π‐Facial Selectivity in the Formation of Tricarbonylchromium(0) Complexes of Estra‐1, 3, 5(10), 6‐tetraenes

The preparation of two η⁶‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation.     

Circular dichroism—LXVIII compounds from valerian—XII: On the chiroptical properties of valepotriates and related compounds

The CD of saturated iridoids containing a 2.9-dioxatricyclo[4.3.1.03,7] decan skeleton derived from valepotriates is determined by the acetal chromophore. For the less symmetric ring system of 1,6-anhydro hexapyranoses the sign of this CD is predictable. The vicinal effect for enones and diketones in this series is appreciable. A new rule for the correlation between the CD around 190–205 nm of enol ethers and their absolute conformation is given; the same reasoning is applicable to explain the known rules for cisoid and transoid vinyl cyclo-propanes.     

Seco-aldehydes from didroval tratum

Primary iodides, obtained from didrovaltratum ($\text{1}$) on treatment with hydriodic acid in methanol, are transformed into seco-aldehydes $\text{5}$ and $\text{6}$ in a fragmentation reaction. Both aldehydes very similar to secologanine yield various condensation products with tryptamine under Pictet-Spengler conditions. The relative and absolute configuration of the crucial intermediate $\text{4}$ was secured by X-ray structure analysis.     

On the cube problem of Las Vergnas

We prove a conjecture of Las Vergnas in dimensions d7: The matroid of the d-dimensional cube C ^d has a unique reorientation class. This extends a result of Las Vergnas, Roudneff and Salaün in dimension 4. Moreover, we determine the automorphism group G ^d of the matroid of the d-cube C ^d for arbitrary dimension d, and we discuss its relation to the Coxeter group of C ^d . We introduce matroid facets of the matroid of the d-cube in order to evaluate the order of G ^d . These matroid facets turn out to be arbitrary pairs of parallel subfacets of the cube. We show that the Euclidean automorphism group W ^d is a proper subgroup of the group G ^d of all matroid symmetries of the d-cube by describing genuine matroid symmetries for each Euclidean facet. A main theorem asserts that any one of these matroid symmetries together with the Euclidean Coxeter symmetries generate the full automorphism group G ^d . For the proof of Las Vergnas' conjecture we use essentially these symmetry results together with the fact that the reorientation class of an oriented matroid is determined by the labeled lower rank contractions of the oriented matroid. We also describe the Folkman-Lawrence representation of the vertex figure of the d-cube and a contraction of it. Finally, we apply our method of proof to show a result of Las Vergnas, Roudneff, and Salaün that the matroid of the 24-cell has a unique reorientation class, too.     

Bestimmung des Aluminiums in niedrig- und hochlegierten Stählen,in Erzen und Schlacken durch Atomabsorption

The measurement is carried out of aqueous solutions. The burner is supplied with a mixture of acetylene and nitrous oxide. Interfering influences by acid and iron concentrations of the sample solution as well as by organic solvents are shown. The standard deviation is ± 0.001%. The agreement with conventional analysis methods is very good. By this procedure a rapid and safe determination of aluminium will be possible.     

Adaption of a fragment analysis technique to an automated high-throughput multicapillary electrophoresis device for the precise qualitative and quantitative characterization of microbial communities

The analysis of microbial communities is of increasing importance in life sciences and bioengineering. Traditional techniques of investigations like culture or cloning methods suffer from many disadvantages. They are unable to give a complete qualitative and quantitative view of the total amount of microorganisms themselves, their interactions among each other and with their environment. Obviously, the determination of static or dynamic balances among microorganisms is of fast growing interest. The generation of species specific and fluorescently labeled 16S ribosomal DNA (rDNA) fragments by the terminal restriction fragment length polymorphism (T-RFLP) technique is a suitable tool to overcome the problems other methods have. For the separation of these fragments polyacrylamide gel sequencers are preferred as compared to capillary sequencers using linear polymers until now because of their higher electrophoretic resolution and therefore sizing accuracy. But modern capillary sequencers, especially multicapillary sequencers, offer an advanced grade of automation and an increased throughput necessary for the investigation of complex communities in long-time studies. Therefore, we adapted a T-RFLP technique to an automated high-throughput multicapillary electrophoresis device (ABI 3100 Genetic Analysis) with regard to a precise qualitative and quantitative characterization of microbial communities.     

Solid-State Photocyclodimerization of 1-Thiocoumarin (= 2H-1-Benzothiopyran-2-one)

Irradiation (λ > 390 nm) of 2H-1-benzothiopyran-2-one ( 1 ) in the solid state affords selectively 6aα,6bα,12bα,12cα -tetrahydrocyclobuta[1,2-c:4,3-c′]bis[1]benzothiopyran -6,7-dione ( 2 ), the head-to-head (HH) cis-cisoid-cis-dimer, while irradiation of 1 in the solid state using shorter wavelengths (λ > 340 nm) affords a mixture of all four cis-fused tricyclic dimers 2 – 5 . These results represent a novel wavelength effect in solid-state photochemistry.     

TDPAC studies on181Hf implanted into diamond

¹⁸¹Hf ions were implanted at (900±10)K into (100) cleaved single crystal diamonds. After subsequent annealing residence site parameters were determined for the implanted ions employing the (133 keV)–(482 keV) cascade in¹⁸¹Ta in TDPAC technique. Fractions of 5% each were determined that experience axially symmetric electric field gradients (EFG) V_zz(1)=5.5×10¹⁷ V cm^–2 and V_zz(2)=9.6×10¹⁷ V cm^–2, respectively. The bulk of the ions are strongly disturbed by still higher electric field gradients.     

Light‐Driven Coordination‐Induced Spin‐State Switching: Rational Design of Photodissociable Ligands

The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin‐state switching to isolated molecules at room temperature (light‐driven coordination‐induced spin‐state switching, or LD‐CISSS). Whereas bistability and hysteresis in conventional spin‐crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD‐CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel–porphyrin as the transition‐metal complex and 3‐phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni–porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72 % paramagnetic Ni–porphyrin after irradiation at 365 nm, 32 % paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD‐CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light‐controlled magnetic levitation are conceivable applications.     

From Ion‐Like Ethylzinc Aluminates to [EtZn(arene)2]+[Al(ORF)4]− Salts

Attempts to prepare previously unknown simple and very Lewis acidic [RZn]⁺[Al(OR^F)₄]^? salts from ZnR₂, AlR₃, and HO?R^F delivered the ion‐like RZn(Al(OR^F)₄) (R=Me, Et; R^F=C(CF₃)₃) with a coordinated counterion, but never the ionic compound. Increasing the steric bulk in RZn⁺ to R=CH₂CMe₃, CH₂SiMe₃, or Cp*, thus attempting to induce ionization, failed and led only to reaction mixtures including anion decomposition. However, ionization of the ion‐like EtZn(Al(OR^F)₄) compound with arenes yielded the [EtZn(arene)₂]⁺[Al(OR^F)₄]^? salts with arene=toluene, mesitylene, or o‐difluorobenzene (o‐DFB)/toluene. In contrast to the ion‐like EtZn(η³‐C₆H₆)(CHB₁₁Cl₁₁), which co‐crystallizes with one benzene molecule, the less coordinating nature of the [Al(OR^F)₄]^? anion allowed the ionization and preparation of the purely organometallic [EtZn(arene)₂]⁺ cation. These stable materials have further applications as, for example, initiators of isobutene polymerization. DFT calculations to compare the Lewis acidities of the zinc cations to those of a large number of organometallic cations were performed on the basis of fluoride ion affinity. The complexation energetics of EtZn⁺ with arenes and THF was assessed and related to the experiments.