The reactions of Me2MCl2 (M = Si, Ge, Sn), Si2Me4Cl2, Si2Me2Cl3, Si2Me2Cl4 and CH2(SiCl2Me)2, and suitable mixtures thereof, with H2S / NEt3 and Li2E (E = Se, Te) have been investigated and lead to a variety of new group 14 chalcogenide systems. 相似文献
Abstract Alkyl- or arylbis(trimethylsilyl)phosphines as well as tris(trimethylsilyl)phosphine and the corresponding arsines react with acyl chlorides to give [1-(trimethylsiloxy)alkylidene]phosphines 1 and -arsines 2; most of their 2,2-dimethylpropylidene derivatives are thermally stable at room temperature. With the same class of phosphines as starting compounds and carbon disulfide [bis(trimethylsilylsulfano)methylidene]phosphines 3 are formed, whereas [(dialkylamino)methylidene]-4 and [diarylmethylidene]phosphines 5 or the corresponding arsines 6 and 7 can be obtained from acyl amides or ketones.1相似文献
One-hundred-two years ago, on 21 April 1910, the Austrian chemist Carl Auer von Welsbach published a short comment on a fundamental discovery he had made in the field of nuclear sciences. He reported that “jonium” (230Th) was able to induce radioactivity in other materials if stored in contact with the ionium sample. He was well aware that this observation was “not quite in agreement with current theories”, because, as a basic principle, a radioactive substance cannot activate an inactive substance. Since he could not remove any superficial contamination, he concluded that the previously inactive materials had become radioactive themselves. Auer von Welsbach predicted that this observation “might be of importance for the mysterious field of radioactivity research”. In fact, we believe that in this experiment he incidentally discovered neutron activation and the production of artificial radionuclides (24 years before I. Curie and F. Joliot) or even induced nuclear fission. The neutron source in his experiments is yet unknown and shall be identified in this project. The neutrons could have been produced from nuclear reactions with impurities of beryllium in the sample. Auer von Welsbach may even have observed nuclear fission 29 years before O. Hahn, F. Straßmann, L. Meitner and O. R. Frisch. In any case, he may have noticed the effects of neutron radiation—22 years before its discovery by J. Chadwick. The main aim of this interdisciplinary project (of which preliminary results are presented herein) is to repeat the 1910-experiment and to identify the source of the neutrons. It will be equally important to investigate the historical reasons and circumstances why Auer’s report remained mostly uncommented in the scientific community. The hypothetical consequences are worth discussion: Auer’s publication could have started the “nuclear age” much earlier than it finally began, with all the consequences for mankind. 相似文献
Following Mie theory, nanoparticles made of a high‐refractive‐index dielectric, such as silicon, exhibit a resonator‐like behavior and very rich resonance spectra. Which electric or magnetic particle mode is excited depends on the wavelength, the refractive‐index contrast relative to the environment, and the geometry of the nanoparticle itself. In addition, the spatial structure of the impinging light field plays a major role in the excitation of the nanoparticle resonances. Here, it is shown that, by tailoring the excitation field, individual multipole resonances can be selectively addressed while suppressing the excitation of other particle modes. This enables a detailed study of selected individual resonances without interference by the other modes.
Rare examples of heavier alkali metal manganates [{(AM)Mn(CH2SiMe3)(N‘Ar)2}∞] (AM=K, Rb, or Cs) [N‘Ar=N(SiMe3)(Dipp), where Dipp=2,6-iPr2-C6H3] have been synthesised with the Rb and Cs examples crystallographically characterised. These heaviest manganates crystallise as polymeric zig-zag chains propagated by AM⋅⋅⋅π-arene interactions. Key to their preparation is to avoid Lewis base donor solvents. In contrast, using multidentate nitrogen donors encourages ligand scrambling leading to redistribution of these bimetallic manganate compounds into their corresponding homometallic species as witnessed for the complete Li - Cs series. Adding to the few known crystallographically characterised unsolvated and solvated rubidium and caesium s-block metal amides, six new derivatives ([{AM(N‘Ar)}∞], [{AM(N‘Ar)⋅TMEDA}∞], and [{AM(N‘Ar)⋅PMDETA}∞] where AM=Rb or Cs) have been structurally authenticated. Utilising monodentate diethyl ether as a donor, it was also possible to isolate and crystallographically characterise sodium manganate [(Et2O)2Na(nBu)Mn[(N‘Ar)2], a monomeric, dinuclear structure prevented from aggregating by two blocking ether ligands bound to sodium. 相似文献
Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of 13C NMR spectra and generally precludes the observation of 15N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of 13C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced 13C NMR spectra indicate that the 13C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of 15N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine. 相似文献
Neutral [Ru(η6-arene)Cl2{Ph2P(CH2)3SPh-κP}] (arene = benzene, indane, 1,2,3,4-tetrahydronaphthalene: 2a, 2c and 2d) and cationic [Ru(η6-arene)Cl(Ph2P(CH2)3SPh-κP,κS)]X complexes (arene = mesitylene, 1,4-dihydronaphthalene; X = Cl: 3b, 3e; arene = benzene, mesitylene, indane, 1,2,3,4-tetrahydronaphthalene, and 1,4-dihydronaphthalene; X = PF6: 4a–4e) complexes were prepared and characterized by elemental analysis, IR, 1H, 13C and 31P NMR spectroscopy and also by single-crystal X-ray diffraction analyses. The stability of the complexes has been investigated in DMSO. Complexes have been assessed for their cytotoxic activity against 518A2, 8505C, A253, MCF-7 and SW480 cell lines. Generally, complexes exhibited activity in the lower micromolar range; moreover, they are found to be more active than cisplatin. For the most active ruthenium(II) complex, 4b, bearing mesitylene as ligand, the mechanism of action against 8505C cisplatin resistant cell line was determined. Complex 4b induced apoptosis accompanied by caspase activation. 相似文献