Spiroborate-Based Host Materials with High Triplet Energies and Ambipolar Charge-Transport Properties

Organic light-emitting diodes (OLEDs) receive considerable attention because of their commercial use in flat panel displays. Herein, highly efficient spiroborate-based host materials are reported for use in blue OLEDs. Our designed spiroborates ( SBOX ) were simple to synthesize and exhibited high triplet excitation energies, narrow S-T gaps, and balanced charge carrier mobilities. A blue OLED containing one of the designed spiroborates, SBON , as a host exhibited a high external quantum efficiency (27.6 %) and low turn-on voltage (3.7 V) compared to those observed using 3,3′-di(9H-carbazol-9-yl)-1,1′-biphenyl (17.6 % and 4.5 V, respectively), indicating their potential as host materials in OLEDs.     

Molecularly Dispersed Donors in Acceptor Molecular Crystals for Photon Upconversion under Low Excitation Intensity

For real‐world applications of photon upconversion based on the triplet–triplet annihilation (TTA‐UC), it is imperative to develop solid‐state TTA‐UC systems that work effectively under low excitation power comparable to solar irradiance. As an approach in this direction, aromatic crystals showing high triplet diffusivity are expected to serve as a useful platform. However, donor molecules inevitably tend to segregate from the host acceptor crystals, and this inhomogeneity results in the disappointing performance of crystalline state TTA‐UC. In this work, a series of cast‐film‐forming acceptors was developed, which provide both regular acceptor alignment and soft domains of alkyl chains that accommodate donor molecules without segregation. A typical triplet sensitizer, Pt^II octaethylporphyrin (PtOEP), was dispersed in these acceptor crystals without aggregation. As a result, efficient triplet energy transfer from the donor to the acceptor and diffusion of triplet excitons among regularly aligned anthracene chromophores occurred. It resulted in TTA‐UC emission at low excitation intensities, comparable to solar irradiance.     

Asymmetric Total Synthesis of Heronamides A–C: Stereochemical Confirmation and Impact of Long‐Range Stereochemical Communication on the Biological Activity

Heronamides are biosynthetically related metabolites isolated from marine‐derived actinomycetes. Heronamide C shows potent antifungal activity by targeting membrane phospholipids possessing saturated hydrocarbon chains with as‐yet‐unrevealed modes of action. In spite of their curious hypothesized biosynthesis and fascinating biological activities, there have been conflicts in regard to the reported stereochemistries of heronamides. Here, we describe the asymmetric total synthesis of the originally proposed and revised structures of heronamide C, which unambiguously confirmed the chemical structure of this molecule. We also demonstrated nonenzymatic synthesis of heronamides A and B from heronamide C, which not only proved the postulated biosynthesis, but also confirmed the correct structures of heronamides A and B. Investigation of the structure–activity relationship of synthetic and natural heronamides revealed the importance of both long‐range stereochemical communication and the 20‐membered macrolactam ring for the biological activity of these compounds.     

Generalized inverse of linear transformations: a geometric approach

A generalized inverse of a linear transformation A:

→

, where

and

are arbitrary finite dimensional vector spaces, is defined using only geometrical concepts of linear transformations. The inverse is uniquely defined in terms of specified subspaces $\text{L}$ ?

, $\text{M}$ ?

and a linear transformation N satisfying some conditions. Such an inverse is called the $\text{LM}$N-inverse. A Moore-Penrose type inverse is obtained by choosing N = 0. Some optimization problems are considered by choosing

and

as inner product spaces. Our results extend without any major modification of proofs to bounded linear operators with closed range on Hilbert spaces.     

A multi-moment finite volume formulation for shallow water equations on unstructured mesh

A novel and accurate finite volume method has been presented to solve the shallow water equations on unstructured grid in plane geometry. In addition to the volume integrated average (VIA moment) for each mesh cell, the point values (PV moment) defined on cell boundary are also treated as the model variables. The volume integrated average is updated via a finite volume formulation, and thus is numerically conserved, while the point value is computed by a point-wise Riemann solver. The cell-wise local interpolation reconstruction is built based on both the VIA and the PV moments, which results in a scheme of almost third order accuracy. Efforts have also been made to formulate the source term of the bottom topography in a way to balance the numerical flux function to satisfy the so-called C-property. The proposed numerical model is validated by numerical tests in comparison with other methods reported in the literature.     

