Reaction of cholesterol 5,6-epoxides with simulated gastric juice

Cholesterol 5α,6α-epoxide (α-epoxide) and cholesterol 5β,6β-epoxide (β-epoxide) were individually suspended in simulated gastric juice (pH 1.2) at 37 C, and their reaction was followed by gradient high performance liquid chromatography (HPLC) with flame ionization (FID) detection. Both epoxides reacted rapidly in the aqueous acid medium. The α-epoxide formed 6β-chlorocholestane-3β,5α-diol (α-chlorohydrin) and 5α-cholestane-3β,5,6β-triol (triol), while the β-epoxide formed 5α-chlorocholestane-3β,6β-diol (β-chlorohydrin) and triol. The isomeric chlorohydrins reacted further to form the triol. In mildly alkaline aqueous medium, each chlorohydrin reverted to the epoxide from which it was formed. The data suggest that both epoxides, which have been reported to have adverse health effects in animals, would be largely hydrolyzed in the stomach and to the triol, which also has been reported to have biological activity. The data furher suggest that residual chlorohydrins surviving stomach residence can be expected to revert to epoxide in the more alkaline intestinal environment.     

Kinematic viscosity of biodiesel components (fatty acid alkyl esters) and related compounds at low temperatures

Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats is, has undergone rapid development and acceptance as an alternative diesel fuel. Kinematic viscosity is one of the fuel properties specified in biodiesel standards, with 40 °C being the temperature at which this property is to be determined and ranges of acceptable kinematic viscosity given. While data on kinematic viscosity of biodiesel and related materials at higher temperatures are available in the literature, this work reports on the kinematic viscosity of biodiesel and a variety of fatty acid alkyl esters at temperatures from 40 °C down to −10 °C in increments of 5 °C using the appropriately modified standard reference method ASTM D445. Investigating the low-temperature properties of biodiesel, including viscosity, of biodiesel and its components is important because of the problems associated with the use of biodiesel under these conditions. Such data may aid in developing biodiesel fuels optimized for fatty ester composition. An index termed here the low-temperature viscosity ratio (LTVR) using data at 0 °C and 40 °C (divide viscosity value at 0 °C by viscosity value at 40 °C) was used to evaluate individual compounds but also mixtures by their low-temperature viscosity behavior. Compounds tested included a variety of saturated, monounsaturated, diunsaturated and triunsaturated fatty esters, methyl ricinoleate, in which the OH group leads to a significant increase in viscosity as well as triolein, as well as some fatty alcohols and alkanes. Esters of oleic acid have the highest viscosity of all biodiesel components that are liquids at low temperatures. The behavior of blends of biodiesel and some fatty esters with a low-sulfur diesel fuel was also investigated.     

Volatile compounds of original African black and white shea butter from Tchad and Cameroon

Shea butter is used as an edible vegetable fat in many African countries. It can be utilized as a substitute or complete replacement for cocoa butter in various applications and plays an important role in traditional African medicinal practice. Although detection of volatile compounds by solid‐phase micro‐extraction gas‐chromatography mass‐spectroscopy (SPME‐GC‐MS) is a very reliable and reproducible technique, which can be used as an important part of authenticity checking, production monitoring and contamination detection, no published data about volatile compounds of shea butter are available so far. In this investigation, the characteristic volatiles in the headspace of original African shea butter samples were identified by using SPME‐capillary‐GC coupled to a mass selective detector. Almost 100 different volatile components were identified, e.g. fatty acids, saturated and unsaturated aldehydes and ketones, terpenes, and typical Maillard reaction products such as methylfuranes and pyrazines. Furthermore, the samples have been olfactorily evaluated by a panel of professional flavorists and trained analytical chemists. It can be stated that variations in processing conditions of shea butter result in considerable differences in the composition of headspace volatiles, detected by SPME‐GC‐MS and human olfaction.     

Effect of Ionic Substitution on the Thermal Expansion of ZrTiO4

New oxide compounds with α-PbO₂ structure have been synthesized by solid-state reactions. These are derived from ZrTiO₄ and HfTiO₄ by a different kind of ionic substitution. The thermal expansion behavior of these phases was investigated by means of a dilatometer and an X-ray heating diffractometer. These measurements revealed rather low expansion for some of the Zr(Me³⁺/Me⁵⁺)O₄, solid solutions. This behavior is attributed to their high expansion anisotropy, which leads to extended formation of microcracks.     

Synergistic Sex Pheromone Components of White-Spotted Tussock Moth, Orgyia thyellina

In 1996, the exotic white-spotted tussock moth (WSTM), Orgyia thyellina (Lepidoptera: Lymantriidae), was discovered in Auckland, New Zealand. Because establishment of WSTM would threaten New Zealand's orchard industry and international trade, eradication of WSTM with microbial insecticide was initiated. To monitor and complement eradication of WSTM by capture of male moths in pheromone-baited traps, pheromone components of female WSTM needed to be identified. Coupled gas chromatographic–electroantennographic detection analysis of pheromone gland extract revealed several compounds that elicited responses from male moth antennae. Mass spectra of the two most EAD-active compounds suggested, and comparative GC-MS of authentic standards confirmed, that they were (Z)-6-heneicosen-11-one (Z6–11-one) and (Z)-6-heneicosen-9-one, the latter termed here thyellinone. In field experiments in Japan, Z6–11-one plus thyellinone at a 100:5 ratio attracted WSTM males, whereas either ketone alone failed to attract a single male moth. Addition of further candidate pheromone components did not enhance attractiveness of the binary blend. Through the 1997–1998 summer, 45,000 commercial trap lures baited with 2000 g of Z6–11-one and 100 g of thyellinone were deployed in Auckland towards eradication of the residual WSTM population.Dedicated to my dear mother in honor of her 75th birthday     

