Hydration and anomalous solubility of the Bell-Lavis model as solvent

We address the investigation of the solvation properties of the minimal orientational model for water originally proposed by [Bell and Lavis, J. Phys. A 3, 568 (1970)]. The model presents two liquid phases separated by a critical line. The difference between the two phases is the presence of structure in the liquid of lower density, described through the orientational order of particles. We have considered the effect of a small concentration of inert solute on the solvent thermodynamic phases. Solute stabilizes the structure of solvent by the organization of solvent particles around solute particles at low temperatures. Thus, even at very high densities, the solution presents clusters of structured water particles surrounding solute inert particles, in a region in which pure solvent would be free of structure. Solute intercalates with solvent, a feature which has been suggested by experimental and atomistic simulation data. Examination of solute solubility has yielded a minimum in that property, which may be associated with the minimum found for noble gases. We have obtained a line of minimum solubility (TmS) across the phase diagram, accompanying the line of maximum density. This coincidence is easily explained for noninteracting solute and it is in agreement with earlier results in the literature. We give a simple argument which suggests that interacting solute would dislocate TmS to higher temperatures.

Enzyme Microheterogeneous Hydration and Stabilization in Supercritical Carbon Dioxide

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

Mejillonesite, a new acid sodium, magnesium phosphate mineral, from Mejillones, Antofagasta, Chile

Mejillonesite, ideally NaMg(2)(PO(3)OH)(PO(4))(OH)center dot H(5)O(2), is a new mineral approved by the CNMNC (IMA 2010-068). It occurs as isolated crystal aggregates in thin zones in fine-grained opal-zeolite aggregate on the north slope of Cerro Mejillones, Antofagasta, Chile. Closely associated minerals are bobierrite, opal, clinoptilolite-Na, clinoptilolite-K, and gypsum. Mejillonesite forms orthorhombic, prismatic, and elongated thick tabular crystals up to 6 mm long, usually intergrown in radiating aggregates. The dominant form is pinacoid {100}. Prisms {hk0}, {h0l}, and {0kl} are also observed. The crystals are colorless, their streak is white, and the luster is vitreous. The mineral is transparent. It is non-fluorescent under ultraviolet light. Mohs' hardness is 4, tenacity is brittle. Cleavage is perfect on {100}, good on {010} and {001}, and fracture is stepped. The measured density is 2.36(1) g/cm(3); the calculated density is 2.367 g/cm(3). Mejillonesite is biaxial (-), alpha= 1.507(2), beta= 1.531(2), gamma= 1.531(2), 2V(meas) = 15(10)degrees, 2V(calc) = 0 degrees (589 nm). Orientation is X= a, Z= elongation direction. The mineral is non-pleochroic. Dispersion is r> v, medium. The IR spectrum contains characteristic bands of the Zundel cation (H(5)O(2)(+), or H(+)center dot 2H(2)O) and the groups P-OH and OH(-). The chemical composition is (by EDS, H(2)O by the Alimarin method, wt%): Na(2)O 9.19, MgO 26.82, P(2)O(5) 46.87, H(2)O 19, total 101.88. The empirical formula, based on 11 oxygen atoms, is Na(0.93)Mg(2.08)(PO(3)OH)(1.00) (PO(4)) (OH)(0.86) .0.95H(5)O(2) The strongest eight X-ray powder-diffraction lines [d in angstrom(I)(hkl)] are: 8.095(100)(200), 6.846(9) (210), 6.470(8)(111), 3.317(5)(302), 2.959(5)(132), 2.706(12)(113), 2.157(19)(333), and 2.153(9) (622). The crystal structure was solved on a single crystal (R = 0.055) and gave the following data: orthorhombic, Pbca, a = 16.295(1), b = 13.009(2), c = 8.434(1) angstrom, V= 1787.9(4) angstrom(3), Z = 8. The crystal structure of mejillonesite is based on a sheet (parallel to the b-c plane) formed by two types of MgO(6) octahedra, isolated tetrahedra PO(4) and PO(3)OH whose apical vertices have different orientation with respect to the sheet. The sheets are connected by interlayer, 5-coordinated sodium ions, proton hydration complexes, and hydroxyl groups. The structure of mejillonesite is related to that of angarfite, NaFe(5)(3+)(PO(4))(4)(OH)(4).4H(2)O and bakhchisaraitsevite, Na(2)Mg(5)(PO(4))(4)center dot 7H(2)O.

