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%.

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.

Lithium Ion Electro-Insertion and Spectroelectrochemical Properties of Films from Hexaniobate

Layer-by-layer (LbL) films from K(2)Nb(6)O(17)(2-) and polyallylamine (PAH) and dip-coating films of H(2)K(2)Nb(6)O(17) were prepared on a fluorine-doped tin-oxide (FTO)-coated glass. The atomic force microscopy (AFM) images were carried out for morphological characterization of both materials. The real surface area and the roughness factor were determined on the basis of pseudocapacitive processes involved in the electroreduction/electrooxidation of gold layers deposited on these films. Next, lithium ion insertion into these materials was examined by means of electrochemical and spectroelectrochemical measurements. More specifically, cyclic voltammetry and current pulses under visible light beams were used to investigate mass transport and chromogenic properties. The lithium ion diffusion coefficient (D(Li)) within the LbL matrix is significantly higher than that within the dip-coating film, ensuring high storage capacity of lithium ions in the self-assembled electrode. Contrary to the LbL film, the potentiodynamic profile of absorbance change (Delta A) as a function of time is not similar to that obtained in the case of current density for the dip-coating film. Aiming at analyzing the rate of the coloration front associated with lithium ion diffusion, a spectroelectrochemical method based on the galvanostatic intermittent titration technique (GITT) was employed so as to determine the ""optical"" diffusion coefficient (D(op)). In the dip-coating film, the method employed here revealed that the lithium ion rate is higher in diffusion pathways formed from K(2)Nb(6)O(17)(2-) sites that contribute more significantly to Delta A. Meanwhile, the presence of PAH contributed to the increased ionic mobility in diffusion pathways in the LbL film, with low contribution to the electrochromic efficiency. These results aided a better understanding of the potentiodynamic profile of the temporal change of absorbance and current density during the insertion/deinsertion of lithium ions into the electrochromic materials.

A New Indirect Electroanalytical Method to Monitor the Contamination of Natural Waters with 4-Nitrophenol Using Multiwall Carbon Nanotubes

The electrochemical detection of the hazardous pollutant 4-nitrophenol (4-NP) at low potentials, in order to avoid matrix interferences, is an important research challenge. This study describes the development, electrochemical characterization and utilization of a multiwall carbon nanotube (MWCNT) film electrode for the quantitative determination of 4-NP in natural water. Electrochemical impedence spectroscopy measurements showed that the modified surface exhibits a decrease of ca. 13 times in the charge transfer resistance when compared with a bare glassy carbon (GC) surface. Voltammetric experiments showed the possibility to oxidize a hydroxylamine layer (produced by the electrochemical reduction of 4-NP on the GC/MWNCT surface) in a potential region which is approximately 700 mV less positive than that needed to oxidize 4-NP, thus minimizing the interference of matrix components. The limit of detection for 4-NP obtained using square-wave voltammetry (0.12 mu mol L(-1)) was lower than the value advised by EPA. A natural water sample from a dam located in Sao Carlos (Brazil) was spiked with 4-NP and analyzed by the standard addition method using thee GC/MWCNT electrode, without any further purification step. the recovery procedure yielded a value of 96.5% for such sample, thus confirming the suitability of the developed method to determine 4-NP in natural water samples. The electrochemical determination was compared with that obtained by HPLC with UV-vis detection.

V(2)O(5) nanoparticles obtained from a synthetic bariandite-like vanadium oxide: Synthesis, characterization and electrochemical behavior in an ionic liquid

Highly stable and crystalline V(2)O(5) nanoparticles with an average diameter of 15 nm have been easily prepared by thermal treatment of a bariandite-like vanadium oxide, V(10)O(24)center dot 9H(2)O. Their characterization was carried out by powder X-ray diffractometry (XRD). Fourier transform infrared (FT-IR) and Raman spectroscopies, and transmission electron microscopy (TEM). The fibrous and nanostructured film obtained by electrophoretic deposition of the V(2)O(5) nanoparticles showed good electroactivity when submitted to cyclic voltammetry in an ionic liquid-based electrolyte. The use of this film for the preparation of a nanostructured electrode led to an improvement of about 50% in discharge capacity values when compared with similar electrodes obtained by casting of a V(2)O(5) xerogel. (C) 2009 Elsevier Inc. All rights reserved.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Pt film electrodes prepared by the Pechini method for electrochemical decolourisation of Reactive Orange 16

Electrochemical decolourisation of Reactive Orange 16 was carried out in an electrochemical flow-cell, using as working electrodes a Pt thin film deposited on a Ti substrate (Pt/Ti) prepared by the Pechini method and a pure platinum (Pt) foil. Using the Pt/Ti electrodes better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (lambda = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L(-1) NaCl + 0.5 mol L(-1) H(2)SO(4) solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L(-1) NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction, was 0.024 min(-1) and 0.069 min(-1), for Pt and Pt/Ti electrodes, respectively.

