Crystal structure of the new FeSe(1-x) superconductor

The newly discovered superconductor FeSe(1-x) (x approximately 0.08, T(c)(onset) approximately 13.5 K at ambient pressure rising to 27 K at 1.48 GPa) exhibits a structural phase transition from tetragonal to orthorhombic below 70 K at ambient pressure-the crystal structure in the superconducting state shows remarkable similarities to that of the REFeAsO(1-x)F(x) (RE = rare earth) superconductors.     

Doping dependence of the pressure response of Tc in the SmO(1-x)F(x)FeAs superconductors

The superconducting transition temperature of the high-Tc SmO1-xFxFeAs superconductors increases monotonically as the F-doping level x increases to 0.20. High-pressure magnetization experiments reveal a strong sensitivity of Tc to interatomic distances in the underdoped regime (x 相似文献   

Secondary Metabolites,including a New 5,6-Dihydropyran-2-One,Produced by the Fungus Diplodia corticola. Aphicidal Activity of the Main Metabolite,Sphaeropsidin A

An undescribed 5,6-dihydropyran-2-one, namely diplopyrone C, was isolated and characterized from the cultures of an isolate of the fungus Diplodia corticola recovered from Quercus suber in Algeria. The structure and relative stereostructure of (5S,6S,7Z,9S,10S)-5-hydroxy-6-(2-(3-methyloxiran-2-yl)vinyl)-5,6-dihydro-2H-pyran-2-one were assigned essentially based on NMR and MS data. Furthermore, ten known compounds were isolated and identified in the same cultures. The most abundant product, the tetracyclic pimarane diterpene sphaeropsidin A, was tested for insecticidal effects against the model sucking aphid, Acyrthosiphon pisum. Results showed a toxic dose-dependent oral activity of sphaeropsidin A, with an LC₅₀ of 9.64 mM.     

Rydberg states with quantum Monte Carlo

Calculations on Rydberg states are performed using quantum Monte Carlo methods. Excitation energies and singlet-triplet splittings are calculated for two model systems, the carbon atom (3P and 1P) and carbon monoxide ((1Sigma and 3Sigma). Kohn-Sham wave functions constructed from open-shell localized Hartree-Fock orbitals are used as trial and guide functions. The fixed-node diffusion quantum Monte Carlo (FN-DMC) method depends strongly on the wave function's nodal hypersurface. Nodal artefacts are investigated for the ground state of the carbon atom. Their effect on the FN-DMC results can be analyzed quantitatively. FN-DMC leads to accurate excitation energies but to less accurate singlet-triplet splittings. Variational Monte Carlo calculations are able to reproduce the experimental results for both the excitation energies and the singlet-triplet splittings.     

Magnetic-fluorescent nanocomposites for biomedical multitasking

Fluorescent magnetite nanocomposites based on magnetic nanoparticles, a polyhedral octaaminopropylsilsesquioxane and a porphyrin derivative have been prepared. The intracellular uptake of the nanocomposites by macrophage and bone osteoblast cells, and their potential as MRI contrast agents, has been demonstrated.     

A full multiple scattering model for the analysis of time-resolved X-ray difference absorption spectra

A full multiple theoretical model (MXAN) is applied to fit picosecond difference X-ray absorption spectra at the ruthenium L(3) edge upon photoexcitation of aqueous [RuII(bpy)3]2+. We show that fitting difference spectra allows an increase in sensitivity, such that slight structural changes can be retrieved, which are not detected in fitting full spectra. The Ru-N bond distances of the excited complex in the (3)MLCT state are in good agreement with recently published values. The implementation of the present approach to L-edge spectra and its high sensitivity opens opportunities for its extension to a large class of experiments where difference X-ray absorption spectra are recorded.     

Development of a convenient new synthetic route to [3]ferrocenophanones

[3]Ferrocenophanone rac-8 was prepared by several non-Friedel-Crafts pathways starting from a Mannich-type coupling of 1,1'-diacetylferrocene followed by catalytic hydrogenation. Hydride abstraction from the resulting alpha-dimethylamino[3]ferrocenophane rac-14 with B(C6F5)3 followed by hydrolysis gave the ketone rac-8. Several variants of the Sommelet reaction, using ethylglyoxylate, formaldehyde or hexamethylenetetramine (urotropine) as the "oxidizing" reagent gave the alpha-[3]ferrocenophanone 8 in good to excellent yield. Some variants of these reactions were also used for the preparation of the pure enantiomer (R)-8. The electrochemical behaviour of 8 has been investigated and compared with related derivatives.     

