Sodium halides as the source of electrophilic halogens in green synthesis of 3-halo- and 3,n-dihalobenzo[b]thiophenes

A convenient methodology for the synthesis of mono- and di-halogenated benzo[b]thiophenes is described herein, which utilizes copper(II) sulfate pentahydrate and various sodium halides in the presence of substituted 2-alkynylthioanisoles. The proposed method is facile, uses ethanol as a green solvent, and results in uniquely substituted benzo[b]thiophene structures with isolated yields up to 96%. The most useful component of this methodology is the selective introduction of bromine atoms at every available position (2–7) around the benzo[b]thiophene ring, while keeping position 3 occupied by a specific halogen atom such as Cl, Br or I. Aromatic halogens are useful reactive handles; therefore, the selective introduction of halogens at specific positions would be valuable in the targeted synthesis of bioactive molecules and complex organic materials via metal-catalyzed cross coupling reactions. This work is a novel approach towards the synthesis of dihalo substituted benzo[b]thiophene core structures, which provides a superior alternative to the current methods discussed herein.     

Synthesis of new di-anchoring organic sensitizer based on quinoxaline acceptor for dye-sensitized solar cells

New quinoxaline-based organic sensitizer bearing di-anchoring group for dye-sensitized solar cells (DSSCs) was synthesized from diethyl 4,5-diaminophthaltate, in which was prepared under mild condition by using Takehito’s method. The synthesized sensitizer was compared with mono-anchoring sensitizer through absorption spectra, emission spectra, J-V curve, and IPCE spectra, indicating the di-anchoring group leads to a noticeable improvement of J_sc value owing to more efficient intramolecular charge transfer and channel number increment.     

Site-selective C–H nitration of N-aryl-7-azaindoles under palladium(II) catalysis

The site-selective C–H nitration reaction of 7-azaindoles with t-butyl nitrite under palladium catalysis is described. This protocol provides an efficient method for the construction of ortho-nitrated N-aryl-7-azaindoles with excellent site-selectivity and functional group compatibility. The formed 7-azaindole derivatives can be readily transformed into 7-azaindoles containing an aniline functional group under palladium-catalyzed hydrogenation conditions.     

Hydrodechlorination of chlorophenols over Pd catalysts supported on zeolite Y,MCM-41 and graphene

Hydrodechlorination (HDC) reaction of chlorophenols was carried out using Pd catalysts supported over zeolite Y, MCM-41 or graphene. Pd-MCM-41 and Pd-Y zeolite were prepared by impregnation and ion-exchange method, respectively. Pd-graphene (Pd-G) was prepared by hydrazine hydrate reduction of palladium ion dispersed on graphene oxide. The catalysts were characterized by several analytical tools such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). These catalysts were subjected to HDC reaction of chlorophenols, such as 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP) and 3,4-dichlorophenol (3,4-DCP). The reaction rate of HDC of chlorophenols catalyzed by Pd catalysts with various solid bases, such as KF/Al₂O₃ (alumina), sodium acetate (NaOAc) and K₂CO₃ was compared. First, Pd-MCM-41 and Pd-Y catalysts were compared. 2,4- and 3,4-DCPs were completely decomposed within 6 h, in the case of Pd-MCM-41 with NaOAc. Using Pd-Y instead of Pd-MCM-41 with NaOAc, much faster decomposition was observed. Faster decomposition of 4-CP and DCPs was observed with NaOAc base than K₂CO₃ or KF/Al₂O₃ under the same condition. In the case of Pd-Y with KF/Al₂O₃, slower decomposition of 4-CP and DCPs was observed. These base effects were interpreted using the solubility of NaCl and KCl in alcohol and the basic sites of KF/Al₂O₃. Because the solubility of NaCl is known to be larger than KCl solubility in alcohol, byproduct NaCl could be easily dissolved and ionized in solvents. For Pd-Y with KF/Al₂O₃, the small pore size of Y zeolite can interfere with the diffusion of HCl to KF/Al₂O₃ basic site. Second, three catalysts, including Pd-graphene, were compared. 2,4-DCP was decomposed within 2 h using Pd-G with either K₂CO₃, NaOAc or KF/Al₂O₃. Pd-G catalyst showed the highest catalytic activity among Pd-G, Pd-MCM-41 and Pd-Y catalysts. The high activity and stability of the Pd-G could be attributed to the strong metal–support interaction with an electron-deficient site and a critical Pd particle size (ca. 3.5 nm) of Pd-G nanocatalyst with a stronger resistance to the deactivation and good affinity toward aromatic organic molecules, especially phenols. The progress of HDC reaction was monitored by gas chromatography with flame ionization detection (GC/FID), and a feasible degradation process could be explained by analyzing the degradation products such as phenol, cyclohexanone and cyclohexanol from resulting GC chromatograms. The effect of reaction temperature on HDC in Pd-G catalyst was also discussed. In conclusion, Pd-G is an efficient catalyst for decomposition of chlorophenols and can be applied to remediation of chlorophenol-contaminated water under mild conditions.     

