Materials Formed by Combining Inorganic Glasses and Metal-Organic Frameworks

Here, we propose the combination of glassy or crystalline metal-organic frameworks (MOFs) with inorganic glasses to create novel hybrid composites and blends.The motivation behind this new composite approach is to improve the processability issues and mechanical performance of MOFs, whilst maintaining their ubiquitous properties. Herein, the precepts of successful composite formation and pairing of MOF and glass MOFs with inorganic glasses are presented. Focus is also given to the synthetic routes to such materials and the challenges anticipated in both their production and characterisation. Depending on their chemical nature, materials are classified as crystalline MOF-glass composites and blends. Additionally, the potential properties and applications of these two classes of materials are considered, the key aim being the retention of beneficial properties of both components, whilst circumventing their respective drawbacks.     

Coupled ab initio potential energy surfaces for the two lowest 2A′ electronic states of the C2H molecule

Realistic two-valued potential energy surfaces for the reaction C(³P) + CH(X²Π) → C₂ + H have been constructed from a set of high level ab initio data describing the first two ²A′ electronic states of the C₂H system. These states have linear equilibrium configurations, known as the X ²Σ⁺ and A²Π states, and are coupled by a conical intersection. They lead to the formation of C₂(X¹Σ⁺ _g) and C₂(a³Π_u) considering an adiabatic dissociation process. The ab initio calculations are of the multireference configuration interaction variety and were carried out using a polarized triple-zeta basis set. Using the ab initio adiabatic energies and the matrix elements of the dipole moment, a 2 × 2 diabatic representation of the electronic Hamiltonian was built. Each element of this Hamiltonian matrix was expressed within the double many-body expansion (DMBE) scheme which is based, in this case, on the extended Hartree-Fock approximate correlation energy model (EHFACE). The analytical adiabatic potential energy surfaces are then obtained as the eigenvalues of this matrix, and display correctly the Σ/Π conical intersection. Moreover, the non-adiabatic couplings given by our analytical model are compared with the ab initio ones, and good qualitative agreement is observed.     

Long‐Range Electrostatics‐Induced Two‐Proton Transfer Captured by Neutron Crystallography in an Enzyme Catalytic Site

Neutron crystallography was used to directly locate two protons before and after a pH‐induced two‐proton transfer between catalytic aspartic acid residues and the hydroxy group of the bound clinical drug darunavir, located in the catalytic site of enzyme HIV‐1 protease. The two‐proton transfer is triggered by electrostatic effects arising from protonation state changes of surface residues far from the active site. The mechanism and pH effect are supported by quantum mechanics/molecular mechanics (QM/MM) calculations. The low‐pH proton configuration in the catalytic site is deemed critical for the catalytic action of this enzyme and may apply more generally to other aspartic proteases. Neutrons therefore represent a superb probe to obtain structural details for proton transfer reactions in biological systems at a truly atomic level.     

Evaluation of a new maintenance concept for the preservation of highways

Asphalt roads gradually deteriorate over time and need mendingto remain in a good state. Inspections are performed to obtaininformation about the current state of the road; when the levelof damage reaches the established standards, the road is repairedthrough a maintenance action that is considered most cost-effective.Because of economies of scale, it is to a certain extent economicalto limit the number of maintenance services by integrating neighbouringsegments into a homogeneous section which is completely repaired.In this report we consider the question of whether it is economicallyjustified to adopt a maintenance concept in which the road isoccasionally regenerated from junction to junction with a distanceof several kilometers. The big advantage of junction-to-junctionmaintenance is that it can be done within special road barrierconstructions which reduce the road capacity only slightly,so that the road can be maintained 24 hours a day.     

A Note on the Formation and Rise of a Bubble from a Submerged Nozzle, Including Effects of Bulk- and Surface-Dilatational Viscosity

A model of the formation, detachment, and rise of a bubble from a submerged orifice is derived, based upon a study using a modified form of the Rayleigh–Plesset equation. Similar models have previously been proposed by Oguz and Prosperetti (1), Avramidis and Jiang (2), and also Chakraborty and Tuteja (3). We seek to re-examine these models and implement a number of additional physical features. In particular, we demonstrate the relative importance of the surface dilatational viscosity of surfactant added to the liquid in the growth and detachment of the bubble from the orifice. It is found that “large” surface dilatational viscosities significantly increase the time to detachment of the bubble. In addition, through a drastic reduction in the rate of radial expansion of the bubble in the early stages of development (given an initial condition on the radial velocity for “fast” bubble growth), the rise velocity of the bubble centroid at this time is greater with a large surface dilatational viscosity than when this property is neglected.     

Crystal Structures and Ionic Conductivities of Ternary Derivatives of the Silver and Copper Monohalides: I. Superionic Phases of Stoichiometry MA4I5:RbAg4I5, KAg4I5, and KCu4I5

The superionic properties of the compounds RbAg₄I₅, KAg₄I₅ and KCu₄I₅ have been investigated by powder neutron diffraction and complex impedance spectroscopy. RbAg₄I₅ and KAg₄I₅ have room-temperature ionic conductivities of σ=0.21(6) and 0.08(5) Ω⁻¹ cm⁻¹, respectively, which increase gradually on increasing temperature. KCu₄I₅ is only stable in the temperature range between 515(5) K and its melting point of 605 K, and its ionic conductivity is σ=0.61(8) Ω⁻¹ cm⁻¹, at T=540 K. At lower temperatures, KCu₄I₅ disproportionates into KI+4CuI and the ionic conductivity falls by over three orders of magnitude. Least-squares refinements of the powder neutron diffraction data for RbAg₄I₅ at ambient temperature confirm the reported structure (space group P4₁32, Z=4, a=11.23934(3) Å), though with some differences in the preferred locations of the mobile Ag⁺. KAg₄I₅ and KCu₄I₅ are found to adopt the same basic structure as RbAg₄I₅, with the I− forming a β-Mn-type sublattice, with the K⁺ located in a distorted octahedral environment and the Ag⁺(Cu⁺) predominantly distributed over two sites which are tetrahedrally co-ordinated to I⁻. The implications for the conduction mechanism within these compounds are discussed, using a novel maximum entropy difference Fourier technique to map the distribution of the Ag⁺(Cu⁺) within the unit cell.     

Evolution of Concentrated Vortices in a Viscous Fluid

Evolution of the vortices of monopole and dipole types in a viscous fluid is considered numerically. Theory and numerical results are compared for some particular exact solutions. A good agreement is obtained for the dipole vortices (viscous Chaplygin-Lamb vortices) moving with variable velocities due to viscosity. For the monopole type vortices, the agreement is more or less good only at an initial stage of their evolution; while in the long-lime asymptotics the law of vorticity decay other than the theoretical one is discovered. The reason for such a discrepancy is discussed. The interactions of dipole vortices with each other and with rigid boundaries are studied too. The stability of dipole vortices with complex internal structures is considered briefly.     

由重构矩阵存储精度引起的波前重构误差的研究

 采用Southwell区域法波前重构模型对泽尼克多项式的前几项进行了波前重构的数值模拟, 研究了由重构矩阵存储精度原因而引起的波前重构误差。结果表明,对于前六项,以8Bit的数据精度来存储重构矩阵就能保证波前重构误差不超过1.0%,而对于具有更高阶的泽尼克多项式,比8Bit更高的数据精度不会使误差减小。对一个测量所得的波前进行了研究,所得结果和上述结论相符合。