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. [ , 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.

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: pK = 4.392 ± 0.

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.

New insights on the spectrophotometric determination of melatonin pK values and melatonin-βCD 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 pK values, in a completely protected aqueous medium, were estimated as 5.777±0.

Effective mercury(II) bioremoval from aqueous solution, and its electrochemical determination.

This work proposed mercury elimination using agricultural waste (Allium Cepa L.). The biomass removed 99.

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.

Electrochemical quantification of the antioxidant capacity of medicinal plants using biosensors.

The working area of a screen-printed electrode, SPE, was modified with the enzyme tyrosinase (Tyr) using different immobilization methods, namely entrapment with water-soluble polyvinyl alcohol (PVA), cross-linking using glutaraldehyde (GA), and cross-linking using GA and human serum albumin (HSA); the resulting electrodes were termed SPE/Tyr/PVA, SPE/Tyr/GA and SPE/Tyr/HSA/GA, respectively. These biosensors were characterized by means of amperometry and EIS techniques. From amperometric evaluations, the apparent Michaelis-Menten constant, Km', of each biosensor was evaluated while the respective charge transfer resistance, Rct, was assessed from impedance measurements.

Guest-host complex formed between ascorbic acid and β-cyclodextrin immobilized on the surface of an electrode.

This work deals with the formation of supramolecular complexes between ascorbic acid (AA), the guest, and β-cyclodextrin (β-CD), the host, that was first potentiodynamically immobilized on the surface of a carbon paste electrode (CPE) throughout the formation of a β-CD-based conducting polymer (poly-β-CD). With the bare CPE and the β-CD-modified CPE, an electrochemical study was performed to understand the effect of such surface modification on the electrochemical response of the AA. From this study it was shown that on the modified-CPE, the AA was surface-immobilized through formation of an inclusion complex with β-CD, which provoked the adsorption of AA in such a way that this stage became the limiting step for the electrochemical oxidation of AA.

Deprotonation mechanism and acidity constants in aqueous solution of flavonols: a combined experimental and theoretical study.

Four flavonols, namely quercetin, morin, kaempferol, and myricetin, were studied using spectrophotometry (UV-vis) in aqueous solution. The study was performed varying the pH to analyze the stability of these compounds, and to estimate their acidity constants. In addition, the deprotonation mechanisms were studied using computational chemistry within the density functional theory framework.

Solid-contact Hg(II)-selective electrode based on a carbon-epoxy composite containing a new dithiophosphate-based ionophore.

The experimental results herein concern a novel ion-selective electrode manufactured with an inner solid contact based on a new ligand O,O'-(2,2'-biphenylene)dithiophosphate pentyl (PenDTF). This electrode displays high selectivity toward the Hg(II) ion even in the presence of different divalent ions. The electrode also exhibited a good Nernstian response to Hg(II) (33.

Determination of oxytetracycline in milk samples by polymer inclusion membrane separation coupled to high performance liquid chromatography.

The determination of oxytetracycline in milk samples using a polymer inclusion membrane concept with high performance liquid chromatography (HPLC) was studied. The membranes developed are composed by cellulose acetate as polymer base, Cyanex 923 as carrier and o-nitrophenyl octyl ether as plasticizer. In the optimal conditions, the method exhibits good linearity in the range 0.

Searching for Computational Strategies to Accurately Predict pKas of Large Phenolic Derivatives.

Twenty-two reaction schemes have been tested, within the cluster-continuum model including up to seven explicit water molecules. They have been used in conjunction with nine different methods, within the density functional theory and with second-order Møller-Plesset. The quality of the pKa predictions was found to be strongly dependent on the chosen scheme, while only moderately influenced by the method of calculation.

Kinetics and mechanism of the electrochemical formation of iron oxidation products on steel immersed in sour acid media.

From electrochemical techniques (cyclic voltammetry, potential steps, and EIS), XRD, and SEM-EDX, the kinetics and mechanism of anodic film formation applying anodic potential steps on steel immersed in sour acid media was determined. It was found, from a thermodynamic analysis, based on equilibrium phase diagrams of the system considered in this work, that iron oxidation may produce different new solid phases, depending on the applied potential, the first being the iron oxidation associated with formation of FeS((c)) species, which in turn can be reoxidized to FeS(2(c)) or even to Fe(2)O(3(c)) at higher potential values. From analysis of the corresponding experimental potentiostatic current density transients, it was concluded that the electrochemical anodic film formation involves an E(1)CE(2) mechanism, whereby the first of the two simultaneous processes were the Fe electrochemical oxidation (E(1)) followed by FeS precipitation (C) that occurs by 3D nucleation and growth limited by mass transfer reaction and FeS oxidation (E(2)) forming a mix of different stoichiometry iron sulphides and oxides.

Enzyme entrapment by β-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), β-cyclodextrin (β-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/β-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/β-CD, SPE/GOx, SPE/β-CD/GOx, SPE/MWCNT/β-CD, SPE/MWCNT/GOx and SPE/MWCNT/β-CD/GOx were tested separately.

