Tensid- und Interpolyelektrolytkomplexe semiflexibler Polyelektrolyte

Hochgeladene semiflexible kationische und anionische Polyelektrolyte wurden mit niedermolekularen Tensiden zu Polyelektrolyt-Tensid-Komplexen (PETK) umgesetzt und in organischen Lösungsmitteln mit Streumethoden und Rasterkraftmikroskopie charakterisiert. Die synthetisierten PETK wurden anschließend, mit dem Ziel einer strukturkontrollierten Komplexbildung, für die Bildung von Interpolyelektrolytkomplexen (IPEK) in organischen Lösungsmitteln verwendet und anhand ihres Komplexbildungsverhaltens mit wässrigen Systemen verglichen. Die Umsetzung von zylindrischen Polymerbürsten mit Poly(styrolsulfonat)-, bzw. Poly(2-vinylpyridinium)-Seitenketten mit entgegengesetzt geladenen Tensiden verlief, trotz einer Graftingdichte von eins, quantitativ. Mit Streumethoden konnte gezeigt werden, dass die gebildeten PETK in Lösung als molekulare Zylinder vorliegen. Die Synthese von pUC19-DNA-Tensidkomplexen (DNA-TK), die sich in Alkoholen gut lösen, ist nur in stark basischer Lösung gelungen. Während der Charakterisierung der DNA-TK mit Streumethoden zeigte sich eine starke Abhängigkeit des Trägheitsradius von dem Verhältnis DNA-/Salz+. Die Bildung von IPEK aus hochgeladenen Polyelektrolyt-Bürsten bzw. PETK-Bürsten wurde an verschiedenen Beispielen in Wasser und DMF durchgeführt und mit Streumethoden verfolgt. Alle Systeme zeigten ein zu der IPEK-Bildung von linearen Polyelektrolyten analoges Komplexbildungsverhalten. Bei der Komplexierung von Poly(styrolsulfonat)-Bürsten-Tensidkomplexen mit kommerziellen Polyamidoamin-G5-Dendrimeren (PAMAM) oder Poly(ethylenoxid) modifizierten Poly(ethylenimin)-Bürsten hingegen wurden über den gesamten Gewichtsbruchbereich mit Streumethoden und AFM zylindrische Aggregate gefunden, die den Dimensionen der Poly(styrolsulfonat)-Bürsten-Tensidkomplexe entsprechen. Durch statistische Höhenanalyse der AFM-Bilder wurde ein linearer Zusammenhang zwischen der Komplexhöhe und dem Gewichtsbruch an PAMAM, bzw. PEI-PEO gefunden, der auf die Zunahme der Molmasse der Komplexe durch Wachstum entlang des Zylinderdurchmessers hindeutet. Die Bildung von Aggregaten, mit mehr als einem Polyanion, wurde nicht beobachtet.

Effects of pH and acid concentration on erosive dissolution of enamel, dentine, and compressed hydroxyapatite

The aims of this study were to determine the effects of pH and acid concentration on the dissolution of enamel, dentine, and compressed hydroxyapatite (HA) in citric acid solutions (15.6 and 52.1 mmol l(-1) ; pH 2.45, 3.2, and 3.9), using a pH-stat system. After an initial adjustment period, the dissolution rates of enamel and HA were constant, while that of dentine decreased with time. The dissolution rate increased as the pH decreased, and this was most marked for enamel. To compare substrates, the rate of mineral dissolution was normalized to the area occupied by mineral at the specimen surface. For a given acid concentration, the normalized dissolution rate of HA was always less than that for either dentine or enamel. The dissolution rate for dentine mineral was similar to that for enamel at pH 2.45 and greater at pH 3.2 and pH 3.9. The concentration of acid significantly affected the enamel dissolution rate at pH 2.45 and pH 3.2, but not at pH 3.9, and did not significantly affect the dissolution rates of dentine or HA at any pH. The variation in response of the dissolution rate to acid concentration/buffer capacity with respect to pH and tissue type might complicate attempts to predict erosive potential from solution composition.

