Synthesis and structure-activity relationship of diene modified analogs of<Emphasis Type="Italic"> Matsucoccus</Emphasis> sex pheromones

The biological activity of the Matsucoccus spp. sex pheromones and diene modified analogs has been tested in forests of Israel and Portugal in order to explore the structure-activity relationship of the pine bast scale pheromone/kairomone system. The response of the adult predatory bugs, Elatophilus hebraicus and E. crassicornis and of the brown lacewing, Hemerobius stigma is more selective than that of the conspecific Matsucoccus males. The removal of the terminal methyl group from the diene terminus of both pheromones 1 and 2 eliminates all kairomonal activity but retains moderate pheromonal activity. Addition of a methyl group to the diene terminus of pheromones 1 and 2 sustains full pheromonal and kairomonal activities of the Elatophilus spp. but eliminates entirely the kairomonal activity of H. stigma. Subtle designed alterations in the structure of the diene group, typical of all Matsucoccus pheromones, change the mode of the kairomonal activity markedly.     

Anatomical localization and stereoisomeric composition of <Emphasis Type="Italic">Tribolium castaneum</Emphasis> aggregation pheromones

We report that the abdominal epidermis and associated tissues are the predominant sources of male-produced pheromones in the red flour beetle, Tribolium castaneum and, for the first time, describe the stereoisomeric composition of the natural blend of isomers of the aggregation pheromone 4,8-dimethyldecanal (DMD) in this important pest species. Quantitative analyses via gas chromatography–mass spectrometry showed that the average amount of DMD released daily by single feeding males of T. castaneum was 878 ± 72 ng (SE). Analysis of different body parts identified the abdominal epidermis as the major source of aggregation pheromone; the thorax was a minor source, while no DMD was detectable in the head. No internal organs or obvious male-specific glands were associated with pheromone deposition. Complete separation of all four stereoisomers of DMD was achieved following oxidation to the corresponding acid, derivatization with (1R, 2R)- and (1S, 2S)-2-(anthracene-2,3-dicarboximido)cyclohexanol to diastereomeric esters, and their separation on reversed-phase high-performance liquid chromatography at −54°C. Analysis of the hexane eluate from Porapak-Q-collected volatiles from feeding males revealed the presence of all four isomers (4R,8R)/(4R,8S)/(4S,8R)/(4S,8S) at a ratio of approximately 4:4:1:1. A walking orientation bioassay in a wind tunnel with various blends of the four synthetic isomers further indicated that the attractive potency of the reconstituted natural blend of 4:4:1:1 was equivalent to that of the natural pheromone and greater than that of the 1:1 blend of (4R,8R)/(4R,8S) used in commercial lures.     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

Human intake of PCDDs, PCDFs, and dioxin like PCBs in Japan, 2001 and 2002

PCDDs, PCDFs, and dioxin like PCBs (dioxin) surveillance results derived from regular environmental monitoring as well as other dioxin surveys by national and local governmental bodies in Japan were collected and analyzed. Several thousand data for air and soil in fiscal year 2001 (from 01/04/2001 to 31/03/2002) and 2002, water (from the sea, rivers and lakes), sediment (from the sea, rivers and lakes), ground water, aquatic organisms, purified water from water purification plants, raw water from water purification plants, human breast milk, and human blood in fiscal 2001, and total diet study (TDS) and various kinds of foodstuff in fiscal 1998-2002 were collected. Average human uptake of dioxin in Japan in fiscal 2001 was estimated at 1.68 pg-TEQ/kg-bw/day, while uptake in fiscal 2002 was estimated at 1.52 pg-TEQ/kg-bw/day. Diet accounted for more than 90% of the total intake. Contributions of inhalation and soil ingestion were relatively small. Age-group-specific contribution of various foodstuff to total dietary intake was also estimated. The estimates of intake through fish and shellfish accounted for approximately 45-70% of total dietary intake in each age group. Monte Carlo simulation was conducted, using the data of the air and soil concentrations in fiscal 2001 and the total diet study data in fiscal 1998-2001, in order to obtain information on the variability of dioxin intake; The estimated average, median, 5th percentile and 95th percentile of the intake distribution were 1.78, 1.69, 0.95 and 2.91 pg-TEQ/kg-bw/day, respectively. This study found that the average total intake estimates in Japan in both fiscal 2001 and 2002 were estimated to be below tolerable daily intake level (TDI) defined by the Ministry of Health, Labour and Welfare, Japan (i.e. 4 pg-TEQ/kg-bw/day). The 95th percentile of the dioxin intake distributions estimated with Monte Carlo simulation using the data of the air and soil concentrations in fiscal 2001 and TDS data in fiscal 1998-2001 was also below the Japanese TDI.     

Improvement of reporter gene assay for highly sensitive dioxin detection using protoplastic yeast with inactivation of CWP and PDR genes

Environmental Science and Pollution Research - A yeast reporter gene assay system with improved performance for dioxin detection was established. Since yeast reporter gene assays are relatively...