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Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
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The traditional chemical industry has become a largely mature industry with many commodity products based on established technologies. Therefore, new product and market opportunities will more likely come from speciality chemicals, and from new functionalities obtained from new processing technologies as well as new microstructure control methodologies. It is a well-known fact that in addition to its molecular structure, the microstructure of a material is key to determining its properties. Controlling structures at the micro- and nano-levels is therefore essential to new discoveries. For this article, we define nanotechnology as the controlled manipulation of nanomaterials with at least one dimension less than 100nm. Nanotechnology is emerging as one of the principal areas of investigation that is integrating chemistry and materials science, and in some cases integrating these with biology to create new and yet undiscovered properties that can be exploited to gain new market opportunities. In this article market opportunities for nanotechnology will be presented from an industrial perspective covering electronic, biomedical, performance materials, and consumer products. Manufacturing technology challenges will be identified, including operations ranging from particle formation, coating, dispersion, to characterization, modeling, and simulation. Finally, a nanotechnology innovation roadmap is proposed wherein the interplay between the development of nanoscale building blocks, product design, process design, and value chain integration is identified. A suggestion is made for an R&D model combining market pull and technology push as a way to quickly exploit the advantages in nanotechnology and translate these into customer benefits. 相似文献
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Simplicial complexes X provide commutative rings A(X) via the Stanley- Reisner construction. We calculated the cotangent cohomology, i.e., T1 and T2 of A(X) in terms of X. These modules provide information about the deformation theory of the algebro geometric objects assigned to X. 相似文献
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On the basis of the general class of solutions of 6D vacuum Einstein equations and using well-known results of the 6D geometric model of electroweak and gravitational interactions, the variations of fundamental physical constants and their influence on the observed red-shift of galaxies are investigated. By considering the interpretation of extra components of the 6D metric as reproducing the properties of matter in the 4D curved space-time, the effective quantities of matter are obtained. In particular, the states of dust and radiation are shown. The corresponding 5D models were also investigated. 相似文献
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Geometric (Clifford) algebra provides an efficient mathematical language for describing physical problems. We formulate general relativity in this language. The resulting formalism combines the efficiency of differential forms with the straightforwardness of coordinate methods. We focus our attention on orthonormal frames and the associated connection bivector, using them to find the Schwarzschild and Kerr solutions, along with a detailed exposition of the Petrov types for the Weyl tensor. 相似文献
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Arthur G. Maki John C. Grecu Brenda Winnewisser Manfred Winnewisser 《Journal of Molecular Spectroscopy》2003,222(2):198-212
High-resolution spectra of 15N12C12C15N and 14N13C13C14N have been measured and analyzed from 200 to 3600 cm−1. All the vibrational levels below 900 cm−1 have been observed and characterized. The Fermi resonance between ν2 and 2ν4 has been studied and the resonance constant has been determined for several cases. Several Σ− states have been directly observed for the first time for each isotopomer, the (0001111)0f, (0011111)0f, and (0002222)0f states. The pattern of the energy levels for clusters of l-type resonance coupled levels, such as 0001131,3, has been determined for cyanogen for the first time. Among other things this involved the determination of the vibrational l-type resonance constant, r45. Many of the power series constants, αi and xij, and higher order constants have been determined. 相似文献
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Humberto César Chaves Fernandes Arthur Rodrigo Barros da Rocha 《International Journal of Infrared and Millimeter Waves》2003,24(7):1171-1176
The use of photonic materials has been used in the theory of optical waves. The PBG (Photonic Band Gap) theory and material, was developed recently for optical frequencies and can be easily applied to millimeter waves, microwaves and planar antenna frequencies. The presence of photonic materials as substrate in antennas has some good characteristics such as, supression of light spontaneous emission and suppression of surface waves, allowing the application in planar antenna array. In this work an elaborate analysis using the full wave Transverse Transmission Line - TTL method, that provides efficient and concise results is applied to the planar antennas array with PBG substrate. 相似文献