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Chain Packing (chain + packing)
Selected AbstractsTemperature and Pressure Effects on Local Structure and Chain Packing in cis -1,4-Polybutadiene from Detailed Molecular Dynamics SimulationsMACROMOLECULAR THEORY AND SIMULATIONS, Issue 5 2006Georgia Tsolou Abstract Summary: We present results for the temperature and pressure dependence of local structure and chain packing in cis -1,4-polybutadiene (cis -1,4-PB) from detailed molecular dynamics (MD) simulations with a united-atom model. The simulations have been executed in the NPT statistical ensemble with a parallel, multiple time step MD algorithm, which allowed us to access simulation times up to 1 µs. Because of this, a 32 chain C128cis -1,4-PB system was successfully simulated over a wide range of temperature (from 430 to 195 K) and pressure (from 1 atm to 3 kbar) conditions. Simulation predictions are reported for the temperature and pressure dependence of the: (a) density; (b) chain characteristic ratio, Cn; (c) intermolecular pair distribution function, g(r), static structure factor, S(q), and first peak position, Qmax, in the S(q) pattern; (d) free volume around each monomer unit along a chain for the simulated polymer system. These were thoroughly compared against available experimental data. One of the most important findings of this work is that the component of the S(q) vs. q plot representing intramolecular contributions in a fully deuterated cis -1,4-PB sample exhibits a monotonic decrease with q which remains completely unaffected by the pressure. In contrast, the intermolecular contribution exhibits a distinct peak (at around 1.4 Å,1) whose position shifts towards higher q values as the pressure is raised, accompanied by a decrease in its intensity. 3D view of the simulation box containing 32 chains of C128cis -1,4-polybutadiene at density ,,=,0.849 g,·,cm,3 and the conformation of a single C128cis -1,4-PB chain fully unwrapped in space. [source] Synthesis, Morphology, and Properties of Poly(3-hexylthiophene)- block -Poly(vinylphenyl oxadiazole) Donor,Acceptor Rod,Coil Block Copolymers and Their Memory Device ApplicationsADVANCED FUNCTIONAL MATERIALS, Issue 18 2010Yi-Kai Fang Abstract Novel donor,acceptor rod,coil diblock copolymers of regioregular poly(3-hexylthiophene) (P3HT)- block -poly(2-phenyl-5-(4-vinylphenyl)-1,3,4-oxadiaz-ole) (POXD) are successfully synthesized by the combination of a modified Grignard metathesis reaction (GRIM) and atom transfer radical polymerization (ATRP). The effects of the block ratios of the P3HT donor and POXD pendant acceptor blocks on the morphology, field effect transistor mobility, and memory device characteristics are explored. The TEM, SAXS, WAXS, and AFM results suggest that the coil block fraction significantly affects the chain packing of the P3HT block and depresses its crystallinity. The optical absorption spectra indicate that the intramolecular charge transfer between the main chain P3HT donor and the side chain POXD acceptor is relatively weak and the level of order of P3HT chains is reduced by the incorporation of the POXD acceptor. The field effect transistor (FET) hole mobility of the system exhibits a similar trend on the optical properties, which are also decreased with the reduced ordered P3HT crystallinity. The low-lying highest occupied molecular orbital (HOMO) energy level (,6.08 eV) of POXD is employed as charge trap for the electrical switching memory devices. P3HT- b -POXD exhibits a non-volatile bistable memory or insulator behavior depending on the P3HT/POXD block ratio and the resulting morphology. The ITO/P3HT44 - b - POXD18/Al memory device shows a non-volatile switching characteristic with negative differential resistance (NDR) effect due to the charge trapped POXD block. These experimental results provide the new strategies for the design of donor-acceptor rod-coil block copolymers for controlling morphology and physical properties as well as advanced memory device applications. [source] Matrimid®/MgO mixed matrix membranes for pervaporationAICHE JOURNAL, Issue 7 2007Lan Ying Jiang Abstract For the first time, porous Magnesium oxide (MgO) particles have been applied to generate mixed matrix membranes (MMM) for the dehydration of iso-propanol by pervaporation. A modified membrane fabrication procedure has been developed to prepare membranes