A Facile Generation of a Cyclopropylzinc Compound from an Alkenylzinc Derivative and Its Reaction with Electrophiles

The one-pot synthesis of cyclopropyl compounds from 1-alkynes has been achieved by direct cyclopropanation of a 1-alkenylzinc species upon treatment with iodomethylzinc and trapping of the cyclopropylzinc intermediate with allyl bromide in the presence of CuCN⋅2 LiCl (see reaction scheme). This method proceeds under mild conditions and in good yield.     

The first total synthesis of hibarimicinone,a potent v-Src tyrosine kinase inhibitor

The first total synthesis of hibarimicinone has been achieved. The polyhydroxydecalin moieties (AB and GH rings) have been synthesized from sulfonylenone 4 derived from d-arabinose. The chiral biaryl 20 was coupled with two polyhydroxydecalins 11 by Michael–Dieckmann type condensation to give the eight rings system. Aromatization and oxidation with Ag⁺ gave quinone 24, and the subsequential transannular etheration gave the hibarimicinone skeleton. Deprotection and tautomerization were performed in one pot to give hibarimicinone (1).     

Analysis of antimony around the abandoned Tsugu mine in Aichi Prefecture by neutron activation analysis

At Tsugu mine in Aichi Prefecture, antimony was mined and smelted until 1956. The amounts of antimony present in the soil of the abandoned mine were measured to enable us to detect any traces of the operation of the mine and to measure the level of environmental contamination with antimony. The quantity of antimony in rings of hinoki and sugi was also measured to obtain information about chronological changes in environmental conditions. The quantity of antimony in the samples was determined by INAA. The antimony concentrations in eight soil samples at different points in the Tsugu mine area were 8–17,000 ppm.     

Synthesis of dicarboxylate oligosaccharide multilayer terminal functionality upon poly(lysine) dendrimer scaffolding

A reactive three‐layered dendrimer containing carboxyl groups was synthesized by the coupling of dicarboxylic acid and a highly reactive, two‐layered glycopeptide dendrimer. Lactose, maltose, or maltotriose was reacted with the poly(lysine) dendrimer in its third and fourth generations by reductive amination and afforded two‐layered glycolysine dendrimers. The reaction was conducted in a borate buffer (pH 9.0). ¹H NMR, ¹³C NMR, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analyses were applied for the determination of the structures of the products. When an excess amount of the oligosaccharide and a long reaction time were used, the degree of substitution increased to 1.5–2.0 against an amino group. For the preparation of highly reactive, multilayered dendrimers for an antigen carrier, C6 hydroxy groups of the oligosaccharides were selectively esterified by adipic acid and suberic acid to give 6‐O‐adipoyl oligosaccharide–poly(lysine) dendrimers and 6‐O‐suberoyl oligosaccharide–poly(lysine) dendrimers. The reactivity of these multilayered dendrimers was examined by a model reaction with phenylalanine ethyl ester. The dendrimer showed high reactivity, providing phenylalanine ethyl ester–dicarboxylate oligosaccharide–poly(lysine) dendrimers with a considerably high proportion of phenylalanine residues. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3622–3633, 2002     

Novel chiral recognition beyond the limitation due to the law of mass action: highly enantioselective chiral sensing based on non-linear response in phase transition events

Based on non-linear response in phase transition events exhibiting a sharp transmittance change, an intelligent chiral sensor capable of chirality amplification in aqueous media was designed and constructed as poly(N-isopropylacrylamide) having chiral pseudo-18-crown-6. Both sensitivity and selectivity of the sensor surmount the limitation due to the law of mass action.     

Possibility of heat sterilization of liposomes

Several kinds of liposomes were sterilized at 121 degrees C for 20 min. They tended to aggregate after heat sterilization (HS) in saline, while no aggregation was observed in an isotonized sugar or polyol solution. The dispersions containing egg phosphatidylcholine (EggPC) with a high peroxide value (POV) turned slightly yellowish after HS. This color change was prevented by using EggPC with a low POV, hydrogenated EggPC (H-EggPC) or dipalmitoylphosphatidylcholine (DPPC). Nitrogen gas bubbling at neutral pH also prevented the color change, but vitamin E did not. The particle size of the EggPC liposomes extruded through a 0.4 micron membrane filter did not change significantly after HS, whereas the H-EggPC or DPPC liposomes extruded through a 0.8 micron membrane filter tended to be reduced in size. On this change the type of medium had a considerable influence. The anionic 6-carboxyfluorescein leaked from the negatively charged liposomes (EggPC/cholesterol (Chol)/egg phosphatidylglycerol) during HS, while no leakage was observed from the positively charged liposomes (EggPC/Chol/stearylamine) not only during HS but also during a long period of storage. It was suggested that sterilization of liposomes by heating was practicable as well as that by filtration, if the liposomes were prepared as follows: the charged liposomes made of lipids with low POV's were dispersed in a sugar or polyol solution adjusted to nearly pH 6.5, where the amount of dissolved oxygen was minimized. An ionic water-soluble drug had to be encapsulated in the oppositely charged liposomes.     

Specific Adhesion of 3T3‐L1 Fibroblast onto Uridine‐Containing Polystyrene

A hydrophobic 96‐well multiplate was incubated with aqueous poly(uridine 5′‐p‐styrenesulfonate) (PUSS). Analysis of the PUSS‐coated surface indicated that the surface incubated at higher polymer concentration (50 mg·mL^–1) was hydrophilic while the surface incubated at lower polymer concentration (1 mg·mL^–1) was hydrophobic. Adhesion of 3T3‐L1, which has GalTase on the cell membrane, on the hydrophobic PUSS‐coated surface was greater than on the non‐coated surface. 3T3‐L1 adhesion on the hydrophilic PUSS‐coated surface was even greater. On the other hand, the adhesion of HeLa cells, which did not show GalTase on the cell membrane, on the hydrophilic surface was quite weak. It may well be said that the 3T3‐L1 adhesion on the hydrophilic PUSS‐coated surface was GalTase‐mediated.     

Silica gel with continuous macropores prepared from water glass in the presence of poly(acrylic acid)

Monolithic silica gel with macropores was prepared in the solution of water glass and polyacrylic acid (HPAA) by freezing transitional structures of phase separation. In the system, phase separation proceeds between silica polymers and HPAA, so that the porous morphology varies from closed macropores to particle aggregates through bicontinuous morphology, where both macropores and silica skeleton are three-dimensionally interconnected, with increasing HPAA/silica ratio. In addition, we can control the macropore size in bicontinuous morphology by varying the concentration of both silica and HPAA, or by changing the molecular weight of HPAA. The pore size distribution is quite sharp indicating the presence of pores with the same size all through the monolithic samples.