Dielectric Dispersion of Water in the Frequency Range from 10 mHz to 30 MHz

We investigate the dielectric dispersion of water, specially in the low-frequency range, by using the impedance spectroscopy technique. The frequency dependencies of the real R and imaginary Z parts of the impedance Could not be explained by means of the Usual description of the dielectric properties of the water as all insulating liquid containing ions. This is due to the incomplete knowledge of the parameters entering in the fundamental equations describing the evolution of the system, and oil the mechanisms regulating the exchange of charge of the cell with the external circuit. We propose a simple description of our experimental data based on the model of Debye, by invoking a dc conductivity of the cell, related to the nonblocking character of the electrodes. A discussion on the electric Circuits able to simulate the cell under investigation, based oil bulk and Surface elements, is also reported. We find that the simple circuit formed by a series of two parallels of resistance and capacitance is able to reproduce the experimental data concerning the real and imaginary part of the electrical impedance of the cell for frequency larger than 1 Hz. According to this description, one of the parallels takes into account the electrical properties of interface between the electrode and water, and the other of the bulk. For frequency lower than 1 Hz, a good agreement with the experimental data is obtained by simulating the electrical properties of the interface by means of the constant phase element.

Polarization and Spectral Shift of Benzophenone in Supercritical Water

Monte Carlo simulation and quantum mechanics calculations based on the INDO/CIS and TD-DFT methods were utilized to study the solvatochromic shift of benzophenone when changing the environment from normal water to supercritical (P = 340.2 atm and T = 673 K) condition. Solute polarization increases the dipole moment of benzophenone, compared to gas phase, by 88 and 35% in normal and supercritical conditions, giving the in-solvent dipole value of 5.8 and 4.2 D, respectively. The average number of solute-solvent hydrogen bonds was analyzed, and a large decrease of 2.3 in normal water to only 0.8 in the supercritical environment was found. By using these polarized models of benzophenone in the two different conditions of water, we performed MC simulations to generate statistically uncorrelated configurations of the solute surrounded by the solvent molecules and subsequent quantum mechanics calculations on these configurations. When changing from normal to supercritical water environment, INDO/CIS calculations explicitly considering all valence electrons of the 235 solvent water molecules resulted in a solvatochromic shift of 1425 cm(-1) for the most intense transition of benzophenone, that is, slightly underestimated in comparison with the experimentally inferred result of 1700 cm(-1). TD-B3LYP/6-311+G(2d,p) calculations on the same configurations but with benzophenone electrostatically embedded in the 320 water molecules resulted in a solvatochromic shift of 1715 cm(-1) for this transition, in very good agreement with the experimental result. When using the unpolarized model of the benzophenone, this calculated solvatochromic shift was only 640 cm(-1). Additional calculations were also made by using BHandHLYP/6-311+G(2d,p) to analyze the effect of the asymptotic decay of the exchange functional. This study indicates that, contrary to the general expectation, there is a sizable solute polarization even in the low-density regime of supercritical condition and that the inclusion of this polarization is important for a reliable description of the spectral shifts considered here.

Solvatochromism in Binary Mixtures: First Report on a Solvation Free Energy Relationship between Solvent Exchange Equilibrium Constants and the Properties of the Medium

