Clockwise-counterclockwise differentiation on the upper rim of a monofunctional gamma-cyclodextrin: efficient topological control in the syntheses of capped cyclodextrins

Intramolecular condensation of 6(A)-(N-dansyl-l-cysteine)-gamma-cyclodextrin occurred only at 6(B)-OH of the many OH groups to afford the corresponding lactone with an exo-topology.     

Crystal structure and peroxidase activity of myoglobin reconstituted with iron porphycene

The incorporation of an artificially created metal complex into an apomyoglobin is one of the attractive methods in a series of hemoprotein modifications. Single crystals of sperm whale myoglobin reconstituted with 13,16-dicarboxyethyl-2,7-diethyl-3,6,12,17-tetramethylporphycenatoiron(III) were obtained in the imidazole buffer, and the 3D structure with a 2.25-A resolution indicates that the iron porphycene, a structural isomer of hemin, is located in the normal position of the heme pocket. Furthermore, it was found that the reconstituted myoglobin catalyzed the H2O2-dependent oxidations of substrates such as guaiacol, thioanisole, and styrene. At pH 7.0 and 20 degrees C, the initial rate of the guaiacol oxidation is 11-fold faster than that observed for the native myoglobin. Moreover, the stopped-flow analysis of the reaction of the reconstituted protein with H2O2 suggested the formation of two reaction intermediates, compounds II- and III-like species, in the absence of a substrate. It is a rare example that compound III is formed via compound II in myoglobin chemistry. The enhancement of the peroxidase activity and the formation of the stable compound III in myoglobin with iron porphycene mainly arise from the strong coordination of the Fe-His93 bond.     

Catalytic enantioselective allylation of ketoimines

A general catalytic allylation of simple ketoimines was developed using 1 mol % of CuF.3PPh(3) as catalyst, 1.5 mol % of La(O(i)Pr)(3) as the cocatalyst, and stable and nontoxic allylboronic acid pinacol ester as the nucleophile. This reaction constituted a good template for developing the first catalytic enantioselective allylation of ketoimines. In this case, using LiO(i)Pr as the cocatalyst produced higher enantioselectivity and reactivity than La(O(i)Pr)(3). Thus, using the CuF-cyclopentyl-DuPHOS complex (10 mol %) and LiO(i)Pr (30 mol %) in the presence of (t)BuOH (1 equiv) produced high enantioselectivity up to 93% ee from a range of aromatic ketoimines. Mechanistic studies indicated that LiO(i)Pr accelerates the reaction by increasing the concentration of an active nucleophile, allylcopper.     

Do-it-yourself computational astronomy

We overview our GRAPE (GRAvity PipE) and GRAPE-DR project to develop dedicated computers for astrophysical N-body simulations. The basic idea of GRAPE is to attach a custom-build computer dedicated to the calculation of gravitational interaction between particles to a general-purpose programmable computer. By this hybrid architecture, we can achieve both a wide range of applications and very high peak performance. GRAPE-6, completed in 2002, achieved the peak speed of 64 Tflops. The next machine, GRAPE-DR, will have the peak speed of 2 Pflops and will be completed in 2008. We discuss the physics of stellar systems, evolution of general-purpose high-performance computers, our GRAPE and GRAPE-DR projects and issues of numerical algorithms.     

Design of a rate- and time-programming drug release device using a hydrogel: pulsatile drug release from κ-carrageenan hydrogel device by surface erosion of the hydrogel

We have found that a repetitive pulsatile drug release with a certain time interval is observed from a monolithic hydrogel device by surface erosion of the hydrogel. As a model system of pulsatile drug release, dibucaine hydrochloride and κ-carrageenan hydrogel were chosen as a drug and a device, respectively. Electrostatic interactions between dibucaine hydrochloride and κ-carrageenan polymer segments are strong, since dibucaine hydrochloride is positively charged and each disaccharide repeating unit of κ-carrageenan chains has one sulfate group. Dibucaine hydrochloride was loaded into the hydrogel by immersing dry κ-carrageenan hydrogel disks in a dibucaine hydrochloride solution for 24 h. The pulsed release of dibucaine hydrochloride from the device was observed every 50 min between 30 and 250 min after the release starts. The weight of κ-carrageenan hydrogel decreases in an oscillatory manner with time in distilled water. The oscillatory changes observed in the hydrogel weight in distilled water are considered to be caused by influx and efflux of water molecules into and from the surface and core of the hydrogel and by polymer liberation from the hydrogel. This phenomenon was well explained by our kinetic model [Colloids and Surfaces B 8 (1996) 93–100]. The time interval between pulses observed in drug release coincides with that observed in the oscillatory weight change of the hydrogel. From these, it was concluded that the pulsatile release of dibucaine hydrochloride from the device was caused by the pulsatile liberation of swollen κ-carrageenan hydrogel from the surface of the device.     

