Chemiluminometric evaluation of melatonin and selected melatonin precursors' interaction with reactive oxygen and nitrogen species.

Melatonin is a hormone, a derivative of tryptophan, that possesses a potent scavenging capacity for the most reactive and dangerous free radicals, being an important protection against oxidative stress. In this work, an automated flow-based procedure for assessment of melatonin, tryptophan, and 5-hydroxytryptophan scavenging capacity was developed. The presented methodology involved a multi-pumping flow system and exploited the ability of selected compounds to inhibit the chemiluminescence reaction of luminol with hydrogen peroxide, hydroxyl radical, and peroxynitrite anion. The system was based on the use of several solenoid actuated micro-pumps as the only active components of the flow manifold. This enabled the reproducible insertion and efficient mixing of very low volumes of sample and reagents as well as the transportation of the sample zone toward detection for monitoring the chemiluminometric response. Furthermore, the high versatility of the proposed multi-pumping flow system allowed the implementation of distinct reactions for the in-line generation of the different reactive species assayed without requiring physical reconfiguration. The results obtained demonstrated that 5-hydroxytryptophan is the most potent scavenger, followed by melatonin and tryptophan. The developed multi-pumping flow system exhibited good measurement precision (relative standard deviations typically <2%, n=10), low operational costs, and low reagent consumption.

Simultaneous chemiluminometric determination of levodopa and benserazide in a multi-pumping flow system with multivariate calibration.

An automated multi-pumping flow system is proposed for the simultaneous chemiluminometric determination of benserazide and levodopa using multivariate calibration methods. The developed methodology is based on chemiluminescence (CL) emission generated by the reaction of benserazide with luminol, and on a concurrent inhibiting effect of levodopa on this reaction. A multi-pumping flow system comprising multiple solenoid micro-pumps as the only active components was developed to implement a stopped-flow approach for signal acquisition and processing. Artificial neural networks were used to establish a relationship between the CL emission profile and the concentration of both drugs. The concentration values used to establish the experimental calibration samples were varied between 5 and 30 mg l(-1) for levodopa and between 2.5 and 20 mg l(-1) for benserazide. The proposed method was successfully applied to the simultaneous determination of levodopa and benserazide in pharmaceutical formulations combining both drugs.

Functionalized magnetite particles for adsorption of colloidal noble metal nanoparticles.

Magnetite (inverse spinel type) particles have been surface-modified with siliceous shells enriched in dithiocarbamate groups. The deposition of colloidal noble metal nanoparticles (Au, Ag, Pt, Pd) onto the modified magnetites can be performed by treating the respective hydrosols with the magnetic sorbents, thus allowing their uptake from water under a magnetic gradient. In particular, for Au colloids, these magnetic particles are very efficient sorbents that we ascribe to the strong affinity of sulfur-containing groups at the magnetite surfaces for this metal. Considering the extensive use of Au colloids in laboratorial and industrial contexts, the approach described here might have an impact on the development of nanotechnologies to recover this precious metal. En route to these findings, we varied several operational parameters in order to investigate this strategy as a new bottom-up assembly method for producing plasmonic-magnetic nanoassemblies.

Chemiluminometric determination of propranolol in an automated multicommutated flow system.

In this work, a fully automated analytical methodology for the chemiluminometric determination of propranolol hydrochloride in pharmaceutical preparations is proposed. The developed procedure was based on the oxidation of propranolol by potassium permanganate in acidic medium and was implemented in a multicommutated flow system. The combined automated actuation of syringe pumps and two-way solenoid valves, under computer control, assured a high versatility in terms of sample and reagent manipulation and an effective run-time control of all analytical parameters, including a time-based insertion that enabled a significant solutions saving and the exploitation of different strategies for sample/reagent mixing. The calibration graph was linear over the range 20-150 mg l(-1) of propranolol hydrochloride with a relative standard deviation lower than 1.6% (n = 7). The results were in agreement with those obtained by the reference procedure with a relative deviation between -3.8 and 3.7% and a sampling rate of about 27 samples h(-1).

Application of quantum dots as analytical tools in automated chemical analysis: a review.

Colloidal semiconductor nanocrystals or quantum dots (QDs) are one of the most relevant developments in the fast-growing world of nanotechnology. Initially proposed as luminescent biological labels, they are finding new important fields of application in analytical chemistry, where their photoluminescent properties have been exploited in environmental monitoring, pharmaceutical and clinical analysis and food quality control. Despite the enormous variety of applications that have been developed, the automation of QDs-based analytical methodologies by resorting to automation tools such as continuous flow analysis and related techniques, which would allow to take advantage of particular features of the nanocrystals such as the versatile surface chemistry and ligand binding ability, the aptitude to generate reactive species, the possibility of encapsulation in different materials while retaining native luminescence providing the means for the implementation of renewable chemosensors or even the utilisation of more drastic and even stability impairing reaction conditions, is hitherto very limited. In this review, we provide insights into the analytical potential of quantum dots focusing on prospects of their utilisation in automated flow-based and flow-related approaches and the future outlook of QDs applications in chemical analysis.

Automatic multi-pumping flow system for the chemiluminometric screening of scavenging capacity against singlet oxygen.

