Perquinolines A–C: Unprecedented Bacterial Tetrahydroisoquinolines Involving an Intriguing Biosynthesis

Metabolic profiling of Streptomyces sp. IB2014/016‐6 led to the identification of three new tetrahydroisoquinoline natural products, perquinolines A–C ( 1 – 3 ). Labelled precursor feeding studies and the cloning of the pqr biosynthetic gene cluster revealed that 1 – 3 are assembled by the action of several unusual enzymes. The biosynthesis starts with the condensation of succinyl‐CoA and l ‐phenylalanine catalyzed by the amino‐7‐oxononanoate synthase‐like enzyme PqrA, representing rare chemistry in natural product assembly. The second condensation and cyclization events are conducted by PqrG, an enzyme resembling an acyl‐CoA ligase. Last, ATP‐grasp RimK‐type ligase PqrI completes the biosynthesis by transferring a γ‐aminobutyric acid or β‐alanine moiety. The discovered pathway represents a new route for assembling the tetrahydroisoquinoline cores of natural products.     

Catalytic Formal [2π+2σ] Cycloaddition of Aldehydes with Bicyclobutanes: Expedient Access to Polysubstituted 2-Oxabicyclo[2.1.1]hexanes

Synthesis of bicyclic scaffolds has attracted tremendous attention because they are playing an important role as saturated bioisosteres of benzenoids in modern drug discovery. Here, we report a BF₃-catalyzed [2π+2σ] cycloaddition of aldehydes with bicyclo[1.1.0]butanes (BCBs) to access polysubstituted 2-oxabicyclo[2.1.1]hexanes. A new kind of BCB containing an acyl pyrazole group was invented, which not only significantly facilitates the reactions, but can also serve as a handle for diverse downstream transformations. Furthermore, aryl and vinyl epoxides can also be utilized as substrates which undergo cycloaddition with BCBs after in situ rearrangement to aldehydes. We anticipate that our results will promote access to challenging sp³-rich bicyclic frameworks and the exploration of BCB-based cycloaddition chemistry.     

Allosteric and Chelate Cooperativity in Divalent Crown Ether/Ammonium Complexes with Strong Binding Enhancement

A thorough thermodynamic analysis by isothermal titration calorimetry of allosteric and chelate cooperativity effects in divalent crown ether/ammonium complexes is combined with DFT calculations including implicit solvent on the one hand and large‐scale molecular dynamics simulations with explicit solvent molecules on the other. The complexes studied exhibit binding constants up to 2×10⁶ m ^?1 with large multivalent binding enhancements and thus strong chelate cooperativity effects. Slight structural changes in the spacers, that is, the exchange of two ether oxygen atoms by two isoelectronic methylene groups, cause significantly stronger binding and substantially increased chelate cooperativity. The analysis is complemented by the examination of solvent effects and allosteric cooperativity. Such a detailed understanding of the binding processes will help to efficiently design and construct larger supramolecular architectures with multiple multivalent building blocks.     

Development and applications of a new IR-radiation heating in thermal desorption mass spectrometry TDMS

 An infra-red radiation heating was developed for applications in thermal desorption mass spectrometry (TDMS), avoiding disadvantages of the various types of sample heatings used so far. In a first application D₂-desorption profiles were determined from deuterium doped vanadium samples. Thereby a linear relationship could be found between the amount of detected deuterium and known D-concentrations. D₂-desorption profiles from D doped Si showed 2 maxima corresponding to different desorption processes. In another application characteristic TD mass spectra were obtained for a solvent agent of an adhesive. The further investigation of the desorption behaviour of a specific fragment yielded a relationship between the detected amount of this species and the adhesive strengths of polycarbonate foils. Received: 19 September 1996/Revised: 9 January 1997/Accepted: 14 January 1997     

Novel low‐loss waveguide delay lines using Vernier ring resonators for on‐chip multi‐λ microwave photonic signal processors

In this paper, novel photonic delay lines (DLs) using Vernier/non‐identical ring resonators (VRRs) are proposed and demonstrated, which are capable of simultaneous generation of multiple different delays at different wavelengths (frequencies). The simple device architectures and full reconfigurability allow the DLs to be integrated with other functional building blocks in photonic integrated circuits to realize on‐chip, complex multi‐λ microwave photonic signal processors with reduced system complexity. To prove the concept, DLs using VRRs in cascaded and coupled configurations have been fabricated in TriPleX^TM waveguide technology, which enables a very low delay‐induced loss of approximately 0.18 dB/100 ps. The fabricated DLs demonstrated simultaneous generation of four incremental delays, where a maximum incremental step of 550 ps and a corresponding top delay of 1650 ps were measured for a bandwidth up to 1 GHz. To our knowledge, this is the first report on VRRs for delay generation functionalities.