[2,3]‐Wittig Rearrangement of Enantiomerically Enriched 3‐Substituted 1‐Propenyloxy‐1‐phenyl‐2‐propen‐1‐yl Carbanions: Effect of Heteroatoms and Conjugating Groups on Planarization of an α‐Oxy‐Benzylcarbanion through a Double Bond

Don't get trapped : The effect of conjugating electron‐withdrawing groups and α‐anion‐stabilizing heteroatom substituents on configurational stability of chiral carbanions through a double bond was examined on the basis of extent of chirality transfer in intramolecular trapping in [2,3]‐Wittig rearrangement of chiral 3‐substituted 1‐propenyloxy‐1‐phenyl‐2‐propen‐1‐yl carbanions (see scheme).

     

Increased expression and phosphorylation of liver glutamine synthetase in well-differentiated hepatocellular carcinoma tissues from patients infected with hepatitis C virus

Hepatocellular carcinoma (HCC) is one of the most common fatal cancers, and chronic infection with hepatitis C virus (HCV) is thought to be one of the main causes in Japan. To identify diagnostic or therapeutic biomarkers for HCC associated with HCV (HCV-HCC), we tried to elucidate the factors related to the products from cancerous tissues of HCV-infected patients. From proteomic differential display analysis of liver tissue samples from HCV-HCC cancerous tissues and corresponding non-cancerous tissues from patients, three protein spots of the same molecular mass (42 kDa), whose expression increased in well-differentiated cancerous tissues, were detected. Although their pI were different, they were identified as glutamine synthetase (GS) by PMF with MALDI-TOF MS and by Western blotting using anti-GS specific mAb. Immunohistochemical analysis showed that tumor tissue consists of two parts, GS-positive cell and GS-negative cell regions, suggesting that GS-producing cells grew in the tumor tissue as a nodule in nodules. The tryptic peptides of the most acidic GS isoform lost the signal of 899.5 Da, corresponding a peptide of SASIRIPR, and gained a signal of 1059.5 Da, which was submitted to PSD analysis. PSD analysis showed the neutral loss by elimination of two phosphate groups, supposed to be on serine residues of the 899.5-Da peptide, from serine 320 to arginine 327 in GS. PMF followed by PSD analysis is thought to be useful for the determination of phosphorylation sites of proteins showing molecular heterogeneity.     

Effect of ultrasonic irradiation on nucleation phenomena in a Na2HPO4.12H2O melt being used as a heat storage material

The effect of ultrasound on nucleation phenomena in the heat storage material Na2HPO4.12H2O was investigated by determining the primary nucleation probability and induction time, and by looking at heat generation phenomena in the initial stage of nucleation. The experimental results show that the primary nucleation probability dramatically increased, and the induction time decreased under the ultrasound irradiation, and in addition, the rate of temperature rise was dependent upon the ultrasonic output. Based on these results and the theoretical relationship between the number of primary nuclei and the heat generation rate, it is proposed that the number of primary nuclei depends upon the ultrasonic output.     

Two-body decays of gluino at full one-loop level in the quark-flavour violating MSSM

We study the two-body decays of the gluino at full one-loop level in the Minimal Supersymmetric Standard Model with quark-flavour violation (QFV) in the squark sector. The renormalisation is done in the \(\overline{\mathrm{DR}}\) scheme. The gluon and photon radiations are included by adding the corresponding three-body decay widths. We discuss the dependence of the gluino decay widths on the QFV parameters. The main dependence stems from the \(\tilde{c}_R \)–\( \tilde{t}_R\) mixing in the decays to up-type squarks, and from the \(\tilde{s}_R \)–\( \tilde{b}_R\) mixing in the decays to down-type squarks due to the strong constraints from B-physics on the other quark-flavour-mixing parameters. The full one-loop corrections to the gluino decay widths are mostly negative and of the order of about ?10%. The QFV part stays small in the total width but can vary up to ?8% for the decay width into the lightest \(\tilde{u}\) squark. For the corresponding branching ratio the effect is somehow washed out by at least a factor of two. The electroweak corrections can be as large as 35% of the SUSY QCD corrections.     

