Synthesis of dragmacidin D via direct C-H couplings

Dragmacidin D, an emerging biologically active marine natural product, has attracted attention as a lead compound for treating Parkinson's and Alzheimer's diseases. Prominent structural features of this compound are the two indole-pyrazinone bonds and the presence of a polar aminoimidazole unit. We have established a concise total synthesis of dragmacidin D using direct C-H coupling reactions. Methodological developments include (i) Pd-catalyzed thiophene-indole C-H/C-I coupling, (ii) Pd-catalyzed indole-pyrazine N-oxide C-H/C-H coupling, and (iii) acid-catalyzed indole-pyrazinone C-H/C-H coupling. These regioselective catalytic C-H couplings enabled us to rapidly assemble simple building blocks to construct the core structure of dragmacidin D in a step-economical fashion.     

Oxygen nonstoichiometry, thermo-chemical stability and lattice expansion of La0.6Sr0.4FeO3 − δ

The oxygen nonstoichiometry of La_0.6Sr_0.4FeO_3 − δ was measured at intermediate temperatures (773 to 1173 K) between 1 bar and the decomposition oxygen partial pressure by thermogravimetry and coulometric titration. The decomposition of the ABO₃ perovskite phase was found to occur at low oxygen partial pressures (below 10^− 20 bar). Using an atmosphere-controlled high-temperature XRD setup, the rhombohedral lattice parameters were obtained between 10^− 4 and 1 bar at 773 to 1173 K. A phase transition from rhombohedral to cubic might be expected to occur at high temperatures and for δ near the plateau at δ = [Sr] / 2. The lattice expansion was separated into “pure” thermal and chemically induced expansion by combining the lattice parameters with the oxygen nonstoichiometry data. The linear thermal expansion was formulated with a “pure” thermal expansion coefficient of α_th = 11.052 · 10^− 6 K^− 1 and a chemical expansion coefficient of α_chem = 1.994 · 10^− 2.The results were compared with previous data obtained for La_0.6Sr_0.4Co_1 − yFe_yO_3 − δ with y = 0.2-0.8. La_0.6Sr_0.4FeO_3 − δ was confirmed to show the highest thermo-chemical stability. While the chemical expansion of La_0.6Sr_0.4Co_1 − yFe_yO_3 − δ seems little affected by the iron content, the thermal expansion coefficient was the lowest for La_0.6Sr_0.4FeO_3 − δ.     

Optimization of the depth resolution for profiling SiO2/SiC interfaces by dual-beam TOF-SIMS combined with etching

To examine precise depth profiles at the interface of SiO₂/SiC, a high resolution that can detect slight discrepancies in the distribution is needed. In this study, an experimental method to achieve a high resolution of less than 1 nm was developed by using dual-beam time-of-flight secondary ion mass spectrometry (TOF-SIMS). The analysis was preceded by the following three steps: (1) determination of the optimal analytical conditions of the analysis beam (Bi⁺) and sputtering beam (Cs⁺), (2) verification of the etching methods to thin the SiO₂ layer, and (3) confirmation of the benefits of the low-energy sputtering beam directed toward SiO₂/SiC samples. By using the secondary ion intensity peak-to-valley ratio of BN⁻ and BO⁻ of a sample with delta-doped boron multilayers, the appropriate Bi⁺/Cs⁺ condition for a high depth resolution was determined for each energy level of the sputtering beam. Upon verification of the etching methods to thin the SiO₂ layer, slight discrepancies were found between samples that were obtained with different etching methods. The difference in the roughness values of the etched surfaces was proactively utilized for the performance confirmation of the low-energy sputtering beam by means of precise observation of the profiles at the SiO₂/SiC interface. The use of a Cs beam with a low energy between 0.25 and 0.5 keV enabled the detection of slight discrepancies in the roughness of less than 1 nm between samples. The aforementioned method has the potential to accurately detect discrepancies in the intrinsic distribution at the SiO₂/SiC interface among samples.     

Comparison between quantitative and subjective assessments of chemotherapy-induced peripheral neuropathy in cancer patients: A prospective cohort study

Objective: Chemotherapy-induced peripheral neuropathy (CIPN) is a common adverse event experienced by cancer patients. In general, CIPN is evaluated subjectively based on patient self-assessment or clinician-reported scales; evidence supporting the utility and validity of quantitative sensory tests (QST) is lacking in this patient population. The aim of this study was to objectively assess CIPN of lower extremities by QSTs, and to evaluate the concordance between QSTs and subjective assessments. Methods: In this prospective cohort study, outpatients with cancer receiving chemotherapy were recruited at a single university hospital. We assessed CIPN at the lower extremities at baseline and three months after baseline. The QSTs were performed by applying a monofilament and a tuning fork to determine touch and vibration thresholds, respectively, at the affected site. Subjective assessments were performed based on the visual analog scale (VAS) and the National Cancer Institute Common Terminology Criteria for Adverse Events (CTCAE) toxicity grade. Kappa coefficients were calculated to evaluate the concordance between QSTs and subjective assessments. Results: After exclusion and drop-outs during follow-up, nineteen patients were included in the analysis. The prevalence of patients with abnormal sensation was 37% based on QSTs, 32% based on the VAS, and 14% based on CTCAE grading, respectively. Kappa coefficients were 0.32 between QSTs and VAS, and 0.28 between QSTs and CTCAE. Conclusions: The concordance rates between quantitative and subjective assessments were low. CIPN should be assessed using both quantitative and subjective assessments.     