We have employed UV-vis spectroscopy in order to investigate details of the solvation of six solvatochromic indicators, hereafter designated as ""probes"", namely, 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (RB); 4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB; 2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr,, respectively. These can be divided into three pairs, each includes two probes of similar pK(a) in water and different lipophilicity. Solvation has been studied in binary mixtures, BMs, of water, W, with 12 protic organic solvents, S, including mono- and bifunctional alcohols (2-alkoxyethanoles, unsaturated and chlorinated alcohols). Each medium was treated as a mixture of S, W, and a complex solvent, S-W, formed by hydrogen bonding. Values of lambda(max) (of the probe intramolecular charge transfer) were converted into empirical polarity scales, E(T)(probe) in kcal/mol, whose values were correlated with the effective mole fraction of water in the medium, chi w(effective). This correlation furnished three equilibrium constants for the exchange of solvents in the probe solvation shell; phi(W/S) (W substitutes S): phi(S-W/W) (S-W substitutes W), and phi(S-W/S) (S-W substitutes S), respectively. The values of these constants depend on the physicochemical properties of the probe and the medium. We tested, for the first time, the applicability of a new solvation free energy relationship: phi = constant + a alpha(BM) + b beta(BM) + s(pi*(BM) + d delta) + p log P(BM), where a, b, s, and p are regression coefficients alpha(BM), beta(BM), and pi*(BM) are solvatochromic parameters of the BM, delta is a correction term for pi*, and log P is an empirical scale of lipophilicity. Correlations were carried out with two-, three-, and four-medium descriptors. In all cases, three descriptors gave satisfactory correlations; use of four parameters gave only a marginal increase of the goodness of fit. For phi(W/S), the most important descriptor was found to be the lipophilicity of the medium; for phi(S-W/W) and phi(S-W/S), solvent basicity is either statistically relevant or is the most important descriptor. These responses are different from those of E(T)(probe) of many solvatochromic indicators in pure solvents, where the importance of solvent basicity is usually marginal, and can be neglected.

Nuclear magnetic resonance water relaxation time changes in bananas during ripening: a new mechanism

BACKGROUND: Nuclear magnetic resonance studies of banana fragments during ripening show an increase on the water transverse relaxation time (T(2)) and a decrease in water self-diffusion coefficient (D). As T(2) and D are normally directly correlated, we studied these two properties in intact bananas during ripening, in an attempt to rule out the effect of injury on the apparent discrepancies in the behavior of T(2) and D. RESULTS: The results show that injury in bananas causes a decrease in T(2) of the water in vacuoles (T(2vac)). They also show that T(2vac) increased and D decreased during ripening, ruling out the injury effect. To explain the apparent discrepancies, we propose a new hypothesis for the increase in T(2) values, based on the reduction of Fe(3+) ions to Fe(2+) by galacturonic acid, produced by the hydrolysis of pectin and a decrease in internal oxygen concentration during ripening. CONCLUSION: As injury alters T(2) values it is necessary to use intact bananas to study relaxation times during ripening. The novel interpretation for the increase in T(2vac) based on reduction of Fe(+3) and O(2) concentration is an alternative mechanism to that based on the hydrolysis of starch in amyloplasts. (C) 2010 Society of Chemical Industry

Qualitative spectroscopic characterization of the matrix-silane coupling agent interface across metal fibre reinforced ion exchange resin composite membranes

The characterization of novel metal reinforced electro-dialysis ion exchange membranes, for water desalination, by attenuated total reflectance Fourier transform infrared spectroscopy mapping is presented in this paper. The surface of the porous stainless steel fibre meshes was treated in order to enhance the amount of surface oxide groups and increase the material hydrophilicity. Then, the metal membranes were functionalized through a sol-gel reaction with silane coupling agents to enhance the affinity with the ion exchange resins and avoid premature metal oxidation due to redox reactions at the metal-polymer interface. Polished cross sections of the composite membranes embedded into an epoxy resin revealed interfaces between metallic frameworks and the silane layer at the interface with the ion exchange material. The morphology of the metal-polymer interface was investigated with scanning electron microscopy and Fourier transform infrared micro-spectroscopy. Fourier transform infrared mapping of the interfaces was performed using the attenuated total reflectance mode on the polished cross-sections at the Australian Synchrotron. The nature of the interface between the metal framework and the ion exchange resin was shown to be homogeneous and the coating thickness was found to be around 1 μm determined by Fourier transform infrared micro-spectroscopy mapping. The impact of the coating on the properties of the membranes and their potential for water desalination by electro-dialysis are also discussed.

