive to be used in the fabrication of low cost and disposable devices. In the present work, gold-leaf sheets, usually employed in decorative crafts and wedding candies, is introduced as an inexpensive source of gold. Planar-disc and nanoband gold electrodes were simply and easily manufactured by combining gold leaf and polyimide tape. The planar disc electrode exhibited electrochemical behavior similar to that of a commercial gold electrode in 0.2molL-1 H2SO4; cyclic voltammetry of a 1mmolL-1 solution of potassium ferricyanide (K3[Fe(CN)6]) in 0.2molL-1 KNO3, using this novel electrode, displayed an 80mV difference between the oxidation and reduction peak potentials. The electrode also delivers promising prospects for the development of wearable devices. When submitted to severe mechanical deformation, this electrode exhibited neither loss of electrical contact nor significant variation in electrode response, even after fifteen bending and/or folding cycles. The thickness of the gold-leaf sheet facilitates the production of nanoband electrodes with behavior similar to that of ultramicroelectrodes. The electrode surface is easily renewed by cutting a thin slice off its end with a razor blade; this process led to limiting currents that were reproducible, presenting a relative standard deviation (RSD) of 3.8% (n = 5).

Methods for determination of glycerol and its electrooxidation products (neutral diols and carboxylates) by capillary electrophoresis (CE) with dual capacitively coupled contactless conductivity detectors (C

An EC-CE-C

Concurrently with ethanol, many other compounds can be formed during the fermentation of grains and fruits. Among those, methanol is particularly important (because of its toxicity) and is typically formed at concentrations much lower than ethanol, presenting a particular challenge that demands the implementation of separation techniques. Aiming to provide an alternative to traditional chromatographic approaches, a hybrid electrophoresis device with electrochemical preprocessing and contactless conductivity detection (hybrid EC-CE-C4D) is herein described. The device was applied to perform the electro-oxidation of primary alcohols, followed by the separation and detection of the respective carboxylates. According to the presented results, the optimum conditions were obtained when the sample was diluted with 2 mmol L–1 HNO3 and then electro-oxidized by applying a potential of 1.4 V for 60 s. The oxidation products were then electrokinetically injected by applying a potential of 3 kV for 4 s and separated u...

An EC-CE-C4D flow system was applied to the investigation of electrocatalytic processes by monitoring carboxylic acids formed during the electro-oxidation at various potentials of primary alcohols (mixture of 1 mmol L−1 of ethanol, n-propanol, n-butanol and n-pentanol) in acidic, neutral and alkaline media. The electro-oxidation was carried out on gold and platinum disk electrodes (3 mm of diameter) in a thin-layer electrochemical flow cell. Products were sampled 50 μm apart from the electrode directly into the capillary. All the generated carboxylates were determined in near real time (less than 2 min) by CE-C4D in counter-flow mode, with Tris/HCl buffer solution (pH 8.6) as BGE. Long sequences of 5 min experiments were run automatically, exploring the applied potential, electrolysis time and solution composition. Electro-oxidation at 1.5 V (vs. Ag/AgCl quasi-reference) during 50 s in acidic medium was found appropriate for both Pt and Au electrodes when the determination of alcohols after derivatization is intended. A noteworthy selectivity effect was observed on the Au electrode. The signal corresponding to pentanoate is similar on both electrodes while the signal of ethanoate (acetate) is four times larger on gold than on platinum. The carboxylate signals were lower in alkaline medium (below the determination limit on Pt) than in acidic and neutral media. On gold, the formation of carboxylates was anticipated (0.85 V in alkaline medium vs. 1.40 V in neutral medium). The automatic online monitoring of electrochemical processes by EC-CE-C4D holds great potential to investigate ionic/ionizable intermediates/products of new electrocatalysts and/or alternative fuels. This article is protected by copyright. All rights reserved

The simultaneous determination of cationic, anionic, and neutral analytes in a real sample was demonstrated by coupling electrochemical (EC) derivatization with counter-EOF CE-C(4) D. An EC flow cell was used to oxidize alcohols from an antiseptic mouthwash sample into carboxylic acids at a platinum electrode in acid medium. The carboxylates formed in the derivatization process and other sample ingredients, such as benzoate, saccharinate, and sodium ions, were separated in counter-flow mode and detected in one run in Tris-HCl buffer, pH 8.6. Fewer than 5 min were needed to complete each analysis with the automated flow system comprising solenoid pumps for the management of solutions. Insights into the electrochemistry of benzoic acid, present in the sample matrix, were also gained by EC-CE-C(4) D; more specifically, by applying potentials higher than 1.47 V to the platinum electrode, some formiate and minute amounts of salicylate were detected.

