Bioaccumulation, temporal trend, and geographical distribution of synthetic musks in the marine environment

Bioaccumulation of synthetic musks in a marine food chain was investigated by analyzing marine organisms at various trophic levels, including lugworm, clam, crustacean, fish, marine mammal, and bird samples collected from tidal flat and shallow water areas of the Ariake Sea, Japan. Two of the polycyclic musks, HHCB and AHTN, were the dominant compounds found in most of the samples analyzed, whereas nitro musks were not detected in any of the organisms, suggesting greater usage of polycyclic musks relative to the nitro musks in Japan. The highest concentrations of HHCB were detected in clams (258-2730 ng/g lipid wt.), whereas HHCB concentrations in mallard and black-headed gull were low, and comparable with concentrations in fish and crab. These results are in contrast to the bioaccumulation pattern of polychlorinated biphenyls; for which a positive correlation between the concentration and the trophic status of organisms was found. Such a difference in the bioaccumulation is probably due to the metabolism and elimination of HHCB in higher trophic organisms. Temporal trends in concentrations of synthetic musks were examined by analyzing tissues of marine mammals from Japanese coastal waters collected during 1977-2005. HHCB concentrations in marine mammals have shown significant increase since the early 1990s, suggesting a continuous input of this compound into the marine environment. Comparison of the time trend for HHCB with those for PCBs and PBDEs suggested that the rates of increase in HHCB concentrations were higher than the other classes of pollutants. To examine the geographical distribution of HHCB, we have analyzed tissues of fish, marine mammals, and birds collected from several locations. Synthetic musks were not detected in a sperm whale (pelagic species) from Japanese coastal water and in eggs of south polar skua from Antarctica. While the number of samples analyzed is limited, these results imply a lack of long-range transportation potential of synthetic musks in the environment.     

PACAP-mediated sperm-cumulus cell interaction promotes fertilization

The developing acrosome in spermatids contains pituitary adenylate cyclase-activating polypeptide (PACAP). However, the role of the acrosomal PACAP remains unclear because it has not been detected in mature spermatids and sperm. We reinvestigated whether the sperm acrosome contains PACAP. An antiserum produced against PACAP reacted to the anterior acrosome in epididymal sperm fixed under mild conditions, suggesting that PACAP acts on oocytes and/or cumulus cells at the site of fertilization. Immunolabeling and RT-PCR demonstrated the presence of PACAP type I receptor, a PACAP-specific receptor, in postovulatory cumulus cells. To investigate the role of PACAP in fertilization, we pretreated cumulus-oocyte complexes with the polypeptide. At a low concentration of sperm, the fertilization rate was significantly enhanced by PACAP in a dose-dependent manner. Sperm penetration through the oocyte investment, cumulus layer, and zona pellucida was also enhanced by PACAP. The enhancement was probably due to an enhancement in sperm motility and the zona-induced acrosome reaction, which were stimulated by a cumulus cell-releasing factor. Indeed, PACAP treatment increased the secretion of progesterone from the cumulus-oocyte complexes. These results strongly suggest that in response to PACAP, cumulus cells release a soluble factor that probably stimulates sperm motility and the acrosome reaction, thereby promoting fertilization.     

Chemical analysis and acetylcholinesterase inhibitory effect of anthocyanin-rich red leaf tea (cv. Sunrouge)

