Synthesis of 2,7‐Carbazolenevinylene‐Based Copolymers and Characterization of Their Photovoltaic Properties

New electroactive and photoactive conjugated copolymers consisting of alternating 2,7‐carbazole and oligothiophene moieties linked by vinylene groups have been developed. Different oligothiophene units have been introduced to study the relationship between the polymer structure and the electronic properties. The resulting copolymers are characterized by UV‐vis spectroscopy, size‐exclusion chromatography, and thermal and electrochemical analyses. Bulk heterojunction photovoltaic cells from different copolymers and a soluble fullerene derivative, [6,6]‐phenyl‐C₆₁ butyric acid methyl ester, have been fabricated, and promising preliminary results are obtained. For instance, non‐optimized devices using poly(N‐(4‐octyloxyphenyl)‐2,7‐carbazolenevinylene‐alt‐3″,4″‐dihexyl‐2,2′;5′,2″;5″,2″′;5″′,2″″‐quinquethiophenevinylene 1″,1″‐dioxide) as an absorbing and hole‐carrier semiconductor exhibit power conversion efficiency up to 0.8 % under air mass (AM) 1.5 illumination. These features make 2,7‐carbazolenevinylene‐based and related polymers attractive candidates for solar‐cell applications.     

Luminescence properties of anodic aluminum oxide films with organic luminophores embedded into pores

Luminescence properties of porous anodic aluminum oxide films formed in a 0.6 M solution of citric acid and luminescence of paraterphenyl, perylene, coumarin 7, and rhodamine 6G dyes adsorbed by the films are investigated. The nature of emitting centers in anodic aluminum oxide is revealed. Intense photoluminescence of all tested dyes embedded into pores of anodic aluminum oxide has been found. A redshift of fluorescence spectra of dyes adsorbed by the matrix and emergence of an additional longwave band have been detected. Data obtained can be used in developing new thin-film luminescent coatings for future applications in optoelectronics and molecular electronics. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No 4, pp. 483–488, July–August, 1997.     

Linear and Nonlinear Optical Properties Of Racemic (±)2-(α-Methylbenzylamino)-5-Nitropyridine Single Crystals

Linear and nonlinear optical properties of racemic (±)2-(α-methylbenzylamino)-5-nitropyridine ((±)MBANP) single crystals have been comprehensively investigated and compared with those of the enantiomorph (–)2-(α-methylbenzylamino)-5-nitropyridine ((–)MBANP) crystals. (±)MBANP crystal exhibits very high chemical and physical stability, but relatively small nonlinear optical coefficients (d₃₁ = 6.8 pm/V, d₃₂ = 4.7 pm/V, d₃₃ = 0.84 pm/V). A comparison between the nonlinear optical coefficients of (±)MBANP and (–)MBANP demonstrates the validity of the oriented-gas model in molecular crystals that neglects all the contributions from intermolecular interaction.     

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     

Reintroduced solids increase inhibitor levels in a pretreated corn stover hydrolysate

Following detoxification of the liquid hydrolysate produced in a corn stover pretreatment process, inhibitor levels are seen to increase with the re-addition of solids for the ensuing hydrolysis and fermentation processes. The solids that were separated from the slurry before detoxification of the liquor contain approx 60% (w/w) moisture, and contamination occurs owing to the diffusion of inhibitors from the moisture entrained in the porous structure of the corn stover solids into the bulk fluid. This evidence suggests the need for additional separation and detoxification steps to purge residual inhibitors entrained in the moisture in the solids. An overliming process to remove furans from the hydrolysate failed to reduce total organic acids concentration, so acids were removed by treatment with an activated carbon powder. Smaller carbon doses proved more efficient in removing organic acids in terms of grams of acid removed per gram of carbon powder. Sugar adsorption by the activated carbon powder was minimal.     

