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21.
Conclusions Prototropic rearrangement in the phenyl radical cannot proceed under ordinary conditions in view of the high energy barrier.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 460–462, February, 1979. 相似文献
22.
Self-sensitisation of photo-oxygen evolution occurs in aqueous dispersions of silver zeolites. In presence of Cl?, chlorine is the photoproduct in acidic medium, and the same type of self-sensitisation occurs. Self-sensitisation means that systems which are first insensitive to light of a certain wavelength become photo-active after they have been illuminated by light of higher energy. For a better understanding of silver zeolites, we have carried out EH-MO calculations on the 6–6 subunit (SBU) of a zeolite, on the 6–6 SBU with an Ag-atom in the center, on the 6–6 SBU with one Ag-atom in the center and one outside on top of the hexagon, and finally on another with one Ag-atom in the center and two Ag-atoms outside, each on top of a hexagon. The Ag0 in the cage of the 6–6 SBU is significantly polarized by the 6–6 SBU environment. The energy barrier to escape the 6–6 SBU is 0.8 eV for Ag0 and 0.5 eV for Ag+. The HOMO of the Ag(6–6 SBU) is a totally symmetric 5s* orbital and the LUMO is a 5pz* type. 5pz*←5s* electronic excitation reduces the energy barrier and allows an (Ag0)* to exit the 6–6 SBU, provided the excited-state lifetime is long enough. The MO picture predicts low-energy charge-transfer transitions from the zeolite framework to the 5s* orbital. The highest occupied orbitals of the zeolite framework are localized on the O-atoms. Interactions between an Ag-atom in the 6–6 SBU and one or two external Ag-atoms are discussed. 相似文献
23.
24.
Häussermann U Amerioun S Eriksson L Lee CS Miller GJ 《Journal of the American Chemical Society》2002,124(16):4371-4383
This work presents a detailed, combined experimental and theoretical study on the structural stability of s-p bonded compounds with the BaAl4 structure type (space group I4/mmm, Z = 2) as part of a broad program to investigate the complex questions of structure formation and atomic arrangements in polar intermetallics. From ab initio calculations employing pseudopotentials and a plane wave basis set, we extracted optimized structural parameters, binding energies, and the electronic structure of the systems AeX(III)4, AeX(II)2X(IV)2, AeX(II)2X(III)2 (Ae = Ca, Sr, Ba; X(II) = Mg, Zn; X(III) = Al, Ga; X(IV) = Si, Ge). For all systems we found a pronounced pseudo-gap in the density of states separating network X42- bonding from antibonding electronic states that coincides with the Fermi level for an electron count of 14 electrons per formula unit, the optimum value for stable BaAl4-type polar intermetallics. However, the synthesis and structural characterization (from X-ray single crystal and powder diffraction data) of the new compounds AeZn2-Al2+, AeZn2-deltaGa2+delta (Ae = Ca, Sr, Ba; delta = 0-0.2) and AeMg0.9Al3.1, AeMg1.7Ga2.3 (Ae = Sr, Ba) manifested that electron deficiency is rather frequent for BaAl4-type polar intermetallics. The site preference for different "X" elements in the ternary systems was quantified by calculating "coloring energies", which, for some systems, was strongly dependent on the size of the electropositive Ae component. The Ae2+ cations decisively influence the nearest neighbor distances in the encapsulating polyanionic networks X4(2-) and the structures of these networks are surprisingly flexible to the size of the Ae component without changing the overall bonding picture. A monoclinically distorted variant of the BaAl4 structure occurs when the cations become too small for matching the size of encapsulating X4(2-) cages. An even larger size mismatch leads to the formation of the EuIn4 structure type. 相似文献
25.
The occurrence of electrochemical processes during the operation of an electrospray ionization (ESI) source is well established. In the positive ion mode, electrons are drawn from the ESI metal capillary to a high voltage power supply. These electrons are the product of charge-balancing oxidation reactions taking place at the liquid/metal interface of the ion source. In a recent study, (Anal. Chem.2001, 73, 4836-4844), our group has shown that the introduction of a ground loop can dramatically enhance the rate of these oxidation processes. Such a ground loop can be introduced by connecting the sample infusion syringe (or the liquid chromatography column, in the case of LC-MS studies) to ground. The magnitude of the ground loop current can be controlled by the electrolyte concentration in the analyte solution, and by the dimensions of the capillary connecting the syringe needle and the ESI source. Using ferrocene as a model system, it is demonstrated that the introduction of such a ground loop can significantly enhance the signal intensity of analytes that form electrochemically ionized species during ESI. However, analytes that form protonated molecular ions, such as reserpine, also show higher signal intensities when a ground loop is introduced into the system. This latter observation is attributed to the occurrence of electrolytic solvent (acetonitrile and/or water) oxidation processes. These reactions generate protons within the ion source, and thus facilitate the formation of [M + nH](n+) ions. Overall, this work provides an example of how the careful control of electrochemical parameters can be exploited to optimize signal intensities in ESI-MS. 相似文献
26.
