High-resolution molecular ion

the mass observed for the molecular ion of CO, for example, is the sum of the exact formula masses of the most abundant isotope of carbon and of oxygen. This differs from a molecular weight of CO based on atomic weights that are the average of 

Appendix A lists molecular and fragment formulas in order of the unit masses. Under each unit mass, the formulas are listed in the standard Chemical Abstract system. The formula mass (FM) to four decimal places is given for each formula. Appendix A is designed for browsing, on the assumption that the student has a unit molecular mass from a unit-resolution mass spectrometer and clues from other spectra. Note that the table includes only C, H, N, and O. 

A unique molecular formula (or fragment formula) can often be derived from a sufficiently accurate mass measurement alone (high-resolution mass spectrometry). This is possible because the nuclide masses are not integers (see Table 2.2). For example, we can distinguish at a unit mass of 28 among CO, N2, CH2N, and C2H4. 

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For most of the Problems in this text, the unit-resolution molecular ion, used in conjunction with IR and NMR, will suffice for determining the molecular formula by browsing in Appendix A. For several more difficult Problems, the high-resolution formula masses— for use with Appendix A (see Section 2.4.2)—have been supplied. 

We think that ion channels have the physical properties suggested by the fractal interpretation because the fractal properties are so clearly present in the experimental data, and these properties are consistent with the extensive experimental and theoretical studies of globular proteins. However, this issue can only be resolved by future work that includes X-ray diffraction and NMR, which are needed to determine the three-dimensional structure of the channel protein at high resolution molecular dynamic simulations, which are needed to determine the dynamics of the motions within the channel and molecular biology, which can test our ideas of channel structure and dynamics by purposeful alterations of the channel. 

The presence of non-CLA peaks, particularly 21 0 and also 20 2 isomers, in the GC profile of the CLA methyl ester region from cheese made identification of CLA isomers difficult without using high-resolution selected-ion recording (SIR) GC-MS of the molecular ion of CLA (Figure 2.9B) (Eulitz et al., 1999 Roach et al., 2000). The 21 0 is often at similar concentrations to the minor CLA isomers and can elute anywhere between llc,13f-18 2 and 10c,12c-18 2 depending on the GC conditions... 

These days, remarkably high-resolution spectra are obtained for positive and negative ions using coaxial-beam spectrometers and various microwave and IR absorption teclmiques as described earlier. Infonnation on molecular bond strengths, isomeric fonus and energetics may also be obtained from the teclmiques discussed earlier. The kinetics of cluster-ion fonuation, as studied in a selected-ion flow tube (SIFT) or by high-pressure... 

In general terms, the main function of the magnetic/electric-sector section of the hybrid is to be able to resolve m/z values differing by only a few parts per million. Such accuracy allows highly accurate measurement of m/z values and therefore affords excellent elemental compositions of ions if these are molecular ions, the resulting compositions are in fact molecular formulae, which is the usual MS mode. Apart from accurate mass measurement, full mass spectra can also be obtained. The high-resolution separation of ions also allows ions having only small mass differences to be carefully selected for MS/MS studies. 

By high-resolution mass spectrometry, ions of known mass from a standard substance can be separated from ions of unknown mass derived from a sample substance. By measuring the unknown mass relative to the known ones through interpolation or peak matching, the unknown can be measured. An accurate mass can be used to obtain an elemental composition for an ion. If the latter is the molecular ion, the composition is the molecular formula. 

This hybrid is used in one form to measure highly accurate m/z values to obtain excellent elemental compositions of ions and therefore molecular formulae from molecular ions in the other form, it is used to obtain MS/MS data at high resolution. 

Diphenylthiirene 1-oxide and several thiirene 1,1-dioxides show very weak molecular ions by electron impact mass spectrometry, but the molecular ions are much more abundant in chemical ionization mass spectrometry (75JHC21). The major fragmentation pathway is loss of sulfur monoxide or sulfur dioxide to give the alkynic ion. High resolution mass measurements identified minor fragment ions from 2,3-diphenylthiirene 1-oxide at mje 105 and 121 as PhCO" and PhCS, which are probably derived via rearrangement of the thiirene sulfoxide to monothiobenzil (Scheme 2). 

