Copolymerization of (Meth)acrylates with Olefins Using Activators Regenerated by Electron Transfer for Atom Transfer Radical Polymerization (ARGET ATRP)

Summary: Controlled copolymerization of polar (meth)acrylates with non-polar olefin monomers (1-octene, norbornene, vinylcyclohexane) was studied by ARGET (activators regenerated by electron transfer) ATRP (atom transfer radical polymerization). When a normal ATRP of n-butyl acrylate (nBA) and 1-octene was conducted, the polymerization resulted in relatively low conversion, limited control over the polymerization process and high polydispersity (PDI > 1.6). This was due to formation of a dormant species, by reaction of 1-octene radicals with Cu(II) deactivator, that could not be reactivated. However, in ARGET ATRP with 10 ppm amounts of Cu-based catalyst, higher yields and a better controlled copolymerization was obtained (PDI < 1.4), because the low concentration of Cu(II) deactivator reduced the formation of the non-reactive dormant species. The influence of the amount of Cu catalyst, ligand structure, initiators with different halogens, the reaction temperature, and monomer feed ratio were also investigated for ARGET ATRP. In copolymerization of (meth)acrylates with non-polar alkenes, the level of control and the total conversion in ARGET ATRP were higher than those for normal ATRP.     

On Numerical Simulation of Interlaminar Failure of Composites

This paper deals with one of the most dangerous failure modes in fiber reinforced composites, namely delamination. The laminated structure is modeled by a solid–shell finite element. The mechanical modeling of delamination onset and propagation is based upon a cohesive zone model implemented into a cohesive element located between laminae of a composite structure. The numerical simulations are accomplished within the commercial software package ABAQUS by the implementation of a user–written finite element. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Great Attractor and the Shapley Concentration

We develop a non-linear relativistic model of the Shapley Concentration (SC) and its environs, including the Great Attractor (GA) and the Local Group (LG). We take the Shapley Concentration as a major attractive centre, and we use the Lemaître–Tolman model. We constrain our model with present day observations, plus the requirement that it have a physically reasonable evolution from small perturbations at last scattering. We investigate possible mass and velocity distributions, and we find that the peculiar velocity maximum near the SC is ~800 km/s inwards, the density between GA and SC must be about ~0.9 times background, the mass of the GA is probably 4–6 × 10¹⁵ M_⊙, the SC’s contribution to the LG motion is negligible, and the value of the cosmological constant is not significant on this scale.     

Canonical Sasakian Metrics

Let M be a closed manifold of Sasaki type. A polarization of M is defined by a Reeb vector field, and for any such polarization, we consider the set of all Sasakian metrics compatible with it. On this space we study the functional given by the square of the L ²-norm of the scalar curvature. We prove that its critical points, or canonical representatives of the polarization, are Sasakian metrics that are transversally extremal. We define a Sasaki-Futaki invariant of the polarization, and show that it obstructs the existence of constant scalar curvature representatives. For a fixed CR structure of Sasaki type, we define the Sasaki cone of structures compatible with this underlying CR structure, and prove that the set of polarizations in it that admit a canonical representative is open. We use our results to describe fully the case of the sphere with its standard CR structure, showing that each element of its Sasaki cone can be represented by a canonical metric; we compute their Sasaki-Futaki invariant, and use it to describe the canonical metrics that have constant scalar curvature, and to prove that only the standard polarization can be represented by a Sasaki-Einstein metric. During the preparation of this work, the first two authors were partially supported by NSF grant DMS-0504367.     

