Ladderlike ferromagnetic spin coupling network on a pi-conjugated pendant polyradical

A poly(9,10-anthryleneethynylene)-based polyradical with two pendant stable phenoxyls in one anthracene skeleton was newly synthesized via polymerization of the corresponding bromoethynylanthracene monomer using a Pd(0) catalyst. The average molecular weight of the polymer reached M(n) = 5 x 10(3) and was soluble in common organic solvents. The polyradical was prepared from the corresponding hydroxyl precursor polymer and was appropriately stable at room temperature. The ESR spectrum of the corresponding monomeric radical suggested an effectively delocalized spin density distribution on the backbone anthracene. The magnetization and the static magnetic susceptibility of the polyradical were measured using a SQUID magnetometer. The large average spin quantum number (S = (5)/(2)) of the polyradical indicated that the ferromagnetic spin coupling network of the polyradical had spread throughout the pi-conjugated chain and that it was considerably insensitive to spin defects.     

Relationship of stereochemical and skeletal diversity of small molecules to cellular measurement space

Systematic and quantitative measurements of the roles of stereochemistry and skeleton-dependent conformational restriction were made using multidimensional screening. We first used diversity-oriented synthesis to synthesize the same number (122) of [10.4.0] bicyclic products (B) and their corresponding monocyclic precursors (M). We measured the ability of these compounds to modulate a broad swath of biology using 40 parallel cell-based assays. We analyzed the results using statistical methods that revealed illuminating relationships between stereochemistry, ring number, and assay outcomes. Conformational restriction by ring-closing metathesis increased the specificity of responses among active compounds and was the dominant factor in global activity patterns. Hierarchical clustering also revealed that stereochemistry was a second dominant factor; whereas the stereochemistry of macrocyclic appendages was a determinant for bicyclic compounds, the stereochemistry of the carbohydrates was a determinant for the monocyclic compounds of global activity patterns. These studies illustrate a quantitative method for measuring stereochemical and skeletal diversity of small molecules and their cellular consequences.     

Gomadalactones A, B, and C: novel 3-oxabicyclo[3.3.0]octane compounds in the contact sex pheromone of the white-spotted longicorn beetle, Anoplophora malasiaca

The ether extract of the females of white-spotted longicorn beetle Anoplophora malasiaca showed activity as contact sex pheromone to males. The extract was fractionated, and a pheromonal activity was revealed only when three fractions; n-hexane, n-hexane/EtOAc 9:1, and EtOAc were blended. The relative structures of gomadalactone A, B, and C, three active components isolated from the EtOAc fraction, were determined by spectroscopic studies to be (1S^∗,4R^∗,5S^∗)-5-hydroxy-4-[(E)-7-hydroxy-4-methylhept-3-enyl]-4,8-dimethyl-3-oxabicyclo[3.3.0]octan-7-en-2,6-dione, (1R^∗,4R^∗,5R^∗)-5-hydroxy-4-[(E)-7-hydroxy-4-methylhept-3-enyl]-4,8-dimethyl-3-oxabicyclo[3.3.0]octan-7-en-2,6-dione, and (1S^∗,4R^∗,5S^∗,8S^∗)-5-hydroxy-4-[(E)-7-hydroxy-4-methylhept-3-enyl]-4,8-dimethyl-3-oxabicyclo[3.3.0]octan-2,6-dione, respectively.     

Adsorption of metal ions on crosslinked poly(4-vinylpyridine) resins prepared with a metal ion as template

Poly(4-vinylpyridine) (PVP) was crosslinked with 1,4-dibromobutane with a metal ion as template. The adsorption behavior of copper, cobalt, zinc, and cadmium ions on the obtained resin (DBQP) was studied. The DBQP resin prepared with a metal ion as template preferentially adsorbed the metal ion used as template. The stability constant of the copper complex of DBQP was largest for the DBQP resin prepared with a copper ion as template, which was due to its large entropy change for the complexation.     

