Electron-density-dependent fused-sphere surfaces derived from pseudopotential calculations

Fused-sphere surfaces can be used to mimic a molecular boundary associated with a constant value of the electron density. The simplest of such fused-sphere models are constructed by using the atomic radii for the spherical isodensity surfaces of individual atoms. In this work, we discuss the extension of this model to molecules containing atoms beyond the second row. In these many- electron systems, the computation of electron densities is usually simplified by adopting a pseudopotential (or effective-core potential) approach. Here, we discuss the performance of large- and small-core pseudo-potential calculations as a tool to derive atomic radii. Our results provide an optimum set of variable radii that can be used to build fused-sphere surfaces. This continuum of surfaces provides a simple approximation to the low-electron-density regions around molecules with heavy atoms.     

Host-guest interactions template: the synthesis of a [3]catenane

Formation of a [3]catenane containing dibenzo-24-crown ether wheels and a large dipyridiniumethane ring is templated by formation of a host-guest adduct between the [3]catenane and the external crown ether.     

The ordered phase of methylammonium lead chloride CH3ND3PbCl3

The perovskite-structured compound methylammonium lead chloride orders into a low-temperature phase of space group Pnma, in which at 80 K each of the orthorhombic axes , and is doubled with respect to the room temperature disordered cubic phase (). The structure was solved by ab initio methods using the programs EXPO and FOX. This unusual cell basis for space group Pnma is not that of a standard tilt system. This phase, in which the methylammonium ions, are ordered shows distorted octahedra. The octahedra possess a bond angle variance of 60.663°² and a quadratic elongation of 1.018, and are more distorted than those in the ordered phase of methylammonium lead bromide. There is also an alternating long and short Pb-Cl bond along a, due to an off-center displacement of Pb within the octahedron. This suggests that the most rigid unit is actually the methylammonium cation, rather than the PbCl₆ octahedra, in agreement with existing spectroscopic data.     

Detecting Reaction Pathways and Computing Reaction Rates in Condensed Phase

Methods for the computation of rate constants that characterize classical reactions occurring in the condensed phase are discussed. While microscopic expressions for these transport properties are well known, their computation presents challenges for simulation since reactive events often occur rarely, and the long time scales that are typical for reactive processes are not accessible using simple molecular dynamics methods. Furthermore, the underlying free energy surface is very complex with many saddle points that prevent sampling of possible reaction pathways. As a result, the reaction coordinate may be a complex many-body function of the system’s degrees of freedom. Since there is not an a priori way to define a “good” reaction coordinate, methods are being developed to assist in a systematic construction of a reaction coordinate. These methods are reviewed and examples of non-trivial reaction coordinates are presented.     

Complexation of well-controlled low-molecular weight polyelectrolytes with antisense oligonucleotides

The influences of polymer-related properties such as molecular weight, charge density, counter ion, and hydrophilic block on the complexation of polyelectrolytes and a fluorescein-labeled oligonucleotide (ON) were investigated. A series of well-defined and well-controlled 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) polymers and block copolymers were prepared using living anionic and radical polymerization methods. Fluorescence measurement was used to reveal the effects of polymer molecular weight, charge density, and counter ion type on the complexation. PolyDMAEMA samples having double molecular weights of the chosen oligonucleotide gave the optimal complexation performance. Kinetic studies showed that high-molecular weight/high-charge density polymer samples produced very stable complexes. The fully charged polyDMAEMA displayed the strongest binding with the ON. These complexes were therefore less sensitive to the changes in the environment. PolyDMAEMA–DMSQ samples had slightly higher complexation ability than polyDMAEMA–MCQ (DMSQ: dimethylsulfate quat; MCQ: methylchloride quat). Both poly(DMAEMA-b-HEMA) and poly(DMAEMA–MCQ-b-PEG) block copolymers showed good complexation ability and steric stability [HEMA: 2-hydroxyethyl methacrylate; PEG: poly(ethylene glycol)]. PEG, but not HEMA block, enhanced the effectiveness of polyDMAEMA–MCQ binding with the ON.     

