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21.
Rebeca G. Castillo Justin T. Henthorn Jeremy McGale Dimitrios Maganas Serena DeBeer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):13065-13075
In recent years, X-ray emission spectroscopy (XES) in the Kβ (3p-1s) and valence-to-core (valence-1s) regions has been increasingly used to study metal active sites in (bio)inorganic chemistry and catalysis, providing information about the metal spin state, oxidation state and the identity of coordinated ligands. However, to date this technique has been limited almost exclusively to first-row transition metals. In this work, we present an extension of Kβ XES (in both the 4p-1s and valence-to-1s [or VtC] regions) to the second transition row by performing a detailed experimental and theoretical analysis of the molybdenum emission lines. It is demonstrated in this work that Kβ2 lines are dominated by spin state effects, while VtC XES of a 4d transition metal provides access to metal oxidation state and ligand identity. An extension of Mo Kβ XES to nitrogenase-relevant model complexes shows that the method is sufficiently sensitive to act as a spectator probe for redox events that are localized at the Fe atoms. Mo VtC XES thus has promise for future applications to nitrogenase, as well as a range of other Mo-containing biological cofactors. Further, the clear assignment of the origins of Mo VtC XES features opens up the possibility of applying this method to a wide range of second-row transition metals, thus providing chemists with a site-specific tool for the elucidation of 4d transition metal electronic structure. 相似文献
22.
23.
Coclite Giuseppe Maria Dipierro Serena Maddalena Francesco Valdinoci Enrico 《Journal of Nonlinear Science》2020,30(4):1285-1305
The formation of singularities in finite time in nonlocal Burgers’ equations, with time-fractional derivative, is studied in detail. The occurrence of finite-time singularity is proved, revealing the underlying mechanism, and precise estimates on the blowup time are provided. The employment of the present equation to model a problem arising in job market is also analyzed.
相似文献24.
We use a recently published method for the renormalization of the self-energy to calculate the self-energy of 6s and 8d levels
to all orders in Zα. We demonstrate the accuracy of the method and its potential for high-n, low-Z applications. We also show that this method is perfectly suited for the evaluation of the two-electron self-energy (self-energy
screening). For the first time, evaluation of the screening of the 1s electron by a second one in either the 1s,2s, 2p1/2 or 2p3/2 shells has been performed, for 30 ⩽ Z ⩽92.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
25.
Serena Gabrielli Genny Pastore Francesca Stella Enrico Marcantoni Fabrizio Sarasini Jacopo Tirill Carlo Santulli 《Molecules (Basel, Switzerland)》2021,26(24)
A poly(urethane-acrylate) polymer (PUA) was synthesized, and a sufficiently high molecular weight starting from urethane-acrylate oligomer (UAO) was obtained. PUA was then loaded with two types of powdered ligno-cellulosic waste, namely from licorice root and palm leaf, in amounts of 1, 5 and 10%, and the obtained composites were chemically and mechanically characterized. FTIR analysis of final PUA synthesized used for the composite production confirmed the new bonds formed during the polymerization process. The degradation temperatures of the two types of waste used were in line with what observed in most common natural fibers with an onset at 270 °C for licorice waste, and at 290 °C for palm leaf one. The former was more abundant in cellulose (44% vs. 12% lignin), whilst the latter was richer in lignin (30% vs. 26% cellulose). In the composites, only a limited reduction of degradation temperature was observed for palm leaf waste addition and some dispersion issues are observed for licorice root, leading to fluctuating results. Tensile performance of the composites indicates some reduction with respect to the pure polymer in terms of tensile strength, though stabilizing between data with 5 and 10% filler. In contrast, Shore A hardness of both composites slightly increases with higher filler content, while in stiffness-driven applications licorice-based composites showed potential due to an increase up to 50% compared to neat PUA. In general terms, the fracture surfaces tend to become rougher with filler introduction, which indicates the need for optimizing interfacial adhesion. 相似文献
26.
Margadonna S Takabayashi Y McDonald MT Kasperkiewicz K Mizuguchi Y Takano Y Fitch AN Suard E Prassides K 《Chemical communications (Cambridge, England)》2008,(43):5607-5609
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. 相似文献
27.
Takabayashi Y McDonald MT Papanikolaou D Margadonna S Wu G Liu RH Chen XH Prassides K 《Journal of the American Chemical Society》2008,130(29):9242-9243
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 = 0.12) with the pressure coefficient of Tc, d(ln Tc)/dP being strongly positive. However, as the doping level increases further to x = 0.15, we find that this sensitivity is strongly suppressed and at the same time, d(ln Tc)/dP sharply switches over to assume negative values with Tc decreasing with increasing applied pressure. The abrupt change in the pressure response of the superconducting properties of the SmO1-xFxFeAs phases coincides with the putative existence of a quantum critical point (QCP) near x approximately 0.14, as proposed by resistivity and Hall effect measurements. 相似文献
28.
Corr SA O'Byrne A Gun'ko YK Ghosh S Brougham DF Mitchell S Volkov Y Prina-Mello A 《Chemical communications (Cambridge, England)》2006,(43):4474-4476
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. 相似文献
29.
Tebben L Neumann M Kehr G Fröhlich R Erker G Losi S Zanello P 《Dalton transactions (Cambridge, England : 2003)》2006,(14):1715-1720
[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. 相似文献
30.
Valli L Casilli S Giotta L Pignataro B Conoci S Borovkov VV Inoue Y Sortino S 《The journal of physical chemistry. B》2006,110(10):4691-4698
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. 相似文献