958 resultados para crystal and ligand fields


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Iron nanostructures with morphology ranging from discrete nanoparticles to nearly monodisperse hierarchical nanostructures have been successfully synthesized using solvated metal atom dispersion (SMAD) method. Such a morphological evolution was realized by tuning the molar ratio of ligand to metal. Surface energy minimization in confluence with strong magnetic interactions and ligand-based stabilization results in the formation of nanospheres of iron. The as-prepared amorphous iron nanostructures exhibit remarkably high coercivity in comparison to the discrete nanoparticles and bulk counterpart. Annealing the as-prepared amorphous Fe nanostructures under anaerobic conditions affords air-stable carbon-encapsulated Fe(0) and Fe3C nanostructures with retention of the morphology. The resulting nanostructures were thoroughly analyzed by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and Raman spectroscopy. TGA brought out that Fe3C nanostructures are more robust toward oxidation than those of a-Fe. Finally, detailed magnetic studies were carried out by superconducting quantum interference device (SQUID) magnetometer and it was found that the magnetic properties remain conserved even upon exposure of the annealed samples to ambient conditions for months.

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The objective of the present work is to study the effect of electrical process Parameters (duty cycle and frequency) on morphological, structural, and in-vitro corrosion characteristics of oxide films formed on zirconium by plasma electrolytic oxidation in an electrolyte system consisting of 5 g/L of trisodium orthophosphate. The oxide films fabricated on zirconium by systematically varying the duty cycle and frequency are characterized for its phase composition, surface morphology, chemical composition, roughness, wettability, surface energy, scratch resistance, corrosion resistance, apatite forming ability and osteoblast cell adhesion. X-ray diffraction pattern of all the oxide films showed the predominance of m-ZrO2 phase. Dense and uniform films with thickness varying from 9 to 15 mu m and roughness in the range of 0.62 to 1.03 mu m are formed. Porosity of oxide films is found to be increased with an increase infrequency. The water contact angle results demonstrated that the oxide films exhibited similar hydrophilicity to zirconium substrate. All oxide films showed improved corrosion resistance, as indicated by far lower corrosion current density and passive corrosion potential compared to the zirconium substrate in simulated body fluid environment, and among the four different combinations of duty cycle and frequency employed in the present study, the oxide film formed at 95% duty cycle and 50 Hz frequency (HDLF film) showed superior pitting corrosion resistance, which can be attributed to its pore free morpholOgy. Scratch test results showed that the HDLF oxide film adhered firmly to the substrate by developing a notable scratch resistance at 19.5 +/- 1.2.N. Besides the best corrosion resistance and scratch retistance, the HDLF film also showed good apatite forming ability and osteo sarcoma cell adhesion on its surface. The HDLF oxide film on zirconium with superior surface characteristics is believed to be useful for various types of implants in the dental and orthopedic fields. (C) 2015 Elsevier B.V. All rights reserved.

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Synthesis of 2-amino-1,3,4-oxadiazole derivatives of N-Cbz(benzyloxycarbonyl)/Boc-protected amino/peptide acids under sonication is described. The conditions involved in the present protocol are simple, mild, and racemization free. The utility of 2-amino group in the substituted oxadiazoles for the incorporation of peptide and ureido bonds to obtain hybrid peptidomimetics is also delineated. The 2-amino-1,3,4-oxadiazole 3b was obtained as a single crystal, and its molecular structure has been confirmed through X-ray crystallographic study.

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In this paper, we try to establish the equivalence or similarity in the thermal and physiochemical changes in precursor droplets (cerium nitrate) in convective and radiative fields. The radiative field is created through careful heating of the droplet using a monochromatic light source (CO2 laser). The equivalence is also established for different modes of convection like droplet injected into a high-speed flow and droplet experiencing a convective flow due to acoustic streaming (levitated) only. The thermophysical changes are studied in an aqueous cerium nitrate droplet, and the dissociation of cerium nitrate to ceria is modeled using modified Kramers' reaction rate formulation. It is observed that vaporization, species accumulation, and chemical characteristics obtained in a convectively heated droplet are retained in a radiatively heated droplet by careful adjustment of the laser intensity. The timescales and ceria yield match reasonably well for both the cases. It is also noted that similar conclusions are drawn in both levitated droplet and a nonlevitated droplet.

