The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides – A Simple and Versatile Approach to ortho‐Functionalized Arylphosphine Oxides

Alkyldiphenylphosphine oxides typically undergo α‐deprotonation with alkyllithium reagents. Here, the lithiation of differentially branched alkyldiphenylphosphine oxides was investigated and a diverse, but predictable reactivity was found. γ‐Branched derivatives undergo selective directed ortho‐metalation (DoM) using butyllithium and TMEDA as an additive. With decreasing degree of γ‐branching α‐lithiation becomes predominant. The ortho‐phosphinoyllithium intermediates are subject to functionalization and C C bond forming reactions, thus providing a convenient approach to new phosphine oxides and phosphine‐borane complexes, which have a good potential for an approach to new ligands for catalysis.

     

Synthesis of poly(N‐isopropylacrylamide) by distillation precipitation polymerization and quantitative grafting on mesoporous silica

In this work, syntheses of thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM) with different molecular weights were carried out in ethanol by distillation precipitation polymerization (DPP) technique. The synthesized polymers were fully characterized by attenuated total reflection Fourier‐transform infrared (ATR‐FTIR) spectroscopy, nuclear magnetic resonance spectroscopy, and size exclusion chromatography techniques. The lower critical solution temperatures of the polymers were determined with differential scanning calorimetry. A simple and versatile method for the in situ synthesis and grafting of PNIPAM on mesoporus silica nanoparticles (MSNs) with improved control over quantitative grafting is devised. The PNIPAM grafted MSNs were characterized with ATR‐FTIR, thermogravimetric analysis, transmission electron microscopy, and dynamic light scattering analyses. From the results obtained it is showed that quantitative grafting of PNIPAM on MSNs from 1 to 20% by weight can be tuned by manipulating the in situ DPP reaction conditions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44181.     

Evaluation of thermal and mechanical properties of rubber compositions based on SBR extended with safe oils

The extender oil usually employed in compositions of rubbers based on styrene and butadiene (SBR) 1712 is the distilled aromatic extract (DAE). In this work, this oil was substituted by oils with low levels of polycyclic aromatic hydrocarbons (PAHs): treated residual aromatic extract (TRAE) and two naphthenic oils from different suppliers (HN1 and HN2). This substitution was performed in response to REACH Regulation (EC No. 1907/2006 European Parliament and the Council of December 18, 2006, Annex XVII), which state that the sum of individual PAHs should be below 10 mg/kg and the levels of benzo (a) pyrene (BaP) should not exceed 1 mg/kg. Infrared spectroscopy was employed to characterize the structure of crude oils and respective SBR compositions. Thermal properties of the materials were evaluated by thermogravimetry and differential scanning calorimetry. Mechanical properties as tension tests, hardness, abrasion resistance, and resilience were also determined. The final results showed that it is possible to replace the extender oil DAE for any of the oils tested, specially the naphthenic HN1, without any loss of the properties evaluated in this study for the SBR compositions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mathematical model of gentamicin sulfate release from a bioactive textile material as a transdermal system under in vitro conditions

A mathematical model was developed to estimate the release of gentamicin sulfate from a bioactive textile material as a transdermal system for wound dressing. The gentamicin sulfate released from the antibiotic/chitosan hydrogel complexes was measured in vitro by the Franz diffusion cell technique. The diffusive transport of gentamicin sulfate through three connected compartments, that is, chitosan hydrogel, membrane, and solution, was considered by the formulation of a model based on Fick's second law. Initially, the total amount of gentamicin sulfate was placed within an already swollen chitosan hydrogel. The value of the diffusivity coefficient of the drug through the chitosan hydrogel was calculated for every initial amount of the active substance. For the initial concentration of gentamicin sulfate, which was lower than 2.81 × 10⁴ μg/mL, the diffusion coefficient was approximately constant. A higher amount of gentamicin sulfate in the hydrogel reduced its own transport as a consequence of an increase in the intensity of the interaction field between the molecules of gentamicin sulfate. The model provides the possibility of optimizing the process of drug release by ensuring a compromise between a higher value of the diffusivity coefficient and a desirable amount of gentamicin sulfate and a constant concentration within the solution over 48 h. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of selenium on lipid alternations in pigment-forming yeasts