Mangiferin and Hesperidin Transdermal Distribution and Permeability through the Skin from Solutions and Honeybush Extracts (Cyclopia sp.)—A Comparison Ex Vivo Study

Polyphenolic compounds—mangiferin and hesperidin—are, among others, the most important secondary metabolites of African shrub Cyclopia sp. (honeybush). The aim of this study was to compare the percutaneous absorption of mangiferin and hesperidin from solutions (water, ethanol 50%, (v/v)) and extracts obtained from green and fermented honeybush (water, ethanol 50%, (v/v)). Research was performed with the Bronaugh cells, on human dorsal skin. The mangiferin and hesperidin distributions in skin layers (stratum corneum, epidermis, and dermis) and in acceptor fluid (in every 2, 4, 6, and 24 h) were evaluated by HPLC–Photodiode Array Coulometric and Coulometric Electrochemical Array Detection. The transdermal distribution of hesperidin was also demonstrated by fluorescence microscopy. Results indicated that mangiferin and hesperidin were able to cross the stratum corneum and penetrate into the epidermis and dermis. An advantage of hesperidin penetration into the skin from the water over ethanol solution was observed (451.02 ± 14.50 vs. 357.39 ± 4.51 ng/cm²), as well as in the mangiferin study (127.56 ± 9.49 vs. 97.23 ± 2.92 ng/cm²). Furthermore, mangiferin penetration was more evident from nonfermented honeybush ethanol extract (189.85 ± 4.11 ng/cm²) than from solutions. The permeation of mangiferin and hesperidin through the skin to the acceptor fluid was observed regardless of whether the solution or the honeybush extract was applied. The highest ability to permeate the skin was demonstrated for the water solution of hesperidin (250.92 ± 16.01 ng/cm²), while the hesperidin occurring in the extracts permeated in a very low capacity. Mangiferin from nonfermented honeybush ethanol extract had the highest ability to permeate to the acceptor fluid within 24 h (152.36 ± 8.57 ng/cm²).     

Perfect plasticity as a zero relaxation limit of plasticity with isotropic hardening

This work presents an approximation result for elasto‐perfect plasticity in the dynamical setting of the problem. We prove that the model of perfect plasticity with isotropic hardening converges to the Prandlt–Reuss model. Copyright © 2001 John Wiley & Sons, Ltd.     

Fractionation of Lycopodiaceae Alkaloids and Evaluation of Their Anticholinesterase and Cytotoxic Activities

In view of the abundant evidence that Lycopodiaceae alkaloids, including the well-known huperzine A (HupA), are among the potent acetylcholinesterase (AChE) inhibitors, an attempt was made to search for new compounds responsible for this property. For this purpose, three plant species belonging to the Lycopodiaceae family, commonly found in the Euro-Asia region, were subjected to the isolation of bioactive compounds, their identification and subsequent evaluation of their anticholinesterase and cytotoxic activities. Methanolic extracts of two Lycopodium and one Hupezia species were obtained via optimized pressurized liquid extraction (PLE) and then pre-purified using innovative gradient vacuum liquid chromatography (gVLC). For the first time, three sorbents of different porosity packed in polypropylene cartridges and mobile phase systems of different polarity were used to elute the target compounds. This technique proved to be a rapid tool for the obtainment of alkaloid fractions and allowed one to select the appropriate process conditions to yield potent AChE inhibitors in each of the species studied. More than 100 collected fractions were analyzed via HPLC/ESI-QTOF-MS, which enabled one to detect more than 50 compounds, including several new ones previously unreported. Some of them were present in high purity fractions (60–90% of the established purity). TLC bioautography assays proved that the analyzed species are rich sources of AChE inhibitors, but H. selago showed the highest anti-AChE activity. Additionally, the modified silanized silica gel sorbent used allowed one to isolate L. clavatum alkaloids more efficiently using an aqueous reversed-phase solvent system. Furthermore, the tested extracts from the three plant extracts were found to be safe, as they did not exhibit cytotoxicity to skin fibroblasts.     

Macromolecular engineering by controlled/living ionic and radical polymerizations

Various methods for the synthesis of well‐defined (co)polymers with controlled dimension, polydispersity, topology, composition and functionality are discussed. They include controlled/living vinyl polymerization using anionic, cationic and radical intermediates being in equilibria with dormant species. Special emphasis is placed on the radical polymerization and on the needs for the comprehensive structure property correlation.