Detector mass spectrometic

These three examples illustrate technology developments over time (dual-channel detector, diode array detector, mass spectrometer). Note that while the overall methodology is very similar (methanolic extracts, methanol-based, acidified solvents used for HPLC, detection of eluted compounds), the exact conditions for successful separation need to be defined for each system. 

Individual compound identification in all GC methods with the exception of GC/MS relies on the compound retention time and the response from a selective or non-selective detector. There is always a degree of uncertainty in a compound s identity and quantity, particularly when non-selective detectors are used or when the sample matrix contains interfering chemicals. To reduce this uncertainty, confirmation with a second column or a second detector is necessary. Analyses conducted with universal detectors (mass spectrometer or diode array) do not require confirmation, as they provide highly reliable compound identification. 

The scan speed, the pulse amplitude in DPV was optimized and an inhibition calibration curve was obtained using carbofuran as reference pesticide. The linear range was observed to be 1 nM to 1 pM. A lowest detection limit of 9 nM has been achieved using this AChE immobilized tetracyanoquinodimethane (TCNQ)/NF modified SPE. In the case of carbofuran contaminated water samples, the detection limit was observed to be 20 nM and the developed sensor has a good analytical performance in comparison with the results obtained by standard methods using gas chromatography coupled to a Finningan Mat 800 ion trap detector mass spectrometer (GC-ITDMS). 

There s No Detector Which Is More Sensitive than a Mass Spec. This phrase touches the same misapprehension as the previous one. Sensitivity and the LoD and LoQ in mass spectrometry are not by default superior to any other detector. Under favorable conditions, like high ion formation yield and good ion transmission through the mass analyzer to the mass detector, mass spectrometers are indeed very powerful, allowing LoQs down to a femto- or even attomol level. However, in case of poorly ionizable analytes, an inappropriate ionization principle and/or perhaps not the most sensitive MS instrument design, there maybe other detection principles that are clearly in favor, for instance electrochemical or fluorescence detection. 

A unique feature of TRMS is that both identities and quantities of ions may be studied in the time domain. For an engineer, the relationship between conventional MS measurements and TRMS is like the relationship between multimeters and oscilloscopes multimeters only indicate average electric properties while oscilloscopes measure and record fast changes in electrical signals over time. By analogy, TRMS uses a high-performance chemical detector (mass spectrometer) to study the dynamic phenomena of atoms, molecules, and ions during reactions. 

Options exist for increasing the selectivity of real-time volatile analysis. Modifying ionization conditions may allow selective ionization of groups of compounds, depending on the potential for further analyte-analyte interactions and charge transfer. More precise selectivity may be obtained at the detector (mass spectrometer) level itself, via the use of accurate mass analysis and MS/MS. 

The chromatogram can finally be used as the series of bands or zones of components or the components can be eluted successively and then detected by various means (e.g. thermal conductivity, flame ionization, electron capture detectors, or the bands can be examined chemically). If the detection is non-destructive, preparative scale chromatography can separate measurable and useful quantities of components. The final detection stage can be coupled to a mass spectrometer (GCMS) and to a computer for final identification. 

Figure Bl.7.4. Schematic diagram of a reverse geometry (BE) magnetic sector mass spectrometer ion source (1) focusing lens (2) magnetic sector (3) field-free region (4) beam resolving slits (5) electrostatic sector (6) electron multiplier detector (7). Second field-free region components collision cells (8) and beam deflection electrodes (9).

Another approach to mass analysis is based on stable ion trajectories in quadnipole fields. The two most prominent members of this family of mass spectrometers are the quadnipole mass filter and the quadnipole ion trap. Quadnipole mass filters are one of the most connnon mass spectrometers, being extensively used as detectors in analytical instnunents, especially gas clnomatographs. The quadnipole ion trap (which also goes by the name quadnipole ion store, QUISTOR , Paul trap, or just ion trap) is fairly new to the physical chemistry laboratory. Its early development was due to its use as an inexpensive alternative to tandem magnetic sector and quadnipole filter instnunents for analytical analysis. It has, however, staned to be used more in die chemical physics and physical chemistry domains, and so it will be described in some detail in this section. 

