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31.
The problems of field evaporation (FE) and field desorption (FD) from surface of oxide high-temperature superconductors (HTSC) of 123, 2212 and 2223 type are discussed. Wide-angle atom probe, usual time-of-flight atom probe and field ionization magnet mass-spectrometer have been used in these experiments. The main purpose of the investigation was to search for effects connected with phase transition. Therefore, the experiments were carried out over a wide range of temperatures: from T of solid nitrogen to room T.

Composition of pure, contaminated and deep corroded surface and typical species of FE and FD spectra have been studied. The bond energies between some atoms (or clusters) and the surface have been estimated on the basis of experimental results and FE theory. From these estimations, and from discovering of correlated ion pairs, it was concluded that the redistribution of local bonds should be taken into consideration in this case. The increase of FE rate was observed at cryogenic temperatures. Various versions are discussed to explain these effects. Some of them are connected with phase transition.

A detailed study of FD of water protonized clusters is performed and the catalytic activity of HTSC crystal surfaces is discussed.  相似文献   

32.
We consider a four-dimensional generalization of Hess–Appel’rot system and costruct its Lax pair. Both classical and algebro-geometric integration procedure are proceeded. The algebro-geometric integration is based on deep facts from geometry of Prym varieties such as the Mumford relation and Mumford-Dalalyan theory. The integration is similar to the integration of Lagrange bitop which has recetly been performed by the authors.  相似文献   
33.
以硅溶胶和氧氯化锆为硅源和锆源,采用水热合成的方法制得具有ZSM-5结构的Zr-Si分子筛;用0.5mol/L的硫酸处理该分子筛,并在550℃焙烧,制得具有ZSM-5结构的SO4^2-/ZrO2-SiO2分子筛型的固体超强酸。采用XRD、SEM、TG、IR、NH3-PHD和指示剂法对其结构和酸性进行表征。结果表明,该SO4^2-/ZrO2-SiO2具有ZSM-5结构和超强酸性,其酸强度大于-13.75,且具有良好的热稳定性。  相似文献   
34.
35.
Starting from optically active methylferrocene-- and--carboxylic acids (1 a and1 b) of known absolute configuration and enantiomeric purity about 15 chiral ferrocenes (of each isomeric series— and ) were obtained by suitable ligand transformations. Thereby (almost) all possible chiral combinations of the ligands CH3, COOH (COO), COOCH3, CN and NH2 (NH3 +) were accessible which are necessary for a potential test of approximations of chirality functions for compounds with basic symmetry C5v. The chiroptical properties of these disubstituted ferrocenes are recorded.Preliminary tests using a shortened Ansatz revealed large discrepancies between calculated () and found [M]D-values. Possible reasons for this failure are discussed.

61. Mitt. über Ferrocenderivate

39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).

60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975).  相似文献   
36.
Due to the high safety risks, chemistry instructors avoid demonstrating many remarkable experiments based on the addition of a liquid to a solid. Well-known examples of such demonstrations are various pyrotechnic mixtures of potassium chlorate and sugar (sucrose), which are usually activated with a drop of concentrated sulfuric acid. Other attractive demonstrations are the addition of water to freshly prepared magnesium phosphide and addition of water to burning magnesium. In all of these demonstrations the reaction that takes place immediately is very vigorous and can be hazardous for the instructor. Because chemistry teachers and instructors usually try to avoid performing experiments that include a hazard, a number of highly attractive experiments may remain unknown to the public. Using a simple homemade device called a safety dropper, one can perform all of these experiments with complete safety, both for the audience and the demonstrator. Details for performing some of these experiments as well as for the construction of the safety dropper are given in this paper. Video clips of demonstrations are included as an aid for inexperienced instructors.  相似文献   
37.
Radiation-induced solid-state polymerization of cyclohexene sulfide has been investigated. Differential thermal analysis shows that this compound has a phase transition point at ?74°C and behaves as a plastic crystal in the temperature range from ?74 to ?20°C (melting point). By rapid cooling, this plastic crystal was easily supercooled, and below ?166°C a glassy crystal, i.e., a supercooled nonequilibrium state of plastic crystal, was obtained. In-source polymerization proceeded in the plastic crystalline state. Postpolymerization of glassy crystalline monomer irradiated at ?196°C occurred above ?166°C (glass transition point) during subsequent heating.  相似文献   
38.
The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr4 to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr4 conversion into bimolecular complex Br2?SeBr2, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using 1H NMR method.  相似文献   
39.
[reaction: see text] The macrocyclic 18-diazo-1,4,7,10,13,16-hexaoxacyclononadeca-17,19-dione (3-diazo-2,4-dioxo-19-crown-6, 1) readily forms complexes with potassium (2, stability constant in methanol is K(K+) = 229 +/- 25 M(-1)) and sodium ions (3, K(Na+) = 84.2 +/- 7.9 M(-1) in methanol). According to B3LYP/6-31G+(d,p) calculations and temperature-dependent 1H NMR spectroscopy, the predominant conformation of 1 has a Z,Z arrangement of the diazo and carbonyl groups. The X-ray crystal structure analysis showed that the potassium complex (2) has the same Z,Z arrangement, while the sodium analogue (2) exists in conformation with Z,E geometry of the diazodicarbonyl moiety. Direct 254 nm photolysis of diazo compounds 1-3 in methanol results in the formation of 3-methoxy-2,4-dioxo-19-crown-6 (5), the product of the insertion of corresponding alpha,alpha'-dicarbonylcarbene into the O-H bond of the solvent. The triplet-sensitized photolysis of diazomalonates 1-3 produces 2,4-dioxo-19-crown-6 (6), which is apparently formed via the triplet state of the intervening carbene.  相似文献   
40.
The mechanism for methane formation in methyl-coenzyme M reductase (MCR) has been investigated using the B3LYP hybrid density functional method and chemical models consisting of 107 atoms. The experimental X-ray crystal structure of the enzyme in the inactive MCR(ox1)(-)(silent) state was used to set up the initial model structure. The calculations suggest a mechanism not previously proposed, in which the most remarkable feature is the formation of an essentially free methyl radical at the transition state. The reaction cycle suggested starts from a Michaelis complex with CoB and methyl-CoM coenzymes bound and with a squareplanar coordination of the Ni(I) center in the tetrapyrrole F(430) prosthetic group. In the rate-limiting step the methyl radical is released from methyl-CoM, induced by the attack of Ni(I) on the methyl-CoM thioether sulfur. In this step, the metal center is oxidized from Ni(I) to Ni(II). The resulting methyl radical is rapidly quenched by hydrogen-atom transfer from the CoB thiol group, yielding the methane molecule and the CoB radical. The estimated activation energy is around 20 kcal/mol, which includes a significant contribution from entropy due to the formation of the free methyl. The mechanism implies an inversion of configuration at the reactive carbon. The size of the inversion barrier is used to explain the fact that CF(3)-S-CoM is an inactive substrate. Heterodisulfide CoB-S-S-CoM formation is proposed in the final step in which nickel is reduced back to Ni(I). The suggested mechanism agrees well with experimental observations.  相似文献   
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