Isotopomer mass

S 0 0)2 isotopomer (mass spectral analysis of the parent ion can not distinguish the two possibilities, vida infra). For the scrambling", or O-atom addition case, two possibilities exist. The first is that oxygenation of the first sulfur is by molecular addition and the subsequent formation of 3... 

The relative abundances of the sample and spike isotopomers are given at the masses shown, not the abundances of all possible isotopomer masses. 

This teclnhque can be used both to pennit the spectroscopic detection of molecules, such as H2 and HCl, whose first electronic transition lies in the vacuum ultraviolet spectral region, for which laser excitation is possible but inconvenient [ ], or molecules such as CH that do not fluoresce. With 2-photon excitation, the required wavelengdis are in the ultraviolet, conveniently generated by frequency-doubled dye lasers, rather than 1-photon excitation in the vacuum ultraviolet. Figure B2.3.17 displays 2 + 1 REMPI spectra of the HCl and DCl products, both in their v = 0 vibrational levels, from the Cl + (CHg) CD reaction [ ]. For some electronic states of HCl/DCl, both parent and fragment ions are produced, and the spectrum in figure B2.3.17 for the DCl product was recorded by monitoring mass 2 (D ions. In this case, both isotopomers (D Cl and D Cl) are detected. 

Mass spectrometry (MS) in its various forms, and with various procedures for vaporization and ionization, contributes to the identification and characterization of complex species by their isotopomer pattern of the intact ions (usually cation) and by their fragmentation pattern. Upon ionization by the rough electron impact (El) the molecular peak often does not appear, in contrast to the more gentle field desorption (FD) or fast-atom bombardment (FAB) techniques. An even more gentle way is provided by the electrospray (ES) method, which allows all ionic species (optionally cationic or anionic) present in solution to be detected. Descriptions of ESMS and its application to selected problems are published 45-47 also a representative application of this method in a study of phosphine-mercury complexes in solution is reported.48... 

Unknown 14. Calculate the percentage of isotopomers in the sample of acetophenone with the following mass spectra ... 

The measurements of the labeled metabolites may be performed with GC- or LC-MS, or by NMR. Because it is the most commonly used method, we will only consider GC-MS based approaches here. Obviously and unfortunately, it is not possible to directly measure the isotopomer enrichments by GC-MS, because the apparatus only yields total masses of molecules or fractions thereof, but not directly the position of a label. Each MS peak is produced by all isotopomers with the same molecular weight that is, the same number of labeled carbon positions. Sometimes this concept is also called mass isotopomers [264]. In a so-called retrobiosynthetic approach, it has been shown that the labeling state of many intracellular pools can be determined indirectly by measuring the labels in macromolecular biomass components at steady state for example, the labeling state of alanine from hydrolyzed protein reflects the label of pyruvate [265]. Using this approach, it is possible to quantify fluxes into storage components. 

Huege et al. [271] cultivated Arabidopsis plants in 13C02 atmosphere, transferred the plants to normal atmosphere, and monitored the dilution of isotopes in several metabolite pools. Through evaluation of the mass isotopomer distribution, metabolite partitioning processes could be monitored. However, due to the lack of absolute metabolite concentrations, no absolute fluxes could be calculated. Nevertheless, building upon this method, suitable approaches for flux analysis in autotrophic tissue might be derived in the future. 

The alkene loss from ionized cycloalkyl-substituted nitrobenzenes has been studied by isotopic labelling and collision activation mass spectrometry77. The reaction path was found to depend highly on the placement of the nitro group. The ortho nitro-substituted phenylcyclopropane and its isotopomers were studied. 

Another classical case with respect to ort/zo-effects is found for 2-nitrostyrene78. The conceivable regio- and stereo-specifically labelled 2-nitrostyrenes have, in addition to the ring-labelled isotopomer, been studied by collision activation mass spectrometry79. Undoubtedly, the most striking result was the nearly equal contribution of both (in the neutral molecule diastereotopic) hydrogens of the fi-carbon. 

Obviously, there is an isotope effect on the vibrational frequency v . For het-eroatomic molecules (e.g. HC1 and DC1), infrared spectroscopy permits the experimental observation of the molecular frequencies for two isotopomers. What does one learn from the experimental observation of the diatomic molecule frequencies of HC1 and DC1 To the extent that the theoretical consequences of the Born-Oppenheimer Approximation have been correctly developed here, one can deduce the diatomic molecule force constant f from either observation and the force constant will be independent of whether HC1 or DC1 was employed and, for that matter, which isotope of chlorine corresponded to the measurement as long as the masses of the relevant isotopes are known. Thus, from the point of view of isotope effects, the study of vibrational frequencies of isotopic isomers of diatomic molecules is a study involving the confirmation of the Born-Oppenheimer Approximation. 

The vibrational frequencies of isotopic isotopomers obey certain combining rules (such as the Teller-Redlich product rule which states that the ratio of the products of the frequencies of two isotopic isotopomers depends only on molecular geometry and atomic masses). As a consequence not all of the 2(3N — 6) normal mode frequencies in a given isotopomer pair provide independent information. Even for a simple case like water with only three frequencies and four force constants, it is better to know the frequencies for three or more isotopic isotopomers in order to deduce values of the harmonic force constants. One of the difficulties is that the exact normal mode (harmonic) frequencies need to be determined from spectroscopic information and this process involves some uncertainty. Thus, in the end, there is no isotope independent force field that leads to perfect agreement with experimental results. One looks for a best fit of all the data. At the end of this chapter reference will be made to the extensive literature on the use of vibrational isotope effects to deduce isotope independent harmonic force constants from spectroscopic measurements. 

The second rule for isotopomer harmonic frequencies is the so-called Sum Rule which follows from Equation 3.A1.8. Equation 3.A1.8 relates the sum of the squares of all the frequencies to the sum of the diagonal matrix elements of the (FG) matrix diagonalized to obtain the frequencies. When mass weighted Cartesian displacement coordinates are used to calculate the vibration frequencies, this means that the sum of the A s (A = 4n2v12)can be found as follows (Equation3.51)... 

In Chapter 3, a formula was presented which connects the normal vibrational frequencies of two rigid-rotor-harmonic-oscillator isotopomers with their respective atomic masses m , molecular masses Mi and moments of inertia (the Teller-Redlich product rule). If this identity is substituted into Equation 4.77, one obtains... 

We have seen that Equation 4.95 for (s2/si)f involves the difference between the sums of the squares of the frequencies for two isotopomers. Consider now two isotopic atoms X and with masses ma and mp and two isotopomers AX and AXP with mp > ma. Then, from Equations 4.95 and 4.99, according to the first quantum correction... 

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