Chelation of cadmium ions by phytochelatin synthase: role of the cysteine-rich C-terminal.

The interactions between Cd(2+) and the C-terminal region of phytochelatin (PC) synthase using recombinant wild-type and mutant PC synthase were studied. We show that site-directed mutagenesis of Cys residues at C(358)C(359)XXXC(363)XXC(366) motif decreases the number of Cd(2+) and other heavy metal ions interacting with the enzyme, and that the motif binds the metals discriminatingly. The optimum binding ratio of PC synthase to Cd(2+) was also determined. The findings indicate that Cys exists as a free SH residue and that it is involved in the regulation of PC enzyme activity by transferring the metals into closer proximity with the catalytic domain. These results are important in understanding heavy metal detoxification mechanisms in higher plants, a step towards phytoremediated-applications.     

Kinetics of hydrogen abstraction reaction between trifluoromethyl formate and OH radical: A theoretical investigation

Kinetics and mechanism of the hydrogen abstraction reaction between trifluoromethyl formate, CF₃OCHO, and OH radical have been investigated by using ab initio molecular orbital theory up to G2(MP2) level. The hydrogen abstraction rate constant has been calculated for the first time over a temperature range of 250–450 K by using standard transition state theory including the tunneling correction. Arrhenius parameters of the reaction have been estimated from the temperature dependence of the calculated rate constant. The calculated value for the rate constant (2.0 × 10^?14 cm³ molecule^?1 s^?1) at 298 K is found to be in very good agreement with the recent experimental results. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 500–507, 2002     

A third order dispersive flow for closed curves into almost Hermitian manifolds

We discuss a short-time existence theorem of solutions to the initial value problem for a third order dispersive flow for closed curves into a compact almost Hermitian manifold. Our equations geometrically generalize a physical model describing the motion of vortex filament. The classical energy method cannot work for this problem since the almost complex structure of the target manifold is not supposed to be parallel with respect to the Levi-Civita connection. In other words, a loss of one derivative arises from the covariant derivative of the almost complex structure. To overcome this difficulty, we introduce a bounded pseudodifferential operator acting on sections of the pullback bundle, and eliminate the loss of one derivative from the partial differential equation of the dispersive flow.     

Experimental investigation on tunnel sonic boom

Upon the entrance of a high-speed train into a relatively long train tunnel, compression waves are generated in front of the train. These compression waves subsequently coalesce into a weak shock wave so that a unpleasant sonic boom is emitted from the tunnel exit. In order to investigate the generation of the weak shock wave in train tunnels and the emission of the resulting sonic boom from the train tunnel exit and to search for methods for the reduction of these sonic booms, a 1300 scaled train tunnel simulator was constructed and simulation experiments were carried out using this facility.In the train tunnel simulator, an 18 mm dia. and 200 mm long plastic piston moves along a 40 mm dia. and 25 m long test section with speed ranging from 60 to 100 m/s. The tunnel simulator was tilted 8° to the floor so that the attenuation of the piston speed was not more than 10 % of its entrance speed. Pressure measurements along the tunnel simulator and holographic interferometric optical flow visualization of weak shock waves in the tunnel simulator clearly showed that compression waves, with propagation, coalesced into a weak shock wave. Although, for reduction of the sonic boom in prototype train tunnels, the installation of a hood at the entrance of the tunnels was known to be useful for their suppression, this effect was confirmed in the present experiment and found to be effective particularly for low piston speeds. The installation of a partially perforated wall at the exit of the tunnel simulator was found to smear pressure gradients at the shock. This effect is significant for higher piston speeds. Throughout the series of train tunnel simulator experiments, the combination of both the entrance hood and the perforated wall significantly reduces shock overpressures for piston speeds ofu _p ranging from 60 to 100 m/s. These experimental findings were then applied to a real train tunnel and good agreement was obtained between the tunnel simulator result and the real tunnel measurements.     

