Proton controlled intramolecular communication in dinuclear ruthenium(II) polypyridine complexes

The synthesis and characterization of two dinuclear ruthenium polypyridyl complexes based on the bridging ligands 5,5'-bis(pyridin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and 5,5'-bis(pyrazin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and of their mononuclear precursors are reported. The dinuclear compounds have been prepared by a Ni(0) catalyzed coupling of a mononuclear ruthenium(II) polypyridyl complex containing a brominated triazole moiety. Electrochemical and photophysical studies indicate that, in these dinuclear complexes, the protonation state of the bridge may be used to tune the intercomponent interaction between the two metal centers and that these species act as proton driven three-way molecular switches that can be read by electrochemical or luminescence techniques.     

Über Chalkogenidhalogenide des Chroms Synthese,Kristallstruktur und Magnetismus von Chromsulfidbromid,CrSBr

Chalkogenidehalides of Chromium. Synthesis, Crystal Structure, and Magnetism of Chromiumsulfidebromide, CrSBr CrSBr is obtained from chromium metal and S₂Br₂ in a sealed quartz ampoule at 880°C. It forms air stable, black crystals. The crystal structure determination (space group Pmmn, lattice constants a = 476.7(2), b = 350.6(2), c = 796.5(4) pm, Z = 2, R = 0.026) shows, that CrSBr crystallizes in the FeOCl structure type. The structure consists of layers which are stacked perpendicular to the c axis. The layers are formed by distorted, edge sharing CrS₄Br₂ octahedra. The interatomic distances are Cr? S 239.7 and 241.5 pm, Cr? Br 249.4 pm. To explain the unusual temperature factor of the Br atom the structure determination was additionaly carried out at 205 K and 118 K. A linear decrease of the coefficients of the anisotropic temperature factors of all atoms was found. The coefficients can be extrapolated to zero for 0 K. This shows the large displacement parameter U₁₁ of the Br atom to be caused by thermal vibrations. Even under forced conditions CrSBr does not form intercalation compounds with pyridine or tetracyanoethylene. CrSBr shows a marked antiferromagnetic behavior with a Néel temperature of 132 K and a critical field of 0.35 Tesla at 4.2 K.     

Solvent mediated interactions close to fluid-fluid phase separation: microscopic treatment of bridging in a soft-core fluid

Using density functional theory we calculate the density profiles of a binary solvent adsorbed around a pair of big solute particles. All species interact via repulsive Gaussian potentials. The solvent exhibits fluid-fluid phase separation, and for thermodynamic states near to coexistence the big particles can be surrounded by a thick adsorbed "wetting" film of the coexisting solvent phase. On reducing the separation between the two big particles we find there can be a "bridging" transition as the wetting films join to form a fluid bridge. The effective (solvent mediated) potential between the two big particles becomes long ranged and strongly attractive in the bridged configuration. Within our mean-field treatment the bridging transition results in a discontinuity in the solvent mediated force. We demonstrate that accounting for the phenomenon of bridging requires the presence of a nonzero bridge function in the correlations between the solute particles when our model fluid is described within a full mixture theory based upon the Ornstein-Zernike equations.     

Quantitative validation of different protein precipitation methods in proteome analysis of blood platelets

For the preparation of proteins for proteome analysis, precipitation is frequently used to concentrate proteins and to remove interfering compounds. Various methods for protein precipitation are applied, which rely on different chemical principles. This study compares the changes in the protein composition of human blood platelet extracts after precipitation with ethanol (EtOH) or trichloroacetic acid (TCA). Both methods yielded the same amount of proteins from the platelet preparations. However, the EtOH-precipitated samples had to be dialyzed because of the considerable salt content. To characterize single platelet proteins, samples were analyzed by two-dimensional fluorescence differential gel electrophoresis. More than 90% of all the spots were equally present in the EtOH- and TCA-precipitated samples. However, both precipitation methods showed a smaller correlation with nonprecipitated samples (EtOH 74.9%, TCA 79.2%). Several proteins were either reduced or relatively enriched in the precipitated samples. The proteins varied randomly in molecular weight and isoelectric point. This study shows that protein precipitation leads to specific changes in the protein composition of proteomics samples. This depends more on the specific structure of the protein than on the precipitating agent used in the experiment.     

Pyrolysis studies of aromatic polyesters

The products of pyrolysis, at 400°C in vacuo (1 Pa), of poly(ethyleneterephthalate) (PET) and poly(butyleneterephthalate) (PBT) were studied. The products were identified by gas chromatography/mass spectrometry technique. The highly volatile products of PET contained acetaldehyde, benzene, toluene, styrene and ethylbenzene and in the case of PBT, butadiene, tetrahydrofuran, vinylcyclohexene and ethylbenzene were the major products. A qualitative analysis of the products of low volatility revealed that the main components were benzoic acid, terephthalic acid, monovinyl esters of terephthalic acid and higher oligomers in the case of PET, whereas benzoic acid, monobutenyl esters of terephthalic acid and higher oligomers were the main products from PBT. The results obtained were in good agreement with those obtained from pyrolysis experiments, carried out directly in the mass spectrometer. Mechanisms to explain the occurrence of the different products are proposed.     

