Influence of TiO2 nanoparticles content as reinforce material to enhance the mechanical and corrosion resistance properties of Sn and Sn-Ag alloy for dental applications.

This study evaluated the influence of the TiO2 nanoparticles (NPs) on the mechanical and chemical performance of Sn and Sn-Ag alloys. The XRD (X-ray diffraction) and HR-TEM (high resolution-transmission electron microscopy) methods were used to characterize the NPs synthesized by the sol-gel microwave process. The chemical composition of the alloys was Sn, Sn+3TiO2 NPs, Sn-5Ag+1.5TiO2 NPs, Sn-10Ag, and Sn-10Ag+3TiO2 NPs, obtained from an experimental factorial design (EFD). A statistical model was used to determine the mechanical and chemical properties, showing the Vickers hardness response surface, tensile strength, wear, and corrosion resistance. The wear and corrosion tests for the various alloy compositions were performed using human artificial saliva solution. The results indicated that the Sn-10Ag+3TiO2 NPs exhibited the highest mechanical performance due to their increased hardness (380 HV), tensile strength (370 N), and wear resistance (0.34 × 10-3 mm3 Nm-1); in all the cases, the inclusion of TiO2 NPs enhanced the corrosion resistance of the alloys. According to the American Dental Association (ADA), Sn-10Ag+3TiO2 NPs alloy could be classified as a possible type IV restorative material.

Mechanism and Kinetics of Palladium Nanoparticles Electrochemical Formation onto Glassy Carbon, from a Deep Eutectic Solvent (Reline).

From electrochemical potentiodynamic and potentiostatic techniques, the electrodeposition mechanism and kinetics of palladium nanoparticles (PdNPs) onto a glassy carbon electrode (GCE), from Pd(II) ions dissolved in the choline chloride-urea deep eutectic solvent (reline) at 343 K, are reported for the first time. From the analysis of the potentiostatic current density transients, using the model developed by Palomar-Pardavé et al. [ Electrochim. Acta, 2005, 50, 4736-4745], it shows that the PdNPs electrodeposition occurs by multiple 3D nucleation and diffusion controlled-growth with the simultaneous reduction of residual water on the PdNPs growing surfaces. This model renders not just the quantification of the palladium nucleation kinetics parameters, but it effectively allows deconvolving the individual contributions to the total current and, thus, from the integration of the j-t plots of these contributions. It was demonstrated that the charge amount of each process depends on the deposition time and applied overpotential. From SEM images, it was possible to verify that the palladium deposits were constituted by PdNPs and from XPS measurements that these PdNPs were formed by a metallic palladium (core) and Pd(OH)2 (shell).

Spectro-electrochemical characterization and quantification of Rutin in aqueous media.

From UV-Vis spectrophotometric measurements the acidity constants of Rutin in aqueous media, at 25 °C and 0.1 M ionic strength, were determined as: pK1 = 4.392 ±â€¯0.167, pK2 = 7.130 ±â€¯0.050, pK3 = 8.661 ±â€¯0.042 and pK4 = 12.354 ±â€¯0.020 and the molar absorptivity coefficients of all the Rutin pH-dependent species were reported as a function of wavelength. Furthermore, the electrochemical behavior of Rutin at neutral pH was investigated using a bare carbon paste electrode, CPE. It was found that both: Rutin electrochemical oxidation and reduction are reversible, adsorption-controlled processes, involving 2 electron transfers. Moreover, the bare CPE was used for the electrochemical quantification of Rutin in neutral aqueous media, displaying the following features: (1.078 ±â€¯0.440) µM, (3.594 ±â€¯0.400) µM and (0.308 ±â€¯0.014) µA µM-1 for the detection and quantification limits and sensitivity, respectively, within the 1-11 µM linear range. Meanwhile the spectrophotometric method displayed the following analytical features: (3.385 ±â€¯1.318) µM, (11.283 ±â€¯3.114) µM and (0.0120 ±â€¯0.0001) AU µM-1 for the detection and quantification limits and sensitivity, respectively within the 11-110 µM linear range. In like manner, the bare CPE is also shown as a robust electrochemical sensor that allows Rutin quantification even in the presence of ascorbic acid, commonly found in Rutin samples.

