Preferential Conversion Research Articles

Application of a SUGAR model to analyse sugar accumulation in peach cultivars that differ in glucose–fructose ratio

SUMMARYA SUGAR model, which was established to predict the partitioning of carbon into sucrose, glucose, fructose and sorbitol in fruit mesocarp of peach cultivars (Prunus persica (L.) Batch) with normal glucose: fructose ratio (G:F) of 0·8–1·5, was evaluated and extended for peach cultivars with a high G:F ratio of 1·5–7·8. The extended model (SUGARb) is more generic and assumes a high G:F ratio to be due to preferential transformation of sorbitol into glucose, preferential utilization of fructose or preferential conversion of fructose into glucose. The simulated seasonal variations in sugars via the SUGARb-model-matched experimental data for three normal and three high G:F cultivars well, and accurately exhibited G:F ratio characteristics. The relative rates of sucrose transformation into glucose and fructose differed according to cultivar but not according to G:F status. Compared with hexosephosphate interconversion, a lower production rate of fructose than glucose from sorbitol, and/or a higher utilization rate of fructose than that of glucose might be preferential alternatives for forming high G:F ratios in the high G:F cultivars studied in the present study, which is discussed in the light of recent results on enzyme activities.

NO Reduction Over Noble Metal Ionic Catalysts

In last 40 years, catalysis for NOx removal from exhaust gas has received much attention to achieve pollution free environment. CeO2 has been found to play a major role in the area of exhaust catalysis due to its unique redox properties. In last several years, we have been exploring an entirely new approach of dispersing noble metal ions in CeO2 and TiO2 for redox catalysis. We have extensively studied Ce1−xMxO2−δ (M = Pd, Pt, Rh), Ce1−x−yAxMyO2−δ (A = Ti, Zr, Sn, Fe; M = Pd, Pt) and Ti1−xMxO2−δ (M = Pd, Pt, Rh, Ru) catalysts for exhaust catalysis especially NO reduction and CO oxidation, structure–property relation and mechanism of catalytic reactions. In these catalysts, lower valent noble metal ion substitution in CeO2 and TiO2 creates noble metal ionic sites and oxide ion vacancy. NO gets molecularly adsorbed on noble metal ion site and dissociatively adsorbed on oxide ion vacancy site. Dissociative chemisorption of NO on oxide ion vacancy leads to preferential conversion of NO to N2 instead of N2O over these catalysts. It has been demonstrated that these new generation noble metal ionic catalysts (NMIC) are much more catalytically active than conventional nano crystalline noble metal catalysts especially for NO reduction.

Phenothiazines are slowly oxidizable substrates of horseradish peroxidase

Reactions of peroxidase oxidation of triftazine and thioproperazine have been investigated in the presence of horseradish peroxidase using steady state kinetic methods. It has been shown that phenothiazines are slowly oxidizable substrates for horseradish peroxidase. kcat and Km values have been determined in the range of pH from 4.5 to 7.5. The study of co-oxidation of phenothiazines and o-dianisidine (ODN) revealed that in the presence of aminazine and ODN in the reaction medium both substances follow sequential oxidation. ODN oxidation was not observed until full conversion of aminazine. At pH 4.5-5.5 thioproperazine bound to the enzyme-substrate complex and caused a nticompetitive inhibition of peroxidase. At pH>5.5 sequential substrate oxidation with preferential thioproperazine conversion occurred. In the range of pH from 4.5 to 7.5 triftazine did not influence ODN oxidation.

ICHNOLOGY OF SILICEOUS FACIES IN THE EOCENE TALLAHATTA FORMATION (EASTERN UNITED STATES GULF COASTAL PLAIN): IMPLICATIONS FOR DEPOSITIONAL CONDITIONS, STORM PROCESSES, AND DIAGENESIS

The Eocene Tallahatta Formation exposed in the eastern United States Gulf coastal plain includes enigmatic siliceous facies characterized by variably indurated claystone, porcelanite, and subordinate thin sandstone and siltstone beds. Ichnosedimentologic studies at localities in eastern Mississippi and Alabama indicate that these strata accumulated in middle-shelf settings (offshore transition). Sandstone and siltstone beds record storm events of variable magnitude. Moderately diverse Cruziana ichnofacies assemblages that reflect overall hospitable fair-weather conditions characterize most mudrock intervals; however, periodically oxygen-deficient or otherwise unfavorable conditions are indicated locally by unbioturbated mudrock. Storm beds associated with bioturbated mud typically contain mixed Cruziana-Skolithos ichnofacies assemblages reflecting the work of both opportunistic(?) and fair-weather tracemakers. In contrast, ichnofabrics of storm beds that were not disrupted by fair-weather bioturbation likely record short-term colonization of substrates by organisms that were transported, sorted, and redeposited by storm currents. Ichnofabrics and diagenesis of the siliceous facies are linked. Ichnofossils locally influenced silica cementation in some storm beds, whereas preferential conversion to porcelanite of siliceous clay intervals immediately below and above many storm beds dramatically enhanced the visibility of fair-weather ichnofabrics.

