Yb(OTf)3-catalyzed cyclization of an N-silylenamine with 2-methylene-1,3-cyclohexanedione to afford a 7,8-dihydroquinolin-5(6H)-one derivative and its application to the one-pot conversion to a 2,3,5-trisubstituted quinoline derivative

A catalytic amount of ytterbium triflate (Yb(OTf)₃) promotes the cyclization of an N-silylenamine with in situ generated 2-methylene-1,3-cyclohexanedione and 2-methylenecyclohexanone to produce the corresponding 2,3-disubstituted 7,8-dihydroquinolin-5-one and 5,6,7,8-tetrahydroquinolin-5-one in moderate to good yields. A one-pot conversion of 7,8-dihydroquinolin-5-one to the quinoline derivative also proceeded in good yield.     

Ferroelectric phase transitions in Pb2xSn2(1-x)P2Se6 system

Heat capacities of the Pb_2xSn_2(1-x)P₂Se₆ crystals (x=0, 0.098, 0.251, 0.402 and 1.0) were measured using an adiabatic calorimeter at temperatures between 10 and 350 K. In the crystal of x=0, two heat capacity anomalies corresponding to the ferroelectric commensurate - intermediate incommensurate(C-IC) phase transition temperature T _i, and the incommensurate - paraelectric (IC-N) phase transition temperature T _c, were observed at 193.24±0.10 and 220.07±0.15 K, respectively. The phase transition temperatures decreased with an increase in Pb²⁺ concentration. The anomaly at Ti disappeared at x=0.251 in the mixed systems of the Pb_2xSn_2(1-x)P₂Se₆. In the crystal of Pb₂P₂Se₆ (x=1.0), no phase transition was observed. The normal heat capacities for the mixed crystals were determined by least squares fitting of the Debye and Einstein functions to the experimental data. The anomalous heat capacities gave the phase transition entropies of 8.5 and 1.5 J mol^-1 K^-1 for x=0. The large transition entropies are consistent with an order-disorder mechanism in the ferroelectric-paraelectric phase transitions in x=0. This revised version was published online in August 2006 with corrections to the Cover Date.     

Chemical release control: Schiff bases of vinylbenzaldehyde and functional amines

Schiff base (SB) monomers of vinylbenzaldehyde with functional amines were prepared. Copolymers of SB monomers with N-vinyl-2-pyrrolidone soluble in aqueous solutions were obtained in most cases. However, p-aminobenzenesulfonamide monomer resulted in gel formation. Thus, the reaction of vinylbenzaldehyde copolymer with the sulfonamide was used instead of the copolymerization. The hydrolytic behaviors of SB monomers and copolymers to liberate respective amines were structure dependent and, for most copolymers, the rates were lower than those of the corresponding monomers.     

Thermodynamically stable vesicle formation from glycolipid biosurfactant sponge phase

Thermodynamically stable vesicle (L(alpha1)) formation from glycolipid biosurfactant sponge phase (L(3)) and its mechanism were investigated using a "natural" biocompatible mannosyl-erythritol lipid-A (MEL-A)/L-alpha-dilauroylphosphatidylcholine (DLPC) mixture by varying the composition. The trapping efficiency for calcein and turbidity measurements clearly indicated the existence of three regions: while the trapping efficiencies of the mixed MEL-A/DLPC assemblies at the compositions with X(DLPC)< or =0.1 or X(DLPC)> or =0.8 were almost zero, the mixed assemblies at the compositions with 0.1 or =0.8 were multilamellar vesicles (L(alpha)) with diameter from 2 to 10 microm. Meanwhile, dynamic light scattering (DLS) measurement revealed that the average size of the vesicles at the composition of X(DLPC)=0.3 was 633.2 nm, which is remarkably small compared to other compositions. Moreover, the mixed vesicle solution at the composition of X(DLPC)=0.3 was slightly bluish and turbid and kept its dispersion stability at 25 degrees C for more than 3 months, indicating the formation of a thermodynamically stable vesicle (L(alpha1)). These results exhibited the formation of a thermodynamically stable vesicle (L(alpha1)) with a high dispersibility from the MEL-A/DLPC mixture. The asymmetric distribution of MEL-A and DLPC in the two vesicle monolayers caused by the difference in geometrical structures is very likely to have changed their self-assembled structure from a sponge phase (L(3)) to a thermodynamically stable vesicle (L(alpha1)).     

Evaluation of molecular structure in Langmuir monolayers of zinc stearate and zinc 12-hydroxystearate by IR external reflection spectroscopy

 In situ polarized Fourier transform IR external reflection spectra of Langmuir monolayers of zinc stearate and zinc 12-hydroxystearate on a water surface were recorded for various surface areas, and their molecular structures were estimated. In the zinc stearate monolayer, the wavenumbers and the absorbances of the antisymmetric and symmetric methylene stretching bands did not change during monolayer compression, which means that orientational and conformational changes of the hydrocarbon chain did not occur. However, wavenumber changes of the antisymmetric and symmetric carboxylate stretching bands were observed during surface compression. The change in the binding nature of the zinc cation to the carboxylate group was speculated. Moreover, it was elucidated that the structure of the hydrocarbon chain in the zinc 12-hydroxystearate monolayer was different from that in the zinc stearate monolayer. Received: 21 March 2001 Accepted: 6 July 2001     

Effects of poly(ethylene glycol) (PEG) concentration on the permeability of PEG-grafted liposomes

Poly(ethylene glycol)-grafted liposomes (PEG-liposomes) were prepared from dipalmitoylphosphatidylcholine (DPPC) with various amounts of distearoyl-N-monomethoxy poly(ethylene glycol)-succinyl-phosphatidylethanolamines (DSPE-PEG) with PEG molecular weights of 1000, 2000, 3000 and 5000. The effects of DSPE-PEG concentration on the permeability of PEG-liposomes were investigated using carboxyfluorescein (CF). In the gel state, the CF leakage from PEG-liposomes was decreased with increasing mole fractions of DSPE-PEG for all PEG molecular weights. In the liquid-crystalline state, the CF leakage from PEG-liposomes containing DSPE-PEG1000 gradually increased with increasing mole fractions of DSPE-PEG, while that of PEG-liposomes whose molecular weight in PEG units was above 2000 rapidly decreased by the addition of DSPE-PEG. Furthermore, no effect of PEG molecular weight on CF leakage was observed. The relationship between the fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) (or 1-(4-trimethylammoniumphenyl)-6-phenyl-1,3,5-hexatriene (TMA-DPH)) and the mole fraction of DSPE-PEG for PEG-liposomes was also investigated. No significant changes in fluorescence polarization of DPH for liposomal bilayer membranes was observed in the gel and liquid-crystalline states due to the addition of DSPE-PEG, while that of TMA-DPH was decreased compared with that of liposomes without DSPE-PEG in both states.     

Positive muons in [Co(NH3)6]Cl3 and [Co(ND3)6]Cl3

We have carried out SR experiments on [Co(NH₃)₆]Cl₃ and [Co(ND₃)₆]Cl₃. At 293 K, all the muons implanted into the complexes were in the diamagnetic state. The observed Gaussian-type muon spin relaxation function proved that the internal magnetic field was caused by nuclear dipole moments of the atoms in the complexes. In addition, another exponential-type muon spin relaxation function was observed in [Co(ND₃)₆]Cl₃ below 50 K.