John P. Bartley

Comprehensive chemical profiling of gramineous plant root exudates using high-resolution NMR and MS

Root exudates released into soil have important functions in mobilizing metal micronutrients and for causing selective enrichment of plant beneficial soil micro-organisms that colonize the rhizosphere. Analysis of plant root exudates typically has involved chromatographic methods that rely on a priori knowledge of which compounds might be present. In the research reported here, the combination of multinuclear and 2-D NMR with GC-MS and high-resolution MS provided de novo identification of a number of components directly in crude root exudates of different plant types. This approach was applied to examine the role of exudate metal ion ligands (MIL) in the acquisition of Cd and transition metals by barley and wheat. The exudation of mugineic acids and malate was enhanced by Fe deficiency. which in turn led to an increase in the tissue content of Cu, Mn, and Zn. The presence of elevated Cd maintained at a free activity pCd of 8.8 (10(-8.8) M), resulted in reduced phytosiderophore production by Fe deficient plants. The buffer morpholinoethane sulfonate (MES), which is commonly used in chelator-buffering nutrient solutions, was detected in the root exudate mixture, suggesting uptake and re-secretion of this compound by the roots. The ability to detect this compound in complex mixtures containing organic acids, amino acids, and other substances suggests that the analytical methods used here provide an unbiased method for simultaneous detection of all major components contained in root exudates.

Effects of drying on flavour compounds in Australian-grown ginger (Zingiber officinale).

The volatile compounds responsible for the flavour of Australian-grown ginger have been extracted using supercritical carbon dioxide. Both fresh and dried ginger samples have been examined and the major effects of the drying process are a reduction in gingerol content, an increase in terpene hydrocarbons and the conversion of some monoterpene alcohols to their corresponding acetates. © 2000 Society of Chemical Industry

Computer simulation of the corrosion inhibition of copper in acidic solution by alkyl esters of 5-carboxybenzotriazole

A series of alkyl esters (methyl, butyl, hexyl, and octyl) synthesised from a mixture of 4- and 5-carboxybenzotriazole (4-CBTAH and 5-CBTAH) inhibited copper corrosion in aerated solution (pH � 0). Inhibition efficiency (IE%) of the protonated esters (CBTAH þ -R) increased with hydrocarbon chain length and this is attributed to chemisorption (through azole ring N) and increased physical adsorption as more methyl groups are introduced. A modelling package employing molecular mechanics and molecular dynamics has been used to simulate the docking of a single protonated species (5-CBTAH þ -R) onto a clean copper (1 1 0) surface. A decrease in potential energy was associated with the flattening of the ester ring system onto the surface and further decreases in energy were associated with the extension of the aliphatic chain onto the surface. The crude binding energy (Ebind) of each ester with the surface was estimated and this energy also increased regularly with carbon chain length. The study suggests that molecular modelling and calculation of Ebind of a single molecule on a specified metallic surface can be used to predict the inhibition performance of compounds whose structures change in a regular way. 2002 Elsevier Science Ltd. All rights reserved.

Retention of volatile organic flavour/fragrance components in the concentration of liquid foods by osmotic distillation

Abstract Nine types of hydrophobic microporous membranes were tested for their influence on the retention of a range of volatile organic species when model aqueous solutions of the latter were subjected to osmotic distillation. Similar studies were carried out on Gordo grape juice and Valencia orange juice. Gas chromatography–mass spectrometry head-space analyses of the feed materials coupled with scanning electron microscopy and image analyses of the membranes used indicated that lower organic volatiles flux to water flux ratios occurred when pore sizes at the membrane surface were relatively large. The results have been interpreted in terms of differences in feed-membrane and stripper-membrane boundary layer resistances to organic volatiles transport resulting from different degrees of liquid intrusion into the membrane pores.

Volatile Constituents from the Leaves of Chenopodium ambrosioides L.

