Electrochemical impedance spectroscopy investigation of the electrochemical behaviour of copper coated with artificial patina layers and submitted to wet and dry cycles

Due to rain events historical monuments exposed to the atmosphere are frequently submitted to wet and dry cycles. During drying periods wetness is maintained in some confined regions and the corrosion product layer, generally denominated patinas, builds up and gets thicker. The aim of this study is to use electrochemical impedance spectroscopy (EIS) to investigate the electrochemical behaviour of pure copper coated with two artificial patina layers and submitted either to continuous or to intermittent immersion tests, this latter aiming to simulate wet and dry cycles. The experiments were performed in 0.1 mol dm(-3) NaCl solution and in artificial rainwater containing the most significant pollutants of the city of Sao Paulo. The results of the continuous immersion tests in the NaCl solution have shown that the coated samples behave like a porous electrode with finite pore length. On the other hand, in the intermittent tests a porous electrode response with semi-infinite pore length can be developed. The results were interpreted based on the model of de Levie and a critical comparison with previous interpretations reported in the literature for similar systems is presented. (C) 2011 Elsevier Ltd. All rights reserved.

Soil density evaluated by spectral reflectance as an evidence of compaction effects

Soil compaction, reflected by high bulk density, is an environmental degradation process and new technologies are being developed for its detection. Despite the proven efficiency of remote sensing, it has not been widely used for soil density. Our objective was to evaluate the density of two soils: a Typic Quartzpisament (TQ) and a Rhodic Paleudalf (RP), using spectral reflectance obtained by a laboratory spectroradiometer between 450 and 2500 nm. Undisturbed samples were taken at two depths (0-20 and 60-80 cm), and were artificially compacted. Spectral data, obtained before and after compaction, were compared for both wet and dried compacted samples. Results demonstrated that soil density was greater in RP than in TQ at both depths due to its clayey texture. Spectral data detected high density (compacted) from low density (non-compacted) clayey soils under both wet and dry conditions. The detection of density in sandy soils by spectral reflectance was not possible. The intensity of spectral reflectance of high soil bulk density (compacted) samples was higher than for low density (non-compacted) soils due to changes in soil structure and porosity. Dry samples with high bulk density showed differences in the spectral intensity, but not in the absorption features. Wet samples in equal condition had statistically higher reflectance intensity than that of the low soil bulk density (non-compacted), and absorption differences at 1920 nm, which was due to the altered position of the water molecules. Soil line and spectral reflectance used together could detect soil bulk density variations for the clay soil. This technique could assist in the detection of high soil density in the laboratory by providing new soil information.

Leaf area index estimation with MODIS reflectance time series and model inversion during full rotations of Eucalyptus plantations

The leaf area index (LAI) of fast-growing Eucalyptus plantations is highly dynamic both seasonally and interannually, and is spatially variable depending on pedo-climatic conditions. LAI is very important in determining the carbon and water balance of a stand, but is difficult to measure during a complete stand rotation and at large scales. Remote-sensing methods allowing the retrieval of LAI time series with accuracy and precision are therefore necessary. Here, we tested two methods for LAI estimation from MODIS 250m resolution red and near-infrared (NIR) reflectance time series. The first method involved the inversion of a coupled model of leaf reflectance and transmittance (PROSPECT4), soil reflectance (SOILSPECT) and canopy radiative transfer (4SAIL2). Model parameters other than the LAI were either fixed to measured constant values, or allowed to vary seasonally and/or with stand age according to trends observed in field measurements. The LAI was assumed to vary throughout the rotation following a series of alternately increasing and decreasing sigmoid curves. The parameters of each sigmoid curve that allowed the best fit of simulated canopy reflectance to MODIS red and NIR reflectance data were obtained by minimization techniques. The second method was based on a linear relationship between the LAI and values of the GEneralized Soil Adjusted Vegetation Index (GESAVI), which was calibrated using destructive LAI measurements made at two seasons, on Eucalyptus stands of different ages and productivity levels. The ability of each approach to reproduce field-measured LAI values was assessed, and uncertainty on results and parameter sensitivities were examined. Both methods offered a good fit between measured and estimated LAI (R(2) = 0.80 and R(2) = 0.62 for model inversion and GESAVI-based methods, respectively), but the GESAVI-based method overestimated the LAI at young ages. (C) 2010 Elsevier Inc. All rights reserved.

