Syntheses and characterization of carbazole based new low‐band gap copolymers containing highly soluble benzimidazole derivatives for solar cell application

Newly designed 2H‐benzimidazole derivatives which have solubility groups at 2‐position have been synthesized and incorporated into two highly soluble carbazole based alternating copolymers, poly[2,7‐(9‐(1′‐octylnonyl)‐9H‐carbazole)‐alt‐5,5‐(4′,7′‐di(thien‐2‐yl)‐2H‐benzimidazole‐2′‐spirocyclohexane)] (PCDTCHBI) and poly[2,7‐(9‐(1′‐octylnonyl)‐9H‐carbazole)‐alt‐5,5‐(4′,7′‐di(thien‐2‐yl)‐2H‐benzimidazole‐2′‐spiro‐4′′‐((2′′′‐ethylhexyl)oxy)‐cyclohexane)] (PCDTEHOCHBI) for photovoltaic application. These alternating copolymers show low‐band gap properties caused by internal charge transfer from an electron‐rich unit to an electron‐deficient moiety. HOMO and LUMO levels are –5.53 and –3.86 eV for PCDTCHBI, and –5.49 and –3.84 eV for PCDTEHOCHBI, respectively. Optical band gaps of PCDTCHBI and PCDTEHOCHBI are 1.67 and 1.65 eV, respectively. The new carbazole based the 2H‐benzimidazole polymers show 0.11–0.13 eV lower values of band gaps as compared to that of carbazole based benzothiadiazole polymer, poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)] (PCDTBT), while keeping nearly the same deep HOMO levels. The power conversion efficiencies of PCDTCHBI and PCDTEHOCHBI blended with [6,6]phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) are 1.03 and 1.15%, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Fluorescent sensing system for palladium(II) based on the Heck reaction

In this paper, we report a fluorescent sensing system based on the palladium-catalyzed Heck reaction between N-methyl vinylpyridinium and 4-bromo-N,N′-dimethylaniline. Generation of a new fluorophore as a product enhances fluorescence and permits selective detection of palladium(II) among other metal species.     

Stable single-frequency fiber ring laser for 25-GHz ITU-T grids utilizing saturable absorber filter

A stable single-frequency fiber ring laser is proposed that operates in a single mode for more than an hour by incorporating unpumped erbium-doped fiber (EDF) as a saturable absorber filter and optimizing the length of EDF used as gain medium. This laser can be continuously tuned to 25-GHz spacing that precisely matches the ITU-T grids by temperature control of etalon filter. This laser had a signal-to-source spontaneous emission ratio higher than 70 dB, and lasing frequencies of 361 channels was matched to ITU-T grids with excellent flatness. Frequency offset from the ITU-T grid was less than 0.14 GHz. The linewidth and the relative intensity noise value was less than 1.3 kHz and 130 dB/Hz (above 250 kHz), respectively.     

Highly monodisperse crosslinked polymethylmethacrylate microparticles by dispersion polymerization

Highly monodisperse polymethylmethacrylate (PMMA) microparticles crosslinked with carboxylic group-containing urethane acrylates (CUA) were produced by simple dispersion polymerization in methanol solution. In contrast to conventional crosslinkers, the CUA employed as a crosslinker was excellent for maintaining the monodispersity of PMMA microparticles even at moderate crosslinker concentrations (to about 5 wt%). It was believed that the CUA helped form the monomer-swellable surface of primary particles, because of the structurally long tetramethylene oxide groups in the molecule. Carboxylic groups in the molecular backbone resulted in larger primary particles by increasing the solubility of the monomer mixture in the medium. Owing to these larger primary particles, the crosslinked PMMA particles showed lower polymerization rates than the linear ones during particle growth. However, at high CUA concentrations (about 10 wt%), bimodal distributions were observed. This was attributed to the high crosslinking density of the primary particle surfaces. Therefore, monomer diffusion toward the polymer phase was restricted, resulting in more favorable secondary nucleation in the medium. Received: 12 May 1998 Accepted: 19 August 1998     

Electrorheological properties of carbon nanotube/polyelectrolyte self‐assembled polystyrene particles by layer‐by‐layer assembly

Sulfonated polystyrene (PS) particles were prepared by the sulfonation of PS microspheres with H₂SO₄. Then, composite particles were synthesized by layer‐by‐layer (LbL) self‐assembly with funtionalized multiwall carbon nanotubes (fMCNTs) and polyelectrolytes on sulfonated PS particles. The amount of fMCNTs on PS particles was adjusted by controlling the number of fMCNT layers by LbL self‐assembly. Composite particles were characterized by ζ‐potential analysis, scanning electron microscopy, and thermal analysis. The electrorheological (ER) properties of composite particles in insulating oil was investigated with varying the number of fMCNT layers under controlled electric fields. It was observed that the number of fMCNT layers was a critical factor to determine the ER properties of composite particles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1058–1065, 2008     

