Copper and Silver Carbene Complexes without Heteroatom‐Stabilization: Structure,Spectroscopy, and Relativistic Effects

Salts of a copper and a silver carbene complex were prepared from dimesityl diazomethane, made possible by the steric shielding of the N‐heterocyclic carbene (NHC) ancillary ligand IPr**. The mint‐green complex [IPr**Ag=CMes₂]⁺[NTf₂]^? is the first isolated silver carbene complex without heteroatom donor substituents. Single‐crystal X‐ray diffraction provides evidence for a predominant carbenoid character, and supports the postulation of such reactive species as intermediates in silver‐catalyzed C? H activation reactions. The greenish yellow copper carbene complex [IPr**Cu=CMes₂]⁺[NTf₂]^? has spectroscopic properties in between the isostructural silver complex and the already reported emerald green gold carbene complex. A comparison in the Group 11 series indicates that relativistic effects are responsible for the strong σ bond and the significant π back‐bonding in the gold carbene moiety.     

12C+12C fusion reactions near the Gamow energy

The fusion reactions 12C(12C,alpha)20Ne and 12C(12C,p)23Na have been studied from E=2.10 to 4.75 MeV by gamma-ray spectroscopy using a C target with ultralow hydrogen contamination. The deduced astrophysical S(E)* factor exhibits new resonances at E< or =3.0 MeV, in particular, a strong resonance at E=2.14 MeV, which lies at the high-energy tail of the Gamow peak. The resonance increases the present nonresonant reaction rate of the alpha channel by a factor of 5 near T=8x10(8) K. Because of the resonance structure, extrapolation to the Gamow energy EG=1.5 MeV is quite uncertain. An experimental approach based on an underground accelerator placed in a salt mine in combination with a high efficiency detection setup could provide data over the full EG energy range.     

Mikrochemie

Ohne Zusammenfassung     

Iterative algorithms for part grouping and loading in cellular reconfigurable manufacturing systems

A reconfigurable manufacturing system (RMS), one of state-of-the-art manufacturing system technologies, is the one designed at the outset for rapid changes in its hardware and software components in order to quickly adjust its production capacity and functionality in response to market or system changes. In this study, we consider a cellular RMS with multiple reconfigurable machining cells (RMCs), each of which has numerical control machines, a setup station, and an automatic material handling and storage system. Each machine within the RMC has an automatic tool changer and a tool magazine of a limited capacity. Two important operational problems, part grouping and loading, are considered in this study. Part grouping is the problem of allocating parts to RMCs, and loading is the problem of allocating operations and their cutting tools to machines within the RMC. An integer programming model is suggested to represent the two problems at the same time for the objective of balancing the workloads assigned to machines. Then, due to the complexity of the problem, we suggest two iterative algorithms in which the two problems are solved repeatedly until a solution is obtained. Computational experiments were done on various test instances and the results are reported.     

The C-Glycosyltransferase UrdGT2 is unselective toward d- and l-configured nucleotide-bound rhodinoses

UrdGT2 is a d-olivosyltransferase from the metabolic pathway of urdamycin A, an angucycline antitumor and antimicrobial drug. The remarkable feature of this biocatalyst is its ability to set up C-glycosidic bonds. Using an in vivo system suitable to deliver the trideoxysugar rhodinose in both d- and l- configuration we could verify that both have been accepted as substrates and attached to the urdamycin polyketide backbone via a C-glycosidic bond. Regardless of the stereochemistry, these C-glycosides served as acceptor for a subsequent glycosylation step to yield the novel urdamycins R and S with di-rhodinosyl side chains at C-9 of the polyketide moiety.     

Linearly polarised photon beams at ELSA and measurement of the beam asymmetry in \pi^{0}_{} photoproduction off the proton

At the electron accelerator ELSA a linearly polarised tagged photon beam is produced by coherent bremsstrahlung off a diamond crystal. Orientation and energy range of the linear polarisation can be deliberately chosen by accurate positioning of the crystal with a goniometer. The degree of polarisation is determined by the form of the scattered electron spectrum. Good agreement between experiment and expectations on the basis of the experimental conditions is obtained. Polarisation degrees of % are typically achieved at half of the primary electron energy. The determination of is confirmed by measuring the beam asymmetry, , in photoproduction and by a comparison of the results to independent measurements using laser backscattering.     

Biosynthesis of the orthosomycin antibiotic avilamycin A: deductions from the molecular analysis of the avi biosynthetic gene cluster of Streptomyces viridochromogenes Tü57 and production of new antibiotics.

Background: Streptomyces viridochromogenes Tü57 is the producer of avilamycin A. The antibiotic consists of a heptasaccharide side chain and a polyketide-derived dichloroisoeverninic acid as aglycone. Molecular cloning and characterization of the genes governing the avilamycin A biosynthesis is of major interest as this information might set the direction for the development of new antimicrobial agents.Results: A 60-kb section of the S. viridochromogenes Tü57 chromosome containing genes involved in avilamycin biosynthesis was sequenced. Analysis of the DNA sequence revealed 54 open reading frames. Based on the putative function of the gene products a model for avilamycin biosynthesis is proposed. Inactivation of aviG4 and aviH, encoding a methyltransferase and a halogenase, respectively, prevented the mutant strains from producing the complete dichloroisoeverninic acid moiety resulting in the accumulation of new antibiotics named gavibamycins.Conclusions: The avilamycin A biosynthetic gene cluster represents an interesting system to study the formation and attachment of unusual deoxysugars. Several enzymes putatively responsible for specific steps of this pathway could be assigned. Two genes encoding enzymes involved in post-PKS tailoring reactions were deleted allowing the production of new analogues of avilamycin A.