Correlation between physical properties and conformational rigidity of some aromatic polyimides having pendant phenolic groups

Soluble polyimides based on an aromatic diamine containing pendant phenolic group and four different dianhydrides have been synthesized by two-step polycondensation reaction in solution. The polyimides were easily soluble in polar organic solvents and even in less polar solvents and showed high thermal stability, with initial decomposition temperature being above 420 °C. Monte Carlo method was used to calculate conformational rigidity parameters of these polyimides. Some physical properties such as solubility, glass transition temperature and initial decomposition temperature were investigated and compared with those of related polyimides which did not contain any pendant groups based on the same dianhydrides and a diamine without pendant phenolic group. All data were discussed in relation to the rigidity of the chain.

     

The Pr2Se3-PrSe2 system: Studies of the phase relationships and the modulated crystal structure of PrSe1.85

Thermochemical investigations have been carried out to elucidate the phase relationships in the system Pr₂Se₃-PrSe₂ and to construct the p_Se-T-x diagram. The result of the tensimetric and thermogravimetric studies showed the thermal decomposition of PrSe₂ to be a step-wise process due to the formation of a sequence of discrete intermediate phases with the compositions PrSe_1.9, PrSe_1.85, PrSe_1.8, and Pr₂Se₃. PrSe_1.85 and PrSe_1.8 have been previously considered as selenium-deficient non-stoichiometric phases. Conclusions derived from the thermodynamic study were verified by X-ray diffraction and electron microscopy studies on single crystals of PrSe_1.85 which were obtained from reactions of praseodymium and selenium in stoichiometric amounts in a KCl flux at 1070 K. A two-dimensional modulation could be observed for PrSe_1.85 in X-ray and high-resolution transmission electron microscopy. The structure of PrSe_1.85 was solved and refined in superspace group P4/n()(β-α)00 with lattice parameters of a=4.137(1) Å, c=8.398(2) Å of the basic unit cell and α=β=0.293(1). The origin of the modulation can be attributed to a site occupancy wave and a charge density wave in its planar selenium layer. The experimentally determined magnetic moments indicate Pr³⁺ for the polyselenides PrSe₂, PrSe_1.9 and PrSe_1.85.     

Effect of electron-donating and electron-withdrawing groups on peptide/single-walled carbon nanotube interactions

Nano-1, a designed peptide, has been demonstrated to efficiently disperse individual single-walled carbon nanotubes (SWNTs) by folding into an amphiphilic alpha-helix wherein the phenylalanine (Phe) residues on the hydrophobic face of the helix interact via pi-stacking with the aromatic surface of the SWNT. In this study, the ability of electron-donating (hydroxyl) and electron-withdrawing (nitro) groups on the phenyl ring of Phe to affect the interactions between the peptide and SWNTs is examined by substituting the Phe residues in the nano-1 sequence with tyrosine and p-nitro-phenylalanine, respectively. Atomic force microscopy measurements and optical absorption spectroscopy revealed that the ability to disperse individual SWNTs increases with increasing electron density of the aromatic residue on the hydrophobic face of the amphiphilic helical peptides. Scanning tunneling spectroscopy (STS) and Raman analyses were used to examine the effect of noncovalent protein functionalization on the electronic properties of SWNTs. Small shifts in the Raman G band peak for the peptide/SWNT composites, as well as weak features that appear near the Fermi energy (Ef) in the STS dI/dV spectra of the peptide-coated SWNTs, are suggestive of a weak charge-transfer interaction between the peptides and the SWNTs.     

Fast microfluidic temperature control for high resolution live cell imaging

One major advantage of using genetically tractable model organisms such as the fission yeast Schizosaccharomyces pombe is the ability to construct temperature-sensitive mutations in a gene. The resulting gene product or protein behaves as wildtype at permissive temperatures. At non-permissive or restrictive temperatures the protein becomes unstable and some or all of its functions are abrogated. The protein regains its function when returning to a permissive temperature. In principle, temperature-sensitive mutation enables precise temporal control of protein activity when coupled to a fast temperature controller. Current commercial temperature control devices do not have fast switching capability over a wide range of temperatures, making repeated temperature changes impossible or impractical at the cellular timescale of seconds or minutes. Microfabrication using soft-lithography is emerging as a powerful tool for cell biological research. We present here a simple disposable polydimethylsiloxane (PDMS) based microfluidic device capable of reversibly switching between 5 °C and 45 °C in less than 10 s. This device allows high-resolution live cell imaging with an oil immersion objective lens. We demonstrate the utility of this device for studying microtubule dynamics throughout the cell cycle.     