Characterization and properties of blended cement matrices containing activated bamboo leaf wastes

The worldwide production of bamboo generates large volumes of leaf wastes, which are deposited in landfills or burned in an uncontrolled manner, with negative effects in the environment. The ash obtained by calcining of the bamboo leaf waste, shows good qualities as supplementary cementing material for the production of blended cements. The current paper shows a detailed scientific study of a Brazilian bamboo leaf ash (BLA) calcined at 600 degrees C in small scale condition, by using different techniques (XRF, XRD, SEM/EDX, FT-IR, TG/DTG) and technical study in order. to analyse the behaviour of this ash in blended cements elaborated with 10% and 20% by mass of BLA. The results stated that this ash shows a very high pozzolanic activity, with a reaction rate constant K of the order of 10(-1)/h and type I CSH gel was the main hydrated phase obtained from pozzolanic reaction. The BLA blended cements (10% and 20%) complied with the physical and mechanical requirements of the existing European standards. (c) 2012 Elsevier Ltd. All rights reserved.

PHYSIOLOGICAL QUALITY OF OSMOPRIMED EGGPLANT SEEDS

Eggplant seeds germination can be slow and uneven, justifying the use of pre-germinative treatments to improve the performance of seed lots. One option of treatment is the controlled hydration of seeds by priming. In this way, this study aimed to evaluate the performance of eggplant seeds cv. Embu submitted to different methodologies of priming. The seeds used in the experiment were stored in cold chamber (15 degrees C and 55% RH) in paper bags. The research was carried out at Central Laboratory of Seeds/UFLA. The seeds were submitted to the priming in aerated solutions varying the following factors: temperature (15 degrees C and 25 degrees C), time (24, 48 and 72 hours) and solution (water, PEG, KNO3 and PEG+KNO3). Seeds were washed in running water and dried at 30 degrees C, until the return to the initial moisture content, around 10%. The variables analyzed were percentage of germination, percentage of emergence, speed index of emergence and electrical conductivity. The treatments were arranged in a completely randomized design, according to a factorial arrangement 2x3x4+1 (control - seeds without priming). The results showed that priming improves the vigour of eggplant seeds with no effect on viability; the priming in water or KNO3 is efficient to improve the seed vigour and priming in water or KNO3 may use temperature of 15 degrees C or 25 degrees C for 24, 48 or 72 hours.

Effect of EVA on the fresh properties of cement paste

The improved workability effect of latex in dry mortars has not been fully clarified. The purpose of this research was to investigate the influence cif the EVA copolymer on the cement hydration and on the rheological properties of cement pastes. The results pointed to a minor influence of EVA on cement hydration and to a ball-bearing effect. In fact, the shear thinning behavior of reference paste at 15 min after mixing changed to shear thickening owing to the EVA addition. This behavior could be explained by the decrease in the interparticle separation distance as consequence of the solid content increase in case of shearing detachment of weakly adhered EVA particles from the cement particles surfaces. The expected EVA plasticizing effect was observed at 60 min. Such behavior points to the stabilization of EVA on the cement particles surfaces, thus resulting in a steric barrier effect. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of cations/polycations on the efficiency of formation of a hybrid bilayer membrane that mimics the inner mitochondrial membrane

We aim in this study to characterize the effect of cations and polycations on the formation of hybrid bilayer membranes (HBMs), especially those that mimic the inner mitochondrial membrane (IMM), with a proper composition of phosphatidylcholine (PC), phosphatidylethanolamine (PE) and cardiolipin (CL) adsorbed on an alkanethiol monolayer. HBMs are versatile membrane mimetics that show promising results in sensor technology. Its formation depends on the fusion of vesicles on hydrophobic surfaces, a process that is not well understood at the molecular level. Our results showed to which extend and in which condition the presence of cations and polycations facilitate the formation of HBMs. The required time for lipid layer formation was reduced several times and the lipid layer reaches the expected thickness of 19.5 +/- 1.8 angstrom, in contrast to only 2 +/- 1.5 angstrom usually observed in the absence of cations. In the presence of specific concentrations of spermine and Ca2+ the amount of adsorbed phospholipids on the thiol layer increased nearly 70% compared to that observed when Na+ was used at concentrations 10 times higher. Divalent cations and polycations adsorb specifically on the lipid headgroups destabilizing the hydration forces, facilitating the process of vesicle fusion and formation of lipid monolayers. The concepts and conditions described in the manuscript will certainly help the development of the field of membrane biosensors. (C) 2011 Elsevier B.V. All rights reserved.

Efficacy of Cosmetic Formulations Containing Dispersion of Liposome with Magnesium Ascorbyl Phosphate, Alpha-Lipoic Acid and Kinetin

The present study aimed to evaluate the photoprotective effects of cosmetic formulations containing a dispersion of liposome with magnesium ascorbyl phosphate (MAP), alpha-lipoic acid (ALA) and kinetin, as well as their effects on the hydration and viscoelastic skin properties. The photoprotection was determined in vitro (antioxidant activity) and in vivo on UV-irradiated hairless mouse skin. The hydration effects were performed with the application of the formulations under study on the forearm of human volunteers and skin conditions were analyzed before and after a single application and daily applications during 4 weeks in terms of transepidermal water loss (TEWL), skin moisture and viscoelastic properties. The raw material under study possessed free-radical scavenging activity and the formulation with it protected hairless mouse skin barrier function against UV damage. After 4 weeks of application on human skin, the formulation under study enhanced stratum corneum skin moisture and also showed hydration effects in deeper layers of the skin. Thus, it can be concluded that the cosmetic formulation containing a dispersion of liposome with MAP, ALA and kinetin under study showed photoprotective effects in skin barrier function as well as pronounced hydration effects on human skin, which suggests that this dispersion has potential antiaging effects.