Quantum interference and diffraction of parametric down-converted biphotons

We present two-photon diffraction and interference experiments utilizing parametric down-converted photon pairs (biphotons) and a transmission grating. The biphoton exhibits a diffraction-interference pattern equivalent to an effective single particle with half wavelength of the constituent photons.     

Photon polarization entanglement induced by Biexciton: experimental evidence for violation of Bell's inequality

We have investigated the polarization entanglement between photon pairs generated from a biexciton in a CuCl single crystal via resonant hyperparametric scattering. The pulses of a high repetition pump are seen to provide improved statistical accuracy and the ability to test Bell's inequality. Our results clearly violate the inequality and thus manifest the quantum entanglement and nonlocality of the photon pairs. We also analyzed the quantum state of our photon pairs using quantum state tomography.     

Fermionic solutions of chiral Gross–Neveu and Bogoliubov–de Gennes systems in nonlinear Schrödinger hierarchy

The chiral Gross–Neveu model or equivalently the linearized Bogoliubov–de Gennes equation has been mapped to the nonlinear Schrödinger (NLS) hierarchy in the Ablowitz–Kaup–Newell–Segur formalism by Correa, Dunne and Plyushchay. We derive the general expression for exact fermionic solutions for all gap functions in the arbitrary order of the NLS hierarchy. We also find that the energy spectrum of the n  -th NLS hierarchy generally has n+1$n+1$ gaps. As an illustration, we present the self-consistent two-complex-kink solution with four real parameters and two fermion bound states. The two kinks can be placed at any position and have phase shifts. When the two kinks are well separated, the fermion bound states are localized around each kink in most parameter region. When two kinks with phase shifts close to each other are placed at distance as short as possible, the both fermion bound states have two peaks at the two kinks, i.e., the delocalization of the bound states occurs.     

Molecular g-tensors from analytical response theory and quasi-degenerate perturbation theory in the framework of complete active space self-consistent field method

The molecular g-tensor is an important spectroscopic parameter provided by electron para magnetic resonance (EPR) measurement and often needs to be interpreted using computational methods. Here, we present two new implementations based on the first-order and second-order perturbation theories to calculate the g-tensors within the complete-active space self-consistent field (CASSCF) wave function model. In the first-order method, the quasi-degenerate perturbation theory (QDPT) is employed for constructing relativistic CASSCF states perturbed with the spin–orbit coupling operator, which is described effectively in one-electron form with the flexible nuclear screening spin–orbit approximation introduced recently by us. The second-order method is a newly reported approach built upon the linear response theory which accounts for the perturbation with respect to external magnetic field. It is implemented with the coupled–perturbed CASSCF (CP-CASSCF) approach, which provides an equivalent of untruncated sum-over-states expansion. The comparison of the performances between the first-order and second-order methods is shown for various molecules containing light to heavy elements, highlighting their relative strength and weakness. The formulations of QDPT and CP-CASSCF approaches as well as the derivation of the second-order Douglas–Kroll–Hess picture change of Zeeman operators are given in detail.     

Electron Spin Resonance (ESR) Dating of Calcareous Fault Gouge of the Ushikubi Fault, Central Japan

The ages of fault events of active faults have been estimated using electron spin resonance (ESR) signals of siliceous gouges. This technique of ESR method is limited by obtaining only ages that are greater than tens of millennia. So this study focuses on developing a new technique of using calcareous gouges to gain an insight into the ages of latest seismogenic event within the Holocene. For the first time, signal B of the ESR method has been used to estimate the age of the Ushikubi fault from calcareous gouge. This technique proved reliable because the mean age (1.9 ka) obtained agrees with previous works on indirect age determination of latest fault events by utilizing radiocarbon dating in the study area. However, the result from the ESR technique showed an increase relative to the age of 1 ka that was obtained by the radiocarbon dating method. This disparity may be due to a high dose rate value of 50 Gy/h of artificial irradiation that was used to determine the equivalent dose (ED). Moreover, isochronal experiment revealed that the gouge did not comprise pure carbonates but consisted of a mixture of calcite and quartz grains. A younger age value would have been obtained if a lower artificial irradiation dose rate and a relatively pure carbonate fault gouge were used in the ED determination.