Bis-phenol A Cyclophanes: Synthesis, Crystal Structures and Binding Studies

The synthesis and structural characterisation of three new macrocyclicbis-phenol A cyclophane ethers are described. The solid state structuresof two of the cyclophanes were determined by single crystal X-raydiffraction. Cyclophane 3 crystallises in the orthorhombic spacegroup Pbca with unit cell dimensions of a = 11.533(7), b = 29.383(8),c = 14.927(8) Å and cyclophane 4 in the monoclinic spacegroup P2₁/n with cell dimensions of a = 11.585(4), b = 11.839(2), c = 18.866(2) Å, = 94.48(2)°.The X-ray crystalstructures reveal distorted conformations, thus supporting the weak bindingof quats in solution observed by the NMR studies. In the crystalline state bothmacrocycles were found to form self-complementary dimers held together byweak intermolecular - and CH- interactions. The bindingbehaviour towards a series of tetralkylammonium cations was determinedby ¹H NMR titration in CDCl₃ solution. The interactions between the hosts and the quats were clearly detectable but too weak to be translated into meaningful equilibrium constants.     

Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO2 bond fission and C-NO2 to CONO isomerization. Electronic excitation or charging of FOX-7 disfavors CONO formation and, thus, terminates this channel of decomposition. However, if CONO is formed from the neutral FOX-7 molecule, charge trapping and/or excitation results in spontaneous splitting of an NO group accompanied by the energy release. Intramolecular hydrogen transfer is found to be a rare event in FOX-7 unless free electrons are available in the vicinity of the molecule, in which case HONO formation is a feasible exothermic reaction with a relatively low energy barrier. The effect of charged and excited states on other possible reactions is also studied. Implications of the obtained results to FOX-7 decomposition in condensed state are discussed.     

Behaviour of Extractives in Norway Spruce (Picea abies) Bark during Pile Storage

The current practices regarding the procurement chain of forest industry sidestreams, such as conifer bark, do not always lead to optimal conditions for preserving individual chemical compounds. This study investigates the standard way of storing bark in large piles in an open area. We mainly focus on the degradation of the most essential hydrophilic and hydrophobic extractives and carbohydrates. First, two large 450 m³ piles of bark from Norway spruce (Picea abies) were formed, one of which was covered with snow. The degradation of the bark extractives was monitored for 24 weeks. Samples were taken from the middle, side and top of the pile. Each sample was extracted at 120 °C with both n-hexane and water, and the extracts produced were then analysed chromatographically using gas chromatography with flame ionisation or mass selective detection and high-performance liquid chromatography. The carbohydrates were next analysed using acidic hydrolysis and acidic methanolysis, followed by chromatographic separation of the monosaccharides formed and their derivatives. The results showed that the most intensive degradation occurred during the first 4 weeks of storage. The levels of hydrophilic extractives were also found to decrease drastically (69% in normal pile and 73% in snow-covered pile) during storage, whereas the decrease in hydrophobic extractives was relatively stable (15% in normal pile and 8% in snow-covered pile). The top of the piles exhibited the most significant decrease in the total level of extractives (73% in normal and snow-covered pile), whereas the bark in the middle of the pile retained the highest amount of extractives (decreased by 51% in normal pile and 47% in snow-covered pile) after 24-week storage.     

Anomalous dependence of particle size on supersaturation in the preparation of iron nanoparticles from iron pentacarbonyl

Anisotropic colloidal particles consisting of different compositions and geometry are useful for various applications. These include optical biosensing, antireflective coatings and electronic displays. In this work we demonstrate a simple and cost-effective method for fabricating anisotropic colloidal particles bearing a snowman-like shape. This is achieved by first settling the positively-charged polystyrene latex (PSL) colloids and negatively-charged silica colloids in deionized water onto a glass substrate, forming heterodoublets. The temperature is then raised above the glass transition temperature of the polymer. As a result, the silica particle spontaneously rises to the top of the PSL particle forming a snowman like structure. We have extended this method to different sizes and shown that the structure of the hybrid particles can be tuned by adjusting the size ratio between the silica and the PSL colloids. The surface coverage of the PSL, and hence of the snowman particles, on the glass substrate can also be varied by changing the ionic strength of the solution during the adhesion of PSL to the glass.     