Investigation of hybrid ion-exchange membranes reinforced with non-woven metal meshes for electro-dialysis applications

Salt and solvent permeations across ion-exchange membranes used in electro-dialysis are directly related to the membrane material structure and chemistry. Although primarily used for aqueous effluents desalination, electro-dialysis was recently shown to be a promising technology for industrial wastewater and co-solvent mixtures purification. The harsh working conditions imposed by these liquid effluents, including high suspended solids, require the development of more chemically and mechanically resistant membranes. In this study, commercial porous stainless steel media filters (240 μm thick) were used as a backbone to prepare hybrid ion-exchange membranes by casting ion-exchange materials within the porous metal structure. The surface of the metal reinforcements was modified by plasma treatment prior to sol-gel silane grafting to improve the interface between the metal and the ion-exchange resins. The morphology of novel hybrid materials and the interface between the metal fibers and the ion-exchange material have been characterized using techniques such as scanning electron microscopy and FTIR mapping. The thickness of the silane coating was found to lie between 1 and 2 μm while water contact angle tests performed on membrane surfaces and corrosion test behaviors revealed the formation of a thin passivating oxide layer on the material surfaces providing anchoring for the silane grafting and adequate surface energy for the proper incorporation of the ion-exchange material. The hybrid membranes desalination performance were then tested in a bench top electro-dialysis cell over a range of flow rate, current densities and salt concentration conditions to evaluate the ability of the novel hybrid materials to desalinate model streams. The performance of the hybrid membranes were benchmarked and critically compared against commercially available membranes (Selemion™). Although the salt transfer kinetics across the hybrid ion-exchange composite membranes were shown to be comparable to that of the commercial membranes, the low porosity of the stainless steel reinforcements, around 60%, was shown to impede absolute salt permeations. The hybrid ion-exchange membranes were however found to be competitive at low current density and low flow velocity desalination conditions.

Investigation of hybrid ion-exchange membranes reinforced with non-woven metal meshes for electro-dialysis applications

Salt and solvent permeations across ion-exchange membranes used in electro-dialysis are directly related to the membrane material structure and chemistry. Although primarily used for aqueous effluents desalination, electro-dialysis was recently shown to be a promising technology for industrial wastewater and co-solvent mixtures purification. The harsh working conditions imposed by these liquid effluents, including high suspended solids, require the development of more chemically and mechanically resistant membranes. In this study, commercial porous stainless steel media filters (240. μm thick) were used as a backbone to prepare hybrid ion-exchange membranes by casting ion-exchange materials within the porous metal structure. The surface of the metal reinforcements was modified by plasma treatment prior to sol-gel silane grafting to improve the interface between the metal and the ion-exchange resins. The morphology of novel hybrid materials and the interface between the metal fibers and the ion-exchange material have been characterized using techniques such as scanning electron microscopy and FTIR mapping. The thickness of the silane coating was found to lie between 1 and 2. μm while water contact angle tests performed on membrane surfaces and corrosion test behaviors revealed the formation of a thin passivating oxide layer on the material surfaces providing anchoring for the silane grafting and adequate surface energy for the proper incorporation of the ion-exchange material. The hybrid membranes desalination performance were then tested in a bench top electro-dialysis cell over a range of flow rate, current densities and salt concentration conditions to evaluate the ability of the novel hybrid materials to desalinate model streams. The performance of the hybrid membranes were benchmarked and critically compared against commercially available membranes (Selemion™). Although the salt transfer kinetics across the hybrid ion-exchange composite membranes were shown to be comparable to that of the commercial membranes, the low porosity of the stainless steel reinforcements, around 60%, was shown to impede absolute salt permeations. The hybrid ion-exchange membranes were however found to be competitive at low current density and low flow velocity desalination conditions.

