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Abstract: The oxidative coupling reaction between aromatic amines and 3-methylbenzothiazolin-2-one hydrazone (MBTH) in the presence of cerium(IV) has been extensively used with quantitative analytical purposes. Nevertheless, a literature survey reveals that different wavelengths (visible range) can be used to monitor the reaction products when using MBTH and Ce(IV) as colour developing reagents. In the present work, the oxidative coupling reaction of indapamide (an oral antihypertensive diuretic drug) with MBTH in the presence of cerium(IV) was evaluated using distinct reaction approaches and was implemented in an automated multipumping flow system. The developed methodology was applied in the spectrophotometric control of the drug in pharmaceutical formulations. The optimization of the proposed multipumping flow system was performed by using an experimental design approach, namely by exploiting a Plackett–Burman factorial design and a central cubic faces design. This work revealed the formation of products with different reaction kinetics, chemical stabilities and absorbance spectra, depending on the sequence of addition of the reagents. By exploiting a specific sequence in the addition of reagents, the proposed automatic system allowed the rapid quantification of indapamide in pharmaceutical formulations, with a determination rate of about 25h−1, and a relative deviation under 2.1% when comparing with the reference procedure. Detection limit was approximately 1mgL−1. [Copyright &y& Elsevier]

Abstract: The determination of hydrogen peroxide (H2O2) and the evaluation of scavenging capacity against this species were performed using five colorimetric reactions, which were adapted to flow injection analysis. The reactions chosen were based on the oxidation of iodide (I− method), on the formation of titanium-peroxide complex (TiP method), on the formation of titanium-xylenol orange-peroxide complex (TiXoP method), on the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB method) and on the co-oxidation of phenol-4-sulfonic acid and 4-aminoantipyrine (PSA/4-AAP method). The operational conditions were studied in order to improve the sensitivity of each method. Concerning to the method sensitivity, the ranking order was TMB method>I− method>TiXoP method ∼PSA/4-AAP method>TiP method. All methods showed an excellent repeatability (RSD<2%) and, except for I− method, relative deviations from the reference method were <1.9%. The FIA manifolds were adapted to perform the determination of scavenging capacity against H2O2 and glutathione (GSH) was applied as model compound. TiP and TiXoP methods were not suitable as no inhibition or an increase of analytical signal was attained. PSA/4-AAP method was chosen for further application to dietary phenolics and pharmaceutical compounds, providing IC50 values for those compounds that are fast reacting antioxidants. [Copyright &y& Elsevier]

Abstract: This work reports the development of an automatic methodology based on the use of 1-anilinonaphthalene-8-sulfonate (ANS) as an interfacial fluorescent probe for detecting the hydrophobic environment shift around the probe, caused by the hydrolytic action of PLA2 on the liposomes. The implementation of this reaction in a sequential injection analysis (SIA) system along with the use of the mixing chambers permitted the evaluation of PLA2 activity and assessment of the inhibitory effect of the non-steroidal anti-inflammatory drugs (NSAIDs) on PLA2 activity. Several studies were performed with the aim of establishing the appropriate flow system configuration: the liposome substrate; PLA2 and ANS optimum concentrations and incubation times before and after the enzyme addition. Based on these studies, the optimum reaction conditions were selected. It was shown that PLA2 is effectively inhibited by the NSAIDs tested (meloxicam, tolmetin and ibuprofen) and by the α-lipoic acid, used as a positive control. Results obtained from the flow system are in agreement with those provided by the comparison batch procedures. The proposed methodology is in fact more efficient and rapid than the comparison batch experiments, enabling the exact timing of fluidic manipulations and precise control of the reaction conditions. [Copyright &y& Elsevier]

Abstract: The present work describes the development of a fast and robust sequential injection fluorimetric procedure for the determination of Sn in juices of canned fruits. The developed automatic methodology is based on the complexation of Sn with 8-hydroxyquinoline-5-sulfonic acid (HQSA) to form a fluorimetric product (λ exc =354nm; λ em =510nm). The influence of dimethylsulfoxide (DMSO) and cetylpyridinium bromide (CPB) on the sensitivity of the fluorimetric determination was evaluated. Linear calibration plots were obtained for Sn concentrations between 1 and 10mgL−1, with a detection limit of 0.38mgL−1. In each analytical cycle 0.006mg of HQSA and 0.47mg of CPB were consumed and 1.5mL of effluent was generated. The developed methodology was applied to the determination of Sn in juices of canned fruits and the results complied with those furnished by an electrothermal atomic absorption spectrometry comparison procedure, with relative deviations lower than 5.2%. The automatic procedure exhibited good precision (R.S.D.<1.4%) and the sampling rate was about 70 determinations per hour. [Copyright &y& Elsevier]

