Applying sequential injection analysis (SIA) and response surface methodology for optimization of Fenton-based processes

This work presents the use of sequential injection analysis (SIA) and the response surface methodology as a tool for optimization of Fenton-based processes. Alizarin red S dye (C.I. 58005) was used as a model compound for the anthraquinones family, whose pigments have a large use in coatings industry. The following factors were considered: [H₂O₂]:[Alizarin] and [H₂O₂]:[FeSO₄] ratios and pH. The SIA system was designed to add reagents to the reactor and to perform on-line sampling of the reaction medium, sending the samples to a flow-through spectrophotometer for monitoring the color reduction of the dye. The proposed system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 99.7% of the dye was degraded and the TOC content was reduced to 35% of the original value. Low reagents consumption and high sampling throughput were the remarkable features of the SIA system.     

Pre-evaluation of metal ions as a catalyst on chemiluminometric sequential injection analysis with luminol-H2O2 system

Catalytic effect of metal ions on luminol chemiluminescence (CL) was investigated by sequential injection analysis (SIA). The SIA system was set up with two solenoid micropumps, an eight-port selection valve, and a photosensor module with a fountain-type chemiluminescence cell. The SIA system was controlled and the CL signals were collected by a LabVIEW program. Aqueous solutions of luminol, H₂O₂, and a sample solution containing metal ion were sequentially aspirated to the holding coil, and the zones were immediately propelled to the detection cell. After optimizing the parameters using 1 × 10⁻⁵ M Fe³⁺ solution, catalytic effect of some metal species was compared. Among 16 metal species examined, relatively strong CL responses were obtained with Fe³⁺, Fe²⁺, VO²⁺, VO₃⁻, MnO₄⁻, Co²⁺, and Cu²⁺. The limits of detection by the present SIA system were comparable to FIA systems. Permanganate ion showed the highest CL sensitivity among the metal species examined; the calibration graph for MnO₄⁻ was linear at the concentration level of 10⁻⁸ M and the limit of detection for MnO₄⁻ was 4.0 × 10⁻¹⁰ M (S/N = 3).     

Sensing hydrogen peroxide involving intramolecular charge transfer pathway: A boronate-functioned styryl dye as a highly selective and sensitive naked-eye sensor

The synthesis, properties and applications of a novel boronate-functioned styryl dye, BSD, as a colorimetric sensor for hydrogen peroxide is presented. The dye displayed remarkable color change from colorless (λ_max = 391 nm) to deep red (λ_max = 522 nm) in the presence of H₂O₂ and the behavior could be rationalized by the chemoselective H₂O₂-mediated transformation of arylboronate to phenolate, resulting in the release of the merocyanine dye which featured with strong intramolecular charge transfer (ICT) absorption band. The absorption increment of merocyanine at λ_max = 522 nm (? = 87000 L mol⁻¹ cm⁻¹) is linear with the concentration of H₂O₂ in the range of 1.0 × 10⁻⁷-2.5 × 10⁻⁵ mol L⁻¹ with the detection limit of 6.8 × 10⁻⁸ mol L⁻¹ under optimum conditions. There is almost no interference by other species that commonly exist due to the specific deprotection of H₂O₂ towards arylboronate group on BSD. The chromogenic sensor has been applied to the detection of trace amounts of hydrogen peroxide in rain water.     

Factors influencing level of hydrogen peroxide in exhaled breath condensate

Hydrogen peroxide (H₂O₂) in exhaled breath condensate (EBC) has been proposed as a marker for oxidative stress in the airways. The aim of the present study was to evaluate the measurement of H₂O₂ in EBC with or without use of a nose clip, and the influence of mouth rinsing, sampling time and storage.An elevated H₂O₂ level was seen during nasal breathing compared to mouth breathing with nose clip (3.4 pmol/s vs. 2.1 pmol/s, p = 0.02). Breathing through the mouth, using a nose clip, was therefore practiced in all experiments. The H₂O₂ levels were increased when mouth rinsing was performed using an acid buffer (1.4 pmol/s vs. 1.9 pmol/s, p = 0.03). 15 min sampling time decreased the H₂O₂ output by almost 50% compared with 2 min sampling time (1.2 vs. 0.6 pmol/s, p = 0.03). When samples were left unattended for 15 min no change in H₂O₂ concentration in the EBC was seen.We found no significant differences in H₂O₂ levels between samples stored for 4 weeks at − 80 °C and samples analysed directly; however, a significant decrease in the levels was seen for samples stored for 4 weeks at − 20 °C.In conclusion, the method of EBC collection and storage plays an important role in reducing variability within and between individuals.     