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Cocrystals and eutectics are different yet related crystalline multi-component adducts with diverse applications in pharmaceutical and materials fields. Recently, they were shown to be alternate products of cocrystallization experiments. Whereas a cocrystal shows distinct diffraction, spectroscopic and thermal signatures as compared to parent components, the hallmark of a eutectic is its low melting nature. However, in certain cases, there can be a problem when one resorts to design a cocrystal and assess its formation vis-A -vis a eutectic. In the absence of a gold standard method to make a cocrystal, it is often difficult to judge how exhaustive should the cocrystallization trials be to ensure the accomplishment of a desired/putative cocrystal. Further, a cocrystal can manifest with intermolecular interactions and/or crystal structure similar to that of its parent compounds such that the conventional diffraction and spectroscopic techniques will be of little help to conclusively infer the formation of cocrystal in the lack of single crystals. Such situations combined with low melting behavior of a combination brings the complication of resolving the combination as a cocrystal or eutectic since now both the adducts share common features. Based on the curious case of Caffeine-Benzoic acid combination, this study aims to unfold the intricate issues related to the design, formation and characterization of cocrystals and eutectics for a way forward. The utility of heteronuclear seeding methodology in establishing a given combination as a cocrystal-forming one or a eutectic-forming one in four known systems is appraised.

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The performance of combustion driver ignited by multi-spark plugs distributed along axial direction has been analysed and tested. An improved ignition method with three circumferential equidistributed ignitors at main diaphragm has been presented, by which the produced incident shock waves have higher repeatability, and better steadiness in the pressure, temperature and velocity fields of flow behind the incident shock, and thus meets the requirements of aerodynamic experiment. The attachment of a damping section at the end of the driver can eliminate the high reflection pressure produced by detonation wave, and the backward detonation driver can be employed to generate high enthalpy and high density test flow. The incident shock wave produced by this method is well repeated and with weak attenuation. The reflection wave caused by the contracted section at the main diaphragm will weaken the unfavorable effect of rarefaction wave behind the detonation wave, which indicates that the forward detonation driver can be applied in the practice. For incident shock wave of identical strength, the initial pressure of the forward detonation driver is about 1 order of magnitude lower than that of backward detonation.

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In the current paper, we have primarily addressed one powerful simulation tool developed during the last decades-Large Eddy Simulation (LES), which is most suitable for unsteady three-dimensional complex turbulent flows in industry and natural environment. The main point in LES is that the large-scale motion is resolved while the small-scale motion is modeled or, in geophysical terminology, parameterized. With a view to devising a subgrid-scale(SGS) model of high quality, we have highlighted analyzing physical aspects in scale interaction and-energy transfer such as dissipation, backscatter, local and non-local interaction, anisotropy and resolution requirement. They are the factors responsible for where the advantages and disadvantages in existing SGS models come from. A case study on LES of turbulence in vegetative canopy is presented to illustrate that LES model is more based on physical arguments. Then, varieties of challenging complex turbulent flows in both industry and geophysical fields in the near future-are presented. In conclusion; we may say with confidence that new century shall see the flourish in the research of turbulence with the aid of LES combined with other approaches.

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A large-eddy simulation with transitional structure function(TSF) subgrid model we previously proposed was performed to investigate the turbulent flow with thermal influence over an inhomogeneous canopy, which was represented as alternative large and small roughness elements. The aerodynamic and thermodynamic effects of the presence of a layer of large roughness elements were modelled by adding a drag term to the three-dimensional Navier-Stokes equations and a heat source/sink term to the scalar equation, respectively. The layer of small roughness elements was simply treated using the method as described in paper (Moeng 1984, J. Atmos Sci. 41, 2052-2062) for homogeneous rough surface. The horizontally averaged statistics such as mean vertical profiles of wind velocity, air temperature, et al., are in reasonable agreement with Gao et al.(1989, Boundary layer meteorol. 47, 349-377) field observation (homogeneous canopy). Not surprisingly, the calculated instantaneous velocity and temperature fields show that the roughness elements considerably changed the turbulent structure within the canopy. The adjustment of the mean vertical profiles of velocity and temperature was studied, which was found qualitatively comparable with Belcher et al. (2003, J Fluid Mech. 488, 369-398)'s theoretical results. The urban heat island(UHI) was investigated imposing heat source in the region of large roughness elements. An elevated inversion layer, a phenomenon often observed in the urban area (Sang et al., J Wind Eng. Ind. Aesodyn. 87, 243-258)'s was successfully simulated above the canopy. The cool island(CI) was also investigated imposing heat sink to simply model the evaporation of plant canopy. An inversion layer was found very stable and robust within the canopy.

