Structural phase transition of Gd3RuO7

Structural phase transition of trigadorinium ruthenium heptaoxide, Gd(3)RuO(7), has been investigated by in situ high-temperature single-crystal X-ray diffraction. A small shrinkage in b-length and an expansion in c-length were observed between 363 and 383 K with increasing temperature. No significant change occurred in a-length within experimental errors. The changes were essentially reversible against temperature. Structures of the high-temperature modification have been determined at 423, 773, and 1223 K assuming the orthorhombic Cmcm symmetry. The structure of the low-temperature modification has been determined at 293 K, assuming the orthorhombic P2(1)nb symmetry with doubled unit cell along the b-axis of the high-temperature modification. The transition from high- to low-temperature modification can be structurally characterized by tilts about axes close to the c-axis of the unit cell occurring on half of the RuO(6) octahedra. These octahedral tilts couple with a reduction in coordination number of the Gd atom bridging the adjacent RuO(6) single chains along the b-axis. The present study also revealed the presence of structural disorder in the high-temperature Cmcm modification that had not been reported for the archetypal Cmcm structures of lanthanide ruthenates (Ln(3)RuO(7)) and osmates (Ln(3)OsO(7)) in the literature. The disorder includes a dynamical or static distribution of one-third of Gd atoms in the unit cell, which is presumably linked to the libration of the octahedral tilts about the axes close to c.     

Formation mechanism of one-dimensional Si islands on a H/Si(001) surface

The formation mechanism of one-dimensional Si islands on a H/Si(001)-(2x1) surface is studied using scanning tunneling microscopy/spectroscopy and first-principles calculations. We observed that one-dimensional islands that are made from dimer chains are formed at the initial growth stages similar to the bare Si(001) surface. It is found that the number of odd-numbered dimer chains is larger than that of even-numbered dimer chains. We propose the growth processes of the two types of growth edges to explain the observation.     

Chiral Biomineralization: Mirror‐Imaged Helical Growth of Calcite with Chiral Phosphoserine Copolypeptides

The O‐phospho‐L ‐serine [Ser(P)] containing peptides and proteins play an important role in controlling the morphology of biominerals. The poly[Ser(P)] and copoly[Ser(P)^xAsp^y] affect the calcium carbonate (CaCO₃) morphology and polymorph. The CaCO₃ helical structures were obtained in the presence of copoly[Ser(P)⁷⁵Asp²⁵]. When the L ‐copolymer was used as an additive, a clockwise P twisted spiral morphology was formed. On the other hand, when using D ‐copolymer, a counterclockwise M twisted spiral morphology was obtained.

Optical micrographs of chiral morphologies of CaCO₃ in the presence of a) L ‐copolymer and b) D ‐copolymer.     

Coherent-phonon-assisted excitation transfer via optical near fields in dilute magnetic semiconductor nanostructures

Optical near-field (ONF) phenomena observed in nanoscale systems have been applied to nano-fabrication and nano-photoelectronic devices for the last decade. Excitation transfer (ET) is an elementary process caused by ONF interaction localized at the nanoscale in real space. Recently, we have observed spin-dependent ET controlled by an external field and discovered the sign of assistance of phonons. In this work, we elucidate that the assistance of coherent phonons in ET originates from two types of mechanism: energy resonance between exciton levels renormalized by phonon effects and enhancement by phase matching between coherent oscillation of populations and phonon oscillation. This study will stimulate the development of the application of ET via a ONF to nano-photoelectronic devices.     

Proton‐Transfer Reaction Dynamics and Energetics in Calcification and Decalcification

CaCO₃‐saturated saline waters at pH values below 8.5 are characterized by two stationary equilibrium states: reversible chemical calcification/decalcification associated with acid dissociation, Ca²⁺+HCO₃^??CaCO₃+H⁺; and reversible static physical precipitation/dissolution, Ca²⁺+CO₃^2??CaCO₃. The former reversible reaction was determined using a strong base and acid titration. The saturation state described by the pH/P_CO2‐independent solubility product, [Ca²⁺][CO₃^2?], may not be observed at pH below 8.5 because [Ca²⁺][CO₃^2?]/([Ca²⁺][HCO₃^?]) ?1. Since proton transfer dynamics controls all reversible acid dissociation reactions in saline waters, the concentrations of calcium ion and dissolved inorganic carbon (DIC) were expressed as a function of dual variables, pH and P_CO2. The negative impact of ocean acidification on marine calcifying organisms was confirmed by applying the experimental culture data of each P_CO2/pH‐dependent coral polyp skeleton weight (Wskel) to the proton transfer idea. The skeleton formation of each coral polyp was performed in microspaces beneath its aboral ectoderm. This resulted in a decalcification of 14 weight %, a normalized CaCO₃ saturation state Λ of 1.3 at P_CO2 ≈400 ppm and pH ≈8.0, and serious decalcification of 45 % and Λ 2.5 at P_CO2 ≈1000 ppm and pH ≈7.8.     

