7,7,8,8‐Tetraaryl‐o‐quinodimethane Stabilized by Dibenzo Annulation: A Helical π‐Electron System That Exhibits Electrochromic and Unique Chiroptical Properties

When two benzene rings are fused to a tetraaryl‐o‐quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron‐donating alkoxy groups, 1 undergo reversible two‐electron oxidation to 2 ²⁺, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec‐butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b ²⁺ and 2 c ²⁺, which represents an efficient method for enhancing circular‐dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X‐ray analysis of dication 2 ²⁺ revealed π–π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response.     

Defect Engineering and Anisotropic Modulation of Ionic Transport in Perovskite Solid Electrolyte LixLa(1−x)/3NbO3

Solid electrolytes, such as perovskite Li_3xLa_2/1−xTiO₃, Li_xLa_(1−x)/3NbO₃ and garnet Li₇La₃Zr₂O₁₂ ceramic oxides, have attracted extensive attention in lithium-ion battery research due to their good chemical stability and the improvability of their ionic conductivity with great potential in solid electrolyte battery applications. These solid oxides eliminate safety issues and cycling instability, which are common challenges in the current commercial lithium-ion batteries based on organic liquid electrolytes. However, in practical applications, structural disorders such as point defects and grain boundaries play a dominating role in the ionic transport of these solid electrolytes, where defect engineering to tailor or improve the ionic conductive property is still seldom reported. Here, we demonstrate a defect engineering approach to alter the ionic conductive channels in Li_xLa_(1−x)/3NbO₃ (x = 0.1~0.13) electrolytes based on the rearrangements of La sites through a quenching process. The changes in the occupancy and interstitial defects of La ions lead to anisotropic modulation of ionic conductivity with the increase in quenching temperatures. Our trial in this work on the defect engineering of quenched electrolytes will offer opportunities to optimize ionic conductivity and benefit the solid electrolyte battery applications.     

Quantification of Intracellular Thiols by HPLC-Fluorescence Detection

Biothiols, such as cysteine and glutathione, play important roles in various intracellular reactions represented by the redox equilibrium against oxidative stress. In this study, a method for intracellular thiol quantification using HPLC-fluorescence detection was developed. Thiols were derivatized with a thiol-specific fluorescence derivatization reagent, viz. ammonium 7-fluoro-2,1,3-benzoxadiazole-4-sulfonate (SBD-F), followed by reversed-phase separation on an InertSustain AQ-C18 column. Six different SBD-thiols (homocysteine, cysteine, cysteinylglycine, γ-glutamylcysteine, glutathione, and N-acetylcysteine as an internal standard) were separated within 30 min using a citric buffer (pH 3.0)/MeOH mobile phase. The calibration curves of all the SBD-thiols had strong linearity (R² > 0.999). Using this developed method, the thiol concentrations of human chronic myelogenous leukemia K562 cell samples were found to be 5.5–153 pmol/1 × 10⁶ cells. The time-dependent effect of a thiol scavenger, viz. N-ethyl maleimide, on intracellular thiol concentrations was also quantified. This method is useful for elucidating the role of intracellular sulfur metabolism.     

Isotopic dependence of the giant monopole resonance in the even-A 112-124Sn isotopes and the asymmetry term in nuclear incompressibility

The strength distributions of the giant monopole resonance (GMR) have been measured in the even-A Sn isotopes (A=112-124) with inelastic scattering of 400-MeV alpha particles in the angular range 0 degrees -8.5 degrees . We find that the experimentally observed GMR energies of the Sn isotopes are lower than the values predicted by theoretical calculations that reproduce the GMR energies in 208Pb and 90Zr very well. From the GMR data, a value of Ktau = -550 +/- 100 MeV is obtained for the asymmetry term in the nuclear incompressibility.     

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two-Step Iron(II) Spin Crossover Switchable by Temperature,Light, and Pressure

A two-step hysteretic Fe^II spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3-CNpy)₂][Re(CN)₈]}⋅H₂O ( 1 ) (3-CNpy=3-cyanopyridine) assembly consisting of cyanido-bridged Fe^II-Re^V square grid sheets bonded by Cs⁺ ions. The presence of two non-equivalent Fe^II sites and the conjunction of 2D bimetallic coordination network with non-covalent interlayer interactions involving Cs⁺, [Re^V(CN)₈]³⁻ ions, and 3-CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin-transition phenomenon could be tuned by an external pressure giving the room-temperature range of SCO, as well as by visible-light irradiation, inducing an efficient recovery of the high-spin Fe^II state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable Fe^II SCO effect.     

Inclusion Complex Formation of Thiacalix[4]arene and Xe in Aqueous Solution Studied by Hyperpolarized 129Xe NMR

The inclusion complex formation of 4-sulfothiacalix[4]arene sodium salt (STCAS) and Xe has been investigated by using hyperpolarized ¹²⁹Xe NMR spectroscopy. Our new continuous-flow type hyperpolarizing system has advantageous capabilities that can supply hyperpolarized gases continuously and directly to a sample solution in a NMR tube. Consequently saturated Xe concentration in the aqueous solution of STCAS is maintained during the NMR experiment, and ¹²⁹Xe NMR spectra can be obtained in remarkably short time. STCAS concentration dependence of ¹²⁹Xe chemical shift has been analyzed in an elaborated way by a computer method as well as a simple graphic method that we have proposed. The association constant K:13.6±0.8 M⁻¹ at 25 °C was obtained, and further analysis of the temperature dependence has successfully given thermodynamic parameters of enthalpy (ΔH) and entropy (ΔS) for the inclusion complex formation: ΔH = −11.9±1.9 kJ mol⁻¹ and ΔS = −17.4±5.8 JK⁻¹ mol⁻¹. The energetic aspects of complex formation are discussed from the size effect and from the molecular theory of standard entropy, and a release of definite number of water molecules from STCAS cavity is suggested in the inclusion complex formation with Xe.     

Time-of-flight studies of emission of μt from frozen hydrogen films

In recent TRIUMF experiments, a μ^- beam is stopped in a solid hydrogen film with a small fraction of T₂. The Ramsauer-Townsend (RT) mechanism allows μt to escape into vacuum with a few eV of energy. To study the emission process, an imaging system was used to determine the position of muon decays. Experimental histograms are in good agreement with a Monte Carlo simulation. This revised version was published online in August 2006 with corrections to the Cover Date.     

High-speed wavelength-division multiplexing quantum key distribution system

A high-speed quantum key distribution system was developed with the wavelength-division multiplexing (WDM) technique and dedicated key distillation hardware engines. Two interferometers for encoding and decoding are shared over eight wavelengths to reduce the system's size, cost, and control complexity. The key distillation engines can process a huge amount of data from the WDM channels by using a 1 Mbit block in real time. We demonstrated a three-channel WDM system that simultaneously uses avalanche photodiodes and superconducting single-photon detectors. We achieved 12 h continuous key generation with a secure key rate of 208 kilobits per second through a 45 km field fiber with 14.5 dB loss.