A compact permanent‐magnet system for measuring magnetic circular dichroism in resonant inelastic soft X‐ray scattering

A compact and portable magnet system for measuring magnetic dichroism in resonant inelastic soft X‐ray scattering (SX‐RIXS) has been developed at the beamline BL07LSU in SPring‐8. A magnetic circuit composed of Nd–Fe–B permanent magnets, which realised ～0.25 T at the center of an 11 mm gap, was rotatable around the axis perpendicular to the X‐ray scattering plane. Using the system, a SX‐RIXS spectrum was obtained under the application of the magnetic field at an angle parallel, nearly 45° or perpendicular to the incident X‐rays. A dedicated sample stage was also designed to be as compact as possible, making it possible to perform SX‐RIXS measurements at arbitrary incident angles by rotating the sample stage in the gap between the magnetic poles. This system enables facile studies of magnetic dichroism in SX‐RIXS for various experimental geometries of the sample and the magnetic field. A brief demonstration of the application is presented.     

Adaptive exponential approximation of optical density ratio using third-order regression equations for depth profiling of a blood inclusion in a skin tissue model

We propose the use of the third-order multiple regression equations in approximating an optical density ratio with an adaptive exponential function for measuring depth and thickness of a blood inclusion embedded in a skin tissue model. To ensure accuracy of the exponential approximation, we investigated numerically various relations of optical density ratios versus depth and thickness, on the basis of Monte Carlo simulations for a layered skin tissue model. The third-order multiple regression analysis based on the relations above was used to derive regression equations for the determination of depth and thickness. Experiments with skin tissue phantoms were used to assess this approach.     

Synthetic Study of (−)‐Norzoanthamine: Construction of the ABC Ring Moiety

Throw your hat in the ring : A highly diastereoselective synthesis of the ABC rings of (?)‐norzoanthamine has been achieved starting from the (?)‐Hajos–Parrish ketone (see scheme). Three asymmetric quaternary carbon centers on the C ring were constructed by a 1,4‐addition, and an intramolecular Diels–Alder reaction provided a trans‐decalin scaffold on the AB rings.

     

A comparative mechanistic analysis of the stereoselectivity trends observed in the oxidation of chiral oxazolidinone-functionalized enecarbamates by singlet oxygen, ozone, and triazolinedione

The stereoselectivity in the reactions of the E/Z enecarbamates 1, equipped with the oxazolidinone chiral auxiliary, has been examined for singlet oxygen (¹O₂), ozone (O₃), and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) in a variety of solvents as a function of temperature. The oxidative cleavage of the alkenyl functionality by ¹O₂ and O₃ releases the enantiomerically enriched methyldesoxybenzoin (MDB) product. The extent (% ee) as well as the sense (R vs S) of the stereoselectivity in the MDB formation depends on the electronic nature of the oxidant. A high stereoselectivity, substantially dependent on solvent and temperature, is displayed for the reactions with ¹O₂, whereas the ground-state reactants O₃ and PTAD are rather unaffected by solvent and temperature variations. The present comparative analysis clearly substantiates our hypothesis of stereoselective vibrational quenching of the attacking ¹O₂, whereas O₃ and PTAD are only subject to steric impositions. The electronically excited ¹O₂ is sensitive to all three stereochemically relevant structural characteristics embodied in the chiral enecarbamates, namely the R/S configuration at the C₄ position of the oxazolidinone chiral auxiliary, the Z/E geometry of the ‘alkene’ functionality, and R/S configuration at the C_3′ position of the enecarbamate side chain.     

Thermodynamics of interactions of vancomycin and synthetic surrogates of bacterial cell wall

Glycopeptide antibiotics, including vancomycin, form complexes via a set of five hydrogen bonds with the acyl-l-Lys-d-Ala-d-Ala portion of the peptidyl stems of the bacterial cell wall peptidoglycan. This complexation deprives the organism from the ability to cross-link peptidyl stems of the peptidoglycan, leading to bacterial cell death. Four synthetic fragments as surrogates of the components of the bacterial cell wall have been prepared in our lab in multistep syntheses. These synthetic samples were used in investigations of the thermodynamics properties (DeltaG degrees , DeltaH degrees , and TDeltaS degrees ) for the complexation with vancomycin by isothermal titration calorimetry (ITC). Complexation with the glycopeptide analogues is largely enthalpy-driven (formation of five hydrogen bonds), and in the analogues with a single peptidyl stem, the complexation is 1:1. The complexation is more complicated with an approximately 2 kDa cell wall surrogate (compound 4), which possesses two peptidyl stems. The data were suggestive of interactions between the two vancomycin molecules, with an entropic penalty attributable to restriction of molecular movements within the complex due to restriction of motion of the highly mobile acyl-d-Ala-d-Ala moiety of the peptidyl stems. These data were reconciled with the recently determined NMR solution structure for the peptidoglycan fragment 4 and its implications for the larger cell wall.     