Heart failure (HF) is a clinical condition that presents high morbidity and mortality and is one of the main reasons for hospital admissions all over the world. Although biochemical processes that occur in the body during heart failure are known, this syndrome is still associated to poor prognosis. Exhaled breath analysis has emerged as a promising noninvasive tool in different clinical conditions and, recently, it has been also tested in patients with HF. This review presents the main breath HF biomarkers, which reflect metabolic changes that occur in this complex syndrome. It also discusses the diagnostic and prognostic value of exhaled breath compounds for HF and makes a short description of the main technologies involved in this analysis. Some perspectives on the area are presented as well.

A closer look at particles of a solid oxygen-based bleach household product is proposed, both figuratively and literally, to help develop observation and critical thinking skills and to link everyday life to chemistry concepts like acid–base equilibrium, redox reactivity, gas laws, gas volumetry, stoichiometry, and morphology of a heterogeneous solid mixture. In a microchemical approach, students learn to discriminate particles by their morphology under an optical (or low-cost USB) microscope and to investigate how they react with (a) hypochlorite solution (or household chlorine bleach); and (b) acetic acid (or vinegar). Aware of the ingredients listed on the product’s label, and searching for the structure and formula of percarbonate (2Na2CO3·3H2O2), a hydrogen peroxide–sodium carbonate adduct, they end up concluding that the particles showing effervescence with both reagents consist of sodium percarbonate, and those bubbling only in contact with acetic acid are sodium carbonate, while other minor ingred...

Background The identification of new biomarkers of heart failure (HF) could help in its treatment. Previously, our group studied 89 patients with HF and showed that exhaled breath acetone (EBA) is a new noninvasive biomarker of HF diagnosis. However, there is no data about the relevance of EBA as a biomarker of prognosis. Objectives To evaluate whether EBA could give prognostic information in patients with heart failure with reduced ejection fraction (HFrEF). Methods After breath collection and analysis by gas chromatography-mass spectrometry and by spectrophotometry, the 89 patients referred before were followed by one year. Study physicians, blind to the results of cardiac biomarker testing, ascertained vital status of each study participant at 12 months. Results The composite endpoint death and heart transplantation (HT) were observed in 35 patients (39.3%): 29 patients (32.6%) died and 6 (6.7%) were submitted to HT within 12 months after study enrollment. High levels of EBA (≥3.7μg/L, 50th percentile) were associated with a progressively worse prognosis in 12-month follow-up (log-rank = 11.06, p = 0.001). Concentrations of EBA above 3.7μg/L increased the risk of death or HT in 3.26 times (HR = 3.26, 95%CI = 1.56–6.80, p = 0.002) within 12 months. In a multivariable cox regression model, the independent predictors of all-cause mortality were systolic blood pressure, respiratory rate and EBA levels. Conclusions High EBA levels could be associated to poor prognosis in HFrEF patients.

A thin-layer electrochemical flow cell coupled to capillary electrophoresis with contactless conductivity detection (EC-CE-C(4)D) was applied for the first time to the derivatization and quantification of neutral species using aliphatic alcohols as model compounds. The simultaneous electrooxidation of four alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) to the corresponding carboxylates was carried out on a platinum working electrode in acid medium. The derivatization step required 1 min at 1.6 V vs. Ag/AgCl under stopped flow conditions, which was preceded by a 10 s activation at 0 V. The solution close to the electrode surface was then hydrodynamically injected into the capillary, and a 2.5 min electrophoretic separation was carried out. The fully automated flow system operated at a frequency of 12 analyses per hour. Simultaneous determination of the four alcohols presented detection limits of about 5 × 10(-5) mol L(-1). As a practical application with a complex matrix, ethanol concentrations were determined in diluted pale lager beer and in nonalcoholic beer. No statistically significant difference was observed between the EC-CE-C(4)D and gas chromatography with flame ionization detection (GC-FID) results for these samples. The derivatization efficiency remained constant over several hours of continuous operation with lager beer samples (n = 40).

