Thermospray technique, interfacing with HPLC

Particle beam LC-MS is a rapidly developing complimentary interface to thermospray techniques and provides a method of linking conventional HPLC systems with eluant flow-rates of 0.3-1.0mlmin , to an El ion source to obtain the classical El spectra which can be compared to conventional reference spectra (Figure 7.12). A capillary GC column may be connected to the same interface [10]. LC eluant enters the interface together with a stream of helium to form an aerosol of droplets which move through the desolvation chamber maintained at room temperature and pressure. The... 

Continuous flow FAB has been demonstrated for HPLC detection of the components of ditallowdimethylammonium chloride fabric softener. In this technique, the matrix substance is added to the HPLC colunrn effluent prior to introduction to the MS. MS-MS was demonstrated for confirmation of identity. While continuous flow FAB is typically performed with aqueous HPLC systems, the solubility of dialkyl quats is such that normal phase HPLC with nonpolar solvents is preferred. Lawrence was able to adapt a FAB system to this analysis, using a matrix solution of 75 25 glycerol/methanol (118). The use of FAB for analysis of surfactants has dropped off sharply with the availability of electrospray and thermospray interfaces for HPLC-MS. 

A group of techniques employing differential selection of solute ions relies on nebulisation and ionisation of the eluent, with some discrimination of ion selection in favour of the solute. Main representatives are APCI [544] and thermospray [545]. In a thermospray interface a supersonic jet of vapour and small droplets is generated out of a heated vaporiser tube. Controlled, partial vaporisation of the HPLC solvent occurs before it enters the ion source. Ionisation of nonvolatile analytes takes place by means of solvent-mediated Cl reactions and ion evaporation processes. Most thermospray sources are fitted with a discharge electrode. When this is used, the technique is called plasmaspray (PSP) or discharge-assisted thermospray. In practice, many... 

In thermospray interfaces, the column effluent is rapidly heated in a narrow bore capillary to allow partial evaporation of the solvent. Ionisation occurs by ion-evaporation or solvent-mediated chemical ionisation initiated by electrons from a heated filament or discharge electrode. In the particle beam interface the column effluent is pneumatically nebulised in an atmospheric pressure desolvation chamber this is connected to a momentum separator where the analyte is transferred to the MS ion source and solvent molecules are pumped away. Magi and Ianni (1998) used LC-MS with a particle beam interface for the determination of tributyl tin in the marine environment. Florencio et al. (1997) compared a wide range of mass spectrometry techniques including ICP-MS for the identification of arsenic species in estuarine waters. Applications of HPLC-MS for speciation studies are given in Table 4.3. 

Whilst the object of this chapter has been to show the extent and type of HPLC technique that is used today in today s environmental laboratories, there are a number of less routine techniques that may or may not have an impact on routine environmental monitoring. One of the most potentially important of these is the use of LC-MS. The problems associated with using LC-MS for trace analysis are twofold one is the usual LC-MS problem of interfacing the second is that of sensitivity of detector. The interfacing problem may well continue to have partial (compared with GC-MS interfacing) solutions such as FAB, and thermospray, etc. However, even given the advances arising from electrospray interfaces the answer may well be to move away from LC-MS to supercritical fluids and SFC-MS. 

The emergence of thermospray ionization heralded a first ideal interface for a wide range of molecules [30,31]. With the introduction of this interface, LC/MS was accepted as a routine analytical technique. A major beneficiary of this interface was the pharmaceutical industry, which used this system to characterize drugs and metabolites. The construction and basic principle of thermospray ion source was discussed in Section 2.14 briefly, it consists of a heated probe, a desolvation chamber, and an ion extraction skimmer. When passed through a resistively heated capillary, the HPLC effluent, emerges as a mist of fine droplets into a heated desolvation chamber. Ionization of the solute molecules occurs by direct evaporation of the preformed ions or solvent-mediated chemical ionization. Thus, unlike the interfaces discussed above, the thermospray system acts as an ion source as well as an interface. Thermospray is ideally suited to coupling with conventional wide-bore columns. It is, however, confined primarily to reversed-phase HPLC separations, and it is less compatible with nonvolatile... 

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