MoO2Cl2] as catalyst for hydrosilylation of aldehydes and ketones

The high valent molybdenum-dioxo complex [MoO2Cl2] catalyzes the addition of dimethylphenylsilane to aldehydes and ketones to afford the corresponding dimethylphenylsilyl ethers in quantitative yield.     

Electrospinning of Hyperbranched Poly-L-Lysine/Polyaniline Nanofibers for Application in Cardiac Tissue Engineering

Electrospun polyaniline nanofibers are one of the most promising materials for cardiac tissue engineering due to their tunable electroactive properties. Moreover, the biocompatibility of polyaniline nanofibes can be improved by grafting of adhesive peptides during the synthesis. In this paper, we describe the biocompatible properties and cardiomyocytes proliferation on polyaniline electrospun nanofibers modified by hyperbranched poly-L-lysine dendrimers (HPLys). The microstructure characterization of the HPLys/polyaniline nanofibers was carried out by scanning electron microscopy (SEM). It was observed that the application of electrical current stimulates the differentiation of cardiac cells cultured on the nanofiber scaffolds. Both electroactivity and biocompatibility of the HPLys based nanofibers suggest the use this material for culture of cardiac cells and opens the possibility of using this material as a biocompatible electroactive 3-D matrix in cardiac tissue engineering.     

A close analysis of metal-enhanced fluorescence of tryptophan induced by silver nanoparticles: wavelength emission dependence

In the last few years, silver nanoparticles have been proposed as a promising alternative for the label-free detection of proteins via metal-enhanced fluorescence. Generally, the aromatic amino acid tryptophan is most frequently used in this type of studies, because the intrinsic fluorescence of proteins is usually dominated by tryptophan emissions. In the present study, we evaluated the fluorescence behavior of tryptophan in the presence of a silver colloid with nanoparticles of 100 nm in diameter. The results showed that a nanoparticles concentration of 32 mg L^?1 induced maximum fluorescence enhancement. However, the metal-enhanced fluorescence was dependent on the emission wavelength of tryptophan, and this phenomenon was closely related to the metal surface reabsorption process (inner filter effect), suggesting that the plasmon resonance reabsorption effect should be taken into account in analyses involving protein studies by metal-enhanced fluorescence.     

Incorporation of Baccharis dracunculifolia DC (Asteraceae) leaf extract into phosphatidylcholine-cholesterol liposomes improves its anti-inflammatory effect in vivo

The aerial parts of Baccharis dracunculifolia (BdE) is used in the Brazilian folk medicine to treat inflammatory conditions. Here we examined the ability of free and liposomal BdE to modulate reactive oxygen species generation in human neutrophils in vitro and zymosan-induced acute joint inflammation in Wistar rats. We prepared biocompatible liposomes of soya phosphatidylcholine and cholesterol with low diameter, homogeneous size distribution, and neutral surface charge. Free BdE decreased joint swelling, total leucocyte and neutrophil infiltration, and the synovial levels of tumour necrosis factor-α and interleukins 6 and 1β. Incorporation of BdE into liposomes preserved its capacity to inhibit the neutrophil superoxide anion and total reactive oxygen species generation, and improved its anti-inflammatory effect in vivo by decreasing the effective BdE dose by nearly sixfold. The same liposome type lowered the effective dose of caffeic acid by nearly sixteenfold. Therefore, incorporation of BdE into phosphatidylcholine-cholesterol liposomes improves its anti-inflammatory effect.     

Thermal and photochemical effects on the structure,morphology, thermal and optical properties of PVA/Ni0.04Zn0.96O and PVA/Fe0.03Zn0.97O nanocomposite films

Ni_0.04Zn_0.96O and Fe_0.03Zn_0.97O with average diameter of 23 and 19 nm, respectively, have been synthesized by a modified sol–gel method to be used in the preparation of (100 − x)/x poly(vinyl alcohol)/oxide nanocomposite films, with x = 0, 1, 3 and 5 (in wt.%). A 125 W-Hg vapor lamp with emission above 254 nmwas used to irradiate PVA/Ni_0.04Zn_0.96O and PVA/Fe_0.03Zn_0.97O films. The effect on their structural, thermal, morphological and optical properties was studied by TG, DSC, DRX, AFM, UV–vis and PL spectrophotometry. The Ni_0.04Zn_0.96O addition on PVA films decreases the thermal stability of the polymer in inert and in oxidative atmosphere. In contrast, the Fe_0.03Zn_0.97O presence in the PVA films seems to increase the thermal stability of the polymer. The characteristic peak of the crystalline phase of PVA and wurtzite phase of the zinc oxide were identified through X-ray diffraction in both films. The crystallinity of the PVA film increases with UV irradiation and with the presence of Ni_0.04Zn_0.96O and Fe_0.03Zn_0.97O. The roughness of the PVA film was not modified by the addition of the doped oxides; however, it increases after UV irradiation, more significantly in the films containing the oxides. The PVA film exhibits absorption around 280 nm characteristic of π–π^∗ transitions related to carbonyl groups from residuals acetate, while the 95/05 PVA/Ni_0.04Zn_0.96O and 95/05 PVA/Fe_0.03Zn_0.97O nanocomposite films show absorption at the visible region which is characteristics of the band gap reduction of the doped oxides. The photoluminescence of PVA was modified by the presence of the oxides in the film. These nanocomposite films are interesting due to their thermal, mechanical (flexible) properties and low cost of production. In addition they are also able to exhibit peculiar optical properties showing potential to be used in photonic devices, gas sensors and organic solar cell applications.     

