New aplysiatoxin derivatives from the Okinawan cyanobacterium Moorea producens

The marine cyanobacterium Moorea producens is a rich source of diverse compounds that possess a variety of biological activities. In the present study, eight new aplysiatoxin derivatives, namely 6, 8–13, and 15, along with aplysiatoxin (1), debromoaplysiatoxin (2), 3-methoxyaplysiatoxin (3), anhydroaplysiatoxin (4), anhydrodebromoaplysiatoxin (5), oscillatoxin B2 (7), and 30-methyloscillatoxin D (14) were isolated and identified from the Okinawan M. producens. In cytotoxicity and diatom growth inhibition tests, the fifteen compounds tested (1–15) showed moderate or no activity at a concentration of 10?μg/mL.     

High‐Pressure Synthesis of A2NiO2Ag2Se2 (A=Sr,Ba) with a High‐Spin Ni2+ in Square‐Planar Coordination

Square‐planar coordinate Ni²⁺ ions in oxides are exclusively limited to a low‐spin state (S=0) owing to extensive crystal field splitting. Layered oxychalcogenides A₂Ni^IIO₂Ag₂Se₂ (A=Sr, Ba) with the S=1 NiO₂ square lattice are now reported. The structural analysis revealed that the Ni²⁺ ion is under‐bonded by a significant tensile strain from neighboring Ag₂Se₂ layers, leading to the reduction in crystal field splitting. Ba₂NiO₂Ag₂Se₂ exhibits a G‐type spin order at 130 K, indicating fairly strong in‐plane interactions. The high‐pressure synthesis employed here possibly assists the expansion of NiO₂ square lattice by taking the advantage of the difference in compressibility in oxide and selenide layers.     

Disulfide‐Unit Conjugation Enables Ultrafast Cytosolic Internalization of Antisense DNA and siRNA

Development of intracellular delivery methods for antisense DNA and siRNA is important. Previously reported methods using liposomes or receptor‐ligands take several hours or more to deliver oligonucleotides to the cytoplasm due to their retention in endosomes. Oligonucleotides modified with low molecular weight disulfide units at a terminus reach the cytoplasm 10 minutes after administration to cultured cells. This rapid cytoplasmic internalization of disulfide‐modified oligonucleotides suggests the existence of an uptake pathway other than endocytosis. Mechanistic analysis revealed that the modified oligonucleotides are efficiently internalized into the cytoplasm through disulfide exchange reactions with the thiol groups on the cellular surface. This approach solves several critical problems with the currently available methods for enhancing cellular uptake of oligonucleotides and may be an effective approach in the medicinal application of antisense DNA and siRNA.     

Mechanochromism,Twisted/Folded Structure Determination,and Derivatization of (N‐Phenylfluorenylidene)acridane

(N‐Phenylfluorenylidene)acridane (Ph‐FA) compounds with electron‐withdrawing and ‐donating substituents (H, MeO, Ph, NO₂, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N‐aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p‐NO₂‐C₆H₄‐FA could be crystallographically characterized, which enabled the charge transfer from the electron‐donating acridane moiety to the electron‐accepting fluorenylidene moiety to be understood. Ground‐state mechanochromism, thermochromism, vapochromism, and proton‐induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph‐FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors.     

The First Study on the Reactivity of Water Vapor in Metal–Organic Frameworks with Platinum Nanocrystals

We first studied the reactivity of H₂O vapor in metal–organic frameworks (MOFs) with Pt nanocrystals (NCs) through the water–gas shift (WGS) reaction. A water‐stable MOF, UiO‐66, serves as a highly effective support material for the WGS reaction compared with ZrO₂. The origin of the high catalytic performance was investigated using in situ IR spectroscopy. In addition, from a comparison of the catalytic activities of Pt on UiO‐66, where Pt NCs are located on the surface of UiO‐66 and Pt@UiO‐66, where Pt NCs are coated with UiO‐66, we found that the competitive effects of H₂O condensation and diffusion in the UiO‐66 play important roles in the catalytic activity of Pt NCs. A thinner UiO‐66 coating further enhanced the WGS reaction activity of Pt NCs by minimizing the negative effect of slow H₂O diffusion in UiO‐66.     

