Isotopes dilution

A more detailed study of the nitration of quinolinium (l) in 80-05 % sulphuric acid at 25 °C, using isotopic dilution analysis, has shown that 3-) 5-) 6-, 7- and 8-nitroquinoline are formed (table 10.3). Combining these results with the kinetic ones, and assuming that no 2- and 4-nitration occurs, gives the partial rate factors listed in table 10.4. Isoquinolinium is 14 times more reactive than quinolinium. The strong deactivation of the 3-position is in accord with an estimated partial rate factor of io for hydrogen isotope exchange at the 3-position in the pyridinium ion. It has been estimated that the reactivity of this ion is at least 10 less than that of the quinolinium ion. Based on this estimate, the partial rate factor for 3-nitration of the pyridinium ion would be less than 5 x io . 

Two other techniques that depend only on base SI units are coulometry and isotope-dilution mass spectrometry. Coulometry is discussed in Chapter 11. Isotope-dilution mass spectroscopy is beyond the scope of an introductory text, however, the list of suggested readings includes a useful reference. 

Por a review of isotope dilution mass spectrometry see the following article. 

Eassett, J. D. Paulsen, P. J. Isotope Dilution Mass Spectrometry for Accurate Elemental Analysis, Anal. Chem. 1989, 61, 643A-649A. 

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. 

Isotope Dilution Another important quantitative radiochemical method is isotope dilution. In this method of analysis a sample of analyte, called a tracer, is prepared in a radioactive form with a known activity. Ax, for its radioactive decay. A measured mass of the tracer, Wf, is added to a sample containing an unknown mass, w, of a nonradioactive analyte, and the material is homogenized. The sample is then processed to isolate wa grams of purified analyte, containing both radioactive and nonradioactive materials. The activity of the isolated sample, A, is measured. If all the analyte, both radioactive and nonradioactive, is recovered, then A and Ax will be equal. Normally, some of the analyte is lost during isolation and purification. In this case A is less than Ax, and... 

The concentration of insulin in a production vat is determined by the method of isotope dilution. A 1.00-mg sample of insulin labeled with with an activity of 549 cpm, is added to a 10.0-mL sample taken from the production vat. After homogenizing the sample, a portion of the insulin is separated and purified, yielding 18.3 mg of pure insulin. The activity for the isolated insulin is measured at 148 cpm. How many milligrams of insulin are in the original sample ... 

Equations 13.31 and 13.32 are only valid if the radioactive element in the tracer has a half-life that is considerably longer than the time needed to conduct the analysis. If this is not the case, then the decrease in activity is due both to the effect of dilution and the natural decrease in the isotope s activity. Some common radioactive isotopes for use in isotope dilution are listed in Table 13.1. 

An important feature of isotope dilution is that it is not necessary to recover all the analyte to determine the amount of analyte present in the original sample. Isotope dilution, therefore, is useful for the analysis of samples with complex matrices, when a complete recovery of the analyte is difficult. 

Geiger counter (p. 643) half-life (p. 643) isotope dilution (p. 646)... 

Radiochemical methods of analysis take advantage of the decay of radioactive isotopes. A direct measurement of the rate at which a radioactive isotope decays may be used to determine its concentration in a sample. For analytes that are not naturally radioactive, neutron activation often can be used to induce radioactivity. Isotope dilution, in which a radioactively labeled form of an analyte is spiked into the sample, can be used as an internal standard for quantitative work. 

Isotopic dilution analysis is widely used to determine the amounts of trace elements in a wide range of samples. The technique involves the addition to any sample of a known quantity (a spike) of an isotope of the element to be analyzed. By measuring isotope ratios in the sample before and after addition of the spike, the amount of the trace element can be determined with high accuracy. The method is described more fully in Figure 48.13. 

Although isotope-dilution analysis can be very accurate, a number of precautions need to be taken. Some of these are obvious ones that any analytical procedure demands. For example, analyte preparation for both spiked and unspiked sample must be as nearly identical as possible the spike also must be intimately mixed with the sample before analysis so there is no differential effect on the subsequent isotope ration measurements. The last requirement sometimes requires special chemical treatment to ensure that the spike element and the sample element are in the same chemical state before analysis. However, once procedures have been set in place, the highly sensitive isotope-dilution analysis gives excellent precision and accuracy for the estimation of several elements at the same time or just one element. 