Abstract: The estimation of the time since death known as postmortem interval (PMI) is a main issue in the field of forensic science and legal medicine. In this work it is proposed a sequential injection system for the determination of hypoxanthine and potassium in the same sample of vitreous humor since the concentrations of both parameters change with PMI and the vitreous humor has been regarded as the ideal extracellular fluid for these kinds of determinations. By measuring both parameters the accuracy of estimation of PMI can be increased, and the effects of factors which influence the values in postmortem chemistry minimized. Hypoxanthine determination is based on its oxidation to uric acid (290nm), catalyzed by immobilized xanthine oxidase, and the quantification of potassium levels in vitreous humor was performed using a tubular potassium ion-selective electrode. With a unique analytical cycle both analytes were evaluated being potassium levels determined during the degradation of hypoxanthine in the enzymatic reactor. Working concentration ranges between 6.04–40.00μmolL−1 and 7.00×10−5 to 1.00×10−1 mmolL−1 were obtained, for hypoxanthine and potassium, respectively. The method proved to be reproducible with R.S.D. <5% for hypoxanthine and <3% for potassium. Sampling rate was approximately 30 per hour for the sequential determination of both parameters being 15 and 60 determinations per hour if hypoxanthine or potassium, where evaluated independently. Statistical evaluation at the 95% confidence level showed good agreement between the results obtained, for the vitreous humor samples, with both the SIA system and the comparison batch procedures. Moreover the methodology has low environmental impact in agreement with the demands of green analytical chemistry as only 2.7mL of chemical waste is produced during both determinations. [Copyright &y& Elsevier]

Abstract: Multi-pumping flow systems exploit pulsed flows delivered by solenoid pumps. Their improved performance rely on the enhanced radial mass transport inherent to the pulsed flow, which is a consequence of the establishment of vortices thus a tendency towards turbulent mixing. This paper presents several evidences of turbulent mixing in relation to pulsed flows, such as recorded peak shape, establishment of fluidized beds, exploitation of flow reversal, implementation of relatively slow chemical reactions and/or heating of the reaction medium. In addition, Reynolds number associated with the GO period of a pulsed flow is estimated and photographic images of dispersing samples flowing under laminar regime and pulsed flow conditions are presented. [Copyright &y& Elsevier]

Abstract: Cyclooxygenases (COXs) are the key enzymes in the biosynthesis of prostanoids. COX-1 is a constitutive enzyme while the expression of COX-2 is highly stimulated in the event of inflammatory processes, leading to the production of large amounts of prostaglandins (PGs), in particular PGE2 and PGI2, which are pro-inflammatory mediators. Lipoxygenases (LOXs) are enzymes that produce hydroxy acids and leukotrienes (LTs). 5-LOX metabolizes arachidonic acid to yield, among other products, LTB4, a potent chemoattractant mediator of inflammation. The aim of the present work was to evaluate the anti-inflammatory potential of 2-styrylchromones (2-SC), a chemical family of oxygen heterocyclic compounds, vinylogues of flavones (2-phenylchromones), by studying their COX-1 and COX-2 inhibitory capacity as well as their effects on the LTB4 production by stimulated human polymorphonuclear leukocytes (PMNL). Some of the tested 2-SC were able to inhibit both COX-1 activity and LTB4 production which makes them dual inhibitors of the COX and 5-LOX pathways. The most effective compounds in this study were those having structural moieties with proved antioxidant activity (3′,4′-catechol and 4′-phenol substituted B-rings). This type of compounds may exhibit anti-inflammatory activity with a wider spectrum than that of classical non-steroidal anti-inflammatory drugs (NSAIDs) by inhibiting 5-LOX product-mediated inflammatory reactions, towards which NSAIDs are ineffective. [Copyright &y& Elsevier]

Abstract: The role and importance of antioxidants in different fields, ranging from physiology to food technology, have become evident in the past years, requiring adequate analytical methodologies. Therefore, the determination of antioxidant capacity as a routine or screening analysis fosters its automation. In this context, several flow injection methods based on scavenging of 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulphonate) radical cation (ABTS +) or 2,2-diphenyl-1-picrylhydrazyl radical (DDPHd on the determination of total reducing capacity have been proposed. The objective of the present review is to critically compare the different approaches, regarding their degree of automation, their performance vs. the respective batch procedure and its applicability to real samples. [Copyright &y& Elsevier]

