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.

     

Adsorption of dissolved organic matter onto activated carbon--the influence of temperature, absorption wavelength, and molecular size

In this study, batch and column adsorption experiments with granular activated carbon (GAC) were carried out for removing dissolved organic matter (DOM) of a pond water at different water temperatures (5, 20, and 35 °C). The water was characterized before and after the adsorption step using UV/VIS spectroscopy and size-exclusion chromatography (SEC) combined with diode array detection (DAD). DOM breakthrough of GAC filters has been found to be slower at higher water temperatures, the DOM removal being most effective at 35 °C. UV/VIS spectra and SEC chromatograms of water samples treated at different water temperatures indicate that an increase in temperature especially supports the adsorption of small DOM molecules as well as molecules absorbing at higher wavelengths, specifying aromatic structures of DOM. SEC-DAD has been demonstrated to be an efficient method for characterizing DOM of natural waters and for detecting relative changes of DOM during the water treatment process.     

Breakthrough behavior of granular ferric hydroxide (GFH) fixed-bed adsorption filters: modeling and experimental approaches

Breakthrough curves (BTC) for the adsorption of arsenate and salicylic acid onto granulated ferric hydroxide (GFH) in fixed-bed adsorbers were experimentally determined and modeled using the homogeneous surface diffusion model (HSDM). The input parameters for the HSDM, the Freundlich isotherm constants and mass transfer coefficients for film and surface diffusion, were experimentally determined. The BTC for salicylic acid revealed a shape typical for trace organic compound adsorption onto activated carbon, and model results agreed well with the experimental curves. Unlike salicylic acid, arsenate BTCs showed a non-ideal shape with a leveling off at c/c0 approximately 0.6. Model results based on the experimentally derived parameters over-predicted the point of arsenic breakthrough for all simulated curves, lab-scale or full-scale, and were unable to catch the shape of the curve. The use of a much lower surface diffusion coefficient D(S) for modeling led to an improved fit of the later stages of the BTC shape, pointing on a time-dependent D(S). The mechanism for this time dependence is still unknown. Surface precipitation was discussed as one possible removal mechanism for arsenate besides pure adsorption interfering the determination of Freundlich constants and D(S). Rapid small-scale column tests (RSSCT) proved to be a powerful experimental alternative to the modeling procedure for arsenic.     

A Spider's Fang: How to Design an Injection Needle Using Chitin‐Based Composite Material

Spiders mainly feed on insects. This means that their fangs, which are used to inject venom into the prey, have to puncture the insect cuticle that is essentially made of the same material, a chitin‐protein composite, as the fangs themselves. Here a series of structural modifications in the fangs of the wandering spider Cupiennius salei are reported, including texture variation in chitin orientation and arrangement, gradients in protein composition, and selective incorporation of metal ions (Zn and Ca) and halogens (Cl). These modifications influence the mechanical properties of the fang in a graded manner from tip to base, allowing it to perform as a multi‐use injection needle that can break through insect cuticle, which is made of a chitin composite as well.     

Monocrystalline spinel nanotube fabrication based on the Kirkendall effect

There is a deep interest in methods to fabricate hollow nanocrystals for potential application as high-efficiency catalysts or drug-delivery agents. Tubular one-dimensional nanocrystals have been prepared for a wide variety of materials, including semiconductors, metals, ferroelectrics and magnetite. They can be produced by rolling up layered materials or via an axial growth in a rolled-up form, coating pores in templates or by eliminating the core of a core-shell nanowire. The Kirkendall effect, a classical phenomenon in metallurgy, was recently applied to explain the formation of hollow spherical nanocrystals. Although the experimental demonstration and theoretical treatment mainly concern binary compounds and planar interfaces or nanoscale spherical interfaces, the fabrication route provided by the Kirkendall effect should be generic, and should also work for high-aspect-ratio hollow cylinders (that is, nanotubes) or even more complex superstructures. In this letter, we report, for the first time, on ultra-long single-crystal ZnAl(2)O(4) spinel nanotubes (total diameter: approximately 40 nm, wall thickness: approximately 10 nm) fabricated through a spinel-forming interfacial solid-state reaction of core-shell ZnO-Al(2)O(3) nanowires involving the Kirkendall effect. Our results simultaneously represent an extension of applying the Kirkendall effect in fabricating hollow nano-objects from zero-dimensional to multidimensional, and from binary to ternary systems.     

Discrimination of single mutations in cancer-related gene fragments with a surface acoustic wave sensor

Here, we report on using a surface acoustic wave sensor for the highly sensitive and accurate detection of individual point mutations in cancer-related gene DNA fragments from single injections. Our sensor measures both the mass and viscosity signals and, thus, allows discriminating between mass effects resulting from hybridization of short DNA strands and viscosity effects due to increasing amounts of DNA deposited on the sensor. Single nucleotide exchanges or deletions are distinguished reliably and with exceeding simplicity from the wild-type sequences, on the basis of differences in their dissociation or association rates starting at low nanomolar concentrations. Mutant oligonucleotides were identified immediately from viewing the recorded signal and without further processing of the data. Multiple repeated binding cycles were possible over days without affecting sensitivity. To achieve signal amplification, our new bioassay can also apply multiple hybridization steps based on sandwich hybridizations. Kinetic evaluations gave insight into the physicochemical properties of the fragments used that explain the differences in their binding processes.     

Fixierung von β-Cyclodextrinderivaten auf Polyesterfasermaterial

Fixation of β-Cyclodextrinderivatives on Polyester Fibres . Syntheses of derivatives of β-cyclodextrin are described which aimed at a partial substitution of OH-groups by hydrophobic moieties. According to such substitution it can be envisaged that those derivatives are applicable to polyester fabric treatment by conventional dispersion dyeing methods. By applying such textile finishing agents it can be expected to impart hydrophilic properties to the fabric due to unsubstituted OH-groups of the cyclodextrin but still remaining complexation ability due to the cyclodextrin inner torus. The success of anchoring of the derivatives onto polyester and methods for evidence of cyclodextrin derivatives on the polyester surface (iodine incorporation, fluorescence activity of dyestuffs included, FT-IR-spectroscopy) are given.