Structure of single-molecule single crystals of isotactic polystyrene and their radiation resistance

The structure of single-molecule single crystals of isotactic polystyrene (i-PS) was investigated by electron diffraction (ED). The nanoscale single-molecule single crystals were found to be more resistant to electron irradiation when compared to the larger crystals of many molecules, as indicated by both observation of ED and high-resolution electron microscopy with increasing radiation dose. It is proposed that since the single-molecule single crystals are very small, the secondary electrons escape more frequently from the crystal so that the radiation damage is reduced. Lattice imaging was achieved at room temperature in the case of single-molecule single crystals because of their stability to electron irradiation. Published 1998 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

J Polym Sci B: Polym Phys 36 : 105–112, 1998     

Small angle x-ray analysis of the effect of temperature on the self-assembling columnar structures formed by a polymethacrylate with highly tapered side groups and by one of its low molar mass precursors

Small angle X-ray methods have been used to investigate the self-assembling columnar structures formed by a polymethacrylate with large highly tapered side groups, and by one of its low molar mass precursors. The polymer is poly{2-{2-[2-(2-methacryloyloxyethoxy)ethoxy] ethoxy}ethyl-3, 4, 5-tris(p-dodecyloxybenzyloxy)-benzoate} (H12-ABG-4EO-PMA); the precursor is 2-{2-[2-(2-hydroxyethoxy)-ethoxy]ethoxy}-ethyl-3, 4, 5-tris(p-dodecyl-oxybenzyloxy)benzoate (H12-ABG-4EO-OH). Both the polymer and the precursor form three dimensionally ordered structures at room temperature, consisting of hexagonally packed cylinders with diameters in the region of 60 and 53Å, respectively, in which the interiors of the columns probably have helical arrays of the stacked tapered groups. At higher temperatures these are converted to columnar hexagonal (ϕ_h) liquid crystalline phases. At temperatures close to this transition for the precursor we detect two coexisting columnar structures, with the ϕ_h structure having a diameter approximately 1Å higher than that in the solid state. For the polymer, the data are not so well resolved, and coexisting phases cannot be resolved. However, the changes in column dimensions are larger than for the precursor. Conversion of the room temperature phase to the ϕ_h phase at 40°C results in an increase of 3Å in the diameter, which then declines by approximately the same amount as the temperature rises to 90°C, close to the isotropization point. Cooling to room temperature does not immediately restore the room temperature structure. Rather, we obtain a quenched ϕ_h structure, with a column diameter almost 10% higher. These dimensional changes correlate well with the changes in diameter with temperature seen for the bulk fiber, and suggest a continuous rearrangement of the interiors of the columns in the ϕ_h phase, such as a partial unwinding of a disordered helical structure.     

Deep level emission of ZnO nanoparticles deposited inside UV opal

The temperature-dependent photoluminescence spectra of zinc oxide (ZnO) nanocrystals deposited inside the ultraviolet (UV) opal were studied. ZnO was grown in the voids between FCC packed SiO₂ spheres using spray pyrolysis under ultrasonic vibration in the solution containing a zinc nitrate precursor. The ZnO nanoparticles inside opal matrix with UV photonic band-gap exhibit suppression of the excitonic emission and enhancement of the deep level emission. Suppression of the excitonic lines is due to the inhibition of spontaneous emission, while enhancement and broadening of the DL emission in the green spectral region is due to Purcell effect. The infiltration of ZnO nanoparticles inside the photonic crystal may be a useful technique to increase its emission efficiency in the selected spectral region.     

Preparation and characterization of MPEG–PCL diblock copolymers with thermo‐responsive sol–gel–sol phase transition

MPEG–PCL diblock copolymers consisting of methoxy polyethylene glycol (MPEG, 750 g/mol) and poly(?‐caprolactone) (PCL) were synthesized by ring‐opening polymerization. Aqueous solutions of the synthesized diblock copolymers were prepared by dissolving the MPEG–PCL diblock copolymers at concentrations in the range of 0–20 wt %. When the PCL molecular weight was 3000 or greater, the polymer was only partially soluble in water. As the temperature was increased from room temperature, the diblock copolymer solutions showed two phase transitions: a sol‐to‐gel transition and a gel‐to‐sol transition. The sol‐to‐gel phase transition temperature decreased substantially with increasing PCL length. The sol–gel–sol transition with the increase in temperature was confirmed by monitoring the viscosity as a function of temperature. The temperature ranges of the phase transitions measured by the tilting method were in full agreement with those determined from the viscosity measurements. The maximum viscosity of the copolymer solution increased with increasing hydrophobicity of the diblock copolymer and with increasing copolymer concentration. X‐ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses revealed that the diblock copolymers exhibited crystalline domains that favored the formation of an aggregated gel because of the tight aggregation and strong packing interactions between PCL blocks. Scanning electron micrographs of the diblock copolymer solutions in the sol state showed interconnected polyhedral pore structures, whereas those of the gel state revealed a fibrillar‐like morphology. Atomic force microscope (AFM) studies of the sol and gel surfaces showed that the sol surface was covered with fine globular particles, whereas the gel surface was covered with particles in micron‐scale irregular islets. These findings are consistent with uniform mixing of the diblock copolymer and water in the sol state, and aggregation of PCL blocks in the gel state. In conclusion, we confirm that the MPEG–PCL diblock copolymer solution exhibited a sol–gel–sol transition as a function of temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5413–5423, 2006     

