Detectors spectrometry

Figure Bl.23.4. Schematic diagram of TOE scattermg and recoiling spectrometry (TOF-SARS) illustrating the plane of scattering fonned by the ion beam, sample and detector. TOE spectra (a) are collected with fixed...

In contrast to IR and NMR spectroscopy, the principle of mass spectrometry (MS) is based on decomposition and reactions of organic molecules on theii way from the ion source to the detector. Consequently, structure-MS correlation is basically a matter of relating reactions to the signals in a mass spectrum. The chemical structure information contained in mass spectra is difficult to extract because of the complicated relationships between MS data and chemical structures. The aim of spectra evaluation can be either the identification of a compound or the interpretation of spectral data in order to elucidate the chemical structure [78-80],... 

Detectors Most of the detectors used in HPLC also find use in capillary electrophoresis. Among the more common detectors are those based on the absorption of UV/Vis radiation, fluorescence, conductivity, amperometry, and mass spectrometry. Whenever possible, detection is done on-column before the solutes elute from the capillary tube and additional band broadening occurs. 

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 modem mass spectrometry, ion collectors (detectors) are generally based on the electron multiplier and can be separated into two classes those that detect the arrival of all ions sequentially at a point (a single-point ion collector) and those that detect the arrival of all ions simultaneously (an array or multipoint collector). This chapter compares the uses of single- and multipoint ion collectors. For more detailed discussions of their construction and operation, see Chapter 28, Point Ion Collectors (Detectors), and Chapter 29, Array Collectors (Detectors). In some forms of mass spectrometry, other methods of ion detection can be used, as with ion cyclotron instmments, but these are not considered here. 

There is potential confusion in the use of the word array in mass spectrometry. Historically, array has been used to describe an assemblage of small single-point ion detectors (elements), each of which acts as a separate ion current generator. Thus, arrival of ions in one of the array elements generates an ion current specifically from that element. An ion of any given m/z value is collected by one of the elements of the array. An ion of different m/z value is collected by another element. Ions of different m/z value are dispersed in space over the face of the array, and the ions are detected by m/z value at different elements (Figure 30.4). 

After acceleration through an electric field, ions pass (drift) along a straight length of analyzer under vacuum and reach a detector after a time that depends on the square root of their m/z values. The mass spectrum is a record of the abundances of ions and the times (converted to m/z) they have taken to traverse the analyzer. TOP mass spectrometry is valuable for its fast response time, especially for substances of high mass that have been ionized or selected in pulses. 

In conventional mass spectrometry with electric and magnetic sectors arranged in-hne (see Chapter 26), an ion beam consists of a stream of ions of all m/z values, which is separated into individual m/z values by the magnetic sector before being collected by single-point or multipoint detectors (see Chapters 28 and 29). 

Photoacoustic spectrometry (pas) differs from the other methods in that the detector is a microphone. This makes pas wavelength independent. 

Confirmation of the identities of nitrosamines generally is accompHshed by gas chromatography—mass spectrometry (gc/ms) (46,87). High resolution gc/ms, as well as gc/ms in various single-ion modes, can be used as specific detectors, especially when screening for particular nitrosamines (87) (see Analytical LffiTHODS Trace and residue analysis). 

K. Debertin and R. G. Helmer, Gamma- and X-raj Spectrometry With Semiconductor Detectors North-HoUand, Amsterdam, the Netherlands, 1988. 

The use of separation techniques, such as gel permeation and high pressure Hquid chromatography interfaced with sensitive, silicon-specific aas or ICP detectors, has been particularly advantageous for the analysis of siUcones in environmental extracts (469,483—486). Supercritical fluid chromatography coupled with various detection devices is effective for the separation of siUcone oligomers that have molecular weights less than 3000 Da. Time-of-flight secondary ion mass spectrometry (TOF-sims) is appHcable up to 10,000 Da (487). 

Fast concentration and sample injection are considered with the use of a theory of vibrational relaxation. A possibility to reduce a detection limit for trinitrotoluene to 10 g/cnf in less than 1 min is shown. Such a detection limit can by obtained using selective ionization combined with ion drift spectrometry. The time of detection in this case is 1- 3 s. A detection technique based on fluorescent reinforcing polymers, when the target molecules strongly quench fluorescence, holds much promise for developing fast detectors. 

After adequate analitical prepai ation according to standai d EPA method 608 samples were analysed gas chromatographic on a gas chromatograph 8500 Perkin Elmer, in glass and capilar columns using a capture electron detector and mass spectrometry, temperature program. 

The recent development and comparative application of modern separation techniques with regard to determination of alkylphosphonic acids and lewisite derivatives have been demonstrated. This report highlights advantages and shortcomings of GC equipped with mass spectrometry detector and HPLC as well as CE with UV-Vis detector. The comparison was made from the sampling point of view and separation/detection ability. The derivatization procedure for GC of main degradation products of nerve agents to determine in water samples was applied. Direct determination of lewisite derivatives by HPLC-UV was shown. Also optimization of indirect determination of alkylphosphonic acids in CE-UV was developed. Finally, the new instrumental development and future trends will be discussed. 

Coupling of analytical techniques (detectors) to high-performance liquid chromatographic (HPLC) systems has increased in the last tree decades. Initially, gas chromatography was coupled to mass spectrometry (MS), then to infrai ed (IR) spectroscopy. Following the main interest was to hyphenate analytical techniques to HPLC. 

Identification of stmctures of toxic chemicals in environmental samples requires to use modern analytical methods, such as gas chromatography (GC) with element selective detectors (NPD, FPD, AED), capillary electrophoresis (CE) for screening purposes, gas chromatography/mass-spectrometry (GC/MS), gas chromatography / Fourier transform infra red spectrometry (GC/FTIR), nucleai magnetic resonance (NMR), etc. 

R. Woldseth. X-Ray Energy Spectrometry Kevex Corporation, San Carlos, 1973. A good introduction with emphasis on detectors and electronics. Most of the applications refer to X-ray tube sources. Unfortunately the book is out of print, but many industrial laboratories may have copies. 

---