Compact optical duplicate system for satellite-ground laser communications: application of averaging effects

In recent years, there has been considerable interest in satellite-ground laser communication due to an increase in the quantity of data exchanged between satellites and the ground. However, improving the quality of this data communication is necessary as laser communication is vulnerable to air fluctuation. We first verify the spatial and temporal averaging effects using light beam intensity images acquired from middle-range transmission experiments between two ground positions and the superposition of these images using simulations. Based on these results, we propose a compact and lightweight optical duplicate system as a multi-beam generation device with which it is easy to apply the spatial averaging effect. Although an optical duplicate system is already used for optical correlation operations, we present optimum design solutions, design a compact optical duplicate system for satellite-ground laser communications, and demonstrate the efficacy of this system using simulations.     

Extended Fluorochromism of Anthracene Trimers with a meta‐Substituted Triphenylamine or Triphenylphosphine Core

Combining meta‐triphenylamine or triphenylphosphine with three anthracene fluorophores gives rise to fluorescent non‐planar triskelions 1 and 2 . The emissive properties of 1 are highly solvatochromic, yielding blue to pale green and even pale yellow fluorescence, whereas the blue emission of 2 is solvent‐insensitive. Anthracene trimers 1 and 2 are both emissive in the solid state, displaying yellow and pale green fluorescence, respectively, with moderate quantum yields.     

Suppressed speckle contrast of blue light emission out of white lamp with phosphors excited by blue laser diodes for high-brightness lighting applications

The speckle contrast of blue light emission out of high-brightness white lamps using phosphors excited by InGaN/GaN blue laser diodes is evaluated as a measure of coherence. As a result, speckle contrast of as low as 1.7%, the same level as a blue light emitting diode, is obtained. This implies that the original blue laser light can be converted into incoherent light through lamp structures without any dynamic mechanisms. This unique speckle-free performance is considered to be realized by multiple scattering inside the lamp structure, the multi-longitudinal mode operation of the blue laser diodes, and the use of multiple laser diodes. Such almost-incoherent white lamps can be applied for general lighting without any nuisance of speckle noise and should be categorized as lamps rather than lasers in terms of laser safety regulation.     

Correction of quadratic phase error in two-wavelength digital holographic interferometry using laser diodes

We present the correction of a quadratic phase error in two-wavelength digital holographic interferometry using laser diodes. This phase error arises from numerical reconstructions of wavefronts from digital holograms based on the Fresnel diffraction integral. To correct the quadratic phase error, it is numerically produced by computer on the basis of the theoretical prediction and is subtracted from the phase difference map in two-wavelength digital holographic interferometry. Experimental results show that the method of correction in this paper is useful for two-wavelength digital holographic interferometry using laser diodes.     

Peptide Chirality Sensing by a Cyclodextrin–Polythiophene Conjugate

A new cyclodextrin–polythiophene conjugate ( CDPT ) has been prepared by attaching permethyl-α-cyclodextrins to polythiophene (PT) through a hexamethylene tether. Circular dichroism spectral examination of CDPT revealed that only a weak positive Cotton effect (Δε=0.1 M ⁻¹ cm⁻¹) was induced at the main band of the PT in dimethyl sulfoxide and similarly weak bisignate signals in pure and aqueous methanol solutions, which indicates that the α-cyclodextrins appended to PT with a long tether are ineffective in inducing a homochiral structure in the PT backbone. Nevertheless, enantiomeric amino acids and dipeptides added to an aqueous methanolic solution of CDPT caused chirality-dependent hypochromic changes in the UV/Vis spectra, which enabled us to sense these species and quantitatively determine the enantioselectivity by observing the difference in absorbance upon interaction with pairs of enantiomers. Enantiomeric d,d /l,l -dipeptide pairs rather than D /L -amino acid pairs were better differentiated in general, the highest dd /ll selectivity of 13.7 being observed for Phe-Phe.