Mesomorphic polyacrylates containing isomeric methyl-substituted azobenzene mesogens

The synthesis and characterization are reported of two new series of structurally isomeric polyacrylates containing the azobenzene moiety spaced away from the backbone by a hexamethylene spacer and substituted in 4-position with linear alkoxy groups (C₁? C₆, C₁₀) and with a lateral methyl group in 2′- or 3′-position. Thermal optical and X-ray analyses of the prepared polymer samples, with molecular weight ranging from 50 × 10³ to 35 × 10⁴ Dalton (M?_w/M?_n = 2?3), provide evidences for the establishment of liquid crystalline behavior in the melt in a fairly broad range of temperature. In any case, quenching from the mesophase allows for the lock-in of the liquid crystalline structure in the glassy state. The presence of the lateral methyl-substitutents causes a drop as high as 50–100 K. in the stability of the mesophase with respect to the corresponding samples of the methyl-unsubstituted series. A parallel depletion of the smectogenic character is also observed. Typical even-odd effects on the isotropization temperature and relevant thermodynamic parameters have been detected along with the formation of interdigitated smectic structures.     

Oxo-biodegradable carbon backbone polymers - Oxidative degradation of polyethylene under accelerated test conditions

Oxo-biodegradation of carbon-only backbone polymers is receiving ever increasing attention for the practical implications that some re-engineered thermoplastic polymer formulations based on conventional biostable polymeric materials may satisfy in terms of environmental friendliness and acceptance by commodity plastic manufacturers.In this respect, as part of our continuing activity in the area of bioactive polymeric materials for biomedical and environmental applications, we report the results of an investigation of the effects of different degradation conditions on the oxidative degradation of polyethylene (PE) film samples containing pro-oxidant additives and formulated according to a proprietary technology. The effects of temperature and relative humidity have been evaluated by monitoring, with time, several parameters associated to oxidation and cleavage of the macromolecules, such as the weight variation due to oxygen uptake, film wettability, carbonyl index, molecular weight and the extractability with polar solvents of oxidized PE samples.     

Surface patterning and biological evaluation of semi-interpenetrated poly(HEMA)/poly(alkyl β-malolactonate)s

Semi-interpenetrating hydrogel networks were prepared by radical polimerization of monomer HEMA, co-monomer EGDMA as cross-linking agent and in the presence of 1 wt % of poly(alkyl β-malolactonate)s. Biological evaluation in terms of cell adhesion and proliferation of the prepared materials showed the ability of HEMA-based hydrogels to sustain a good cell adhesion and proliferation. Moreover, a method based on soft-lithography to obtained surface microstructured semi-interpenetrating hydrogel networks was developed, thus allowing for further investigation of the influence of surface topography on cell behavior.     

Symmetric Block Oligomers. Gelation characteristics by DSC

Symmetrical block oligomers having in common terminal groups (A) consisting of polyoxyethylene (20) stearyl ether are materials of pharmaceutical and cosmetic interest. Phase properties of their aqueous systems and amounts of water typologies were determined by differential scanning calorimetry (DSC). The overall amount of water absorbed by each investigated oligomer was not significantly influenced by the type of central bridging block, whereas the amount of free water decreased with increasing oligomer concentration in the gel. A number of 60–70 moles of water was found to solvate the oligomer chain. The oligomers studied presented a thermo-reversible gelation with and precipitation under determined temperature conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Control of surface properties using fluorinated polymer brushes produced by surface-initiated controlled radical polymerization

Surface-grafted styrene-based homopolymer and diblock copolymer brushes bearing semifluorinated alkyl side groups were synthesized by nitroxide-mediated controlled radical polymerization on planar silicon oxide surfaces. The polymer brushes were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and time-dependent water contact angle measurements. Angle-resolved XPS studies and water contact angle measurements showed that, in the case of the diblock copolymer brushes, the second block to be added was always exposed at the polymer-air interface regardless of its surface energy. Values of z*/Rg were estimated based on the radius of gyration, Rg, of the grafted homopolymer or block copolymer chains for the grafted brushes and thickness of the brush, z*. The fact that z*/Rg > 1 suggests that all these brushes are stretched. These results support the idea that after grafting the first block onto the surface the nitroxide-end capped polymer chains were able to polymerize the second block in a "living" fashion and the stretched brush so formed was dense enough that the outermost block in all cases completely covers the surface. NEXAFS analysis showed a relationship between the surface orientation of the fluorinated side chains and brush thickness with thicker brushes having more oriented side chains. Time-dependent water contact angle measurements revealed that the orientation of the side chains of the brush improved the surface stability toward reconstruction upon prolonged exposure to water.     

Photochromic liquid-crystalline polymers. Main chain and side chain polymers containing azobenzene mesogens

Abstract

Two classes of thermotropic polymers were synthesized containing the trans-azobenzene unit as both a mesogenic and a photochromic group. In the former class (I) the azobenzene unit is incorporated into the main chain of substituted polymalonates, while in the latter class (II) it is appended as a side chain substituent to a polyacrylate backbone. The liquid-crystalline properties of the polymers were studied as a function of the chemical structure. All of the prepared polymers I have smectic phases. Polymers II are nematic and/or smectic, or cholesteric when including a chiral residue R'. Polymers I and II when radiated at 348 nm in chloroform solution undergo trans-to-cis isomerization of the azobenzene moiety. The calculated rate constants are comparable with those of low molar mass model compounds, and indicate that the macromolecular structure does not significantly affect the photoisomerization rate.     

