Alberto N. Araújo

Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment

Pharmaceuticals are biologically active and persistent substances which have been recognized as a continuing threat to environmental stability. Chronic ecotoxicity data as well as information on the current distribution levels in different environmental compartments continue to be sparse and are focused on those therapeutic classes that are more frequently prescribed and consumed. Nevertheless, they indicate the negative impact that these chemical contaminants may have on living organisms, ecosystems and ultimately, public health. This article reviews the different contamination sources as well as fate and both acute and chronic effects on non-target organisms. An extensive review of existing data in the form of tables, encompassing many therapeutic classes is presented.

Optical sensors and biosensors based on sol–gel films

The sol-gel technology is being increasingly used for the development of optical sensors and biosensors, due to its simplicity and versatility. By this process, porous thin films incorporating different chemical and biochemical sensing agents are easily obtained at room temperature, allowing final structures with mechanical and thermal stability as well as good optical characteristics. In this article, an overview of the state-of-the-art of sol-gel thin films-based optical sensors is presented. Applications reviewed include sensors for determination of pH, gases, ionic species and solvents, as well as biosensors.

Determination of Fe(III) and total Fe in wines by sequential injection analysis and flame atomic absorption spectrometry

The sequential determination of Fe(III) and total Fe in Portuguese table wines by sequential injection analysis (SIA) with flame atomic absorption spectrometry (FAAS) at a sampling rate of 18 samples h -1 is described. The determination of Fe(III) is based on the extraction with MIBK of the complex formed between Fe(III) and thiocyanate by using an on-line device for gravimetric analysis previously described for FIA systems, as liquid-liquid extraction module for organic phases less dense than water. Afterwards, the determination of total iron is accomplished by sending a small sample aliquot directly to the FAAS nebulizer. The injection of about 1.8 ml of sample enabled the determination of Fe(III) ranging between 0.10-6.00 mg l -1 . The injection of sample volumes of 83, 125, or 333 μl enabled the determination of total iron contents ranging between 1.50-15.00, 0.50-10.00, or 0.25-5.00 mg l -1 , respectively. The linear regression analysis of the results obtained for the two parameters with the proposed procedure and those provided by the reference methods (colorimetry for Fe(III) and FAAS for total Fe) led to the following relationships: [SIA] = 0.05(±0.31) + 0.98(±0.10) x [colorim.] for Fe(III) and [SIA] = -0.14(±0.29) + 1.03(±0.04) x [FAAS] for total Fe.

Multicommutation in flow analysis. Part 2. Binary sampling for spectrophotometric determination of nickel, iron and chromium in steel alloys

Multicommutation flow systems for the spectrophotometric determination of nickel, iron and chromium in acid solutions of steel alloys employing a binary sampling approach are described. Dimethylglyoxime, salicylic acid and diphenylcarbazide were used as chromogenic reagents for nickel, iron and chromium, respectively. The flow networks were designed with active devices in order to provide facilities to handle reagent solutions employing a single pumping channel to propel all reagent solutions. Interference caused by iron on the nickel determination was suppressed on-line by using triethanolamine as masking agent. For sample concentrations ranging from 5 to 50 mg/l, the proposed method is characterized by a throughput of 60 determinations per hour and a relative standard deviation of about 1%. Consumptions of potassium peroxodisulphate and dimethylglyoxime solutions were 56 and 78 μl per determination, respectively. Iron and chromium were determined sequentially, with a reagent consumption of 80 μl and 26 μl, respectively. For sample concentrations ranging from 25 to 200 mg/l Fe and 20 to 60 mg/l Cr a throughput of 130 determinations per hour was achieved. Results compared well with those obtained by inductively coupled argon plasma atomic emission spectrometry.

Sequential injection chromatographic determination of ambroxol hydrochloride and doxycycline in pharmaceutical preparations

A new separation method based on a novel reversed-phase sequential injection chromatography (SIC) technique was used for simultaneous determination of ambroxol hydrochloride and doxycycline in pharmaceutical preparations in this contribution. The coupling of short monolith with SIA system results in an implementation of separation step to until no-separation low-pressure method. A Chromolith((R)) Flash RP-18e, 25-4.6mm column (Merck, Germany) and a FIAlab((R)) 3000 system (USA) with a six-port selection valve and 5ml syringe were used for sequential injection chromatographic separations in our study. The mobile phase used was acetonitrile-water (20:90, v/v), pH 2.5 adjusted with 98% phosphoric acid, flow rate 0.48mlmin(-1), UV detection was at 213nm. The validation parameters have shown good results: linearity of determination for both compounds including internal standard (ethylparaben) >0.999; repeatability of determination (R.S.D.) in the range 0.5-5.4% at three different concentration levels, detection limits in the range 0.5-2.0mugml(-1), and recovery from the pharmaceutical preparation in the range 99.3-99.9%. The chromatographic resolution between peak compounds was >5.0 and analysis time was <9min under the optimal conditions. The method was found to be applicable for routine analysis of the active compounds ambroxol hydrochloride and doxycycline in various pharmaceutical preparations.