Relating MODIS vegetation index time-series with structure, light absorption and stem production of fast-growing Eucalyptus plantations

By allowing the estimation of forest structural and biophysical characteristics at different temporal and spatial scales, remote sensing may contribute to our understanding and monitoring of planted forests. Here, we studied 9-year time-series of the Normalized Difference Vegetation Index (NDVI) from the Moderate Resolution Imaging Spectroradiometer (MODIS) on a network of 16 stands in fast-growing Eucalyptus plantations in Sao Paulo State, Brazil. We aimed to examine the relationships between NDVI time-series spanning entire rotations and stand structural characteristics (volume, dominant height, mean annual increment) in these simple forest ecosystems. Our second objective was to examine spatial and temporal variations of light use efficiency for wood production, by comparing time-series of Absorbed Photosynthetically Active Radiation (APAR) with inventory data. Relationships were calibrated between the NDVI and the fractions of intercepted diffuse and direct radiation, using hemispherical photographs taken on the studied stands at two seasons. APAR was calculated from the NDVI time-series using these relationships. Stem volume and dominant height were strongly correlated with summed NDVI values between planting date and inventory date. Stand productivity was correlated with mean NDVI values. APAR during the first 2 years of growth was variable between stands and was well correlated with stem wood production (r(2) = 0.78). In contrast, APAR during the following years was less variable and not significantly correlated with stem biomass increments. Production of wood per unit of absorbed light varied with stand age and with site index. In our study, a better site index was accompanied both by increased APAR during the first 2 years of growth and by higher light use efficiency for stem wood production during the whole rotation. Implications for simple process-based modelling are discussed. (C) 2009 Elsevier B.V. All rights reserved.

Quantitative Determination of Dimethylaminoethanol in Cosmetic Formulations by Nuclear Magnetic Resonance Spectroscopy

A nuclear magnetic resonance (NMR) spectroscopic method was validated for the quantitative determination of dimethylaminoethanol (DMAE) in cosmetic formulations. The linearity in the range from 0.5000 to 1.5000 g (DMAE salt/mass maleic acid) presents a correlation coefficient > 0.99 for all DMAE salts. The repeatability (intraday), expressed as relative standard deviation, ranged from 1.08 to 1.44% for samples and 1.31 to 1.88% for raw materials. The detection limit and quantitation limit were 0.0017 and 0.0051 g for DMAE, 0.0018 and 0.0054 g for DMAE bitartrate, and 0.0023 and 0.0071 g for DMAE acetamidobenzoate, respectively. The proposed method is simple, precise, and accurate and can be used in the quality control of raw materials and cosmetic gels containing these compounds as active substances.

Rutin association with ethylhexyl methoxycinnamate and benzophenone-3: In vitro evaluation of the photoprotection effectiveness by reflectance spectrophotometry

There is a world tendency to the development of sunscreens possessing reduced concentration of UV filters and, yet, with high UVA-UVB protection. This research work proposes the development and in vitro efficacy evaluation of sunscreens containing rutin, an antioxidant flavonol, associated or not to UVA (benzophenone-3) and UVB (ethylhexyl methoxycinnamate) filters. Formulations were in vitro assayed by reflectance spectrophotometry with integrated sphere, regarding the following parameters: estimated sun protection factor (SPF), critical wavelength (nm) and UVA/UVB ratio. Rutin 0.1% w/w photoprotection efficacy presented dependent of the concentration and presence of the UVA and UVB filters, and it was verified synergism on the SPF elevation, from 7.34 +/- 0.24 to 9.97 +/- 0.18, when the flavonoid was associated with the filters in minimum concentrations. Isolated rutin exerted UVA protection superior to the formulation not added to UV filters and their associations.

