The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid

(Figure Presented) Mixed micelles of cetyltrimethylammonium bromide (CTABr) or dodecyltrimethylammonium bromide (DTABr) and the α-nucleophile, lauryl hydroxamic acid (LHA) accelerate dephosphorylation of bis(2,4-dinitrophenyl) phosphate (BDNPP) over the pH range 4-10. With a 0.1 mole fraction of LHA in DTABr or CTABr, dephosphorylation of BDNPP is approximately 10 4-fold faster than its spontaneous hydrolysis, and monoanionic LHA - is the reactive species. The results are consistent with a mechanism involving concurrent nucleophilic attack by hydroxamate ion (i) on the aromatic carbon, giving an intermediate that decomposes to undecylamine and 2,4-dinitrophenol, and (ii) at phosphorus, giving an unstable intermediate that undergoes a Lossen rearrangement yielding a series of derivatives including N,N-dialkylurea, undecylamine, undecyl isocyanate, and carbamyl hydroxamate. © 2009 American Chemical Society.

Chemical and biological characterization of four new linear cationic α-helical peptides from the venoms of two solitary eumenine wasps

Four novel peptides were isolated from the venoms of the solitary eumenine wasps Eumenes rubrofemoratus and Eumenes fraterculus. Their sequences were determined by MALDI-TOF/TOF (matrix assisted laser desorption/ionization time-of-flight mass spectrometry) analysis, Edman degradation and solid-phase synthesis. Two of them, eumenitin-R (LNLKGLIKKVASLLN) and eumenitin-F (LNLKGLFKKVASLLT), are highly homologous to eumenitin, an antimicrobial peptide from a solitary eumenine wasp, whereas the other two, EMP-ER (FDIMGLIKKVAGAL-NH 2) and EMP-EF (FDVMGIIKKIAGAL-NH 2), are similar to eumenine mastoparan-AF (EMP-AF), a mast cell degranulating peptide from a solitary eumenine wasp. These sequences have the characteristic features of linear cationic cytolytic peptides; rich in hydrophobic and basic amino acids with no disulfide bond, and accordingly, they can be predicted to adopt an amphipathic α-helix secondary structure. In fact, the CD (circular dichroism) spectra of these peptides showed significant α-helical conformation content in the presence of TFE (trifluoroethanol), SDS (sodium dodecylsulfate) and asolectin vesicles. In the biological evaluation, all the peptides exhibited a significant broad-spectrum antimicrobial activity, and moderate mast cell degranulation and leishmanicidal activities, but showed virtually no hemolytic activity. © 2011 Elsevier Ltd.

Dinâmica de cátions na raiz e folhas de berinjela cultivada sobre doses crescentes de potássio oriundas de duas fontes

This study was conducted at the Department of Plant Production, Sector Horticulture, UNESP - Botucatu, SP, Brazil, in order to assess the dynamics of cationic nutrients in roots and leaves and effects on dry matter production of roots and shoots in eggplant grown on conditions of increasing doses of potassium from two distinct sources (KCl and K 2SO 4). The experiment was arranged in randomized blocks in factorial 2 × 4 (two sources of potassium, KCl and K 2SO 4 and four doses of each source equivalent, 250, 500, 750 and 1000 kg ha -1 K 2O) comprising eight treatments with three replicates. For the experiment we used Oxisol medium texture (615 g of sand, silt 45 g and 340 g clay per kg soil). The characteristics evaluated were: soil electrical conductivity, mass of shoot and root material, content and ratio of K +, Ca 2+ and Mg 2+ in roots and leaves of eggplant. We conclude that excessive doses of sources of K 2O affected the production of dry matter of roots and shoots, as well as electrical conductivity. The accumulation and the relationship of Ca2+/K+, Mg 2+/K + were affected by increased K + concentration; K 2SO 4 was the fertilizer that was less damaging.