Decadienoates: Sex Pheromone Components of Nettle Caterpillars Darna trima and D. bradleyi

This study was undertaken to identify sex pheromone components of nettle caterpillars Darna trima and Darna bradleyi (Lepidoptera: Limacodidae) whose larvae defoliate oil palm, Elaeis guineensis, in southeast Asia. Coupled gas chromatographic–electroantennographic detection (GCEAD) analyses of pheromone gland extracts revealed two antennally active compounds produced by female D. trima and two by female D. bradleyi. Molecular structures of these candidate pheromone components were identified by electron-impact and chemical-ionization mass spectrometry; retention-index calculations on DB-5, DB-23, and DB-210 columns; microanalytical treatments, as well as syntheses of "auxilliary" compounds that facilitated identification of the compounds. The compounds from D. trima were 2-methylbutyl (E)-7,9-decadienoate (A) and (E)-2-hexenyl (E)-7,9decadienoate (B); from D. bradleyi we identified methyl (E)-7,9-decadienoate (C), and isobutyl (E)-7,9-decadienoate (D). In field experiments in Malaysia, (S)-2-methylbutyl (E)-7,9-decadienoate (SA) in combination with B proved to be essential and synergistic pheromone components for attraction of male D. trima. (R)-2-Methylbutyl (E)-7,9-decadienoate (RA) had no behavioral activity. Compound D singly attracted male D. bradleyi, but addition of C to D at a 1 : 10 ratio significantly enhanced attractiveness of the bait. Synthetic pheromone blends were more effective trap baits than unmated female moths and could be developed for monitoring populations of D. trima and D. bradleyi in Asian oil palm plantations.     

(<Emphasis Type="Italic">Z,Z</Emphasis>)-6,9-Heneicosadien-11-One: Major Sex Pheromone Component Of Painted Apple Moth, <Emphasis Type="Italic">Teia anartoides</Emphasis>

(Z, Z)-6,9-Heneicosadien-11-one (Z6Z9-11-one-21Hy) was identified as the major sex pheromone component of the painted apple moth (PAM), Teia anartoides (Lepidoptera: Lymantriidae), on the basis of (1) comparative gas chromatographic-electroantennographic detection (GC-EAD) analyses, GC-mass spectrometry (MS), high-performance liquid chromatography (HPLC)-MS, and HPLC-UV/visible spectroscopy of pheromone gland extracts and authentic standards; (2) GC-EAD analyses of effluvia of calling females; and (3) wind tunnel and field trapping experiments with a synthetic standard. In field experiments in Australia, synthetic Z6Z9-11-one-21Hy as a single component attracted male moths. Wind tunnel experiments suggested that a 4-component blend consisting of Z6Z9-11-one-21Hy, (6Z,9R,10S)-cis-9,10-epoxy-heneicosene (Z6-9R10S-epo-21Hy), (E, E)-7,9-heneicosadien-6,11-dione (E7E9-6,11-dione-21Hy), and 6-hydroxy-(E, E)-7,9-heneicosadien-11-one (E7E9-6-ol-11-one-21Hy) (all present in pheromone gland extracts) might induce more males to orient toward, approach, and contact the source than did Z6Z9-11-one-21Hy as a single component. Additional experiments are needed to determine conclusively whether or not Z6-9R10S-epo-21Hy, E7E9-6,11-dione-21Hy, and E7E9-6-ol-11-one-21Hy might be minor sex pheromone components of PAM. Moreover, attractiveness of synthetic pheromone and virgin PAM females needs to be compared to determine whether synthetic pheromone could replace PAM females as trap baits in the program to monitor eradication of exotic PAM in New Zealand.     

Sex phermone components of mulberry looper,Hemerophila atrilineata butler (lepidoptera: Geometridae)

(6Z-9S, 10R)-Epoxy-octadecene (SR-1) and (3Z, 6Z-9S, 10R)-epoxy-octadecadiene (SR-2) are sex pheromone components of the mulberry looper (MBL),Hemerophila atrilineata Butler. Compounds extracted from female MBL pheromone glands were identified by coupled gas chromatographic-electroantennographic detection (GC-EAD) and GC-mass spectrometry. In field experiments in China,SR-2,RS-2, or both combined were hardly attractive, butSR-2 in combination withSR-1 attracted significant numbers of MBL males. Synergistic behavioral activity ofSR-1 plusSR-2, but not of corresponding antipode mixtures, indicates enantiospecificity of MBL pheromone communication. Because blends of racemic and enantiospecific (SR)1 plus2 were similarly attractive, racemic1 plus2 may have potential for mass trapping or confusion of MBL males in commercial mulberry plantations.     

CREEP DEFORMATION OF INTERMETALLIC ALLOYS

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