Improved properties of polyfluorenevinylenes by introduction of carbazole units

New electroluminescent polyfluorenevinylenes (PFV) copolymers with carbazole group, CzPFVs, have been synthesized by the GILCH polymerization. The carbazole groups were introduced as pendant to increase the electron rich ability of the copolymers. All CzPFVs exhibited absorption spectra with maximum peaks at around 417 nm. In the PL emission spectra of CzPFVs, maximum peaks around 463 nm and shoulder peaks around 490–500 nm were exhibited. By adjusting the feed ratios of carbazole groups in the CzPFVs, it is possible to have the higher current density and brightness, and the lower turn‐on voltage due to increasing hole injection ability. The maximum luminescence of CzPFV9 was 2003 cd/m² at 7 V. The introduction of carbazole contents in PFVs can enhance the device performance to result in stable PL and EL spectra with high current density and brightness due to the increased hole injection ability and reduced interchain interaction between polymer backbones. Especially, the 1:1 mixture of CzPFV10 and PVK didn't show aggregation effect in PL spectra even after annealing the thin film at 80 °C up to 60 min, since the interchain interaction among polymer backbones with fluorenevinylene units was reduced. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4407–4419, 2008     

Pulse width modulation for analog fiber-optic communications

The pulse width modulation (PWM) technique has been revisited and analyzed to evaluate its merits for application to analog signal transmission in fiber-optic links. Fourier analysis of the PWM signal reveals that it can be used as a vehicle to launch an analog signal onto optical fiber when a symmetrical natural sampling process is used. The SNR of the modulated signal depends on the timing jitter of the carrier pulses and a wide-band (45 MHz) SNR of 45 dB has been obtained with a commercially available multimode laser transmitter. A linear dynamic range of over 50 dB has been experimentally demonstrated. The full fiber bandwidth can be utilized by using a very high pulse carrier frequency, while a more popular pulse frequency modulation technique provides about a 10-MHz analog signal bandwidth when 1 km of multimode fiber is used in conjunction with a short wavelength (0.87 μm) LED transmitter. Analog transmission capability was experimentally demonstrated by constructing a simple video link using common laboratory equipment. The performance of the video link supports the PWM modulation theory developed here and elsewhere. The experimental results indicated that PWM is potentially very attractive for low-cost broad-band local area network (LAN) application, including future highly interactive offices, hospitals, and automated factory floors.     

Biocompatible microspheres based on acetylated polysaccharide prepared from water-in-oil-in-water (W1/O/W2) double-emulsion method for delivery of type II diabetic drug (exenatide)

Polysaccharide microspheres (PAMs) from acetylated pullulan were designed for the long-term delivery of peptide/protein drugs, as an alternative to a PLGA depot system. Three kinds of samples were obtained according to their different degrees of acetylation (0.8(PA1), 1.5(PA2), 2.3(PA3) acetyl groups in one glucose unit in pullulan), and then utilized to prepare a microsphere via a water-in-oil-in-water (W₁/O/W₂) emulsion method. The mean particle size of PAMs was shown to be in a range between 35 and 110 μm, as determined by a particle size analyzer. In order to evaluate their potential as a depot for protein/peptide delivery, exenatide, a drug used for the treatment of type II diabetes, was employed. The encapsulation efficiency of exenatide in PAMs was 69.1%, 80.4%, and 90.3% in PAM 1, PAM 2, and PAM 3, respectively. Although the release of exenatide from the PLGA microspheres evidenced a fast and high-burst behavior, PAMs evidenced a sustained release profile for 21 days. After 16 days, the released peptide was found to have a molecular weight almost identical to that of native exenatide, indicating that the stability of the peptide in the PAMs was maintained. The tissue reaction evidenced by the PAM was characterized by minimal foreign body reaction and minimal configurations of immune cells such as neutrophils and macrophages, but that of the PLGA microspheres was characterized by relatively elevated inflammation. On the basis of these results, we have concluded that the PAM may provide new insights into the development of new protein/peptide depots in long-term delivery.     

Autogenic synthesis of green- and red-emitting single-phase Pr(2)O(2)CO(3) and PrO(1.833) luminescent nanopowders

This Article reveals a rare synthesis of pure Pr(2)O(2)CO(3) (POC) nanopowder by thermolysis (700 °C) of a single chemical precursor in an autogenic reaction. The autogenic thermolysis of praseodymium acetate is a solvent-free, efficient, and straightforward approach yielding luminescent POC nanoparticles. The as-prepared POC nanopowder converted to PrO(1.833) (PO) powder via combustion. Methodical morphological, structural, and compositional characterizations of POC and PO powders are carried out, supported by mechanistic elucidation and the photoluminescent properties.