Adsorption of anionic amphiphilic polyelectrolytes onto amino-terminated solid surfaces

The adsorption behavior of several amphiphilic polyelectrolytes of poly(maleic anhydride-alt-styrene) functionalized with naphthyl and phenyl groups, onto amino-terminated silicon wafer has been studied by means of null- ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The maximum of adsorption, Gamma(plateau), varies with the ionic strength, the polyelectrolyte structure and the chain length. Values of Gamma(plateau) obtained at low and high ionic strengths indicate that the adsorption follows the ""screening-reduced adsorption"" regime. Large aggregates were detected in solution by means of dynamic light scattering and fluorescence measurements. However. AFM indicated the formation of smooth layers and the absence of aggregates. A model based on a two-step adsorption behavior was proposed. In the first one, isolated chains in equilibrium with the aggregates in solution adsorbed onto amino-terminated surface. The adsorption is driven by electrostatic interaction between protonated surface and carboxylate groups. This first layer exposes naphtyl or phenyl groups to the solution. The second layer adsorption is now driven by hydrophobic interaction between surface and chains and exposes carboxylate groups to the medium, which repel the forthcoming chain by electrostatic repulsion. Upon drying some hydrophobic naphtyl or phenyl groups might be oriented to the air, as revealed by contact angle measurements. Such amphiphilic polyelectrolyte layers worked well for the building-up of multilayers with chitosan. (C) 2010 Elsevier Ltd. All rights reserved.

Investigating the formation and the properties of monoalkyl carbonates in aqueous medium using capillary electrophoresis with capacitively coupled contactless conductivity detection

Although alkyl carbonic acids (ACAs) and their salts are referred to as instable species in aqueous medium, we demonstrate that a monoalkyl carbonate (MAC) can in fact be easily formed from bicarbonate and an alcohol even in the presence of a high amount of water. A CE system with two capacitively coupled contactless conductivity detectors (C(4)Ds) was used to obtain different parameters about these species and their reactions. Based on the mobilities obtained for a series of alcohols ranging from 1 to 5 carbons, the coefficients of diffusion and the hydrodynamic radii were calculated. When compared with the equivalent carboxylates, MACs have radii systematically smaller. Although the precise pK(a) values of the ACAs could not be obtained, because of the fast decomposition in acid medium, it was possible, for the first time, to show that they are below 4.0. This result suggests that the acidity of an ACA is quite similar to the first hydrogen of H(2)CO(3). Using a new approach to indirectly calibrate the C(4)D, the kinetic constants and the equilibrium constants of formation were also obtained. The results suggest that the increase in the chain length makes the MACs less stable and more inert.

Microwave-Assisted Derivatization of Cellulose in an Ionic Liquid: An Efficient, Expedient Synthesis of Simple and Mixed Carboxylic Esters

Microwave (MW)-assisted cellulose dissolution in ionic liquids (ILs) has routinely led either to incomplete biopolymer solubilization, or its degradation. We show that these problems can be avoided by use of low-energy MW heating, coupled with efficient stirring. Dissolution of microcrystalline cellulose in the IL 1-allyl-3-methylimidazolium chloride has been achieved without changing its degree of polymerization; regenerated cellulose showed pronounced changes in its index of crystallinity, surface area, and morphology. MW-assisted functionalization of MCC by ethanoic, propanoic, butanoic, pentanoic, and hexanoic anhydrides has been studied. Compared with conventional heating, MW irradiation has resulted in considerable decrease in dissolution and reaction times. The value of the degree of substitution (DS) was found to be DS(ethanoate) > DS(propanoate) > DS(butanoate). The values of DS(pentanoate) and DS(hexanoate) were found to be slightly higher than DS(ethanoate). This surprising dependence on the chain length of the acylating agent has been reported before, but not rationalized. On the basis of the rate constants and activation parameters of the hydrolysis of ethanoic, butanoic, and hexanoic anhydrides in aqueous acetonitrile (a model acyl transfer reaction), we suggest that this result may be attributed to the balance between two opposing effects, namely, steric crowding and (cooperative) hydrophobic interactions between the anhydride and the cellulosic surface, whose lipophilicity has increased, due to its partial acylation. Four ethanoate-based mixed esters were synthesized by the reaction with a mixture of the two anhydrides; the ethanoate moiety predominated in all products. The DS is reproducible and the IL is easily recycled. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 134-143, 2010

