Electrocatalytic Properties of a Novel Poly‐1‐Naphthylamine‐Modified Electrode Using Ascorbic Acid as Molecule Probe

A glassy carbon electrode was modified with an electropolymerized film of 1‐naphthylamine in aqueous solution. The electrocatalytic properties of this modified electrode (ME) were investigated using ascorbic acid (AA) as probe molecule. The electrochemical behavior of AA in buffer solution was examined by voltammetry and amperometry. The results showed that the ME exhibited good electrocatalytic activity towards the oxidation of AA, as a consequence, it can be used as amperometric sensor of this analyte in a flow injection system with good sensitivity. Calibration curves were linear over the concentration range 0.05–1.50 mM with a phosphate buffer solution pH 3 as the carrier, the detection limit was 1 ppm (S/N=3). The methods were applied to the determination of AA in beverages and pharmaceutical products. A good correlation with a reference method was attained.     

Training American listeners to perceive Mandarin tones

Auditory training has been shown to be effective in the identification of non-native segmental distinctions. In this study, it was investigated whether such training is applicable to the acquisition of non-native suprasegmental contrasts, i.c., Mandarin tones. Using the high-variability paradigm, eight American learners of Mandarin were trained in eight sessions during the course of two weeks to identify the four tones in natural words produced by native Mandarin talkers. The trainees' identification accuracy revealed an average 21% increase from the pretest to the post-test, and the improvement gained in training was generalized to new stimuli (18% increase) and to new talkers and stimuli (25% increase). Moreover, the six-month retention test showed that the improvement was retained long after training by an average 21% increase from the pretest. The results are discussed in terms of non-native suprasegmental perceptual modification, and the analogies between L2 acquisition processes at the segmental and suprasegmental levels.     

Acoustic analyses and perceptual data on anticipatory labial coarticulation in adults and children

The present study investigated anticipatory labial coarticulation in the speech of adults and children. CV syllables, composed of [s], [t], and [d] before [i] and [u], were produced by four adult speakers and eight child speakers aged 3-7 years. Each stimulus was computer edited to include only the aperiodic portion of fricative-vowel and stop-vowel syllables. LPC spectra were then computed for each excised segment. Analyses of the effect of the following vowel on the spectral peak associated with the second formant frequency and on the characteristic spectral prominence for each consonant were performed. Perceptual data were obtained by presenting the aperiodic consonantal segments to subjects who were instructed to identify the following vowel as [i] or [u]. Both the acoustic and the perceptual data show strong coarticulatory effects for the adults and comparable, although less consistent, coarticulation in the speech stimuli of the children. The results are discussed in terms of the articulatory and perceptual aspects of coarticulation in language learning.     

An Alternative Approach to Quantify Partition Processes in Confined Environments: The Electrochemical Behavior of PRODAN in Unilamellar Vesicles

Herein, we investigate the behavior of the electroactive molecular probe 6‐propionyl‐2‐dimethyl amino naphthalene (PRODAN) in large unilamellar vesicles (LUV) formed with the phospholipid 1,2‐di‐oleoyl‐sn‐glycero‐3‐phosphatidylcholine (DOPC) by using cyclic voltammetry (CV). The CV studies in pure water confirm our previous spectroscopic results that PRODAN self‐aggregates due to its low water solubility. Moreover, the electrochemical results also reveal that the PRODAN aggregated species are non‐electroactive within the studied electrochemical potential region. In DOPC LUV media, the redox behavior of PRODAN shows how the LUV bilayer interacts with PRODAN aggregated species to form PRODAN monomer species. Moreover, the electrochemical response of PRODAN allows us to propose a model for explaining the electrochemical experimental results and—in conjunction with our measurements—for calculating the value of the partition constant (K_p) of PRODAN between the water and LUV bilayer pseudophases. This value coincides with that obtained through an independent technique. Moreover, our electrochemical model allows us to calculate the diffusion coefficient (D) for the DOPC LUV, which coincides with the D value obtained through dynamic light scattering (DLS). Thus, our data clearly show that electrochemical measurements could be a powerful alternative approach to investigate the behavior of nonionic electroactive molecules embed in a confined environment such as the LUV bilayer. Moreover, we believe that this approach can be used to investigate the behavior of non‐optical molecular drugs embedded in bilayer media.     

