Size dependence of crystallization within spherical microdomain structures

We have investigated the size dependence of crystallization within spherical microdomains formed in various poly(ε-caprolactone)-block-polybutadiene diblock copolymers (PCL-b-PB). The crystallinity (χ) and melting temperature (T_m) of the PCL block are considerably lower than those of PCL homopolymer, and χ decreases steadily and T_m decreases only slightly with decreasing radius of PCL spheres (R) for a series of PCL-b-PB with a same molecular weight (M_n). When PCL-b-PB is compared with the similar R but different M_n, χ is significantly different, suggesting that the sphere size is not the unique factor to control crystallization within spherical microdomains.     

Separation of endocrine disruptors from aqueous solutions by pervaporation: Dioctylphthalate and butylated hydroxytoluene in mineral water

We examined the existence of endocrine disruptors in mineral water, ultrapure water, and tap water. GC/MS analysis revealed that dioctylphthalate (di‐n‐octylphthalate and di(2‐ethylhexyl)phthalate) in the water was found to be on the order of parts per billion. The dioctylphthalate concentration remained consistent for mineral water of the same brand, regardless of whether it was bottled in a PET bottle or a glass bottle. Therefore, the dioctylphthalate contamination in mineral water originated from the manufacturing line of the mineral water and not as a result of leaching from PET bottles. Butylated hydroxytoluene (BHT), an oxidization prevention agent in plastics, was detected at 2.05 ± 0.1 ppb in the mineral water bottled in glass bottles, but was not detected in the mineral water bottled in PET bottles. BHT contamination in the mineral water in the glass bottles is likely to have originated from the cap of the glass bottles, as the caps were sealed with polyethylene. We further investigated the feasibility of separating dioctylphthalate and BHT from the mineral water by pervaporation using hydrophobic polydimethylsiloxane membranes. We found that trace amounts (on the order of parts per billion) of organic chemicals such as dioctylphthalate and BHT in aqueous solutions can be removed and concentrated by the pervaporation using polydimethylsiloxane membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1737–1742, 2004     

Circulating Organ-Specific MicroRNAs Serve as Biomarkers in Organ-Specific Diseases: Implications for Organ Allo- and Xeno-Transplantation

Different cell types possess different miRNA expression profiles, and cell/tissue/organ-specific miRNAs (or profiles) indicate different diseases. Circulating miRNA is either actively secreted by living cells or passively released during cell death. Circulating cell/tissue/organ-specific miRNA may serve as a non-invasive biomarker for allo- or xeno-transplantation to monitor organ survival and immune rejection. In this review, we summarize the proof of concept that circulating organ-specific miRNAs serve as non-invasive biomarkers for a wide spectrum of clinical organ-specific manifestations such as liver-related disease, heart-related disease, kidney-related disease, and lung-related disease. Furthermore, we summarize how circulating organ-specific miRNAs may have advantages over conventional methods for monitoring immune rejection in organ transplantation. Finally, we discuss the implications and challenges of applying miRNA to monitor organ survival and immune rejection in allo- or xeno-transplantation.     

Mechano-catalytic overall water splitting on some mixed oxides

Simple transition metal oxides such as NiO, Co₃O₄, Fe₃O₄ and Cu₂O were found to catalytically decompose water into H₂ and O₂ by mechanical energy. The reaction is regarded as “mechano-catalytic” overall water splitting” and is a quite novel catalytic reaction. In this paper, some general aspects on the mechano-catalytic overall water splitting are reviewed on simple oxides. In addition, recent results on the mechano-catalytic activity of a groups of mixed oxides, wolramite-type oxides with a formula of ABO₄ (A=Fe, Co, Ni and Cu, etc., B=W, Mo), are shown. AWO₄ (A=Fe, Co, Ni and Cu) decomposed water into H₂ and O₂ under the supply of mechanical energy, indicating that mechano-catalytic overall water splitting proceeded on wolframite-type compounds containing 3d-transition metals. AMoO₄ (A=Fe, Co, Ni) also decomposed water into H₂ and O₂ under supply of mechanical energy. The reaction properties on wolframite-type oxides are discussed.     

The structural characterization and hydroformylation activity of the tri-rhodium complex [Rh3(μ2-dppm)2(μ2-CO)3(K-CO)3]BF4

Rh₂(cod)₂(μ₂-dppm)(μ₂-Cl)]BF₄ (1) rearranges under carbon monoxide to give [Rh₃(μ₂-dppm)₂(μ₂-CO)₃(K¹-CO)₃]BF₄ (2). Complex 2 has been structurally characterized by single crystal X-ray crystallography. The hydroformylation activities of 1 and 2 were compared for substrates styrene and 1-hexene and the activity of 2 found to be unexpectedly high.     

