NMR and molecular orbital studies of isomerism and tautomerism in oximes of 2-acyl cyclic 1,3-diones.

Molecular orbital calculations and 13C and 15N NMR experiments have been performed on the O-methyl oximes of two types of 2-acyl cyclic 1,3-diones. One (III; X = CH2) was based on cyclohexane, and the other (X = O) on pyran. The data indicate that both the cyclohexane and pyran compounds prefer to exist as the oxime, rather than the enamine isomer. Two equivalent, interconverting, keto-enol tautomers exist in the cyclohexane compound. The pyran compound exists as the lactone-enol tautomer. Our results have implications in the design of herbicidal compounds and drugs containing similar tautomeric systems.

Solution volume and seed number: Often overlooked factors in allelopathic bioassays.

Cucumber seeds were germinated under various combinations of solution volume and seed number with a range of ferulic acid concentrations. At each concentration, radicle growth decreased as the relative amount of ferulic acid available per seed increased from χ (25 seeds/5 ml) to 5χ (5 seeds/5 ml) to 19χ (25 seeds/95 ml). With 2.0 mM ferulic acid in buffered solution, radicle lengths after 48 hr ranged from 71 to 47% of control. The amount of ferulic acid remaining in 2.0 mM solution after 48 hr was directly proportional to the amount initially available per seed, and ranged from 9 to 91%. Solution volume and seed number also significantly affected inhibition by vanillic acid, caffeic acid, and juglone. With 0.1 mM juglone, radicle lengths after 48 hr were 88% of control with 25 seeds/5 ml, 68% with 5 seeds/5 ml, and 56% with 25 seeds/90 ml. The data demonstrated that lower phytotoxin concentrations can produce equivalent or greater inhibitory effects than higher concentrations when the amount available per seed for uptake is greater. Equivalent inhibition of radicle growth was observed with 1.0 mM (5 seeds/5 ml) and 2.0 mM (25 seeds/5 ml) ferulic acid. Available literature on herbicides indicates that similar effects occur in greenhouse and field studies.

Investigation of some amino acid analogues and metabolites as inhibitors of wool and hair growth.

Sheep were given intravenous infusions of ethionine together with cycloleucine or reduced glutathione, in attempts to prevent the inhibition of wool growth by ethionine. Other sheep were given cycloleucine alone to measure effects on wool growth. Twenty-two compounds related to cystine, methionine, ethionine, lysine, phenylalanine and tyrosine were given as intravenous infusions to sheep to investigate their potential as depilatory agents. Nineteen of these compounds were also tested in mice during their first cycle of hair growth. The concurrent administration of cycloleucine with ethionine prevented the weakening of wool fibres caused by ethionine, but reduced glutathione was ineffective. Cycloleucine weakened wool fibres, as judged subjectively, and caused a small reduction in fibre diameter. Selenocystine and selenomethionine caused some hair loss in mice but selenocystine was also toxic. Both seleno-amino acids were toxic for sheep; selenocystine was lethal at 0.025 mmol kg-0.75 and selenomethionine at 0.09 mmol kg-0.75. Doses that permitted survival of sheep did not have depilatory effects. However, the presence of autophagic vacuoles in the cytoplasm of follicle bulb cells of sheep indicated that a toxic dose of selenocystine had potential depilatory activity. Other compounds investigated did not induce loss of wool or hair. Some compounds, notably 3-methylthiopropionic acid and S-(2-aminoethyl)-L-cysteine, were toxic to mice but not sheep. The methionine analogue, methoxinine (O-methyl-DL-homoserine), caused a substantial reduction in the strength of wool fibres and a prolonged alteration of the crimp pattern. It is suggested tentatively that cycloleucine inhibits methionine adenosyltransferase and thereby reduces or prevents the formation of S-adenosylethionine. The failure of various compounds related to methionine and ethionine to have any depilatory activity in sheep supports the view that ethionine influences wool growth via the formation of S-adenosylethionine.