Palladium-catalyzed allylic oxidation of olefins by t-butyl hydroperoxide and tellurium(IV) oxide

Treatment of several cyclic olefins, β-pinene, allylbenzene, and estragole with palladium(II) salt in acetic acid in the presence of t-butyl hydroperoxide and tellurium(IV) oxide afforded mainly the corresponding allylic acetates. The reaction proceeded catalytically with palladium(II) salt, t-BuOOH working as a reoxidizing agent.     

Carbon-13 NMR spectra of some epoxides derived from dicyclopentadiene

The ¹³C NMR spectra of a series of epoxides derived from endo- and exo-dicyclopentadiene and their partially hydrogenated compounds were determined to examine the substituent effects arising from the introduction of the oxirane ring in comparison with those found in other ring systems. The ¹³C signals of some epoxides were assigned by using lanthanide shift reagents. Characteristic substituent effects exerted by an oxirane ring were demonstrated. Marked steric γ-effects of ?8—13 ppm were observed at the bridge carbon signal in the bicyclo[2.2.1]heptane skeleton. Differences were found in the substituent effects between endo- and exo-dicyclopentadiene epoxides, and have been discussed in relation to the molecular geometry.     

Optomechanical wavelength and energy conversion in high- double-layer cavities of photonic crystal slabs

We demonstrate that ultrasmall double-layer photonic-crystal-slab cavities exhibit a very high-Q value for a wide range of the layer spacing, which enables us to realize unique optomechanical coupling. By mechanically varying the separation, we can achieve extraordinarily large wavelength conversion. In addition, the light stored in the cavity can generate a large radiation force. We show that this system exhibits extremely high energy conversion efficiency between optical and mechanical energy, leading to a novel approach for the optomechanical control of light and matter.     

Effects of pressure and temperature on the solubility of monosodium L-glutamate monohydrate in water

Abstract

The solubility of monosodium L-glutamate monohydrate (MSG.H₂O) in water was measured at pressures in the range of 0.10-300MPa and 298.15K. The density of MSG solution at high concentrations and heat of solution at saturated concentration were also measured at atmospheric pressure. The solubility, m_s, increased with increasing pressure and the pressure coefficient, Θ_p, [?(? In m_s,? p)_T] at 0.10 MPa was (2.0 ± 0.1) × 10-¹⁰Pa-1. It agrees well with (2.1 ±0.2)× 10-¹⁰ Pa-¹ thermodynamically estimated using the partial molar volume, the activity coefficient of the solute in solution, and the molar volume of the crystal. The excellent agreement at 0.10MPa gives us confidence in the solubility data at higher pressures. The heat of solution data and other pertinent values were used to calculate the temperature coefficient of solubility, Θ_T [? (? In m_s/?(1/T))_p], by a thermodynamic equality. The resulting Θ_T compares well with the data directly measured by Ogawa.     

Dibenzoarsepins: Planarization of 8π‐Electron System in the Lowest Singlet Excited State

Dibenzo[b,f]arsepins possessing severely distorted cores compared to those of other heteropins were synthesized. These derivatives exhibited dual photoluminescence in the green‐to‐red region (500–700 nm) and the near‐ultraviolet region (<380 nm), which could be attributed to the planarization of the arsepin core in the lowest singlet excited (S₁) state. The computational approach for the assessment of the aromatic indices revealed that the dibenzoarsepins studied show aromaticity (8π system) in the S₁ states in line with Baird's rule. The lone pair electrons of the arsenic atoms play a crucial role in the aromaticity in the S₁ states.     

An Unprecedented Cyclization Mechanism in the Biosynthesis of Carbazole Alkaloids in Streptomyces

Carquinostatin A (CQS), a potent neuroprotective substance, is a unique carbazole alkaloid with both an ortho‐quinone function and an isoprenoid moiety. We identified the entire gene cluster responsible for CQS biosynthesis in Streptomyces exfoliatus through heterologous production of CQS and gene deletion. Biochemical characterization of seven CQS biosynthetic gene products (CqsB1–7) established the total biosynthetic pathway of CQS. Reconstitution of CqsB1 and CqsB2 showed that the synthesis of the carbazole skeleton involves CqsB1‐catalyzed decarboxylative condensation of an α‐hydroxyl‐β‐keto acid intermediate with 3‐hydroxybutyryl‐ACP followed by CqsB2‐catalyzed oxidative cyclization. Based on crystal structures and mutagenesis‐based biochemical assays, a detailed mechanism for the unique deprotonation‐initiated cyclization catalyzed by CqsB2 is proposed. Finally, analysis of the substrate specificity of the biosynthetic enzymes led to the production of novel carbazoles.     

Radial breathing modes of single-walled carbon nanotubes in resonance Raman spectra at high temperature and their chiral index assignment

Radial breathing modes (RBMs) in resonance Raman spectra from single-walled carbon nanotubes (SWCNTs) on a SiO₂/Si (0 0 1) substrate are studied between 25 and 720 °C. A change in the relative intensity of each RBM peak with temperature is observed, which originates from the temperature dependence of the resonance condition of nanotubes. For 25 °C, each RBM peak is reasonably assigned on the basis of data in the literature [J. Maultzsch, H. Telg, S. Reich, F. Hennrich, C. Thomsen, Phys. Rev. B 72 (2005) 205438]. By taking into account the temperature-dependent behavior of the relative intensity of the RBM peaks, each RBM peak is successfully assigned even for 720 °C. It is found that most of the observed RBM peaks for a laser excitation energy of E_exc = 1.96 eV are from chiral SWCNTs. These results make it possible to discuss further details of the chirality-dependent growth behavior observed for in situ Raman spectroscopy.