Red swamp crayfish (Procambarus clarkii) were placed for a period of 7 days in Bayou Trepagnier, a Louisiana waterway which received petroleum-laden effluents from a manufacturing complex several decades ago. However, coolant water from the plant continued to be released into the bayou until 1995. Analyses of sediments at the exposure site revealed heavy contamination by lead, chromium, and copper, while concentrations of arsenic and cadmium were very low. Significant bioaccumulation of lead was observed in the hepatopancreas and gills of 7-day-exposed crayfish, whereas chromium accumulated the most in the gills and blood. Concentrations of copper in the crayfish did not change during the course of the study, suggesting that this essential metal constituent of the respiratory pigment is successfully regulated even when crayfish are exposed to relatively high levels of copper in the sediments. There was no metal accumulation in the abdominal muscle of the crayfish. That damage to the hepatopancreas occurred during the exposure is suggested by histopathological studies which revealed swollen and vacuolated R cells and an increase in the pH of the digestive juices. Blood glucose levels, as well as ovarian and hepatopancreatic indices, were unchanged. This study demonstrates that accumulation of nonessential metals in crayfish tissues in a wetland environment contaminated by mixed pollution (metals and hydrocarbons) reflects the concentrations of metals in the sediment.
1,3,5-Tris(5-substituted sa1icylamino)cyclohexanes (H,L; R = H, NO, or OMe) have been synthesized by Schiffbase condensation between cis-1.3.5-triaminocyclohexane and a substituted salicylaldehyde, followed by reduction with KBH,. Reaction of these compounds with gallium(lll), indium(ll1) and iron(ii1) salts gave neutral six-co-ordinate N,O, complexes of type [ML] ( M = Ga, In or Fe). The complexes have been characterized by a combination of infrared, l H and 13C-{lH} NMR and mass spectroscopy. The distribution coefficients between octan-1 -01 and water indicate that the complexes are lipophilic. The electronic absorption spectra of the high-spin iron( 111) complexes show ligand-tometal charge-transfer bands in the 450-500 nm range. The structures of five of the complexes have been confirmed by single-crystal X-ray crystallography.
The reaction of P4S10 with acyloins, RC(O)CH(OH)R, in refluxing dioxane, followed by the addition of alkylating agents, forms dithiolene thiophosphoryl thiolate compounds, (R2C2S2)P(S)(SR'), which are readily isolated and purified. The compounds that have been prepared and identified spectroscopically are those with R = p-anisyl, R' = Me (1); R = p-anisyl, R' = Bz (2); R = Ph, R' = Me (4); R = Et, R' = Bz (5). Compounds 1, 2, and 4 were structurally characterized by X-ray crystallography and found to possess a tetrahedral coordination geometry about the phosphorus atom, with overall Cs symmetry. In each case, the mirror plane bisects the dithiolene S-P-S chelate and contains the thiophosphoryl bond, which ranges in length from 1.9241(8) to 1.9361(7) A. The use of 2-(bromomethyl)naphthalene as organic electrophile in the P4S10/acyloin reaction produced bis(2-methylnaphthalenyl) disulfide as the only identifiable product. The substitution of Lawesson's reagent for P4S10 in reactions with acyloins produced deoxy acyloin rather than products resulting from chalcogen exchange. Compounds 1-2 and 4-5 are Group 5 analogues of 1,3-dithiol-2-ones, (R2C2S2)C=O, and undergo a similar hydrolysis in aqueous base to liberate ene-1,2-dithiolate dianions from which corresponding metal dithiolene complexes may be prepared. Deprotection of 1 in MeO-/MeOH, followed by the addition of NiCl2.6H2O and then I2, produces square planar [Ni(S2C2(C6H4-p-OCH3)2)2] (8) in 93% yield. A high-resolution structure of 8 (P) reveals dithiolene C-C and C-S bond lengths that are clearly indicative of the thionyl radical monoanionic nature of the ligand. The use of isolated (R2C2S2)P(S)(SR') compounds as a dithiolene ligand source for the preparation of metal dithiolene complexes offers the advantages of clean reactivity and high yield.
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