Melanin Biosynthesis From Dopamine. II. A Mass Spectrometric and Collisional Spectroscopic Investigation

Electron impact (EI) and fast atom bombardment (FAB) mass spectrometry together with collisional activation (CA) experiments were applied to the study of the oxidation pathway of dopamine by tyrosinase. In order to prevent attachment of the protein to the highly reactive intermediates, ultrafiltration was employed to remove the enzyme at different reaction times. FAB, privileging molecular species formation, was successfully used for identification of transient intermediates and their relative concentrations with respect to time, directly in the reaction mixture. The presence of isobaric molecular species made chromatographic separation necessary. Further EI mass spectrometry and collision spectroscopy led to structural identification of pure components. Of these, dopamine-o-quinone, leucoaminochrome, and aminochrome semiquinone were characterized for the first time as real intermediates in dopamine melanogenesis, in agreement with previous hypotheses. This approach elucidated the pathway of dopamine melanogenesis.     

The impact of sarcoptic mange Sarcoptes scabiei on the British fox Vulpes vulpes population

• 1 Disease epizootics can significantly influence host population dynamics and the structure and functioning of ecological communities. Sarcoptic mange Sarcoptes scabiei has dramatically reduced red fox populations Vulpes vulpes in several countries, including Britain, although impacts on demographic processes are poorly understood. We review the literature on the impact of mange on red fox populations, assess its current distribution in Britain through a questionnaire survey and present new data on resultant demographic changes in foxes in Bristol, UK.
• 2 A mange epizootic in Sweden spread across the entire country in < 10 years resulting in a decline in fox density of up to 95%; density remained lowered for 15–20 years. In Spain, mange has been enzootic for > 75 years and is widely distributed; mange presence was negatively correlated with habitat quality.
• 3 Localized outbreaks have occurred sporadically in Britain during the last 100 years. The most recent large‐scale outbreak arose in the 1990s, although mange has been present in south London and surrounding environs since the 1940s. The questionnaire survey indicated that mange was broadly distributed across Britain, but areas of perceived high prevalence (> 50% affected) were mainly in central and southern England. Habitat type did not significantly affect the presence/absence of mange or perceived prevalence rates. Subjective assessments suggested that populations take 15–20 years to recover.
• 4 Mange appeared in Bristol's foxes in 1994. During the epizootic phase (1994–95), mange spread through the city at a rate of 0.6–0.9 km/month, with a rise in infection in domestic dogs Canis familiaris c. 1–2 months later. Juvenile and adult fox mortality increased and the proportion of females that reproduced declined but litter size was unaffected. Population density declined by > 95%.
• 5 In the enzootic phase (1996–present), mange was the most significant mortality factor. Juvenile mortality was significantly higher than in the pre‐mange period, and the number of juveniles classified as dispersers declined. Mange infection reduced the reproductive potential of males and females: females with advanced mange did not breed; severely infected males failed to undergo spermatogenesis. In 2004, Bristol fox population density was only 15% of that in 1994.

     

Collisional Spectroscopy in Structural Characterization of Melanins: I. A First Study on |C8H7ON|+· Ions Originating From Pyrolysis of Biosynthetic and Synthetic Tryptophan Melanins

The structural investigation of four bio- and synthetic melanins, obtained by the action of polyphenol oxidase from potatoes and Psalliota campestris mushrooms and of tyrosinase from Sepia officinalis on tryptophan, or by means of performic oxidation, has been carried out by thermal decomposition performed in the ion source of a mass spectrometer. The structural characterization of the ionic species |C₈H₇ON|⁺· common and abundant for all the examined compounds, has been obtained by accurate mass measurements and collisional spectroscopy. These mass spectrometric techniques have shown unequivocally for ionic species | C₈H₇ON| ⁺· the structure of 2-indolinone.