Simultaneous monitoring of amoxicillin and paracetamol in synthetic biological fluids using a 3D printed disposable electrode with a lab-made conductive filament.

In this work, we are pleased to present for the first time a 3D-printed electrochemical device using a lab-made conductive filament based on graphite (Gr) and polylactic acid (PLA) polymer matrix for the simultaneous detection of amoxicillin (AMX) and paracetamol (PAR). The sensor was properly characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). Compared to the commercial glassy carbon electrode (GCE), the superior performance of the 3D-Gr/PLA electrode was verified with a 3.8-fold more favored charge transfer. A differential pulse voltammetry (DPV) method was proposed providing a linear working range of 4 to 12 µmol L-1 for both analytes and a limit of detection (LOD) of 0.80 and 0.51 µmol L-1 for AMX and PAR, respectively. Additionally, repeatability studies (n = 5, RSD < 5.7%) indicated excellent precision, and recovery percentages ranging from 89 to 109% when applied to synthetic human urine, saliva, and plasma samples, attested to the accuracy of the method. The studies also indicate that the sensor does not suffer significant interference from common substances (antibiotics and biomarkers) present in the biological fluids, which makes it a promising analytical tool considering its low-cost, ease of manufacturing, robustness, and electrochemical performance.

Cost-effective protocol to produce 3D-printed electrochemical devices using a 3D pen and lab-made filaments to ciprofloxacin sensing.

A novel conductive filament based on graphite (Gr) dispersed in polylactic acid polymer matrix (PLA) is described to produce 3D-electrochemical devices (Gr/PLA). This conductive filament was used to additively manufacture electrochemical sensors using the 3D pen. Thermogravimetric analysis confirmed that Gr was successfully incorporated into PLA, achieving a composite material (40:60% w/w, Gr and PLA, respectively), while Raman and scanning electron microscopy revealed the presence of defects and a high porosity on the electrode surface, which contributes to improved electrochemical performance. The 3D-printed Gr/PLA electrode provided a more favorable charge transfer (335 Ω) than the conventional glassy carbon (1277 Ω) and 3D-printed Proto-pasta® (3750 Ω) electrodes. As a proof of concept, the ciprofloxacin antibiotic, a species of multiple interest, was selected as a model molecule. Thus, a square wave voltammetry (SWV) method was proposed in the potential range + 0.9 to + 1.3 V (vs Ag|AgCl|KCl(sat)), which provided a wide linear working range (2 to 32 µmol L-1), 1.79 µmol L-1 limit of detection (LOD), suitable precision (RSD < 7.9%), and recovery values from 94 to 109% when applied to pharmaceutical and milk samples. Additionally, the sensor is free from the interference of other antibiotics routinely employed in veterinary practices. This device is disposable, cost-effective, feasibly produced in financially limited laboratories, and consequently promising for evaluation of other antibiotic species in routine applications.

Electrochemical monitoring of levofloxacin using a silver nanoparticle-modified disposable device based on a lab-made conductive ink.

The emergence of bacteria genetically resistant to first- and second-generation fluoroquinolones has resulted in increased consumption of levofloxacin (LEV) in human and veterinary medicine. In this regard, the development of low cost and good sensitivity electrochemical devices has been highly required. Thus, in this work, we propose the development of a disposable electrochemical device (DED) using a lab-made conductive ink based on graphite powder and nail polish immobilized on a rigid polyvinyl chloride support (transparent sheet). Additionally, a simple and quick protocol for the electrodeposition of silver nanoparticles was used in order to improve the electroanalytical performance of the sensor (2.75-fold). A differential pulse voltammetry (DPV) method was optimized and the sensor was applied for LEV monitoring in pharmaceutical formulation samples, synthetic urine and simulated body fluid. The method showed a wide linear working range ranging from 0.5 to 50 µmol L-1 and a detection limit of 68.3 nmol L-1. Furthermore, the precision was adequate (RSD < 4.7%), while the accuracy was evaluated through spiked samples with percent recovery ranging from 93 to 103%. The sensor was also shown to be selective for LEV against other electroactive antibiotic species, thus demonstrating suitable characteristics for electroanalytical applications.

