Self-assembly of chemically linked rod-disc mesogenic liquid crystals.

A series of new molecular discs (RDn, here n is the number of carbon atoms between the rod and disc mesogens) was synthesized via the chemical attachment of six cyanobiphenyl calamitic (rod) mesogens (R) linked to the triphenyl discotic (disc) mesogen (D) with a series of six alkyl chain linkages (n = 6-12). In this study, phase structures, transitions, and liquid crystalline (LC) behavior of the RD12 compound with 12 carbon atoms in each alkyl chain linkage between the rod and disc mesogens were investigated. Differential scanning calorimetry, polarized light microscopy, wide-angle X-ray diffraction (WAXD), and selected area electron diffraction (SAED) allowed us to identify three ordered phases below the isotropization temperature: nematic (N) LC and K1 and K2 crystalline phases. On the basis of the structural results obtained via 2D WAXD experiments on oriented samples and SAED experiments on single crystals, the K1 crystalline unit cell was determined to be triclinic with the dimensions of a = 1.36 nm, b = 1.45 nm, c = 2.11 nm, alpha = 85 degrees, beta = 100 degrees, and gamma = 50 degrees. The K2 phase was metastable with respect to the K1 phase. It also possessed a triclinic unit cell with a = 1.40 nm, b = 1.51 nm, c = 1.92 nm, alpha = 87 degrees, beta = 117 degrees, and gamma = 62 degrees. Molecular packing models for the crystalline phases were proposed on the basis of the diffraction results. In the whole range of ordered structures, it was found that RD12 molecular discs are intercalated. Both triphenyl discotic mesogens and cyanobiphenyl calamitic mesogens are completely interdigitated.

Formation of nanostructured materials via coalescence of amphiphilic hollow particles.

A new, simplified route to amphiphilic core-shell nanotubes, microfibers, and microrods has been developed that does not involve the traditional utilization of well-defined block copolymers. Thus, amphiphilic graft copolymers (PEI-g-PMMA) are prepared by an aqueous free radical polymerization that self-assemble in situ to form uniform core-shell nanoparticles. The hydrophobic homopolymer (PMMA) that is also formed is incorporated in the cores. Slight cross-linking of the shells followed by extraction of the homopolymer results in hollow nanoparticles that coalesce to form nanotubes. When the shells are not cross-linked, the hollow particles coalesce to form microrods and microfibers. The sizes and shapes of the micromaterials can be controlled by varying the experimental conditions.

Phase behaviors and supra-molecular structures of a series of symmetrically tapered bisamides.

A series of symmetrically tapered 1,4-bis[3,4,5-tris(alkan-1-yloxy)benzamido] benzene bisamides (CPhBA, where is the number of carbon atoms in the alkyl chains, = 10, 12 and 16), was synthesized in order to investigate the effect of alkyl chain length on supra-molecular ordered structures induced by hydrogen (H)-bonding and micro-phase separation. These bisamides consist of a rigid aromatic bisamide core with three flexible alkyl chains at each end of the core. Major phase transitions and their origins in CPhBA bisamides were studied with differential scanning calorimetry, one-dimensional (1D) wide angle X-ray diffraction (WAXD), infrared spectroscopy, and solid-state carbon-13 nuclear magnetic resonance experiments. The structures of these compounds in different phases were identified using 2D WAXD from oriented samples and were also confirmed by selected area electron diffractions in transmission electron microscopy from stacked single crystals and by computer simulations. All of the CPhBA bisamides in this series formed a highly ordered oblique columnar () phase and a low-ordered oblique columnar () phase, similar to a recent report on C14PhBA. The two main driving forces in the formation of these two supra-molecular columnar structures were identified: One was the H-bond formation between N-H and C[double bond, length as m-dash]O groups, and the other was the micro-phase separation between the bisamide cores and the alkyl chains. With increasing the length of alkyl tails, the isotropization temperature decreased, while the disordering temperature of the alkyl tails increased. The 2D lattice structures perpendicular to the columnar axis also increasingly deviated from the pseudo-hexagonal packing with increasing the alkyl tail length. However, the alkyl tail length did not have a significant influence on the packing along the columnar axis direction. Utilizing polarized optical microscopy, the phase identifications were also supported by the observation of texture changes and molecular arrangements inside of the micro-sized domains.

Multiwalled carbon nanotubes with chemically grafted polyetherimides.

Covalent attachment of a non-fluorinated polyetherimide onto the surface of carboxylic acid-functionalized multiwalled carbon nanotubes (MWNTs) has been achieved via grafting reactions. This confirms for the first time that the grafting reaction occurs at the nanotube surface when the carboxylic acid-functionalized MWNTs react with the polyetherimide with amine-terminated groups, through both amide and imide linkages formed at the interface between the carbon nanotubes and the polyetherimide. Additionally, an increase in the average molecular weight is detected in gel permeation chromatography when the polyetherimide is chemically attached onto the nanotubes. More interestingly, the chemical bonding at the interface provides much better interfacial adhesion and mechanical stress transfer, evidenced by a significant improvement in mechanical properties. As a result of the chemical attachment, the carbon nanotube-reinforced polyetherimide composite films have enhanced electrical conductivity, thermal deformation temperatures, and mechanical properties.

