Enantioselective acylation of secondary alcohols catalyzed by chiral N-heterocyclic carbenes

[reaction: see text] The synthetic utility of chiral N-heterocyclic carbenes, which have been used mainly in transition metal-catalyzed reactions as a ligand, was demonstrated by the enantioselective acylation of secondary alcohols.     

Aggregation states and surface wettability in films of poly(styrene-block-2-perfluorooctyl ethyl acrylate) diblock copolymers synthesized by atom transfer radical polymerization

Well-defined poly(styrene-block-2-perfluorooctyl ethyl acrylate) [P(St-b-PFA)] copolymers with various chemical compositions were synthesized by atom transfer radical polymerization. Films of P(St-b-PFA) were structurally characterized, from bulk to surface, on the basis of transmittance electron microscopic observation and small-angle X-ray scattering, X-ray photoelectron spectroscopic, and contact angle measurements. For a comparison, poly(styrene-random-2-perfluorooctyl ethyl acrylate) [P(St-ran-PFA)] copolymers were also synthesized by conventional free radical polymerization. While P(St-b-PFA) with the 2-perfluorooctyl ethyl acrylate (PFA) content higher than 18.7 mol % formed a typical phase-separated cylinder structure, P(St-b-PFA) with a lower PFA content and P(St-ran-PFA) were in a miscible state. Since the perfluoroalkyl groups possess extremely low surface energy, they were preferentially segregated at the film surface, resulting in the formation of the PFA surface layer. This was the case for all P(St-b-PFA) films examined, although the aggregation state at the surface was strongly dependent on the PFA content. In the case of the P(St-b-PFA) with the PFA content higher than 18.7 mol %, both advancing and receding contact angles for water were 120 degrees and even larger with almost no hysteresis. In addition, extremely excellent oil-repellent surface properties such as advancing and receding contact angles for dodecane of 76 degrees and 75 degrees were also observed. However, these intriguing liquid-repellent properties were not observed for the films of miscible P(St-b-PFA) and P(St-ran-PFA). Therefore, it can be concluded that the internal structure beneath the surface as well as the surface itself should be deeply considered to design excellent and stable liquid-repellent materials.     

Supramolecular nanocarrier of siRNA from PEG-based block catiomer carrying diamine side chain with distinctive pKa directed to enhance intracellular gene silencing

An siRNA nanocarrier formed through self-assembly of PEG-based block catiomer possessing two distinct amino groups with different pKa values in a side chain was developed. This design provided the carrier with a sufficient siRNA complexation and an assumed buffering capacity in the endosomes, allowing it to exhibit remarkable gene knockdown abilities as well as sufficient serum tolerability.     

Laser-driven vehicles – from inner-space to outer-space

Laser-supported propulsion of a micro-airplane with a water-covered ablator is demonstrated. The repetitive use of an overlay structure is experimentally demonstrated with a specially designed water supply. Various transparent overlays are investigated by the CIP-based hydrodynamic code and by experiments using a pendulum and using a semi-conductor load cell. A momentum-coupling efficiency of ∼10⁴ N s/MJ is achieved by water–exotic-target experiments, in agreement with the simulation code, which predicts a maximum efficiency of ∼10⁵ N s/MJ. The concept of laser-supported propulsion can also be used for driving a Mach 5 airplane in the stratosphere, a micro-ship inside the human body, and a robot in a nuclear power reactor accident, during which large numbers of neutrons make electronic devices useless. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-3/5734-2165, E-mail: yabe@mech.titech.ac.jp     

Versatile and cooperative reactivity of a triruthenium polyhydride cluster. A computational study

The reaction of a trinuclear polyhydride complex Ru3H5(C5H5)3 with cyclopentadiene, C5H6, has been studied computationally. A mechanism for the experimentally observed selective C-C bond activation is proposed. All three Ru centers participate in various steps of the mechanism. The catalytic involvement of two cluster hydrides in the transformation of the C5Hn fragment is emphasized.     

Some remarks on the universal cover of an open K3 surface

 We shall give, in an optimal form, a sufficient numerical condition for the finiteness of the fundamental group of the smooth locus of a normal K3 surface. We shall moreover prove that, if the normal K3 surface is elliptic and the above fundamental group is not finite, then there is a finite covering which is a complex torus. Received: 13 April 2001 / Published online: 16 October 2002 RID="⋆" ID="⋆" Supported by Korea Research Foundation Grant(KRF-2001-041-D00025) Mathematics Subject Classification (2000): 14J28     

Optical guidance of terrawatt laser pulses by the implosion phase of a fast Z-pinch discharge in a gas-filled capillary

A new method of optical guidance by the implosion phase of a fast Z-pinch discharge in a gas-filled capillary is proposed. An imploding plasma column has a concave electron-density profile in the radial direction, just before a stagnation phase driven by a converging current sheet and a shock wave. The feasibility of optical guidance of a high-intensity (>1 x 10(17) W/cm(2)) Ti:sapphire laser pulse by use of this method over a distance of 2 cm, corresponding to 12.5 times the Rayleigh length, has been experimentally demonstrated. The guiding-channel formation process was directly probed with a He-Ne laser beam. The electron density in the fully ionized channel was estimated to be 2.0 x 10(17) cm(-3) on the axis and 7.0 x 10(17) cm(-3) on the peaks of the channel edge, with a diameter of 70 mum, as indicated by the experimental results, which were corroborated by a magnetohydrodynamics simulation.     

Theoretical study of resonant tunneling in rectangular double-, triple-, quadruple-, and quintuple-barrier structures

The transmission coefficient and the resonance condition in the one-dimensional rectangular double-, triple-, quadruple-, and quintuple-barrier structures are derived theoretically under the assumption of the constant tunneling effective mass. It is found that the resonance energies are different from the eigenvalues in the quantum well due to coupling between wells in the multiple-barrier (much more than triple-barrier) structures. It is confirmed that the transmission spectrum is a Lorentzian near to energies of resonance.