Ab initio calculations using conventional (HF/6-31G and MP2/6-31G) and density functional theory (B-LYP/6-31G) methods have been used to determine the structures of the [n]fulvene and [n,m]fulvalene (n, m = 3, 5, 7) series of molecules, with particular emphasis on heptafulvalene (n = m = 7: 12). Calculations have also been performed on the parent cycloalkenes: cyclopropene, cyclopentadiene, and cycloheptatriene (1-3, respectively). All the fulvenes (n = 3, 5, 7: 4-6, respectively) and the smaller fulvalenes (n = 3, m= 3, 5, 7: 7-9, respectively, and n = m = 5: 10) are found to be planar. Pentaheptafulvalene (n = 5, m = 7: 11) adopts a very slightly nonplanar C(s)() arrangement of the five- and seven-membered rings. Heptafulvalene (12) is predicted to have an anti-folded C(2)(h)() structure, in accord with the X-ray crystal structure. We propose that the underlying reason for 11 and 12 adopting nonplanar conformations is the proximity of the H(2) and H(2)(') hydrogen atoms which promotes a distortion of the rings away from planarity at the central fulvalenic C=C double bond. In the process, pi-overlap is lost but this is partially regained by pyramidalization of the carbon centers in the seven-membered ring(s). The degree of folding is substantially more pronounced in 12 than in 11. Our calculated dipole moments, pi-electron distributions, bond alternation parameters, and energy comparisons indicate that the unknown smallest fulvalene, triafulvalene (7), is highly destabilized with localized bonding while triapentafulvalene (8), which is also unknown, is predicted to be stabilized and quite delocalized, consistent with Hückel 4n + 2 considerations.

We show that reproductively mature male sea lampreys release a bile acid that acts as a potent sex pheromone, inducing preference and searching behavior in ovulated female lampreys. The secreted bile acid 7alpha,12alpha,24-trihydroxy-5alpha-cholan-3-one 24-sulfate was released in much higher amounts relative to known vertebrate steroid pheromones and may be secreted through the gills. Hence, the male of this fish species signals both its reproductive status and location to females by secreting a pheromone that can act over long distances.

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Abstract-Estrogenic discharges are known or suspected to be present in many United Kingdom estuaries and are also occurring from offshore oil and gas installations. The aim of this study was to establish whether estrogens and their mimics are present in marine waters at concentrations that can produce biological responses in fish and, if so, to discover whether the effects are likely to be harmful to populations and communities through changes in reproductive and other physiological processes. Laboratory studies and extensive field surveys were carried out with the euryhaline flounder (Platichthys flesus), using the amount of yolk protein vitellogenin in the blood of free-living male fish as an indicator of exposure to estrogens. Exposure to the synthetic estrogen ethynylestradiol for 3 weeks confirmed that the vitellogenin response was made and showed that this species is about one order of magnitude less sensitive than the freshwater species rainbow trout. The fish did not respond to the estrogen mimic nonylphenol at concentrations of 30 g/L. Wild male flounder were sampled from four contaminated United Kingdom estuaries: the Tyne, Crouch, Thames, and Mersey. Fish from one or more sites in each estuary had significantly elevated concentrations of vitellogenin in their blood when compared to concentrations in fish from the clean control estuary (Alde River). Vitellogenin concentrations in the Tyne and Mersey fish were four and six orders of magnitude greater, respectively, than control concentrations. Elevated vitellogenin concentrations were also seen in some male flounder caught in coastal areas. Approximately 20% of male fish from the Mersey estuary contained oocytes in their testes, but this intersex condition was not seen elsewhere. The implications of these findings for fish populations are discussed.

Synthetic progestins are widely used as a component in both contraceptives and in hormone replacement therapy (HRT), both on their own and in combination with EE2. Their presence in the environment is now established in wastewater effluent and river water and this has led to concerns regarding their potential effects on aquatic organisms living in these waters. We carried out in vivo experiments to determine the potencies of four different synthetic progestins on the reproductive capabilities of the fathead minnow (Pimephales promelas). We then performed a series of in vitro assays to try and determine the reason for the effects seen in the in vivo experiments. In the first experiment, fathead minnow exposed to a single concentration of 100 ng/L of either Levonorgestrel or Gestodene stopped spawning almost completely. The same nominal concentration of Desogestrel and Drospirenone did not affect reproduction (21 d NOECs of 100 ng/L). The second experiment investigated two progestins of different potency: Gestodene at 1, 10, and 100 ng/L and Desogestrel at 100 ng/L, 1 μg/L, and 10 μg/L. Gestodene concentrations as low as 1 ng/L had significant effects on reproduction over 21 d, whereas concentrations of Desogestrel at or above 1 μg/L were required to significantly reduce egg production. The synthetic progestins also masculinized the female fish in a concentration-dependent manner. Results from yeast-based in vitro assays demonstrated that the progestins are all strongly androgenic, thereby explaining the masculinization effects. The results strongly suggest that synthetic progestins merit serious consideration as environmental pollutants.

A review of case material from the Cornell University College of Veterinary Medicine from 1988 to 1996 identified 20 dogs and one cat with definitive or presumed erythema multiforme. An additional 24 dogs and five cats with definitive or presumed erythema multiforme were found in the veterinary literature. Erythema multiforme accounted for only 0.40% and 0.11%, respectively, of all the canine and feline dermatology cases examined over a 9‐year period. German Shepherd dogs and Pembroke Welsh Corgis appeared predisposed. The condition was manifested as a vesiculobullous and/or ulcerative dermatosis in the majority of dogs and cats. In dogs, the most commonly affected body sites included the ventrum (especially axillae and groin), mucocutaneous junctions, oral cavity, pinnae, and footpads. Histopathological findings in cutaneous and mucocutaneous biopsy specimens were consistent with previously published criteria. In dogs, erythema multiforme occurred more frequently in patients receiving drug therapy. In cats, all cases of erythema multiforme were presumed to be drug related. Elimination of the associated trigger factor and supportive care usually resulted in resolution of the erythema multiforme within 1–2 weeks. Four dogs with severe idiopathic erythema multiforme were successfully managed with glucocorticoids or azathioprine.

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