A modelling study of transient, buoyancy-driven exchange flow over a descending barrier

Results are presented from a series of model studies of the transient exchange flow resulting from the steady descent of an impermeable barrier separating initially-quiescent fresh and saline water bodies having density ρ0 and ρ0 + (Δρ)0, respectively. A set of parametric laboratory experiments has been carried out (i) to determine the characteristic features of the time-dependent exchange flow over the barrier crest and (ii) to quantify the temporal increase in the thickness and spatial extent of the brackish water reservoir formed behind the barrier by the outflowing, partly-mixed saline water. The results of the laboratory experiments have been compared with the predictions of a theoretical model adapted from the steady, so-called maximal exchange flow case and good qualitative agreement between theory and experiment has been demonstrated. The comparisons indicate that head losses of between 7% and 3% are applicable to the flow over the ridge crest in the early and late stages, respectively, of the barrier descent phase, with these losses being attributed to mixing processes associated with the counterflowing layers of fresh and saline water in the vicinity of the ridge crest. The experimental data show (and the theoretical model predictions confirm) that (i) the dimensionless time of detection tdet (g′/Hb)1/2 of the brackish water pool fed by the dense outflow increases (at a given distance from the barrier) with increasing values of the descent rate parameter g'Hb/(dhb/dt)2 and (ii) the normalised thickness δ(x,t)/Hb of the pool at a given reference station increases monotonically with increasing values of the modified time (t - tdet)/(Hb/g′) 1/2, with the rate of thickening decreasing with increasing values of the descent rate parameter g'Hb (dhb/dt)2. Here, g′ = (g/ρ0) (Δρ)0 is the modified gravitational acceleration, Hb is the mean depth of the water and dhb/dt denotes the rate of descent of the barrier height hb with elapsed time t after the two water bodies are first brought into contact. © 2004 Kluwer Academic Publishers.

Facet selectivity in gold binding peptides: exploiting interfacial water structure

Peptide sequences that can discriminate between gold facets under aqueous conditions offer a promising route to control the growth and organisation of biomimetically-synthesised gold nanoparticles. Knowledge of the interplay between sequence, conformations and interfacial properties is essential for predictable manipulation of these biointerfaces, but the structural connections between a given peptide sequence and its binding affinity remain unclear, impeding practical advances in the field. These structural insights, at atomic-scale resolution, are not easily accessed with experimental approaches, but can be delivered via molecular simulation. A current unmet challenge lies in forging links between predicted adsorption free energies derived from enhanced sampling simulations with the conformational ensemble of the peptide and the water structure at the surface. To meet this challenge, here we use an in situ combination of Replica Exchange with Solute Tempering with Metadynamics simulations to predict the adsorption free energy of a gold-binding peptide sequence, AuBP1, at the aqueous Au(111), Au(100)(1 × 1) and Au(100)(5 × 1) interfaces. We find adsorption to the Au(111) surface is stronger than to Au(100), irrespective of the reconstruction status of the latter. Our predicted free energies agree with experiment, and correlate with trends in interfacial water structuring. For gold, surface hydration is predicted as a chief determining factor in peptide-surface recognition. Our findings can be used to suggest how shaped seed-nanocrystals of Au, in partnership with AuBP1, could be used to control AuNP nanoparticle morphology.

Gas exchange rates, plant height, yield components, and productivity of upland rice as affected by plant regulators

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Differential responses between mature and young leaves of sunflower plants to oxidative stress caused by water deficit

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photosynthetic limitations caused by different rates of water-deficit induction in Glycine max and Vigna unguiculata

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Leaf gas exchange and fruit yield in sweet orange trees as affected by citrus variegated chlorosis and environmental conditions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Anodic Stripping Voltammetric Determination of Lead (II) and Cadmium (II) by Using a Carbon Nanotubes Paste Electrode Modified with Ion Exchange Synthetic Resin

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

CO2 assimilation, photosynthetic light response curves, and water relations of 'Pêra' sweet orange plants infected with Xylella fastidiosa

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)