Mass spectrometers direct insertion

How are low vapor pressure solid samples introduced into the source of a mass spectrometer (direct insertion probe). 

Kankare, J.J. Simple Temperature Programmer for a Mass Spectrometer Direct Insertion Probe. Anal. Chem. 1974, 46, 966-967. 

It has been observed in this laboratory, as in many others, that compounds, which volatilize from the mass spectrometer direct insertion probe at a certain temperature under electron impact conditions, will often volatilize at a lower temperature (50°C or more) if the analysis is carried out under chemical ionization conditions with reagent gas sweeping around the probe tip and then into the source. For sulfuric acid deposited on a Fluoropore filter, a decrease in volatilization temperature of approximately 70°C has been observed for sulfuric acid when the analysis is carried out in the chemical ionization mode. The elution profile is sharper and better defined than that obtained under electron impact conditions. 

Steam-solvent distillation using diethyl ether has been used to remove and analyse for odour and taint from additives in food packaging films. Another technique that has been used is vacuum/thermal extraction. This procedure has been applied to polyamides and fluorocarbon polymers. The procedure is used for the direct isolation or release of volatile components from a polymeric matrix and may involve the combined use of vacuum and heat, as for example in the mass spectrometer direct insertion probe or during dry vacuum distillation. Alternatively, the volatiles may be swept from the heated sample by a flow of inert gas for concentration by freeze trapping and/or collection on to a solid adsorbent prior to thermal or solvent desorption for GC or mass spectrometric (MS) examination. 

Fig. 2. Schematic diagram of the high-resolution double-focusing mass spectrometer. The insert shows an enlarged view of the ion extraction optics for the high-extraction-efficiency mode. P, pusher electrode C, collision chamber B, electron beam (z direction) S, collision chamber exit slit S2, penetrating field extraction slit S3, grounded slit S4 and Ss, deflector electrodes.

The prepared sample must then be introduced into the MS. Liquid samples, usually weakly acidified solutions, can be converted into an aerosol by aspiration into the ICP/MS carrier gas in a mixing tube and inserted as a vapor. Alternatively, the prepared solutions can be applied to a TIMS filament and dried (see Section 17.5.1). The filament is subsequently inserted into the mass spectrometer. Direct volatilization from a furnace is an alternative for some elements. Ablation of a solid surface by a laser followed by direct injection of the aerosol is discussed in Section 17.7.2. 

Direct-exposure probe. Provides for insertion of a sample on an exposed surface, such as a flat surface or a wire, into (rather than up to the entrance of) the ion source of a mass spectrometer. 

Direct-inlet probe. A shaft or tube having a sample holder at one end that is inserted into the vacuum system of a mass spectrometer through a vacuum lock to place the sample near to, at the entrance of, or within the ion source. The sample is vaporized by heat from the ion source, by heat applied from an external source, or by exposure to ion or atom bombardment. Direct-inlet probe, direct-introduction probe, and direct-insertion probe are synonymous terms. The use of DIP as an abbreviation for these terms is not recommended. 

The liquid jet from the DLI probe has to be initiated at atmospheric pressure, i.e. before insertion of the interface into the mass spectrometer, and, for best performance, the spray direction has to be coaxial to the probe. Any deviation from this, however slight, tends to produce changes in the mass spectrum obtained. 

Cl and El are both limited to materials that can be transferred to the ion source of a mass spectrometer without significant degradation prior to ionisation. This is accomplished either directly in the high vacuum of the mass spectrometer, or with heating of the material in the high vacuum. Sample introduction into the Cl source thus may take place by a direct insertion probe (including those of the desorption chemical ionisation type) for solid samples a GC interface for reasonably volatile samples in solution a reference inlet for calibration materials or a particle-beam interface for more polar organic molecules. This is not unlike the options for El operation. 