Liquid–Vapor Interface of Formic Acid Solutions in Salt Water: A Comparison of Macroscopic Surface Tension and Microscopic in Situ X-ray Photoelectron Spectroscopy Measurements

The liquid–vapor interface is difficult to access experimentally but is of interest from a theoretical and applied point of view and has particular importance in atmospheric aerosol chemistry. Here we examine the liquid–vapor interface for mixtures of water, sodium chloride, and formic acid, an abundant chemical in the atmosphere. We compare the results of surface tension and X-ray photoelectron spectroscopy (XPS) measurements over a wide range of formic acid concentrations. Surface tension measurements provide a macroscopic characterization of solutions ranging from 0 to 3 M sodium chloride and from 0 to over 0.5 mole fraction formic acid. Sodium chloride was found to be a weak salting out agent for formic acid with surface excess depending only slightly on salt concentration. In situ XPS provides a complementary molecular level description about the liquid–vapor interface. XPS measurements over an experimental probe depth of 51 Å gave the C 1s to O 1s ratio for both total oxygen and oxygen from water. XPS also provides detailed electronic structure information that is inaccessible by surface tension. Density functional theory calculations were performed to understand the observed shift in C 1s binding energies to lower values with increasing formic acid concentration. Part of the experimental −0.2 eV shift can be assigned to the solution composition changing from predominantly monomers of formic acid to a combination of monomers and dimers; however, the lack of an appropriate reference to calibrate the absolute BE scale at high formic acid mole fraction complicates the interpretation. Our data are consistent with surface tension measurements yielding a significantly more surface sensitive measurement than XPS due to the relatively weak propensity of formic acid for the interface. A simple model allowed us to replicate the XPS results under the assumption that the surface excess was contained in the top four angstroms of solution.

Geochemistry of DSDP Hole 83-504B minerals

Leg 83 of the Deep Sea Drilling Project has deepened Hole 504B to over 1 km into basement, 1350 m below the seafloor (BSF). The hole previously extended through 274.5 m of sediment and 561.5 m of pillow basalts altered at low temperature (< 100°C), to 836 m BSF. Leg 83 drilling penetrated an additional 10 m of pillows, a 209-m transition zone, and 295 m into a sheeted dike complex. Leg 83 basalts (836-1350 m BSF) generally contain superimposed greenschist and zeolite-facies mineral parageneses. Alteration of pillows and dikes from 836 to 898 m BSF occurred under reducing conditions at low water/rock ratios, and at temperatures probably greater than 100°C. Evolution of fluid composition resulted in the formation of (1) clay minerals, followed by (2) zeolites, anhydrite, and calcite. Alteration of basalts in the transition zone and dike sections (898-1350 m BSF) occurred in three basic stages, defined by the opening of fractures and the formation of characteristic secondary minerals. (1) Chlorite, actinolite, pyrite, albite, sphene, and minor quartz formed in veins and host basalts from partially reacted seawater (Mg-bearing, locally metal-and Si-enriched) at temperatures of at least 200-250°C. (2) Quartz, epidote, and sulfides formed in veins at temperatures of up to 380°C, from more evolved (Mg-depleted, metal-, Si-, and 18O-enriched) fluids. (3) The last stage is characterized by zeolite formation: (a) analcite and stilbite formed locally, possibly at temperatures less than 200°C followed by (b) formation of laumontite, heulàndite, scolecite, calcite, and prehnite from solutions depleted in Mg and enriched in Ca and 18O, at temperatures of up to 250°C. The presence of small amounts of anhydrite locally may be due to ingress of relatively unaltered seawater into the system during Stage 3. Alteration was controlled by the permeability of the crust and is characterized by generally incomplete recrystallization and replacement reactions among secondary minerals. Secondary mineralogy in the host basalts is strongly controlled by primary mineralogy. The alteration of Leg 83 basalts can be interpreted in terms of an evolving hydrothermal system, with (a) changes in solution composition because of reaction of seawater fluids with basalts at high temperatures; (b) variations in permeability caused by several stages of sealing and reopening of cracks; and (c) a general cooling of the system, caused either by the cooling of a magma chamber beneath the spreading center and/or the movement of the crust away from the heat source. The relationship of the high-temperature alteration in the transition zone and dike sections to the low-temperature alteration in the overlying pillow section remains uncertain.

Reversible active switching of the mechanical properties of a peptide film at a fluid-fluid interface

Designer peptides have recently been developed as building blocks for novel self-assembled materials with stimuli-responsive properties. To date, such materials have been based on self-assembly in bulk aqueous solution or at solid-fluid interfaces. We have designed a 21-residue peptide, AM1, as a stimuli-responsive surfactant that switches molecular architectures at a fluid-fluid interface in response to changes in bulk aqueous solution composition. In the presence of divalent zinc at neutral pH, the peptide forms a mechanically strong 'film state'. In the absence of metal ions or at acid pH, the peptide adsorbs to form a mobile 'detergent state'. The two interfacial states can be actively and reversibly switched. Switching between the two states by a change in pH or the addition of a chelating agent leads to rapid emulsion coalescence or foam collapse. This work introduces a new class of surfactants that offer an environmentally friendly approach to control the stability of interfaces in foams, emulsions and fluid-fluid interfaces more generally.

