Preparation of monolayers of [MnIII6CrIII]3+ single-molecule magnets on HOPG,mica and silicon surfaces and characterization by means of non-contact AFM

We report on the characterization of various salts of [Mn^III₆Cr^III]³⁺ complexes prepared on substrates such as highly oriented pyrolytic graphite (HOPG), mica, SiO₂, and Si₃N₄. [Mn^III₆Cr^III]³⁺ is a single-molecule magnet, i.e., a superparamagnetic molecule, with a blocking temperature around 2 K. The three positive charges of [Mn^III₆Cr^III]³⁺ were electrically neutralized by use of various anions such as tetraphenylborate (BPh₄^-), lactate (C₃H₅O₃^-), or perchlorate (ClO₄^-). The molecule was prepared on the substrates out of solution using the droplet technique. The main subject of investigation was how the anions and substrates influence the emerging surface topology during and after the preparation. Regarding HOPG and SiO₂, flat island-like and hemispheric-shaped structures were created. We observed a strong correlation between the electronic properties of the substrate and the analyzed structures, especially in the case of mica where we observed a gradient in the analyzed structures across the surface.     

Stereoisomere Aromastoffe

Zusammenfassung 5-Alkyl-substituierte-Lactone finden sich als aromarelevante Substanzen in tierischen Fetten, aber auch in einigen Früchten. Vor kurzem gelang die erste direkte gaschromatographische Stereodifferenzierung einiger-Lactone an der chiralen Phase Oktakis(3-O-butyryl-2,6-di-O-pentyl)--cyclodextrin [4]. Es wird nun die Enantiomerentrennung der-Lactone bis zu den langkettigen Verbindungen-Trideca-(-C₁₃-)- und-Tetradeca-(-C₁₄-)-lacton aufgezeigt. Über optisch reine Referenzsubstanzen konnte die Elutionsfolge S(I), R(II) der drei wichtigsten aromarelevanten Vertreter dieser-Lactonklasse bestimmt werden. Die Enantiomerenverteilung der C₈-, C₁₀-, C₁₂--Lactone im Wasserdampfdestillat verschiedener Milchprodukte (Milch, Sahne, Butter), in Margarine sowie im Kokosnußfleisch wurde exemplarisch mit Hilfe der HRGC, auch unter Einsatz der multidimensionalen Gaschromatographie (MDGC), untersucht. Es zeigten sich charakteristische, substratspezifische Enantiomerenverteilungen. Die Verteilungsmuster der untersuchten Spiegelbildisomeren aus Kokosnüssen unterschieden sich wesentlich von denen der Milchprodukte.

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Stereoisomeric flavour compoundsXLVII. Direct chirospecific HRGC-analysis of natural -lactones

Summary 5-Alkylated-lactones are well known flavour compounds in animal fats and also some special kinds of fruit. Recently, the first direct stereo-differentiation of chiral-lactones was reported using Oktakis(3-O-butyryl-2,6-di-O-pentyl)--cyclodextrin as the chiral stationary phase [4]. The enantiomeric separation of-lactones up to the long-chain compounds-trideca-(-C_13–) and-tetradeca-(-C_14–)-lactone is demonstrated. By means of optically pure references, the order of elution S(I), R(II) was determined for the important flavour compounds-octa-,-deca-, and-dodecalactone. Analysis of the steam distillate of some dairy products (milk, cream, butter), of margarine and of coconut has been carried out, in order to yield the enantiomeric distribution of C₈-, C₁₀- and C₁₂--lactones by HRGC and multidimensional gas chromatography. Characteristic and product-specific ratios of-lactone enantiomers are detected. The pattern of enantiomeric composition of-octa-,-deca-,-dodecalactone in coconuts differs completely from that found in the dairy products.

