High-Spin Polyphenoxyls Attached to Star-Shaped Poly(phenylenevinylene)s

Star-shaped poly(1,2-phenylenevinylene)s 4-substituted with multiple pendant phenoxyls (2 and 3) were synthesized by polymerizing 2-bromo-4-(acetoxyphenyl)styrene in the presence of 1,3,5-triiodobenzene or 1,3,5-tris(3',5'-diiodophenyl)benzene as the core via a simple one-pot Heck reaction and subsequent hydrolysis, phenolate formation, and heterogeneous oxidation. ESR spectra indicated a delocalized spin distribution into the core parts of the star-shaped molecules. The polyradicals, 2 and 3, were in a high-spin state at low temperature, and the ferromagnetic behavior was enhanced for the polyradical with a higher molecular weight. Although an average S of 3 remained at 3/2 to 4/2, the polyradical 2 even with a spin concentration of 0.8 spin/unit revealed an average S of 7/2 to 8/2. The 1,3,5-benzene core acted as an effective magnetic coupler to align the spins of the pendant phenoxyls through the star-shaped pi-conjugated backbone.     

Effect of ageing atmospheres on the changes in surface free energies of oxygen plasma-treated polyethylene films

The changes in the surface properties of oxygen plasma-treated polyethylene films during ageing in various atmospheres (water, dry nitrogen gas, and hexane) were studied from the viewpoint of the interaction of the surface functional groups formed on the films and the ageing media. The XPS (x-ray photoelectron spectroscopy) and the SSIMS (static secondary ion mass spectrometry) spectra indicated the formation of polar groups containing oxygen such as C=O on the film surface. The changes in the critical surface tension (_C) of the film with ageing time were largely affected by the ageing atmospheres: the _C value of the film aged in water increased, and those of the films aged in nitrogen gas and hexane decreased with an increase in ageing time. These different tendencies among the ageing media could be understood reasonably with examining the surface free energy ratios (the total energy, _S ^tot , the dispersion force component, _S ^d / _S ^tot , the polar component, _S ^p / _S ^tot , the hydrogen bonding component, _S ^h / _S ^tot ) of the films. The ageing in water of which _L is large gave the films with higher _S ^p / _S ^tot values, suggeting that the overturn and/or the orientation of the polar groups toward the water phase occurred so as to minimize the discrepancy of the surface free energy between the polymer surface and water. On the other hand, the ageing in nitrogen gas and hexane media of which _L are small gave the films with lower _S ^p / _S ^tot and _S ^h / _S ^tot values, suggesting the overturn and/or the orientation of the polar groups into the bulk polymer.     

First total synthesis of a new sesquiterpenoid natural product, (±)-3-(2,4-dihydroxybenzoyl)-4,5-dimethyl-5-(4,8-dimethyl-3(E),7(E)-nonadien-1-yl)tetrahydro-2-furanone

An efficient and stereodefined process is described for the first preparation of a new prenyl-benzoylfuranone type sesquiterpenoid, (±)-3-(2,4-dihydroxybenzoyl)-4,5-dimethyl-5-(4,8-dimethyl-3(E),7(E)-nonadien-1-yl)tetrahydro-2-furanone. The synthetic strategy is based on nucleophilic addition of organometallic reagents to the functionalized ketoamides elaborated from dihydroxyacetone dimer for the stereoselective construction of the key quaternary carbon center in the target compound.     

Drying dissipative structures of the aqueous suspensions of monodisperse bentonite particles

Macroscopic and microscopic dissipative structural patterns formed in the course of drying the fractionated and monodisperse bentonite particles (plate-like in their shape) in aqueous deionized suspension and in the presence of NaCl have been studied on a cover glass. The patterns coexisted with the broad ring of the hill accumulated with the particles and with the round hills are formed around the outside edges of the film and in the center, respectively, in the macroscopic scale. By the addition of NaCl the pattern shifts from the broad ring to the round hill in the center. The spoke-like cracks, which have been observed for the suspensions of the spherical particles so often hitherto, are not observed at all for the bentonite suspensions. The characteristic convection flow of the particles and the interactions among the particles and substrate are important for the macroscopic pattern formation. Wrinkled, branch-like and/or star-like fractal patterns are observed in the microscopic scale. These patterns are determined mainly by the electrostatic and polar interactions between the particles and/or between the particle and the substrate in the course of drying.     

Self-organized lipid-porphyrin bilayer membranes in vesicular form: nanostructure,photophysical properties,and dioxygen coordination

