An insight into the mechanism of the aerobic oxidation of aldehydes catalyzed by N-heterocyclic carbenes.

N-Heterocyclic carbene catalysis for the aerobic oxidation and esterification of aromatic aldehydes was monitored by ESI-MS (MS/MS) and the key intermediates were intercepted and characterized using the charge-tag strategy.

A major QTL for durable leaf rust resistance widely exploited in durum wheat breeding programs maps on the distal region of chromosome arm 7BL.

A recombinant inbred line (RIL) population and a set of advanced lines from multiple crosses were used to investigate the leaf rust (Puccinia triticina Eriks.) resistance carried by the durum wheat cultivar Creso and its derivatives (Colosseo and Plinio). One hundred seventy-six RILs from the cross Colosseo x Lloyd were tested under artificial rust inoculation in the field. The response at the seedling stage was also investigated. A major QTL (QLr.ubo-7B.2) for leaf rust resistance controlling both the seedling and the adult open field based-response was mapped on 7BL, with the favourable allele inherited from Colosseo. QLr.ubo-7B.2 showed R2 and LOD peak values for the area under disease progress curve (AUDPC) equal to 72.9% and 44.5, respectively. The presence and location of QLr.ubo-7B.2 was validated by a linkage disequilibrium-based test using two-year field data of 62 advanced lines from 21 crosses with Creso, Colosseo or Plinio as resistance donors. QLr.ubo-7B.2 maps in a gene-dense region (7BL10-0.78-1.00) carrying several genes/QTLs in wheat and barley for resistance to rusts and other fungal diseases.

Solid-supported reagents for multi-step organic synthesis: preparation and application.

Since the early days of combinatorial chemistry solid-phase organic synthesis has been the method of choice for the production of large libraries. Solution-phase synthesis is again gaining importance especially for the synthesis of parallel arrays of smaller, focussed libraries containing single compounds with high degrees of purity. In the field of solution-phase library generation, the use of solid-supported reagents, catalysts and scavengers is emerging as a leading strategy, combining the advantages of both solid-phase organic synthesis (e.g. allowing the employment of an excess of reagent without the need for additional purification steps) and solution-phase chemistry (e.g. the ease of monitoring the progress of the reactions by applying LC-MS, TLC or standard NMR techniques). An account of some of the most recent advances in this area of research will be presented.

Combined application of analytical techniques for the characterization of polymer supported species

The combined application of a diverse range of analytical techniques is described for the complete analysis of polymer supported molecules. These techniques permit complete description of the FTIR, (1)H NMR, and (13)C NMR spectra. The comparison of supported bicyclo[2.2.2]octane derivatives with analogous species prepared using polymer supported reagents is made.

Interspecies differences in mixed function oxidase activity in birds: Relationship between feeding habits, detoxication activities and organochlorine accumulation.

The relationship between feeding habits and interspecies differences in the detoxication ability of the mixed function oxidase (MFO) system was investigated in birds. The role of MFO (particularly aldrin epoxidase activity) in the detoxication/bioaccumulation of organochlorines was also investigated. Euriphagic (yellow-legged herring gull (Larus cachinnans), black-headed gull (Larus ridibundus), jackdaw (Corvus monedula), magpie (Pica pica) and stenophagic (cormorant (Phalacrocorax carbo), coot (Fulica atra) and sparrow (Passer italiae)) species were collected in northern and central Italy. The following liver microsomal monooxygenase activities were measured: aldrin epoxidase, ethoxyresorufin dealkylation (EROD), benzyloxyresorufin dealkylation (BROD) and pentoxyresorufin dealkylation (PROD). NADPH-and NADH-cytochrome c reductase (NAD(P)H-CYT-CRED) and NADH-ferricyanide reductase (NADH-FERRIRED) activities were also measured in the liver microsomal fraction. Glutathione concentration (GSH) was measured in the liver cytosolic fraction. As a marker of liver damage gamma-glutamyl transpeptidase (GGTP) activity was assayed in the serum. The residues of organochlorines (HCB, pp'DDTs and PCBs) were determined in muscle samples. Omnivorous species, particularly the yellow-legged herring gull, had the highest aldrin epoxidase activities. In the yellow-legged herring gull the activity was approximately twice as high as in the jackdaw (p < 0.05), black-headed gull (p < 0.05) and coot (p < 0.05). Values five times lower were detected in the specialist fish-eater, the cormorant (p < 0.001). The lowest values of aldrin epoxidase activity were detected in the sparrow. Feeding habits were found to be related to evolutionary interspecies differences in MFO activity. A significant statistical correlation (r = 0.656) was found between the 'omnivore index' and MFO detoxication activity expressed as aldrin epoxidation. Organochlorines, and particularly PCBs, were higher in cormorants and yellow-legged herring gulls from a polluted lagoon than in the other species analysed (black-headed gull p < 0.01; sparrow p < 0.001; jackdaw p < 0.01; coot p < 0.001). Levels of pp'DDE were much higher in the cormorant and sparrow than in the other birds. Knowledge of the different species-specific detoxication abilities was found to be a useful tool for the identification of species potentially at risk in environments with high pollution by chlorinated hydrocarbons, or in general contaminants metabolized by the MFO system.

Blood esterase inhibition in birds as an index of organophosphorus contamination: field and laboratory studies.