Catalysis and proton-conduction of novel phosphate glasses

The performance of phosphate glasses as a catalyst for water decomposition and a proton conductor was investigated. Glasses with a composition of 30Na₂O–10BaO–30P₂O₅–(30?x)WO₃–xNb₂O₅ (5 < x < 25) decompose water vapor and generate hydrogen at 500 °C. The best decomposition performance was observed on a specimen with the Nb₂O₅ composition of x = 15. A part of hydrogen produced on the glass surface changes to protons by reducing W⁶⁺ ions and penetrates into the glass. The electron is the dominant charge carrier in the electric conduction of W-rich glasses, whereas proton conduction is predominant in Nb-rich glasses in hydrogen atmosphere. A Raman scattering experiment revealed that Nb contributes to depolymerize the –P–O–P– chains in the phosphate glass producing non-bridging oxygen. A possible model was proposed for the water decomposition and proton conduction processes.     

Defect chemical and statistical thermodynamic studies on oxygen nonstoichiometric Nd2 − xSrxNiO4 + δ

In order to elucidate how oxygen content changes in Nd_2 − xSr_xNiO_4 + δ (x = 0, 0.2, 0.4), defect chemical and statistical thermodynamic analyses were carried out. The relationship among δ, P(O₂), and T were analyzed by a defect equilibrium model. Since Nd_2 − xSr_xNiO_4 + δ shows metal like band conduction at high temperatures, chemical potential of hole is expressed by the integration of the Fermi-Dirac distribution function and the density of state. The nonstoichiometric variation of oxygen content in Nd_2 − xSr_xNiO_4 + δ can be explained by the defect equilibrium model with a regular solution approximation. Partial molar entropy and partial molar enthalpy of oxygen are calculated from the nonstoichiometric data and Gibbs–Helmholtz equation. The relationship among defect structure, defect equilibrium, and thermodynamic quantities is elucidated by the statistical thermodynamic model. Thermodynamic quantities are calculated by the statistical thermodynamic model with the results of defect chemical analysis and compared with those obtained from experimental results. Thermodynamic quantities calculated by the statistical thermodynamic model can explain rough tendency of those obtained from the δ–T–P(O₂) relationship.     

Ultrastructural characteristics of the gerbil pterygoid medial muscle after experimental occlusal alteration

Ten male young adult gerbils Meriones unguiculatus weighing 55g were divided in two groups: experimental (n=5) animals submitted to exodontia of the left upper molars, and sham-operated were used as control (n=5) group. The aim of the present study was to investigate the ultrastructural effects of occlusal alteration induced by unilateral exodontia on medial pterygoid muscle. After 60 days, the animals were sacrificed by perfusion intracardially with a modified Karnovsky solution after anesthetized with overdose of urethane (3g/kg i.p.). The small samples of this muscle were fixed in 2.5% glutaraldehyde solution and post-fixed in 1% buffered osmium tetroxide solution, dehydrated in ascending concentration of ethanol, and embedded in Spurr resin. Several micrographs data showed that in this period of time, the unilateral teeth extraction was able to induce modifications on the medial pterygoid muscle fibers and capillaries at ultrastructural levels as compared to control muscles and to the ones in the contralateral side of the experimental animals. Ultrastructural changes suggest that injury was greater in the hypofunctional muscle, ipsilateral to teeth extraction.     

Direct observation of dark excitons in individual carbon nanotubes: inhomogeneity in the exchange splitting

We report the direct observation of spin-singlet dark excitons in individual single-walled carbon nanotubes through low-temperature micro-magneto-photoluminescence spectroscopy. A magnetic field (B) applied along the tube axis brightened the dark state, leading to the emergence of a new emission peak. The peak rapidly grew in intensity with increasing B at the expense of the originally dominated bright exciton peak and became dominant at B>3 T. This behavior, universally observed for more than 50 tubes of different chiralities, can be quantitatively modeled by incorporating the Aharonov-Bohm effect and intervalley Coulomb mixing. The directly measured dark-bright splitting values were 1-4 meV for tube diameters 1.0-1.3 nm. Scatter in the splitting value emphasizes the role of the local environment surrounding a nanotube in determining its excitonic fine structure.     

Transition from spherical to deformed shapes of nuclei in the Monte Carlo shell model

The transition from spherical to deformed shapes is studied in terms of large-scale shell-model calculations for Ba isotopes as a function of valence nucleon number with fixed single-particle space and Hamiltonian. A new version of the Monte Carlo shell model is introduced so as to incorporate pairing correlations efficiently, by utilizing condensed pair bases. The energy levels and electromagnetic matrix elements are described in agreement with experiments throughout the transitional region. The orbital M1 sum rule is calculated as a measure of the deformation evolution, and the Q-phonon picture is shown to be reasonable from spherical to deformed nuclei.