The use of a gold disc microelectrode for the determination of copper in human sweat

A novel approach of using a gold disc microelectrode to analyze sweat samples for copper ions by anodic square wave stripping voltammetry (SW stripping voltammetry) is described. Sweat was collected from the lower back of four subjects after physical exercise and the sample volume required for the determinations was 100 μL. Under the optimized conditions, the calibration plot was linear over the range 1-100 μmol L⁻¹ Cu(II) with a limit of detection of 0.25 μmol L⁻¹. The precision was evaluated by carrying out five replicate measurements in a 1 μmol L⁻¹ Cu(II) solution and the standard deviation was found to be 1.5%. Measurements were performed by inserting the microelectrode into sweat drops and Cu(II) concentrations in the analyzed samples ranged from 0.9 to 28 μmol L⁻¹. Values obtained by the proposed voltammetric method agreed well with those found using graphite furnace atomic absorption spectroscopy (GFAAS).     

Sensitive Determination of the Diquat Herbicide in Fresh Food Samples on a Highly Boron‐Doped Diamond Electrode

The highly boron‐doped diamond electrode (HBDD) combined with square wave voltammetry (SWV) was used in the development of an analytical procedure for diquat determination in potato and sugar cane samples and lemon, orange, tangerine and pineapple juices. Preliminary experiments realised in a medium of 0.05 mol L^?1 Na₂B₄O₇ showed the presence of two voltammetric peaks around ?0.6 V and around ?1.0 V vs. Ag/AgCl/Cl^? 3.0 mol L^?1, where the first peak could be successfully used for analytical proposes due the facility in the electrode surface renovation. After the experimental and voltammetric optimisation, the calculated detection and quantification limits were 1.6×10^?10 mol L^?1 and 5.3×10^?10 mol L^?1 (0.057 µg L^?1 and 0.192 µg L^?1, respectively), which are lower than the maximum residue limit established for fresh food samples by the Brazilian Sanitary Vigilance Agency. The proposed methodology was used to determine diquat residues in potato and sugar cane samples and lemon, orange, tangerine and pineapple juices and the calculated recovery efficiencies indicated that the proposed procedure presents higher robustness, stability and sensitivity, good reproducibility, and is very adequate for diquat determination in complex samples.     

Thermodynamic study of 1,2,3-triphenylbenzene and 1,3,5-triphenylbenzene

The energetic study of 1,2,3-triphenylbenzene (1,2,3-TPhB) and 1,3,5-triphenylbenzene (1,3,5-TPhB) isomers was carried out by making use of the mini-bomb combustion calorimetry and Knudsen mass-loss effusion techniques. The mini-bomb combustion calorimetry technique was used to derive the standard (p° = 0.1 MPa) molar enthalpies of formation in the crystalline state from the measured standard molar energies of combustion for both isomers. The Knudsen mass-loss effusion technique was used to measure the dependence with the temperature of the vapour pressure of crystalline 1,2,3-TPhB, which allowed the derivation of the standard molar enthalpy of sublimation, by application of the Clausius–Clapeyron equation. The sublimation study of 1,3,5-TPhB had been performed previously. From the combination of data obtained by both techniques, the standard molar enthalpies of formation in the gaseous state, for both isomers, at T = 298.15 K, were calculated. The results indicate a higher stability of the 1,3,5-TPhB isomer relative to 1,2,3-TPhB, similarly to the terphenyls. Nevertheless, the 1,2,3-TPhB isomer is not as energetically destabilized as one might expect, supporting the existence of a π–π displacive stacking interaction between both pairs of outer phenyl rings. The volatility difference between the two isomers is ruled by the enthalpy of sublimation. The volatility of the 1,2,3-TPhB is two orders of magnitude higher than the 1,3,5-TPhB isomer, at T = 298.15 K.     

134.

Thermal behaviour of malonic acid,sodium malonate and its compounds with some bivalent transition metal ions     

F.J. Caires  L.S. Lima  C.T. Carvalho  R.J. Giagio  M. Ionashiro 《Thermochimica Acta》2010,497(1-2):35-40

Characterization, thermal stability and thermal decomposition of transition metal malonates, MCH₂C₂O₄·nH₂O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as, the thermal behaviour of malonic acid (C₃H₄O₄) and its sodium salt (Na₂CH₂C₂O₄·H₂O) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, TG-FTIR system, elemental analysis and complexometry. The dehydration, as well as, the thermal decomposition of the anhydrous compounds occurs in a single step. For the sodium malonate the final residue up to 700 °C is sodium carbonate, while the transition metal malonates the final residue up to 335 °C (Mn), 400 °C (Fe), 340 °C (Co), 350 °C (Ni), 520 °C (Cu) and 450 °C (Zn) is Mn₃O₄, Fe₂O₃, Co₃O₄, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity, thermal behaviour and identification of some gaseous products evolved during the thermal decomposition of these compounds.     

