Improved Metal Cation Optosensing Membranes through the Incorporation of Sulphated Polysaccharides.

Optosensing chitosan-based membranes have been applied for the detection of heavy metals, especially in drinking water. The novelty of this study is based on the use of sulphated polysaccharides, in such optosensing membranes, aiming at an improved analytical performance. The sulphated polysaccharides, such as ulvan, fucoidan and chondroitin sulfate, were extracted from by-products and wastes of marine-related activities. The membranes were developed for the analysis of aluminum. The variation in the visible absorbance of the sensor membranes after the contact between the chromophore and the aluminum cation was studied. The membranes containing sulphated polysaccharides showed improved signals when compared to the chitosan-only membrane. As for the detection limits for the membranes containing ulvan, fucoidan and chondroitin sulfate, 0.17 mg L-1, 0.21 mg L-1 and 0.36 mg L-1 were obtained, respectively. The values were much lower than that obtained for the chitosan-only membrane, 0.52 mg L-1, which shows the improvement obtained from the sulphated polysaccharides. The results were obtained with the presence of CTAB in analysis solution, which forms a ternary complex with the aluminum cation and the chromophore. This resulted in an hyperchromic and batochromic shift in the absorption band. When in the presence of this surfactant, the membranes showed lower detection limits and higher selectivity.

Effect of the calcination temperature on the photocatalytic efficiency of acidic sol-gel synthesized TiO2 nanoparticles in the degradation of alprazolam.

We report a comparative study on the photodegradation of the widely used benzodiazepine psychoactive drug alprazolam (8-chloro-1-methyl-6-phenyl-4H-[1,2,4]triazolo[4,3-a][1,4]benzodiazepine, ALP) using direct photolysis, and titanium dioxide photocatalyzed reaction. Titanium dioxide photocatalysts were prepared as nanoparticles by acidic sol-gel methods, calcined at two different temperatures, and their behavior compared with P25 (Degussa type) TiO2. Efficient photodegradation was observed in the photocatalytic process, with over 90% degradation after 90 minutes under optimized conditions. Triazolaminoquinoline, 5-chloro-(5-methyl-4H-1,2,4-triazol-4-yl)benzophenone, triazolbenzophenone, and α-hydroxyalprazolam were identified as the degradation products by fluorescence spectroscopy and HPLC-MS. A comparison with the literature suggests that 8H-alprazolam may also be formed. Good mineralization was observed with TiO2 photocatalysts. ALP photodegradation with TiO2 follows pseudo-first order kinetics, with rates depending on the photocatalyst used. The effects of the quantity of the photocatalyst and concentration of alprazolam were studied.

Understanding the interaction between trivalent lanthanide ions and stereoregular polymethacrylates through luminescence, binding isotherms, NMR, and interaction with cetylpyridinium chloride.

Complexation of isotactic, syndiotactic, and atactic poly(methacrylic acid), PMA, with trivalent lanthanide ions has been studied in water at a degree of neutralization 0.5. Metal ion binding is shown by quenching of cerium(III) fluorescence, enhancement of Tb(III) luminescence, and lanthanide-induced line broadening in the PMA (1)H NMR spectra. Comparison with lanthanide-acetate complexation suggests carboxylate binds in a bidentate fashion, while Ce(III) luminescence quenching suggests an ≈3:1 carboxylate:metal ion stoichiometry, corresponding to charge neutralization. The presence of both free and bound Ce(III) cations in PMA solutions is confirmed from luminescence decays. Studies of Tb(3+) luminescence lifetime in H2O and D2O solutions show complexation is accompanied by loss of 5-6 water molecules, indicating that each bidentate carboxylate replaces two coordinated water molecules. The behavior depends on pH and polyelectrolyte stereoregularity, and stronger binding is observed with isotactic polyelectrolyte. Binding of cetylpyridinium chloride, CPC, in these systems is studied by luminescence, NMR, and potentiometry. NMR and Tb(3+) luminescence lifetime studies show the strongest binding with the isotactic polymer. Binding of surfactant to poly(methacrylate) in the presence of lanthanides is noncooperative, i.e., it binds to the free sites; binding isotherms in the presence of lanthanides are shifted to higher free surfactant concentrations, compared with sodium ions, have lower slopes and show a clear two-step binding mechanism. While CPC readily replaces the Na(+) ions of poly(methacrylate) and binds very strongly (low critical association concentrations), exchange is much more difficult with the strongly bound trivalent lanthanide ions. Effects of tacticity are seen, with surfactant interacting most strongly with isotactic chains in the initial stages of binding, while in the final stages of binding the interaction is strongest with atactic poly(methacrylate).