Sequential injection analysis system for on-line monitoring of l-cysteine concentration in biological processes

A sequential injection analysis (SIA) system was developed to monitor the concentration of l-cysteine in biological processes on-line. It is based on the redox reaction of l-cysteine with iron(III) in the presence of 1,10-phenanthroline (phen) and the detection of the red-iron(II)-phen complex with a spectrophotometry. The system was fully automated using software written in the LabVIEW™ development environment. A number of system variables such as the flow rate of the carrier buffer solution, the volume ratio of the sample to the reagents, and the reaction coil length, etc., were evaluated to increase the sensitivity and performance of the SIA system. Under partially optimized operating conditions the performance of the SIA system was linear up to a concentration of l-cysteine of 1 mM (R² = 0.998) with a detection limit of 0.005 mM and a sample frequency of 15 hr⁻¹. The SIA system was employed to monitor the concentration of l-cysteine on-line in a continuously stirred reactor and a fermentation process of Saccharomyces cerevisiae. The on-line monitored data were in good agreement with the off-line data measured by a HPLC with a fluorescence detector (n = 15, R² = 09899).     

A rare multi-coordinate tellurite, NH4ATe4O9·2H2O (ARb or Cs): The occurrence of TeO3, TeO4, and TeO5 Polyhedra in the same material

Two new tellurites, NH₄RbTe₄O₉·2H₂O and NH₄CsTe₄O₉·2H₂O have been synthesized and characterized. The compounds were synthesized hydrothermally, in near quantitative yields, using the alkali metal halide, TeO₂, and NH₄OH as reagents. The iso-structural materials exhibit layered, two-dimensional structural topologies consisting of TeO_x (x=3, 4, or 5) polyhedra separated by NH₄⁺, H₂O, Rb⁺ or Cs⁺ cations. Unique to these materials is the presence of TeO₃, TeO₄, and TeO₅ polyhedra. Thermogravimetric and infrared spectroscopic data are also presented. Crystal data: NH₄RbTe₄O₉·2H₂O: Monoclinic I2/a (no. 15), a=18.917(3) Å, b=6.7002(11) Å, c=21.106(5) Å, β=101.813(2)°, V=2618.5(9) Å³, Z=8; NH₄CsTe₄O₉·2H₂O: Monoclinic I2/a (no. 15), a=18.9880(12) Å, b=6.7633(4) Å, c=21.476(2) Å, β=102.3460(10)°, V=2694.2(3) Å³, Z=8.     

Similarities and differences of epoxide, aldehyde and peroxide initiators for Cp2TiCl-catalyzed styrene living radical polymerizations

Cp₂TiCl is the first example of a single electron transfer (SET) agent that both provides initiating radicals from three different types of functionalities (i.e. radical ring opening of epoxides and reduction of aldehydes and peroxides) and doubles as mediator for the living radical polymerization of styrene (St) by reversibly endcapping the growing polymer chains. An initiator (I) comparison was performed using 1,4-butanediol diglycidyl ether (BDE), benzaldehyde (BA) and benzoyl peroxide (BPO) as models. The investigation of the effect of reaction variables was carried out over a wide range of experimental conditions ([Cp₂TiCl₂]/[I] = 0.5/1-4/1; [Zn]/[Cp₂TiCl₂] = 0.5/1-3/1, [St]/[I] = 50/1-400/1 and T = 60-130 °C) to reveal living polymerization features such as a linear dependence of molecular weight on conversion and narrow molecular weight distribution (M_w/M_n) for each initiator class. However, progressively lower polydispersities and larger initiator efficiencies are obtained with increasing the [Cp₂TiCl₂]/[I] and [Zn]/[Cp₂TiCl₂] ratios and with decreasing temperature. Accordingly, optimum conditions correspond to [St]/[I]/[Cp₂TiCl₂]/[Zn] = [50-200]/[1]/[2-3]/[4-6] at 70-90 °C. By contrast to peroxides, aldehydes and the more reactive epoxides provide alcohol end groups useful in block or graft copolymers synthesis.     