Development of a 3D disposable device for the electrochemical determination of diclofenac in different matrices.

In this work, the development of a disposable electrochemical device (US$ 0.02 per electrode) using a 3D printed support (3Ds) of acrylonitrile butadiene styrene (ABS) insulating filament with a composite material (CM) based on graphite and nail polish, immobilized on the support surface, was described for the electrochemical determination of diclofenac (DCF). The device was compared to the commercial glassy carbon electrode (GCE) and showed superior electroanalytical performance with approximately 1.8-fold higher current density. Additionally, an amperometric method for DCF determination in tap water, synthetic urine, and pharmaceutical formulation samples with the proposed electrode, using a flow injection analysis (FIA-AD) system, was developed. The optimized method presented excellent detectability (LOD = 0.47 µmol L-1), with excellent precision and accuracy (relative standard deviation < 5.6%) and percent recovery from spiked samples ranging from 89 to 106%. In addition, the sensor showed optimal analytical frequency with approximately 108 injections per hour, which demonstrates the potential of this system using the proposed disposable electrode for implementation in routine analysis and quality control with good selectivity and sensitivity.

Determination of hydroquinone and benzoquinone in pharmaceutical formulations: critical considerations on quantitative analysis of easily oxidized compounds.

Hydroquinone is a skin-lightening agent used as an active ingredient in topical dermatological formulations prescribed for treating cutaneous diseases caused by hyperpigmentation. Despite being widely used, some toxicological aspects have been associated with these products, mainly due to overdosage and long-term use combined with the easy oxidation of hydroquinone. In this work, an investigative study has been done to gather enough data for selecting a quantitative analytical method for quality control purposes that considers the ease of oxidation not only within the product but also during the experimental procedures. After studying the influence of pH, reversibility, sampling, and standard solution preparation on the redox reaction between hydroquinone and benzoquinone by using spectroscopic, electrophoretic, and electroanalytical measurements, a reliable, fast, and selective chronoamperometric method was achieved. The optimized method was used for the analysis of samples, previously diluted in Britton-Robinson (BR) buffer (pH 5.5) and methanol (1 : 9, v/v), by applying a potential fixed at 0.4 V. A glassy-carbon working electrode, lab-made Ag/AgCl(sat) and platinum wire as a reference electrode and auxiliary electrodes, respectively, and BR buffer (pH 5.5) as supporting electrolyte were the additional experimental conditions used. Analytical performance parameters were verified to confirm the applicability of the new method (LOD 4.22 µmol L-1 and LOQ 14.1 µmol L-1; recovery mean value of 100% with 0.22% RSD). A gel topical formulation containing 4% (w/w) hydroquinone was analyzed through the developed method for determination of dosage and oxidation traces, and a content of 3.53 ± 0.095% (w/w) was found with no indications of degradation.

A pencil graphite-based disposable device for electrochemical monitoring of sulfanilamide in honey and water samples.

The present paper reports a simple, fast, and inexpensive process of manufacturing a disposable pencil graphite electrode (PGE) from widely available materials, which showed a reproducibility of at least 7.5%. The electrode was compared to the commercial glassy carbon electrode (GCE) and showed superior electroanalytical performance for sulfanilamide (SFA) with approximately 3.9-fold higher current density. Additionally, a displacement of the oxidation peak from approximately 80 mV to more cathodic regions was observed. Therefore, a method based on square wave voltammetry (SWV) was developed for the determination of the antimicrobial SFA in honey and tap water samples using the proposed sensor. The optimized method presented good detectability (LOD = 2.37 µmol L-1), with excellent precision and accuracy (relative standard deviation < 4.2%) and percent recovery from spiked samples ranging from 92 to 97%. In addition, the sensor did not suffer significant interference from sample matrix components and other commonly evaluated antimicrobials, which demonstrates the potential of these electrodes for implementation in routine analysis and quality control.

3D-printed electrode an affordable sensor for sulfanilamide monitoring in breast milk, synthetic urine, and pharmaceutical formulation samples.

