Lembehsterols A and B,novel sulfated sterols inhibiting thymidine phosphorylase,from the marine sponge Petrosia strongylata

Lembehsterols A (1) and B (2), two novel sulfated sterols, were isolated from the marine sponge Petrosia strongylata. Both sterols showed inhibitory activity against thymidine phosphorylase, which is an enzyme related to angiogenesis in solid tumors. The structures of these sulfated sterols were established on the basis of chemical and physicochemical evidence.     

Determination of strontium in biological samples by atomic emission spectrometry with electrothermal atomization

Summary Strontium showed a high atomic emission in a molybdenum microtube. The addition of hydrogen in the argon gas atmosphere served to increase the atomic emission. No interferences from less than 5 ng of potassium, calcium and magnesium were found. Other elements also had no interferences at the concentration levels usually found in biological samples. Samples were digested with nitric acid in a Uni-Seal decomposition vessel. The results obtained showed good agreement with the certified values. Atomic emission spectrometry with a molybdenum microtube atomizer permits a simple and sensitive determination of strontium in biological samples (coefficient of variation 2.5% for 10 pg Sr).

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Strontiumbestimmung in biologischem Material durch Atomemissions-Spektrometrie mit elektrothermischer Atomisierung

Zusammenfassung Eine hohe Atomemission wurde für Strontium bei Verwendung einer Molybdän-Mikroröhre beobachtet. Durch Wasserstoffzusatz zum Argon konnte sie noch weiter erhöht werden. Weniger als 5 ng K, Ca und Mg verursachen keine Störung. Andere Elemente stören nicht in den Konzentrationsbereichen, wie sie üblicherweise in biologischen Materialien vorkommen. Der Aufschluß der Proben wurde mit Salpetersäure in Uni-Seal-Gefäßen vorgenommen. Die erhaltenen Werte stimmten gut mit zertifizierten Daten überein. Die vorgeschlagene Methode ermöglicht eine einfache und empfindliche Strontiumbestimmung in biologischen Proben (Variationskoeffizient 2,5% bei 10 pg Sr).

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This work was supported by the Ministry of Education, Science and Culture of Japan through a Grant-in-Aid for Special Project Research.     

Discrimination of the geometrical isomers of 2,3-, 2,5-, and 2,6-dimethylpiperazines based on 1 H?Nmr spectral data

¹ H-Nmr spectra of cis and trans isomers of 2,3-, 2,5-, and 2,6-dimethylpiperazines were taken at various temperatures. The spectra of geometrical isomers bearing the ae or ea dimethyl groups showed broadening at lower temperatures. It was clarified that the measurement of the spectra at lower temperatures is useful for the discrimination of the geometrical isomers of dimethylpiperazines.     

Excited state property of hardly photodissociable heme-CO adduct studied by time-dependent density functional theory

While most of CO-bound hemes are easily photodissociated with a quantum yield of nearly unity, we occasionally encounter a CO-heme which appears hardly photodissociable under the ordinary measurement conditions of resonance Raman spectra using CW laser excitation and a spinning cell. This study aims to understand such hemes theoretically, that is, the excited-state properties of the five-coordinate heme-CO adduct (5cH) as well as the 6c heme-CO adduct (6cH) with a weak axial ligand. Using a hybrid density functional theory, we scrutinized the properties of the ground and excited spin states of the computational models of a 5cH and a water-ligated 6cH (6cH-H(2)O) and compared these properties with those of a photodissociable imidazole-ligated 6cH (6cH-Im). Jahn-Teller softening for the Fe-C-O bending potential in the a(1)-e excited state was suggested. The excited-state properties of 6cH-Im and 5cH were further studied with time-dependent DFT theory. The reaction products of 6cH-Im and 5cH were assumed to be quintet and triplet states, respectively. According to the time-dependent DFT calculations, the Q excited state of 6cH-Im, which is initially a pure pi-pi state, crosses the Fe-CO dissociative state (2A') without large elongation of the Fe-CO bond. In contrast, the Q state of the 5cH does not cross the Fe-CO dissociative state but results in the formation of the excited spin state with a bent Fe-C-O. Consequently, photoisomerization from linear to bent Fe-C-O in the 5cH is a likely mechanism for apparent nonphotodissociation.     

