Extractive spectrophotometric determination of Cobalt(II) in synthetic and pharmaceutical samples using Cyanex 923.

Cyanex 923 has been proposed as a sensitive analytical reagent for the direct extractive spectrophotometric determination of cobalt(II). Cobalt(II) forms a blue-colored complex with Cyanex 923 in the organic phase. The maximum absorbance of the complex is measured at 635 nm. Beer's law was obeyed in the range 58.9 - 589.0 microg of cobalt. The molar absorptivitiy and Sandell's sensitivity of the complex was calculated to be 6.79 x 10920 l mol(-1) cm(-1) and 0.088 microg cm(-2), respectively. The nature of the extracted species was found to be Co(SCN)2 x 2S. An excellent linearity with a correlation coefficient value of 0.999 was obtained for the Co(II)-Cyanex 923 complex. Stability and regeneration of the reagent (Cyanex 923) for reuse is the main advantage of the present method. The method was successfully applied to the determination of cobalt in synthetic mixtures and pharmaceutical samples was found to give values close to the actual ones. Standard alloy samples, such as high-speed tool BCS 484 and 485, have been tested for the determination of cobalt for the purpose of validating the present method. The results of the proposed method are comparable with atomic absorption spectrometry and were found to be in good agreement.     

Crystal structure of the 4-chromanone derivative.

The title compound was extracted from a natural product and its structure was characterized by an X-ray diffraction method. It crystallizes in the tetragonal space group P41 with cell parameters a = 15.832(10)A, c = 11.622(10)A, Z = 4; the final residual factor is R1 = 0.0769. The structure has both intra and intermolecular hydrogen bonds.     

A sequential injection system for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples.

A sequential injection methodology for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples is proposed. A single manifold is used for the determination of the three analytes, and the same protocol sequence allows the sequential determination of calcium and magnesium (the sum corresponds to the water hardness). The determination of both metals is based on their reaction with cresolphtalein complexone; mutual interference is minimized by using 8-hydroxyquinoline for the determination of calcium and ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) for the determination of magnesium. Alkalinity determination is based on a reaction with acetic acid, and corresponding color change of Bromcresol Green. Working ranges of 0.5 - 5 mg dm(-3) for Ca, 0.5 - 10 mg dm(-3) for Mg, and 10 - 100 mg HCO3- dm(-3), for alkalinity have been achieved. The results for water samples were comparable to those of the reference methods and to a certified reference water sample. RSDs lower than 5% were obtained, a low reagent consumption and a reduced volume of effluent have been accomplished. The determination rate for calcium and magnesium is 80 h(-1), corresponding to 40 h(-1) per element, while 65 determinations of alkalinity per hour could be carried out.     

Addition–fragmentation chain transfer: Molecular weight distributions and retardation in the system methyl methacrylate/methyl α‐(bromomethyl)acrylate

A detailed investigation of addition–fragmentation chain transfer (AFCT) in the free‐radical polymerization of methyl methacrylate (MMA) in the presence of methyl α‐(bromomethyl)acrylate (MBMA) was carried out to elucidate mechanistic details with efficient macromonomer synthesis as an underlying goal. Advanced modeling techniques were used in connection with the experimental work. Curve fitting of simulated and experimental molecular weight distributions with respect to the rate coefficient for addition of propagating radicals to MBMA (k_add) over 60–120 °C resulted in E_add = 21.7 kJ mol^?1 and A_add = 2.18 × 10⁶ M^?1 s^?1 and a very weak temperature dependence of the chain‐transfer constant (E_add ≈ E_p). The rate coefficient for fragmentation of adduct radicals at 60 °C was estimated as k_f ≈ 39 s^?1 on the basis of experimental data of the MMA conversion and the concentration of 2‐carbomethoxy‐2‐propenyl end groups. The approach developed is generic and can be applied to any AFCT system in which copolymerization does not occur and in which the resulting unsaturated end groups do not undergo further reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2640–2650, 2004     

