气相和溶液中金属离子与腺嘌呤配位选择性的理论研究

在B3LYP/6-31G(d,p)水平,全优化Mg2+、Ca2+、Mn2+、Co2+、Zn2+、Cu2+、Ni2+、Cd2+ (用有效实势(ECP) 方法处理)与腺嘌呤(A) N(1)、N(7)位点配位的两类配合物气相结构,通过相互作用能和自由能分析分别得出两位点对所研究金属离子的选择性顺序;后采用Onsager模型,优化其在水溶液(=78.39)中的结构,讨论溶剂效应对上述顺序的影响;通过相对自由能分析分别得出气相和溶液中,同种金属对两位点的选择性规律。溶液中金属离子与N(7)位配位的相对优选顺序为:Co2+ > Mg2+ > Cd2+ > Ca2+ > Zn2+ > Mn2+ > Ni2+ > Cu2+。     

On Bonding,Structure, and Stability of Ternary Hydrides A2MH2 (A = Li,Na; M = Pd,Pt)

Bonding, structure, and stability of solid A₂MH₂ with A = Li, Na; M = Pd, Pt were investigated with a relativistically corrected density-functional approach, which reliably describes the trends among these four compounds. In order to examine the influence of the ligands (A) and of the crystalline environment, calculations were also made for free A₂MH₂ molecules and MH₂^2– ions. The free MH₂^2– complex is held together by strong bonds between formally closed shell atomic units because of strong M-d,s hybridization. The M–H bonds are further stabilized by the alkali metal ion ligands and by the crystal surrounding. The crystal field expands the H–A distance and enhances the H–A polarity. Relativistic effects contribute to M–H bonding in the solid state. The experimentally determined bond lengths and their trends are in accordance with theory. Due to relativistic and lanthanide effects, the Pt–H bond length becomes nearly as short as the Pd–H one. The small Li ion causes a distortion of the Li₂PtH₂ crystal resulting in an even shorter Pt–H bond length. In the gas-phase, A₂PtH₂ is more stable against dissociation than A₂PdH₂. The stability of the solid compounds is strongly influenced by the cohesive energy of the metal M, and also by the nature of the alkali metal. The evaluated enthalpies of formation favor increasing stability of solid A₂MH₂ against disproportionation into M and AH from Pt to Pd and from Li to Na. This is in agreement with experimental findings. The assignment of the experimental vibrational excitations should be reconsidered.     

Über die Oxidsilicate M2O[SiO4] der schweren Lanthanoide (M = Dy–Lu) im A‐Typ

On the Oxide Silicates M₂O[SiO₄] of the Heavy Lanthanides (M = Dy–Lu) with the A‐Type Structure By reacting the sesquioxides M₂O₃ of the heavy lanthanides (M = Dy–Lu) with SiO₂ and CsCl as flux (molar ratio 1 : 1 : 4; 700 °C, 7 d) in evacuated silica ampoules, it is possible to expand the series of lanthanide oxide silicates M₂O[SiO₄] with the A‐type structure (to date known with M = La–Tb) down to lutetium. The most important structural features, besides isolated ortho‐silicate anions [SiO₄]^4–, form oxygen‐centred (M³⁺)₄ tetrahedra, which are condensed to a two‐dimensional network [O(M1)_1/1(M2)_3/3)]⁴⁺ by sharing common edges and corners. The adaption of the structure (with coordination numbers of seven and nine, respectively, for the M³⁺ cations) to the smaller ionic radii of the heavy lanthanides is shown with help of X‐ray single‐crystal data. The influence of temperature on the stability of the products will be discussed.     

Formation of Fe i –B pairs in silicon at high temperatures

We report on the detection of Fe _i –B pairs in heavily B doped silicon using ⁵⁷Fe emission Mössbauer spectroscopy following implantation of radioactive ⁵⁷Mn⁺ parent ions (T _1/2?=?1.5 min) at elevated temperatures >?850 K. The Fe _i –B pairs are formed upon the dissociation of Fe _i –V pairs during the lifetime of the Mössbauer state (T _1/2?=?100 ns). The resulting free interstitial Fe_i diffuses over sufficiently large distances during the lifetime of the Mössbauer state to encounter a substitutional B impurity atom, forming Fe _i –B pairs, which are stable up to ～1,050 K on that time scale.     

Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

New group 10 metalloorganic complexes are proposed as the basis of new catalysts for the formation of carbon‐phosphorous bonds. Density functional theory (DFT) is applied, using multiple DFT functionals, to model molecular geometry as well as electron density distribution in the highest occupied molecular orbitals (HOMOs) expected to carry out a reductive catalytic cycle. DFT/M06 analysis predicts a robust planar geometry, regardless of alteration of major components. Precursors for rapid catalyst generation should begin with an electron‐withdrawing monodentate ligand. Palladium and platinum catalysts have lower chemical hardness, but the electron distribution in the HOMO of the nickel‐based catalyst is preferred for reductive catalytic mechanisms. Both electron density and chemical hardness, however, are affected by the choice of metal ion and the composition of the monodentate ligand bound to it. Group 10 metalloorganic complexes are modeled as precursors for generating new catalysts for a minimally wasteful method of forming bonds commonly found in biochemically active compounds. Suitable precursors have an accessible metal center, as well as significant the HOMO/LUMO involvement at the metal center. All complexes studied offer similar geometries, but precursor transformation into catalyst depends on the electron‐withdrawing ligand being exchanged. Catalyst turn over number is predicted to depend primarily on the central metal. © 2016 Wiley Periodicals, Inc.     

Higher regularity for free boundary and tangential derivative problems and global solutions to regular reflections for the unsteady transonic small disturbance (UTSD) equations

We establish C^2,α$C^{2,\alpha }$-estimates for solutions of a class of quasilinear elliptic equations with free boundary and tangential derivative boundary problems. Using this regularity result we show the existence of global solutions to regular shock reflections for the unsteady transonic small disturbance (UTSD) equation. We also present Lipschitz estimates near the degenerate Dirichlet boundary (the sonic boundary) for the UTSD equation.     

A gas-kinetic scheme for shallow-water equations with source terms

In this paper, the Kinetic Flux Vector Splitting (KFVS) scheme is extended to solving the shallow water equations with source terms. To develop a well-balanced scheme between the source term and the flow convection, the source term effect is accounted in the flux evaluation across cell interfaces. This leads to a modified gas-kinetic scheme with particular application to the shallow water equations with bottom topography. Numerical experiments show better resolution of the unsteady solution than conventional finite difference method and KFVS method with little additional cost. Moreover, some positivity properties of the gas-kinetic scheme is established.     

Étude du contrôle du décollement sur un profil d'aile par mesures PIV et analyse PODStudy of separation control on a wing profile using PIV measurements and POD analysis

The purpose of this study is the active control of flow separation on an ONERA D airfoil, using continuous blowing microjets. Particle Image Velocimetry (PIV) is used to measure velocity fields at midspan around the airfoil in both controlled and uncontrolled cases. Post-processing based on Proper Orthogonal Decomposition (POD) is developed to exhibit the main energetic features of the flow. Therefore, the detailed study of the POD modes for separated and stalled cases leads to a better understanding of the control mechanisms. Moreover, the POD basis computed for uncontrolled and controlled cases, opens the way to optimisation of control strategies. To cite this article: J. Favier, A. Kourta, C. R. Mecanique 334 (2006).     

More QACs,more questions: Recent advances in structure activity relationships and hurdles in understanding resistance mechanisms

Quaternary ammonium compounds (QACs) are a class of antimicrobials that have been around for over a century; nevertheless, they have found continued renewal in the structures to which they can be appended. Ranging from antimicrobial polymers to adding novel modes of action to existing antibiotics, QACs have found ongoing use due to their potent properties. However, resistance against QACs has begun to emerge, and the mechanism of resistance is still only partially understood. In this review, we aim to summarize the current state of the field and what is known about the mechanisms of resistance so that the QACs of the future can be designed to be evermore efficacious and utilized to unearth the remaining mysteries that surround bacteria’s resistance to them.