Analyzers time-of-flight

Kinsel, G. R. Gimon-Kinsel, M. E. Gillig, K. J. Russell, D. H. Investigation of the dynamics of matrix-assisted laser desorption/ionization ion formation using an electrostatic analyzer/time-of-flight mass spectrometer. J. Mass Spectrom. 1999, 34, 684-690. 

Before ehding this presentation on mass spectrometry, we should cite the existence of spectrometers for which the method of sorting ions coming from the source is different from the magnetic sector. These are mainly quadripolar analyzers and, to a lesser degree, analyzers measuring the ion s time of flight. 

After ions have been formed by El, they are examined for mass and abundance by the analyzer part of the mass spectrometer, which can incorporate magnetic sectors, electric sectors, qua-drupoles, time-of-flight tubes, and so on. The region in which the ions are first formed is called... 

The term Q/TOF is used to describe a type of hybrid mass spectrometer system in which a quadrupole analyzer (Q) is used in conjunction with a time-of-flight analyzer (TOP). The use of two analyzers together (hybridized) provides distinct advantages that cannot be achieved by either analyzer individually. In the Q/TOF, the quadrupole is used in one of two modes to select the ions to be examined, and the TOF analyzer measures the actual mass spectrum. Hexapole assemblies are also used to help collimate the ion beams. The hybrid orthogonal Q/TOF instrument is illustrated in Figure 23.1. 

Commercial mass analyzers are based almost entirely on quadrupoles, magnetic sectors (with or without an added electric sector for high-resolution work), and time-of-flight (TOE) configurations or a combination of these. There are also ion traps and ion cyclotron resonance instruments. These are discussed as single use and combined (hybrid) use. 

Almost any type of analyzer could be used to separate isotopes, so their ratios of abundances can be measured. In practice, the type of analyzer employed will depend on the resolution needed to differentiate among a range of isotopes. When the isotopes are locked into multielement ions, it becomes difficult to separate all of the possible isotopes. For example, an ion of composition CgHijOj will actually consist of many compositions if all of the isotopes ( C, C, H, H, 0, O, and 0) are considered. To resolve all of these isotopic compositions before measurement of their abundances is difficult. For low-molecular-mass ions (HjO, COj) or for atomic ions (Ca, Cl), the problems are not so severe. Therefore, most accurate isotope ratio measurements are made on low-molecular-mass species, and resolution of these even with simple analyzers is not difficult. The most widely used analyzers are based on magnets, quadrupoles, ion traps, and time-of-flight instruments. 

Once inside the hot plasma, which is at a temperature of about 8000 K and contains large numbers of energetic electrons and ions, the sample molecules are broken down into their constituent elements, which appear as ions. The ions are transported into a mass analyzer such as a quadrupole or a time-of-flight instrument for measurement of m/z values and ion abundances. 

If samples are introduced batchwise, then each one enters the flame as a plug, and the elements are measured transiently. If more than one m/z ration must be examined, the analyzer needs to be a quadrupole or time-of-flight instrument. 

Hybrid time-of-flight (TOF) mass spectrometers make use of a TOF analyzer placed at right angles to a main ion beam. Ions are deflected from this beam by a pulsed electric fleld at right angles to the ion beam direction. The deflected ions travel down the TOF tube for analysis. Hybrid TOF mass spectrometers have many advantages arising from the combination of two techniques, neither of which alone would be as useful. 

If, just before the ion beam reaches the ion detector, a pusher electrode is used alongside it to deflect the beam at right angles (orthogonal) to its original direction into the flight tube of a time-of-flight sector (TOP analyzer), the m/z values can be measured by the TOP section. 

Upon emerging from the quadrupole, the ions are accelerated through about 40 V and focused into the time-of-flight (TOF) analyzer. A pusher electrode is sited alongside this focused ion beam. Application of a pulse of high electric potential (about 1 kV) to the pusher electrode over a period of about 3 ps causes a short section of the ion beam to be detached and accelerated into the TOF analyzer. A positive potential is used to accelerate positively charged ions and vice versa. 

In a time-of-flight (TOF) mass spectrometer, ions formed in an ion source are extracted and accelerated to a high velocity by an electric field in an analyzer consisting of a long, straight drift tube. The ions pass along the tube until they reach a detector. 

Since the distance from the source to the detector is fixed, the time taken for an ion to traverse the analyzer in a straight line is proportional to its velocity and hence its mass (strictly, proportional to the square root of its m/z value). Thus each m/z value has its characteristic time of flight from the source to the detector. 

In time-of-flight (TOF) mass spectrometers, a pulse of ions is accelerated electrically at zero time. Having attained a maximum velocity, the ions drift along the flight tube of the analyzer. The times of arrival of ions at a detector are noted. 

Scanning techniques are carried out differently with such hybrid instruments as the triple quadrupole analyzer, the Q/TOF (quadrupole and time-of-flight), and double magnetic-sector instruments. 

Laser-desorption mass spectrometry (LDMS) or matrix-assisted laser desorption ionization (MALDI) coupled to a time-of-flight analyzer produces protonated or deprotonated molecular ion clusters for peptides and proteins up to masses of several thousand. 

Almost any kind of mass analyzer can be used to measure the isotope m/z values and abundances, but the usual ones are based on magnetic sectors, quadrupoles, and time-of-flight. 

Mass spectrometer configuration. Multianalyzer instruments should be named for the analyzers in the sequence in which they are traversed by the ion beam, where B is a magnetic analyzer, E is an electrostatic analyzer, Q is a quadrupole analyzer, TOP is a time-of-flight analyzer, and ICR is an ion cyclotron resonance analyzer. For example BE mass spectrometer (reversed-geometry double-focusing instrument), BQ mass spectrometer (hybrid sector and quadrupole instrument), EBQ (double-focusing instrument followed by a quadrupole). 

Time-of-flight analyzer. A device that measures the flight time of ions with an equivalent kinetic energy over a fixed distance. 

Q/TOF, used for two mass analyzers (quadrupole and time-of-flight) used in combination QQQ (or QqQ)- a triple quadrupole analyzer (if q is used, it means the central quadrupole is also a collision cell)... 

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