Mass instrumentation

With the advent of accurate mass instruments, access to a reference database or library of compounds with the exact masses of precursor and product ions is becoming increasingly important. Many instrument manufacturers, as well as independent companies or institutions, are developing software that allows chemists to manage this type of information for specific applications such as proteomics or chemical contaminants. Examples of online resources that may be useful for searching for unknown residues based on molecular formulas obtained from accurate mass data inciude Metlin from the Scripps Center for Mass Spectrometry and ChemSpider from the Royal Society of Chemistry. " ... 

In the absence of compound-specific fragmentation to drive selectivity, metabolite detection on nominal mass instruments becomes significantly more difficult. Typically, significant ambiguity exists in nominal MS data due to the presence of endogenous interferences, isobaric with metabolites, which... 

Fig. 6 Exact masses of coumarate and rhamnose and their residues when incorporated into biological molecules. Both of these groups are common in plants, and they have the same nominal mass. They can be distinguished by accurate mass instruments...

For calculation of the volumetric flow rate only the cross section area of the pipe is to be known. In order to give flow under standard conditions the temperature and pressure must be measured, and for conversion to mass flow the composition or density of the gas must be determined. These process parameters are often monitored by calibrated instrumentation. 

The mass spectrometer tends to be a passive instrument in these applications, used to record mass spectra. In chemical physics and physical chemistry, however, the mass spectrometer takes on a dynamic function as a... 

Most instruments are configured with a fixed value for the radius of curvature, r, so changing the value of B selectively passes ions of particular values of momentum, mv, tlirough tlie magnetic sector. Thus, it is really the momentum that is selected by a magnetic sector, not mass. We can convert this expression to one involving the accelerating potential. 

Magnetic sectors can be used on their own, or in conjunction with energy analysers to fomi a tandem mass spectrometer. The unique features of the reverse geometry instrument are presented from this point. 

Figure Bl.7.7. Summary of the other collision based experiments possible with magnetic sector instruments (a) collision-mduced dissociation ionization (CIDI) records the CID mass spectrum of the neutral fragments accompanying imimolecular dissociation (b) charge stripping (CS) of the incident ion beam can be observed (c) charge reversal (CR) requires the ESA polarity to be opposite that of the magnet (d) neutiiralization-reionization (NR) probes the stability of transient neutrals fonned when ions are neutralized by collisions in the first collision cell. Neutrals surviving to be collisionally reionized in the second cell are recorded as recovery ions in the NR mass spectrum.

Aside from the smgle mass filter, the most connnon configuration for quadnipole mass spectrometers is the triple-quadnipole instrument. This is the simplest tandem mass spectrometer using quadnipole mass filters. Typically, the... 

A connnon approach has been to measure the equilibrium constant, K, for these reactions as a fiinction of temperature with the use of a variable temperature high pressure ion source (see section (Bl.7.2)1. The ion concentrations are approximated by their abundance in the mass spectrum, while the neutral concentrations are known from the sample mlet pressure. A van t Hoff plot of In K versus /T should yield a straight Ime with slope equal to the reaction enthalpy (figure B1.7.11). Combining the PA with a value for basicityG at one temperature yields a value for A.S for the half-reaction involving addition of a proton to a species. While quadnipoles have been tire instruments of choice for many of these studies, other mass spectrometers can act as suitable detectors [19, 20]. 

A sehematie diagram of a SIFT apparatus is shown in figure Bl.7.12. The instrument eonsists of five basie regions, the ion soiiree, initial quadnipole mass filter, flow tube, seeond mass filter and finally the deteetor. The heart of the instrument is the flow tube, whieh is a steel tube approximately 1 m long and 10 em in diameter. The pressure in the flow tube is kept of the order of 0.5 Torr, resulting in earrier gas flow rates of... 

Another instrument used in physical chemistry research that employs quadnipole mass filters is the guided ion beam mass spectrometer [31]. A schematic diagram of an example of this type of instrument is shown in figure B 1.7.13. A... 

