One-Pot Synthesis of Enantioenriched β-Amino Secondary Amides via an Enantioselective [4+2] Cycloaddition Reaction of Vinyl Azides with N-Acyl Imines Catalyzed by a Chiral Brønsted Acid

A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides.     

Formation of One‐Dimensional Helical Columns and Excimerlike Excited States by Racemic Quinoxaline‐Fused [7]Carbohelicenes in the Crystal

A series of quinoxaline‐fused [7]carbohelicenes (HeQu derivatives) was designed and synthesized to evaluate their structural and photophysical properties in the crystal state. The quinoxaline units were expected to enhance the light‐emitting properties and to control the packing structures in the crystal. The electrochemical and spectroscopic properties and excited‐state dynamics of these compounds were investigated in detail. The first oxidation potentials of HeQu derivatives are approximately the same as that of unsubstituted reference [7]carbohelicene (Heli), whereas their first reduction potentials are shifted to the positive by about 0.7 V. The steady‐state absorption, fluorescence, and circular dichroism spectra also became redshifted compared to those of Heli. The molecular orbitals and energy levels of the HOMO and LUMO states, calculated by DFT methods, support these trends. Moreover, the absolute fluorescence quantum yields of HeQu derivatives are about four times larger than that of Heli. The structural properties of the aggregated states were analyzed by single‐crystal analysis. Introduction of appropriate substituents (i.e., 4‐methoxyphenyl) in the HeQu unit enabled the construction of one‐dimensional helical columns of racemic HeQu derivatives in the crystal state. Helix formation is based on intracolumn π‐stacking between two neighboring [7]carbohelicenes and intercolumn CH ??? N interaction between a nitrogen atom of a quinoxaline unit and a hydrogen atom of a helicene unit. The time‐resolved fluorescence spectra of single crystals clearly showed an excimerlike delocalized excited state owing to the short distance between neighboring [7]carbohelicene units.     

Controllable Electronic Structures and Photoinduced Processes of Bay‐Linked Perylenediimide Dimers and a Ferrocene‐Linked Triad

A series of perylene‐3,4,9,10‐bis(dicarboximide) (PDI) dimers linked through the bay regions was systematically synthesized to examine the electronic structures and photophysical properties in dependence on the distance and orientation between the two PDI units. The spectroscopic and electrochemical measurements suggested that the coupling value of a directly linked PDI dimer (PDI)₂ is much larger than those of para‐ and meta‐phenylene‐bridged PDI dimers p‐(PDI)₂ and m‐(PDI)₂. The width of Davydov splitting was quantitatively evaluated to compare the coupling values between the two PDI units in these dimers by absorption spectroscopy in frozen 2‐methyl‐THF. Excimer formation of PDI dimers induced the strong fluorescence quenching and large red‐shifts. Femtosecond transient absorption revealed a broad absorption derived from an excimer in the range from about 600 nm to the near‐IR region. The rate constants of formation and decay of the excimer are strongly dependent on the coupling values. Time‐resolved measurements on ferrocene‐linked p‐(PDI)₂ revealed a competition between the photoinduced processes of electron transfer and excimer formation in PhCN, which is in sharp contrast with the sole electron‐transfer process in toluene.     

Czochralski-growth of germanium crystals containing high concentrations of oxygen impurities

Oxygen-containing germanium (Ge) single crystals with low density of grown-in dislocations were grown by the Czochralski (CZ) technique from a Ge melt, both with and without a covering by boron oxide (B₂O₃) liquid. Interstitially dissolved oxygen concentrations in the crystals were determined by the absorption peak at 855 cm⁻¹ in the infrared absorption spectra at room temperature. It was found that oxygen concentration in a Ge crystal grown from melt partially or fully covered with B₂O₃ liquid was about 10¹⁶ cm⁻³ and was almost the same as that in a Ge crystal grown without B₂O₃. Oxygen concentration in a Ge crystal was enhanced to be greater than 10¹⁷ cm⁻³ by growing a crystal from a melt fully covered with B₂O₃; with the addition of germanium oxide powder, the maximum oxygen concentration achieved was 5.5×10¹⁷ cm⁻³. The effective segregation coefficients of oxygen in the present Ge crystal growth were roughly estimated to be between 1.0 and 1.4.     

Analytical Solutions of Electromagnetic Fields from Current Dipole Moment on Spherical Conductor in a Low-Frequency Approximation

We analytically derive the solutions for electromagnetic fields of electric current dipole moment, which is placed in the exterior of the spherical homogeneous conductor, and is pointed along the radial direction. The dipole moment is driven in the low frequency f = 1 kHz and high frequency f = 1 GHz regimes. The electrical properties of the conductor are appropriately chosen in each frequency. Electromagnetic fields are rigorously formulated at an arbitrary point in a spherical geometry, in which the magnetic vector potential is straightforwardly given by the Biot- Savart formula, and the scalar potential is expanded with the Legendre polynomials, taking into account the appropriate boundary conditions at the spherical surface of the conductor. The induced electric fields are numerically calculated along the several paths in the low and high frequeny excitation. The self-consistent solutions obtained in this work will be of much importance in a wide region of electromagnetic induction problems.     