A major example of isotope-dilution analysis lies in the procedure itself, which does not require any quantitative isolation of the elements being investigated. The relation between the abundance of the element under investigation and the spike is such that, once the spike has been intimately mixed with the sample, any losses of sample have no effect on the result (Figure 48.14). 

It is not necessary that there be two isotopes in both the sample and the spike. One isotope in the sample needs to be measured, but the spike can have one isotope of the same element that has been produced artificially. The latter is often a long-lived radioisotope. For example, and are radioactive and all occur naturally. The radioactive isotope does not occur naturally but is made artificially by irradiation of Th with neutrons. Since it is commercially available, this last isotope is often used as a spike for isotope-dilution analysis of natural uranium materials by comparison with the most abundant isotope ( U). 

IKES. ion kinetic energy spectroscopy IRMS. isotope ratio mass spectrometry ISDMS. isotope dilution mass spectrometry ITMS. ion trap mass spectrometry LA. laser ablation... 

Isotope Dilution Assay. An isotope dilution assay for biotin, based on the high affinity of avidin for the ureido group of biotin, compares the binding of radioactive biotin and nonradio active biotin with avidin. This method is sensitive to a level of 1—10 ng biotin (82—84), and the radiotracers typically used are p C]biotin (83), [3H]biotin (84,85) or an I-labeled biotin derivative (86). A variation of this approach uses I-labeled avidin (87) for the assay. 

ICPMS is uniquely able to borrow a quantitation technique from molecular mass spectrometry. Use of the isotope dilution technique involves the addition of a spike having a different isotope ratio to the sample, which has a known isotope ratio. This is usefiil for determining the concentration of an element in a sample that must undergo some preparation before analysis, or for measuring an element with high precision and accuracy. ... 

A solution of 3j5-hydroxy-5a-androstan-7-one (10, 50 mg) in methanol-OD (4 ml) is saturated with deuterium oxide containing 5 % sodium deuterioxide (prepared by reacting sodium with deuterium oxide) and heated under reflux for 3 days. (If the heated solution becomes turbid due to supersaturation, a few drops of methanol-OD should be added until a clear solution is obtained. The use of a drying-tube on top of the condenser is advisable to avoid isotope dilution from moisture.)... 

Radioactivity. Methods based on the measurement of radioactivity belong to the realm of radiochemistry and may involve measurement of the intensity of the radiation from a naturally radioactive material measurement of induced radioactivity arising from exposure of the sample under investigation to a neutron source (activation analysis) or the application of what is known as the isotope dilution technique. 

Isotopic dilution. A known amount of the element being determined, containing a radioactive isotope, is mixed with the sample and the element is isolated in a pure form (usually as a compound), which is weighed or otherwise determined. The radioactivity of the isolated material is measured and compared with that of the added element the weight of the element in the sample can then be calculated. 

D. with EDTA, (s) 678, 690 Iron ware, 97 wire, 262, 376 Isotopic dilution 132... 

The isotope dilution principle, first employed by Hevesy and Hobbie (133) in 1932 for the determination of lead in ores, was applied by Schoenheimer et al. (241) to the determination of amino acids. [Shemin and Foster (248) have reviewed this topic.] An N15-amino acid derivative was added to a protein hydrolyzate, a sample of the amino acid to be determined was isolated and purified, the excess N15 in this product was estimated with the mass spectrograph, and the grams of amino acid originally present were calculated from Equation 2. 

Other methods involve isotopic dilution, kinetic resolution, relaxation rates of diastereomeric complexes, luminescence. ... 

Since the carrier effect is not general for all analytes and all additives, quantitative studies using the particle-beam interface should only be carried out after a very careful choice of experimental conditions and standard(s) to be used, with isotopic-dilution methodology being advocated for the most accurate results. 

The particle-beam interface has been developed primarily to provide El spectra from HPLC eluates but may be combined with other ionization techniques such as CL If quantitative studies are being undertaken, a detailed study of experimental conditions should be undertaken. Isotope-dilution methodology is advocated for the most accurate results. 

Oxidation of [2- C]acetone produced the following yields of products identified by isotope dilution analysis... 

Very little hydrogen peroxide was found as a product (by isotope dilution analysis), and it was ruled out as an intermediate by addition of 0-labelled H2O2 before reaction. 

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