Electrochemical Behaviour of the AA2024 Aluminium Alloy Modified with Self-Assembled Monolayers/Polyaniline Double Films

The electrochemical characteristics of the AA2024 aluminium alloy modified with octadecyltrimethoxysilane (ODTMS) + polyaniline (PANi) and propiltrimethoxysilane (PTMS) + (PANi) were studied in the present work. The results show that the different protective coatings shift the values of corrosion and pit potentials to more positive values making the system nobler and indicate that the double film ODTMS + PANi present the best protection against corrosion characteristics, that is probably due to the two contributions: anodic protection associated with the barrier effect.

The validity of n-alkanes to estimate intake and digestibility in Nellore beef cattle fed a tropical grass (Brachiaria brizantha cv. Marandu)

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

Effect of vesicles of dimethyldioctadecylammonium chloride and phospholipids on the rate of decarboxylation of 6-nitrobenzisoxazole-3-carboxylate

Sonicated mixtures of dimethyldioctadecylammonium chloride (DODAC), egg phosphatidylcholine (PC), dimyristoyl phosphatidylcholine (DMPC), and dipalmitoyl phosphatidylcholine (DPPC) were used to analyze vesicle effects on the rate of decarboxylation of 6-nitrobenzisoxazol-3-carboxylic acid (Nboc). Electron microscopic images of the vesicles were obtained with trehalose, a know cryoprotector. Phase diagrams and phase transitions temperatures of the vesicle bilayers were determined. Nboc decarboxylation rates increased in the presence of vesicles prepared with both phospholipids and DODAC/phospholipid mixtures. Quantitative analysis of vesicular effects was done using pseudophase models. Phospholipids catalyzed up to 140-fold while the maximum catalysis by DODAC/lipid vesicles reached 800-fold. Acceleration depends on alkyl chain length, fatty acid insaturation of the lipids, and the DODAC/phospholipid molar ratio. Catalysis is not related to the liquid crystalline-gel state of the bilayer and may be related to the relative position of Nboc with respect to the interface.

Structural Changes of Conjugated Pt-Containing Polymetallaynes Exposed to Gamma Ray Radiation Doses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Protocatechuic Acid Alkyl Esters: Hydrophobicity As a Determinant Factor for Inhibition of NADPH Oxidase

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

Bioprospecção química da esponja callyspongia vaginalis (Callyspongiidae)

Recently, marine organisms have attracted attention because of the complexity and potent biological activity from your secondary metabolites. Our planet has 80% it surface covered by oceans and seas, therefore, housing a wide number of different forms of life, among them, the sponges. These sessile and filtrating animals, according to numerous researches, come showing like true chemistry factories. The substances from these animals, sometimes show as news targets to therapeutics agents, and some countries has already use them for treatment of some diseases. Further of the secondary metabolites, the polysaccharides of marine origin also have been target of studies, because the presence of the sulfates groups in its molecules. Polysaccharides with differents biological activities have been related in a large number of researches. Actually, many studies show the sponges as source of promising medicine. These studies inspire new researches, because the few number of sponges species studied until now. Because of that, the present work shows the chemistry prospection of the sponge Callyspongia vaginalis. Chromatographic methods in silica gel allowed the isolations of two secondary metabolites: the known β- sitosterol and a ceramide, no reported in the genus Callyspongia, previously. The analysis of the their lipid extracts show different kinds of fatty acids with a variety of chain length (saponifiable fraction), and others metabolites like Lupenone and stigmasterol, also unprecedented in the genus. The Polysaccharide characterization and the elucidation of the secondary metabolites acquired through of chromatography analysis (CC, molecular exclusion) and spectrometric (NMR 1H and 13C, mass, IR), respectively and comparison with literature data