Heart failure (HF) is associated with poor prognosis, and the identification of biomarkers of its severity could help in its treatment. In a pilot study, we observed high levels of acetone in the exhaled breath of patients with HF. The present study was designed to evaluate exhaled acetone as a biomarker of HF diagnosis and HF severity.Of 235 patients with systolic dysfunction evaluated between May 2009 and September 2010, 89 patients (HF group) fulfilled inclusion criteria and were compared with sex- and age-matched healthy subjects (control group, n = 20). Patients with HF were grouped according to clinical stability (acute decompensated HF [ADHF], n = 59; chronic HF, n = 30) and submitted to exhaled breath collection. Identification of chemical species was done by gas chromatography-mass spectrometry and quantification by spectrophotometry. Patients with diabetes were excluded.The concentration of exhaled breath acetone (EBA) was higher in the HF group (median, 3.7 μg/L; interquartile range [IQR], 1.69-10.45 μg/L) than in the control group (median, 0.39 μg/L; IQR, 0.30-0.79 μg/L; P.001) and higher in the ADHF group (median, 7.8 μg/L; IQR, 3.6-15.2 μg/L) than in the chronic HF group (median, 1.22 μg/L; IQR, 0.68-2.19 μg/L; P.001). The accuracy and sensitivity of this method in the diagnosis of HF and ADHF were about 85%, a value similar to that obtained with B-type natriuretic peptide (BNP). EBA levels differed significantly as a function of severity of HF (New York Heart Association classification, P.001). There was a positive correlation between EBA and BNP (r = 0.772, P.001).EBA not only is a promising noninvasive diagnostic method of HF with an accuracy equivalent to BNP but also a new biomarker of HF severity.

Um sistema automatizado de analise foi projetado pelo acoplamento de microamostrador difusional baseado em uma membrana capilar microporosa (CMDS) com a separacao por eletroforese capilar (CE) e deteccao condutometrica sem contato (C4D). O volume interno do CMDS, da ordem de 30 µL, combinado com a demanda de nanolitros dos equipamentos de CE-C4D, levou a concepcao de um sistema automatizado de gerenciamento de fluido de baixo custo e livre de manutencao recorrente, baseado em bombas de aquario e valvulas de estrangulamento controladas via software, uma interface CMDS-CE de pequeno volume e um equipamento robusto de CE operado com injecao hidrodinâmica. Como exemplo de aplicacao do sistema, foi demonstrada a amostragem conjunta de acido formico e acido acetico no ar, com elevados fatores de pre-concentracao em fase liquida, e quantificacao por CE-C4D a uma frequencia de operacao ininterrupta de 10 analises completas por hora. Os limites de deteccao estimados foram de 1,2 µg m-3 para o acido formico e 3,0 µg m-3 de acido acetico no ar, com resposta linear no intervalo de concentracao usual desses analitos em fase gasosa da atmosfera.

Analysis by capillary electrophoresis (CE) of nanoliter samples taken 0.05 mm away from the electrode/solution interface assisted in the evaluation of glycerol electrooxidation on noble metals (Pt, Au and Pd). The fully automated all electrochemical flow system generates a conductometric electropherogram every few minutes, while exploring experimental parameters. Products like glycerate, glycolate, formate and hydroxymalonate were observed in different ratios by changing the electrocatalyst and the applied potential. On Pd, dissolved oxygen oxidizes glycerol at zero current. This new approach holds promise for fast in situ study of reaction products of heterogeneous catalysis reactions and electrode processes in general.

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-C⁴D). 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-C⁴D 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-C⁴D 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.

Vast quantities, on the order of megatons, of pollutants are emitted monthly to the atmosphere both by natural and anthropogenic sources. The evaluation of rainwater composition has great importance in understanding the atmospheric chemical composition, as water drops scavenge particles and soluble atmospheric pollutants. Most students are aware that SO2 is one of the pollutants related to the acidification of the atmosphere owing to its oxidation in the gas or liquid phase that produces sulfate and H+, but the situation is more complex in the presence of other common pollutants such as ammonia or formaldehyde. To give insight into the chemistry occurring in the gas and liquid phases, a demonstration is described where the pH of a “raindrop” is monitored during absorption of SO2 followed by exposure to H2O2, with or without previous contact with gaseous CH2O. The effect of the presence of alkalinizing substances such as NH3 in the atmosphere is evaluated as well. The raindrop is simulated by the wet bulb ...

A dynamic atmosphere generator with a naphthalene emission source has been constructed and used for the development and evaluation of a bioluminescence sensor based on the bacteria Pseudomonas fluorescens HK44 immobilized in 2% agar gel (107 cell mL−1) placed in sampling tubes. A steady naphthalene emission rate (around 7.3 nmol min−1 at 27 °C and 7.4 mL min−1 of purified air) was obtained by covering the diffusion unit containing solid naphthalene with a PTFE filter membrane. The time elapsed from gelation of the agar matrix to analyte exposure (“maturation time”) was found relevant for the bioluminescence assays, being most favorable between 1.5 and 3 h. The maximum light emission, observed after 80 min, is dependent on the analyte concentration and the exposure time (evaluated between 5 and 20 min), but not on the flow rate of naphthalene in the sampling tube, over the range of 1.8–7.4 nmol min−1. A good linear response was obtained between 50 and 260 nmol L−1 with a limit of detection estimated in 20 nmol L−1 far below the recommended threshold limit value for naphthalene in air.

