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571.
Samuel Andrejčák Dr. Péter Kisszékelyi Dr. Michal Májek Prof. Dr. Radovan Šebesta 《European journal of organic chemistry》2023,26(5):e202201399
Arylboronates are helpful building blocks in organic synthesis. Here, we present an efficient mechanochemical synthesis of arylboronates from arene diazonium salts. Importantly, this transformation was significantly enhanced by sodium chloride, which probably promotes the decomposition of diazonium salts via anion exchange. Chloride anions also participate in the formation of strongly reducing Cl−B anion radical intermediate that promotes radical chain reaction. The reaction proceeds more efficiently with a small amount of polar solvent as a liquid-assisted grinding additive. Quantum chemical calculations support the mechanistic proposal. 相似文献
572.
Matjaž Žaucer Danilo Pumpernik Milan Hladnik Andrej Ažman 《Chemical physics letters》1976,44(1):58-60
The magnetic susceptibility of hydrogen fluoride is calculated with four different basis sets of gauge invariant atomic orbitals (GIAO's). The Roothaan equations are solved for various values of the magnetic field strength and the susceptibility is deduced by a numerical differentiation of the energy. 相似文献
573.
We consider chains of dimensionless masses connected by breakable bistable links. A non-monotonic piecewise linear constitutive relation for each link consists of two stable branches separated by a gap of zero resistance. Mechanically, this model can be envisioned as a ”twin-element” structure which consists of two links (rods or strands) of different lengths joined by the ends. The longer link does not resist to the loading until the shorter link breaks. We call this construction the waiting link structure. We show that the chain of such strongly non-linear elements has an increased in-the-large stability under extension in comparison with a conventional chain, and can absorb a large amount of energy. This is achieved by two reasons. One is an increase of dissipation in the form of high-frequency waves transferring the mechanical energy to heat; this is a manifestation of the inner instabilities of the bonds. The other is delocalization of the damage of the chain. The increased stability is a consequence of the distribution of a partial damage over a large volume of the body instead of its localization, as in the case of a single neck formation in a conventional chain. We optimize parameters of the structure in order to improve its resistance to a slow loading and show that it can be increased significantly by delocalizing a damage process. In particular, we show that the dissipation is a function of the gap between the stable branches and find an optimal gap corresponding to maximum energy consumption under quasi-static extension. The results of numerical simulations of the dynamic behavior of bistable chains show that these chains can withstand without breaking the force which is several times larger than the force sustained by a conventional chain. The formulation and results are also related to the modelling of compressive destruction of a porous material or a frame construction which can be described by a two-branched diagram with a large gap between the branches. We also consider an extension of the model to multi-link chain that could imitate plastic behavior of material. 相似文献
574.
A statistical theory of conjugated macro- and microphase separation in flexile polydisperse block copolymer systems with a given arbitrary molecular structural distribution is developed in the mean field approximation. A special attention is paid to recognizing and calculating all terms having the least order of magnitude to be taken into account. To this end a special procedure is elaborated enabling to distinguish between strongly and weakly fluctuating order parameters characterizing polydisperse systems and to construct explicitly a one-field parametrization of the free energy of the systems under investigation. The contribution of so-called higher harmonics and effect of a redistribution of macromolecules among coexisting phases are taken into account therewith by a proper renormalization of the fourth vertex of the corresponding effective hamiltonian. In order to compare the presented approach and other existing theories phase diagrams of molten polydisperse diblock copolymer are built numerically in approximations corresponding to different theories. It is shown that our rigorous approach results in phase diagrams qualitatively different from the conventional ones. In particular, we predict the existence of one-phase region having a quasicrystal symmetry and regions of coexistence of this phase with disordered phase and one having the symmetry of the body-centered-oubic lattice as well as a considerable shrinking of the region of the existence of the lamellar phase. 相似文献