Oxidations of 4- and 3-Aminopyridinepentaammineruthenium(ii) Complexes by Ethylenediaminetetraacetatocobaltate(III)

Redox reactions of Co(edta)^? with Ru(NH₃)₅L²⁺ (L = 3- and 4-aminopyridine (AmPy)) were found to follow an outer-sphere electron transfer mechanism. The specific rate constants are (3.26 ± 0.03) × 10² and (3.07 ± 0.04) × 10₃ M^?1S^?1, for L = 3- and 4-AmPy, respectively, at μ, = 0.10 M LiClO₄, pH = 8.0 (tris) and T = 25 °C. The rate constants of oxidations for a series of Ru(NH₃)₅L²⁺ complexes are higher than those of the corresponding Fe(CN)₅L_3- complexes by factors of 4 to 15 even after corrections for differences in reduction potentials and in charges of the complexes. Nonadiabaticity in the reactions of Fe(CN)₅L3 complexes may account for the difference in the relative reactivities.     

Morphology-controlled nonaqueous synthesis of anisotropic lanthanum hydroxide nanoparticles

The preparation of lanthanum hydroxide and manganese oxide nanoparticles is presented, based on a nonaqueous sol-gel process involving the reaction of La(OiPr)₃ and KMnO₄ with organic solvents such as benzyl alcohol, 2-butanone and a 1:1 vol. mixture thereof. The lanthanum manganese oxide system is highly complex and surprising results with respect to product composition and morphology were obtained. In dependence of the reaction parameters, the La(OH)₃ nanoparticles undergo a shape transformation from short nanorods with an average aspect ratio of 2.1 to micron-sized nanofibers (average aspect ratio is more than 59.5). Although not directly involved, KMnO₄ plays a crucial role in determining the particle morphology of La(OH)₃. The reason lies in the fact that KMnO₄ is able to oxidize the benzyl alcohol to benzoic acid, which presumably induces the anisotropic particle growth in [0 0 1] direction upon preferential coordination to the ±(1 0 0), ±(0 1 0) and ±(−110) crystal facets. By adjusting the molar La(OiPr)₃-to-KMnO₄ ratio as well as by using the appropriate solvent mixture it is possible to tailor the morphology, phase purity and microstructure of the La(OH)₃ nanoparticles. Postsynthetic thermal treatment of the sample containing La(OH)₃ nanofibers and β-MnOOH nanoparticles at the temperature of 800 °C for 8 h yielded polyhedral LaMnO₃ and worm-like La₂O₃ nanoparticles as final products.     

Direct electrochemistry and electrocatalysis of hemoglobin in gelatine film modified glassy carbon electrode

Direct electrochemical and electrocatalytic behavior of hemoglobin (Hb) immobilized on glass carbon electrode (GCE) containing gelatine (Gel) films was investigated. The characteristics of Hb/Gel film modified GC electrode were performed by using SEM microscopy, UV-vis spectroscopy and electrochemical methods. The immobilized Hb showed a couple of quasi-reversible redox peak with a formal potential of −0.38 V (versus SCE) in 0.1 M pH 7.0 PBS. The formal potential changed linearly from pH 4.03 to 8.41 with a slope value of −52.0 mV pH⁻¹, which suggested that a proton transfer was accompanied with each electron transfer (ET) in the electrochemical reaction. The Hb/gelatine/GCE displayed a rapid amperometric response to the reduction of H₂O₂ and nitrite.     

密度泛函理论和从头算方法对富勒烯分子静电势的比较研究

分别在Hartree-Fock和密度泛函B3LYP理论下,用6-31G*基组研究了C60和C70分子的静电势,比较了这方法计算得到上述分子静电势值的大小,静电势图形和静电势差值曲线,分析了富勒烯的电子相关效应.     