A simple and sensitive spectrophotometric flow method for determination of low concentrations of the flotation collector O-ethyldithiocarbonate (ethyl xanthate, CH3CH2-O-CS2 − ) in solutions is described. The method is based on ethyl xanthate detection at 301 nm in medium of NaOH 50 mmol L −1 . By injection of 200L of sample, the analytical method shows linear response for the ethyl xanthate concentration from 0.5 up to 500mol L −1 . Successive injections of 4mol L −1 ethyl xanthate (n = 23) show a coefficient of variation lower than 0.6%, denoting high repeatability. The detection limit is 0.3mol L −1 . At a flow rate of 2.0 mL min −1 , a frequency of 120 injections/h of ethyl xanthate can be attained. By introduction of a tangential dialysis cell in the FIA system, the manual sample filtration step with 0.22m filter was eliminated and the residual interference of suspended material, was completely overcome even for unfiltered sludge suspension samples, an important advantage that compensates for the frequency reduction to 25 injections/h elevation and detection limit elevation to 2mol L −1 , still outreaching for many applications. Potential applications of the method embrace the at line determination of ethyl xanthate in the ore processing industry, control of the concentration at its optimal level during the flotation process, as well as monitoring of residues in the effluents. © 2007 Elsevier B.V. All rights reserved.

A novel microreactor for TiO2-assisted photocatalysis in a microfluidic electrochemical cell was designed and constructed by a technology that can be reproduced in any chemical laboratory. The cell is obtained by a two-step thermal transfer of laser printed masks onto gold CD-Rs, a subtractive one to define the electrodes, and an additive one to define the channels. The TiO2 nanoparticles are physically embedded in a gold matrix by electrodeposition from a solution of ions of this metal also containing colloidal suspension of anatase. This modification is conducted in the assembled microfluidic cell, with minimum material and time consumption. A 100 mW UV-LED (365 nm) is focused on the modified electrode and irradiation of the sample in the thin layer microreactor is conducted under stopped flow condition. The Cu–EDTA complex served as model system to demonstrate the in situ photocatalytic digestion of organic matter followed by the voltammetric determination of the metal ion in aqueous solution. The voltammetric wave of 1.0 × 10−3 mol L−1 Cu(II) in acetate buffer (pH 4.7) at the gold electrode is suppressed by EDTA in the −0.3 to 0.8 vs. Ag/AgCl region. Irradiation of the bare electrode at 365 nm does not recover the wave, while irradiation of the TiO2-modified gold electrode causes the recovery of the copper wave, proving the photocatalytic destruction of the chelating agent. Diffusion transport to/from the modified electrode rapidly enrolls the whole volume of sample in the thin-layer above the electrode (about 19 nL), so that in less than four minutes the recorded voltammogram become indistinguishable from that of a copper ion solution without EDTA. This novel in situ sample pre-treatment approach is very promising, deserving further research aiming its integration in micro-TAS. Keywords: Photocatalytic digestion, Microfluidic cell, TiO2 immobilization, Modified gold electrode, Cu(II) detection, Photocatalysis with UV-LED, Flow voltammetry