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Fracture appearance, surface and nanomechanics properties of antibacterial ceramics contairing rare earth phosphate composite antibacterial materials were characterized and measured by SEM, AFM and Nanoindenter, respectively. Results show that grain of fracture surface of antibacterial ceramics grows uniform refinement topography of bubble break-up appears at the surface, which is flat and has liquid character, by adding the phosphate composite containing rare earth, nevertheless needle-like crystal and granular outgrowth form at fracture surface and surface of common ceramics, respectively. Young's modulus of antibacterial ceramic film is 74. 397 GPa and hardness is 8. 134 GPa, which increses by 4.4﹪ and 1.6﹪ comparing with common ceramics, respectively. Loading curves of two kind of ceramics have obvious nonlinear character under 700 nm and linear character between 700 ~ 1000 nm, and unloading curve have obvious linear character.

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Many physical experiments have shown that the domain switching in a ferroelectric material is a complicated evolution process of the domain wall with the variation of stress and electric field. According to this mechanism, the volume fraction of the domain switching is introduced in the constitutive law of ferroelectric ceramic and used to study the nonlinear constitutive behavior of ferroelectric body in this paper. The principle of stationary total energy is put forward in which the basic unknown quantities are the displacement u (i) , electric displacement D (i) and volume fraction rho (I) of the domain switching for the variant I. Mechanical field equation and a new domain switching criterion are obtained from the principle of stationary total energy. The domain switching criterion proposed in this paper is an expansion and development of the energy criterion. On the basis of the domain switching criterion, a set of linear algebraic equations for the volume fraction rho (I) of domain switching is obtained, in which the coefficients of the linear algebraic equations only contain the unknown strain and electric fields. Then a single domain mechanical model is proposed in this paper. The poled ferroelectric specimen is considered as a transversely isotropic single domain. By using the partial experimental results, the hardening relation between the driving force of domain switching and the volume fraction of domain switching can be calibrated. Then the electromechanical response can be calculated on the basis of the calibrated hardening relation. The results involve the electric butterfly shaped curves of axial strain versus axial electric field, the hysteresis loops of electric displacement versus electric filed and the evolution process of the domain switching in the ferroelectric specimens under uniaxial coupled stress and electric field loading. The present theoretic prediction agrees reasonably with the experimental results given by Lynch.

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Modeling results are presented concerning the characteristicsoflaminar and turbulentargonplasmajetsimpingingnormally upon a flat plate (workpiece) in ambient air. It is found that the presence of the flat plate significantly enhances the entrainment rate of ambient air into the jets and affects on the flow and temperature fields in the near-plate region of the jets. At comparatively large distances between the plate and the jet inlet, the axial gradients of the plasma parameters in the laminarplasmaimpinging-jets assume values much less than those in the turbulentplasmaimpinging-jets.

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Various families of exact solutions to the Einstein and Einstein-Maxwell field equations of General Relativity are treated for situations of sufficient symmetry that only two independent variables arise. The mathematical problem then reduces to consideration of sets of two coupled nonlinear differential equations.

The physical situations in which such equations arise include: a) the external gravitational field of an axisymmetric, uncharged steadily rotating body, b) cylindrical gravitational waves with two degrees of freedom, c) colliding plane gravitational waves, d) the external gravitational and electromagnetic fields of a static, charged axisymmetric body, and e) colliding plane electromagnetic and gravitational waves. Through the introduction of suitable potentials and coordinate transformations, a formalism is presented which treats all these problems simultaneously. These transformations and potentials may be used to generate new solutions to the Einstein-Maxwell equations from solutions to the vacuum Einstein equations, and vice-versa.

