Palladium-catalyzed intramolecular hydroarylation of 4-benzofuranyl alkynoates. Approach to angelicin derivatives

Intramolecular hydroarylation of 4-benzofuranyl alkynoates using Pd(OAc)(2) as catalyst took place selectively and efficiently, giving angular furocoumarin derivatives in high yields. The parent angelicin was obtained in 80% yield by this method. The starting 4-benzofuranyl alkynoates were easily accessible from readily available 4-hydroxybenzofurans and alkynoic acids.     

Efficient total synthesis of manzacidin B

The highly diastereoselective synthesis of the marine natural product, (?)-manzacidin B, is described. A novel copper-catalyzed aldol reaction of the α-methylserine-derived aldehyde with an isocyanoacetate possessing (1R)-camphorsultam as the chiral auxiliary proceeded in a highly diastereoselective manner to give the (4R,5R,6R)-adduct, which was converted into manzacidin B in a few steps.     

Electrochemical Gene‐Function Analysis for Single Cells with Addressable Microelectrode/Microwell Arrays

To each his own : An addressable electrochemical device consisting of orthogonally arranged rows and columns of electrodes has been constructed to monitor protein expression in genetically engineered cells at the single‐cell level. The response based on redox cycling reflected the different expression levels of the enzyme from individual HeLa cells transfected with a plasmid vector including secreted alkaline phosphatase.

     

α,α′‐Diarylacenaphtho[1,2‐c]phosphole P‐Oxides: Divergent Synthesis and Application to Cathode Buffer Layers in Organic Photovoltaics

A divergent method for the synthesis of α,α′‐diarylacenaphtho[1,2‐c]phosphole P‐oxides has been established; α,α′‐dibromoacenaphtho[c]phosphole P‐oxide, which was prepared through a Ti^II‐mediated cyclization of 1,8‐bis(trimethylsilylethynyl)naphthalene, underwent a Stille coupling with three different kinds of aryltributylstannanes to afford the α,α′‐diarylacenaphtho[c]phosphole P‐oxides in moderate to good yields. X‐ray crystallographic analyses and UV/Vis absorption/fluorescence measurements have revealed that the degree of π‐conjugation, the packing motif, the electron‐accepting ability, and the thermal stability of the acenaphtho[c]phosphole π‐systems are finely tunable with the α‐aryl substituents. All the P?O and P?S derivatives exhibited high stability in their electrochemically reduced state. To use this class of arene‐fused phosphole π‐systems as n‐type semiconducting materials, we evaluated device performances of the bulk heterojunction organic photovoltaics (OPV) that consist of poly(3‐hexylthiophene), an indene‐C₇₀ bisadduct, and a cathode buffer layer. The insertion of the diarylacenaphtho[c]phosphole P‐oxides as the buffer layer was found to improve the power conversion efficiency of the polymer‐based OPV devices.     

Hepatic parenchymal enhancement at Gd-EOB-DTPA-enhanced MR imaging: correlation with morphological grading of severity in cirrhosis and chronic hepatitis

The aim was to clarify whether enhancement effects of the liver parenchyma in the hepatobiliary phase (HP) of gadolinium-ethoxybenzyl-diethylenetriamine pentaacetic acid (Gd-EOB-DTPA)-enhanced MR imaging were correlated with the morphological grading of the severity in cirrhosis. A total of 62 patients with chronic hepatitis or cirrhosis underwent Gd-EOB-DTPA-enhanced MR imaging. Relative enhancement (RE) of liver parenchyma was calculated from signal intensity (SI) measurements obtained at precontrast images (SIpre) and 20-min postcontrast HP images (SIpost) as: (SIpost-SIpre)/SIpre. Morphological MR grades of severity in cirrhosis were divided into four groups. Then, RE of liver parenchyma and morphologic MR grading were correlated. Regarding the morphologic severity of cirrhosis, the numbers of patients with MR grade 1, 2, 3 and 4 were 14 (23%), 7 (11%), 28 (45%) and 13 (21%), respectively. The mean REs of liver parenchyma in each group of MR morphologic grade 1, 2, 3 and 4 were 0.71±0.21, 0.62±0.16, 0.70±0.22 and 0.77±0.18, respectively. There was no significant correlation between the MR grading of morphologic severity and the RE of liver parenchyma at 20-min HP. Hepatic parenchymal enhancement in the HP of Gd-EOB-DTPA-enhanced MR imaging did not necessarily decrease according to the severity of morphologic changes in cirrhosis. This fact may suggest that the hepatic uptake of Gd-EOB-DTPA depends on the preserved hepatocytes function rather than the severity of morphologic changes in cirrhosis.     

