Under certain circumstance, natural orbitals of excited states have quite unusual hybrid behavior, which is drastically different from that of the familiar cononical orbitals, and gives ambiguous results for the one-electron properties. We show that a simple 2×2 density matrix obtained from a multiconfiguration self-consistent-field calculation is sufficient to reveal the NO behavior in this situation. 相似文献
Growth of large-area, few-layer graphene has been reported recently through the catalytic decomposition of methane (CH(4)) over a Cu surface at high temperature. In this study, we used ab initio calculations to investigate the minimum energy pathways of successive dehydrogenation reactions of CH(4) over the Cu (111) surface. The geometries and energies of all the reaction intermediates and transition states were identified using the climbing image nudged elastic band method. The activation barriers for CH(4) decomposition over this Cu surface are much lower than those in the gas phase; furthermore, analysis of electron density differences revealed significant degrees of charge transfer between the adsorbates and the Cu atoms along the reaction path; these features reveal the role of Cu as the catalytic material for graphene growth. All the dehydrogenation reactions are endothermic, except for carbon dimer (C(2)) formation, which is, therefore, the most critical step for subsequent graphene growth, in particular, on Cu (111) surface. 相似文献
Lipid rafts being rich in cholesterol and sphingolipids are considered to provide ordered lipid environment in the neuronal membranes, where it is hypothesized that the cleavage of amyloid precursor protein (APP) to Aβ (1-40) and Aβ (1-42) takes place. It is highly likely that the interaction of lipid raft components like cholesterol, sphingomylein or GM1 leads to nucleation of Aβ and results in aggregation or accumulation of amyloid plaques. One has investigated surface pressure-area isotherms of the lipid raft and Aβ (1-40) Langmuir monolayer. The compression-decompression cycles and the stability of the lipid raft Langmuir monolayer are crucial parameters for the investigation of interaction of Aβ (1-40) with the lipid raft Langmuir monolayer. It was revealed that GM1 provides instability to the lipid raft Langmuir monolayer. Adsorption of Aβ (1-40) onto the lipid raft Langmuir monolayer containing neutral (POPC) or negatively charged phospholipid (DPPG) was examined. The adsorption isotherms revealed that the concentration of cholesterol was important for adsorption of Aβ (1-40) onto the lipid raft Langmuir monolayer containing POPC whereas for the lipid raft Langmuir monolayer containing DPPG:cholesterol or GM1 did not play any role. In situ UV-vis absorption spectroscopy supported the interpretation of results for the adsorption isotherms. 相似文献
Data-driven, model-free analytics are natural choices for discovery and forecasting of complex, nonlinear systems. Methods that operate in the system state-space require either an explicit multidimensional state-space, or, one approximated from available observations. Since observational data are frequently sampled with noise, it is possible that noise can corrupt the state-space representation degrading analytical performance. Here, we evaluate the synthesis of empirical mode decomposition with empirical dynamic modeling, which we term empirical mode modeling, to increase the information content of state-space representations in the presence of noise. Evaluation of a mathematical, and, an ecologically important geophysical application across three different state-space representations suggests that empirical mode modeling may be a useful technique for data-driven, model-free, state-space analysis in the presence of noise.
Herein, we have specifically designed two metalated porous organic polymers ( Zn-POP and Co-POP ) for syngas (CO+H2) production from gaseous CO2. The variable H2/CO ratio of syngas with the highest efficiency was produced in water medium (without an organic hole scavenger and photosensitizer) by utilizing the basic principle of Lewis acid/base chemistry. Also, we observed the formation of entirely different major products during photocatalytic CO2 reduction and water splitting with the help of the two catalysts, where CO (145.65 μmol g−1 h−1) and H2 (434.7 μmol g−1 h−1) production were preferentially obtained over Co-POP & Zn-POP , respectively. The higher electron density/better Lewis basic nature of Co-POP was investigated further using XPS, XANES, and NH3-TPD studies, which considerably improve CO2 activation capacity. Moreover, the structure–activity relationship was confirmed via in situ DRIFTS and DFT studies, which demonstrated the formation of COOH* intermediate along with the thermodynamic feasibility of CO2 reduction over Co-POP while water splitting occurred preferentially over Zn-POP . 相似文献
A sensitive and selective liquid chromatography-tandem mass spectrometry (LC-MS-MS) method for the determination of quetiapine was developed and validated over the linearity range 1-1500 ng/mL with 0.1 mL of plasma using clozapine as the internal standard. Detection was performed on a triple-quadrupole tandem mass spectrometer using positive electrospray ionization and quantification was performed by selected reaction monitoring mode. The MS-MS ion transitions monitored were m/z 384.1 → 253.1 and 327.0 → 270.0 for quetiapine and clozapine, respectively. The between- and within-run precision was less than 7.44% and accuracy was less than 10.2%. The lower limit of quantification was 1 ng/mL. The extraction recoveries of quetiapine were over 90%. The method is proved to be accurate and specific, and was applied to the pharmacokinetic study in healthy Chinese volunteers. 相似文献
In this paper, CeO2 and cobalt-doped CeO2 nanorods synthesized by surfactant free co-precipitation method. The microstructures of the synthesized products were characterized by XRD, FESEM and TEM. The structural properties of the grown nanorods have been investigated using electron diffraction and X-ray diffraction. High resolution transmission electron microscopy studies show the polycrystalline nature of the Co-doped cerium oxide nanorods with a length of about 300?nm and a diameter of about 10?nm were produced. The X-ray Photoelectron spectrum confirms the presence of cobalt in cerium oxide nanorods. From BET, the specific surface area of the CeO2 (Co-doped) nanostructures (131 m2?g??) is found to be significantly higher than that of pure CeO2 (52 m2?g??). The Co-doped cerium nanorods exhibit an excellent photocatalytic performance in rapidly degrading azodyes acid orange 7 (AO7) in aqueous solution under UV illumination. 相似文献
High-entropy alloys (HEAs) have been attracting extensive research interests in designing advanced nanomaterials, while their precise control is still in the infancy stage. Herein, we have reported a well-defined PtBiPbNiCo hexagonal nanoplates (HEA HPs) as high-performance electrocatalysts. Structure analysis decodes that the HEA HP is constructed with PtBiPb medium-entropy core and PtBiNiCo high-entropy shell. Significantly, the HEA HPs can reach the specific and mass activities of 27.2 mA cm−2 and 7.1 A mgPt−1 for formic acid oxidation reaction (FAOR), being the record catalyst ever achieved in Pt-based catalysts, and can realize the membrane electrode assembly (MEA) power density (321.2 mW cm−2) in fuel cell. Further experimental and theoretical analyses collectively evidence that the hexagonal intermetallic core/atomic layer shell structure and multi-element synergy greatly promote the direct dehydrogenation pathway of formic acid molecule and suppress the formation of CO*. 相似文献