Magnetic domain structure in Fe78.8−xCoxCu0.6Nb2.6Si9B9 nanocrystalline alloys studied by Lorentz microscopy

The magnetic domain structures of Fe_78.8−xCo_xCu_0.6Nb_2.6Si₉B₉ (x=0, 20, 40, 60) alloys are investigated by Lorentz microscopy coupled with the focused ion beam method. The specimen prepared using the FIB method is found to have a considerably more uniform thickness compared to that prepared using the ion-milling method. In Fe_38.8Co₄₀Cu_0.6Nb_2.6Si₉B₉ and Fe_18.8Co₆₀Cu_0.6Nb_2.6Si₉B₉ alloys, 180° domain walls extending in the direction of the induced magnetic anisotropy are observed. Analysis with Lorentz microscopy reveals that the width of the magnetic domains decreases with an increase in the cobalt content or the induced magnetic anisotropy K_u, that is, the domain width d is proportional to the induced magnetic anisotropy (K_u)^−1/4. On the other hand, in the in situ Lorentz microscopy observation as a function of temperature, magnetic ripple structures are found to appear in a localized area due to the fluctuation of magnetization vectors from 423 K. It is observed that the induced magnetic anisotropy caused by the applied magnetic field at 803 K is not suppressed by the magnetic ripple structures observed at 423–443 K.     

ESR studies of electrochemically prepared poly(3-methylthienylene) films

ESR measurements have been performed on samples of poly(3-methylthienylene, poly(3-methylthienylene) perchlorate, and poly(3-methylthienylene) iodide. The ESR lines observed are concluded to come from defects in the π-conjugated system. It is deduced that the current carriers in the doped film are spinless and the role of bipolarons in the conduction mechanism is suggested.     

Catalytic roles of active-site amino acid residues of coenzyme B12-dependent diol dehydratase: protonation state of histidine and pull effect of glutamate

The hydrogen abstraction and the OH migration processes catalyzed by diol dehydratase are discussed by means of a quantum mechanical/molecular mechanical method. To evaluate the push effect of His143 and the pull effect of Glu170, we considered three kinds of whole-enzyme model, the protonated and two unprotonated His143 models. A calculated activation energy for the hydrogen abstraction by the adenosyl radical is 15.6 (13.6) kcal/mol in the protonated (unprotonated) His143 model. QM/MM calculational results show that the mechanism of the OH migration is significantly changed by the protonation of His143. In the protonated His143 model, the OH group migration triggered by the full proton donation from the imidazolium to the migrating OH group occurs by a stepwise OH abstraction/re-addition process in which the water production reduces the barrier for the C-O bond cleavage. On the other hand, the OH migration in the unprotonated His143 model proceeds in a concerted manner, as we previously proposed using a simple model including only K+ ion and substrate. The latter mechanism seems to be kinetically more favorable from the calculated energy profiles and is consistent with experimental results. The activation barrier of the OH group migration step is only 1.6 kcal/mol reduced by the hydrogen-bonding interaction between the O2 of the substrate and unprotonated His143. Thus, it is predicted that His143 is not protonated, and therefore the main active-site amino acid residue that lowers the energy of the transition state for the OH group migration is determined to be Glu170.     

Siloxyallenes revisited. A useful functional intermediate for the synthesis of (Z)-β-branched Morita-Baylis-Hillman type adducts and (Z)-chalcones

Siloxyallenes proved to be a useful functional intermediate in the preparation of (Z)-β-branched Morita-Baylis-Hillman type adducts by the reaction of aldehydes with silylacetylenes or siloxypropynes. Various (Z)-chalcones were stereoselectively synthesized from siloxypropynes via siloxyallenes.     

Isolation of an inclusion complex of naphthol and its benzoate as an intermediate in the solvent-free benzoylation reaction of naphthol

Solvent-free benzoylation of naphthol was found to proceed via an inclusion complex intermediate of the naphthol and its benzoate by IR spectral monitoring.     

