Studies on the terpenoids and related alicyclic compounds—XXII: Stereochemical study on the angular hydroxylation of polycyclic ketones using benzeneseleninic anhydride

Introduction of an OH group to the tertiary carbon of simple ketones (1, 2 and 6), furanoeremophilane-type ketones (12–19), and tricyclic ketones (20–22) by the use of benzeneseleninic anhydride is described. 10β-Hydroxy compounds were obtained in the case of 12–14 and 20–22. 10α-Hydroxy compounds were obtained in the case of 15 and 16. In the hydroxylation reaction of polycyclic ketones using benzeneseleninic anhydride, the results suggest that the thermodynamically more stable product was usually produced as the major product.     

Cellulose synthesizing terminal complexes in the ascidians

The structure of cellulose synthesizing terminal complexes (TCs) has been investigated in different species of ascidians. The linear-shaped TCs consisting of two types of membrane particles were found in four species belonging to two orders including previous data . A relationship between the length of TCs and the size of produced cellulose microfibrils was found within the same order. The density and localization patterns of TCs coincided with the arrangement of cellulose microfibrils in the innermost layer of the tunic, that is outer protective tissue and a major cellulosic component in the ascidians. This suggests that the shape and dimension of the microfibril bundle is influenced by an arrangement of TCs in the epidermal cell membrane.     

Roles of the proximal hydrogen bonding network in cytochrome P450cam-catalyzed oxygenation

Structural and functional roles of the hydrogen bonding network that surrounds the heme-thiolate coordination of P450(cam) from Pseudomonas putida were investigated. A hydrogen bond between the side chain amide of Gln360 and the carbonyl oxygen of the axial Cys357 was removed in Q360L. The side chain hydrogen bond and the electrostatic interaction between the polypeptide amide proton of Gln360 and the sulfur atom of Cys357 were simultaneously removed in Q360P. The increased electron donation of the axial thiolate in Q360L and Q360P was evidenced by negative shifts of their reduction potentials by 45 and 70 mV, respectively. Together with the results on L358P in which the amide proton at position 358 was removed (Yoshioka, S., Takahashi, S., Ishimori, K., Morishima, I. J. Inorg. Biochem. 2000, 81, 141-151), we propose that the side chain hydrogen bond and the electrostatic interaction of the amide proton with the thiolate ligand cause approximately 45 and approximately 35 mV of positive shifts, respectively, of the redox potential of the heme in P450(cam). The resonance Raman spectra of the ferrous-CO form of the Q360 mutants showed a downshifted Fe-CO stretching mode at 482 approximately 483 cm(-)(1) compared with that of wild-type P450(cam) at 484 cm(-)(1). The Q360 mutants also showed the upshift by 4 approximately 5 cm(-)(1) of the Fe-NO stretching mode in the ferrous-NO form. These Raman results indicate the increase in the sigma-electron donation of the thiolate ligand in the reduced state of the Q360 mutants and were in contrast to the increased pi-back-donation of the thiolate in L358P having an upshifted Fe-CO stretching mode at 489 cm(-)(1). The catalytic activities of the Q360 mutants for the unnatural substrates were similar to those of the wild-type enzyme, indicating that the increased sigma-electron donation does not promote the O-O bond heterolysis in the Q360 mutants, although the increased pi-electron donation in L358P promoted the heterolysis of the O-O bond. We conclude that the functions of the proximal hydrogen bonding network in P450(cam) are to stabilize the heme-thiolate coordination, and to regulate the redox potential of the heme iron. Furthermore, we propose that the pi-electron donation, not the sigma-electron donation, of the thiolate ligand promotes the heterolysis of the O-O bond of dioxygen.     