Abstract: 2-Styrylchromones (2-SC) are a chemical family of oxygen heterocyclic compounds, vinylogues of flavones (2-phenylchromones), whose occurrence in nature has been reported. Recently, several 2-SC derivatives were demonstrated to have antioxidant properties, namely, xanthine oxidase inhibition, hepatoprotection against pro-oxidant agents in cellular and non-cellular systems and scavenging activity against reactive oxygen and reactive nitrogen species (ROS and RNS). Considering these antioxidant properties, it may be hypothesised that the electrochemical redox behaviour of 2-SC contributes significantly to their activity. To test this hypothesis, the electrochemical behaviour of different 2-SC was studied, together with a number of flavonoids with well-known antioxidant activities, by cyclic voltammetry, and the results correlated to their ability to scavenge ROS and RNS. The results obtained showed that 2-SC with a catecholic B-ring have a low oxidation peak potential corresponding to the oxidation of the 3′,4′-OH (catechol) moiety. The compounds with a phenolic B-ring have a common peak, with oxidation potential values of about +0.4/+0.5V versus Ag/AgCl, corresponding to the oxidation of the 4′-OH. The oxidation of the hydroxyl substituents in the A-ring generated peaks of higher potentials (+0.7/+0.8V vs Ag/AgCl). The results from the scavenging assays were in agreement with those obtained from the cyclic voltammetry, that is, higher scavenging effects corresponded to lower values of oxidation potentials, with significant correlation coefficients. The values obtained for the studied flavonoids are in accordance with the literature, and reflect their relative antioxidant activity, when compared to the studied 2-SC. Thus, in this family of compounds, oxidation potentials obtained by cyclic voltammetry seem to be applicable as a general indicator of radical scavenging activity. [Copyright &y& Elsevier]

Abstract: The concept of multi-commutation in flow analysis is revisited, and emphasis is given to recent methodological and applicative achievements. Multi-commutation is compatible with different flow patterns (unsegmented, segmented, pulsed, tandem) and amenable to concentration-oriented feedback mechanisms. Its exploitation has led to significant attainments mainly in relation to versatility of the flow system. Characteristics and potentialities of the multi-commuted flow systems are discussed, and guidelines for assisting methodological implementation are given. The number of applications has experienced remarkable increase during last years; therefore, the applicative part of this review is focused on the recent noteworthy applications, mainly in relation to environmental, agronomical, pharmaceutical, biological, food and industrial samples. [Copyright &y& Elsevier]

Abstract: Several of the most commonly used methods for in vitro determination of antioxidant capacity are reviewed in the present paper. The chemical principles of methods based either on biological oxidants (peroxyl radical, superoxide radical anion, hydrogen peroxide, hydroxyl radical, hypochlorous acid, singlet oxygen, nitric oxide radical, and peroxynitrite) or on non-biological assays (scavenging of 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulphonate) radical cation (TEAC assay), scavenging of 2,2-diphenyl-1-picrylhydrazyl radical (DPPHferric reducing antioxidant power (FRAP assay), Folin–Ciocalteu reducing capacity (FC assay), electrochemical total reducing capacity) are outlined and critically discussed. The scope of application, the advantages and shortcomings of each method are also highlighted. [Copyright &y& Elsevier]

Abstract: The proposed flow system was developed in order to minimize the drawbacks related to the PGEs determination by quadrupole-inductively coupled plasma-mass spectrometry (Q-ICP-MS). It was intended not only to lower the limits of detection (LODs) but also to eliminate the interferences originating from some atomic and molecular ions produced in the argon plasma. This was accomplished by means of an on-line sample clean-up/pre-concentration step, using a chelating resin (Metalfix™ Chelamine™) in which Rh, Pd and Pt were preferably retained when compared with the interfering species. The results obtained by using the developed flow system in the analysis of urine samples are presented. With a sampling rate of 9 samples h−1 (i.e., 27 determinations) and a sample consumption of ca. 10mL, the developed flow system allowed linear calibration plots up to 100ngL−1 with detection limits of 1.2ngL−1 (Rh), 0.4ngL−1 (Pd) and 0.9ngL−1 (Pt). Repeatability studies showed good precision (R.S.D.%, n =5): 3.7% (Rh); 2.6% (Pd) and 2.4% (Pt), for 10ngL−1; 2.4% (Rh); 1.4% (Pd) and 1.9% (Pt), for 50ngL−1; and 1.3% (Rh); 0.58% (Pd) and 0.62% (Pt), for 100ngL−1. By spiking human urine samples, recovery tests were performed, and the values obtained ranged between 89% and 105% (Rh); 90% and 104% (Pd); and 93% and 105% (Pt). [Copyright &y& Elsevier]

