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PubMed2005

Carbon isotope fractionation in the reductive dehalogenation of carbon tetrachloride at iron (hydr)oxide and iron sulfide minerals.

Compound-specific isotope analysis (CSIA) is used increasingly in contaminant hydrology in the attempt to assess the nature as well as the extent of in situ transformation reactions. Potentially, variations of stable isotope ratios along a contaminant plume may be used to quantify in situ degradation. In the present study, the abiotic dehalogenation of CCl4 by Fe(II) present at the surface of different iron minerals has been characterized in terms of the reaction rates and carbon isotopic fractionation (delta13C) of carbon tetrachloride (CCl4) as well as the yields and isotopic signatures of chloroform (CHCl3), one of the main transformation products. The abiotic reductive dehalogenation of CCl4 was associated with substantial carbon isotopic enrichment effects. The observed enrichment factors, e, correlated neither with the surface-normalized reaction rate constants nor with the type of products formed but fell into two distinctly different ranges for the two principal groups of minerals studied. With iron (hydr)oxide minerals (goethite, hematite, lepidocrocite, and magnetite) and with siderite, the e-values for CCl4 dehalogenation were remarkably similar (-29 +/- 3 per thousand). Because this value matches well with the theoretical estimates for the cleavage of an aliphatic C-Cl bond, we suggest that dissociative electron transfer to CCl4 controls the reaction rates for this group of iron minerals. Conversely, CCl4 transformation by different preparations of the iron sulfide mackinawite was accompanied by a significantly lower carbon istotopic fractionation (e = -15.9 +/- 0.3 per thousand), possibly due to the presence of nonfractionating rate-determining steps or a significantly different transition state structure of the reaction. Isotopically sensitive branching of the reaction pathways (i.e., the effect of different product distributions on isotope fractionation of CCl4) did not play a significant role in our systems. The extensive data set presented in this study opens new perspectives toward an improved understanding of the factors that determine reaction mechanisms and isotopic fractionation of dehalogenation reactions by Fe(II) at iron containing minerals.

Carbon Isotopes↗
PubMed2005

New evaluation scheme for two-dimensional isotope analysis to decipher biodegradation processes: application to groundwater contamination by MTBE.

Compound-specific analysis of stable carbon and hydrogen isotopes was used to assess the fate of the gasoline additive methyl tert-butyl ether (MTBE) and its major degradation product tert-butyl alcohol (TBA) in a groundwater plume at an industrial disposal site. We present a novel approach to evaluate two-dimensional compound-specific isotope data with the potential to identify reaction mechanisms and to quantify the extent of biodegradation at complex field sites. Due to the widespread contaminant plume, multiple MTBE sources, the presence of numerous other organic pollutants, and the complex biogeochemical and hydrological regime atthe site, a traditional mass balance approach was not applicable. The isotopic composition of MTBE steadily changed from the source regions along the major contaminant plume (-26.4% to +40.0% (carbon); -73.1% to +60.3% (hydrogen)) indicating substantial biodegradation. Constant carbon isotopic signatures of TBA suggest the absence of TBA degradation at the site. Published carbon and hydrogen isotope fractionation data for biodegradation of MTBE under oxic and anoxic conditions, respectively, were examined and used to determine both the nature and the extent of in-situ biodegradation along the plume(s). The coupled evaluation of two-dimensional compound-specific isotope data explained both carbon and hydrogen fractionation data in a consistent way and indicate anaerobic biodegradation of MTBE along the entire plume. A novel scheme to reevaluate empiric isotopic enrichment factors (epsilon) in terms of theoretically based intrinsic carbon (12k/13k) and hydrogen (1k/2k) kinetic isotope effects (KIE) is presented. Carbon and hydrogen KIE values, calculated for different potential reaction mechanisms, imply that anaerobic biodegradation of MTBE follows a SN2-type reaction mechanism. Furthermore, our data suggest that additional removal process(es) such as evaporation contributed to the overall MTBE removal along the plume, a phenomenon that might be significant also for other field sites at tropic or subtropic climates with elevated groundwater temperatures (25 degrees C).

Bacteria, Anaerobic↗
PubMed2006

Isotopic criteria in the characterization of aromatic molecules. 2. Influence of the chemical elaboration process.

