Blue myoglobin reconstituted with an iron porphycene shows extremely high oxygen affinity

Myoglobin will be a good scaffold for engineering a function into proteins. To modulate the physiological function of myoglobin, almost all approaches have been demonstrated by site-directed mutagenesis, however, there are few studies which show a significant improvement in the function. In contrast, we focused on the replacement of heme in the protein with an artificial prosthetic group. Recently, we prepared a novel myoglobin reconstituted with an iron porphycene as a structural isomer of mesoheme. The bluish colored reconstituted myoglobin is relatively stable and the deoxymyoglobin reversibly binds ligands. Interestingly, the O2 affinity of the reconstituted myoglobin, 1.1 x 109 M-1, is a significant 1,400-fold higher than that of the native myoglobin. Furthermore, the unfavorable autoxidation kinetics show 7-fold decrease in rate for the reconstituted myoglobin relative to the native myoglobin, indicating the stable oxy-form against autoxidation. The net results come from the slow dissociation of the O2 ligand in the reconstituted myoglobin, koff = 0.11 s-1, because of the formation of strong hydrogen bond between His64 and negatively charged dioxygen. The present study indicates that the replacement of native heme with an artificially created prosthetic group will give us a unique function into a hemoprotein.     

Electromagnetic Properties of Lanthanum Manganese Oxides Doped with Iron

The mechanism of GMR effects in La(Mn_1–x Fe _x )O₃ (x=0, 0.01, 0.03) oxides has been investigated by means of magnetic measurements, resistivity measurements in magnetic field and Mössbauer spectroscopy. For the x=0.01 sample, the GMR behavior is similar to that of the conventional (La, A)MnO₃ (A: divalent cations) oxides. For the x=0.03 sample, even though the temperature dependence of the Mössbauer spectra was similar to that of the x=0.01 sample, the mechanism for the occurrence of the GMR effect seems to be different. The x=0 sample shows a similar behavior to the x=0.03 sample. A thermal stabilization of spin fluctuation is proposed for the x=0 and x=0.03 sample.     

Hyperspaces of Normed Linear Spaces with the Attouch–Wets Topology

Let Cld _AW (X) be the hyperspace of nonempty closed subsets of a normed linear space X with the Attouch–Wets topology. It is shown that the space Cld _AW (X) and its various subspaces are AR's. Moreover, if X is an infinite-dimensional Banach space with weight w(X) then Cld _AW (X) is homeomorphic to a Hilbert space with weight 2 ^w(X).     

Oxygen ion conduction in 12CaO·7Al2O3: O2− conduction mechanism and possibility of O− fast conduction

12CaO·7Al₂O₃ (C12A7) with a unique nano-porous structure and free O^2? ions entrapped in sub-nanometer-sized cages is a fast oxygen-ion-conducting material. These free O^2– may be replaced by various oxygen-related species, OH^?, O^2? and O^?, by tuning the atmosphere during the heat treatment. We examined the conduction mechanism for stoichiometric C12A7 (C12A7:O^2?), in which O^2? ions exist as counter anions in sub-nanometer-sized cages, by Raman measurement of C12A7:O^2? annealed in a dry ¹⁸O₂ atmosphere. It was revealed that the primary ion conducting species is an O^2? ion which diffuses via exchange with O^2? in the cage wall. An experimental result on the sample containing O^? ions implied that O^? is more mobile than O^2? in C12A7. Ab initio calculations on the diffusion paths of O^2? and O^? ions in C12A7 supported the above experimental results.     

Evaluation and comparison of three novel microbubbles: Enhancement of ultrasound-induced cell death and free radicals production

Three novel lipid-shell-type microbubbles (MBs), AS-0100, BG6356A and BG6356B, have been evaluated for their impact on ultrasound (US)-induced cell death and free radicals production. Previously studied and well-characterized US exposure conditions were employed in which human myelomonocytic lymphoma U937 cells were exposed to 1 MHz pulsed US beam (0.3 W/cm², 10% duty factor) for 1 min with or without MBs. Three different concentrations of each MB were used. Apoptosis and cell lysis were assessed by examining phosphatidylserine externalization and by counting viable cells, respectively, 6 h post-exposure. Free radicals production and scavenging activities were evaluated using electron paramagnetic resonance (EPR)-spin trapping. The results showed that only AS-0100 and BG6356A were able to enhance the US-induced apoptosis, mainly by increasing the secondary necrosis. Apoptosis and cell lysis seemed to depend more on mechanical forces exerted by oscillating MBs while free radicals played a trivial role. BG series MBs exhibited pronounced scavenging activities. Generally, despite the need for further optimization, AS-0100 and BG6356A appear to be promising as adjuncts in cases where US-induced cell death is required.     

