Nickel adsorption in two Oxisols and an Alfisol as affected by pH, nature of the electrolyte, and ionic strength of soil solution

Background, aim, and scope The retention of potentially toxic metals in highly weathered soils can follow different pathways that variably affect their mobility and availability in the soil-water-plant system. This study aimed to evaluate the effects of pH, nature of electrolyte, and ionic strength of the solution on nickel (Ni) adsorption by two acric Oxisols and a less weathered Alfisol. Materials and methods The effect of pH on Ni adsorption was evaluated in surface and subsurface samples from a clayey textured Anionic `Rhodic` Acrudox ( RA), a sandy-clayey textured Anionic `Xantic` Acrudox (XA), and a heavy clayey textured Rhodic Kandiudalf (RK). All soil samples were equilibrated with the same concentration of Ni solution (5.0 mg L(-1)) and two electrolyte solutions (CaCl(2) or NaCl) with different ionic strengths (IS) (1.0, 0.1 and 0.01 mol L(-1)). The pH of each sample set varied from 3 to 10 in order to obtain sorption envelopes. Results and discussion Ni adsorption increased as the pH increased, reaching its maximum of nearly pH 6. The adsorption was highest in Alfisol, followed by RA and XA. Competition between Ni(2+) and Ca(2+) was higher than that between Ni(2+) and Na(+) in all soil samples, as shown by the higher percentage of Ni adsorption at pH 5. At pH values below the intersection point of the three ionic strength curves (zero point of salt effect), Ni adsorption was generally higher in the more concentrated solution (highest IS), probably due to the neutralization of positive charges of soil colloids by Cl(-) ions and consequent adsorption of Ni(2+). Above this point, Ni adsorption was higher in the more diluted solution (lowest ionic strength), due to the higher negative potential at the colloid surfaces and the lower ionic competition for exchange sites in soil colloids. Conclusions The effect of ionic strength was lower in the Oxisols than in the Alfisol. The main mechanism that controlled Ni adsorption in the soils was the ionic exchange, since the adsorption of ionic species varied according to the variation of pH values. The ionic competition revealed the importance of electrolyte composition and ionic strength on Ni adsorption in soils from the humid tropics. Recommendations and perspectives The presence of NaCl or CaCl(2) in different ionic strengths affects the availability of heavy metals in contaminated soils. Therefore, the study of heavy metal dynamics in highly weathered soils must consider this behavior, especially in soils with large amounts of acric components.

Platinum nanoparticle-modified electrodes, morphologic, and electrochemical studies concerning electroactive materials deposition

The present work describes the synthesis of platinum nanoparticles followed by their electrophoretic deposition onto transparent fluorine-doped tin oxide electrodes. The nano-Pt-modified electrodes were characterized by voltammetric studies in acidic solutions showing a great electrocatalytic behavior towards H(+) reduction being very interesting for fuel cell applications. Morphological characterization was performed by atomic force microscopy on different modified electrodes showing a very rough surface which can be tuned by means of time of deposition. Also, nickel hydroxide thin films were galvanostatically grown onto these electrodes showing an interesting electrochemical behavior as sharper peaks, indicating a faster ionic exchange from the electrolyte to the film.

Tailored Media for Homogeneous Cellulose Chemistry: Ionic Liquid/Co-Solvent Mixtures

Co-solvents can minimize two of the major problems associated with the use of ionic liquids (ILs) as solvents for homogeneous derivatization of cellulose: high viscosity and limited miscibility with non-polar reagents or reaction products. Thus, the effects of 18 solvents and 3 binary solvent mixtures on cellulose solutions in three ILs were systematically studied with respect to the solution phase behavior. The applicable limits of these mixtures were evaluated and general guidelines for the use of co-solvents in cellulose chemistry could be advanced: Appropriate co-solvents should have EN T values (normalized empirical polarity) > 0.3, very low ``acidity`` (alpha < 0.5), and relatively high ""basicity`` (beta >= 0.4). Moreover, novel promising co-solvents and binary co-solvent mixtures were identified.

Adsorption of amyloglucosidase from Aspergillus niger NRRL 3122 using ion exchange resin

Amyloglucosidase enzyme was produced by Aspergillus niger NRRL 3122 from solid-state fermentation, using deffated rice bran as substrate. The effects of process parameters (pH, temperature) in the equilibrium partition coefficient for the system amyloglucosidase - resin DEAE-cellulose were investigated, aiming at obtaining the optimum conditions for a subsequent purification process. The highest partition coefficients were obtained using 0.025M Tris-HCl buffer, pH 8.0 and 25ºC. The conditions that supplied the highest partition coefficient were specified, the isotherm that better described the amyloglucosidase process of adsorption obtained. It was observed that the adsorption could be well described by Langmuir equation and the values of Qm and Kd estimated at 133.0 U mL-1 and 15.4 U mL-1, respectively. From the adjustment of the kinetic curves using the fourth-order Runge-Kutta algorithm, the adsorption (k1) and desorption (k2) constants were obtained through optimization by the least square procedure, and the values calculated were 2.4x10-3 mL U-1 min-1 for k1 and 0.037 min-1 for k2 .

