Synthesis and two-electron redox behavior of diazuleno[2,1-a:1,2-c]naphthalenes

The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement.     

Magnetic properties of amorphous Mn x B100−x alloys

Magnetic properties of amorphous Mn _x B_100–x alloys ranging fromx = 30 to 70 under high magnetic fields and low ac magnetic fields in the temperature range from 4.2 K to room temperature have been investigated. Samples which have Mn concentrations of aboutx = 40–60 show spin-glass-like properties in the low-temperature region. This spin-glass characteristics result from a frustration in the spin system which is caused by the competition of ferromagnetic and antiferromagnetic interactions between randomly distributed Mn atoms. Both magnetization at 4.2 K and paramagnetic momentP _eff as a function of Mn concentration show a peak aroundx 44 which drops rapidly towards both sides of the Mn content.     

Swelling-shrinking behavior of a polyampholyte gel composed of positively charged networks with immobilized polyanions

Polyampholyte gels were prepared by free radical polymerization of aqueous monomer solutions with the following composition: 69% N-isopropylacrylamide (thermosensitive neutral monomer), 1% N,N'-methylenebisacrylamide (cross-linker), 15% 1-vinylimidazole (cationic monomer), and either 15% acrylic acid (AAc, anionic monomer) or poly(acrylic acid) (PAAc, polyanion). We thus obtained two sorts of polyampholyte gels; that is, G1 with immobilized PAAc and G2 with randomly copolymerized AAc. The equilibrium swelling ratio (Qe) was studied as a function of the pH, NaCl concentration, and temperature. Also studied was the kinetics of swelling and shrinking in response to a sudden pH change. The significant results obtained were as follows: (i) A fully collapsed state was observed at pH 4.5-9.0 for G1 and at pH 4.5-7.0 for G2. (ii) Below and above these pH ranges, both gels were in a swollen state; therefore, an isoelectric point (pI) appeared in a wide pH range. (iii) At alkaline pH regions where a hysteresis was observed in the Qe versus pH curves of G1 and G2 as the pH was first increased then decreased, G1 exhibited very slow swelling-shrinking kinetics. (iv) An increase in the NaCl concentration allowed the gel to swell at pH approximately pI (antipolyelectrolyte behavior) but to shrink at pHs below and above the pI range (polyelectrolyte behavior). (v) The magnitude of the salt-induced shrinking of G1 is smaller than that of G2 at pH 10 and at NaCl concentrations > 0.01 M. (vi) At pH 10, an increase in the temperature from 35 to 50 degrees C led to a shrinking change of G1 but not of G2. These results were found to be explicable in terms of a different distribution of negative charges within the polyampholyte gel network.     

Wild ginseng grows in Myanmar

Ginseng, the underground parts of plants of Panax species, has been used in oriental traditional medicine for centuries. Unfortunately, because of extensive exploitation over thousands of years, the natural source of these species has been almost exhausted. Recently, we have found a wild ginseng growing in Myanmar. Here, by a combination of chemical composition study and gene sequence analysis, we unambiguously demonstrate that the wild ginseng is actually P. zingiberensis, commonly known as ginger ginseng. This ginseng was an indigenous to the southwestern China. However, now it is seriously threatened to brink of extinction and is put on the highest level of protection in China. Therefore, an appropriate protection measure is highly recommended to preserve this valuable resource, since this Myanmar ginseng might turn out to be the last P. zingiberensis, which could ever be seen in the planet.     

Cyclocopolymerization of diallyl ether with sulfur dioxide in acetone

The radical polymerization of diallyl ether (DAE) with sulfur dioxide produced soluble copolymers whose composition was between 1:1 and 2:1 in SO₂. The overall rate was maximum at a 2:1 feed composition in SO₂. A cyclocopolymerization scheme, which was based on cross propagations and the intramolecular cyclization of DAE radical, was applied. The energy of activation was larger for the uncyclized DAE radical in undergoing the cross propagation with SO₂ than in undergoing the intramolecular cyclization with the pendent allylic group by 40 kJ/mol. Formation of rings made of DAE and SO₂ and 3,4-disubstituted-tetrahydrofuran rings by the cyclized DAE units on the main chain was proposed on the basis of the ¹H-NMR spectra.     

Efficient synthesis of a 4,5-epoxy-2-cyclohexen-1-one derivative bearing a spirolactone via a Diels-Alder reaction with high pi-facial selectivity: a synthetic study towards scyphostatin

The Diels-Alder reaction of spirolactones with cyclopentadiene afforded the adduct with high pi-facial selectivity; a hydrophilic analogue of scyphostatin was synthesized from the Diels-Alder adduct.