Fabrication of polymer Langmuir-Blodgett films containing regioregular poly(3-hexylthiophene) for application to field-effect transistor

Semiconducting thin films consisting of regioregular poly(3-hexylthiophene) (RR-PHT) and poly(N-dodecylacrylamide) (pDDA) were constructed by the Langmuir-Blodgett (LB) technique. A mixture of RR-PHT and pDDA spread from a chloroform solution on a water surface forms a stable monolayer, which can be transferred onto solid substrates by the LB method, yielding a well-defined polymer LB film. Surface morphology studies of the LB film indicate that the RR-PHT is dispersed uniformly throughout the surface. The polymer thin film was chemically doped by contacting with FeCl3 acetonitrile solution, and a conductivity of 5.6 S/cm was achieved. Further, the LB film was utilized as the semiconducting film in the field-effect transistor (FET), and mobilities of 2.2 x 10(-4) and 4.4 x 10(-4) cm2 V(-1) s(-1) were obtained by analyzing the saturated and linear regions of the current-voltage characteristic, respectively.     

Cationic ring‐opening polymerization of monothiocarbonate with a norbornene group

This work deals with the cationic ring‐opening polymerization of cyclic thiocarbonates with a norbornene or norbornane moiety, that is, 5,5‐(bicyclo[2.2.1]hept‐2‐ene‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC1 ) or 5,5‐(bicyclo[2.2.1]heptane‐5,5‐ylidene)‐1,3‐dioxane‐2‐thione ( TC2 ), respectively. The reaction of TC1 initiated by trifluoromethanesulfonic acid (TfOH), methyl trifluoromethanesulfonate (TfOMe), boron trifluoride etherate (BF₃OEt₂), or triethyloxonium tetrafluoroborate (Et₃OBF₄) afforded unidentified products; however, TC1 underwent cationic ring‐opening polymerization with methyl iodide as an initiator to afford polythiocarbonate because the propagating end was stabilized by the covalent‐bonding property. The polymerization of TC2 initiated by TfOH, TfOMe, BF₃OEt₂, or Et₃OBF₄ afforded polythiocarbonate with good solubility in common organic solvents and a narrow molecular weight distribution because of the absence of a double‐bond moiety. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1698–1705, 2002     

Phase morphology of hydrolysable polyurethanes derived from aqueous dispersions

Biodegradable polyurethanes are an interesting alternative to many applications that involve plastics since they can minimize environmental problems caused by the low rates of natural degradation of synthetic polymers. In addition, since waterborne polyurethanes are based on aqueous dispersions, they restrict the use of organic solvents during processing and application of the polymer, thus contributing furthermore to reduce environmental damage. In this work, aqueous anionic polyurethane dispersions (PUD) with tailorable susceptibility for hydrolysis were synthesized by progressively replacing polypropylene glycol (PPG) with a biodegradable polycaprolactone diol (PCL) as soft segments. The hard segments were formed by extending isophorone diisocyanate (IPDI) with hydrazine (HZ). Dimethylol propionic acid (DMPA) was used as ionic center and triethyl amine (TEA) as neutralizer. The degree of phase separation was evaluated mainly by infrared spectroscopy (FTIR) and small angle X-ray scattering (SAXS). The results indicated that phase separation between hard and soft segments of poly(ester-urethane) is more significant than that of poly(ether-urethane). Data obtained from SAXS experiments indicated that phase separation within soft domains can also be present in samples containing both polyester and polyether soft segments. Hydrolytic degradation of the polymers in buffer solution of pH 7.4 and alkaline solution was performed as an initial test. The results showed that the fraction of polyester soft segments in the polyurethanes can be used to tailor the susceptibility of the materials to hydrolytic attack. Polyurethanes having higher contents of polyester were more promptly hydrolytically degraded than polyurethanes containing only polyether segments.     

Peroxotungstate immobilized on ionic liquid-modified silica as a heterogeneous epoxidation catalyst with hydrogen peroxide

Peroxotungstate immobilized on ionic liquid-modified SiO2 is capable of heterogeneously epoxidizing a wide range of olefins with the maintenance of the catalytic activity of homogeneous analogue. The epoxidation was immediately stopped by the removal of the catalyst, and no tungsten species could be found in the filtrate after the removal of the catalyst. These results can rule out any contribution to the observed catalysis from the tungsten species that leached into the reaction solution, and the observed catalysis is truly heterogeneous in nature. Furthermore, the catalyst was reusable without the loss of the catalytic performance.     