Zinc(II) phthalocyanines immobilized in mesoporous silica Al-MCM-41 and their applications in photocatalytic degradation of pesticides.

In the present study the authors investigated a set of three new zinc(II) phthalocyanines (zinc(II) tetranitrophthalocyanine (ZnTNPc), zinc(II) tetra(phenyloxy)phthalocyanine (ZnTPhOPc) and the tetraiodide salt of zinc(II)tetra(N,N,N-trimethylaminoethyloxy) phthalocyaninate (ZnTTMAEOPcI)) immobilized into Al-MCM-41 prepared via ship-in-a-bottle methodology. The samples were fully characterized by diffuse reflectance-UV-vis spectroscopy (DRS-UV-vis), luminescence, thermogravimetric analysis (TG/DSC), N(2) adsorption techniques and elemental analysis. A comparative study was made on the photocatalytic performance upon irradiation within the wavelength range 320-460nm of these three systems in the degradation of pesticides fenamiphos and pentachlorophenol. ZnTNPc@Al-MCM-41 and ZnTTMAEOPcI@Al-MCM-41 were found to be the most active systems, with the best performance observed with the immobilized cationic phthalocyanine, ZnTTMAEOPcI@Al-MCM-41. This system showed high activity even after three photocatalytic cycles. LC-MS product characterization and mechanistic studies indicate that singlet oxygen ((1)O(2)), produced by excitation of these immobilized photosensitizers, is a key intermediate in the photocatalytic degradation of both pesticides.

Estimate of the digestibility, assimilability and intestinal permeability of butyltins occurring in wine.

An estimate of the digestibility and assimilability of butyltins occurring in contaminated wines (Port, red and white) was obtained by means of in vitro studies of gastrointestinal digestion. The influence of the wine matrix on the intestinal permeability was explored by studying the accumulation of butyltins in Caco-2 monolayers either when these species are dissolved in buffer only or in the dialysates of digested wines. Some important information about the fate of the butyltin compounds ingested from contaminated wines could be achieved. Only a very small fraction of the ingested DBT and TBT, the two most toxic forms, appear to be able to reach the epithelium as judged by the small dialyzable fraction found (<2%). This is probably independent from the food/drink matrix introducing these contaminants, since the influence of the involved enzymes appear to be dominant, especially for DBT and TBT. Additionally, the intestinal permeability of the three butyltins was also very low, the wine matrix possibly having a hindrance effect in a few cases.

Optimization of supercritical fluid extraction of pesticide residues in soil by means of central composite design and analysis by gas chromatography-tandem mass spectrometry.