New insights on the spectrophotometric determination of melatonin pKa values and melatonin-ßCD inclusion complex formation constant.

Using UV-Vis spectrophotometry a stability study of melatonin at different pH values was done in aqueous media, finding that at acidic pH melatonin is unstable when interacting with the environment, however it becomes stable protecting it from light and oxygen. From the UV-Vis spectra and SQUAD software, melatonin pKa values, in a completely protected aqueous medium, were estimated as 5.777±0.011 and 10.201±0.024. Using the same techniques, the melatonin and ß-cyclodextrin inclusion complex formation constants were assessed at pH3, 7 and 11.5, giving the values of log ß=(3.07±0.06), (2.94±0.01) and (3.07±0.06) M-1, respectively. From the global acidity formation constants and the complexes' formation constants, the molar fractions were determined for each species of MT and MT-ßCD, to build the molar fraction-[ßCD]-pH 3D diagram and the molar fraction-pH 2D diagrams, where it was possible to observe the predominance of the MT species with and without ßCD. A voltammetric study at pH3, allowed obtaining a value of log ß=(3.15±0.01) M-1, which corroborates that obtained through UV-Vis spectrophotometry, supporting strongly the rationale behind using simple, straightforward techniques.

Quercetin spectrofluorometric quantification in aqueous media using different surfactants as fluorescence promoters.

Quercetin spectrofluorometric quantification was carried out in aqueous media (pH 7) using micelles of surfactants, namely: CTAB, SDS and TX100 as promoters of quercetin fluorescence, having a critical micelle concentration, CMC, of: 0.94 ± 0.03, 7.7 ± 0.6 and 0.18 ± 0.3 mM, respectively, measured through UV-Vis spectrophotometry. The thermodynamic binding constant, K, for the quercetin-surfactants' micelles supramolecular complex was estimated to be (log(K/M-1)) = 2.87 ± 0.02, 2.78 ± 0.04 and 2.80 ± 0.04, respectively, from fluorescence spectrophotometry. With the aid of these parameters it was possible to construct species distribution diagrams and choose the experimental conditions where quercetin can be quantified in aqueous media from fluorescence measurements. The best lowest limit of detection (0.244 ± 0.092) µM was achieved with CTAB micelles while the best sensitivity (2.919 ± 0.054) M-1 corresponded to SDS.

Spectrophotometric quantification of the thermodynamic constants of the complexes formed by dopamine and Cu(II) in aqueous media.

The thermodynamic constants of the complex Cu(II)-dopamine in aqueous solution were evaluated from spectrophotometric data using the software SQUAD. It was found that there exist Cu(II):DA complexes with 1:1 and 1:2 stoichiometries and that their predominance depends on both the solution pH and the [Cu(II)]/[DA] ratio. Moreover, it is shown that the solubility of Cu(OH)2(s) increases drastically when these complexes are thermodynamically stable.

Enzyme entrapment by ß-cyclodextrin electropolymerization onto a carbon nanotubes-modified screen-printed electrode.

A novel enzyme entrapment approach based on an electropolymerization process utilizing multi-walled carbon nanotubes (MWCNT), ß-cyclodextrin (ß-CD) and glucose oxidase (GOx) is shown. Dopamine (DA) quantification is presented using a screen-printed electrode modified by electropolymerization of cyclodextrin with glucose oxidase, SPE/MWCNT/ß-CD-GOx. In order to show the relevance of the enzyme entrapment strategy controlled by electropolymerization to develop a specific and efficient biosensor, the various parts composing the electrode: SPE, SPE/ß-CD, SPE/GOx, SPE/ß-CD/GOx, SPE/MWCNT/ß-CD, SPE/MWCNT/GOx and SPE/MWCNT/ß-CD/GOx were tested separately. It was shown that although DA determination can be achieved with all of them, the electrodes modified with MWCNT presented better analytical features that those built without MWCNT, the best being the one including all components. This biosensor displayed good reproducibility, repeatability, and prolonged life-time under cold storage conditions. Its DA limit of detection (LOD) was 0.48±0.02 µA in a linear range of 10-50 µM with a sensitivity of 0.0302±0.0003 µA µM(-1) that makes it comparable or even better than many other electrodes reported in the literature. Moreover, it was also shown that using this electrode, DA quantification can be done in the presence of interfering agents such as ascorbic and uric acid. These findings demonstrate that the approach employed is feasible for enzyme entrapment and may find applications in other biosensing systems, where better sensitivity, stability and fast response are required.