Air pollution is a major risk for human health. Acetaldehyde is an environmental pollutant present in tobacco smoke, vehicle exhaust and several food products. Formation of DNA adducts has been regarded as a critical factor in the mechanisms of acetaldehyde mutagenicity and carcinogenesis. Acetaldehyde reacts with 2'-deoxyguanosine in DNA to primarily form N(2)-ethylidene-2'-deoxyguanosine (N(2)-ethylidene-dGuo). The subsequent reaction of N(2)-ethylidene-dGuo with another molecule of acetaldehyde gives rise to 1,N(2)-propano-2´-deoxyguanosine (1,N(2)-propanodGuo). In this study, on-line reverse-phase high-performance liquid chromatography (HPLC) separation with tandem mass spectrometry detection was utilized for the accurate quantification of 1,N(2)-propanodGuo and 1,N(2)-etheno-2'-deoxyguanosine (1,N(2)-edGuo) in tissues of rats exposed to 12 ppb, 33 ppb and 96 ppb acetaldehyde in atmospheric air for 50 days. A significant increase in the levels of 1,N(2)-propanodGuo was observed in lung tissues of rats exposed to 12 ppb (7.8/10(8) dGuo); 33 ppb (8.9/10(8) dGuo) and 96 ppb (11.6/10(8) dGuo) compared to controls (4.2/10(8) dGuo). For comparative purposes, the levels of 1,N(2)-etheno-2'-deoxyguanosine (1,N(2)-edGuo), which is produced from a,b-unsaturated aldehydes formed during the lipid peroxidation process were also measured. Elevated levels of 1,N(2)-edGuo were observed only in lung tissues of animals exposed to 96 ppb acetaldehyde. 1,N(2)-propanodGuo also differed quantitatively in liver but not in brain. The monitoring of 1,N(2)-propanodGuo levels in tissues provides important information on acetaldehyde genotoxicity and may contribute to the elucidation of the mechanisms associated with acetaldehyde exposure and cancer risk. Supported byFAPESP:2011/10048-5, CAPES, INCT Redoxoma:573530/2008-4,NAP Redoxoma: 2011.1.9352.1.8, CEPID Redoxoma:2013/07937-8.

O presente trabalho começa por uma apresentação monográfica do fenômeno de adsorção, que dá acesso à bibliografia existente sobre o assunto. Numa extensa parte experimental desenvolveu-se um eletrodo de amálgama gotejante e um eletrodo de gota pendente mercúrio capaz de gerar gotas com área reprodutível dentro de ± 0,1%. Fez-se, também, a implantação da técnica da cronocoulometria, com os recursos disponíveis neste Instituto de Química. Realizou-se um estudo polarográfico preliminar onde se observaram diversos efeitos inibitivos sobre a reação de eletrodo do Cd(II), ligados á presença dos fenantrolino complexos de Cd(II) e de Fe(II), com participação de ânions. O sistema cádmio(II)/piridina/cloreto foi estudado potenciometricamente, tendo sido avaliadas as seguintes constantes globais de estabilidade βij = ‌CdpyiClj‌/‌Cd‌ ‌py‌ i‌Cl‌j (i, número de ligantes piridina, e j, de cloreto): β01 = 25,36, β02 = 96,0, β03 = 48,3, β04 = 65,8, β10 = 23,5, β11 = 550, β12 = 2600, β13 = 550, β14 = 1100, β20 = 690, β21 = 9740, β22 = 9400, β30 = 270, β31 = 3500, β32 = 37400, β40 = 8450, β41 = 54400. Para chegar às constantes de equilíbrio usou-se um processo iterativo de cálculo. As medidas foram realizadas com um eletrodo de amálgama gotejante, após comprovar-se que o eletrodo íon-seletivo de cádmio de estado sólido é inadequado para esta finalidade. Empregou-se um novo tipo de diagramas para representar a contribuição percentual das espécies formadas, em função dos dois ligantes. Estudou-se, através da cronocoulometria, a adsorção do sistema Cd(II)/py/Cl-, em diversas condições, fixando a concentração do metal e do cloreto e variando-se a concentração de py. Ficou estabelecido que a adsorção dos complexos é um processo competitivo com a dos ligantes. Há sempre um máximo de adsorção na faixa de 0,1 a 0,5 M de py. Encontraram-se evidências de que as espécies mistas neutras são preferencialmente adsorvidas. The present thesis starts with the monographic discussion of the adsorption phenomena, with several references. There is an extensive experimental part referred to the development of a simple dropping amalgam electrode, a hanging mercury drop electrode whose area is reproductible within 0,1%, and the introduction of the double step chronocoulometric method w1th the resources of this Chemistry Institute, was done. In a preliminary polarographic study, several inhibiting effects on the Cd(II) electrode reaction, due to the presence of cadmium(II) and iron(II) complexes of phen participation of some anions has been observed. A potentiometric study of the cadmium(II)/pyridine//chloride system lead to the evaluation of the overall stability, βij = ‌CdpyiClj‌/‌Cd‌ ‌py‌ i‌Cl‌j (i, number of py ligands and j of chloride ones): β01 = 25,36, β02 = 96,0, β03 = 48,3, β04 = 65,8, β10 = 23,5, β11 = 550, β12 = 2600, β13 = 550, β14 = 1100, β20 = 690, β21 = 9740, β22 = 9400, β30 = 270, β31 = 3500, β32 = 37400, β40 = 8450, β41 = 54400. To obtain the equilibrium constants from the experimental data, an iterative calculation process was used. The measurements has been made with an amalgam electrode, after unsucessfull tests with a solid state cadmium ion selective electrode. A new type of diagram was used to present the percent distribution of the species with the change in the concentration of the ligands, in substitution to the predominance area diagram. In add1tion, the chronocoulometric study of the Cd(II)/ /py/Cl- system was done at several experimental conditions, by fixing the concentration of the metal and the chloride, and changing in wide extension the pyridine concentration. The adsorption of the complexes is a competitive process with the free ligands, and allways exhibits a maxima between .1 and .5M pyridine. There are strong evidences indicating that the neutral mixed species are preferabbly adsorbed.

