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1.
Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
2.
Julia K Pruns Jens-Peter Vietzke Manfred Strassner Claudius Rapp Ulrich Hintze Wilfried A K?nig 《Rapid communications in mass spectrometry : RCM》2002,16(3):208-211
A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards. 相似文献
3.
The versatile behavior of a trihydrazidophosphoradamantane allowing the synthesis of a variety of neutral, mono- or di-cationic water-soluble molecules of potential interest for biphasic catalysis is reported. 相似文献
4.
In this paper we construct an example of a word metric on an infinite cyclic subgroup. This example shows that subexponential
distortion does not obstruct non-trivial growth of connected radii. This answers a question of Gromov [6]. The constructed
metric has other pathological properies. Specifically, its asymptotic cone depends on the choice of ultrafilter and scaling
sequence.
The work has been partially supported by the Swiss National Science Foundation. 相似文献
5.
We build a metric space which is homeomorphic to a Cantor set but cannot be realized as the attractor of an iterated function system. We give also an example of a Cantor set K in R3 such that every homeomorphism f of R3 which preserves K coincides with the identity on K. 相似文献
6.
Milan Medved? 《Journal of Mathematical Analysis and Applications》2002,267(2):643-650
A criterion for the nonexplosion of solutions to semilinear evolution equations on Banach spaces is proved. The result is obtained by applying a modification of the Bihari type inequality to the case of a weakly singular nonlinear integral inequality. 相似文献
7.
We consider the one-dimensional steady-state semiconductor deviceequations modelling a pnpn device. There are two relevant scalingsof the equations corresponding to small and large applied voltages.In both scalings, the semiconductor equations can be consideredas singularly perturbed. It turns out that the small-voltagescaling breaks down for current values between two saturationcurrents. In that interval, the large-voltage scaling has tobe employed. For both scalings, we derive the first-order termsof an asymptotic expansion and show that the reduced problemhas a solution. An example verifies that the current-voltagecurves obtained have the expected qualitative structure. 相似文献
8.
Could simple intraannular-arm macrocyclic systems exist in enantiopure stable forms? The effective synthesis of two representative compounds of such a class, their resolution into enantiomers, and experiments justifying their stability toward racemization are presented. 相似文献
9.
Micha? Chmielewski 《Tetrahedron letters》2004,45(31):6007-6010
Comparison of the anion binding properties of a series of uncharged macrocyclic tetraamides reveal significant effects of the receptor's size on the strength of its anion complexes. This study allowed for estimation of the optimal size of a macroring for complexation of common anions. 相似文献
10.
Takayuki Yaegashi Shinya Yodoya Masahiko Nakamura Hiroki Takeshita Katsuhiko Takenaka Tomoo Shiomi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):999-1007
Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (Rp) equation was Rp ∝ [DEA]1.1[AIBN]0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r1 = 5.83 and r2 = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004 相似文献