Raman and infrared spectra of the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers of β-carotene: Key bands distinguishing stretched or terminal-bent configurations form central-bent configurations

Raman and infrared spectra in the region of 1800-150 cm⁻¹ were recorded for a set of cis-trans isomers of d̃-carotene, i.e. the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers. Spectral comparison revealed Raman and infrared key bands which (1) distinguish stretched or terminal-bent configurations (all-trans, 7-cis and 9-cis) from central-bent configurations (13-cis and 15-cis), and (2) distinguish unmethylated 7-cis and 15-cis configuratios. Keybands (1) include Raman bands at 1160 and 1140 cm⁻¹ and infrared bands at 825 and 775 cm⁻¹ (the intensity varies with the position of the cis-bend) Key bands (2) include Raman bands at 1274 and 962 cm⁻¹ and an infrared band at 741 cm⁻¹ (characteristic of the 7-cis configuration), and also a Raman band at 1247 cm⁻¹ and an infrared band at 775 cm⁻¹ (characteristic of the 15-cis configuration). The normal modes for the key bands were determined by a set of normal coordinate calculations for the isomeric configurations of a simplified model of d̃-carotene. The key bands were mainly related to the C H in-plane bendings, coupled with the CC or C C stretching, or to the C H out-of-plane wagging vibrations, some of which coupled with the CC torsion.     

Luminescence imaging of biological subjects during X-ray irradiations lower energy than Cerenkov-light threshold

It is commonly thought that UV or visible-light luminescence imaging of biological subjects during X-ray irradiation at the energy below 120 keV is impossible because the secondary electrons produced in this energy range do not emit Cerenkov light. Contrary to this consensus, we found UV or visible-light luminescence imaging of the subjects were possible with X-ray irradiations of this energy range. We placed one of the biological subjects in a black box; visible-light luminescence images were measured with a high-sensitivity, cooled charge coupled device (CCD) camera during X-ray irradiation at energy below 120 keV. We also conducted the imaging of air without subjects during irradiation of the same X-ray. The biological subjects emitted visible-light luminescence, and the imaging was possible with the irradiation of the X-ray below 120 keV. The luminescence images were observed in only the X-ray irradiated areas. Also air luminescence images could be obtained and the intensity of the luminescence measured from the images was proportionally increased with the exposure dose. UV or visible-light luminescence imaging of biological subjects was possible during X-ray irradiations lower energy than the Cerenkov-light threshold. The phenomenon was different from general X-ray fluorescence because wavelength of the luminescence is UV or visible-light. The luminescence imaging method is promising for estimating the irradiated area with X-ray, which could be used for interventional radiology (IVR). Also air luminescence imaging would be applied to the exposure dose distribution measurements for X-ray of diagnostic X-ray systems.     

Phase-locked laser system for a metastable states qubit in 40 Ca+

We describe the development of a phase-locked laser system tailored to an ion-trap-based quantum information processor with (40)Ca(+). Laser outputs from an extended cavity diode laser and a Ti:sapphire laser with output laser wavelengths of approximately 850 and 854 nm, respectively, were phase locked and used to excite a Raman transition between the D(3/2) and D(5/2) metastable states qubit. Development and the performance of the laser system are described. We also compare the characteristics and the benefits of the developed qubit coupling with those in the conventional approaches.     

Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

Preparation of polymethyl methacrylate with well-controlled stereoregularity by anionic polymerization in an ionic liquid solvent

This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using ¹H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA.     

Measurement on Spot Size Dependence of Dense WDM Dielectric Multilayer Filters

We present the spot size dependence of dielectric multilayer filters for use in dense WDM systems. We found large dependences of filter performances on the spot size and the incident angle of input light, which should be important for miniaturizing multi-channel add/drop filters.     

Magneto-Optical Measurement of Organic Conductor Using Rotational Cavity System

We have developed a new magneto-optical measurement system using a rotational cavity system equipped with a millimeter vector network analyzer and a 14 T solenoid type super conducting magnet. The measurement can be performed in the transmission configuration down to 1.6 K. The results of the precise angular dependence measurement of quasi-one-dimensional organic conductor (DMET)₂I₃ using the new system are shown, and its Fermi surface will be discussed in connection with the previous reports.     