     

Comparative molecular profiling of the PPARα/γ activator aleglitazar: PPAR selectivity, activity and interaction with cofactors

Peroxisome proliferator-activated receptors (PPARs) are a family of nuclear hormone receptors that control the expression of genes involved in a variety of physiologic processes, through heterodimerization with retinoid X receptor and complex formation with various cofactors. Drugs or treatment regimens that combine the beneficial effects of PPARα and γ agonism present an attractive therapeutic strategy to reduce cardiovascular risk factors. Aleglitazar is a dual PPARα/γ agonist currently in phase III clinical development for the treatment of patients with type 2 diabetes mellitus who recently experienced an acute coronary event. The potency and efficacy of aleglitazar was evaluated in a head-to-head comparison with other PPARα, γ and δ ligands. A comprehensive, 12-concentration dose-response analysis using a cell-based assay showed aleglitazar to be highly potent, with EC(50) values of 5 nM and 9 nM for PPARα and PPARγ, respectively. Cofactor recruitment profiles confirmed that aleglitazar is a potent and balanced activator of PPARα and γ. The efficacy and potency of aleglitazar are discussed in relation to other dual PPARα/γ agonists, in context with the published X-ray crystal structures of both PPARα and γ.     

Fragmentation and bond strength of airborne diesel soot agglomerates

Background  

The potential of diesel soot aerosol particles to break up into smaller units under mechanical stress was investigated by a direct impaction technique which measures the degree of fragmentation of individual agglomerates vs. impact energy. Diesel aerosol was generated by an idling diesel engine used for passenger vehicles. Both the aerosol emitted directly and aerosol that had undergone additional growth by Brownian coagulation ("aging") was investigated. Optionally a thermo-desoption technique at 280°C was used to remove all high-volatility and the majority of low-volatility HC adsorbates from the aerosol before aging.     

Model based scenario studies to optimize the regional nitrogen balance and reduce leaching of nitrate and sulfate of an agriculturally used water catchment

Oxidation of pyrite by nitrate (autotrophic denitrification) was identified as the main cause for sulfate increase in drinking water wells in an agriculturally used watershed, located in the north of Lower Saxony (Germany). Nitrate, which inducts this microbial catalyzed process, is drained into ground water predominantly from agricultural fertilization. The increase of sulfate in the ground water can only be stopped by reducing nitrate leaching into the ground water. To analyze the negative influence of agricultural fertilization on the quality of ground water different fertilization strategies were deducted for an investigated area of 890 ha. Calculated on the basis of nutrient balance of soil surface, the current average nitrogen balance in the investigated area amounts to 91 kg N ha^-1 a⁻¹. Farm-gate balance of nutrients is a strong indicator for assessing potential nutrient losses caused by leaching. This indicator shows comparable accuracy to the calculated nutrient balance of soil surface which demands, however, much more data input for calculations. Nitrate concentrations in seepage water in 2 m depth layer of the soil from agricultural fields were simulated with the model HERMES for the whole investigated area (agricultural land + forest). The nitrate concentration in seepage water was calculated for the whole area on the basis of farm-gate nutrient balance as an annual average, which amounts to 14.0 mg NO₃–N l⁻¹ (62 mg NO₃ l⁻¹). In order to keep the nitrate concentration of the ground water below the threshold value for drinking water (EU-water directive: 11.3 mg NO₃–N l⁻¹ (50 mg NO₃ l⁻¹) and to limit pyrite oxidation, different scenarios with simulation studies to optimize fertilization measures were developed. Only those scenarios which assured reduction of an average nitrate concentration in the drainage water below 11.3 mg NO₃–N l⁻¹ (50 mg NO₃ l⁻¹) without profit cuts for the farms were analyzed.

Production and Bioactivity of Common Lichen Metabolites as Exemplified by <Emphasis Type="Italic">Heterodea muelleri</Emphasis> (Hampe) Nyl.

