Many-body effect in the M45–N23N45–N45N45N45 coincidence spectroscopy spectra of metallic elements around Cd

The quasi-particle approximation for the 4p4d state of the metallic elements around Cd breaks down because of very rapid 4p4d–4d³ super Coster–Kroning (sCK) decay of the 4p hole in the presence of the spectator 4d hole. Here the underbar is a hole. As a result, the 4p4d multiplet coupling breaks down. We can examine the presence or absence of the 4p4d multiplet by Auger-electron sCK-electron coincidence spectroscopy measurement of the 3d–4p4d–4d³ Auger-preceded sCK transitions. We collect the sCK-electrons in coincidence with the Auger-electrons of a selected kinetic energy (KE) and vice versa. If the multiplet coupling breaks down and does not exist, the coincidence sCK-electron (or Auger-electron) lines shift as much as the Auger-electron (or sCK-electron) analyzer's selected KE is varied. We can determine not only the three 4d-hole sCK final-state energy but also the presence or absence of the 4p4d multiplet by Auger-electron sCK-electron coincidence spectroscopy. The unique capability of the coincidence measurement by which one can determine the correlation between an Auger-electron and a sCK electron generated, respectively, by creation and annihilation of the same Auger two-hole final state is very useful, even when the quasi-particle approximation of the two-hole state breaks down.     

Direct Fabrication Methods of Surface Relief Electro-Optic Gratings in Azo-Polymer Films

Two fabrication methods of surface relief electro-optic (EO) gratings in azo-polymer films are described: surface deformation by a continuous wave laser and laser ablation by a pulse laser. In the fabrication process, the periodic intensity modulation of laser beams is formed by an interference fringe or a phase mask. The surface relief EO grating is fabricated by poling the surface relief grating (SRG) after the SRG fabrication process. The linear dependence of an applied voltage in the modulation efficiency of the first-order diffraction beam is observed. The proposed methods are effective for highly-efficient surface relief EO grating fabrication.     

Synthesis and crosslinking reaction of a novel polymer containing benzoxazine and phenyleneethynylene moieties in the main chain

A novel polymer, poly( 1 ) containing benzoxazine and phenyleneethynylene moieties in the main chain with number‐average molecular weights ranging from 1400 to 9800 was obtained quantitatively by the Sonogashira–Hagihara coupling polymerization of the corresponding iodophenyl‐ and ethynylphenyl‐substituted monomer 1 . Poly( 1 ) was heated at 200 °C under N₂ for 2 h to obtain the cured polymer, poly( 1 )′ via the ring‐opening polymerization of the benzoxazine moieties. The structures of the polymer before and after curing were confirmed by ¹H‐NMR, IR, and UV–vis absorption and reflectance spectroscopies. Poly( 1 )′ was thermally more stable than monomer 1 and poly( 1 ). A specimen was prepared from a mixture of poly( 1 ) and phenol‐diaminodiphenylmethane type benzoxazine 2 by heating at 200 °C for 2 h under N₂. The poly( 1 )/ 2 resin was thermally stable than bisphenol‐A type benzoxazine resin 3 . Poly( 1 ) exhibited XRD peaks corresponding to the d‐spacings of 1.26–0.98 and 0.40 nm, assignable to the repeating monomer unit and alignment of polymer molecules, respectively. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2581–2589     

Evaluation of measurement uncertainty in the elemental analysis of sintered silicon carbide using laser ablation in liquid—inductively coupled plasma mass spectrometry with external calibration and isotope dilution

Accreditation and Quality Assurance - The goal of this study was to evaluate the uncertainty of elemental analytical methods that use laser ablation in liquid (LAL) as a pretreatment. After LAL...     

Computer-Generated Holograms Based on the Three-Dimensional Fourier Spectrum

A method to synthesize a computer-generated hologram (CGH) of real-existing objects from projection images is proposed. Different from other similar methods, our method enables the synthesis of a CGH with only one-dimensional (1-D) mechanical scanning of the objects. Our method is connected with the three-dimensional (3-D) Fourier spectrum of the objects by the 3-D central slice theorem (CST). Two efficient recording techniques for projection images and numerical experiments to verify our principle is discussed. A comparison between the two techniques is also presented from the viewpoint of diffraction efficiency. © 2005 The Optical Society of Japan     

High-speed wavelength-division multiplexing quantum key distribution system

A high-speed quantum key distribution system was developed with the wavelength-division multiplexing (WDM) technique and dedicated key distillation hardware engines. Two interferometers for encoding and decoding are shared over eight wavelengths to reduce the system's size, cost, and control complexity. The key distillation engines can process a huge amount of data from the WDM channels by using a 1 Mbit block in real time. We demonstrated a three-channel WDM system that simultaneously uses avalanche photodiodes and superconducting single-photon detectors. We achieved 12 h continuous key generation with a secure key rate of 208 kilobits per second through a 45 km field fiber with 14.5 dB loss.     

