Chemistry of organosilicon compounds : CXIX. Preparation and some reactions of 1,2-disilacyclobutenes

Two new 1,2-disilacyclobutenes have been prepared by the reaction of tetramethyldisilene with acetylenes. Several reactions of these new 1,2-disilacyclobutenes including oxidation, silylene insertion, iron carbonyl insertion, and addition to acetylenes and dienes are reported.     

Synthesis of deterministic phase codes for phase shifter in holography

A new family of a deterministic phase coding suitable for a phase shifter in holography is proposed. For a phase shifter with matrix-shaped sampling elements, in which phase is shifted by the amount of 0, π/2, π, or 3π/2, new deterministic codes satisfy the two following conditions: (1) nearly uniformity of the Fourier transformed image before insertion of an object, and (2) a constant phase difference (π/2 or -π/2) between the nearest neighbor sampling elements. The diminished fluctuation of the simulated reconstruction image, as well as uniformity of the Fourier transformed image, is experimentally shown as expected from the above conditions. This indicates a novel phase coding for a phase shifter in recording high density and high quality holograms.     

The isolation and structure elucidation of new cassane diterpene-acids from Caesalpinia crista L. (Fabaceae), and review on the nomenclature of some Caesalpinia species

New cassane diterpene-acids, neocaesalpins H and I, were isolated from the leaves of Caesalpinia crista (Fabaceae), and their structures were deduced on the basis of the spectroscopic and chemical basis. These compounds were characterized as having an alpha,beta-butenolide hemiacetal ring that is rare in nature. The lacking of 5-hydroxy group also distinguished neocaesalpins H and I from cassane diterpenes (caesalpins) occurring in other Caesalpinia species from the phytochemical viewpoint. The nomenclature of three Caesalpinia species was also reviewed, and it was found that some species belonging to the genus Caesalpinia are improperly named and should be changed to valid names.     

Synthesis and evaluation of 5-thio-L-fucose-containing oligosaccharide

5-Thio-L-fucose-containing trisaccharide H-type II was synthesized. The 3',4'-O-isopropylidene-2-azido-2-deoxylactoside derivative, which was prepared from lactose by azidonitration of lactal, was used as a starting material. By regio- and stereoselective 5-thio-L-fucosylation of the 6,6'-dibenzoate 5 with 5-thiofucosyl trichloroacetimidate 6 and subsequent deprotection gave the 5-thio-L-fucose-containing H-type II 1. Conformational analysis of the 5-thio-L-fucose-containing H-type II and the native H-type II was carried out through NOESY experiments. The observed NOE values between N-acetylglucosamine and galactose, and galactose and fucose were same for these two trisaccharides. However, NOE values between fucose and N-acetylglucosamine were significantly different. Binding of the 5-thio-L-fucose-containing H-type II to lectins and antibodies were in some case stronger and in some case weaker than those of the native trisaccharide.     

Titanosilicate molecular sieve for size-screening photocatalytic conversion

Titanosilicate molecular sieves, when activated by ultraviolet light irradiation in water in the presence of molecular oxygen, catalyze a conversion of molecules having a size close to the pore of the catalysts but are inactive for molecules having much larger or smaller size. This unprecedented size-screening photocatalytic activity is triggered by a combination of H2O-induced shortened lifetime of active species (charge-transfer excited state of tetrahedrally coordinated titanium oxide) and restricted diffusion of a molecule inside the pore. This catalytic property demonstrates a potential utility of the catalyst for selective transformation of molecules that is associated with a size reduction of molecules, so-labeled "molecular shave" transformation.     

Conformation of solvent N,N-dimethylpropionamide in the coordination sphere of the zinc(II) ion studied by Raman spectroscopy and DFT calculations

Solvation structure of the zinc(II) ion in N,N-dimethylpropionamide (DMPA) was studied by Raman spectroscopy at varying temperature and by quantum mechanical calculations. No significant ion-pair formation was found for the Zn(ClO4)2 solution in the molality range m(Zn) < 1.5 mol kg(-1), and the solvation number of the zinc(II) ion was determined to be 4, indicating that 6-coordination of DMPA is sterically hindered. Interestingly, DMPA molecules are under equilibrium between planar cis and nonplanar staggered conformers, and the latter is more preferred in the coordination sphere, while the reverse is the case in the bulk. The DeltaG degrees , DeltaH degrees , and TDeltaS degrees values of conformational change from planar cis to nonplanar staggered in the coordination sphere were obtained to be -0.9, -8.5, and -7.5 kJ mol(-1), respectively. Density functional theory (DFT) calculations show that the planar cis conformer is more favorable than the nonplanar staggered one in the 1:2 cluster, as is the case for a single DMPA molecule and H(DMPA)+, indicating that there hardly occurs solvent-solvent interaction through the metal ion in the Zn2+-DMPA 1:2 cluster. On the other hand, the SCF energy of [Zn(planar cis-DMPA)4-n(nonplanar staggered DMPA)n]2+ (n = 0-4) decreases with increasing n, implying that the nonplanar staggered conformer is preferred in the solvate ion. It is thus concluded that solvent-solvent interaction through space, or solvation steric effect, plays a crucial role in the conformational equilibrium in the coordination sphere of the four-solvate metal ion.     

Surfactant-promoted novel reductive synthesis of supported metallic Cu nanoclusters and their catalytic performances for selective dehydrogenation of methanol

We have found a surfactant-promoted novel reductive synthesis of metallic Cu nanoclusters on metal oxides under hydrothermal synthesis conditions, which are active for the selective dehydrogenation of methanol.     

Existence of stable equilibrium point for dynamical systems of Volterra type

This paper presents sufficient conditions for the existence of a nonnegative and stable equilibrium point of a dynamical system of Volterra type, (1) $\text{(}\text{d}\text{dt}\text{) x}{}_{\mathrm{i}}\text{(t) = ?x}{}_{\mathrm{i}}\text{(t)[f}{}_{\mathrm{i}}\text{(x}{}_1\text{(t),…, x}{}_{\mathrm{n}}\text{(t)) ? q}{}_{\mathrm{i}}\text{], i = 1,…, n}$, for every q = (q₁,…, q_n)^T?Rⁿ. Results of a nonlinear complementarity problem are applied to obtain the conditions. System (1) has a nonnegative and stable equilibrium point if (i) f(x) = (f₁(x),…,f_n(x))^T is a continuous and differentiable M-function and it satisfies a certain surjectivity property, or (ii), f(x) is continuous and strongly monotone on R₊₀ⁿ.