Abstract: In this paper, a flow-through optosensor based on diffuse reflectance spectroscopy and multivariate regression modelling is proposed for simultaneous multiresidue determination of trace level concentrations of nitro-substituted phenols. The optrode integrates on-line anion-exchange sorptive preconcentration and matrix removal with direct detection of sorbed species onto the sensing layer and chemometric deconvolution of overlapped spectra. After recording of the reflectometric spectrum, fast chemosensor regeneration is accomplished with an acidic methanolic eluent followed by a metered volume of alkaline solution. The full automation of the analytical procedure is ensured by flow-programming as executed via a software-controlled multisyringe pump and a set of multiposition and solenoid valves. Under the optimized chemical and physical variables, the 3σ blank detection limits for 2-, and 4-nitrophenol and 2,4-dinitrophenol were 0.69, 0.42 and 0.37μgL−1, respectively, for a sample loading volume of 4.0mL with enrichment factors of 73, 74 and 81, respectively, and repeatability better than 3.0%. The analytical applicability of the optosensing system was asserted by the satisfactory results attained in its application to monitoring of nitrophenol derivatives in spiked environmental waters including highly saline matrices via the standard additions method. [Copyright &y& Elsevier]

Abstract: Nowadays, the trend towards more compact, smarter and simpler devices is generally recognized as one of the most challenging aspects in the development of analytical instrumentation. Modern flow-based procedures do not escape this tendency. The level of integration and automation and the operational functionality of Multi-pumping flow systems (MPFS) would, in most of the situations, meet this requirement. The essential elements of MPFS are multiple solenoid actuated micro-pumps strategically positioned in the flow manifold, which are accountable for solutions insertion, propelling and commutation, conditioning the establishment and subsequent detection of the reaction zone. Being the only active components of the flow manifold they provide a great operational simplicity and assure a straightforward run-time control of important analytical variables. Moreover, the reduction of active components minimizes the probability of occurrence of equipment failures, malfunctions or errors. The low size and low cost of solenoid micro-pumps make them ideal tools to build up compact environmentally friendly analytical systems, which are characterized by low solutions consumptions and the minimisation of hazardous waste generation. Furthermore, the reproducible pulsed flowing stream produced by micro-pumps actuation has proven to be a valuable feature regarding sample/reagent mixing and reaction zone homogenisation. [Copyright &y& Elsevier]

Abstract: A tubular bismuth film electrode (BFE), installed as part of a multisyringe flow injection system, was used as an amperometric detector to determine the concentration of diclofenac sodium in pharmaceutical formulations. A tubular voltammetric detection cell was employed, in which the hydrodynamic flow conditions were not disturbed. This automated method allows the continuous regeneration of the BFE, preventing passivation of the detector and improving the sensitivity of detection. The influence of several variables on this sensitivity, such as the injection volume, deposition time and flow rate were evaluated; a two-level factorial experimental design was employed for this. In optimal conditions, the linear range of the calibration curve varied from 6.0–50.0μmolL−1, with a detection limit of 4.3μmolL−1. A sampling rate of 90determinations/h was achieved; the relative standard deviation of analytical repeatability was <3.5%. After 30 injections the bismuth film on the electrode surface was automatically renewed. The method was validated by comparing the results obtained with those provided by RP-HPLC; no significant difference were seen (p <0.05). [Copyright &y& Elsevier]

