Electrostatic control of regioselectivity via ion pairing in a Au(i)-catalyzed rearrangement

Ion pairing controls regioselectivity in a Au(i)-catalyzed rearrangement by favoring the more polar product-determining transition state.

Enrichment of an Endosulfan-Degrading Mixed Bacterial Culture

ABSTRACT An endosulfan-degrading mixed bacterial culture was enriched from soil with a history of endosulfan exposure. Enrichment was obtained by using the insecticide as the sole source of sulfur. Chemical hydrolysis was minimized by using strongly buffered culture medium (pH 6.6), and the detergent Tween 80 was included to emulsify the insecticide, thereby increasing the amount of endosulfan in contact with the bacteria. No growth occurred in control cultures in the absence of endosulfan. Degradation of the insecticide occurred concomitant with bacterial growth. The compound was both oxidized and hydrolyzed. The oxidation reaction favored the alpha isomer and produced endosulfate, a terminal pathway product. Hydrolysis involved a novel intermediate, tentatively identified as endosulfan monoaldehyde on the basis of gas chromatography-mass spectrometry and chemical derivatization results. The accumulation and decline of metabolites suggest that the parent compound was hydrolyzed to the putative monoaldehyde, thereby releasing the sulfite moiety required for growth. The monoaldehyde was then oxidized to endosulfan hydroxyether and further metabolized to (a) polar product(s). The cytochrome P450 inhibitor, piperonyl butoxide, did not prevent endosulfan oxidation or the formation of other metabolites. These results suggest that this mixed culture is worth investigating as a source of endosulfan-hydrolyzing enzymes for use in enzymatic bioremediation of endosulfan residues.

Absorption, Translocation, and Metabolism of14C-Chlorsulfuron in Canada Thistle (Cirsium arvense)

Absorption of14C-chlorsulfuron {2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] carbonyl] benzenesulfonanide} by Canada thistle [Cirsium arvense(L.) Scop. # CIRAR] was 39% following foliar treatment and 16% when added to a nutrient solution in which the plants were growing. Translocation from the treated organ was limited regardless of treatment method; 10% of the applied14C moved out of the treated leaf and 10% moved from the roots to other parts of the plant following absorption from the nutrient solution. When applied as a foliar treatment,14C-chlorsulfuron had not been metabolized by Canada thistle 48 h later. However, when14C-chlorsulfuron was added to the nutrient solution and absorbed by the roots, nearly 25% of the14C in the plants was present as a polar product(s), 13% had an Rf value identical to benzenesulfonamide standards, and the remaining 62% was chlorsulfuron. Chlorsulfuron was not transformed similarly in a nutrient solution after 6 days in the absence of plants. Suppression of regrowth was the primary injury symptom observed following chlorsulfuron application. Chlorsulfuron also reduced whole plant weight and root bud number and weight.

Fat metabolism in higher plants. β-hydroxylation of fatty acids by a soluble preparation from maturing avocado mesocarp

1. An avocado supernatant fraction converted fatty acids of medium chain length (C8–C12) into a polar product. 2. The product was identified as the β-hydroxy derivative of the substrate by g.l.c. and t.l.c. analysis. 3. For hydroxylation of the fatty acids, CoA, ATP and molecular oxygen were required. Acyl carrier protein gave some stimulation. The reaction took place with oxygen alone if acyl-CoA was the substrate. 4. Hydroxylation was maximal with decanoic acid but dodecanoic acid and octanoic acid were also very active. Acids of shorter or longer chain lengths were not hydroxylated. 5. NAD+ concentration caused complete inhibition at 0.5mm and may be an important control mechanism for the reaction in vivo. 6. The reaction was inhibited by iodoacetamide and by bipyridyl and carbon monoxide, indicating involvement of thiol and heavy metal groups.