An environmentally friendly methodology is proposed for the analysis of pesticides in soil samples based on supercritical fluid extraction (SFE) and analysis at high selectivity and sensitivity, by gas chromatography-tandem mass spectrometry (GC-MS-MS). The pesticides investigated are among the most commonly used in intensive horticulture activities comprising organochlorine and organophosphorous insecticides, triazine and acetanilide herbicides, amongst others. An experimental design approach was used for modelling SFE and optimised extraction conditions were derived for the total pesticides extraction or for specific sub-groups of interest. Pesticide residues could be detected in soils in the sub-ppb range (0.1-3.7microgkg(-1)), with quite good precision (4.2-15.7%) and extraction efficiency (80.4-106.5%). The analysis of soil samples from an intensive horticulture area in Póvoa de Varzim, north of Portugal, revealed the presence of persistent pesticides, parent compounds and degradation products among the following: endosulfan, endosulfan sulfate, dieldrin, 4,4'-DDE, 4,4'-DDD, atrazine, alachlor, metolachlor, chlorpyrifos, pendimethalin and lindane. The important features to point out are the easy interpretation of chromatograms and straightforward confirmation of analytes that greatly facilitates the analyst judgement on the contamination of the sample.

A comparative study of water soluble 5,10,15,20-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin and its metal complexes as efficient sensitizers for photodegradation of phenols.

5,10,15,20-Tetrakis(2,6-dichloro-3-chlorosulfophenyl)porphyrin and its tin and zinc complexes were synthesized with high yields and fully characterized. The corresponding water-soluble 5,10,15,20-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrins were obtained by hydrolysis with water. An extensive photophysical study of the new water soluble porphyrinic compounds was carried out including absorption and fluorescence spectra, fluorescence quantum yields, triplet absorption spectra, triplet lifetimes, triplet and singlet oxygen quantum yields. These sensitizers were successfully used in the photodegradation of 4-chlorophenol and 2,6-dimethylphenol. A comparison is made of their efficiencies, and some mechanistic considerations are highlighted.

On the low-lying excited states of sym-triazine-based herbicides.

We report a joint computational and luminescence study on the low-lying excited states of sym-triazines, namely, 1,3,5-triazine (1) and the ubiquitous herbicides atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (2)] and ametryn [6-methylthio-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (3)]. Geometrical structures, energetics, and transition and state properties of I and 2 were computed at the TD-DFT, CASSCF, and CASPT2 levels of theory. The fluorescence and phosphorescence emission spectra, lifetimes, and fluorescence quantum yields were measured for the three compounds, and from these, the energies of the lowest excited states and their corresponding radiative rates were determined. The predictions from CASPT2 calculations are in good agreement with the experimental results obtained from the luminescence studies and allow the interpretation of different absorption and emission features.

Estimation of the human intestinal permeability of butyltin species using the Caco-2 cell line model.

The main objective of the work was the setup of the Caco-2 human intestinal cell-line model for the study of the intestinal permeation of monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT). The study was focused in gathering information on (a) the relative permeability of butyltins, (b) their possible permeation routes (paracellular/transcellular) and (c) the eventual interactions between the different butyltins when occurring as a mixture. The presence of basolateral serum protein greatly influenced the permeability, causing a large net clearance, but the apparent permeability (Papp) values were comparable to that of phenolred, suggesting a low in vivo permeability of the butyltins. The found permeability pattern correlates well with the general in vivo toxicity pattern (trialkyltin>dialkyltin>>monoalkyltin). The accumulation pattern (DBT>TBT>MBT) was different from that of permeability and may be an important element regarding the elucidation of some specific strong toxic effects caused by the dialkyltins in several species. The transport of MBT and DBT was found to be dependent on the paracellular route status. An interaction between the butyltin compounds in a mixture was found for the accumulation results (the accumulation was significantly higher for the three compounds when in a mixture). A set of useful information about the butyltin accumulation and transport by the epithelial Caco-2 cell line was, thus, achieved, constituting a starting point for future research on the permeability of butyltins from contaminated food and beverages.

Photooxidation of 4-chlorophenol sensitised by iron meso-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin in aqueous solution.