Pyrolysis mass spectroscopy was conducted with a Hewlett-Packard model 5985B gas chromatograph/quadrupole mass spectrometer, operated at sslO- Torr and 70eV electron-impact ionization energy. Samples were introduced into the mass spectrometer via a glass lined direct insertion probe (DIP). The samples were decomposed in the DIP to a nominal temperature of 300°C at a heating rate of 30°C/min. 

Direct insertion probe pyrolysis mass spectrometry (DPMS) utilises a device for introducing a single sample of a solid or liquid, usually contained in a quartz or other non-reactive sample holder, into a mass spectrometer ion source. A direct insertion probe consists of a shaft having a sample holder at one end [70] the probe is inserted through a vacuum lock to place the sample holder near to the ion source of the mass spectrometer. The sample is vaporized by heat from the ion source or by heat from a separate heater that surrounds the sample holder. Sample molecules are evaporated into the ion source where they are then ionized as gas-phase molecules. In a recent study, Uyar et al. [74] used such a device for studying the thermal stability of coalesced polymers of polycarbonate, PMMA and polylvinyl acetate) (PVAc) [75] and their binary and ternary blends [74] obtained from their preparation as inclusion compounds in cyclodextrins. 

Direct introduction of a sample, either in solid or liquid state, in the ion source of a mass spectrometer may be achieved through two procedures the first one is based on the use of a direct insertion probe (DIP) the second one necessitates a direct exposure probe (DEP). Direct introduction followed by heating of the sample in the ion source of the mass spectrometer is also known as direct temperature resolved mass spectrometry (DTMS). 

The most straightforward tool for the introduction of a sample into a mass spectrometer is called the direct inlet system. It consists of a metal probe (sample rod) with a heater on its tip. The sample is inserted into a cmcible made of glass, metal, or silica, which is secured at the heated tip. The probe is introduced into the ion source through a vacuum lock. Since the pressure in the ion source is 10-5 to 10-6 torr, while the sample may be heated up to 400°C, quite a lot of organic compounds may be vaporized and analyzed. Very often there is no need to heat the sample, as the vapor pressure of an analyte in a vacuum is sufficient to record a reasonable mass spectrum. If an analyte is too volatile the cmcible may be cooled rather than heated. There are two main disadvantages of this system. If a sample contains more than one compound with close volatilities, the recorded spectrum will be a superposition of spectra of individual compounds. This phenomenon may significantly complicate the identification (both manual and computerized). Another drawback deals with the possibility of introducing too much sample. This may lead to a drop in pressure, ion-molecule reactions, poor quality of spectra, and source contamination. 

Fig. 11.1. Conceptual diagrams of a mass spectrometer showing the various functional components. The top diagram represents instruments that employ conventional modes of ionization such as El or Cl. In such instruments, the sample introduction process (for example, direct insertion probe) bridges the atmospheric pressure/high-vacuum interface. The bottom diagram represents instruments that employ the recently developed API techniques such as ESI. Ions are formed outside the vacuum envelope of the instrument and transported into the instrument through the API interface.

The instrumental design is similar to that of other mass spectrometers described above, with the end of the GC column directly inserted into the ion... 

Mass-spectral (MS) Analysis. Mass spectral analyses were obtained using a computerized Finnigan Model 1015 gas chromatograph-mass spectrometer (GC-MS) operated at 70 eV. Samples were introduced via direct insertion probe or by utilizing the GC-MS combination, both operated over a programmed temperature range. 

Junk, G.A. Svec, H.J. A Vacuum Lock for the Direct Insertion of Samples into a Mass Spectrometer. Anal. Chem. 1965, S7, 1629-1630. 

Mass spectrometry. (+)Fast atom bombardment (FAB) mass spectrometry was carried out with a JEOL JMS-SX/SX102A mass spectrometer. Dried samples were dissolved in methanol-water, mixed with (thio-) glycerol, and applied to a direct insertion probe. During the high resolution FAB-MS measurements, a resolving power of 10,000 (10% valley definition) was used. Cesium iodide, glycerol, or polyethylene oxide (MWav = 600) was used to calibrate the mass spectrometer. 

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