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.

Amperometric biosensor based on a high resolution photopolymer deposited onto a screen-printed electrode for phenolic compounds monitoring in tea infusions.

An amperometric biosensor based on laccase, from Trametes versicolor (LTV), was developed and optimized for monitoring the phenolic compounds content in tea infusions. The fungal enzyme was immobilized by entrapment within polyvinyl alcohol photopolymer PVA-AWP (azide-unit pendant water-soluble photopolymer) onto disposable graphite screen-printed electrodes (SPE). Sensitivity optimization in terms of pH, temperature and applied potential was carried out.

Determination of pKa values of tenoxicam from 1H NMR chemical shifts and of oxicams from electrophoretic mobilities (CZE) with the aid of programs SQUAD and HYPNMR.

In this work it is explained, by the first time, the application of programs SQUAD and HYPNMR to refine equilibrium constant values through the fit of electrophoretic mobilities determined by capillary zone electrophoresis experiments, due to the mathematical isomorphism of UV-vis absorptivity coefficients, NMR chemical shifts and electrophoretic mobilities as a function of pH. Then, the pK(a) values of tenoxicam in H(2)O/DMSO 1:4 (v/v) have been obtained from (1)H NMR chemical shifts, as well as of oxicams in aqueous solution from electrophoretic mobilities determined by CZE, at 25 degrees C. These values are in very good agreement with those reported by spectrophotometric and potentiometric measurements.

Deprotonation mechanism of new antihypertensive piperidinylmethylphenols: a combined experimental and theoretical study.

Four new antihypertensive piperidinylmethylphenol compounds were synthesized for their potential antihypertensive and antiarhythmic properties. The pKa values were determined experimentally, with the aid of the program SQUAD, by capillary zone electrophoresis (CZE) at T=298.15 K and 0.

Acetylcholinesterase-based biosensors for quantification of carbofuran, carbaryl, methylparaoxon, and dichlorvos in 5% acetonitrile.

Amperometric acetylcholinesterase biosensors have been developed for quantification of the pesticides carbofuran, carbaryl, methylparaoxon, and dichlorvos in phosphate buffer containing 5% acetonitrile. Three different biosensors were built using three different acetylcholinesterase (AChE) enzymes-AChE from electric eel, and genetically engineered (B394) and wild-type (B1) AChE from Drosophila melanogaster. Enzymes were immobilized on cobalt(II) phthalocyanine-modified electrodes by entrapment in a photocrosslinkable polymer (PVA-AWP).

Automated resolution of dichlorvos and methylparaoxon pesticide mixtures employing a Flow Injection system with an inhibition electronic tongue.

An amperometric biosensor array has been developed to resolve pesticide mixtures of dichlorvos and methylparaoxon. The biosensor array has been used in a Flow Injection system, in order to operate automatically the inhibition procedure. The sensors used were three screen-printed amperometric biosensors that incorporated three different acetylcholinesterase enzymes: the wild type from Electric eel and two different genetically modified enzymes, B1 and B394 mutants, from Drosophila melanogaster.

Sensitive amperometric biosensor for dichlorovos quantification: Application to detection of residues on apple skin.

This paper presents the construction of an amperometric biosensor for the highly sensitive detection of the organophosphorus insecticide dichlorvos, based on the inhibition of acetylcholinesterase (AChE). The sensitivity of three AChEs from different sources were tested and compared: AChEs from Electric eel (Ee) and genetically engineered (B394) and wild type (B1) from Drosophila melanogaster (Dm). The enzymes were immobilized by entrapment in a photocrosslinkable PVA-SbQ polymer on a screen printed graphite electrode.

Development of a capillary electrophoresis method for the characterization of "palo azul" (Eysenhardtia polystachya).

The tree Eysenhardtia polystachya (Ortega) Sarg. has quite a wide popular use within the traditional Mexican medicine as herbal remedy. Popular practices constitute a relevant enough basis to design optimum analytical methods in order to determine basic principles of diverse medicinal plants.

Experimental correlation between the pKa value of sulfonphthaleins with the nature of the substituents groups.

This work presents the results obtained from a spectrophotometry study performed on some indicators of the sulfonphtaleins like phenol red (PR), thymol blue (TB), bromothymol blue (BTB), xylenol orange (XO) and methylthymol blue (MTB). During the first stage the acidity constants of some of the indicators were determined using the data from spectrophotometry, potentiometry and with the use of the software SQUAD. These were as follows: for the equilibrium 2H+BTB<-->H(2)BTB, log beta(2)=15.

UV-visible spectroscopic and electrochemical study of the complex formation between Fe(II) and 5-amino-1,10-phenantroline (5-Aphen) in aqueous solution.

The system Fe(II)-5-Aphen-H(2)O was studied. The spectroscopic and electrochemical results show that only one stable complex between Fe(II) and 5-Aphen forms, having a 1:3 stoichiometric ratio. The spectrophotometry study allowed determination of the formation constant of the complex (logbeta(3)=23.