A CO Adsorption Site Change Induced by Copper Substitution in a Ruthenium Catalyst for Enhanced CO Oxidation Activity

Ru is an important catalyst in many types of reactions. Specifically, Ru is well known as the best monometallic catalyst for oxidation of carbon monoxide (CO) and has been practically used in residential fuel cell systems. However, Ru is a minor metal, and the supply risk often causes violent fluctuations in the price of Ru. Performance‐improved and cost‐reduced solid‐solution alloy nanoparticles of the Cu‐Ru system for CO oxidation are now presented. Over the whole composition range, all of the Cu_xRu_1?x nanoparticles exhibit significantly enhanced CO oxidation activities, even at 70 at % of inexpensive Cu, compared to Ru nanoparticles. Only 5 at % replacement of Ru with Cu provided much better CO oxidation activity, and the maximum activity was achieved by 20 at % replacement of Ru by Cu. The origin of the high catalytic performance was found as CO site change by Cu substitution, which was investigated using in situ Fourier transform infrared spectra and theoretical calculations.     

A pyrazine-bridged linear pentanuclear copper(II) complex and related tri- and dinuclear complexes showing various coordination structures and magnetic couplings

Sterically bulky pyrazines have been successfully utilized for the preparation of discrete oligo-nuclear TBP (trigonal bipyramidal), SqP (square pyramidal), and Oh (octahedral) copper(II) complexes. We have synthesized a unique linear pentanuclear complex [{Cu(hfac)₂}₅(μ-2-butyl-3-methylpyrazine)₄]. The two terminal copper(II) ions have a SqP structure while the three inner ions have an Oh one. The solvent molecule was incorporated in the clearance of the lattice. From another reaction under harsh conditions, we separated [{Cu(hfac)₂}₃(μ-2-butyl-3-methylpyrazine)₂], which can be regarded as the central moiety of the pentanuclear one. We also prepared a dinuclear complex [{Cu(hfac)₂}₂(μ-tetramethylpyrazine)], in which the pyrazine nitrogen atoms were located at TBP equatorial positions. Single-crystal EPR measurements supported its compressed TBP structure. The exchange coupling was antiferromagnetic with J_TBP–TBP/k_B = −3.6 K. The linear trinuclear [{Cu(hfac)₂}₃(μ-2,3,5-trimethylpyrazine)₂], having two TBP Cu ions with an intervening Oh Cu ion, showed very weak antiferromagnetic coupling. DFT calculations on these compounds indicated that the σ-type orbital overlap between the Cu and N atoms is essential for superexchange interactions.     

Selectivity in substrate–enzyme complexation studied by surface forces measurement

The selectivity of substrate in substrate–enzyme complexation of heptaprenyl diphosphate synthase was directly investigated using colloidal probe atomic force microscopy (AFM). This enzyme is composed of two dissociable subunits, which exhibits a catalytic activity only when they are associated together in the presence of a cofactor, Mg²⁺, and a substrate, farnesyl diphosphate (FPP). We have recently succeeded to directly demonstrate a specific interaction involved in this enzyme reaction and obtain new insights into the molecular mechanism of the reaction using the approach based on the colloidal probe AFM. The AFM measurement showed the adhesive force between the subunits only in the presence of both Mg²⁺ and FPP. In this study, we studied the substrate selectivity in the complexation by monitoring the adhesive force. The substrates studied are pyrophosphate (PPi), isopentenyl diphosphate (IPP), geranyl diphosphate (GPP), farnesyl monophosphate (FP), and farnesyl geranyl diphosphate (FGPP). No adhesion was observed in the case of PPi, IPP, and GPP. On the other hand, the significant adhesion was observed for phosphate derivatives, which bear prenyl units longer than three. This is in good agreement with the selectivity of the substrates by this enzyme, which catalyzes the condensation reaction of four IPP molecules with FPP to give heptaprenyl (C₃₅) diphosphates. Our study showed a useful methodology for examining the elemental processes of biological reactions.