Studies on in-vivo capacity of thyroxine deiodinating system in rat liver: biliary excretion of several iodothyronines after increasing loading doses of thyroxine.

Eighteen male rats were inserted with polyethylene tubings into bile duct and femoral vein and two rats each were injected a series of doses from 5 to 1280 micrograms L-thyroxine into a venous cannula. The bile was collected for three subsequent 2-hr periods and the excretion of total thyroxine (T4), triiodothyronines (T3 and rT3) and all diiodothyronines (3,3'-T2, 3,5-T2 and 3',5'-T2) was estimated as well as that of conjugated T4 and T3. The excretion of all compounds was considerably increased as early as within the first 2-hr period. Almost linear dose-response relationship was found between the dose of T4 and its biliary excretion up to the dose of 640 micrograms, only smaller increase being observed after 1280 micrograms T4. Similar relationship was found also in the excretion of diiodothyronines, while that of triiodothyronines after 1280 micrograms T4 was slightly less than after 640 micrograms T4. The excretion of rT3 was consistently about twice as high as that of T3. The data on diiodothyronine excretion suggested a preferential conversion of rT3 to 3',5'-T2 and that of T3 to 3,5-T2 over that to 3,3'-T2. The ratio of 3,5-T2/T3 after different doses of T4 was about 2--4 times higher than that of 3',5'-T2/rT3 suggesting the higher deiodination rate of T3 than that of rT3.

Pharmacology and therapeutic efficacy of capecitabine: focus on breast and colorectal cancer

Capecitabine (N -pentyloxycarbonyl-5-deoxy-5-fluorocytidine), an oral prodrug of 5-fluorouracil, has provided compelling efficacy data for the treatment of metastatic breast cancer and stage III or IV colorectal cancer, both as monotherapy and in combination regimens. The preferential conversion of capecitabine to 5-fluorouracil in neoplastic tissues renders this fluoropyrimidine particularly appealing for clinical use. The enzyme thymidine phosphorylase, which mediates the final step of the capecitabine activation pathway, is expressed in higher concentration in neoplastic than in healthy tissues. This makes capecitabine more tumor specific than other chemotherapeutic agents. Accordingly, capecitabine is generally well tolerated. In particular, the incidence of myelosuppression and alopecia is low, and the most common side effects, hand-foot syndrome and diarrhea, are usually manageable. Given its good toxicity profile, capecitabine was assessed in combination with several chemotherapeutic or biologic agents. In addition, the observation that thymidine phosphorylase is upregulated after treatment with other anticancer drugs, namely taxanes, provided a rationale for the prominent antitumor activity recently observed for the combination of capecitabine with these agents. This review provides an evidence-based update of clinical trials investigating the role of capecitabine in the treatment of breast and colorectal cancer, with special emphasis on pharmacological and safety issues that form the basis of currently used schedules.

Microstrain Sensitivity of Orbital and Electronic Phase Separation inSrCrO3

An orbital ordering transition and electronic phase coexistence have been discovered in SrCrO3. This cubic, orbitally-degenerate perovskite transforms to a tetragonal phase with partial orbital order. The tetragonal phase is antiferromagnetic below 35-40 K, whereas the cubic phase remains paramagnetic at low temperatures. The orbital ordering temperature (35-70 K) and coexistence of the two electronic phases are very sensitive to lattice strain. X-ray measurements show a preferential conversion of the most strained regions in the cubic phase. This reveals that small fluctuations in microstrain are sufficient to drive long range separation of competing electronic phases even in undoped cubic oxides.

