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At least 127 records · Page 7Linked to original sources

Stable isotope analysis of safety matches using isotope ratio mass spectrometry--a forensic case study.

Isotope ratio mass spectrometry (IRMS) was used to assess what contribution the technique could make towards the comparative analysis of matchstick samples within the 'normal' framework of a forensic investigation. A method was developed to allow the comparison of samples submitted as a result of an investigation, with the added advantage of rapid sample turn-around expected within this field. To the best of our knowledge this is the first time that wooden safety matches have been analysed using IRMS. In this particular case, bulk stable isotope analysis carrried out on a 'like-for-like' basis could demonstrate conclusively that matches seized from a suspect were different from those collected at the scene of crime. The maximum delta13C variability observed within one box was 2.5 per thousand, which, in conjunction with the error of measurement, was regarded to yield too wide an error margin as to permit differentiation of matchsticks based on 13C isotopic composition alone given that the 'natural' 13C abundance in wood ranges from -20 to -30 per thousand. However, from the delta2H values obtained for crime scene matches and seized matches of -114.5 per thousand and -65 per thousand, respectively, it was concluded that the matches seized were distinctly different from those collected at the crime scene.

Journal Article↗

High-precision, automated stable isotope analysis of atmospheric methane and carbon dioxide using continuous-flow isotope-ratio mass spectrometry.

Small-scale developments have been made to an off-the-shelf continuous-flow gas chromatography/isotope-ratio mass spectrometry (CF-GC/IRMS) system to allow high-precision isotopic analysis of methane (CH(4)) and carbon dioxide (CO(2)) at ambient concentrations. The repeatability (1sigma) obtainable with this system is 0.05 per thousand for delta(13)C of CH(4), 0.03 per thousand for delta(13)C of CO(2), and 0.05 per thousand for delta(18)O of CO(2) for ten consecutive analyses of a standard tank. An automated inlet system, which allows diurnal studies of CO(2) and CH(4) isotopes, is also described. The improved precision for CH(4) analysis was achieved with the use of a palladium powder on quartz wool catalyst in the combustion furnace, which increased the efficiency of oxidation of CH(4) to CO(2). The automated inlet further improved the precision for both CH(4) and CO(2) analysis by keeping the routine constant. The method described provides a fast turn-around in samples, with accurate, reproducible results, and would allow a long-term continuous record of CH(4) or CO(2) isotopes at a site to be made, providing information about changing sources of the gases both seasonally and interannually.

Air Pollution↗

Acquired hydrocephalus. II. Diagnostic and prognostic value of quantitative isotope ventriculography (QIV), lumbar isotope cisternography (LIC), pneumoencephalography, and continuous intraventricular pressure recording (CIP).

The diagnostic and prognostic values of quantitative isotope ventriculography (QIV), lumbar isotope cisternography (LIC), pneumoencephalography (PEG), and continuous intraventricular pressure recording (CIP) were assessed on the basis of the clinical course in 160 patients suspected of having acquired hydrocephalus. The diagnostic value of a given method is defined as its reliability in the diagnosis of hydrocephalus. The reliability in the selection of hydrocephalic patients who will improve on shunt operation is designated as the prognostic value of the method concerned. As the diagnoses are based on isotopic procedures, the diagnostic values of these procedures cannot be assessed. QIV is of greater prognostic value than the other methods of examination. The presence of plateau waves in CIP is a rare, but prognostically valuable sign. The prognostic value of B waves is also good, whereas their diagnostic value is slight. Both from diagnostic and prognostic points of view, PEG is of less value is communicating hydrocephalus on account of the many false findings.

Cerebral Ventricles↗

Dual isotope separation technique for radioassay. The effect of cross counting between two simultaneously counted isotopes.

A theoretical model, describing the effects of cross counting on the dual-isotope-corrected bound count rate and on the precision with which it is estimated, is presented. Experimental support for the validity of the model is given. The bound count rate is shown to be independent of the amount of marker isotope incorrectly counted as label isotope. The precision with which the bound count rate is estimated appears to be dependent on the size of this cross counting correction, although other factors such as pipetting errors are of more importance. Implications for the choice of assay system are discussed.

Cobalt Radioisotopes↗

Evidence of a systematic deviation of the isotopic composition of neon from commercial sources compared with its isotopic composition in air.