The structure of polytetraruthenated nickel porphyrin was unveiled for the first time by electrochemistry, Raman spectroelectrochemistry, and a hydroxyl radical trapping assay. The electrocatalytic active material, precipitated on the electrode surface after successive cycling of [NiTPyP{Ru(bipy)2Cl}4](4+) species in strong aqueous alkaline solution (pH 13), was found to be a peroxo-bridged coordination polymer. The electropolymerization process involves hydroxyl radicals (as confirmed by the characteristic set of DMPO/(•)OH adduct EPR peaks) as reaction intermediates, electrocatalytically generated in the 0.80-1.10 V range, that induce the formation of Ni-O-O-Ni coordination polymers, as evidenced by Raman spectroelectrochemistry and molecular modeling studies. The film growth is halted above 1.10 V due to the formation of oxygen gas bubbles.

Eduardo Fausto de Almeida Neves, Professor Emeritus of the Universidade Federal de São Carlos and formerly Full Professor at the Instituto de Química - Universidade de São Paulo (USP), São Paulo, Brazil, was born in November 7, 1933 in Pedra Azul, MG, and deceased in July 2, 2006 in São Carlos, SP. He graduated under supervision of Professor Paschoal Senise, pioneer of Analytical Chemistry at USP, and developed his post-doctoral work at Caltech, USA, with Professor Fred Anson. His brilliant career as teacher, scientist, supervisor and mentor resulted in a prolific science school in Analytical Chemistry, with some sixty PhDs and masters supervised by him, amplified to over four hundred in the 2nd to 4th generations (still growing), spread throughout the country and nucleating new research groups. The contents of a hundred papers reflect Prof. Eduardo's wide range of scientific interests. Passionate inclination for creative intellectual activity, rooted in profound knowledge of all branches of Chemistry, broadminded thinking, sound experimentation, generous scientific cooperation and true friendship - that's why friends, colleagues and students referred to him as "master" or "my guru".

The metropolitan area of Sao Paulo (MASP), with 18 million inhabitants, is one of the largest urban areas of the world, with serious environmental problems, including atmospheric pollution. Even though there is an official network monitoring the air quality, it does not include data on the chemical composition of precipitation. However, some research groups have sampled and measured common analytes in rainwater on several sites at MASP during restricted periods. Eventually, available data of pH values and ion concentrations in rainwater since 1983 in the city of Sao Paulo have been compiled and are, now, discussed in this work, which, besides showing possible trends, gives support for future studies planned in MASP. A decreasing trend of rainwater free acidity in Sao Paulo occurred along the 2 decades considered. Since 1995, no monthly volume weight mean (VWMm) pH values below 4.5 have been observed which, in part, reflects the gradual decrease in the atmospheric concentrations of the SO2, with annual average of 65 μg m−3 in 1983 and 15 μg m−3 in 2003. Scarce data on sulfate concentration in the rain shows a similar decay from 33±35 μmol L−1 in 1989–1990 to 19±18 μmol L−1 in 2002–2003. Despite the fact that no significant trends can be inferred in the limited nitrate database, for ammonium, high concentrations (47±42 μmol L−1 of NH4+) have been observed in recent years, indicating the contribution of the NH3 present in the Sao Paulo's atmosphere to the neutralization of the rain acidity.

A chemometric method for analysis of conductometric titration data was introduced to extend its applicability to lower concentrations and more complex acid-base systems. Auxiliary pH measurements were made during the titration to assist the calculation of the distribution of protonable species on base of known or guessed equilibrium constants. Conductivity values of each ionized or ionizable species possibly present in the sample were introduced in a general equation where the only unknown parameters were the total concentrations of (conjugated) bases and of strong electrolytes not involved in acid-base equilibria. All these concentrations were adjusted by a multiparametric nonlinear regression (NLR) method, based on the Levenberg-Marquardt algorithm. This first conductometric titration method with NLR analysis (CT-NLR) was successfully applied to simulated conductometric titration data and to synthetic samples with multiple components at concentrations as low as those found in rainwater (approximately 10 micromol L(-1)). It was possible to resolve and quantify mixtures containing a strong acid, formic acid, acetic acid, ammonium ion, bicarbonate and inert electrolyte with accuracy of 5% or better.

