The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Notiz über Parachloraldehyd

Ohne Zusammenfassung     

Simultaneous determination of trace cadmium and mercury in Chinese herbal medicine by non-dispersive atomic fluorescence spectrometry using intermittent flow vapor generator.

A method was proposed for the simultaneous determination of trace cadmium and mercury by vapor generation non-dispersive atomic fluorescence spectrometry using an intermittent flow system. The effects of the parameters on the performance were studied systematically. The parameters such as acid concentration of the reaction medium, flow rate of the carrier gas and shield gas, the observation height and the atomizer temperature, etc. which affected the sensitivity, were optimized. Ascorbic acid, cobalt ion and thiourea were used as enhancement reagents or masking agents to enhance the generation efficiency of the volatile species of Cd and Hg. The mechanisms of their effects on vapor generation were investigated. In the presence of thiourea and ascorbic acid, the influences of some coexisting elements on the determination of cadmium and mercury were investigated. The detection limits (3sigma) were 0.010 microg l(-1) for Cd and 0.019 microg l(-1) for Hg, respectively. The relative standard deviations for Cd and Hg at 1.00 microg l(-1) were 2.6% and 0.97% (n = 11), respectively. The proposed method has been satisfactorily applied to the determination of trace cadmium and mercury in Chinese herbal medicine.     

Untersuchungen über Papaverin

Ohne Zusammenfassung     

Boiling heat transfer characteristics of nanofluids in a flat heat pipe evaporator with micro-grooved heating surface

An experimental study was performed to understand the nucleate boiling heat transfer of water–CuO nanoparticles suspension (nanofluids) at different operating pressures and different nanoparticle mass concentrations. The experimental apparatus is a miniature flat heat pipe (MFHP) with micro-grooved heat transfer surface of its evaporator. The experimental results indicate that the operating pressure has great influence on the nucleate boiling characteristics in the MFHP evaporator. The heat transfer coefficient and the critical heat flux (CHF) of nanofluids increase greatly with decreasing pressure as compared with those of water. The heat transfer coefficient and the CHF of nanofluids can increase about 25% and 50%, respectively, at atmospheric pressure whereas about 100% and 150%, respectively, at the pressure of 7.4 kPa. Nanoparticle mass concentration also has significant influence on the boiling heat transfer and the CHF of nanofluids. The heat transfer coefficient and the CHF increase slowly with the increase of the nanoparticle mass concentration at low concentration conditions. However, when the nanoparticle mass concentration is over 1.0 wt%, the CHF enhancement is close to a constant number and the heat transfer coefficient deteriorates. There exists an optimum mass concentration for nanofluids which corresponds to the maximum heat transfer enhancement and this optimum mass concentration is 1.0 wt% at all test pressures. The experiment confirmed that the boiling heat transfer characteristics of the MFHP evaporator can evidently be strengthened by using water/CuO nanofluids.     

4-Amino-imidazole durchThorpe-Cyclisierung

The alkylation of arylaminomethylenecyanamides1 or cyano-imidothiocarbamates2 with -halogen carbonyl compounds followed by base catalysed cyclization yields substituted 4-amino-imidazoles4. Imidazo[4,5-d]pyrimidones5, 6 and imidazo[4,5-b]pyridines7 can be obtained from4.     

The electrocapillarity of polyacrylates

Summary The electrocapillary properties of polyacrylic acid have been studied by two methods. Exploratory measurements have been made of the effect of the polymer on the differential capacity of a mercury drop in 0.1 m sodium perchlorate. They showed that the polymer was strongly adsorbed over a wide range of potentials but that it did not appear to form a monolayer. The surface excess of polymer obtained from drop weight data showed a maximum at very low concentrations and then a decline at higher concentrations. The bulk of the work was carried out by making surface tension measurements, using a sessile mercury drop, in solutions of a fraction of polyacrylic acid (mol. wt. 7.02×10⁴) in potassium chloride at 0.01, 0.1, 0.2, and 0.5 m at 25°C.The data have been used to evaluate the surface excesses of the polymer and of the inorganic ions. The distribution of K⁺ and Cl^– in the electrical double layer and the contact adsorption of Cl^– on the mercury were very little affected by the presence of the polymer. The surface excess of polymer was always found to be greatest at low concentrations, to decrease steeply at first as the concentration was increased and then to decrease more slowly at higher concentrations.Possible explanations of this behaviour are discussed and it is concluded that the rapid decrease is a consequence of molecular weight dispersion and the stronger adsorption of high molecular weight polymer. The slow decrease in surface excess at higher concentrations may be a result of configurational changes of the polymer molecules.Surface pressure data show that, despite this decrease in the surface excess, the surface coverage reaches a high level at very low polymer concentrations and then continues to increase slowly as the concentration of polymer is increased. This apparent contradiction is due to changes in configuration of the adsorbed polymer molecules. At higher bulk concentrations the chain configurations are more compact and each adsorbed molecule makes more contacts with and so occupies a greater area of the mercury surface than at low concentrations.The conclusion is reached that the surface excess of polymer is mostly contained in a layer probably more than 1000 Å thick. It consists of a concentrated and entangled mass of polymer chains. Relatively few of these chains are in contact with the mercury at any istant. The concentration in this surface layer decreases steadily with increasing distance from the mercury surface and it merges without discontinuity into the bulk solution.With 10 figures in 22 details     

Stereochemie von Metallocenen, 40. Mitt.

Starting from optically active methylferrocene-- and--carboxylic acids (1 a and1 b) of known absolute configuration and enantiomeric purity about 15 chiral ferrocenes (of each isomeric series— and ) were obtained by suitable ligand transformations. Thereby (almost) all possible chiral combinations of the ligands CH₃, COOH (COO^–), COOCH₃, CN and NH₂ (NH₃ ⁺) were accessible which are necessary for a potential test of approximations of chirality functions for compounds with basic symmetry C_5v. The chiroptical properties of these disubstituted ferrocenes are recorded.Preliminary tests using a shortened Ansatz revealed large discrepancies between calculated () and found [M]_D-values. Possible reasons for this failure are discussed.

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61. Mitt. über Ferrocenderivate

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39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).

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60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975).