This paper describes a simple and cost-effective method for manufacturing a 3D-printed electrode. This electrode presented a similar design to commercial electrodes, where a stereolithography printer was used to build the electrode body using an acrylic resin. The electroactive surface was filled by a 3D-pen using a carbon black integrated polylactic acid (CB/PLA) conductive filament. After a simple and fast (400 s) surface treatment, the 3D-printed CB/PLA electrode was combined with Differential Pulse Voltammetry (DPV) technique for sulfanilamide (SAA) determination. The developed electroanalytical method was applied to breast milk, synthetic urine, and otologic solution samples, showing excellent analytical performance with a detection limit of 12 nmol L-1, wide linear range from 1 to 39.2 µmol L-1, and good precision (RSD = 1.8%, n = 10). In addition, the sensor provides fantastic selectivity towards other antibiotic classes, and when applied in spiked samples, recovery values between 93 and 108% were obtained, which demonstrated good accuracy as well as the absence of matrix effect. It is highlighted that no laborious sample preparation steps were required (simple dilution in supporting electrolyte). Thus, the proposed 3D-printed device proves to be a promising analytical tool for routine analysis.

Batch injection analysis with amperometric detection for fluoroquinolone determination in urine, pharmaceutical formulations, and milk samples using a reduced graphene oxide-modified glassy carbon electrode.

In this work, the batch injection analysis system with amperometric detection using reduced graphene oxide as a modifier of glassy carbon electrode (GCE) was investigated for the simple, fast, and sensitive monitoring of levofloxacin (LEVO) and ciprofloxacin (CIPRO) in samples of pharmaceutical formulations, synthetic urine, and milk (low- and high-fat content). LEVO and CIPRO were quantified in seven samples using amperometric measurements at +1.10 V vs Ag/AgCl, KCl(sat). The developed methods showed excellent analytical performance with limits of detection of 0.30 and 0.16 µmol L-1, linear range from 3.0 to 50 µmol L-1 and 1.0 to 50 µmol L-1, relative standard deviation below 9.7 and 3.1%, and recovery ranges ranging from 80 to 107% and from 78 to 109% for LEVO and CIPRO, respectively. In addition, the minimum sample preparation (simple dilution) combined with a high analytical frequency (130 to 180 analyses per hour) can be highlighted. Thus, the methods are promising for implementation in routine analysis and quality control to different samples.

Adsorptive stripping voltammetric determination of chloramphenicol residues in milk samples using reduced graphene oxide sensor.

In this paper, the electrochemical response of chloramphenicol (CHL) was investigated on a bare glassy carbon electrode (GCE) and after modification with reduced graphene oxide (GCE/rGO). Preliminary studies by cyclic voltammetry demonstrated an adsorption-controlled mass transport regime of CHL species and a pH-dependent behavior on both electrode surfaces. An adsorptive stripping differential pulse voltammetry (AdSDPV) method was proposed and under optimized instrumental conditions, a comparison of the analytical characteristics of both sensors was performed. The GCE/rGO sensor showed an increase in sensitivity (10-fold), and an anticipation of the reduction potential (200 mV), compared to the bare electrode, due to the adsorptive character (pre-concentration of the CHL species) and the electrocatalytic effect of the nanomaterial. The method was applied to skimmed and whole milk samples, which were simply diluted (50-fold) in supporting electrolyte. The results by AdSDPV using GCE/rGO showed adequate detectability (0.22 µmol L-1), good precision with a 6% relative standard deviation (RSD) and satisfactory recovery ranging from 93 to 108%. The obtained results were statistically similar (95% confidence level) with those performed through ultra-fast liquid chromatography (UFLC). Furthermore, the sensor showed an improvement in the analytical performance for CHL detection, when compared to other sensors reported in the literature. Therefore, the developed method is reliable and promising for implementation in monitoring CHL residues in milk samples.

Electrochemical methods for the determination of antibiotic residues in milk: A critical review.

