Chemical nature of larval osmeterial secretions of papilionid butterflies in the generaParnassius,Sericinus andPachliopta

Volatile components of the larval osmeterial secretion ofParnassius glacialis (Parnassiinae, Parnassiini) consisted of isobutyric acid, 2-methylbutyric acid, and their methyl esters. In contrast, the osmeterial exudate ofSericinus montela (Parnassiinae, Zerynthiini) was characterized as monoterpene hydrocarbons comprising-myrcene (Major),-pinene, sabinene, limonene, and-phellandrene, whereas that ofPachliopta aristolochiae (Papilioninae, Troidini) was composed of numerous sesquiterpene hydrocarbons, including-himachalene,-amorphene, and germacrene-A, and a few oxygenated sesquiterpenoids. In these three species, the chemical nature of the secretions of the last and the penultimate instars was essentially of similar quality, suggesting that the three genera,Parnassius, Sericinus, andPachliopta, are assigned to homogeneous types.     

Compact electrostatic levitator for diffraction measurements with a two axis diffractometer and a laboratory x-ray source

A compact electrostatic levitator was developed for the structural analysis of high-temperature liquids by x-ray diffraction methods. The size of the levitator was 200 mm in diameter and 200 mm in height and can be set up on a two axis diffractometer with a laboratory x-ray source, which is very convenient in performing structural measurements of high-temperature liquids. In particular, since the laboratory x-ray source allows a great amount of user time, preliminary or challenging experiments can be performed with trial and error, which prepares and complements synchrotron x-ray experiments. The present small apparatus also provides the advantage of portability and facility of setting. To demonstrate the capability of this electrostatic levitator, the static structure factors of alumina and silicon samples in their liquid phases were successfully measured.     

Identification of chemical oviposition stimulants from rice grain forSitophilus zeamais motschulsky (Coleoptera,Curculionidae)

Chemical components stimulating oviposition bySitophilus zeamais in rice grain were isolated from rice bran and were found to be a mixture of ferulates, diglycerides, and free sterols. Oviposition preference of the species can be induced by synergistic action of these compounds.     

Chemical and Chromatic Bases for Preferential Visiting By the Cabbage Butterfly, Pieris rapae, to Rape Flowers

Scent and coloration of corolla were examined as floral attributes responsible for preferential visiting by the cabbage butterfly, Pieris rapae, to rape flower, Brassica rapa. Floral volatile components that release the flower-visiting behavior of the butterfly were identified by chemical analyses, electroantennography (EAG), and two behavioral bioassays: proboscis extension reflex (PER) in response to odor and attraction to artificial flowers. GC and GC-MS analyses of the headspace volatiles from the flowers revealed the presence of six aromatic compounds, benzaldehyde, phenylacetaldehyde, benzyl alcohol, 2-phenylethanol, phenylacetonitrile, and indole in decreasing order of quantity. Of these, phenylacetaldehyde elicited the highest response in the PER assay. While benzyl alcohol, 2-phenylethanol, benzaldehyde, and phenylacetonitrile evoked moderate responses, the PER-eliciting activity of indole was very weak. In two-choice behavioral bioassays, artificial flowers scented with any one of these PER-active compounds attracted significantly more butterflies than control (unscented) flowers, whereas those treated with indole were almost inactive. The EAG activities of the six chemicals were not high and were about the same at a low dose (1 g), but phenylacetaldehyde elicited a much stronger response from both sexes at higher doses (10 and 100 g). An overall profile of EAG responses at a dose of 100 g was analogous to that of PER performance, suggesting that floral volatiles may be involved in close-range location or recognition of flowers rather than long-range attraction. By spectroscopic and UV-photographic examinations of rape flower, the central part of the corolla was found to absorb UV rays in marked contrast to the other parts, which reflected near-UV rays (_max = 350 nm). This indicates that the flower is endowed with a conspicuous nectar guide that is probably an important visual stimulus for attracting foraging adults of P. rapae. Consequently, the present findings strongly suggest that this elaborate pollination strategy of rape flower, characterized by its good combination of olfactory and visual attractiveness, accounts for preferential visiting by the cabbage butterfly to the flower.     

Pyrrolizidine Alkaloids Mediate Host-Plant Recognition by Ovipositing Females of an Old World Danaid Butterfly, Idea leuconoe

A giant danaid butterfly, Idea leuconoe, specializes on apocynaceous plants such as Parsonsia laevigata, which has been reported to contain pyrrolizidine alkaloids. Females of I. leuconoe deposited eggs in response to methanolic extract of P. laevigata, and subsequent bioassay-guided fractionation of the extract revealed that phytochemicals crucial for host recognition by ovipositing females are Parsonsia-specific macrocyclic pyrrolizidine alkaloids including parsonsianine, parsonsianidine, and 17-methylparsonsianidine. Parsonine, another P. laevigata pyrrolizidine component with a keto-dihydropyrrolizine moiety that is closely related in structure to male pheromones of the butterfly, and several nonhost pyrrolizidine alkaloids were entirely inactive. We interpret these data as strong evidence for an ancestral association through herbivory between danaid butterflies and pyrrolizidine alkaloids.     