Results are reported of a study concerning the variation in isotopic composition of a limited number of neon samples of commercial origin and the resulting influence on the temperature of the triple point of this element. All seven neon samples investigated were found to contain more 22Ne than neon in air, and the amount fraction of 22Ne varied by as much as 0.2% from sample to sample. This variation corresponds to a range of triple-point temperatures (Ttp) of more than 200 microK, much larger than the state-of-the-art uncertainty in the realization of this phase transition for metrological purposes. Deviations in the amount fractions of 21Ne were irrelevant, as far as their effect on T(tp) is concerned, though they may have relevance to other isotope studies. Ratios of amounts of neon isotopes at IRMM-Geel were obtained using the same measurement procedures, and instrumentation developed in the framework of the redetermination of the Avogadro constant and all significant sources of uncertainty were taken into account. The repeatability of the ion current ratio measurements on individual samples was 5 x 10(-5) relative. All uncertainty statements are made following the ISO/BIPM Guide to the Expression of Uncertainty in Measurements. Whereas these results proved unexpected, a more comprehensive study will follow incorporating a much wider range of samples of commercial origin.

Letter↗

A new form of kinetic isotope effect. Dynamic effects on isotopic selectivity and regioselectivity.

The intramolecular H/D kinetic isotope effect in the ene reaction of singlet oxygen with tetramethylethylene is studied using quasiclassical direct dynamics calculations on a B3LYP/6-31G* potential energy surface. Starting from the area of the energy surface around a valley-ridge inflection point, random trajectories lead to predominantly H abstraction over D abstraction, despite the symmetry of the surface and the absence of a barrier to either reaction. This demonstrates a new form of kinetic isotope effect, unrelated to the usual effect of zero-point energies on barriers. Dynamics calculations on the reaction of cis-2-pentene predict the experimentally observed mixture of regioisomeric products, while the minimum-energy path leads to only one product. For energy surfaces containing two adjacent saddle points, dynamics effects are important for understanding both product and isotopic selectivity, and this should be considered in the interpretation of experimental results.

Alkenes↗

Isotopic self-exchange reactions of water: evaluation of the rule of the geometric mean in liquid-vapor isotope partitioning.

Deviations from the random distribution of hydrogen isotopes among isotopic species of liquid and vapor water (the rule of the geometric mean) were critically assessed theoretically and experimentally from the triple to critical point of water. A third-order polynomial equation of the classical near-critical expansion was used to accurately describe the liquid-vapor isotope fractionation of H2O and D2O on the basis of their equations of state. It was found that experimental data for the enthalpy of mixing of H2O-D2O can be used to calculate accurately the deviation from the rule of the geometric mean in liquid and vapor water, ln(KD(v)/KD(l)). A new equation obtained in this study shows that the value of ln(KD(v)/KD(l)) smoothly decreases from +0.009 to 0 with increasing temperature from the triple to critical temperature of water. In contrast, the equation available in the literature and that derived from mass spectrometric measurements of liquid-vapor partitioning of H2O and HDO show complex behavior, including maximum, minimum, and crossover.

Journal Article↗

In situ Os isotopes in abyssal peridotites bridge the isotopic gap between MORBs and their source mantle.

Abyssal peridotites are assumed to represent the mantle residue of mid-ocean-ridge basalts (MORBs). However, the osmium isotopic compositions of abyssal peridotites and MORB do not appear to be in equilibrium, raising questions about the cogenetic relationship between those two reservoirs. However, the cause of this isotopic mismatch is mainly due to a drastic filtering of the data based on the possibility of osmium contamination by sea water. Here we present a detailed study of magmatic sulphides (the main carrier of osmium) in abyssal peridotites and show that the 187Os/188Os ratio of these sulphides is of primary mantle origin and can reach radiogenic values suggesting equilibrium with MORB. Thus, the effect of sea water on the osmium systematics of abyssal peridotites has been overestimated and consequently there is no true osmium isotopic gap between MORBs and abyssal peridotites.

Journal Article↗

Computational evidence that the inverse kinetic isotope effect for reductive elimination of methane from a tungstenocene methyl-hydride complex is associated with the inverse equilibrium isotope effect for formation of a sigma-complex intermediate.

Calculations on [H2Si(C5H4)2]W(Me)H demonstrate that the interconversion between [H2Si(C5H4)2]W(Me)H and the sigma-complex [H2Si(C5H4)2]W(sigma-HMe) is characterized by normal kinetic isotope effects for both reductive coupling and oxidative cleavage; the equilibrium isotope effect, however, is inverse and is the origin of the inverse kinetic isotope effect for the overall reductive elimination of methane.

Journal Article↗

VLDL apolipoprotein B-100, a potential indicator of the isotopic labeling of the hepatic protein synthetic precursor pool in humans: studies with multiple stable isotopically labeled amino acids.

