The use of isotopes

Radioactive and non-radioactive isotopes have proved to be of great value in providing insight into the mechanism of catalytic reactions. They have been used less frequently to provide information about reaction kinetics. Deuterium, tritium, carbon-14, nitrogen-15 and oxygen-18 are the most commonly used isotopes. 

The use of deuterium has been reviewed by Taylor and more recently by Emmett et It can be obtained commercially in a sealed flask or prepared 

Deuterium and its exchange products are normally detected by mass spectrometry (the use of mass spectrometers is discussed in the next section). 

The other modifications of hydrogen which have been employed in kinetic measurements are para-hydtogGti and or/Ao-hydrogen. These modifications are not isotopes in the normal sense, differing only in the direction of their nuclear spins. At room temperature, the equilibrium mixture of ortho and para hydrogen (normal hydrogen) contains 25 % para-hydrogen. As the temperature is lowered, 

Analysis of hydrogen mixtures with a thermal conductivity cell is well established. The most accurate measurements are obtained by use of a thermal conductivity gauge with the walls immersed in liquid nitrogen and the wire heated to 160° K. This is the teniperature when the difference in the rotational specific heats of orth h and para-hydrogen is a maximum . Various modifications of thermal conductivity gauges have been made to improve their convenience in use . A room temperature flow analyser based on a thermal conductivity cell has been developed by Weitzel and White which is claimed to be as sensitive as low temperature units. Bridge current and temperature must be controlled very carefully, but the unit is relatively insensitive to changes in pressure and flow rate. 

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The use of isotopic substitution to detennine stmctures relies on the assumption that different isotopomers have the same stmcture. This is not nearly as reliable for Van der Waals complexes as for chemically bound molecules. In particular, substituting D for H in a hydride complex can often change the amplitudes of bending vibrations substantially under such circumstances, the idea that the complex has a single stmcture is no longer appropriate and it is necessary to think instead of motion on the complete potential energy surface a well defined equilibrium stmcture may still exist, but knowledge of it does not constitute an adequate description of the complex. 

The proportionality between the concentration of chromophores and the measured absorbance [Eqs. (6.8) and (6.9)] requires calibration. With copolymers this is accomplished by chemical analysis for an element or functional group that characterizes the chromophore, or, better yet, by the use of isotopically labeled monomers. 

Cu/ Zn0/Si02 catalyst reduced at 700 K [3.147]. These LEIS spectra were obtained at three different ion doses - 3 x 3.41 x 10 and 8.67 x 10 Ne" cm . Because of the use of isotopically enriched Cu and Zn, and of Ne" ions as projectiles, Cu and Zn can clearly be separated in the LEIS spectrum. Strong dose-dependence is apparent. Eig. 3.60b shows the dose-dependent surface concentrations of Cu and Zn. At low doses (<1.5 x lO " Ne cm ) the Zn concentration remains constant whereas the Cu concentration increases. At these low doses a hydroxyl layer on top of the catalyst is sputtered. The Zn signal stays constant despite removal of the adsorbate, indicating that at the virgin surface the Zn concentration was even higher. 

For a review of the use of isotopic labeling to study Friedel-Crafts reactions, see Roberts, R.M. Gibson, T.L. Isot. Org. Chem., 1980, 5, 103. 

This selectivity allows the use of isotopically labelled analytes as internal standards and this, coupled with high sensitivity, allows very accurate and precise quantitative determinations to be carried out. 

The preparation of antibodies specific for the individual plasma proteins has greatly facilitated their smdy, allowing the precipitation and isolation of pure proteins from the complex mixmre present in tissues or plasma. In addition, the use of isotopes has made possible the determination of their pathways of biosynthesis and of their turnover rates in plasma. 

Example illustrates the use of isotopic molar masses and natural abundances to calculate the molar mass of elemental iron. 

SlEKMANN L (1979) Determination of steroid hormones by the use of isotope dilution mass spectrometry a definitive method in clinical chemistry. J Steroid Biochem 11 117-123. 

Fritz P, Drimmie RJ, Frape SK, O Shea K (1987) The isotopic composition of precipitation and groundwater. In Canada International Symposium on the Use of Isotope Techniques in Water Resources Development. IAEA Symposium, Vienna 299 539-550 Frumkin A, Ford DC, Schwarcz HP (1999) Continental oxygen isotopic record of the last 170,000 years in Jerasalem. (JuatRes 51 317-327... 

It is also important to note that matrix-related effects, either signal enhancement or more commonly signal suppression, can have a pronounced effect on quantitative measurements. Based on these observations, the use of isotope-labeled standards is helpful to achieve accurate analytical measurement data on the diastereoisomers. Several methods found in the open literature include use of both 13C-labeled and d18-labeled surrogates as recovery and/or instrument standards [118],... 

The characteristics of nuclei described here are intimately related to how certain species figure prominently in chemistry (such as dating materials by determining their carbon-14 content). The use of isotopic tracers is a technique that finds applications in all areas of chemistry. 

The analytical detectability applying a CL method should, in principle, be comparable to that obtained using radioactive labels, without all the disadvantages related to the use of isotopic labeling. In fact, assuming reasonable values for the quantum efficiency of the chemiluminescent reaction (Cl 0.01), for the overall photon collection efficiency of the optical system-CCD camera assembly (T) 0.01%), and for the intensity of the lowest detectable CL signal (about... 

Finally, in many cases the acidity equilibria cannot be measured but the rate of proton transfer or transmetallation can be measured to give an ionic or ion pair kinetic acidity. Studies using the rates of proton transfer have included the use of isotopes such as tritium and deuterium5,6. The rate is then used to calculate the Brpnsted slope, a, by plotting the logarithm of the proton transfer rate against the pK, as determined by the equilibrium acidity, for a series of compounds. From this plot, the approximate pKa of an unknown compound can be determined by comparison of the same type of compounds. 

Final remarks. The 14C-KIE and 2H-SKIE data presented in this Section (VLB) clearly indicate the usefulness of isotope effect methodology in studies of mechanistic details of thermally induced Claisen rearrangement, which provides a synthetic route to y,5-unsaturatcd carbonyl compounds. The primary and secondary 14C KIE supplement strongly the deuterium SKIE. Especially easy for interpretation are 14C and 2H isotope... 

The use of isotopically labelled organogermanium compounds in spectroscopic studies... 

Isotope Methods. The isotopes of calcium have relatively short half-lives and are readily counted using liquid scintillation or gamma counters as appropriate to the nuclide. Calcium isotopes may be quantitated in the excreta, blood, tissues or in the whole body. This has made them useful for many nutritional metabolic studies. However, because of safety concerns, radioactive isotopes are cumbersome to work with and many researchers are unwilling to administer them to human beings. This has limited the use of isotopes to those studies in which alternate methods are not available or are imprecise. Methodologies for stable isotopes of calcium, which may be safely used in human being, are becoming available for use in metabolism studies. These will be practical alternatives to radioactive isotopes in the future. 

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