Embryonic development and larval stages of Steindachneridion parahybae (Siluriformes: Pimelodidae) - implications for the conservation and rearing of this endangered Neotropical species

Steindachneridion parahybae is a freshwater catfish endemic to the Paraiba do Sul River and is classified as an endangered Neotropical species. An increasing number of conservation biologists are incorporating morphological and physiological research data to help conservation managers in rescue these endangered species. This study investigated the embryonic and larval development of S. parahybae in captivity, with emphasis in major events during the ontogeny of S. parahybae. Broodstocks were artificially induced to reproduce, and the extrusion occurred 200-255 degree-hours after hormonal induction at 24 degrees C. Larval ontogeny was evaluated every 10 minutes under microscopic/stereomicroscopic using fresh eggs samples. The main embryogenic development stages were identified: zygote, cleavage, including the morula, blastula, gastrula phase, organogenesis, and hatching. The extruded oocytes showed an average diameter of 1.10 +/- 0.10 mm, and after fertilization and hydration of eggs, the average diameter of eggs increased to about 1.90 +/- 0.60 mm, characterized by a large perivitelline space that persisted up to embryo development, the double chorion, and the poles (animal and vegetative). Cell division started about 2 minutes after fertilization (AF), resulting in 2, 4, 8 (4 x 2 arrangement of cells), 16 (4 x 4), 32 (4 x 8) and 64 (2 x 4 x 8) cells. Furthermore, the blastula and gastrula stages followed after these cells divisions. The closed blastopore occurred at 11 h 20 min AF; following the development, the organogenetic stages were identified and subdivided respectively in: early segmentation phase and late segmentation phase. In the early segmentation phase, there was the establishment of the embryonic axis, and it was possible to distinguish between the cephalic and caudal regions; somites, and the optic vesicles developed about 20 h AF. Total hatching occurred at 54 h AF, and the larvae average length was 4.30 +/- 0.70 mm. Gradual yolk sac reduction was observed during the first two days of larval development. The first feeding occurred at the end of the second day. During the larval phase, cannibalism, heterogeneous larval growth and photophobia were also observed. This information will be important in improving the artificial reproduction protocols of S. parahybae in controlled breeding programs.

Interfacial concentrations of chloride and bromide in zwitterionic micelles with opposite dipoles: Experimental determination by chemical trapping and a theoretical description

Interfacial concentrations of chloride and bromide ions, with Li+, Na+, K+, Rb+, Cs+, trimethylammonium (TMA(+)), Ca2+, and Mg2+ as counterions, were determined by chemical trapping in micelles formed by two zwitterionic surfactants, namely N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and hexadecylphosphorylcholine (HDPC) micelles. Appropriate standard curves for the chemical trapping method were obtained by measuring the product yields of chloride and bromide salts with 2,4,6-trimethyl-benzenediazonium (BF4) in the presence of low molecular analogs (N,N,N-trimethyl-propane sulfonate and methyl-phosphorylcholine) of the employed surfactants. The experimentally determined values for the local Br- (Cl-) concentrations were modeled by fully integrated non-linear Poisson Boltzmann equations. The best fits to all experimental data were obtained by considering that ions at the interface are not fixed at an adsorption site but are free to move in the interfacial plane. In addition, the calculation of ion distribution allowed the estimation of the degree of ion coverage by using standard chemical potential differences accounting for ion specificity. (C) 2012 Elsevier Inc. All rights reserved.

Immediate and long-term effects of polysaccharides-based formulations on human skin

A new trend in cosmetic formulations is the use of biotechnological raw materials as the polysaccharides from Klebsiella pneumoniae, which are supposed to enhance cell renewal, improve skin hydration and micro-relief. Botanical extracts of Myrtus communis leaves contain different sugars, which may provide the same benefits. Thus, the objective of this study was to evaluate through objective and subjective analysis the immediate and long-term effects of cosmetic formulations containing polysaccharides biotechnologically-originated and / or the ones contained in Myrtus communis extracts. Three polysaccharide-based and placebo formulations were applied on the forearm skin of 40 volunteers. Skin hydration, transepidermal water loss (TEWL), viscoelasticity and skin micro-relief measurements were made before and 2 hours after a single application and after 15 and 30 day-periods of daily applications. Answers to a questionnaire about perceptions of formulation cosmetic features constituted the subjective analysis. All polysaccharide-based formulations enhanced skin hydration. Formulations with isolated or combined active substances improved skin barrier function as compared to placebo, in the short and long term studies. Formulations containing Myrtus communis extracts had the highest acceptance. Results suggest that daily use of formulations containing these substances is important for protection of the skin barrier function.

