Determinação voltamétrica de ciclamato de sódio em produtos dietéticos empregando um eletrodo de diamante dopado com boro

The use of square-wave voltammetry in conjunction with a cathodically pre-treated diamond electrode for the analytical determination of sodium cyclamate is described. The samples were analyzed as received in a 0.5 mol L-1 H2SO4 solution in the concentration range from 5.0 × 10-5 mol L-1 to 4.1 × 10-4 mol L-1, with a detection limit of 4.8 × 10-6 mol L-1. The RSD was smaller than 1.2 % and the proposed method was applied with success in the determination of sodium cyclamate in several dietary products.

Avaliação da influência de sulfetos solúveis na complexação do cobre em águas superficiais empregando métodos voltamétricos

In this work a sulfide quantification protocol using voltammetric methods was developed to evaluate the effect of dissolved sulfides on copper complexation. On the basis of pH, sulfide release from the dissociation of specific metal sulfide complexes can be electrochemically measured and then removed (as H2S) by a N2 purge. Cathodic stripping square wave voltammetry (CSSWV) was conducted to quantify Cu sulfides complexes which dissociate at pH < 5.0 during the process of acid titration.

Especiação de cobre e zinco em urina: importância dos metais em doenças neurodegenerativas

Metals such as copper and zinc are essential for the development and maintenance of numerous enzymatic activities, mitochondrial functions, neurotransmission, and also for memorization and learning. However, disruption in their homeostasis can cause neurodegenerative disorders such as the Alzheimer and Parkinson diseases. In this work, the speciation of copper and zinc in urine samples was carried out. To this end, free and total metal concentrations were determined by square wave anodic stripping voltammetry using a glassy carbon electrode coated with bismuth film. The digestion of the samples was performed in a microwave with the addition of oxidant reagents.

INVESTIGAÇÃO DO USO DE ELETRODO DE CARBONO VÍTREO MODIFICADO COM HEXACIANOFERRATO DE RUTÊNIO PARA DETECÇÃO DE PROCAÍNA

A glassy carbon electrode modified with ruthenium hexacyanoferrate (RuOHCF) was investigated as an electrocatalyst for the detection of procaine with the aim of quantification in pharmaceutical and forensic samples. The RuOHCF films were prepared by electrochemical deposition, and the parameters used in this process (concentration of RuCl3, K3Fe(CN)6, temperature, and number of cyclic voltammograms recorded in the modification step) were carefully optimized. Based on the optimal conditions achieved, the RuOHCF modified electrode allows the determination of procaine at 0.0 V with a detection limit of 11 nmol L-1using square wave voltammetry.

BIOSSENSOR ELETROQUÍMICO BASEADO NA ENZIMA TIROSINASE PARA A DETERMINAÇÃO DE FENOL EM EFLUENTES

AbstractThis work describes the development of a biosensor based on the tyrosinase enzyme (Tyr) for the determination of phenol (PHEN) in laboratory effluent samples derived from ammoniacal nitrogen analysis of the water samples from the Muquém dam in the city of Cariús, CE, using square-wave voltammetry (SWV). The electrode modification consisted of the immobilization of gold nanoparticles, multi-walled carbon nanotubes, cobalt phthalocyanine, and Tyr on a glassy carbon electrode. The electrolyte, pH, enzyme quantity, and voltammetric parameters were optimized to detect PHEN. The analytical curves presented a linear range from 4.97 × 10-6 mol L-1 to 6.10 × 10-5 mol L-1, and the detection limit (DL) and quantitation limit (QL) values were 4.81 × 10-6 mol L-1 and 4.97 × 10-6mol L-1, respectively. The repetition of measurements with the same biosensor and repetition for three other prepared biosensors exhibited a relative standard deviation (RSD) of 5.50 and 1.75%, respectively. The percentage recovery of PHEN in effluent samples varied from 86.40 to 105.04%. The stability of the biosensor was evaluated (at 21 days) with satisfactory results, showing 97.86% of the initial response. Moreover, the DL and recovery percentages agreed with the established values from CONAMA and ABNT, respectively. Thus, the electrode configuration developed seems a promising tool in the detection and quantification of PHEN in complex samples.

