Anisotropic nanoparticles of precise microstructure polyolefins

Nanoparticles of precisely branched polyethylenes possess a distinct oblate shape resulting from a crystalline lamella in the particle as revealed by SAXS and TEM, and display controllable and well-behaved thermal behaviour.     

How lipid unsaturation, peroxyl radical partitioning, and chromanol lipophilic tail affect the antioxidant activity of α-tocopherol: direct visualization via high-throughput fluorescence studies conducted with fluorogenic α-tocopherol analogues

The preparation of two highly sensitive fluorogenic α-tocopherol (TOH) analogues which undergo >30-fold fluorescence intensity enhancement upon reaction with peroxyl radicals is reported. The probes consist of a chromanol moiety coupled to the meso position of a BODIPY fluorophore, where the use of a methylene linker (BODIPY-2,2,5,7,8-pentamethyl-6-hydroxy-chroman adduct, H(2)B-PMHC) vs an ester linker (meso-methanoyl BODIPY-6-hydroxy-2,5,7,8-tetramethylchromane-2-carboxylic acid, H(2)B-TOH) enables tuning their reactivity toward H-atom abstraction by peroxyl radicals. The development of a high-throughput fluorescence assay for monitoring kinetics of peroxyl radical reactions in liposomes is subsequently described where the evolution of the fluorescence intensity over time provides a rapid, facile method to conduct competitive kinetic studies in the presence of TOH and its analogues. A quantitative treatment is formulated for the temporal evolution of the intensity in terms of relative rate constants of H-atom abstraction (k(inh)) from the various tocopherol analogues. Combined, the new probes, the fluorescence assay, and the data analysis provide a new method to obtain, in a rapid, parallel format, relative antioxidant activities in phospholipid membranes. The method is exemplified with four chromanol-based antioxidant compounds differing in their aliphatic tails (TOH, PMHC, H(2)B-PMHC, and H(2)B-TOH). Studies were conducted in six different liposome solutions prepared from poly- and mono-unsaturated and saturated (fluid vs gel phase) lipids in the presence of either hydrophilic or lipophilic peroxyl radicals. A number of key insights into the chemistry of the TOH antioxidants in lipid membranes are provided: (1) The relative antioxidant activities of chromanols in homogeneous solution, arising from their inherent chemical reactivity, readily translate to the microheterogeneous environment at the water/lipid interface; thus similar values for k(inh)(H(2)B-PMHC)/k(inh)(H(2)B-TOH) in the range of 2-3 are recorded both in homogeneous solution and in liposome suspensions with hydrophilic or lipophilic peroxyl radicals. (2) The relative antioxidant activity between tocopherol analogues with the same inherent chemical reactivity but bearing short (PMHC) or long (TOH) aliphatic tails, k(inh)(PMHC)/k(inh)(TOH), is ~8 in the presence of hydrophilic peroxyl radicals, regardless of the nature of the lipid membrane into which they are embedded. (3) Antioxidants embedded in saturated lipids do not efficiently scavenge hydrophilic peroxyl radicals; under these conditions wastage reactions among peroxyl radicals become important, and this translates into larger times for antioxidant consumption. (4) Lipophilic peroxyl radicals show reduced discrimination between antioxidants bearing long and short aliphatic tails, with k(inh)(PMHC)/k(inh)(TOH) in the range of 3-4 for most lipid membranes. (5) Lipophilic peroxyl radicals are scavenged with the same efficiency by all four antioxidants studied, regardless of the nature of their aliphatic tail or the lipid membrane into which they are embedded. These data underpin the key role the lipid environment plays in modulating the rate of reaction of antioxidants characterized by similar inherent chemical reactivity (arising from a conserved chromanol moiety) but differing in their membrane mobility (structural differences in the lipophilic tail). Altogether, a novel, facile method of study, new insights, and a quantitative understanding on the critical role of lipid diversity in modulating antioxidant activity in the lipid milieu are reported.     

Morphology and toughness of coextruded PS/PMMA multilayers

The micromechanical behaviour of multilayered tapes made of two brittle incompatible amorphous polymers PS and PMMA was studied by means of an optical and a High Voltage Electron Microscope (HVEM). Microlayers of PS and PMMA were coextruded with varying number of layers: 64, 512 and 4096 layers. Mechanical properties of the PS/PMMA tapes were also examined. An increase in layer numbers was found to lead to a decrease in layer thickness that, in turn, resulted in: a) formation of thicker and longer crazes and, therefore, increased volume of the material involved in the plastic deformation; b) a noticeable increase in strength and strain at break (i.e. of toughness) of the samples. Enhanced toughness of the multilayered tapes is accounted for by massive cooperating crazing and yielding of both PS and PMMA phases.     

Charge form factor and cluster structure of the 6Li nucleus

The charge form factor of the 6Li nucleus is considered on the basis of its cluster structure. The charge density of ⁶Li is presented as a superposition of two terms. One of them is a folded density and the second one is a sum of the ⁴He and deuteron densities. Using the available experimental data for ⁴He and deuteron charge form factors, a satisfactory agreement of the calculations within the suggested scheme is obtained with the experimental data for the charge form factor of ⁶Li, including those in the region of large transferred momenta.      

Differentiation of neurons from neural precursors generated in floating spheres from embryonic stem cells

Background  

Neural differentiation of embryonic stem (ES) cells is usually achieved by induction of ectoderm in embryoid bodies followed by the enrichment of neuronal progenitors using a variety of factors. Obtaining reproducible percentages of neural cells is difficult and the methods are time consuming.     

Convenient synthesis of some 2‐substituted 4(3H)‐quinazolinone derivatives

A series of 2‐substituted‐4(3H)‐quinazolinones 13‐20 has been synthesized in good yields using the reaction of double lithiated 2‐methylquinazolinone‐4 with a variety of aromatic aldehydes. They have been easily transformed in high yields into the corresponding 2‐substituted conjugated derivatives 21‐28 bearing terminal aryl groups by F₃CCOOH mediated dehydration.     

Chevron morphology in deformed semicrystalline polymers

Chevron morphology was observed using transmission electron microscopy in various semicrystalline polymers deformed in tensile experiments. The morphological and mechanical prerequisites for chevron structure formation in semicrystalline polymers were revealed. It was demonstrated that chevron folding is a common deformation mode which can appear in real, i.e. globally unoriented or partially oriented samples, in areas where the lamellar stacks are oriented perpendicular to the deformation direction. Similarities with the behaviour of other layered systems were found. The mechanism of chevron formation is discussed in the light of the fundamental statements of the folding theories and is related to the specific microstructure of the polymers. The effect of boundary conditions, deformation temperature and macroscopic strain on the characteristics of the chevron structure is described.     

Elastic properties of oriented polymers, blends and reinforced composites using the microindentation technique

The elastic behaviour of poly(ethylene terephthalate) (PET) and nylon 6 (PA6), their blends (1:1 by weight) and microfibrillar-reinforced composites of the previously mentioned homopolymers has been investigated by means of load-displacement analysis from indentation experiments. The dependence of the elastic modulus of the homopolymers upon the degree of crystallinity and the crystal size, as derived from indentation experiments, is discussed. A linear correlation between the elastic modulus anisotropy and the microindentation hardness anisotropy values is also found to apply for the oriented materials. The results reveal that the indentation modulus values of the PET/PA6 blends follow the parallel additivity model of the individual components. The use of the additivity law is also shown to provide a value, otherwise not accessible from direct measurements, of the modulus of the microfibrils within the microfibrillar-reinforced composites.