Deep investigation on different effects of Cl- in transformation of reactive species in Fe(II)/NH2OH/PDS and Fe(II)/NH2OH/H2O2 systems.

Hydroxylamine (NH2OH) has been verified to efficiently strengthen pollutants oxidation in Fe(II)/peroxydisulfate (PDS) and Fe(II)/H2O2 systems. However, the different effects of hydroxylamine salts types were rarely recognized. Herein, the effects of two commonly used hydroxylamine salts (i.e. NH2OH·HCl and (NH2OH)2·H2SO4) on oxidation kinetics and reactive species composition were compared in Fe(II)/PDS and Fe(II)/H2O2 systems for the first time. Pseudo first order kinetics could only describe benzoic acid (BA) oxidation well in Fe(II)/NH2OH/H2O2 system, which was related to the different concentration changes of Fe(III) determined by [Formula: see text] . Hydroxylamine salts types influenced not kinetic rules, but reaction rates of target compounds. The empirical reaction rate constant of BA in Fe(II)/NH2OH·HCl/PDS system was 141.5% of that in Fe(II)/(NH2OH)2·H2SO4/PDS system under the same concentration of NH2OH (1.4 mM), while the apparent reaction rate constant in Fe(II)/NH2OH·HCl/H2O2 system was 68% of that in Fe(II)/(NH2OH)2·H2SO4/H2O2 system. This opposite effect resulted from the differences in primary reactive species compositions and their interactions with Cl-. Reactive species identification indicated that Cl- would decrease the contribution of ferryl ion (Fe(IV)) and transform sulfate radical (SO4·-) to hydroxyl radical (·OH) in Fe(II)/NH2OH/PDS system, while it competitively consumed the only reactive species ·OH in Fe(II)/NH2OH/H2O2 system. This study highlights the importance of reductants types on strengthening Fenton oxidation and offers a reference for reasonable construction of the relevant systems.

Performance evaluation of a capillary electrophoresis electrochemical chip integrated with gold nanoelectrode ensemble working and decoupler electrodes.

This paper presents a capillary electrophoresis poly(methyl methacrylate) (PMMA) based microchip for electrochemical detection applications featuring embedded gold nanoelectrode ensemble (GNEE) working and decoupler electrodes. In fabricating the microchip, the GNEE films are pressed directly onto the metallic electrode structures using a hot embossing technique, and the microfluidic channels are then sealed using a low-temperature azeotropic solvent bonding method. The detection performance of the microchip is evaluated using dopamine and catechol analytes for illustration purposes. The experimental results show that the GNEE working electrode provides a significantly higher signal response than that obtained from a bulk gold electrode when applied to the detection of dopamine analyte. Compared to a conventional bulk palladium decoupler electrode, the GNEE decoupler electrode reduces both the amplitude of the charge current (3.5 nA vs. 18.7 nA) and the baseline drift at higher separation voltages. The measured baseline current drift for the microchip equipped the proposed GNEE decoupler electrode is around three times smaller than the microchip with the palladium decoupler electrode under the applied separation electric field from 40 V/cm to 240 V/cm. Finally, when detecting a mixture of 1mM dopamine and 1mM catechol, the calculated signal response of the microchip with a GNEE decoupler electrode is approximately five times higher than that obtained from a microchip with a bulk Pd decoupler electrode, resulting in the detection limit of 1 microM for the proposed GNEE-based microchip device. Overall, the results indicate that the proposed capillary electrophoresis-electrochemical detection (CE-ED) microchip with embedded GNEE working and decoupler electrodes provides an ideal solution for sample detection in lab-on-a-chip and micro total analysis applications.

Poly(methyl methacrylate) microchip device integrated with gold nanoelectrode ensemble for in-column biochemical reaction and electrochemical detection.

This paper proposes a poly(methyl methacrylate) (PMMA) based microchip with an integrated gold nanoelectrode ensemble (GNEE) and a quartet-T loading channel for in-column urea/urease reactions and electrochemical detections. The on-chip GNEE electrode is fabricated using an electrodeless deposition process on a thin polycarbonate (PC) film and bonded directly onto a PMMA substrate to carry out high-performance electrochemical detections. The in-column bio-catalytic reaction of urea/urease is successfully demonstrated utilizing a novel approach based on the different electrokinetic mobilities of urea and urease in capillary electrophoresis (CE) channel. The experimental results significantly show that the GNEE electrode provides a better detection response for the reaction product of ammonia (NH(4)(+)) than a conventional planar gold electrode. The detection results demonstrate a satisfactory determination coefficient (R(2) value) and high reproducibility with a detection limit of 14.8 and 62.8 microM while detecting standard ammonia solution and the urea/urease reaction product of NH(4)(+), respectively. These results confirm the capability of the proposed device for the high-resolution CE-electrochemical detection (CE-ED) of bioanalytical reactions.