EFFECT OF ZEOLITE CRYSTALLITE SIZE ON Pt/KL CATALYSTS USED FOR THE AROMATIZATION OF n-OCTANE

The effects of varying zeolite crystallite size in n-octane aromatization over Pt/KL have been studied on a series of catalysts. Various KL zeolites were synthesized via microwave-hydrothermal treatment, which allows for good control of crystallite morphology. Zeolites with different crystallite sizes were prepared by varying aging time (17–24 h), amount of barium (0–445 ppm), and seeding (0–8 wt%). The results showed that higher aging time resulted in smaller zeolite crystallite size, whereas the addition of barium resulted in larger crystallite size. Moreover, the addition of seeding reduced the crystallite size from 1.47 to 0.94 μm. Pt supported on different zeolite catalysts (Pt/KL) was prepared by vapor phase impregnation (VPI). The fresh catalysts were characterized by DRIFTS of adsorbed CO and volumetric hydrogen chemisorption. The results indicated that Pt clusters are well dispersed inside the zeolite channel in all the catalysts prepared. The aromatization of n-octane was tested on the different catalysts at 500°C and atmospheric pressure. It was found that the catalytic activity of all catalysts dropped rapidly after about 200 min on stream due to coke plugging inside the pore of the KL zeolite. It was also observed that less ethylbenzene (EB) and o-xylene (OX) were obtained as the conversion increased because both EB and OX are converted to smaller molecules such as benzene, toluene, etc., by secondary hydrogenolysis. Furthermore, the EB/OX ratio increases with zeolite crystallite size due to an enhanced preferential conversion of the larger OX molecules compared to the narrower EB as their path through the pores is restricted.

Human Pharmacokinetics and Interconversion of Enantiomers of MK‐0767, a Dual PPARα/γ Agonist

MK-0767, a dual peroxisome proliferator-activated receptor (PPAR) alpha/gamma agonist, has been studied as a potential treatment of type 2 diabetes and dyslipidemia. The pharmacokinetics and interconversion of (+)-(R)-MK-0767 and (-)-(S)-MK-0767 were evaluated following oral administration of each single enantiomer and the racemate to healthy subjects. The results demonstrate that, consistent with in vitro experiments, chiral inversion occurs rapidly in vivo, and interconversion equilibrium favors (+)-(R). After all treatments, a stable ratio (R/S) of 2 to 2.5 was achieved within 8 hours in most individuals, congruent with model-based estimates of interconversion half-life. In addition, the pharmacokinetics of each enantiomer were generally similar regardless of treatment. Modeling and simulation of enantiomer disposition suggest that the observed predominance of (+)-(R)-MK-0767 in plasma may result from differential volumes of distribution between (-)-(S) and (+)-(R), preferential conversion from (-)-(S) to (+)-(R), or a combination of these, but not faster clearance of (-)-(S) compared to (+)-(R).

Effects of diet and metamorphosis upon the sterol composition of the butterfly Morpho peleides

Whole body sterol metabolism in insects has seldom been studied. We were able to design an appropriate study at a butterfly farm in Belize. We collected six larvas of butterfly (Morpho peleides), their food (leaves of Pterocarpus bayessii), and their excretions. In addition, six adult butterflies were collected. The sterols of the diet, the larva, and adult butterfly were analyzed by gas-liquid chromatography. The structures of these sterols were identified by digitonin precipitation, GC-MS, and NMR. Four sterols (cholesterol, campesterol, stigmasterol, and sitosterol) and a sterol mixture were found in the food, the body, and the excreta of the larva. The tissue sterol content of the larva was 326 microg. They consumed 276 microg of sterols per day. Their excretion was 185 microg per day as sterols. The total tissue sterol contents of the larva and butterfly were similar, but they had different sterol compositions, which indicated interconversion of sterols during development. There was a progressive increase in the cholesterol content from larva to butterfly and a decrease in the content of sitosterol and other plant sterols, which were likely converted to cholesterol. Our data indicated an active sterol metabolism in butterfly larva. Diet played an important role in determining its sterol composition. During metamorphosis, there was an interconversion of sterols. This is the first paper documenting the fecal sterol excretion in insects as related to dietary intakes.

Innovations in oxidation catalysis leading to a sustainable society

The strategic principles that enable simple, open-structure solid catalysts to be systematically designed so as to oxidize selectively a wide range of organic compounds in air or oxygen under mild conditions, and often without use of solvent are outlined. Illustrated examples of specific reactions, that utilize single-site catalysts that permit these conversions, include: preferential conversion of cyclohexane to adipic acid, toluene to either benzaldehyde or benzoic acid, linear alkanes to terminally oxyfunctionalized products, alkenes to epoxides, ketones to lactones, methanol to formaldehyde and ammonia to hydroxylamine, the last reaction under in situ conditions. Single-site catalysts open up methods for the future avoidance of ecologically harmful procedures, which are still publicized in modern textbooks, that use aggressive stoichiometric oxidants such as CrO 3/H 2SO 4, pyridinium chlorochromate, SeO 2, KMnO 4 and KHSO 5.

