Stereoselective synthesis of c3-c12 dihydropyran portion of antitumor laulimalide using copper-catalyzed oxonium ylide formation-[2,3] shift

Copper-catalyzed oxonium ylide formation-[2,3] shift of (5S,7R)-5-allyloxy-1-diazo-8-(p-methoxybenzyloxy)-7-methyl-2-octanone (3) proceeded in tetrahydrofuran-dichloromethane (4 : 1) under reflux with an excellent stereoselectivity (97 : 3) to give (2R,6S)-2-allyl-6-[(2R)-3-(p-methoxybenzyloxy)-2-methylpropyl]-3-dihydropyranone (2) as a major isomer in 82% yield. The resultant pyranone (2) was converted to the key intermediate (1) of the Mulzer's laulimalide synthesis and its derivatives (14, 15).     

Ionic liquid crystal as a hole transport layer of dye-sensitized solar cells

Use of a new ionic liquid crystal, 1-dodecyl-3-methylimidazolium iodide, and iodine as an electrolyte of dye-sensitized solar cells leads to a high short circuit photocurrent density and a high light-to-electricity conversion efficiency, due to a self-assembled structure of the imidazolium cations, resulting in high conductivity of the electrolyte.     

Synthesis and structure of 16 pi octaalkyltetraphenylporphyrins

The oxidized octaethyltetraphenylporphyrin (1, OETPP) and the corresponding newly prepared octaisobutyltetraphenylporphyrin (3, OisoBuTPP) could be isolated from the reaction of OETPPLi2 (or OisoBuTPPLi2) with SOCl2. The X-ray analysis and the characteristic UV-vis spectra of 1 and 3 revealed that these are the first examples of 16 pi nonaromatic porphyrins.     

Excited states of phosphorescent platinum(II) complexes containing N wedge C wedge N-coordinating tridentate ligands: spectroscopic investigations and time-dependent density functional theory calculations

The absorption and emission spectra of the Pt(II) complexes containing N wedge C wedge N-coordinating tridentate ligands, platinum(II) 1,3-di(2-pyridyl)benzene chloride [Pt(dpb)Cl] and platinum(II) 3,5-di(2-pyridyl)toluene chloride [Pt(dpt)Cl], together with their corresponding free ligands, 1,3-di(2-pyridyl)benzene (dpbH) and 3,5-di(2-pyridyl)toluene (dptH), have been analyzed by density functional theory (DFT) for the ground state and time-dependent DFT (TDDFT) for the excited states. T(1)(A(1)) and S(1)(B(2)) of the complexes (in C(2)(v) symmetry) were assigned on the basis of the calculated excitation energies as well as comparison of the experimental spectroscopic properties and the calculated states' characteristics. The calculated excitation energies for T(1) and S(1) of the complexes as well as those for T(1) of the free ligands were in good agreement with their observed values within 600 cm(-1). The d-pi* characters of the excited states were evaluated from the change in electron densities between the ground and excited states by Mulliken population analysis; values of 25% for T(1) and 32% for S(1) were obtained for both complexes. The calculated values of d-pi* character were found to be consistent with the reported emission lifetimes as well as the observed emission energy shifts from the corresponding free ligands. Most spectroscopic properties of the complexes and the free ligands, which include solvatochromic shift, Stokes shifts, methyl substitution shifts, and emission spectra profiles, were well explained from the calculation results.     

Fixed point properties for semigroup of nonexpansive mappings on Fréchet spaces

In this paper, we shall establish a fixed point property on Fréchet spaces for left reversible semitopological semigroups generalizing some classical results.     

Synthesis of proton conductive inorganic–organic hybrid membranes through copolymerization of dimethylethoxyvinylsilane with vinylphosphonic acid

Proton conductive inorganic–organic hybrid membranes were synthesized from dimethylethoxyvinylsilane (DMEVS), vinylphosphonic acid (VPA) and 3-glycidoxypropyltrimethoxysilane (GPTMS) through copolymerization followed by sol–gel process. The ratio of phosphorus to silicon in the copolymer almost corresponded to the charged molar ratio of VPA to DMEVS when the ratio of VPA to DMEVS was below 1/2. Self-standing, homogeneous, highly transparent membranes were synthesized from DMEVS–VPA copolymer and GPTMS via sol–gel condensation. Differential thermal analysis-thermogravimetry analyses indicated that these membranes were thermally stable up to 200 °C. The results of Fourier transform infrared and ¹³C NMR revealed that phosphonic acid groups of VPA were chemically bound to organosiloxane network. The copolymerization and condensation of (DMEVS–VPA)/GPTMS were confirmed by ³¹P and ²⁹Si NMR spectra. The proton conductivity of the hybrid membranes increased with phosphonic acid content. The membrane of (DMEVS–VPA)/GPTMS showed a remarkable conductivity of 6.3 × 10⁻² S cm⁻¹ at 130 °C and 100% relative humidity.     

Subwavelength-size solid immersion lens

We report on the fabrication and characterization of nanoscale solid immersion lenses (nano-SILs) with sizes down to a subwavelength range. Submicrometer-scale cylinders fabricated by electron-beam lithography are thermally reflowed to form a spherical shape. Subsequent soft lithography leads to nano-SILs on transparent substrates for optical characterization. The optical characterization is performed using a high-resolution interference microscope with illumination at 642 nm wavelength. The focal spots produced by the nano-SILs show both spot-size reduction and enhanced optical intensity, which are consistent with the immersion effect.     

Development of ultra-short pulse VUV laser system for nanoscale processing

We have developed intense vacuum ultraviolet (VUV) radiation sources for advanced material processing, such as photochemical surface reactions and precise processing on a nanometer scale. We have constructed a new VUV laser system to generate sub-picosecond pulses at the wavelength of 126 nm. A seed VUV pulse was generated in Xe as the 7th harmonic of a 882-nm Ti:sapphire laser. The optimum conversion was achieved at the pressure of 1.2 Torr. The seed pulse will be amplified by the Ar₂^*\mathrm{Ar}_{2}^{*} media generated by an optical-field-induced ionization Ar plasma produced by the Ti:sapphire laser. We have obtained a gain coefficient of g=0.16 cm⁻¹. Our developing system will provide VUV ultra-short pulses with sub-μJ energy at a repetition rate of 1 kHz.     

Observation of vacuum-ultraviolet Ar2* radiation gain at 126 nm produced by an ultrashort high-intensity laser pulse propagating in a hollow fiber

We observed a small-signal gain of Ar2* emission at 126 nm by use of a hollow fiber to guide the high-intensity laser propagation in high-pressure Ar. The small-signal gain coefficient was measured to be 0.05 cm(-1) at 126 nm. Kinetic analysis revealed that the electrons produced by the high-intensity laser through an optical-field-induced ionization process initiated the Ar2* production processes. The increase in the emission intensity was measured to be exp(2.5), with an increase in the fiber length.