with higher separation efficiency. FESEM and DSC characterizations confirm that the MMMs produced have intimate polymer/particle interface; the nanosize crystallites on MgO surface may interfere with the polymer chain packing and induce chains rigidification upon the particle surface. It is observed that Matrimid®/MgO MMMs generally have higher selectivity, but lower permeability relative to the neat Matrimid® dense membrane. The highest selectivity is obtained with MMM containing 15 wt. % MgO. The selective sorption and diffusion of water in the MgO particles, and the polymer/particle interface properties combine to lead to the earlier phenomena. The investigation on the effect of feed water composition on the pervaporation performance reveals that the addition of MgO can show the selectivity-enhancing effects if the feed water concentration is lower than 30 wt. %. In the dehydration of isopropanol aqueous solution with 10 wt. % water, the selectivity of the MMMs is around 2,000, which is more than twice of 900 of neat polymeric membrane. This makes MMMs extremely suitable for breaking the azeotrops of water/iso-propanol. Gas permeation tests are also conducted using O2 and N2 to determine the microscopic structure of the MMMs, and to investigate the relationship between pervaporation and gas separation performance. © 2007 American Institute of Chemical Engineers AIChE J, 2007 [source] Raman and Fourier transform infrared study of phytol effects on saturated and unsaturated lipid multibilayersJOURNAL OF RAMAN SPECTROSCOPY, Issue 1 2003M. Picquart Abstract The effects of phytol on DPPC and OPPC multilayers were investigated using FT-IR and Raman spectroscopy. The results were compared with those obtained with ,-tocopherol (,-T) and ,-tocopherol acetate (,-TA). The chain packing was analyzed using Raman intensity ratios measured in the CH2 stretching region, whereas the number of gauche bonds introduced by phytol was estimated by the measure of the FT-IR absorbance of the CH2 wagging progression modes. It is shown that the chain packing is reduced and that gauche rotamer formation is promoted by phytol in the gel phase. Phytol has a very similar effect on the acyl chains of DPPC to ,-T but does not have the same impact on the CO stretching vibrations of this lipid. The results indicate that phytol perturbs the interfacial region of DPPC causing dehydration or a conformational modification of the ester groups. Furthermore, the modification of the OPPC chain order induced by phytol is slightly different with respect to ,-T. It is concluded that (1) a hydrogen bond between the hydroxyl group of ,-T and the phospholipid carbonyl groups may not necessarily be associated with the stabilization of the membrane, (2) the studied phytyl compounds may be located more or less close to the membrane interface, (3) the presence of the chromanol ring may strongly influence the location of vitamin E within the membrane and, consequently, its capacity to catch free radicals and (4) the hydroxyl group, chroman moiety and phytyl chain all play a crucial role that determines the effects of ,-T on lipid acyl chains and its location within membranes, which in turn can affect its biological function. Copyright © 2002 John Wiley & Sons, Ltd. [source] Polyvinyl-Locked versus Free Quaterthiophene: Effect of Spatial Constraints on the Electronic Properties of n -HexylquaterthiopheneCHEMPHYSCHEM, Issue 18 2007Manuela Melucci Dr. Abstract A soluble, low-weight fraction of poly(,-vinyl,,- n -hexyl-quaterthiophene), PT4Hex, having n -hexylquaterthiophenes as side-chain groups, is prepared by free-radical polymerization of ,-vinyl,,-n-hexyl-quaterthiophene and the corresponding properties compared to those of free di- n -hexylquaterthiophene (T4Hex). Optical analysis (absorption and emission) and X-ray diffraction data indicate that in the polyvinyl-locked architecture the quaterthiophene pendants adopt a cofacial arrangement with a mutual distance close enough for ,,, orbitals to overlap (,4 Å). As a consequence of the close chain packing, a shift of the reduction potential of about 0.5 V toward less negative values with respect to free T4Hex, is found for PT4Hex films. Due to its enhanced electron affinity, PT4Hex displays an electron-acceptor behavior when blended with alkylated and silylated quaterthiophenes acting as donors. [source] | |||||||||||||