Conformational polymorphism and amphiphilic properties of resorcinarene octapodands

o-Nitroaniline functionalized resorcinarene octapodands 1-5 with pendant methyl, ethyl, pentyl, nonyl or 1-decenyl groups, respectively, were synthesized and their structural properties investigated using X-ray crystallography and NMR spectroscopy. The upper rim of each podand is identical containing flexible side arms, in which rotation around the -OCH(2)CH(2)N- linkers create excellent possibilities for polymorphism. Two conformational polymorphs of acetone solvate of 2 were identified containing different side arm orientation and crystal packing. Compound 1 crystallized from acetone and nitromethane yielding two pseudopolymorphs with different packing motifs. The longer alkyl chains of 3-5 lead to differences in solubility and induce amphiphilic properties, which were studied at the air-water interface using the Langmuir-film technique. Crystals of amphiphilic compound 5, which has hydrophobic alkyl tails at the lower rim and hydrophilic nitroaniline groups at the upper rim, showed an interesting packing motif with alternating aromatic and aliphatic layers. Versatile structures of the octapodands in solid state and in solution serve as an example of how conformational flexibility can be utilized in crystal engineering and creating self-assembling monolayer structures.     

Characterization of ARC/CL wheat flour, pork meat and skim milk powder reference materials for contents of toxic elements

Summary Wheat flour, pork meat and skim milk powder reference materials (RM) prepared and employed for the activities of the Sub-network on Trace Element Status in Food of the FAO European Cooperative Research Network on Trace Elements were subjected to an interlaboratory comparison study on the contents of Pb, Cd and Hg. The homogeneity of the above materials had earlier been shown to be within 2% for several essential elements and within 5 to 10% for Pb and Cd. An interlaboratory comparison study was conducted involving 17 reference laboratories recognized for their reliability and specialized in heavy metal determinations in biological materials. A total of seven methods based on four different analytical principles were employed to determine the contents of the above heavy metals. After the exclusion of outliers, the recommended concentration values expressed as the medians ±95% confidence limits were established. All of the recommended values reported here fell into category A, i.e. values recommended with a high degree of confidence according to the certification criteria established by Pszonicki. The present materials contain very low naturally occurring levels of all the heavy metals studied and have been successfully employed in the analytical quality control program of the above FAO study during the past five years.     

Crystal structure of a CsF-uranyl-salen complex. An unusual cesium-chlorine coordination

Complexation of CsF with the ditopic uranyl-salen receptor results in a solid-state structure, in which the coordination sphere of cesium is filled by ligation to one of the chlorine atoms of the solvent chloroform. This X-ray structure is the first example of chloroform ligation to an alkali-metal ion.     

First principles calculation of the mechanical compression of two organic molecular crystals

The mechanical compression curves for the organic molecular crystals 1,1-diamino-2,2-dinitroethylene and beta-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (beta-HMX) are calculated using the Hartree-Fock approximation to the solutions of the many-body Schr?dinger equation for a periodic system as implemented in the computer program CRYSTAL. No correction was made for basis set superposition error. The equilibrium lattice parameters are reproduced to within 1% of reported experimental values. Pressure values on the isotherm also agree well with reported experimental values. To obtain accurate results, the relaxation of all the atomic coordinates as well as the lattice parameters under a fixed volume constraint was required.     

Electrostatics of the ferroelectric phases of BaTiO3

Extensive theoretical calculations are reported here on the electrostatics of the three ferroelectric phases of BaTiO₃ using the static polarizable point-ion model. For each structure the following quantities have been calculated: monopole and dipole fields at ionic sites, field gradients, spontaneous polarization, high frequency dielectric constant and the Coulomb energy terms. The parameters of the model have been fitted on the basis of the experimental information on the tetragonal structure and then treated as constants for all the studied structures. The use of the experimental positional parameters of the orthorhombic structure gives such exceptional behaviour for all the calculated quantities that a redetermination of the structural parameters for this phase is suggested. Numerical study of the changes in the Coulomb energy as a function of the macroscopic depolarization potential demonstrated that the most stable state is achieved with the value zero for the potential.     

Analytical quality control program used by the trace elements in foods and diets sub-network of the FAO European cooperative network on trace elements

Summary The analytical quality control program employed by the ongoing FAO study on 14 trace elements in nationally representative staple foods of European countries is presented. The analytical quality control used is based on: 1) precautions taken to avoid trace element contaminations or losses during sampling and sample handling; and, 2) on methods used to guarantee that the actual determinations yield correct results. The precautions are presented. A number of certified biological reference materials (RMs) were used to validate the analytical methods employed. The following staple food RMs were also prepared: wheat flour, potato powder, animal muscle (pork) and milk powder. They were tested for homogeneity and subjected to an interlaboratory comparison study on the basis of which recommended values for trace element concentrations were defined. Further, the mean relative standard deviation for the 95% confidence limits of the medians in all RMs was below 5% for Ca, Mg and Zn; below 10% for Mn; below 15% for Fe, Cu and Se; and below 25% for Mo and Ni. These RMs were used to control the analytical quality of the trace element determinations in the actual samples. It is concluded that important contaminations were avoided in sampling and sample handling and that use of the RMs described was necessary to guarantee the analytical quality of the results.