Nucleation and growth kinetics of electrodeposited sulfate-doped polypyrrole: determination of the diffusion coefficient of SO(4)(2-) in the polymeric membrane.

A kinetic study for the electrosynthesis of polypyrrole (Ppy) doped with SO(4)(2-) ions is presented. Ppy films were electrochemically polymerized onto a graphite-epoxy resin electrode. Experimental current density transients (j-t) were obtained for three different potentiometric behaviors: anionic, cationic, and a combination. Theoretical models were used to fit the experimental j-t data to determine the nucleation and growth processes controlling the polymer synthesis. It was encountered that, in all cases, pyrrole electropolimerization involves two concomitant processes, namely, a Ppy diffusion limited multiple 3D nucleation and growth and pyrrole electro-oxidation on the growing surface of the Ppy nuclei. SEM analysis of the electrodes surfaces reveals that Ppy deposition occurred over most of the electrode surface by multiple nucleation of hemispheres, as the theoretical model used for the analysis of the current transients required. Hemispherical particles formed the polymeric film displaying different sizes. The order for the particle size was as follows: anionic > anionic-cationic > cationic. These results are congruent with those obtained by theoretical analysis of the corresponding current transients. Analysis of the impedance measurements recorded on the anionic Ppy film, immersed in an aqueous solution with different sulfate ion concentrations evidenced that SO(4)(2-) ions diffuse through the Ppy film provoking a decrease of its electrical resistance and an increase of its dielectric constant. From the Warburg impedance coefficient, the sulfate coefficient of diffusion in the Ppy film was 1.38 x 10(-9) cm(2) s(-1).

Stable and sensitive flow-through monitoring of phenol using a carbon nanotube based screen printed biosensor.

A stable and sensitive biosensor for phenol detection based on a screen printed electrode modified with tyrosinase, multiwall carbon nanotubes and glutaraldehyde is designed and applied in a flow injection analytical system. The proposed carbon nanotube matrix is easy to prepare and ensures a very good entrapment environment for the enzyme, being simpler and cheaper than other reported strategies. In addition, the proposed matrix allows for a very fast operation of the enzyme, that leads to a response time of 15 s. Several parameters such as the working potential, pH of the measuring solution, biosensor response time, detection limit, linear range of response and sensitivity are studied. The obtained detection limit for phenol was 0.14 x 10(-6) M. The biosensor keeps its activity during continuous FIA measurements at room temperature, showing a stable response (RSD 5%) within a two week working period at room temperature. The developed biosensor is being applied for phenol detection in seawater samples and seems to be a promising alternative for automatic control of seawater contamination. The developed detection system can be extended to other enzyme biosensors with interest for several other applications.

Cr(VI) and Cr(VI)-diphenylcarbazide removal from aqueous solutions using an iron rotating disc electrode.

This paper presents the results of the investigation on the removal of Cr(VI) and the complex Cr(VI)-diphenylcarbazide from aqueous solutions using an electrochemical reactor, with iron electrodes. A maximum value of 99% Cr(VI) removal from aqueous solutions is observed for both Cr(VI) and Cr(VI)-diphenylcarbazide, at initial concentrations from 150 to 800 mg l(-1). Cyclic voltammetry experiments of water show the presence of electroactive species in the oxidation and reduction zones previous to the treatment and how this presence diminishes as the electrochemical treatment is applied to the wastewater. UV-Vis analyses corroborate the improvement on the quality of aqueous solutions treated. Finally, scanning electron microscopy and energy dispersion spectra show that Cr and Fe are present as constituents of the sludge formed during the electrochemical treatment. It was demonstrated that the use of electrochemical methods for the treatment of Cr(VI) and Cr(VI)-diphenylcarbazide aqueous solutions is an effective and economical method.

