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Isotopic labels deuterium

A quite different use of isotopes in mechanistic studies involves their use as labels for ascertaining the location of a given atom involved in a reaction. As in kinetic experiments, the isotopic substitution will not qualitatively affect the course of the reaction. The nuclei most commonly used for isotopic tracer experiments in organic chemistry are deuterium, tritium, and the and isotopes of carbon. There are several means of locating isotopic labels. Deuterium can frequently be located by analysis of NMR spectra. In contrast to the normal isotope, deuterium... [Pg.220]

The first mass spectrometric investigation of the thiazole ring was done by Clarke et al. (271). Shortly after, Cooks et al., in a study devoted to bicydic aromatic systems, demonstrated the influence of the benzo ring in benzothiazole (272). Since this time, many studies have been devoted to the influence of various types of substitution upon fragmentation schemes and rearrangements, in the case of alkylthiazoles by Buttery (273) arylthiazoles by Aune et al. (276), Rix et al. (277), Khnulnitskii et al. (278) functional derivatives by Salmona el al. (279) and Entenmann (280) and thiazoles isotopically labeled with deuterium and C by Bojesen et al. (113). More recently, Witzhum et al. have detected the presence of simple derivatives of thiazole in food aromas by mass spectrometry (281). [Pg.81]

Substitution of deuterium for hydrogen at the a carbon atom of an aldehyde or a ketone is a convenient way to introduce an isotopic label into a molecule and is readily carried out by treating the carbonyl compound with deuterium oxide (D2O) and base... [Pg.768]

Isotopically Labeled Compounds. The hydrogen isotopes are given special names H (protium), H or D (deuterium), and H or T (tritium). The superscript designation is preferred because D and T disturb the alphabetical ordering in formulas. [Pg.216]

Below — 140°C, the EPR spectrum observed was that of the cyclopropylmethyl radical. If the photolysis was done above — 140°C, however, the spectmm of a second species was seen, and above — 100°C, this was the only spectmm observed. This second spectmm could be shown to be that of the 3-butenyl radical. This study also established that the 3-butenyl radical did not revert to the cyclopropylmethyl radical on being cooled back to — 140°C. The conclusion is that the ring opening of the cyclopropyl radical is a very facile process and that the lifetime of the cyclopropyl radical above — 100°C is very short. Even though the equilibrium favors the 3-butenyl radical, the reversible ring closure can be detected by isotopic labeling experiments, which reveal the occurrence of deuterium migration ... [Pg.669]

A disadvantage of this technique is that isotopic labeling can cause unwanted perturbations to the competition between pathways through kinetic isotope effects. Whereas the Born-Oppenheimer potential energy surfaces are not affected by isotopic substitution, rotational and vibrational levels become more closely spaced with substitution of heavier isotopes. Consequently, the rate of reaction in competing pathways will be modified somewhat compared to the unlabeled reaction. This effect scales approximately as the square root of the ratio of the isotopic masses, and will be most pronounced for deuterium or... [Pg.220]

Further evidence for different reaction pathways is obtained in isotope labelling experiments, illustrated in fig.6. Here we present a comparison of the effects of preadsorbing various amounts of deuterium with methyl groups cm the two metal surfaces. [Pg.332]

