Controlled morphology and photoreduction characteristics of polyoxometalate(POM)/lipid complexes and the effect of hydrogen bonding at molecular interfaces

Supramolecular complexes consisting of anionic polyoxometalate (POM) and chiral, cationic lipids are newly developed. They give nanofibers, helical ribbons, and nanotapes in organic media depending on the chemical structure of lipid molecules. Lipid ammonium groups exert significant influence on their photoreduction characteristics.     

Non‐hybridization single nucleotide polymorphism detection and genotyping assay through direct discrimination of single base mutation by capillary electrophoretic separation of single‐stranded DNA

The significant demands for single nucleotide polymorphism detection and genotyping assays have grown. Most common assays are based on the recognition of the target sequence by the hybridization with its specific probe having the complementary sequence of the target. Herein, a simple, label‐free, and economical non‐hybridization assay was developed for single nucleotide polymorphism detection and genotyping, based on the direct discrimination of single base mutation by simple capillary electrophoresis separation for single‐stranded DNA in an acidic electrophoretic buffer solution containing urea. Capillary electrophoresis separation of single‐base sequential isomers of DNA was achieved due to charge differences resulting from the different protonation properties of the DNA bases. Single nucleotide polymorphism detection and genotyping were achieved by discriminating the electropherogram pattern change, that is, peak number in the electropherogram, obtained by the proposed method. The successful practical application of the proposed method was demonstrated through single nucleotide polymorphism detection and genotyping on a known gene region of 84‐mer, in which guanine to adenine single‐base mutation is commonly observed, using a human hair sample in combination with genomic DNA extraction, polymerase chain reaction amplification, DNA purification from polymerase chain reaction products, and capillary electrophoresis separation.     

Interfacial Polycondensation in Aqueous and Non-Aqueous Systems

Abstract

Interfacial polycondensation in aqueous and non-aqueous systems has been investigated in order to synthesize various polyamides having functional groups. Rigid aromatic polyamides having pyridine moieties (PPy) were synthesized by interfacial polycondensation using an aqueous system and the solution properties of PPy in concentrated sulfuric acid were investigated in terms of solution viscosity and lyotropic behavior. Interfacial polycondensation in a non-aqueous system using two immiscible solvents was found to be useful for the synthesis of aromatic polyesters and copolyesters.     

Photosensitive fluorinated polyimides with a low dielectric constant based on reaction development patterning

The fluorinated polyimide PI(6FDA/HFBAPP) was prepared by the reaction of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane (HFBAPP) in 1‐methyl‐2‐pyrrolidone/toluene. A multiblock copolyimide with both fluorinated and rigid‐rod segments, PI(6FDA/HFBAPP)(BPDA/2‐DMB), was prepared by the addition of a second dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and a second diamine, 2,2′‐dimethylbenzidine (2‐DMB), to the polyimide main chain. The potential lithographic performance of photosensitive polyimides composed of nonphotosensitive fluorine‐containing polyimides and photosensitive diazonaphthoquinone (DNQ) was studied on the basis of a new imaging principle recently proposed by our laboratory, that is, reaction development patterning. Neat PI(6FDA/HFBAPP) showed a low dielectric constant (?) of 2.41 and a low dissipation factor (tan δ) of 0.0027 at 20 GHz, and a 10‐μm resolution of the fluorinated polyimide/DNQ system was demonstrated with reactive development with a solution including ethanolamine after ultraviolet exposure. Although slight changes in the dielectric properties were observed in the presence of DNQ residues, these values (? = 2.63 and tan δ = 0.0033 at 20 GHz) were low enough for use in microelectronic applications. However, PI(6FDA/HFBAPP)(BPDA/2‐DMB), having a lower coefficient of thermal expansion (CTE; 33 ppm/°C) than PI(6FDA/HFBAPP) (49 ppm/°C), exhibited good positive photosensitivity, whereas the relatively low‐CTE multiblock copolyimide displayed a much higher ? value (3.48 at 1 MHz) than the highly fluorinated polyimide (2.88 at 1 MHz). A film consisting of PI(6FDA/HFBAPP)(BPDA/2‐DMB) and the remaining DNQ derivatives showed a CTE value comparable to that of the neat polyimide film. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 861–871, 2003     

Algorithms for finding distance-edge-colorings of graphs

For a bounded integer ℓ, we wish to color all edges of a graph G so that any two edges within distance ℓ have different colors. Such a coloring is called a distance-edge-coloring or an ℓ-edge-coloring of G. The distance-edge-coloring problem is to compute the minimum number of colors required for a distance-edge-coloring of a given graph G. A partial k-tree is a graph with tree-width bounded by a fixed constant k. We first present a polynomial-time exact algorithm to solve the problem for partial k-trees, and then give a polynomial-time 2-approximation algorithm for planar graphs.     

Newly designed hydrogel with both sensitive thermoresponse and biodegradability

The synthesis and characterization of thermoresponsive hydrogels on the basis of N‐isopropylacrylamide (IPAAm) copolymers crosslinked with biodegradable poly(amino acids) are described. This hydrogel was prepared with two kinds of reactive IPAAm‐based copolymers containing poly(amino acids) as the side‐chain groups and activated ester groups. We introduced the graft chains by decarboxylation polymerization of amino acid N‐carboxyanhydrides initiated from lateral amino groups in the PIPAAm copolymer. The hydrogels easily crosslinked with degradable poly(amino acid) chains by only mixing the copolymer aqueous solutions. The gelling method in this study would provide some of the following innovative features: (1) no necessary removal of unreacted monomers and so forth, (2) simpler loading of drugs into the hydrogels (only mixing when gelling), and (3) easier insertion into the body. On the basis of the swelling ratio measurement of the hydrogel, large volume changes dependent on temperature changes were observed. Moreover, the enzymatic temperature‐dependent degradation was confirmed. The results suggested that these hydrogels could be used for an injectable or implantable matrix of temperature‐modulated drug release. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 779–787, 2003     

Progresses of coal liquefaction catalysts in Japan

Research and development of catalysts and their performances for coal liquefaction are reviewed, enphasizing the contribution of recent 20 years from Japan. A variety of iron based catalysts were extensively examined to define the pyrrhotite as the active species produced in the liquefaction process. Synthetic pyrite, synthesized hydroxy ferric oxide, finely ground pyrite and limonite have been applied in the process development of coal liquefaction. Iron impregnation onto coal particles using waste water was examined also in a continuous-flow reactor. Finer particles were found to reduce significantly the amount of the catalyst to obtain the same oil yield. Usefulness of such catalysts is proved in the continuous operation of a large scale pilot plant. Iron, iron–nickel, and iron–molybdenum sulfides were found to be active catalysts when they are supported on nano-particles of carbon. Catalysts for recovery and repeated use and for selective aromatic ring opening are under current research.     

A convergent total synthesis of epolactaene: an application of the bridgehead oxiranyl anion strategy

The generation and reaction of a lactone-derived oxiranyl anion is described. The aldol-type reaction of the epoxylactone and aldehydes was accomplished by a two-step procedure via the trimethylsilyl epoxylactone. The application of this methodology to the total synthesis of (+)-epolactaene and its analogs is described.