Understanding cage effects in the n-alkane conversion on zeolites

Molecular simulations are used to provide insight into published catalytic reactivity data for zeolites that exhibit a cage effect, the selective and preferential conversion of short-chain rather than long-chain n-alkanes. This paper demonstrates that understanding cage effects for ERI-, AFX-, and FER-type zeolites requires consideration of four components: (1) adsorption thermodynamics, (2) adsorption kinetics, (3) conversion at the exterior surface of the catalysts, and (4) coke-induced modifications to the pore texture. By breaking down the Gibbs free energy of adsorption into its enthalpic and entropic contributions, we can further elucidate the influence of the zeolite topology on the adsorption of n-alkanes with different hydrocarbon chain lengths. This analysis indicates that zeolite topologies with cages accessible through windows < 0.47 nm wide are particularly prone to exhibiting a cage effect, because they impose a high thermodynamic penalty on the adsorption of molecules that are too long to fit comfortably in a single cage. This improved understanding of the cage effect could facilitate its renewed use in commercial practice.

Bridging the gap between liquid and vapor phase hydrocracking

Research aimed at fundamental understanding of industrial reactions often leads to important differences, or so-called gaps, between laboratory and industrial conditions. Vapor and liquid phase hydrocracking of parapur, a mixture of linear alkanes in the range from C 9 to C 14, has been performed on a Pt/H-USY zeolite at temperatures between 503 and 533 K, total pressures between 1 and 7.7 MPa and molar inlet hydrogen to hydrocarbon ratios from 3 to 300. At these conditions ideal hydrocracking occurs, except for the heaviest components at the highest temperatures, lowest pressures and highest molar inlet hydrogen to hydrocarbon ratios. The individual component product distributions obtained at vapor and liquid phase conditions were identical to those reported in the literature for pure n-alkane hydrocracking. A preferential conversion of the heavier hydrocarbons in the mixture was observed for vapor phase parapur hydrocracking. At liquid phase conditions this preferential conversion of heavier hydrocarbons is still observed, but much less pronounced. A single kinetic model accounting for all these features allows to adequately describe both vapor and liquid phase parapur hydrocracking. It suffices to account explicitly for (i) the non-ideality of the fluid phase, (ii) the destabilization of the physisorbed phase in the catalyst micropores and (iii) the increased strength of the acid sites at the liquid phase conditions. The last two effects are quantified by so-called physisorption and protonation excess.

Adsorption-Driven Photocatalytic Activity of Mesoporous Titanium Dioxide

Titanium dioxide with a mesoporous structure, when photoactivated in water, demonstrates an unprecedented photocatalytic activity, driven strongly by an adsorption degree of molecules onto the catalyst surface, which promotes a preferential conversion of a well-adsorbed molecule. This catalyzes a selective transformation of a well-adsorbed molecule into a less-adsorbed molecule, so-labeled "stick-and-leave" transformation, which promotes a direct hydroxylation of benzene to phenol, one of the most difficult synthetic reactions, with very high selectivity (>80%) and using water as a source of oxidant.

The Yeast Phospholipid N-Methyltransferases Catalyzing the Synthesis of Phosphatidylcholine Preferentially Convert Di-C16:1 Substrates Both in Vivo and in Vitro

Phosphatidylcholine (PC) is an important and abundant structural component of the membranes of eukaryotic cells. In the yeast Saccharomyces cerevisiae, the primary route for the biosynthesis of PC consists of three consecutive methylation steps of phosphatidylethanolamine (PE) catalyzed by the phospholipid N-methyltransferases Cho2p and Opi3p. To investigate how these biosynthetic enzymes contribute to the composition of the PC species profile, the precursor-product relationships between PE and newly synthesized PC were determined at the level of the molecular species by using electrospray ionization tandem mass spectrometry and stable isotope labeling. In vivo labeling of yeast cells for 10 min with [methyl-D3]methionine revealed the preferential methylation of di-C16:1 PE over a range of PE species compositions. A similar preferential conversion of di-C16:1 PE to PC was found in vitro upon incubating isolated microsomes with S-adenosyl[methyl-D3]methionine. Yeast opi3 and cho2 deletion strains were used to distinguish between the substrate selectivities of Cho2p and Opi3p, respectively. Both biosynthetic enzymes were found to participate in the speciesselective methylation with Cho2p contributing the most. The combined results indicate that the selective methylation of PE species by the methyltransferases plays an important role in shaping the steady-state profile of PC molecular species in yeast.