Modeling, Structural, and Spectroscopic Studies of Lanthanide-Organic Frameworks

In this paper, we report the hydrothermal synthesis of three lanthanide-organic framework materials using as primary building blocks the metallic centers Eu(3+), Tb(3+), and Gd(3+) and residues of mellitic acid: [Ln(2)(MELL)(H(2)O)(6)] (where Ln(3+) = Eu(3+), Tb(3+), and Gd(3); hereafter designated as (1), (2) and (3)). Structural characterization encompasses single-crystal X-ray diffraction studies, thermal analysis, and vibrational spectroscopy, plus detailed investigations on the experimental and predicted (using the Sparkle/AM1 model) photophysical luminescent properties. Crystallographic investigations showed that the compounds are all isostructural, crystallizing in the orthorhombic space group Pnnm and structurally identical to the lanthanum 3D material reported by the group of Williams. (2) is highly photoluminescent, as confirmed by the measured quantum yield and lifetime (37% and 0.74 ms, respectively). The intensity parameters (Omega(2), Omega(4), and Omega(6)) of (1) were first calculated using the Sparkle/AM1 structures and then employed in the calculation of the rates of energy transfer (W(ET)) and back-transfer (W(BT)). Intensity parameters were used to predict the radiative decay rate. The calculated quantum yield derived from the Sparkle/AM1 structures was approximately 16%, and the experimental value was 8%. We attribute the registered differences to the fact that the theoretical model does not consider the vibronic coupling with O-H oscillators from coordinated water molecules. These results clearly attest for the efficacy of the theoretical models employed in all calculations and open a new window of interesting possibilities for the design in silico of novel and highly efficient lanthanide-organic frameworks.

Flow-injection amperometric determination of dopamine in pharmaceuticals using a polyphenol oxidase biosensor obtained from soursop pulp

The amperometric determination of dopamine (Do) in pharmaceuticals formulations by flow injection analysis (FIA) is proposed. An enzymatically modified carbon paste electrode constituted by 25% (w/w) of polyphenol oxidase obtained from Annona muricata L. tissue, 30% (w/w) of graphite, 30% (w/w) of silicone and 15% (w/w) of 7,7,8,8 tetracyanoquinodimethane (TCNQ), was used as flow-through detector. The flow amperometric detection was carried out at a potential of 0.10 V (vs. Ag/AgCl) when an injected sample volume of 250 microl was inserted on a 0.3 M phosphate buffer carrier solution (pH 7.8) flowing at 2.5 ml/min. The developed biosensor showed good stability and reproducibility, enabling up to 500 determinations in 60 days, without considerable loss of enzymatic activity. The FIA system presented a linear response to Do concentrations in the interval from 2 x 10(-2) to 2 x 10(-4) M, with relative standard deviations lower than 1.5%. The kinetic parameter K(M) for the soluble and immobilized enzyme was 1.45 x 10(-2) and 1.91 x 10(-2) M, respectively. In the analyses of different commercially pharmaceutical formulations a relative deviation lower than about 3.4% was obtained.

Multicommutation in flow analysis. Part 3. Spectrophotometric kinetic determination of creatinine in urine exploiting a novel zone sampling approach

Zone sampling performed on a single analytical channel and associated with the stopped-flow approach was proposed and applied to the spectrophotometric kinetic determination of creatinine in urine based on Jaffes reaction. The flow network comprised microcomputer controlled three-way solenoid valves. With multicommutation, the potentialities of zone sampling and stopped-flow were expanded, and the design of the flow set up was simplified. Influence of the main related parameters such as system configuration, reagent concentrations, temperature and timing were studied. The proposed system handled about 24 samples per hour. Baseline drift was not observed during extended operation periods (8 h). Sample pretreatment was not required. Results were reproducible (R.S.D. < 3%) and in agreement with those obtained in a batch procedure.

An efficient non-mediated amperometric biosensor for nitrite determination

In this paper we propose the construction of a new non-mediated electrochemical biosensor for nitrite determination in complex samples. The device is based on the stable and selective cytochrome c nitrite reductase (ccNiR) from Desulfovibrio desulfuricans, which has both high turnover and heterogeneous electron transfer rates. In opposition to previous efforts making use of several redox mediators, in this work we exploited the capacity of ccNiR to display a direct electrochemical response when interacting with pyrolytic graphite (PG) surfaces. To enable the analytical application of such bioelectrode the protein was successfully incorporated within a porous silica glass made by the sol-gel process. In the presence of nitrite, the ccNiR/sol-gel/PG electrode promptly displays catalytic currents indicating that the entrapped ccNiR molecules are reduced via direct electron transfer. This result is noteworthy since the protein molecules are caged inside a non-conductive silica network, in the absence of any mediator species or electron relay. At optimal conditions, the minimum detectable concentration is 120 nM. The biosensor sensitivity is 430 mA M(-1) cm(-2) within a linear range of 0.25-50 microM, keeping a stable response up to two weeks. The analysis of nitrites in freshwaters using the method of standard addition was highly accurated.

Application of amperometric sol-gel biosensor to flow injection determination of glucose

A glucose biosensor with enzyme immobilised by sol-gel technology was constructed and evaluated. The glucose biosensor reported is based on encapsulated GOX within a sol-gel glass, prepared with 3-aminopropyltriethoxy silane, 2-(3,4-epoxycyclohexyl)-ethyltrimetoxy silane and HCl. A flow system incorporating the amperometric biosensor constructed was developed for the determination of glucose in the 1x10(-4)-5x10(-3) moll(-1) range with a precision of 1.5%. The results obtained for the analysis of electrolytic solution for iv administration and human serum samples showed good agreement between the proposed method and the reference procedure, with relative error <5%.