Effects of the extraction conditions on the yield and composition of rice bran oil extracted with ethanol-A response surface approach

Rice bran oil was obtained from rice bran by solvent extraction using ethanol. The influence of process variables, solvent hydration (0-24% of water, on mass basis), temperature (60-90 degrees C), solvent-to-rice bran mass ratio (2.5:1 to 4.5:1) and stirrer speed (100-250 rpm) were analysed using the response surface methodology. The extraction yield was highly affected by the solvent water content, and it varied from 8.56 to 20.05 g of oil/100 g of fresh rice bran (or 42.7-99.9% of the total oil available) depending on the experimental conditions. It was observed that oryzanol and tocols behave in different ways during the extraction process. A larger amount of tocols is extracted from the solid matrix in relation to gamma-oryzanol. It was possible to obtain values from 123 to 271 mg of tocols/kg of fresh rice bran and 1527 to 4164 mg of oryzanol/kg of fresh rice bran, indicating that it is feasible to obtain enriched oil when this renewable solvent is used. No differences in the chemical composition of the extracted oils were observed when compared to the data cited in the literature. (C) 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Liquid-liquid equilibria for systems composed of rice bran oil and alcohol-rich solvents: Application to extraction and deacidification of oil

The liquid-liquid equilibria of systems composed of rice bran oil, free fatty acids, ethanol and water were investigated at temperatures ranging from 10 to 60 degrees C. The results of the present study indicated that the mutual solubility of the compounds decreased with an increase in the water content of the solvent and a decrease in the temperature of the solution. The experimental data set was correlated by applying the UNIQUAC model. The average variance between the experimental and calculated compositions was 0.35%, indicating that the model can accurately predict behavior of the compounds at different temperatures and degrees of hydration. The adjustment of interaction parameters enables both the simulation of liquid-liquid extractors for deacidification of vegetable oil and the prediction of phase compositions for the oil and alcohol-rich phases that are generated during cooling of the stream exiting the extractor (when using ethanol as the solvent). (C) 2012 Elsevier Ltd. All rights reserved.

Structure and electronic properties of hydrated mesityl oxide: a sequential quantum mechanics/molecular mechanics approach

The hydration of mesityl oxide (MOx) was investigated through a sequential quantum mechanics/molecular mechanics approach. Emphasis was placed on the analysis of the role played by water in the MOx syn-anti equilibrium and the electronic absorption spectrum. Results for the structure of the MOx-water solution, free energy of solvation and polarization effects are also reported. Our main conclusion was that in gas-phase and in low-polarity solvents, the MOx exists dominantly in syn-form and in aqueous solution in anti-form. This conclusion was supported by Gibbs free energy calculations in gas phase and in-water by quantum mechanical calculations with polarizable continuum model and thermodynamic perturbation theory in Monte Carlo simulations using a polarized MOx model. The consideration of the in-water polarization of the MOx is very important to correctly describe the solute-solvent electrostatic interaction. Our best estimate for the shift of the pi-pi* transition energy of MOx, when it changes from gas-phase to water solvent, shows a red-shift of -2,520 +/- 90 cm(-1), which is only 110 cm(-1) (0.014 eV) below the experimental extrapolation of -2,410 +/- 90 cm(-1). This red-shift of around -2,500 cm(-1) can be divided in two distinct and opposite contributions. One contribution is related to the syn -> anti conformational change leading to a blue-shift of similar to 1,700 cm(-1). Other contribution is the solvent effect on the electronic structure of the MOx leading to a red-shift of around -4,200 cm(-1). Additionally, this red-shift caused by the solvent effect on the electronic structure can by composed by approximately 60 % due to the electrostatic bulk effect, 10 % due to the explicit inclusion of the hydrogen-bonded water molecules and 30 % due to the explicit inclusion of the nearest water molecules.

Structure and anomalous solubility for hard spheres in an associating lattice gas model

In this paper we investigate the solubility of a hard-sphere gas in a solvent modeled as an associating lattice gas. The solution phase diagram for solute at 5% is compared with the phase diagram of the original solute free model. Model properties are investigated both through Monte Carlo simulations and a cluster approximation. The model solubility is computed via simulations and is shown to exhibit a minimum as a function of temperature. The line of minimum solubility (TmS) coincides with the line of maximum density (TMD) for different solvent chemical potentials, in accordance with the literature on continuous realistic models and on the "cavity" picture. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4743635]