Ladderlike ferromagnetic spin coupling network on a pi-conjugated pendant polyradical

A poly(9,10-anthryleneethynylene)-based polyradical with two pendant stable phenoxyls in one anthracene skeleton was newly synthesized via polymerization of the corresponding bromoethynylanthracene monomer using a Pd(0) catalyst. The average molecular weight of the polymer reached M(n) = 5 x 10(3) and was soluble in common organic solvents. The polyradical was prepared from the corresponding hydroxyl precursor polymer and was appropriately stable at room temperature. The ESR spectrum of the corresponding monomeric radical suggested an effectively delocalized spin density distribution on the backbone anthracene. The magnetization and the static magnetic susceptibility of the polyradical were measured using a SQUID magnetometer. The large average spin quantum number (S = (5)/(2)) of the polyradical indicated that the ferromagnetic spin coupling network of the polyradical had spread throughout the pi-conjugated chain and that it was considerably insensitive to spin defects.     

Measurement of bisphenol A in human serum by gas chromatography/mass spectrometry

The purpose of this study is to establish an easy and accurate method for the determination of bisphenol A (BPA) in the human serum. The samples were applied to the C₁₈ solid phase extraction (SPE) column for clean up of samples. The BPA is conjugated with tetrabutylammonium hydrogen sulfate as the counter ion in alkali solution. The ion paired BPA is moves from the aqueous phase to the organic phase as an ion paired extraction. BPA extracted from human serum were derivatized with pentafluorobenzyl bromide (PFBBr). The derivative was analyzed by gas chromatography (GC)/mass spectrometry (MS) using negative chemical ionization (NCI). The instrumental detection limit of BPA was 5 pg/ml (10 fg). The instrumental response between 0.01 and 100 pg/ml of BPA standards was linear (r²=0.998). The recovery of BPA spiked into human serum was 101.0±4.63 (1 pg/ml) and 100.9±3.75 (10 pg/ml), respectively. The concentration of BPA in the human serum from 20 individuals was 0.54 pg/ml.     

A novel method for synthesis of silica nanoparticles

A sequential method has been used, for the first time, to prepare monodisperse and uniform-size silica nanoparticles using ultrasonication by sol-gel process. The silica particles were obtained by hydrolysis of tetraethyl orthosilicate (TEOS) in ethanol medium and a detailed study was carried out on the effect of different reagents on particle sizes. Various-sized particles in the range 20-460 nm were synthesized. The reagents ammonia (2.8-28 mol L(-1)), ethanol (1-8 mol L(-1)), water (3-14 mol L(-1)), and TEOS (0.012-0.12 mol L(-1)) were used and particle size was examined under scanning electron microscopy and transmission electron microscopy. In addition to the above observations, the effect of temperature on particle size was studied. The results obtained in the present study are in agreement with the results observed for the electronic absorption behavior of silica particles, which was measured by UV-vis spectrophotometry.     

Strategy for Designing New Li+ ion Specific Receptors. A Combination of Theoretical Calculations and Experimental Techniques

Our strategy for designing new receptor molecules specific for Li+ ions is to combine two methods, theoretical calculations and the experimental technique. In developing the Li+ ion-specific receptors, we regarded crown ether derivatives of a 12-membered ring and side arms with functional groups as building blocks. This strategy worked well to synthesize new receptor molecules which selectively bind and transport the Li+ ion.     

Amine side arm effect on the ion selectivity of 12-crown-O3N derivatives with an amine arm in aqueous and acetonitrile solutions

Molecular geometries of crown ether derivatives play an important role in capturing and transporting alkali metal ions such as Li⁺ and Na⁺. As selectivity of the ions is observed in solution, it is necessary to know their molecular structures in solutions. Recently, we investigated stable conformations of 12-crown-O₃N and its alkali ion complexes in aqueous and acetonitrile solutions. In the present study, we applied a procedure similar to that in previous papers to investigate the side arm effect of 12-crown-O₃N with an amine arm for capturing Li⁺ and Na⁺ in the two solutions. It was confirmed that the stable structures of Li⁺ and Na⁺ complexes in solutions, especially the geometry of the amine side arm, are highly solvent-dependent. This conformational difference is the key to understanding the high Li⁺ selectivity of 12-crown-O₃N derivatives with an amine side arm in acetonitrile.