Most valued natural aromatic molecules can be substituted by their low-cost chemical counterparts. Isotopic methods, which offer the most powerful tool to infer the origin of a molecule, are applied to the characterization of a large number of chemical aromatic species. Isotopic affiliation between precursors and products is investigated in several types of reactions: oxidation of benzyl chloride and benzyl alcohol and hydrolysis of benzylidene chloride and cinnamaldehyde. The isotopic parameters strongly depend not only on the type of process but, for a given process, on the experimental conditions of the reaction. Kinetic isotope effects occurring in several formylation reactions are estimated. It is shown that, in the drastic experimental conditions of many industrial processes, the benzenic hydrogen atoms may be affected by exchange phenomena. Consequently, the site-specific isotopic parameters of the ring fragment of chemical species are usually much less stable than those of the corresponding natural molecules biosynthesized in mild environments. The isotope ratios of substituents such as CH3, CH2Cl, and CHO are more resistant to exchange and provide useful criteria for characterizing both the raw materials and the process. It is shown in particular that radical hydrogen abstraction in toluene to produce benzyl chloride induces relatively moderate fractionation effects. In contrast, oxidation reactions frequently produce strong fractionation effects. In particular, industrial direct oxidation of toluene into benzaldehyde is characterized by deuterium enrichments at the formyl site, which may exceed 900 ppm. Taking into account the large magnitude and high variability of many fractionation effects occurring in chemical reactions, the isotopic fingerprint may provide unambiguous criteria, not only for excluding a natural origin and characterizing the type of process, but also for differentiating molecules synthesized by a given process in different industrial contexts. The isotopic fingerprint may therefore be used by manufacturers as a powerful label for characterizing their production batches.

Acrolein↗
PubMed2005

Multiple isotope effect study of the acid-catalyzed hydrolysis of methyl formate.

Multiple isotope effects have been measured for the acid-catalyzed hydrolysis of methyl formate in 0.5 M HCl at 20 degrees C. The isotope effects in the present investigation include the carbonyl carbon (13k = 1.028 +/- 0.001), the carbonyl oxygen (18k = 0.9945 +/- 0.0009), the nucleophile oxygen (18k = 0.995 +/- 0.001), and the formyl hydrogen ((D)k = 0.81 +/- 0.02). Determination of the carbonyl carbon, carbonyl oxygen, and formyl hydrogen isotope effects was performed via isotopic analysis of residual substrate. However, determination of the oxygen nucleophile isotope effect required analysis of the oxygen atoms of the product (formic acid), which exchange with the solvent (water) under acid conditions. This necessitated measurement of the rate of exchange of these oxygen atoms under the conditions for hydrolysis (k(ex) = 0.0723 min(-1)) and correction of the raw isotope ratios measured during the nucleophile-O isotope effect experiment. These results, along with the previously reported isotope effect for the leaving oxygen (18k = 1.0009) and the ratio of the rate of hydrolysis to that of exchange of the carbonyl oxygen with water (k(h)/k(ex) = 11.3), give a detailed picture of the transition-state structure for the reaction.

Catalysis↗
PubMed1994

Comparison of stable isotopes and radioisotopes in the measurement of iron absorption in healthy women.

1. Stable isotope methods are being used to investigate the absorption of dietary iron. In order to be certain that this new methodology is accurate, we have compared results obtained using stable isotopes and inductively coupled plasma mass spectrometry with those determined using a radioisotope and whole body counting. 2. The stable isotope 54Fe (2.8 mg) was given to 10 healthy non-pregnant women. Six women received the isotope in aqueous form, and four took it with a meat meal. The 54Fe served as a carrier for 10 ng of the radioisotope 59Fe. An ampoule (200 micrograms) of the isotope 57Fe or 58Fe was then given intravenously, and in serum samples taken over the next 10 h the ratios of the stable iron isotopes were measured by inductively coupled plasma mass spectrometry and the oral iron absorption was calculated. This was then compared with the results obtained by using a whole body counter to measure (on day 0 and day 14) the gamma-activity emitted by the radioisotope. 3. The mean iron absorption measured by both methods ranged from 8% to 45%. Measurement of the post-absorptive serum enrichment of the stable isotopes provided estimates of absorption from both aqueous and food iron which were similar to that yielded by whole body counting, the mean difference being -1.5% (95% confidence interval -5.2 to 2.1%). Absorption estimated by stable isotopes exhibited the same inverse relationship with the serum ferritin level (body iron stores) to that known to exist with whole body counting.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗
PubMed2006

Isotopic evidence for large gaseous nitrogen losses from tropical rainforests.