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]. 

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. 

Figure Bl.7.17. (a) Schematic diagram of a single acceleration zone time-of-flight mass spectrometer, (b) Schematic diagram showing the time focusing of ions with different initial velocities (and hence initial kinetic energies) onto the detector by the use of a reflecting ion mirror, (c) Wiley-McLaren type two stage acceleration zone time-of-flight mass spectrometer.

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). 

Figure Bl.7.18. (a) Schematic diagram of the trapping cell in an ion cyclotron resonance mass spectrometer excitation plates (E) detector plates (D) trapping plates (T). (b) The magnetron motion due to tire crossing of the magnetic and electric trapping fields is superimposed on the circular cyclotron motion aj taken up by the ions in the magnetic field. Excitation of the cyclotron frequency results in an image current being detected by the detector electrodes which can be Fourier transfonned into a secular frequency related to the m/z ratio of the trapped ion(s).

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... 

If the molecules could be detected with 100% efficiency, the fluxes quoted above would lead to impressive detected signal levels. The first generation of reactive scattering experiments concentrated on reactions of alkali atoms, since surface ionization on a hot-wire detector is extremely efficient. Such detectors have been superseded by the universal mass spectrometer detector. For electron-bombardment ionization, the rate of fonnation of the molecular ions can be written as... 

FIGURE 13 44 Diagram of a gas chromatograph When connected to a mass spectrometer as in GC/MS the effluent is split into two streams as it leaves the column One stream goes to the detector the other to the mass spectrometer (Adapted with permission from H D Durst and G W Gokel Experimental Organic Chemistry Inti eti McGraw Hill New York 1987)... 

Two common detectors, which also are independent instruments, are Fourier transform infrared spectrophotometers (FT-IR) and mass spectrometers (MS). In GC-FT-IR, effluent from the column flows through an optical cell constructed... 

Gas chromatography also can be used for qualitative purposes. When using an FT-IR or a mass spectrometer as the detector, the available spectral information often can be used to identify individual solutes. 

Time, Cost, and Equipment Analysis time can vary from several minutes for samples containing only a few constituents to more than an hour for more complex samples. Preliminary sample preparation may substantially increase the analysis time. Instrumentation for gas chromatography ranges in price from inexpensive (a few thousand dollars) to expensive (more than 50,000). The more expensive models are equipped for capillary columns and include a variety of injection options and more sophisticated detectors, such as a mass spectrometer. Packed columns typically cost 50- 200, and the cost of a capillary column is typically 200- 1000. 

An AutoSpec-TOF mass spectrometer has a magnetic sector and an electron multiplier ion detector for carrying out one type of mass spectrometry plus a TOF analyzer with a microchannel plate multipoint ion collector for another type of mass spectrometry. Either analyzer can be used separately, or the two can be run in tandem (Figure 20.4). 

In one instrument, ions produced from an atmospheric-pressure ion source can be measured. If these are molecular ions, their relative molecular mass is obtained and often their elemental compositions. Fragment ions can be produced by suitable operation of an APCI inlet to obtain a full mass spectrum for each eluting substrate. The system can be used with the effluent from an LC column or with a solution from a static solution supply. When used with an LC column, any detectors generally used with the LC instrument itself can still be included, as with a UV/visible diode array detector sited in front of the mass spectrometer inlet. 

TOF mass spectrometers are very robust and usable with a wide variety of ion sources and inlet systems. Having only simple electrostatic and no magnetic fields, their construction, maintenance, and calibration are usually straightforward. There is no upper theoretical mass limitation all ions can be made to proceed from source to detector. In practice, there is a mass limitation in that it becomes increasingly difficult to discriminate between times of arrival at the detector as the m/z value becomes large. This effect, coupled with the spread in arrival times for any one m/z value, means that discrimination between unit masses becomes difficult at about m/z 3000. At m/z 50,000, overlap of 50 mass units is more typical i.e., mass accuracy is no better than about 50-100 mass... 

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