PICOSECOND LASER PHOTOLYSIS OF SQUID RHODOPSIN AT ROOM AND LOW TEMPERATURES

Abstract. Squid rhodopsin extracted with 2% digitonin (pH 10.5 or 7.0) was excited with a 347 nm light pulse from a mode-locked ruby laser at room temperature. Within 19 ps after the excitation, absorbance at 430 nm due to hypsorhodopsin increased and subsequently decreased with a decay time of 45 ± 10 ps. Absorbance at 550 nm due to bathorhodopsin increased with a rise time of 50 ± 10 ps. These results are the first observations of hypsorhodopsin at room temperature and clearly show that hypsorhodopsin is a precursor of bathorhodopsin which has been considered to be the earliest photoproduct in the photobleaching process of rhodopsin.
Hypsorhodopsin appeared with a rise time of 70 ± 10 ps at 421 nm at liquid nitrogen temperature without any bathorhodopsin being observed during the formation of hypsorhodopsin. An experiment using an N₂ laser showed that squid bathorhodopsin converted to lumirhodopsin with a decay time of about 300 ns at room temperature.     

First observation of clusters for solvated tropylium ions

We have first observed clusters for solvated tropylium ions (Tr+(ROH)n) which were isolated from ROH-CH3CN (1:1 by vol.; R = Me, Et, and Prn) solutions by using a specially designed mass spectrometer and found the clear-cut essential features concerning the solvation structure around Tr+.     

Syntheses of potential metabolites of a potent kappa-opioid receptor agonist, TRK-820

Chemical syntheses of three kinds of potential metabolites of TRK-820, a potent kappa-opioid receptor agonist, were described. One of the potential metabolites 2, 17-N-dealkylated TRK-820, was synthesized starting from noroxycodone through 8 steps in 21% total yield. Glucuronidation of intermediate 10 and compound 1, the free base of TRK-820, was carried out stereoselectively to give 3-O-beta-D-glucuronides 15 and 16 in good yields, respectively. Syntheses of potential conjugated metabolites 3 and 4 were accomplished through 10 steps and 2 steps in 11% and 43% total yields, respectively. Among the potential metabolites of TRK-820, compounds 2 and 4 were identified as metabolites in human hepatocytes. The results of pharmacological studies of compounds 2, 3, and 4 are described.     

Caged bulky organic dyes in a polyaromatic framework and their spectroscopic peculiarities

Host–guest structures and properties have been widely studied using relatively small dyes (<1 nm) without bulky groups, due to their smooth incorporation, efficient host–guest interactions, and high analytical accessibility. In this report, on the other hand, three types of sterically demanding organic dyes trapped by a polyaromatic cage were investigated by spectroscopic analyses on the basis of supramolecular interactions. Coumarins with two bulky substituents are bound by the cage in aqueous solution. The resultant caged dyes show unusual emission enhancement, depending on the difference of a single heteroatom in their substituents. The color of perylene bisimides with two bulky substituents is remarkably changed from yellow to red upon caging. This peculiarity stems from the twist of the substituents in the cage, revealed by the combination of absorption and theoretical studies. Furthermore, tetrasubstituted, bulky porphyrins are caught by the cage in aqueous solution. The caged bulky dyes also display altered color and absorption properties, which remain intact even under acidic conditions. In contrast to typical covalent functionalization and previous host–guest studies toward small and non-bulky dyes, the unusual, non-covalent spectroscopic modulation of the large and bulky dyes can be accomplished for the first time by the present cage, featuring a prolate polyaromatic framework with four openings.

Here we report that the open large cavity of an M₂L₄ polyaromatic cage can efficiently bind sterically demanding organic dyes with coumarin, perylene bisimide, and porphyrin cores in aqueous solution. The spectroscopic properties of the caged dyes are largely modulated in the cavity.