The nitrogen isotopic composition (15N/14N) of forested ecosystems varies systematically worldwide. In tropical forests, which are elevated in 15N relative to temperate biomes, a decrease in ecosystem 15N/14N with increasing rainfall has been reported. This trend is seen in a set of well characterized Hawaiian rainforests, across which we have measured the 15N/14N of inputs and hydrologic losses. We report that the two most widely purported mechanisms, an isotopic shift in N inputs or isotopic discrimination by leaching, fail to explain this climate-dependent trend in 15N/14N. Rather, isotopic discrimination by microbial denitrification appears to be the major determinant of N isotopic variations across differences in rainfall. In the driest climates, the 15N/14N of total dissolved outputs is higher than that of inputs, which can only be explained by a 14N-rich gas loss. In contrast, in the wettest climates, denitrification completely consumes nitrate in local soil environments, thus preventing the expression of its isotope effect at the ecosystem scale. Under these conditions, the 15N/14N of bulk soils and stream outputs decrease to converge on the low 15N/14N of N inputs. N isotope budgets that account for such local isotopic underexpression suggest that denitrification is responsible for a large fraction (24-53%) of total ecosystem N loss across the sampled range in rainfall.

Models, Biological↗
PubMed1998

Counting individual sulfur atoms in a protein by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry: experimental resolution of isotopic fine structure in proteins.

A typical molecular ion mass spectrum consists of a sum of signals from species of various possible isotopic compositions. Only the monoisotopic peak (e.g., all carbons are 12C; all nitrogens are 14N, etc.) has a unique elemental composition. Every other isotope peak at approximately integer multiples of approximately 1 Da higher in nominal mass represents a sum of contributions from isotope combinations differing by a few mDa (e.g., two 13C vs. two 15N vs. one 13C and one 15N vs. 34S, vs. 18O, etc., at approximately 2 Da higher in mass than the monoisotopic mass). At sufficiently high mass resolving power, each of these nominal-mass peaks resolves into its isotopic fine structure. Here, we report resolution of the isotopic fine structure of proteins up to 15.8 kDa (isotopic 13C,15N doubly depleted tumor suppressor protein, p16), made possible by electrospray ionization followed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass analysis at 9.4 tesla. Further, a resolving power of m/Deltam50% approximately 8,000,000 has been achieved on bovine ubiquitin (8.6 kDa). These results represent a 10-fold increase in the highest mass at which isotopic fine structure previously had been observed. Finally, because isotopic fine structure reveals elemental composition directly, it can be used to confirm or determine molecular formula. For p16, for example, we were able to determine (5.1 +/- 0.3) the correct number (five) of sulfur atoms solely from the abundance ratio of the resolved 34S peak to the monoisotopic peak.

Animals↗
PubMed1999

Calcium isotope fractionation between soft and mineralized tissues as a monitor of calcium use in vertebrates.

Calcium from bone and shell is isotopically lighter than calcium of soft tissue from the same organism and isotopically lighter than source (dietary) calcium. When measured as the (44)Ca/(40)Ca isotopic ratio, the total range of variation observed is 5.5 per thousand, and as much as 4 per thousand variation is found in a single organism. The observed intraorganismal calcium isotopic variations and the isotopic differences between tissues and diet indicate that isotopic fractionation occurs mainly as a result of mineralization. Soft tissue calcium becomes heavier or lighter than source calcium during periods when there is net gain or loss of mineral mass, respectively. These results suggest that variations of natural calcium isotope ratios in tissues may be useful for assessing the calcium and mineral balance of organisms without introducing isotopic tracers.

Animals↗
PubMed2002

Survey of stable sulfur isotope ratios (34S/32S) of sulfite and sulfate in foods.

A study was conducted to determine the natural abundance sulfur isotope ratios in foods containing sulphite preservatives. This involved determining (1) the accuracy and repeatability of sulfur isotope ratios measured using an elemental analyser (EA) coupled to an isotope ratio mass spectrometer (IRMS); and (2) the isotope ratios of 21 samples of commercially available S(IV) oxo-anion compounds, nine samples of S(VI) sulfate salts and the isotope ratios of the sulfate obtained by modified Monier-Williams distillation of SO(2) from 33 retail foods containing sulfite preservatives. The sulfur isotope ratio data for SO(2) recovered from foodstuffs showed a large spread of results, which suggested that the SO(2) derived from sulfite preservatives does not have a distinctive sulfur signature ratio. The range of results (3.1-52.1) overlapped with that found for a range of commercially available sulfite and sulfate reagents commonly used to preserve food (sulfites 2.5-13.7, sulfates 10.0-16.9). Whilst the variability in isotope ratios originated from the food samples themselves, evidence from the analysis of SO(2) gas suggested that isotope fractionation during dissolution, reaction and recovery was also a confounding factor.