The work deals with lipid modifications of pigment-forming yeasts Rhodotorula and Sporobolomyces growing under presence of selenium. This metal in the medium significantly prolonged lag-phase of all cultures and enlarged yeast cells. Total, neutral, and membrane yeast lipids (phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, and phosphatidylinositol) consisted of predominantly palmitic, palmitoleic, stearic, oleic, linoleic, and linolenic acids. Selenium activated fatty acid unsaturation mainly in phosphatidylcholine due to elevated levels of linoleic and linolenic acids. Because biosynthesis of C18 unsaturated fatty acids in Rhodotorula and Sporobolomyces species may be associated with phosphatidylcholine moieties, selenium might be involved to the induction of membranebound fatty acid Δ¹² and Δ¹⁵ desaturases in red yeasts. Oppositely, neutral lipids (primarily triacylglycerols) did not show such intensive changes in fatty acid composition as their polar counterparts. These observations could be applied for preparation of selenized red yeasts containing carotenoid pigments with enhanced accumulation of linoleic and linolenic acids.     

Cryptanalysis of the Tillich�CZ��mor Hash Function

At CRYPTO ’94, Tillich and Zémor proposed a family of hash functions, based on computing a suitable matrix product in groups of the form SL₂(\mathbbF_2ⁿ)SL_{2}(\mathbb{F}_{2^{n}}). We show how to construct collisions between palindromic bit strings of length 2n+2 for Tillich and Zémor’s construction. The approach also yields collisions for related proposals by Petit et al. from ICECS ’08 and CT-RSA ’09.     

Data dissemination in wireless broadcast channels: Network coding versus cooperation

Network coding and cooperative diversity have each extensively been explored in the literature as a means to substantially improve the performance of wireless networks. Yet, little work has been conducted to compare their performance under a common framework. Our goal in this paper is to fill in this gap. Specifically, we consider a single-hop wireless network consisting of a base station and N receivers. We perform an asymptotic analysis, as N → ∞, of the expected delay associated with the broadcasting of a file consisting of K packets. We show that if K is fixed, cooperation outperforms network coding, in the sense that the expected delay is proportional to K (and thus within a constant factor of the optimal delay) in the former case while it grows logarithmically with N in the latter case. On the other hand, if K grows with N at a rate at least as fast as (logN)^r, for r ≫ 1, then we show that the average delay of network coding is also proportional to K and lower than the average delay of cooperation if the packet error probability is smaller than 0.36. Our analytical findings are validated through extensive numerical simulations.     

Polyaniline nanotubes: conditions of formation

The courses of aniline oxidation with ammonium peroxydisulfate in aqueous solutions of strong (sulfuric) and in weak (acetic) acids, followed by temperature and acidity changes, are different. In solutions of sulfuric acid, granular polyaniline (PANI) was produced; in solutions of acetic acid, PANI nanotubes were obtained. The external diameter of the nanotubes was 100–300 nm, the internal cavity 20–100 nm, and the length extended to several micrometres. The morphology of PANI, granular or tubular, depends on the acidity conditions during the reaction rather than on the chemical nature of the acid. PANI nanotubes were also produced when aniline was oxidized in the absence of any acid. The bulk conductivity of PANI prepared in solutions of acetic acid was 0.08–0.27 S cm^?1, depending on the acid concentration. Protonated PANI prepared in sulfuric and acetic acids were deprotonated with ammonium hydroxide to obtain PANI bases and the ammonium salt of the protonating acid. FTIR spectroscopy showed the differences in the molecular structure of the PANI bases. Irrespective of whether the polymerization was performed in solutions of sulfuric or acetic acid, PANI had hydrogen sulfate counter‐ions only. The PANI morphology is thus not controlled by the nature of counter‐ions. The acidity of the reaction medium determines the protonation of monomer, oligomer and polymer species. The chemistry of aniline oxidation is likely to be affected especially by the protonation of an intermediate in the pernigraniline form. It is proposed that, in the course of aniline oxidation, pH‐dependent self‐assembly of aniline oligomers predetermines the final PANI morphology. Copyright © 2005 Society of Chemical Industry