Formation of polymer vesicles by liquid crystal amphiphilic block copolymers

We report the formation of polymer vesicles (or polymersomes) by a new class of amphiphilic block copolymers in which the hydrophobic block is a side-on nematic liquid crystal polymer. Two series of these block copolymers, named PEG-b-PA444 and PEG-b-PMAazo444, with different hydrophilic/hydrophobic ratios were synthesized and characterized in detail. Polymersomes and nanotubes were formed by adding water into a solution of copolymers in dioxane. Polymersomes in water were finally obtained by dialyzing the resulting mixture against water. These self-assemblies have been studied by classical TEM and cryo-TEM. For the PEG-b-PA444 series, polymersomes were observed for hydrophilic/hydrophobic ratios ranging from 40/60 to 19/81. For PEG-b-PMAazo444 series, polymersomes were observed for hydrophilic/hydrophobic ratios ranging from 26/74 to 18/82. For a PEG-b-PA444 sample with hydrophilic/hydrophobic ratio equal to 25/75, a tubular morphology with tube diameter of typically 100 nm and tube length of up to 10 mum was also observed together with polymersomes during addition of water into the polymer solution in dioxane.     

Crystallization of a melt spun Fe-Ni based metallic glass

The crystallization kinetics of a melt spun Fe-Ni based alloy has been investigated, with both isothermal and continuous heating experiments, by means of differential scanning calorimetry. The alloy presents two separated crystallization processes. In order to perform the kinetic analysis of a melt spun metallic glass and to decide which kinetic model agrees better with the experimental crystallization data as the crystallized fraction x. We compare the experimental dependence of ln(k0f(x)) vs. (1-x) and that predicted, assuming different model equations for f(x). Both crystallization processes follow the JMAE equation and the master curve is the same for isothermal and non-isothermal data. This revised version was published online in July 2006 with corrections to the Cover Date.     

3-Amino-2-quinoxalinecarbonitrile. New fused quinoxalines with potential cytotoxic activity

Starting with 3-amino-2-quinoxalinecarbonitrile 1,4-dioxide 1 , a new series of quinoxaline derivatives was prepared through chemical modifications of the 2-cyano and 3-amino groups. Nitration of 3-amino-2-quin-oxalinecarbonitrile 3 afforded the 7-nitro derivative 6 . Diazotation of 3 gave the 3-chloro compound 9 . 2,3-Quinoxalinedicarbonitrile 14 was obtained from 9 . Pyridazino[4,5-b]quinoxalines 15 and 16 were prepared by condensing 14 with hydrazine hydrate. A triazolo[4,5-b]quinoxaline 18 , a isothiazolo[4,5-b]quinoxaline 20 and two pyrazolo[3,4-b]quinoxalines 21 and 22 were identified. Compounds were tested as cytotoxic agents both in oxic and in hypoxic cells.     

All‐in‐one Layer: Anisotropic Emission due to Light‐Induced Orientation of a Multifunctional Polymer

An efficient procedure to create oriented polymer films with strongly anisotropic properties is described. It is based on a two‐step process combining a photochemical and a thermal aligning step. The orientation of the polymer parallel or perpendicular to linearly polarised incident light can be adjusted. The method presented allows for simple fabrication of films with anisotropic absorption and emission characteristics with a dichroism of 0.7 and a fluorescence anisotropy of about 8.

     

Polysulfonylamine. CLXXVIII Onium‐Salze des Benzol‐1,2‐di(sulfonyl)amins (HZ): Eine zweite Kristallform des Ammonium‐Salzes NH4Z·H2O und Kristallstruktur des Bis(triphenylphosphoranyliden)ammonium‐Salzes [Ph3PNPPh3]Z

Polysulfonylamines. CLXXVIII. Onium Salts of Benzene‐1,2‐di(sulfonyl)amine (HZ): A Second Crystal Form of the Ammonium Salt NH₄Z·H₂O and Crystal Structure of the Bis(triphenylphosphoranylidene)ammonium Salt [Ph₃PNPPh₃]Z A dimorphic form of NH₄Z·H₂O, where Z^? is N‐deprotonated ortho‐benzenedisulfonimide, has been obtained and structurally characterized (previously known form 1A : monoclinic, P2₁/c, Z′ = 1; new polymorph 1B : monoclinic, P2₁/n, Z′ = 1). Both structures are dominated by an abundance of classical hydrogen bonds N⁺–H/O–H···O=S/OH₂, whereby the anionic N^? function does not act as an acceptor. The major difference between the dimorphs arises from the topology of the hydrogen bond network, which is two‐dimensional in 1A , leading to a packing of discrete lamellar layers, but three‐dimensional in 1B . Moreover, the latter network is reinforced by a set of weak C–H··O/N hydrogen bonds, whereas the layered structure of 1A displays only one independent C–H···O bond, providing a link between adjacent layers. The compound [Ph₃PNPPh₃]Z ( 2 , monoclinic, P2₁/c, Z′ = 1) is the first structurally authenticated example of an ionic Z^? derivative in which the cation contains neither metal bonding sites nor strong hydrogen bond donors. This structure exhibits columns of anions, surrounded by four parallel columns of cations, giving a square array. The large cations are associated into a three‐dimensional framework via weak C–H···C(π) interactions and an offset face‐to‐face phenyl interaction, while the anions occupy tunnels in this framework and are extensively bonded to the surrounding cations by C–H···O/N^? hydrogen bonds and C–H···C(π) interactions.     

