A proof of the homotopy push-out and pull-back lemma

The homotopy push-out and pull-back lemma of Iwase (1998) is a generalized version of Theorem 1.1 of Ganea (1965) and the Theorem of Rutter (1971) whose proofs were given under the simply-connectivity condition. The purpose of this paper is to give a proof in the general case.

     

Impact of cell-voltage on energy and power performance of supercapacitors with single-walled carbon nanotube electrodes

We report the energy and power voltage-dependencies of supercapacitors using single-walled carbon nanotube electrodes. The energy density was dependent on the cell-voltage cubed (up to 4 V: E = 1.43 × V³). The cubic relationship was attributed to the linear increase of the capacitance as a function of voltage, enabled by electrochemical doping. Furthermore, while up to 3.5 V, the maximum power rating of the nanotube electrodes increased as a function of the cell-voltage squared, beyond 3.5 V, a decline in power was observed as a result of depletion of the electrolyte's ions.     

Measurement of the tau lepton mass and an upper limit on the mass difference between tau+ and tau-

The mass of the tau lepton has been measured in the decay mode tau-->3pinutau using a pseudomass technique. The result obtained from 414 fb-1 of data collected with the Belle detector is Mtau=[1776.61+/-0.13(stat)+/-0.35(sys)] MeV/c2. The upper limit on the relative mass difference between positive and negative tau leptons is |Mtau+-Mtau-|/Mtau<2.8 x 10-4 at 90% confidence level.     

Photo-switchable spin-crossover iron(III) compound based on intermolecular interactions

Iron(III) spin-crossover compounds, [Fe(qnal)₂]CF₃SO₃·MeOH (1·MeOH) and [Fe(qnal)₂]CF₃SO₃·acetone (1·acetone) were prepared and their spin transition properties were characterized by magnetic susceptibility measurement, Mössbauer spectroscopy and single crystal analysis. Two iron(III) compounds exhibited abrupt spin transition with thermal hysteresis loop (T _1/2?? = 115 K and T _1/2?? = 104 K for 1·MeOH, and T _1/2?? = 133 K and T _1/2?? = 130 K for 1·acetone). Single crystal analysis revealed both of the structures in high-spin (HS) and low-spin (LS) states for 1·acetone. The difference of bond length between the HS and LS states for 1·acetone was ~0.10 Å, which was corresponding to that of typical iron(III) SCO compounds. Specially, it showed strong intermolecular interactions by ???C?? stacking formed between the neighbor complexes leading to 2-D sheet. Both 1·MeOH and 1·acetone exhibited LIESST effect when it was illuminated at 1000 nm. We also confirmed that the introduction of strong intermolecular interactions, such as ???C?? stacking, can play an important role in LIESST effect.     

Confinement in carbon nanospace-induced production of KI nanocrystals of high-pressure phase

An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure.     

1D and 2D assembly structures by imidazole···chloride hydrogen bonds of iron(II) complexes [Fe(II)(HL(n-Pr))3]Cl·Y (HL(n-Pr) = 2-methylimidazol-4-yl-methylideneamino-n-propyl; Y = AsF6, BF4) and their spin states

Two Fe(II) complexes fac-[Fe(II)(HL(n-Pr))(3)]Cl·Y (Y = AsF(6) (1) and BF(4) (2)) were synthesized, where HL(n-Pr) is 2-methylimidazole-4-yl-methylideneamino-n-propyl. Each complex-cation has the same octahedral N(6) geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[Fe(II)(HL(n-Pr))(3)](2+) with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) are hydrogen-bonded to three Cl(-) ions or, from the viewpoint of the Cl(-) ion, one Cl(-) ion is hydrogen-bonded to three neighbouring fac-[Fe(II)(HL(n-Pr))(3)](2+) cations. The 3?:?3 NH···Cl(-) hydrogen bonds between Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) and Cl(-) generate two kinds of assembly structures. The directions of the 3?:?3 NH···Cl(-) hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) enantiomorphs are bridged by two NH···Cl(-) hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[Fe(II)(HL(n-Pr))(3)](2+)···Cl(-)}(3) giving a smaller cavity, in which Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) species with the same chirality are linked by NH···Cl(-) hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and M?ssbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T(c↓) = 125.5 K and T(c↑) = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.     

Entropy of Hadamard spaces

We consider a geodesically complete and proper Hadamard metric measure space X endowed with a Borel measure. Assuming that there exists a certain non-amenable group of isometry of X which acts freely, properly discontinuously and cocompactly on X and preserves the measure we show that the topological entropy of the geodesic flow on the orbit space is positive.     

Exopeptidase degradation for the analysis of phosphorylation site in a mono-phosphorylated peptide with matrix-assisted laser desorption/ionization mass spectrometry.

The utility of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) coupled with a peptide ladder sequencing method employing exopeptidase degradation for the analysis of phosphorylation site in a mono-phosphorylated peptide is investigated. MALDI-TOFMS analysis of time-dependent exopeptidase digestion using carboxypeptidase W and aminopeptidase M of the mono-phosphorylated 33-48 fragment isolated from a beta-casein tryptic digestion mixture allowed for the sequencing analysis from both the C-terminus and N-terminus. Negative ion detection MALDI-TOFMS made it possible to clearly measure the peptide ladder of mono-phosphorylated peptide by the strong negative charge localized at the phosphoric acid group. Since exopeptidase activity was suppressed by the existence of a phosphorylated amino acid residue, the termination exopeptidase degradation therefore suggested the existence of a phosphorylated amino acid residue at that site. This peptide ladder sequencing method using exopeptidases was effective for the identification of the site of a phosphorylated amino acid residue by a simple MALDI-TOFMS analysis in the negative ion detection mode.     

On-line liquid chromatography and circular dichroism detection of stereo-isomers of alpha-tocopherol derivatives generated by an electrochemical reaction

The electrochemical oxidation of (+/-)-alpha-tocopherol on a porous graphite electrode was performed in the presence of methanol, and successive separation and detection of the products were performed by an on-line liquid chromatography/mass spectrometry system. Three products were identified, one of which was determined to be alpha-tocopheryl quinone, because its m/z was 469 [M+Na](+). The other two products showed identical mass and UV spectra, and were suspected to be diastereomers of 9-methoxy-alpha-tocopheron, because their molecular weights were m/z 483 [M+Na](+), and also because it is known that the chemical oxidation of alpha-tocopherol by benzoyl peroxide or N-bromosuccinimide in the presence of methanol should provide 9-methoxy-alpha-tocopheron. To confirm that these two compounds were diastereomers, a circular dichroism detector was used. The signs of both peaks detected by the circular dichroism detector at 230 nm were opposite. In addition to observations of identical mass and ultraviolet spectra, these results indicated that the two products were diastereomers of 9-methoxy-alpha-tocopheron, whose stereochemistry is different at the newly generated chiral center of the 9-position. The on-line use of a circular dichroism detector with an electrochemical cell/liquid chromatography system may expand the utility of the system to study the metabolism of a chiral drug.