Biosynthesis of Indole Diterpene Lolitrems: Radical‐Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.     

Module-based assembly of copper(II) chloranilate compounds: syntheses, crystal structures, and magnetic properties of [[Cu(2)(CA)(terpy)(2)][Cu(CA)(2)]](n)() and [[Cu(2)(CA)(terpy)(2)(dmso)(2)][Cu(CA)(2)(dmso)(2)](EtOH)](n)(H(2)CA = chloranilic acid, terpy = 2,2':6',2' '-terpyridine, dmso = dimethyl sulfoxide)

Two new copper(II) compounds of chloranilate and 2,2':6',2' '-terpyridine have been synthesized, and the structures have been solved by the single-crystal X-ray diffraction method. The crystal structure of [[Cu(2)(CA)(terpy)(2)][Cu(CA)(2)]](n)(1), where H(2)CA = chloranilic acid and terpy = 2,2':6',2' '-terpyridine, consists of two modules, the dimer unit [Cu(2)(CA)(terpy)(2)](2+) and the anionic mononuclear unit [Cu(CA)(2)](2)(-), forming an alternated chain. The chain is stabilized by semicoordinating and additional but efficient secondary bonding interactions. The crystal structure of [[Cu(2)(CA)(terpy)(2)(dmso)(2)][Cu(CA)(2)(dmso)(2)](EtOH)](n)(2), where dmso = dimethyl sulfoxide, consists of solvent molecules and two discrete modules, the dimer unit [Cu(2)(CA)(terpy)(2)(dmso)(2)](2+) and the anionic mononuclear unit [Cu(CA)(2)(dmso)(2)](2)(-). The dimer units form a layer by secondary bonding interactions, and the monomer units and ethanol molecules are introduced between the layers. The magnetic properties of 1 and 2 have been investigated in the temperature range 2.0-300 K. A weak ferromagnetic interaction was observed in 1, J(a) = 2.36 cm(-)(1) and zJ(b) = -0.68 cm(-)(1) while no exchange coupling was observed in 2.     

Classical in-plane negative magnetoresistance and quantum positive magnetoresistance in undoped InSb thin films on GaAs (1 0 0) substrates

Magnetoresistance (MR) effects have been investigated in perpendicular and parallel magnetic fields at 300, 80 K and liquid He temperatures for undoped InSb thin films 0.1–2.3 μm thick grown on GaAs(1 0 0) substrates by MBE. At high temperatures, the intrinsic carriers show the parabolic negative MR observable only in magnetic fields parallel to the film. The skipping-orbit effect due to surface boundary scattering in the classical orbits in the plane vertical to the film has been argued to be responsible for the negative MR. At low temperatures (T=80 K), the transport is dominated by the two-dimensional (2D) electrons in the accumulation layers at the InSb/GaAs(1 0 0) hetero interface; MR is positive and shows a logarithmic increase with anisotropy between parallel and perpendicular field orientation, arising from the 2D weak anti-localization (WAL) that reflects the interplay between the spin-Zeeman effect and strong spin–orbit interaction caused by the asymmetric potential at the interface (Rashba term). The zero-field spin splitting energy of Δ₀13 meV, the electron effective mass of m^*0.10m₀ seven times of the band edge mass in bulk InSb and the effective g-factor of |g^*|15 in the accumulation layer have been inferred from fits of MR for the 0.1 μm thick film to the 2D WL theory.     

Photon number squeezing of ultrabroadband laser pulses generated by microstructure fibers

To the best of our knowledge, we demonstrate for the first time the generation of photon number squeezing by spectral filtering for ultrabroadband light generated by microstructure fibers at 800 nm. A maximum squeezing of 4.6 dB is observed, corresponding to 10.3 dB after correcting for detection losses. We numerically analyzed the quantum dynamics of ultrashort laser pulse propagation through optical fibers by solving a nonlinear quantum Schr?dinger equation that included Raman scattering, especially for the quantum correlation of photon number fluctuation among frequency modes in broadband pulses.     

Optical interconnection between different spatial modes using double phase conjugate mirror with polarization alignment system

We propose a fundamental interconnection method using a polarization alignment system for waveguides having different spatial modes. In addition, as an example for the verification of the fundamental operation, we demonstrate an interconnection between a photonic crystal fiber and a laser that have obviously different spatial modes. The polarization alignment system operates synergistically with a self-written waveguide formed with a double phaseconjugate mirror. This technique enables us to interconnect a photonic crystal fiber with a laser source without complicated and time-consuming optical alignment. In this method, although it is not necessary to perform an external control for interconnection, the waveguide most suitable for connection is formed autonomously in a Sn₂P₂S₆:Sb crystal developed for this purpose. There was a marked reduction in the polarization dependence of coupling efficiency, compared with that observed using a stand-alone double phase-conjugate mirror.     

Quantitative T(1)(ρ) imaging using phase cycling for B0 and B1 field inhomogeneity compensation

T_1ρ imaging is useful in a number of clinical applications. T_1ρ preparation methods, however, are sensitive to non-uniformities of the B₀ magnetic field and the B₁ RF field. These common system imperfections can result in image artifacts and quantification errors in T_1ρ imaging. We report on a phase-cycling method which can eliminate B₁ RF inhomogeneity effects in T_1ρ imaging. This method does not only correct for image artifacts but also for T_2ρ contamination caused by B₁ RF inhomogeneity. The presence of B₀ magnetic field inhomogeneity can compromise the effectiveness of this method for B₁ RF inhomogeneity correction. We demonstrate that, by combining the spin-locking scheme reported by Dixon et al. (Myocardial suppression in vivo by spin locking with composite pulses. Magn Reson Med 1996; 36:90-94) with phase cycling, we can simultaneously correct B₀ magnetic field inhomogeneity effects and B₁ RF inhomogeneity effects in T_1ρ imaging. Phantom and in vivo data sets are used to demonstrate the proposed methods and to compare them with other existing T_1ρ preparation methods.     

A system for measuring absolute frequencies of up to 4.25 THz using a Josephson point contact

A system for measuring the absolute frequency of a far-infrared (FIR) laser is described. Josephson point contacts have been utilized in the system as a frequency harmonic mixer connecting microwaves and optically pumped CH₃OH laser lines. The Josephson point contacts are capable of generating beat signals of 90 GHz microwaves and FIR waves of up to 4.25 THz. To measure the frequency of the beat signals from the Josephson junction with a frequency counter, tracking oscillators have been developed, which tracks the beat signals by phase locking and regenerate clean signals for frequency counting. It is shown that the absolute frequency can be measured to an accuracy of about 100 Hz by using the tracking oscillators.     

Relation between Hall-magnetohydrodynamics and the kinetic Alfvén wave

Effects of a finite ion temperature on the Hall magnetohydrodynamics (MHD), which breaks down for a finite ion temperature, are clarified in terms of a rigorous three-field kinetic dispersion relation. The MHD mode equation becomes anisotropic with respect to the ion pressure because of the double adiabaticity in ion dynamics.