Biodiesel Production by Amorphous Carbon Bearing SO3H, COOH and Phenolic OH Groups, a Solid Brønsted Acid Catalyst

A solid Brønsted acid of amorphous carbon bearing SO₃H, COOH and phenolic OH groups has been studied as a catalyst for biodiesel production. The carbon material functions as a stable and efficient catalyst for the formation of biodiesel from oleic acid at 353 K; the catalytic performance is 70–80% that of sulfuric acid. The carbon material also exhibits remarkable catalytic performance for transesterification of triolein at 403 K, maintaining high catalytic activity even in the presence of water. These results suggest that this catalyst can directly convert crude vegetable oils composed of triglycerides, free higher fatty acids and water into biodiesel with minimal energy consumption.     

Active Polymer Gel Actuators

Many kinds of stimuli-responsive polymer and gels have been developed and applied to biomimetic actuators or artificial muscles. Electroactive polymers that change shape when stimulated electrically seem to be particularly promising. In all cases, however, the mechanical motion is driven by external stimuli, for example, reversing the direction of electric field. On the other hand, many living organisms can generate an autonomous motion without external driving stimuli like self-beating of heart muscles. Here we show a novel biomimetic gel actuator that can walk spontaneously with a worm-like motion without switching of external stimuli. The self-oscillating motion is produced by dissipating chemical energy of oscillating reaction. Although the gel is completely composed of synthetic polymer, it shows autonomous motion as if it were alive.     

Influence of the methyl group on the dielectric constant of boron carbon nitride films containing it

LSI interconnect insulators made using low dielectric constant (low-k) materials are required for high performance devices with a small RC delay. We investigated a boron carbon nitride film containing the methyl group (Me–BCN) using tris-di-methyl-amino-boron (TMAB: B[N(CH₃)₂]₃) gas as a low-k material. In addition, we studied the influence of the methyl group on the dielectric constant (k-value) and the properties of the Me–BCN films. It was found that the k-value of the Me–BCN films decreases with increasing number of C–H bonds due to the methyl group (CH₃). The number of O–H bonds due to water incorporation is suppressed by increasing the number of C–H bonds. Consequently, we suggested that a lower k-value can be realized by the suppression of water invasion by a hydrophobic surface due to methyl bonds. Thus, the control of the methyl group is important to achieve a low-k material using Me–BCN films.     

Effect of heating process on the formation of nanoparticles of elastin model polypeptide, (GVGVP)251, by gamma-ray crosslinking

Nanoparticles were prepared by the thermosensitive aggregation of the elastin model polypeptide, (GVGVP)₂₅₁, and gamma-ray crosslinking. Three different heating processes, “slow heating,” “fast heating,” and “heat shock,” were used for the aggregation of the peptide, followed by gamma-ray crosslinking. Only the “heat shock” process successfully yielded stable nanoparticles with diameters of less than ca. 150 nm and a narrow size distribution. Circular dichroism (CD) spectrometry showed that this polypeptide formed a type-II β-turn structure when the temperature was increased to above the cloudy point in the case of the “heat shock” process; suggesting that this structure might contribute to stable nanoparticle formation by gamma-rays. CD spectrometry also suggested that this structure would be affected during the formation of stable crosslinked particles.     

Screening of Inhibitors Targeting Heat Shock Protein 47 Involved in the Development of Idiopathic Pulmonary Fibrosis

Heat shock protein 47 (HSP47), a collagen-specific molecular chaperone, is causally related to fibrotic diseases, including idiopathic pulmonary fibrosis. The identification of Compounds that interfere with the HSP47-collagen interaction is essential for the development of relevant therapeutics. Herein, we prepared human HSP47 as a soluble fusion protein expressed in E. coli and established an assay system for HSP47 inhibitor screening. We screened a natural and synthetic Compound library established at Nagasaki University. Among 1023 Compounds, 13 exhibited inhibitory activity against human HSP47, of which three inhibited its function in a dose-dependent manner. Epigallocatechin-3-O-gallate, one of these three Compounds, is a typical polyphenol Compound derived from tea leaves. Structurally related Compounds were synthesized and examined for their activity, revealing a hydroxyl group at A-ring position 5 as important for its activity. The present findings provide valuable insight for the development of natural product-derived therapeutics for fibrotic diseases, including idiopathic pulmonary fibrosis.