Structural and functional characteristics of selected soft wheat starches

Starches from eight soft wheat samples (two parent lines and six offspring) were isolated; relationships between their structures and properties were examined. Branch chain-length distributions of amylopectins were determined by using high-performance anion exchange chromatography equipped with an amyloglucosidase reactor and a pulsed amperometric detector (HPAEC-ENZ-PAD). Results showed that the average chain length of the eight samples varied at DP 25.6-26.9. Starch samples of lines 02, 60, 63, 95, and 114 consisted of amylopectins with more long chains (DP greater than or equal to 37) and longer average chain length (DP 26.2-26.9) than that of other samples. These starch samples of longer branch chain length displayed higher gelatinization temperatures (55.3-56.5degreesC) than that of other samples (54.4-54.9degreesC) and higher peak viscosity (110-131 RVU) and lower pasting temperature (86.3-87.6degreesC) than others (83-100 RVU and 88.2-88.9degreesC, respectively). The M-w of amylopectins, determined by using high-performance size exclusion chromatography equipped with multiangle laser-light scattering and refractive index detectors (HPSEC-MALLS-RI), were similar for all samples (6.17 x 10(8) to 6.97 x 10(8)). There were no significant differences in amylose and phosphorus contents between samples. These results indicated that physical properties of wheat starch were affected by the branch-chain length of amylopectin.

Thermotropic phase behavior in aqueous mixtures of dioctadecyldimethylammonium bromide and alkyltrimethylammonium bromide surfactant series studied by differential scanning calorimetry

The effect of the micelle-forming surfactant series alkyltrimethylammonium bromide (C(n)TAB, n = 12, 14, 16 and 18) on the thermotropic phase behavior of dioctadecyldimethylammonium bromide (DODAB) vesicles in water was investigated by differential scanning calorimetry at constant 5.0 mM total surfactant concentration and varying individual surfactant concentrations. The pre-, post- and main transition temperatures (T-s, T-p and T-m), melting enthalpy (Delta H) and peak width of the main transition (Delta T-1/2) are reported as a function of the surfactant molar fraction. No clear dependence of these parameters on the C(n)TAB chain length was found. At 5 mM, neat DODAB in water exhibits two transition temperatures, T-s = 32.1 and T-m = 42.7 degrees C, as obtained from the DSC upscans, but not a clear T-p. For every n, except n = 12, T-s vanishes as CnTAB concentration increases and approaches CMC. T-m behaves differently for different n, the longer C(14)TAB and C(16)TAB decrease, while C(18)TAB increases T-m with increasing concentration. The data indicate that changes in T-m, T-s, T-p and Delta H of the transition are related not only to the extent of C(n)TAB affinity to DODAB but also to the surfactant chain length. Accordingly, C18TAB yields a more compact bilayer, thus increasing T-m, while C(14)TAB and C(1G)TAB yield a less organized bilayer and reduce T-m. C(12)TAB does not much affect T-s and T-m, although it yields T-p approximate to 51.6 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

Motional heterogeneities in siloxane/poly(ethylene glycol) ormolyte nanocomposites studied by C-13 solid-state exchange NMR

C-13 exchange solid-state NMR methods were used to study two families of siloxane/poly-(ethylene glycol) hybrid materials: Types I and II, where the polymer chains interact with the inorganic phase through physical (hydrogen bonds or van der Waals forces) or chemical (covalent bonds) interactions, respectively. These methods were employed to analyze the effects of the interactions between the organic and inorganic phases on the polymer dynamics in the milliseconds to seconds time scale, which occurs at temperatures below the motional narrowing of the NMR line width and around the polymer glass transition. Motional heterogeneities associated with these interactions and evidence of both small and large amplitude motions were directly observed for both types of hybrids. The results revealed that the hindrance to the slow molecular motions of the polymer chains due to the siloxane structures depends on the chain length and the nature of the interaction between the organic and inorganic phases.