Thermal behavior of cellulose fibers with enzymatic or Na<Subscript>2</Subscript>CO<Subscript>3</Subscript> treatment

Summary New regenerated cellulose fibers were developed during the last decades as environmentally friendly systems. In this work, three fibers: lyocell, modal and viscose were subjected to an enzymatic treatment. Likewise, different lyocell fibers were washed in a Na₂CO₃ solution under severe conditions. Analysis was performed by means of differential scanning calorimetry, thermogravimetry and scanning electron microscopy. In all samples, at low temperature, water desorption was detected. Furthermore, thermal analysis shows wide exothermic processes that began between 250 and 300°C corresponding to the main thermal degradation and it is associated to a depolymerization and decomposition of the regenerated cellulose. It is accompanied with mass more than 60% mass loss. Kinetic analysis was performed and activation energy values 152-202 kJ mol^-1 of the main degradation process are in agreement with literature values of cellulose samples.     

Identification of triterpenoid compounds of Centella asiatica by thin-layer chromatography and mass spectrometry

The identification of the four principal triterpenoid components of Centella asiatica has been achieved by TLC on silica gel plates and mass spectrometry, as a modification of the method described in the European Pharmacopoeia (5th edn). A combination of ethyl acetate and methanol as the mobile phase was found to be successful in separating these compounds from the rest of the main components of the extract. The spots were detected with anisaldehyde solution. The separated compounds were confirmed by MALDI -TOF mass spectrometry.     

Photoreactive main‐chain liquid‐crystalline polyesters: Synthesis,characterization, and photochemistry

Three series of semiflexible and rigid main‐chain polyesters containing photoreactive mesogenic units derived from p‐phenylenediacrylic acid (PDA) and cinnamic acid have been synthesized by high‐temperature polycondensation. The thermal and mesomorphic properties of the polymers have been determined. The photochemical behavior of polymer P‐[1]‐T, which contains a PDA unit, has been studied both in solution and in films. In solution, [2+2] photocycloaddition, E/Z photoisomerization, and photo‐Fries rearrangement can take place. In contrast, the dominant process in spin‐coated films is the [2+2] photocycloaddition reaction, which causes crosslinking of the polymer. In films, the photochemistry and induction of anisotropy are strongly influenced by the aggregation of the PDA phenylester unit. A dichroism of about 0.2 has been induced in films by irradiation with linearly polarized UV light, and thus the capability of these films to induce optical anisotropy and align liquid crystals has been demonstrated. Liquid‐crystalline cells have been made with polarized irradiated films of P‐[1]‐T as aligning layers. A commercial liquid‐crystalline mixture has been used for this study, and a similar liquid‐crystalline order determined by polarized Fourier transform infrared to a commercial cell with rubbed polyimide as an aligning layer has been detected. Because of crosslinking of the irradiated P‐[1]‐T photoaligning layer, the photoinduced anisotropy is stable at high temperatures, and the liquid‐crystalline molecules are insoluble in the irradiated polymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4907–4921, 2005     

Lattice-Boltzmann simulations of flow through Fontainebleau sandstone

We report preliminary results from simulations of single-phase and two-phase flow through three-dimensional tomographic reconstructions of Fontainebleau sandstone. The simulations are performed with the lattice-Boltzmann method, a variant of lattice-gas cellular-automation models of fluid mechanics. Simulations of single-phase flow on a sample of linear size 0.2 cm yield a calculated permeability in the range 1.0–1.5 darcys, depending on direction, which compares qualitatively well with a laboratory measurement of 1.3 darcys on a sample approximately an order of magnitude larger. The sensitivity of permeability calculations to sample size, grid resolution, and choice of model parameters is quantified empirically. We also present a qualitative study of immiscible two-phase flow in a sample of linear size 0.05 cm; simulations of both drainage and imbibition are presented.