Barium Sulfate↗
PubMed1989

The use of stable isotopes in mineral nutrition research.

Stable isotopes are valuable tools for research on mineral bioavailability and metabolism. They can be used as tracers with no exposure to radiation and they do not decay over time. Attempts to use stable isotopes of minerals as metabolic tracers were first described only 25 years ago. There were relatively few reports of their use over the next 15 years, but interest in stable isotopes has expanded markedly in the last 10 years. The advantages of stable isotope tracers are so great that scientists have been willing to accept the laborious and costly nature of mineral isotope analysis, and substantial progress has been made in the field. New applications for stable isotopes and new analytical methods have been introduced recently. However, limitations to the approach and methodological problems remain to be resolved. This review describes early work in the field and discusses the advantages and disadvantages of stable isotope tracers and of the various methods of analysis. Information discovered with stable isotopes is reviewed, and probable future applications are discussed.

Biological Availability↗
PubMedDate not supplied

Strontium isotopic identification of water-rock interaction and ground water mixing.

87Sr/86Sr ratios of ground waters in the Bighorn and Laramie basins' carbonate and carbonate-cemented aquifer systems, Wyoming, United States, reflect the distinctive strontium isotope signatures of the minerals in their respective aquifers. Well water samples from the Madison Aquifer (Bighorn Basin) have strontium isotopic ratios that match their carbonate host rocks. Casper Aquifer ground waters (Laramie Basin) have strontium isotopic ratios that differ from the bulk host rock; however, stepwise leaching of Casper Sandstone indicates that most of the strontium in Casper Aquifer ground waters is acquired from preferential dissolution of carbonate cement. Strontium isotope data from both Bighorn and Laramie basins, along with dye tracing experiments in the Bighorn Basin and tritium data from the Laramie Basin, suggest that waters in carbonate or carbonate-cemented aquifers acquire their strontium isotope composition very quickly--on the order of decades. Strontium isotopes were also used successfully to verify previously identified mixed Redbeds-Casper ground waters in the Laramie Basin. The strontium isotopic compositions of ground waters near Precambrian outcrops also suggest previously unrecognized mixing between Casper and Precambrian aquifers. These results demonstrate the utility of strontium isotopic ratio data in identifying ground water sources and aquifer interactions.

Environmental Monitoring↗
PubMed1990

Stable carbon isotope analysis of nucleic acids to trace sources of dissolved substrates used by estuarine bacteria.

The natural abundance of stable carbon isotopes measured in bacterial nucleic acids extracted from estuarine bacterial concentrates was used to trace sources of organic matter for bacteria in aquatic environments. The stable carbon isotope ratios of Pseudomonas aeruginosa and nucleic acids extracted from cultures resembled those of the carbon source on which bacteria were grown. The carbon isotope discrimination between the substrate and total cell carbon from bacterial cultures averaged 2.3% +/- 0.6% (n = 13). Furthermore, the isotope discrimination between the substrate and nucleic acids extracted from bacterial cultures was 2.4% +/- 0.4% (n = 10), not significantly different from the discrimination between bacteria and the substrate. Estuarine water samples were prefiltered through 1-micron-pore-size cartridge filters. Bacterium-sized particles in the filtrates were concentrated with tangential-flow filtration and centrifugation, and nucleic acids were then extracted from these concentrates. Hybridization with 16S rRNA probes showed that approximately 90% of the nucleic acids extracted on two sample dates were of eubacterial origin. Bacteria and nucleic acids from incubation experiments using estuarine water samples enriched with dissolved organic matter from Spartina alterniflora and Cyclotella caspia had stable carbon isotope values similar to those of the substrate sources. In a survey that compared diverse estuarine environments, stable carbon isotopes of bacteria grown in incubation experiments ranged from -31.9 to -20.5%. The range in isotope values of nucleic acids extracted from indigenous bacteria from the same waters was similar, -27.9 to -20.2%. Generally, the lack of isotope discrimination between bacteria and nucleic acids that was noted in the laboratory was observed in the field.(ABSTRACT TRUNCATED AT 250 WORDS)

Bacteria↗
PubMed2005

Hereditary hemochromatosis is reflected in the iron isotope composition of blood.

