7-Substituted prostaglandin analogues. A new synthetic approach

Starting from methyl 7-oxo-7-(1-cyclopentene)-heptanoate, a simple synthesis of the methyl esters of 7-oxo- and 7-hydroxy-9,11-dideoxy-PGF ₁ as a model for 7-substituted prostaglandin analogues is described.

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7-Substituierte Prostaglandin-Analoge — ein neuer Syntheseweg

Zusammenfassung Ausgehend von Methyl-7-oxo-7-(1-cyclopenten)-heptanoat wird eine einfache Synthese der Methylester von 7-Oxo- und 7-Hydroxy-9,11-dideoxy-PGF ₁ als Modellverbindungen für 7-substituierte Prostaglandinanaloge beschrieben.

     

Advanced approaches for the characterization of a de novo designed antiparallel coiled coil peptide

We report here an advanced approach for the characterization of the folding pattern of a de novo designed antiparallel coiled coil peptide by high-resolution methods. Incorporation of two fluorescence labels at the C- and N-terminus of the peptide chain as well as modification of two hydrophobic core positions by Phe/[15N,13C]Leu enable the study of the folding characteristics and of distinct amino acid side chain interactions by fluorescence resonance energy transfer (FRET) and NMR spectroscopy. Results of both experiments reveal the antiparallel alignment of the helices and thus prove the design concept. This finding is also supported by molecular dynamics simulations. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in combination with NMR experiments was used for verification of the oligomerization equilibria of the coiled coil peptide.     

Triarylborane ammonia complexes as ideal precursors for arylzinc reagents in asymmetric catalysis

[reaction: see text] The value of arylboranes as precursors for arylzinc reagents in asymmetric catalysis is demonstrated. Kinetic studies on the transmetalation reaction with zinc reagents rationalize the observed differences of three classes of arylboranes in catalytic applications. By using the stable and easily accessible triarylborane ammonia complexes, an array of chiral diarylmethanols in high yield and enantioselectivity was synthesized.     

Über einige neue Bispirane

We have obtained four new bispirane systems in which both spiroatoms are vicinal atoms in cyclopropane or cyclobutane rings and in which the heterocyclic component has the basic structure of 1,4-dioxep-2-ene. We have shown that from two possibilities (bispiran, propellan) the general reaction leads only to a bispiran system. To the bispiran2 exhibiting the highest hyperchromism we ascribed the bispirocoplanar conformation (Fig. 1).

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Mit 3 Abbildungen     

Fluorescence Analysis in Microarray Technology

Fluorescence has been the preferred choice for data quantification in biomedical microarray formats since their earliest days. As much as the formats have grown and evolved over the years, the methods in optical analysis have become ever more sophisticated and complex in order to produce more and better output. This review will provide an insight into the most common methods and the state-of-the-art of all areas in microarray fluorescence analysis. Starting with an overview on microarray formats with a focus on their demands on the readout, the most common and useful organic fluorescent stains are discussed before proceeding on to other approaches; the use of semiconductor nanocrystals (quantum dots), polymer and silica nanoparticles and fluorescent proteins. Ways to enhance the intrinsically low signal on biochips have become increasingly important as they offer a sound approach towards the detection of low concentration sample content. The three main categories are presented: amplification using DNA, enzymes, and dendrimers. As much diversity as on the microarrays themselves can be found at the detection device. Standard optical microarray detectors, and non-standard methods using fluorescence anisotropy, fluorescence lifetime imaging (FLIM) and fluorescence resonance energy transfer (FRET), and their advantages and disadvantages are discussed.     

Assessing weak intramolecular donor-acceptor interactions using 1H-117Sn J-HMQC spectroscopy