Electrochemical nitration of naphthalene in the presence of nitrite ion in aqueous non-ionic surfactant solutions

The nitration of naphthalene (NapH) at a Pt electrode in aqueous NaNO₂ solutions both in the absence and presence of a non-ionic surfactant, Brij®35 (polyoxyethylene (23) dodecanol), has been studied. The electrochemical behaviour of the reactants NapH and NaNO₂ and a mixture of the two was investigated by cyclic voltammetry (CV) to determine the optimal electrolysis conditions. The peak current of NapH decreases with increasing NaNO₂ concentration, indicating that the oxidation product of the NO₂⁻ ion interacts with the NapH radical cation (NapH⁺). Controlled potential electrolysis (CPE) was carried out and the products were analysed by HPLC. The main products detected in the micellar medium were 1-nitronaphthalene, 2-nitronaphthalene, 1,2-naphthoquinone, and 1,4-naphthoquinone. In the absence of Brij 35, the naphthoquinones were produced but no nitration products were obtained. In both cases, unknown products are inferred by mass balance, which are believed to be derived from the oxidation of 1,1′-binaphthyl (BinapH) formed by NapH⁺ coupling in both micellar and aqueous media. A mechanism of nitration by the attack of NO₂ to NapH⁺ is proposed. The higher selectivity for formation of 2-nitronaphthalene in comparison to non-aqueous homogeneous media is attributed to the effect of the micellar microenvironment.     

First Observation of z-Dependent Electron-Beam Microbunching Using Coherent Transition Radiation

We report the first measurements of the electron-beam microbunching z dependence in a self-amplified spontaneous-emission (SASE) free-electron laser (FEL) experiment by the observation of visible wavelength coherent transition radiation (CTR). In this case the fundamental SASE wavelength was at 537 nm, and the CTR exhibited an exponential intensity growth similar to the SASE radiation. In addition, we observed for the first time structure in the CTR angular distribution patterns that may be useful for optimizing SASE FEL performance.     

Anodic oxidation of 1-naphthylamine in acetonitrile

The anodic oxidation of 1-naphthylamine (ArNH₂) has been studied at the platinum electrode in acetonitrile by controlled potential electrolysis, chronopotentiometry, cyclic voltammetry, cyclic voltammetry and spectrometric methods. From the electrochemical data a complex ECE type of mechanism is inferred with an overall efficiency of one electron per molecule of ArNH₂. The electrochemical steps are reversible and the chemical process seems to follow second order kinetics and is extremely fast. The cation radical produced in the first charge transfer step suffers fast decomposition to give dimers which are easier to oxidize than ArNH₂. The dimeric products were identified by comparison with authentic samples. Further complications arise due to slow reactions of the oxidized dimers. Electrochemical studies in basic media (pyridine and 2,6-lutidine) and acid media (anhydrous trifluoroacetic acid) were also performed.     

Optimization of the electrodeposition of copper on poly-1-naphthylamine for the amperometric detection of carbohydrates in HPLC

A modified electrode consisting of copper dispersed in a poly-1-naphthylamine (p-1-NAP/Cu) film on a glassy carbon electrode was used as an amperometric detector for the on-line analysis of various carbohydrates separated by high performance liquid chromatography. The results obtained with this new sensor were compared to those obtained with a modified electrode based on the same polymer but with copper ions incorporated at open circuit, as described in a previous paper. In this new modified electrode the copper microparticles were electrochemically deposited into the polymeric matrix by single potential step chronoamperometry. A nucleation and growth mechanism was proposed to explain the current transients of copper electrodeposition. The experimental results were fitted to the proposed mechanism by using a mathematical equation that considers three-dimensional growth and progressive nucleation, assuming a no overlap and no diffusion mechanism. Cyclic voltammetric experiments showed that the electrodeposited copper microparticles provided a catalytic surface suited for the oxidation of glucose and several carbohydrates. The sensitivity of the electrode was influenced by the amount of copper electrodeposited, which in turn depended on the applied overpotential used for the deposition of copper. Liquid chromatographic experiments were carried out to test the analytical performance of these electrodes for the determination of various carbohydrates.     

Effect of column material on sorption isotherms obtained by inverse gas chromatography

The dependence of sucrose sorption isotherm data obtained by inverse gas chromatography on column material was studied. Columns made of polyamide glass, copper and stainless steel were used. The results obtained indicate that the interaction between water vapour and the column wall cannot be ignored when products with very low equilibrium moisture content are considered.