Highly Pure Synthesis,Spectral Assignments,and Two‐Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units

Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ⁽²⁾) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.     

Study of transient photorefractive beam coupling in high- and low-molar-mass liquid crystal mixtures

We observed transient signals of Bragg grating formation in high-performance photorefractive high- and low-molar-mass liquid crystal mixtures (HL-LCMs). These transient signals including oscillation-like behavior can be explained by a complex time constant in the case of a finite applied dc field. The time constant for the space-charge field to reach its steady state and the oscillation frequency are estimated. Received: 30 October 1998 / Revised version: 14 December 1998 / Published online: 24 February 1999     

Catalytic activation of nucleophile precursors with metal acetates in alcohol media and applications to enantioselective Michael addition reactions

Nickel(II) acetate tetrahydrate works as catalyst to activate nucleophile precursors in Michael addition reactions. Use of alcohol media is essential for the high catalytic activation of nucleophile precursors. Catalytic enantioselective reactions using a chiral nickel(II) acetate tetrahydrate between dimedone and α,β-unsaturated amide acceptors provide a useful synthetic access to enantiomers of enol lactones through the carbon-carbon bond formation.     

Far infrared optical properties of high Tc superconductors LnBa2Cu3Ox (Ln=Y, Ho, Er, Sm, GD, Dy, Eu, Pr)

Systematic measurements of the far infrared reflection spectra of high T_c superconductors LnBa₂Cu₃O_x for various Ln as shown in the title were performed. Infrared reflection spectra of tetragonal LnBa₂Cu₃O_x exhibit Reststrahlen vibration near 640, 590, 530, 355 and 250 cm^–1, common to these materials, and the spectra of the orthorhombic LnBa₂Cu₃O_x exhibit the characteristics of free carriers except PrBa₂Cu₃O_x with weak phonon structures near 617, 570, 317 and 285 cm^–1. PrBa₂Cu₃O_x is not a superconductor, and it has no characteristic broad band due to free carriers for all x in the range of 6 to 7. Lattice dynamical calculation was performed by the use of the shell model and the calculated results express quite well the characteristic features of infrared experiments.     

m × n] metal ion arrays templated by coordination cages

Three-dimensional m × n arrays of metal ion clusters can be assembled as aromatic stacks of planar polynuclear metal complexes within columnar coordination cages. The polynuclear complexes and cage height program the final array structures of the metal ion clusters. Cyclic trinuclear Au(I) complexes (m = 3) assembled into trigonal prismatic arrays (n = 1-3) within the cages and the array structures were clearly shown by X-ray crystallographic analysis. A silver-sandwiched hetero-Au(3)-Ag-Au(3) cluster was also prepared by treating a hexanuclear Au(3)-Au(3) cluster with Ag(I) ion.     

Pneumatic handling of droplets on-demand on a microfluidic device for seamless processing of reaction and electrophoretic separation

Sequential operations of pre-separation reaction process by picoliter droplets and following electrophoretic separation process were realized in a single microfluidic device with pneumatic handling of liquid. The developed device consists of a fluidic chip made of PDMS, an electrode substrate, and a temperature control substrate on which thin film heater/sensor structures are fabricated. Liquid handling, including introduction of liquid samples, droplet generation, and merging of droplets, was implemented by pneumatic manipulation through microcapillary vent structures, allowing air to pass and stop liquid flow. Since the pneumatic manipulations are conducted in a fully automated manner by using a programmable air pressure control system, the user simply has to load liquid samples on each liquid port of the device. Droplets of 420 pL were generated with an accuracy of ± 2 pL by applying droplet generation pressure in the range of 40-100 kPa. As a demonstration, a binding reaction of a 15 mer ssDNA with a peptide nucleic acid oligomer used as an oligoprobe followed by denaturing electrophoresis to discriminate a single-base substitution was performed within 1.5 min. By exploiting the droplet-on-demand capability of the device, the influence of various factors, such as reaction time, mixing ratio and droplet configurations on the ssDNA-peptide nucleic acid binding reaction in the droplet-based process, was studied toward realization of a rapid detection method to discriminate rapid single-base substitution.     

Efficient decoherence-free entanglement distribution over lossy quantum channels

We propose and demonstrate a scheme for boosting the efficiency of entanglement distribution based on a decoherence-free subspace over lossy quantum channels. By using backward propagation of a coherent light, our scheme achieves an entanglement-sharing rate that is proportional to the transmittance T of the quantum channel in spite of encoding qubits in multipartite systems for the decoherence-free subspace. We experimentally show that highly entangled states, which can violate the Clauser-Horne-Shimony-Holt inequality, are distributed at a rate proportional to T.