It has recently been shown that the iron isotopic composition of blood differs between individuals and sexes, which is supposed to reflect individual differences in iron metabolism. We hypothesized that patients suffering from hereditary hemochromatosis would demonstrate alterations in the iron isotopic composition of blood due to persistent up-regulation of intestinal iron absorption. Blood from 30 patients with homozygous C282Y hemochromatosis was analyzed for iron isotopic composition by a newly developed technique using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Blood of patients with hemochromatosis is characterized by a higher 56Fe/54Fe isotope ratio than blood of healthy individuals, which are either members of an age-matched control group (n = 10; P < .001) or young adults (n = 36; P < .001). In patients with hereditary hemochromatosis, the 56Fe/54Fe isotope ratio of blood significantly correlates with total-body iron accumulation, severity of clinical disease, and the need for regular phlebotomies to prevent iron reaccumulation. We conclude that blood of patients with hereditary hemochromatosis contains more of the heavier iron isotopes than blood of healthy individuals. The primary determinant of the iron isotopic composition of blood appears to be isotope-sensitive iron absorption in the intestine and the efficiency of this process.

Adult↗
PubMed2006

High-resolution quantitative imaging of mammalian and bacterial cells using stable isotope mass spectrometry.

BACKGROUND: Secondary-ion mass spectrometry (SIMS) is an important tool for investigating isotopic composition in the chemical and materials sciences, but its use in biology has been limited by technical considerations. Multi-isotope imaging mass spectrometry (MIMS), which combines a new generation of SIMS instrument with sophisticated ion optics, labeling with stable isotopes, and quantitative image-analysis software, was developed to study biological materials. RESULTS: The new instrument allows the production of mass images of high lateral resolution (down to 33 nm), as well as the counting or imaging of several isotopes simultaneously. As MIMS can distinguish between ions of very similar mass, such as 12C15N- and 13C14N-, it enables the precise and reproducible measurement of isotope ratios, and thus of the levels of enrichment in specific isotopic labels, within volumes of less than a cubic micrometer. The sensitivity of MIMS is at least 1,000 times that of 14C autoradiography. The depth resolution can be smaller than 1 nm because only a few atomic layers are needed to create an atomic mass image. We illustrate the use of MIMS to image unlabeled mammalian cultured cells and tissue sections; to analyze fatty-acid transport in adipocyte lipid droplets using 13C-oleic acid; to examine nitrogen fixation in bacteria using 15N gaseous nitrogen; to measure levels of protein renewal in the cochlea and in post-ischemic kidney cells using 15N-leucine; to study DNA and RNA co-distribution and uridine incorporation in the nucleolus using 15N-uridine and 81Br of bromodeoxyuridine or 14C-thymidine; to reveal domains in cultured endothelial cells using the native isotopes 12C, 16O, 14N and 31P; and to track a few 15N-labeled donor spleen cells in the lymph nodes of the host mouse. CONCLUSION: MIMS makes it possible for the first time to both image and quantify molecules labeled with stable or radioactive isotopes within subcellular compartments.

Adipocytes↗
PubMed2003

Isotopic measurements of uranium using inductively coupled plasma cavity ringdown spectroscopy.

Inductively coupled plasma cavity ringdown spectroscopy (ICP-CRDS) is applied to isotopic measurements of uranium. We have successfully obtained the isotopic-resolved spectra of uranium at three different atomic/ionic transition lines, 286.57, 358.49, and 409.01 nm. Of the three lines, the largest isotope shift of approximately 9 pm was measured at the 286.57 ionic line. Isotopic-resolved spectra were recorded in ratio of 1:1 (235U/238U, 2.5 micrograms/mL) and at the natural abundance ratio of 0.714% (235U/238U, 1.25 micrograms/mL 235U). The smallest measurable isotope shift of approximately 3 pm was determined for the 409.01 nm ion spectral line. Detection limits (DL) were obtained under optimized ICP operating conditions to be in the range of 70-150 ng/mL, except for the 238U component of the 286.57 nm line (300 ng/mL). This latter result was determined to be due to a strong, previously unreported, absorption interference from the argon plasma. The 235U isotope component (DL 70 ng/mL) was found to be unaffected. This work demonstrates the applicability of ICP-CRDS for uranium isotopic measurements. The potential of development of a field-deployable, on-line uranium isotope monitor using plasma-CRDS is discussed.

Gases↗
PubMedDate not supplied

Selenium stable isotope ratios in California agricultural drainage water management systems.

