Enhancement of electroluminescence intensity in poly(3-alkylthiophene) with different alkyl side-chain length by doping of fluorescent dye

Electroluminescent diodes utilizing poly(3-alkylthiophene) (PAT) containing fluorescent dyes have been fabricated and their unique enhancement of emission characteristics have been studied. Remarkable enhancement of the electroluminescence efficiency has been observed for diodes with PAT doped with oxadiazole derivative (2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole; PBD) and perylene derivative (N,N′ - Bis(2,5 - di - tert - butylphenyl) - 3,4,9,10 - perylenedi- carboximide; BPPC). The mechanism of emission enhancement by doping of PBD into PAT has been discussed with different alkyl side-chain lengths. © 1997 John Wiley & Sons, Ltd.     

Miscibility of Polyoxymethylene Blends as Revealed by High-resolution Solid-state 13C-NMR Spectroscopy

The miscibility of polyvinylphenol (PVPh) or terpenephenol (TPh) with polyoxymethylene (POM) was examined by high-resolution solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. It was found that the driving force for the mixing of POM and PVPh is the hydrogen-bonding interaction between the phenolic OH group of PVPh and the ether oxygen of POM, and that the mixing is preferentially induced in the noncrystalline phase. ¹H relaxation time experiments indicated that POM/PVPh blends were homogeneous on a scale of 20–30 nm but heterogeneous on a scale of 2–3 nm. On the other hand, Fourier transform infrared and cross-polarization/magic-angle-spinning ¹³C-NMR (nuclear magnetic resonance) spectra revealed that POM and TPh are also mixed in the noncrystalline phase through the intermolecular hydrogen-bonding interaction, while some fraction of POM is still crystallizable. Moreover, the domain size of the micro-phase separation was estimated to be about 1 nm by the direct ¹H spin-diffusion measurements, suggesting almost homogeneous mixing on a molecular level in the noncrystalline phase. © 1997 John Wiley & Sons, Ltd.     

Multiple cluster model (MCM) for surface reaction systems

Multiple cluster model (MCM) for investigating surface reactions is formulated. In this model the reaction center, where electron correlation effects often play a key role, is described by an accurate high‐level approximation, and bulk effects such as the lattice distortion energy are evaluated using a simple low‐level approximation. Therefore, the MCM can properly simulate the potential energy hypersurface of the surface reaction system with a feasible computational cost. Since there exists no fixed atom in the MCM, we can rigorously characterize the stationary point (the minimum energy point or the transition state) on the potential energy hypersurface by vibrational frequency analysis. The MCM can be applied not only to surface systems, but also to various large systems. A detailed comparison of the MCM with the integrated molecular orbital+molecular mechanics (IMOMM), the integrated molecular orbital+molecular orbital (IMOMO), and ONIOM developed by Morokuma and co‐workers is also presented. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 403–413, 1999     

Low temperature deposited Zr-B film applicable to extremely thin barrier for copper interconnect

We have prepared thin Zr-B films at low temperatures as a new material applicable to an extremely thin barrier against Cu diffusion in Si-ULSI metallization. The obtained Zr-B films mainly consist of the ZrB₂ phase with a nanocrystalline texture on SiO₂ and a fiber texture on Cu. The resistivity of the Zr-B films depends on the substrate of SiO₂ or Cu. The constituent ratio of B/Zr is almost 2, though the contaminants of oxygen, nitrogen, and carbon are incorporated in the film. The nanocrystalline structure of the Zr-B film on SiO₂ is stable due to annealing at temperatures up to 500 °C for 30 min. We applied the 3-nm thick Zr-B film to a diffusion barrier between Cu and SiO₂, and the stable barrier properties were confirmed. We can demonstrate that the thin Zr-B film is a promising candidate for thin film application to a metallization material in Si-ULSIs.     