Peptide surfactants (Pepfactants) for switchable foams and emulsions

We have developed a series of sustainable peptide surfactants (Pepfactants) capable of stabilizing foams and emulsions in a stimuli-responsive manner, based on the reversible formation of a mechanically strong interfacial film. Under conditions where the interfacially adsorbed peptide forms a mechanically strong film state, foam or emulsion stabilization occurs as a direct result of the film strength. Under conditions where the interfacially adsorbed peptide forms a mobile detergent state, foam or emulsion stabilization is either reduced, or does not occur. Preformed foams or emulsions stabilized by Pepfactants undergo rapid phase coalescence when the film state is converted to the detergent state. Switching between film and detergent states is readily and reversibly achieved by a change in the bulk solution composition, such as a change in pH, or the addition or sequestering of metal ions. Copyright © 2007 Curtin University of Technology and John Wiley & Sons, Ltd.

Electrical conductivity and mineral composition of the imbibition solution of bean seeds during storage

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

Ni catalyst on mixed support of CeO2-ZrO2 and Al2O3: Effect of composition of CeO2-ZrO2 solid solution on the methane steam reforming reaction

In this study, catalysts containing 5 wt.% Ni deposited on a support composed of a CeO2-ZrO2 solid solution deposited on alumina were tested in the steam reforming of methane. The supports, with various ratios of Ce to Zr, were prepared by co-precipitation of the oxide precursors, followed by calcination in synthetic air. The catalysts were then prepared by Ni impregnation of the supports. The prepared solids were characterized by temperature-programmed reduction with H-2 (TPR-H-2), in situ X-ray diffraction (XRD) and X-ray absorption near-edge structure (XANES) spectroscopy. The XRD analysis confirmed the formation of a solid solution between ZrO2 and CeO2. In the catalytic tests, it was found that catalysts with higher Ce content did not exhibit deactivation during 6 h of reaction. The catalyst with highest Ce content, Ni(0.8Ce0.2Zr)AI, provided the best result, with the highest rate of conversion of methane and the lowest carbon deposition, which may be partly due to the smaller Ni-0 crystallites in this sample and also the segregated CeO2 particles may have favored H2O adsorption which could lead to higher C gasification. (C) 2012 Elsevier B.V. All rights reserved.

Effect of fructans-based fat replacer on chemical composition, starch digestibility and sensory acceptability of corn snacks

To develop a convenience healthy food snack the partially hydrogenated vegetable fat, used as the flavour fixative agent, was replaced by a non-fat-flavouring solution enriched with inulin and oligofructose. The effects of this replacement on chemical composition, in vitro rate of starch digestion and sensory acceptability were assessed. The new snack presented low-fat levels (0.1 per cent) and around a sevenfold increase in dietary fibre (15.3 per cent of dietary fibre, being 13.3 per cent of fructans) when compared with the traditional ones. The enrichment with fructans reduced the predicted Glycaemic Index by 25 per cent, thus indicating that this dietary fibre contributes effectively towards delaying the in vitro glycaemic response. Fructans-enriched snack presented overall acceptability score (6.6 ± 1.7) similar to the traditional one, flavoured with fatty fixative agent (7.4 ± 1.4). The healthy low-fat fibre-enriched snack produced presented the high sensory acceptability typical for this food product type

Composition and orientation effects on the final recrystallization texture of coarse-grained Nb-containing AISI 430 ferritic stainless steels

Composition and orientation effects on the final recrystallization texture of three coarse-grained Nb-containing AISI 430 ferritic stainless steels (FSSs) were investigated. Hot-bands of steels containing distinct amounts of niobium, carbon and nitrogen were annealed at 1250 degrees C for 2h to promote grain growth. In particular, the amounts of Nb in solid solution vary from one grade to another. For purposes of comparison, the texture evolution of a hot-band sheet annealed at 1030 degrees C for 1 min (finer grain structure) was also investigated. Subsequently, the four sheets were cold rolled up to 80% reduction and then annealed at 800 degrees C for 15 min. Texture was determined using X-ray diffraction and electron backscatter diffraction (EBSD). Noticeable differences regarding the final recrystallization texture and microstructure were observed in the four investigated grades. Results suggest that distinct nucleation mechanisms take place within these large grains leading to the development of different final recrystallization textures. (c) 2011 Elsevier B.V. All rights reserved.