Ethane-bridged zinc porphyrin dimers in Langmuir-Shäfer thin films: structural and spectroscopic properties

This work reports on the structural and spectroscopic properties of ethane-bridged Zn porphyrin dimers (1) in Langmuir-Sch?fer (LS) thin films by combining scanning force microscopy (SFM) with film balance, UV-vis absorption, fluorescence, and nanosecond laser flash photolysis measurements. Results show that depending on the surface pressure the Langmuir films of pure 1 can be arranged in two different condensed phases, whereas SFM of the LS films shows characteristic fractal networks constituted by nanoscopic aggregates. The spectral findings agree with a picture in which 1 is apparently present in the anti conformation but aggregated in a sort of H-type structure whose optical features resemble those of the syn conformer. This type of structure is not responsive to light stimuli. By diluting 1 in arachidic acid the porphyrin aggregation is significantly minimized with 1 exhibiting almost exclusively the anti conformation. As a result the LS films become photoresponsive, showing fluorescence emission and triplet-triplet transient absorption.     

Open-shell localized Hartree-Fock method based on the generalized adiabatic connection Kohn-Sham formalism for a self-consistent treatment of excited states

An effective exact-exchange Kohn-Sham approach for the treatment of excited electronic states, the generalized adiabatic connection open-shell localized Hartree-Fock (GAC-OSLHF) method is presented. The GAC-OSLHF method is based on the generalized adiabatic connection Kohn-Sham formalism and therefore capable of treating excited electronic states, which are not the energetically lowest of their symmetry. The method is self-interaction free and allows for a fully self-consistent computation of excited valence as well as Rydberg states. Results for atoms and small- and medium-size molecules are presented and compared to restricted open-shell Hartree-Fock (ROHF) and time-dependent density-functional results as well as to experimental data. While GAC-OSLHF and ROHF results are quite close to each other, the GAC-OSLHF method shows a much better convergence behavior. Moreover, the GAC-OSLHF method as a Kohn-Sham method, in contrast to the ROHF approach, represents a framework which allows also for a treatment of correlation besides an exchange by appropriate functionals. In contrast to the common time-dependent density-functional methods, the GAC-OSLHF approach is capable of treating doubly or multiply excited states and can be easily applied to molecules with an open-shell ground state. On the nodal planes of the energetically highest occupied orbital, the local multiplicative GAC-OSLHF exchange potential asymptotically approaches a different, i.e., nonzero, value than in other regions, an asymptotic behavior which is known from exact Kohn-Sham exchange potentials of ground states of molecules.     

Competitive Gold‐Promoted Meyer–Schuster and oxy‐Cope Rearrangements of 3‐Acyloxy‐1,5‐enynes: Selective Catalysis for the Synthesis of (+)‐(S)‐γ‐Ionone and (−)‐(2S,6 R)‐cis‐γ‐Irone

We report a simple, highly stereoselective synthesis of (+)‐(S)‐γ‐ionone and (‐)‐(2S,6R)‐cis‐γ‐irone, two characteristic and precious odorants; the latter compound is a constituent of the essential oil obtained from iris rhizomes. Of general interest in this approach are the photoisomerization of an endo trisubstituted cyclohexene double bond to an exo vinyl group and the installation of the enone side chain through a [(NHC)Au^I]‐catalyzed Meyer–Schuster‐like rearrangement. This required a careful investigation of the mechanism of the gold‐catalyzed reaction and a judicious selection of reaction conditions. In fact, it was found that the Meyer–Schuster reaction may compete with the oxy‐Cope rearrangement. Gold‐based catalytic systems can promote either reaction selectively. In the present system, the mononuclear gold complex [Au(IPr)Cl], in combination with the silver salt AgSbF₆ in 100:1 butan‐2‐one/H₂O, proved to efficiently promote the Meyer–Schuster rearrangement of propargylic benzoates, whereas the digold catalyst [{Au(IPr)}₂(μ‐OH)][BF₄] in anhydrous dichloromethane selectively promoted the oxy‐Cope rearrangement of propargylic alcohols.