High Mass Resolution

All have molecular weights of 226 to the nearest integer (C = 12, H = 1, S = 32), but the exact molecular weights differ slightly. A resolution of 2500 is necessary to separate molecules 1, 2 and 3 but 75,000 is required to separate molecule 4 from molecule 3 which explains why high resolution mass spectrometers are sdiiglit. 

Fisher, I.P. and P. Fisher (1974), Analysis of high boiling petroleum streams by high resolution mass spectrometry . Talanta, Vol. 21, p. 867. 

Exact Mass Differences. If the exact mass of the parent or fragment ions are ascertained with a high-resolution mass spectrometer, this relationship is often useful for combinations of C, H, N, and O (Table 1.15b) ... 

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. 

High resolution mass spectrometry (qv) has been used with extracts of a series of coals to indicate the association of different heteroatoms (27). Various types of chromatography (qv) have also been used to identify the smaller species that can be extracted from coal. 

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). 

The degradation of 2,6-xylenol (2,6-dimethylphenol) by bacteria produces a metabolite with elemental composition C8///0O2 as determined by high-resolution mass spectrometry Which carbon skeleton and which relative configuration are deducible from the NMR experiments 44, all obtained from one 1.5 mg sample ... 

The C NMR spectrum of the metabolite shows 16 signals instead of 8 as expected from the elemental composition determined by high-resolution mass spectrometry. Moreover, aromaticity of the 2,6-xylenol is obviously lost after metabolism because two ketonic carbonyl carbon atoms (5c = 203.1 and 214.4) and four instead of twelve carbon signals are observed in the shift range of trigonal carbon nuclei (5c = 133.1, 135.4, 135.6 and 139.4) in the C NMR spectra. To conclude, metabolism involves oxidation of the benzenoid ring. 

Unlike the stable molecule N2O, the sulfur analogue N2S decomposes above 160 K. In the vapour phase N2S has been detected by high-resolution mass spectrometry. The IR spectrum is dominated by a very strong band at 2040 cm [v(NN)]. The first ionization potential has been determined by photoelectron spectroscopy to be 10.6 eV. " These data indicate that N2S resembles diazomethane, CH2N2, rather than N2O. It decomposes to give N2 and diatomic sulfur, S2, and, hence, elemental sulfur, rather than monoatomic sulfur. Ab initio molecular orbital calculations of bond lengths and bond energies for linear N2S indicate that the resonance structure N =N -S is dominant. 

The male sex hormone testosterone contains C, H, and O and has a mass of 288.2089 amu as determined by high-resolution mass spectrometry. What is the likely molecular formula of testosterone ... 

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. 

Camphor, a saturated monoketone from the Asian camphor tree, is used among other things as a moth repellent and as a constituent of embalming fluid. If camphor has M+ = 152.1201 by high-resolution mass spectrometry, what is its molecular formula How many rings does camphor have ... 

B Nicotine is a diamino compound isolated from dried tobacco leaves. Nicotine has two rings and M + = 162.1157 by high-resolution mass spectrometry. Give a molecular formula for nicotine, and calculate the number of double bonds. 

The molecular formulas of PMs (Table 9.5) obtained by high-resolution mass spectrometry in collaboration with Prof. Y. Kishi, Harvard University, indicate that PMs are formed by the condensation of three molecules of PS and two molecules of methylamine, with the removal of four water molecules. No study has been made on their conformational isomers. 

Both compounds were non-fluorescent. Compound KM-1 was similar to PMs in the absorption maximum (A.max 488 nm) but not in the spectral shape, whereas KM-2 was similar to PMs in the spectral shape but not in the absorption maximum at 515 nm (Fig. 9.10). The chemical structures of KM-1 and KM-2 have been determined by high-resolution mass spectrometry and NMR spectrometry (Fig. 9.11 Stojanovic, 1995). 

Structure determination of luciferin. Once a luciferin is obtained in a sufficient purity, the determination of luciferin structure should be attempted most of the important properties of luciferin are usually already obtained during the course of purification as a necessity. The structural study is considerably more straightforward than the extraction and purification, due to the availability of advanced methods, such as high-resolution mass spectrometry and various NMR techniques. If help or collaboration is needed in structure determination, the attractiveness of a luciferin will make it easy to find a good collaborator. However, the purified luciferin is usually an extremely precious material considering the effort spent in preparing it. To avoid accidental loss of the purified material, the chosen collaborator must have solid knowledge and experience in structure determination a criterion to be considered is that the person has successfully done the structure determination of at least one new natural product. 

The four-sector mass spectrometer is the ultimate in MS-MS instrumentation and consists of two high-resolution mass spectrometers in series. The strength of these instruments is in terms of their high-mass and high-resolution capabilities for both precursor-ion selection and product-ion analysis. Their cost, however, precludes their primary use for LC-MS and therefore they will not be considered any further here [12]. 

High-resolution mass spectrometers have been used to obtain electrospray spectra and have the added advantage that they allow the direct determination of the charge state of the ions being observed, e.g. if the apparent separation of the and isotopic contributions is 0.1 Da, the charge state is 10, while if it is 0.05 Da, the charge state is 20, etc. 

High-resolution mass spectrometer A mass spectrometer capable of high resolution and measuring m/z ratios with high accuracy to enable the atomic composition of an ion to be determined. 

In addition to high sensitivity, a requirement for any acceptable analytical method is high specificity because at very low levels few confirmatory procedures can be used to establish the identity of a particular compound. A method which uniquely combines high sensitivity with high specificity is high resolution mass spectrometry. We have used this method as the basis for an approach which we believe will make possible a meaningful assessment of TCDD levels in the environment. 

The following is a procedure recommended for elucidating the structure of complex organic molecules. It uses a combination of different NMR and other spectroscopic techniques. It assumes that the molecular formula has been deduced from elemental analysis or high-resolution mass spectrometry. Computer-based automated or interactive versions of similar approaches have also been devised for structural elucidation of complex natural products, such as SESAMI (systematic elucidation of structures by using artificial machine intelligence), but there is no substitute for the hard work, experience, and intuition of the chemist. 

Advanced techniques like molecularly imprinted polymers (MIPs), infrared/near infrared spectroscopy (FT-IR/NIR), high resolution mass spectrometry, nuclear magnetic resonance (NMR), Raman spectroscopy, and biosensors will increasingly be applied for controlling food quality and safety. 

Figure 7a demonstrates that FTMS can simultaneously detect ions over a broad mass range. This is the actual high resolution mass spectrum, not a stick plot. This spectrum was obtained when a mixture of CO,, C H., and acetone was leaked into the chamber and ionized by the electron beam. The total sample pressure was... 

The position of the methyl group of 25b,c was deduced from high-resolution mass analysis as shown in Figs. 1 and 2. The mass fragmentation pattern of 25b was quite different from that of 25c, thus assuring the differ-... 

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