The photosensitised degradation of 4-chlorophenol (4-CP) by iron meso-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin (FeTDCPPS) has been studied in aerated aqueous solution, and is shown to lead to formation of p-benzoquinone (BQ) and p-hydroquinone (HQ) as main photoproducts. In deaerated solution no p-benzoquinone was formed. The photolysis products were identified by high performance liquid chromatography (HPLC) and UV-visible spectroscopy. The photodegradation in aerated solution was also carried out in the presence of sodium azide (NaN(3)) as a singlet oxygen [(1)O(2)((1)[capital Delta](g))] quencher, and showed a significant decrease in the rate of photolysis, suggesting under these conditions, that Type II sensitisation is one of the dominant mechanisms of 4-CP degradation. Support for this comes from laser flash photolysis and time-resolved singlet oxygen phosphorescence measurements. However, these also show direct reaction between the excited porphyrin and 4-CP, indicating that there are two mechanisms involved in the chlorophenol photodegradation.

Aqueous solutions of uranium(VI) as studied by time-resolved emission spectroscopy: a round-robin test.

Results of an inter-laboratory round-robin study of the application of time-resolved emission spectroscopy (TRES) to the speciation of uranium(VI) in aqueous media are presented. The round-robin study involved 13 independent laboratories, using various instrumentation and data analysis methods. Samples were prepared based on appropriate speciation diagrams and, in general, were found to be chemically stable for at least six months. Four different types of aqueous uranyl solutions were studied: (1) acidic medium where UO2(2+)aq is the single emitting species, (2) uranyl in the presence of fluoride ions, (3) uranyl in the presence of sulfate ions, and (4) uranyl in aqueous solutions at different pH, promoting the formation of hydrolyzed species. Results between the laboratories are compared in terms of the number of decay components, luminescence lifetimes, and spectral band positions. The successes and limitations of TRES in uranyl analysis and speciation in aqueous solutions are discussed.

Deactivation processes of the lowest excited state of [UO2(H2O)5]2+ in aqueous solution.

A detailed analysis of the photophysical behaviour of uranyl ion in aqueous solutions at room temperature is given using literature data, together with results of new experimental and theoretical studies to see whether the decay mechanism of the lowest excited state involves physical deactivation by energy transfer or a chemical process through hydrogen atom abstraction. Comparison of the radiative lifetimes determined from quantum yield and lifetime data with that obtained from the Einstein relationship strongly suggests that the emitting state is identical to that observed in the lowest energy absorption band. From study of the experimental rate and that calculated theoretically, from deuterium isotope effects and the activation energy for decay support is given to a deactivation mechanism of hydrogen abstraction involving water clusters to give uranium(v) and hydroxyl radicals. Support for hydroxyl radical formation comes from electron spin resonance spectra observed in the presence of the spin traps 5,5-dimethyl-1-pyrroline N-oxide and tert-butyl-N-phenylnitrone and from literature results on photoinduced uranyl oxygen exchange and photoconductivity. It has previously been suggested that the uranyl emission above pH 1.5 may involve an exciplex between excited uranyl ion and uranium(v). Evidence against this mechanism is given on the basis of quenching of uranyl luminescence by uranium(v), together with other kinetic reasoning. No overall photochemical reaction is observed on excitation of aqueous uranyl solutions, and it is suggested that this is mainly due to reoxidation of UO2+ by hydroxyl radicals in a radical pair. An alternative process involving oxidation by molecular oxygen is analysed experimentally and theoretically, and is suggested to be too slow to be a major reoxidation pathway.

On the kinetics and energetics of one-electron oxidation of 1,3,5-triazines.

One-electron oxidation of 1,3,5-triazines is observed with both excited uranyl ion (*UO2(2+)) and sulfate radical anion (SO4.-) in aqueous solution, but not with Tl2+, indicating that the standard reduction potentials E degree of 1,3,5-triazine radical cations are = 2.3 +/- 0.1 V vs. NHE, consistent with theoretical calculations; this suggests that if triazines inhibit electron transfer during photosynthesis, they would need to act on the reductive part of the electron transport chain.

Pb and Cu speciation and bioavailability in port wine.

