First preparation and structural determination of 1,1-disubstituted dibenzo[bc,fg][1,4]silathiapentalene derivatives by x-ray crystallographic analysis and MO calculations

1,1-Dimethyldibenzo[bc,fg][1,4]silathiapentalene ( 1a ) was prepared by treatment of 1,9-bis(methyl-sulfinyl)dibenzothiophene with EtMgBr or of dibenzothiophene with n-butyllithium, and then with dimethyl dichlorosilane. The structure of 4,4-dimethyl-dibenzo[bc,fg][1,4]silathiapentalene 1-oxide ( 2 ), obtained by oxidation of compound 1a with mCPBA, was determined by X-ray crystallographic analysis. The structure of compound 2 determined experimentally was compared to the structure obtained by semiempirical molecular orbital calculations (AM1). The MO calculations of compound 1a and its phenyl analog 1b were also performed by AM1 to evaluate their structures. © 1996 John Wiley & Sons, Inc.     

Effect of Dissolved Oxygen on the Reduction of Stable Nitroxide by Ascorbic Acid: In Vitro Model for Acute Hypoxia Ischemia

The reaction between 3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl (PCAM), which is a blood–brain-barrier (BBB) permeable stable cyclic nitroxide, and ascorbic acid was examined in a low dissolved oxygen-phosphate buffer (low DO-PB, 0.1 mM DO) under 8% oxygen in a glove bag or in an ordinal dissolved oxygen-phosphate buffer (ordinal DO-PB, 0.3 mM DO) under 21% oxygen in an open atmosphere with and without diethylenetriaminepentaacetic acid (DTPA). In PB with DTPA, no difference was observed between the results in the low DO-PB and those in the ordinal DO-PB. In the ordinal DO-PB without DTPA, the rate constant of the PCAM decrease was half that in the low DO-PB without DTPA. The present results indicate that high DO and coexisting transition metal ions caused the oxidation of ascorbic acid, which degraded the PCAM reduction. The stable nitroxide-ascorbic acid system without DTPA was found to be applicable to an in vitro model for the acute hypoxia ischemia.     

Wavelet processing and digital interferometric contrast to improve reconstructions from X‐ray Gabor holograms

In this work, the application of an undecimated wavelet transformation together with digital interferometric contrast to improve the resulting reconstructions in a digital hard X‐ray Gabor holographic microscope is shown. Specifically, the starlet transform is used together with digital Zernike contrast. With this contrast, the results show that only a small set of scales from the hologram are, in effect, useful, and it is possible to enhance the details of the reconstruction.     

Position magnifying sensor

This paper describes the application of multiple beam shearing interferometry to a position magnifying sensor. A multiple beam shearing interferometer (MBSI) with a shear plate wedged in the vertical direction produces sharp multiple beam fringes. When the lateral displacement of a point source (which gives rise to the input beam of the MBSI) or its image occurs in the horizontal direction, these fringes move vertically in a magnified manner. This characteristic was used in a position magnifying sensor to detect the displacement of a point image. The advantages of the sensor include a large displacement magnification (more than a hundred times) and a large working distance.     

Application of Protonic Acid-Doped Silica Gels to Electric Double-Layer Capacitors

Silica gels doped with several protonic acids such as HClO₄, H₂SO₄ and H₃PO₄ have been prepared by the sol-gel method and totally solid electric double-layer capacitors have been successfully fabricated using the highly proton-conductive silica gels as an electrolyte and activated carbon powder (ACP) hybridized with the silica gels as a polarizable electrode. It was found that the addition of HClO₄, which had the highest value of acid dissociation constant among these three acids, most effectively increased the proton conductivity of the resultant acid-doped silica gels. Tablets of the HClO₄-doped silica gels exhibited conductivities as high as 10^–5–10^–2 S cm^–1 at room temperature in dry N₂ atmosphere. One of the capacitors fabricated using the protonic acid-doped silica gels had a capacitance of 44 F/(gram of total ACP in the capacitor), which was comparable to those of conventional capacitors using liquid electrolytes.     

Steric bulk at position 454 in Saccharomyces cerevisiae lanosterol synthase influences B-ring formation but not deprotonation

[reaction: see text] Lanosterol synthase converts oxidosqualene to the tetracyclic sterol precursor lanosterol. The mutation experiments described here show that an active-site valine residue in lanosterol synthase contributes to cyclization control through steric effects. Mutating to smaller alanine or glycine residues allows formation of the monocyclic achilleol A, whereas the leucine and isoleucine mutants make exclusively lanosterol. The phenylalanine mutant is inactive.     

Synthesis of 3‐Acyl‐4‐alkenylpyrrolidines by Platinum‐Catalyzed Hydrative Cyclization of Allenynes

A series of nitrogen‐tethered allenynes (‘5‐aza‐1,2‐dien‐7‐ynes’) 1 were transformed to the corresponding 3‐acyl‐4‐alkenylpyrrolidines 3 when treated with a catalytic amount of PtCl₂ in MeOH at 70°. Initial Pt‐promoted cyclization forms a nonclassical carbocationic intermediate. In contrast to the cycloisomerization in toluene, which produced the bicyclic cyclobutenes 2 , the intermediate is intercepted by addition of an oxygen nucleophile to achieve the formal hydrative cyclization.     

Self-assembly of photochromic diarylethenes with amphiphilic side chains: reversible thermal and photochemical control

Diarylethene derivatives with hexaethylene glycol side chains were synthesized and their self-assembling and photochromic reactivity were investigated. The diarylethenes showed photochromism in organic solvents and even in water. The aqueous solution of the compounds turned turbid quickly upon heating. The clouding behavior was investigated using 1H NMR spectroscopy, dynamic light scattering, and absorption spectroscopy. It was revealed that, in the aqueous solution, the compounds self-assembled into aggregates, and the aggregates were loosened by raising the temperature. The cloud-point temperature of the closed-ring isomer was 5-7 degrees C lower than that of the open-ring isomer. When asymmetric methyl groups were introduced in the amphiphilic side chains, induced circular dichroism (ICD) was observed upon irradiation with UV light in water. This ICD was explained by the difference in the self-assembling behavior between the open- and the closed-ring isomers. It was suggested that the closed-ring isomers assembled into a chiral nanostructure.