Quantification of chlorpheniramine maleate enantiomers by ultraviolet spectroscopy and chemometric methods

Chlorpheniramine maleate (CLOR) enantiomers were quantified by ultraviolet spectroscopy and partial least squares regression. The CLOR enantiomers were prepared as inclusion complexes with beta-cyclodextrin and 1-butanol with mole fractions in the range from 50 to 100%. For the multivariate calibration the outliers were detected and excluded and variable selection was performed by interval partial least squares and a genetic algorithm. Figures of merit showed results for accuracy of 3.63 and 2.83% (S)-CLOR for root mean square errors of calibration and prediction, respectively. The ellipse confidence region included the point for the intercept and the slope of 1 and 0, respectively. Precision and analytical sensitivity were 0.57 and 0.50% (S)-CLOR, respectively. The sensitivity, selectivity, adjustment, and signal-to-noise ratio were also determined. The model was validated by a paired t test with the results obtained by high-performance liquid chromatography proposed by the European pharmacopoeia and circular dichroism spectroscopy. The results showed there was no significant difference between the methods at the 95% confidence level, indicating that the proposed method can be used as an alternative to standard procedures for chiral analysis.

The Reflectance Signature of Canopy Components: Implications for the Interpretation of Remotely Sensed Images

The reflectance signatures of plantation pine canopy and understorey components were measured using a spectro-radiometer. The aim was to establish whether differences observed in the reflectance signature of stressed and unstressed pine needles were consistent with observed differences in the reflectance of multispectral Landsat Thematic Mapper (TM) images of healthy and stressed forest. Because overall scene reflectance includes the contribution of each scene component, needle reflectance may not be representative of canopy reflectance. In this investigation, a limited dataset of reflectance signatures from stressed and unstressed needles confirmed the negative relationship between pine needle health and reflectance which was observed in visible red wavelengths. However, the reflectance contribution from bushes, pine needle litter and bare soil tended to reinforce this relationship suggesting that in this instance, overall scene reflectance is comprised of the proportional reflectance of each scene component. In near infrared wavelengths, differences between healthy and stressed needle reflectance suggested a strong positive relationship between reflectance and tree health. For Landsat TM images, previous research had only observed a weak positive relationship between stand health and near infrared reflectance in these pine canopies. This suggests that for multispectral Landsat TM images, reflectance of near infrared light from pine canopies may be affected by other factors which may include the scattering of light within canopies. These results are seen as promising for the use of hyperspectral images to detect stand health, provided that pixel reflectance is not influenced by other scene components.

Free volume and water uptake in a copolymer hydrogel series

A copolymer of X-hydroxyethyl methacrylate (HEMA) with 2-ethoxy ethyl methacrylate (EEMA) was synthesized and the molecular mobility, free volume, and density properties examined as a function of composition. These properties were correlated with the equilibrium water uptake in order to determine which of the properties were most influential in causing high water sorption, as these materials are suitable candidates for hydrogel systems. It was found that the polar HEMA repeat unit results in a rigid, glassy sample at room temperature due to the high degree of hydrogen bonding between chains whereas high EEMA content leads to rubbery samples with subambient glass transition temperatures. The free volume properties on the molecular scale measured by positron annihilation Lifetime spectroscopy (PALS) showed that higher HEMA content led to smaller, fewer holes and a lower free volume fraction than EEMA. Therefore the high water uptake of HEEMA-containing copolymers is largely related to the high polarity of the HEMA unit compared to EEMA, despite the low content of free volume into which the water can initially diffuse. Trends in density with copolymer composition, as measured on a macroscopic level, differs to that seen by PALS and indicates that the two techniques are measuring different scales of packing. (C) 1998 John Wiley & Sons, Inc.