Abstract: The work here described aimed to find out the location of the different species of two families of pharmaceutical substances, namely two β-blockers (atenolol and nadolol) and two benzodiazepines (midazolam and nitrazepam) in synthetic (sodium dodecyl sulphate, SDS) and natural (bile salts-sodium cholate and sodium deoxycholate) micellar aggregate solutions. Electronic spin resonance spectroscopy studies were carried out, at 25°C and at an ionic strength of 0.10M in NaCl, using 5-, 12- and 16-doxylstearic acid probes (AS). The immobilization degree of solubilized stearic acid spin probes was found to vary with the position of the nitroxide group in the sequence 5-doxylstearic acid>12-doxylstearic acid>16-doxylstearic acid for SDS and 12-doxylstearic acid>5-doxylstearic acid>16-doxylstearic acid for both bile salts investigated. Therefore, from the rotational correlational time values obtained, it can be inferred that the structure of bile salt micelles is markedly different from that of SDS micelles and the results suggest that the bile salt micelles studied have similar structure independently of differences in the molecular structure of the respective bile salts. Drug location studies were performed at pH 4.0 (SDS solutions) or 7.0 (bile salt solutions) and 10.8 in order to study the effect of the drug ionisation on its relative position on micelles. The results have shown that drug location is controlled by the (i) drug hydrophilicity and acid/base properties, with the more soluble compound in water (atenolol) exhibiting smaller variation of rotational correlational time (in SDS and bile salts solutions), and with both β-blockers exhibiting smaller deviations in the protonated forms and (ii) the bile salt monomers, with the dihydroxylic bile salt (deoxycholate) producing larger differences. The work described herein allow us to conclude that the (protonated) β-blockers are probably located on the surface of the detergent micelles, and linked to them by means of essentially electrostatic forces, while the (neutral) benzodiazepines are probably located deeper in the interior of the micelles. [Copyright &y& Elsevier]

Abstract: 2-Styrylchromones are a small group of naturally occurring chromones, vinylogues of flavones (2-phenylchromones). Natural and synthetic 2-styrylchromones have been tested in different biological systems, showing activities with potential therapeutic applications. In particular, the potential and hitherto understudied antioxidant behavior of these compounds has been raised as a matter of interest. Thus the present work consisted in the study of the in vitro scavenging activities for reactive oxygen species (ROS) and reactive nitrogen species (RNS) of various 2-styrylchromone derivatives and structurally similar flavonoids. Some of the studied 2-styrylchromones proved to be extremely efficient scavengers of the different ROS and RNS, showing, in some cases, IC50s under 1μM. The hydroxylation pattern of 2-styrylchromones, especially in the B-ring but also in the A ring, modulates the activity of these compounds, the catecholic derivatives being the most effective scavengers. The styryl pattern also contributes to their observed outstanding antioxidant activity. In conclusion, the scavenging activities for ROS/RNS of 2-styrylchromone derivatives, here shown for the first time, provide novel and most promising compounds to be applied as antioxidants. [Copyright &y& Elsevier]

Abstract: In the present work, an automatic flow procedure for the sequential spectrophotometric determination of Folin-Ciocalteu reducing capacity (FC assay) and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS +) scavenging capacity expressed as the trolox equivalent (TEAC assay) is proposed for a comparative study of antioxidant properties in food products. Exploiting the flexibility of flow management associated to the computer control offered by multisyringe flow injection analysis, both methodologies were carried out in the same manifold using gallic acid and trolox as standard compounds. The proposed system configuration allowed the performance of each method separately or in tandem, providing 24 determinations per hour, which accounts for its application in routine analysis. The present methodology was applied to a large number of beverages (n =72), namely red and white wines, herbal and tea infusions, juices and beers. The results obtained showed that FC reducing capacity and TEAC values of red wines were significantly different from those obtained for the other beverages, while tea infusions provided significantly higher TEAC values when compared to white wines, herbal infusions, juices and beers. A good correlation was found between TEAC and FC reducing capacity (R >0.9) for red wines, herbal and tea infusions, and beers. For these beverages, similar slope values were found (106–140mgL−1 of gallic acid per mM of Trolox), except for beers that showed a higher response for FC assay. These results provided evidence that the correlation between these assays vary according to the type of sample, reinforcing the idea that more than one method should be used for evaluation of antioxidant capacity. [Copyright &y& Elsevier]