Food web structure in a tropical stream ecosystem

This study investigated the structure and properties of a tropical stream food web in a small spatial scale, characterizing its planktonic, epiphytic and benthic compartments. The study was carried out in the Potreirinho Creek, a second-order stream located in the south-east of Brazil. Some attributes of the three subwebs and of the conglomerate food web, composed by the trophic links of the three compartments plus the fish species, were determined. Among compartments, the food webs showed considerable variation in structure. The epiphytic food web was consistently more complex than the planktonic and benthic webs. The values of number of species, number of links and maximum food chain length were significantly higher in the epiphytic compartment than in the other two. Otherwise, the connectance was significantly lower in epiphyton. The significant differences of most food web parameters were determined by the increase in the number of trophic species, represented mainly by basal and intermediate species. High species richness, detritus-based system and high degree of omnivory characterized the stream food web studied. The aquatic macrophytes probably provide a substratum more stable and structurally complex than the sediment. We suggest that the greater species richness and trophic complexity in the epiphytic subweb might be due to the higher degree of habitat complexity supported by macrophyte substrate. Despite differences observed in the structure of the three subwebs, they are highly connected by trophic interactions, mainly by fishes. The high degree of fish omnivory associated with their movements at different spatial scales suggests that these animals have a significant role in the food web dynamic of Potreirinho Creek. This interface between macrophytes and the interconnections resultant from fish foraging, diluted the compartmentalization of the Potreirinho food web.

Kinetics of the reaction of alkylamines with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in organic solvents

The following sequence of substitution reactions was studied spectrophotometrically in organic solvents: RNH2 + TCNQ →-HCN 7-substituted TCNQ →-HCN +RNH2 7.7-disubstituted TCNQ where R = butyl, octyl, dodecyl, and hexadecyl. The production of 7-(alkylamino)-7,7,8-tricyanoquinodimethanes proceeds via the formation of the anion radical of TCNQ (TCNQ-·) whose rate of appearance was found to be a function of the chain length of R, reaching a maximum for octylamine. The formation of TCNQ-· was sensitive to the solvent polarity and electron-donor power and was associated with a small enthalpy and a highly negative entropy of activation. Above a certain [C8H17NH2] the rate of disappearance of TCNQ-· was independent of the amine concentration, and the reaction had a much higher enthalpy and entropy of activation. The occurrence of tautomerism precluded an investigation of the conversion of 7-(octylamino)-7,8,8-tricyanoquinodimethane into 7,7-bis(octylamino)-8,8-dicyanoquinodimethane. A study of the reaction of octylamine with 7-morpholino-7,8,8-tricyanoquinodimethane (which does not exist in tautomeric forms) showed that the second substitution step proceeds with the same mechanism as the first one. The only difference between the two compounds (TCNQ and its monosubstituted morpholino derivative) is one of reactivity. © 1985 American Chemical Society.

Investigation of New Ion Conducting Ormolytes Silica-Polypropyleneglycol

Two groups of hybrid organic-inorganic composites exhibiting ionic conduction properties, so called ORMOLYTES (organically modified electrolytes), have been prepared by the sol-gel process. The first group has been prepared from mixture of a lithium salt and 3-isocyanatopropyltriethoxysilane(IsoTrEOS),O,O′-bis(2-aminopropyl) polypropyleneglycol. These materials produce chemical bonds between the organic (polymer) and the inorganic (silica) phases. The second group has been prepared by an ultrasonic method from a mixture of tetraethoxysilane (TEOS), polypropyleneglycol and a lithium salt. The organic and inorganic phases are not chemically bonded in these samples. The Li+ ionic conductivity, σ, of all these materials has been studied by AC impedance spectroscopy up to 100°C. Values of σ up to 10-6 Ω-1·cm-1 have been found at room temperature. A systematic study of the effects of lithium concentration, polymer chain length and the polymer to silica weight ratio on σ shows that there is a strong dependence of σ on the preparation conditions. The dynamic properties of the Li+ ion and the polymer chains as a function of temperature between -100 and 120°C were studied using 7Li solid-state NMR measurements. The ionic conductivity of both families are compared and particular attention is paid to the nature of the bonds between the organic and inorganic components.