Densities and Viscosities of Tris(acetylacetonato)cobalt(III) Complex Solutions in Various Solvents

The densities and the viscosities of tris(acetylacetonato)cobalt(III) solutions in acetonitrile, dichloromethane, chloroform, tetrachloromethane, benzene, toluene, ethylbenzene, and p-xylene were measured in the dilute concentration regions at several temperatures ranging from 278 to 313 K under ambient pressure. The partial molar volumes of the solvents and solute were calculated. They are independent of concentration and increase slightly as the temperature increases. The viscosity A- and B-coefficients of the Jones-Dole equation were obtained. The A-coefficients were found to be zero within experimental error. The B-coefficients are positive and decrease as the temperature increases. Thermodynamic quantities of activation for viscous flow were calculated on the basis of Eyring’s viscosity equation. From the quantities obtained in this study, along with some information from the literature, it is suggested that structure-making interactions occur between the segments of the complex and the solvent molecules. These interactions include electrostatic interactions between the local charge on the complex and the dipole moment of the solvent in solutions of acetonitrile and dichloromethane, interlocking packing interactions along C ₃-axis of the complex with solvent in solutions of chloroform and tetrachloromethane, and π-electron interactions between the chelate ring of the complex and the solvent in solutions of benzene, toluene, ethylbenzene, and p-xylene.     

Binding of Multivalent Anionic Porphyrins to V3 Loop Fragments of an HIV‐1 Envelope and Their Antiviral Activity

Interactions of multivalent anionic porphyrins and their iron(III) complexes with cationic peptides, V3_Ba‐L and V3_IIIB, which correspond to those of the V3 loop regions of the gp120 envelope proteins of the HIV‐1_Ba‐L and HIV‐1_IIIB strains, respectively, are studied by UV/Vis, circular dichroism, ¹H NMR, and EPR spectroscopy, a microcalorimetric titration method, and anti‐HIV assays. Tetrakis(3,5‐dicarboxylatophenyl)porphyrin (P1), tetrakis[4‐(3,5‐dicarboxylatophenylmethoxy)phenyl]porphyrin (P2), and their ferric complexes (Fe^IIIP1 and Fe^IIIP2) were used as the multivalent anionic porphyrins. P1 and Fe^IIIP1 formed stable complexes with both V3 peptides (binding constant K>10⁶ M ^?1) through combined electrostatic and van der Waals interactions. Coordination of the His residues in V3_Ba‐L to the iron center of Fe^IIIP1 also played an important role in the complex stabilization. As P2 and Fe^IIIP2 form self‐aggregates in aqueous solution even at low concentrations, detailed analysis of their interactions with the V3 peptides could not be performed. To ascertain whether the results obtained in the model system are applicable to a real biological system, anti‐HIV‐1_BA‐L and HIV‐1_IIIB activity of the porphyrins is examined by multiple nuclear activation of a galactosidase indicator (MAGI) and 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assays. There is little correlation between chemical analysis and actual anti‐HIV activity, and the size rather than the number of the anionic groups of the porphyrin is important for anti‐HIV activity. All the porphyrins show high selectivity, low cytotoxicity, and high viral activity. Fe^IIIP1 and Fe^IIIP2 are used for the pharmacokinetic study. Half‐lives of these iron porphyrins in serum of male Wistar rats are around 4 to 6 h owing to strong interaction of these porphyrins with serum albumin.     

Thermal carbosilylation of endohedral dimetallofullerene La(2)@I(h)-C(80) with silirane

Thermal carbosilylation of endohedral dimetallofullerene La(2)@I(h)-C(80) with silirane (silacyclopropane) is reported herein for the first time. Two diastereomers of the carbosilylated La(2)@I(h)-C(80) have been isolated and characterized. The fascinating molecular structure of one diastereomer of the carbosilylated derivatives has been determined unambiguously using X-ray crystallographic analysis. Detailed characteristics of the molecular structures including their metal atom movements have also been revealed using NMR spectroscopic studies and computational calculations. Results revealed that two La atoms move dynamically inside the carbon sphere. Furthermore, electrochemical study has demonstrated that carbosilylation is effective to fine-tune the La(2)@I(h)-C(80) electronic properties.     