The calculus of differential forms is used as a tool for generation of similarity solutions and generalized similarity solutions. It is further used to find the invariance group of the equations; this in turn leads to various finite transformations that give new, physically distinct solutions from old. Some of the above results are then generalized to the case of three independent variables.

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The control role of the relative phase between the probe and driving fields on the gain and dispersion in an open Lambda-type inversionless lasing system with spontaneously generated coherence (SGC) is investigated. It is shown that the inversionless gain and dispersion are quite sensitive to variation in the relative phase; by adjusting the value of the relative phase, electromagnetically induced transparency (EIT), a high refractive index with zero absorption and a larger inversionless gain can be realized. It is also shown that, in the contributions to the inversionless gain ( absorption) and dispersion, the contribution from SGC is always much larger than that from the dynamically induced coherence for any value of the relative phase. Our analysis shows that variation in the SGC effect will cause the spectrum regions and values of the inversionless gain and dispersion to vary evidently. We also found that, under the same conditions, the values of the inversionless gain and dispersion in the open system are evidently larger than those in the corresponding closed system; EIT occurs in the open system but cannot occur in the closed system.

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Assembling a nervous system requires exquisite specificity in the construction of neuronal connectivity. One method by which such specificity is implemented is the presence of chemical cues within the tissues, differentiating one region from another, and the presence of receptors for those cues on the surface of neurons and their axons that are navigating within this cellular environment.

Connections from one part of the nervous system to another often take the form of a topographic mapping. One widely studied model system that involves such a mapping is the vertebrate retinotectal projection-the set of connections between the eye and the optic tectum of the midbrain, which is the primary visual center in non-mammals and is homologous to the superior colliculus in mammals. In this projection the two-dimensional surface of the retina is mapped smoothly onto the two-dimensional surface of the tectum, such that light from neighboring points in visual space excites neighboring cells in the brain. This mapping is implemented at least in part via differential chemical cues in different regions of the tectum.

The Eph family of receptor tyrosine kinases and their cell-surface ligands, the ephrins, have been implicated in a wide variety of processes, generally involving cellular movement in response to extracellular cues. In particular, they possess expression patterns-i.e., complementary gradients of receptor in retina and ligand in tectum- and in vitro and in vivo activities and phenotypes-i.e., repulsive guidance of axons and defective mapping in mutants, respectively-consistent with the long-sought retinotectal chemical mapping cues.

The tadpole of Xenopus laevis, the South African clawed frog, is advantageous for in vivo retinotectal studies because of its transparency and manipulability. However, neither the expression patterns nor the retinotectal roles of these proteins have been well characterized in this system. We report here comprehensive descriptions in swimming stage tadpoles of the messenger RNA expression patterns of eleven known Xenopus Eph and ephrin genes, including xephrin-A3, which is novel, and xEphB2, whose expression pattern has not previously been published in detail. We also report the results of in vivo protein injection perturbation studies on Xenopus retinotectal topography, which were negative, and of in vitro axonal guidance assays, which suggest a previously unrecognized attractive activity of ephrins at low concentrations on retinal ganglion cell axons. This raises the possibility that these axons find their correct targets in part by seeking out a preferred concentration of ligands appropriate to their individual receptor expression levels, rather than by being repelled to greater or lesser degrees by the ephrins but attracted by some as-yet-unknown cue(s).

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The control role of the relative phase between the probe and driving fields on gain, dispersion and populations in an open V-type three-level system with spontaneously generated coherence is studied. The result shows that by adjusting the value of the relative phase, the transformation between lasing with inversion and lasing without inversion (LWI) can be realized and high dispersion (refractive index) without absorption can be obtained. The shape and value range of the dispersion curve are similar to those of the gain curve, and this similarity is closely related to the relative phase. The effects of the atomic exit and injection rates and the incoherent pump rate on the control role of the relative phase are also analysed. It is found easier to get LWI by adjusting the value of the relative phase using the open system rather than the closed system, and using an incoherent pump rather than without using the incoherent pump. Moreover the open system can give a larger LWI gain than the closed system.