STM/STS study of electronic states in highly underdoped Bi2212

Local density of states (LDOS) and the lattice structure of highly underdoped Bi₂Sr₂CaCu₂O_8+δ with T_c = 22 K and 30 K were investigated by a low temperature scanning tunneling microscope. The modulation structure of the Bi–O surface was strongly depressed in the highly underdoped samples. The depression was observed only in the samples subject to the strong reduction annealing process, suggesting that the strong reduction in excess oxygen could destroy the modulation structure. At a time, patch-like inhomogeneity in the gap map sometimes disappeared, indicating that the existence of excess oxygen has an important role in the patch formation. Analysis on the LDOS with various doping levels showed that there was no crossover energy, which separates a pseudogap and a superconducting gap and is proportional to T_c.     

Quasi-Nambu-Goldstone modes in Bose-Einstein condensates

We show that quasi-Nambu-Goldstone (NG) modes, which play prominent roles in high energy physics but have been elusive experimentally, can be realized with atomic Bose-Einstein condensates. The quasi-NG modes emerge when the symmetry of a ground state is larger than that of the Hamiltonian. When they appear, the conventional vacuum manifold should be enlarged. Consequently, topological defects that are stable within the conventional vacuum manifold become unstable and decay by emitting the quasi-NG modes. Contrary to conventional wisdom, however, we show that the topological defects are stabilized by quantum fluctuations that make the quasi-NG modes massive, thereby suppressing their emission.     

Oxidation of Zn in UHV environment at low temperature

Thermal oxidation of polycrystalline Zn foils at 5 × 10⁻⁷ Torr oxygen pressure and at room temperature, 50 °C, 70 °C, 90 °C and 110 °C was studied. In situ photoemission spectroscopy using synchrotron light with photon energy of 57 eV was used to monitor the formation of ZnO and to determine the thickness of the oxide overlayer. At the initial oxidation, the oxidation rate follows a two-stage logarithmic equation and later trends to saturate at a certain thickness depending on the oxidation temperature. The saturated thickness was found to increase with the oxidation temperature. The two-stage oxidation process may be governed by two kinds of space charge presumably formed in the thin oxide overlayer.     

Scanning ion conductance microscopy for imaging biological samples in liquid: a comparative study with atomic force microscopy and scanning electron microscopy

The present study was designed to show the applicability of scanning ion conductance microscopy (SICM) for imaging different types of biological samples. For this purpose, we first applied SICM to image collagen fibrils and showed the usefulness of the approach-retract scanning (ARS)/hopping mode for such samples with steep slopes. Comparison of SICM images with those obtained by AFM revealed that the ARS/hopping SICM mode can probe the surface topography of collagen fibrils and chromosomes at nanoscale resolution under liquid conditions. In addition, we successfully imaged cultured HeLa cells, with 15 μm in height by ARS/hopping SICM mode. Because SICM can obtain non-contact (or force-free) images, delicate cellular projections were visualized on the surface of the fixed cell. SICM imaging of live HeLa cells further demonstrated its applicability to study the morphological dynamics associated with biological processes on the time scale of minutes under liquid conditions. We further applied SICM for imaging the luminal surface of the trachea and succeeded in visualizing the surface of both ciliated and non-ciliated cells. These SICM images were comparable with those obtained by scanning electron microscopy. Although the dynamic mode of AFM provides better resolution than the ARS/hopping mode of SICM in some samples, only the latter can obtain contact-free images of samples with steep slopes, rendering it an important tool for observing live cells as well as unfixed or fixed soft samples with complicated shapes. Taken together, we demonstrate that SICM imaging, especially using an ARS/hopping mode, is a useful technique with unique capabilities for imaging the three-dimensional topography of a range of biological samples under physiologically relevant aqueous conditions.     

Synthesis, Characterization, and Crystal Structure of a (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) Complex with a Dinucleating Hexapyridine Ligand, 1,2-Bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane. The First Example of a Discrete (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) Complex with a Dinucleating Ligand

A mononucleating tripyridine ligand, 2-(bis(2-pyridyl)methyl)-6-methylpyridine (L(1)), and a dinucleating hexapyridine ligand, 1,2-bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane (L(2)), have been prepared. The reaction of a carbanion of 2,6-lutidine with 2-bromopyridine affords L(1) which is converted to L(2) quantitatively by treating with tert-butyllithium and 1,2-dibromoethane. (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) complexes [Fe(2)(O)(OAc)(2)(L(1))(2)](ClO(4))(2) (1) and [Fe(2)(O)(OAc)(2)L(2)](ClO(4))(2) (2) have been synthesized and characterized by means of infrared, UV/vis, mass, and M?ssbauer spectroscopies and by measuring magnetic susceptibility and cyclic voltammograms. All the spectral data are consistent with the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure in both 1 and 2. A relatively strong molecular ion peak at m/z 865 corresponding to [{Fe(2)O(OAc)(2)L(2)}(ClO(4))](+) in a FAB mass spectrum of 2 suggests the stabilization of the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure by L(2) in a solution state. The compound 2.DMF.2-PrOH.H(2)O, chemical formula C(44)Cl(2)Fe(2)H(51)N(7)O(16), crystallizes in the monoclinic space group C2/c with a = 22.034(6) ?, b = 12.595(5) ?, c = 20.651(7) ?, beta = 121.49(2) degrees, and Z = 4. The cation has 2-fold symmetry with the bridging oxygen atom on the 2-fold axis: Fe-(&mgr;-O) = 1.782(5) ?, Fe-O-Fe = 123.6(6) degrees, and Fe.Fe = 3.142(3) ?. The diiron(III) core structure of 2 seems to be stabilized by encapsulation of the ligand. Compound 2 is the first example of a discrete (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) complex with a dinucleating ligand.     

