Preparation of chiral 5-deazaflavin derivatives and their asymmetric reduction of ethyl benzoylformate

1,5-Dihydro-5-deazaflavin derivatives possessing a chiral substituent at N(3) position were synthesized, with which moderate asymmetric induction was observed in the reduction of ethyl benzoylformate.     

Beta-1,3-glucan polysaccharide (schizophyllan) acting as a one-dimensional host for creating supramolecular dye assemblies

We have demonstrated that one-dimensional supramolecular dye assemblies with a uniform diameter can be created by utilizing schizophyllan (SPG) as a one-dimensional host. In the supramolecular nanofibers, the dye molecules are assembled into the different aggregation modes depending on the preparation procedures. The findings establish that SPG is useful for creating the supramolecular nanofibers, where temporal superstructures can be stabilized by the SPG-specific helical higher-order structure. [structure: see text].     

Modified alpha-beta chimeric oligoDNA bearing a multi-conjugate of 2,2-bis(hydroxymethyl)propionic acid-anthraquinone-polyamine exhibited improved and stereo-nonspecific triplex-forming ability

Novel alpha-beta chimeric oligonucleotides bearing a propionic acid derivative of an anthraquinone-polyamine conjugate in the "linker" region sequence-specifically formed a substantially stable alternate-stranded triplex with dsDNA almost regardless of the stereochemistry of the derivative.     

An Unprecedented Cyclization Mechanism in the Biosynthesis of Carbazole Alkaloids in Streptomyces

Carquinostatin A (CQS), a potent neuroprotective substance, is a unique carbazole alkaloid with both an ortho‐quinone function and an isoprenoid moiety. We identified the entire gene cluster responsible for CQS biosynthesis in Streptomyces exfoliatus through heterologous production of CQS and gene deletion. Biochemical characterization of seven CQS biosynthetic gene products (CqsB1–7) established the total biosynthetic pathway of CQS. Reconstitution of CqsB1 and CqsB2 showed that the synthesis of the carbazole skeleton involves CqsB1‐catalyzed decarboxylative condensation of an α‐hydroxyl‐β‐keto acid intermediate with 3‐hydroxybutyryl‐ACP followed by CqsB2‐catalyzed oxidative cyclization. Based on crystal structures and mutagenesis‐based biochemical assays, a detailed mechanism for the unique deprotonation‐initiated cyclization catalyzed by CqsB2 is proposed. Finally, analysis of the substrate specificity of the biosynthetic enzymes led to the production of novel carbazoles.     

An Unusual Skeletal Rearrangement in the Biosynthesis of the Sesquiterpene Trichobrasilenol from Trichoderma

The skeletons of some classes of terpenoids are unusual in that they contain a larger number of Me groups (or their biosynthetic equivalents such as olefinic methylene groups, hydroxymethyl groups, aldehydes, or carboxylic acids and their derivatives) than provided by their oligoprenyl diphosphate precursor. This is sometimes the result of an oxidative ring‐opening reaction at a terpene‐cyclase‐derived molecule containing the regular number of Me group equivalents, as observed for picrotoxan sesquiterpenes. In this study a sesquiterpene cyclase from Trichoderma spp. is described that can convert farnesyl diphosphate (FPP) directly via a remarkable skeletal rearrangement into trichobrasilenol, a new brasilane sesquiterpene with one additional Me group equivalent compared to FPP. A mechanistic hypothesis for the formation of the brasilane skeleton is supported by extensive isotopic labelling studies.     

Efficient and low-noise single-photon detection in 1550 nm communication band by frequency upconversion in periodically poled LiNbO3 waveguides

We demonstrate 1500 nm band single-photon detection with low dark-count noise and a potentially high efficiency, which may allow long distance and high-bit-rate quantum key distribution. By developing frequency upconversion devices based on periodically poled lithium niobate waveguides, which are specifically designed to use a pump wavelength longer than that of communication-band photons, we completely eliminate the dark-count noise caused by parasitic nonlinear processes in the waveguide. We observed an internal conversion efficiency as high as 40% and demonstrated scaling down to the single photon level while maintaining a background dark-count rate of 10(2)s(-1).     

X-ray Crystallographic Observation of Chiral Transformations within a Metal–Peptide Pore

Porous metal complexes enable single-crystal X-ray crystallographic observation of included guests or reaction intermediates through simple soaking with the guests/substrates. Previous studies on this technique have often encountered difficulties in the observation of chiral structures because the host frameworks had no chirality. We synthesized a new metal–peptide porous complex through a folding-and-assembly strategy and utilized the chiral pore for trapping chiral guests. Chiral alcohols and ketones were successfully included within the pore. Crystallographic analyses clearly revealed not only their chemical structures but also chiral transformation events within the pore such as fixed conformations or an unstable hemiacetal formation.     

In situ observation of formation of misfit dislocations in pseudomorphic monolayer overgrowth of metals and non-metals

Epitaxial overgrowth in cases of deposit and substrate combinations of PbSe/PbS, Au/Pd and Pd/Au were observed in situ in an electron microscope. It was found that the growth proceeds with the very characteristic features of monolayer overgrowth as implied by the theory of Frank and Van der Merwe; no indication of nucleation was observed and the formation of misfit dislocations was noticed over the whole area of films at certain critical thicknesses of the overgrowths. Points were noted which distinguish the monolayer overgrowth from the case where misfit dislocations are introduced in nucleated islands, to which Matthews has counted the growth processes in these combinations. The importance of climb motion as well as slip motion was stressed as the mechanism of introduction of misfit dislocations. Some results of electron diffraction and electron microscopy of films prepared in separate evaporation units were also quoted. These were to examine the relation between misfit dislocation density and mean lattice parameter and the effect of degree of vacuum on the growth mode and to indicate that the same growth mode takes place for some other combinations of IV–VI compounds, SnTe/PbSe, PbTe/PbS and PbTe/PbSe.