Isotopic tracer measurements

Information on the steps in a reaction mechanism can be extended significantly by isotopic tracer measurements, especially by transient tracing [see Happel et al. (54,55)]. Studies by Temkin and Horiuti previously referenced here have been confined to steady-state isotopic transfer techniques. Modeling with transient isotope data is often more useful since it enables direct determination of concentrations of intermediates as well as elementary step velocities. When kinetic rate equations alone are used for modeling, determination of these parameters is more indirect. 

Not all mixed valence compounds show intervalence bands. Those that show not the slightest evidence for them are often called class 1. In class 2 intervalence compounds the intervalence-transfer band may well dominate the visible spectrum, swamping the spectra of the individual ions. However, these may be seen the important point is that the different ions retain their chemical individuality. Soluble Prussian blue is a case in point. This contains Fe and Fe bridged by CN ligands. Isotopic tracer measurements show that there is no doubt—the Fe" is bonded to the N atom of the CN ligand and the Fe to the C. If radioactive Fe is used in the preparation and the compound subsequently decomposed, the activity remains in the iron of the same valence state in which it was incorporated. A class 3 also exists, exemplified by the IJ anion, in which it is not possible to associate a unique valence state to individual metal ions typically, but as our example shows, not always, they are structurally indistinguishable. When they form an... 

Three common quantitative applications of radiochemical methods of analysis are considered in this section the direct analysis of radioactive isotopes by measuring their rate of disintegration, neutron activation, and the use of radioactive isotopes as tracers in isotope dilution. 

Nuclear reaction analysis (NRA) is used to determine the concentration and depth distribution of light elements in the near sur ce (the first few lm) of solids. Because this method relies on nuclear reactions, it is insensitive to solid state matrix effects. Hence, it is easily made quantitative without reference to standard samples. NRA is isotope specific, making it ideal for isotopic tracer experiments. This characteristic also makes NRA less vulnerable than some other methods to interference effects that may overwhelm signals from low abundance elements. In addition, measurements are rapid and nondestructive. 

NRA is an effective technique for measuring depth profiles of light elements in solids. Its sensitivity and isotope-selective character make it ideal for isotopic tracer experiments. NRA is also capable of profiling hydrogen, which can be characterized by only a few other analytical techniques. Future prospects include further application of the technique in a wider range of fields, three-dimensional mapping with microbeams, and development of an easily accessible and comprehensive compilation of reaction cross sections. 

The neutron activation technique mentioned in the preceding paragraph is only one of a range of nuclear methods used in the study of solids - methods which depend on the response of atomic nuclei to radiation or to the emission of radiation by the nuclei. Radioactive isotopes ( tracers ) of course have been used in research ever since von Hevesy s pioneering measurements of diffusion (Section 4.2.2). These techniques have become a field of study in their own right and a number of physics laboratories, as for instance the Second Physical Institute at the University of Gottingen, focus on the development of such techniques. This family of techniques, as applied to the study of condensed matter, is well surveyed in a specialised text... 

Isotope dilution measurements using a and/or spike tracer can be performed separately, or combined with the isotopic composition run. Spike tracers can be measured on an ion counting channel, or alternatively, it may be preferable to concentrate the tracer (provided the spike corrections are small) and measure it on a... 

Cochran JK, Masque P (2003) Short-lived U/Th-series radionuclides in the ocean tracers for scavenging rates, export fluxes and particle dynamics. Rev Mineral Geochem 52 461-492 Cohen AS, O Nions RK (1991) Precise determination of femtogram quantities of radium by thermal ionization mass spectrometry. Anal Chem 63 2705-2708 Cohen AS, Belshaw NS, O Nions RK (1992) High precision uranium, thorium, and radium isotope ratio measurements by high dynamic range thermal ionization mass spectrometry. Inti J Mass Spectrom Ion Processes 116 71-81... 

Unidirectional, first-order transfer rates (day1) between compartments were developed for 6 age groups, and intermediate age-specific values are obtained by linear interpolation. The range of age-specific transfer rate values are given in Table 2-8. The total transfer rate from diffusible plasma to all destinations combined is assumed to be 2,000 day"1, based on isotope tracer studies in humans receiving lead via injection or inhalation. Values for transfer rates in various tissues and tissue compartments are based on measured deposition fractions, or instantaneous fractional outflows of lead between tissue compartments (Leggett 1993). 

In principle to all elements at low (ppb) concentrations. Valuable for first look analysis, at solid samples. Isotopic ratio measurements can distinguish between sources of elements in tracer studies and environmental samples. Use in geological dating based upon isotopic ratios. 