Enzymatic syntheses of unsaturated polyesters based on isosorbide and isomannide

The search for materials produced from renewable sources aiming at the substitution of petroleum‐based derivates is an area of intense investigation. In this work, the enzymatic copolymerization of isosorbide or isomannide with diethyl adipate and fractions of different unsaturated diesters (diethyl itaconate, diethyl fumarate, diethyl glutaconate, and diethyl hydromuconate) were examined using CAL‐B as catalyst. The polyesters prepared using one‐step syntheses were characterized by SEC, NMR, and MALDI‐TOF MS. In addition, syntheses with linear diols were carried out in bulk to evaluate the reactivity of cyclic diols in producing unsaturated polyesters using enzymatic catalysis, as well as to evaluate the occurrence of addition side reactions on the double bonds. Isosorbide and isomannide yielded unsaturated polymers with values in the order of 4,000‐16,000 when fumarate or glutaconate esters were added in 5 mol % ratio against adipate. In all cases MALDI‐TOF confirmed the presence of unsaturated units. Although these polyesters have unreacted double bonds they are prone to crosslinking and ready to further functionalization, like anchoring bioactive molecules. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3881–3891     

Reaction of 2, 3, 4-pentantrione-3-arylhydrazones with N,N-dimethylhydrazine: Formation of substituted 1H-pyrazoles via demethylation

A novel one-step synthesis of 4-arylazo-1H-1, 3, 5-trimethylpyrazoles is accomplished by reaction of N, N-dimethylhydrazine with 2, 3, 4-pentantrione-3-arylhydrazones via an unusual demethylation.     

Determination of alpha-emitting isotopes of uranium and thorium in vegetables and excreta

A radiochemical procedure for the determination of alpha-emitting isotopes of uranium and thorium in vegetables and excreta has been optimized, involving sample dissolution, separation by ionic exchange resin, electrodeposition and alpha-spectroscopy. Uranium and thorium isotopes were determined separately to prevent interference of ²²⁸Th from ²³²U tracer with ²²⁸Th from natural series of 232Th. This procedure was applied to faeces from people living in the Poços de Caldas plateau, a high natural radioactivity region of Brazil, and vegetables from the Laboratory of Environmental Monitoring (EML/DOE). Results show a chemical recovery of 80–95% for uranium and 46–72% for thorium.     

Approximating a class of combinatorial problems with rational objective function

In the late seventies, Megiddo proposed a way to use an algorithm for the problem of minimizing a linear function a ₀ + a ₁ x ₁ + . . . + a _n x _n subject to certain constraints to solve the problem of minimizing a rational function of the form (a ₀ + a ₁ x ₁ + . . . + a _n x _n )/(b ₀ + b ₁ x ₁ + . . . + b _n x _n ) subject to the same set of constraints, assuming that the denominator is always positive. Using a rather strong assumption, Hashizume et al. extended Megiddo’s result to include approximation algorithms. Their assumption essentially asks for the existence of good approximation algorithms for optimization problems with possibly negative coefficients in the (linear) objective function, which is rather unusual for most combinatorial problems. In this paper, we present an alternative extension of Megiddo’s result for approximations that avoids this issue and applies to a large class of optimization problems. Specifically, we show that, if there is an α-approximation for the problem of minimizing a nonnegative linear function subject to constraints satisfying a certain increasing property then there is an α-approximation (1/α-approximation) for the problem of minimizing (maximizing) a nonnegative rational function subject to the same constraints. Our framework applies to covering problems and network design problems, among others.     

Eigenfunctions and Very Singular Similarity Solutions of Odd‐Order Nonlinear Dispersion PDEs: Toward a “Nonlinear Airy Function” and Others

Asymptotic properties of nonlinear dispersion equations (1) with fixed exponents n > 0 and p > n+ 1 , and their (2k+ 1) th‐order analogies are studied. The global in time similarity solutions, which lead to “nonlinear eigenfunctions” of the rescaled ordinary differential equations (ODEs), are constructed. The basic mathematical tools include a “homotopy‐deformation” approach, where the limit in the first equation in ( 1 ) turns out to be fruitful. At n= 0 the problem is reduced to the linear dispersion one: whose oscillatory fundamental solution via Airy’s classic function has been known since the nineteenth century. The corresponding Hermitian linear non‐self‐adjoint spectral theory giving a complete countable family of eigenfunctions was developed earlier in [ 1 ]. Various other nonlinear operator and numerical methods for ( 1 ) are also applied. As a key alternative, the “super‐nonlinear” limit , with the limit partial differential equation (PDE) admitting three almost “algebraically explicit” nonlinear eigenfunctions, is performed. For the second equation in ( 1 ), very singular similarity solutions (VSSs) are constructed. In particular, a “nonlinear bifurcation” phenomenon at critical values {p=p_l(n)}_l≥0 of the absorption exponents is discussed.