Mutually pumped phase conjugate mirror using cross polarized photorefractive coupling

This paper presents a new proposal for a mutually pumped phase conjugate mirror (MPPCM) using cross polarization. In the cross polarized MPPCM, two light beams, whose polarizations are orthogonal to each other, incident on a photorefractive crystal, causing photorefractive interaction to generate phase conjugate waves with an orthogonal polarization to an incident beam. The use of Ar⁺ laser and BaTiO₃ crystal in an experiment for the cross polarized MPPCM found that diffraction efficiency for an extraordinary beam is about 20%. As opposed to a conventional parallel polarized MPPCM in which the use of a beam splitter is required to separate a diffraction beam, the cross polarized MPPCM can efficiently extract phase conjugate waves by means of a polarized beam splitter, demonstrating the advantage of substantially improved efficiency.     

Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo‐Ring Formation with 8π‐6π Electrocyclization

Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo‐ring formation reactions proceed non‐enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo‐ring formation and 8π‐6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non‐enzymatic conversion to shimalactones in the dark.     

Principles of Aggregation-Induced Emission: Design of Deactivation Pathways for Advanced AIEgens and Applications

Twenty years ago, the concept of aggregation-induced emission (AIE) was proposed, and this unique luminescent property has attracted scientific interest ever since. However, AIE denominates only the phenomenon, while the details of its underlying guiding principles remain to be elucidated. This minireview discusses the basic principles of AIE based on our previous mechanistic study of the photophysical behavior of 9,10-bis(N,N-dialkylamino)anthracene ( BDAA ) and the corresponding mechanistic analysis by quantum chemical calculations. BDAA comprises an anthracene core and small electron donors, which allows the quantum chemical aspects of AIE to be discussed. The key factor for AIE is the control over the non-radiative decay (deactivation) pathway, which can be visualized by considering the conical intersection (CI) on a potential energy surface. Controlling the conical intersection (CI) on the potential energy surface enables the separate formation of fluorescent (CI:high) and non-fluorescent (CI:low) molecules [control of conical intersection accessibility ( CCIA )]. The novelty and originality of AIE in the field of photochemistry lies in the creation of functionality by design and in the active control over deactivation pathways. Moreover, we provide a new design strategy for AIE luminogens (AIEgens) and discuss selected examples.     

Conformational analysis of methyl 2-methyl-2-(1-naphthyl)propionate

(S)-2-Methoxy-2-(1-naphthyl)propionic acid (MαNP acid 1) is used for enantioseparation of many secondary alcohols and for determining the stereogenic centers. In the liquid state, based on the ¹H NMR anisotropy effect and reported results, it was shown that the MαNP ester preferred a coplanar relation between the methyl and naphthyl groups and a synperiplanar relation between the Cα-OMe and CO groups. In the case of 1,2,3,4-tetrahydro-4-phenanthrenol, which is a secondary alcohol, the stereogenic center was determined by X-ray analysis. It was shown that MαNP ester adopted similar arrangements in the solid state. However, it was presumed that the strong repulsion between oxygen atoms may be disadvantageous in the solid state. Therefore, we carried out conformational analysis using the simplest MαNP methyl ester to clarify this unique relationship. From detailed results based on the energy surface determined using the RHF/STO-3G basis set, the synperiplanar positional relation was the most stable, and the calculated results agreed with many reported experimental results. At the same time, all conformational isomers of the MαNP methyl ester were used to clarify the internal conversion pathways.     

The dihydro-beta-agarofuran sesquiterpenoids

Dihydro-Beta-agarofuran sesquiterpenoids are a structurally diverse class of natural products based on tricyclic 5,11-epoxy-5Beta,10alpha-eudesman-4-(14)-ene skeleton. Between January 1990 and June 2006, 462 new dihydro-Beta-agarofuran sesquiterpenoids of 74 structural types have been isolated from about 64 species of Celastraceae, 3 species of Hippocrateaceae and one species of Lamiaceae. The present review covers the chemical and biological activity research of dihydro-Beta-agarofuran sesquiterpenoids in the past 16 years. The chemical research includes structural classification into sesquiterpene polyesters and macrolide sesquiterpene pyridine alkaloids, synthesis of dihydro-Beta-agarofuran as well as extraction, isolation and purification methods. The biological activity research includes activities such as multidrug resistance (MDR) reversal activity, HIV inhibition, cytotoxicity, antitumor activity, antifeedant activity and insecticidal activity with some insights to their modes of actions.     

Point spread function measurement of an X‐ray beam focused by a multilayer zone plate with narrow annular aperture

The experimental procedure for obtaining the point spread function (PSF) of a focusing beam generated using an X‐ray multilayer zone plate (MZP) with a narrow annular aperture has been developed. It was possible to reconstruct the PSF by applying the tomographic process to the measured dataset consisting of line spread functions (LSFs) in every radial direction on the focal plane. The LSFs were measured by a knife‐edge scanning method of detecting scattered intensity. In the experimental work, quasi‐monochromatic undulator radiation with a first harmonic energy of 20 keV was directly focused without a monochromator by the MZP, and the PSF was measured using this procedure. As a result, a near diffraction‐limited focused beam size of 46 nm full width at half‐maximum was obtained.     

Periodic nanostructures self-formed on silicon and silicon carbide by femtosecond laser irradiation

Laser-induced periodic surface structures (LIPSS) were formed on Si and SiC surfaces by irradiations with femtosecond laser pulses in air. Different kinds of self-organized structures appeared on Si and SiC at laser fluences slightly higher than the damage threshold, which was measured by confocal laser scanning microscope. The characteristic spatial periodicity of every observed structure was estimated reading the peak values of the 2D Fourier transform power spectra obtained from SEM images. The evolution of the spatial periodicity was finally studied with respect to both the laser fluence and the number of laser pulses. As already observed for metals, the behavior of the spatial periodicity on laser fluence can be related to the parametric decay of laser light into surface plasma waves. Our results suggest a wide applicability of the parametric decay model on different materials, making the model a useful tool in view of different applications of LIPSS.     

Development of Glassy Step‐Growth Thiol‐Vinyl Sulfone Polymer Networks

Thermomechanical properties of neat phosphine‐catalyzed thiol‐Michael networks fabricated in a controlled manner are reported, and a comparison between thiol‐acrylate and thiol‐vinyl sulfone step‐growth networks is performed. When highly reactive vinyl sulfone monomers are used as Michael acceptors, glassy polymer networks are obtained with glass transition temperatures ranging from 30 to 80 °C. Also, the effect of side‐chain functionality on the mechanical properties of thiol‐vinyl sulfone networks is investigated. It is found that the inclusion of thiourethane functionalities, aryl structures, and most importantly the elimination of interchain ester linkages in the networks significantly elevate the network's glass transition temperature as compared with neat ester‐based thiol‐Michael networks.