Cytochrome P450cam-catalyzed oxidation of a hypersensitive radical probe.

trans-1-Phenyl-2-vinylcyclopropane, a hypersensitive radical probe, is oxidized by cytochrome P450cam (CYP101) to a diastereomeric mixture of the corresponding epoxide (81%), (trans-2-phenylcyclopropyl)acetaldehyde (6%), and trans-5-phenyl-2-penten-1,5-diol (13%). trans-5-Phenyl-2-penten-1-ol and (trans-2-phenylcyclopropyl)ethane-1,2-diol are not detectably formed. Authentic standards of all the products have been synthesized and used to establish the identities (or the absence) of the metabolites. Studies with [18O]H2O demonstrate that the oxygens at positions 1 and 5 in the rearranged diol derive from molecular oxygen and water, respectively. Catalytic turnover of the enzyme is required for product formation from the olefin, but incubation of the epoxide metabolite with the enzyme, or with buffer alone, yields both the aldehyde and the rearranged diol products. The absence of trans-5-phenyl-2-penten-1-ol implies that the lifetime of the putative radical intermediate is so short that its existence as a discrete entity is questionable. A cationic intermediate is unlikely but cannot be excluded because the same metabolites are formed in a secondary reaction, even at pH 8.0, from the epoxide. The results provide no evidence for the involvement of radicals or cations in the epoxidation reaction, in agreement with results on the oxidation of olefins in organic solvents by metalloporphyrin catalysts.     

Characterization of Viticultural Terroirs using a Simple Field Model Based on Soil Depth – II. Validation of the Grape Yield and Berry Quality in the Anjou Vineyard (France)

Soil and climate are major constituents of the French notion of Terroir. This concept implies that there is a strong relationship between the composition of the grape, the characteristics of the wine and the territory of production. To study this link, a new method of characterization of the Terroir, including geological and pedological factors, was investigated. It uses a field model based on depth and clay content of soil, together with the degree of weathering of the parent rock. Consequently, for every type of parent rock belonging to a given geologic stage, there are a series of soils that show different stages of pedological evolution. According to the model, three kinds of soils are distinguished with regards to the weathering intensity of the parent rock, that are named weakly weathered rock (WWR), moderately weathered rock (MWR) and strongly weathered rock (SWR). By hypothesis, each soil type is considered as a homogeneous unit for vine production from the viewpoint of ecophysiological factors. Each terroir unit defined by this method is called a Basic Terroir Unit (BTU). To validate this hypothesis, experimental plots planted with Chenin and Cabernet Franc vines were studied over three consecutive seasons (2000–2002), in the Anjou vineyard (Loire Valley – France). The major BTUs developed on the two most important geological systems of Anjou (Brioverian and Ordovician–Devonian), were studied. Results showed that the berries of vines cultivated in WWR were significantly smaller, richer in sugars and anthocyanins and had a Total Phenolic Index higher than those of the vines cultivated in SWR. They also had a lower titratable acidity. Cabernet Franc vines cultivated in MWR had berries with sugar and anthocyanin contents but also total phenolics very close to those of WWR. With Chenin vines there was a good relationship between the global pool of free aromas of berries and the BTU type. The study showed significant relationships between the quality of grapes and the measured values of several ecophysiological variables such as the water supply regime or the timing of budburst.     

The induction of chromosomal damage in rat hepatocytes and lymphocytes II. Alkylation damage and repair of rat-liver DNA after diethylnitrosamine,dimethylnitrosamine and ethyl methanesulphonate in relation to clastogenic effects

Rat-liver DNA alkylation by diethylnitrosamine (DEN), dimethylnitrosamine (DMN) and ethyl methanesulphonate (EMS) was studied in an attempt to relate chromosome-damaging effects of these agents (the formation of micronuclei in hepatocytes; see preceding paper) to specific alkylation patterns. No correlation was observed between the induction of micronuclei and liver DNA N-alkylation, measured as 3- and 7-alkyl-purines. O⁶-Alkylguanine is probably not involved in micronucleus induction because it is lost from DNA too rapidly to explain the much more persistent clastogenic effects. In contrast, both the initial amounts of alkylphosphotriesters and the persistencies of these products roughly paralleled the respective effects on micronucleus induction. The possible involvement of alkylphosphotriesters or other O-alkylation products of comparable stabilities is discussed. Results with DMN suggest that part of the primary DNA methylation damage is converted into a secondary (DNA) lesion and that both the primary and secondary lesion(s) contribute to the process of micronucleus formation.     

The Importance of Hydrodynamics for Protected and Endangered Biodiversity of Lowland Rivers

This paper examines the relationship between protected and endangered riverine species (target species) and hydrodynamics in river-floodplain ecosystems, combining ecological and policy-legal aspects of biodiversity conservation in river management. The importance of different hydrodynamic conditions along a lateral gradient was quantified for various taxonomic groups. Our results show that (i) target species require ecotopes along the entire hydrodynamic gradient; (ii) different parts of the hydrodynamic gradient are important to different species, belonging to different taxonomic groups; (iii) in particular low-dynamic parts are important for many species and (iv) species differ in their specificity for hydrodynamic conditions. Many species of higher plants, fish and butterflies have a narrow range for hydrodynamics and many species of birds and mammals use ecotopes along the entire gradient. Even when focussing only on target species, the entire natural hydrodynamic gradient is important. This means that the riverine species assemblage as a whole can benefit from measures focussing on target species only. River reconstruction and management should aim at re-establishing the entire hydrodynamic gradient, increasing the spatial heterogeneity of hydrodynamic conditions.