Diet changes in the carbon and nitrogen content of the copepod Metridia lucens

Diel changes in the near-surface (0–50 m) abundance, prosomelength, and carbon and nitrogen content of the copepod Metridialucens were measured in Deep Cove, Doubtful Sound, New Zealand(45°27'S, 167°9'E) between 3 and 6 September 1996. Metridialucens showed maximal abundance a night, suggesting a patternof normal diel vertical migration (DVM). The change in abundancesuggested that the descent of the population occurred –1h prior to dawn and the ascent –1 h after dusk. However,a proportion of the population remained near the surface duringthe day. Although there was no diel pattern in the prosome lengthof M.lucens collected near the surface, there was a marked dielcycle in the measured carbon and nitrogen contents, with maximalvalues being measured towards the end of the night prior tothe downward migration. We suggest that this diet cycle in themeasured elemental content was caused by DVM occurring morestrongly in those animals which had a better body condition,i.e. a higher elemental content per unit length.     

Computational Investigations of the Chalcogen-Substituted Carboxylic Acids RC(=O)XH and RC(=X)OH and their Dimers [RC(=O)XH]2 and [RC(=X)OH]2 (X=S, Se, Te)

Semiempirical and ab initio theoretical methods have been used to investigate molecular structures of the chalcogen-substituted carboxylic acid isomers RC(=O)XH (chalcogenol acid) and RC(=X)OH (chalcogenon acid). A recent experimental report suggests that the chalcogenon isomers, although less stable at room temperature, predominate at low temperature in polar solvents and that there is only a small barrier to isomerization between the isomers. Theoretical calculations have been used to locate minimum energy structures of chalcogen-substituted carboxylic acid isomers and to calculate energy differences between pairs of isomers. Carboxylic acids are well known to dimerize, especially in the gas phase and in non-polar solvents. We have, therefore, also calculated energies of dimerization of the chalcogen-substituted acids by optimizing the geometries of the symmetric dimers. We note that the PM3 level of theory is only qualitatively correct for sulfur- and selenium-containing species but fails even qualitatively for the tellurium-containing compounds. Ab initio results confirm the experimental observations and provide good estimates of both isomerization and dimerization energies. We conclude that for many functional groups with tautomers RC(=X)YH and RC(=Y)XH, the more acidic tautomer is the one with the acid proton on the smaller, more electronegative atom, although in many cases this may not be the more stable tautomer.Electronic Supplementary Material available.     

Novel surface lipids of diapausing Manduca sexta pupae. Long chain oxoalcohol esters of acetoacetic, hydroxybutyric, and acetic acids

Ester components in the surface wax from diapausing tobacco hornworm pupae, Manduca sexta L., were separated by thin layer chromatography and gas-liquid chromatography, and characterized by infrared spectroscopy and gas-liquid chromatography-mass spectrometry. Three groups of esters were identified as natural derivatives of acetic acid, acetoacetic acid, and 3-hydroxybutyric acid. The major ester fraction was identified as a mixture of C26 (10%), C27 (5%), and C28 (85%) oxoalcohol esters of acetoacetic acid. The major homolog consisted of equal amounts of 11-oxooctacosanyl 3-oxobutanoate and 12-oxooctacosanyl 3-oxobutanoate. Lesser amounts of 11- and 12-oxooctacosanyl and n-octacosanyl esters of acetic and 3-hydroxybutyric acids were also identified. The chain length distributions of these C26, C27, and C28 oxoalcohol and n-primary alcohol ester moieties, as well as the isomeric ratios for the 11- and 12-oxoalcohol isomers, were similar to the oxoaldehydes and unesterified oxoalcohols previously identified by Buckner et al (Buckner, J. S., Nelson, D. R., Haak, H., and Pomonis, J. G. (1984) J. Biol. Chem. 259, 8452-8470) as lipid components of the surface wax of M. sexta pupae.     

A stable isotope trace method to measure silicic acid uptake by marine phytoplankton.

A tracer method is described that uses the stable isotope ³⁰Si to measure rates of silicic acid uptake by diatom cultures and natural populations of marine phytoplankton. The method involves (i) incubation of organisms requiring silicic acid for growth in the presence of ³⁰Si-labeled silicic acid, (ii) collection of the resulting particulate silicon, (iii) conversion of the particulate silicon to BaSiF₆, (iv) determination of the ³⁰Si content of BaSiF₆ by solid sample mass spectrometry, and (v) calculation of the uptake rate from the ³⁰Si enrichment of the particulate matter during the incubation. The maximum overall error in the uptake rate measurement is ±10%.     

Enzymes of vitamin B6 degradation. Purification and properties of 5-pyridoxic-acid oxygenase from Arthrobacter sp

5-Pyridoxic-acid oxygenase, a cytoplasmic enzyme formed when Arthrobacter Cr-7 is grown with pyridoxine as a sole source of carbon and nitrogen, was purified about 190-fold to homogeneity from fully induced cells. The enzyme catalyzes Reaction a, (Formula: see text) the essential ring-opening step in the degradation of pyridoxine, and provides a second example of an FAD-dependent oxygenase that adds both two hydrogen and two oxygen atoms to its substrate. 5-Pyridoxic-acid oxygenase has an isoelectric point of 4.6, functions optimally between pH 7 and 8, appears to contain a single subunit of Mr = 51,000 and one FAD (but no iron) per subunit, and is readily resolved by precipitation with ammonium sulfate at pH 3.0. FMN and riboflavin do not replace FAD as coenzyme, but their presence enhances a normally minor side reaction (Reaction b) NAD(P)H + H+ + O2----NAD(P)+ + H2O2 (b) catalyzed by the holoenzyme. Reaction b also is enhanced when the poorly utilized analogues, 3-hydroxy-2-methylpyridine-5-carboxylic acid or NADH, replace 5-pyridoxic acid or NADPH, respectively, as substrates in Reaction a. Each of the enzymes required in two different pathways for degradation of pyridoxine to anabolic intermediates has now been studied. A comparison of these two pathways and their enzymes is provided.     

Dehydroheliamine,a trace alkaloid from the saguaro,Carnegiea gigantea (cactaceae)

Extraction of Carnegiea gigantea yielded a new 3,4-dihydroisoquinoline alkaloid, dehydroheliamine; the structure was confirmed by synthesis.     

Dormancy in peach (Prunus persica L.) flower buds

Morphological studies were carried out with peach flower buds collected monthly in 1989 and 1990, from two months before leaf fall (7 March) until two to three weeks before bloom (7/8 August). Chilled (2–4°C for 30 days) and unchilled buds were exposed to 20 to 25°C, 100% RH and continuous light. Gibberellin A₃ (3 ng or 30 ng) was applied to some of the non-chilled cuttings at three days intervals. Then, 12, 19, and 26 days after they were planted, the buds were sampled and processed for histological studies. Cultured flower buds (chilled or unchilled) had accelerated anther and gynoecium morphogenesis after 12 days under controlled conditions, compared to buds processed immediately after collection from the field. Chilling treatment augmented the bud culture effect, while Gibberellin A₃ applications to the excised buds retarded bud morphogenesis to a stage comparable to that of buds collected directly from the field. This, suggests that the comparatively high levels of Gibberellin A_1/3 we previously found in mid winter [15, 18] could be at least one of the factors that controls floral bud dormancy by retarding anther and gynoecium development.