COVALENTLY LINKED TYROSINE-PYROPHEOPHORBIDE a AND TRYPTOPHAN-PYROPHEOPHORBIDE a COMPOUNDS: SYNTHESIS AND PHOTO-INDUCED CROSS COUPLING WITH 1, 4-BENZOQUINONE

Abstract— Tyrosine-linked pyropheophorbide a ( 2 ) and tryptophan-linked pyropheophorbide a ( 3 ) were synthesized. Neither the phenol group of the tyrosine end nor the indole group of the tryptophan end showed upfield shifts as observed for the tyrosine-linked mesoporphyrin II ( 17 ) and the tryptophanlinked mesoporphyrin II ( 18 ). When the keto group at the C-9 of 2 and 3 was reduced to methylene group [tyrosine-linked 9-deoxopyropheophorbide a ( 5 ) and tryptophan-linked 9-deoxopyropheophorbide a ( 6 )], the phenol group of the tyrosine and the indole group of the tryptophan showed upfield shifts, indicating the intramolecular hydrogen bonds between amino acid moieties and the keto group at the C-9 in 2 and 3 . Irradiation of 2 and 1,4-benzoquinone (BQ) in benzene led to a clean formation of a quinone-linked pyropheophorbide a ( 8 ) in 56% yield. Triplet radical pair composed of tyrosine radical and semiquinone radical was assigned as the reaction intermediate for the formation of 8 by means of CIDNP technique. Irradiation of 5 under the identical conditions led to the formation of benzoquinone-linked 9-deoxo-mesopyropheophorbide a ( 10 ) and benzoquinone-linked 9-deoxophylloerythrin a ( 11 ) in 45 and 22%, respectively. Magnesium and zinc complexes of 2 underwent the similar photoaddition reaction much less efficiently. However, irradiation of the tryptophan-linked model compounds 3 and 6 in the presence of BQ did not give the coupling product.     

Electronic second hyperpolarizability of the carbon tetrachloride molecule

The electronic second hyperpolarizability γ of the carbon tetrachloride molecule is calculated by the ab initio molecular orbital method considering electron correlation with large basis sets. The static electronic γ value with the CCSD(T) method is 1.65 times the Hartree-Fock value, indicating a considerable electron correlation effect. Taking account of the frequency dispersion and vibrational effects, we estimate the most probable theoretical γ value at 800 nm to be around 17900au (9.0 × 10^?36 esu). On the other hand, the experimental value recently observed by optical Kerr effect method is 10.6 × 10^?36 esu at 800nm. It is concluded that the major part of the experimental χ⁽³⁾ value of carbon tetrachloride can account for the static electronic hyperpolarizability.     

Measurements on diproton emission from the break-up channels of ~(23)Al and ~(22)Mg

Two-proton relative momentum distributions from the break-up channels 23Al→p+p+21Na and 22Mg→p+p+20Ne at an energy of 60-70 A MeV have been measured together with two-proton opening angles at the projectile fragment separator beamline (RIPS) in the RIKEN Ring Cyclotron Facility. The results demonstrate the existence of diproton emission component from single-step 2He for highly excited 23Al and 22Mg.     

Novelty Filtering Using Phase Conjugate Wave in Organic Dye-Doped Polymer Films

A real-time detection of a moving object was demonstrated by taking the subtraction between cross-polarized phase conjugate waves with fast and slow response times with two kinds of dye-doped phase conjugators. One consists of superposed films of an erythrosin-B-doped film and a methyl-orange-doped film, and the other is a film dispersed with both dyes. The relative phase between cross-polarized phase conjugate waves by the both dye-dispersed films was stable.     

Design Method for Optical Waveguide Filters Having Corrugation Structures by Corrugation Width Modulation

A method to design a corrugated optical waveguide filter by modulating the corrugation width profile is proposed. This method is based on combined applications of the Fourier transformation and the F-matrix formalism. The method achieves the spatial profile of the corrugation width required to design a filter with any specified spectral profile of the reflection coefficient. The idea of the technique is that the spatial variation of the effective refractive index can be transformed, with the help of the F-matrix formalism, to variation of the corrugation width while maintaining a constant amplitude of the refractive index variation. Two examples are given applying the technique to the design of optical waveguide filters with reflectivity profiles of two- and four-rejection bands.     