Influence of the Solvent Evaporation Rate on the Crystalline Phases of Solution-Cast Poly(Vinylidene Fluoride) Films

The influence of the solvent-evaporation rate on the formation of of. and P crystalline phases in solution-cast poly(vinylidene fluoride) (PVDF) films was systematically investigated. Films were crystallized from PVDF/N,N-dimethylformamide solutions with concentrations of 2.5, 5.0, 10, and 20 wt % at different temperatures. During crystallization, the solvent evaporation rate was monitored in situ by means of a semianalytic balance. With this system, it was possible to determine the evaporation rate for different concentrations and temperatures of the solution under specific ambient conditions (pressure, temperature, and humidity). Fourier-Transform InfraRed spectroscopy with Attenuated Total Reflectance revealed the P-phase content in the PVDF films and its dependence on previous evaporation rates. Based on the relation between the evaporation rate and the PVDF phase composition, a consistent explanation for the different amounts of P phase observed at the upper and lower sample surfaces is achieved. Furthermore, the role of the sample thickness has also been studied. The experimental results show that not only the temperature but also the evaporation rate have to be controlled to obtain the desired crystalline phases in solution-cast PVDF films. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 785-791, 2010

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.

Phenolic composition and antioxidant activity of culms and sugarcane (Saccharum officinarum L.) products

The present work reports amounts of flavonoids and phenylpropanoids of culms of three sugarcane varieties and of raw juice, syrup, molasse and VHP sugar. The antioxidant activity of those materials was evaluated by the DPPH and beta-carotene/linoleic acid methods. The predominant phenolics in culms were phenylpropanoids (caffeic, chlorogenic and coumaric acids), while flavones (apigenin, tricin and luteolin derivatives) appeared in lower amounts. Differences were noted either among phenolic profiles of sugarcane culms or between culms and sugarcane products. The antioxidant activities of solutions from most samples were similar or higher than a 80 mu M Trolox solution. (C) 2010 Elsevier Ltd All rights reserved.

Measurement of grain boundary composition for X52 pipeline steel

Analytical electron microscopy was used to measure the composition of grain boundaries (GBs) and interconstituent boundaries (IBs) of X52 pipeline steel using specimens about 40-60 nm in thickness. All elements of interest were examined with the exception of carbon. With this caveat; there was no segregation at proeutectoid ferrite GBs. This indicated that the commonly expected species S and P are not responsible for preferential corrosion of GBs during intergranular stress corrosion cracking of pipeline steels. Manganese was the only species measured to segregate at the IBs. Manganese segregated to the IBs between proeutectoid ferrite and pearlitic cementite, and desegregated from IBs between proeutectoid ferrite and pearlitic ferrite. The pearlitic cementite was Mn rich. There was no Mn segregation at the IBs between pearlitic ferrite and pearlitic cementite. The pattern of Mn segregation could be explained in terms of diffusion in the process zone ahead of the pearlite during the austenite to pearlite transformation and diffusion in the IBs between the proeutectoid ferrite and pearlite. (C) 1998 Acta Metallurgica Inc. Published by Elsevier Science Ltd. All rights reserved.

Ontological changes in the crystallin composition of the eye lenses of the territorial damselfish Parma microlepis and their possible effects on trace-metal accumulation

The eye lenses of Parma microlepis from the rocky barrens of Sydney (New South Wales, Australia) were found to contain Ba, Hg, Rb, and Sr at concentrations above the quantitative detection limits of solution-based inductively-coupled plasma-mass spectrometry (ICP-MS). Lenses were separated into the hard central nucleus and the softer surrounding cortex. Nuclei contained lower (equal for Ba) concentrations of these metals. Biochemical analysis of the protein composition of these lenses revealed differences in the ratio of gamma-crystallin to beta-crystallin in the lens nucleus and cortex. These changes were shown to be attributable both to protein degradation and changes in protein synthesis as fish age. Such changes may lead to the loss of sequestered metals from older cell layers, or change the affinity of new layers for particular trace metals. Differential binding affinities of these crystallins may, therefore, partially account for trace-metal differences observed in the lens nucleus and cortex.