Some new Schiff base ligands giving a NNOS coordination sphere and their nickel(II) complexes: Synthesis,characterization and complex formation

Some new tetradentate ligands with a NNOS coordination sphere were prepared and their corresponding nickel(II) complexes were synthesized and characterized by elemental analysis, IR, ¹H NMR, UV–Vis and mass spectrophotometry. The thermodynamic formation constants of the complexes were measured spectrophotometrically, at a constant ionic strength of 0.1 M (NaClO₄) at 25 °C in DMF solvent. The trend of the complex formation for nickel is as follows:     

Design and performance simulation of a molecular Doppler wind lidar

A mobile molecular Doppler wind lidar at an eye-safe wavelength of 355 nm based on double-edge technique is being built in Hefei （China） for wind measurement from 10-to 40-km altitude. The structure of this lidar system is described. A triple Fabry-Perot etalon is employed as a frequency discriminator whose parameters are optimized. The receiver system is designed to achieve compactness and stability by putting in a standard 19-inch socket bench. Simulation results show that within the wind speed dynamic range of ±100 m/s, the horizontal wind errors due to noise are less than 1 m/s bdow 20-km altitude for 100-m vertical resolution, and less than 5.5 m/s from 20 km up to 40 km for 500-m vertical resolution with 400-mJ laser energy, 30-min temporal resolution, and a 45-cm aperture telescooe.     

APUSM technology for the production of BTX and LPG from pyrolysis gasoline using metal promoted zeolite catalyst

SK Corporation developed an advanced pyrolysis gasoline (pygas) upgrading (APU^SM) technology based on a catalytic process for producing valuable benzene, toluene and xylenes (BTX) and liquefied petroleum gas (LPG) from pygas containing aromatics and non-aromatic hydrocarbons. Hydrodealkylation of heavy aromatics and hydrocracking of non-aromatic hydrocarbons occurred with facility in the conversion of pygas over a proprietary catalyst, metal promoted zeolite. This catalytic process produced benzene and toluene with high purity corresponding to chemical grade while giving mixed xylenes with reduced ethylbenzene. In the present study, we described novel features of the APU^SM technology in terms of the process and catalyst. The influence of the process conditions was also examined. This technology has been commercially proven, and hence is available for licensing through Axens, which is a major engineering and licensing company.     

Enhanced efficiency of polyfluorene derivatives: Organic–inorganic hybrid polymer light‐emitting diodes

Two novel organic–inorganic hybrid polyfluorene derivatives, poly{(9,9′‐dioctyl‐2,7‐fluorene)‐co‐(9,9′‐di‐POSS‐2,7‐fluorene)‐co‐[2,5‐bis(octyloxy)‐1,4‐phenylene]} (PFDOPPOSS) and poly{(9,9′‐dioctyl‐2,7‐fluorene)‐co‐(9,9′‐di‐POSS‐2,7‐fluorene)‐co‐bithiophene} (PFT2POSS), were synthesized by the Pd‐catalyzed Suzuki reaction of polyhedral oligomeric silsesquioxane (POSS) appended fluorene, dioctyl phenylene, and bithiophene moieties. The synthesized polymers were characterized with ¹H NMR spectroscopy and elemental analysis. Photoluminescence (PL) studies showed that the incorporation of the POSS pendant into the polyfluorene derivatives significantly enhanced the fluorescence quantum yields of the polymer films, likely via a reduction in the degree of interchain interaction as well as keto formation. Additionally, the blue‐light‐emitting polyfluorene derivative PFDOPPOSS showed high thermal color stability in PL. Moreover, single‐layer light‐emitting diode devices of an indium tin oxide/poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate)/polymer/Ca/Al configuration fabricated with PFDOPPOSS and PFT2POSS showed much improved brightness, maximum luminescence intensity, and quantum efficiency in comparison with devices fabricated with the corresponding pristine polymers PFDOP and PFT2. In particular, the maximum external quantum efficiency of PFT2POSS was 0.13%, which was twice that of PFT2 (0.06%), and the maximum current efficiency of PFT2POSS was 0.38 cd/A, which again was twice that of PFT2 (0.19 cd/A). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2943–2954, 2006     

Synthesis of metal/polymer colloidal composites by the tailored deposition of silver onto porous polymer microspheres

A new colloidal silver system is presented in which a fine colloidal silver is in situ deposited onto functionalized porous poly(ethylene glycol dimethacrylate) [poly(EGDMA)] microspheres. The effectiveness of the silver deposition has been investigated through an examination of the surface characteristics of poly(EGDMA) microspheres. The result reported in this study demonstrate that the control of the surface area and surface functionality (in this study, a hydroxyl group) of poly(EGDMA) microspheres is an important factor that practically determines the degree of deposition of colloidal silver. X‐ray analysis has shown that silver nanoparticles are dispersed evenly on inner and outer surfaces and have a face center cubic phase. Preservation testing has shown that silver‐containing poly(EGDMA) microspheres have powerful antibacterial properties and, therefore, have significant potential as new preservatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2551–2557, 2004