Electrochemical detection for dynamic analyses of a redox component in droplets using a local redox cycling-based electrochemical (LRC-EC) chip device

This report describes the electrochemical detection of a redox component in droplets using a local redox cycling-based electrochemical (LRC-EC) chip device consisting of 256 sensors. The time-course analyses showed that the redox compound in the droplet was dynamically changed during droplet evaporation or mass transfer through a water/oil interface.     

Current status for light-emitting diode with Eu-doped GaN active layer grown by MBE

Recent progress on light-emitting diode having a Eu-doped GaN active layer is reported. Although the first success on LED using GaN:Eu has been achieved by OMVPE, the factors to be controlled during the crystal growth are not well understood. We found that GaN:Eu co-doped with Mg in NH₃-MBE shows a Eu site which is excited only by the above band-gap excitation. The luminescence intensity is enhanced at least 10 times than that without Mg co-doping. The LED operation fabricated using Mg co-doping technique is successfully demonstrated.     

2,7-Diphenyl[1]benzothieno[3,2-b]benzothiophene, a new organic semiconductor for air-stable organic field-effect transistors with mobilities up to 2.0 cm2 V(-1) s(-1)

Vapor-deposited thin films of a newly developed sulfur-containing heteroarene, 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DPh-BTBT), were used as an active layer of OFETs, which showed excellent FET characteristics in ambient conditions with mobilities of approximately 2.0 cm2 V-1 s-1 and Ion/Ioff of 107.     

High-Resolution Electrochemical Mapping of the Hydrogen Evolution Reaction on Transition-Metal Dichalcogenide Nanosheets

High-resolution scanning electrochemical cell microscopy (SECCM) is used to image and quantitatively analyze the hydrogen evolution reaction (HER) catalytically active sites of 1H-MoS₂ nanosheets, MoS₂, and WS₂ heteronanosheets. Using a 20 nm radius nanopipette and hopping mode scanning, the resolution of SECCM was beyond the optical microscopy limit and visualized a small triangular MoS₂ nanosheet with a side length of ca. 130 nm. The electrochemical cell provides local cyclic voltammograms with a nanoscale spatial resolution for visualizing HER active sites as electrochemical images. The HER activity difference of edge, terrace, and heterojunction of MoS₂ and WS₂ were revealed. The SECCM imaging directly visualized the relationship of HER activity and number of MoS₂ nanosheet layers and unveiled the heterogeneous aging state of MoS₂ nanosheets. SECCM can be used for improving local HER activities by producing sulfur vacancies using electrochemical reaction at the selected region.     

Selenium-Containing π-Conjugated Compounds for Electronic Molecular Materials

Abstract

Novel selenium-containing π-conjugated compounds have been studied for the development of organic metals, superconductors, and field-effect-transistors. Methylenedithiotetraselenafulvalene (MDT-TSF) and its related electron donors are effectively synthesized by the recently developed synthetic method consisting of the one-pot formation of 1,3-diselenole-2-selones, the deprotection/realkylation procedure of the protected tetrachalcogenafulvalene-thiolate and -selenolate, and the ring closing reaction via trans-alkylation on sulfur or selenium atom. These new compounds serve as good electron donors for developing not only highly conducting charge-transfer salts (> 10 ³ S cm^?1) but also superconducting salts. Among six selenium-containing methylenedichalcogeno-tetrachalcogenafulvalenes, we found that four of them can produce superconducting salts, indicating that the present compounds are superior class of electron donors.

For the development of high-performance organic semiconductors for organic field effect transistor (OFET) devices, we focused our attention to selenophene-containing acene-type compounds, namely benzo[1,2-b:4,5-b′]diselenophene (BDS) derivatives hitherto unknown. A new synthetic method for BDS derivatives consisting of double heterocycle-formation on the central benzene ring has been established and has made it possible to synthesize a range of BDS derivatives. Among them, 2,6-diphenyl derivative (DPh-BDS) shows very high hole mobility of 0.17 cm ² /Vs, which is classified into the highest class of field-effect mobility of organic thin films.