Structures of linear poly(ethylene oxide) compounds and potassium complexes in dichloromethane

The H-1 NMR spectra of a series of linear poly(ethylene oxides) compounds (POE compounds) were measured in dichloromethane-d2 at 25 degrees C, where the POE compounds (HO-(CH2CH2O-)n-R) were unsubstituted POE, HEOn (R=H, n=3, 4, 6), and alkyl-substituted POE, DEOn (R=C12H25, n=4, 6, 8) and MeEO6 (R=CH3, n=6). All the peaks of H-1 NMR signals were assigned to each methylene proton of POE. The chemical shifts and coupling constant between vicinal protons were evaluated by a complete spin analysis. The spectral changes of POE compounds by the addition of potassium ion were measured at various metal-to-POE ratios. The chemical shift change of each methylene proton by the formation of the complex was evaluated. The downfield shift of methylene protons caused by the complex formation indicates that the ethylene oxide that the ethylene oxide moiety is coordinating to surround the potassium ion in the same manner as the cyclic crown ether complexes. The results of spin lattice relaxation time measurements of DEO6 suggest that all the methylenes of the ethylene oxides are immobilized by the coordination to the metal ion. Thus, it was confirmed that all oxygens of POE are participating in the complex formation.     

Delineation of malignant glioma by turbo spin echo multislice motion-sensitized driven-equilibrium (TSE-MSDE) with gadolinium-based contrast media: A case report

T1-weighted images by turbo spin echo multislice motion-sensitized driven-equilibrium with gadolinium-based contrast media clearly delineated the brainstem invasion of a malignant glioma in an 80-year-old woman compared with other magnetic resonance imaging sequences.     

Mössbauer study on Fe0.068Ni0.932Cl2 with competing spin anisotropies

Mössbauer measurements on Fe_0.068Ni_0.932Cl₂ were done at temperatures between 55K and 4.2K. We have found that below T_N-50K an observed spectrum is composed of two kinds of spectra and that the composition ratio changes gradually with temperature. The average angle of Fe²⁺ spins, \(\overline {\theta _{Fe} } \) , with the c-axis is smaller than \(\overline {\theta _c } \) by ?15° at each temperature below T_N, where \(\overline {\theta _c } \) is the average angle of total spins with the c-axis in this system obtained from the neutron scattering measurements. This is reasonably understood if we take into account that Fe²⁺ spins have the strong uniaxial anisotropy along the c-axis. We discuss the coexistence of the two kinds of spectra by considering the exchange energy of Fe²⁺ spins and the local magnetic anisotropy.     

Analysis of the release process of phenylpropanolamine hydrochloride from ethylcellulose matrix granules II. effects of the binder solution on the release process

The release properties of phenylpropanolamine hydrochloride (PPA) from ethylcellulose (EC) matrix granules prepared by an extrusion granulation method were examined. The release process could be divided into two parts; the first and second stages were analyzed by applying square-root time law and cube-root law equations, respectively. The validity of the treatments was confirmed by the fitness of a simulation curve with the measured curve. In the first stage, PPA was released from the gel layer of swollen EC in the matrix granules. In the second stage, the drug existing below the gel layer dissolved and was released through the gel layer. The effect of the binder solution on the release from EC matrix granules was also examined. The binder solutions were prepared from various EC and ethanol (EtOH) concentrations. The media changed from a good solvent to a poor solvent with decreasing EtOH concentration. The matrix structure changed from loose to compact with increasing EC concentration. The preferable EtOH concentration region was observed when the release process was easily predictable. The time and release ratio at the connection point of the simulation curves were also examined to determine the validity of the analysis.     

Cytochrome c-crown ether complexes as supramolecular catalysts: cold-active synzymes for asymmetric sulfoxide oxidation in methanol

A series of supramolecular complexes of various cytochrome c proteins with 18-crown-6 derivatives behave as cold-active synzymes in the H2O2 oxidation of racemic sulfoxides. This interesting behavior contrasts with native functionality, where the employed proteins act as electron transfer carriers. ESI-MS. UV, CD, and Raman spectroscopic characterizations reveal that four or five 18-crown-6 molecules strongly bind to the surface of the cytochrome c and also that nonnatural low-spin hexacoordinate heme structures are induced in methanol. Significantly, crown ether complexation can convert catalytically inactive biological forms to catalytically active artificial forms. Horse heart, pigeon breast, and yeast cytochromes c all stereoselectively oxidize (S)-isomers of methyl tolyl sulfoxide and related sulfoxides upon crown ether complexation. These supramolecular catalysts show the highest efficiency and enantiomer selectivity at -40 degrees C in the H202-dependent sulfoxide oxidation, while oxidative decomposition of the heme moieties predominantly occurs at room temperature. The oxidation reactivity of the employed sulfoxides is apparently related to steric constraints and electrochemical oxidation potentials of their S=O bonds. Among the cytochrome c complexes, yeast cytochrome c demonstrates the lowest catalytic activity and degradation reactivity. It has a significantly different protein sequence, suggesting that crown ether complexation effectively activates heme coordination but may additionally alter the native backbone structure. The proper combination of cytochrome c proteins, 18-crown-6 receptors, and external circumstances can be used to successfully generate "protein-based supramolecular catalysts" exhibiting nonbiological reactivities.     