Amino sugar phosphate levels in Giardia change during cyst wall formation.

The parasite Giardia intestinalis exists as a trophozoite (vegetative) that infects the human small intestine, and a cyst (infective) that is shed in host faeces. Cyst viability in the environment depends upon a protective cyst wall, which consists of proteins and a unique beta(1-3) GalNAc homopolymer. UDP-GalNAc, the precursor for this polysaccharide, is synthesized from glucose by an enzyme pathway that involves amino sugar phosphate intermediates. Using a novel method of microanalysis by capillary electrophoresis, the levels of amino sugar phosphate intermediates in trophozoites before encystment, during a period of active encystment and after the peak of encystment were measured. These levels were used to deduce metabolic control of amino sugar phosphates associated with encystment. Levels of amino sugar phosphate intermediates increased during encystment, and then decreased to nearly non-encysting levels. The most pronounced increase was in glucosamine 6-phosphate, which is the first substrate unique in this pathway, and which is the positive effector for the pathway's putative rate-controlling enzyme, UDP-GlcNAc pyrophosphorylase. Moreover, more UDP-GalNAc than UDP-GlcNAc, its direct precursor, was detected at 24 h. It is postulated that the enhanced UDP-GalNAc is a result of enhanced synthesis of UDP-GlcNAc by the pyrophosphorylase, and its preferential conversion to UDP-GalNAc. These results suggest that kinetics of amino sugar phosphate synthesis in encysting Giardia favours the direction that supports cyst wall synthesis. The enzymes involved in synthesis of UDP-GalNAc and its conversion to cyst wall might be potential targets for therapeutic inhibitors of Giardia infection.

Substrate preference in phosphatidylserine biosynthesis for docosahexaenoic acid containing species.

Neuronal membranes contain high levels of phosphatidylserine (PS) and docosahexaenoic acid (22:6n-3, DHA). In this study, substrate preference in PS synthesis was determined to gain insight on the biochemical basis for concentrating PS in neuronal membranes where 22:6n-3 is highly enriched. We first established an in vitro assay method using unilamellar vesicles (LUV) of deuterium-labeled substrates and reversed-phase HPLC/electrospray ionization (ESI) mass spectrometry. The PS production by the incubation of deuterium-labeled substrate and microsomal fractions was monitored. We found that tissue-specific substrate preference exists in PS synthesis. Microsomes from the cerebral cortex synthesized PS from 18:0,22:6-PC most favorably among the PC substrates tested, followed by 18:0,22:5-PC, resulting in the PC substrate preference in the order of 18:0,22:6 > 18:0,22:5 > 18:0,20:4 = 18:0,18:1. Liver microsomes also preferred 18:0,22:6-PC as the substrate in PS synthesis but did not use 18:0,22:5-PC favorably. The 18:0,22:5-PC species was converted to PS at the similar extent as 18:0,20:4- or 18:0,18:1-PC species in the liver. Both brain and liver microsomes showed a preference for 18:0 over 16:0 as the sn-1 fatty acid. From these data it was deduced that preferential conversion of 18:0,22:6-PC to the corresponding PS species is at least partly responsible for concentrating PS in neuronal tissues where 22:6n-3 is particularly abundant. The distinctive preference for 18:0,22:5-PS observed with brain microsomes may help to maintain PS at a high level in the brain when 22:6n-3 is replaced by 22:5n-3 as in the case of n-3 fatty acid deficiency.

Capillary electrophoresis to assess drug metabolism induced in vitro using single CYP450 enzymes (Supersomes): application to the chiral metabolism of mephenytoin and methadone.