Radiation use efficiency increases when the diffuse component of incident radiation is enhanced under shade

Theoretical analyses have shown the radiation use efficiency of maize, soybean, and peanut to increase with a decrease in the level of incident radiation and an increase in the proportion of diffuse radiation. This study compared the growth and radiation use efficiency of Panicum maximum cv. Petrie (green panic) and Bothriochloa insculpta cv. Bisset (creeping bluegrass) beneath shading treatments (birdguard and solarweave shadecloths) with that in full sunlight. A level of incident radiation reduced by 25% under birdguard shadecloth decreased final yield and final leaf area index, but increased canopy leaf nitrogen concentration and radiation use efficiency (19-14%) (compared with the full sun treatment). A similar level of reduced incident radiation under solarweave shadecloth (which provided an increased proportion of diffuse radiation), increased final yield and radiation use efficiency (46-50%). An understanding of the effects of composition of incident radiation on radiation use efficiency of tropical grasses enables more accurate estimation of potential pasture growth in shaded environments. It also has impact upon crop production in glasshouses and greenhouses.

Iron(III) and iron(II) complexes of 1-thia-4,7-diazacyclononane ([9]aneN(2)S) and 1,4-dithia-7-azacyclononane ([9]aneNS(2)). X-Ray structural analyses, magnetic susceptibility, Mossbauer, EPR and electronic spectroscopy

The complexes [Fe([9]aneN(2)S)(2)][ClO4](2), [Fe([9]aneN(2)S)(2)][ClO4](3) and [Fe([9]aneNS(2))(2)][ClO4](2) ([9]aneN(2)S = 1-thia-4. 7-diazacyclononane and [9]aneNS(2) = 1,4-dithia-7-azacyclononane) have been prepared and the latter two characterised by X-ray crystallography. The Mossbauer spectra (isomer shift/mm s(-1), quadrupole splitting/mm s(-1), 4.2 K) for [Fe([9]aneN(2)S)(2)][ClO4](2) (0.52, 0.57), [Fe([9]aneN(2)S)(2)][ClO4](3) (0.25, 2.72) and [Fe([9]aneNS(2))(2)][ClO4](2) (0.43, 0.28) are typical for iron(II) and iron(III) complexes. Variable-temperature susceptibility measurements for [Fe([9]aneN(2)S)(2)][ClO4](2) (2-300 K) revealed temperature-dependent behaviour in both the solid state [2.95 mu(B) (300 K)-0.5 mu(B) (4.2 K)] and solution (Delta H degrees 20-22 kJ mol(-1), Delta S degrees 53-60 J mol(-1) K-1). For [Fe([9]aneN(2)S)(2)][ClO4](3) in the solid state [2.3 mu(B) (300 K)-1.9 mu(B) (4.2 K)] the magnetic data were fit to a simple model (H = -lambda L . S + mu L-z) to give the spin-orbit coupling constant (lambda) of -260 +/- 10 cm(-1). The solid-state X-band EPR spectrum of [Fe([9]aneN(2)S)(2)][ClO4](3) revealed axial symmetry (g(perpendicular to) = 2.607, g(parallel to) = 1.599). Resolution of g(perpendicular to) into two components at Q-band frequencies indicated a rhombic distortion. The low-temperature single-crystal absorption spectra of [Fe([9]aneN(2)S)(2)][ClO4](2) and [Fe([9]aneNS(2))(2)][ClO4](2) exhibited additional bands which resembled pseudotetragonal low-symmetry splitting of the parent octahedral (1)A(1g) --> T-1(2g) and (1)A(1g) ---> T-1(1g) transitions. However, the magnitude of these splittings was too large, requiring 10Dq for the thioether donors to be significantly larger than for the amine donors. Instead, these bands were tentatively assigned to weak, low-energy S --> Fe-II charge-transfer transitions. Above 200 K, thermal occupation of the high-spin T-5(2g) ground state resulted in observation of the T-5(2g) --> E-5(g) transition in the crystal spectrum of [Fe([9]aneN(2)S)(2)][ClO4](2). From a temperature-dependence study, the separation of the low-spin (1)A(1g) and high-spin T-5(2g) ground states was approximately 1700 cm(-1). The spectrum of the iron(III) complex [Fe([9]aneN(2)S)(2)][ClO4](3) is consistent with a low-spin d(5) configuration.