Fourier transform millimeter-wave spectroscopy of the ethyl radical in the electronic ground state

The pure rotational spectrum of the ethyl radical (C2H5) has been detected for the first time with the Fourier transform millimeter-wave spectrometer. The ethyl radical is produced by discharging the C2H5I gas diluted in Ar. The 1(01)-0(00) rotational transition of the ethyl radical is observed in the frequency range from 43,680 to 43,780 MHz. The observed spectrum shows a very complicated pattern of the fine and hyperfine structures of a doublet radical with the nuclear spins of five protons. The fine and hyperfine components are assigned with the aid of measurements of the Zeeman splittings. As a result, the 22 lines are ascribed to the transitions in the ground vibronic state (A2"). The rotational constant, the spin-rotation interaction constant, and hyperfine interaction constants are determined by the least-squares fit. The Fermi contact term of the alpha-proton is determined to be -64.1654 MHz in the gas phase, indicating that the structure of the -CH2 is essentially planar. The present rotational spectroscopic study further supports that the methyl group of the ethyl radical can be regarded as a nearly free internal rotor with a low energy barrier. A few unassigned lines still remain, which may be vibrational satellites of the internal rotation mode.     

ENERGY TRANSFER FROM PHYCOBILINS TO CHLOROPHYLL a IN HEAT-STRESSED CELLS OF Anacystis nidulans: CHARACTERIZATION OF THE LOW TEMPERATURE 683 nm FLUORESCENCE EMISSION BAND*

Abstract— Heat-induced changes of the characteristics of fluorescence spectra of Anacystis nidulans cells were studied after 39°C-grown cells were heated at 55°C. Heat-treatment of the cells induced no changes in the absorption properties or photosystem I-catalyzed cytochrome oxidation, but induced a dramatic change in the fluorescence characteristics of the cells. The low temperature fluorescence emission spectra of heated cells showed a large increase of fluorescence emission at683–685 nm (F683) and at 695 nm, while the bands at 660 nm (allophycocyanin) and at 718 nm (chlorophyll a of photosystem I) were not affected when the cells were excited with light absorbed by phycobilins. When the cells were heated for various periods, a progressive increase of the intensity of F683 occurred with the loss in oxygen evolution capacity. The increase of the F683 band was observed prior to the increase of the F695 band. Quenching of emission spectra by the addition of quinones indicates that the F683 band emanated mainly from a long wavelength form of allophycocyanin. Excitation spectra of heated cells measured at 77 K showed that light absorbed by phycobilins was effective in exciting F685, F695, and F715 emission. A possible energy distribution pathway in Anacystis nidulans is discussed.     

Evidence for epitaxial arrangement and high conformational order of an organic monolayer on Si(111) by sum frequency generation spectroscopy

The structure of an octadecyl monolayer formed on a hydrogen-terminated Si(111) surface in neat octadecene was studied by infrared-visible sum frequency generation (SFG) spectroscopy. The SFG spectra in the CH vibration region were dominated by peaks corresponding to those of the methyl group, confirming that the monolayer is essentially in the all-trans conformation. The shapes of the spectra were strongly dependent on the azimuthal angle, and the strength of the asymmetric vibration mode obtained from the theoretical fitting shows threefold symmetry with respect to the azimuthal angle, suggesting the epitaxial arrangement of the monolayer with the Si(111) substrate. The orientation angle of the methyl group estimated from SFG anisotropy was in good agreement with the theoretical prediction.     

Highly phosphorescent bis-cyclometalated iridium complexes: synthesis, photophysical characterization, and use in organic light emitting diodes.

