Organocatalytic Activation of the Leaving Group in the Intramolecular Asymmetric SN2′ Reaction

A Brønsted‐acid‐catalyzed intramolecular enantioselective S_N2′ reaction was developed utilizing trichloroacetimidate as a leaving group. The findings indicated that dual activation of the substrates is operative. This metal‐free allylic alkylation allows highly enantioselective access to 2‐vinylpyrrolidines bearing various substituents.     

Anionic ring-opening polymerization of silacyclobutane derivatives

Anionic polymerizations of 1,1-dimethylsilacyclobutane, 1,1-diethylsilacyclobutane and 1-methyl-1-phenylsilacyclobutane were investigated. Addition of 5 mol % of butyllithium to a solution of 1,1-dimethylsilacyclobutane in THF-hexane (1 : 1) at −48°C provided poly(1,1-dimethylsilabutane) in 99% yield. M_n and M_w/M_n of the obtained polymer were 2400 and 1.10. This polymerization proceeded with a living nature. M_n increased in proportion as the yield of polymer increased. Addition of the second fresh feed of the monomer to the reaction mixture restarted polymerization of the second monomer at the same rate as in the initial stage. Addition of styrene to the living poly(1,1-dimethylsilabutane) provided a poly(1,1-dimethylsilabutane-b-styrene) block copolymer. It was also found that a polymerization of 1,1-diethylsilacyclobutane in THF-hexane at −48°C showed a living nature. In contrast, a polymerization of 1-methyl-1-phenylsilacyclobutane in THF at −78°C did not show a living nature. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3207–3216, 1997     

Water‐dispersible microgel modified with methacryloyl groups by ionic bonding on the surface and the photopolymer microgel

A novel water‐dispersible reactive microgel, which had a diameter of 40–90 nm, was synthesized for photopolymer materials. The microgels have segments with substituted ammonium groups, to provide water solubility, in their polymer networked structure. It has unsaturated groups connected to the quaternary nitrogens by ionic bonding (I‐type microgel). The I‐type microgel was compared with one that has methacryloyl groups connected with the quaternary nitrogens of the microgel by covalent bonding (C‐type microgel). The I‐type microgels were able to separately control the modified amount of quaternary nitrogen and methacryloyl group. In the presence of 2,4‐diethylthioxantone as a photoinitiator and pentaerthritol triacrylate as a crosslinker, the photopolymer containing the C‐type or I‐type microgels had sensitivity high enough for practical use. Not only the amount of the methacryloyl group of the microgel but the amount of the quaternary nitrogen affected the sensitivity and the rate of polymerization of the water‐dispersible photopolymer containing the I‐type microgels. Copyright © 2000 John Wiley & Sons, Ltd.     

Global existence and nonexistence of solutions for second-order nonlinear differential equations

This paper deals with the global existence and nonexistence of solutions of the second-order nonlinear differential equation (φ(x^′))^′+λφ(x)=0${(\phi (x^{\prime }))}^{\prime }+\lambda \phi (x)=0$ satisfying x(0)=_x0$x(0)=x_0$ and x^′(0)=_x1$x^{\prime }(0)=x_1$, where λ   is a positive parameter and φ:(−ρ,ρ)→(−σ,σ)$\phi :(-\rho ,\rho )\to (-\sigma ,\sigma )$ with 0<ρ?∞$0<\rho ?\infty$ and 0<σ?∞$0<\sigma ?\infty$ is strictly increasing odd bijective and continuous on (−ρ,ρ)$(-\rho ,\rho )$. Necessary and sufficient conditions are obtained for the initial value problem to have a unique global solution which is oscillatory and periodic. Examples are given to illustrate our main result. Finally, a nonexistence result for the equation with a damping term is discussed as an application to our result.     