Catalytic enantioselective arylations: boron to zinc exchange as a powerful tool for the generation of transferable aryl groups

The transmetalation between boron and zinc is of great importance for application in organic synthesis, since it allows the formation of new carbon-carbon bonds between organometallic units and electrophiles. The direct arylation of aldehydes or more scarcely ketones, in a catalytic, enantioselective manner using chiral catalysts has been described recently. The enantiomerically enriched diarylmethanols obtained in these reactions are valuable precursors for important bioactive molecules. This review provides a synopsis of this ever-growing field and highlights some of the challenges that still remain.

A concise enantioselective synthesis of (+)-endo-brevicomin accomplished by a tellurium/metal exchange reaction

A homoenolate generated by tellurium/lithium exchange reaction was employed in a straightforward enantioselective synthesis of (+)-endo-brevicomin in 70% yield and 84.4% e.e.

Synthesis of diaryl selenides using electrophilic selenium species and nucleophilic boron reagents in ionic liquids

We described herein the use of imidazolium ionic liquids [bmim]PF(6) and [bmim]BF(4) in the selective, metal and catalyst-free synthesis of unsymmetrical diaryl selenides by electrophilic substitution in arylboron reagents with arylselenium halides (Cl and Br) at room temperature. This is a general substitution reaction and it was performed with arylboronic acids or potassium aryltrifluoroborates bearing electron-withdrawing or electron-donating groups, affording the corresponding diaryl selenides in good to excellent yields. The ionic liquid [bmim][PF(6)] was easily recovered and utilized for further substitution reactions.

Ionic and Histological Studies of Salivary Glands in Rats with Diabetes and Their Glycemic State After Laser Irradiation

Objectives: To evaluate the effect of laser irradiation (LI) on the glycemic state and the histological and ionic parameters of the parotid and submandibular glands in rats with diabetes. Methods: One hundred twenty female rats were divided into eight groups. Diabetes was induced by administration of streptozotocin and confirmed later according to results of glycemia testing. Twenty-nine days after the induction, the parotid and submandibular glands of the rats were irradiated with 5, 10, and 20 J/cm(2) using a laser diode (660nm/100mW) (without diabetes: C5, C10, and C20; with diabetes: D5, D10, and D20, respectively). On the following day, the rats were euthanized, and blood glucose determined. Histological and ionic analyses were performed. Results: Rats with diabetes without irradiation (D0) showed lipid droples accumulation in the parotid gland, but accumulation decreased after 5, 10, and 20 J/cm(2) of laser irradiation. A decrease in fasting glycemia level from 358.97 +/- 56.70 to 278.33 +/- 87.98mg/dL for D5 and from 409.50 +/- 124.41 to 231.80 +/- 120.18 mg/dL for D20 (p < 0.05) was also observed. Conclusion: LI should be explored as an auxiliary therapy for control of complications of diabetes because it can alter the carbohydrate and lipid metabolism of rats with diabetes.

AFFINE INTERVAL EXCHANGE TRANSFORMATIONS WITH FLIPS AND WANDERING INTERVALS

There exist uniquely ergodic affine interval exchange transformations of [0,1] with flips which have wandering intervals and are such that the support of the invariant measure is a Cantor set.

Phase transitions and spatially ordered counterion association in ionic-lipid membranes: A statistical model

We propose a statistical model to account for the gel-fluid anomalous phase transitions in charged bilayer- or lamellae-forming ionic lipids. The model Hamiltonian comprises effective attractive interactions to describe neutral-lipid membranes as well as the effect of electrostatic repulsions of the discrete ionic charges on the lipid headgroups. The latter can be counterion dissociated (charged) or counterion associated (neutral), while the lipid acyl chains may be in gel (low-temperature or high-lateral-pressure) or fluid (high-temperature or low-lateral-pressure) states. The system is modeled as a lattice gas with two distinct particle types-each one associated, respectively, with the polar-headgroup and the acyl-chain states-which can be mapped onto an Ashkin-Teller model with the inclusion of cubic terms. The model displays a rich thermodynamic behavior in terms of the chemical potential of counterions (related to added salt concentration) and lateral pressure. In particular, we show the existence of semidissociated thermodynamic phases related to the onset of charge order in the system. This type of order stems from spatially ordered counterion association to the lipid headgroups, in which charged and neutral lipids alternate in a checkerboard-like order. Within the mean-field approximation, we predict that the acyl-chain order-disorder transition is discontinuous, with the first-order line ending at a critical point, as in the neutral case. Moreover, the charge order gives rise to continuous transitions, with the associated second-order lines joining the aforementioned first-order line at critical end points. We explore the thermodynamic behavior of some physical quantities, like the specific heat at constant lateral pressure and the degree of ionization, associated with the fraction of charged lipid headgroups.

Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles

This work describes an easy synthesis (one pot) of MFe(2)O(4) (M = Co, Fe, Mn, and Ni) magnetic nanoparticles MNPs by the thermal decomposition of Fe(Acac)(3)/M(Acac)(2) by using BMI center dot NTf(2) (1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) or BMI center dot PF(6) (1-n-butyl-3-methylimidazolium hexafluorophosphate) ionic liquids (ILs) as recycling solvents and oleylamine as the reducing and surface modifier agent. The effects of reaction temperature and reaction time on the features of the magnetic nanomaterials (size and magnetic properties) were investigated. The growth of the MNPs is easily controlled in the IL by adjusting the reaction temperature and time, as inferred from Fe(3)O(4) MNPs obtained at 150 degrees C, 200 degrees C and 250 degrees C with mean diameters of 8, 10 and 15 nm, respectively. However, the thermal decomposition of Fe(Acac)(3) performed in a conventional high boiling point solvent (diphenyl ether, bp 259 degrees C), under a similar Fe to oleylamine molar ratio used in the IL synthesis, does not follow the same growth mechanism and rendered only smaller NPs of 5 nm mean diameter. All MNPs are covered by at least one monolayer of oleylamine making them readily dispersible in non-polar solvents. Besides the influence on the nanoparticles growth, which is important for the preparation of highly crystalline MNPs, the IL was easily recycled and has been used in at least 20 successive syntheses.

DNA-based ionic conducting membranes

Deoxyribonucleic acid based gel solid electrolytes were prepared and their electric properties were characterized. Their ionic conductivity is in the range of 10(-4)-10(-5) S/cm at room temperature and increases linearly in function of temperature, obeying an Arrhenius-like relationship. The present study, combined with the literature data, suggests that the electrical conduction mechanism in these membranes involve ion motion and/or charge hopping, promoted most likely by a significant interaction between the membrane components. The good conductivity results, as found here, together with the good transparency and good adhesion to the electrodes show that the DNA-based gel polymer electrolytes are very promising materials for application in various electrochromic devices. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3610951]

Lower Bounds on the Exchange-Correlation Energy in Reduced Dimensions

Bounds on the exchange-correlation energy of many-electron systems are derived and tested. By using universal scaling properties of the electron-electron interaction, we obtain the exponent of the bounds in three, two, one, and quasione dimensions. From the properties of the electron gas in the dilute regime, the tightest estimate to date is given for the numerical prefactor of the bound, which is crucial in practical applications. Numerical tests on various low-dimensional systems are in line with the bounds obtained and give evidence of an interesting dimensional crossover between two and one dimensions.

Physical signatures of discontinuities of the time-dependent exchange-correlation potential

The exact exchange-correlation (XC) potential in time-dependent density-functional theory (TDDFT) is known to develop steps and discontinuities upon change of the particle number in spatially confined regions or isolated subsystems. We demonstrate that the self-interaction corrected adiabatic local-density approximation for the XC potential has this property, using the example of electron loss of a model quantum well system. We then study the influence of the XC potential discontinuity in a real-time simulation of a dissociation process of an asymmetric double quantum well system, and show that it dramatically affects the population of the resulting isolated single quantum wells. This indicates the importance of a proper account of the discontinuities in TDDFT descriptions of ionization, dissociation or charge transfer processes.

Contribution of the second Landau level to the exchange energy of the three-dimensional electron gas in a high magnetic field

We derive a closed analytical expression for the exchange energy of the three-dimensional interacting electron gas in strong magnetic fields, which goes beyond the quantum limit (L=0) by explicitly including the effect of the second, L=1, Landau level and arbitrary spin polarization. The inclusion of the L=1 level brings the fields to which the formula applies closer to the laboratory range, as compared to previous expressions, valid only for L=0 and complete spin polarization. We identify and explain two distinct regimes separated by a critical density n(c). Below n(c), the per particle exchange energy is lowered by the contribution of L=1, whereas above n(c) it is increased. As special cases of our general equation we recover various known more limited results for higher fields, and we identify and correct a few inconsistencies in some of these earlier expressions.