Asymmetric Kumada-Corriu cross-coupling reaction with Pd2(dba)3 and an N-Ar axially chiral mimetic-type ligand catalyst

A catalyst comprised of Pd₂(dba)₃·CHCl₃ and an N-Ar axially chiral mimetic-type ligand, (S)-N-[2-(diphenylphosphanyl)naphthalene-1-yl]-2-(piperidinylmethyl)piperidine, provides good enantioselectivities for the asymmetric Kumada-Corriu cross-coupling reaction of 1-phenylethylmagnesium chloride and E-β-bromostyrene derivatives with which it is more difficult to achieve high enantioselectivity. Furthermore, in the case of styrene derivatives bearing both vinyl and aryl bromide groups, the chemoselective asymmetric cross-coupling reaction of the vinyl bromide group is observed. This N-Ar axially chiral mimetic-type ligand allows easy synthesis of a wide variety of analogues, and starting from the initial ligand, the enantioselectivity of coupling products is improved by modifying the structure in the ligand.     

Dynamic analyses on induced-fit gaseous guest binding to organic crystals with a quartz-crystal microbalance

The inclusion behavior of gaseous guest molecules in a solid apohost, an orthogonal anthracene-bis(resorcinol)tetraol (1), was investigated with a quartz-crystal microbalance (QCM). Compound 1 forms crystals composed of molecular sheets bound together by an extensive hydrogen-bonded network. An apohost of 1 was cast onto a QCM and the binding of gaseous guest molecules was followed as a function of time by observing the decrease in the oscillation frequency, which is directly related to the increase in mass. Ethyl acetate and methyl ethyl ketone were significantly included into the apohost, whereas benzene and cyclohexane were simply adsorbed onto the surface of the solid; all these guests have similar vapor pressures at 25 degrees C. On the other hand, a host analogue 2, a tetramethoxy derivative of 1, barely included these guest molecules. The inclusion amount and the rate of inclusion of ethyl acetate or methyl ethyl ketone showed a drastic increase above a threshold concentration of guests in the gas phase. Thus, the structure of the apohost changed cooperatively in order to bind guest molecules above the threshold guest concentration. This cooperativity of the binding behavior was kinetically analyzed.     

Application of thin-layer chromatography with flame ionization detection to the characterization of organic extracts from diesel exhaust particulates

Thin-layer chromatography with flame ionization detection has been applied to the analysis of organic extracts of diesel exhaust particulates. Non-volatile organics whose boiling points are higher than ca. 300 degrees C can be analyzed, with a detection limit of ca. 0.03 micrograms and a relative standard deviation of ca. 10%. The organic extracts are separated into aliphatics , aromatics and polars by the development procedure with n-hexane, and the polars can be separated further by using toluene as the solvent. Some examples of application are presented.     

Clinical evaluation of population pharmacokinetic parameters in phenytoin dosage adjustment

We investigated the influence of the population pharmacokinetic parameters on the performance of the Bayesian feedback method in predicting the phenytoin (PHT) dosage needed to achieve a desired PHT serum concentration. Population pharmacokinetic parameters studied were taken from reports by Sheiner et al. (I), Grasela et al. (II), Miller et al. (III), and the authors (IV). The predictive abilities of the Bayesian feedback method were evaluated by using retrospective data from 70 patients. The mean prediction error, mean absolute prediction error (MAE), and root mean squared error (RMSE) served as measures of prediction bias and precision. The precision of the initial estimates based on the population parameter set IV was superior to those of other initial estimates studied. The performance of the Bayesian feedback method to predict PHT dosage at the steady state was relatively insensitive to bias in the estimates of the population parameters. However, the revised estimates derived from the Bayesian feedback method using the population parameter set IV with one feedback gave the lowest MAE and RMSE in predicting PHT dosage.     

