Optical properties of transparent barium titanate nanoparticle/polymer hybrid synthesized from metal alkoxides

A transparent BaTiO₃ particle/polymer hybrid was synthesized from a Ba–Ti double alkoxide modified with an organic ligand and its refractive index and second harmonic generation were studied. BaTiO₃ particles modified with 2-vinyloxyethanol (ethylene glycol monovinyl ether, EGMVE) were polymerized with methyl methacrylate (MMA) yielding the transparent BaTiO₃ particle/poly MMA hybrid. X-ray photoelectron spectra indicated that the formation of chemical bonds between BaTiO₃ nanoparticles and the organic matrix. The refractive indexes of the hybrid films depended on the crystallite size of BaTiO₃ nanoparticles and the volume fractions of BaTiO₃ and polymer phases. The hybrid film synthesized at BaTiO₃/8EGMVE/30H₂O/PMMA revealed a refractive index of 1.65 at 589 nm with an Abbe number of 54. The hybrid film exhibited a second harmonic wave of 532 nm on irradiation with a fundamental wave of 1,064 nm.     

On Fermion Grading Symmetry for Quasi-Local Systems

We discuss fermion grading symmetry for quasi-local systems with graded commutation relations. We introduce a criterion of spontaneously symmetry breaking (SSB) for general quasi-local systems. It is formulated based on the idea that each pair of distinct phases (appeared in spontaneous symmetry breaking) should be disjoint not only for the total system but also for every complementary outside system of a local region specified by the given quasi-local structure. Under a completely model independent setting, we show the absence of SSB for fermion grading symmetry in the above sense. We obtain some structural results for equilibrium states of lattice systems. If there would exist an even KMS state for some even dynamics that is decomposed into noneven KMS states, then those noneven states inevitably violate our local thermal stability condition.     

Diastereoselective Synthesis of Open‐Chain Secondary Alkyllithium Compounds and Trapping Reactions with Electrophiles

A practical stereoselective iodide–lithium exchange was used in the first general preparation of functionalized stereodefined acyclic secondary nonstabilized lithium reagents from the corresponding secondary alkyl iodides. These lithium reagents react with various electrophiles including carbon electrophiles with high retention of configuration. Kinetic data on the configurational stability of these acyclic alkyllithium reagents are given. This methodology offers a new entry to chiral synthons for the stereoselective synthesis of open‐chain molecules.     

Cooperative Catalysis of Metal and O?H⋅⋅⋅O/sp3‐C?H⋅⋅⋅O Two‐Point Hydrogen Bonds in Alcoholic Solvents: Cu‐Catalyzed Enantioselective Direct Alkynylation of Aldehydes with Terminal Alkynes

Catalyst–substrate hydrogen bonds in artificial catalysts usually occur in aprotic solvents, but not in protic solvents, in contrast to enzymatic catalysis. We report a case in which ligand–substrate hydrogen‐bonding interactions cooperate with a transition‐metal center in alcoholic solvents for enantioselective catalysis. Copper(I) complexes with prolinol‐based hydroxy amino phosphane chiral ligands catalytically promoted the direct alkynylation of aldehydes with terminal alkynes in alcoholic solvents to afford nonracemic secondary propargylic alcohols with high enantioselectivities. Quantum‐mechanical calculations of enantiodiscriminating transition states show the occurrence of a nonclassical sp³‐C? H???O hydrogen bond as a secondary interaction between the ligand and substrate, which results in highly directional catalyst–substrate two‐point hydrogen bonding.     

Radical polymerization behavior of N-vinylsaccharin

Synthesis and radical polymerization behavior of N-vinylsaccharin (1) are described. Radical homopolymerization of 1 was carried out in the presence of a radical initiator for 24 h to afford the polymer containing a saccharin moiety in the side group, which was insoluble in common organic solvents. Among the copolymers of 1 with various vinyl monomers such as vinyl acetate (VAc), methyl acrylate (MA), acrylonitrile (AN), and styrene (St), only the copolymer [copoly(1-St)] obtained from 1 and St was soluble in common organic solvents. In the copolymerization of 1 and St, the Q and e values of 1 were estimated to be 0.10 and −1.60, respectively. These values are similar to those of N-vinylphthalimide (Q = 0.36, e = −1.52). The reaction of copoly(1-St) with LiAlH₄ was carried out in THF for 24 h to convert the saccharin moiety into the ring-opened structure bearing hydroxy and sulfonamide groups. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3419–3426, 1999     

Schiff base copper(II) chelate as a tool for immobilization of protein

In our previous report a new methodology for intermolecular cross-linking or bridging of protein utilizing a spontaneous chelate formation process was proposed. In this paper the reliability of the process as a tool for protein immobilization has been further evaluated. The chromatographic behavior of tryptophan in a column packed with Sepharose coupled with salicylaldehyde residue showed that the alpha-amino acid was bound tightly to the gel in the presence of copper(II) ion and was eluted by the addition of ethylenediaminetetraacetate (EDTA). It was also proved that subtilisin modified with an alpha-amino acid residue was immobilized on the column, and this binding was reversed by the addition of EDTA as well.     

Some Aspects of Quantum Entanglement for CAR Systems

We show some distinct features of quantum entanglement for bipartite CAR systems such as the failure of triangle inequality of von Neumann entropy and the possible change of our entanglement degree under local operations. Those are due to the nonindependence of CAR systems and never occur in any algebraic independent systems. We introduce a new notion half-sided entanglement.     

Further measurement of the 7Be(p,γ)8B cross section at low energies with the coulomb dissociation of 8B

We have measured the dissociation of ⁸B in the Coulomb field of ²⁰⁸Pb at E_in=51.9 MeV/nucleon and extracted the cross section of the ⁷Be(p,γ)⁸B reaction at 0.4 ≤ E_rel≤ 3 MeV, which is of importance for the ⁸B solar-neutrino production rate. The extracted astrophysical S₁₇ factors are consistent with our earlier Coulomb dissociation measurement, and agree with the values deduced from the direct capture measurements by Filippone et al., Vaughn et al. and Hammache et al. The S factor at zero energy was extracted to be 18.9±1.8 eV-b with the help of theoretical energy-dependence. Received: 15 August 1998     

Optical Control of Cytokine Production Using Photoswitchable Galactosylceramides

α-Galactosylceramides are glycosphingolipids that show promise in cancer immunotherapy. After presentation by CD1d, they activate natural killer T cells (NKT), which results in the production of a variety of pro-inflammatory and immunomodulatory cytokines. Herein, we report the synthesis and biological evaluation of photochromic derivatives of KRN-7000, the activity of which can be modulated with light. Based on established structure–activity relationships, we designed photoswitchable analogues of this glycolipid that control the production of pro-inflammatory cytokines, such as IFN-γ. The azobenzene derivative α-GalACer-4 proved to be more potent than KRN-7000 itself when activated with 370 nm light. Photolipids of this type could improve our mechanistic understanding of cytokine production and could open new directions in photoimmunotherapy.