The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
Tunneled metal oxides such as α-Mn8O16 (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K+ ions (which act as structure-stabilizing dopants) and H2O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K+-doped α-Mn8O16 (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H2O displaces K+ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K2+ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li+/Na+ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K2+) in the tunnels of hollandite.相似文献
The combinatorial integral approximation decomposition splits the optimization of a discrete-valued control into two steps: solving a continuous relaxation of the discrete control problem, and computing a discrete-valued approximation of the relaxed control. Different algorithms exist for the second step to construct piecewise constant discrete-valued approximants that are defined on given decompositions of the domain. It is known that the resulting discrete controls can be constructed such that they converge to a relaxed control in the \(\hbox {weak}^*\) topology of \(L^\infty \) if the grid constant of this decomposition is driven to zero. We exploit this insight to formulate a general approximation result for optimization problems, which feature discrete and distributed optimization variables, and which are governed by a compact control-to-state operator. We analyze the topology induced by the grid refinements and prove convergence rates of the control vectors for two problem classes. We use a reconstruction problem from signal processing to demonstrate both the applicability of the method outside the scope of differential equations, the predominant case in the literature, and the effectiveness of the approach.
Results from 5D induced-matter and membrane theory with null paths are extended to show that a particle obeys the 4D Klein-Gordon equation but with a variable mass. The Dirac equation also follows, but raises concerns about 4D quantization in the two natural 5D gauges, and reopens the question of a Regge-like trajectory for the spin angular momenta and squared masses of gravitationally-dominated systems. 相似文献
In this paper, integration of interference phenomenon into femtosecond laser micromachining was reported as the femtosecond laser pulses were reshaped spatially to perform ablation. The generation of circular interference pattern was demonstrated by overlapping infrared femtosecond laser pulses. The interference pattern was subsequently focused on a copper substrate to ablate microstructures of concentric circular rings. The present technique is expected to open up new applications in the areas of rapid fabrication of micro-Fresnel lenses, hybrid microlenses and lens arrays. 相似文献
In order to describe the dynamics of the t–J model, two different families of first-order Lagrangians in terms of the generators of the Hubbard algebra are found. Such families correspond to different dynamical second-class constrained systems. The quantization is carried out by using the path-integral formalism. In this context the introduction of proper ghost fields is needed to render the model renormalizable. In each case the standard Feynman diagrammatics is obtained and the renormalized physical quantities are computed and analyzed. In the first case a nonperturbative large-N expansion is considered with the purpose of studying the generalized Hubbard model describing N-fold-degenerate correlated bands. In this case the 1/N correction to the renormalized boson propagator is computed. In the second case the perturbative Lagrangian formalism is developed and it is shown how propagators and vertices can be renormalized to each order. In particular, the renormalized ferromagnetic magnon propagator coming from our formalism is studied in details. As an example the thermal softening of the magnon frequency is computed. The antiferromagnetic case is also analyzed, and the results are confronted with previous one obtained by means of the spin-polaron theories. 相似文献
By making creep and recoverable creep measurements of a nearly monodisperse low molecular weight poly(methyl phenyl siloxane) sample, we have found on decreasing temperature towardsTg that there is continuously a change in the viscoelastic spectrum concomitant with a decrease of the steadystate recoverable compliance. This behavior is exactly the same as previously observed in low molecular weight poly(styrene), proving that this spectacular anomaly in the viscoelasticity of low molecular weight polymers is general and deserves an explanation. Photon correlation spectroscopic measurements performed on the same sample have extended the observation of the viscoelastic response to shorter times and the result corroborates the trend of variation established by the creep data.Dedicated to Prof.Dr. E. W. Fischer on his 65th Birthday. Prof.Dr. Fischer is known for his valuable contribution to fosterine, international collaboration of research in polymer science. This work is an example of his contribution because it would not be possible without him bringing us together. One of us (KLN) would like to take this opportunity to thank Prof. Dr. Fischer for his unwaiving support of the 1st (Crete) and the 2nd (Alicante) International Discussion Meeting on Relaxations in Complex Systems 相似文献
Investigated is the dependency of the crack tip opening displacement (CTOD) on the local microstructure of the heat affected zone in high-strength low-alloy (HSLA) microalloyed steel. Since the initiation of the crack tip location could not be controlled in fatigue, any possible correlation between heat iput in welding and fracture toughness could be smeared. Modified CTOD data are defined; they show that the fracture resistance of the weld joint decreased as the heat input increased. 相似文献