Nonvolatile Me(3)P-like P-donor ligand: synthesis and properties of 4-phenyl-1-phospha-4-silabicyclo[2.2.2]octane

[reaction: see text] A new trialkylphosphine ligand with Me(3)P-like steric and electronic properties, 4-phenyl-1-phospha-4-silabicyclo[2.2.2]octane (Ph-SMAP), was synthesized. Given a phenyl group at the silicon atom, the Ph-SMAP ligand displayed nonvolatility with retention of Me(3)P-like properties. The new ligand was air-stable, crystalline, and easy to handle.     

Absolute asymmetric photoreactions of aliphatic amino acids by circularly polarized synchrotron radiation: critically pH-dependent photobehavior

The absolute asymmetric photoreaction (AAP) of racemic aliphatic amino acids, such as alanine (Ala) and leucine (Leu), by left- and right-handed circularly polarized light (l- and r-CPL) irradiation was investigated in aqueous solutions at various pHs, by using the Onuki-type polarizing undulator installed in an electron storage ring. The magnitude of the optical purity (op) generated and the enantiomer-enriching mechanism operative in the AAP were found to be entirely dependent on the ionic state (and thus pH) of the amino/carboxylic acid moieties. At pH 1, the op of Ala and Leu determined by circular dichroism (CD) spectral measurement gradually developed with CPL irradiation, according to Kagan's equation. In contrast, irradiation at pH 7 gave op's much smaller than the theoretical values predicted by Kagan's equation. However, it turned out that the photodecomposition at pH 7 produces the corresponding alpha-hydroxycarboxylic acids stereoselectively, the CD sign of which is just opposite to that of the remaining amino acid, thus affording the apparently small op. It is concluded that, irrespective of solution pH, the AAP of amino acid proceeds upon CPL irradiation. At pH 1, the photodecomposition of valine, Leu, and isoleucine occurs via a Norrish type II mechanism, which is also applicable to other amino acids possessing a gamma-hydrogen. In the case of amino acids lacking a gamma-hydrogen, such as glycine and Ala, the photodecomposition mechanism is a photodeamination/hydroxylation and a Norrish type I reaction. At pH 7, the main photoproducts were ammonia and alpha-hydroxycarboxylic acids that were produced via photodeamination.     

Phosphorus Ligands with a Large Cavity: Synthesis of Triethynylphosphines with Bulky End Caps and Application to the Rhodium‐Catalyzed Hydrosilylation of Ketones

Trialkynylphosphines substituted with bulky triarylsilyl groups at the alkyne termini were synthesized. The new phosphines P(C?CSiAr₃)₃ (Ar=3,5‐tBu₂‐4‐MeOC₆H₂, 3,5‐(Me₃Si)₂C₆H₃) are uncrowded near the phosphorus atom but bulky in the distal region. As a result, they contain a large cavity, at the bottom of which the phosphine lone‐pair electrons are located. The compounds are stable to oxidation by air and hydrolysis. DFT calculations suggested that the triethynylphosphines are good π‐acceptor ligands, comparable with P(OAr)₃. The trialkynylphosphines reacted with [{RhCl(cod)}₂] (P/Rh=1.1:1) to give selectively the monophosphine–rhodium complex [RhCl(cod)P(C?CSiAr₃)₃]. X‐ray crystal‐structure analysis revealed that the {RhCl(cod)} fragment is fully accommodated by the cavity of the phosphine ligand. Compared to the effect of analogues with smaller end caps and PPh₃, the trialkynylphosphines accelerated markedly the rhodium‐catalyzed hydrosilylation of ketones with a triorganosilane. It is proposed that the higher catalytic activity observed with the holey phosphines is a result of the preferential formation of a monophosphine–rhodium species.     

Formation mechanism of a multihollow structure within submicron-sized styrene/methacrylic acid copolymer particles by the stepwise acid/alkali method

 The formation mechanism of a multihollow structure within submicron-sized styrene/methacrylic acid copolymer particles by the stepwise alkali/acid method, which we proposed in 1990, was discussed thermodynamically from the viewpoint of interfacial free energy. Received: 6 March 2001 Accepted: 17 May 2001