Four adult men received a 48-h constant intravenous infusion of [2H4]lysine, [2H3]leucine, L-[ring-13C6]phenylalanine, and L-[1,2,3,-13C3]alanine. Subjects ingested hourly meals for two 12-h periods, separated to two 12-h fasting periods. The isotopic enrichments of free amino acids in venous plasma and in VLDL apolipoprotein B-100 (apoB)-bound amino acids, plasma alpha-keto isocaproic acid (alpha-KIC) and plasma pyruvic acid (PYR) were measured by negative chemical ionization gas chromatography-mass spectrometry. By 7 h of infusion, all four amino acids achieved an equilibrium isotopic enrichment (EIE) in plasma and in apoB. In the fed state, the EIE of the amino acids in apoB was lower than that in plasma free amino acids. The ratio EIE-apoB:EIE-plasma differed significantly among amino acids in the fed state (alanine 0.30; lysine 0.64; leucine 0.70; phenylalanine 0.81). In the postabsorptive state, the EIE-apoB:EIE-plasma ratio rose significantly compared with the fed state (alanine 0.38; lysine 0.73; leucine 0.94; phenylalanine 1.05). Plasma PYR and apoB-alanine were in isotopic equilibrium irrespective of nutritional state. The EIE-apoB-leucine:EIE-plasma-alpha-KIC ratio rose from 0.75 in the fed state to near 1 in the postabsorptive state. We conclude that the contribution of systemic amino acids to apoB-100 synthesis is sensitive to nutritional state, and that systemic essential amino acids seem to be preferentially incorporated into apoB.

Adult↗

Comparison of isotopic equilibrium and dual isotope blood ratio methods for measurement of cholesterol absorption in rats.

The dual isotope plasma ratio method (IRM) was applied to eight 3-month-old rats fed a semipurified diet. 1 month later, the isotopic equilibrium method (IEM) was substituted and was continued for 2 months. The animals were therfore 6 months old at the end of the isotope experiment. The IRM was then applied to a second group of eight 6-month-old rats. No difference was seen between the absorption coefficient of cholesterol measured by the IRM in rats of the first (73 +/- 2%) and of the second groups (72 +/- 4%) or by the IEM (69 +/- 1%). A critical discussion of both techniques is presented.

Animals↗

A selective unsaturated hydrocarbon subtraction technique for stable carbon isotopic analysis of atmospheric methyl chloride, methyl bromide, and C2-C5 saturated hydrocarbons using continuous-flow isotope ratio mass spectrometry.

Using continuous-flow isotope ratio mass spectrometry, we have developed a new analytical system which enables us to determine the stable carbon isotopic composition of CH3Cl, CH3Br, and C2-C5 saturated hydrocarbons in gas samples even if they contain substantial amounts of unsaturated hydrocarbons, using an I2O5 reagent for their selective subtraction. The analytical precision of the delta13C determinations is better than 0.5 per thousand for >300 pmolC injections and better than 5 per thousand for 20 pmolC injections. Using the system, delta13C values for CH3Cl and CH3Br were found in burning exhaust that contain a substantial quantity of unsaturated hydrocarbons. CH3Cl and CH3Br measured in exhaust from burning rice plants exhibit highly 13C-depleted values of -56.6 +/- 1.3 per thousand and -48.6 +/- 3.9 per thousand, respectively, while saturated hydrocarbons exhibit delta13C values (-26.4 to -28.9 per thousand) that are comparable with the total delta13C value of the parent material (rice plant; -28.0 per thousand). Using the system, we can determine the delta13C values of methyl halides and hydrocarbons in many kinds of gas samples.

Air Pollutants↗

Application of the combination of isotope ratio monitoring with isotope dilution mass spectrometry to the determination of glucose in serum.

Isotope ratio monitoring combined with n((13)C)/n((12)C) isotope dilution mass spectrometry (IRM/IDMS) provides results of low uncertainty of the order of 0.1% if it is applied to the analysis of simple mixtures as found in organic chemistry, even if only low (13)C spike additives to the sample are used. If the method is applied to the analysis of systems that require large-scale sample preparation prior to the measurement, such as the determination of glucose in serum, the results obtained exhibit a higher uncertainty that is comparable to that of the conventional gas chromatography/isotope dilution mass spectrometry (GC/IDMS) method. The reason for this observation is that the small contribution that the IRM/IDMS method makes to the uncertainty budget of the result is superimposed on a large contribution due to the sample preparation. It appears therefore that the IRM/IDMS method has no advantage over the conventional GC/IDMS method. However, if a series of measurements is carried out, and if a suitable experimental design is chosen, the IRM/IDMS method can provide valuable additional information. The influence of sample preparation on each individual result can be quantified as its deviation from the average value of all results of the series. From these data conclusions can be drawn for an improvement in sample preparation.

Algorithms↗

An electron paramagnetic resonance method for quantification of copper isotopes in proteins: application to a mixed-isotope derivative of laccase.