Excitation wavelength dependence of the Raman-Stokes shift of N,N-dimethyl-p-nitroaniline

Raman spectra of N,N-dimethly-p-nitroaniline have been measured in various solvents. The Raman-Stokes shift of the band assigned to the NO2 stretching mode excited at 488 nm was found to be linearly dependent on the pi-pi* absorption band center. Furthermore, it is found that the Raman-Stokes shift of the NO2 stretching mode is dependent upon the excitation wavelength. The extent of the shift when excited at 355 versus 488 nm is almost linearly dependent on the vibrational bandwidth of the NO2 mode. The phenomenon is interpreted as the result of the solvation state selective excitation of the vibrational mode as in the case of phenol blue [Yamaguchi et al., J. Chem. Phys. 109, 9075 (1998); 109, 9084 (1998)].     

MOF‐on‐MOF: Oriented Growth of Multiple Layered Thin Films of Metal–Organic Frameworks

The precise alignment of multiple layers of metal–organic framework (MOF) thin films, or MOF‐on‐MOF films, over macroscopic length scales is presented. The MOF‐on‐MOF films are fabricated by epitaxially matching the interface. The first MOF layer (Cu₂(BPDC)₂, BPDC=biphenyl‐4,4′‐dicarboxylate) is grown on an oriented Cu(OH)₂ film by a “one‐pot” approach. Aligned second (Cu₂(BDC)₂, BDC=benzene 1,4‐dicarboxylate, or Cu₂(BPYDC)₂, BPYDC=2,2′‐bipyridine‐5,5′‐dicarboxylate) MOF layers can be deposited using liquid‐phase epitaxy. The co‐orientation of the MOF films is confirmed by X‐ray diffraction. Importantly, our strategy allows for the synthesis of aligned MOF films, for example, Cu₂(BPYDC)₂, that cannot be grown on a Cu(OH)₂ surface. We show that aligned MOF films furnished with Ag nanoparticles show a unique anisotropic plasmon resonance. Our MOF‐on‐MOF approach expands the chemistry of heteroepitaxially oriented MOF films and provides a new toolbox for multifunctional porous coatings.     

Light-induced conformational change and product release in DNA repair by (6-4) photolyase

Proteins of the cryptochrome/photolyase family share high sequence similarities, common folds, and the flavin adenine dinucleotide (FAD) cofactor, but exhibit diverse physiological functions. Mammalian cryptochromes are essential regulatory components of the 24 h circadian clock, whereas (6-4) photolyases recognize and repair UV-induced DNA damage by using light energy absorbed by FAD. Despite increasing knowledge about physiological functions from genetic analyses, the molecular mechanisms and conformational dynamics involved in clock signaling and DNA repair remain poorly understood. The (6-4) photolyase, which has strikingly high similarity to human clock cryptochromes, is a prototypic biological system to study conformational dynamics of cryptochrome/photolyase family proteins. The entire light-dependent DNA repair process for (6-4) photolyase can be reproduced in a simple in vitro system. To decipher pivotal reactions of the common FAD cofactor, we accomplished time-resolved measurements of radical formation, diffusion, and protein conformational changes during light-dependent repair by full-length (6-4) photolyase on DNA carrying a single UV-induced damage. The (6-4) photolyase by itself showed significant volume changes after blue-light activation, indicating protein conformational changes distant from the flavin cofactor. A drastic diffusion change was observed only in the presence of both (6-4) photolyase and damaged DNA, and not for (6-4) photolyase alone or with undamaged DNA. Thus, we propose that this diffusion change reflects the rapid (50 μs time constant) dissociation of the protein from the repaired DNA product. Conformational changes with such fast turnover would likely enable DNA repair photolyases to access the entire genome in cells.     

Study on excited states of hexamethoxybenzene-NO+ charge-transfer complex: incorporation of excited radical cation

A charge-transfer (CT) complex of NOBF₄ and hexamethoxybenzene (HMB), which gives out HMB^?+ as a “fluorescent radical cation probe,” upon one-electron oxidation, has been designed to explore the excited state dynamics of contact radical ion pairs by laser-induced fluorescence and femtosecond transient absorption spectroscopic techniques. The acetonitrile solution of the CT complex showed weak fluorescence with a similar spectrum to that observed for free excited HMB radical cation (HMB^?+*), suggesting the formation of HMB^?+* upon the one-photonic excitation of the CT complex. The laser-power dependence of the fluorescence intensity supported the one-photonic excitation event. We have also observed a short-lived transient species but no long-lived species by femtosecond laser flash photolysis of the CT complex. The lifetime (6.5 ps) was in good accordance with its fluorescence quantum yield (2.5 × 10^?5) and was able to assign the transient species to the fluorescent state, an excited radical ion pair [HMB ^?+*/NO^?]. All the events were completed within the inner sphere and the short lifetime of the transient species could be attributed to rapid back-electron transfer. It is concluded that the excited radical cation character in the excited state of the CT complex originates from the radical ion character in the CT complex in the ground state and that a relatively long lifetime of HMB^?+* facilitates its observation even in the contact ion pair.