Electrical conductivity of poly(ethylene terephthalate)/expanded graphite nanocomposites prepared by in situ polymerization

Nanocomposites based on poly(ethylene terephthalate) (PET) and expanded graphite (EG) have been prepared by in situ polymerization. Morphology of the nanocomposites has been examined by electronic microscopy. The relationship between the preparation method, morphology, and electrical conductivity was studied. Electronic microscopy images reveal that the nanocomposites exhibit well dispersed graphene platelets. The incorporation of EG to the PET results in a sharp insulator‐to‐conductor transition with a percolation threshold (?_c) as low as 0.05 wt %. An electrical conductivity of 10^?3 S/cm was achieved for 0.4 wt % of EG. The low percolation threshold and relatively high electrical conductivity are attributed to the high aspect ratio, large surface area, and uniform dispersion of the EG sheets in PET matrix. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Vibrational Spectra of Magnesium Hydrogenphosphate Trihydrate and of its Manganese Analogue

Abstract

The infrared (IR) and Raman spectra of MgHPO₄. 3H₂O and of a series of partially deuterated analogues as well as the IR spectra of MnHPO₄. 3H₂O have been recorded and interpreted. The analysis of the IR spectra in the HOD bending region rules out the possibility of existence of H₃OC⁺ ions in the structure.     

Structure of amyloid aggregates of lysozyme from small-angle X-ray scattering data

The structure of filament amyloid aggregates of hen egg white lysozyme in water has been investigated by the small-angle X-ray scattering method. The experimental data are described by different cylindrical models, among which the best agreement is reached with the long helix model. A comparison of the results with the small-angle neutron scattering data reveals the influence of the heavy component of the solvent (a H₂O/D₂O mixture) on the structure of the filaments.     

Cluster integrals of convex molecule systems

Cluster integrals assigned to particles interacting via the Kihara non-spherical potential are studied theoretically. An exact formula is derived which allows one to consider the effect of molecular shape separately from the effect of soft interactions. Employing the proposed formalism, the cluster integrals are analysed. The approach is applied to determine the third virial coefficient and an efficient computational method is developed. The third virial coefficient was calculated for a combination of molecules with hard cores of prolate spher-ocylindrical- and spherical shapes interacting via the square-well, triangle-well and 12-6 pair potentials. Comparison with numerical results obtained by Monte Carlo integration is made and fair agreement is found.     

Rearrangement of hexadecane molecules confined in the nanopores of a controlled pore glass using positron annihilation and differential scanning calorimetry

The solidification/melting of cetane confined in nine silica glasses with specific controlled pores (CPG) with different pore sizes (r _p ranging from 3.7–72 nm) has been studied. Samples with variable coefficient of filling of cetane were prepared and analyzed. Combining the indication of the evolving solidification heats (via differential scanning calorimetry, DSC) with the lifetime spectra of positron annihilation, the mechanism of filling of cetane molecules in the pores of the hosting silica glass matrices has been searched. Three independent solidification effects—three independent DSC peaks—were observed in each measuring cycle, namely one crystallization exotherm Rb of the bulk-cetane (if present) and two crystallization sub-peaks Rc1 and Rc2 of the confined cetane in the case of continuous cooling. The temperatures of both Rc1 and Rc2 effects decrease on decreasing the r _p of the CPG matrix. The mutual relation between Rc1 and Rc2 has been analyzed. The kinetics of all three steps of the solidification in the continuous-cooling as well as isothermal regimes have been specified.     

Photophysics of Push–Pull Distyrylfurans,Thiophenes and Pyridines by Fast and Ultrafast Techniques

Time‐resolved transient absorption and fluorescence spectroscopy with nano‐ and femtosecond time resolution were used to investigate the deactivation pathways of the excited states of distyrylfuran, thiophene and pyridine derivatives in several organic solvents of different polarity in detail. The rate constant of the main decay processes (fluorescence, singlet–triplet intersystem crossing, isomerisation and internal conversion) are strongly affected by the nature [locally excited (LE) or charge transfer (CT)] and selective position of the lowest excited singlet states. In particular, the heteroaromatic central ring significantly enhances the intramolecular charge‐transfer process, which is operative even in a non‐polar solvent. Both the thiophene and pyridine moieties enhance the S₁→T₁ rate with respect to the furan one. This is due to the heavy‐atom effect (thiophene compounds) and to the ¹(π,π)*→³(n,π)* transition (pyridine compounds), which enhance the spin‐orbit coupling. Moreover, the solvent polarity also plays a significant role in the photophysical properties of these push–pull compounds: in fact, a particularly fast ¹LE*→¹CT* process was found for dimethylamino derivatives in the most polar solvents (time constant, τ≤400 fs), while it takes place in tens of picoseconds in non‐polar solvents. It was also shown that the CT character of the lowest excited singlet state decreased by replacing the dimethylamino side group with a methoxy one. The latter causes a decrease in the emissive decay and an enhancement of triplet‐state formation. The photoisomerisation mechanism (singlet/triplet) is also discussed.     

Green chromatography separation of analytes of greatly differing properties using a polyethylene glycol stationary phase and a low-toxic water-based mobile phase

A simple, rapid, and environmentally friendly HPLC method was developed and validated for the separation of four compounds (4-aminophenol, caffeine, paracetamol, and propyphenazone) with different chemical properties. A “green” mobile phase, employing water as the major eluent, was proposed and applied to the separation of analytes with different polarity on polyethylene glycol (PEG) stationary phase. The chromatography separation of all compounds and internal standard benzoic acid was performed using isocratic elution with a low-toxicity mobile phase consisting of 0.04 % (v/v) triethylamine and water. HPLC separation was carried out using a PEG reversed-phase stationary phase Supelco Discovery HS PEG column (15?×?4 mm; particle size 3 μm) at a temperature of 30 °C and flow rate at 1.0 mL min^?1. The UV detector was set at 210 nm. In this study, a PEG stationary phase was shown to be suitable for the efficient isocratic separation of compounds that differ widely in hydrophobicity and acid–base properties, particularly 4-aminophenol (log P, 0.30), caffeine (log P, ?0.25), and propyphenazone (log P, 2.27). A polar PEG stationary phase provided specific selectivity which allowed traditional chromatographic problems related to the separation of analytes with different polarities to be solved. The retention properties of the group of structurally similar substances (aromatic amines, phenolic compounds, and xanthine derivatives) were tested with different mobile phases. The proposed green chromatography method was successfully applied to the analysis of active substances and one degradation impurity (4-aminophenol) in commercial preparation. Under the optimum chromatographic conditions, standard calibration was carried out with good linearity correlation coefficients for all compounds in the range (0.99914–0.99997, n?=?6) between the peak areas and concentration of compounds. Recovery of the sample preparation was in the range 100?±?5 % for all compounds. The intraday method precision was determined as RSD, and the values were lower than 1.00 %.

Bead Cellulose

Abstract

A new polymeric structure has been developed which fills a blank in available hydrophilic supports for separation processes.

Bead cellulose is a pure regenerated cellulose which is prepared by a modified viscose procedure. It is characterized by a regular spherical shape of individual particles, controlled porosity, accessibility for high molecular weight substances, high deformation stability and adequate chemical reactivity.

Diverse uses of this new material are described, viz., physical supports, chromatographic materials, dried preparations and various derivatives with different functions like ion exchangers, metal chelating adsorbents, chemisorbents, affinity adsorbents, immobilized enzymes. Bead cellulose can also be coupled with various active substances giving composite systems.