Photooxygenation of pyrazin-2(1h)-ones

1-Alkyl-5,6-diphenylpyra2in-2(1H)-ones (1a-b) reacted with singlet oxygen in dichloromethane to afford the stable endoperoxide (1a-b), while in methanol to afford the 1:1-adduct (3a-b) of the endoperoxide (2a-b) and methanol.     

Partial molar enthalphy of formation of solid solution in transition metal sulfides by a combustion calorimetry

The combustion calorimetry on the NbS system has been carried out under an oxygen atmosphere at 453°C using a Calvet-type twin calorimeter. The partial molar enthalphies of the formation of solid solution for both 2S-NbS_x and 3S-NbS_x phase on the NbS system has been determined.     

Biferrocene-M(mnt)2 charge-transfer complexes (M = Ni, Co; mnt = maleonitriledithiolate). structure, valence states, and magnetic properties

Charge-transfer salts of branched-alkyl biferrocenes, (1',1' '-R2-1,1' '-biferrocene)[Ni(mnt)2] (1a, R = isopropyl; 2a, R = dineopentyl) and (1',1' '-R2-1,1' '-biferrocene)2[Co(mnt)2]2 (1b, R = isopropyl; 2b, R = dineopentyl), were prepared. Their valence states were investigated using X-ray crystallography and M?ssbauer spectroscopy. Complexes 1a and 1b show segregated-stack crystal structures that contain columns of acceptors, whereas structures of 2a and 2b, which contain bulky donors, are rather discrete. All of the complexes contain mixed-valent biferrocenium monocations. A two-step valence transition was found in complex 1a. The crystal contains two crystallographically independent cations: one undergoes valence localization below room temperature; the other undergoes valence localization below ca. 130 K. The former transition is derived from asymmetry of the crystal environment around the cation, whereas the latter one is caused by symmetry lowering coupled with a spin-Peierls transition (T(C) = 133.2 K) associated with the dimerization of the acceptors. This compound was found to exhibit a dielectric response based on valence tautomerization. Other complexes (1b, 2a, and 2b) show a valence-trapped state. In all complexes, charge localization was found to occur through local electrostatic interactions between the donor's cationic moiety and the acceptor's electronegative moieties.     

Brittle fracture and spinnability of viscous materials

Conclusion In both cases, brittle fracture and dropping breakdown, only very little deformation or elongation was observed in the experiments mentioned above, and limiting conditions were obtained reproducibly with respect to rate of extension and temperature. The brittle limits give the condition where the viscous resistance due to locally concentrated stress, i. e. the grip effect (5) exceeds cohesion of the materials, and development of the surface of separation is followed. At the dropping limits, the viscosities of the liquids may be too small to resist shrinking by surface tension with respect to the rate of extension. Although the theory of spinnability proposed here may be only tentative, it can be pointed out that surface tension plays some important role in spinning of viscous liquids of lower molecules. Concerning higher molecules, rubber-like elasticity as well as viscosity may become more important (6).

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Zusammenfassung Für beide Fälle, spröden Bruch und stufenweiser Bruch, wurde nur sehr geringe Deformation oder Verlängerung beobachtet und Grenzbedingungen hinsichtlich Dehnungsgeschwindigkeit und Temperatur reproduzierbar erhalten. Die Bruchgrenzen geben die Bedingungen, bei denen der viskose Widerstand entsprechend den lokalen Spannungskonzentrationen, d. h. entsprechend den grip-Effekt die Kohäsion des Materials übersteigt, und die Entwickelung der Trennfläche wird verfolgt. Bei der Grenzbelastung für das Absinken der Spannung mag die Viskosität der Flüssigkeiten zu gering sein, um dem Schrumpfen durch Oberflächenspannung im Vergleich mit der Dehnungsgeschwindigkeit entgegen zu wirken. Obgleich die Theorie der Spinnbarkeit, hier vorgeschlagen, nur einen Versuch darstellt, kann behauptet werden, daß die Oberflächenspannung beim Spinnen viskoser Flüssigkeiten mit kleineren Molekülen eine wichtige Rolle spielt. Für höhermolekulare Substanzen wird neben der Viskosität auch die Gummielastizität ausschlaggebend.