Information about the speciation of Pb and Cu in different types of Port wines (white, single-year and blended aged red, and young red wines) was gathered to estimate their respective bioavailabilities to man. For this purpose, wines were subjected to in vitro simulated gastrointestinal digestion, and the following properties were studied in the wines and its gastric and intestinal digests: (1) average conditional stability constant (K(av)) of the Cu complexes (by potentiometry), of the strongest Pb complexes (those inert to cathodic voltammetry, K'(av)), and of the respective ligand concentrations (CC or CC(inert)); (2) the distribution of the metal among the different groups of compounds of different molecular weights and/or polarities in the different bands separated by reverse phase high-performance liquid chromatography; (3) the total metal concentration present in the wines and the respective fractions present in the soluble and in the dialyzable fractions of the digest (an estimation of the assimilable fraction). The study showed that the complexing affinity for Pb (expressed by either CC(inert) or K'(av)) of white and very aged red Port wines was lower than for the remainder of the wines. For Cu, the strength of the ligands in the white wines was lower (

Assessment of the Pb and Cu in vitro availability in wines by means of speciation procedures.

The speciation of Pb and Cu in white and red table wines was investigated, in order to estimate their respective bioavailability to man. For this purpose, wines were subjected to in vitro gastrointestinal digestion, and the following properties were studied in the wines and in their gastric and intestinal digests: (1) the average conditional stability constant (Kav) of the strongest complexes (those inert to cathodic voltammetry) and of the respective ligand concentration (CCinert); (2) the distribution of the metal among the different bands of reverse phase high performance liquid chromatography (RP-HPLC) (groups of compounds of different molecular weight and/or polarity); (3) the total metal concentration and metal present in the soluble and in the dialyzable fractions of the digest. The CCinert of the red wines and the respective digests were much greater than those of the white wines and their digests. The conditional stability constants of the strongest soluble complexes after the digestion ranged between 5.9 and 6.1 for Pb. These parameters could not be determined for Cu. After the digestion the dialyzable metal fraction (a relative index of the metal potentially available for interaction with the inner biologic ligands) was only 16% of the total Pb in red wine, 62% in white Verde and 75% in white wine. For Cu the dialyzable metal fraction was 45% of the total metal in red wine, 64% in white Verde and 98% in white wine.

The influence of Cu concentration on ethanolic fermentation by Saccharomyces cerevisiae.

In the present work, the influence of Cu concentration on alcoholic fermentation by Saccharomyces cerevisiae was studied in white grape musts and in YNB medium containing glucose. In the YNB medium, the yield of ethanol, relative to the control, doubled in the presence of 0.50 and 1.0 mM Cu. As for production of ethanol from musts, only minor effects were observed at different Cu concentrations, which indicates that Cu levels do not effect changes in fermentation, and, therefore, are below any toxic level regarding the yeast performance.

Role of polyphenols in copper complexation in red wines.

Four monovarietal red wines, Tinta Roriz, Tinta Barroca, Touriga Nacional, and Touriga Francesa, were studied for their complexometric properties toward copper. For the purpose, ion selective electrode potentiometric titrations were carried out, and the data were treated by two methods suitable for heterogeneous ligands: the Scatchard plot, which provided the complexation capacity (CC(total) = maximum number of moles of sites per liter), and the differential equilibrium function (DEF), which provided the conditional stability constants of the sites effectively involved in the metal complexation (K(DEF)) at a given titration point. The different wines displayed similar properties: CC(total) ranged from 4.5x10(-3) (Tinta Barroca) to 4.9x10(-3) M (Touriga Francesa), and log K(DEF) values were between 4.2 and 6.5. The range of log(|Cu|(bound)/CC(total)) = log theta embraced in the titration was between -0.2 and -1.9. With regard to the natural levels of copper, from 4.4x10(-7) (Tinta Roriz) to 1.3x10(-6) M (Touriga Nacional), and ligands (CC(total)) in the wines, it can be expected that copper will be strongly complexed in the studied wines (log K(DEF) > 6). Studies carried out, in parallel, for solutions of isolated seed tannins and skin polyphenols (mainly anthocyans) showed that their contribution to the CC(total) of the wines was <40% for tannins and <2% for skin polyphenols. However, skin polyphenols were shown to be much stronger copper ligands (log K(DEF) = 6.7, log theta = -1.5) than tannins (log K(DEF) = 4.5, log theta = -1.5).

