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251.
Amendola V Colasson B Fabbrizzi L Rodriguez Douton MJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(17):4988-4997
Dicationic ligands incorporating two 2,2'-bipyridine units and two imidazolium moieties, [1](2+) and [2](2+), form stable chelate complexes with Cu(II) and Cu(I) in acetonitrile solution. Each Cu(II) complex binds two X(-) ions according to two stepwise equilibria, the first involving the Cu(II) centre and the second involving the bis-imidazolium compartment. Cu(I) complexes are able to host only one NO(3)(-) ion in the bis-imidazolium cavity, while other anions induce demetallation. Thus, in the presence of one equivalent of NO(3)(-), the Cu(II)/Cu(I) redox change makes the anion translocate quickly and reversibly from one binding site to the other within the [Cu(II,I)(1)](4+/3+) system, as demonstrated by cyclic voltammetry and controlled-potential electrolysis experiments. 相似文献
252.
Density functional theory was employed to investigate the water-gas-shift reaction (WGS, CO+H2O-->H2+CO2) on Au29 and Cu29 nanoparticles seen with scanning tunneling microscopy in model AuCeO2(111) and CuCeO2(111) catalysts. Au(100) and Cu(100) surfaces were also included for comparison. According to the calculations of the authors, the WGS on these systems operate via either redox or associative carboxyl mechanism, while the rate-limiting step is the same, water dissociation. The WGS activity decreases in a sequence: Cu29>Cu(100)>Au29>Au(100), which agrees well with the experimental observations. Both nanoparticles are more active than their parent bulk surfaces. The nanoscale promotion on the WGS activity is associated with the low-coordinated corner and the edge sites as well as the fluxionality of the particles, which makes the nanoparticles more active than the flat surfaces for breaking the O-H bond. In addition, the role of the oxide support during the WGS was addressed by comparing the activity seen in the calculations of the authors for the Au29 and Cu29 nanoparticles and activity reported for XCeO2(111) and XZnO(000i)(X=Cu or Au) surfaces. 相似文献
253.
Graciani J Fdez Sanz J Asaki T Nakamura K Rodriguez JA 《The Journal of chemical physics》2007,126(24):244713
This work presents a detailed experimental and theoretical study of the oxidation of TiN(001) using a combination of synchrotron-based photoemission and density functional theory (DFT). Experimentally, the adsorption of O2 on TiN(001) was investigated at temperatures between 250 and 450 K. At the lowest temperature, there was chemisorption of oxygen (O(2,gas)-->2O(ads)) without significant surface oxidation. In contrast, at 450 K the amount of O2 adsorbed increased continuously, there was no evidence for an oxygen saturation coverage, a clear signal in the Ti 2p core level spectra denoted the presence of TiOx species, and desorption of both N2 and NO was detected. The DFT calculations show that the adsorption/dissociation of O2 is highly exothermic on a TiN(001) substrate and is carried out mainly by the Ti centers. A high oxygen coverage (larger than 0.5 ML) may induce some structural reconstructions of the surface. The exchange of a surface N atom by an O adatom is a highly endothermic process (DeltaE=2.84 eV). However, the overall oxidation of the surface layer is thermodynamically favored due to the energy released by the dissociative adsorption of O2 and the formation of N2 or NO. Both experimental and theoretical results lead to conclude that a TiN+mO2 -->TiOx + NO reaction is an important exit channel for nitrogen in the oxidation process. 相似文献
254.
This review is concerned with recent studies of electrospray ionisation-mass spectrometry (ESI-MS) of selected small molecular mass drugs and their application in qualitative and quantitative analytical methods using the techniques liquid chromatography mass spectrometry (LC-ESI-MS) and capillary electrophoresis mass spectrometry (CE-ESI-MS). The publications reviewed are taken from the Web of Knowledge database for the year 2006. The drugs have molecular mass less than 1000 Da and are chosen according to selected drug classifications in which they give ESI signals primarily as [M+H]+ ions. The drug classifications are antibiotics/antibacterials, steroids, anti-tumour drugs, erectile dysfunction agents, anti-epileptic drugs, antiasthmatic drugs, psychoactive drugs and miscellaneous drugs. Details are given on the fragmentations, where available, that these ionic species exhibit in-source and in ion trap, triple quadrupole and time-of-flight mass spectrometers. Analytical methods for the detection and determination of these small molecular mass drug molecules are also discussed, where appropriate, under the particular drug classifications. Analytical information on, for example, sample concentration techniques, separation conditions, recoveries from biological media and limits of detection/quantitation (LODs and LOQs) are provided. 相似文献
255.