Intrinsic vacancy-induced nanoscale wire structure in heteroepitaxial Ga2Se3/Si(001)

A highly anisotropic growth morphology is found for heteroepitaxial gallium sesquiselenide (Ga2Se3) on the lattice matched substrate, arsenic-terminated Si(001). Scanning tunneling microscopy of Ga2Se3 films reveals nanoscale, wirelike structures covering the surface in parallel lines, less than 1 nm wide and up to 30 nm long. Core-level photoemission spectroscopy and diffraction reveals the local structure of buried Ga and Se atoms to reflect the bulk, defected zinc-blende structure of beta-Ga2Se3, which contains ordered 110 arrays of Ga vacancies. These ordered vacancy lines are proposed to be responsible for the observed growth anisotropy in heteroepitaxial Ga2Se3.     

Microwave EPR spectroscopy of cobalt-doped germanium cuprate

Resonance magnetoabsorption spectra of CuGeO₃ single crystals containing 2% Co impurity have been studied in the frequency range 60–360 GHz in magnetic fields of up to 16 T and in the temperature interval 2–60 K with the magnetic field B aligned parallel to the a crystallographic axis. In addition to the Cu²⁺ chain resonance, a new absorption line (unobserved previously in doped CuGeO₃ and deriving apparently from the Co²⁺ ions) was detected in EPR spectra. Quantitative analysis of the spectra suggests that the spin-Peierls transition occurs in about 10% Cu²⁺ chains, while the spin-Peierls state in the remaining 90% chains is completely destroyed by cobalt doping. The results obtained reveal considerable deviations from the universally accepted scenario of CuGeO₃ doping and are discussed within alternative theoretical models, namely, the quantum critical behavior (based on the EPR theory for quasi-one-dimensional systems) and a three-dimensional antiferromagnet with the Néel temperature lowered by disorder.     

Building a Simple Model of a Pulse-Frequency-Modulation Photosensor and Demonstration of a 128 x 128-pixel Pulse-Frequency-Modulation Image Sensor Fabricated in a Standard 0.35-$mUm Complementary Metal-Oxide Semiconductor Technology

We present a simple model of the pulse-frequency-modulation (PFM) photosensor that provides explicit relationships between circuit parameters and output characteristics. The model treats the PFM photosensor with a feedback loop as an open loop circuit. Several characteristics such as output pulse frequency for light intensity and photosensitivity are expressed by device parameters of a photodiode, reset transistor, and chain of inverters. The relationships derived from the proposed model help us to comprehend the results by simulation program with integrated circuit emphasis (SPICE) or experiments. We design and fabricate a 128 x 128-pixel PFM image sensor with photosensitivity of 0.15 Hz/lux. As a demonstration, a figure of a dinosaur is captured using the fabricated image sensor to discuss its operation. Characteristics of a normal pixel and white and black defect pixels are measured and discussed based on the results of formulations.     

Ruthenium catalyzed addition reaction of carboxylic acid across olefins without beta-hydride elimination

The cationic ruthenium catalyst (Cp*RuCl2)2/AgOTf/Ligand promotes the addition reaction of carboxylic acids across olefins without beta-hydride elimination.     

Adsorption of thiolates to singly coordinated sites on Au111 evidenced by photoelectron diffraction

The adsorption structure of methylthiolate (CH3S) adsorbed on Au(111), a long-standing controversial issue, has been unambiguously determined by scanned-energy and scanned-angle S 2p photoelectron diffraction. The methylthiolate molecules are found to occupy atop sites with a S-Au distance of 2.42 +/- 0.03 A. The angular distribution of the S 2p photoelectrons due to forward scattering reveals that the S-C bond is inclined by approximately 50 degrees from the surface normal towards both the [211] and [121] (nearest-neighbor thiolate) directions.