Oscillation criteria for second-order damped nonlinear differential equations with p-Laplacian

This paper is concerned with the oscillation problem for the nonlinear differential equation with a damping term,

     

Oscillation constant of second-order non-linear self-adjoint differential equations

Our concern is to solve the oscillation problem for the non-linear self-adjoint differential equation (a(t)x’)’+b(t)g(x)=0, where g(x) satisfies the signum condition xg(x)>0 if x≠0, but is not assumed to be monotone. Sufficient conditions and necessary conditions are given for all non-trivial solutions to be oscillatory. The obtained results show that the number 1/4 is a critical value for this problem. This paper takes a different approach from most of the previous research. Proof is given by means of phase plane analysis of systems of Liénard type. Examples are included to illustrate the relation between our theorems and results which were given by Cecchi, Marini and Villari. Received: January 5, 2001?Published online: June 11, 2002     

Gadolinium-based hybrid nanoparticles as a positive MR contrast agent

A new nanoparticulate inorganic-organic hybrid-type positive contrast agent (CA), PGP/dextran-K01, was synthesized based on a GdPO4 inorganic core as a relaxation-time-shortening moiety and a dextran-coating, which generates monodispersibility in water, a high relaxation-time-shortening effect by retaining a large number of water molecules in proximity of the core and toxicity reduction in in-vivo studies. This PGP/dextran-K01 nanoparticle has high r1 and r2 values and a significantly low r2/r1 value, 1.1, which is unprecedented and which is the lowest value among existing nanoparticulate CAs indicating that PGP/dextran-K01 is a positive contrast agent. Because of this low r2/r1 value and the nanoparticulate shape, PGP/dextran-K01 will be a useful clinical substitute for negative CAs based on iron oxides.     

Experimental evidence of interatomic coulombic decay from the auger final states in argon dimers

Interatomic Coulombic decay (ICD) from an Auger-final dicationic state is observed in the Ar dimer. A 2p inner-shell vacancy created by photoionization is replaced with 3s and 3p vacancies via intra-atomic Auger decay. The Auger-final dicationic state is subject to ICD in which one of the 3p electrons in the same Ar atom fills the 3s vacancy while one of the 3p electrons from the neighboring Ar atom is emitted as an ICD electron. This ICD process is unambiguously identified by electron-ion-ion coincidence spectroscopy in which the kinetic energy of the ICD electron and the kinetic energy release between Ar+ and Ar2+ are measured in coincidence.     

Reactive ketimino radical acceptors: intermolecular alkyl radical addition to imines with a phenolic hydroxyl group

Intermolecular carbon radical addition to the carbon-nitrogen double bond of ketimines was studied. In the study on the reactivity of various aldimines, we found that the aldimine 7 having a phenolic hydroxyl group shows an excellent reactivity toward nucleophilic carbon radicals. A remarkable effect of phenolic hydroxyl group is assumed to be the stabilization of intermediate aminyl radical provided by a hydroxyl group. The screening of reactive ketimino acceptors showed that ketimines 15, 17, and 19 having a phenolic hydroxyl group exhibit excellent reactivities. The radical addition to ketimines 15, 17, and 19 took place regioselectively at the imino carbon to give the C-alkylated products without the formation of N-alkylated products. Enantioselective ethyl radical addition to ketimine 15 using chiral box ligand and Zn(OTf)2 gave the diethylated product 30 in 80% ee.     

Elastic/adhesive double-layered PLA-PEG multiblock copolymer membranes for postoperative adhesion prevention

Tissue adhesions cause severe and life-threatening conditions, including pain, infertility, and heart defects. The purpose of this study is to develop an anti-adhesion membrane that sticks onto the injured tissues or organs in order to avoid the suturing of the membrane which may lead to the unnecessary tissue adhesion. We previously developed poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) multiblock copolymers as soft, water absorbable, and quickly degradable biomaterials. The copolymer with the highest PEG content adsorbs body fluid in vivo and sticks to the tissues. In the present study thin film and nanofiber mat were prepared from the copolymer and evaluated in vitro and in vivo. The hydrophilicity and the degradation rate increased with the increased PEG content of the multiblock copolymers. The copolymer with PEG content of 88% (LE(m)-88) was quickly swollen, become viscous, and rapidly collapsed in PBS, which was suitable feature for adhesion prevention material without suturing. Various double layered membranes with different characteristics were evaluated in vivo by applying onto the cecum scrubbed with abrasive paper, and onto the heart surface after pericardium removal. LE(m)-88 was swollen with tissue fluid and had a hydrogel-like nature. LE(m)-88 film/LE(m)-32 film double layered membrane was found to be the most effective in preventing tissue adhesion in cecum model. This excellent performance was confirmed in the rat heart adhesion model. In both models, the LE(m)-32 support film was detached from the site of application, which leads to the healing without adhesion.