135.

A new oxovanadium(IV)–cucurbit[6]uril complex: Properties and potential for confined heterogeneous catalytic oxidation reactions     

Silvânia Marilene de Lima  Jorge Antonio Gómez  Valéria P. Barros  Greice de S. Vertuan  Marilda das Dores Assis  Carlos Frederico de Oliveira Graeff  Grégoire Jean-François Demets 《Polyhedron》2010

This work presents a new oxovanadium(IV)–cucurbit[6]uril complex, which combines the catalytic properties of the metal ion with the size-excluding properties of the macrocycle cavity. In this coordination compound, the VO²⁺${\text{VO}}^{2+}$ ions are coordinated to the oxygen atoms located at the rim of the macrocycle in slightly distorted square-pyramidal configurations, which are in fact _C2v$C_{2v}$ symmetries. This combination results in a size-selective heterogeneous catalyst, which is able to oxidize linear alkanes like n-pentane at room temperature, but not styrene, cyclohexane or z-cyclooctene, which are too big to enter the cucurbit[6]uril cavity. The results presented here contribute to understanding the mechanism of alkane catalytic oxidation by oxovanadium(IV) complexes.     

136.

pH effect on the photochemistry of 4-methylcoumarin phosphate esters: caged-phosphate case study     

Pinheiro AV  Parola AJ  Baptista PV  Lima JC 《The journal of physical chemistry. A》2010,114(49):12795-12803

There are numerous reports of coumarin ester derivatives, in particular phosphate esters, as photocleavable cages in biological systems. Despite the comprehensive analysis of the photocleavage mechanism, studies of 4-methylcoumarin caged phosphates and/or nucleotides were always performed at constant pH. In this work, we present the study of the pH effect on the photochemistry of (7-diethylaminocoumarin-4-yl)methyl phosphate (DEACM-P). Fluorescence and photocleavage quantum yields, as well as the fluorescence decay times were measured as a function of the pH. It was found that the pH produces significant changes in the overall photochemical quantum yield of DEACM-P, and the observed changes are complementary to those obtained from the fluorescence quantum yield. Deprotonation of DEACM-HPO(4)(-) to yield DEACM-PO(4)(2-), produces a decrease in the photochemical quantum yield (from 0.0045 to 0.0003) and an increase in the fluorescence quantum yield (from 0.072 to 0.092). Moreover, from the analysis of the decay times, we have also found that hydroxyl ion is not only relevant, but it is mechanistically involved in the photoreaction of DEACM-HPO(4)(-).     

137.

On-line renewable solid-phase extraction hyphenated to liquid chromatography for the determination of UV filters using bead injection and multisyringe-lab-on-valve approach     

Hugo M. Oliveira  Marcela A. Segundo  José L.F.C. Lima  Manuel Miró  Victor Cerdà 《Journal of chromatography. A》2010,1217(22):3575-3582

For the first time, an automatic sample pre-treatment/detection method is proposed for the multiclass determination of UV filters (namely, benzophenone-3, ethylhexylmetoxycinnamate, butylmethoxydibenzoylmethane and homosalate) in environmental samples. The new methodology comprises in-line solid-phase extraction (SPE) of the target analytes by exploiting the bead injection (BI) concept in a mesofluidic lab-on-valve (LOV) format, with subsequent determination by liquid chromatography (LC). The proposed microanalytical system, using a multisyringe burette as propulsion unit, automatically performed the overall SPE steps, including the renewal of the sorbent in each analytical cycle to prevent sample cross-contamination and the post-extraction adjustment of the eluate composition to prevent chromatographic band broadening effects. In order to expedite the LC separation, a C₁₈ monolithic column was applied and an accelerated isocratic elution was carried out by using a cationic surfactant as mobile phase additive. The LOV-BI-LC method was proven reliable for handling and analysis of complex matrices, e.g., spiked swimming pool water and seawater, with limits of detection ranging between 0.45 and 3.2 μg L⁻¹ for 9 mL sample volume. Linear calibration was attained up to 160 μg L⁻¹ for homosalate and up to 35 μg L⁻¹ for the other target analytes, with good reproducibility (RSD < 13%, for 5 different SPE columns). The hyphenated scheme is able to process a given sample simultaneously and within the same time frame than the chromatographic separation/determination of the formerly pre-treated sample, providing concentration values every 9 min. Hence, the sample throughput was enhanced up to 33 times when compared with previously reported off-line SPE methods. A drastic reduction in reagent consumption and effluent production was also attained, contributing to the development of an environment-friendly analyzer.     

138.

