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221.
222.
4-Substituted tetrahydro-3,6-pyridazinedione 3-hydrazones (2) (or their 3-hydrazino tautomers 3), useful intermediates in the synthesis of bicyclic pyridazine derivatives, were prepared in satisfactory yields in the reaction of the corresponding alkyl 3-substituted 3-cyanopropionates with hydrazine hydrate. 相似文献
223.
The reaction of various organometallics with 2-nitro-1-phenylsulfonylpropene 2a and 2-nitro-1-phenylthiopropene 2b was investigated. While in the case of lithium and magnesium organyls the addition products 4 were formed, transmetallation with CuCN led exclusively to (E)-nitro olefins 3. 相似文献
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225.
Dr. Benjamin Frank Dr. Thomas P. Cotter Dr. Manfred E. Schuster Prof. Dr. Robert Schlögl Dr. Annette Trunschke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):16938-16945
The effect of the gas‐phase chemical potential on surface chemistry and reactivity of molybdenum carbide has been investigated in catalytic reactions of propane in oxidizing and reducing reactant mixtures by adding H2, O2, H2O, and CO2 to a C3H8/N2 feed. The balance between surface oxidation state, phase stability, carbon deposition, and the complex reaction network involving dehydrogenation reactions, hydrogenolysis, metathesis, water‐gas shift reaction, hydrogenation, and steam reforming is discussed. Raman spectroscopy and a surface‐sensitive study by means of in situ X‐ray photoelectron spectroscopy evidence that the dynamic formation of surface carbon species under a reducing atmosphere strongly shifts the product spectrum to the C3‐alkene at the expense of hydrogenolysis products. A similar response of selectivity, which is accompanied by a boost of activity, is observed by tuning the oxidation state of Mo in the presence of mild oxidants, such as H2O and CO2, in the feed as well as by V doping. The results obtained allow us to draw a picture of the active catalyst surface and to propose a structure–activity correlation as a map for catalyst optimization. 相似文献
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227.
Meike Koenig Tadas Kasputis Daniel Schmidt Keith B. Rodenhausen Klaus-Jochen Eichhorn Angela K. Pannier Mathias Schubert Manfred Stamm Petra Uhlmann 《Analytical and bioanalytical chemistry》2014,406(28):7233-7242
A combined setup of quartz crystal microbalance and generalized ellipsometry can be used to comprehensively investigate complex functional coatings comprising stimuli-responsive polymer brushes and 3D nanostructures in a dynamic, noninvasive in situ measurement. While the quartz crystal microbalance detects the overall change in areal mass, for instance, during a swelling or adsorption process, the generalized ellipsometry data can be evaluated in terms of a layered model to distinguish between processes occurring within the intercolumnar space or on top of the anisotropic nanocolumns. Silicon films with anisotropic nanocolumnar morphology were prepared by the glancing angle deposition technique and further functionalized by grafting of poly-(acrylic acid) or poly-(N- isopropylacrylamide) chains. Investigations of the thermoresponsive swelling of the poly-(N-isopropylacrylamide) brush on the Si nanocolumns proved the successful preparation of a stimuli-responsive coating. Furthermore, the potential of these novel coatings in the field of biotechnology was explored by investigation of the adsorption of the model protein bovine serum albumin. Adsorption, retention, and desorption triggered by a change in the pH value is observed using poly-(acrylic acid) functionalized nanostructures, although generalized ellipsometry data revealed that this process occurs only on top of the nanostructures. Poly-(N-isopropylacrylamide) is found to render the nanostructures non-fouling properties. 相似文献
228.
Walter MJ Lupton JM Becker K Feldmann J Gaefke G Höger S 《Physical review letters》2007,98(13):137401
Simultaneous surface enhanced Raman scattering (SERS) and fluorescence is demonstrated from single conjugated polymer chains. As resonance enhancement of SERS depends on the spectral overlap of the polymer's absorption and the incident laser, resonance Raman and fluorescence effectively probe the absorbing and emitting part of the polymer, respectively. The optical phonon energies change along the polymer chain, providing a window to spatially track excited state relaxation. Whereas a mean spatial redistribution of the excitation is witnessed by a change in vibronic fingerprint following interchromophoric energy transfer, intrachromophoric exciton self-trapping leaves the vibrations unchanged. 相似文献
229.
Dr. Bhupendra Goswami Dr. Thomas J. Feuerstein Dr. Ravi Yadav Dr. Ralf Köppe Dr. Sergei Lebedkin Prof. Dr. Manfred M. Kappes Prof. Dr. Peter W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4401-4411
The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L- H ( L =[Ph2P{N(R)CH(CH3)Ph}2]), L′ -H ( L′ =[Ph2P{NDipp}{N(R)CH(CH3)Ph}]), (Dipp=2,6-iPr2C6H3), and L′′ -H ( L′′ =[Ph2P{N(R)CH(CH3)naph}2]), (naph=naphthyl) is presented. The resulting structures [ L 2Ca], [ L′ 2Ca], and [ L′′ 2Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue–green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [ L′′ 2Ca] is assigned to the fluorescence of naphthyl groups, the PL of [ L 2Ca] and [ L′ 2Ca] is contributed by long-lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5–295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved. 相似文献
230.
Maria Haimerl Dr. Christian Graßl Dr. Michael Seidl Dr. Martin Piesch Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18129-18134
The reactivity of white phosphorus and yellow arsenic towards two different nickel nacnac complexes is investigated. The nickel complexes [(L1Ni)2tol] ( 1 , L1=[{N(C6H3iPr2-2,6)C(Me)}2CH]−) and [K2][(L1Ni)2(μ,η1 : 1-N2)] ( 6 ) were reacted with P4, As4 and the interpnictogen compound AsP3, respectively, yielding the homobimetallic complexes [(L1Ni)2(μ-η2,κ1:η2,κ1-E4)] (E=P ( 2 a ), As ( 2 b ), AsP3 ( 2 c )), [(L1Ni)2(μ,η3 : 3-E3)] (E=P ( 3 a ), As ( 3 b )) and [K@18-c-6(thf)2][L1Ni(η1 : 1-E4)] (E=P ( 7 a ), As ( 7 b )), respectively. Heating of 2 a , 2 b or 2 c also leads to the formation of 3 a or 3 b . Furthermore, the reactivity of these compounds towards reduction agents was investigated, leading to [K2][(L1Ni)2(μ,η2 : 2-P4)] ( 4 ) and [K@18-c-6(thf)3][(L1Ni)2(μ,η3 : 3-E3)] (E=P ( 5 a ), As ( 5 b )), respectively. Compound 4 shows an unusual planarization of the initial Ni2P4-prism. All products were comprehensively characterized by crystallographic and spectroscopic methods. 相似文献