Several antibiotics have been applied to veterinary medicine due to their broad-spectrum of antibacterial activity and prophylactic power. Residues of these antibiotics can be accumulated in dairy cattle, in addition to promoting contamination of the environment and, in more serious cases, in milk, causing a public health problem. Different regulatory agencies establish maximum residue limits for these antibiotics in milk, so it becomes important to develop sensitive analytical methods for monitoring these compounds. Electrochemical techniques are important analytical tools in analytical chemistry because they present low cost, simplicity, high sensitivity, and adequate analytical frequency (sample throughput) for routine analyses. In this sense, this review summarizes the state of the art of the main electrochemical sensors and biosensors, instrumental techniques, and sample preparation used for the development of analytical methods, published in the last five years, for the monitoring of different classes of antibiotics: aminoglycosides, amphenicols, beta-lactams, fluoroquinolones, sulfonamides, and tetracyclines, in milk samples. The different strategies to develop electrochemical sensors and biosensors are critically compared considering their analytical features. The mechanisms of electrochemical oxidation/reduction of the antibiotics are revised and discussed considering strategies to improve the selectivity of the method. In addition, current challenges and future prospects are discussed.

Simultaneous determination of cadmium, lead and copper in chocolate samples by square wave anodic stripping voltammetry.

In this work, an effective and simple method is proposed for the simultaneous determination of cadmium, lead and copper in chocolate samples by Square Wave Anodic Stripping Voltammetry (SWASV). An ultrasonic bath was used for the extraction of cadmium, lead and copper from fourteen chocolate samples using HNO3 solution (7 mol L-1). The electrochemical system consisted of a cell with three electrodes and HCl solution (10 mmol L-1) as the supporting electrolyte. An efficient extraction of the metals (~100%) was attained after 1 h of ultrasonic pre-treatment. Quantitative analysis was carried out by the standard addition method. Good linearity, precision and accuracy were obtained in the range of concentrations examined. The accuracy was evaluated by means of a reference sample of spiked skim milk powder (BCR 151) to prove the reliability of the method. Detection limits (LOD) of 0.089, 0.059 and 0.018 µg g-1 were found for cadmium, copper and lead, respectively, in the chocolate samples. Concentrations in chocolate samples were 4.30-138 µg g-1 for Cu and 0.83-27.9 µg g-1 for Pb, with no significant Cd. The simultaneous determination brings advantages to other methods already reported for chocolate analysis and the samples preparation proposed avoids the traditional sample mineralization step. These characteristics show this new method is especially attractive for case studies and routine analysis.

Simultaneous determination of strobilurin fungicides residues in bean samples by HPLC-UV-AD using boron-doped diamond electrode.

The aim of this paper was the development of a method for the determination of six strobilurins (fungicides) using boron-doped diamond (BDD) electrode with amperometric detection (AD) homemade coupled to high performance liquid chromatography (HPLC/UV-Vis). HPLC separation of fungicides was performed in a C18 reverse phase column using both UV and AD detectors at 200 mn and 1.9 V, respectively. The linear range for each strobilurin was from 5 to 15 mg L-1 and the correlation coefficients for all the compounds were above 0.997. Both detectors presented adequate detectability (LOD ranging from 1.33 to 1.57 µg kg-1) respecting the limits pre-established by regulatory agencies. The method was validated presenting good values of recovery and accuracy. In the spiked samples the recoveries ranged from 61.6% (trifloxystrobin) to 98.8% (azoxystrobin) for UV and 62.3% (trifloxystrobin) to 95.2% (azoxystrobin) for AD. In blanks spikes the recovery varied from 77.8% (picoxystrobin) to 88.4% (kresoxim-methyl) for UV and 76.7% (picoxystrobin) to 87.1% (dimoxystrobin) for AD. The method showed good precision (RSD < 10%). The results obtained by amperometric and UV detections were statistically comparable. Seven bean samples were analyzed to detect fungicide residues.

Direct analysis of ascorbic acid in food beverage samples by flow injection analysis using reduced graphene oxide sensor.

In this paper, a simple, sensitive and precise electroanalytical method was developed using flow injection analysis (FIA) with amperometric detection and reduced graphene oxide sensor for ascorbic acid determination in samples of multivitamin beverages, milk, fermented milk, and milk chocolate. The advantages of this sensor include a potential displacement of 450 mV and a 2-fold peak current increase for electrochemical oxidation of ascorbic acid, which resulted in a highly sensitive method. No interference of sample matrix was observed, avoiding solvent extraction procedures (samples were only diluted). The FIA allowed a high analytical frequency, approximately 96 injections per hour, together with adequate detection limit of 4.7 µmol L-1. Good precision (RSD < 7%) and accuracy (recoveries between 91 and 108%) evidenced the robustness of the method. The method was compared with ultra-fast liquid chromatography (UFLC) obtaining statistically similar results (95% confidence level). The ascorbic acid content in samples varied from 0.065 to 2.53 mmol L-1.