The risk of agranulocytosis associated with the use of pyrazolone drugs at therapeutical doses and for short periods of time has been considered to be very low. However, little or no attention at all has been devoted to the possible hindrance of neutrophil burst and scavenging of neutrophil-generated reactive oxygen species (ROS) by these compounds. Such an effect could be beneficial in the case of overactivation of neutrophils but could also be highly detrimental if the number of circulating neutrophils is already decreased. Thus, the aim of the present study was to evaluate the putative inhibitory effect of the pyrazolones dipyrone, aminopyrine, isopropylantipyrine, and antipyrine against human neutrophil burst and their scavenging activity against O2•−, H2O2, HO•, ROO•, and HOCl. The obtained results showed that dipyrone and aminopyrine prevent phorbol-12-myristate-13-acetate-induced neutrophil burst with high efficiency, while isopropylantipyrine had little effect and antipyrine had no effect at all. Dipyrone and aminopyrine were highly potent scavengers of HO and HOCl, while, in accordance with the neutrophil burst results, isopropylantipyrine had little effect and antipyrine had no effect at all against these two ROS. None of the studied pyrazolones was capable of scavenging O2•− or H2O2, while dipyrone was shown to be the most reactive against ROO•. [Copyright &y& Elsevier]

Abstract: In the present work, an automatic method based on multi-syringe flow injection analysis (MSFIA) was developed for the determination of total antioxidant capacity, measured as the cumulative capacity of the compounds present in the sample to scavenge free radicals, using the 2,2-diphenyl-1-picrylhydrazyl (DPPHn. The determination is based on the colour disappearance due to the scavenging of DPPHxidant compounds monitored spectrophotometrically at 517nm. The influence of initial DPPHation and sample dilution in the present methodology was studied. It was verified that the amount of DPPH by antioxidant standards (ascorbic and caffeic acids) was independent of the initial concentration of radical except for situations where DPPHant molar ratio was lower than the stoichiometric value. Furthermore, the sample dilution factor plays an important role for achieving results comparable to those from end-point batch method since the exhausting of scavenging ability of the sample should take place during the period of absorbance measurement. The proposed method was applied to several food products and the total antioxidant capacity was expressed as Vitamin C equivalent antioxidant capacity (VCEAC). The results obtained by the proposed method ranged from 1.1 to 318mg of ascorbic acid/100ml and they were statistically comparable to those provided by the batch method. The detection limit was 0.34mg of ascorbic acid/100ml and the determination frequency was about 13h−1 with an excellent repeatability (R.S.D.<1%, n =10). [Copyright &y& Elsevier]

Abstract: In this work, a fully automated flow system exploiting the advantages of the association of multi-pumping, multicommutation, binary sampling and merging zones, to accomplish the sequential determination of copper in serum and urine by flame atomic absorption spectrometry, is described. The developed flow system allowed multiple tasks, such as serum samples preparation (samples and standard solutions viscosity adjustment), serum copper (SCu) measurement, urine copper (UCu) pre-concentration and its subsequent elution and measurement, to be carried out sequentially. The implemented flow manifold presented a modular configuration consisting on two quasi-independent modules, each one accountable for a specific sample manipulation and whose combined operation under computer control enabled the determination of copper in a wide concentrations range. Once optimised and with a sample consumption of about 0.250mL of serum and 7mL of urine, the developed flow system allowed linear calibration plots up to 5mgL−1 with a detection limit of 0.035mgL−1 for SCu and linear calibration plots up to 300μgL−1 with a detection limit of 0.67μgL−1 for UCu. The sampling rate varied according to the module employed and was about 360determinationsh−1 (SCu module), 12determinationsh−1 (UCu module) or 24determinationsh−1 (12 urine and 12 serum samples; UCu and SCu modules simultaneously). Repeatability studies (R.S.D.%, n =10) showed good precision for UCu at concentrations of 25μgL−1 (2.54%), 50μgL−1 (0.90%) and 100μgL−1 (1.62%) as well as for SCu at concentrations of 0.25mgL−1 (8.11%), 1mgL−1 (3.11%) and 5mgL−1 (0.90%). A comparative evaluation showed a good agreement between the results obtained in the analysis of UCu and SCu (n =18) by both the developed methodology and the reference procedures. Accuracy was further evaluated by means of the analysis of reference samples (Seronorm™ Trace Elements Urine and Seronorm™ Trace Elements Serum) and the obtained results complied with the certified values. [Copyright &y& Elsevier]

Abstract: A sensitive sequential injection analysis (SIA) methodology for the fluorimetric determination of naproxen is proposed. The developed automatic analytical procedure is based on the complexation of naproxen with β-cyclodextrin (β-CD) yielding an enhanced fluorimetric signal (λ ex =280nm, λ em =356nm). Linear calibration plots were obtained for naproxen concentrations up to 1×10−5 moll−1. The developed methodology exhibited a good precision, with a R.S.D.<2.1% (n =15). The detection limit of the determination was 1.9×10−7 moll−1 with a sampling rate of about 70h−1. The automatic method was applied to the determination of naproxen in pharmaceutical formulations. The obtained results were compared with those furnished by the reference procedure and the relative deviations were lower than 3.6%. No interference was found from the excipients usually used in solid pharmaceutical formulations. [Copyright &y& Elsevier]