High mass resolution techniques are used to separate peaks at the same nominal mass by the very small mass differences between them. As an example, a combination of Si and H to form the molecular ion Si H , severely degrades the detection limit of phosphorous ( P) in a silicon sample. The exact mass of phosphorous ( P) is 31.9738 amu while the real masses of the interfering Si H and Si H2 molecules are 31.9816 amu and 31.9921 amu, respectively. Figure 8 shows a mass... 

High-mass resolution is needed to separate mass interferences of molecular and atom ions. Because of the mass defect of the binding energy of the nucleus, atomic ions have a slightly smaller mass than the corresponding molecular ions. To observe this typical mass resolutions between 5000 and 10000 are necessary. 

Write molecular formulas for compounds that show the following molecular ions in their high-resolution mass spectra. Assume that C, H, N, and O might be present, and use the exact atomic masses given in Section 12.2. 

X-Ray diffraction from single crystals is the most direct and powerful experimental tool available to determine molecular structures and intermolecular interactions at atomic resolution. Monochromatic CuKa radiation of wavelength (X) 1.5418 A is commonly used to collect the X-ray intensities diffracted by the electrons in the crystal. The structure amplitudes, whose squares are the intensities of the reflections, coupled with their appropriate phases, are the basic ingredients to locate atomic positions. Because phases cannot be experimentally recorded, the phase problem has to be resolved by one of the well-known techniques the heavy-atom method, the direct method, anomalous dispersion, and isomorphous replacement.1 Once approximate phases of some strong reflections are obtained, the electron-density maps computed by Fourier summation, which requires both amplitudes and phases, lead to a partial solution of the crystal structure. Phases based on this initial structure can be used to include previously omitted reflections so that in a couple of trials, the entire structure is traced at a high resolution. Difference Fourier maps at this stage are helpful to locate ions and solvent molecules. Subsequent refinement of the crystal structure by well-known least-squares methods ensures reliable atomic coordinates and thermal parameters. 

There are three main reasons for this choice. Firstly, it becomes more and more difficult to obtain recordable, molecular-ion signals from un-derivatized carbohydrates as their M, increases significantly above 3000. Secondly, the mass spectrometers that have been used in all high-mass-carbofiydrate studies published at the time of writing this article are not capable of very sensitive analysis above —3800 mass units (see later). Thirdly, at masses >4000, it is usually not practicable to work at the resolution necessary for adjacent peaks to appear as separate signals in the spectrum. To do so would require that the source and collector slits be narrowed to such a degree that there would be an unacceptable loss in sensitivity. Thus, spectra acquired at mass >4000 are usually composed of unresolved clusters. 

Fig. 6.—One of the Molecular-ion Clusters Obtained from a Sample of Deuteropermethy-lated. Cyclic /3(l- 2)-Glucans (see Section VI,S). [All high-mass samples give unresolved clusters of this type if the mass spectrometer is operated at low resolution. The peak is 6 mass units wide at half height. The mass is assigned by using the mass marker, which gives marks every 4 mass units, as shown. The center of the peak corresponds to the chemical molecular weight of an [M + NKJ species.]...

Figure 1 shows narrow range high resolution scans of the molecular ion region of NDMA, recorded near the maximum of the GC peaks, present in one of the beer samples prepared in the AOAC collaborative study. The peak at m/z 74.0480 represents approximately 0.15 ng of NDMA injected on the column, corresponding to a concentration of 0.6 yg/kg of beer. Use of high resolution MS permitted confirmation of the identity and amount of nitrosamine without additional cleanup of the concentrate prepared by the AOAC method. Sample quantity requirements were comparable to those of the TEA. 

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