Sulfonated poly(aryl ether ketone)s containing naphthalene moieties obtained by direct copolymerization as novel polymers for proton exchange membranes

A series of sulfonated poly(aryl ether ketone)s (SPAEKs) were prepared by aromatic nucleophilic polycondensation of 2,6‐dihydroxynaphthalene with 5,5′‐carbonyl‐bis(2‐fluorobenzenesulfonate) and 4,4′‐difluorobenzophenone. The structure and degree of sulfonation (DS) of the SPAEKs were characterized using ¹H NMR spectroscopy. The experimentally observed DS values were close to the expected values derived from the starting material ratios. The thermal stabilities of the SPAEKs were characterized by thermogravimetric analysis, which showed that in acid and sodium salt forms they were thermally stable in air up to about 240 and 380 °C, respectively. Transparent membranes cast from the directly polymerized SPAEKs exhibited good mechanical properties in both dry and hydrated states. The dependence of water uptake and of membrane swelling on the DS at different temperatures was studied. SPAEK membranes with a DS from 0.72 to 1.60 maintained adequate mechanical properties after immersion in water at 80 °C for 24 h. The proton conductivity of SPAEK membranes with different degrees of sulfonation was measured as a function of temperature. The proton conductivity of the SPAEK films increased with increased DS, and the highest room temperature conductivity (4.2 × 10^?2 S/cm) was recorded for a SPAEK membrane with a DS of 1.60, which further increased to 1.1 × 10^?1 S/cm at 80 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2866–2876, 2004     

Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

A series of sulfonated poly(aryl ether ether ketone ketone)s statistical copolymers with high molecular weights were synthesized via an aromatic nucleophilic substitution polymerization. The sulfonation content (SC), defined as the number of sulfonic acid groups contained in an average repeat unit, could be controlled by the feed ratios of monomers. Flexible and strong membranes in sodium sulfonate form could be prepared by the solution casting method, and readily transformed to their proton forms by treating them in 2 N sulfuric acid. The polymers showed high T_gs, which increased with an increase in SC. Membranes prepared from the present sulfonated poly(ether ether ketone ketone) copolymers containing the hexafluoroisopropylidene moiety (SPEEKK‐6F) and copolymers containing the pendant 3,5‐ditrifluoromethylphenyl moiety (SPEEKK‐6FP) had lower water uptakes and lower swelling ratios in comparison with previously prepared copolymers containing 6F units. All of the polymers possessed proton conductivities higher than 1 × 10^?2 S/cm at room temperature, and proton conductivity values of several polymers were comparable to that of Nafion at high relative humidity. Their thermal stability, oxidative stability, and mechanical properties were also evaluated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2299–2310, 2006     

Boron trifluoride-methanol complex—mild and powerful reagent for deprotection of labile acetylated amines

A set of amino-group possessing cyanine dyes is obtained from their N-acetyl derivatives via deprotection with boron trifluoride-methanol complex in good yields.     

Metal-polymer PVDF/nickel composites and evaluation of their dielectric and thermal properties

Dielectric properties, thermal stability and sub-molecular structure of metal-polymer composites on the basis of polyvinylidene fluoride (PVDF) modified by sub-micro sized nickel powder were studied in this work by different methods such as dielectric spectroscopy, resistivity measurement, breakdown strength measurement, differential scanning calorimetry and optical microscopy. It was found that modification of PVDF by nickel particles results in the increase of both the volume resistivity by a factor of 1.24…15 and the melting and decomposition temperature by 5 °C and 48 °C for composite with an optimal nickel content compared with non-modified PVDF.     

Variable-frequency EPR study of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) single crystal at 9.6, 36, and 249.9 GHz: structural phase transition

