Pd-catalyzed coupling reaction of acid chlorides with terminal alkynes using 1-(2-pyridylethynyl)-2-(2-thienylethynyl)benzene ligand

In the presence of 1-(2-pyridylethynyl)-2-(2-thienylethynyl)benzene as a ligand, the direct synthesis of alkynones has accomplished by a Pd-catalyzed coupling reaction of acid chlorides with terminal acetylenes under mild conditions.     

Metastable decomposition and hydrogen migration of ethane dication produced in an intense femtosecond near-infrared laser field

We investigated a formation channel of triatomic molecular hydrogen ions from ethane dication induced by irradiation of intense laser fields (800 nm, 100 fs, ～1 × 10(14) W∕cm(2)) by using time of flight mass spectrometry. Hydrogen ion and molecular hydrogen ion (H,D)(n)(+) (n = 1-3) ejected from ethane dications, produced by double ionization of three types of samples, CH(3)CH(3), CD(3)CD(3), and CH(3)CD(3), were measured. All fragments were found to comprise components with a kinetic energy of ～3.5 eV originating from a two-body Coulomb explosion of ethane dications. Based on the signal intensities and the anisotropy of the ejection direction with respect to the laser polarization direction, the branching ratios, H(+):D(+) = 66:34, H(2)(+):HD(+):D(2)(+) = 63:6:31, and H(3)(+):H(2)D(+):HD(2)(+):D(3)(+) = 26:31:34:9 for the decomposition of C(2)H(3)D(3)(2+), were determined. The ratio of hydrogen molecules, H(2):HD:D(2) = 31:48:21, was also estimated from the signal intensities of the counter ion C(2)(H,D)(4)(2+). The similarity in the extent of H∕D mixture in (H,D)(3)(+) with that of (H,D)(2) suggests that these two dissociation channels have a common precursor with the C(2)H(4)(2+)...H(2) complex structure, as proposed theoretically in the case of H(3)(+) ejection from allene dication [A. M. Mebel and A. D. Bandrauk, J. Chem. Phys. 129, 224311 (2008)]. In contrast, the (H,D)(2)(+) ejection path with a lower extent of H∕D mixture and a large anisotropy is expected to proceed essentially via a different path with a much rapid decomposition rate. For the Coulomb explosion path of C-C bond breaking, the yield ratios of two channels, CH(3)CD(3)(2+)→ CH(3)(+) + CD(3)(+) and CH(2)D(+) + CHD(2)(+), were 81:19 and 92:8 for the perpendicular and parallel directions, respectively. This indicates that the process occurs at a rapid rate, which is comparable to hydrogen migration through the C-C bond, resulting in smaller anisotropy for the latter channel that needs H∕D exchange.     

Chiral porphyrin dimer with a macrocyclic cavity for intercalation of aromatic guests

Chiral diporphyrin receptor 1, which has a macrocyclic cavity to sandwich aromatic guest molecules via double π-π stacking interactions, enabled the naked-eye detection of an aromatic explosive as well as chiral discrimination in NMR.     

In-situ Observation of Tissue Laser Ablation Using Optical Coherence Tomography

In laser ablation of biological tissue, tomography of the tissue surface is necessary for measurement of the crater shape and the crater depth. In this paper, we demonstrate in-situ observation of biological-tissue surface in laser ablation by optical coherence tomography (OCT). Depth of a crater of human tooth is measured by these OCT images, and then the ablation rate of 0.21 μm/pulse is determined.     

A lens formula for an electrostatic lens accompaning pre- and after electric fields

The virtual object and image are introduced in order to apply the usual lens formula to an electrostatic lense accompaning pre- and/or electric fields. In case of the uniform electric field, their positions are simply expressed as a function of the accelerating or decelerating potential ratio.     

Preparation of poly(ethylene glycol)-modified poly(amido amine) dendrimers encapsulating gold nanoparticles and their heat-generating ability

Loading of HAuCl4 in poly(amido amine) G4 dendrimers having poly(ethylene glycol) (PEG) grafts at all chain ends and subsequent reduction with NaBH4 yielded PEG-modified dendrimers encapsulating gold nanoparticles (Au NPs) of ca. 2 nm diameter. The Au NPs held in the dendrimers were stable in aqueous solutions and dissolved readily, even after freeze-drying. Despite their small particle size, the heat-generating ability of Au NPs held in the dendrimer was comparable to that of widely used Au NPs with ca. 11 nm diameter under visible light irradiation. The observed excellent colloidal stability, high heat-generating ability and their biocompatible surface confirm that the PEG-modified dendrimers encapsulating Au NPs are a promising tool for photothermal therapy and imaging.     

Modelling and experimental validation of enantioseparation of racemic phenylalanine via a hollow fibre-supported liquid membrane

This paper reports on the enantioseparation of racemic phenylalanine or D-phenylalanine and Lphenylalanine via a hollow fibre-supported liquid membrane (HFSLM) and the results are compared with the mathematical model. The enantioseparation results, of 80 % and 73 %, showed the highest extraction and stripping of l-phenylalanine from the feed phase and the enantiomeric excess (% ee) of 60 % from 6 mmol L^?1 of initial rac-phenylalanine in the feed solution. The optimum parameters were feed solution at pH 5, 6 mmol L^L?1 of O,O′-dibenzoyl-(2S,3S)-tartaric acid ((+)-DBTA) as the extractant in octanol as the liquid membrane, and deionised water as the stripping solution. Equal flow-rates of feed and stripping solutions of 100 mL min^L?1 were adjusted in a batch operation mode for 50 min at ambient temperature. From the calculation, the equilibrium constants of extraction (K _ex) and mass transfer coefficients in the feed phase (k _f) and in the liquid membrane phase (k _m) were found to be 1.81 L mmol^?2, 3.50 × 10^?2 cm s^?1, and 1.40 × 10^?2 cm s^?1, respectively. Finally, the change in concentrations of d,l-phenylalanine over time in the feed and stripping solutions by mathematical model were estimated and compared with the experimental results. The values thus calculated were in agreement with the experimental data with the average deviation of approximately 3 %.     

High resolution flux‐difference‐splitting scheme on adaptive grid for open‐channel flows

The effectiveness and usefulness of further enhancing the shock resolution of a second‐order accurate scheme for open‐channel flows by using an adaptive grid is investigated. The flux‐difference‐splitting (FDS) scheme based on the Lax–Wendroff numerical flux is implemented on a fixed as well as on a self‐adjusting grid for this purpose. The grid‐adjusting procedure, developed by Harten and Hyman, adjusts the grid by averaging the local characteristic velocities with respect to the signal amplitude in such a way that a shock always lies on a mesh point. This enables a scheme capable of perfectly resolving a stationary shock to capture a shock that moves from mesh point to mesh point. The Roe's approximate Jacobian is used for conservation and consistency, while theoretically sound treatment for satisfying entropy inequality conditions ensures physically realistic solutions. Details about inclusion of source terms, often left out of analyses for the homogeneous part of governing equations, are also explained. The numerical results for some exacting problems are compared with analytical as well as experimental results for examining improvements in resolution of discontinuities by the adaptive grid. Copyright © 2001 John Wiley & Sons, Ltd.