Capillary electrophoresis (CE) with multiwavelength absorbance detection is demonstrated to be an effective tool for the assessment of in vitro drug metabolism studies using microsomes containing single human cytochrome P450 enzymes (CYPs) expressed in baculovirus-infected insect cells (Supersomes). Mephenytoin (MEPH), dextromethorphan, diclofenac, caffeine, and methadone (MET) were successfully applied as test substrates for CYP2C19, CYP2D6*1, CYP2C9*1, CYP1A2, and CYP3A4, respectively. For each system, the CE-based assay could be shown to permit the simultaneous analysis of the parent drug and its targeted metabolite. Using a chiral micellar electrokinetic capillary chromatography assay, the aromatic hydroxylation of MEPH catalyzed by CYP2C19 could thereby be confirmed to be highly stereoselective, an aspect that is in agreement with data obtained via urinary analysis after intake of racemic MEPH by extensive metabolizer phenotypes. The MET to 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) conversion was investigated with a chiral zone electrophoresis assay. Incubation of racemic and nonracemic MET with CYP3A4 revealed no stereoselectivity for the transformation to EDDP, whereas no EDDP formation was observed with CYP1A2. CYP2C9 and CYP2C19 provided enhanced formation of R-EDDP and CYP2D6 incubation resulted in the preferential conversion to S-EDDP. Investigations using racemic MET and human liver microsomes revealed a modest stereoselectivity with an R/S EDDP ratio < 1 which is similar to the in vivo findings in urine.

Prolonged lipopolysaccharide inhibits leukotriene synthesis in peritoneal macrophages: mediation by nitric oxide and prostaglandins

Resident rat peritoneal macrophages synthesize a variety of prostanoids and leukotrienes from arachidonic acid. Overnight treatment with lipopolysaccharide (LPS) induces the synthesis of cyclooxygenase-2 (COX-2) and an altered prostanoid profile that emphasizes the preferential conversion of arachidonic acid to prostacyclin and prostaglandin E 2. In these studies, we report that exposure to LPS also caused a strong suppression of 5-lipoxygenase but not 12-lipoxygenase activity, indicated by the inhibition of synthesis of both leukotriene B 4 and 5-hydroxyeicosatetraenoic acid (5-HETE), but not of 12-HETE. Inhibition of 5-lipoxygenase activity by LPS was both time- and dose-dependent. Treatment of macrophages with prostaglandin E 2 partially inhibited leukotriene synthesis, and cyclooxygenase inhibitors partially blocked the inhibition of leukotriene generation in LPS-treated cells. In addition to COX-2, nitric oxide synthase (NOS) was also induced by LPS. Treatment of macrophages with an NO donor mimicked the ability of LPS to significantly reduce leukotriene B 4 synthesis. Inhibition of NOS activity in LPS-treated cells blunted the suppression of leukotriene synthesis. Inhibition of both inducible NOS and COX completely eliminated leukotriene suppression. Finally, macrophages exposed to prolonged LPS demonstrated impaired killing of Klebsiella pneumoniae and the combination of NOS and COX inhibitors restored killing to the control level. These results indicate that prolonged exposure to LPS severely inhibits leukotriene production via the combined action of COX and NOS products. The shift in mediator profile, to one that minimizes leukotrienes and emphasizes prostacyclin, prostaglandin E 2 and NO, provides a signal that reduces leukocyte function, as indicated by impaired killing of Gram-negative bacteria.

Competition between Fe(III)-Reducing and Methanogenic Bacteria for Acetate in Iron-Rich Freshwater Sediments

The kinetics of acetate uptake and the depth distribution of [2-14C]acetate metabolism were examined in iron-rich sediments from a beaver impoundment in northcentral Alabama. The half-saturation constant (Km) determined for acetate uptake in slurries of Fe(III)-reducing sediment (0.8 mM) was more than 10-fold lower than that measured in methanogenic slurries (12 mM) which supported comparable rates of bulk organic carbon metabolism and Vmax values for acetate uptake. The endogenous acetate concentration (Sn) was also substantially lower (1.7 mM) in Fe(III)-reducing vs methanogenic (9.0 mM) slurries. The proportion of [2-14C]acetate converted to 14CH4 increased with depth from ca 0.1 in the upper 0.5 cm to ca 0.8 below 2 cm and was inversely correlated (r2 = 0.99) to a decline in amorphous Fe(III) oxide concentration. The results of the acetate uptake kinetics experiments suggest that differences in the affinity of Fe(III)-reducing bacteria vs methanogens for acetate can account for the preferential conversion of [2-14C]acetate to 14CO2 in Fe(III) oxide-rich surface sediments, and that the downcore increase in conversion of [2-14C]acetate to 14CH4 can be attributed to progressive liberation of methanogens from competition with Fe(III) reducers as Fe(III) oxides are depleted with depth.