The electrochemical effect of acid functionalisation of carbon nanotubes to be used in sensors development

The electrochemical behaviour of multi-walled carbon nanotubes was compared with that of glassy carbon, and the differences were investigated by cyclic voltammetry and electrochemical impedance spectroscopy before and after acid pre-treatment. The electrochemical techniques showed that acid functionalisation significantly improves the electrocatalytic properties of carbon nanotubes. These electrocatalytic properties enhance the analytical signal, shift the oxidation peak potential to a less positive value, and the charge-transfers rate increase of both dopamine and K(4)[Fe(CN)(6)]. The functionalisation step and the resulting appearance of edge planes covered with different chemical groups were confirmed by FTIR measurements. Carbon nanotubes after acid pre-treatment are a potentially powerful analytical tool for sensor development. (C) 2010 Elsevier B.V. All rights reserved.

Direct Electrochemical Determination of Glyphosate at Copper Phthalocyanine/Multiwalled Carbon Nanotube Film Electrodes

A copper phthalocyanine/multiwalled carbon nanotube film-modified glassy carbon electrode has been used for the determination of the herbicide glyphosate (Gly) at -50 mV vs. SCE by electrochemical oxidation using differential pulse voltamtnetry (DPV). Cyclic voltammetry and electrochemical impedance spectroscopy showed that Gly is adsorbed on the metallic centre of the copper phthalocyanine molecule, with formation of Gly-copper ion complexes. An analytical method was developed using DPV in pH 7.4 phosphate buffer solution, without any pretreatment steps: Gly was determined in the concentration range of 0.83-9.90 mu mol L(-1), with detection limit 12.2 nmol L(-1) (2.02 mu g L(-1))

Reliability of a method for evaluating porosity in denture base resins

Background: The method of porosity analysis by water absorption has been carried out by the storage of the specimens in pure water, but it does not exclude the potential plasticising effect of the water generating unreal values of porosity. Objective: The present study evaluated the reliability of this method of porosity analysis in polymethylmethacrylate denture base resins by the determination of the most satisfactory solution for storage (S), where the plasticising effect was excluded. Materials and methods: Two specimen shapes (rectangular and maxillary denture base) and two denture base resins, water bath-polymerised (Classico) and microwave-polymerised (Acron MC) were used. Saturated anhydrous calcium chloride solutions (25%, 50%, 75%) and distilled water were used for specimen storage. Sorption isotherms were used to determine S. Porosity factor (PF) and diffusion coefficient (D) were calculated within S and for the groups stored in distilled water. anova and Tukey tests were performed to identify significant differences in PF results and Kruskal-Wallis test and Dunn multiple comparison post hoc test, for D results (alpha = 0.05). Results: For Acron MC denture base shape, FP results were 0.24% (S 50%) and 1.37% (distilled water); for rectangular shape FP was 0.35% (S 75%) and 0.19% (distilled water). For Classico denture base shape, FP results were 0.54% (S 75%) and 1.21% (distilled water); for rectangular shape FP was 0.7% (S 50%) and 1.32% (distilled water). FP results were similar in S and distilled water only for Acron MC rectangular shape (p > 0.05). D results in distilled water were statistically higher than S for all groups. Conclusions: The results of the study suggest that an adequate solution for storing specimens must be used to measure porosity by water absorption, based on excluding the plasticising effect.

Adhesion to Er : YAG laser-prepared dentin after long-term water storage and thermocycling

This in vitro study evaluated the microtensile bond strength of a resin composite to Er:YAG-prepared dentin after long-term storage and thermocycling. Eighty bovine incisors were selected and their roots removed. The crowns were ground to expose superficial dentin. The samples were randomly divided according to cavity preparation method (I-Er:YAG laser and II-carbide bur). Subsequently, an etch & rinse adhesive system was applied and the samples were restored with a resin composite. The samples were subdivided according to time of water storage (WS)/number of thermocycles (TC) performed: A) 24 hours WS/no TC; B) 7 days WS/500 TC; C) 1 month WS/2,000 TC; D) 6 months WS/12,000 TC. The teeth were sectioned in sticks with a cross-sectional area of 1.0-mm(2), which were loaded in tension in a universal testing machine. The data were subjected to two-way ANOVA, Scheffe and Fisher`s tests at a 5% level. In general, the bur-prepared group displayed higher microtensile bond strength values than the laser-treated group. Based on one-month water storage and 2,000 thermocycles, the performance of the tested adhesive system to Er:YAG-laser irradiated dentin was negatively affected (Group IC), while adhesion of the bur-prepared group decreased only within six months of water storage combined with 12,000 thermocycles (Group IID). It may be concluded that adhesion to the Er:YAG laser cavity preparation was more affected by the methods used for simulating degradation of the adhesive interface.