Preparation and medical application of magnetic beads conjugated with bioactive molecules

Ferrite nanobeads were synthesized from an aqueous solution utilizing Fe²⁺ to Fe³⁺ oxidation for use as magnetic carriers in bioscreening, bio-molecular recognition and anti-cancer diagnosis and therapy. The beads had a crystal structure that was intermediate between Fe₃O₄ and γ-Fe₂O₃. Functional biomolecules were strongly conjugated onto the surfaces of the ferrite beads via COOH and SH groups. The addition of ferrite seed crystals (3-8 nm in size) together with a disaccharide enabled the synthesis of monodisperse, spherical ferrite beads with average diameters (d¯) between 50 and 150 nm and relative deviation Δd/d¯=9-16%. Hollow ferrite nano-spheres (d¯=150-450 nm, Δd/d¯≈10%) were prepared using silica spheres as templates, which were dissolved in NaOH solution. Ferrite beads 40 nm in size were encapsulated in polymer spheres of styrene and polymerized glycidyl methacrylate (poly-GMA), 184±9 nm in diameter. They were used for high throughput bioscreening system for affinity purification of target proteins which make specific bindings to anti-cancer drugs, porphyrins, environment hormones, etc.     

Stereoselective synthesis and absolute configuration of the C33-C42 fragment of symbiodinolide

Cross-metathesis of methyl ester which was prepared from symbiodinolide with ethylene was performed to give the C33-C42 degraded fragment. This fragment was estimated to be (36S,40S)-diol by the modified Mosher method. Stereoselective synthesis of the (36S,40S)-diol and its diastereomer (36R,40S)-diol was achieved from l-aspartic acid. Synthetic bis-(S)- and (R)-MTPA esters which were derivatized from the (36S,40S)-diol exhibited spectroscopic data identical with those of bis-(S)- and (R)-MTPA esters derived from the degraded product. Thus, the absolute stereochemistry of the C33-C42 fragment was elucidated to be (36S,40S).     

Bifunctional Heterogeneous Catalysis of Silica–Alumina‐Supported Tertiary Amines with Controlled Acid–Base Interactions for Efficient 1,4‐Addition Reactions

We report the first tunable bifunctional surface of silica–alumina‐supported tertiary amines (SA–NEt₂) active for catalytic 1,4‐addition reactions of nitroalkanes and thiols to electron‐deficient alkenes. The 1,4‐addition reaction of nitroalkanes to electron‐deficient alkenes is one of the most useful carbon–carbon bond‐forming reactions and applicable toward a wide range of organic syntheses. The reaction between nitroethane and methyl vinyl ketone scarcely proceeded with either SA or homogeneous amines, and a mixture of SA and amines showed very low catalytic activity. In addition, undesirable side reactions occurred in the case of a strong base like sodium ethoxide employed as a catalytic reagent. Only the present SA‐supported amine (SA–NEt₂) catalyst enabled selective formation of a double‐alkylated product without promotions of side reactions such as an intramolecular cyclization reaction. The heterogeneous SA–NEt₂ catalyst was easily recovered from the reaction mixture by simple filtration and reusable with retention of its catalytic activity and selectivity. Furthermore, the SA–NEt₂ catalyst system was applicable to the addition reaction of other nitroalkanes and thiols to various electron‐deficient alkenes. The solid‐state magic‐angle spinning (MAS) NMR spectroscopic analyses, including variable‐contact‐time ¹³C cross‐polarization (CP)/MAS NMR spectroscopy, revealed that acid–base interactions between surface acid sites and immobilized amines can be controlled by pretreatment of SA at different temperatures. The catalytic activities for these addition reactions were strongly affected by the surface acid–base interactions.     

Mass selective ejection by axial resonant excitation from a linear ion trap

We describe a new mass selective ejection method from a linear ion trap, which we call axial resonant excitation (AREX). A set of vane lenses are inserted between each quadrupole rod to produce electrostatic potential that is approximately harmonic along the central axis of the quadrupole field. After ions with specific m/z are resonantly oscillated in the axial direction, the ions are mass selectively ejected in the axial direction. At a high scan rate of 11 Th/ms, AREX achieved a high ejection efficiency of more than 60%, which is more than three times higher than a conventional mass selective axial ejection method from a linear trap using fringing field.     

Synthesis and characterization of bromonium ylides and their unusual ligand transfer reactions with N-heterocycles

Stable aliphatic bromonium ylides (RfSO2)2C--Br+C6H4-p-CF3 (Rf = CF3, CF3(CF2)3) have been synthesized and structurally characterized for the first time. X-ray crystallographic analyses indicated a ylide structure with an sp2 hybridization of the ylide carbanions and with little double-bond character for the ylidic bond. The bromonium ylides selectively undergo transfer of the aryl group to nitrogen heterocycles, such as pyridines, yielding N-arylpyridinium salts. This is in a marked contrast to the reaction of the iodonium ylides, which produces pyridinium ylides through transylidations.