Mass separation spectrometer

Separation of ions according to their m/z values can be effected by magnetic and/or electric fields used as mass analyzers, which are described in Chapters 24 through 27. However, apart from measurement of m/z values, there is often a need to be able to transmit ions as efficiently as possible from one part of a mass spectrometer to another without any mass separation. 

In Laser Ionization Mass Spectrometry (LIMS, also LAMMA, LAMMS, and LIMA), a vacuum-compatible solid sample is irradiated with short pulses ("10 ns) of ultraviolet laser light. The laser pulse vaporizes a microvolume of material, and a fraction of the vaporized species are ionized and accelerated into a time-of-flight mass spectrometer which measures the signal intensity of the mass-separated ions. The instrument acquires a complete mass spectrum, typically covering the range 0— 250 atomic mass units (amu), with each laser pulse. A survey analysis of the material is performed in this way. The relative intensities of the signals can be converted to concentrations with the use of appropriate standards, and quantitative or semi-quantitative analyses are possible with the use of such standards. 

In quadrupole-based SIMS instruments, mass separation is achieved by passing the secondary ions down a path surrounded by four rods excited with various AC and DC voltages. Different sets of AC and DC conditions are used to direct the flight path of the selected secondary ions into the detector. The primary advantage of this kind of spectrometer is the high speed at which they can switch from peak to peak and their ability to perform analysis of dielectric thin films and bulk insulators. The ability of the quadrupole to switch rapidly between mass peaks enables acquisition of depth profiles with more data points per depth, which improves depth resolution. Additionally, most quadrupole-based SIMS instruments are equipped with enhanced vacuum systems, reducing the detrimental contribution of residual atmospheric species to the mass spectrum. 

Principles and Characteristics Analytical multistage mass spectrometry (MSn) relies on the ability to activate and dissociate ions generated in the ion source in order to identify or obtain structural information about an unknown compound and to analyse mixtures by exploiting two or more mass-separating steps. A basic instrument for the currently most used form, tandem mass spectrometry (MS/MS), consists of a combination of two mass analysers with a reaction region between them. While a variety of instrument set-ups can be used in MS/MS, there is a single basic concept involved the measurement of the m/z of ions before and after a reaction in the mass spectrometer the reaction involves a change in mass and can be represented as ... 

One of the most interesting aspects of ion trap mass spectrometers is represented by the possibility of carrying out multi mass separation steps with only one analyzer (see Section 2.9). 

In addition to neutral loss scans, mass spectrometers can be used to detect other compounds in a different manner. Acylcamitines are fatty acid esters of carnitine. The masses of acylcamitines differ by the size of the fatty acid attached to it. The tandem mass spectrometer can detect these selectively as well because they all produce a similar product, in this case an ion rather than a molecule. Because it is an ion, it can be detected by the second mass separation device. The ion has a mass of 85 Da and is common to all acylcamitines. Performing a precursor ion scan of 85 Da (essentially a scan of only molecules that produce the 85 ion) reveals a selective analysis of acylcar-nitines, as shown in Fig. 14.2. Additional scans have been added to more selectively detect basic amino acids, free carnitine, short chain acylcamitines and a hormone, thyroxin (T4) which has amino acid components. 

Mass separator, 74 443 Mass spectrometer, 75 647-648, 650-665 Mass spectrometry (ms, MS), 75 647-670. See also Tandem mass spectrometry applications of, 75 666-669 archaeological materials, 5 743 biochemical, 75 666-668 concepts and definitions related to, 75 647-650... 

Mass spectrometry (MS) has changed its appearance in the scientific world considerably during recent years. At the beginning of the 20 century first applications in physics were described. Gradually MS methods entered more and more into the fields of biology, biochemistry and biomedicine and became a major tool in life sciences. Mass spectrometers consist of a sequence of functional units for sample introduction, ion formation, mass separation, and detection. The data handling is carried out by computers. Currently, a variety of different mass spectrometric techniques are used for the analysis of biomolecules (Fig. 6). 

Figure 14.1 Schematic view of a mass spectrometer. Its basic parts are ion source, mass analyzer, and detector. Selected principles realized in modern mass spectrometers are assigned El—electron impact. Cl—chemical ionization, FAB—fast atom bombardment, ESI—electrospray ionization, MALDI—matrix-assisted laser desorption/ionization. Different combinations of ion formation with mass separation can be realized.