Highly sensitive determination of a polymeric hindered amine light stabilizer in polypropylene by reactive thermal desorption-gas chromatography using nitrogen-specific detection

Highly sensitive and specific determination of trace amounts of a polymeric hindered amine light stabilizer (HALS) in polypropylene (PP) materials could be established by improving reactive thermal desorption-gas chromatography (RTD-GC) in the presence of an organic alkali, tetramethylammonium hydroxide. By using nitrogen-phosphorus detection, highly selective detection of the HALS-related components was attained. In addition, the use of a polar poly(ethylene glycol) separation column alleviated the adsorption of minor specific pyrolysis products. This modified RTD-GC method allowed the determination of the polymeric HALS (Mr 1900) in PP even for trace concentrations between 100 and 500 ppm, through observing selectively the characteristic products containing a tetramethylpiperidine moiety, which had been impossible to detect under the previous RTD-GC conditions using a non-polar separation column and conventional flame ionization detection.     

Radical addition to "cation pool". Reverse process of radical cation fragmentation

The reaction of an N-acyliminium ion with an alkyl iodide and hexabutyldistannane took place to give the alkylation product. A mechanism involving the addition of an alkyl radical to an N-acyliminium ion to produce the corresponding radical cation has been suggested.     

Conductometric titration of nitrate by formation of the silver-1,10-phenanthroline-nitrate ternary complex

Nitrate forms an insoluble ternary complex, Ag(phen)(2)NO(3), with silver in the presence of 1,10-phenanthroline (phen). A simple and direct conductometric titration of nitrate, based on the formation of this ternary complex, has been investigated. The sample solution is adjusted to pH 4.3 with acetate buffer and titrated with 0.1M Ag(phen)(+)(2) complex solution in 40% ethanol-water mixture. The relative error is less than 0.5% and relative standard deviation less than 0.4%. The effect of ammonium ion and urea has also been studied. The method has been successfully applied to determination of nitrate-nitrogen in fertilizer.     

Synthesis of 12-deoxyroyleanone, cryptoquinone, 11,14-dihydroxy-8,11,13-abietatrien-7-one, and related derivatives from dehydroabietic acid

Naturally occurring abietane quinones and hydroquinone, namely, 12-deoxyroyleanone (1a), cryptoquinone (4a), and 11,14-dihydroxyabieta-8,11,13-trien-7-one (5a), together with the epimers of tryptoquinones D (2) and F (3), were first synthesized from dehydroabietic acid (6).     

Static and dynamic structures of spherical nonionic surfactant micelles during the disorder-order transition

We have investigated the static and dynamic structures of nonionic surfactant micelles, a C(12)E(8)/water binary system, during the disorder-order transition using small angle x-ray scattering, static light scattering, and dynamic light scattering techniques. In the disordered phase, the micelles have spherical shape and intermicellar interactions are governed by the hard core and weak long ranged attractive potentials. With increase of the micellar concentration, the disordered micelles transform to the three characteristic ordered micellar phases, a hexagonally close packed lattice, a body centered cubic lattice, and an A15 lattice having area-minimizing structure. The stability of these phases is well explained by balance of a close packing rule and a minimal-area rule proposed by Ziherl and Kamien [Phys. Rev. Lett. 85, 3528 (2000)]. The role of hydrodynamic interactions in surfactant micellar solutions was compared with that in hard sphere colloidal particle suspensions.     

Molecular mechanics (MM3) calculations on lithium amide compounds

The MM3 force field has been extended to deal with the lithium amide molecules that are widely used as efficient catalysts for stereoselective asymmetric synthesis. The MM3 force field parameters have been determined on the basis of the ab initio MP2/6-31G* and/or DFT (B3LYP/6-31G*, B3-PW91/6-31G*) geometry optimization calculations. To evaluate the electronic interactions specific to the lithium amides derived from the diamine molecules properly, the Lewis bonding potential term for the interaction between the lithium atom and the nonbonded adjacent electronegative atom such as nitrogen was introduced into the MM3 force field. The bond dipoles were evaluated correctly from the electronic charges on the atoms calculated by fitting to the electrostatic potential at points selected. The MM3 results on the molecular structures, conformational energies, and vibrational spectra show good agreement with those from the quantum mechanical calculations.