Based on results of a former study in 2005, this investigation aimed at quantifying UV- and cold temperature stress-induced changes within the secondary metabolite production of the cultured mycobiont of the lichen Heterodea muelleri (Hampe) Nyl. The chemical profiles of the mycobiont cultures and the lichen thallus were determined by high-performance liquid chromatography (HPLC) and thin layer chromatography (TLC) analyses. The voucher specimen of H. muelleri produced diffractaic acid as a major polyketide and barbatic acid as a satellite compound, whereas the untreated mycobiont did not contain any detectable secondary metabolites. While UV-C stress caused a general increase in substance formation, cold temperature stress resulted in a strong activation of barbatic acid biosynthesis. A further series of experiments focused on the effect of diffractaic and barbatic acids on the growth of the symbiotic photobiont Trebouxia jamesii; usnic acid was similarly tested. Pure substances were obtained from mycobiont cultures by performing preparative TLC. A determined quantity of algae was incubated on BBM plates that contained three different concentrations of the pure lichen metabolites. The growth of the photobionts was monitored over a period of 1 mo to evaluate the impact of each substance on the cultured algae. While diffractaic and usnic acid had no noticeable effect, barbatic acid strongly inhibited algal growth and resulted in cell death.     

PTR-MS assessment of photocatalytic and sorption-based purification of recirculated cabin air during simulated 7-h flights with high passenger density

Four different air purification conditions were established in a simulated 3-row 21-seat section of an aircraft cabin: no air purifier; a photocatalytic oxidation unit with an adsorptive prefilter; a second photocatalytic unit with an adsorptive prefilter; and a two-stage sorption-based air filter (gas-phase absorption and adsorption). The air purifiers placed in the cabin air recirculation system were commercial prototypes developed for use in aircraft cabin systems. The four conditions were established in balanced order on 4 successive days of each of 4 successive weeks during simulated 7-h flights with 17 occupants. Proton-transfer reaction mass spectrometry was used to assess organic gas-phase pollutants and the performance of each air purifier. The concentration of most organic pollutants present in aircraft cabin air was efficiently reduced by all three units. The photocatalytic units were found to incompletely oxidize ethanol released by the wet wipes commonly supplied with airline mealsto produce unacceptably high levels of acetaldehyde and formaldehyde.     

Genetic transformation of auxotrophic mutants of the filamentous yeast Trichosporon cutaneum using homologous and heterologous marker genes

A transformation system for the filamentous yeast Trichosporon cutaneum based on auxotrophic markers is presented and techniques for the induction, isolation and characterization of mutants are described. A number of auxotrophic mutants were isolated and characterized by using biosynthetic precursors and/or inhibitors. A mutant unable to grow in the presence of ornithine could be complemented successfully by spheroplast transformation experiments using the cloned Aspergillus nidulans ornithine transcarbamoylase gene (argB gene) as selection marker with an efficiency of 5-100 transformants per microgram of DNA. In these transformants the heterologous argB gene was present in multiple tandem copies and the transforming DNA was found to remain stable after more than 50 generations in non-selective media. The same mutant could be complemented by a T. cutaneum cosmid gene library and a complementary cosmid was subsequently isolated from this library by a sib-selection strategy. This cosmid transformed T. cutaneum spheroblasts with an efficiency of 50-200 colonies per microgram of DNA. Southern blot analyses were consistent with the view that the transforming sequences became stably integrated into the host genome at the homologous site.     

Measurement techniques for magnetic resonance imaging of fast relaxing nuclei

In this review article, techniques for sodium (²³Na) magnetic resonance imaging (MRI) are presented. These techniques can also be used to image other nuclei with short relaxation times (e.g., ³⁹K, ³⁵Cl, ¹⁷O). Twisted projection imaging, density-adapted 3D projection reconstruction, and 3D cones are preferred because of uniform k-space sampling and ultra-short echo times. Sampling density weighted apodization can be applied if intrinsic filtering is desired. This approach leads to an increased signal-to-noise ratio compared to postfiltered acquisition in cases of short readout durations relative to T ₂ ^* relaxation time. Different MR approaches for anisotropic resolution are presented, which are important for imaging of thin structures such as myocardium, cartilage, and skin. The third part of this review article describes different methods to put more weighting either on the intracellular or the extracellular sodium signal by means of contrast agents, relaxation-weighted imaging, or multiple-quantum filtering.