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排序方式: 共有140条查询结果,搜索用时 15 毫秒
41.
Tobias Santowski Alexander G. Sturm Dr. Kenrick M. Lewis Dr. Thorsten Felder Prof. Dr. Max C. Holthausen Prof. Dr. Norbert Auner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3809-3815
The Müller–Rochow direct process (DP) for the large-scale production of methylchlorosilanes MenSiCl4−n (n=1–3) generates a disilane residue (MenSi2Cl6−n, n=1–6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes MexSiHyClz (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution. 相似文献
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43.
Modulation of Relaxivity,Suspension Stability,and Biodistribution of Dendronized Iron Oxide Nanoparticles as a Function of the Organic Shell Design
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Aurélie Walter Audrey Parat Antonio Garofalo Sophie Laurent Luce Vander Elst Robert N. Muller Tao Wu Emilie Heuillard Eric Robinet Florent Meyer Delphine Felder‐Flesch Sylvie Begin‐Colin 《Particle & Particle Systems Characterization》2015,32(5):552-560
Nanoparticles (NPs) with a mean diameter of 10 nm are functionalized with three dendrons: D1 a PEGylated PAMAM dendron of generation 0.5, D2 a hydrophilic oligoethyleneglycol‐derivatized dendron (D2) displaying a phosphonic acid at the focal point, and D2–2P the same dendron than D2 but with two phosphonic acid anchoring agents. Their grafting is confirmed by IR spectroscopy and elemental analysis. All dendronized NPs are stable over a long period of time in suspensions in water and in different physiological media and display a mean hydrodynamic diameter smaller than 50 nm whatever the molecule architecture. NMRD profiles and relaxivity measurements highlight the influence of the molecule architecture on the water diffusion close to the magnetic core thus influencing the relaxation properties at low magnetic field. The high hydrophilic architecture of the dendron D2 by contrast to dendron D1 allows maintaining the colloidal stability in different conditions while ensuring a very good accessibility of water molecule close to the magnetic core. Coupling of a fluorescent dye on dendrons have allowed investigating the biodistribution of dendronized NPs, which are found to be quickly eliminated through urinary and hepatobiliary pathways within 4 h. Furthermore, no enhanced permeation and retention effect in tumors can be observed. 相似文献
44.
Lukin O Gramlich V Kandre R Zhun I Felder T Schalley CA Dolgonos G 《Journal of the American Chemical Society》2006,128(27):8964-8974
The synthesis of "designer" dendrimers and dendrons with sulfonimide units at every branching point is reported. The synthesis is based on a series of (regio)selective functionalization reactions of amines and sulfonamides allowing precise control of the dendrimers' shape, the number of branches in each generation, and their peripheral decoration with functional groups. In principle, structurally different branches can be incorporated at any position within the dendrimer structure at will. Structurally perfect symmetrical and two-faced "Janus"-type dendrimers, as well as dendrimers and dendrons with intended interstices were synthesized on a preparative scale and fully characterized. Oligosulfonimide dendrons of various generations bearing an aryl bromide functional group at their focal points were attached to a p-phenylene core with the aid of Suzuki cross-coupling reactions resulting in dendrimers with photoactive terphenyl cores. The structure and the high purity of all dendritic sulfonimides were confirmed by means of (1)H and (13)C NMR, electrospray ionization mass spectrometry (ESI-MS), and elemental analysis. The utility of MALDI-TOF mass spectrometry for the analytical characterization of these dendrimers was evaluated in comparison to electrospray ionization. Two model branched oligosulfonimides were characterized in the solid state by single-crystal X-ray analysis. Reaction selectivities and conformation of sulfonimide branching points were rationalized by DFT calculations. 相似文献
45.
46.
Armaroli N Accorsi G Felder D Nierengarten JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(10):2314-2323
The rhenium(I) and ruthenium(II) complexes of a fullerene-substituted bipyridine ligand have been prepared. Electrochemical studies indicate that some ground state electronic interaction between the fullerene subunit and the metal-complexed moiety are present in the Re(I) but not the Ru(II) complex. The photophysical properties have been investigated by steady-state and time-resolved UV/Vis-NIR luminescence spectroscopy and nanosecond laser flash photolysis in CH2Cl2 solution, and compared to those of the corresponding model compounds. Excitation of the methanofullerene moiety in the dyads does not lead to excited state intercomponent interactions. Instead, excitation of the metal-complexed unit shows that the lowest triplet metal-to-ligand-charge-transfer excited state ((3)MLCT) centered on the Re(I)- or Ru(II)-type unit is quenched with a rate constant of about 2.5 x 10(8) s(-1). The quenching is attributed to an electron-transfer (ElT) process leading to the reduction of the carbon sphere, as determined by luminescence spectroscopy for the Ru(II) dyad. Experimental detection of electron transfer in the Re(I) dyad is prevented due to the unfavorable absorption of the metal-complexed moiety relative to the fullerene unit. However, it can be postulated on the basis of energetic/kinetic arguments and by comparison with the Ru(II)-type array. The primary ElT process is followed by charge-recombination to give the lowest-lying fullerene triplet excited state (3C60) with quantitative yield, as determined by sensitized singlet oxygen luminescence experiments. Direct (3)MLCT-->3C60 triplet-triplet energy-transfer (EnT) does not successfully compete with ElT since it is highly exoergonic and located in the Marcus inverted region. The quantum yield of singlet oxygen sensitization (Phi(delta)) of the Re(I)-based dyad is found to be lower (0.80) than for the corresponding Ru(II) derivative (1.0). This is likely to be the consequence of different conformational structures for the two dyads, rather than a different yield of 3C60 formation. 相似文献
47.