Fine structure and transition probabilities of the 2p 5 nl bound excited states of Ne atom

We present a semi-empirical calculational procedure for thep ⁵ nl bound excited states of rare gas atoms based on the use of an LS-dependent orbital for an excitednl electron outside a frozen Hartree-Fockp ⁵ core. The spin-orbit interaction is accounted for approximately using a localized Hartree potential. The contribution from the long-range core polarization is estimated by using a parametrized potential. A model potential is also introduced to represent partially the short-range multi-electron interactions for thep ⁵ np levels. The energy levels are calculated by diagonalizing the Hamiltonian matrix following anLS →jl transformation. The calculated fine structure of the Nep ⁵ ns,p ⁵ np,p ⁵ nd, andp ⁵ nf ¦ (jl)KJ〉 levels are in close agreement with the observed level splittings. The transition probabilities are also in agreement with earlier theoretical and experimental results.     

SUPER TOUGH GELS WITH A DOUBLE NETWORK STRUCTURE

 Living tissues work with fantastic functions in soft and wet gel-like state. Thus, hydrogels have attracted much attention as excellent soft & wet materials, suitable for making artificial organs for medical treatments.However, conventional hydrogels are mechanically too weak for practical uses. We have created double network (DN) hydrogels with extremely high mechanical strength in order to overcome this problem. DN gels are interpenetrating network (IPN) hydrogels consisting of rigid polyelectrolyte and soft neutral polymer. Their excellent mechanical properties cannot be explained by the standard fracture theories. In this paper, we discuss about the toughening mechanism of DN gels in accordance with their characteristic behavior, such as large hysteresis and necking phenomenon. We also describe the results on tissue engineering application of DN gels.     

Irradiation effects on hydrases for biomedical applications

To apply an irradiation technique to sterilize “Hybrid” biomedical materials including enzymes, we selected papain, a well-characterized plant endopeptidase as a model to examine durability of enzyme activity under the practical irradiation condition in which limited data were available for irradiation inactivation of enzymes. Dry powder and frozen aqueous solution of papain showed significant durability against ⁶⁰Co-gamma irradiation suggesting that, the commercial irradiation sterilizing method is applicable without modification. Although irradiation of unfrozen aqueous papain solution showed an unusual change of the enzymatic activity with the increasing doses, and was totally inactivated at 15 kGy, we managed to keep the residual activity more than 50% of initial activity after 30-kGy irradiation, taking such optimum conditions as increasing enzyme concentration from 10 to 100 mg/ml and purging with N₂ gas to suppress the formation of free radicals.     

A theoretical study of the dehydration and the dehydrogenation processes of alcohols on metal oxides using MOPAC

Using a semi-empirical molecular orbital method, PM3, and 2-propanol as an example, the dehydration and the dehydrogenation processes of alcohol on oxide catalysts were studied. The catalysts addressed here were four kinds of oxides (Al₂O₃, SiO₂, ZnO, CdO) whose reaction selectivities had been experimentally determined. The usual models consisting of a surface metal ion, several oxide ions and an isopropoxy group were used in calculations. For the dehydration, heats of formation of the models were calculated at each point of the process where the distance between a β-hydrogen of the group and a basic site (i.e. oxygen of the group or a surface oxide ion) or a metal ion was gradually shortened, or where the length of the C–O bond of the group was gradually increased. A reasonable dehydration mechanism was estimated by comparing activation energies calculated from the transitions of the heats of formation. The most probable dehydrogenation mechanism was also estimated in a similar way by gradually making an -hydrogen close to a surface oxide ion, the metal ion or a surface proton. It was concluded that the dehydration proceeds by scission of the C–O bond of the group after its oxygen was attacked by some electrophile on the surface and that the dehydrogenation proceeds by a mechanism in which an -hydrogen of the group was extracted by the metal ion.

Based on the dehydration mechanism thus deduced, alkoxy groups generated by adsorption of the primary, secondary and tertiary alcohols on SiO₂ were calculated in order to estimate the activation energies of their decompositions. In result, the order of the energies was found to be in good agreement with that of the decomposition rates experimentally determined by Kitahara. This agreement gives support to the validity of the mechanism deduced for the dehydration of alcohol.     

Direct cycloauration of 1-(2-pyridylamino and 2-pyrimidinylamino)naphthalene and 2-(p-toluidino)quinoline with sodium tetrachloroaurate(III)

1-(2-Pyridylamino and 2-pyrimidinylamino)naphthalene (abbreviated as Hpyn and Hpmn, respectively) and 2-(p-toluidino)quinoline (Htlq) were directly cycloaurated with Na[AuCl₄] to give [AuCl₂L] (L = pyn, pmn, or tlq). These complexes were characterized spectroscopically and the square planar structure of [AuCl₂(pmn)] was determined by X-ray analysis. The naphthalene ring was aurated at position 2, forming a six-membered auraheterocycle with concomitant coordination of the pyrimidine-N atom. The trans influence of the carbon donor was clearly reflected in the Au–Cl bond lengths; 2.372(2) trans to C and 2.275Å trans to N. Similar square planar structures were suggested for the other two complexes.