Amperometric Determination of Hydrogen Peroxide in Whitening Gels Using Boron-doped Diamond Electrode.

The aim of this work was to develop an electrochemical cell and a methodology based on an amperometric determination of hydrogen peroxide in whitening gel samples under a boron-doped diamond electrode using flow injection analysis. Different parameters were evaluated to obtain the best conditions of analysis: among them, the flow of electrolyte at 2.8 mL min-1, the loop sampling 175 µL (28.5 cm), an analytical length of 159 µL (25 cm) and an applied potential of +0.60 V vs. Ag/AgCl(sat). The proposed method was suitable in terms of precision of results (RSD <10%); the accuracy was confirmed in the analysis of the gels through addition and recovery studies with results between 74 and 107%. The method was then applied to the analysis of tooth-whitening gel samples, acquired in different cities of the region. Regarding the results, a medium concentration value of 2.39% (w/w) was observed.

Synthesis, characterization, cytotoxic and antitubercular activities of new gold(I) and gold(III) complexes containing ligands derived from carbohydrates.

Novel gold(I) and gold(III) complexes containing derivatives of D-galactose, D-ribose and D-glucono-1,5-lactone as ligands were synthesized and characterized by IR, (1)H, and (13)C NMR, high resolution mass spectra and cyclic voltammetry. The compounds were evaluated in vitro for their cytotoxicity against three types of tumor cells: cervical carcinoma (HeLa) breast adenocarcinoma (MCF-7) and glioblastoma (MO59J) and one non-tumor cell line: human lung fibroblasts (GM07492A). Their antitubercular activity was evaluated as well expressed as the minimum inhibitory concentration (MIC90) in µg/mL. In general, the gold(I) complexes were more active than gold(III) complexes, for example, the gold(I) complex (1) was about 8.8 times and 7.6 times more cytotoxic than gold(III) complex (8) in MO59J and MCF-7 cells, respectively. Ribose and alkyl phosphine derivative complexes were more active than galactose and aryl phosphine complexes. The presence of a thiazolidine ring did not improve the cytotoxicity. The study of the cytotoxic activity revealed effective antitumor activities for the gold(I) complexes, being more active than cisplatin in all the tested tumor cell lines. Gold(I) compounds (1), (2), (3), (4) and (6) exhibited relevant antitubercular activity even when compared with first line drugs such as rifampicin.

A novel functionalisation process for glucose oxidase immobilisation in poly(methyl methacrylate) microchannels in a flow system for amperometric determinations.

Different materials like glass, silicon and poly(methyl methacrylate) (PMMA) are being used to immobilise enzymes in microchannels. PMMA shows advantages such as its low price, biocompatibility and attractive mechanical and chemical properties. Despite this, the introduction of reactive functional groups on PMMA is still problematic, either because of the complex chemistry or extended reaction time involved. In this paper, a new methodology was developed to immobilise glucose oxidase (GOx) in PMMA microchannels, with the benefit of a rapid immobilisation process and a very simple route. The new procedure involves only two steps, based on the reaction of 5.0% (w/w) polyethyleneimine (PEI) with PMMA in a dimethyl sulphoxide medium, followed by the immobilisation of glucose oxidase using a solution containing 100U enzymes and 1.0% (v/v) glutaraldehyde. The reactors prepared in this way were evaluated by a flowing system with amperometric detection (+0.60V) based on the oxidation of the H2O2 produced by the reactor. The microreactor proposed here was able to work with high bioconversion and a frequency of 60 samples h(-1), with detection and quantification limits of 0.50 and 1.66µmol L(-1), respectively. Michaelis-Menten parameters (Vmax and KM) were calculated as 449±47.7nmol min(-1) and 7.79±0.98mmol. Statistical evaluations were done to validate the proposed methodology. The content of glucose in natural and commercial coconut water samples was evaluated using the developed method. Comparison with spectrophotometric measurements showed that both methodologies have a very good correlation (tcalculated, 0.05, 4=1.35