The new electrolytic dissolution in batch of aluminum alloys samples as grains or turns and the determination of Fe, Cu, Mn, Mg, Cr, Ni, Zn, Pb and Ti by ICP OES was investigated. In on-line electrodissolution procedures described in the literature, samples were restricted to be in the form of solid blocks or plates with one polished flat face. Here, the sample was loaded in the barrel of a modified disposable syringe (the anodic semi-cell) and pressed with a modified plunger fitted with a platinum disk to establish electrical contact with the analyte. This arrangement was introduced in a beaker containing the electrolyte (1 mol L−1 HNO3) and a platinum wire as the cathode. The resulting solution from electrodissolution (0.6 A) was used for the ICP OES determinations. The influence of the aluminum concentration increase on the determination of the elements was evaluated. Electrodissolution of certified reference materials and commercial samples revealed relative errors lower than 10% for the elements Fe, Cu, Mg, Ni, Cr, Zn and Ti (when their content is above 0.1%). Higher inaccuracies (>10%) were observed for Mn and for Fe in B.C.S. 268/1 reference material certified. The proposed method presented a relative standard deviations (R.S.D.) lower or circa 10% to all of the elements (except Pb). In comparison with traditional acid dissolution, the proposed electrodissolution method is relatively fast (about 30 min), it is clean (there is no projection of solution) and simple (heating and fumes exhaust system were not necessaries).

A simple and reliable FIA-potentiometric system for rapid assays of chloride in certain food samples is described and evaluated. The system is constituted by an aquarium air pump to propel the carrier solution, a manually operated injector, a homemade dialysis flow cell, a solid-state chloride detector (Ag/AgCl), a reference electrode and a multimeter connected to a microcomputer for data acquisition. The dialysis unit enables direct analysis of liquid food samples without any other previous treatment. The principal novelties are the precision (R.S.D. of 1.2% for whole milk) and rapidity (90 determinations/h) of FIA measurements near and below the lower end of the linear (Nernstian) response region of the chloride ion-selective electrode (ISE), with an estimated detection limit (3 s) of 0.4 mg L −1 Cl − in the sample injected in donor stream. Data of peak potential versus sample chloride concentration (donor stream) was accurately fitted with a quadratic polynomial over the range between 4 and 1000 mg L −1 (r 2 = 0.9999) and used as a calibration curve. The method was applied to the determination of chloride in milk and in coconut water samples. The validation of the results was done by comparison with a NIST reference material (milk) or by capillary electrophoresis (coconut water). For all analysis, no significant difference at a 95% confidence level was observed. © 2005 Elsevier B.V. All rights reserved.

An original, simple and sensitive flow-injection spectroelectroanalytical method for the determination of chlorpromazine in pure form or in pharmaceutical formulations is described. The method is based on the formation of a stable cationic radical by electro-oxidation in sulfuric acid medium (0.1 mol l−1), monitored in situ at λ = 524 nm. The determination of chlorpromazine hydrochloride in pure form or in pharmaceutical formulations was explored, considering the amperometric and the absorptiometric signal. The association of these two signals enhanced the selectivity of the analysis and proved decisive when other electroactive compounds or excipients like ascorbic acid were present in the formulation. The analytical parameters have been evaluated and the results obtained using standard additions are in agreement with the reference methods.

The forensic analysis of lead in gunshot residues (GSR) sampled on the hands of potential shooters is rendered faster, simpler and less expensive by a new batch injection analysis (BIA) method, based on differential pulse anodic stripping voltammetry (DPASV). A simple “J” shaped adaptor was designed to direct the flux of the analyte injected with a micropipettor onto the hanging mercury drop electrode of any commercial electrode stand. Sampling methods for GSR were compared and lifting with adhesive tape was elected for field use. The tapes are glued on polyethylene screens and stored in capped vials. Sampling with multiple strips provides coarse mapping of the distribution of lead on the shooter's hands. After a dissolution/extraction step with chloroform/aqueous 0.10 mol L−1 HCl, 100 μL of the aqueous phase are injected during 25 s for accumulation of lead on the HMDE at −0.60 V (vs. Ag/AgCl). A detection limit of 20 ng/mL of Pb(II), outreaching for GSR analysis, is reached without oxygen removal, at a frequency of 20 injections per hour. Results for sequences of shootings with a revolver and a pistol are presented.