Yet another proof of Marstrand’s theorem     

Yuri Lima  Carlos Gustavo Moreira 《Bulletin of the Brazilian Mathematical Society》2011,42(2):331-345

In a paper from 1954 Marstrand proved that if K ⊂ ℝ² is a Borel set with Hausdorff dimension greater than 1, then its one-dimensional projection has positive Lebesgue measure for almost-all directions. In this article, we give a combinatorial proof of this theorem, extending the techniques developed in our previous paper [9].     

139.

Multimode vibrational couplings in resonant positron annihilation     

d'A Sanchez S  Lima MA  Varella MT 《Physical review letters》2011,107(10):103201

The mechanisms for multimode vibrational couplings in resonant positron annihilation are not well understood. We show that these resonances can arise from positron-induced distortions of the potential energy surface (target response to the positron field). Though these distortions can transfer energy into single- and multiquantum vibrations, they have so far been disregarded as a pathway to resonant annihilation. We also compare the existing annihilation theories and show that the currently accepted model can be cast as a special case of the Feshbach annihilation theory.     

140.

3D elemental distribution images in biological samples by XRFµCT     

G. R. Pereira  H. S. Rocha  C. Calza  M. J. Anjos  I. Lima  C. A. Pérez  R. T. Lopes 《X射线光谱测定》2011,40(4):260-264

An X‐ray transmission microtomography (CT) system combined with an X‐ray fluorescence microtomography (XRFµCT) system was implemented in the Brazilian Synchrotron Light Laboratory (LNLS), Campinas, Brazil. The aim of this work was to determine the elemental distribution in biological samples (breast, prostate and lung samples) in order to verify the concentration of some elements correlated with characteristics and pathology of each tissue observed by the transmission CT. The experiments were performed at the X‐ray fluorescence beamline (D09B‐XRF) of the Brazilian Synchrotron Light Laboratory, Campinas, Brazil. A quasi‐monochromatic beam produced by a multilayer monochromator was used as an incident beam. The sample was placed on a high‐precision goniometer and translation stages that allow rotating as well as translating it perpendicularly to the beam. The fluorescence photons were collected with an energy dispersive HPGe detector placed at 90° to the incident beam, while transmitted photons were detected with a fast Na(Tl) scintillation counter placed behind the sample on the beam path. The CT images were reconstructed using a filtered‐back projection algorithm and the XRFµCT images were reconstructed using a filtered‐back projection algorithm with absorption corrections. The 3D images were reconstructed using the 3D‐DOCTOR software. Results from the 3D visualization showed that the distribution of iron, copper and zinc is different and heterogeneous from the analyzed samples. Copyright © 2011 John Wiley & Sons, Ltd.     

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Thermal behaviour of malonic acid,sodium malonate and its compounds with some bivalent transition metal ions

Characterization, thermal stability and thermal decomposition of transition metal malonates, MCH₂C₂O₄·nH₂O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as, the thermal behaviour of malonic acid (C₃H₄O₄) and its sodium salt (Na₂CH₂C₂O₄·H₂O) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, TG-FTIR system, elemental analysis and complexometry. The dehydration, as well as, the thermal decomposition of the anhydrous compounds occurs in a single step. For the sodium malonate the final residue up to 700 °C is sodium carbonate, while the transition metal malonates the final residue up to 335 °C (Mn), 400 °C (Fe), 340 °C (Co), 350 °C (Ni), 520 °C (Cu) and 450 °C (Zn) is Mn₃O₄, Fe₂O₃, Co₃O₄, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity, thermal behaviour and identification of some gaseous products evolved during the thermal decomposition of these compounds.     

A new oxovanadium(IV)–cucurbit[6]uril complex: Properties and potential for confined heterogeneous catalytic oxidation reactions

This work presents a new oxovanadium(IV)–cucurbit[6]uril complex, which combines the catalytic properties of the metal ion with the size-excluding properties of the macrocycle cavity. In this coordination compound, the VO²⁺${\text{VO}}^{2+}$ ions are coordinated to the oxygen atoms located at the rim of the macrocycle in slightly distorted square-pyramidal configurations, which are in fact _C2v$C_{2v}$ symmetries. This combination results in a size-selective heterogeneous catalyst, which is able to oxidize linear alkanes like n-pentane at room temperature, but not styrene, cyclohexane or z-cyclooctene, which are too big to enter the cucurbit[6]uril cavity. The results presented here contribute to understanding the mechanism of alkane catalytic oxidation by oxovanadium(IV) complexes.     

pH effect on the photochemistry of 4-methylcoumarin phosphate esters: caged-phosphate case study

