Rhodium‐Catalyzed Intramolecular Hydroarylation of 1‐Halo‐1‐alkynes: Regioselective Synthesis of Semihydrogenated Aromatic Heterocycles

The regioselective intramolecular hydroarylation of (3‐halo‐2‐propynyl)anilines, (3‐halo‐2‐propynyl) aryl ethers, or (4‐halo‐3‐butynyl) aryl ethers was efficiently catalyzed by Rh₂(OCOCF₃)₄ to give semihydrogenated aromatic heterocycles, such as 4‐halo‐1,2‐dihydroquinolines, 4‐halo‐3‐chromenes, or 4‐(halomethylene)chromans, in good to excellent yields. Some synthetic applications taking advantage of the halo‐substituents of the products are also illustrated.     

Ligand exchange as the first irreversible step in the nickel-catalyzed cross-coupling reaction of Grignard reagents

Mechanistic studies of the Ni-catalyzed cross-coupling reaction of Grignard reagents through analysis of kinetic isotope effects and theoretical calculations indicated that the product-to-substrate ligand exchange process is the first irreversible step and affects the turnover efficiency and selectivity of the reaction. On the other hand, the oxidative addition step is the first irreversible step in Pd catalysis. This finding has useful implications for the development of efficient Ni catalysis and also illustrates the importance of the catalyst turnover step that has so far received less attention than subsequent catalytic steps.     

Identical-location Transmission Electron Microscopy of Pt Nanoparticle Electrocatalysts Using Iridium-coated Au Grids for Fuel Cell Durability Tests Simulating Start-up and Shutdown Conditions

In an identical-location TEM (IL-TEM) analysis of an electrocatalyst, an Au grid is usually selected owing to its chemical stability under potential cycling conditions. A potential cycle between 1.0 and 1.5 V is applied to the catalyst-cast Au grid for cathode durability testing that simulates the start-up and shutdown conditions of fuel cells. Because of the redox potential of Au (1.36 V vs. RHE), the grid dissolves and redeposits on the catalyst under the applied potential, making it complicated to evaluate the catalyst nanoparticle shape and size after degradation. We fabricated an Au grid coated with an iridium oxide layer (Ir-coated Au grid) to suppress the dissolution of Au. The Ir-coated Au grid with carbon support was compared to the Au grid to confirm the effect of the iridium oxide layer. No Au deposition was observed, even after 3000 cycles at 60 °C for the Ir-coated Au grid, but Au was deposited on carbon on the Au grid after 1000 cycles. Consequently, the alkylamine-modified Pt nanoparticle catalyst (unwashed catalyst) was observed along with the Ir-coated Au grid using IL-TEM under durability tests simulating start-up and shutdown conditions. A catalyst with less alkylamine content was prepared by butylamine washing (washed catalyst) and observed using IL-TEM for comparison. The Pt nanoparticles of the washed catalyst aggregated and changed their morphology after 1000 cycles, while the alkylamine-modified nanoparticles of the unwashed catalyst almost maintained their original size and shape up to 1000 cycles. The Ir-coated gold grids allow proper IL-TEM analysis of catalysts in durability tests without the interference of Au dissolution.     

Palladium(0)-catalyzed direct cross-coupling reaction of allylic alcohols with aryl- and alkenylboronic acids

Allylic alcohols can be used directly for the palladium(0)-catalyzed allylation of aryl- and alkenylboronic acids with a wide variety of functional groups. A triphenylphosphine-ligated palladium catalyst turns out to be most effective for the cross-coupling reaction and its low loading (less than 1 mol%) leads to formation of the coupling product in high yield. The Lewis acidity of the organoboron reagents and poor leaving ability (high basicity) of the hydroxyl group are essential for the cross-coupling reaction. The reaction process is atom-economical and environmentally benign, because it needs neither preparation of allyl halides and esters nor addition of stoichiometric amounts of a base. Furthermore, allylic alcohols containing another unsaturated carbon-carbon bond undergo arylative cyclization reactions leading to cyclopentane formation.     

Synthesis, characterization, DNA-binding study and anticancer properties of ternary metal(II) complexes of edda and an intercalating ligand

A series of ternary metal(ii) complexes {M(phen)(edda); 1a (Cu), 1b (Co), 1c (Zn), 1d (Ni); H(2)edda = N,N(')-ethylenediaminediacetic acid} of N,N'-ethylene-bridged diglycine and 1,10-phenanthroline were synthesized and characterized by elemental analysis, FTIR, UV-visible spectroscopy and magnetic susceptibility measurement. The interaction of these complexes with DNA was investigated using CD and EPR spectroscopy. MTT assay results of 1a-1c , screened on MCF-7 cancer cell lines, show that synergy between the metal and ligands results in significant enhancement of their antiproliferative properties. Preliminary results from apoptosis and cell cycle analyses with flow cytometry are reported. seems to be able to induce cell cycle arrest at G(0)/G(1). The crystal structure of 1a is also included.     