The synthesis and photophysical study of a family of cyclometalated iridium(III) complexes are reported. The iridium complexes have two cyclometalated (C(**)N) ligands and a single monoanionic, bidentate ancillary ligand (LX), i.e., C(**)N2Ir(LX). The C(**)N ligands can be any of a wide variety of organometallic ligands. The LX ligands used for this study were all beta-diketonates, with the major emphasis placed on acetylacetonate (acac) complexes. The majority of the C(**)N2Ir(acac) complexes phosphoresce with high quantum efficiencies (solution quantum yields, 0.1-0.6), and microsecond lifetimes (e.g., 1-14 micros). The strongly allowed phosphorescence in these complexes is the result of significant spin-orbit coupling of the Ir center. The lowest energy (emissive) excited state in these C(**)N2Ir(acac) complexes is a mixture of (3)MLCT and (3)(pi-pi) states. By choosing the appropriate C(**)N ligand, C(**)N2Ir(acac) complexes can be prepared which emit in any color from green to red. Simple, systematic changes in the C(**)N ligands, which lead to bathochromic shifts of the free ligands, lead to similar bathochromic shifts in the Ir complexes of the same ligands, consistent with "C(**)N2Ir"-centered emission. Three of the C(**)N2Ir(acac) complexes were used as dopants for organic light emitting diodes (OLEDs). The three Ir complexes, i.e., bis(2-phenylpyridinato-N,C2')iridium(acetylacetonate) [ppy2Ir(acac)], bis(2-phenyl benzothiozolato-N,C2')iridium(acetylacetonate) [bt2Ir(acac)], and bis(2-(2'-benzothienyl)pyridinato-N,C3')iridium(acetylacetonate) [btp2Ir(acac)], were doped into the emissive region of multilayer, vapor-deposited OLEDs. The ppy2Ir(acac)-, bt2Ir(acac)-, and btp2Ir(acac)-based OLEDs give green, yellow, and red electroluminescence, respectively, with very similar current-voltage characteristics. The OLEDs give high external quantum efficiencies, ranging from 6 to 12.3%, with the ppy2Ir(acac) giving the highest efficiency (12.3%, 38 lm/W, >50 Cd/A). The btp2Ir(acac)-based device gives saturated red emission with a quantum efficiency of 6.5% and a luminance efficiency of 2.2 lm/W. These C(**)N2Ir(acac)-doped OLEDs show some of the highest efficiencies reported for organic light emitting diodes. The high efficiencies result from efficient trapping and radiative relaxation of the singlet and triplet excitons formed in the electroluminescent process.     

First total synthesis of the antitumor compound (-)-kazusamycin A and absolute structure determination

The first total synthesis of kazusamycin A, a potent antitumor compound from an actinomycete, has been achieved, and its absolute structure was determined. Paterson's stereoselective aldol reaction was successfully applied to construct the contiguous chiral centers by using an originally designed optically active 2-acyl-1,3-propanediol derivative.     

Effect of floc structure on the rate of shear coagulation

We derived a mathematical expression for the temporal evolution of the number of particles due to shear coagulation, covering the later stage by expanding the initial stage approximation to take into account the formation of floc structure. In the derivation, it is assumed that flocculation proceeds through binary collisions between identical fractal flocs. The capture efficiency between flocs is calculated on the basis of trajectory analysis, which is determined by viscous hydrodynamic interaction between flocs and van der Waals attractive forces between two primary particles located at colliding points of flocs. The validity of the derived equation was tested by a coagulation experiment using polystyrene sulfate latex particles under conditions of rapid coagulation. The experiment was carried out in a laminar Couette flow generated in the gap between two concentric cylinders. Careful and direct observation of flocculation under microscopy provided the data on the fractal dimension as well as the temporal evolution of number concentration of flocs. The measured rate of coagulation gradually increases in accordance with the formation of the fractal structure of flocs. This behavior agreed very well with the prediction based on the derived equation.     

Properties of low temperature swelling hydrogels prepared with partially saponified PVA and drug release using the hydrogels

The hydrogels prepared by the crosslinking of partially saponified poly(vinyl alcohol) (PVA) which has low critical solution temperature (LCST) in water showed characteristics of swelling at low temperature and shrinkage at high temperature. The hydrogels showed repeatable swelling–shrinking behavior. The hydrogels containing release substances such as cyanocobalamin, p‐acetamidophenol, insulin and ovalbumin were prepared by dipping these aqueous solutions and the release substances were studied. Insulin and ovalbumin were not absorbed by the hydrogels when the use of partially PVA with the degrees of polymerization (DPs) of 540 were prepared, but absorbed by the hydrogels with DPs of 1860. The size of the polymer network prepared with a higher DP was suitable for the absorption of insulin and ovalbumin. In accordance with release substances, the release patterns were different. In this way, the polymer network sizes and their swelling behaviors of partially saponified PVAs were estimated. Copyright © 2003 John Wiley & Sons, Ltd.