Multifrequency electron paramagnetic resonance studies on the Mn(2+) impurity ion in a mixed single crystal NH(4)Cl(0.9)I(0.1) were carried out at 9.62 (X-band) in the range 120-295 K, at 35.87 (Q-band) at 77 and 295 K, and at 249.9 GHz (far-infrared band) at 253 K. The high-field EPR spectra at 249.9 GHz are well into the high-field limit leading to a considerable simplification of the spectra and their interpretation. Three magnetically inequivalent, but physically equivalent, Mn(2+) ions with their respective magnetic Z-axes oriented along the crystallographic [100], [010], [001] axes were observed. Simultaneous fitting of EPR line positions observed at X-, Q-, and far infra-red bands was performed using a least-squares procedure and matrix diagonalization to estimate accurately the Mn(2+) spin-Hamiltonian parameters. The temperature variation of the linewidth and peak-to-peak intensities of the EPR lines indicate the presence of lambda-transitions in the mixed NH(4)Cl(0.9)I(0.1) crystal at 242 and 228 K consistent with those observed in the pure NH(4)Cl and NH(4)I crystals, respectively. A superposition-model analysis of the spin-Hamiltonian parameters reveals that the local environment of the Mn(2+) ion is considerably reorganized to produce axially symmetric crystal fields about the respective Z-axes of the three magnetically inequivalent ions as a consequence of the vacancy created due to charge-compensation when the divalent Mn(2+) ion substitutes for a monovalent NH(4)(+) ion in the NH(4)Cl(0.9)I(0.1) crystal. This reorganization is almost the same as that observed in NH(4)Cl and NH(4)I single crystals, although the latter two are characterized by different, simple cubic and face-centered cubic, structures.     

Dynamical Analysis of Schrödinger Operators with Growing Sparse Potentials

We consider discrete half-line Schrödinger operators H with potentials of the form V(n)=S(n)+Q(n). Here Q is any compactly supported real function, if n=L_N and S(n)=0 otherwise, where (0,1) and L_N is a very fast growing sequence. We study in a rather detailed manner the time-averaged dynamics exp(–itH) for various initial states . In particular, for some we calculate explicitly the intermittency function ^–(p) which turns out to be nonconstant. The dynamical results obtained imply that the spectral measure of H has exact Hausdorff dimension for all boundary conditions, improving the result of Jitomirskaya and Last.Acknowledgement I would like to thank F. Germinet for useful discussions.     

Identifying the underlying structure and dynamic interactions in a voting network

We analyse the structure and behaviour of a specific voting network using a dynamic structure-based methodology which draws on Q-Analysis and social network theory. Our empirical focus is on the Eurovision Song Contest over a period of 20 years. For a multicultural contest of this kind, one of the key questions is how the quality of a song is judged and how voting groups emerge. We investigate structures that may identify the winner based purely on the topology of the network. This provides a basic framework to identify what the characteristics associated with becoming a winner are, and may help to establish a homogenous criterion for subjective measures such as quality. Further, we measure the importance of voting cliques, and present a dynamic model based on a changing multidimensional measure of connectivity in order to reveal the formation of emerging community structure within the contest. Finally, we study the dynamic behaviour exhibited by the network in order to understand the clustering of voting preferences and the relationship between local and global properties.     

Controllable propagation of light pulses in Er-doped fibers with saturable absorption

We report controllable (slow or fast) propagation of low-intensity probe-light pulses through erbium-doped fiber periodically saturated by the synchronized master-pulse sequence. These two pulse sequences could have significantly different carrier wavelengths within the fundamental absorption spectrum 1470-1570 nm of Er(+3) ions. The effect of fractional delay or advancement grew with the fiber optical absorption at the probe wavelength and could be significantly stronger than that at the saturating wavelength. The probe-pulse advancement was observed in the case when the saturating and probe waves were modulated approximately in antiphase. The observed effects are explained in the framework of a simple model of a periodically saturated homogeneously broadened absorption line.     

Superacid mediated hydroxyalkylation reaction of 1,2,3‐indanetrione: a theoretical study

Energies of mono‐ and multiprotonation for 1,2,3‐indanetrione and ninhydrin in triflic acid (TFSA) media were estimated at PBE0/aug‐cc‐pvtz//6‐31+G** level of theory. The reactivity of formed intermediates in the reaction of aromatic electrophilic substitution has been studied at the same level of theory. It appears that the basicity of carbonyl groups in 1,2,3‐indanetrione is extremely low due to mutual influences of carbonyl groups. Carbonyl 2 is the least basic but the most reactive in accordance with experiment. Calculations demonstrated that monoprotonated intermediates are the principal reactive species in the reaction of hydroxyalkylation of 1,2,3‐indanetrione in TFSA. A new isomerization mechanism of 2,2‐diaryl‐1,3‐indanediones to 3‐(diarylmethylene)isobenzofuranones in TFSA media has been proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

Supersymmetry and cohomology of graph complexes

Letters in Mathematical Physics - I describe a combinatorial construction of the cohomology classes in compactified moduli spaces of curves $$widehat{Z}_{I}in H^{*}left( bar{mathcal...