Chemiluminescence in the reaction of the RuII trisbipyridyl complex with dimethyldioxirane

The reaction of dimethyldioxirane (1) with the Ru^II trisbipyridyl complex accompanied by chemiluminescence (CL) was studied. It is established that the intensity of CL and the rate of its decay increase proportionally with the concentration of Ru^II. The bimolecular rate constant (k ₂) of the reaction of1 with Ru^II was determined. The activation parameters (E _a and logA) for this reaction were calculated from the temperature dependence ofk ₂. The excitation yield of Ru^II* (η _Ru ^* ) was estimated. The quenching of Ru^II* by dioxirane was studied, and the bimolecular quenching constant and the coefficient of excitation regeneration were determined. It was suggested that the catalysis of the decomposition of1 and the excitation of Ru^II occurvia a mechanism of chemically initiated electron exchange. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1138–1142, June, 1997.     

Direct Visualization of Electromagnetic Microfields by Superposition of Two Kinds of Electron Holograms

A new electron holographic method is presented to directly visualize pure phase objects such as electromagnetic microfields, which is achieved by superposition of two kinds of electron holograms. The method is very simple and is twice as sensitive as the conventional double-exposure electron holography and the four-electron-wave interference. Using this technique, an electric field around a charged latex sphere and a magnetic field around a barium ferrite particle have been directly observed.     

Quantitative High Resolution Electron Microscopy

 With the resolution becoming sufficient to reveal individual atoms, HREM is now entering the stage where it can compete with X-ray methods to quantitatively determine atomic structures of materials without much prior knowledge, but with the advantage of being applicable to aperiodic objects such as crystal defects. In our view the future electron microscope will be characterised by a large versatility in experimental settings under computer control such as the illumination conditions (TEM-STEM), CBED, detecting conditions (diffraction, image, ptychography) and many other tunable parameters such as focus (g), voltage, spherical aberration (C _s ), beam tilt, etc. Since modern detectors can detect single electrons, also the counting statistics is known. The only limiting factor in the experiment will be the total number of electrons that interact with the object during the experiment due to the limitations in the exposure time or in the object damage. However, instrumental potentialities will never be exploited fully if not guided by an experimental strategy. Here intuitive guidelines can be very deceptive. For instance an image made with the best electron microscope (C _s  = 0) at the best focus (g = 0) from the best object (phase object) would show no contrast at all. Hence, questions such as what is the best C _s , focus, object thickness, etc. can only be answered properly if done using a method of experiment design.     

The Physical Basis of the VSEPR Model

The VSEPR model is a consequence of the correlation of same-spin electrons resulting from the operation of the Pauli exclusion principle. Although the VSEPR rules can be interpreted in terms of an orbital model they do not provide the physical basis for the model.     

Ion pair generation rates near planar3H and63Ni electron capture detector foils

The ion-pair generation rate (ionization topography) in plasmas from⁶³Ni and particularly Ti³H₄ foils, as used in electron capture detectors, was measured at room temperature using large, parallel plates of low backscattering ability in nitrogen gas of varying density. For one atmosphere pressure, the fall-off of ion pair formation as calculated from the exponential region equalsN ₀·e ^–0.19d for⁶³Ni andN ₀·e ^–1.4d for³H (whereN ₀ is the initial ionization rate immediately adjacent to the foil andd is the distance from the foil in mm). The experimentally measured half ranges (distances from the foil within which 50% of all possible ion pairs are created) are 2.7 mm for⁶³Ni and 0.27 mm for³H. The half ranges calculated from the exponential region where there is less interference from electron backscattering, are 3.7 and 0.5 mm, respectively. The latter values are considered closer to the true, unimpeded ionization topography near planar⁶³Ni and³H foils.Material taken from doctoral thesis     

Activated bis- and tetrafluoroaromatic compounds containing bis-phenylquinoxaline fragments

New activated bis- and tetrafluoroaromatic compounds containing the bis-phenylquinoxaline fragments, viz., methylene-bis-6(7),6"(7")-{2-(p-fluoro)phenyl-3[4-(p-fluorobenzoyl)phenyl]quinoxalines}, were prepared according to multistep procedures with the use of chloral as the starting compound. The presence of the activating carbonyl groups in the para positions with respect to two fluorine atoms opens up the possibility of the use of these monomers for the synthesis of high-molecular-weight aromatic quinoxaline-containing polyether ketones.