Spatial correlation between the composition of the clay fraction and contents of available phosphorus of an Oxisol at hillslope scale

Relief is regarded as the abiotic factor most strongly influencing pedogenic processes at a local scale. The spatial correlations between the composition of the clay fraction (iron - Fe and aluminum - Al oxides, kaolinite and organic matter - OM) and contents of available phosphorus (P) of an Oxisol were evaluated at hillslope scale under sugarcane cultivation. A total of 119 samples were collected at intersection points on a 100. ×. 100. m georeferenced grid of regularly spaced points 10. m apart in the 0.2-0.4. m depth in an area consisting of two landform components namely: component I (an area with a linear hillslope curvature), and component II (one with a concave-convex hillslope curvature). Soil OM and available P contents were subjected to descriptive statistics and geostatistical analyses in order to assess their variability and spatial dependence. All attributes studied were spatially dependent. Available phosphorus had positive spatial correlation with high crystalline goethite, hematite and gibbsite. Identifying small hillslope curvatures is useful with a view to better understanding their relationships with soil organic matter and available phosphorus, as well as kaolinite and Fe and Al oxide attributes. A simple correlation analysis by itself is inadequate to relate attributes, which requires a supplemental, geostatistical technique. © 2012 Elsevier B.V..

Thermal stability of ionene polymers

Two different cationic polymers of the same chemical type and with very similar chemical structures were reacted with a natural bentonite over a wide range of polymer/clay ratios. This study involved the synthesis of cationic aliphatic ammonium polyionenes, specifically 3,6-ionene and 3,6-dodecylionene. Ionenes are ion-containing polymers that contain quaternary nitrogen atoms in the main macromolecular chain as opposed to a pendant chain. The CHN content, basal spacing, and elemental composition of each of the polymer-clay complexes were analyzed by X-ray diffraction, X-ray fluorescence, and thermogravimetry. All the polycations reacted to form interlayer complexes with clay, which displaced more Na+ and little Ca2+. Sodium and calcium were both present as interlayer cations in the clay and its complexes. The TG/DTG curves show that both polymers underwent thermal degradation in more than one stage. Specifically, 3,6-ionene was found to undergo two stages of decomposition and 3,6-dodecylionene undergo three stages. The behavior of the TG/DTG curves and the activation energy values suggest that 3,6-dodecylionene (E = 174,85 kJ mol-1) complexes have greater thermal stability than 3,6-ionene (E = 115,52 kJ mol-1) complexes. The mechanism of degradation suggests a direct interaction with the dodecyl chain containing 12 carbons, which are present in 3,6-dodecylionene but not in 3,6-ionene. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Enhanced bulk and superficial hydrophobicities of starch-based bionanocomposites by addition of clay

In this work, thermoplastic starch (TPS)-clay bionanocomposites were obtained by an innovative methodology using a combination of methodologies commonly used in the composites and nanocomposites preparations. The main objectives or novelties were to confirm efficiency of the processing methodology by field emission gun scanning electron microscopy and investigate the effect of clay content on the spectroscopic, bulk and surface hydrophilic/hydrophobic properties of these bionanocomposites. Raman and FTIR spectroscopies confirmed the changes in the spectroscopic properties of the TPS bionanocomposites with the addition of the clay materials. Water absorption and contact angle measurements were also used to analyze the effect of the clay content on the hydrophilic properties of the TPS bionanocomposites. The results also showed that the addition of the cloisite-Na+ clay increased the bulk and surface hydrophobicities of the TPS matrix, which may increase its industrial application, particularly in manufacturing of food containers. © 2013 Elsevier B.V.

O uso de bambu e metal clay no design de jóias de arte

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Alterações de propriedades físicas e químicas e das frações húmicas de um nitossolo vermelho na sucessão milheto-soja em semeadura direta

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo de um depósito de argila ball clay de Tambaú (SP), para aplicação na indústria cerâmica de revestimentos

Pós-graduação em Geologia Regional - IGCE

Polymer-clay nanocomposites thermal stability: experimental evidence of the radical trapping effect

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

Clay mineralogy and magnetic susceptibility of Oxisols in geomorphic surfaces

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

Characterization of Rhinodrilus alatus hemoglobin (HbRa) and its subunits: Evidence for strong interaction with cationic surfactants DTAB and CTAC

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Outlining precision boundaries among areas with different variability standards using magnetic susceptibility and geomorphic surfaces

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

Nanocomposites based on LbL films of polyaniline and sodium montmorillonite clay

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synergy between polyaniline and OMt clay mineral in Langmuir-Blodgett films for the simultaneous detection of traces of metal ions

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