MassBank: a public repository for sharing mass spectral data for life sciences

MassBank is the first public repository of mass spectra of small chemical compounds for life sciences (<3000 Da). The database contains 605 electron‐ionization mass spectrometry(EI‐MS), 137 fast atom bombardment MS and 9276 electrospray ionization (ESI)‐MSⁿ data of 2337 authentic compounds of metabolites, 11 545 EI‐MS and 834 other‐MS data of 10 286 volatile natural and synthetic compounds, and 3045 ESI‐MS² data of 679 synthetic drugs contributed by 16 research groups (January 2010). ESI‐MS² data were analyzed under nonstandardized, independent experimental conditions. MassBank is a distributed database. Each research group provides data from its own MassBank data servers distributed on the Internet. MassBank users can access either all of the MassBank data or a subset of the data by specifying one or more experimental conditions. In a spectral search to retrieve mass spectra similar to a query mass spectrum, the similarity score is calculated by a weighted cosine correlation in which weighting exponents on peak intensity and the mass‐to‐charge ratio are optimized to the ESI‐MS² data. MassBank also provides a merged spectrum for each compound prepared by merging the analyzed ESI‐MS² data on an identical compound under different collision‐induced dissociation conditions. Data merging has significantly improved the precision of the identification of a chemical compound by 21–23% at a similarity score of 0.6. Thus, MassBank is useful for the identification of chemical compounds and the publication of experimental data. Copyright © 2010 John Wiley & Sons, Ltd.     

Eine trockene Methode zur Bestimmung von Zink in Messing, Bronze und anderen ?hnlichen Legierungen

Ohne Zusammenfassung     

Ablation process of silica glass induced by laser plasma soft X-ray irradiation

Silica glass can be machined by irradiation with laser plasma soft X-rays on nano- and micrometer scale. We have investigated the ablation process of silica glass induced by laser plasma soft X-ray irradiation. We observed ionic and neutral species emitted from silica surfaces after irradiation. Dominant ions and neutrals are O⁺ and Si⁺ ions and Si, O, SiO and Si₂ neutrals, respectively. The ions have kinetic energies of 13 and 25 eV, which are much higher than those of particles emitted by evaporation. The energy of laser plasma soft X-rays absorbed to silica glass at a fluence of 1.4 J/cm² is estimated to be 380 kJ/cm³, which is higher than the binding energy of SiO₂ of 76 kJ/cm³. These results suggest that the most of the bonds in silica glass are broken by absorption of laser plasma soft X-rays, that several percent of the atoms are ionized, and that neutral atoms are emitted together with repulsive ions. The process possibly enables us to fabricate nano structures.     

Enzyme-catalyzed resolution of 3,8-dioxatricyclo[3.2.1.0]octane-6-carboxylic esters and the application to the synthesis of 3-epishikimic acid

3,8-Dioxatricyclo[3.2.1.0^2,4]octane-6-carboxylic acid, whose racemic form is readily available on a large scale, is a versatile starting material for the synthesis of carbasugars and carbocyclic biologically active natural products. In this study, the enzyme-catalyzed kinetic resolution was attempted on a variety of corresponding carboxylic esters. The hydrophobic and hydrophilic properties of ester substituents greatly affected the rate of reaction and the enantioselectivity. Hydrolysis of the corresponding 2′-chloroethyl ester with pig liver esterase worked well in a highly enantioselective manner (E = 116) to give the hydrolyzate (90.6% ee) and unreacted ester recovery (99.4% ee). The hydrolyzate is a precursor for (−)-oseltamivir phosphate, and a route to (3S,4S,5R)-(−)-3-epishikimic acid was developed from the recovered ester.     

Hydrothermal Synthesis and Crystal Structure of a New BariumVanadium Bronze Ba1+xV8O21 with a Tunnel Structure

A barium vanadium bronze Ba_1+xV₈O₂₁ has been hydrothermally synthesized and structurally characterized. Hydrothermal treatment of a suspension of VO₂ powders in Ba(NO₃)₂ solution at 350°C yielded a fibrous brown compound having nonstoichiometric composition Ba_1+xV₈O₂₁ (x=0.13). Single-crystal X-ray diffractometry revealed the monoclinic system C2/m with a=15.144(6), b=3.596(4), c=14.972(3) Å, β=90.08(3)°, and Z=2, with the refinement based on 2021 reflections with I>3σ(I) converged to R=0.054 and R_w=0.046. A new tunnel-type bronze structure was disclosed in which VO₆ octahedra and VO₅ trigonal bipyramids form a V–O framework with a tunnel cavity running along [010]. The Ba atom partially occupies the tunnel site with more than half occupancy of 56.6%, which causes displacement of the Ba atom and further displacement of V and O atoms along the tunnel axis. Ba_1+xV₈O₂₁ is the first tunnel-type barium vanadium bronze whose structure has been fully determined.