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71.
Hassan Rabaâ Bernd Engels Thomas Hupp A. Stephen K. Hashmi 《International journal of quantum chemistry》2007,107(2):359-365
A general scheme for the endo‐ and exo‐cyclization of furan reactivity with [L ‐AuIII, IClx] with (x = 3, 1 and L ‐acetylene and vinylidene) complexes is investigated using density functional theory (DFT) code. Two conceivable mechanisms via a [4 + 2] Diels–Alder process or carbene complex are analyzed. According to the activation energy values of the gold (III and I) catalyst, the first mechanism, which implies the Diels–Alder reaction of AuIII, is thermodynamically favored and gives more evidence of the intramolecular addition of the furan with the alkynes. The second mechanism, presumably assisted by the spontaneous formation of the exo‐vinylidene complexes and intermediates of gold (III, I) by forming the carbene complex, is kinetically favored. Additionally, we compare our results with other structures with intramolecular additions that exhibit the quasi‐similarity of gold analogue structures. Differences in activation energies are observed, according to the functional used. Finally, we probe the solvent effects, which decrease the energy barrier in the path. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
72.
Wolfgang Schwack Bernd Brüger Steven Nyanzi 《Fresenius' Journal of Analytical Chemistry》1995,351(2-3):297-300
The differential pulse-polarographic (DPP) determination of both CS2 and COS gases, after their absorption in a methanolic piperidine reagent and the subsequent application of this technique to the residue analysis of dithiocarbamate fungicides is described. Rectilinear calibration curves for both CS2 and COS in the respective regions of 1.5–9.2 and 2.1–12.6 mol/l were obtained. The DPP method has been successfully applied to the determination of thiram residues on apples after a hot acid hydrolysis of the fruits. 相似文献
73.
Bernd Wegner 《Journal of Geometry》1994,50(1-2):186-201
For a closed plane curve the centers of distance functions are considered satisfying the condition that the function attains at least two absolute minima along. From the topology of the closure of this set some information on specific vertices of the curve can be obtained. If a simply closed curve has a finite number of vertices only, then the structure of this set is given by a tree, composed from regular arcs, such that the end points of this tree belong to minimal osculating circles of, which entirely are located in the interior of. Furthermore, the curve can be reconstructed from this set as the envelope of a suitable family of circles. These relations are used to give alternative proofs and extensions of several known vertex theorems for closed curves.Dedicated to N. Stephanidis on occasion of his 65. birthday 相似文献
74.
The job-shop problem is one of the most difficult NP-hard scheduling problems. A 10×10-problem published in 1963 has been solved only recently by Carlier and Pinson using a branch and bound method. Other branch and bound algorithms have been developed recently. The efficiency of all these branch and bound methods relies on the concept of immediate selection which allows to introduce order relations on the setI of all operations to be processed on the same machine before branching. We present new algorithms for immediate selection. Among them are
- anO(max {n logn,f})-algorithm for fixing all disjunctions induced by cliques;
- anO(n 2)-algorithm based on concepts which are different from those used by Carlier and Pinson.
75.
Itzhak I. Maor Katharina Kruppa Adi Rozencweig Amir Sterzer Frank Steinbach Vadim Beilin Bernd Breidenstein Gennady E. Shter Meirav Mann-Lahav Armin Feldhoff Gideon S. Grader 《Advanced functional materials》2023,33(49):2304464
Calcium cobaltite Ca3Co4−xO9+δ (CCO) is a promising p-type thermoelectric (TE) material for high-temperature applications in air. The grains of the material exhibit strong anisotropic properties, making texturing and nanostructuring mostly favored to improve thermoelectric performance. On the one hand multitude of interfaces are needed within the bulk material to create reflecting surfaces that can lower the thermal conductivity. On the other hand, low residual porosity is needed to improve the contact between grains and raise the electrical conductivity. In this study, CCO fibers with 100% flat cross sections in a stacked, compact form are electrospun. Then the grains within the nanoribbons in the plane of the fibers are grown. Finally, the nanoribbons are electrospun into a textured ceramic that features simultaneously a high electrical conductivity of 177 S cm−1 and an immensely enhanced Seebeck coefficient of 200 µV K−1 at 1073 K are assembled. The power factor of 4.68 µW cm−1 K−2 at 1073 K in air surpasses all previous CCO TE performances of nanofiber ceramics by a factor of two. Given the relatively high power factor combined with low thermal conductivity, a relatively large figure-of-merit of 0.3 at 873 K in the air for the textured nanoribbon ceramic is obtained. 相似文献
76.
Theorem 3 gives a condition when two -weights can be ``pasted' together to yield another -weight. It is subsequently used in Example 6 to give an example that shows that a necessary condition by Gohberg, Krupnik, and Spitkovsky is not sufficient.
77.
Bernd Siebert 《Mathematische Annalen》1993,296(1):269-283
This and the second part of the paper are to a great extent parts of my thesis [Si] which also appeared as preprint Mathematica Gottingensis 5/92. This work was partly supported by the S7B170 Geometrie und Analysis in Göttingen 相似文献
78.
In this B3 LYP model study, homoleptic nickel(0) ethyne complexes have been predicted as the catalyst resting state for the title reaction. Ethyne ligand coupling of Ni(C(2)H(2))(3) yields monoethyne nickelacyclopentadiene in the rate-determining step. Ethyne coordination is followed by insertion of an ethyne ligand into the Ni--C sigma bond. A highly strained monoethyne trans-nickelacycloheptatriene is formed. This trans intermediate is unable to reductively eliminate benzene without prior isomerization to a cis-structure. Instead, it rapidly collapses to a nickelacyclononatetraene. Ethyne coordination induces reductive elimination to the cyclooctatetraene complex Ni(eta(2)-C(2)H(2))(eta(2)-C(8)H(8)), followed by facile ligand exchange. Other ethyne coupling pathways have been computed to be less favored. The cyclooctatetraene ligand binds significantly weaker to nickel(0) than ethyne, both for mononuclear, and for dinuclear species. For this reason, C--C bond formation steps at Ni(2)(micro-cot) fragments have been predicted to feature prohibitively high overall reaction barriers. 相似文献
79.
Boron subhalide cluster dianions B6X 2- 6 (X = Cl, Br, I) are electrochemically oxidized in two steps. According to cyclic voltammograms, the first step is chemically reversible and yields the corresponding radical anions B6X .- 6. The electron transfer is nearly diffusion controlled. The second, slower electron-transfer step leads to a species which we assume to be the hitherto not yet described neutral compounds B6X 2- 6. The voltammograms indicate a coupled fast catalytic reaction, producing the radical anions in a reduction by an electrolyte component. Computer simulations of the cyclic voltammograms reveal mechanistic details of the redox reactions, as well as quantitative values for formal potentials, rate constants, and diffusion coefficients. The results are compared to other BnXn redox systems. 相似文献
80.
1,3-Dienes and electron deficient alkenes are coupled in a one pot carbon-carbon bond formation reaction under mild conditions. 相似文献