Application of residue distribution along the sequence for discriminating outer membrane proteins

Discriminating outer membrane proteins from other folding types of globular and membrane proteins is an important problem both for detecting outer membrane proteins from genomic sequences and for the successful prediction of their secondary and tertiary structures. In this work, we have systematically analyzed the distribution of amino acid residues in the sequences of globular and outer membrane proteins. We observed that the occurrence of two neighboring aliphatic and polar residues is significantly higher in outer membrane proteins than in globular proteins. From the information about the dipeptide composition we have devised a statistical method for discriminating outer membrane proteins from other globular and membrane proteins. Our approach correctly picked up the outer membrane proteins with an accuracy of 95% for the training set of 337 proteins. On the other hand, our method has correctly excluded the globular proteins at an accuracy of 79% in a non-redundant dataset of 674 proteins. Furthermore, the present method is able to correctly exclude alpha-helical membrane proteins up to an accuracy of 87%. These accuracy levels are comparable to other methods in the literature. The influence of protein size and structural class for discrimination is discussed.     

New principle of magnetophoretic velocity mass analysis.

We propose a novel principle of velocity mass analysis of a micro-particle using magnetophoretic force. The new method can determine the mass of a particle from its magnetophoretic velocity change in a high magnetic field gradient in a low viscous medium such as air. In the present study, the new principle was demonstrated by the magnetophoretic acceleration of an aqueous manganese(II) chloride micro-droplet and the deceleration of a water micro-droplet in the atmosphere. The observed velocity change was analyzed taking into account the mass of the droplet through the acceleration term of the equation of motion. The experimental results proved that the inertia force in the magnetophoretic velocity of a micro-particle could be detected in air. The present method provided an innovative mass analysis method without any ionization of the sample.     

Helix unwinding process in the chiral smectic C phase of MHPOBC as observed by conoscopy

Conoscopic studies have been made on the helix unwinding process in the chiral smectic C phase of MHPOBC. The unwinding process is rather unique in the sense that abrupt changes of the biaxiality and apparent tilt angle are followed by further gradual changes before the complete helix unwinding. The process is qualitatively explained by simulating the conoscopic images using the 4 ×4 matrix method with consideration of model molecular distributions, by taking account of both the ferroelectric and dielectric coupling between molecules and a field. The transmittance loss due to selective reflection was also measured under the application of a stepwise d.c. field. The shift of the dip position due to the loss, toward a longer wavelength region, was observed at low field. In contrast, the emergence of a transmittance loss at the same wavelength as that of an unperturbed state was observed. This phenomenon is explained by the ferroelectric deformation of a helix with the pitch unchanged.     

Raman microprobe spectrometer installed in a super-conducting magnet.

A Raman microprobe spectrometer that could be installed in the bore of a cryogen free super-conducting magnet (10 T) was designed and constructed for the investigation of the external magnetic field effect on the Raman spectra of molecular aggregates in solutions and at interfaces. The performance of the present instrument was demonstrated by measuring the magnetic field effect (0 - 10 T) on the resonance Raman spectra of diprotonated meso-tetra-(sulfonatophenyl)porphine aggregates in an acidic solution. The Raman shifts of the aggregates were not significantly influenced even in 10 T. However, the relative intensity of 1123 cm(-1) peak (nu(C(a)-N)) was interestingly enhanced about 20% under the magnetic fields higher than 2.5 T.     

A highly efficient total synthesis of (R)-(+)-muscopyridine by intramolecular [4+2] cycloaddition of bisketene

A highly efficient total synthesis of (R)-(+)-muscopyridine 1 has been accomplished in 12 steps with 40% overall yield. A highlight of the synthesis is the intramolecular [4+2] cycloaddition of bisketene to afford a bridged pyrone and ring transformation of the pyrone to afford pyridine derivatives.