Three-dimensional solution structure of alpha-conotoxin MII by NMR spectroscopy: Effects of solution environment on helicity

alpha-Conotoxin MII, a 16-residue polypeptide from the venom of the piscivorous cone snail Conus magus, is a potent and highly specific blocker of mammalian neuronal nicotinic acetylcholine receptors composed of alpha 3 beta 2 subunits. The role of this receptor type in the modulation of neurotransmitter release and its relevance to the problems of addiction and psychosis emphasize the importance of a structural understanding of the mode of interaction of MII with the alpha 3 beta 2 interface. Here we describe the three-dimensional solution structure of MIT determined using 2D H-1 NMR spectroscopy. Structural restraints consisting of 376 interproton distances inferred from NOEs and 12 dihedral restraints derived from spin-spin coupling constants were used as input for simulated annealing calculations and energy minimization in the program X-PLOR. The final set of 20 structures is exceptionally well-defined with mean pairwise rms differences over the whole molecule of 0.07 Angstrom for the backbone atoms and 0.34 Angstrom for all heavy atoms. MII adopts a compact structure incorporating a central segment of alpha-helix and beta-turns at the N- and C-termini. The molecule is stabilized by two disulfide bonds, which provide cross-links between the N-terminus and both the middle and C-terminus of the structure. The susceptibility of the structure to conformational change was examined using several different solvent conditions. While the global fold of MII remains the same, the structure is stabilized in a more hydrophobic environment provided by the addition of acetonitrile or trifluoroethanol to the aqueous solution. The distribution of amino acid side chains in MII creates distinct hydrophobic and polar patches on its surface that may be important for the specific interaction with the alpha 3 beta 2 neuronal nAChR. A comparison of the structure of MII with other neuronal-specific alpha-conotoxins provides insights into their mode of interaction with these receptors.

The solution structure of a copper(II) compound of a new cyclic octapeptide by EPR spectroscopy and force field calculations

A new cyclic octapeptide, cyclo(Ile-Ser-(Gly)Thz-Ile-Thr-(Gly)Thz) (PatN), related to patellamide A, has been synthesized and reacted with copper(II) and base to form mono- and dinuclear complexes. The coordination environments around copper(TI) have been characterized by EPR spectroscopy. The solution structure of the thermodynamically most stable product, a purple dicopper(TI) compound, has been examined by simulating weakly dipole-dipole coupled EPR spectra based upon structural parameters obtained from force field (MM and MD) calculations. The MM-EPR method produces a saddle-shaped structure for [Cu-2(PatN)(OH2)(6)] that is similar to the known solution structure of patellamide A and the known solid-state structure of [Cu-2(AscidH(2))CO3(OH2)(2)]. Compared with the latter, [Cu-2(PatN)] has no carbonate bridge and a significantly flatter topology. The MM-EPR approach to solution-structure determination for paramagnetic metallopeptides may find wide applications to other metallopeptides and metalloproteins.

Synthesis of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2), a hydroxo-bridged copper(II) complex of N,N '-dimethyl-1-thia-4,7-diazacyclononane (Me-2[9]aneN(2)S). X-ray structural analysis, magnetic susceptibility, EPR and visible spectroscopy

The bis(mu-hydroxo) complex [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)](PF6)(2) (Me-2[9]aneN(2)S = N,N'-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me-2[9]aneN(2)S)(MeCN)] (PF6) with dioxygen at -78 degrees C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Angstrom, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu ... Cu 2.866(1) Angstrom. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46+/-5 cm(-1), g = 2.01+/-0.01 and theta = -0.58+/-0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g(parallel to) 2.300, g(perpendicular to) 2.063; A(parallel to) 156.2 x 10(-4) cm(-1), A(perpendicular to) 9.0 x 10(-4) cm(-1)) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a sigma(S)-->Cu-II LMCT transition at c. 34000 cm(-1). The single-crystal spectrum of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2) (273 K) reveals d-->d transitions at 14500 and 18300 cm(-1) and a weak pi(S)-->Cu-II charge-transfer band at approximately 25000 cm(-1).