LC-APCI

III) East LC-APCI-MS/MS analysis using a short luonolitliie separation eoluiun eoupled to a triple-quadiupole luass speetroiueter operating in luultiple reaetion luonitoring (MRM) detention luode. 

An on-line chromatography/atmospheric pressure chemical ionization tandem mass spectrometry (LC-APCI/MS/MS) methods was developed for rapid screen of pharmacokinetics of different drugs, including 5 (98RCM1216). The electron impact mass spectrum of 5 and ethyl 9,10-difluoro-3-methyl-7-oxo-2,3-dihydro-7Ff-pyrido[l,2,3- fe]-l,4-benzoxazine-6-carboxylate was reported (97MI28). Electron impact/Fourier transform... 

Immunosorbents have also found applicability in on-line SPE analysis. An antibody is immobilized on to a silica support and used as an affinity ligand to retain targeted analytes. Components not recognized by the antibody are not retained and some degree of selectivity is attained. Recoveries of 87-103% were obtained for atrazine, simazine, DEA, propazine, and terbuthylazine at the 0.2 xgL concentration level when using immunosorbent SPE (80 mg silica and 2 mg anti-atrazine and anti-chlortoluron antibodies) on-line with LC/APcI-MS however, this method is not applicable to DIA (0% recovery). This compound may be better retained when using an... 

Instrument HPLC HPLC HPLC HPLC HPLC LC/APCI-MS... 

Applications APCI-MS is often more widely applicable than ESI-MS to the analysis of classes of compounds with a low molecular weight, such as basic drugs and their metabolites, antibiotics, steroids, oestrogens, benzodiazepines, pesticides, surfactants, and most other organic compounds amenable to El. LC-APCI-MS has been used to analyse PET extracts obtained by a disso-lution/precipitation procedure [147]. Other applications of hyphenated APCI mass spectrometric techniques are described elsewhere LC-APCI-MS (Section 7.33.2) and packed column SFC-APCI-MS (Section 73.2.2) for polar nonvolatile organics. 

Applications With the current use of soft ionisation techniques in LC-MS, i.e. ESI and APCI, the application of MS/MS is almost obligatory for confirmatory purposes. However, an alternative mass-spectrometric strategy may be based on the use of oaToF-MS, which enables accurate mass determination at 5 ppm. This allows calculation of the elemental composition of an unknown analyte. In combination with retention time data, UV spectra and the isotope pattern in the mass spectrum, this should permit straightforward identification of unknown analytes. Hogenboom et al. [132] used such an approach for identification and confirmation of analytes by means of on-line SPE-LC-ESI-oaToFMS. Off-line SPE-LC-APCI-MS has been used to determine fluorescence whitening agents (FWAs) in surface waters of a Catalan industrialised area [138]. Similarly, Alonso et al. [139] used off-line SPE-LC-DAD-ISP-MS for the analysis of industrial textile waters. SPE functions here mainly as a preconcentration device. 

LC-APCI-MS is a derivative of discharge-assisted thermospray, where the eluent is ionised at atmospheric pressure. In an atmospheric pressure chemical ionisation (APCI) interface, the column effluent is nebulised, e.g. by pneumatic or thermospray nebulisation, into a heated tube, which vaporises nearly all of the solvent. The solvent vapour acts as a reagent gas and enters the APCI source, where ions are generated with the help of electrons from a corona discharge source. The analytes are ionised by common gas-phase ion-molecule reactions, such as proton transfer. This is the second-most common LC-MS interface in use today (despite its recent introduction) and most manufacturers offer a combined ESI/APCI source. LC-APCI-MS interfaces are easy to operate, robust and do not require extensive optimisation of experimental parameters. They can be used with a wide variety of solvent compositions, including pure aqueous solvents, and with liquid flow-rates up to 2mLmin-1. 

B-QITMS. LC-APCI-ToFMS is still in an early stage of development. LC-API-MS is more general purpose than LC-PB-MS these techniques are complementary. 