The mechanisms of ion formation are usually studied with measurements of mass separated ion energy distributions using a magnetic sector mass spectrometer.144,145 For a liquid metal ion source, both atomic ions and cluster ions of all sizes are emitted. If the total ion current is large, neutral atoms and small droplets may also be emitted. There is little question that most of the atomic ions in a liquid metal ion source at low... 

Fig. 8.1.1 Simple illustrations of a various mass spectrometers, a The triple-quadrupole tandem mass spectrometer (top panel). The middle set of quadrupoles are part of the collision cell (CC) and do not perform mass separation. MSI and MS2 indicate the first and second quadrupole mass separation devices, respectively. The bold arrow shows the path of ions, b Ion-trap mass spectrometer (middle left). The charged sections of the ion trap are not elliptical as drawn, but rather hyperbolic. The diagram is also two-dimensional, whereas the ion trap is three-dimensional. The ion path is such that ions enter the device and are trapped until a specific voltage ejects these ions, c Time of Flight mass spectrometer with a Reflectron (middle left). Ions are separated by the time it takes to pass through the instrument. The Reflectron improves/focuses the ions, d Hybrid Tandem mass spectrometer (bottom). The diagram shows that a quadrupole instrument can be combined with a different type of mass spectrometer, forming a tandem hybrid instrument...

Finally, it is important to note there are many other instruments and configurations that are often referred to as tandem mass spectrometers. There are hybrid instruments that use another form of mass separation, time-of-flight (TOF) mass spectrometry. TOF mass spectrometry separates ions based on the time it takes to... 

Ionization is very important in that you have to have ions to detect and measure mass. Today, electrospray ionization is used this is a process where a streaming liquid is ionized and this imparts ionization of the molecules dissolved within it. However, large amounts of liquid or uncharged molecules are not desirable in a mass spectrometer operating in a vacuum. Hence, electrospray ionization is optimized such that nearly all of the solvent/spray is removed and only charged molecules enter the mass-separation devices. You may ask how I ensure that only the molecules I am interested in make it to the mass spectrometer rather than all of the other molecules that may be present in the mix. This is an important concept, since... 

This fundamental equation explains that the velocity of heavier ions (iq of ions with mass m,) is lower than of lighter ions (v2 of ions with mass m2, with m, > m2). Equation (10) is used directly in time resolved measurements, for example in time-of-flight mass spectrometers (ToF-MS). The charged ions of the extracted and accelerated ion beam are separated by their mass-to-charge ratio, m/z, in the mass analyzer. Mass-separated ion beams are subsequently recorded by an ion detection system either as a function of time or simultaneously. Mass spectrometers are utilized for the determination of absolute masses of isotopes, atomic weights, relative abundance of isotopes and for quite different applications in survey, trace, ultratrace and surface analysis as discussed in Chapters 8 and 9. 

Figure 1.2 Principle of the operation of a mass spectrometer including sample introduction system, ion source, mass separator (e.g., a magnetic sector field) and ion detector system (e.g., double ion collectors for simultaneous measurements of two separated ion beams).

Another type of dynamic mass spectrometer is the time-of-flight (ToF) analyzer. In 1946, Stephens presented his concept of the linear time-of-flight mass spectrometer (ToF-MS) as the simplest mass separation technique at an American Physical Society meeting in Cambridge, MA.49 Cameron and Eggers first published the design and showed mass spectra for linear ToF-MS in... 

Although for many elements the degree of ionization is about 100 % only 1 in 104 to 1 in 106 atoms7 in the original sample are detected due to the extensive loss of ions that occurs during their transport from the plasma via the mass separation system to the ion detector (due to different ion transmission of mass spectrometers). 

Mass spectrometry (MS) is an analytical method based on the determination of atomic or molecular masses of individual species in a sample. Information acquired allows determination of the nature, composition, and even structure of the analyte. Mass spectrometers can be classified into categories based on the mass separation technique used. Some of the instruments date back to the beginning of the twentieth century and were used for the study of charged particles or ionised atoms using magnetic fields, while others of modest performance, such as bench-top models often used in conjunction with chromatography, rely on different principles for mass analysis. Continuous improvements to the instruments, miniaturisation and advances in new ionisation techniques have made MS one of the methods with the widest application range because of its flexibility and extreme sensitivity. 

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