The analysis of volatile trace compounds in landfill gases,compost heaps and forest air

Landfill gas, cryotrapped on a loop fashioned from a length of a capillary gas chromatography (GC) column, was examined for volatile organometallic compounds (VOMCs) and for volatile organic compounds (VOCs) by using GC–mass spectrometry (MS). A large number of organic components were present and many were identified, but the only VOMCs present in high enough concentrations to be detected were trimethylstibine and tetramethyltin. The use of inductively coupled plasma (ICP)‐MS as an element‐specific detector allowed the identification of a number of other organometallic species in the landfill gas, including trimethylarsine and trimethylbismuth, and, for the first time, butyltrimethyltin and dibutyldimethyltin. The presence of molybdenum hexacarbonyl was confirmed. Gas from a large‐scale compost heap and from compost incubated in the laboratory contained iodomethane but no common VOMCs (GC–ICP‐MS). Only VOCs were present in forest air (GC–MS). Copyright © 2003 John Wiley & Sons, Ltd.     

Electrical properties and memory effect in the field effect transistor based on organic ferroelectric insulator and pentacene

We have fabricated a field effect transistor (FET) based on an organic ferroelectric insulator and molecular conductor, and investigated the electrical properties and memory effects on the PEN-FET. We have observed a drastic change in the drain current at around the coercive electric fieldE _c of the organic ferroelectric insulator in not only a FET (PEN-FET) based on a pentacene (PEN) film but also a FET (IPEN-FET) based on an iodine doped PEN film. The magnitude of the change of the drain current for the IPEN-FET is 200 times larger than that for the PEN-FET. It is expected from these results that the PEN-FET (especially the IPEN-FET) is an improvement in such devices, since it operates at a low gate electric field accompanied by the appearance of the spontaneous polarization in the organic ferroelectric insulator. In addition, we have found that the drain current for the PEN-FET does not return to the initial drain current ofE _G =0 V/cm for more than one week, even if the gate electric field is changed to 0 V/cm from 500 V/cm(>E _c ). From these results, it is suggested that the PEN-FET becomes a memory device.     

Laser spectroscopic investigation of a new precursor-type polyparaphenylenevinylene

Optical, structural and morphological properties of thin films of polyparaphenylenevinylene (PPV) formed by an alkyl sulfinyl precursor route have been studied. Thin films were fabricated on an optical glass and on quartz glass either by spin-coating of the precursor solution or by layer-by-layer deposition using Langmuir–Blodgett technique. PPV precursor films were also spin-coated on gold-coated glass in order to study thin-film optical parameters by surface plasmon spectroscopy. We have been successful in forming about 40 precursor mono layers on quartz glass by Langmuir–Blodgett technique using optimized surface pressure and dipping conditions. After thermal conversion of the precursor layers good quality fluorescent PPV films of yellow colour have been obtained. Optical characterization of the films was carried out by linear absorption and emission spectroscopy, ellipsometry, and surface plasmon spectroscopy. Structural and morphological studies on the thin films were carried out by using X-ray scattering and atomic force microscopy. Wave-guided travelling-wave laser action has been achieved in a PPV film on quartz glass. The sample was transversally pumped with picosecond laser pulses (wavelength 347.15 nm, duration 35 ps). Laser emission occurred at 550 nm for pump pulse energy densities above .     

An Efficient Method for the Synthesis of 3-Cyano-6-hydroxy-2(1H)-pyridinones under Microwave Irradiation and Solvent-free Conditions

Summary. Three component condensation of alkylacetoacetates, primary amines, and alkyl cyanoacetates catalyzed by solid supports under microwave irradiation gave N-alkyl 3-cyano-6-hydroxy-2(1H)-pyridinones with high yields. Upon carrying out the reaction under the same condition on acidic alumina, zeolite HY, silica gel, and montmorillonite K-10, the best yields were achieved by silica gel. Corresponding author. E-mail: balalaie@yahoo.com Received August 28, 2002; accepted September 3, 2002