It is demonstrated that long-range nJ(1H,117Sn) coupling constants down to 0.3 Hz, can be accurately quantified from non-linear fitting of the sine modulation of the associated 1H-117Sn correlation cross-peak intensities sampled as a function of the heteronuclear antiphase coherence preparation time in the 1H-117Sn J-HMQC pulse sequence. The contribution of additional, undesired modulations is illustrated and assessed using the product operator formalism, and is traced back to contributions that arise from miss-setting of the wandering 180 degrees pulse angle in the constant time period. The power of the method and its use in the characterization of weak intramolecular donor-acceptor interactions are illustrated by the determination of long-range nJ(1H,117Sn) coupling constants of bis[3-(dimethylamino)propyl]tin derivatives, [Me2N(CH2)3]2SnR2 (', R = Me; 3, R = Ph; 4, R = t-Bu). By comparing these with the values found for the corresponding bis(4-methylpentyl)tin derivatives, [Me2CH(CH2)3]2SnR2 (2', R = Me; 3', R = Ph), which lack such interactions, the use of long-range coupling constants to detect intramolecular donor-acceptor interactions is evaluated. It is concluded that nJ(1H,117Sn) couplings up to six bonds through an organic carbon chain can be quantified, whether donor-acceptor interactions are present or not. Furthermore, evidence is presented that, when two scalar coupling pathways co-exist, the pathway involving an intramolecular donor-acceptor interaction can have opposite sign, thus decreasing the overall coupling constant to a value smaller than that actually measured in the absence of a donor-acceptor interaction, where only one coupling pathway is active. There is nevertheless clear numerical value discrimination in the series of compounds investigated between long-range couplings in derivatives without weak intramolecular donor-acceptor interactions and those where such interactions can exist.     

Molecular gradients: an efficient approach for optimizing the surface properties of biomaterials and biochips

A variety of molecular gradients of alkanethiols with the structure HS-(CH(2))(m)-X (m = 15; X = COOH, CH(2)NH(2), or CH(3)) and oligo(ethylene glycol)-terminated alkanethiols with the structures HS-(CH(2))(15)-CO-NH-Eg(n) (n = 2, 4, or 6), HS-(CH(2))(15)-CO-NH-Eg(2)-(CH(2))(2)-NH-CO-(CH(2))(4)-biotin, and HS-(CH(2))(15)-CO-NH-Eg(6)-CH(2)-COOH were prepared on polycrystalline gold films. These gradients were designed to serve as model surfaces for fundamental studies of protein adsorption and immobilization phenomena. Ellipsometry, infrared spectroscopy, and X-ray photoelectron spectroscopy, operating in scanning mode, were used to monitor the layer composition, gradient profiles, tail group conformation, and overall structural quality of the gradient assemblies. The gradient profiles were found to be 4-10 mm wide, and they increased in width with increasing difference in molecular complexity between the thiols used to form the gradient. The oligo(ethylene glycol) thiols are particularly interesting because they can be used to prepare so-called conformational gradients, that is, gradients that display a variation in oligo(ethylene glycol) chain conformation from all trans on the extreme Eg(2,4) sides, via an amorphous-like phase in the mixing regimes, to helical at the extreme Eg(6) sides. We demonstrate herein a series of experiments where the above gradients are used to evaluate nonspecific binding of the plasma protein fibrinogen, and in agreement with previous studies, the highest amounts of nonspecifically bound fibrinogen were observed on all-trans monolayers, that is, on the extreme Eg(2,4) sides. Moreover, gradients between Eg(2) and a biotinylated analogue have been prepared to optimize the conditions for the immobilization of streptavidin. Ellipsometry and infrared spectroscopy reveal high levels of immobilization over a fairly broad range of compositions in the gradient regime, with a maximum between 50 and 60% of the biotinylated analogue in the monolayer. A pI gradient composed of (NH(3)(+)/COO(-))-terminated thiols was also prepared and evaluated with respect to its ability to separate differently charged proteins, pepsin, and lysozyme, on a solid surface.     

Crystal structure, oxidation state and magnetism of La1.2Sr2.4RuO7: a new member of the [A2O][AnBn−1O3n] series of hexagonal perovskites

Single crystals of the new compound La_1.2Sr_2.4RuO₇, an oxide related to the hexagonal perovskites, were grown from a BaCl₂ flux. The structure was solved by single crystal X-ray diffraction. La_1.2Sr_2.4RuO₇ crystallizes in the space group with a=5.760(1) Å and c=18.273(3) Å. It is one of the rare examples of oxides with isolated RuO₆-octahedra. The structure consists of alternating layers of RuO₆-octahedra and trigonal (La,Sr)O₆-prisms. These prisms are capped by one additional oxygen ion, which occupies a distorted position within the (La,Sr)O₆-layers. La_1.2Sr_2.4RuO₇ is the second member of the general [A₂O][A_nB_n−1O_3n] family of hexagonal perovskites with n=2 and the first ruthenate possessing this structure. XANES investigations, bond valence sum calculations and magnetic measurements show that ruthenium takes the oxidation state +5. Although the ruthenium ions have quite long distances, a medium strong antiferromagnetic interaction between these paramagnetic centers was observed.