Stereoselectivity of superacid-catalyzed Pictet-Spengler cyclization reactions

[reaction: see text] High stereoselectivities were found in a wide range of superacid-catalyzed Pictet-Spengler cyclization reactions. Particularly in the cases of 2-alkyl-N-benzylidene-2-phenethylamines, an enhanced stereoselectivity was observed under the superacid conditions as compared with the corresponding weak acid (TFA)-catalyzed (monocationic) cyclization reaction of the N-benzylidene-2-(3',4'-dimethoxy)phenethylamines that bear electron-donating groups on the cyclizing aromatic ring. The computational study also supported the energetic favorability of the cyclization of the N,N-diprotonated imine and revealed a significantly early transition-state structure.     

Iron-catalyzed regio- and stereoselective ring opening of [2.2.1]- and [3.2.1]oxabicyclic alkenes with a Grignard reagent

[reaction: see text] Arylative and alkenylative ring-opening reactions of a [2.2.1]- or [3.2.1]oxabicyclic alkene with a Grignard reagent take place in the presence of a catalytic amount of iron(III) chloride and a stoichiometric amount of TMEDA to produce a highly substituted 3-cyclohexen-1-ol or 3-cyclohepten-1-ol in good yield with high regio- and stereoselectivity.     

Equivalent cross relaxation rate image for decreasing a false negative case of sentinel lymph node biopsy

In the breast carcinamas, sentinel lymph node biopsy (SLNB) attracts attention as technique to be settled by axillary lymph node metastasis, but existence of a false negative case is a problem. Equivalent cross relaxation rate image (ECRI) is the measurement method that we can evaluate a change of organization structure quantitatively by magnetic resonance imaging. We executed axillary ECRI as a purpose with decreasing a false negative case of SLNB. ECRI related to a macroscopic image, and it was possible to evaluate yes or no of axillary lymph node metastasis. ECRI is the useful method to evaluate adaptability of SLNB.     

Dielectric breakdown of rubber materials by femtosecond irradiation

We report the reversible micro-structuring of a synthetic rubber polymer (cis1,4-polybutadiene (PB)) by femtosecond laser illumination. Visco-elastic relaxation of the optically damaged region was observed. The recovery time, typically 10²–10⁴ ms, can be varied by changing the irradiation pulse energy. Multi-shot-induced damage recovers on the much longer scale of 10¹–10² s. It was found that the doping of PB by 4 wt. % of pentazadiene ([4-NO₂]–phenyl–N=N–N(C₃H₇)–N=N–phenyl–[4-NO₂]) reduces the threshold of light-induced photo-modification by 20%. This is explained by photo-induced (homolytic) cleavage of the pentazadiene bonds and formation of gaseous N₂, which facilitates material failure at the irradiated spot. The recovery of optical transmission can be applied to optical memory, optical and micro-mechanical applications. The underlying mechanism of the phenomenon is discussed in terms of anelastic α- and β-relaxation (polymer backbone and chains/coils relaxation, respectively). Received: 11 October 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +81-88/656-7598, E-mail: misawa@eco.tokushima-u.ac.jp     

Three-dimensional micro-channels in polymers: one-step fabrication

We report on the femtosecond laser fabrication of micro-channels of sub-micrometer cross section recorded in polymethylmethacrylate (PMMA) films in a single processing step. Both axial lengths of an elliptical cross section smaller than 0.4 m were achieved for a fabrication irradiance close to the dielectric breakdown of PMMA. Femtosecond pulsed irradiation was scanned along the three-dimensional (3D) patterns inside the film. Channels have a self-formed densified cladding and can be 3D stacked into any pre-designed pattern and can extend over a mm length. These features are prospective for micro-total analysis system (-TAS) chip fabrication, micro- or nano-fluidic studies, and photonic applications such as photonic crystals . PACS 42.70.-a; 42.70.Jk; 81.16.-c; 81.40.-z; 82.35.Lr     

Fluctuation and relaxation of macrovariables

Assuming that a macrovariable follows a Markovian process, the extensive property of its probability distribution is proved to propagate. This is a generalization of the Gaussian properties of the equilibrium distribution to nonequilibrium nonstationary processes. It is basically a WKB-like asymptotic evaluation in the inverse of the size of the macrosystem. Evolution of the variable along the most probable path and fluctuation properties around the path are considered from a general point of view with an emphasis on the relation of nonlinearity of evolution and the associated fluctuation. Anomalous behavior of the fluctuation is discussed in connection with unstable, critical, or marginal states. A general treatment is given for the asymptotic properties of relaxation eigenmodes.     

Reductive displacement of the nitro group into hydrogen in primary α-nitroketones

The nitrogroup in primary α-nitroketones is converted into hydrogen with aluminum chloride and ethanethiol.