Variation in estrogenic activity among fractions of a commercial nonylphenol by high performance liquid chromatography

Estrogenic activity by recombinant yeast screen assay of the commercial NP was considerably higher when compared with that of n-nonylphenol (n-NP). Fractionation of the commercial NP by high performance liquid chromatography (HPLC) afforded seven isomers: 4-(1,3-dimethyl-1-propyl-butyl)-phenol, 4-(1,1,3-trimethyl-hexyl)-phenol, 4-(1,1-dimethyl-3-ethyl-pentyl)-phenol, 4-(1,1,4-trimethyl-hexyl)-phenol, 4-(1-methyl-1-propyl-pentyl)-phenol, 4-(1,1,2-trimethyl-hexyl)-phenol and 4-(1-ethyl-1-methyl-hexyl)-phenol. The structures of these isomers were determined by GC-MS and nuclear magnetic resonance spectroscopy (NMR). All of these isomers possessed tertiary alpha-carbon in their chemical structures. Another tertiary NP, 4-(1,1-dimethyl-heptyl)-phenol was synthesized in the present study and this synthetic NP also exhibited the estrogenic activity. One fractionated compound was identified as one of decylphenol, 4-(1-ethyl-1,4,4-trimethyl-pentyl)-phenol. The isomer, 4-(1,1,4-trimethyl-hexyl)-phenol exhibited the highest estrogenic activity corresponding to 1/10000 that of 17beta-estradiol (E2). The activity of n-NP was the least. This suggests that it may be possible to develop a technical NP mixture with relatively low estrogenic activity.     

Microbial phytotoxins as potential herbicides

Abstract

Microbes are sources of a diverse array of phytotoxic compounds. These compounds are generally structurally different from commercial herbicides, targeting different molecular sites of action within the plant. These novel structures and sites can be excellent leads for the discovery and development of safer synthetic herbicides. Microbial phytotoxins are often more environmentally benign than synthetic herbicides. Examples of phytotoxins from fungi (AAL‐toxin, cornexistin, cyperin, and tentoxin) with novel structures and sites of action are discussed. AAL‐toxin is toxic to a wide variety of weeds at very low dose rates. AAL‐toxin and many of its analogues kill plants by inhibiting a ceramide synthase‐like enzyme, causing rapid accumulation of free sphingoid bases that disrupt membranes. Cornexistin appears to be metabolically cnverted to an inhibitor of certain aspartate amino transferase isoenzymes. Its activity can be reversed by feeding aspartate and glutamate or with tricarboxylic acid cycle intermediates. Its activity is much like that of (aminooxy)acetate. Cyperin is a diphenylether phytotoxin that inhibits protoporphyrinogen oxidase, but does not kill plants by this mechanism. It appears to have other effects on porphyrin metabolism. Tentoxin is toxic by two mechanisms. It disrupts chloroplast development by inhibiting the processing of a nuclear‐coded plastid protein, and it also inhibits photophosphorylation by acting as an energy transfer inhibitor of coupling factor 1 ATPase. Other examples of phytotoxins from microbes with promise as herbicides will be mentioned.     

Adjustment of web-building initiation to high humidity: a constraint by humidity-dependent thread stickiness in the spider Cyrtarachne

Cyrtarachne is an orb-weaving spider belonging to the subfamily Cyrtarachninae (Araneidae) which includes triangular-web-building Pasilobus and bolas spiders. The Cyrtarachninae is a group of spiders specialized in catching moths, which is thought to have evolved from ordinary orb-weaving araneids. Although the web-building time of nocturnal spiders is in general related to the time of sunset, anecdotal evidence has suggested variability of web-building time in Cyrtarachne and its closely related genera. This study has examined the effects of temperature, humidity, moonlight intensity, and prey (moths) availability on web-building time of Cyrtarachne bufo, Cyrtarachne akirai, and Cyrtarachne nagasakiensis. Generalized linear mixed model (GLMM) have revealed that humidity, and not prey availability, was the essential variable that explained the daily variability of web-building time. Experiments measuring thread stickiness under different humidities showed that, although the thread of Cyrtarachne was found to have strong stickiness under high humidity, low humidity caused a marked decrease of thread stickiness. By contrast, no obvious change in stickiness was seen in an ordinary orb-weaving spider, Larinia argiopiformis. These findings suggest that Cyrtarachne adjusts its web-building time to favorable conditions of high humidity maintaining strong stickiness, which enables the threads to work efficiently for capturing prey.     