Thermal analysis of PVA/CNTs 2D membrane

The power–time curves of micellar formation of two anionic surfactants, sodium laurate (SLA) and sodium dodecyl sulfate (SDS), in N,N-dimethyl acetamide (DMA) in the presence of various long-chain alcohols (1-heptanol, 1-octanol, 1-nonanol and 1-decanol) were measured by titration microcalorimetry at 298 K. The critical micelle concentrations (CMCs) of SLA and SDS under various conditions at 298 K were obtained based on the power–time curves. Thermodynamic parameters (, and ) for micellar systems at 298 K were evaluated according to the power–time curves and the mass action model. The influences of the number of carbon-atom and the concentration of alcohol were investigated. Moreover, combined the thermodynamic parameters at 303, 308 and 313 K in our previous work and those of 298 K in the present work for SLA and SDS in DMA in the presence of long-chain alcohols, an enthalpy–entropy compensation effect was observed. The values of the enthalpy of micellization calculated by direct and indirect methods were made a comparison.     

The effects of hydrogen bonding on the liquid crystalline behavior of semiflexible poly(urethaneester)s

The peculiar liquid crystalline behavior of two poly(urethane-ester)s TDI-C6C4 and TDI-C6C8 is reported. Evidence is provided of the formation of two nematic mesophases, a cybotactic nematic and a conventional nematic mesophase, in TDI-C6C8 and of one cybotactic nematic mesophase in TDI-C6C4. IR spectroscopy indicates that different hydrogen bonded and non-bonded structures occur with varying temperature. The transition from the nematic cybotactic mesophase to the nematic mesophase, or to the isotropic phase, is accompanied by a substantial decrease of the strength of the hydrogen bonds. This is also reflected in the dynamic-mechanical behavior of these poly(urethane-ester)s which is similar to the one of slightly crosslinked thermoreversible networks.     

Polystyrene microspheres having epoxy functional dangling chains linked by hydrolytically stable bonds via ATRP

We report application of copper‐mediated atom transfer radical polymerization in graft copolymerization of glycidyl methacrylate (GMA) from N‐bromosulfonamide groups on polystyrene‐divinyl benzene (PS‐DVB) microspheres (210–420 μm). The surface initiator groups were introduced by simple modification of crosslinked PS‐DVB (10% mol/mol) beads in three steps: (i) chlorosulfonation, (ii) sulfamidation with propylamine, and (iii) bromination. Initiation from surface‐bound N‐bromosulfonamide groups showed first‐order kinetics (k = 1.04 × 10^?4 s^?1 in toluene at 70 °C) and gave poly(GMA) graft chains linked to the surface by hydrolytically stable sulfonamide bonds. High graft yields were attained (up to 294.4% within 21 h) while retaining the epoxy groups. Epoxy content of the resulting product (5.41 mmol g^?1) revealed an average 17 GMA repeating units in the graft per initiation site. Taking advantage of the hydrolytic stability of sulfonamide linkages and well‐known reactivity of the epoxy groups on dangling chains, “the hair‐like structure” of the polymer beads prepared can be considered when devising more efficient functional polymers as catalysts or reagent carriers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6708–6716, 2006     

Oxidation and biodegradation of polyethylene films containing pro-oxidant additives: Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation

Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation on the oxidation and biodegradation of linear low density poly(ethylene) PE-LLD films containing pro-oxidant were examined. To achieve oxidation and degradation, films were first exposed to the sunlight for 93 days during the summer months followed by their incubation with fungal strains previously isolated from the soil based on the ability to grow on the oxidized PE-LLD as a sole carbon source. Some films were also thermally aged at temperatures ranging between 45°C and 65 °C, either before or after fungal degradation. Films with pro-oxidant additives exhibited a higher level of oxidation as revealed by increase in their carbonyl index (COi). In addition to increase in the COi, films showed a slight increase in crystallinity and melting temperature (T_m), considerably lower onset degradation temperatures, and a concomitant increase in the % weight of the residues. The level of oxidation observed in thermally aged films was directly proportional to the aging temperature. The PE-LLD films with pro-oxidant exposed to sunlight followed by thermal aging showed even higher rate and extent of oxidation when subsequently subjected to fungal biodegradation. The higher oxidation rate also correlated well with the CO₂ production in the fungal biodegradation tests. Similar films oxidized and aged but not exposed to fungal biodegradation showed much less degradation. Microscopic examination showed a profuse growth and colonization of fungal mycelia on the oxidized films by one strain, while another spore-producing strain grew around the film edges. Data presented here suggest that abiotic oxidation of polymer's carbon backbone produced metabolites which supported metabolic activities in fungal cells leading to further biotically-mediated polymer degradation. Thus, a combined impact of abiotic and biotic factors promoted the oxidation/biodegradation of PE-LLD films containing pro-oxidants.