Abstract: In this work a simple, fast, sensitive and selective flow-based procedure for the chemiluminometric determination of carvedilol, a recent non-cardioselective β-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 1.2×10−7 to 3.0×10−6 moll−1 (r >0.999, n =6), was obtained, with a detection limit of 8.7×10−9 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. [Copyright &y& Elsevier]

Abstract: 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 3.2×10−4, 1.1×10−3, and 8.8×10−8 molL−1 for Trolox, ascorbic acid, and resveratrol, respectively. With lucigenin, linear calibration plots up to 2×10−5 molL−1 of Trolox and 5.7×10−5 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 70h−1), and versatility should be highlighted. The proposed system can be used in distinct analytical circumstances without requiring physical reconfiguration. [Copyright &y& Elsevier]

Abstract: This works reports the development of a pulsed flow sequential injection analysis (SIA) system based on the utilisation of pulse generating solenoid micro-pumps, which replace the conventional solutions propelling units commonly used in SIA systems. The influence on sample/reagent zones interpenetration and reaction zone formation of the reproducible pulsed flow produced by micro-pumps operation, which is characterised by a chaotic solutions movement, was comparatively evaluated with the typical laminar flow conditions of conventional SIA systems. The enhanced sample/reagent mixing provided by the controlled pulsed flow was favourably applied in the implementation of a SIA methodology for the fluorimetric determination of indomethacin in pharmaceutical preparations upon alkaline hydrolysis in micellar medium. Linear calibration plots were obtained for indomethacin concentrations up to 10-5moll-1 with a 3σ detection limit of about 1.6×10-8moll-1. The obtained results complied with those furnished by the reference procedure (RD≤2.3%) and exhibited good reproducibility (RSD&#60;1.2%, n=15). Sampling rate was about 30 samples per hour. [Copyright &y& Elsevier]

Abstract: A novel sampling approach in flow analysis exploiting the multi-pumping concept is proposed and applied to the spectrophotometric determination of glucose and fructose in invert sugar syrups. The samples are collected in gelatin capsules and brought to the laboratory. The capsules are placed directly into the dissolution chamber of a flow-batch system, therefore, the manual sample dissolution step is not required. All the involved analytical steps, including the capsule dissolution under acidic conditions, are efficiently controlled by using discretely actuated solenoid micro-pumps. Glucose and fructose determinations involve sugar oxidation by periodate and evaluation of the remaining periodate by monitoring the tri-iodide complex formed after addition of potassium iodide. The proposed system is very stable, handles about 50 samples per hour and requires 28.8μg NaIO4 and 2.5mg KI per determination. Precise results (R.S.D.<2%) in agreement with HPLC are obtained. [Copyright &y& Elsevier]

Abstract: An automatic system that performs two analytical procedures, allowing the evaluation of the relative antioxidant capacity of wine samples, was developed. Automation was carried out using a sequential injection analysis (SIA) system that allowed, thanks to its versatility, the development of two methodologies. One is based on the decolorization assay of the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical, using a spectrophotometric detector. A second methodology allowed the evaluation of the hydrogen peroxide scavenging activity by measuring the oxidation of homovanylic acid (HVA) to its fluorescent dimer, using a fluorescent detector. The developed automatic methodologies were evaluated using trolox as standard and subsequently using other antioxidant substances as gallic acid, caffeic acid, ascorbic acid, catechin and taxifolin which are abundant in wine and whose antioxidant activities were compared to that shown by trolox. The spectrophotometric and fluorimetric assays showed linearity intervals between 0.001 and 0.01mM, and 0.001 and 0.008mM of trolox, respectively. The evaluation of the antioxidant power of 20 white and red wine samples, from different Portuguese wine producing regions, was carried out sequentially, in the automatic system. The results were expressed in trolox equivalent antioxidant capacity (TEAC) and presented, for the ABTS and hydrogen peroxide scavenging activity methodologies, detection limits of 8.4×10-7 and 1.4×10-4mM and relative standard deviation (R.S.D. (%)) in the range 0.6–2.4 and 1–1.8, respectively. [Copyright &y& Elsevier]