A microband lactate biosensor fabricated using a water-based screen-printed carbon ink

The present study demonstrated for the first time that screen-printed carbon microband electrodes fabricated from water-based ink can readily detect H₂O₂ and that the same ink, with the addition of lactate oxidase, can be used to construct microband biosensors to measure lactate. These microband devices were fabricated by a simple cutting procedure using conventional sized screen-printed carbon electrodes (SPCEs) containing the electrocatalyst cobalt phthalocyanine (CoPC). These devices were characterised with H₂O₂ using several electrochemical techniques. Cyclic voltammograms were found to be sigmoidal; a current density value of 4.2 mA cm⁻² was obtained. A scan rate study revealed that the mass transport mechanism was a mixture of radial and planar diffusion. However, a further amperometric study under quiescent and hydrodynamic conditions indicated that radial diffusion predominated. A chronoamperometric study indicated that steady-state currents were obtained with these devices for a variety of H₂O₂ concentrations and that the currents were proportional to the analyte concentration. Lactate microband biosensors were then fabricated by incorporating lactate oxidase into the water-based formulation prior to printing and then cutting as described. Voltammograms demonstrated that lactate oxidase did not compromise the integrity of the electrode for H₂O₂ detection. A potential of +400 mV was selected for a calibration study, which showed that lactate could be measured over a dynamic range of 1-10 mM which was linear up to 6 mM; a calculated lower limit of detection of 289 μM was ascertained. This study provides a platform for monitoring cell metabolism in-vitro by measuring lactate electrochemically via a microband biosensor.     

“Oxidative etching-aggregation” of silver nanoparticles by melamine and electron acceptors: An innovative route toward ultrasensitive and versatile functional colorimetric sensors

An innovative and versatile functional colorimetric sensor for melamine (MA) and H₂O₂ was developed with simplicity, excellent selectivity and ultrasensitivity. The detection mechanism was based on the “oxidative etching-aggregation” of silver nanoparticles (AgNPs) by the cooperation effect of MA and electron acceptors such as H₂O₂, ozone or Fe(NO₃)₃. The detection limits of this method for MA could reach as low as 0.08 nM, 0.16 nM and 3 nM when H₂O₂, ozone or Fe(NO₃)₃ was used as an electron acceptor, respectively. When using H₂O₂ as a typical electron acceptor, the method enabled the detection of H₂O₂ with a detection limit of 0.2 nM. This proposed method offered a new way to design MA and H₂O₂ sensors and might be easily extended to detect other nucleophilic reagents and electron acceptors based on colorimetric sensors.     

A luminol-based micro-flow-injection electrochemiluminescent system to determine reactive oxygen species

A flow injection analysis (FIA) system with electrochemiluminescent (ECL) detection has been established. Based on a specially designed flow-through ECL cell with a very simple structure, the system possesses rapid response and high sensitivity. With luminol as the ECL reagent, the response of hydrogen peroxide (H₂O₂) was investigated on the developed FIA-ECL system. After optimizing the experimental conditions, such as the electric parameters, the buffer condition and the flow rate, it was demonstrated that the developed FIA-ECL system works well for quantified assays. Compared with reported works, the present results indicate that the developed FIA-ECL system has the lowest limit of detection (S/N = 3) of 3.0 × 10⁻⁹ mol/L for H₂O₂, which is equal to the level of chemiluminescence (CL). The developed system was successfully used to monitor the yield of reactive oxygen species (ROSs) in water vapour during the work of an ultrasonic humidifier with H₂O₂ as index. And the amount of ROSs in some other real samples, including tap water, drinking water and river water was detected with recoveries from 92.0% to 106%.