Reductive PET-fragmentation-cyclization processes of bicyclo[n.3.0]alkanones: synthesis of angular quasi-triquinane and propellane systems

Bicyclo[3.3.0]octanone and bicyclo[4.3.0]nonanone derivatives with a cyclopropane unit in the α-position and an unsaturated side chain in the γ-position of the carbonyl group undergo fragmentation-cyclization processes leading to quasi-triquinane systems upon reductive photoinduced electron transfer (PET). For example, the new angular triquinane derivative 6 and the new propellane derivative 12 were synthesized in one step from these starting materials in moderate to good yields.     

Dual-label autoradiographic analysis of human skin fibroblast and myoblast proteins by two-dimensional polyacrylamide gel electrophoresis using immobilised pH gradients in the first dimension

Horizontal two-dimensional polyacrylamide gel electrophoresis with immobilised pH gradients in the first dimension has been applied to the analysis of human skin fibroblast and muscle myoblast total cell proteins. Excellent two-dimensional separations of skin fibroblast proteins were obtained using pH 4-10 immobilised pH gradient gels with a long interelectrode distance (16 cm), but resolution was degraded, particularly of the more acidic proteins, by the use of shorter (10 cm) gels. Improved resolution of acidic and basic proteins was obtained using separate pH 4-7 and pH 7-10 immobilised pH gradient gels respectively in the first dimension. Two-dimensional protein maps of skin fibroblast proteins were visualised both by silver staining and by autoradiography of samples labelled synthetically with [35S]methionine. Horizontal two-dimensional electrophoresis, using pH 4-7 and pH 7-10 immobilised pH gradient gels in the first dimension, was applied to the analysis of protein samples from skin fibroblasts and muscle myoblasts dual-labelled synthetically with [35S]methionine and [75Se]selenomethionine in an attempt to identify sets of proteins specific to each cell type. In addition, two-dimensional maps or protein samples derived from normal individuals and patients with Duchenne muscular dystrophy were compared to search for protein changes associated with the disease state. Although sets of qualitative protein spot differences were observed by visual inspection of the two-dimensional gels, more rigorous qualitative and quantitative analysis of the patterns using a computerised analysis system will be required to obtain the maximum amount of information from these data.     

Triphenylphosphan-Nickel(0)-Komplexe mit Isocyanid-Liganden — [(RNC)nNi(PPh3)4–n] (n = 1–3)

Triphenylphosphane Nickel(0) Complexes with Isocyanide Ligands — [(RNC)_nNi(PPh₃)_4–n] (n = 1–3) Synthesis and properties of the isocyanide triphenylphosphane nickel(0) complexes [(RNC)Ni(PPh₃)₃], [(RNC)₂Ni(PPh₃)₂] and [(RNC)₃Ni(PPh₃)] (R = ^tBu, Cy, PhCH₂, p-TosCH₂) are described. I.r. and ³¹P n.m.r. spectra were recorded and the X-ray crystal structure of [(PhCH₂NC)₂Ni(PPh₃)₂] was determined.     

Mass spectrometric studies of organophosphorus compounds: III—Remarkable migration of chalcogen on electron impact of organophosphorus compounds

The mass spectra of several dibenzo (d.f)-1,3,2,-dioxaphosphorepines of the type where X=0, S, Se and R=2,2′-biphenylylene, have been studied. Dibenzochalcogen ions [RX]⁺˙ stemming directly from [M]⁺˙ were observed with high intensities, indicating specific migration of X from phosphorus to carbon with simultaneous destruction of the dioxaphosphorepine ring. Simple cleavage of P? Y as usually observed in similar organophosphorus compounds is not a common process here.     

A new heterocyclic structure. The 6H-[1,3]benzoxathiepino[5,4-d]pyrimidine 5,5-dioxide

The novel benzoxathiepinopyrimidines 6a-d were synthesized by ring transformations of 3-chloromethylsulfonylchromone ( 2 ) with amidines 3a-d .     

Über die Uranylverbindungen des Natrium-cyklohexyldithiocarbaminats

Zusammenfassung Na-cyklohexyldithiocarbaminat reagiert im p_H-Bereich 6,6 bis 7,2 mit Uranylsalzen unter Bildung eines in Wasser mit gelber Farbe lösliehen Komplexes, der bei p_H 6,6 ein Absorptionsmaximum bei 392 bis 394 nm besitzt. Die wäßrige Lösung wird durch Zusatz von Alkalilauge bis zum p_H 8 bis 9 momentan entfärbt.Es wird ein Kaliumdoppelsalz KUO₂(S₂HCNC₆H₁₁)₃ · 3 H₂O beschrieben; ferner wird über die Umwandlung des Calciumdoppelsalzes beim Kochen mit NaOH berichtet.

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Summary Sodium cyolohexyldithiooarbamate reacts, in the p_H range 6.6 to 7.2, with uranium salts to yield a complex which gives a yellow aqueous solution. The absorption maximum is at 392–394 nm at p_H 6.6. The aqueous solution loses its color immediately when caustic alkali is added to raise the p_H to 8 or 9.A potassium double salt, KUO₂(S₂HCNC₆H₁₁)₃ · 3 H₂O is described. A report is also given of the transformation of the calcium double salt on boiling with NaOH.

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Résumé Le dithiocarbamate de cyclohexylsodium réagit dans le domaine de p_H 6,6 à 7,2 sur les sels d'uranyle avec formation d'un complexe coloré en jaune, soluble dans l'eau, qui possède à p_H 6,6 un maximum d'absorption pour 392–394 nm. Par addition de lessive alcaline jusqu'à p_H 8 à 9 on décolore momentanément la solution aqueuse.On décrit un sel double de potassium KUO₂(S₂HCNC₆H₁₁)₃ · 3 H₂O; on rend compte, de plus, de la transposition du sel double de calcium par chauffage avec la soude.

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Gewidmet zur 100. Wiederkehr des Geburtstages vonFriedrich Emich.     

Über magnetische Beeinflussung der Polarisation der Resonanzfluoreszenz

1. Historical remarks concerning magnetic influence on the polarization of resonance fluorescence and its explanation as the Zeeman effect. 2. Rotation of the plane of polarization of the resonance fluorescence of Hg by weak magnetic fields and determination of the lifetime of the excited state. 3. Experiments concerning the excitation of the resonance fluorescence of Hg by light with different kinds and directions of polarization.     

电解池电阻和容抗的快速测定仪

利用锁定放大器, 恒电势仪, 压控频率正弦波信号发生器等组装成电解池电阻和容抗的快速测定仪。可以快速地自动测是和绘出阻抗谱图和电阻/容抗～时间图。采用微小恒定振幅正弛交流电流(<10 μA)作为微扰, 数据可能较为可靠。给出了线路及所需滤波器元件的数据, 说明仪器各部份之间的干扰可以减少。测定了滴汞电极在1 mol L~(-1)Na_2SO_4溶液中及1 mol L~(-1)Na_2SO_4被正庚醇饱和的溶液中的微分电容～电势数值。证明仪器工作良好。另外, 从实验数据和理论分析, 均表明D.C.Grahame的被广泛引用的有关经典数据有误。本文做了修正。还测定了半导体氧化铁电极在光照下黑暗中的阻抗谱图和氧化银电极充电和停止充电后开路下的电阻～时间图, 显示了仪器在电化学研究中利用的可能性。