Effect of pressure and temperature on the molecular interaction of polar lubricant containing oleic acid in polypropylene glycol observed by infrared spectroscopy

In this work, we have investigated the infrared spectra of polar lubricant in order to explore the molecular interaction under high pressure and temperature conditions using diamond anvil cell. Polypropylene glycol and oleic acid were used as base oil and additive, respectively. Stretching vibration mode of polar functional groups, such as ν _O–H and ν _C═O, was found to be sensitive to pressure and temperature. The peak positions of the vibration mode were shifted clearly to lower wavenumber as pressure increases, and temperature increase induced a slight shift to higher wavenumber. These results indicate that hydrogen bonding between lubricant molecules of base oil and additive was influenced by pressure and temperature. And furthermore, the dependency of the peak shift was discontinuous and affected mainly by pressure. These results imply a structural change on the basis of the molecular interaction of the lubricating molecules at elastohydrodynamic lubrication contacts. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of volatile organic contamination on head-disk interface tribology and a method for its reduction

Volatile organic contamination is known to be one of the factors to cause the failure of head-disk interface (HDI). Therefore, reduction of its harmful effects and improvement of the stability and reliability of HDI is becoming an important issue. In this study, the effects of some model compounds of volatile organic contamination on the tribological characteristics of HDI were systematically investigated using a contact start/stop (CSS) tester. The slider surface after the CSS tests was analyzed using Time-of-Flight Secondary Ion Mass Spectroscopy (TOF-SIMS). Transfer of lubricating oil onto the slider surface was detected after the CSS tests. The organic contaminants promoted the transfer and resulted in high and unstable friction force. Fluorinated self-assembled monolayers (SAMs) were applied on the slider surface for reducing the transferred amount of the lubricating oil. Tribological performance of the slider coated with the SAMs and the transfer amount of lubricating oil onto the slider surface in the presence of contaminant was investigated. The friction force was low and stable in the case of the SAMs coated slider even under environmental contaminant. This result could be explained by the reduction of the transferred lubricating oil because the SAMs that coated on the slider surface were low surface energy.     

Tribological Behaviors of 52100 Steel in Carbon Dioxide Atmosphere

The tribological behavior of 52100 steel in a carbon dioxide (CO₂) atmosphere was investigated using a reciprocating ball-on-disk tribometer. X-ray photoelectron spectroscopy (XPS) was used to identify the adsorbed surface layers and tribochemical products. We found that CO₂can substantially reduce friction and wear of the steel. Adsorbed and reacted surface layers containing iron carbonate and/or bicarbonate play an important role in reducing friction. A disk, exposed once to CO₂atmosphere, also shows a low friction for a long time even in a vacuum environment. An optimum CO₂pressure exists for effectively reducing friction and wear. A low-pressure CO₂atmosphere is insufficient to produce iron carbonate. In contrast, high pressure engenders serious chemical wear.     

Tribological Characteristics and Tribochemical Reactions of Various Ceramics Lubricated with HFC-134a Gas

The role of tribochemical products in the friction and wear reduction of ceramics with different fractional ionic character in CF₃CH₂F (HFC-134a) gas was investigated using a ball-on-disk type tribometer. Without exposure to air, the wear tracks on the disks were characterized with the aid of a micro-spot X-ray Photoelectron Spectroscope (XPS) whose analytical chamber was connected to the friction chamber of the tribometer. Further, the adsorption and desorption behaviors of HFC-134a molecules on the nascent surfaces of the ceramics were studied using an adsorption test apparatus in high vacuum. It was found that the lubricating effect of HFC-134a gas was closely related to the fractional ionic or covalent characters of the ceramics. HFC-134a gas was more effective in lubricating ionic ceramics than the covalent ceramics. XPS analysis revealed that metal fluorides were mainly formed on the frictional surfaces of the ionic ceramics, whereas the composition of the tribochemical products on the frictional surfaces of the other ceramics was complicated. The adsorption tests proved that HFC-134a was decomposed to an olefin CF₂=CHF on the nascent surfaces of the ionic ceramic Al₂O₃ and the covalent ceramics. However, the formation of organic fluorine-containing compounds was not detected on the frictional surfaces of the ionic ceramics by XPS. This result implies that the mechanism of tribochemical reactions is strongly dependent on the bond type of ceramics. It is concluded that the low friction and wear of the ionic ceramics in HFC-134a gas result from the metal fluorides formed with high surface concentration on the sliding surfaces.