Various LC-PB-MS and LC-APCI-MS comparisons have been reported on polymer additive extracts [540, 563,629,630]. The complementary character of the El and APCI modes was confirmed. Yu et al. [630] compared LC-PB-MS and RPLC-UV-APCI-MS for detection and identification of unknown additives (in the 252 to 696 Da range) in an acetonitrile extract from PP (containing Irganox 1076, Naugard XL-1 and a degradation product, NC-4, 3-(3,5-di-f-butyl-4-hydroxyphenyl) propanoic acid, 7,9-di-f-butyl-l-oxaspiro [4,5] deca-6,9-diene-2,8-dione and octadecanol-1). Comparison was based on El data (identification of chemical structure), APCI (MW information CID spectrum with limited fragmentation) and PDA (210 nm). The components were identified by El and confirmed by APCI- (with better sensitivity and linearity) MS and PDA showed... 

The degradation products of Irganox 1010, (MA4, cf Scheme 7.9) from extrusion of PE in mild processing conditions were characterised using LC-APCI-MS [635]. Various decomposition reactions of Irganox 1010 may be envisaged ... 

LC-APCI-MS confirms these degradation pathways. Table 7.67 shows that one or two d i-/ - b u ly 1-4- hydroxy -phenylpropionate side-chains are lost by hydrolysis of the ester groups. 

Figure 7.32 shows the identification of an oxidation product of Irganox 1330 by means of APCI-MS. LC-APCI-MS/MS (high-resolution sector field-ion trap hybrid) has also been used for the analysis (elemental composition and structure) of Irganox PS 802 [636]. 

There is no single LC-MS interface that is ideally suited for all compounds of interest to analytical chemists. It is evident that LC-APCI-MS and LC-PB-MS are currently the LC-MS methods most frequently used for polymer/additive analysis. The two techniques are compared in Table 7.69. When PB and API interfacing techniques are used, much more structural information can be obtained, and unambiguous identification... 

Table 7.69 Comparison of LC-PB-MS and LC-APCI-MS in polymer/additive analysis...

Whereas the components of (known) test mixtures can be attributed on the basis of APCI+/, spectra, it is quite doubtful that this is equally feasible for unknown (real-life) extracts. Data acquisition conditions of LC-APCI-MS need to be optimised for existing universal LC separation protocols. User-specific databases of reference spectra need to be generated, and knowledge about the fragmentation rules of APCI-MS needs to be developed for the identification of unknown additives in polymers. Method development requires validation by comparison with established analytical tools. Extension to a quantitative method appears feasible. Despite the current wide spread of LC-API-MS equipment, relatively few industrial users, such as ICI, Sumitomo, Ford, GE, Solvay and DSM, appear to be somehow committed to this technique for (routine) polymer/additive analysis. 

Fig. 2.7.6. (-)-LC-APCI-MS-MS daughter ion spectra of two C10-alkyldiglucosides (parent ion mjz 481) (Reprinted with permission from [3], Copyright 2000, American...

An industrial blend of ethylene oxide (EO) PEMS marketed as a personal care product was examined by positive ion FIA-APCI-MS and LC-APCI-MS-MS (Fig. 2.8.8) [41]. The FIA-APCI-MS spectrum without LC separation (Fig. 2.8.8(a)) is dominated by ions corresponding to unreacted PEG (m/z 520, 564, 608, 652,...), whilst the ions corresponding to the PEMS (m/z 516, 560, 604, 648,...) could only be clearly observed following LC separation (Fig. 2.8.8(b)). Comparison of the TIC chromatograms of PEMS and PEG (Fig. 2.8.8(c) and (h)) demonstrates the dominance of the PEG by-products in the commercial formulation. It is unclear whether the observed relative intensities are representative of the actual amounts or of the different ionisation efficiencies, due to the confidential nature of the product composition. However, the spectra indicate a trisiloxane surfactant structure of that shown in Fig. 2.8.2 (R = Ac) and FIA-MS analysis of another commercial formulation of this product showed good spectra dominated by the silicone surfactants [48], indicating that the PEG by-product composition can vary significantly in commercially available PEMS formulations. 

Fig. 4.3.4. Effect of composition of a technical mixture used for calibration in the quantification of APEO concentrations of influents and effluents from a wastewater treatment plant. (A) LC-ESI-MS (B) LC-APCI-MS.

Invariably, results obtained for the separate LAS congeners showed that the data obtained with LC-APCI-MS (laboratory 1) were again lower than those obtained with LC-ESI-MS (laboratories 2 and 4), varying between 10% and more than 50% less than the mean of the two higher values. For Ci3LAS the value obtained with APCI was only 16% of the mean of the two values obtained with an ESI-MS interface. Between the two laboratories using ESI-MS, a... 

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