COMPARAÇÃO DE PROCESSAMENTOS MATEMÁTICOS DE DADOS VOLTAMÉTRICOS: APLICAÇÃO NA DETERMINAÇÃO SIMULTÂNEA DE FLUOROQUINOLONAS

This paper describes a comparative study between the procedures of deconvolution and the second-order derivative of square wave voltammograms to achieve separation of the voltammetric peaks of levofloxacin (LEVO) and norfloxacin (NOR), for their simultaneous quantification in urine samples. The obtained results indicate that the use of second-derivative voltammograms coupled with carbon screen-printed electrodes is the most efficient approach for completely separating the voltammetric peaks of LEVO and NOR. In addition, this approach has produced detection limits lower than 1.0 µmol L-1 and a wide linear range for both drugs. The proposed method was successfully used to simultaneously determine LEVO and NOR in spiked human and bovine urine samples with recovery percentages close to 100% for all analyzed samples.

Kaarihitsauksen suojakaasun tunnistus ja virtauksen mittaus ultraäänellä

Kaasukaarihitsauksessa suojakaasuna käytetään yleensä argonin ja hiilidioksidin tai argonin ja heliumin seoksia. Suojakaasu vaikuttaa useisiin hitsausominaisuuksiin, jotka puolestaan vaikuttavat hitsauksen laatuun ja tuottavuuteen. Automaattisella suojakaasun tunnistuksella ja virtausmäärän mittauksella voitaisiin tehdä hitsauksesta paitsi käyttäjän kannalta yksinkertaisempaa, myös laadukkaampaa. Työn tavoite on löytää mahdollisimman edullinen ja kuitenkin mahdollisimman tarkasti kaasuseoksia tunnistava menetelmä, jota voitaisiin hyödyntää MIG/MAG-hitsauskoneeseen sisäänrakennettuna. Selvä etu on, jos menetelmällä voidaan mitata myös kaasun virtausmäärä. Äänennopeus kaasumaisessa väliaineessa on aineen atomi- ja molekyylirakenteesta ja lämpötilasta riippuva ominaisuus, joka voidaan mitata melko edullisesti. Äänennopeuden määritys perustuu ääniaallon kulkuajan mittaamiseen tunnetun pituisella matkalla. Kaasun virtausnopeus on laskettavissa myötä- ja vastavirtaan mitattujen kulkuaikojen erotuksen avulla. Rakennettu mittauslaitteisto koostuu kahdesta ultraäänimuuntimesta, joiden halkaisija on 10 mm ja jotka toimivat sekä lähettimenä että vastaanottimena. Muuntimet ovat 140 mm:n etäisyydellä toisistaan virtauskanavassa, jossa suojakaasu virtaa yhdensuuntaisesti äänen kanssa. Virtauskanava on putki, jossa on käytetty elastisia materiaaleja, jotta ääniaaltojen eteneminen kanavan runkoa pitkin minimoituisi. Kehitetty algoritmi etsii kahden lähetetyn 40 kHz:n taajuisen kanttiaaltopulssin aiheuttaman vasteen perusteella ääniaallon saapumisajanhetken. Useiden mittausten, tulosten lajittelun ja suodatuksen jälkeen tuntemattomalle kaasulle lasketaan lämpötilakompensoitu vertailuluku. Tuntematon kaasu tunnistetaan vertailemalla lukua tunnettujen kaasuseosten mitattuihin vertailulukuihin. Laitteisto tunnistaa seokset, joissa heliumin osuus argonissa on enintään 50 %. Hiilidioksidia sisältävät argonin seokset puolestaan tunnistetaan puhtaaseen hiilidioksidiin asti jopa kahden prosenttiyksikön tarkkuudella. Kaasun tilavuusvirtausmittauksen tarkkuus on noin 1,0 l/min.

Chaos and Unpredictability in the Vibration of an Elasto-Plastic Beam

This contribution discusses the nonlinear dynamics of a pin-ended elasto-plastic beam with both kinematic and isotropic hardening. An iterative numerical procedure based on the operator split technique is developed in order to deal with the nonlinearities in the equations of motion. Free and forced responses for harmonic sinusoidal and square wave excitations are investigated. Numerical simulations present many interesting behaviors such as jump phenomena, sensitivity to initial conditions, chaos and transient chaos. These results indicate that there are practical problems in predicting the response of the beam even when periodic steady state response is expected.