Quality assurance system for a decomposition method as demonstrated for the Wickbold combustion technique

 A five-step model for a quality assurance system is developed for an internal quality control check. It includes the quality control of the decomposition method and the detection method as steps belonging together. The Wickbold combustion technique as decomposition method in combination with atomic absorption spectrometry was chosen. The vaporization of the elements mercury, arsenic, lead, antimony and selenium is based on combustion in an oxyhydrogen flame. To check the efficiency of the analytical system, the uncertainty of results was calculated on the basis of the "Guide to the Expression of Uncertainty in Measurement". Received: 13 January 1997 · Accepted: 29 March 1997     

One-dimensional magnetism and crystal structure ofcatena-di-bromobis(3,5-dimethylpyridine)copper(II)

Summary Crystals ofcatena-di--bromobis(3,5-dimethylpyridine)copper(II) are monoclinic, space group P2₁/a. The unit cell constants area=13.900(2),b=14.416(2),c=4.097(1) Å,=93.49(2)°, V=819.4 ų and Z=2. The structure was determined from powder data using a Guinier-Johansson focussing powder camera. The structure was solved using a simplex method for function minimization to a conventional R-value of 0.13.The structure consists of infinite linear chains parallel toc in which the copper coordination is distorted elongated octahedral. Cu-Br distances were found to be 2.449(7) and 3.286(7) Å, whereas the Cu-N bond length is 2.02(2) Å. All distances are in the range usually observed for this type of compounds.The antiferromagnetic superexchange interactions between adjacent Cu^II ions (J = –21 cm^–1) has been compared with those observed in structural similar CuBr₂L₂ compounds. The differences in observed J-values are discussed briefly, in relation to the structural variations. It appears that very small changes in structural parameters strongly affect the magnetic exchange.     

The discovery of two kinds of ion pairs

The discovery and implications of the existence of two kinds of ion pairs in solutions of carbanion salts is described. Also discussed are the factors controlling tight–loose ion pair equilibrium: the nature of the carbanion and its counterion, temperature, pressure, solvent, and cation‐complexing additives. A few examples are presented of the effect of these ionic species on the mechanisms of anionic polymerization and proton transfer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3655–3667, 2004     

Ueber die Titration der Schwefels?ure mit Benzidinchlorhydrat

Zusammenfassung In Vorstehendem wurde zunächst die Ausführung der von einem von uns ausgearbeiteten Schwefelsäuretitration mittelst Benzidinchlorhydrats nochmals genau beschrieben, sodann wurden die Bedingungen festgestellt, unter denen verschiedene Schwefelsäuremengen am genauesten zu bestimmen waren. Es hat sich dabei herausgestellt, dass die Schwefelsäure bis zu 0,01g H₂SO₄ herunter nach der beshriebenen Methode auf 1–2 genau bestimmt werden kann. Die Anwendung der Methode auf verschiedene Fälle (Ammoniumsulfat, Alaun, Zinksulfat-heptahydrat, Mohr'sches Salz, Mangansulfat-tetrahydrat), wobei die Metalle in einigen Fällen vorher ausgefällt wurden, bestätigten die zuvor festgestellten Regeln; ausserdem wurde gezeigt, dass beim Ausfällen von Zink, Eisen und Mangan nach dem angegebenen Verfahren Schwefelsäure nicht mitgerissen wird. Die Zeit, welche eine derartige Bestimmung, auch wenn die beschriebenen Ausfällungen vorgenommen werden müssen, bei einiger Uebung erfordert, ist sehr kurz, weil alles Auswaschen und so weiter in Fortfall kommt, so dass auch hier ein Vortheil gegenüber dem gewichtsanalytischen Verfahren vorhanden ist.     

Insight into the extractability of metals from soils using an implementation of the linear adsorption isotherm model

This paper deals with an often overlooked artifact in sequential and single extraction of metals from soils, viz. the volume to mass (V/m) ratio as a potential source for inadequate extraction yields. We offer a theoretical framework to get a grip on this intricate parameter and came up with a model based on a linear adsorption isotherm to derive the correct maximal metal extractability for a certain extractant. We verified the model experimentally using 0.1 mol l⁻¹ nitric acid for extraction of seven metals (Cr, Co, Cu, Cd, Pb, Ni and Zn) from an urban soil sample, and concluded that commonly used V/m ratios in the range of 10-40 ml g⁻¹ may give as much as 50% too low extraction yields. Thus, a strong caveat is in place as to be very critical what V/m ratios to use and preferably apply the model derived to obtain the correct maximal extractability using a variable V/m ratio method.