     

Decay studies of K isomers in 254No

A detailed $ \gamma$ spectroscopic decay study of two K isomers in ²⁵⁴No was performed. In addition to the previously reported $ \gamma$ lines two new transitions of E = 778 , 856keV could be attributed to the decay pattern of ^254m1No ( T _1/2 = 275±7 ms). The population of an excited band built up on this isomer ( $\ensuremath K^{\pi} =8^{-}$ by the decay of ^254m2No ( T _1/2 = 198±13 μs) could be proven by measuring delayed $ \gamma$ - $ \gamma$ coincidences between transitions stemming from the decay of both isomeric states. The energies of the band members could be established up to $\ensuremath I^{\pi} = 15^{-}$ . A spontaneous fission branch of (2.0±1.2)×10^-4 was measured for ^254m1No , an upper limit of $ \le$ 1.2×10^-4 was estimated for ^254m2No . These values demonstrate the high stability of multi-quasiparticle configurations against spontaneous fission. Evidence for an $ \alpha$ decay branch of ^254m1No in the order of 1×10^-4 was found.     

Electrostatic potential screened by a two-dimensional electron system: a real-space observation by scanning-tunneling spectroscopy

Scanning-tunneling spectroscopy at 5 K was used to investigate the electrostatic potential profile on the Si(111)-square root of 3 x square root of 3 Ag surface at subnanometer spatial resolution. The potential was measured from an energy-level shift of electronic states on the surface. The potential images obtained reveal that the potential drops around the steps and Ag adsorbates, upon which positive charges are presumably accumulated. The profiles of the reduced potentials are explained with the screening of potential due to the charges by two-dimensional electron gas (2DEG) existing on the surface. The Friedel oscillation, which results from the screening and has a period of the half Fermi wavelength of the 2DEG, was also observed in the potential images.     

Procedure for increasing the detection responses of estrogens in LC–MS based on introduction of a nitrobenzene moiety followed by electron capture atmospheric pressure chemical ionization

A practical procedure for determining estrogens in biological fluids has been studied using liquid chromatography–electron capture atmospheric pressure chemical ionization–mass spectrometry combined with derivatization. Among the commercially available reagents (4-nitrobenzoyl chloride, 2,4-dinitrofluorobenzene, 4-nitrobenzenesulfonyl chloride and 4-nitrobenzyl bromide), 4-nitrobenzenesulfonyl chloride was of the most practical use; it rapidly and quantitatively reacted with estrogens and increased the detection responses by 8–23 times. The derivatization method allowed the reproducible and accurate quantification of serum and urine estrone and estradiol of a pregnant woman, which is useful for diagnosis of the fetoplacental function, with small amounts (10 μl) of sample and a simple pretreatment procedure. Tatsuya Higashiis Associate Professor of the Laboratory of Clinical Analytical Sciences (Professor Kazutake Shimada’s research group) at the Graduate School of Natural Science and Technology of Kanazawa University. He received the Japan Society for Analytical Chemistry Award for Young Scientists in 2003 and the Pharmaceutical Society of Japan Award for Young Scientists in 2006. His current research interests are the development of methods for increasing sensitivity in LC-MS to detect and characterize trace amounts of biologically active steroids, such as estrogens, androgens and neuroactive steroids.     

Morphological Study of hydroxypropyl cellulose films prepared from thermotropic melt under shear

A strain-induced crystallization behavior of hydroxypropyl cellulose (HPC) from the thermotropic liquid-crystalline state is described based on morphological observations by electron microscopy. It is shown that originally round-shaped particles behave as a structure unit in formation of a variety of supermolecular architectures of HPC films prepared from the thermotropic melt under shear. In an oriented HPC film obtained under weak shear, many round particles are elongated and aligned in the direction of shear (SD), but with their bodies bent to some degree. As deformation increases further, fibrillation occurs on the surface of the elongated particles, and then the resulting fibrils are arranged in a zigzag fashion along the SD to form a banded structure. In some cases, a pleated arrangement of fibrils is noticeable between bands. The structural transformation mechanism of thermotropic HPC under shear is discussed in detail on the basis of the morphological evidence.     

Chemical Interactions of Cryptic Actinomycete Metabolite 5‐Alkyl‐1,2,3,4‐tetrahydroquinolines through Aggregate Formation

Organisms often produce secondary metabolites as a mixture of biosynthetically related congeners. However, why are metabolites with minor chemical variations produced simultaneously? 5‐Alkyl‐1,2,3,4‐tetrahydroquinolines (5aTHQs) are small, lipophilic metabolites produced by Streptomyces nigrescens HEK616 when cultured with Tsukamurella pulmonis TP‐B0596. A mixture of 5aTHQs forms aggregates that show enhanced membrane affinity and biological activity. The ability to form aggregates and membrane‐binding activity is regulated by the length of the alkyl chains. Aggregates with long alkyl chains were too stable to fuse with lipid membranes. However, if inactive 5aTHQ congener was mixed with active congener, the mixture showed increased membrane affinity, enabling cellular entry and biological activity. Therefore, it is shown that sloppiness in a biosynthetic pathway, by which minor structural variations can be produced, is functionally rational, as the metabolites show synergistic action.