An automated multi-pumping flow system was developed for the in-line generation of singlet oxygen ((1)O(2)) and subsequent assessment of the scavenging capacity against this reactive species. (1)O(2) was generated by dismutation of hydrogen peroxide catalyzed by molybdate ions. The evaluation of the scavenging capacity was based on the inhibition of the chemiluminescence reaction of luminol with (1)O(2). The proposed system used solenoid micro-pumps as the only active components of the flow manifold, enabling the reproducible insertion and efficient mixing of sample and reagents as well as the transportation of the sample zone towards detection for chemiluminescence measurement, assuring a strictly reproducible timing of all analytical tasks. Several compounds were evaluated as possible (1)O(2) scavengers. The obtained results showed that only ascorbic acid, dipyrone and tryptophan exhibited scavenging capacity, with IC(50) values of 3.36 × 10(-5), 7.84 × 10(-5) and 1.28 × 10(-2) mol L(-1), respectively.

Mathematical modeling of dispersion in single interface flow analysis.

This work describes the optimization of the recently proposed fluid management methodology single interface flow analysis (SIFA) using chemometrics modelling. The influence of the most important physical and hydrodynamic flow parameters of SIFA systems on the axial dispersion coefficients estimated with the axially dispersed plug-flow model, was evaluated with chemometrics linear (multivariate linear regression) and non-linear (simple multiplicative and feed-forward neural networks) models. A D-optimal experimental design built with three reaction coil properties (length, configuration and internal diameter), flow-cell volume and flow rate, was adopted to generate the experimental data. Bromocresol green was used as the dye solution and the analytical signals were monitored by spectrophotometric detection at 614 nm. Results demonstrate that, independent of the model type, the statistically relevant parameters were the reactor coil length and internal diameter and the flow rate. The linear and non-linear multiplicative models were able to estimate the axial dispersion coefficient with validation r(2)=0.86. Artificial neural networks estimated the same parameter with an increased accuracy (r(2)=0.93), demonstrating that relations between the physical parameters and the dispersion phenomena are highly non-linear. The analysis of the response surface control charts simulated with the developed models allowed the interpretation of the relationships between the physical parameters and the dispersion processes.

A catalytic multi-pumping flow system for the chemiluminometric determination of metformin.

A multi-pumping flow system for the chemiluminometric determination of the hypoglycaemic drug metformin was implemented. The developed methodology was based on the metformin-induced inhibition (metformin acts as a Cu(II) scavenger) of the catalytic effect of Cu(II) ions on the chemiluminescent reaction between luminol and hydrogen peroxide. The flow manifold configuration was based on the utilisation of multiple solenoid-actuated micro-pumps that were simultaneously accountable for sample/reagent introduction and reaction zone formation/propulsion, thus resulting in a fully automated, simple and highly selective multi-pumping flow system. A versatile sample manipulation allowed the establishment of distinct sampling strategies with low reagent consumption. The characteristic pulsed flow ensured an effective sample/reagent mixing leading to a better and faster reaction zone homogenisation and thus improved analytical signals. Linear calibration plots were obtained for metformin hydrochloride concentrations ranging from 5 to 15 mg L(-1) with a relative standard deviation lower than 2.0% (n=5). Detection limit was 0.94 mg L(-1), and the sampling rate was about 95 determinations per hour. The developed methodology was applied to the analysis of pharmaceutical formulations and the obtained results were in agreement with those furnished by the reference method with relative percentage deviations of lower than 1.5%.

Chemiluminometric determination of carvedilol in a multi-pumping flow system.

In this work a simple, fast, sensitive and selective flow-based procedure for the chemiluminometric determination of carvedilol, a recent non-cardioselective beta-blocker with noteworthy antioxidant activity, is proposed. The developed methodology takes advantage of the antioxidant capacity of carvedilol to inhibit the chemiluminescence response resulting from the oxidation of luminol by hypochlorite, by acting as a hypochlorite scavenger. The analytical process was implemented in a multi-pumping flow system that employs multiple solenoid actuated micro-pumps as the only active components. These acted as solution insertion, propelling and commuting units assuring an easily controlled, low cost, compact and reliable analytical system. A linear working range for carvedilol concentrations ranging from 1.2x10(-7) to 3.0x10(-6)moll(-1) (r>0.999, n=6), was obtained, with a detection limit of 8.7x10(-9)moll(-1). The system handles about 65 samples per hour yielding precise results (R.S.D.<1.3%, n=10). Recoveries within 95 and 104% were obtained.

Evaluation of the total antioxidant capacity by using a multipumping flow system with chemiluminescent detection.

An automated flow-based procedure for assessment of total antioxidant capacity was developed. It involved a multipumping flow system, a recent approach to flow analysis, and exploited the ability of selected compounds to inhibit the chemiluminescence reactions of luminol or lucigenin with hydrogen peroxide. The system included several discretely actuated solenoid micropumps as the only active components of the flow manifold. This enabled the reproducible insertion and efficient mixing of very low volumes of sample and reagents as well as the transportation of the sample zone toward a flow-through luminometer, where the chemiluminometric response was monitored. With luminol as the chemiluminogenic reagent, linearity of the analytical curves was noted up to 3.2x10(-4), 1.1x10(-3), and 8.8x10(-8) molL-1 for Trolox, ascorbic acid, and resveratrol, respectively. With lucigenin, linear calibration plots up to 2x10(-5) molL-1 of Trolox and 5.7x10(-5)molL-1 of ascorbic acid were obtained. As favorable analytical figures of merit, the measurement precision (RSD typically between 0.2 and 2.0%, n=10), low operational costs, low reagent consumption, sampling rate (160 and 70 h-1), and versatility should be highlighted. The proposed system can be used in distinct analytical circumstances without requiring physical reconfiguration.