Photo-Absorption and photochemical decomposition of copper and alkaline-earth ß-diketonates as source gases of high-Tc superconducting films

For low-temperature deposition of oxide films relating to Bi-Sr-Ca-Cu-O superconductors, photo-absorption and -decomposition properties were examined with respect to copper and alkaline-earth ß-diketonates. It was confirmed that all ß-diketonates examined were promising as source materials for photochemical vapour deposition (photo-CVD) using a low-pressure mercury lamp, in view of their large light absorption coefficients at wavelength 254 nm. The light irradiation was effective for the formation of highly crystalline oxide films at temperatures below 600 °C. By combining two sources, Ca₂CuO₃ and SrCuO₂ films were prepared. Photo-CVD of c-axis oriented Bi₂Sr₂CuO_x film was achieved by the irradiation of ternary sources of Bi(C₆H₅)₃ and strontium and copper ß-diketonates at 500 °C.     

Synthesis of large macrocyclic tetraaza compounds with a methylene backbone: Cyclo[-NH- (CH2)n-]4, (n = 6, 7, 8, 9 and 10). The formation of 28-, 32-, 36-, 40- and 44-membered rings

A series of macrocyclic tetraamines with 28-, 32-, 36-, 40- and 44-membered rings have been efficiently prepared from the corresponding ditosylamide and monobromoalcohol derivatives in 6 steps via a double condensation reaction. Overall yields were: 41, 41, 46, 29, and 33%, respectively, for 1,8,15,22-tetraazacyclooctacontane ( 11a ), 1,9,17,25-tetraazacyclodotriacontane ( 11b ), 1,10,19,28-tetraazacyclohexatriacontane ( 11c ), 1,11,21,31-tetraazacyclotetracontane ( 11d ) and 1,12,23,34-tetraazacyclotetratetracontane ( 11e ).     

Revaluation of the correlation of isomer shift with Np-O bond length in various neptunyl(V and VI) compounds

Summary The correlations of isomer shifts in various neptunyl(V and VI) compounds with crystallographic structures were revaluated. A linear correlation between the isomer shifts of neptunyl(VI) compounds and Np-O bond lengths of neptunyl group has been demonstrated. On the other hand, it has been evidenced that the isomer shifts of neptunyl(V) compounds are correlated much stronger with the mean Np-O distances in the crystals than the lengths in neptunyl(V) group.     

Cross-linking chemistry and biology: development of multifunctional photoaffinity probes

An efficient method of photoaffinity labeling has been developed based on rationally designed multifunctional photoprobes. Photoaffinity techniques have been used to elucidate the protein structure at the interface of biomolecules by the photochemical labeling of interacting sites. However, the identification of labeled sites within target proteins is often difficult. Novel biotinyl bioprobes bearing a diazirine photophore have contributed significantly to the rapid elucidation of ligand binding sites within proteins, thereby extending conventional photoaffinity methods. This article discusses the synthesis and applications of various photoprobes bearing a biotin, including strategies using cleavable linkages between photophores. The combination of photoaffinity methods with chip technology is also described as a novel entry to rapid affinity-based screening of inhibitors. This review focuses on a rapid and reliable photoaffinity method utilizing diazirine-based multifunctional photoprobes with numerous potential applications in functional proteomics of biomolecular interactions.     

Neutron diffraction study of crystal structure and antiferromagnetic ordering in the heavy fermion compound CePd2Al3

Nuclear and magnetic structures of an annealed polycrystalline sample of the heavy-fermion compound CePd₂Al₃ prepared by arc-melting were investigated by neutron powder diffraction. The chemical structure corresponds well to the ordered hexagonal PrNi₂Al₃-type structure. The antiferromagnetic structure of CePd₂Al₃ with an ordered magnetic moment _Ce=0.47(2) _B at saturation is remarkably similar to that in the heavy fermion superconductor UPd₂Al₃. The additional incommensurate magnetic structures reported previously both for UPd₂Al₃ and CePd₂Al₃ are not observed in the present sample of CePd₂Al₃. At 1.4 K the magnetoresistivity of CePd₂Al₃ measured up to 14 T indicates only one field-induced phase transition at 3.0 T.     

Synthesis of Indolones via Radical Cyclization of N‐(2‐Halogenoalkanoyl)‐Substituted Anilines

The radical reactions of N‐(2‐halogenoalkanoyl)‐substituted anilines (anilides) of type 1 have been investigated under various conditions. Treatment of compounds 1a – 1o with Bu₃SnH in the presence of (2,2′‐azobis(isobutyronitrile) (AIBN) afforded a mixture of the indolones (oxindoles) 2a – 2o and the reduction products 5a – 5o (Table 1). In contrast, the N‐unsubstituted anilides 1p – 1s, 1u , and 1v gave the corresponding reduction products exclusively (Table 1). Similar results were obtained by treatment of 1 with Ni powder (Table 2) or wth Et₃B (Table 3). Anilides with longer N‐(phenylalkyl) chains such as 6 and 7 were inert towards radical cyclization, with the exception of N‐benzyl‐2‐bromo‐N,2‐dimethylpropanamide ( 6b ), which, upon treatment with Ni powder in i‐PrOH, afforded the cyclized product 9b in low yield (Table 4). Upon irradiation, the extended anilides 6, 7, 10 , and 11 yielded the corresponding dehydrobromination products exclusively (Table 5).     

Plaunol A and B,new anti-ulcer diterpenelactones from Crotonsublyratus

Two new diterpenelactones named plaunol A ($\text{2}$) and B ($\text{3}$) exhibiting anti-Shay ulcer activity were isolated from Thai medicinal plant, $\text{Croton}$$\text{sublyratus}$. Structure of $\text{2}$ was determined by X-ray analysis of its $\text{p}$-bromobenzoate and structure of $\text{3}$ was deduced from the results of chemical correlation and the spectral data.