Electro-optic light modulation with holographic gratings stored in a Cu-diffused LiNbO3 plate

Investigations have been made on the electro-optic modulation of a laser beam using Bragg reflection from holographic gratings stored in a Cu-diffused LiNbO₃ plate. A new device configuration is proposed which makes it possible to use the holographic recording characteristics of LiNbO₃ more effectively than previous other devices. A modulation of about 50% with a 45° deflection angle was obtained at an applied voltage of 500 V.     

Duality theorem for the stochastic optimal control problem

We prove a duality theorem for the stochastic optimal control problem with a convex cost function and show that the minimizer satisfies a class of forward–backward stochastic differential equations. As an application, we give an approach, from the duality theorem, to h$h$-path processes for diffusion processes.     

Cu-diffused layers in LiNbO3 for reversible holographic storage

Some holographic recording characteristics of Cu-diffused layers fabricated in Rh-doped LiNbO₃ have been examined in comparison with those fabricated in undoped lithium niobate.The diffusion layers, whose thickness depends on the diffusion temperature, are found to be enormously susceptible to optically-induced refractive index changes and to be able to attain a high diffraction efficiency. A distinguished difference is found between the persistence of holograms stored in Rh-doped and undoped LiNbO₃.     

Covariance kernel and the central limit theorem in the total variation distance

We modify and generalize the idea of covariance kernels for Borel probability measures on R^d, and study the relation between the central limit theorem in the total variation distance and the convergence of covariance kernels.     

A simple and reliable monitoring system for 3H and 14C in radioactive airborne effluent

Summary A simple and reliable sampling system for ³H and ¹⁴C in airborne release from nuclear facilities was designed. The sampling system can collect ³H and ¹⁴C simultaneously with a condensation technique using a commercially available cold trap equipment and a CO₂ absorption technique using an organic alkali monoethanolamine solution, respectively. In situ performance tests for the effluent from a reprocessing plant showed that the system has high and stable efficiencies for collecting ³H and ¹⁴C for a one-week batch sampling at a sampling flow rate of 0.4 l ^. min^-1. These collection techniques also provided a simple procedure of following sample preparation for activity measurements by liquid scintillation counting. The detectable concentrations of the proposed monitoring method were 3.0 Bq ^. m^-3 for ³H and 1.6 Bq ^. m^-3 for ¹⁴C, respectively. The sensitivity would be on an acceptable level for routine monitoring of airborne release at nuclear facilities.     

Spatial confinement effect on the atomic structure of solid argon

Molecules confined in nanopores show unusual behavior not seen in bulk systems. The present paper reports on molecular dynamics simulations of unusual freezing behavior in confined Ar. Similar to bulk Ar, liquid Ar confined in pores with a diameter D>15sigma (5.1 nm), where sigma is the diameter of the Ar atom, crystallizes when the cooling rate is lower than a critical value (Qc). We also find that the spatial confinement does not have significant influence on Qc when D>15sigma (5.1 nm). In the pore of 10sigma (3.4 nm) in diameter, on the other hand, the behavior is dramatically changed. Crystalline Ar does not appear inside the pore even when the system is cooled at a rate lower than the Qc in the bulk system by over two orders of magnitude. Instead, amorphous Ar characterized by local icosahedral configurations is formed in the pore. We further find that, even when crystalline Ar is formed outside the pore, it does not grow deeply into the pore. This supports that the amorphous Ar is actually the most stable phase in the pore. It is well known that Ar is a poor glass former. Our finding that even such an amorphous Ar is the most stable in the pore suggests that, in any system, it is possible to prepare amorphous structure selectively by using nano-molds.     

(2,5)-Ene cyclization catalyzed by mesoporous solid acids: isotope labeling study and ab initio calculation for continuum from concerted to stepwise ene mechanism

(2,5)-Ene reactions catalyzed by mesoporous solid acids are reported from the mechanistic point of view. The continuum (2,5)-ene mechanism from the concerted to the cationic cyclization followed by 1,2-hydride shift is evaluated. The solid-acid-catalyzed cyclization of the oxonium ion intermediate 4 derived from cyclic allylic lactol ether 3 bearing allylic hydroxy group affords the (2,5)-ene product as the enol form, eventually tautomerizing to the corresponding aldehyde 6. The continuum from the concerted to stepwise mechanism is experimentally and theoretically verified in the present ene cyclization of the oxonium ion intermediate such as 4. The stepwise cyclization leading to aldehyde 6 is thus shown to associate with the concerted version as a result of the stabilization of the beta-hydroxycarbenium ion intermediate.     

Direct Deprotonative Functionalization of α,α-Difluoromethyl Ketones using a Catalytic Organosuperbase

The deprotonative functionalization of α,α-difluoromethyl ketones is described herein. Using a catalytic organosuperbase and a silane additive, the corresponding difluoroenolate could be generated and trapped with aldehydes to deliver various α,α-difluoro-β-hydroxy ketones in high yields. This new strategy tolerates numerous functional groups and represents the access to the difluoroenolate by direct deprotonation of the difluoromethyl unit. The diastereoselective version of the reaction was also investigated with d.r. up to 93 : 7. Several transformations were performed to demonstrate the synthetic potential of these α,α-difluoro-β-hydroxy ketones. In addition, this method has been extended to the use of other electrophiles such as imines and chalcogen derivatives, and a difluoromethyl sulfoxide as nucleophile, thus leading to a diversity of difluoromethylene compounds.     

Piano-Stool Ruthenium N-Heterocyclic Carbene Complexes for gem-Specific Catalytic Dimerization of Terminal Alkynes

A series of piano-stool Ru−NHC (NHC=N-heterocyclic carbene) complexes have been prepared and characterized. The NHC ligands used herein have varying wingtip groups, showing the impact of steric congestion on the selectivity for the catalytic dimerization of terminal alkynes.