BACKGROUND: The purpose of this study was to evaluate the effects of leaf order or crop season on anthocyanins and other chemicals in the anthocyanin‐rich tea cultivar ‘Sunrouge’ (Camellia sinensis x C. taliensis) by using high‐performance liquid chromatography, and to study the effect of ‘Sunrouge’ extract on acetylcholinesterase (AChE) activity in human neuroblastoma SK‐N‐SH cells. RESULTS: The total anthocyanin content was higher in the third (3.09 mg g^?1) than in the second (2.24 mg g^?1) or first crop season (1.79 mg g^?1). The amount of anthocyanins contained in the stem was high (1.61 mg g^?1). In the third crop season, the concentrations of delphinidin‐3‐O‐β‐D ‐(6‐(E)‐p‐coumaroyl)galactopyranoside (DCGa), cyanidin‐3‐O‐β‐D ‐(6‐(E)‐p‐coumaroyl)galactopyranoside, delphinidin‐3‐O‐β‐D ‐galactopyranoside, delphinidin‐3‐O‐β‐D ‐(6‐O‐(Z)‐p‐coumaroyl)galactopyranoside, cyanidin‐3‐O‐β‐D ‐galactoside, and delphinidin‐3‐O‐β‐D ‐glucoside were 1.57 mg g^?1, 0.52 mg g^?1, 0.40 mg g^?1, 0.22 mg g^?1, 0.14 mg g^?1, and 0.11 mg g^?1, respectively. DCGa accounted for about 50% of the anthocyanins present. The suppressive effect of ‘Sunrouge’ water extract on AChE activity in human neuroblastoma SK‐N‐SH cells was the strongest among the three tea cultivars (‘Sunrouge’, ‘Yabukita’ and ‘Benifuuki’). CONCLUSION: These results suggested that ‘Sunrouge’ might protect humans from humans from AChE‐related diseases by suppressing AChE activity. To obtain sufficient amounts of anthocyanins, catechins and/or caffeine for a functional food material, ‘Sunrouge’ from the third crop season should be used. Copyright © 2012 Society of Chemical Industry     

Synthesis and application of fluorescein- and biotin-labeled molecular probes for the chemokine receptor CXCR4

The design, synthesis, and bioevaluation of fluorescence- and biotin-labeled CXCR4 antagonists are described. The modification of D-Lys8 at an epsilon-amino group in the peptide antagonist Ac-TZ14011 derived from polyphemusin II had no significant influence on the potent binding of the peptide to the CXCR4 receptor. The application of the labeled peptides in flow cytometry and confocal microscopy studies demonstrated the selectivity of their binding to the CXCR4 receptor, but not to CXCR7, which was recently reported to be another receptor for stromal cell-derived factor 1 (SDF-1)/CXCL12.     

Improvement of carrier diffusion length in silicon nanowire arrays using atomic layer deposition

To achieve a high-efficiency silicon nanowire (SiNW) solar cell, surface passivation technique is very important because a SiNW array has a large surface area. We successfully prepared by atomic layer deposition (ALD) high-quality aluminum oxide (Al₂O₃) film for passivation on the whole surface of the SiNW arrays. The minority carrier lifetime of the Al₂O₃-depositedSiNW arrays with bulk silicon substrate was improved to 27 μs at the optimum annealing condition. To remove the effect of bulk silicon, the effective diffusion length of minority carriers in the SiNW array was estimated by simple equations and a device simulator. As a result, it was revealed that the effective diffusion length in the SiNW arrays increased from 3.25 to 13.5 μm by depositing Al₂O₃ and post-annealing at 400°C. This improvement of the diffusion length is very important for application to solar cells, and Al₂O₃ deposited by ALD is a promising passivation material for a structure with high aspect ratio such as SiNW arrays.     

Drying of Sewage Sludge During Composting in an Updraft Dryer with the Concept of Using Self-Energy Generated Within the System

An innovative technology for sewage treatment systems is proposed. A mixture of sewage sludge and char particle is subjected to drying in the progress of composting in an updraft column. Exothermic heat generated during composting is utilized for energy of sludge drying. The char particle in the mixture contributes to enhancement of composting and drying rate. This study presents drying and composting behaviors of sludge to examine the effect of char addition. A fundamental drying experiment was carried out by hot-air heating of the sample in a small vessel. The drying characteristic curve for a mixture of sludge and char was greater than the sample of only sludge over a whole period if the drying rates were compared with the same moisture content. The drying behavior could be analyzed with a reasonable agreement by the water front receding model. The enhancement effect of drying and composting of sludge by char addition was confirmed by examination using a pilot scale of the updraft column whose volume was 50 m³. Sludge with 400% dry base (80% wet base) in moisture content could be dried successfully to lower moisture content than 67% dry base (40% wet base) only by exothermic heat during composting without supplying any auxiliary energy from the outside, and the treatment time was reduced by mixing char in sludge. The behavior was analyzed with a satisfactory agreement by a theoretical model employing moisture diffusion parameters determined from the drying characteristic curve.     