Avaliação da liberação de íon fluoreto de cimentos ionoméricos antes e após a recarga e com proteção da superfície / Fluoride ion release from glass ionomer cements before and after recharge and surface protection

Objetivo: Avaliar a liberação de íon fluoreto de 2 cimentos de ionômerode vidro (CIV) anidro e 2 modificados por resina composta antes e apósrecarga com fluoreto de sódio neutro a 2% por 4min. e após a proteçãoda superfície do CIV Maxxion R com um adesivo odontológico, umverniz cavitário e um esmalte incolor para unhas.Métodos: Com uma matriz de aço inox com 2mm x 6mm,confeccionou-se 5 corpos de prova de cada material, que foramimersos em 5mL de água deionizada, trocada a cada 24h. Foramrealizadas leituras em um potenciômetro nos dias 1, 2, 9 e 17 na 1ª e 2ªetapas, e as amostras foram tamponadas com solução TISAB III. Na 2ªetapa, as amostras foram submetidas à recarga e novamente imersasem 5mL de água deionizada. Na 3ª etapa foi realizada a proteção dasuperfície dos CIVs e feitas leituras nos 5min., 24h, 48h e 72h. Utilizouseos testes estatísticos Post Hoc de Tukey e t Student (p<0,05).Resultados: Observou-se diferença estatisticamente significante aocomparar a 1ª com a 2ª etapas em todos os materiais, exceto no dia 2para o Vidrion R e para o VitroFil LC. Na 3ª etapa observou-se que emtodos os materiais, comparando os primeiros 5 min. com os outrostempos, as diferenças entre as médias da liberação das concentraçõesde íon fluoreto foram estatisticamente significantes. Ao 0comparar osdemais tempos, tanto o verniz quanto o esmalte incolor para unhasapresentou diferença estatisticamente significante entre 24h e 48h,bem como em 24h e 72h.Conclusão: Os CIVs anidros tiveram maior efetividade na liberação deíon fluoreto e na recarga em comparação com os CIVs modificados porresina composta e o Maxxion R apresentou um comportamentohomogêneo e estatisticamente significante nas duas etapas. Todos osmateriais protetores testados foram eficazes, e o esmalte incolor paraunhas apresentou o melhor comportamento...

Objective: To evaluate fluoride ion release from two anhydrous glassionomer cements (GICs) and two resin-modified GICs (RMGICs) before and after recharge with 2% neutral sodium fluoride for 4 min and after surface protection of the Maxxion R GIC with an adhesive system, a cavity varnish and a colorless nail polish. Method: A stainless steel 2x6 mm matrix was used for fabricating 5 specimens of each material, which were immersed in 5 mL of deionized water, renewed every 24 h. Measurements with a potentiometer were performed on days 1, 2, 9 and 17, in the 1st and 2nd phases, and thespecimens were buffered with a TISAB III solution. In the 2nd phase, thespecimens were subjected to recharge and immersed again in 5 mL ofdeionized water. In the 3rd phase, the GIC surfaces were protected andreadings were made at 5 min, 24 h, 48 h and 72 h. TukeyÆs post-hoc and StudentÆs t tests were used for statistical analyses (p<0.05). Results: There was statistically significant difference in the comparison between the 1st and 2nd phases for all materials, except at day 2 for Vidrion R and VitroFil LC. In the 3rd phase, it was observed that for all materials, comparison of the first 5 min with the other times revealedstatistically significant differences among the means of fluoride ionrelease. In the comparison with the other times, both the varnish and the colorless nail polish presented statistically significant differencebetween 24 and 48 h as well as between 24 and 72 h. Conclusion: The anhydrous GICs were more effective in fluoride ion release and recharge compared with the RMGICs. Maxxion R presented a homogeneous and statistically significant behavior in both phases. All materials for surface protection were efficient and the colorless nail polish had the best behavior...

Differential amperometric determination of hydrogen peroxide in honeys using flow-injection analysis with enzymatic reactor.