Probably the simplest mass spectrometer is the time-of-fiight (TOP) instrument [36]. Aside from magnetic deflection instruments, these were among the first mass spectrometers developed. The mass range is theoretically infinite, though in practice there are upper limits that are governed by electronics and ion source considerations. In chemical physics and physical chemistry, TOP instniments often are operated at lower resolving power than analytical instniments. Because of their simplicity, they have been used in many spectroscopic apparatus as detectors for electrons and ions. Many of these teclmiques are included as chapters unto themselves in this book, and they will only be briefly described here. 

In the simplest fomi, reflects the time of flight of the ions from the ion source to the detector. This time is proportional to the square root of the mass, i.e., as the masses of the ions increase, they become closer together in flight time. This is a limiting parameter when considering the mass resolution of the TOP instrument. 

The final velocity of these two ions will be the same, but their final flight times will differ by the above turnaround time, This results in a broadening of the TOF distributions for each ion mass, and is anotiier limiting factor when considering the mass (time) resolution of the instrument. 

Time-of-flight mass spectrometers have been used as detectors in a wider variety of experiments tlian any other mass spectrometer. This is especially true of spectroscopic applications, many of which are discussed in this encyclopedia. Unlike the other instruments described in this chapter, the TOP mass spectrometer is usually used for one purpose, to acquire the mass spectrum of a compound. They caimot generally be used for the kinds of ion-molecule chemistry discussed in this chapter, or structural characterization experiments such as collision-induced dissociation. Plowever, they are easily used as detectors for spectroscopic applications such as multi-photoionization (for the spectroscopy of molecular excited states) [38], zero kinetic energy electron spectroscopy [39] (ZEKE, for the precise measurement of ionization energies) and comcidence measurements (such as photoelectron-photoion coincidence spectroscopy [40] for the measurement of ion fragmentation breakdown diagrams). 

In the other types of mass spectrometer discussed in this chapter, ions are detected by having them hit a detector such as an electron multiplier. In early ICR instruments, the same approach was taken, but FT-ICR uses a very different teclmique. If an RF potential is applied to the excitation plates of the trapping cell (figure B 1.7.18(b)) equal to the cyclotron frequency of a particular ion m/z ratio, resonant excitation of the ion trajectories takes place (without changing the cyclotron frequency). The result is ion trajectories of higher... 

Guilhaus M 1995 Principles and instrumentation in time-of-flight mass spectrometry physical and instrumental concepts J. Mass Spectrom. 30 1519-32... 

Benninghoven A, Rudenauer F G and Werner H W 1987 Secondary Ion Mass Spectrometry, Basic Concepts, Instrumental Aspects, Applications and Trends (New York Wiley)... 

Specinfo, from Chemical Concepts, is a factual database information system for spectroscopic data with more than 660000 digital spectra of 150000 associated structures [24], The database covers nuclear magnetic resonance spectra ( H-, C-, N-, O-, F-, P-NMR), infrared spectra (IR), and mass spectra (MS). In addition, experimental conditions (instrument, solvent, temperature), coupling constants, relaxation time, and bibliographic data are included. The data is cross-linked to CAS Registry, Beilstein, and NUMERIGUIDE. 

Present day techniques for structure determination in carbohydrate chemistry are sub stantially the same as those for any other type of compound The full range of modern instrumental methods including mass spectrometry and infrared and nuclear magnetic resonance spectroscopy is brought to bear on the problem If the unknown substance is crystalline X ray diffraction can provide precise structural information that m the best cases IS equivalent to taking a three dimensional photograph of the molecule... 

Measurements are made using appropriate equipment or instruments. The array of equipment and instrumentation used in analytical chemistry is impressive, ranging from the simple and inexpensive, to the complex and costly. With two exceptions, we will postpone the discussion of equipment and instrumentation to those chapters where they are used. The instrumentation used to measure mass and much of the equipment used to measure volume are important to all analytical techniques and are therefore discussed in this section. 

---