Unusual Reactivities of ortho-Hydroxy-β-nitrostyrene

Nitrostyrene derivatives are widely used in organic syntheses as a substrate for Michael addition, photoisomerization and cycloaddition. In contrast, ortho-hydroxy derivatives exhibit unusual behaviors in these reactions. Conjugate addition proceeded upon treatment of the ortho-hydroxy-β-nitrostyrene with an amine; however, subsequent C–C bond cleavage readily occurred to afford the corresponding imine. Moreover, conversion of the trans-isomer to a cis-isomer did not occur efficiently, even when UV light was irradiated. We studied these unusual behaviors of β-nitrostyrene, focusing on the role of the ortho-hydroxy group.     

Chemical composition and phase identification of sodium titanate nanostructures grown from titania by hydrothermal processing

Fine titanium dioxide particles were hydrothermally treated in a sodium hydroxide aqueous solution. The treatment extended from 1 to 6 days leading to belt-like and wire-like structures of a metastable phase of sodium titanate, with typical widths and diameters between 8 and 40 nm, and lengths from 100 nm to several micrometers. These conclusions are supported by X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy. The latter method revealed two set of space fringes with characteristic distances of 0.29 and 0.34 nm. These distances could correspond to the lattice spacing of and planes in Na₂Ti₆O₁₃ compounds. The nanomaterial was found to be stable up to temperatures as high as 200 or depending on the reaction time and the concentration.     

Spectroscopy of light nuclei with skyrme-type interactions

Deformed Hartree-Fock calculations are performed for some light nuclei in a large configuration space consisting of first four major shells. The interaction employed is the modified Skyrme interaction in which the deformed density is replaced by the band averaged scalar density that makes the Hamiltonian rotationally invariant rendering the spectroscopic calculations feasible. It is shown that the introduction of density dependence spreads out the energy spectra and that the Skyrme variant SIV which has a weak density dependence gives best overall agreement for energy spectra and the available data for the electromagnetic properties of the nuclei studied. It is found that the maximum contribution to the energy of any state in the low lying spectrum comes from thes-state attractive ands-state repulsive parts of the Skyrme interaction. It is also shown that when two-body density dependent version of Skyrme interaction is used, the Koopmans theorem no longer holds.     

Fortschritte in der Auswertung von Markierungsversuchen an dynamischen Systemen

In einem dynamischen System vollziehen sich kontinuierlich ablaufende Stoffwandlungen, deren Ausgangsstoffe dem System ständig zufließen und deren Folgeprodukte das System kontinuierlich verlassen. Es wird das Verhalten eines solchen Systems mit drei Pools bei Markierungsexperimenten untersucht. Die Ergebnisse dieser mathematischen Untersuchungen werden auf die Erforschung des Stickstoffstoffwechsels laktierender Rinder mit Hilfe des stabilen Isotops ¹⁵N angewandt. In diesem Fall enthält das dynamische System zwei kleine stoffwechselaktive Pools und einen großen, niclit intensiv am Stoffwechsel beteiligten Körpereiweiβ-Pool.     

1H, 13C and 15N NMR spectral analysis of substituted 1,2,3,4‐tetrahydro‐pyrido[1,2‐a]pyrimidines

The NMR spectroscopic data of a series of thirty‐four 3‐acylpyrido[1,2‐a]pyrimidinium salts are analyzed, which were prepared as either perchlorates or chlorides. Methyl group substituted 3‐aroyltetrahydropyrido[1,2‐a]pyrimidines with the methyl substituent in positions 6, 8 and 9 as well as both in positions 6 and 8 were investigated bearing various aroyl substituents. Unequivocal assignment of all resonances was achieved via two‐dimensional ¹H,¹H‐COSY measurements, ¹H,¹³C and ¹H,¹⁵N HSQC as well as HMBC experiments, and important diagnostic CH and NH couplings in the heteroaromatic ring system are evaluated. The influence of the methyl substituents was analyzed on the proton, carbon and nitrogen shifts. A significant effect of the counter ion on some chemical shifts of the nuclei under discussion of the pyridopyrimidines is found, allowing the indirect detection of the anion, which is confirmed by direct measurement of the ³⁵Cl nucleus of the perchlorates. Copyright © 2013 John Wiley & Sons, Ltd.     

HCSE method for detection of small carbon–carbon couplings and their signs,comparison with SLAP pulse sequence

Performance of homonuclear coupling sign edited (HCSE) experiment applied to detection of signed carbon–carbon couplings is discussed using a set of already measured samples of nine monosubstituted benzenes. It is shown that coupling sign detection is insensitive to the settings of carbon–carbon polarization transfer delays. The HCSE spectra of ten from the total of 43 measured carbon–carbon couplings were considerably influenced by relaxations and proton–proton strong couplings. These effects are quantitatively discussed. The results of HCSE and SLAP experiments are compared. It is shown that the two methods may complement each other in detection of signed carbon–carbon couplings. Copyright © 2013 John Wiley & Sons, Ltd.     

Efficient synthesis of the C/D rings of atisine-type C20-diterpenoid alkaloids

A bicyclo[2.2.2]octane C/D ring system,with a lactonic ring at C-8 and C-9,of the atisine-type C₂₀-diterpenoid alkaloids,was successfully synthesized,using an oxidative dearomatization/intramolecular Diels-Alder reaction.     

Selective lighting up of segments around Gly,Ala and Ser/Thr in proteins

Direct detection of ¹³C nucleus can be used as a valuable alternative where ¹H detection poses a challenge due to relaxation effects, chemical exchange and poor chemical shift dispersion. In this context, we have designed a suite of 2D ¹³C^α‐detected hNCA experiments that provide sequential correlations of ¹³C^α with ¹⁵N on one hand and efficient spectroscopic labeling of certain groups of residues, namely, Gly, Ala, Ser and Thr, on the other. These residues act as checkpoints in the sequential walk, which in turn offer new possibilities of backbone assignment of small proteins from a set of 2D experiments, thereby providing great economy in terms of spectrometer time. The direct identification of peptide segments around Gly, Ala, Ser and Thr residues along a protein chain will be highly valuable for deriving important information on sites of ligand binding, phosphorylation, inhibitor/substrate binding, understanding protein folding pathways, comprehending local conformational dynamics etc. without having to obtain complete sequence‐specific assignments, which can be time consuming and at times formidable, especially in large proteins. We have illustratively demonstrated the multifaceted applications of these variants of 2D experiments on ubiquitin and M‐crystallin. We foresee that these 2D hNCA experiments will provide economic and efficient strategies for studying the structure and function of proteins. Copyright © 2012 John Wiley & Sons, Ltd.