Development of butt welding of polymeric materials based on softening and stirring effects by hot tool

In this study, new butt welding technique was proposed to join polymeric materials in which the polymeric material is softened by a heated tool due to the Joule effect heating of the electric current flow through the tool, and the coalescence of material is done by the stirring action due to the tool rotation. A 3 mm-thick Polycarbonate (PC) sheets were joined in various joining conditions, from which joining mechanism, mechanical properties of joints and process parameters affecting joint performance were investigated. In the experiments, in situ observation with a CCD camera and material temperature measurement during the process, as well as the observation of surface appearance and cross section of the joint and tensile test were performed for these purposes. It was shown from the in situ observation and material temperature measurement that the molten and softened region is formed around the weld tool. It was also shown that sufficient heat input was required to form sound joints with acceptable performance, which depended upon the joining speed and amount of electric current flow through the tool. The observation of joint appearance and cross section revealed that the joint with comparable thickness to base material was obtained under the condition of revolution pitch below 0.08 mm, defined by the ratio of joining speed to tool rotation. It is noticed that joints obtained from the proper conditions have the same mechanical properties as the base material, and that the process parameters of this method were tool rotation speed, welding speed and amount of electric current. These results suggest proposed method is useful for joining the polymeric materials.     

Catalytic dehydration of 1,2-propanediol into propanal

Vapor-phase catalytic dehydration of 1,2-propanediol was investigated over several catalysts, such as acidic oxides and supported heteropoly acids. These acids catalyze the dehydration of 1,2-propanediol to produce propanal. In particular, silica-supported silicotungstic acid showed the highest catalytic activity in the formation of propanal. At low conversions, however, propanal reacted with another 1,2-propanediol to produce a cyclic acetal (2-ethyl-4-methyl-1,3-dioxolane). Such acetal formation reduced the selectivity to propanal. Under optimum reaction conditions, 100% conversion was attained with propanal selectivity higher than 93 mol% at 200 °C.     

Differences in Sterol Composition between Male and Female Gonads of Dominant Limpet Species

The present study demonstrated here for the first time that there are statistically significant differences in sterol composition between male and female gonads of the dominant limpets Cellana grata and Cellana toreuma, which are intertidal gastropods. Among 11 different sterols identified in this study, unusually high levels (11.2–19.8% of total sterols) of the Δ⁸-sterols 5α-cholest-8-en-3β-ol (zymostenol) and 5α-cholesta-8,24-dien-3β-ol (zymosterol), which have never been reported in aquatic invertebrate gonads, were present in only the male gonads.     

Effective Coke Removal in Methane to Benzene (MTB) Reaction on Mo/HZSM-5 Catalyst by H2 and H2O Co-addition to Methane

The catalytic dehydro-aromatization reaction over Mo/HZSM-5 catalyst was drastically stabilized by the co-addition of 5.4% H₂ and 1.8% H₂O to methane feed at 750 °C, 0.3 MPa and methane space velocity of 3000 mL g⁻¹ h⁻¹, suppressing the coke formation effectively, compared with single hydrogen or steam addition.     

Chemical response of Picea glehnii seed-epiphytic Penicillium species to Pythium vexans under in vitro competitive conditions for mycelial growth

The potential protection of Picea glehnii seedlings from damping-off by seed-epiphytic Penicillium species was investigated. We studied the chemical response of seed-epiphytic Penicillium species (Pen. cyaneum, Pen. damascenum, and Pen. implicatum) to Pythium vexans, a damping-off fungus, in vitro. Penicillium species were cultured singly or cocultured with Pyt. vexans for 14 or 18 d, and mycelial growth, pH of culture filtrate, antifungal activity of the culture filtrate against Pyt. vexans, and the amount of antifungal compound produced by each Penicillium species, were examined. The filtrate of both the single culture of Penicillium and the coculture of Penicillium and Pyt. vexans showed antifungal activity against Pyt. vexans. In a coculture with Pyt. vexans, Pen. cyaneum produced an antifungal compound (patulin) as in the single culture. Pen. damascenum cocultured with Pyt. vexans produced an antifungal compound (citrinin), as it did in the single culture and in larger amounts on day 10. Pen. implicatum produced two antifungal compounds, frequentin and palitantin, and the ratio of frequentin (with higher antifungal activity than palitantin) to palitantin was higher in the coculture with Pyt. vexans than in the single culture. Our results indicate that these Penicillium species have the ability to produce antifungal compounds and to keep antifungal activity under competitive condition with Pyt. vexans. The chemical response of these Penicillium species to Pyt. vexans may contribute to protect P. glehnii seedlings from damage by Pyt. vexans.     

Allelopathic Effects of Volatile Monoterpenoids Produced by <Emphasis Type="Italic">Salvia leucophylla</Emphasis>: Inhibition of Cell Proliferation and DNA Synthesis in the Root Apical Meristem of <Emphasis Type="Italic">Brassica campestris</Emphasis> Seedlings

Salvia leucophylla, a shrub observed in coastal south California, produces several volatile monoterpenoids (camphor, 1,8-cineole, -pinene, -pinene, and camphene) that potentially act as allelochemicals. The effects of these were examined using Brassica campestris as the test plant. Camphor, 1,8-cineole, and -pinene inhibited germination of B. campestris seeds at high concentrations, whereas -pinene and camphene did not. Root growth was inhibited by all five monoterpenoids in a dose-dependent manner, but hypocotyl growth was largely unaffected. The monoterpenoids did not alter the sizes of matured cells in either hypocotyls or roots, indicating that cell expansion is relatively insensitive to these compounds. They did not decrease the mitotic index in the shoot apical region, but specifically lowered mitotic index in the root apical meristem. Moreover, morphological and biochemical analyses on the incorporation of 5-bromo-2-deoxyuridine into DNA demonstrated that the monoterpenoids inhibit both cell-nuclear and organelle DNA synthesis in the root apical meristem. These results suggest that the monoterpenoids produced by S. leucophylla could interfere with the growth of other plants in its vicinity through inhibition of cell proliferation in the root apical meristem.     