An amphiphilic tetraphenylporphyrin and its iron complex bearing four phospholipid substituents, in which a trimethylolethane residue connects the two acyl chains (lipid-porphyrins), have been synthesized. The free-base lipid-porphyrin 6a self-organizes in aqueous media to form spherical unilamellar vesicles with a diameter of 100 nm and a uniform thickness of 10 nm, which corresponds to twice the length of the molecule. In the visible absorption spectrum, the porphyrin Soret band was significantly red-shifted (12 nm) relative to that of the monomer in benzene/MeOH solution due to the excitonic interaction of the porphyrin chromophores. The [symbol: see text]-A isotherm of 6a gave an area per molecule of 2.2 nm2, which allowed the estimation of the number of molecules in a single vesicle (2.3 x 10(4)). Double-layered Langmuir-Blodgett (LB) films of 6a on a glass surface exhibited an absorption spectrum identical to that of the 6a vesicles in bulk aqueous solution, and this suggests that they contain similar geometric arrangements of the porphyrin moieties. Exciton calculations on the basis of our structural model reproduced the bathochromic shift of the Soret band well. In the photophysical properties of the 6a vesicles, the characteristics of J-aggregated porphyrins substantially predominate: strong fluorescence and extremely short triplet lifetime. The iron complex 6b with a small molar excess of 1-dodecylimidazole (DIm) also formed spherical unilamellar vesicles (100 nm phi). Scanning force microscopy after evaporation on a graphite surface revealed 6b/DIm vesicles with a vertical height of 19.8 nm, which coincided with the thickness of the double bilayer membranes. The ferrous 6c formed a bis(DIm)-coordinated low-spin FeII complex under an N2 atmosphere. Upon addition of O2 to this solution, a kinetically stable O2 adduct was formed at 37 degrees C with a half-life of 17 h. Distinct gel-phase (liquid-crystal) transitions of the lipid-porphyrin membranes were clearly observed; the free base 6a displayed a higher transition temperature (56 degrees C) than the iron complex. Magnetic circular dichroism and infrared spectroscopic studies proved that molecular O2 coordinates to the self-organized lipid-porphyrinatoiron(II) vesicles in aqueous media.     

Surface free energies of styrene-acrylic acid copolymer plates prepared in various frames

Styrene (St)-acrylic acid (AA) copolymer plates were synthesized in the frames made of glass, aluminum (Al) and poly(difluoroethylene) (PDFE). Surface properties of the prepared copolymer plates were characterized with regard to critical surface tension ( _C ), chemical components by IR analysis and surface energies (total energy, _S ; dispersion force components, _S ^d ; polar component, _S ^p ; hydrogen bonding component, _S ^h ) and the following results were obtained.The _C values of the copolymer plates increased with AA content and also depended on the sort of the used frame. The increasing order of the _C values of the copolymer plates corresponded to those of the used frames, namely, PDFE frame < Al frame < Glass frame.The prepared copolymer plates with low AA contents (ca. 10 mol%) were enriched in the AA moiety in the surface layer regardless of the kind of the used frame.The total and the individual components of the surface free energies of the copolymer plates were largely affected by the property of the used frame. The glass frame gave the plate with higher _S ^h values suggesting preferential orientation of the polar site of AA component.     

Coordination reaction of cobaloxime with 4-vinylpyridine-styrene copolymer

The equilibrium constants of the coordination reaction of chlorodimethylformamide·cobaloxime with 4-vinylpyridine–styrene copolymers (PPS) were determined. The constants for PPS, which contain 20–50% 4-vinylpyridine (4VP) unit, measured about 1.3 × 10⁵ liter/mole larger than those in the pyridine system (6.8 × 10⁴ liter/mole). When the polymer ligand is 4VP homopolymer or contains less than 20% 4VP unit, K values are lower. The rate constants (k_f) of the coordination reactions of the cobaloxime with polymer ligands were also measured in dimethylformamide (DMF) and benzene. In DMF k_f decreased with an increase in 4VP unit content of the polymer ligand; in benzene it was increased by the 4VP fraction. These results can be explained by the variation in conformation of the polymer chain in each solvent. The effect of the polymer chain on complexation was discussed on the basis of the kinetic data.     

Computational examination of the electrophilic reaction on oxidative polymerization of phenyltrimethylsilane with sulfur chloride

Phenyltrimethylsilane possesses a higher HOMO energy (–9.34 eV) than nonsubstituted benzene (>0.41 eV). The π electron of the phenyltrimethylsilane localizes on the benzene ring at the ipso position rather than at the para position. Two center energies calculated by the MNDO-PM3 method indicate that the C? Si bond is facilitated to cleave in comparison with the C? H (para position) one of the benzene ring. Phenyltrimethylsilane and phenyl bis(trimethylsilane) were polymerized with sulfur chloride through the cationic oxidative polymerization. The product is isolated as oligo(p-phenylene sulfide), with a melting point of 150–190°C. An electrophile attacks the carbon atom linked to the Si atom in phenyltrimethylsilane. The new synthetic route of PPS can be established on the basis of the computational calculation.     

Preparation of dehydrated powder of hemoglobin vesicles

The carbonyl hemoglobin (CO-Hb), which was used to prevent denaturation (metHb) during the preparation of samples, was encapsulated into lipid vesicles constituted from unsaturated phospholipid, cholesterol and unsaturated fatty acid. Unsaturated components were polymerized by γ-irradiation to enhance the stability of bilayer membrane. An aqueous dispersion of resulting Hb vesicles was freeze-dried in the presence of saccharides (50–200 mM) to obtain a dehydrated powder of Hb vesicles. Change in the vesicle size, the leakage of encapsulated Hb and the oxidation of Hb to metHb were not observed. Therefore, the long-term storage of Hb vesicles can be realized as a dry powder.     

Radical copolymerization of proto-hemin dimethyl ester

Iron(III) proto-porphyrin IX dimethyl ester (HDME) can copolymerize with π-conjugated monomers binding at one end of the polymer chain. Apparent Q, e values of HDME were Q = 70 and e = ?0.17. The copolymerization of HDME with π-unconjugated monomer was feasible by using π-conjugated monomer as a third component. When unconjugated vinylimidazoles were used as monomers, the obtained ternary copolymers of HDME formed intramacromolecular complexes of iron(II) porphyrin with vinylimidazole residues, which gave stable carbon monoxide adducts.