Nuclei, sensitivity

The product of isotopic abundance and relative sensitivity determines the overall sensitivity to detection of the isotope relative to hydrogen with its 99.985% natural abundance and unit relative sensitivity. Low y nuclei may be quite difficult to detect as sensitivity is proportional to y (e.g., Fe which is 3 x 10 times less sensitive than protons for equal numbers of nuclei). Sensitivity may be enhanced by repetitive spectral accumulation as the signal-to-noise (S/N) ratio is proportional to the square root of the number of accumulations. It requires 10 accumulations to give a Fe signal 1/50 the S/N of protons - a daunting task. 

Inverse geometry Term used to describe the construction of a probe that has the 1H receiver coils as close to the sample as possible and the X nucleus coils outside these 1H coils. Such probes tend to give excellent sensitivity for 1H spectra at the expense of X nucleus sensitivity in 1-D techniques. They offer a lot of compensation in terms of sensitivity of indirectly detected experiments. 

Selective probe heads are used for optimal sensitivity for a particular nucleus. Sensitivity of a selective H probe head is normally greater than that of a switchable probe head with indirect observation. With a selective X-nucleus (a nucleus other than proton) probe head, decoupling of protons is normally possible. Because of their limited usefulness, selective probe heads are rare in NMR laboratories. Other probe heads are also available, for example, those for triple resonance experiments and experiments utilizing pulsed-field gradients. In addition to their suitability for 2-D experiments, the gradients are particularly suitable for solvent suppression (20). 

Figure Bl.11.1. Resonance frequencies for different nuclei in a field of 14.1 T. Widths indicate the quoted range of shifts for each nucleus, and heights mdicate relative sensitivities at the natural isotopic abundance, on a log scale covering approximately six orders of magnitude. Nuclei resonatmg below 140 MHz are not shown.

The available sensitivity depends strongly on the equipment as well as the sample. H is the nucleus of choice for most experiments. 1 mg of a sample of a medium-sized molecule is adequate for almost all types of H-only spectra, and with specialized equipment one can work with nanogram quantities. At this lower level, the... 

Similar experiments exist to correlate the resonances of different types of nucleus, e.g. C with H, provided that some suitable couplings are present, such as It is necessary to apply pulses at both the relevant frequencies and it is also desirable to be able to detect either nucleus, to resolve different peak clusters. Detection tlirough the nucleus with the higher frequency is usually called reverse-mode detection and generally gives better sensitivity. The spectrum will have the two different chemical shift scales along its axes... 

The negative sign in equation (b 1.15.26) implies that, unlike the case for electron spins, states with larger magnetic quantum number have smaller energy for g O. In contrast to the g-value in EPR experiments, g is an inlierent property of the nucleus. NMR resonances are not easily detected in paramagnetic systems because of sensitivity problems and increased linewidths caused by the presence of unpaired electron spins. 

Forward recoil spectrometry (FRS) [33], also known as elastic recoil detection analysis (ERDA), is fiindamentally the same as RBS with the incident ion hitting the nucleus of one of the atoms in the sample in an elastic collision. In this case, however, the recoiling nucleus is detected, not the scattered incident ion. RBS and FRS are near-perfect complementary teclmiques, with RBS sensitive to high-Z elements, especially in the presence of low-Z elements. In contrast, FRS is sensitive to light elements and is used routinely in the detection of Ft at sensitivities not attainable with other techniques [M]- As the teclmique is also based on an incoming ion that is slowed down on its inward path and an outgoing nucleus that is slowed down in a similar fashion, depth infonuation is obtained for the elements detected. 

Carbon-13 nmr. Carbon-13 [14762-74-4] nmr (1,2,11) has been available routinely since the invention of the pulsed ft/nmr spectrometer in the early 1970s. The difficulties of studying carbon by nmr methods is that the most abundant isotope, has a spin, /, of 0, and thus cannot be observed by nmr. However, has 7 = 1/2 and spin properties similar to H. The natural abundance of is only 1.1% of the total carbon the magnetogyric ratio of is 0.25 that of H. Together, these effects make the nucleus ca 1/5700 times as sensitive as H. The interpretation of experiments involves measurements of chemical shifts, integrations, andy-coupling information however, these last two are harder to determine accurately and are less important to identification of connectivity than in H nmr. 

Other Nuclei. Although most nmr experiments continue to involve H, or both, many other nuclei may also be utilized Several factors, including the value of I for the nucleus, the magnitude of the quadmpolar moment, the natural abundance and magnetogyric ratio of the isotope, or the possibihty of preparing enriched samples, need to be considered. The product of the isotopic parameters can be compared to the corresponding value for providing a measure of relative sensitivity or receptivity. Table 1 summarizes these factors for a number of isotopes. More complete information may... 

Although the natural abundance of nitrogen-15 [14390-96-6] leads to lower sensitivity than for carbon-13, this nucleus has attracted considerable interest in the area of polypeptide and protein stmcture deterrnination. Uniform enrichment of is achieved by growing protein synthesi2ing cells in media where is the only nitrogen source. reverse shift correlation via double quantum coherence permits the... 

An important concept is the shadow cone, which is a region where no ions can penetrate due to the ion—nucleus repulsion (see Figure 2). This effect makes ion scattering surface sensitive. The size of the shadow cone / jCan be calculated for the classical Coulomb potential as ... 

The mtroducuon of a tnfluoromethanethio group into an aromatic nng has a synthetic importance The reaction of tnfluoromethanethio copper with aryl bro mides and iodides provides a convenient route to the synthesis of aryltn fluoromethane sulfides The reaction is not sensitive to the type of substituents or the aromahc nucleus Selectivity can be achieved accordmg to the type of halogen or the aromatic rmg, because iodides react at lower temperatures than bromides, whereas chlondes do not react [f J] (equation 12) (Table 5)... 

Chemical shift (Section 13.4) A measure of how shielded the nucleus of a particular atom is. Nuclei of different atoms have different chemical shifts, and nuclei of the same atom have chemical shifts that are sensitive to their molecular environment. In proton and carbon-13 NMR, chemical shifts are cited as 8, or parts per million (ppm), from the hydrogens or carbons, respectively, of tetramethylsilane. 

Curiously, the ring expansion fails in sulfuric, trifluoroacetic, trichloroacetic, and orthophos-phoric acid. The reaction is sensitive to substituents both in the TV-aryl group and in the 2-and 3-positions of the indole nucleus. For example, 3-methyl-l-phenylindole yields a mixture of 10-methyl-5//-dibenz[/t,/]azepine (34% mp 129-131X) and 2-mcthyl-l-phenylindole (57%). In contrast, 2-methyl-l-phenylindole and 2,3-dimethyl-l-phcnylindole fail to ring expand. The reaction also fails with electron-withdrawing groups (N02 and CF3) in the TV-phenyl ring. 

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