Copper(II) complexation properties and surfactant activity of 3-[N, N-bis(2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid and N-(2-Hydroxyethyl)piperazine-N'-2-hydroxypropanesulfonic acid pH buffers which may affect trace metal speciation in in vitro studies.

Disadvantages of the some zwitterionic pH buffers are (i) that they can interact with metal ions as well as protons, and (ii) that they may have a surfactant effect in chemical or in vitro biological or biochemical studies. This has to be taken into account when a buffer is selected. Here, the copper-complexing capacity and the surfactant activity of three compounds, 3-[N,N-bis (2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid (DIPSO), N-(2-hydroxyethyl)piperazine-N'-(2-hydroxypropanesulfonic acid) (HEPPSO), and piperazine-N,N'-bis(2-ethanesulfonic acid) (Pipes), were investigated. Global stability constants (log betaabc) of copper(II)-buffer complexes were determined, at 25 degrees C, 0.5 M ionic strength, and at 0.8 mM buffer concentration, by pH and pCu ion-selective electrode measurements. Here, betaabc corresponds to the equilibrium: aCu2+ + bL- + cH+ left and right arrow (CuaLbHc)(2a-b+c); HL = DIPSO or HEPPSO; c: +1 = proton; -1 = hydroxide. Using SUPERQUAD constants were calculated, giving: DIPSO: log beta110 = 5.02, log beta120 = 8.99, log beta130 = 13.0, log beta140 = 16.3, log beta14-1 = 9.26, log beta14-2 = 0.645, log beta150 = 20.5, log beta160 = 24.3, log beta16-1 = 16.1, log beta16-2 = 8.98; HEPPSO: log beta110 = 4.29, log beta120 = 8.35, log beta130 = 12.1, log beta140 = 15.9, log beta150 = 19.6, log beta160 = 23.4, log beta16-1 = 14.9. The pKa values were determined at higher buffer concentrations, giving a value 7.33 for DIPSO and 7.84 for HEPPSO at 2.0 mM buffer concentration. Effects of buffer concentration on stability and acidity constants were investigated and compared with measurements using voltammetric and potentiometric stripping analysis, confirming no copper(II) complexation by Pipes. Surfactant activities were determined using alternating current polarography, confirming marked surface activity of 10 mM of DIPSO or HEPPSO.

Electrochemical evidence of surfactant activity of the hepes pH buffer which may have implications on trace metal availability to cultures in vitro.

Hydrogen ion buffers are required for many different types of in vitro biological and chemical studies, but they may not be inert enough, thus interfering with the system under study. N-Hydroxyethylpiperazine-N'-ethanesulfonic acid (Hepes), a zwitterionic buffer in the 7.0-8.0 pH range, has been used in different biological studies. In this work, surfactant activity of Hepes and the buffer's capability to bind copper(II) were investigated through different electrochemical techniques: ion-selective electrode potentiometry, potentiometric stripping analysis, differential pulse anodic stripping voltammetry, normal pulse anodic stripping voltammetry, and alternating current polarography. Hepes concentrations between 0.1 (0.24 g liter-1) and 25 mmol liter-1 (6.0 g liter-1) were studied at pH 8.0 (and at pH 6.5 for comparison). At pH 8.0 Hepes displayed surfactant activity, particularly when magnitude of Hepes > 10 mmol liter-1 (2.4 g liter-1). The ability of Hepes to bind copper(II) was detected when Hepes was in large excess (magnitude of Hepes/magnitude of Cu between 10,000 and 2000). Eventual implications in the bioavailability of copper(II) are also discussed.