Hydrogen peroxide (H2O2) present in honey was rapidly determined by the differential amperometric method in association with flow-injection analysis (FIA) and a tubular reactor containing immobilized enzymes. A gold electrode modified by electrochemical deposition of platinum was employed as working electrode. Hydrogen peroxide was quantified in 14 samples of Brazilian commercial honeys using amperometric differential measurements at +0.60V vs. Ag/AgCl((sat)). For the enzymatic consumption of H2O2, a tubular reactor containing immobilized peroxidase was constructed using an immobilization of enzymes on Amberlite IRA-743 resin. The linear dynamic range in H2O2 extends from 1 to 100 x 10(-6) mol L(-1), at pH 7.0. At flow rate of 2.0 mL min(-1) and injecting 150 microL sample volumes, the sampling frequency of the 90 determinations per hour is afforded. This method is based on three steps involving the flow-injection of: (1) the sample spiked with a standard solution, (2) the pure sample and (3) the enzymatically treated sample with peroxidase immobilized. The reproducibility of the current peaks for hydrogen peroxide in 10(-5) mol L(-1) range concentration showed a relative standard deviation (R.S.D.) better than 1%. The detection limit of this method is 2.9 x 10(-7) mol L(-1). The honey samples analyses were compared with the parallel spectrophotometric determination, and showed an excellent correlation between the methods.

Rapid determination of hydrogen peroxide using peroxidase immobilized on Amberlite IRA-743 and minerals in honey.

Hydrogen peroxide and trace metals (K+, Ca2+, Na+, Mg2+, Mn2+, and Li+) were determined in 14 samples of Brazilian commercial honeys. The method for the determination of H2O2 is based on selective oxidation of H2O2 using an on-line tubular reactor containing peroxidase immobilized on Amberlite IRA-743 resin. Reactors presented high stability for at least 2 weeks under intense use. The results show a simple, accurate, selective, and readily applied method to the determination of H2O2 in honey. The trace metals were determined by capillary zone electrophoresis. Mean contents of 656, 69.1, 71.8, 36.0, 21.4, and 1.70 mg/kg were found, respectively, for K+, Ca2+, Na+, Mg2+, Mn2+, and Li+ in the analyzed honeys. The cations were identified by comparison of the relative migration times of their peaks with the Ba2+ migration time used as reference. The electrophoretic analysis was simple and rapid and did not require any other preparation of sample than dilution and filtration.

Peroxidase immobilized on Amberlite IRA-743 resin for on-line spectrophotometric detection of hydrogen peroxide in rainwater.

The importance of atmospheric hydrogen peroxide (H(2)O(2)) in the oxidation of SO(2) and other compounds has been well established. A spectrophotometric method for the determination of hydrogen peroxide in rainwater is proposed. This method is based on selective oxidation of hydrogen peroxide using an on-line tubular reactor containing peroxidase immobilized on Amberlite IRA-743 resin. The hydrogen peroxide in the presence of phenol, 4-aminoantipyrine and peroxidase, produces a red compound (lambda=505 nm). Beer's law is obeyed in a concentration range of 1-100 microl l(-1) hydrogen peroxide with an excellent correlation coefficient (r=0.9991), at pH 7.0, with a relative standard deviation (R.S.D.) <2%. The detection limit of the method is 0.7 micromol l(-1) (4.8 ng of H(2)O(2) in a 200 microl sample). Measurements of hydrogen peroxide in rain samples were carried out over the period from November 2003 to January 2005, in the central area of the Juiz de Fora city, Brazil. The concentration of H(2)O(2) varied from values lower than the detection limit to 92.5 microl l(-1). The effects of the presence of non-sea salt (NSS) SO(4)(2-), NO(3)(-) and H(+) in the concentration of hydrogen peroxide in the rainwater had been evaluated. The average concentrations of H(2)O(2), NO(3)(-), NSS SO(4)(2-) and SO(4)(2-) are 23.4, 18.9, 7.9 and 10.3 microl l(-1), respectively. The pH values for 82% of the collected samples are greater than 5.0. The spectrophotometeric method developed in this work that uses enzyme immobilized on the resin ion-exchange compared with the amperometric method did not present any significant difference in the results.