Preconcentration technique for nonylphenol using cellulose cotton with homogenous liquid–liquid extraction for liquid chromatographic analysis

A powerful preconcentration method for nonylphenol (NP) has been developed for liquid-chromatography by combining the use of cellulose cotton (solid-phase extraction) with homogeneous liquid–liquid extraction. A 100 ml of sample solution was preconcentrated using cotton, and the eluate obtained (acetonitrile; 5 ml) was further preconcentrated to 50 l within 10 min using a homogeneous liquid–liquid extraction method (volume ratio, 2,000-fold; 100 ml 50 l). The sample concentration increases from preconcentration was 1,599-fold, and NP was extracted into the sedimented phase at 80%. The proposed method was applied to high performance liquid chromatography with fluorescence detection (FL/HPLC); the lowest determination limit obtained was 1.0×10^–9 mol l^–1.     

Synthesis of dl-coriolin

The total synthesis of dl-coriolin has been achieved in a stereoselective way. The key tricyclic intermediate was synthesized from dicyclopentadiene through a route which involved an S_N2 reaction at a neopentylic position.     

Influence of SO2 on the durability of Ag/Al2O3 catalyst in lean NOx reduction by ethyl alcohol

The influence of SO₂ (200 ppm) on the durability of a Ag/Al₂O₃ catalyst for the reduction of NOx with ethyl alcohol was examined. The results strongly suggest that H₂O in diesel engine exhaust is essential for the high durability of Ag/Al₂O₃ catalyst in the presence of SO₂.     

Dissolution behavior of tetrafluoroethylene-based fluoropolymers for 157-nm resist materials

We have synthesized various main-chain fluorinated polymers and studied base-resin properties, such as transparency at 157 nm, solubility in a standard alkaline developer, and lithographic performance. Main-chain-fluorinated polymers were synthesized by copolymerization of tetrafluoroethylene (TFE) with cyclic monomers, especially newly synthesized norbornene derivatives. We studied the correlation between pK_a(OH) and the solubility of the copolymers of TFE and functional (fluoroalkyl alcohol group) norbornenes. Their solubility depends on the pK_a value of the fluoroalkyl alcohol groups.We studied the impact of the polymerization initiators on base-resin properties. High transparency was obtained by using the fluorocarbon initiator. It was also confirmed that the monocyclic component improves dry-etch resistance and that fluorination at the terminal groups improves alkaline solubility.In addition, we found that the development characteristics of TFE/norbornene copolymers were significantly improved by the stereoselective (endo versus exo) partial protection of the hydroxyl groups in the fluoroalkyl alcohol moiety attached to norbornene unit. The polymer protected only in the exo position of the norbornene unit in the copolymer had a higher R_max and a higher contrast. Positive-working resists based on these fluoropolymers were developed and 55 nm dense lines could be delineated by exposure at 157 nm wavelength with an alternating phase shift mask on a 0.9 NA 157 nm exposure tool.     

One-pot synthesis of ω-bromoesters from aromatic aldehydes and diols using pyridinium hydrobromide perbromide

A simple and efficient one-pot procedure has been developed for the synthesis of ω-bromoesters from aromatic aldehydes and diols in the presence of pyridinium hydrobromide perbromide (PHPB) and triethoxymethane in which aldehyde reacts first with diol and the product, cyclic acetal, reacts with PHPB to give the final product, ω-bromoesters.     

Optimal control of ultrafast selection

Optimal laser control for ultrafast selection of closely lying excited states whose energy separation is smaller than the laser bandwidth is reported on the two-photon transition of atomic cesium; Cs(6S-->7D(J), J=5/2 and 3/2). Selective excitation was carried out by pulse shaping of ultrashort laser pulses which were adaptively modulated in a closed-loop learning system handling eight parameters representing the electric field. Two-color fluorescence from the respective excited states was monitored to measure the selectivity. The fitness used in the learning algorithm was evaluated from the ratio of the fluorescence yields. After fifty generations, a pair of nearly transform-limited pulses were obtained as an optimal pulse shape, proving the effectiveness of the "Ramsey fringes" mechanism. The contrast of the selection ratio was improved by approximately 30% from the simple "Ramsey fringes" experiment.