Thermal (blackbody-like) radiation that originated from laser-heated tungsten nanoparticles was measured using optical emission spectroscopy. The nanoparticles were generated via ArF excimer laser-assisted photolytic decomposition of WF6/H2/Ar gas mixtures, and the laser heating was applied parallel to the deposition. The temperature of the nanoparticles was determined, and its dependence on time, with respect to the 15-ns laser pulse (full width at half-maximum, fwhm) and laser fluence (phi), has been presented. At phi > 90 mJ/cm2, the particles reached the melting point (shortly after the laser pulse). Dominant cooling mechanisms, such as evaporation (above approximately 3000 K) and a combination of heat transfer by the ambient gas and radiative cooling (below approximately 3000 K), were observed for the nanoparticles, which were approximately 10 nm in diameter. The degree of inelasticity for the (predominantly) argon-gas collisions and the total emissivity of the particles (in the 2500-3000 K temperature region) could also be derived. The measured cooling rate and temperature data indicate that, depending on experimental parameters, evaporation and surface reactions can have a definite effect on the growth of particles. 相似文献
27.
The monoclinic modification of terbium oxide hydroxide, TbOOH, was prepared using hydrothermal technique. The crystal structure was investigated by three-dimensional single-crystal X-ray analysis and was refined to a conventional R-value of 8.1%. The space group is , No. 11, with a = 6.04 Å, b = 3.69 Å, c = 4.33 Å, and β = 109.0°. The terbium atom is seven coordinated with oxygen atoms, and the structure is not hydrogen bonded.The compound is antiferromagnetic with a Néel temperature of 10°K. Neutron diffraction powder patterns were measured at 300°K and 4.2°K. The magnetic super lattice reflections were indexed on the basis of a monoclinic unit cell with the dimensions aM = 2a, bM = b, cM = c, and βM = β, where a, b, c, and β are the dimensions of the chemical unit cell. The structure contains two independent magnetic atoms. A nonclinear antiferromagnetic arrangement of the spins describes the magnetic structure. The spin at one atom has an angle of 43° with the ac plane and the projection of the spin on the ac plane has an angle of 59° with the a axis. The spin on the other atom has an angle of ?43° with the ac plane, the projection having the same angle of 59° with the a axis. 相似文献
28.
Direct optical detection of singlet oxygen from a single cell 总被引:1,自引:0,他引:1
Zebger I Snyder JW Andersen LK Poulsen L Gao Z Lambert JD Kristiansen U Ogilby PR 《Photochemistry and photobiology》2004,79(4):319-322
Singlet oxygen has been detected in single nerve cells by its weak 1270 nm phosphorescence (a1deltag --> X3sigmag-) upon irradiation of a photosensitizer incorporated in the cell. Thus, one can now consider the application of direct optical imaging techniques to mechanistic studies of singlet oxygen at the single-cell level. 相似文献
29.
Jerald S. Bradshaw Reed M. Izatt James J. Christensen Krzystof E. Krakowiak Bryon J. Tarbet Ronald L. Bruening S. Lifson 《Journal of inclusion phenomena and macrocyclic chemistry》1989,7(2):127-136
Silica gel-bound crown ethers and aza macrocycles have been synthesized with the attaching arm connected to the carbon framework of the macrocycles. The interactions of these bound macrocycles with cations are almost identical to those involving the analogous free macrocycles. This has allowed for predictable cation separation, concentration, and removal processes to be performed on a small scale. Quantum mechanical calculations and NMR measurements indicate that similarly bound chiral macrocycles will be capable of use in separating chiral organic amines.Dedicated to the memory of Professor James J. Christensen who died on 5 September 1987. 相似文献
30.
Hainer?Wackerbarth Rodolphe?Marie Mikala?Grubb Jingdong?Zhang Allan?G.?Hansen Ib?Chorkendorff Claus?B.?V.?Christensen Anja?Boisen Jens?UlstrupEmail author 《Journal of Solid State Electrochemistry》2004,8(7):474-481
We provide a comprehensive study of single- (ss) and double-strand (ds) oligonucleotides with either 25 or 10 bases or base pairs (bp) immobilized on polycrystalline and single-crystal Au(111) surfaces. The study is based on X-ray photoelectron spectroscopy, cyclic and differential pulse voltammetry, interfacial capacitance data, and electrochemical scanning tunnelling microscopy (in situ STM). The sequences used were the 25-bp sequence from the BRCA1 gene (25-mer), while the 10-bp oligonucleotides contained solely linear adenine and thymine sequences. The oligonucleotides were modified by the dimethoxytrityl group (DMT) via a disulfide group [DMT-S-S-ss25-mer and DMT-S-S-ds(AT)10], a pure disulfide group (A10-S-S-T10), or a thiol group [HS-ss25-mer and HS-ds-(AT)10], all via a hexamethylene linker. The overall pattern suggests strategies for controlled adsorption of DNA-based molecules and recognition of complementary strands or other molecules. 相似文献