分子表面随机采样分析法用于药物定量构效关系研究

考虑药物配基与蛋白质受体的3类非键作用模式,利用蒙特卡罗随机采样技术得到了一种分子结构性质表达方法:分子表面随机采样分析(RaSMS).同时,定义了蛋白质原子探针、虚拟受体可及表面、表面随机采样目标面积逼近法等多个相关概念,在理论和算法上对该法进行了可行性分析.在此基础上,对31个标准甾体化合物进行了定量构效关系(QS...     

Structure and magnetic properties of the Al1−xGaxFeO3 family of oxides: A combined experimental and theoretical study

Magnetic properties of the Al_1−xGa_xFeO₃ family of oxides crystallizing in a non-centrosymmetric space group have been investigated in detail along with structural aspects by employing X-ray and neutron diffraction, Mössbauer spectroscopy and other techniques. The study has revealed the occurrence of several interesting features related to unit cell parameters, site disorder and ionic size. Using first-principles density functional theory based calculations, we have attempted to understand how magnetic ordering and related properties in these oxides depend sensitively on disorder at the cation site. The origin and tendency of cations to disorder and the associated properties are traced to the local structure and ionic sizes.     

Determination of the Nanostructure of Polymer Materials by Electron Paramagnetic Resonance Spectroscopy

Electron paramagnetic resonance (EPR) spectroscopy is one the few methods that can characterize structural features in the range between 0.5 and 5 nm in systems that lack long‐range order. Approaches based on EPR spectroscopy provide good structural contrast even in complex materials, as the sites of interest can be selectively labeled or addressed by suitably functionalized spin probes using well established techniques. This article assesses the EPR experiments available for distance measurements on nanoscales in terms of the accessible distance range, precision, and sensitivity. Recommendations are derived for the proper choice of experiment for a given problem. Both simple and sophisticated methods for data analysis are described and their limitations are evaluated. It is discussed which assumptions must be made to extract a pair correlation function from EPR data. Finally, applications to the study of polymer chain conformation and the structure of ionically functionalized diblock copolymers are highlighted.     

2-（1,3-Diphenylpropen-1,3-diolato）-1,3,2-（5-formylbenzo）dioxaborol： A ＇Whole-molecule Disorder＇ Crystal Structure

The boron atom in C22H15BO5 is O,O’-chelated by the anions in a tetrahedral geometry, with the planar five-and six-membered chelate rings being orthogonal to each other. The molecule lies on a two-fold rotation axis. The molecule is disordered with respect to another molecule in a 93:7 ratio; the treatment of the ‘whole-molecule disorder’ by employing a large number of restraints is described. Crystal data: C22H15BO5, monoclinic C2/c, a = 17.1804(5), b = 12.9409(4), c = 9.8842(3) , β = 124.832(2)o, V = 1803.82(9) 3 at –173 K.     

Estimation of surface desorption times in hydrophobically coated nanochannels and their effect on shear-driven and pressure-driven chromatography

The present paper provides a detailed analysis of the analyte-wall adsorption effects in nanochannels, including a random walk study of the analyte-wall collision frequency, and uses these insights to estimate wall desorption times from chromatographic experiments in nanochannels. Using coumarin dye analytes and using a methanol/water mixture buffered at pH 3 in 120-nm deep channels, the surface desorption times on naked fused-silica glass were found to be maximally of the order of 60 to 150 μs, while they were found to be on the order of 100 to 500 μs on a hydrophobically coated wall. These nonzero adsorption and desorption times lead to an additional band broadening when conducting chromatographic separations. Shear-driven flows, requiring a noncoated moving wall and a stationary coated wall, intrinsically turn out to be more prone to this effect than pressure-driven or electro-driven flows for example. The present study also shows that, interestingly, the number of analyte-wall collisions increases with the inverse of the channel depth and not with its second power, as would be expected from the Einstein–Smoluchowski relationship for molecular diffusion.     

The structure of bis(trimethylammonium) undecachlorotriantimonate(III) [(CH3)3NH]2Sb3Cl11 containing a novel antimony(III) anion

The structure of [(CH₃)₃NH]₂Sb₃Cl₁₁ (space group P2₁/n; a = 10.374(2), b = 23.723(5), c = 11.884(2) Å, = 113.46(3)°; V = 2682.9(9) ų) consists of a structurally novel [Sb₃Cl^2– ₁₁] anion and two crystallographically nonequivalent trimethylammonium cations. The anion is composed of three deformed octahedra in the asymmetric part of the unit cell. The octahedra are connected with each other by edges and corners forming a characteristic polyanionic layer. Trimethylammonium cations, one ordered and one disordered, are connected to the inorganic sublattice by N—H···Cl hydrogen bonds.     

Crystal structure of monomethylammonium tribromocadmate(II)

CH₃NH₃CdBr₃ crystallizes in the space group Ccm2₁, a = 13.693(1) Å, b = 7.906(1) Å, c = 6.886(1) Å, V = 745.46(15) ų, Z = 4, D _x = 3.42 Mg m^–3. The structure of the title compound is one-dimensional consisting of infinite chains made of face sharing CdBr₆ octahedra. The methylammonium groups are situated in the space between chains. The cations and anions are joined by hydrogen bonding.     

Structure of phosphonium rhenates(VII)

Four phosphonium rhenates(VII) were prepared and crystallized: (A) 1,2-bis (triphenylphosphonium)ethane rhenate(VII) (Pī, a=8.298(2), b=10.638(3), c= 11.242(3) ?, α=64.96(2), β=80.49(2), γ=88.17(2)°), (B) methyltriphenylphosphonium rhenate(VII) (Pca2₁, a=15.096(3), b=12.627(3), c=19.353(3) ?), (C) benzyltriphenylphosphonium rhenate(VII) (Pī, a=9.648(2), b=11.689(2), c=20.806(3) ?, α=88.44(2), β=84.63(2), γ=77.33(3)°), and (D) orthorhombic form of (iodomethyl)triphenylphosphonium rhenate(VII) (Pca2₁, a=14.952(3), b=13.120(3), c=20.603(4) ?). Each crystal structure consists of separate phosphonium cations and rhenate(VII) anions. In A centrosymmetric 1,2-bis(triphenylphosphonium)ethane cations form layers perpendicular to [011]. In B the cations are set in chains along [100] forming layers perpendicular to [001]. In C two symmetrically-independent cations form double columns along [100] and these columns are arranged in puckered layers perpendicular to [001]. D is almost isomorphous to B. The crystal structures are stabilised by weak C–H⋯O hydrogen bonds as well as phenyl rings interactions. In all crystal structures supramolecular motifs of phenyl rings embraces could be distinguished.     

Stochastic fatigue limits and fatigue life variability for unplasticised PVC pipes

This paper uses the random fatigue limit (RFL) model of Pascual and Meeker to address fatigue limits for PVC pressure pipes. This model differs from previous ways of describing fatigue data for PVC by recognising that the fatigue limit is a stochastic quantity rather than a single valued stress amplitude below which fatigue failures will not occur. By analysing published fatigue data, it is demonstrated that the RFL model is capable of quantifying fatigue limit variability and its influence on fatigue life variability. Moreover, the RFL model was used to illustrate the risks associated with defining fatigue limits based on small quantities of high-cycle fatigue data. In particular, it is shown that fatigue failure can occur below the mean fatigue limit and that the RFL model is capable of quantifying the probability of failure at a given level of stress amplitude.