Abundance in units of atom% is used for tracer measurements. This is an absolute measurement of the number of atoms of the isotope in 100 atoms of the element. For example ... 

We have developed an in vitro digestion procedure, not as a substitute for in vivo studies, but as a useful adjunct. Our initial objective was to develop an in vitro procedure for measuring exchangeability, the fraction of the food mineral which exchanges with an extrinsic isotope tracer added to the food. This was expected to facilitate the measurement of food mineral absorption in humans by the extrinsic tag method. Secondary objectives were to determine if in vitro mineral solubility could be used to estimate potential... 

The reaction mechanism of and active sites for the reaction have been studied using various techniques combined with an isotopic tracer method. Infrared spectra were measured for detection of surface adsorbates on the Cu-ZSM5 zeolites ESR, XPS, phosphorescence, diffuse reflectance UV, and Cu-MASNMR have been used to reveal the states of the copper ions in the catalysts. CO adsorption and TPD experiments have been employed to measure quantitativdy the amounts of Cu ions, NO adsorbed, and O2 remaining on the surface. Based on these investigations, we can propose a reasonable reaction mechanism which includes Cu ions as active sites and NO" species as reaction intermediates. The reaction cycle is suggested to be as foDows elevated temp. + 2NO... 

Isotope ratio measurements are performed whenever the exact ratio, or abundance, of two or more isotopes of an element must be known. For example, the isotopic ratios of lead are known to vary around the world, so it is possible to determine the source of lead in paint, bullets and petrol by knowing the isotopic abundances of the four lead isotopes 204, 206, 207, 208. Another example is the use of stable isotopes as metabolic tracers, where an animal is both fed and injected with an element having artificially enriched isotopes and the fractional absorption of the element can be accurately determined. 

In a discussion of permeability it is important to recognize that we deal with operational definitions, since the act of measurement influences the state of the system. In your case, applying an electrical potential gradient and performing electrodialysis alter the distribution of ionophore within the membrane. I wonder whether you have attempted to measure permeability by isotopic tracer techniques In this method the distribution of ionophore would not be influenced. Furthermore, information can be obtained on the question of carriers versus channels or pores. It should not be difficult to determine the extent of possible isotope interaction between tracer species and abundant species in the membrane as discussed by Kedem and Essig [J. Gen. Physiol., 48, 1047 (1965)]. Positive isotope interaction would tend to suggest the presence of channels or pores, negative isotope interaction the presence of carriers. 

A multiple ion collector device is required for the simultaneous determination of separated ion beams in precise and accurate isotope ratio measurements in order to study, for example, isotope fine variation in Nature or during tracer experiments using enriched stable isotope tracers. In thermal ionization mass spectrometers or in ICP-MS, mostly a system of several Faraday cups (up to 16) and/or ion counters (electron multipliers) is applied. In the photographs in Figures 4.7 and 4.8 examples of multiple ion collector systems are shown from the mass spectrometers MC-ICP-MS... 

Some of the methods for measuring molecular diffusion coefficients, together with a few recent references, are (a) diaphragm cell [60,61] (b) boundary layer interferometry [59] (c) shearing plate interferometry [58] (d) chromatographic peak broadening [60] (e) nuclear magnetic resonance and electron spin resonance [62, 63] (f) electrolyte conductance [64] (g) isotopic tracers [65] and (h) laminar jets [66]. 

The self-diffusion of component 1 in such a system is measured by studying the diffusion of a radioactive isotope tracer of component 1 (i.e., 1) under the condition that while there is a gradient in the tracer s concentration, c i, the sum (ci +c i) and C2 are both uniform. A possible diffusion couple is shown in Fig. 3.2. 

Unlike the Rh-based hydrogenation of a-(acylamino)acrylates, the corresponding Ru chemistry has not been studied extensively. Ru complexes of (S)-BINAP and (S,S)-CHIRAPHOS catalyze the hydrogenation of (Z)-a-(acylamino)cinnamates to give the protected ( -phenylalanine with 92% ee [74] and 97% ee [75], respectively. It is interesting that the Rh and Ru complexes with the same chiral diphosphines exhibit an opposite sense of asymmetric induction (Scheme 1.6) [13,15,56,74,75]. This condition is due primarily to the difference in the mechanisms the Rh-catalyzed hydrogenation proceeds via Rh dihydride species [76], whereas the Ru-catalyzed reaction takes place via Ru monohydride intermediate [77]. The Rh-catalyzed reaction has been studied in more detail by kinetic measurement [78], isotope tracer experiments [79], NMR studies [80], and MO calculations [81]. The stereochemical outcome is understandable by considering the thermodynamic stability and reactivity of the catalyst-enamide complexes. 

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