Calculations of electron inelastic mean free paths. XII. Data for 42 inorganic compounds over the 50 eV to 200 keV range with the full Penn algorithm

We have calculated inelastic mean free paths (IMFPs) for 42 inorganic compounds (AgBr, AgCl, AgI, Al₂O₃, AlAs, AlN, AlSb, cubic BN, hexagonal BN, CdS, CdSe, CdTe, GaAs, GaN, GaP, GaSb, GaSe, InAs, InP, InSb, KBr, KCl, MgF₂, MgO, NaCl, NbC_0.712, NbC_0.844, NbC_0.93, PbS, PbSe, PbTe, SiC, SiO₂, SnTe, TiC_0.7, TiC_0.95, VC_0.76, VC_0.86, Y₃Al₅O₁₂, ZnS, ZnSe, and ZnTe) for electron energies from 50 eV to 200 keV. These calculations were made with energy-loss functions (ELFs) obtained from measured optical constants for 15 compounds while calculated ELFs were utilized for the other 27 compounds. Checks based on ELF sum rules showed that the calculated ELFs were superior to the measured ELFs that we had used previously. Our calculated IMFPs could be fitted to a modified form of the relativistic Bethe equation for inelastic scattering of electrons in matter for energies from 50 eV to 200 keV. The average root-mean-square (RMS) deviation in these fits was 0.60%. The IMFPs were also compared with a relativistic version of our predictive Tanuma-Powell-Penn (TPP-2M) equation. The average RMS deviation in these comparisons was 10.7% for energies between 50 eV and 200 keV. This average RMS deviation is almost the same as that found in a similar comparison for a group of 41 elemental solids (11.9%) although relatively large deviations were found for cubic BN (65.6%) and hexagonal BN (34.3%). If these two compounds are excluded in the comparisons, the average RMS deviation becomes 8.7%. We found generally satisfactory agreement between our calculated IMFPs and values from other calculations and from experiments.     

Stabilization and utilization of nonlinear phenomena based on bifurcation control for slow dynamics

Mechanical systems may experience undesirable and unexpected behavior and instability due to the effects of nonlinearity of the systems. Many kinds of control methods to decrease or eliminate the effects have been studied. In particular, bifurcation control to stabilize or utilize nonlinear phenomena is currently an active topic in the field of nonlinear dynamics. This article presents some types of bifurcation control methods with the aim of realizing vibration control and motion control for mechanical systems. It is also indicated through every control method that slowly varying components in the dynamics play important roles for the control and the utilizations of nonlinear phenomena. In the first part, we deal with stabilization control methods for nonlinear resonance which is the 1/3-order subharmonic resonance in a nonlinear spring-mass-damper system and the self-excited oscillation (hunting motion) in a railway vehicle wheelset. The second part deals with positive utilizations of nonlinear phenomena by the generation and the modification of bifurcation phenomena. We propose the amplitude control method of the cantilever probe of an atomic force microscope (AFM) by increasing the nonlinearity in the system. Also, the motion control of a two link underactuated manipulator with a free link and an active link is considered by actuating the bifurcations produced under high-frequency excitation. This article is a discussion on the bifurcation control methods presented by the author and co-researchers by focusing on the actuation of the slowly varying components included in the original dynamics.     

Simulation of micro/nanometer-scale self-organized lightwave network (SOLNET) using the finite difference time domain method

A simulator for self-organized lightwave network (SOLNET) is developed. The simulator is based on the finite difference time domain method. SOLNET enables us to construct self-aligned coupling waveguides between misaligned micro/nanometer-scale optical devices by self-focusing, which arises from an increase in refractive index induced by write beams in photo-refractive materials. The SOLNET simulator reveals that an L-shaped nanometer-scale optical waveguide of SOLNET is grown from a 0.5-μm-wide optical waveguide when write beams are introduced from the optical waveguide into photo-refractive materials, where a wavelength filter is embedded. The SOLNET simulator also reproduces coupling path construction between a 2-μm-wide optical waveguide and a 0.5-μm-wide optical waveguide having a wavelength filter on the core edge. The optical waveguides are placed with misalignment of 0.5-μm offset. By introducing write beams from the 2-μm-wide optical waveguide, the incident write beams and reflected write beams from the wavelength filter merge into one optical waveguide in the photo-refractive materials, constructing a self-aligned coupling waveguide.     

Coherent transfer of light polarization to electron spins in a semiconductor

We demonstrate that the superposition of light polarization states is coherently transferred to electron spins in a semiconductor quantum well. By using time-resolved Kerr rotation, we observe the initial phase of Larmor precession of electron spins whose coherence is transferred from light. To break the electron-hole spin entanglement, we utilized the big discrepancy between the transverse g factors of electrons and light-holes. The result encourages us to make a quantum media converter between flying photon qubits and stationary electron-spin qubits in semiconductors.