Modified Synthesis and Supramolecular Polymerization of Rim-to-Rim Connected Bisresorcinarenes

The acid-catalyzed condensation reaction of resorcinol and bisdimethoxyacetals gave rise to rim-to-rim connected bisresorcinarenes in good yields. In the presence of ethanol, the homoditopic bisresorcinarenes assembled to form supramolecular polymers via hydrogen bonding interactions. The fibrous morphologies of the supramolecular polymers were confirmed by atomic force microscopy and scanning electron microscopy.     

Copper-catalyzed complete regio- and stereoselective cyclization of 1-aryl-3-sulfanyl-4-oxahepta-1,6-diynes triggered by alkynylation

Copper(I)-catalyzed alkynylation-cyclization of 4-oxahepta-1,6-diynes 1 with a wide variety of terminal alkynes proceeded to give (3E,4Z)-3-(phenylsulfanylmethylene)-4-(2-propynylidene)tetrahydrofuran-2-yl]benzenes 2aa-he in high yields with complete regio- and stereoselectivity.     

Stereocontrolled synthesis of an indole moiety of sespendole and stereochemical assignment of the side chain

Two possible diastereomers of the indole moiety of sespendole were synthesized from 3-hydroxy-4-nitrobenzaldehyde in a highly stereoselective manner. Comparison of (1)H and (13)C NMR spectra of the two synthetic materials with those sespendole leads us to propose that the relative stereochemistry of the epoxyalcohol is syn.     

An Iron(III)-Monoamidate Complex Catalyst for Selective Hydroxylation of Alkane CH Bonds with Hydrogen Peroxide

Selective oxidation: The success of the title reaction is caused by the strong electron donation from the amidate moiety of the dpaq ligand to the iron center (dpaq=2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate). This process facilitates the O?O bond heterolysis of the intermediate Fe(III) OOH species to generate a selective oxidant without forming highly reactive hydroxyl radicals.     

No-go theorem for critical phenomena in large-N(c) QCD

We derive some rigorous results on the chiral phase transition in QCD and QCD-like theories with a large number of colors, N(c), based on the QCD inequalities and the large-N(c) orbifold equivalence. We show that critical phenomena and associated soft modes are forbidden in flavor-symmetric QCD at finite temperature T and finite but not so large quark chemical potential μ for any nonzero quark mass. In particular, the critical point in QCD at a finite baryon chemical potential μ(B)=N(c)μ is ruled out, if the coordinate (T, μ) is outside the pion condensed phase in the corresponding phase diagram of QCD at a finite isospin chemical potential μ(I)=2μ.     

Equilibrium polymerization behavior in the cationic single ring‐opening polymerization of bicyclo orthoesters

The synthesis and cationic polymerization of the following bicyclo orthoesters were examined: 4‐ethyl‐2,6,7‐trioxabicyclo[2.2.2]octane, 1,4‐diethyl‐2,6,7‐trioxabicyclo[2.2.2]octane, 4‐ethyl‐1‐phenyl‐2,6,7‐trioxabicyclo[2.2.2]octane, 4‐ethyl‐1‐(4‐methoxyphenyl)‐2,6,7‐trioxabicyclo[2.2.2]octane, and 4‐ethyl‐1‐(4‐nitrophenyl)‐2,6,7‐ trioxabicyclo[2.2.2]octane. All the monomers underwent equilibrium polymerization, which was confirmed by the relationships between the polymerization temperature and monomer conversion. The obtained polymers afforded the original monomers via an acid‐catalyst treatment with a low reagent concentration in CH₂Cl₂ at 20 °C. The equilibrium monomer concentration was constant, regardless of the initial reagent concentration, in both polymerization and depolymerization. The bicyclo orthoesters with a bulky and electron‐withdrawing substituent showed a larger equilibrium monomer concentration. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3159–3167, 2001