Influence of conformational rigidity on membrane properties of polyimides

Several polyimides were studied with regard to the influence of their conformational rigidity on the packing in glassy state, and consequently on their physical properties such as glass transition temperature and selectivity of gas separation membranes made from these polymers. The values of their physical properties were taken from literature, while the conformational rigidity parameters such as Kuhn segment, characteristic ratio, and occupied, free, and accessible volumes were calculated here and were correlated with physical properties. It was shown that there are correlations between selectivity of gas separation membranes made from these polyimides on one hand, and characteristic ratio, on another hand.     

Direct involvement of the acetato ligand in the reductive elimination step of rhodium-catalyzed methanol carbonylation

For the last step of rhodium-catalyzed methanol carbonylation, high-pressure NMR, and kinetic and experimental data supported by density functional theory calculations are consistent with substitution of I(-) by an AcO(-) ligand on the [RhI(3)(COCH(3))(CO)(2)](-) species followed by reductive elimination of acetic anhydride, which immediately reacts with water to afford acetic acid.     

Study of the chemical mechanism involved in the formation of tungstite in benzyl alcohol by the advanced QEXAFS technique

Insight into the complex chemical mechanism for the formation of tungstite nanoparticles obtained by the reaction of tungsten hexachloride with benzyl alcohol is presented herein. The organic and inorganic species involved in the formation of the nanoparticles were studied by time-dependent gas chromatography and X-ray diffraction as well as by time-resolved in situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy. Principal component analysis revealed two intermediates, which were identified as WCl(4) and WOCl(4) by using linear combination analysis. Quick-scanning extended X-ray absorption fine structure spectroscopy enabled the time-dependent evolution of the starting compound, the intermediates and the product to be monitored over the full reaction period. The reaction starts with fast chlorine substitution and partial reduction during the dissolution of the tungsten hexachloride in benzyl alcohol followed by the generation of intermediates with W=O double bonds and finally the construction of the W-O-W network of the tungstite structure.     

Polyimides Containing Azobenzene Side Units: Properties and Correlation with Conformational Parameters

Two series of aromatic polyimides differing by the bridging group between imide rings, polymers a, b, and c, having C?O linkages and polymers d, e, and f, having C(CF₃)₂ groups, have been obtained by polycondensation reaction of aromatic dianhydrides with aromatic diamines containing substituted azobenzene groups. These polymers with good solubility in polar amidic solvents, were able to form transparent flexible films and showed high thermal stability. Conformational parameters of the polymers were calculated by the Monte Carlo method with allowance for hindered rotation. Several physical properties of these polymers, such as solubility, glass transition temperature (T_g), and initial decomposition temperature (T_onset) were measured and discussed in relation to the volume factor of the macromolecular chains. The volume factor is equal to ratio of the Van der Waals volume of the pendent group to the Van der Waals volume of the repeating unit of the main chain.     

Economic value of greenhouse gases and nitrogen surpluses: Society vs farmers’ valuation

Livestock supply must challenge the growth of final demand in the developing countries. This challenge has to take into account its ecological effects since the dairy and livestock sectors are clearly pointed out as human activities which contribute significantly to environmental deterioration. Therefore, livestock activity models have to include desirable and undesirable outputs simultaneously. Using this perspective, we implement a Data Envelopment Analysis model to evaluate shadow prices of outputs under contradictory objectives between the society and the farmers. We show that farmers are able to reduce pollution significantly if society accepts to balance farmers’ opportunity cost. Finally, we observe that initial levels of the CO₂ tax implemented in European countries are in line with farmers’ valuation while the current level of the CO₂ tax tends to reach the value of pollution targeted by the society.     

Comparative study of polyimides containing different flexible linkages

Two series of polyimides were synthesized based on different aromatic dianhydrides containing various flexible linkages and two aromatic diamines containing ether and nitrile groups. The structure of the polymers was confirmed by FTIR and ¹H NMR spectroscopy. The correlation between some physical properties, such as solubility, thermal stability and glass transition temperature, and conformational rigidity parameters, such as Kuhn segment, characteristic ratio and rigidity parameter p, was studied.