Photoluminescence spectral change in layered titanate oxide intercalated with hydrated Eu3+

A number of interesting photoluminescence properties of titanate layered oxide intercalated with hydrated Eu3+ have been demonstrated. Photoluminescence intensity of Eu3+ decreased rapidly with time during irradiation by UV light having energy higher than the band gap energy of the host TiO (Ti(1.81)O4) layer. This is presumably due to the decrease in energy transfer from the host TiO layer to Eu3+ as a result of the change in the hydration state of water molecules surrounding Eu3+, which is caused by the hole produced in the TiO valence band. When irradiation was discontinued, the emission intensity gradually recovered. The recovery time increased when the water in the interlayer is removed by heat treatment. This indicates that the state of interlayer water changes during irradiation and returns to its initial state after discontinuation of irradiation. The excitation spectra changed drastically at any given wavelength upon irradiation with UV light. A comparison of the excitation spectra before and after irradiation reveals that only the excitation peak at around the irradiation wavelength decreased upon irradiation, as in the case of spectral hole burning. The hydration state of water molecules surrounding Eu3+ presumably changes depending on the irradiation wavelength, leading to the above spectral change because the Eu/TiO film has a superlattice structure producing holes with different energies.     

Anomalous High Pressure Properties in Fullerene Superconductors

Abstract

Correlations among lattice parameter, external pressure, and critical temperature T_c has been surveyed on fullerene superconductors with a wide range of lattice parameters and various valence states. The observed value of dT_c/dP for Na₂Rb_0.5Cs_0.5C₆₀ and Li₃CsC₆₀, having small interfullerene separations, is about a few times lager than that of K₃C₆₀. In contrast, small dT_c/dP values are found in fullerides with expanded unit cells, such as (NH₃)_xNaAA^?C₆₀ (A, A^? = K, Rb and Cs) and A₃Ba₃C₆₀. Interestingly, the chemical and physical pressure effects on T_c are considerably different in these fullerides with large interfullerene spacings. Our results suggest that the pressure dependence is scaled by an interfullerene distance when the interfullerene distances is small, but that this scaling fails when the unit cell is expanded.     

On predicate provability logics and binumerations of fragments of Peano arithmetic

Solovay proved (Israel J Math 25(3–4):287–304, 1976) that the propositional provability logic of any ∑₂-sound recursively enumerable extension of PA is characterized by the propositional modal logic GL. By contrast, Montagna proved in (Notre Dame J Form Log 25(2):179–189, 1984) that predicate provability logics of Peano arithmetic and Bernays–Gödel set theory are different. Moreover, Artemov proved in (Doklady Akademii Nauk SSSR 290(6):1289–1292, 1986) that the predicate provability logic of a theory essentially depends on the choice of a binumeration of the theory which is used to construct the provability predicate. In this paper, we compare predicate provability logics of I∑ _n ’s. For a binumeration α(x) of a recursive theory T, let PL _α(T) be the predicate provability logic of T defined by α(x). We prove that for any natural numbers i, j such that 0 < i < j, there exists a ∑₁ binumeration α(x) of some recursive axiomatization of I∑ _i such that ${{\sf PL}_\alpha({\rm I \Sigma}_i) \nsupseteq \bigcap_{\beta(x)}{\sf PL}_\beta({\rm I \Sigma}_j)}$ PL α ( I Σ i ) ? ? β ( x ) PL β ( I Σ j ) and ${{\sf PL}_\alpha({\rm I \Sigma}_i) \nsubseteq \bigcup_{\beta(x)}{\sf PL}_\beta({\rm I \Sigma}_j)}$ PL α ( I Σ i ) ? ? β ( x ) PL β ( I Σ j ) , where β(x) ranges over all ∑₁ binumerations of recursive axiomatizations of I∑ _j .     

Parameter estimation by decoherence in the double-slit experiment

We discuss a parameter estimation problem using quantum decoherence in the double-slit interferometer. We consider a particle coupled to a massive scalar field after the particle passing through the double slit and solve the dynamics non-perturbatively for the coupling by the WKB approximation. This allows us to analyze the estimation problem which cannot be treated by master equation used in the research of quantum probe. In this model, the scalar field reduces the interference fringes of the particle and the fringe pattern depends on the field mass and coupling. To evaluate the contrast and the estimation precision obtained from the pattern, we introduce the interferometric visibility and the Fisher information matrix of the field mass and coupling. For the fringe pattern observed on the distant screen, we derive a simple relation between the visibility and the Fisher matrix. Also, focusing on the estimation precision of the mass, we find that the Fisher information characterizes the wave-particle duality in the double-slit interferometer.