Mixed systems of hydrophobically modified polyelectrolytes: controlling rheology by charge and hydrophobe stoichiometry and interaction strength

Rheology and phase separation were investigated for aqueous mixtures of two oppositely charged hydrophobically modified polyelectrolytes. The typical phase separation, normally seen for oppositely charged polymer mixtures, is dramatically reduced by the presence of hydrophobic modification, and phase separation is only detected close to the point of charge neutralization. While the two polyelectrolytes separately can give high viscosities and a gel-like behavior, a pronounced maximum in viscosity and storage modulus with the mixing ratio of the polyelectrolytes is observed; the maximum is located between the points of charge and hydrophobe stoichiometry and reflects a combination of hydrophobic and electrostatic association. Lowering the charge density of the anionic polymer leads to a strengthened association at first, but at lower charge densities there is a weakened association due to the onset of phase separation. The strength of the electrostatic interaction was modified by adding salt. Increased ionic strength can lead to phase separation and to increased or decreased viscosity depending on the polyelectrolyte mixing ratio.     

Heck reactions in monoglyme and diglyme using BmimCl as pre‐ligand

Heck reactions between iodobenzene and methyl acrylate were carried out in monoglyme and diglyme as solvents, using different ligands and palladium sources, and good to high yields were obtained in the production of (E)‐substituted olefins. The ionic liquid BmimCl was successfully utilized as pre‐ligand to substitute triphenylphosphine. Copyright © 2007 John Wiley & Sons, Ltd.     

Immobilization of Anti-Galectin-3 onto Polysiloxane–Polyvinyl Alcohol Disks for Tumor Prostatic Diseases Diagnosis

This work aimed to immobilize the antibody anti-galectin-3 onto polysiloxane–polyvinyl alcohol (POS-PVA) support, to evaluate its capacity to capture the serum antigen galectin-3 and to quantify by ELISA the antigen levels in sera from patients with prostatic adenocarcinoma (PA) and benign prostatic hyperplasia (BPH) and healthy individuals. Also, for comparative effect, the galectin-3 expression in the prostate tissue through immunohistochemistry was evaluated. The optical density (galectin-3 level) values established for the sera from PA and BPH patients were lower compared with those found for the healthy individuals. Galectin-3 immunohistochemically showed a significant increase and reduction of the cytoplasmatic protein expression in BPH and PA, respectively, compared with the normal prostate. These results showed that POS-PVA disks could be used as solid phase to immobilize serum galectins and in immunoassays procedures for the correspondent IgG anti-galectins detection in human sera.     

Modification of the electrical properties in Fe-Al2O3 granular thin films due to increased bias potential

We studied the electrical properties in Fe-Al₂O₃ granular films when the injected direct current or bias potential are varied in the low-field regime (eΔV?k_BT). Measurements of the electrical resistance as a function of temperature and applied bias at different temperatures were performed. We found that the electrical properties are best described using variable range hopping. The variation in resistance showed unexpected characteristics in distinct regions of potential. These regions of potential could be due to modification of the electronic localization length. We have shown that the electrical resistance decreases when the applied bias and/or current increases. We associate this behavior of the resistance with the activation of new electronic paths. The total resistance of our samples is reduced as additional parallel electronic paths are formed.     

DYNAMICS OF ROTORS IMMERSED IN ECCENTRIC ANNULAR FLOW. PART 2: EXPERIMENTS

In order to validate the theoretical approach described in Part 1, an extensive experimental study has been performed at Instituto Tecnológico e Nuclear (I.T.N.), using a test rig presenting some improvements over previous experiments by the authors. In agreement with the theoretical model, concentric configurations always display flutter instability of the forward mode only, at velocities much higher than the critical unbalance-excited rotor velocity. Also predicted by theory, an instability of the backward mode may occur at much lower spinning velocities, for some eccentric configurations—which is a conclusion of practical significance. Therefore, rotor-annulus eccentricity is a very important parameter, when stability of the system is addressed. The quantitative agreement of both modal frequencies and damping values, with respect to the rotor spinning velocity, is quite satisfactory at lower velocities. However, it deteriorates somewhat at higher velocities, even for concentric configurations. Discrepancies are discussed, in connection with experimental difficulties (some unavoidable three-dimensional flow effects in the test rig) or other possibly pertinent phenomena (dynamic flow nonlinearities)—which were not accounted for in the theoretical model. However, these problems should not be overstressed, as theoretical instability boundaries are usually fairly close to the experimental results.     

On the determination of the Young’s modulus of thin films using indentation tests

The main difficulty with the characterization of thin coatings using depth-sensing indentation tests is related to the determination of the contributions of the substrate and the film to the measured properties. In this study, three-dimensional numerical simulations of the Vickers hardness test are used in order to examine the influence of the elastic and plastic properties of the substrate and the film on the composite’s Young’s modulus results. The hardness of the film is equal to or higher than the substrate hardness. A study of the stress distributions and the indentation geometry of composites, film/substrate, was performed, taking into account the relative mechanical properties of the film and substrate. In addition, stress evolution during indentation was studied, in order to quantify the critical indentation depth under which the substrate is not elastically deformed. The accurate evaluation of the Young’s modulus of the films using weight functions is also examined: some of these have previously been proposed and one was introduced for this study. Two different fitting procedures were used to compare the results obtained from eight fictive film/substrate combinations using six weight functions. The first procedure, commonly used, considers the substrate’s modulus as a known parameter in the fitting process. In the second, the film and the substrate’s modulus are considered as unknown variables that are calculated simultaneously during the fitting process. The validity of the conclusions obtained using the fictive materials was checked by applying the weight functions to four real composites.     

Product ion studies of some novel arylamine adducts of deoxyguanosine by matrix-assisted laser desorption/ionization and post-source decay.

The product ions of the BH(2)(+) ions formed by the glycosidic cleavage of N-(deoxyguanosin-O(6)-yl)-2-methylaniline, 4-(deoxyguanosin-8-yl)-2-methylaniline, and N-(deoxyguanosin-1-yl)-2-methylaniline have been studied using matrix-assisted laser desorption/ionization (MALDI) and post-source decay (PSD) to identify fragment ions and pathways that may be used to differentiate their structures. All three isomers may be distinguished based on their PSD product ion spectra using only femtomole quantities of sample. N-(Deoxyguanosin-O(6)-yl)-2-methylaniline produces product ions at m/z 107 and 134 that are diagnostic for 2-methylaniline attachment to the O(6) position of guanine. The BH(2)(+) ion from 4-(deoxyguanosin-8-yl)-2-methylaniline yields a product ion formed by the consecutive losses of 17 and 42 u neutral fragments that may be regarded as specific for guanine-arylamine adducts that possess two primary amine groups. The BH(2)(+) ion from 4-(deoxyguanosin-8-yl)-2-methylaniline yields no product ions that correlate with specificity for guanine N1 substitution. However, the product ion abundance ratio of the protonated arylamine to that of the ammonia loss ion may be used to differentiate an adduct formed by N1 substitution from other arylamine adducts of guanine studied thus far.     

Enantioselective heterogeneous catalytic production of alpha-amino acids

Summary In the present paper the heterogeneous catalytic preparation of alpha-amino acids by hydrogenation of the dehydroamino acids catalyzed by palladium is described. Enantiomeric excess of up to 26% was achieved when the hydrogenation was carried out in ethanol at 0.5 MPa, 298 K with substrate concentration kept at 80 mmol L^-1, 50 mol% cinchonidine as modified and triethylamine as addictive.</o:p>