Selenium stable isotope ratios are known to shift in predictable ways during various microbial, chemical, and biological processes, and can be used to better understand Se cycling in contaminated environments. In this study we used Se stable isotopes to discern the mechanisms controlling the transformation of oxidized, aqueous forms of Se to reduced, insoluble forms in sediments of Se-affected environments. We measured 80Se/76Se in surface waters, shallow ground waters, evaporites, digested plants and sediments, and sequential extracts from several sites where agricultural drainage water is processed in the San Joaquin Valley of California. Selenium isotope analyses of samples obtained from the Tulare Lake Drainage District flow-through wetland reveal small isotopic contrasts (mean difference 0.7%) between surface water and reduced Se species in the underlying sediments. Selenium in aquatic macrophytes was very similar isotopically to the NaOH and Na2SO3 sediment extracts designed to recover soluble organic Se and Se(0), respectively. For the integrated on-farm drainage management sites, evaporite salts were slightly (approximately 0.6%) enriched in the heavier isotope relative to the inferred parent waters, whereas surface soils were slightly (approximately 1.4%) depleted. Bacterial or chemical reduction of Se(VI) or Se(IV) may be occurring at these sites, but the small isotopic contrasts suggest that other, less isotopically fractionating mechanisms are responsible for accumulation of reduced forms in the sediments. These findings provide evidence that Se assimilation by plants and algae followed by deposition and mineralization is the dominant transformation pathway responsible for accumulation of reduced forms of Se in the wetland sediments.

Agriculture↗
PubMed1995

Use of stable isotopic selenium as a tracer to follow incorporation of selenium into selenoproteins.

Stable isotopes of selenium (Se) have been used in human studies to measure Se absorption, retention and excretion. The purpose of this study was to examine whether stable Se could also be used to follow the incorporation of Se into selenoproteins and whether selenoproteins are labeled with stable isotopes the same way they are with radioactive Se. Rats fed either a Se-deficient or a high-Se diet were injected with either a radioactive (75Se) or a stable isotope of Se (77Se), and the liver cytosol was chromatographed on Sephadex G-200. Compared with 75Se, a greater percentage of 77Se was incorporated into cytosol, but the distribution and the effect of dietary Se was similar for both isotopes. New Zealand long-eared rabbits were also injected with either 77Se or 75Se, and the plasma was chromatographed. More of the 75Se was incorporated into the plasma, but again the patterns of incorporation were similar for both isotopes. Plasma from a male subject who ingested 60 micrograms of 77Se was chromatographed, and the stable Se was detected in column fractions and showed a distribution similar to that observed for rabbit plasma. Finally, a polyacrylamide gel electrophoresis (PAGE) method was developed that allowed loading of sufficient protein to analyze for 77Se in individual protein fractions. The distribution of 77Se and 75Se in rabbit plasma was similar. Human plasma was electrophoresed by a similar method and peaks of 56 and 23 kDa were detected. These data show that stable isotopes of Se can be used for selenoprotein production in the same way as radioactive isotopes. They also show that, when physiological amounts of stable Se are ingested by humans, the isotope can be detected in blood-borne proteins separated by column chromatography and PAGE.

Adult↗
PubMedDate not supplied

[Intramolecular isotope distribution of metabolites in the glycolytic chain].

Based on the mechanism of the fractionation of carbon isotopes in the glycolytic chain proposed earlier, a method for the qualitative prediction of intramolecular isotope distribution of metabolites synthesized through the glycolytic chain and conjugated reactions was developed. Among them are fatty acids, monoterpenes, hopanoids, branched amino acids, amino acids of the family of trioses, metabolites synthesized by the shikimate pathway, metabolites of the Krebs cycle, amino acids of the family of ketoglutaric and oxalacetic acids. The method was tested by comparing the natural and theoretically predicted isotope distributions of carbon. The model for the description of theoretical isotope distributions is based on oscillations in the glycolytic chain. In the glycolysis phase, an isotope effect of decarboxylation of pyruvate arises, which determines the experimentally observed isotope inhomogeneity of metabolites. The isotope distributions of carbon depend on the sequence of syntheses of metabolites in the cell cycle, which corresponds to the degrees of exhaustion of the pyruvate depot that supplies structural units for the synthesis. In repeated cycles, the syntheses of metabolites occur in phase in addition to the carbon flux passing through the glycolytic chain, a carbon flux entering from the photorespiratory chain is involved in the synt, which is enriched in carbon heavy isotope. This flux is used, in particular, for the formation of carbon fragments of complex molecules.

Amino Acids, Branched-Chain↗