Time-mode spectrometers

Partial pressures were measured using a Dycor M200M quadru-pole mass spectrometer. In its PRESSURE-TIME mode the mass spectrometer displayed and recorded the partial pressures of... 

Both these objections can be overcome by using a time-mode system and spectrometers based on this latter principle have now virtually replaced those operating in the pulse-height analysis mode. 

The original method employed was to scan eitiier the frequency of the exciting oscillator or to scan the applied magnetic field until resonant absorption occiined. Flowever, compared to simultaneous excitation of a wide range of frequencies by a short RF pulse, the scanned approach is a very time-inefficient way of recording the spectrum. Flence, with the advent of computers that could be dedicated to spectrometers and efficient Fourier transfomi (FT) algoritluns, pulsed FT NMR became the nomial mode of operation. 

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. 

Quadmpole mass spectrometers (mass filters) allow ions at each m/z value to pass through the analyzer sequentially. For example, ions at m/z 100, 101, and 102 are allowed to pass one after the other through the quadmpole assembly so that first m/z 100 is transmitted, then m/z 101, then m/z 102, and so on. Therefore, the ion collector at the end of the quadmpole unit needs to cover only one point or focus in space and can be placed immediately behind the analyzer (Figure 30.1). A complete mass spectram is recorded over a period of time (temporally), which is set by the voltages on the quadmpole analyzer. In this mode of operation, the ions are said to be scanned sequentially. The resolution of m/z values is dependent solely on the analyzer and not on the detector. The single-point collector is discussed in detail in Chapter 28. 

Another form of array is called a microchannel plate detector. A time-of-flight (TOP) mass spectrometer collects ions sequentially in time and can use a point detector, but increasingly, the TOP instrument uses a microchannel plate, most particularly in an orthogonal TOP mode. Because the arrays and microchannel plates are both essentially arrays or assemblies of small electron multipliers, there may be confusion over their roles. This chapter illustrates the differences between the two arrays. 

Quantitative mass spectrometry, also used for pharmaceutical appHcations, involves the use of isotopicaHy labeled internal standards for method calibration and the calculation of percent recoveries (9). Maximum sensitivity is obtained when the mass spectrometer is set to monitor only a few ions, which are characteristic of the target compounds to be quantified, a procedure known as the selected ion monitoring mode (sim). When chlorinated species are to be detected, then two ions from the isotopic envelope can be monitored, and confirmation of the target compound can be based not only on the gc retention time and the mass, but on the ratio of the two ion abundances being close to the theoretically expected value. The spectrometer cycles through the ions in the shortest possible time. This avoids compromising the chromatographic resolution of the gc, because even after extraction the sample contains many compounds in addition to the analyte. To increase sensitivity, some methods use sample concentration techniques. 

H-NMR studies were performed on a Bruker MSL-400 spectrometer operating in the Fourier transform mode, using a static multinuclei probehead operating at 400.13 MEtz. A pulse length of 1 iis is used for the 90° flip angle and the repetition time used (1 second) is longer than five times Tjz ( H) of the analyzed samples. 

Since modern FTIR spectrometers can operate in a rapid scan mode with approximately 50 ms time resolution, TRIR experiments in the millisecond time regime are readily available. Recent advances in ultra-rapid scanning FTIR spectroscopy have improved the obtainable time resolution to 5 ms. Alternatively, experiments can be performed at time resolutions on the order of 1-10 ms with the planar array IR technique, which utilizes a spectrograph for wavelength dispersion and an IR focal plane detector for simultaneous detection of multiple wavelengths. ... 

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