Technique to Estimate the Reflectance of a High-Reflectance Dielectric Multilayer Coating Mirror Using Incident Beam Angular Dependence of Its Transmittance

The reflectance of a high-reflectance dielectric multilayer coating mirror tuned to a monochromatic laser wavelength was estimated from its transmittance which was measured with 0.4 ppm accuracy. The transmittance was calculated from its theoretical formula including three parameters (refractive indexes of low and high refractive films (n_L, n_H) and a number of layer units composed of a pair of one low and one high refractive film (N)) which were estimated from the incident beam angular dependence curve of the transmittance. This calculated transmittance agreed with that measured as a ratio of the laser beam power before and after the mirror with 6 ppm difference.     

SiO production from Si(100) and (111) surfaces by reaction with O2 beams

Desorption kinetics of SiO in the reaction of O₂ with Si(100) and (111) surfaces were investigated at surface temperatures between 1000 and 1300 K by using a pulsed molecular beam technique. The gaseous SiO product was detected by a mass spectrometer above 1000 K. At temperatures lower than 1050 K, the SiO signal appeared with an induction time after the O₂ beam irradiation onto the surface, which means that the desorption occurs via sequential steps. The rate constants for two steps were obtained by a computer simulation of the relaxation waveforms of the SiO signal. The values obtained are in the same range as those of D'Evelyn et al. However, they are one order of magnitude larger than those of Yu and Eldridge. The activation energies for the two steps are 2.8 and 2.4 eV for both Si(100) and (111) surfaces. No significant difference between the two kinds of surfaces was found from these values. However, many etch pits were observed on the Si(100) surface after the reaction, while no such etch pits were formed on the Si(111) surface. The planes of the etch pits formed on the (100) surfaces consisted mostly of the {111} facets.     

Total syntheses of both enantiomers of sarcophytols A and T based on stereospecific [2,3]Wittig rearrangement

Both enantiomers of sarcophytols A (1) and T (2), cembranolide diterpenes isolated from a soft coral, were synthesized from a common chiral intermediate, obtained by baker's yeast reduction, using a stereospecific [2,3]Wittig rearrangement as the key step.     

Ultraviolet true zero-order wave plate made of birefringent porous silica

Porous Si made from (110) Si wafers exhibits strong in-plane optical anisotropy (birefringence) in the visible and near-IR ranges. Oxidation of the birefringent porous Si results in the formation of birefringent porous silica. We demonstrate that the degree of the birefringence of porous silica can be controlled by the oxidation condition, and very small birefringence can be achieved. The smallest anisotropy of the refractive index (Δn) is 0.001, which is about ten times smaller than that of quartz. The small birefringence allows us to produce true zero-order wave plates operating in the UV range.     

Aqueous dispersion polymerization: a new paradigm for in situ block copolymer self-assembly in concentrated solution

Reversible addition-fragmentation chain transfer polymerization has been utilized to polymerize 2-hydroxypropyl methacrylate (HPMA) using a water-soluble macromolecular chain transfer agent based on poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC). A detailed phase diagram has been elucidated for this aqueous dispersion polymerization formulation that reliably predicts the precise block compositions associated with well-defined particle morphologies (i.e., pure phases). Unlike the ad hoc approaches described in the literature, this strategy enables the facile, efficient, and reproducible preparation of diblock copolymer spheres, worms, or vesicles directly in concentrated aqueous solution. Chain extension of the highly hydrated zwitterionic PMPC block with HPMA in water at 70 °C produces a hydrophobic poly(2-hydroxypropyl methacrylate) (PHPMA) block, which drives in situ self-assembly to form well-defined diblock copolymer spheres, worms, or vesicles. The final particle morphology obtained at full monomer conversion is dictated by (i) the target degree of polymerization of the PHPMA block and (ii) the total solids concentration at which the HPMA polymerization is conducted. Moreover, if the targeted diblock copolymer composition corresponds to vesicle phase space at full monomer conversion, the in situ particle morphology evolves from spheres to worms to vesicles during the in situ polymerization of HPMA. In the case of PMPC(25)-PHPMA(400) particles, this systematic approach allows the direct, reproducible, and highly efficient preparation of either block copolymer vesicles at up to 25% solids or well-defined worms at 16-25% solids in aqueous solution.     

Aqueous colloidal mesoporous nanoparticles with ethenylene-bridged silsesquioxane frameworks

Aqueous colloidal mesoporous nanoparticles with ethenylene-bridged silsesquioxane frameworks with a uniform diameter of ～20 nm were prepared from bis(triethoxysilyl)ethenylene in a basic aqueous solution containing cationic surfactants. The nanoparticles, which had higher hydrolysis resistance under aqueous conditions, showed lower hemolytic activity toward bovine red blood cells than colloidal mesoporous silica nanoparticles.     

Catalytic dehydrative S-allylation of cysteine-containing peptides in aqueous media toward lipopeptide chemistry

Thiol-containing peptides and cysteine have been successfully S-allylated with various allyl alcohols in aqueous medium containing a catalytic amount of [CpRu(η(3)-C(3)H(5))(2-quinolinecarboxylato)]PF(6). Quick and easy install of 2-propen-l-ol having a long-chain alkyl group at C(2) facilitates the synthesis of a new series of artificial lipopeptides, indicating a potential application to synthetic biology.     

Cu-promoted [2 + 2] cycloaddition of 1,4-bisallenes

The thermal reaction of 1,4-bisallenes with the aid of Cu salt/amine significantly suppressed the formal [3,3] sigmatropic rearrangement resulting in the highly selective formation of the bicyclo[4.2.0]octadiene framework. This reaction could be applied to the one-pot synthesis of bicyclo[4.2.0]octadienes from 1,5-hexadiynes via the Crabbé homologation.