S. Paschen E. Felder H.R. Ott 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,2(2):169-176
We present measurements of the specific heat, the electrical resistivity, the Hall effect, and the magnetic susceptibility
of CeAuAl3, a new heavy-electron compound that crystallizes in an ordered derivative of the tetragonal BaAl4-type structure. For comparison we have also done some of these measurements on the isostructural non-magnetic reference compound
LaAuAl3, which appears to be a simple metal. Below K, CeAuAl3 orders antiferromagnetically and below 1K, we encounter Fermi liquid behaviour with considerably enhanced effective masses,
i.e., a quadratic temperature dependence of the resistivity with a large prefactor and a sizable linear-in-T contribution to the specific heat. This linear-in-T contribution increases by more than a factor 50 from its value at to its value at . Consequently CeAuAl3 develops a heavy-electron ground state, coexisting with antiferromagnetic order. The small energy scales involved in the
problem make CeAuAl3 a good candidate for tuning it, by varying external parameters, towards a quantum critical point. At high temperatures we
observe local moment behaviour. From the temperature dependence of the magnetic susceptibility and the specific heat we have
derived the crystalline-electric-field-split level scheme of the J
=5/2 multiplet. Distinct features in the electrical resistivity provide additional evidence for this level splitting.
Received: 6 November 1997 / Accepted: 17 November 1997 相似文献
48.
We prove a relative version of Kontsevich's formality theorem. This theorem involves a manifold M and a submanifold C and reduces to Kontsevich's theorem if C=M. It states that the DGLA of multivector fields on an infinitesimal neighbourhood of C is L∞-quasiisomorphic to the DGLA of multidifferential operators acting on sections of the exterior algebra of the conormal bundle. Applications to the deformation quantisation of coisotropic submanifolds are given. The proof uses a duality transformation to reduce the theorem to a version of Kontsevich's theorem for supermanifolds, which we also discuss. In physical language, the result states that there is a duality between the Poisson sigma model on a manifold with a D-brane and the Poisson sigma model on a supermanifold without branes (or, more properly, with a brane which extends over the whole supermanifold). 相似文献
49.
Appel R Atoyan GS Bassalleck B Bergman DR Brown DN Cheung N Dhawan S Do H Egger J Eilerts S Felder C Fischer H Gach M Herold W Issakov VV Kaspar H Kraus DE Lazarus DM Leipuner L Lichard P Lowe J Lozano J Ma H Majid W Menzel W Pislak S 《Physical review letters》2000,85(12):2450-2453
We report results of a search for the lepton-family number violating decay K+-->pi(+)&mgr;(+)e(-) from data collected by experiment E865 in 1996 at the Alternating Gradient Synchroton of Brookhaven National Laboratory. We place an upper limit on the branching ratio at 3.9x10(-11) ( 90% C.L.). Together with results based on data collected in 1995 and an earlier experiment, E777, this result establishes a combined 90% confidence level upper limit on the branching ratio at 2.8x10(-11). We also report a new upper limit on the branching ratio for pi(0)-->&mgr;(+)e(-) of 3.8x10(-10) ( 90% C. L.). 相似文献
50.
Picosecond time-resolved fluorescence (TRF) spectroscopy has been used to study transient behavior in 1,6-diphenylhexa-1,3,5-triene (DPH) and 1,8-diphenylocta-1,3,5,7-tetraene (DPO). The observation is reported of short-lived fluorescence lying to shorter wavelengths than the literature spectra for these molecules. From the vibrational structure and the solvent shift of the DPO transient spectrum in benzene with respect to hexane, the pulse-limited feature can be assigned to fluorescence from vibrationally unrelaxed levels of the Bu state. In the DPH case, the relaxation time of the transient feature is greater than the laser pulse autocorrelation width, indicating that the decay of Bu state fluorescence may be limited by vibrational relaxation in the lowest excited (Ag) state. 相似文献