Comparison of Surface Organic Compound Mass Spectrum Patterns by LD-TOFMS for Megalopolis Atmospheric Particles and Diesel Exhaust Particles (DEP)

PM_2.5 and PM₁₀ samples for megalopolis atmospheric particles were collected at Shinjuku, Tokyo in December 1998–January 1999 and August 1999, for two weeks both in winter and summer, with a 24 hr sampling interval. Sampling of PM_2.5 and PM₁₀ in diesel exhaust particles (DEP) was carried out using an automobile exhaust testing system, with a diesel truck placed on a chassis dynamometer. Sampling conditions included idling, constant speed of 40 km hr^-1, M-15 test pattern and 60%-revolution/40%-load of maximum power. Mass spectrums of organic compounds adhering to the surface of the PM_2.5 and PM₁₀ samples were analyzed by laser desorption time-of-flight mass spectrometry (LD-TOFMS, analytical mass range: m/z 1–m/z 380 000). LD-TOFMS analysis of those samples revealed consistently the detection of low-mass organic compounds up to m/z 800. For the megalopolis atmospheric particles, the mass spectrum pattern of wintertime samples was almost the same as that of the summertime samples for both PM_2.5 and PM₁₀. The major peak was m/z 177, and the minor peaks were m/z 84, 94, 101, 163, 189 and 235. The mass spectrum pattern of DEP was the same for all samples under all test conditions. The major peak was m/z 101, and other detected peaks were small.     

Prenatal diagnosis of infantile hypophosphatasia

Prenatal diagnosis was attempted in a pregnant Japanese woman whose son had died of infantile hypophosphatasia, using chorionic villi sampled at 10 weeks of gestation. Southern blot analysis of restriction fragment length polymorphism was used as a guide, with cDNA for the human liver-type alkaline phosphatase as a probe, and BclI as a restriction enzyme. The fetus was found to be a heterozygote; the pregnancy was allowed to continue; and the baby born was phenotypically normal.     

The Effect of Estrogens,River Water,and Treated Wastewater on Vitellogenin Induction of Japanese Medaka1

Abstract: The objective of this study is to evaluate the effect of estrogens on fish endocrine disruption in river water and treated wastewater. Endogenous estrogen estrone (E1), 17β‐estradiol (E2), river water, and treated wastewater were used for exposure tests on male Japanese medaka. Vitellogenin induction in male medaka was regarded as the endpoint of endocrine disruption. The effective concentrations of E1 and E2 on vitellogenin induction in medaka were evaluated by breeding medaka for 14 days in tanks with various concentrations of E1 or E2. Vitellogenin induction increased with elapse of time during exposure, with higher estrogen concentrations causing greater vitellogenin induction. According to the test results, the lowest observed effect concentrations (LOECs) of E1 and E2 were estimated to be 31.6 and 5.0 ng/l, respectively; and the E2 equivalent (EEQ) LOEC value of E1 was 5.2 ng‐E2/l, derived by multiplying the relative potency of E1 by that of E2 as estimated in this study. In continuous exposure tests using river water or treated wastewater, the estrogenic activity, an index of total estrogenic potential measured by yeast screen assay and expressed as EEQ, varied widely during the exposure tests, and significant vitellogenin induction was observed after several days of high levels of estrogenic activity in water. Vitellogenin concentration tended to significantly increase if EEQ exceeded the level of 5 ng‐E2/l. The threshold value was substantially the same as the results for E1 and E2 exposure tests of medaka. Consequently, EEQ over 5 ng‐E2/l was revealed to have the potential to cause endocrine disruption of male medaka. As estrogenic activity exceeding 5 ng‐E2/l was observed in some rivers in Japan, total estrogenic potential needs to be further decreased at wastewater treatment plants to prevent fish endocrine disruption.