Polymerization of (p‐vinylphenyl)hydrogalvinoxyl and formation of a stable polyradical derivative

4‐[(3,5‐Di‐tert‐butyl‐4‐hydroxyphenyl)(3,5‐di‐tert‐butyl‐4‐oxo‐cyclohexa‐ 2,5‐dienylidene)methyl]styrene (abbreviated as (p‐vinylphenyl)hydrogalvinoxyl) was polymerized using AIBN as an initiator to give a bright yellow polymer with M w = 3.2 × 10⁴. The polymer was oxidized to give the corresponding polyradical derivative, whose spin concentration could be increased up to about 70 mol % depending on oxidative conditions. ESR signal line‐width in the solid state was greatly increased below 200 K for the polyradical with a high spin concentration (> 50 mol %). The magnetization and magnetic susceptibility indicated weak antiferromagnetic interaction among the radical sites. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 189–198, 1999     

Oxygen permeability of biodegradable copolycaprolactones

Polycaprolactone is one of the biodegradable polymers with good drug permeability. In the present paper, polycaprolactone and three kinds of copolycaprolactone–polycaprolactone–poly(ethylene oxide)– polycaprolactone triblock copolymer (PCE), polycaprolactone/polycaprolactone‐poly(ethylene oxide)/polylactide tricomponents random block copolymer (PCEL) and polycaprolactone/poly(ethylene terephthalate) random block copolymer (PETCL)– were synthesized. The biodegradation behavior of these polymers were shown by degradation tests in vitro, ex vivo and in vivo. The oxygen permeabilities of these polymers were in the range of 10⁻¹⁰ ∼ 10⁻⁹ cm³ (STP) cm/cm² sec cm Hg. Copolymers PCE and PCEL displayed O₂ and N₂ permeability coefficients (PO₂/PN₂) ratios of about 9. The effects of composition and crystallinity of the copolymers on biodegradability and the oxygen permeability of the polymer were discussed. Copyright © 1999 John Wiley & Sons, Ltd.     

Two‐dimensionally extended aromatic polyamines for optimization of charge‐transporting properties by partial oxidation

This article describes the synthesis of the two‐dimensionally extended aromatic polyamines by polycondensation between the tri‐sec‐amine monomer and p‐phenylenediamine‐based dibromide, the polyradical generation by chemical and electrochemical oxidations, and the hole‐transporting properties. The molecular weights (M_n) of the polyamines, 3a and 3b , were 7700 and 5000, respectively, and both polymers were very soluble in the typical organic solvents, ensuring a good film formation capability by a spin‐coating technique. The thermal stability of the aromatic polyamines, elucidated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), was quite high. More important, the cross‐conjugated structure is essential for the controlled radical generation and the maintenance of the radical stability. Cyclic voltammograms of the neutral polyamines in the presence of 1 vol % of trifluoroacetic acid and the intervalence bands of the partially oxidized polyamines with NOPF₆ revealed that the generated radicals delocalize over the p‐phenylenediamine moieties. The half‐life of the polyradicals was about 12 h even under ambient conditions, which allowed us to fabricate and measure the hole‐only devices. The charge‐transporting properties of the polyamines were dramatically changed by the partial oxidation (20 mol %/aminium unit) with NOPF₆. The neutral polyamines showed the conventional injection‐limit behaviors, whereas the hole‐transporting behaviors of the polyradicals are bulk‐limit and highly dependent on the chemical structure. The efficient hole‐transport of the all‐conjugated poly(aminium cationic radical)s was for the first time realized for the polyradical of 3b . © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4577–4586, 2009     

Oxygen-binding property of hemoglobin films

Oxygenated and deoxygenated hemoglobin films were obtained by drying corresponding hemoglobin solutions with maltose (≧0.3 M). The resulting hemoglobin films were homogeneous and smooth, and the methemoglobin formation in the oxyhemoglobin film was well suppressed. The dry, rigid networks of maltose molecules work to preserve the conformation of hemoglobin against the removal of water. The coordination of oxygen to the deoxygenated hemoglobin film was slow and saturated up to 50%, while nearly 100% saturation was achieved if the film contained a residual moisture of 8.7%.