Ruthenium(III) chloride catalyzed oxidation of pyrene and 2,7-disubstitued pyrenes: an efficient, one-step synthesis of pyrene-4,5-diones and pyrene-4,5,9,10-tetraones.

Pyrene and 2,7-disubstituted pyrenes have been oxidized with ruthenium(III) chloride (RuCl3) and sodium periodate (NaIO4) under very mild conditions to 4,5-diones or 4,5,9,10-tetraones. Thus, the oxidation has been controlled by varying the amount of oxidant and reaction temperature to proceed exclusively at the pyrene 4- and 5-positions or at the 4-, 5-, 9-, and 10-positions.

Amphiphilic core-shell nanoparticles with poly(ethylenimine) shells as potential gene delivery carriers.

Spherical, well-defined core-shell nanoparticles that consist of poly(methyl methacrylate) (PMMA) cores and branched poly(ethylenimine) shells (PEI) were synthesized via a graft copolymerization of methyl methacrylate from branched PEI induced by a small amount of tert-butyl hydroperoxide. The PMMA-PEI core-shell nanoparticles were between 130 to170 nm in diameter and displayed zeta-potentials near +40 mV at pH 7 in 1 mM aqueous NaCl. Plasmid DNA (pDNA) was mixed with nanoparticles and formed complexes of approximately 120 nm in diameter and was highly monodispersed. The complexes were characterized with respect to their particle size, zeta-potential, surface morphology, and DNA integrity. The complexing ability of the nanoparticles was strongly dependent on the molecular weight of the PEI and the thickness of the PEI shells. The stability of the complexes was influenced by the loading ratio of the pDNA and the nanoparticles. The condensed pDNA in the complexes was significantly protected from enzymatic degradation by DNase I. Cytotoxity studies using MTT colorimetric assays suggested that the PMMA-PEI (25 kDa) core-shell nanoparticles were three times less toxic than the branched PEI (25 kDa). Their transfection efficiencies were also significantly higher. Thus, the PEI-based core-shell nanoparticles show considerable potential as carriers for gene delivery.

Assembly of well-aligned multiwalled carbon nanotubes in confined polyacrylonitrile environments: electrospun composite nanofiber sheets.

Highly oriented, large area continuous composite nanofiber sheets made from surface-oxidized multiwalled carbon nanotubes (MWNTs) and polyacrylonitrile (PAN) were successfully developed using electrospinning. The preferred orientation of surface-oxidized MWNTs along the fiber axis was determined with transmission electron microscopy and electron diffraction. The surface morphology and height profile of the composite nanofibers were also investigated using an atomic force microscope in tapping mode. For the first time, it was observed that the orientation of the carbon nanotubes within the nanofibers was much higher than that of the PAN polymer crystal matrix as detected by two-dimensional wide-angle X-ray diffraction experiments. This suggests that not only surface tension and jet elongation but also the slow relaxation of the carbon nanotubes in the nanofibers are determining factors in the orientation of carbon nanotubes. The extensive fine absorption structure detected via UV/vis spectroscopy indicated that charge-transfer complexes formed between the surface-oxidized nanotubes and negatively charged (-CN[triple bond]N:) functional groups in PAN during electrospinning, leading to a strong interfacial bonding between the nanotubes and surrounding polymer chains. As a result of the highly anisotropic orientation and the formation of complexes, the composite nanofiber sheets possessed enhanced electrical conductivity, mechanical properties, thermal deformation temperature, thermal stability, and dimensional stability. The electrical conductivity of the PAN/MWNT composite nanofibers containing 20 wt % nanotubes was enhanced to approximately 1 S/cm. The tensile modulus values of the compressed composite nanofiber sheets were improved significantly to 10.9 and 14.5 GPa along the fiber winding direction at the MWNT loading of 10 and 20 wt %, respectively. The thermal deformation temperature increased with increased MWNT loading. The thermal expansion coefficient of the composite nanofiber sheets was also reduced by more than an order of magnitude to 13 x 10(-6)/ degrees C along the axis of aligned nanofibers containing 20 wt % MWNTs.

Effect of gamma-radiation on a polyanhydride implant containing gentamicin sulfate.

Septacin, a polyanhydride implant containing gentamicin sulfate, was sterilized by gamma-radiation. Its copolymer molecular weight (M(w) by GPC) was increased after this radiation. No cross-linking was shown in the radiated samples as no gel content was found by the filtration method. The chemical structure as detected by 1H NMR for non-radiated and radiated samples was comparable. For samples radiated at higher dose levels (70-100 kGy), the IR spectra showed that the intensity of absorbance attributable to the C-H stretching vibration (at 2852 and 2927 cm(-1)) was attenuated, indicating free-radical formation or loss of hydrogen atoms from C-H bonds. However, the mass spectra for the gamma-radiated and the non-radiated controls after they were completely depolymerized in methylene chloride were virtually identical. Therefore, it could be concluded that the increase in copolymer molecular weight for radiated Septacin was a result of chain extension in the copolymer backbone during radiation. In addition, wide-angle X-ray diffraction and polarizing light microscopy (PLM) revealed a change in the physical structure of the radiated copolymer. There was an increase in crystallinity of the copolymer with increasing radiation doses; the greatest increase in crystallinity occurred at the dose range of 70-80 kGy, which was also shown to result in the greatest molecular-weight increase. The crystalline morphology of the samples as detected by PLM was not altered by gamma-radiation, regardless of the dose levels.