: With the aim of developing a nondestructive biomarker (serum 'B' esterases) for monitoring bird populations exposed to azamethiphos S((6-chloro-2-oxooxazolo(4,5-b)pyridin-3(2H)-yl)methyl) 0,0-dimethyl phosphorothioate (9Cl), parallel laboratory and field studies were performed. In japanese quail (Coturnix coturnix japonica) treated with azamethiphos at 10 mg kg(-1), serum butyrylcholinesterase (BChE) and carboxylesterase (CE) activities were inhibited by 88% and 35%, respectively, after 24 h. A gradual recovery was observed after 48 and 72 h. With a higher dose (50 mg kg(-1)), the birds died, or were killed 3 h after dosing. Serum BChE and brain acetylcholinesterase (AChE), in birds that were sampled at 3 h, were inhibited by 98% and 92%, respectively. Hepatic microsomal and serum CEs were also inhibited. There was a statistically significant correlation (r=0.9808, p<0.001) between the activities of serum BChE and brain AChE. Swallows (Hirundo rustica) nesting in a stable treated with azamethiphos showed a drastic reduction in BChE (56%) and CE (36%) 24 h after treatment of the stable.

Serum esterase inhibition in birds: a nondestructive biomarker to assess organophosphorus and carbamate contamination.

With the aim of proposing a nondestructive biomarker for monitoring the toxicological risk to birds of exposure to the organophosphorus insecticide azamethiphos and the carbamate insecticide methomyl, laboratory studies were performed on serum "B" esterases in Japanese quail (Coturnix coturnix japonica). The birds received two single dose treatments of each compound (azamethiphos and methomyl), i.e., 50 mg/kg and 250 mg/kg respectively. In the first treatment, serum butyrylcholinesterase (BChE) and carboxylesterase (CbE) were drastically inhibited in the azamethiphos-treated group, 24 h after the dose. No inhibition was detected for BChE and CbE activities in the methomyl-treated group, 24 h after the dose. In the second treatment, the birds died or were sacrificed 3 h after the dose. Serum BChE and brain acetylcholinesterase (AChE) were strongly inhibited after treatment with both insecticides. Serum CbE, hepatic microsomal CbE and 7-ethoxyresorufin dealkylation activities were also inhibited. A statistically significant correlation between serum BChE and brain AChE was found at lethal and sublethal doses of these xenobiotics. The experimental results indicate that the nondestructive biomarker BChE can give an early qualitative and semi-quantitative warning of the toxic effects of organophosphate and carbamate insecticides in birds.

Calcified hilar and mediastinal lymph nodes in an AIDS patient with Pneumocystis carinii infection.

An unusual radiologic manifestation of Pneumocystis carinii infection (enlarged, calcified hilar and mediastinal lymph nodes) in a patient with acquired immunodeficiency syndrome is described. This atypical manifestation caused significant diagnostic confusion. Recognition that P carinii infection can cause calcification of hilar and mediastinal lymph nodes may prevent this confusion and facilitate diagnosis and treatment.

An assessment of pollutants in eggs of Audouin's gull (Larus audouinii), a rare species of the Mediterranean sea.

Audouin's gull (Larus audouinii) is a very rare species endemic to the Mediterranean basin. A sub-population of an estimated 130 pairs is breeding in the Tuscan Archipelago, an area heavily polluted by mercury and chlorinated hydrocarbons. Here we present the data from 5 years spent monitoring the contaminant levels in the eggs of this species. Mercury, selenium, polychlorobiphenyls (PCBs) and DDE concentrations are two to five times higher than in similar species, such as the yellow-legged herring gull, nesting in the same area. The annual trends in these contaminant levels are discussed. In view of the endangered status of Audouin's gull, there is a need to observe closely the developing trend of contamination in this species.

Trace elements and chlorinated hydrocarbons in eggs of Pelecanus crispus, a world endangered bird species nesting at Lake Mikri Prespa, North-western Greece.

Eggs of the Dalmatian pelican, Pelecanus crispus, collected from 1984 to 1986 at Lake Mikri Prespa, north-western Greece, contained residues of trace elements and PCBs at low concentrations, and of DDE at rather high concentrations. DDE is negatively related to eggshell thickness. Eggshell thickness was reduced by 12-20% in comparison with the pre-1947 (before DDT use) eggshell thickness. However, this decrease did not affect the reproductive success of this species. The main fish species eaten by the Dalmatian pelican at Lake Mikri Prespa were analyzed for pollutants. All the fish contained low concentrations of residues. The contribution of the diet while the birds are on the wintering grounds is unknown. Recommendations for a monitoring programme of pollutants in eggs of the Dalmatian pelican, a world-endangered species, are proposed.

Long term monitoring of pollutants in eggs of Yellow-legged Herring Gull from Capraia island (Tuscan Archipelago).

Chlorinated hydrocarbons (hexachlorobenzene, lindane, pp'DDE, polychlorinated biphenyls) and trace elements (Hg, Se, Cd, Pb) were determined in eggs of Yellow-legged Herring Gull (Larus cachinnans) collected in an island of the Tyrrhenian Sea during the period 1981-1986. PCBs levels vary on the average between 30.4µg g(-1) d.w. in 1981 to 56.1 µg g(-1) d.w. in 1983. The capillary chromatograms revealed the presence of about 30 somers of PCBs without significant variations in the eggs of the same year; more than 50% of the residues is made up only three isomers: the 22'44'55', the 22'344'5' and the 22'344'55'. Average DDE residues were 7-8 times lower than those of PCBs and declined during the period (from 9.2 µg g(-1) d.w. in 1981 to 4.5 µg g(-1) d.w. in 1986). Cadmium and lead are present in low concentrations. The average levels of mercury and selenium are around 2-2.5 µg g(-1) d.w., and a cumulative correlation, on a molar basis, exists between these two elements.