Fast photoelectrocatalytic degradation of organic matter is proposed as a means to estimate the organic load and in situ sample preparation for concomitant trace metal determination by voltammetry. To prove this concept, a thin-layer type flow-through cell comprising a UV-LED focused on a gold disc working electrode, modified with TiO2 nanoparticles (P25, mainly anatase) embedded into an electrodeposited gold film, was developed and evaluated with the model system Cu(II)-EDTA plus EDTA in excess. Consecutive cyclic voltammograms (−0.3 to +0.7 V vs. Ag/AgCl) exhibited no peaks in the dark, whereas under irradiation (370 nm, ≈150 mW) unchelated copper ions were reduced and reoxidised as usual in anodic stripping voltammetry (ASV), denoting the degradation of EDTA near the interface by photogenerated valence-band free holes or indirectly by ·OH radicals. The photocurrent due to conduction-band electrons withdrawal, additively superimposed on the voltammograms, increased with the electrode potential and with the EDTA concentration, thus allowing an estimation of the organic load in the samples. Full depletion of EDTA from the solution layer was found to be unnecessary and the high ‘baseline’ provided by the photocurrent could be avoided by performing ASV immediately after switching off the LED. Keywords: UV-LED photoelectrochemical cell, Gold–TiO2 electrode, Cu(II)-EDTA photovoltammetry, Trace metal stripping voltammetry, EDTA photooxidation, Photoelectrocatalytic sample treatment

The use of two additional reservoirs to accommodate the electrodes of the power source is proposed to improve the stability of the running electrolyte in capillary electrophoresis. The basic idea is to use salt bridges to connect those reservoirs to the ones containing the capillary ends. Although simple, there are several issues that can be considered in the design and implementation of such system in order to prevent undesired transference of material between the electrolysis and the main reservoirs. The use of a sealed electrolysis reservoir without a gas phase, the use of materials that ensure volume stability, and the use of bridges as long as possible are three basic directions. A compromise is involved in the dimensions of the sectional area of the bridge, because a small area diminishes the amount of a species transferred by diffusion but leads to an undesirable increase of the electrical field during the electrophoretic running. Thus, a bridge composed of a main wide-bore tube connected to a small-bore capillary seems to give the best performance for practical use. A simple electrolysis-separated system was adapted to a preexisting capillary electrophoresis system, and its performance was evaluated with a mixture of tartaric, malic, and succinic acids that was separated in sodium benzoate solution (pH 5.5) using the original equipment and the modified one. Due to the water electrolysis and the small buffering capacity of the electrolyte, there was a significant pH change and consequently changes in the effective mobilities of the analytes and loss of resolution after a few runs using the original equipment. Using the electrolysis-separated system, no significant change in the migration time and resolution was observed even after 15 runs. Besides the freedom to prepare running electrolytes with electroactive species or unbuffered solution, high throughput and the use of small reservoirs, such as the ones used in microfluidic devices, are the main advantages of the system.

Voltammetric approaches for the determination of arsenic and speciation at trace levels are critically appraised in a review covering the literature from 1970 to 2002. Special attention is devoted to stripping modes and to issues related to the choice of working material and supporting electrolyte. A section is dedicated to the management of real samples and aspects of sample preparation. An extensive compilation, organized by real sample type, gathers essential experimental conditions. Potentiometric stripping analysis is introduced for sake of comparison. The coupling of voltammetric detection or preaccumulation with FIA, chromatography, capillary electrophoresis and ICP techniques is also addressed.

The first flow injection spectroelectroanalytical method for the determination of promethazine hydrochloride has been developed. It is based on the in situ detection of a colored cationic radical formed during electroxidation at a gold electrode in sulfuric acid medium (0.1 mol l −1 ) and it offers a number of advantages in terms of simplicity, rapidity, selectivity and sensitivity over many other approaches. The determination of promethazine hydrochloride in pure form or in pharmaceutical formulations was investigated, considering the amperometric and the absortiometric signal. Although the amperometric signal alone can be used for the determination of promethazine in simple formulations like Fenergan (Rhodia-Farma), the photometric signal might become decisive when other electroactive compounds, such as dipyrone, are present in the formulation, e.g. in Lisador (Farmasa). Promethazine was quantified in Fenergan and Lisador . The results obtained using either conventional calibration curves or standard additions, were equivalent to those obtained with the official method recommended in the British Pharmacopoeia (BP) and in agreement with the labeled composition, for Fenergan . For Lisador , the results for promethazine were within 2% of the nominal value informed by the producer and the official method could not be applied due to dipyrone interference.