Fold‐2‐covering triangular embeddings

For a graph G and a positive integer m, G_(m) is the graph obtained from G by replacing every vertex by an independent set of size m and every edge by m² edges joining all possible new pairs of ends. If G triangulates a surface, then it is easy to see from Euler's formula that G_(m) can, in principle, triangulate a surface. For m prime and at least 7, it has previously been shown that in fact G_(m) does triangulate a surface, and in fact does so as a “covering with folds” of the original triangulation. For m = 5, this would be a consequence of Tutte's 5‐Flow Conjecture. In this work, we investigate the case m = 2 and describe simple classes of triangulations G for which G₍₂₎ does have a triangulation that covers G “with folds,” as well as providing a simple infinite class of triangulations G of the sphere for which G₍₂₎ does not triangulate any surface. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 79–92, 2003     

Three-dimensional structure of Saccharomyces cerevisiae inorganic pyrophosphatase complexed with cobalt and phosphate ions

Crystals of Saccharomyces cerevisiae inorganic pyrophosphatase suitable for X-ray diffraction study were grown by cocrystallization of the enzyme with cobalt chloride and imidodiphosphate. Saccharomyces cerevisiae is a metal-dependent enzyme which catalyzes hydrolysis of inorganic pyrophosphate to orthophosphate. The three-dimensional structure of this enzyme was solved by the molecular-replacement method and refined at 1.8 Å resolution to an R factor of 19.5%. Cobalt and phosphate ions were revealed in the active centers of both identical subunits (A and B) of the pyrophosphatase molecule. In subunit B, a water molecule was found between two cobalt ions. It is believed that this water molecule acts as an attacking nucleophile in the enzymatic cleavage of the pyrophosphate bond. It was demonstrated that cobalt ions and a phosphate group occupy only part of the potential binding sites (two chemically identical and crystallographically independent subunits have different binding sites). The arrangement of ligands and the structure of the nucleophile-binding site are discussed in relation to the mechanism of action of the enzyme and the nature of the metal activator.     

Electronic molecule-like spectrum of quantum wells in crossed fields

We show that an electron confined to a single finite parabolic quantum well in crossed electric and magnetic fields can behave as a double quantum well system. The magnetic field is parallel to the heterostructure layers and the electric field is perpendicular to those. For a suitable choice of both fields and quantum well width, the electron can be confined to a double quantum well effective potential that is very similar to the electronic potential model for diatomic molecules. The double quantum well spectrum is calculated using a numerical algorithm based on semiclassical methods. A physical interpretation of this quantum system is given based on the analogy to the electrons bound to diatomic molecules.     

Partial structure elucidation of the most abundant octa and nonachlorotoxaphene congeners in marine mammals by using conventional electron ionization mass spectrometry and mass spectrometry/mass spectrometry

Summary Conventional electron ionization (EI) mass spectrometry (MS) and MS/MS techniques were applied to the analysis of two abundant octa and nonachlorobornanes isolated from seals of the Baltic sea and originating from technical toxaphene. The exact sterical structures of the two compounds were previously determined using nuclear magnetic resonance (NMR) spectroscopy by two independent research groups. The MS and MS/MS data generated in this study allowed partial structure elucidation of these polychlorobornanes, in particular revealing the distribution of the Cl substituents between the six-membered carbon ring, the bridge and the bridgehead in the parent bornane structure. Fragmentation of the six-membered carbon ring and the bridge by retro-Diels-Alder (RDA) and related mechanisms was discovered by studying specific parent/daughter ion transitions. The detailed fragmentation pathways formulated may be applicable to the structure elucidation of other toxaphene congeners and the monitoring of strategic transitions is highly selective for the detection of these compounds in technical toxaphene and in environmental samples.     

On asymptotic approximation of a solution of a boundary-value problem for a nonlinear nonautonomous equation

On the basis of periodic Ateb functions, in the resonance and nonresonance cases, we construct the asymptotic approximation of one-frequency solutions of a boundary-value problem for a nonlinear nonautonomous equation.