Interaction and arrangement of nitrogen and carbon atoms in fcc γ-iron

A Mössbauer effect measurement has been done for Fe?N, Fe?Al?C and Fe?Ni?C austenite in order to study the interaction between the interstitial atoms and their distribution among the octahedral sites of the fcc lattice, together with the influence of Al and Ni atoms. The spectra for Fe?N and Fe?Al?C austenite are decomposed into three components; one singlet γ₀, and two sets of doublet γ₁ and γ₂, with different quadrupole splittings, while no γ₂ component is found in the spectrum for Fe?Ni?C. By analyzing the component ratio in each spectrum, it is concluded that, in Fe?N and Fe?Al?C, the interaction between 2nd nearest neighboring nitrogen or carbon atoms is attractive, and is repulsive between 1st nearest for Fe?N, and that the interaction between 2nd nearest atoms is repulsive for Fe?Ni?C. By measuring the spectra of Fe?Ni?C in magnetic field, the sign of EFG for most of the γ₁ component is determined to be negative.     

Fluorine and chlorine behavior in chlorine-rich volcanic rocks from White Island, New Zealand

Extraordinarily high chlorine-bearing volcanic bombs were erupted from White Island volcano on January 25, 1987. The concentrations of fluorine and chlorine were measured in these paralava bombs and their likely parent rocks. The paralavas contain glass with over 1.0 wt.% and up to 1.7% of chlorine. The F/Cl ratios and their relationship with other constituents show that the fluorine and chlorine in the bombs were derived from hydrothermal fluid, most likely concentrated brine in an active Crater Pool.     

Ligand binding properties of myoglobin reconstituted with iron porphycene: unusual O2 binding selectivity against CO binding

Sperm whale myoglobin, an oxygen storage hemoprotein, was successfully reconstituted with the iron porphycene having two propionates, 2,7-diethyl-3,6,12,17-tetramethyl-13,16-bis(carboxyethyl)porphycenatoiron. The physicochemical properties and ligand bindings of the reconstituted myoglobin were investigated. The ferric reconstituted myoglobin shows the remarkable stability against acid denaturation and only a low-spin characteristic in its EPR spectrum. The Fe(III)/Fe(II) redox potential (-190 mV vs NHE) determined by the spectroelectrochemical measurements was much lower than that of the wild-type. These results can be attributed to the strong coordination of His93 to the porphycene iron, which is induced by the nature of the porphycene ring symmetry. The O2 affinity of the ferrous reconstituted myoglobin is 2600-fold higher than that of the wild-type, mainly due to the decrease in the O2 dissociation rate, whereas the CO affinity is not so significantly enhanced. As a result, the O2 affinity of the reconstituted myoglobin exceeds its CO affinity (M' = K(CO)/K(O2) < 1). The ligand binding studies on H64A mutants support the fact that the slow O2 dissociation of the reconstituted myoglobin is primarily caused by the stabilization of the Fe-O2 sigma-bonding. The IR spectra for the carbon monoxide (CO) complex of the reconstituted myoglobin suggest several structural and/or electrostatic conformations of the Fe-C-O bond, but this is not directly correlated with the CO dissociation rate. The high O2 affinity and the unique characteristics of the myoglobin with the iron porphycene indicate that reconstitution with a synthesized heme is a useful method not only to understand the physiological function of myoglobin but also to create a tailor-made function on the protein.     

Semi-free actions of zero-dimensional compact groups on Menger compacta

Let be the -dimensional universal Menger compactum, a -set in and a metrizable zero-dimensional compact group with the unit. It is proved that there exists a semi-free -action on such that is the fixed point set of every . As a corollary, it follows that each compactum with can be embedded in as the fixed point set of some semi-free -action on .

     

Electron localization and a confined electron gas in nanoporous inorganic electrides

The nanoporous main group oxide 12CaO.7Al(2)O3 (C12A7) can be transformed from a wide-gap insulator to an electride where electrons substitute anions in cages constituting a positive frame. Our ab initio calculations of the electronic structure of this novel material give a consistent explanation of its high conductivity and optical properties. They show that the electrons confined in the inert positive frame are localized in cages and undergo hopping between neighboring cages. The results are useful for the understanding of behavior of confined electron gas of different topology and electron-phonon coupling, and for designing new transparent conductors, electron emitters, and electrides.