N-Alkylation of amines with alcohols catalyzed by a Cp*Ir complex

A new effective catalytic system consisting of [Cp*IrCl₂]₂/K₂CO₃ (Cp*=pentamethylcyclopentadienyl) for the N-alkylation of primary amines with alcohols has been developed. As an example, the reaction of aniline with benzyl alcohol in the presence of [Cp*IrCl₂]₂ (5.0 mol%Ir) and K₂CO₃ (5.0 mol%) in toluene at 110°C for 17 h gave benzylaniline in an isolated yield of 88%.     

Preparation and porous control of amorphous carbons by co-defluorination of perfluorooctane and octafluorotoluene in vapor phases at 423 K

Two types of perfluorocarbon compounds, aliphatic perfluorooctane and aromatic octafluorotoluene, were co-defluorinated using sodium metal, and amorphous carbons were deposited from the vapor phase at very low temperature, 423 K. The products showed morphologies composed of fibrous, platelet, and spherical forms, which were dependent on the mixing ratio of the two. The BET surface areas also correlated well with the ratio of the starting mixtures, indicating that the surface area could be adjusted by changing the mixing ratio of these two compounds. However, when the carbonaceous product was further annealed in situ at 573 or 673 K, the porosities also modified. First the porosity decreased at 573 K, then increased greatly at 673 K, where radical interaction to shrink the pores and crystal growth of template fluoride occurred at 573 K and 673 K, respectively.     

Ultrasound enhances liposome-mediated gene transfection

Previous studies have shown that some series of liposomes, usually containing cationic lipids, are useful tools for gene introduction into cells. To investigate the effect of ultrasound (US) on liposome-mediated transfection, three types of liposomes (designated L1, L2 and L3, in the order of increasing transfection efficiency) containing O,O′-ditetradecanoyl-N-(-trimethylammonioacetyl) diethanolamine chloride, dioleoylphosphatidylethanolamine, and/or cholesterol at varying ratios, were used in this study. HeLa cells were treated with liposome–DNA complexes containing luciferase genes for 2 h before sonication. Optimal US condition for the enhancement was determined to be 0.5 W/cm², 1 MHz continuous wave for 1 min and was above threshold for inertial cavitation based on EPR detection of free radicals. Luciferase expressions 24 h after the treatments were significantly increased by sonication to 2.4 fold with L1, and 1.7 fold with L2. However, with L3, which showed the highest level of expression among the liposomes, significant but minimal enhancement was observed when sonication was done 15 min after the DNA-L3 treatment, suggesting that efficiency of the liposome also determines the proper timing for sonication. The 2 h pre-sonication incubation with liposome–DNA complexes for L1 and L2 (30 min for L3) required to attain enhancement, suggests that US works to enhance transfection only after cells had enough DNA uptake.     

Microstructural evolution of pure copper during friction-stir welding

The microstructural evolution of pure copper during friction-stir welding was found to be principally influenced by welding temperature. At temperatures below ~0.5 T_m (where T_m is melting point), the microstructure was shown to be essentially determined by continuous recrystallization, leading to significant grain refinement and related material strengthening in the stir zone. In contrast, grain structure development at temperatures above ~0.5 T_m was dominated by discontinuous recrystallization producing a relatively coarse grain structure in the stir zone and giving rise to material softening.     

Direct beta-alkylation of secondary alcohols with primary alcohols catalyzed by a CpIr complex

A new catalytic system for beta-alkylation of secondary alcohols has been developed. In the presence of [CpIrCl(2)](2) (Cp = pentamethylcyclopentadienyl) catalyst and base, the reactions of various secondary alcohols with primary alcohols give beta-alkylated higher alcohols in good to excellent yields without any hydrogen acceptor or hydrogen donor. This reaction proceeds via successive hydrogen-transfer reactions and aldol condensation. [reaction: see text]     

Investigation of the dominant hydration structures among the ionic species in aqueous solution: novel quantum mechanics/molecular mechanics simulations combined with the theory of energy representation

In the present work, we have performed quantum chemical calculations to determine preferable species among the ionic complexes that are present in ambient water due to the autodissociation of water molecule. First, we have formulated the relative population of the hydrated complexes with respect to the bare ion (H(3)O(+) or OH(-)) in terms of the solvation free energies of the relevant molecules. The solvation free energies for various ionic species (H(3)O(+), H(5)O(2) (+), H(7)O(3) (+), H(9)O(4) (+) or OH(-), H(3)O(2) (-), H(5)O(3) (-), H(7)O(4) (-), H(9)O(5) (-)), categorized as proton or hydroxide ion in solution, have been computed by employing the QM/MM-ER method recently developed by combining the quantum mechanical/molecular mechanical (QM/MM) approach with the theory of energy representation (ER). Then, the computed solvation free energies have been used to evaluate the ratio of the populations of the ionic complexes to that of the bare ion (H(3)O(+) or OH(-)). Our results suggest that the Zundel form, i.e., H(5)O(2) (+), is the most preferable in the solution among the cationic species listed above though the Eigen form (H(9)O(4) (+)) is very close to the Zundel complex in the free energy, while the anionic fragment from water molecules mostly takes the form of OH(-). It has also been found that the loss of the translational entropy of water molecules associated with the formation of the complex plays a role in determining the preferable size of the cluster.     

Host–guest complexation‐triggered chiroptical change of poly(phenylacetylene)s bearing binaphthocrown ether moieties on the main chain

Diacetylene monomers with respective lengths of the oxyethylene chains were cyclopolymerized with a rhodium catalyst to produce novel poly(phenylacetylene)s bearing a different cavity size of the chiral crown ether in the repeating units ( 2a – c ). In the circular dichroism spectra of the resulting polymers, characteristic Cotton effects were observed in the range from 350 to 500 nm corresponding to the absorption of the conjugated polymer backbone, indicating that the polymers possessed a helical structure with an excess single screw sense induced by the covalently bonded binaphthyl units. The host–guest complexation of 2a – c with achiral guests produced a chiroptical change based on the fluctuation in the main chain conformation. The behavior of the complexation‐induced chiroptical change was essentially dictated by the cavity size of the binaphthocrown ether units. Additionally, a chirality‐responsive helicity change was observed in the case of the complexation of 2a – c with chiral guests, which also depended on the crown ether size. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1197–1206, 2010     

Realignment process of actin stress fibers in single living cells studied by focused femtosecond laser irradiation

Three-dimensional dissection of a single actin stress fiber in a living cell was performed based on multi-photon absorption of a focused femtosecond laser pulse. The realignment process of an actin stress fiber was investigated after its direct cutting by a single-shot femtosecond laser pulse irradiation by high-speed transmission and fluorescence imaging methods. It was confirmed that mechanical force led by the femtosecond laser cutting propagates to entire cell through the cytockelton in a 100 μs time scale. The cut actin stress fiber was realigned in the time scale of a few tens of minutes. The dynamic analysis of the realignment induced by single-shot femtosecond laser gives new information on cell activity.