Opioidergic orofacial antinociception induced by electroacupuncture at acupoint St36

The participation of opioids in the antinociceptive effect of electroacupuncture was evaluated in terms of nociception produced by thermal stimuli applied to the face of male Wistar rats, weighing 180-230 g. Electrical stimulation (bipolar and asymmetric square wave with 0.5 mA intensity for 20 min) of acupoint St36, located in the anterior tibial muscle 10 mm distal to the knee joint, induced antinociception in the present model, which was maintained for 150 min. Acupoint LI4, located in the junction of the first and second metacarpal bones, did not achieve antinociception at any frequency studied (5 Hz: 1.7 ± 0.1; 30 Hz: 1.8 ± 0.1; 100 Hz: 1.7 ± 0.1 vs 1.4 ± 0.2). The antinociception obtained by stimulation of acupoint St36 was only achieved when high frequency 100 Hz (3.0 ± 0.2 vs 1.0 ± 0.1) was used, and not with 5 or 30 Hz (1.2 ± 0.2 and 0.7 ± 0.1 vs 1.0 ± 0.1). The antinociceptive effect of acupuncture occurred by opioid pathway activation, since naloxone (1 and 2 mg/kg, subcutaneously) antagonized it (1.8 ± 0.2 and 1.7 ± 0.2 vs 3.0 ± 0.1).

Non-invasive measurement of trigeminal nerve somatosensory evoked potentials

Whiplash injuries are common yet enigmatic to substantiate clinically. Trigeminal somatosensory evoked potentials (TSEPs) were posited as an indicator of trigeminal nerve conduction damage resulting from whiplash. Alternating polarity square-wave current stimuli were applied transcutaneously in the facial region. 379 recorded pilot trials from 27 participants (8 male and 19 female) were utilized to develop a non-invasive recording capability for TSEPs. Stimulus intensity and artifact, cortical recording sites, stimulation electrode design and placement were explored. Statistically significant differences in amplitude of TSEP waveform components at 13, 19 and 27 ms between uninjured and whiplashed participants were noted. Increased stimulus intensity in whiplashed participants was observed to increase TSEP amplitude. The present methodology and hardware are discussed and directions for future advancement of the current process are outlined.

Electroactive Dipyrromethene-Cu(II) Monolayers Deposited onto Gold Electrodes for Voltammetric Determination of Paracetamol

Dipyrromethene-Cu(II) derivatives possessing two dodecane alkyl chains have been used for the modification of gold electrodes. Electroactive host molecules have been incorporated into a lipophilic dodecanethiol SAM deposited onto gold electrodes through hydrophobic and van der Waals interactions (embedment technique). The presence of dipyrromethene-Cu(II) redox centers on the electrode surface was proved by cyclic voltammetry and Osteryoung square-wave voltammetry. The Au electrodes incorporating redox active Cu(II)-dipyrromethene SAMs were used for the direct voltammetric determination of paracetamol in human plasma.

Elektrochemische und spektroelektrochemische Untersuchungen symmetrischer und unsymmetrischer Spiroverbindungen

In dieser Arbeit wurden elektronische Eigenschaften der sogenannten Spiroverbin-dungen untersucht, die aus zwei durch ein gemeinsames Spiro-Kohlenstoffatom miteinander verbundenen π-Systemen bestehen. Solche Untersuchungen sind notwendig, um die gezielte Synthese organischer Materialien mit bestimmten optischen, elektrischen, photoelektrischen oder magnetischen Eigenschaften zu ermöglichen. Im einzelnen wurden mit Hilfe der Cyclovoltammetrie, Square-Wave-Voltammetrie und Spektroelektrochemie eine Reihe homologer Spiro-p-oligophenyle, sowie symmetrisch und unsymmetrisch substituierte Spiroverbindungen und Spirocyclopentadithiophene unter-sucht. Dabei ergaben sich folgende Einflussfaktoren: Kettenlänge, verschiedene Substituenten (Trimethylsilyl, tert-Butyl, Fluor, Pyridyl, perfluoriertes Pyridyl, Dimethylamino-Gruppe), verschiedene Positionen der Substitution, Lage der Spiroverknüpfung und Art des π-Systems im Spirokern. Die elektronischen Eigenschaften der untersuchten Verbindungen variieren systema-tisch mit der Kettenlänge. So vermindert sich der Betrag der Redoxpotentiale der Spiroverbin-dungen mit Zunahme der Kettenlänge, während die Anzahl der übertragenen Elektronen mit zunehmender Kettenlänge wächst. Die Absorption der neutralen und geladenen Spezies ver-schiebt sich mit steigender Kettenlänge bathochrom. Der Substituenteneinfluss auf die Poten-tiallage hängt davon ab, welcher der Effekte +I, -I, +M, -M überwiegt; dabei spielt auch die Position der Substitution eine Rolle. Weiter lässt sich der Einfluss der Lage der Spiroverknüpfung auf die Redoxpotentiale mit der verschiedenen Coulomb-Abstoßung innerhalb oder/und zwischen Phenylketten bei symmetrisch und unsymmetrisch verknüpften Spiroverbindungen begründen. Schließlich wurden die Redoxmechanismen der untersuchten Spiroverbindungen er-mittelt. Die meisten Verbindungen werden zum Bis(radikalion) reduziert bzw. oxidiert (Me-chanismus A). Nur wenige Verbindungen werden nach Mechanismus B reduziert, in dem das Elektron unter Bildung eines Dianions in die schon einfach reduzierte Molekülhälfte über-geht. Die Unterschiede der Redoxpotentiale, der Lage der Absorption, des Reduktionsme-chanismus der Verbindungen mit unterschiedlichen Spirokernen (Spirobifluoren und Spiro-cyclopentadithiophen) konnten mit den unterschiedlichen elektronischen Strukturen von Phe-nyl- und Thiophenring (aromatisches und heteroaromatisches π System) erklärt werden.