Formation mechanism of element distribution in glass under femtosecond laser irradiation

We report on the formation mechanism of element distribution in glass under high-repetition-rate femtosecond laser irradiation. We simultaneously focused two beams of femtosecond laser pulses inside a glass and confirmed the formation of characteristically shaped element distributions. The results of the numerical simulation in which we considered concentration- and temperature-gradient-driven diffusions were in excellent qualitative agreement with the experimental results, indicating that the main driving force is the sharp temperature gradient. Since the composition of a glass affects its refractive index, absorption, and luminescence property, the results in this study provide a framework to fabricate a functional optical device such as optical circuits with a high-repetition-rate femtosecond laser.     

Axially chiral dicarboxylic acid catalyzed asymmetric semipinacol rearrangement of cyclic β-hydroxy-α-diazo esters

The development of axially chiral dicarboxylic acid catalyzed desymmetrizing asymmetric semipinacol rearrangement of symmetrically substituted six-membered cyclic β-hydroxy-α-diazo esters is reported as a means to give chiral cycloheptanones with good enantioselectivities.     

Analysis of liquid structure without construction of any structure models by the X-ray scattering method.

A simple approach for determining a liquid structure using X-ray scattering data, in which a liquid structure is uniquely evaluated without construction of any plausible structure models, has been applied to liquid acetonitrile, acetone and cyclohexane. For a pair of molecules, a given point within a molecule is located at the origin with a given molecular orientation. The site of the given point of another molecule is defined by the polar coordinates and the molecular orientation is treated by three Eulerian angles. These parameters are optimized by a non-linear least-squares calculation applied to X-ray scattering data. The reliability of the method was examined by determining the liquid structure of polar acetonitrile and the obtained intermolecular interatomic distances are in good agreement with the previously reported values. The method was then successfully applied to the determination of the liquid structure of acetone and cyclohexane. Especially for nonpolar cyclohexane, the construction of a variety of plausible structural models is very difficult. It was revealed that acetone has an ordered liquid arrangement similar to that found in its crystal, although the intermolecular distances in liquid acetone are different from those in the crystal. On the other hand, the liquid structure of cyclohexane is disordered.     

Synthesis and morphology of polyethylene‐block‐poly(methyl methacrylate) through the combination of metallocene catalysis with living radical polymerization

Polyethylene‐block‐poly(methyl methacrylate) (PE‐b‐PMMA) was successfully synthesized through the combination of metallocene catalysis with living radical polymerization. Terminally hydroxylated polyethylene, prepared by ethylene/allyl alcohol copolymerization with a specific zirconium metallocene/methylaluminoxane/triethylaluminum catalyst system, was treated with 2‐bromoisobutyryl bromide to produce terminally esterified polyethylene (PE‐Br). With the resulting PE‐Br as an initiator for transition‐metal‐mediated living radical polymerization, methyl methacrylate polymerization was subsequently performed with CuBr or RuCl₂(PPh₃)₃ as a catalyst. Then, PE‐b‐PMMA block copolymers of different poly(methyl methacrylate) (PMMA) contents were prepared. Transmission electron microscopy of the obtained block copolymers revealed unique morphological features that depended on the content of the PMMA segment. The block copolymer possessing 75 wt % PMMA contained 50–100‐nm spherical polyethylene lamellae uniformly dispersed in the PMMA matrix. Moreover, the PE‐b‐PMMA block copolymers effectively compatibilized homopolyethylene and homo‐PMMA at a nanometer level. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3965–3973, 2003     

Function of vinyl copolymers with pendant porphyrin or metalloporphyrin dimers as photoredox catalyst

Photoredox catalytic functions of water-soluble vinyl copolymers with pendant porphyrin or metalloporphyrin dimers were investigated. With FRA-L-ascorbic acid in aqueous solution, a vinyl copolymer bearing Mg-porphyrin dimer linked with the shortest N,N′-methylenebisamide bridge was found to have a remarkable accelerating effect under illumination of visible light as compared with that bearing Mg-porphyrin monomer and other copolymers with longer dimer bridges as well as vinyl copolymers bearing porphyrin dimers and monomer. A copolymer bearing Zn-porphyrin dimer was much inferior to that bearing monomer. Copolymers with other metals such as Co(II), Ni(II), and Cu(II) were almost inert.