Time‐Resolved Synchrotron Radiation Excited Optical Luminescence: Light‐Emission Properties of Silicon‐Based Nanostructures

The recent advances in the study of light emission from matter induced by synchrotron radiation: X‐ray excited optical luminescence (XEOL) in the energy domain and time‐resolved X‐ray excited optical luminescence (TRXEOL) are described. The development of these element (absorption edge) selective, synchrotron X‐ray photons in, optical photons out techniques with time gating coincide with advances in third‐generation, insertion device based, synchrotron light sources. Electron bunches circulating in a storage ring emit very bright, widely energy tunable, short light pulses (<100 ps), which are used as the excitation source for investigation of light‐emitting materials. Luminescence from silicon nanostructures (porous silicon, silicon nanowires, and Si–CdSe heterostructures) is used to illustrate the applicability of these techniques and their great potential in future applications.     

Analysis of inorganic mercury species associated with airborne particulate matter/aerosols: method development

This paper describes a method for speciation of Hg associated with airborne particulate matter. This method uses a mini-sampler for sample collection and analysis, thermal desorption for separating Hg species, and inductively coupled plasma mass spectrometry (ICP–MS) for identification and quantification of Hg. Coal fly ash spiked with different Hg compounds (e.g. Hg⁰, HgCl₂, HgO, and HgS) was used for qualitative calibration. A standard reference material with a certified value for Hg concentration was used to evaluate the method. When the temperature of the furnace was programmed at a linear rate of increase of 50° min^–1, different Hg compounds could clearly be separated. Three airborne particulate matter samples were collected in parallel in Toronto, ON, Canada and analyzed using this method. Reproducible results were obtained and Hg⁰, HgCl₂, HgO, and HgS species from these samples were detected.     

Fluoroapatite - material for medicine,Growth, morphology and thermoanalytical properties

Fluoroapatite containing glass-ceramics were prepared from Li₂O-CaO-CaF₂-P₂O₅-SiO₂ system. The glass was melted at 1480°C for 1 h. The object of observation was the preparing crystal phase of fluoroapatite in amorphous glass matrix. The morphology of lithium disilicate glass-ceramics was studied by SEM. The crystal growth and thermal properties of fluoroapatite were studied by X-ray diffraction and DTA. The more the content of P₂O₅, the more the presence of fluoroapatite particles. SEM investigation clearly indicated the phase separation and formation of a primary crystalline phase of fluoroapatite in the studied glass-ceramics. DTA curves of the fluoroapatite samples exhibit exothermic effects in the temperature range 337-694°C depending on the composition of the materials. The position of exothermic peak for lithium disilicate on DTA curves moves with increasing specific surfacetowards lower temperatures which points on its preferential surface crystallization. As far as physical qualities are concerned, mainly color and gloss, the best qualities of all observed materials belong to glass-ceramics with 10% P₂O₅. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structuring of edible oils by alternatives to crystalline fat

The structure of many food products is based on networks of crystalline triacylglycerol (TAG) hardstock. These contain high levels of saturated fatty acids, which are among the factors contributing to cardiovascular diseases. Therefore it would be desirable to have alternative routes to structure edible oils.This review starts with general structuring concepts and building blocks which can be found in organic solvents. Subsequently it focuses on the field of edible oil structuring. Among the alternative structuring agents that have received attention in recent years are mono- and diglycerides, fatty acids, fatty alcohols, waxes, wax esters, sorbitan esters, and phytosterols. It is found that the most efficient structuring agents form small, preferably non-spherical particles. Mixing of components often provides superior structuring over use of pure components. Straightforward screening of pure components might be feasible. However, the number of options provided by mixing requires guided screening, for which understanding of the underlying mechanisms is essential. Analytical methods helping to characterise oil structuring and elucidate the structuring mechanisms are discussed.     

Probing in vitro digestion at oil–water interfaces

Interfacial layers have been widely applied to study the formation and stability of emulsion-based systems. However, the application of isolated interfaces to address digestibility of emulsions is often limited because of the complexity of experimental methods and results. This review summarizes the latest developments in analytical methods and literature data on effects of digestion on interfacial layers. Particular emphasis is given to understand the changes on interfacial magnitudes during oral, gastric, and duodenal digestion, either applied separately or sequentially. Limitations of interfacial aspects and key factors that influence emulsion microstructure in bulk and lipid digestion are identified. Understanding the behavior of interfacial layers upon gastrointestinal digestion promotes an accurate tracking of the physiological fate of emulsions.