Figure 16.2 The original design of the ICAT compound. The iodoacetyl group provides reactivity with thiol groups. The isotopically labeled spacer arm typically is substituted with eight deuterium atoms. Figure 16.2 The original design of the ICAT compound. The iodoacetyl group provides reactivity with thiol groups. The isotopically labeled spacer arm typically is substituted with eight deuterium atoms.
Figure 16.4 A more advanced ICAT design uses an acid-cleavable spacer arm to facilitate elution of labeled peptides from a (strept)avidin affinity column. The use of 14C isotopes instead of deuterium labels permits precise reverse phase separations prior to mass spec that show no elution peak time differences between isotope-labeled and normal atom-labeled peptides. Figure 16.4 A more advanced ICAT design uses an acid-cleavable spacer arm to facilitate elution of labeled peptides from a (strept)avidin affinity column. The use of 14C isotopes instead of deuterium labels permits precise reverse phase separations prior to mass spec that show no elution peak time differences between isotope-labeled and normal atom-labeled peptides.
Sections I-V of this chapter deal with the syntheses of unsaturated organic compounds playing an essential role in biochemical processes of life. Numerous polyunsaturated compounds have been synthesized in order to elucidate their physiological role, for instance in brain. However, the main impact on permanent searches for new improved methods of synthesis of isotopically labelled dienes and polyenes comes from nuclear medicine and nuclear pharmacy. The deuterium and carbon-13 labelled polyunsaturated compounds are needed as internal standards in mass spectral determinations of very low concentrations of biologically active substances in biological fluids. [Pg.776]

Internal standards are used in quantitative work in a similar manner to GLC. These are usually homologues or isotopically labelled analogues of the analyte, e.g. deuterium (2H). [Pg.129]

It may be concluded that for reactions where the proton is less or more than one-half transferred in the transition state, i.e. the A—H and H—B force constants are unequal, the primary hydrogen-deuterium kinetic isotope effect will be less than the maximum of seven. The maximum isotope effect will be observed only when the proton is exactly half-way between A and B in the transition state. This relationship is also found for carbon kinetic isotope effects where the isotopically labelled carbon is transferred between two atoms in the reaction10,11. This makes interpreting carbon isotope effects difficult. [Pg.896]

The acidity probes discussed above are the most commonly used. However, the use of many different probes has been reported in the literature. This list includes nitriles, alkanes, amines, water, di-hydrogen, deuterium, isotopically labeled molecules, benzene, etc. Probe molecules can also be used to measure basicity on zeohtes. In this case, weakly acidic molecules such as CO2, pyrrole, acetic acid and halogenated light paraffins have been used. Space does not permit discussion of these in any detail, but information about these probes and their applications can be found in the following references [87, 127-130]. [Pg.135]

For reliable quantification, the deuterium-labelled substrate (ds-phenylethyl-amine) was added to the matrix as internal standard. To circumvent the problem of crystal inhomogenities, 100 acceptable spectra were measured from seven to ten different positions of one sample spot and averaged. The MALDI-MS assay was validated with a gas chromatography-based quantification scheme and was found to be in good compliance. This methodology obviously allows a reliable quantification of the low molecular weight analytes of interest. Nevertheless, the need for isotopically labelled compounds as internal standards is still a bottleneck, as these are usually rather expensive or have to be laboriously synthesized. [Pg.287]


See other pages where Isotopic labels deuterium is mentioned: [Pg.225]    [Pg.333]    [Pg.225]    [Pg.186]    [Pg.225]    [Pg.333]    [Pg.225]    [Pg.186]    [Pg.81]    [Pg.646]    [Pg.660]    [Pg.579]    [Pg.179]    [Pg.646]    [Pg.8]    [Pg.193]    [Pg.109]    [Pg.22]    [Pg.87]    [Pg.106]    [Pg.531]    [Pg.650]    [Pg.653]    [Pg.734]    [Pg.85]    [Pg.28]    [Pg.403]    [Pg.88]    [Pg.319]    [Pg.378]    [Pg.102]    [Pg.4]    [Pg.703]   
See also in sourсe #XX -- [ Pg.47 , Pg.117 , Pg.131 , Pg.174 , Pg.216 , Pg.217 , Pg.224 , Pg.233 , Pg.250 , Pg.264 , Pg.278 , Pg.288 ]

See also in sourсe #XX -- [ Pg.47 , Pg.117 , Pg.131 , Pg.174 , Pg.216 , Pg.217 , Pg.224 , Pg.233 , Pg.250 , Pg.264 , Pg.278 , Pg.288 ]




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