Multifarious injection chamber for molecular structure study (MICOSS) system: development and application for serial femtosecond crystallography at Pohang Accelerator Laboratory X‐ray Free‐Electron Laser

The multifarious injection chamber for molecular structure study (MICOSS) experimental system has been developed at the Pohang Accelerator Laboratory X‐ray Free‐Electron Laser for conducting serial femtosecond crystallography. This system comprises several instruments such as a dedicated sample chamber, sample injectors, sample environment diagnostic system and detector stage for convenient distance manipulation. Serial femtosecond crystallography experiments of lysozyme crystals have been conducted successfully. The diffraction peaks have reached to ～1.8 Å resolution at the photon energy of 9.785 keV.     

The Peierls instability in one-dimensional conductors with arbitrary bandfilling

Mean field calculations of the Peierls instability have been carried out for arbitrary bandfilling both in the case of free electrons as well as for the tightbinding approximation. New expressions for Δ(0) and T_p are derived which change the experimentally derived λ to a more reasonable value. Δ(0)/k_BT_p may differ significantly from the BCS value 1.76 in the tightbinding approximation.     

Diffusion and ionic conductivity in sodium beta alumina

Measurements of sodium tracer diffusion (D_t) and ionic conductivity (σ) have been made on the same single crystals of sodium beta-alumina of composition 1.23 Na₂0.11 Al₂O₃. The σ- measurements were made over the temperature 390–660 K using reversible (liquid sodium) electrodes. A fit to the conductivity data gives $\text{σT = 2470}\text{exp}\text{(?0.142}\text{eV}\text{kT}\text{)Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}\text{K}$. The D_t, measurements employed two techniques, i.e. nondestructive profiling over the temperature range 210–750 K and cation exchange over the temperature range 505–970 K. The results of the two techniques were in close agreement and can be expressed as $\text{D = 2.12 ×10}{}^{\mathrm{?4}}\text{exp}\text{(?0.169}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}{}^{\mathrm{?1}}$ for T>520K and $\text{D = 2.45 × 10}{}^{\mathrm{?4}}\text{exp}\text{(?0.164}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}\text{470}\text{K}$. The “transition” region between 470 and 520 K is not observed in the conductivity measurements. Silver cation exchange was used to determine the number of mobile sodium ions. A comparison of D_t and σ data yielded a Haven ratio that is temperature dependent, ranging in value from 0.45 at 870 K to 0.35 at 370 K.     

Pionic K X-rays in liquid He

Energies and lorentzian widths of pionic K X-ray transitions have been measured in liquid ³He with improved accuracy. The strong interaction on the π³He 1s level is found to be attractive and to produce an increase in the K transition energies of 34 ± 4 eV; the measured lorentzian width is 36 ±7 eV. Measured values are also presented for K X-ray energies in liquid π⁴He and μ⁴He, the lorentzian width of the 1s level in π⁴He, and relative intensities of K X-ray transitions in π³He, π⁴He and μ⁴He. The measurements are compared with those of others and with recent theoretical calculations.     

Tail asymptotics for the fundamental period in the MAP/G/1 queue

This paper studies the tail behavior of the fundamental period in the MAP/G/1 queue. We prove that if the service time distribution has a regularly varying tail, then the fundamental period distribution in the MAP/G/1 queue has also regularly varying tail, and vice versa, by finding an explicit expression for the asymptotics of the tail of the fundamental period in terms of the tail of the service time distribution. Our main result with the matrix analytic proof is a natural extension of the result in (de Meyer and Teugels, J. Appl. Probab. 17: 802–813, 1980) on the M/G/1 queue where techniques rely heavily on analytic expressions of relevant functions. I.-S. Wee’s research was supported by the Korea Research Foundation Grant KRF 2003-070-00008.