There are numerous reports of coumarin ester derivatives, in particular phosphate esters, as photocleavable cages in biological systems. Despite the comprehensive analysis of the photocleavage mechanism, studies of 4-methylcoumarin caged phosphates and/or nucleotides were always performed at constant pH. In this work, we present the study of the pH effect on the photochemistry of (7-diethylaminocoumarin-4-yl)methyl phosphate (DEACM-P). Fluorescence and photocleavage quantum yields, as well as the fluorescence decay times were measured as a function of the pH. It was found that the pH produces significant changes in the overall photochemical quantum yield of DEACM-P, and the observed changes are complementary to those obtained from the fluorescence quantum yield. Deprotonation of DEACM-HPO(4)(-) to yield DEACM-PO(4)(2-), produces a decrease in the photochemical quantum yield (from 0.0045 to 0.0003) and an increase in the fluorescence quantum yield (from 0.072 to 0.092). Moreover, from the analysis of the decay times, we have also found that hydroxyl ion is not only relevant, but it is mechanistically involved in the photoreaction of DEACM-HPO(4)(-).     

On-line renewable solid-phase extraction hyphenated to liquid chromatography for the determination of UV filters using bead injection and multisyringe-lab-on-valve approach

For the first time, an automatic sample pre-treatment/detection method is proposed for the multiclass determination of UV filters (namely, benzophenone-3, ethylhexylmetoxycinnamate, butylmethoxydibenzoylmethane and homosalate) in environmental samples. The new methodology comprises in-line solid-phase extraction (SPE) of the target analytes by exploiting the bead injection (BI) concept in a mesofluidic lab-on-valve (LOV) format, with subsequent determination by liquid chromatography (LC). The proposed microanalytical system, using a multisyringe burette as propulsion unit, automatically performed the overall SPE steps, including the renewal of the sorbent in each analytical cycle to prevent sample cross-contamination and the post-extraction adjustment of the eluate composition to prevent chromatographic band broadening effects. In order to expedite the LC separation, a C₁₈ monolithic column was applied and an accelerated isocratic elution was carried out by using a cationic surfactant as mobile phase additive. The LOV-BI-LC method was proven reliable for handling and analysis of complex matrices, e.g., spiked swimming pool water and seawater, with limits of detection ranging between 0.45 and 3.2 μg L⁻¹ for 9 mL sample volume. Linear calibration was attained up to 160 μg L⁻¹ for homosalate and up to 35 μg L⁻¹ for the other target analytes, with good reproducibility (RSD < 13%, for 5 different SPE columns). The hyphenated scheme is able to process a given sample simultaneously and within the same time frame than the chromatographic separation/determination of the formerly pre-treated sample, providing concentration values every 9 min. Hence, the sample throughput was enhanced up to 33 times when compared with previously reported off-line SPE methods. A drastic reduction in reagent consumption and effluent production was also attained, contributing to the development of an environment-friendly analyzer.     

Yet another proof of Marstrand’s theorem

In a paper from 1954 Marstrand proved that if K ⊂ ℝ² is a Borel set with Hausdorff dimension greater than 1, then its one-dimensional projection has positive Lebesgue measure for almost-all directions. In this article, we give a combinatorial proof of this theorem, extending the techniques developed in our previous paper [9].     

Multimode vibrational couplings in resonant positron annihilation

The mechanisms for multimode vibrational couplings in resonant positron annihilation are not well understood. We show that these resonances can arise from positron-induced distortions of the potential energy surface (target response to the positron field). Though these distortions can transfer energy into single- and multiquantum vibrations, they have so far been disregarded as a pathway to resonant annihilation. We also compare the existing annihilation theories and show that the currently accepted model can be cast as a special case of the Feshbach annihilation theory.     

3D elemental distribution images in biological samples by XRFµCT

An X‐ray transmission microtomography (CT) system combined with an X‐ray fluorescence microtomography (XRFµCT) system was implemented in the Brazilian Synchrotron Light Laboratory (LNLS), Campinas, Brazil. The aim of this work was to determine the elemental distribution in biological samples (breast, prostate and lung samples) in order to verify the concentration of some elements correlated with characteristics and pathology of each tissue observed by the transmission CT. The experiments were performed at the X‐ray fluorescence beamline (D09B‐XRF) of the Brazilian Synchrotron Light Laboratory, Campinas, Brazil. A quasi‐monochromatic beam produced by a multilayer monochromator was used as an incident beam. The sample was placed on a high‐precision goniometer and translation stages that allow rotating as well as translating it perpendicularly to the beam. The fluorescence photons were collected with an energy dispersive HPGe detector placed at 90° to the incident beam, while transmitted photons were detected with a fast Na(Tl) scintillation counter placed behind the sample on the beam path. The CT images were reconstructed using a filtered‐back projection algorithm and the XRFµCT images were reconstructed using a filtered‐back projection algorithm with absorption corrections. The 3D images were reconstructed using the 3D‐DOCTOR software. Results from the 3D visualization showed that the distribution of iron, copper and zinc is different and heterogeneous from the analyzed samples. Copyright © 2011 John Wiley & Sons, Ltd.