The physical character of coal char formed during rapid pyrolysis at high pressure

Rapid pyrolysis was conducted in a drop tube reactor using seven coals under various operating conditions. In addition to dense char, porous chars (network char and cenospheric char) were formed by the rapid pyrolysis under certain conditions. Porous char was mainly composed of film-like carbon and skeleton carbon. The pyrolyzed coal char particles were characterized in detail. Morphology and bulk density of porous char were quite different from the dense char formed under the same conditions, but elemental composition and BET surface area were similar to each other. CO₂ gasification reactivity of porous char was lower than dense char in the later gasification stage, and this was ascribed to the low reactivity of skeleton carbon.     

Preparation and Properties of Carbon/Zeolite Composites with Corrugated Structure

Composites of carbon/zeolite with corrugated structures were prepared by carbonization, steam activation and/or hydrothermal treatment of corrugated paper. No zeolite formation resulted from conventional hydrothermal treatment of the carbonized and activated samples in NaOH solution but zeolite Na P1 was formed by addition of silica to the solution. By contrast, zeolites Na P1 and Na A were formed by the in-situ crystallization method (hydrothermal treatment of solid samples impregnated with NaOH solution). With higher impregnating NaOH concentrations, longer reaction times and higher reaction temperatures, the products changed to sodalite- and cancrinite-type compounds. Hydrothermal treatment was effective in increasing the specific surface area of the products by the formation of zeolite from amorphous calcium aluminosilicate, and also increased the mechanical strength by gluing together the carbon fibers in the samples. The resulting samples showed enhanced adsorption for polar molecules such as ammonia, water vapor and methanol due to the formation of composites of activated carbon with hydrophilic zeolites.     

Syntheses of group 4 transition metal complexes bearing 2-pyridinethiolate ligands and their catalytic activities for ethylene polymerization

Titanium bis(2-pyridinethiolate) complexes, Ti(6-R-SPy)₂(NMe₂)₂ (6-R-SPy = 6-R-2-pyridinethiolate, 3a: R = H; 3b: R = Me; 3c: R = Ph; 3d: R = C₆H₄-4-Me; 3e: R = C₆H₄-4-t-Bu; 3f: R = C₆H₃-3,5-Me₂), and the titanium bis(2-pyridinolate) complexes, Ti(6-Ph-OPy)₂(NMe₂)₂ (6-Ph-OPy = 6-phenyl-2-pyridinolate, 8) were prepared by treating Ti(NMe₂)₄ with 2 equiv. of 6-R-2-pyridinethiol or 6-Ph-2-pyridinol. The cis-configuration of the diamido moieties in the pseudo octahedral geometry was elucidated by X-ray crystallography for 3a. Reaction of M(NMe₂)₄ (M = Ti, Zr) with 4 equiv. of 2-pyridinethiol cleanly gave tetrakis(pyridinethiolate) complexes, M(6-H-SPy)₄·THF (6: M = Ti; 7: M = Zr). The triangular dodecahedral geometries of 6 and 7 were also revealed by X-ray crystallography. These complexes catalyzed ethylene polymerization upon activation with MAO (methylaluminoxane) or MMAO (modified MAO). The catalytic activities of titanium bis(6-aryl-pyridinethiolate) systems were found to be remarkably higher than that of titanium bis(6-methyl-pyridinethiolate) system. Among the complexes synthesized in this study, Ti[6-(C₆H₃-3,5-Me₂)-SPy]₂(NMe₂)₂ (3f)/MMAO showed the highest activity (1200 kg/Ti-mol h atm) for ethylene polymerization at 60 °C under atmospheric pressure. In contrast, the activity of the corresponding 6-aryl-pyridinolate system 8/MMAO was rather low (9.3 kg/Ti-mol h atm). Both the N-S chelating structure and the bulky aryl substituents are essential for the high activities of the 6-aryl-pyridinethiolate complexes.