Synthesis optimization and the properties of 8-hydroxyquinoline ion-exchange resins

The preparation of oxine-containing ion-exchange resins has been treated rigorously. The reactant ratios, nature of cure, degree of cross-linking and hydrophilicity have been evaluated in terms of metal capacity and kinetics of metal uptake. The preparation of a bead polymer with good physical properties is described; stability tests show that the gel polymers must never be allowed to dry, otherwise their advantageous properties are destroyed. Stability towards acids in re-cycling procedures is excellent in terms of metal capacity, but there is some loss in water regain which equates to a slower equilibration rate with constant use.     

Approximate force constant calculations for cis-L2M(CO)4 species

A new procedure based on the criterion of maximum interaction between coupled fundamental vibrational modes has been developed to solve the energy factored force field of cis-L₂M(CO)₄ species. The results for complexes containing a wide range of metal-ligand combinations are compared with the force constants obtained by the Cotton-Kraihanzel and Jernigan methods. The CO stretching frequencies of isotopically-substituted cis-I₂Fe(CO)₄ species have been calculated as a check on the method.     

Paths for the formation of dioxin-type xenobiotics: Quantum-chemical treatment 1. Formation of polychlorobiphenylenes from polychlorobenzenes

The heats of formation of polychloroarynes (PCA's) from polychlorobenzenes (PCB's) have been calculated by the AMI method as a function of the composition and structure of the PCB's according to a two-step scheme including deprotonation with the formation of carbanions (PCCA's, H₁) and dechlorination to PCA's (H₂). The influence of the solvent on H₁ and H₂ has been evaluated in the framework of the solvaton model. It has been shown that the value of H₁ decreases as the number of C1 atoms in the PCB is increased, while H₂ increases along the same series due to the increase in the relative stability of the PCCA as the number of C1 atoms is increased. Although the dimerization of PCA's with the formation of polychlorobiphenylenes (PCBP's) is forbidden by orbital symmetry rules, calculations of fragments of the potential-energy surface have shown that this reaction takes place with an energy barrier amounting to about 1 kcal/mole.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Institute of Organic Chemistry, Bulgarian Academy of Sciences, 1113 Sofia. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 350–355, February, 1992.     

Comparison of glass fragments by neutron activation analysis

A method of comparing glass fragments of potential application to forensic sicence has been developed and evaluated. A representative sample of window glass from England and Wales has been collected and analysed for about 25 elements. An automated radiochemical separation followed by gamma-spectroscopy was used in order to determine the concentration of the maximum number of elements. Frequency distributions of the elemental concentration are shown and used to assess the discrimination of the technique and compare it with the measurement of refractive index. A few simulated cases have been included to demonstrate the possible application to forensic science problems.     

Complex formation of copper(II) with chrome azurol s

The complex formation of copper(II) with chrome azurol S (CAS) was studied by spectrophotometric and potentiometric methods. In the pH range 5–7, two complexes with the composition Cu(H₂O)₂HCAS- and (Cu(H₂O)₂)₂CAS were detected; the stability constants were calculated to be log K = 4.02 ±0.05 and log K = 13.7±0.1, respectively (at 25° and ionic strength 0.1 (KCl)). A comparison is made between the copper(II)-CAS and iron(III)-CAS systems.     

Water-soluble cellulose derivatives prepared by the action of solutions of nitrogen dioxide in dimethylformamide

Cellulose derivatives soluble in water and in dilute alkali were prepared by dissolving a bleached sulfite pulp in solutions of nitrogen dioxide in dimethylformamide (DMF) and heating at 70–90°C for 1–3 hr. No cellulose oxidation was detected. Nitrite esters and apparently also, nitrate esters, were formed with degrees of substitution (DS) ranging from 0.18 to 0.55 and with nitrogen contents ranging from 1.47 to 4.32%. Solution viscosities in water increased with increasing nitrogen content. The degree of polymerization (DP) decreased rapidly in the initial stages of the reaction followed by a slow, gradual decrease with increasing reaction times.     

The Isolation,Structure, and Synthesis of Davana Ether,an Odoriferous Compound of the Oil of Artemisia pallens Wall.

Several stereoisomers of 2,6,10-trimethyl-2:5, 7:10-diepoxy-dodeca-3,5,11-triene ( 3 ) have been isolated from the oil of Artemisia pallens. The synthesis of the isomeric mixture is described.     

Elemental concentration in the cortex and hippocampus of Wistar rats by X-ray total reflection fluorescence with synchrotron radiation

Summary The study of trace element levels is of great importance due to their relevance in agingand several neurodegenerative diseases. This work compares the elemental concentrations in different postnatal ages and between the temporal cortex, entorhinal cortex and hippocampus from Wistar rats, using X-ray total reflection fluorescence with synchrotron radiation. Ten elements were determined in brain samples: Ti, Cr, Mn, Fe, Cu, Zn, (at trace level) and P, S, Cl and K (at major levels). The elements that increased with aging in cortical areas were: S, K, Fe, Cu and Zn. Ca and Zn levels decreased with advancing age in the hippocampus. In addition to this, Ti, Mn and Fe levels were more conspicuous in the entorhinal cortex.     

Atomistic molecular dynamics simulations of chemical force microscopy

Chemical force microscopy and related force measurement techniques have emerged as powerful tools for studying fundamental interactions central to understanding adhesion and tribology at the molecular scale. However, detailed interpretation of these interactions requires knowledge of chemical and physical processes occurring in the region of the tip-sample junction that experiments cannot provide, such as atomic-scale motions and distribution of forces. In an effort to address some of these open issues, atomistic molecular dynamics simulations were performed modeling a chemical force microscope stylus covered with a planar C12 alkylthiolate self-assembled monolayer (SAM) interacting with a solid wall. A complete loading-unloading sequence was simulated under conditions of near-constant equilibrium, approximating the case of infinitely slow tip motion. In the absence of the solid wall, the stylus film existed in a fluid state with structural and dynamic properties similar to those of the analogous planar SAM at an elevated temperature. When the wall was brought into contact with the stylus and pressed against it, a series of reversible changes occurred culminating with solidification of the SAM film at the largest compressive force. During loading, the chemical composition of the contact changed, as much of the film's interior was exposed to the wall. At all tip heights, the distribution of forces within the contact zone was uneven and subject to large local fluctuations. Analysis using the Johnson-Kendall-Roberts, Derjaguin-Muller-Toporov, and Hertz contacts mechanics models revealed significant deviations from the simulation results, with the JKR model providing best overall agreement. Some of the discrepancies found would be overlooked in an actual experiment, where, unlike the simulations, contact area is not separately known, possibly producing a misleading or incorrect interpretation of experimental results. These shortcomings may be improved upon by using a model that correctly accounts for the finite thickness of the compliant components and nonlinear elastic effects.