Acidez Potencial Estimada pelo Método do pH SMP em Solos do Estado da Paraíba

O método do pH SMP, em virtude de sua praticidade analítica, tem sido amplamente utilizado na estimativa da acidez potencial (H+Al), em substituição à solução de acetato de cálcio 0,5 mol L-1 a pH 7,0, em laboratórios de análise de solo no Brasil. No entanto, tornam-se imprescindíveis estudos regionalizados para estimar com segurança os valores da acidez potencial. Este trabalho objetivou ajustar uma equação de regressão com boa capacidade preditiva dos valores de H+Al, a partir da medida do pH(SMP), para solos do Estado da Paraíba, visando sua utilização em análises de rotina para estimar a acidez potencial. Foram utilizadas 90 amostras de solo coletadas nas várias regiões do Estado. Essas amostras foram analisadas para pH(H2O), pH(SMP), H+Al e pH do sobrenadante da solução de acetato de cálcio. Foram observadas estreitas correlações quadrática simples do pH de equilíbrio da suspensão de acetato de cálcio com a acidez potencial e linear simples com o pH(SMP), com elevada capacidade preditiva (R2 = 0,93 e R2 = 0,95, respectivamente). Os resultados permitiram concluir que a acidez potencial (H+Al), expressa em cmolc dm-3 pode ser estimada pelo método do pH(SMP), por meio da equação H+Al = 57,108 -13,338** SMP + 0,7637** SMP2 (R2 = 0,87).

Spin-glass behaviour in mixed metal oxides with a rutile-type structure

We report here on the magnetic properties of compounds of composition Fe1−xCrxSbO4 and Fe1−xGaxSbO4. The introduction of paramagnetic Cr3+ and diamagnetic Ga3+ into the rutile‐related iron antimonate lattice does not destroy the antisite atomic ordering which exists in iron antimonate of composition FeSbO4. The initial slope of the Curie temperature dependence on x is similar in both series, indicating that Fe3+‐Cr3+ interactions are very small. The magnetic susceptibility measurements recorded from the compounds of composition Fe1−xCrxSbO4, x<0.4, and Fe0.9Ga0.1SbO4 show them to behave as spin glasses at low temperatures. The inhibition of compounds of the type Fe1−xCrxSbO4, x>0.4, and Fe1−xGaxSbO4, x>0.1 to undergo a spin‐glass transition above 4.2 K is associated with a dilution effect.

Asymmetric Little spin-Glass model

We study the static properties of the Little model with asymmetric couplings. We show that the thermodynamics of this model coincides with that of the Sherrington-Kirkpatrick model, and we compute the main finite-size corrections to the difference of the free energy between these two models and to some clarifying order parameters. Our results agree with numerical simulations. Numerical results are presented for the symmetric Little model, which show that the same conclusions are also valid in this case.

Evidence of aging in spin glass mean-field models

We study numerically the out-of-equilibrium dynamics of the hypercubic cell spin glass in high dimensionalities. We obtain evidence of aging effects qualitatively similar both to experiments and to simulations of low-dimensional models. This suggests that the Sherrington-Kirkpatrick model as well as other mean-field finite connectivity lattices can be used to study these effects analytically.

In vitro antitumor activity of methotrexate via pH-sensitive chitosan nanoparticles

Nanoparticles with pH-sensitive behavior may enhance the success of chemotherapy in many cancers by efficient intracellular drug delivery. Here, we investigated the effect of a bioactive surfactant with pH-sensitive properties on the antitumor activity and intracellular behavior of methotrexate-loaded chitosan nanoparticles (MTX-CS-NPs). NPs were prepared using a modified ionotropic complexation process, in which was included the surfactant derived from Nα,Nε-dioctanoyl lysine with an inorganic lithium counterion. The pH-sensitive behavior of NPs allowed accelerated release of MTX in an acidic medium, as well as membrane-lytic pH-dependent activity, which facilitated the cytosolic delivery of endocytosed materials. Moreover, our results clearly proved that MTX-CSNPs were more active against the tumor HeLa and MCF-7 cell lines than the free drug. The feasibilty of using NPs to target acidic tumor extracellular pH was also shown, as cytotoxicity against cancer cells was greater in a mildly acidic environment. Finally, the combined physicochemical and pH-sensitive properties of NPs generally allowed the entrapped drug to induce greater cell cycle arrest and apoptotic effects. Therefore, our overall results suggest that pH-sensitive MTX-CS-NPs could be potentially useful as a carrier system for tumor and intracellular drug delivery in cancer therapy.