Carboxylate anions binding and sensing by a novel tetraazamacrocycle containing ferrocene as receptor

A tetraazamacrocycle containing ferrocene moieties has been synthesized and characterized. The tetraprotonated form of this compound was evaluated as a receptor (R) for anion recognition of several substrates (S), Cl-, PF6-, HSO4-, H2PO4- and carboxylates, such as p-nitrobenzoate (p-nbz(-)), phthalate (ph(2-)), isophthalate (iph(2-)) and dipicolinate (dipic(2-)). H-1 NMR titrations in CD3OD indicated that this receptor is not suitable for recognizing HSO4- and H2PO4-, but weakly binds p-nbz(-), and strongly interacts with ph(2-), dipic(2-), and iph(2-) anions forming 1 : 2 assembled species. The largest beta(2) binding constant was determined for ph(2-), followed by dipic(2-) and finally iph(2-). The effect of the anionic substrates on the electron-transfer process of the ferrocene units of R was evaluated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in methanol solution and 0.1 mol dm(-3) (CH3)(4)NCl as the supporting electrolyte. Titrations of the receptor were undertaken by addition of anion solutions in their tetrabutylammonium or tetramethylammonium forms. The protonated ligand exhibits a reversible voltammogram, which shifts cathodically in the presence of the substrates. The data revealed kinetic constraints in the formation of the receptor/substrate entity for dipic(2-), ph(2-) and iph(2-) anions, but not for p-nbz(-). In spite of the slow kinetics of assembled species formation with the ph(2-) substrate, this anion provides the largest redox-response when the supramolecular entity is formed, followed by dipic(2-), iph(2-) and finally p-nbz(-) anions. This trend is in agreement with the H-1 NMR results and the values of the binding constants. Single crystal X-ray structures of the receptor with PF6-, ph(2-), iph(2-) and p-nbz(-) were carried out and showed that supermolecules with a RS2 stoichiometry are formed with the first three anions, but RS4 with p-nbz(-). In all cases the binding occurs outside the macrocyclic cavity via N-H center dot center dot center dot O=C hydrogen bonds for carboxylate anions and N - H center dot center dot center dot F hydrogen bonds for the PF6- anion, which is in agreement with the solution results. The macrocyclic framework adopts different conformations in order to interact with each substrate having Fe center dot center dot center dot Fe intramolecular distances ranging from 10.125(14) to 12.783(15) angstrom.

Spatial offset of test field elements from surround elements affects the strength of motion aftereffects

Static movement aftereffects (MAEs) were measured after adaptation to vertical square-wave luminance gratings drifting horizontally within a central window in a surrounding stationary vertical grating. The relationship between the stationary test grating and the surround was manipulated by varying the alignment of the stationary stripes in the window and those in the surround, and the type of outline separating the window and the surround [no outline, black outline (invisible on black stripes), and red outline (visible throughout its length)]. Offsetting the stripes in the window significantly increased both the duration and ratings of the strength of MAEs. Manipulating the outline had no significant effect on either measure of MAE strength. In a second experiment, in which the stationary test fields alone were presented, participants judged how segregated the test field appeared from its surround. In contrast to the MAE measures, outline as well as offset contributed to judged segregation. In a third experiment, in which test-stripe offset wits systematically manipulated, segregation ratings rose with offset. However, MAE strength was greater at medium than at either small or large (180 degrees phase shift) offsets. The effects of these manipulations on the MAE are interpreted in terms of a spatial mechanism which integrates motion signals along collinear contours of the test field and surround, and so causes a reduction of motion contrast at the edges of the test field.