Efficient synthesis of an aldehyde‐capped polythiophene containing fluorinated electron‐withdrawing groups

To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007     

FTIR spectroscopic study on the interaction between a fluoroionophore and metal ions.

A fluoroionophore sensor, N-[4-(1-pyrene)butyroyl]-L-tryptophan (PLT), has been reported. It can distinguish lead ion from other 12 metal ions via forming a pyrene dimer and it exhibits a very high sensitivity (0.15 microM) in aqueous solution (Chem. Commun., 2006, 2702). When the indole moiety in PLT was changed to benzene, in forming a new fluoroionophore of N-[4-(1-pyrene)butyroyl]-L-phenylalanine (PLP), it could not form a pyrene dimer in response to Pb(2+) in water. The present study describes the spectroscopic clarification of the intrinsic differences of the binding model between PLP and PLT in binding with Pb(2+). The model shows identical chelating bidentate coordination between COO(-) and Pb(2+) both in PLP-Pb and PLT-Pb; however, there is no indication of the interaction between the phenyl ring and the metal ion or the hydrogen bonding between amide groups in PLP-Pb. These differences in the binding model between PLP-Pb and PLT-Pb illustrate that the indole ring in PLT appears to play a crucial role in the high selectivity and sensitivity of PLT to lead(II) ion.     

Stability control of the electrooptic effect with new maleimide copolymers containing photoreactive tricyanopyrrolidene‐based chromophores

New photocrosslinkable maleimide copolymers have been synthesized by the attachment of a tricyanopyrrolidene‐based chromophore. The 2‐(3‐cyano‐4‐(2‐{4‐[hexyl‐(6‐hydroxy‐hexyl)‐amino]‐phenyl}‐vinyl)‐5‐oxo‐1‐{4‐[4‐(3‐oxo‐3‐phenyl‐propenyl)‐ phenoxy]‐butyl}‐1,5‐dihydro‐pyrrol‐2‐ylidene)‐malononitrile chromophore exhibits nonlinear optical activity and contains a chalcone moiety that is sensitive to UV light (λ = 330–360 nm) for crosslink formation. The maleimide monomers have also been functionalized with chalcone moieties. The resultant copolymers exhibit great processability, and one of them shows a maximum electrooptic coefficient of 90 pm/V at 1300 nm. We could control the thermal stability of the electrooptic coefficient with the newly synthesized photoreactive copolymers successfully. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 531–542, 2007     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Photoswitching of holographic polymer-dispersed liquid crystals doped with chiral dopant

Chiral dopants were added to the formulation of holographic polymer-dispersed liquid crystals and the effects studied in terms of grating formation dynamics, morphology, diffraction efficiency, contrast ratio and electro-optical properties of the films. A gradual increase of real-time diffraction efficiency, decrease of droplet size and increase of diffraction efficiency of the composite film were obtained with the addition and increasing content of chiral dopant, due to the increased viscosity of the liquid crystal (LC) doped with the chiral dopant leading to decreased droplet coalescence. The contrast ratio decreased with increasing content of chiral dopant due to the difficult orientation of LC molecules caused by the formation of a helical structure. Addition of a small amount of the chiral dopant increased the driving voltage slightly, whereas the decay time is decreased significantly as a result of the high twisting of the helical structure.     

关于多线性振荡奇异积分在加权Hardy-型空间上的一致估计

本文对一类具有光滑位相函数的多线性振荡奇异积分算子建立了一致的加权（H^1(R^n),L^1(R^n))估计及一致的加权（HKp(R^n),Kp(R^n)估计。     

Effect of C layer on the structures and magnetic properties of (0 0 1)-oriented [C/CoPt]n/Ag films

CoPt/Ag and [C/CoPt]n/Ag thin films have been prepared onto the glass substrates by magnetron sputtering. We investigated the evolution of texture and magnetic properties of CoPt/Ag and [C/CoPt]n/Ag films. The results show that C-doping plays an important role in improving (0 0 1) texture, improving the order parameter S, reducing the intergrain interactions, and making the magnetization reversal mechanism more close to Stoner-Wolfarth rotational mechanism. The growth mechanism of (0 0 1) texture also seems to be related strongly to the films thickness. Our results show that the highly (0 0 1)-oriented films with ordered fct phase have a significant potential for the perpendicular media of extremely high-density recording.     

Investigation of laminar plasma remelting/cladding processing

Investigation of remelting and cladding processing with laminar plasma jets on several metals has been conducted looking for possible development of a new surface modification technique. The remelting tests illustrated that the new method could evidently improve the material microstructure and properties of cast iron. The cladding was done with Al₂O₃ ceramic powder on stainless steel. The energy dispersive spectra (EDS) analysis was used to determine the distribution of the major cladding element in the plasma-processed layers, for which the microstructure observations and hardness measurements were also performed.     

Effect of the Electron-LO-Phonon Coupling on an Exciton Quantum Dot

The influence of the electron-LO-phonon coupling on energy spectrum of the low-lying states ofan exciton inparabolic quantum dots is investigated as a function of dot size. Calculations are made by using the method of few-bodyphysics within the effective-mass approximation. A considerable decrease of the energy in the stronger confinement rangeis found for the low-lying states of an exciton in quantum dots, which results from the confinement of electron-phononcoupling.