Role of Surfactants in Carbon Nanotubes Density Gradient Separation

Several strategies aimed at sorting single-walled carbon nanotubes (SWNT) by diameter and/or electronic structure have been developed in recent years. A nondestructive sorting method was recently proposed in which nanotube bundles are dispersed in water-surfactant solutions and submitted to ultracentrifugation in a density gradient. By this method, SWNTs of different diameters are distributed according to their densities along the centrifuge tube. A mixture of two anionic amphiphiles, namely sodium dodecylsulfate (SIDS) and sodium cholate (SC), presented the best performance in discriminating nanotubes by diameter. We present molecular dynamics studies of the water-surfactant-SWNT system. The simulations revealed one aspect of the discriminating power of surfactants: they can actually be attracted toward the interior of the nanotube cage. The binding energies of SDS and SC on the outer nanotube surface are very similar and depend weakly on diameter. The binding inside the tubes, on the contrary, is strongly diameter dependent: SDS fits best inside tubes with diameters ranging from 8 to 9 angstrom, while SC is best accommodated in larger tubes, with diameters in the range 10.5-12 angstrom. The dynamics at room temperature showed that, as the amphiphile moves to the hollow cage, water molecules are dragged together, thereby promoting the nanotube filling. The resulting densities of filled SWNT are in agreement with measured densities.

Indirect study of (11)B(p,alpha(0))(8)Be and (10)B(p,alpha)(7)Be reactions at astrophysical energies by means of the Trojan Horse Method: recent results

Nuclear (p,alpha) reactions destroying the so-called ""light-elements"" lithium, beryllium and boron have been largely studied in the past mainly because their role in understanding some astrophysical phenomena, i.e. mixing-phenomena occurring in young F-G stars [1]. Such mechanisms transport the surface material down to the region close to the nuclear destruction zone, where typical temperatures of the order of similar to 10(6) K are reached. The corresponding Gamow energy E(0)=1.22 (Z(x)(2)Z(X)(2)T(6)(2))(1/3) [2] is about similar to 10 keV if one considers the ""boron-case"" and replaces in the previous formula Z(x) = 1, Z(X) = 5 and T(6) = 5. Direct measurements of the two (11)B(p,alpha(0))(8)Be and (10)B(p,alpha)(7)Be reactions in correspondence of this energy region are difficult to perform mainly because the combined effects of Coulomb barrier penetrability and electron screening [3]. The indirect method of the Trojan Horse (THM) [4-6] allows one to extract the two-body reaction cross section of interest for astrophysics without the extrapolation-procedures. Due to the THM formalism, the extracted indirect data have to be normalized to the available direct ones at higher energies thus implying that the method is a complementary tool in solving some still open questions for both nuclear and astrophysical issues [7-12].

Carbon nanotubes in nanostructured films: Potential application as amperometric and potentiometric field-effect (bio-)chemical sensors

The assembly of carbon nanotubes (CNTs) into nanostructured films is attractive for producing functionalized hybrid materials and (bio-)chemical sensors, but this requires experimental methods that allow for control of molecular architecturcs. In this study, we exploit the layer-by-layer (LbL) technique to obtain two types of sensors incorporating CNTs. In the first, LbL films of alternating layers of multi-walled carbon nanotubes (MWNTs) dispersed in polyarninoamide (PAMAM) dendrimers and nickel phthalocyanine (NiTsPc) were used in amperometric detection of the neurotransmitter dopamine (DA). The electrochemical properties evaluated with cyclic voltammetry indicated that the incorporation of MWNTs in the PAMAM-NT/NiTsPc LbL films led to a 3-fold increase in the peak current, in addition to a decrease of 50 mV in the oxidation potential of DA. The latter allowed detection of DA even in the presence of ascorbic acid (AA), a typical interferent for DA. Another LbL film was obtained with layers of PAMAM and single-walled carbon nanotubes (SWNTs) employed in field-effect-devices using a capacitive electrolyte-insulator-semiconductor structure (EIS). The adsorption of the film components was monitored by measuring the flat-band voltage shift in capacitance-voltage (C-P) curves, caused by the charges from the components. Constant capacitance (ConCap) measurements showed that the EISPAMAM/SWNT film displayed a high pH sensitivity (ca. 54.5 mV/pH), being capable of detecting penicillin G between 10(-4) mol L(-1) and 10(-2) mol L-1, when a layer of penicillinase was adsorbed atop the PAMAM/SWNT film. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal lens spectrometry in pyroelectric lithium niobate crystals

In this work, the light-induced lens effect due to thermal and/or photorefractive processes was studied in pyroelectric (undoped and Fe(2+)-doped) lithium niobate crystals (LiNbO(3)) using thermal lens spectrometry with a two-beam (pump-probe) mode-mismatched configuration. The measurements were carried out at two pump beam wavelengths (514.5 and 750 nm) to establish a full understanding of the present effects in this material (thermal and/or photorefractive). We present an easy-to-implement method to determine quantitative values of the pyroelectric coefficient (dPs/dT), its contribution to the thermal effect and other thermo-optical parameters like thermal diffusivity (D), thermal conductivity (K) and temperature coefficient of the optical path length change (ds/dT). These measurements were performed in LiNbO(3) and LiNbO(3): Fe (0.1 ppm Fe(2+)) crystals with c axis along the direction of laser propagation.