Theoretical study on second hyperpolarizability for cationic pyridine derivatives

The molecular second hyperpolarizabilities γ of cationic 3- or 4-substituted pyridine derivatives have been investigated. The γ values are calculated by an ab initio molecular orbital (MO) method at correlated levels including CCSD(T). The magnitude of γ for the pyridinium cation is shown to be smaller than that of pyridine. It is found that γ for the pyridinium cation changes dramatically with substitution, whereas γ for neutral pyridine does not show such large substituent effects. This remarkable substituent effect on γ of cationic pyridine derivatives is one of the special features of cationic species.     

6 MeV storage ring dedicated to hard X-ray imaging and far-infrared spectroscopy

The tabletop storage ring, 6 MeV MIRRORCLE, is dedicated to hard X-ray imaging as well as far-infrared (FIR) spectroscopy. In spite of low electron energy, the 6 MeV MIRRORCLE generates hard X-rays ranging from 10 keV up to its electron energy and milliwatt order sub-millimetre range FIR rays. Bremsstrahlung is the mechanism for the hard X-ray generation. Images produced with 11× geometrical magnification display a sharply enhanced edge effect when generated using a 25 mm rod electron target. Bright far-infrared is generated in the same way using a conventional synchrotron light source, but with MIRRORCLE the spectral flux is found to be ∼1000 times greater than that of a standard thermal source. Partially coherent enhancement is observed in the case of FIR output.     

Effect of types of proximal femoral fractures on physical function such as lower limb function and Activities of Daily Living

Objectives: This study aimed to assess physical function such as lower limb function and Activities of Daily Living after surgery for proximal femoral fractures ( unstable medial femoral neck fracture and trochanteric fracture). Methods: This study enrolled 68 patients with proximal femoral fractures. Isometric knee extension strength (IKES), the Japanese Orthopedic Association (JOA) hip score, and the number of days required to develop straight leg raising, transfer, and T-caneassisted gait abilities to become independent were assessed. Patients were classified based on the types of proximal femoral fractures, namely unstable medial femoral neck fracture (bipolar hip arthroplasty [BHA] group), stable trochanteric fracture (S group), and unstable trochanteric fracture (US group). Results: IKES and the JOA hip score were significantly better in the BHA group than in the S and US groups. IKES and the JOA hip score were significantly worse in the US group than in the BHA and S groups. Both transfer and T-cane-assisted gait abilities of patients in the BHA and S groups were indifferent. However, all physical functions were significantly worse in the US group. Conclusions: Our study results suggested that physical therapists plan the different rehabilitation program for the patients with proximal femoral fractures who were classified into three types, namely unstable medial femoral neck fracture, stable trochanteric fracture, and unstable trochanteric fracture, instead of two types.     

新型糖基聚合物的合成及其作为高效液相色谱手性固定相的应用(英文)

Two novel polymers containing glucose units as the main-chain that only differ in terms of their regioregularity were synthesized to evaluate their chiral recognition abilities as chiral stationary phases(CSPs)for high performance liquid chromatography(HPLC).The regioregular polymer(poly-5)shows clear resolution ability for the racemate of cobalt(Ⅲ)acetylacetonate(Co(acac)3),whereas the corresponding regioirregular polymer(poly-3)does not show any chiral recognition for Co(acac)3.The regioregular polymer main-chain seems to play an important role not only in providing an efficient interaction with the racemate but also in expressing the chiral recognition ability as a CSP for HPLC.     

A Bubble Element for the Compressible Euler Equations

In this paper, we present a new Galerkin finite element method with bubble function for the compressible Euler equations. This method is derived from the scaled bubble element for the advection-diffusion problems developed by Simo and his colleagues, which is based on the equivalence between the Galerkin method employing piecewise linear interpolation with bubble functions and the Streamline-Upwind/Petrov Galerkin (SUPG) finite element method using P₁ approximation in the steady advection-diffusion problem. Simo and this author have applied this approach to transient advection-diffusion problems by using a special scaled bubble function called P-scaled bubble, which is designed to work in the transient advection-diffusion problems for any Peclet number from 0 to ∞. The method presented in this paper is an application of this p-scaled bubble element to a pure hyperbolic system.