Membrane-destabilizing activity of pH-responsive cationic lysine-based surfactants: role of charge position and alkyl chain length

Many strategies for treating diseases require the delivery of drugs into the cell cytoplasm following internalization within endosomal vesicles. Thus, compounds triggered by low pH to disrupt membranes and release endosomal contents into the cytosol are of particular interest. Here, we report novel cationic lysine-based surfactants (hydrochloride salts of N¿- and N¿-acyl lysine methyl ester) that differ in the position of the positive charge and the length of the alkyl chain. Amino acid-based surfactants could be promising novel biomaterials in drug delivery systems, given their biocompatible properties and low cytotoxic potential. We examined their ability to disrupt the cell membrane in a range of pH values, concentrations and incubation times, using a standard hemolysis assay as a model of endosomal membranes. Furthermore, we addressed the mechanism of surfactant-mediated membrane destabilization, including the effects of each surfactant on erythrocyte morphology as a function of pH. We found that only surfactants with the positive charge on the ¿-amino group of lysine showed pH-sensitive hemolytic activity and improved kinetics within the endosomal pH range, indicating that the positive charge position is critical for pH-responsive behavior. Moreover, our results showed that an increase in the alkyl chain length from 14 to 16 carbon atoms was associated with a lower ability to disrupt cell membranes. Knowledge on modulating surfactant-lipid bilayer interactions may help us to develop more efficient biocompatible amino acid-based drug delivery devices.

pH Sensitive surfactants from lysine: assessment of their cytotoxicity and environmental behavior

The toxicity and environmental behavior of new pH-sensitive surfactants from lysine are presented. Three different chemical structures are studied: surfactants with one amino acid and one alkyl chain, surfactants with two amino acids on the polar head and one alkyl chain, and gemini surfactants. The pH sensitivity of these compounds can be tuned by modifying their chemical structures. Cytotoxicity has been evaluated using erythrocytes and fibroblast cells. The toxic effects against these cells depend on the hydrophobicity of the molecules as well as their cationic charge density. The effect of hydrophobicity and cationic charge density on toxicity is different for each type of cells. For erythrocytes, the toxicity increases as hydrophobicity and charge density increases. Nevertheless, for fibroblasts cationic charge density affects cytotoxicity in the opposite way: the higher charge density, the lower the toxicity. The effect of the pH on hemolysis has been evaluated in detail. The aquatic toxicity was established using Daphnia magna. All surfactants yielded EC50 values considerably higher than that reported for cationic surfactants based on quaternary ammonium groups. Finally, their biodegradability was evaluated using the CO2 headspace test (ISO 14593). These lysine derivatives showed high levels of biodegradation under aerobic conditions and can be classified as"readily biodegradable compounds".

Boron Leaching Decreases withIncreases on Soil pH

ABSTRACT Management of boron fertilization depends on the magnitude of B leaching in the soil profile, which varies proportionally with the concentration of B in the soil solution, which, in turn, decreases as the soil pH increases due to the higher sorption of B on soil solid surfaces. The objective of this study was to quantify the effect of liming and rates of B applied to the soil on B leaching. The experiment was carried out in the laboratory in 2012, and treatments consisted of a factorial combination of two rates of liming (without and with lime to raise the soil pH to 6.0) and five rates of B (0, 10, 20, 50 and 100 mg kg-1, as boric acid). A Typic Rhodudalf was used, containing 790 g kg-1 clay and 23 g kg-1 organic matter; the pH(H2O) was 4.6. Experimental units were composed of PVC leaching columns (0.10 m in diameter) containing 1.42 kg of soil (dry base). Boron was manually mixed with the top 0.15 m of the soil. After that, every seven days for 15 weeks, 300 mL of distilled water were added to the top of each column. In the percolated solution, both the volume and concentration of B were measured. Leaching of B decreased with increased soil pH and, averaged across the B rates applied, was 58 % higher from unlimed (pH 4.6) than from limed (pH 6.6) samples as a result of the increase in B sorption with higher soil pH. In spite of its high vertical mobility, the residual effect of B was high in this oxisol, mainly in the limed samples where 80 % of B applied at the two highest rates remained in the soil, even after 15 water percolations. Total recovery of applied B, including leached B plus B extracted from the soil after all percolations, was less than 50 %, showing that not all sorbed B was quantified by the hot water extraction method.