Determination of the complexation constants of Pb(II) and Cd(II) with thymol blue using spectrophotometry, SQUAD and the HSAB principle.

This paper presents the results concerning the determination of the formation constants of the complexes between thymol blue, TB, and the metal ions Pb(II) or Cd(II). The experimental procedure was carried out in the presence of a nitrogen atmosphere at 25 degrees C. The spectrophotometry data obtained were processed through the software SQUAD to calculate the complexation constants of the metal-indicator and to establish an adequate base of the models which considered the structure of the indicator, and the actual metal species in the aqueous solutions. For the Pb(II)-TB-H2O system the logK value calculated for the PbTB complex was 5.591+/-0.057 while for the Cd(II)-TB-H2O system, the logK value of the CdTB complex was 5.099+/-0.008. Also, supporting theoretical chemistry results on the chemical hardness of TB molecule were performed to enable establishment of a relative prediction scale of the TB complexation constants ranking in the framework of the Principle of Hard and Soft Acids and Bases or HSAB Principle.

Cd(II) and Pb(II) separation from aqueous solution using clinoptilolite and Opuntia ectodermis.

This work presents the conditions for Pb(II) and Cd(II) removal from aqueous solution using two different sorbent materials, namely, clinoptilolite and Opuntia ectodermis, which were characterized before and after entering into contact with the metal-containing aqueous media, using scanning electron microscopy (SEM), thermal analysis (TGA) and surface area (BET). Metal removal was found to depend on the initial metal concentration in aqueous solution, pH and the mass/volume ratio. The Pb(II) and Cd(II) uptake process was maximum at pH 4 for both sorbents, which showed an adsorption capacity that was adequately described by the Freundlich adsorption isotherm. The Thomas model was used to describe the adsorption data from column studies, the sorption capacity was 12.21 Pb(II) mg per gram of Opuntia ectodermis, while 7.71 Pb(II) mg per gram of clinoptilolite were adsorbed; lower values were obtained for Cd(II) removal. It was demonstrated that the use of low cost materials for the treatment of Pb(II), and Cd(II), containing wastewater is an effective and economical alternative method.

Facilitated transport of Hg(II) through novel activated composite membranes.

The results presented in this work deal with the prime application of activated composite membranes (ACMs) for the transport of Hg(II) ions in a continuous extraction-re-extraction system using di-(2-ethylhexyl)dithiophosphoric acid (DTPA) as carrier. The effects of variables such as the pH, the nature of the acid and the concentration of the casting solutions on the transport of Hg(II) are also investigated. When the ACM was prepared with a 0.5 M DTPA solution and when the feed solution contained 2.5x10(-4) M Hg(II) in 0.1 M HCl, the amount of mercury extracted was greater than 76%. The re-extracted mercury was subsequently recovered by means of a stripping phase comprising 0.3 M thiourea solution in 2 M H2SO4, yielding 54% of the initial amount of mercury after transport had taken place for 180 min.

Cr(VI) removal from wastewater using low cost sorbent materials: roots of Typha latifolia and ashes.

This work presents conditions for hexavalent chromium (Cr(VI)) removal from aqueous solution using different sorbent materials, namely: pyrolytic ashes of an industrial sludge from wastewater treatment and roots of Typha latifolia. The sorbent materials were characterized using scanning electron microscopy (SEM) and surface area using the Brunauer-Emmett-Teller (BET) technique, before and after the contact with the chromium-containing aqueous media. An overall Cr(VI) concentration reduction of 45% was achieved using the roots of Typha latifolia whereas in the case of pyrolytic ashes a 60% removal was observed. The percentage removal was found to depend on the initial Cr(VI) concentration in aqueous solution, pH and temperature. The Cr(VI) uptake process was maximum at pH 2 and a temperature of 40 degrees C for both sorbents. These materials showed a Cr(VI) adsorption capacity that was adequately described by the Langmuir adsorption isotherm. It was demonstrated that the use of waste materials for the treatment of Cr(VI)-containing wastewater is an effective and economical alternative method.