We have developed a method of denaturing a copper-containing protein and sequestering the copper in the form of the bis(acetylacetonato)copper(II) complex. Because of the excellent resolution of the hyperfine structure in the resulting EPR spectrum, the method is useful for determining the 65Cu/63Cu isotope ratio in proteins such as tree laccase. Here we analyzed a mixed isotope sample prepared by reconstituting 63Cu-enriched type 2-depleted laccase with 65Cu(I) and found that it contained only 25% 65Cu. This proves that reconstitution of the type 2 copper is possible under conditions that permit little or no exchange between resident copper and the external pool. However, exchange does occur under reducing conditions when we expose the holoprotein to a large excess of exogenous copper.

Binding Sites↗

Stable-isotope probing of DNA: insights into the function of uncultivated microorganisms from isotopically labeled metagenomes.

Stable-isotope probing (SIP) of environmental genomic DNA allows populations in a natural microbial community to be identified through the incorporation of (13)C- or (15)N-labeled substrates into biomass. The isotopically labeled DNA is retrieved by density gradient centrifugation, and active microorganisms identified by molecular analysis of the DNA. Recent advances have set the stage for DNA-based SIP with higher sensitivities, shorter incubation times, and more relevant substrate concentrations than used previously. The first demonstration of a DNA-SIP-based metagenome analysis has paved the way for hypothesis-driven studies in environmental genomics.

Bacteria↗

Carbonyl 13C NMR spectrum of basic pancreatic trypsin inhibitor: resonance assignments by selective amide hydrogen isotope labeling and detection of isotope effects on 13C nuclear shielding.

The carbonyl region of the natural abundance 13C nuclear magnetic resonance (NMR) spectrum of basic pancreatic trypsin inhibitor is examined, and 65 of the 66 expected signals are characterized at varying pH and temperature. Assignments are reported for over two-thirds of the signals, including those of all buried backbone amide groups with slow proton exchange and all side-chain carbonyl groups. This is the first extensively assigned carbonyl spectrum for any protein. A method for carbonyl resonance assignments utilizing amide proton exchange and isotope effects on nuclear shielding is described in detail. The assignments are made by establishing kinetic correlation between effects of amide proton exchange observed in the carbonyl 13C region with development of isotope effects and in the amide proton region with disappearance of preassigned resonances. Several aspects of protein structure and dynamics in solution may be investigated by carbonyl 13C NMR spectroscopy. Some effects of side-chain primary amide group hydrolysis are described. The main interest is on information about intramolecular hydrogen-bond energies and changes in the protein due to amino acid replacements by chemical modification or genetic engineering.

Amides↗

Continuous flow isotope ratio mass spectrometry for the measurement of nanomole amounts of (13)CO(2) by a reverse isotope dilution method.

A simple method for the determination of nanomole amounts of (13)CO(2) generated from an in vitro reaction is reported. The incubation medium contains a known amount of unlabeled sodium bicarbonate and the gaseous (13)CO(2) enriches the atmosphere upon which a measurement of the isotopic enrichment ((13)CO(2)/(12)CO(2)) is made corresponding to a reverse isotope dilution. The quantification of the (13)CO(2) was performed by gas chromatography/isotope ratio mass spectrometry. This assay was validated in terms of linearity, accuracy and precision using three different substrates which produce (13)CO(2) either by enzymatic reaction [(13)C]urea, sodium [(13)C]formate) or by chemical reaction (sodium [(13)C]bicarbonate). Four calibration curves were tested for each (13)C-labeled substrate, allowing the quantification of (13)CO(2) from 25 pmol to 150 nmol. The dynamics of the assay were obtained as a function of the quantity of unlabeled sodium bicarbonate added to each sample.

Algorithms↗

Deuterium isotope effects in carbohydrates revisited. Cryoprobe studies of the anomerization and NH to ND deuterium isotope induced 13C NMR chemical shifts of acetamidodeoxy and aminodeoxy sugars.

Complete 1H and 13C NMR chemical shift assignments have been generated from a series of acetamidodeoxy and aminodeoxy sugar derivatives. For free sugars, the enhanced sensitivity of an NMR cryoprobe allowed simple 1D and 2D NMR spectra to be obtained from essentially single anomers, before significant mutarotation had occurred. The NMR assignments have been used to characterize deuterium isotope effects on 13C chemical shifts measured under conditions of slow NH to ND exchange in single solutions. Within a range of 0 to -0.138 ppm, beta, gamma, delta, and zeta deuterium isotope effects have been observed, thus providing additional reference data for assignment of the 13C NMR spectra of nitrogenous saccharides.

Amination↗