Chemical Interactions of Cryptic Actinomycete Metabolite 5‐Alkyl‐1,2,3,4‐tetrahydroquinolines through Aggregate Formation

Organisms often produce secondary metabolites as a mixture of biosynthetically related congeners. However, why are metabolites with minor chemical variations produced simultaneously? 5‐Alkyl‐1,2,3,4‐tetrahydroquinolines (5aTHQs) are small, lipophilic metabolites produced by Streptomyces nigrescens HEK616 when cultured with Tsukamurella pulmonis TP‐B0596. A mixture of 5aTHQs forms aggregates that show enhanced membrane affinity and biological activity. The ability to form aggregates and membrane‐binding activity is regulated by the length of the alkyl chains. Aggregates with long alkyl chains were too stable to fuse with lipid membranes. However, if inactive 5aTHQ congener was mixed with active congener, the mixture showed increased membrane affinity, enabling cellular entry and biological activity. Therefore, it is shown that sloppiness in a biosynthetic pathway, by which minor structural variations can be produced, is functionally rational, as the metabolites show synergistic action.     

Fourier domain optical coherence tomography using optical demultiplexers imaging at 60,000,000 lines/s

We describe high-speed Fourier domain optical coherence tomography (OCT) using optical demultiplexers (ODs) for spectral dispersion. The OD enables separation of a narrow spectral band of 14 GHz (0.11 nm) from a broadband incident light at 256 different frequencies in 25.0 GHz intervals centered at 192.2 THz (1559.8 nm). OCT imaging of 60,000,000 axial scans per second was achieved through parallel signal acquisition using 256 balanced photoreceivers to simultaneously detect all the output signals from the ODs in a Fourier domain OCT system. OCT imaging at a 16 kHz frame rate, 1100 A-lines per frame, 3 mm depth range, and 23 microm resolution was demonstrated using a resonant scanner for lateral scanning.     

Catalytic decomposition of trichloroethylene over Pt-/Ni-catalyst under microwave heating

Microwave (MW)-activated catalytic reactor system was studied and the results were compared with that of a conventional system based on the thermal activation method. Trichloroethylene (TCE) was decomposed under various MW-powers supply. Results showed that there is an optimum film thickness that was loaded on supports in MW heating system. The threshold may be within 1-3 μm. Lower temperature cannot activate the catalyst, while higher temperature results in carbon deposition and catalyst deactivation. This means that the dechlorination reaction needs to fix an optimum film MW-power supply in order to avoid the deposition of carbon on the surface of the active phase. MW-activated system is also worth compensating the conventional system in VOCs decomposition reaction.     

Quantitative analysis of optical power budget of bismuth oxide-based erbium-doped fiber

We investigated optical power budget of Bi₂O₃-based erbium-doped fiber (BIEDF). Lateral spontaneous emissions and scattering laser powers in the BIEDF were measured quantitatively by using an integrating sphere. Compared with the power of amplified spontaneous emission and signal detected at the output fiber end, it was found that considerable powers were consumed by the laterally emitting lights. As an optically undetected loss limits power conversion efficiency (PCE) of the fiber amplifier, the effect of nonradiative decay from the termination level of pump excited state absorption (pump ESA) was estimated from decay rate analyses of the relevant levels. The nonradiative loss was comparable to amplified signal power in the BIEDF when pumped with a 980-nm LD. Nonradiative decay following cooperative upconversion (CUP) process is also discussed using rate equations analysis.     

Abdominal apparent diffusion coefficient measurements: effect of diffusion-weighted image quality and usefulness of anisotropic images

This study aimed to assess the effect of diffusion-weighted image (DWI) quality on abdominal apparent diffusion coefficient (ADC) measurements and the usefulness of anisotropic images. Twenty-six patients (10 men and 16 women; mean, 58.1 years) who underwent DW imaging and were diagnosed not to have any abdominal diseases were analyzed. Single-shot spin-echo echo-planar DW imaging was performed, and one isotropic and three orthogonal anisotropic images were created. ADCs were calculated for liver (four segments), spleen, pancreas (head, body, tail) and renal parenchyma. Image quality for each organ part was scored visually. We estimated the correlation between ADC and image quality and evaluated the feasibility of using anisotropic images. ADCs and image quality were affected by motion probing gradient directions in the liver and pancreas. A significant inverse correlation was found between ADC and image quality. The r values for isotropic images were −.46, −.48, −.70 and −.28 for the liver, spleen, pancreas and renal parenchyma, respectively. Anisotropic images had the best quality and lowest ADC in at least one organ part in 17 patients. DWIs with the best quality among isotropic and anisotropic images should be used in the liver and pancreas.     

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.     

Ruthenocene‐Type Complexes of N‐Fused Porphyrins

Ruthenocene‐type hybrid complexes with N‐fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N‐fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X‐ray crystallography. [Ru(NFp)Cp] is a common low‐spin ruthenium(II) complex and shows strong aromaticity. The Ru–Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp₂] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three‐dimensional d–π conjugated system. The HOMO–LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N‐fused porphyrin, in which the HOMO–LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles.     

Enzyme catalytic membrane based on a hybrid mesoporous membrane

Immobilization of glucose oxidase (GOD) within a hybrid mesoporous membrane with 12 nm pore diameter was successfully achieved, resulting in catalytically high efficiency during flow of a glucose solution across the membrane.