Reina M Mancha R Gonzalez-Coloma A Bailen M Rodriguez ML Martinez-Diaz RA 《Natural product research》2007,21(12):1048-1055
Two highly oxygenated hetisine-type diterpenoid alkaloids, delphigraciline (1), 14-hydroxyhetisinone N-oxide (2), and the norditerpenoid alkaloid 8-methoxykarakoline (3), were isolated from a neutral extract of Delphinium gracile. Their structures were elucidated on the basis of spectroscopic data and by comparison with previously reported spectroscopic data of similar alkaloids. Their antiparasitic and insecticidal activities are also discussed. 相似文献
256.
Experimental results of turbulent flows for both, field and laboratory tests are presented. The spatial and temporal resolution
is limited by the measuring instruments, which result in “filtering” out the very small scales, thus observing only macroturbulence.
The experimental field-results have been obtained during the large-scale surf zone experiments carried out in the Ebro Delta,
(Spain), under spilling/plunging breaking waves. The field-measurements include several tests across the surf zone with high
vertical resolution. The measured turbulent properties are compared with state-of-art macroturbulence characteristics and
length parameterisations. Furthermore, a detailed comparison of two-dimensional electromagnetic and three-dimensional ultrasonic
velocity measurements has been carried out for hydraulic jumps in a laboratory flume to validate the field measurements and
to study the frequency response of electromagnetic sensors.
Received: 22 December 1996/Accepted: 8 September 1998 相似文献
257.
MJ Singh DO Kataria N Madhavan P Sugathan JJ Das DK Awasthi AK Sinha R Shanker 《Pramana》1999,53(4):743-764
A projectile ion-recoil ion coincidence technique has been employed to study the multiple ionization and the charge transfer
processes in collisions of 60–120 MeV Si
q+ (q = 4−14) ions with neutral argon atoms. The relative contribution of different ionization channels, namely; direct ionization,
electron capture and electron loss leading to the production of slow moving multiply charged argon recoil ions have been investigated.
The data reported on the present collision system result from a direct measurement in the considered impact energy for the
first time. The total ionization cross-sections for the recoil ions are shown to scale as q
1.7/E
p
0.5
, where E
p is the energy in MeV of the projectile and q its charge state. The recoil fractions for the cases of total- and direct ionizations are found to decrease with increasing
recoil charge state j. The total ionization fractions of the recoils are seen to depend on q and to show the presence of a ‘shell-effect’ of the target. Further, the fractions are found to vary as 1/j
2 upto j = 8+. The average recoil charge state 〈j〉 increases slowly with q and with the number of lost or captured electrons from or into the projectile respectively. The projectile charge changing
cross-sections σ
qq′ are found to decrease with increasing q for loss ionization and to increase with q for direct-and capture ionization processes respectively. The physics behind various scaling rules that are found to follow
our data for different ionization processes is reviewed and discussed. 相似文献
258.
KM Varier AM Vinodkumar NVSV Prasad PV Madhusudhana Rao DL Sastry Lagy T Baby MC Radhakrishna NG Puttaswamy JJ Das P Sugathan N Madhavan AK Sinha DO Kataria 《Pramana》1999,53(3):529-533
Large enhancements have been observed in the sub-barrier fusion cross sections for Ti+Ni systems in our previous studies.
Coupled channel calculations incorporating couplings to 2+ and 3− states failed to explain these enhancements completely. A possibilty of transfer channels contributing to the residual enhancements
had been suggested. In order to investigate the role of relevant transfer channels, measurements of one- and two-nucleon transfer
were carried out for 46,48Ti+61Ni systems. The present paper gives the results of these studies. 相似文献
259.
260.