Zur Bestimmung der organischen Substanz in Tonen

Ohne Zusammenfassung(Aus dem agrikulturchemischen Institut der Universität Göttingen.)     

Der Kolloidton

Ohne Zusammenfassung     

Oxidation-reduction potential of soluble and membrane-bound rabbit liver microsomal cytochrome P-450 LM2

The redox midpoint potentials of rabbit liver microsomal cytochromes P-450 and of soluble and membrane-bound rabbit liver microsomal cytochrome P-450 LM2 were determined using EPR-spectroscopy and absorption difference spectrometry with NADPH or dithionite as reductants. Using EPR, a redox midpoint potential of -0.36 V was obtained both for the low spin and the high spin components of microsomal cytochrome P-450. Spectrophotometrical determinations yielded very similar values: -0.37 V and -0.34 V for the low and high spin signals, respectively. Soluble cytochrome P-450 LM2 had a midpoint potential of -0.32 V. This redox potential was not significantly affected by incorporation of the protein into an artificial membrane structure or, furthermore, by the presence of cytochrome b5 the same membrane.     

Intentions-to-Buy and Claimed Brand Usage

Consumers' expressed Intentions-to-buy different brands are frequently measured in marketing research. Study of several hundred surveys shows that a relationship between the percentage I of consumers expressing such an Intention-to-buy and the percentage U claiming current Usage of the brand can be represented by a single one-parameter relationship I = K √U ± 3. This holds for different brands (large and small) in over 20 product-fields, for different demographic subgroups, for certain different definitions of the Intentions and Usage variables, for some American as well as British data, and even for trends over time.Both the nature of this relationship between I and U and the paradoxical finding that relatively few people express an Intention-to-buy a new brand which is sub-sequently successful and that relatively many people do so for a brand which is slowly dying are explained by the effect of past Usage. Methodological conclusions of the findings are indicated.     

Proton transfer in hydrogen-bonded pyridine/acid systems: the role of higher aggregation

In this work the role of higher molecular aggregation in the proton transfer processes within hydrogen bond (H-bond) is investigated. The H-bonded complex consisting of 4-cyanopyridine (CyPy) with trichloroacetic acid (TCA) has been studied in the solutions of acetonitrile, carbon tetrachloride, chloroform and dichloroethane as solvent by FTIR spectroscopy and quantum chemical DFT calculations. In order to illustrate the effect of increasing H-bond strength FTIR investigations have also been performed on solutions of CyPy with H(2)O, acetic-, trifluoroacetic- and methanesulfonic acids. Proton states in the H-bond have been monitored using vibrational CyPy ring modes in FTIR spectra. The stabilization of the CyPy/TCA complex in its protonated form upon increasing polarity of the solvent has been evidenced. It was shown that formation of the CyPy/(TCA)(2) aggregates in the solutions favors the proton transfer process. An X-ray diffraction study has been performed on a single 1 : 2 co-crystal of pyridine/3,5-dinitrobenzoic acid. The H-bond motif found in this system exhibits the same connectivity by strong hydrogen bonds N-H(+)[dot dot dot]O(-) and O-H[dot dot dot]O as that in the CyPy/(TCA)(2) complex predicted by DFT calculation. Certain discrepancies are observed in C-H[dot dot dot]O connectivity only. The networks of H-bonds in both assemblies differ from those usually pictured for 1 : 2 base/carboxylic acid complexes in the literature.     

Enhanced acidity, photophysical properties and liposome binding of perfluoroalkylated phthalocyanines lacking C-H bonds

The acid-base, spectroscopic, photophysical and liposome-binding properties of the recently synthesized free base, 29H,31H,1,4,8,11,15,18,22,25-octafluoro-2,3,9,10,16,17,23, 24-octakisperfluoro(isopropyl) phthalocyanine, F64PcH2, are reported. The perfluoroalkylation of the phthalocyanine core renders the hydrogen atoms acidic, with a pK(a) = 6. The F64Pc(-2) dianion is detected already at pH 3, by singular-value decomposition analysis of electronic spectra. F64Pc(-2) generates 1O2 with quantum yields phi(delta) = 0.252 (in MeOH) and 0.019 in liposomes. Metallation of the Pc macrocycle to yield F64PcZn increases phi(delta) to 0.606 and 0.126 in MeOH and liposomes, respectively. Surprisingly, F64Pc(-2) (but not F64PcH2 or F64PcZn) binds strongly to liposomes, with a binding constant K(b) = 25 (mg/mL)(-1). The fully protonated F64PcH2, but not the zwitterionic F64Pc(-2), might favor hydrogen bonding, thus reducing its lipophilicity. Similarly, the Lewis acidity of Zn in F64PcZn, and thus its ability to bind water within a hydrophobic perfluoroalkyl pocket, is significantly enhanced by the fluorinated substituents.     

Effect of carbon coating process on the structure and electrochemical performance of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.5</Subscript>O<Subscript>2</Subscript> used as cathode in Li-ion batteries

LiNi_0.5Mn_0.5O₂ powder was synthesized by a coprecipitation method. LiOH.H₂O and coprecipitated [(Ni_0.5Mn_0.5)C₂O₄] precursors were mixed carefully together and then calcined at 900°C. Surface modified cathode materials were obtained by coating LiNi_0.5Mn_0.5O₂ with a thin layer of amorphous carbon using table sugar and starch as carbon source. Both parent and carbon-coated samples have the characteristic layered structure of LiNi_0.5Mn_0.5O₂ as estimated from X-ray diffractometry measurements. Transmission electron microscope showed the presence of C layer around the prepared particles. TGA analysis emphasized and confirmed the presence of C coating around LiNi_0.5Mn_0.5O₂. It is obvious that the carbon coating appears to be beneficial for the electrochemical performance of the LiNi_0.5Mn_0.5O₂. A capacity of about 150 mAh/g is delivered in the voltage range 2.5–4.5 V at current density C/15 for carbon coated LiNi_0.5Mn_0.5O₂ in comparison with about 165 mAh/g obtained for carbon free LiNi_0.5Mn_0.5O₂ at the same current density and voltage window. About 92% and 82% capacity retention was obtained at 50th cycle for coated LiNi_0.5Mn_0.5O₂ using sucrose and starch, respectively; whereas, 75% was retained after only 30th cycle for carbon free LiNi_0.5Mn_0.5O₂. This improvement is mainly attributed to the presence of thin layer of carbon layer that encapsulate the nanoparticles and improve the conductivity and the electrochemical performance of LiNi_0.5Mn_0.5O₂.     

The effect of electrochemically inactive Ti substituted for Ru in Li2Ru1-xTixO3 on structure and electrochemical performance

The approach of substituting electrochemically active with inactive elements has widely been used to improve the electrochemical performance of Li-rich intercal...