The Coordination Chemistry of f-Block Elements in Molten Salts

The coordination chemistry of f-block elements (lanthanide and actinide) in molten salts has become a resounding topic in view of its great importance to the research and development (R&D) of molten salt reactors and pyroprocessing. In this Review article, a general overview of the coordination chemistry of f-block elements in molten salts is provided including past achievements and recent advances. Particular emphases are placed on the oxidation state, speciation, and solution structure of f-block metal ions in molten salts, as well as their relationships with the salt composition. Furthermore, this review briefly discusses the spectroscopic and theoretical methods that complement each other in revealing the coordination properties.     

Functional Groups Assisted Tunable Dielectric Permittivity of Guest-Free Zn-Based Coordination Polymers for Gate Dielectrics

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH₂) and electron-withdrawing (R=NO₂) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L₁)(L₂)]_n ( 1 ) and [Zn(L₁)(L₃)]_n ( 2 ) [L₁=2-(2-pyridyl) benzimidazole (Pbim), L₂=5-aminoisophthalate (Aip), and L₃=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH₂ and NO₂ substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO₂ and NH₂. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.     

Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

An efficient edge based data structure for the compressible Reynolds-averaged Navier–Stokes equations on hybrid unstructured meshes

An efficient edge based data structure has been developed in order to implement an unstructured vertex based finite volume algorithm for the Reynolds-averaged Navier–Stokes equations on hybrid meshes. In the present approach, the data structure is tailored to meet the requirements of the vertex based algorithm by considering data access patterns and cache efficiency. The required data are packed and allocated in a way that they are close to each other in the physical memory. Therefore, the proposed data structure increases cache performance and improves computation time. As a result, the explicit flow solver indicates a significant speed up compared to other open-source solvers in terms of CPU time. A fully implicit version has also been implemented based on the PETSc library in order to improve the robustness of the algorithm. The resulting algebraic equations due to the compressible Navier–Stokes and the one equation Spalart–Allmaras turbulence equations are solved in a monolithic manner using the restricted additive Schwarz preconditioner combined with the FGMRES Krylov subspace algorithm. In order to further improve the computational accuracy, the multiscale metric based anisotropic mesh refinement library PyAMG is used for mesh adaptation. The numerical algorithm is validated for the classical benchmark problems such as the transonic turbulent flow around a supercritical RAE2822 airfoil and DLR-F6 wing-body-nacelle-pylon configuration. The efficiency of the data structure is demonstrated by achieving up to an order of magnitude speed up in CPU times.     

Calcium-based coordination polymers from a solvothermal synthesis of HKUST-1 in 3D printed autoclaves

A mixed-metal 1D coordination polymer [CaCu(HBTC)₂(H2O)₈]_n (where H₃BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu₃(BTC)₂(H₂O)₃]_n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H₂BTC)₂(H₂O)₅]_n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave.     

Flow-induced shear stress and deformation of a core–shell-structured microcapsule in a microchannel

A numerical model was developed and validated to investigate the fluid–structure interactions between fully developed pipe flow and core–shell-structured microcapsule in a microchannel. Different flow rates and microcapsule shell thicknesses were considered. A sixth-order rotational symmetric distribution of von Mises stress over the microcapsule shell can be observed on the microcapsule with a thinner shell configuration, especially at higher flow rate conditions. It is also observed that when being carried along in a fully developed pipe flow, the microcapsule with a thinner shell tends to accumulate stress at a higher rate compared to that with a thicker shell. In general, for the same microcapsule configuration, higher flow velocity would induce a higher stress level over the microcapsule shell. The deformation gradient was used to capture the microcapsule's deformation in the present study. The effect of Young's modulus on the microcapsule shell on the microcapsule deformation was investigated as well. Our findings will shed light on the understanding of the stability of core–shell-structured microcapsule when subjected to flow-induced shear stress in a microfluidic system, enabling a more exquisite control over the breakup dynamics of drug-loaded microcapsule for biomedical applications.     

Alkaline oxygen evolution: exploring synergy between fcc and hcp cobalt nanoparticles entrapped in N-doped graphene

Herein, we report a Mott-Schottky catalyst by entrapping cobalt nanoparticles inside the N-doped graphene shell (Co@NC). The Co@NC delivered excellent oxygen evolution activity with an overpotential of merely 248 mV at a current density of 10 mA cm^–2 with promising long-term stability. The importance of Co encapsulated in NC has further been demonstrated by synthesizing Co nanoparticles without NC shell. The synergy between the hexagonal close-packed (hcp) and face-centered cubic (fcc) Co plays a major role to improve the OER activity, whereas the NC shell optimizes the electronic structure, improves the electron conductivity, and offers a large number of active sites in Co@NC. The density functional theory calculations have revealed that the hcp Co has a dominant role in the surface reaction of electrocatalytic oxygen evolution, whereas the fcc phase induces the built-in electric field at the interfaces with N-doped graphene to accelerate the H⁺ ion transport.     

偏缠绕模的Frobenius性质

主要给出了偏缠绕模的Frobenius性质，推广了缠绕模相应的性质。     

A posteriori error analysis of a quadratic finite volume method for nonlinear elliptic problems

In this article, we construct and analyze a residual-based a posteriori error estimator for a quadratic finite volume method (FVM) for solving nonlinear elliptic partial differential equations with homogeneous Dirichlet boundary conditions. We shall prove that the a posteriori error estimator yields the global upper and local lower bounds for the norm error of the FVM. So that the a posteriori error estimator is equivalent to the true error in a certain sense. Numerical experiments are performed to illustrate the theoretical results.