Characteristics of probe electrospray generated from a solid needle

Probe electrospray ionization (PESI) has recently been developed, in which the electrospray was generated from a solid needle instead of by using a capillary. In this paper, the characteristics of probe electrospray ionization were studied based on the measurement of spray current, optical microscopy, and PESI mass spectrometry. In the experiment, the solid needle was moved up and down a vertical axis, and a small amount of sample was repeatedly loaded to the needle when the tip of the needle touched the surface of the liquid sample at the lowest position. After the application of high voltage, a liquid droplet was formed on the tip of the solid needle probe, with its size was determined by the size of the needle tip. The liquid flow rate to the tip, as indicated by the spray current, depends on the voltage applied to the needle as well as the loaded liquid amount. Stable electrospray can be maintained until the total consumption of liquid sample. The kilohertz current pulsation takes place in the case of overloading the sample to the needle. The influences of the applied voltage and the liquid flow rate on the PESI mass spectra were also examined.     

Glucose sensor using a phospholipid polymer-based enzyme immobilization method

An electroenzymatic glucose sensor based on a simple enzyme immobilization technique was constructed and tested. The glucose sensor measures glucose concentrations as changes of oxygen concentrations induced by enzymatic reactions. The immobilizing procedure was developed with the purpose of producing wearable biosensors for clinical use. Two types of biocompatible polymers, 2-methacryloyloxyethyl phosphorylcholine (MPC) copolymerized with dodecyl methacrylate (PMD) and MPC copolymerized with 2-ethylhexyl methacrylate, were compared as a sensitive membrane of biosensors. The PMD enzyme membrane had a better response time. Linearity, reproducibility, effect of the concentrations of immobilized enzyme and drifts of sensor characteristics in long-term tests were also investigated. The linear characteristics were confirmed with glucose concentration from 0.01 to 2.00 mmol/l, with a coefficient of determination of 0.9999. The average output current for 1 mmol/l and the standard deviation were 0.992 and 0.0283 muA. Significant changes in the sensor's characteristics were not observed for 2 weeks when it was kept in a refrigerator at 4 degrees C. Because of the simple procedure, the enzyme immobilization method is not only useful for wearable devices but also other devices such as micro total analysis systems.     

Inactivation of Saccharomyces cerevisiae by ultrasonic irradiation

We have investigated the inactivation of Saccharomyces cerevisiae (yeast cells) by ultrasonic irradiation. The amplitude on the vibration face contacting the sample solution was used as an indication of the ultrasonic power intensity. The effects of the amplitude on the vibration face and the initial cell numbers on the sonolytic inactivation of yeast cells have been investigated using a horn-type sonicator (27.5 kHz). The inactivation of the yeast cells by ultrasonic irradiation shows pseudo first-order behavior. The inactivation rate constant varied from 0.0007 to 0.145 s(-1) when the amplitude on the vibration face was in the range of 1-7 microm(p-p). The change in the inactivation rate constant as a function of the amplitude on the vibration face was similar to that of the OH radical formation rate under the same conditions. The threshold of this sonicator was 3 microm(p-p) with the amplitude on the vibration face. The initial cell numbers (from 10(2) to 10(5) mL(-1)) had an influence on the inactivation of the yeast cells by ultrasonic irradiation. The inactivation rate constants varied from 0.023 to 6.4 x 10(-3) s(-1), and the inactivation by ultrasonic irradiation was fastest at the lowest initial cell numbers. In a squeeze-film-type sonicator (26.6 kHz), 90% inactivation of the yeast cells was achieved by ultrasonic irradiation for 60 min.     

Transfer of chirality from molecule to phase in self-assembled chiral block copolymers

Here, we report the mechanisms of chiral transfer at various length scales in the self-assembly of enantiomeric chiral block copolymers (BCPs*). We show the evolution of homochirality from molecular chirality into phase chirality in the self-assembly of the BCPs*. The chirality of the molecule in the BCP* is identified from circular dichroism (CD) spectra, while the handedness of the helical conformation in the BCP* is determined from a split-type Cotton effect in vibrational circular dichroism spectra. Microphase separation of the BCP* is exploited to form a helical (H*) phase, and the handedness of helical nanostructure in the BCP* is directly visualized from transmission electron microscopy tomography. As examined by CD and fluorescence experiments, significant induced CD signals and a bathochromic shift of fluorescence emission for the achiral perylene moiety as a chemical junction of the BCPs* can be found while the concentration of the BCPs* in toluene solution is higher than the critical micelle concentration, suggesting a twisting and shifting mechanism initiating from the microphase-separated interface of the BCPs* leading to formation of the H* phase from self-assembly.