Efficient total synthesis of novel bioactive microbial metabolites

Bioactive natural products produced by microbes have almost limitless potential in pharmaceutical applications, and the organic synthesis of such products as lead compounds will result in the creation of new and widely useful pharmaceutical products. A program of discovery of naturally occurring bioactive microbial metabolites has been ongoing at the Kitasato Institute. We have also developed efficient, rational, and highly flexible production methods for generation of target compounds, synthesis of related compounds, elucidation of their structure-activity relationships, and the possible creation of improved bioactive compounds. In this Account, the isolation and total synthesis of naturally occurring bioactive microbial metabolites in order to create novel medicines for specific illnesses is described. This covers diseases and conditions such as atherosclerosis, Alzheimer's disease, cancer, inflammation, and osteoporosis, among others, and focuses on six specific compounds. Pyripyropenes were discovered from Aspergillus fumigatus FO-1289 through our screening of microbial metabolites that strongly inhibit acyl-CoA cholesterol acyltransferase (ACAT) in order to develop a new class of cholesterol-lowering agents. These novel polyoxygenated mixed polyketide-terpenoid (meroterpenoid) metabolites contain a fused pyridyl alpha-pyrone moiety. We carried out the first total synthesis of (+)-pyripyropene A via a flexible, concise, and highly efficient route and also clarified the structure-activity relationships. Arisugacins were discovered from Penicillium sp. FO-4259 by our screening of microbial metabolites that strongly inhibit acetylcholinesterase (AChE) in order to create novel medicines for Alzheimer's disease (AD). Arisugacins are also meroterpenoids. We have achieved the first convergent total synthesis of arisugacins A and B. Lactacystin was isolated from Streptomyces sp. OM-6519 via our screening of microbial metabolites that promote the differentiation of the neuroblastoma cell to further discover new AD medicines. Lactacystin has a novel gamma-lactam thioester structure and is also a selective and strong proteasome inhibitor. We have developed a concise approach to synthesize lactacystin designed to afford easy access to the original compound and a variety of analogs. Macrosphelides were isolated from Microsphaeropsis sp. FO-5050 from our screening of microbial metabolites that inhibit the adhesion of HL-60 cells to human umbilical vein endothelial cells (HUVEC). Macrosphelides are the first 16-membered macrotriolides. Macrosphelides prevent cell-cell adhesion by inhibiting the binding of sialyl Lewis X to E-selectin. We have accomplished the first efficient total synthesis of macrosphelides. Madindolines were isolated from Streptomyces nitrosporeus K93-0711 by our program to discover new interleukin 6 (IL-6) modulators. Madindolines are comprised of a 3a-hydroxyfuroindoline ring connected at nitrogen via a methylene bridge to a cyclopentene-1,3-dione ring. We have developed an efficient and practical total synthesis of madindolines. Madindoline A binds to gp130 selectively and inhibits IL-6 activity. Neoxaline was isolated from Aspergillus japonicus Fg-551. Neoxaline is a member of a novel class of biologically active indole alkaloids characterized by a unique indoline spiroaminal framework and binds to tubulin, which results in inhibition of tubulin polymerization. We have developed a concise stereoselective synthesis of the indoline spiroaminal framework of neoxaline.     

Identification and Field Evaluation of Grape Shoot Volatiles Attractive to Female Grape Berry Moth (<Emphasis Type="Italic">Paralobesia viteana</Emphasis>)

Solid-phase microextraction (SPME) and gas chromatography coupled with electroantennographic detection (GC-EAD) were used to identify volatile compounds from shoots of riverbank grape (Vitis riparia) that attract the female grape berry moth (GBM, Paralobesia viteana). Consistent EAD activity was obtained for 11 chemicals: (Z)-3-hexen-1-yl acetate, (E)-linalool oxide, (Z)-linalool oxide, nonanal, linalool, (E)-4,8-dimethyl-1,3,7-nonatriene, methyl salicylate, decanal, beta-caryophyllene, germacrene-D, and alpha-farnesene. In flight-tunnel tests that involved female GBM and rubber septa loaded with subsets of these 11 compounds, we found that both the 11-component blend and a seven-component blend, composed of (E)-linalool oxide, (Z)-linalool oxide, nonanal, (E)-4,8-dimethyl-1,3,7-nonatriene, decanal, beta-caryophyllene and germacrene-D, elicited equivalent levels of upwind flight as freshly cut grape shoots. The removal of any of the seven compounds from the seven-component blend resulted in a significant decrease in female upwind flight responses. In a field trial with these two synthetic blends, traps equipped with either blend captured more female GBM compared to traps baited with hexane only (control), although the number of females caught was generally low. There were no differences in the number of males captured among treatments. Although in flight-tunnel trials, moths readily flew upwind to both grape shoots and rubber septa loaded with the best lures, they landed on shoots but not on rubber septa. Coupled with relatively low field catches, this suggests that additional host finding cues need to be identified to improve trap efficacy.