Direct insertion

Preparing the Sample Flame and plasma sources are best suited for the analysis of samples in solution and liquid form. Although solids can be analyzed by direct insertion into the flame or plasma, they usually are first brought into solution by digestion or extraction. 

Direct Insertion Methods (Direct Solids Insertion, DSI)... 

In practice, direct insertion of samples requires a somewhat more elaborate arrangement than might be supposed. The sample must be placed on an electrode before insertion into the plasma flame. However, this sample support material is not an electrode in the usual meaning of the term since no electrical current flows through it. Heating of the electrode is done by the plasma flame. The electrode or probe should have small thermal mass so it heats rapidly, and it must be stable at the high temperatures reached in the plasma flame. For these reasons, the sort of materials used... 

These direct-insertion devices are often incorporated within an autosampling device that not only loads sample consecutively but also places the sample carefully into the flame. Usually, the sample on its electrode is first placed just below the load coil of the plasma torch, where it remains for a short time to allow conditions in the plasma to restabilize. The sample is then moved into the base of the flame. Either this last movement can be made quickly so sample evaporation occurs rapidly, or it can be made slowly to allow differential evaporation of components of a sample over a longer period of time. The positioning of the sample in the flame, its rate of introduction, and the length of time in the flame are all important criteria for obtaining reproducible results. 

Solid samples can be analyzed using a plasma torch by first ablating the solid to form an aerosol, which is swept into the plasma flame. The major ablation devices are lasers, arcs and sparks, electrothermal heating, and direct insertion into the flame. 

If samples are largely pure, single substances, then the sample inlet can be quite simple, as with a direct insertion probe or a gas inlet. However, most analyses require assessment of the number of components, their relative proportions, and their chemical structures. This level... 

For solids, there is now a very wide range of inlet and ionization opportunities, so most types of solids can be examined, either neat or in solution. However, the inlet/ionization methods are often not simply interchangeable, even if they use the same mass analyzer. Thus a direct-insertion probe will normally be used with El or Cl (and desorption chemical ionization, DCl) methods of ionization. An LC is used with ES or APCI for solutions, and nebulizers can be used with plasma torches for other solutions. MALDI or laser ablation are used for direct analysis of solids. 

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. 

Another method devised for direct sampling of solids involves direct insertion of the sample into the plasma. In this procedure the sample is delivered through the central tube of the torch. The sample may be premixed with graphite powder. 

In the direct insertion technique, the sample (liquid or powder) is inserted into the plasma in a graphite, tantalum, or tungsten probe. If the sample is a liquid, the probe is raised to a location just below the bottom of the plasma, until it is dry. Then the probe is moved upward into the plasma. Emission intensities must be measured with time resolution because the signal is transient and its time dependence is element dependent, due to selective volatilization of the sample. The intensity-time behavior depends on the sample, probe material, and the shape and location of the probe. The main limitations of this technique are a time-dependent background and sample heterogeneity-limited precision. Currently, no commercial instruments using direct sample insertion are available, although both manual and h ly automated systems have been described. ... 

Vinyl fluorinated zinc reagents can be prepared by two different methods (1) capture of the corresponding vinyllithium reagent at low temperatures with a zinc salt and (2) direct insertion of zinc into a carbon-halogen bond. 

A direct insertion of sulfur dioxide into a C—C bond has been observed under photochemical conditions 3 (equation 72) a related CH insertion followed by an intramolecular sulfinate to carbonyl addition yields the same system 3 (equation 73). A further sulfolene synthesis utilizes a three-component reaction see equation 74 (cf. Section IV below) 35. 

A/E) (Roth, 1972b). In contrast, no polarization is observed in the absence of a sensitizer, despite the fact that ethylbenzene is produced. This is consistent with a direct insertion of singlet methylene into the C—H bond, but it could also arise from an abstraction-recombination mechanism if the lifetime of the intermediate radical-pair were too short to permit a significant amount of Tq-S mixing. 

That this mechanism can take place under suitable conditions has been demonstrated by isotopic labeling and by other means. However, the formation of disproportionation and dimerization products does not always mean that the free-radical abstraction process takes place. In some cases these products arise in a different manner.We have seen that the product of the reaction between a carbene and a molecule may have excess energy (p. 247). Therefore it is possible for the substrate and the carbene to react by mechanism 1 (the direct-insertion process) and for the excess energy to cause the compound thus formed to cleave to free radicals. When this pathway is in operation, the free radicals are formed after the actual insertion reaction. 

Thermally labile compounds may also be studied - for example, the El specffa from the condensation products from the reaction between dimedone and substituted phenylbenzopyrans obtained via a particle-beam interface show less thermal degradation than do the mass spectra obtained using a direct-insertion probe [10]. 

The direct insertion probe consists of a metal sample holder drilled to accept standard melting point capillaries up to 1 inch in length. This is inserted into the ion source through a vacuum lock and may be heated to 250°C at varying rates. 

The reactivity of [TpBut]BeH is summarized in Scheme 17. The Be-H moiety is cleaved by both Mel and I2 to give [TpBut]BeI, and by H2S to give [TpBut]BeSH. Furthermore, [TpBut]BeSH is also obtained by the direct insertion of elemental sulfur into the Be-H bond. 

Section 6.4 deals with other EI-MS analyses of samples, i.e. analyses using direct introduction methods (reservoir or reference inlet system and direct insertion probe). Applications of hyphenated electron impact mass-spectrometric techniques for poly-mer/additive analysis are described elsewhere GC-MS (Section 7.3.1.2), LC-PB-MS (Section 7.3.3.2), SFC-MS (Section 13.2.2) and TLC-MS (Section 7.3.5.4). 

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. 

The DCI probe is particularly attractive for samples that are susceptible to thermal decomposition, although it can equally well be used as a general means of introducing samples into the ionisation source, i.e. as an alternative to the direct insertion probe. The types of sample which benefit most from DCI probing are higher-molecular-weight, less-volatile compounds, organometallics, and any thermally sensitive compounds [40,67]. DCI is considered to be a soft ionisation technique. 

Quantitative analysis using FAB is not straightforward, as with all ionisation techniques that use a direct insertion probe. While the goal of the exercise is to determine the bulk concentration of the analyte in the FAB matrix, FAB is instead measuring the concentration of the analyte in the surface of the matrix. The analyte surface concentration is not only a function of bulk analyte concentration, but is also affected by such factors as temperature, pressure, ionic strength, pH, FAB matrix, and sample matrix. With FAB and FTB/LSIMS the sample signal often dies away when the matrix, rather than the sample, is consumed therefore, one cannot be sure that the ion signal obtained represents the entire sample. External standard FAB quantitation methods are of questionable accuracy, and even simple internal standard methods can be trusted only where the analyte is found in a well-controlled sample matrix or is separated from its sample matrix prior to FAB analysis. Therefore, labelled internal standards and isotope dilution methods have become the norm for FAB quantitation. 

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