ABSTRACT The composition of the essential oil of Chenopodium ambrosioides L. was analyzed by capillary GC and GC/MS. Forty-nine compounds were identified accounting for 96.86% of the oil. The major compounds were limonene (32.5%) and trans-pinocarveol (26.7%).

Purification of ptaquiloside, a carcinogen from Pteridium aquilinum

Ptaquiloside, the major carcinogen of bracken fern (Pteridium aquilinum), was isolated in high yield from milled freeze-dried plant material. Because the compound is unstable, a new method was devised to avoid steps which caused loss of activity. Modern multipulse and 2D NMR techniques allowed confirmation of the previously proposed structure, although some assignments were shown to be incorrect.

Alkaloids of Stephania bancroftii

Abstract Six alkaloids were found in a methanol extract of the rhizomes of Stephania bancroftii : (−)-tetrahydropalmatine, (−)-stephanine, (−)-crebanine, ayuthianine, (+)-sebiferine and (+)-stepharine. Complete assignment of the 1 H and 13 C NMR spectra is reported for several of these compounds for the first time.

Electrospray ionization mass spectrometry of stable nitroxide free radicals and two isoindoline nitroxide dimers

Electrospray ionization (ESI) mass spectra were recorded for a range of substituted isoindoline nitroxides, two isoindoline nitroxide dimers and two piperidinyl nitroxides. In all cases the dominant molecular species arise from oxidation rather than protonation, an unusual process in ESI. Fragment ion spectroscopy was used to establish fragmentation mechanisms for the nitroxides under ESI conditions.

Serine isotopomer analysis by 13C-NMR defines glycine-serine interconversion in situ in the renal proximal tubule

[2-(13)C]glycine metabolism was studied in freshly isolated rat renal proximal tubules. Mitochondrial coupling of the glycine cleavage complex (GC) and serine hydroxymethyltransferase (SHMT) was confirmed by the formation of three serine isotopomers, [2-(13)C]-, [3-(13)C]- and [2,3-(13)C]serine, detected by 13C-NMR. Incubation with different fractions of 13C-labelled glycine altered the labelling pattern of the serine isotopomers predictably and allowed calculation of the 13C-labelled fractions of total glycine and methylene in N5,N10-methylenetetrahydrofolate (m-THF) available for serine metabolism. Within 20 min there was a fall in labelled glycine (to 42 +/- 3, 68 +/- 3 and 93 +/- 2%, (n = 4, mean +/- S.D.) from 50%, 75% and 100% 13C-labelled added glycine respectively), followed by a slow rate of endogenous glycine formation for up to 80 min incubation. The C2 of glycine was the source of more than 90% of the methylene group of m-THF formed. Gas chromatography-mass spectroscopy (GC-MS) showed that greater than 50% of serine formed was unlabelled. GC and SHMT proceeded in the direction of serine formation. Serine isotopomer analysis by NMR and GC-MS allowed the actions of GC and SHMT and de novo contributions to glycine, serine and m-THF to be monitored in situ in fresh renal proximal tubules.

The effect of pretreatment on methanesulfonic acid-catalyzed hydrolysis of bagasse to levulinic acid, formic acid, and furfural

A major challenge that must be overcome for the commercial production of levulinic acid from lignocellulosics is to reduce equipment blockage and corrosion. Methanesulfonic acid (MSA), a relatively low corrosive acid, was used to produce organic acids and furfural from pretreated sugarcane bagasse. In general, the type of pretreatment did not affect levulinic acid yield, though it affected furfural yield. However, soda pretreated bagasse produced the highest yields of levulinic acid (∼75 mol%) and furfural (∼85 mol%), albeit under optimized conditions. Hydrolysis residue consists primarily of lignin that has been modified and/or condensed to humic substances, fatty acids, and oligomeric sugars. A conceptual biorefinery utilizing 1 ton of dry bagasse, alkaline-pretreatment, and MSA as a catalyst produced 165 kg soda lignin, 190 kg and 89 kg of levulinic acid and formic acid respectively, and 40 kg furfural.